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Sugar-metal ion interactions: The coordination behavior of cesium ion with lactose, d -arabinose and l -arabinose
Journal of Molecular Structure 1109 (2016) 179e191
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Journal of Molecular Structure journal homepage: http://www.elsevier.com/locate/molstruc
Sugar-metal ion interactions: The coordination behavior of cesium ion with lactose, D-arabinose and L-arabinose Ye Jiang a, c, Junhui Xue d, Xiaodong Wen a, Yanjun Zhai c, Limin Yang a, *, Yizhuang Xu b, **, Guozhong Zhao e, Kuan Kou e, Kexin Liu a, Jia'er Chen a, Jinguang Wu b a
State Key Laboratory of Nuclear Physics and Technology, Institute of Heavy Ion Physics, School of Physics, Peking University, Beijing, 100871, China Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China c College of Pharmacy, Liaoning University of Traditional Chinese Medicine, Dalian, 116600, China d Department of Chemistry, Renmin University of China, Beijing, 100872, China e Department of Physics, Capital Normal University, Beijing, 100037, China b
a r t i c l e i n f o
a b s t r a c t
Article history: Received 25 September 2015 Received in revised form 23 December 2015 Accepted 4 January 2016 Available online 7 January 2016
The novel cesium chlorideelactose complex (CsCl$C12H22O10 (Cs-Lac), cesium chloride-D-arabinose and Larabinose complexes (CsCl$C5H10O5, Cs-D-Ara and Cs-L-Ara) have been synthesized and characterized using X-ray diffraction, FTIR, FIR, THz and Raman spectroscopies. Csþ is 9-coordinated to two chloride ions and seven hydroxyl groups from five lactose molecules in Cs-Lac. In the structures of CsCl-D-arabinose and CsCl-L-arabinose complexes, two kinds of Csþ ions coexist in the structures. Cs1 is 10coordinated with two chloride ions and eight hydroxyl groups from five arabinose molecule; Cs2 is 9coordinated to three chloride ions and six hydroxyl groups from five arabinose molecules. Two coordination modes of arabinose coexist in the structures. a-D-arabinopyranose and a-L-arabinopyranose appear in the structures of Cs-D-Ara and Cs-L-Ara complexes. FTIR and Raman results indicate variations of hydrogen bonds and the conformation of the ligands after complexation. FIR and THz spectra also confirm the formation of Cs-complexes. Crystal structure, FTIR, FIR, THz and Raman spectra provide detailed information on the structure and coordination of hydroxyl groups to metal ions in the cesium chlorideelactose, cesium chloride-D- and L-arabinose complexes. © 2016 Elsevier B.V. All rights reserved.
Keywords: Cesium Lactose Arabinose Complexation Crystal structure THz
1. Introduction The interactions between metal ions and carbohydrates may be involved in many important biochemical processes, such as the transport and storage of metal ions, stabilization of membrane structures, binding of glycoproteins to cell surfaces, toxic metal metabolism, binding of protein to sugar, and so on [1e3]. It has also been exploited in metal-catalyzed enantioselective synthesis, therapeutic agents, catalysts and diagnostic tracers, etc. [4e9]. A series of crystal structures of metal-sugar complexes have been reported, most of them are related to calcium and lanthanide complexes [10e15]. The coordination structures of metalsaccharides complexes are complicated, even metal-promoted
* Corresponding author. ** Corresponding author. E-mail addresses: [email protected] (L. Yang), [email protected] (Y. Xu). http://dx.doi.org/10.1016/j.molstruc.2016.01.005 0022-2860/© 2016 Elsevier B.V. All rights reserved.
deprotonation of alcoholic OH groups in aqueous solutions of low pH can be observed [16e18]. Na and K ions are the most important metal ions in vivo. Sodium-potassium pump is an important process in life. Transport is related to the binding of Na, K with biological molecules. No crystal structure of K with carbohydrates is available at present. The crystal structures of Na-carbohydrate complexes are limited [19e21], which is not enough to serve as references of the structures of K with saccharides. In the periodic table of the elements, K is located between Na and Cs. K with saccharide may demonstrate properties between Na-saccharide and Cs-saccharide. Thus, the structures of Cs-saccharides complexes are helpful in understanding the physiological nature of Ksaccharide interactions. Here CsCl-lactose, CsCl-D-arabinose and CsCl-L-arabinose complexes are investigated to simulate the interactions between K and carbohydrates. Lactose (C12H22O11) is a disaccharide consisting of D-glucose and D-galactose moieties joined by a b-1-4-glycosidic linkage. The crystal structures of CaBr2-lactose (C12H22O11$CaBr2$7H2O) and
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CaCl2-lactose (C12H22O11$CaCl2$7H2O) have been reported [11,22,23]. Rao group has reported the synthesis and characterization of Fe(III)-lactose [24], Ce-lactose [25], Pr and Nd-lactose and arabinose complexes under alkaline conditions by various spectral and analytical techniques, and appropriate structures are assigned [26]. The interactions of lactose with metal ions in water solution have been studied by employing conductance measurements, ultrasonic velocity, density and viscosity, volumetric parameters, etc. [27e31]. The single crystal structures of CaCl2-b-L-arabinose (C5H10O5$CaCl2$4H2O), CaCl2-a-L -arabinose (C5H10O5$CaCl2$4H2O) prepared in neutral condition, [(en)2Pd2(b-D-Arap1,2,3,4 H4)] under alkaline conditions, and bis(4-dehydro-L-arabinose) calcium methanol bishydrate (Ca(C5H9O5)2$CH3OH$2H2O) have been reported [18,32e34]. The reactions between L-arabinose and Mg2þ, Sr2þ, Ba2þ, Zn2þ, Cd2þ, Hg2þ and UO2þ have been studied in 2 aqueous solution and adducts by means of FTIR, 1H NMR spectroscopy, molar conductivity and X-ray powder diffraction measurements [35e39]. Experimental and theoretical studies of sodium cation interactions with D-arabinose, xylose, glucose, and galactose suggest the possible coordination structures [40]. Interactions of D- or L-arabinose with metal ions in aqueous solution have been investigated by volumetric parameters, 1H NMR and circular dichroism spectra, etc. [41e43]. Crystal structures provide definite information about coordination structures, bond lengths and bond angles of metal-sugar complexes. Here novel structures of cesium chlorideelactose (denoted as Cs-Lac), cesium chloride-D-arabinose (denoted as Cs-DAra) and cesium chloride-L-arabinose (denoted as Cs-L-Ara) are observed. The single crystals of metal-sugar complexes are difficult to prepare. For the compounds that are surely coordination compounds but which cannot form a single crystal for the X-ray analysis, IR, Raman, FIR and THz spectra are effective methods to deduce the unknown structures, so here the relationship between these spectra and crystal structure results is also discussed. The complexity of Cs binding with carbohydrate may be a reference for understanding the mechanism of sodium-potassium pump. 2. Experimental section 2.1. Materials and methods CsCl, lactose, D- and L-arabinose were purchased from J&K company in China, and were used without further purification. 2.2. Synthesis of Cs-Lac, Cs-D-Ara and Cs-L-Ara complex The procedures of preparation of the cesium chlorideelactose complex (Cs-Lac) was as follows: 1.010 g CsCl and 1.027 g lactose were dissolved in 4 ml H2O/6 ml ethanol and heated on a water bath at about 80 C. Small aliquots of EtOH (Analytical Reagent) were periodically added to the solution during the heating process to prolong the reaction time, leading to the formation of the complexes. The total reaction time was about 120 h and about 38 ml H2O/ethanol were used. Then the concentrated solutions were cooled down for crystallization. The Cs-Lac complex is stable, and the percentage yield of the product was about 50%. The same method was applied for the preparation of cesium chloride-D-arabinose (Cs-D-Ara) and cesium chloride-L-arabinose (Cs-L-Ara). For Cs-D-Ara, 0.253 g CsCl and 0.168 g D-arabinose were dissolved in 4 ml H2O/6 ml ethanol and heated on a water bath at about 80 C. The total reaction time was about 120 h and about 60 ml H2O/ethanol were used. The Cs-D-Ara complex is stable, and the percentage yield was about 40%. For Cs-L-Ara, 0.758 g CsCl and 0.451 g L-arabinose were used.
The total reaction time was about 200 h and about 60 ml H2O/ ethanol were used. The Cs-D-Ara complex is stable, and the percentage yield was about 40%. Anal. Calcd for Cs-Lac (CsCl$C12H21O11): C, 28.28; H, 4.15. Found: C, 28.05; H, 4.21. Anal. Calcd for Cs-D-Ara (CsCl$C5H10O5): C, 18.86; H, 3.16. Found: C, 18.12; H, 3.01. Anal. Calcd for Cs-L-Ara (CsCl$C5H10O5): C, 18.86; H, 3.16. Found: C, 18.69; H, 3.07. The characteristic IR bands are as follows: for Cs-Lac, 3422, 3357, 3286, 2979, 2936, 2890, 2866, 1462, 1440, 1420, 1369, 1321, 1283, 1264, 1198, 1166, 1150, 1119, 1094, 1063, 1033, 1018, 987, 916, 903, 876, 846, 786, 771, 722, 688 and 661 cm1. For Cs-D-Ara, 3346, 2940, 2903, 2874, 1460, 1438, 1408, 1389, 1375, 1343, 1300, 1257, 1210, 1139, 1122, 1104, 1079, 1058, 1000, 946, 932, 891, 871, 840, 782 and 696 cm1. For Cs-L-Ara, 3354, 2973, 2940, 2905, 2863, 2825, 1467, 1436, 1390, 1376, 1343, 1302, 1275, 1256, 1214, 1139, 1122, 1104, 1079, 1060, 1034, 1001, 945, 928, 891, 871, 840, 781 and 694 cm1. 2.3. Physical measurements Data for the metal complexes were collected on a Xcalibur, Eos, Gemini diffractometer using fine-focus sealed tube (l ¼ 0.71073 Å) at 105(2) K. Using Olex2, the structures of three metal complexes were solved with the XS structure solution program using direct method and refined with the XL refinement package using least squares minimization. Anisotropic thermal parameters were used for the non-hydrogen atoms and isotropic parameters for the hydrogen atoms. Hydrogen atoms were added geometrically and refined using a riding model [44]. The mid-IR spectra in the 4000600 cm1 region were measured on a Nicolet Magna IN10 spectrometer using micro-IR method at 4 cm1 resolution and 64 scans. The variable temperature FTIR spectra of the metal complexes were measured on a Bruker VERTEX 80v FTIR spectrometer with variable temperature attachment at 4 cm1 resolution and 32 scans. The Elemental analyses were carried out on an Elementar Vario EL spectrometer. The THz absorption spectra in the 0.2e2.6 THz region were recorded on the THz time-domain device of Capital Normal University of China. The experimental apparatus for terahertz transmission measurements was discussed in detail elsewhere [45]. The far-IR spectra of the molecules in the 65050 cm1 region were measured using polyethylene pellet method and were taken on a Bruker VERTEX 80v FTIR spectrometer at room temperature and at 4 cm1 resolution and 32 scans. The Raman spectra were recorded on a Nicolet 6700 FTIR NXR FT-Raman module at 4 cm1 resolution and 256 scans. 3. Results and discussion 3.1. Crystal structures of cesium chlorideelactose complex and cesium chloride-D-, and L-arabinose complexes The crystal structures of cesium chlorideelactose and cesium chloride-D-, and L-arabinose complexes are shown in Fig. 1. All H atoms are not shown here for clarity. The crystal data and structure refinements of Cs-Lac, Cs-D-Ara and Cs-L-Ara complexes are listed in Table 1. The selected bond lengths and bond angles for Cs-Lac, CsD-Ara and Cs-L-Ara complexes are listed in Table S1. The symmetry space group of Cs-Lac is P21, which is the same with a-lactose itself. Csþ is 9-coordinated to two chloride ions, O50 , O60 from one lactose molecule, two O20 atoms from two lactose molecules, O3 and O4 from the fourth lactose molecule and O3 from the fifth lactose in Cs-Lac, so one Csþ is connecting with five lactose molecules. For one lactose molecule, its O50 (the oxygen atom in the ring) and O60 is coordinated to the first cesium ion, O20
Y. Jiang et al. / Journal of Molecular Structure 1109 (2016) 179e191
Fig. 1. The crystal structures of the metal complexes (a) Cs-Lac, (b) Cs-D-Ara, (c) Cs-L-Ara.
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Table 1 Crystal data and structure refinement for Cs-Lac, Cs-D-Ara and Cs-L-Ara complexes. Compound
Cs-Lac
Cs-D-Ara
Cs-L-Ara
Empirical formula CCDC No. Formula weight T(K) Crystal system, space group Unit cell dimensions V (Å3) Reflections collected/ unique Rint Z, Calculated density (Mg/ m3) Absorption coefficient (mm1) F(000) Crystal size (mm3) q range for data collection Limiting indices Completeness to qmax Data/restraints/ parameters Goodness-of-fit on F2 Final R indices [I > 2s (I)] R indices (all data) Largest diff. peak and hole, e$Å3 Flack parameter
CsCl$C12H22O11
CsCl$C5H10O5
CsCl$C5H10O5
1003812 510.66 102.1 Monoclinic, P21
1003813 318.49 97.5 Triclinic, P1
1005408 318.49 102.0 Triclinic, P1
a ¼ 4.85591(13) Å, b ¼ 23.9725(6) Å, c ¼ 7.7387(2) Å a ¼ g ¼ 90 b ¼ 104.664(3) 871.50(4) 6302/3395
a ¼ 5.438(7) Å b ¼ 7.584(2) Å c ¼ 11.7194(18) Å, a ¼ 96.322(17), b ¼ 102.86(5), g ¼ 91.64(5) 467.6(6) 6095/3675
a ¼ 5.4456(3) Å b ¼ 7.5810(4) Å c ¼ 11.7202(7) Å, a ¼ 96.323(5) b ¼ 102.859(5), g ¼ 91.684(4) 468.12(4) 6173/3680
0.0214 2, 1.946
0.0260 2, 2.262
0.0258 2, 2.260
2.333
4.228
4.223
508 0.40 0.30 0.30
304 0.17 0.10 0.08
304 0.40 0.30 0.05
3.21e26.00
3.06e26.00
3.06e25.99
5 h 5, 29 k 29, 9 l 9 99.8%
6 h 6, 9 k 9, 14 l 14 99.9%
6 h 6, 9 k 9, 14 l 14 99.8%
3395/1/230
3675/3/217
3680/3/220
1.108
1.012
1.061
R1 ¼ 0.0228, wR2 ¼ 0.0463
R1 ¼ 0.0242, wR2 ¼ 0.0493
R1 ¼ 0.0280, wR2 ¼ 0.0694
R1 ¼ 0.0233, wR2 ¼ 0.0465
R1 ¼ 0.0250, wR2 ¼ 0.0498
R1 ¼ 0.0283, wR2 ¼ 0.0699
0.49/0.66
0.40/0.54
1.23/0.89
0.007(12)
0.014(16)
0.017(19)
atom is coordinated to the second and the third cesium ions, O3 and O4 are coordinated to the fourth Csþ and O3 is also coordinated to the fifth Csþ, so its O3, O4, O20 , O50 and O60 are involved in the coordination. One chloride ion is connected with two cesium ions. CsO distances are from 3.110 to 3.513 Å; the average CseO distance is 3.240 Å. CsCl distances are 3.5578(10) and 3.6317(9) Å. The CeC bond lengths are 1.496(6), 1.509(5), 1.518(5), 1.519(5), 1.522(5), 1.523(5), 1.525(5) and 1.527(5) Å, CeO bond lengths are 1.388(4), 1.399(4), 1.410(4), 1.422(4), 1.423(4), 1.426(4), 1.427(4), 1.436(4), 1.440(4), 1.443(4) and 1.449(4) Å. The OeCeC bond angles are 106.3(3), 106.7(3), 107.3(3), 107.7(3), 108.9(3), 109.0(3), 109.1(3), 109.2(3), 109.7(3), 109.8(3), 110.1(3), 110.7(3), 111.2(3), 111.6(3), 111.9(3), 112.0(3), 112.1(3), 112.7(3), 112.8(3) and 114.1(3) , CeCeC bond angles are 108.1(3), 108.7(3), 108.8(3), 109.3(3), 110.1(3), 111.6(3), 111.9(3) and 113.7(3) and the bond angle of CeOeC is 112.3(3), 113.6(3) and 116.8(3) for Cs-Lac complex. Here lactose coordinates to five metal ions in Cs-Lac. In the corresponding calciumelactose complexes (CaCl2$C12H22O11$7H2O and CaBr2$C12H22O11$7H2O), O3 and O4 of galactose part, O20 and O30 of glucose part of lactose, and 4 water molecules are coordinated with Ca2þ, so Ca2þ is 8-coordinated, Cl or Br ions are hydrogen bonded [11]. Therefore, lactose has different coordination modes to Csþ and Ca2þ, which may be related to large ion radii of Csþ. Comparison of the stereochemistry of the galactose and glucose moieties in Cs-Lac with that in the crystal structure of a-lactose monohydrate indicates that the Csþ interactions are responsible for
small conformational changes at the Csþ binding sites, which is similar to Ca2þ in Ca-lactose. For example, the bond angle of C1eO1eC40 is 116.8(3) in Cs-Lac, which is similar to 116.88(17) in a-Lactose monohydrate itself [46]. The torsion angles related to coordinated hydroxyl groups have small changes (from 1.5 to 5.9 ): the torsion angles of O5eC50 eC60 eO60 , O10 eC10 eC20 eO20 , O50 eC10 eC20 eO20 , C40 eC30 eC20 eO20 , O30 eC30 eC20 eO20 , O20 eC20 e C10 eO50 , O20 eC20 eC10 eO10 are 62.8(4), 63.4(4), 173.3(3), 178.8(3), 56.3(4), 173.3(3) and 63.4(4) (64.3(2), 57.8(3), 179.21(18), 175.98(19), 62.2(3), 179.21(18) and 57.8(3) in a-Lactose monohydrate) [46]. For D- and L-arabinose, their coordination structures with Csþ are different with the reported crystal structures of Ca-arabinose complexes. D- and L-arabinose complexes have the same coordination structures, so here only CsCl-L-arabinose complex is discussed in detail. Two kinds of Csþ ions coexist in the structure of CsL-Ara. Cs1 is 10-coordinated with five arabinose molecule: O1 and O2 of the first arabinose molecule; O6, O9 and O10 of the second arabinose molecule, O2 from the third arabinose molecule, O8 from the fourth arabinose molecule, O10 from the fifth arabinose molecule, and two chloride ions. Cs2 is 9-coordinated to five arabinose molecules: O3, O5, O6 and O7 from four arabinose molecules, respectively, O3 and O4 from the fifth arabinose molecule, and three chloride ions. The two a-L-arabinopyranose have different coordination manners. For example, the ring oxygen atoms (O5 and O10), O5 is coordinated to Cs210 (the bond length of
Y. Jiang et al. / Journal of Molecular Structure 1109 (2016) 179e191
O5eCs210 is 3.042(4) Å), O10 is coordinated to Cs1 and Cs11 (the bond lengths of O10eCs1 and O10eCs11 are 3.250(4) and 3.398(4) Å). For the two arabinose molecules, all of the hydroxyl groups are involved in the coordination, O1, O4, O5, O7, O8 and O9 are coordinated to one Csþ, O2, O3, O6 and O10 are coordinated to two metal ions. Correspondingly, two kinds of chloride ions exist in the structure of Cs-L-Ara, one is coordinated to two metal ions and the other is connecting with three metal ions. The coordination structures of Cs-D-Ara and Cs-L-Ara are different with Ca-L -arabinose complex (CaCl2,C5H10O5,4H2O), in which Ca2þ is bound to two symmetry related arabinose molecules (through O3 and O4 in one and through O1 and O5 in the other as well as four water molecules) and two chloride ions are hydrogenbonded [31], or bis(4-dehydro-L-arabinose) calcium methanol bishydrate (Ca(C5H9O5)2$CH3OH$2H2O), in which Ca2þ is bound to O1, O2 of two sugar molecules as well as O3, O4 of the other two sugar molecules, and the ligand is 4-dehydro-L-arabinose [18]. On 2þ 2þ the basis of spectral similarities, Mg2þ, Sr2þ, Ba2þ, UO2þ 2 , Zn , Cd 2þ and Hg were found to be six-coordinated or eight-coordinated in the corresponding sugar complexes, binding to two moieties in a similar fashion to that of the Ca(II) ion and the two or four water molecules [35e39]. But here Csþ has different structure compared to other reported metal-arabinose complexes as shown in Fig. 1, each Cs ion is coordinated to five arabinose molecules, chloride ions are also coordinated to Csþ and no water appears in the structure of Cs-L-Ara complex. For Cs-L-Ara complex, the CseO distances are 3.042(4), 3.062(4), 3.132(4), 3.162(4), 3.250(4), 3.268(4), 3.295(4), 3.365(4), 3.398(4), 3.422(4), 3.531(4), 3.545(4), 3.630(4) and 3.652(4) Å (CaeO distances are from 2.328 to 2.703 Å in Ca-L-Ara), CseCl distances are 3.3828(13), 3.5054(14), 3.5862(14), 3.6207(14) and 3.9303(14) Å. The CeC bond lengths are 1.501(8), 1.510(7), 1.516(8), 1.517(8), 1.519(7), 1.521(7), 1.525(7) and 1.528(8) Å, CeO bond lengths are 1.389(6), 1.407(7), 1.425(7), 1.427(7), 1.428(7), 1.434(6), 1.435(6), 1.435(7), 1.436(7) and 1.440(7) Å, CeOeC bond angles are 111.4(4) and 111.9(4) (113.9 for Ca-L-Ara), OeCeO bond angles are 107.0(4) and 107.2(4) (103.4 for Ca-L-Ara). OeCeC bond angles are 107.0(4), 107.0(5), 107.2(5), 107.7(4), 107.8(4), 107.9(4), 108.1(4), 109.6(4), 109.9(4), 110.2(4), 110.4(4), 110.5(4), 110.8(4), 110.9(5), 111.6(4) and 112.2(4) . CeCeC bond angles are 108.4(5), 108.7(5), 111.0(4), 111.5(5), 111.7(4) and 112.1(5) in Cs-L-Ara, respectively. The metal hydroxyl interactions produce small conformational changes in the sugar at the metal-binding sites. For example, the bond angles of CeOeC are 111.4(4) and 111.9(4) in Cs-L-Ara (112.7(6) for arabinose itself, 113.9 for Ca-L-Ara), which show small deviation from the ligand [47], Csþ and Ca2þ introduce different changes of conformation of ligands. a-D-Arabinopyranose and a-L-Arabinopyranose appear in the structures of Cs-D-Ara and Cs-L-Ara complexes. For Cs-L-Ara, the hydrogen bonds data show that ring oxygen atoms (O5 and O10) do not form hydrogen bonds. The only OeH … O hydrogen bond is O7eH7 … O4 [x, y, z1] (171.84 , 2.770 Å). Other hydrogen bonds are OeH … Cl hydrogen bonds: O3eH3 … Cl1 [x1, y, z] (147.46 , 3.117 Å); O9eH9 … Cl1 [x, yþ1, z] (166.10 , 3.159 Å); O2eH1 … Cl1 (155.56 , 3.117 Å); O8eH8 … Cl2 (149.01, 3.100 Å); O6eH6 … Cl2 [xþ1, y1, z] (155.57, 3.033 Å); O1eH1B … Cl1 [x, yþ1, z] (174.61, 3.112 Å); O4eH4A … Cl2 [x, y1, zþ1] (167.22 , 3.142 Å). These OeH … Cl hydrogen bonds are related to the bands at 3352, 3334, 3331, 3328, 3320, 3318 and 3316 cm1 in the second derivative results. The only OeH … O hydrogen bond is related to 3204 cm1 in the IR spectrum. The coordination modes of lactose and arabinose with Ca2þ and þ Cs are shown in Fig. 2 and Table 2, which indicate that lactose and arabinose have different coordination structures with Ca2þ and Csþ. Here lactose, D-arabinose and L-arabinose have novel coordination
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modes in Csþ-complexes, they are coordinated to five cesium ions, even two coordination modes of arabinose coexist to form complicated coordination structures. Chloride ions are coordinated to metal ions and no water molecule exists in the three structures. The structures of cesium with lactose, D-arabinose and L-arabinose are different with calcium ion. For example, for Ca-L-arabinose, Ca2þ is bound to two symmetry related arabinose molecules (through O3 and O4 in one and through O1 and O5 in the other) as well as four water molecules. The observed coordination number is 9 or 10 for Csþ-complexes, but Ca2þ is usually 8-coordinated. The various coordination structures and coordination number difference for Ca2þ and Csþ are related to large ion radii of Csþ. Chloride ion coordinates to Csþ and water molecules are absent in the known Cs-saccharide complexes, but they are coordinated or hydrogen-bonded for some Ca-saccharide complexes. Csþ is inclined to coordinate to several saccharide molecules and one saccharide is coordinated with several Csþ. Cesium complexes with other ligands also can have structures different with other metal ions. For example, cesium chloride-D-ribose, myo-inositol and cholic acid complexes have different coordination structures compared to calcium and lanthanide ions [48,49]. 3.2. FTIR spectra of cesium chlorideelactose complex and cesium chloride-D- and L-arabinose complexes The FTIR spectra of lactose, CsCl-lactose complex, D-arabinose, CsCl-D-arabinose complex, L-arabinose and CsCl-L-arabinose complex are shown in Fig. 3. Compared to the IR spectrum of lactose, the changes in the IR spectrum of Cs-Lac indicate the formation of cesium chlorideelactose complex. For the spectrum of Cs-Lac, in the 3600e2600 cm1 region, 3422, 3357 and 3286 cm1 bands are observed (3524, 3378, 3337 and 3275 cm1 bands for lactose), which are related to the hydrogen bonds after complexation. For investigation of the hydrogen bonds, the variable temperature FTIR spectra of Cs-Lac have been measured and shown in Fig. 4. The variable temperature FTIR spectra and micro-IR spectrum are measured on different spectrometers and using different methods. Absorption water exists for KBr pellet method, so the two FTIR spectra at room temperature have some differences. The weak band at 3521 cm1 can be observed, 3417, 3376, 3355, 3321 and 3286 cm1 bands are identified using KBr pellet on the Bruker FTIR spectrometer (3422, 3357 and 3286 cm1 for micro-IR spectrum). At low temperature (184 C) the bands at 3331 and 3251 cm1 are emphasized, and the peak positions have shifts compared to the spectrum at room temperature (3520, 3447, 3413, 3370, 3348, 3331, 3314, 3281, 3251 cm1 and a weak band at 3389 cm1 for the spectrum at 184 C, but 3521, 3417, 3376, 3355, 3321 and 3286 cm1 for the spectrum at room temperature). At high temperature (200 C) the bands are not so obvious. The hydrogen bond data show that there are 9 hydrogen bonds, including OeH … O and OeH … Cl hydrogen bonds in Cs-Lac. To compare the nOH and the hydrogen bonds data, 10 bands can be observed at 184 C, maybe the bands can be assigned to the hydrogen bonds according to the hydrogen bond distances, i.e., 3520 cm1 is the influence of absorption water, 3447 cm1 (O4eH4 … Cl1 [xþ1, y1/2, -zþ3] (169.99 , 3.111 Å); 3413 cm1 (O10 H10 … Cl1 [xþ1, y, z1], 160.80 , 3.103 Å); 3389 cm1 (O3eH3 … Cl1 [-x, y1/2, -zþ2] (126.74 , 3.055 Å); 3370 cm1 (O3eH3 … O2 (117.33 , 2.868 Å); 3348 cm1 (O6eH6 … O2 [xþ1, y, zþ1] (153.64 , 2.797 Å); 3331 cm1 (O30 H30 … O5 (159.31, 2.735 Å); 3314 cm1 (O2eH2A … O6 [x, y, z1] (160.52 , 2.711 Å); 3281 cm1 (O20 H20 … O60 [xþ1, y, zþ1] (169.39 , 2.702 Å) and 3251 cm1 (O60 H60 … O30 [ x, y, z1] (173.57, 2.702 Å), respectively. The relatively weak bands at 2979, 2945, 2936, 2912, 2890 and 2866 cm1 for Cs-Lac (2985, 2978, 2945, 2933, 2918, 2900 and
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Fig. 2. The coordination modes of lactose and arabinose with metal ions (a) Ca-lactose (b) Cs-lactose; (c) Ca-a-L-arabinose; (d) Ca-b-L-arabinose, (e) bis(4-dehydro-L-arabinose) calcium methanol bishydrate (f) Cs-arabinose; (g) Cs-arabinose. Table 2 The coordination modes of the metal-lactose and arabinose complexes11,18,31. Stoichiometry
C. N.
Space group
OH
Coordination mode
Coordinated H2O
C12H22O11$CaBr2$7H2O C12H22O11$CaCl2$7H2O CsCl$C12H22O11 CaCl2$C5H10O5$4H2O(a-L-arabinose) CaCl2$C5H10O5$4H2O (b-L-arabinose) Ca(C5H9O5)2$CH3OH$2H2O(b-L-arabinose) CsCl$C5H10O5(a-D-arabinose) CsCl$C5H10O5(a-L-arabinose)
8 8 9 8 8 8 10 and 9 10 and 9
P212121 P212121 P21 C2 C2 P43212 P1 P1
4 4 7 4 4 8 8 or 6 8 or 6
2(a) 2(a) 2(b) 2(c) 2(d) 2(e) 2(f) (g) 2(f) (g)
4 4
Cl
2 4 4 2 or 3 2 or 3
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Fig. 3. FTIR spectra of lactose, Cs-Lac, D-arabinose, Cs-D-Ara, L-arabinose and Cs-L-Ara in the 36002600 and 1700650 cm1 region.
2887 cm1 bands for lactose) are related to nCH. The band shifts and the changes of relative intensities indicate the formation of metal complexes and rearrangement of CH chain. No band can be observed in the 1700e1600 cm1 region, which indicate that no water exists in the structure of Cs-Lac. The peak positions and relative intensities of the bands in the 1500600 cm1 region for Cs-Lac are changed compared to lactose.
dCH2 has shifted from 1469 to 1455 cm1 in lactose to 1462 cm1 in Cs-Lac. The nCO, nCC and dCOH localized at 1168, 1143, 1116, 1095,
1084, 1073, 1059, 1037 and 1020 cm1 in the lactose spectrum are shifted to 1166, 1150, 1119, 1094, 1080, 1063, 1033 and 1018 cm1 in the Cs-Lac spectrum, which indicate the coordination of hydroxyl groups to Csþ ion [50e53]. The bands in the 950e800 cm1 region related to dCOH, dCCH and dOCH are located at 846, 876, 903 and
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Fig. 4. The variable temperature FTIR spectra of Cs-Lac, Cs-D-Ara and Cs-L-Ara complexes in the 3600e3000 cm1 region.
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187
Fig. 5. FIR spectra of lactose, Cs-Lac, D-arabinose, Cs-D-Ara, L-arabinose and Cs-L-Ara in the 650e50 cm1 region.
916 cm1 in the Cs-Lac spectrum (876, 899 and 916 cm1 bands for lactose). The shifts are not obvious, so maybe only small conformation changes occur after complexation.
The FTIR spectra of D-arabinose, L-arabinose and their cesium chloride complexes shown in Fig. 3 indicate the formation of cesium chloride-D-arabinose and cesium chloride-L-arabinose
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complexes. The IR spectra of D-arabinose and L-arabinose are similar, and the IR spectra of Cs-D-Ara and Cs-L-Ara are also similar, which indicate that their cesium chloride complexes have similar structures. The nOH vibrations are located at 3530 and 3334 cm1 for D-arabinose (3535 and 3331 cm1 for L-arabinose), and the bands are shifted to 3346 cm1 in Cs-D-Ara (3354 cm1 for Cs-LAra), which indicate the changes of hydrogen bonds after complexation. The nCH vibrations are located at 2998, 2969, 2956, 2939, 2895 and 2863 cm1 in D-arabinose (2997, 2968, 2955, 2939, 2894 and 2867 cm1 in L-arabinose), and the bands are shifted to 2973, 2940, 2903, 2874 and 2833 cm1 in Cs-D-Ara (2973, 2940, 2905, 2863 and 2825 cm1 in Cs-L-Ara), which indicate the changes of CH chain of D-arabinose and L-arabinose after complexation. There is no band at ~1640 cm1, which show that no water exists in the structures of Cs-D-Ara and Cs-L-Ara. The dCH2 band at 1474 cm1 in D-arabinose (1473 cm1 in Larabinose) is shifted to 1460 cm1 in Cs-D-Ara (1467 cm1 in Cs-LAra), which also indicate the changes of CH chain. The bands in the fingerprint region also show fine structures after complexation, which indicate the formation of the metal complexes. For example, the bands at 1372, 1354, 1316, 1257 and 1232 cm1 in D-arabinose (1371, 1354, 1315, 1257 and 1231 cm1 in L-arabinose) related to d(CCH), d(OCH) and d(COH), etc. [38,50,51] are shifted to 1389, 1375, 1343, 1300, 1257 and 1210 cm1 in Cs-D-Ara (1390, 1376, 1343, 1302, 1275, 1256 and 1214 cm1 in Cs-L-Ara), which indicate the conformation changes of the ligands. The bands at 1134, 1104, 1092, 1066 and 1053 cm1 in D-arabinose (1132, 1103, 1090, 1065 and 1051 cm1 in L-arabinose) mainly related to n(CO) and n(CC) are corresponding to 1139, 1122, 1104, 1096, 1079, 1058 and 1036 cm1 in Cs-D-Ara (1139, 1122, 1104, 1079, 1060 and 1034 cm1 in Cs-LAra), which indicate the coordination of hydroxyl groups of the ligands. The bands at 998 and 994 cm1 are related to n(CO) and d(CCO) in L-arabinose, which are shifted to 1001 cm1 in Cs-L-Ara. The band at 893 cm1 in D-arabinose (892 cm1 in L-arabinose) related to n(CC) and d(CH), is shifted to 891 and 871 cm1 in Cs-DAra and Cs-L-Ara. The bands at 785 and 679 cm1 in D-arabinose (784 and 678 cm1 in L-arabinose) are related to t (CO) and d(CCO), which are shifted to 782 and 696 cm1 in Cs-D-Ara (781 and 694 cm1 in Cs-L-Ara). The results show the formation of the metal complexes and the similarity of the structures of CsCl-D- and Larabinose complexes. The variable temperature FTIR spectra of Cs-D-Ara and Cs-L-Ara shown in Fig. 4 indicate the changes of the hydrogen bonds after complexation. In the 3600e3000 cm1 region, the bands at 3507, 3319 and 3204 cm1 at low temperature are observed in Cs-L-Ara, among them the band at 3204 cm1 is a new band. Second derivative results indicate that the 3319 cm1 band has child bands located at 3352, 3334, 3331, 3328, 3320, 3318 and 3316 cm1. At high temperature the peak positions are shifted to higher frequencies (3527 and 3344 cm1). For Cs-D-Ara, the bands are located at 3525 and 3342 cm1 at 187 C, and 3535 and 3347 cm1 at 200 C. No new band appears at low temperature for Cs-D-Ara. The bands at ~3520 cm1 may be related to absorption water.
196 and 175 cm1 are belonging to MO vibrations, 148 and 131 cm1 bands may be related to CseCl vibrations. The bands may be also related to MOeH, MOeC, OMO deformation or out of plane vibrations, etc. The peak positions and relative intensities of the bands in Cs-Lac are changed compared to lactose, which confirm the formation of metal complex. The FIR spectra of D-, L-arabinose and their cesium chloride complexes also indicate the formation of the metal complex. The changes in peak positions and relative intensities are evident after complexation, for example, the bands in the 400e100 cm1 region related to nMeO and nMeCl are shifted from 402, 370, 317, 278, 228, 162, 148 and 115 cm1 in D-arabinose (400, 371, 317, 275, 228, 161, 147 and 113 cm1 in L-arabinose) to 400, 374, 332, 294, 230, 205 and 146 cm1 in Cs-D-Ara (400, 374, 331, 319, 293, 231, 205 and 145 cm1 in Cs-L-Ara), which reflect the changes of the conformation of D- and L-arabinose and the formation of MO and MCl bonds. THz bands are mainly related to lattice vibrations and hydrogen bonds, etc. [55] The THz spectrum of lactose is extensively investigated and the bands at ~0.53, 1.23, 1.42 and 1.86 THz are observed [57e64]. The THz absorption bands of cesium chlorideelactose complex shown in Fig. 6 are located at 0.50, 1.05, 1.52, 1.95, 2.19 and 2.46 THz (17, 35, 51, 65, 73 and 82 cm1) for Cs-Lac. The FIR and THz spectra confirm the formation of the metal complex and the changes of hydrogen bonds. D- and L-arabinose also have similar THz spectra. The bands are located at 1.48, 2.16 and 2.36 THz (49, 72 and 79 cm1) for Darabinose (1.49, 2.16 and 2.34 THz, 50, 72 and 78 cm1 for L-arabinose) [65]. After complexation, the bands are shifted to 1.32, 1.66 and 2.23 THz (44, 55 and 74 cm1) for Cs-D-Ara, 1.31, 1.62 and 2.15 THz (44, 54 and 72 cm1, but the bands are not obvious) for CsL-Ara. The band positions are similar for Cs-D-Ara and Cs-L-Ara, which also indicate that they have the same coordination structures.
3.3. FIR and THz spectra of lactose, cesium chlorideelactose complex, D-, L-arabinose and their cesium chloride complexes FIR and THz are effective methods to determine the formation of metal-ligand complexes [54e56]. The FIR spectra of lactose, D- and L-arabinose and their cesium chloride complexes are shown in Fig. 5. In the 65050 cm1 region the bands of Cs-Lac are located at 614, 557, 480, 444, 433, 423, 390, 357, 293, 256, 196, 175, 148, 131 and 73 cm1. The bands near 200 cm1 are usually assigned as MO vibrations for metal-sugar complexes [54], so the bands at 293, 256,
Fig. 6. THz absorption spectra of Cs-Lac, Cs-L-Ara.
D-arabinose,
Cs-D-Ara, L-arabinose and
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Fig. 7. Raman spectra of lactose, Cs-Lac, L-arabinose and Cs-L-Ara in the 3500e2700 and 1500e100 cm1 region.
3.4. Raman spectra of lactose, L-arabinose and their cesium chloride complexes The Raman spectra of lactose, L-arabinose and their cesium chloride complexes are shown in Fig. 7. The Raman spectra of Darabinose and CsCl-D-Arabinose complex are not shown here because the quality of their Raman spectra is not good for the reason of luminescence effect. For lactose and Cs-Lac, the intensities of nOH are decreased in Raman spectra compared to corresponding IR spectra and the bands are shifted from 3385, 3349, 3296 and 3224 cm1 in lactose to 3427, 3408, 3364 and 3300 cm1 in Cs-Lac. nCH are located at 2980, 2947, 2936, 2918 and 2890 cm1 in lactose, the bands are shifted to 2982, 2947, 2939, 2918 and 2892 cm1 in Cs-Lac. Many bands appear in the fingerprint region, which are related to nCO, nCC, dCCO and dCOC, etc. dCH2 is shifted from 1471 to 1456e1464 cm1; uCH2 is shifted from 1347 to 1335 to 1340 and 1324 cm1, tCH2 is shifted from 1264 to 1273 cm1 [49e52]. nCO, nCC and dCOH located at 1140, 1121, 1088, 1055, 1041 and 1021 cm1 are shifted to 1147, 1119, 1089, 1063, 1039 and 1015 cm1 after complexation, which reflect the coordination of hydroxyl groups of lactose. The bands at 359, 317, 260, 178 and 139 cm1 related to nCseO and nCseCl in Cs-Lac. These bands have different shifts
compared to the spectrum of lactose, which indicate the formation of cesiumelactose complex. The main bands are similar for the IR and Raman spectra of Cs-Lac, for example, the bands related to nCO, nCC and dCOH are located at 1147, 1119, 1089, 1063, 1039 and 1015 cm1 in the Raman spectrum, and 1150, 1119, 1094, 1063, 1033 and 1018 cm1 in the IR spectrum. The Raman spectra of L-arabinose and cesium chloride-Larabinose complex also indicate the formation of metal complex. The weak nOH are located at 3388 cm1 in Cs-L-Ara (3338 cm1 in L-arabinose), and the nCH vibrations are at 2978, 2941, 2907, 2876 and 2853 cm1 (3002, 2958, 2940 and 2891 cm1 for Larabinose), which show the changes of CH chain. The bands at 1379, 1358, 1314 and 1260 cm1 in L-Ara mainly related to dCOH, dCCH and dOCH are shifted to 1376, 1351 and 1260 cm1 in Cs-LAra. The nCC and nCO vibrations mainly located at 1138, 1095 and 1054 cm1 in L-Ara are shifted to 1140, 1081 and 1061 cm1 in Cs-L-Ara. The band at 995 cm1 related to nCO and dCCO is shifted to 1003 cm1 in Cs-L-Ara. The strong band at 844 cm1 in L-Ara has small shift to 843 cm1 in Cs-L-Ara. The bands at 333, 280, 233 and 148 cm1 in Cs-L-Ara mainly related to nMO and nMCl confirms the formation of metal complex. Compared the IR and Raman spectra of Cs-L-Ara, some of the bands are similar, for example, 1376 (1376), 1351 (1343), 1260 (1256), 1140 (1139),
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1081 (1079), 1061 (1060), 1003 (1001), 947 (945), 933 (928), 894 (891), 873 (871), 843 (840), 784 (781) and 699 (694) cm1 in Raman (IR). Raman is sensitive to the nonpolar group, such as CH chain structure, but IR is more clearly show the bind of Csþ with the polar group of carbohydrate. The results confirm the formation of Cs-L-Ara complex.
deposited with the Cambridge Crystallographic Data Centre as supplementary publication with CCDC Nos. 1003812, 1003813 and 1005408. Copies of the data can be obtained free of charge on application with the Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax þ44-1223-336-033; e-mail: [email protected]).
4. Conclusions
References
CsCl-lactose, CsCl-D-arabinose and CsCl-L-arabinose complexes have been obtained and characterized. For CsCl-lactose complex, Cs-Lac, the single crystal structure results show that Csþ is 9coordinated to two chloride ions, O50 , O60 from the first lactose molecule, O20 from the second lactose molecule, O20 from the third lactose molecule, O3 and O4 from the fourth lactose molecule and O3 from the fifth lactose, so one Csþ is connecting with five lactose molecules. For one lactose molecule, its O50 (the oxygen atom in the ring) and O60 is coordinated to one cesium ion, O20 atom is coordinated to two cesium ions, O3 and O4 are coordinated to the fourth Csþ and O3 is also coordinated to the fifth Csþ, so its O3, O4, O20 , O50 and O60 are involved in the coordination. One chloride ion is connecting with two cesium ions. For CsCl-L-arabinose complex, two kinds of Csþ ions coexist in the structures. Cs1 is 10-coordinated with five arabinose molecule: O1 and O2 of the first arabinose molecule; O6, O9 and O10 of the second arabinose molecule, O2 from the third arabinose molecule, O8 from the fourth arabinose molecule, O10 from the fifth arabinose molecule, and two chloride ions. Cs2 is 9-coordinated to O3 of the first arabinose molecule, O5 of the second arabinose molecule, O6 of the third arabinose molecule, O7 of the fourth arabinose molecules, O3 and O4 from the fifth arabinose molecule, and three chloride ions. The two a-L-arabinopyranose molecules have different coordination manners in Cs-L-Ara. CsCl-D-arabinose complex has similar structure with CsCl-L-arabinose. Compared to other metal ions, Csþ often has more complicated coordination structures. Here it can coordinate to five sugar molecules to form novel structures. FTIR, variable temperature FTIR spectra, FIR, THz and Raman spectra confirm the formation of the metal complex and the changes of hydrogen bonds. The crystal structures and spectroscopic results provide detailed information of metalsaccharides interactions. Acknowledgments Financial support from National Natural Science Foundation of China for the grants (21001009 and 50973003), the State Key Project for Fundamental Research of MOST (2011CB808304) and National High-tech R&D Program of China (863 Program) of MOST (2010AA03A406) and the Scientific Research Project of Beijing Municipal Commission of Education and Beijing Natural Science Foundation (Grant No. KZ201310028032) are gratefully acknowledged. The authors thank Prof. Jian Hao (Beijing University of Chemical Technology) and Prof. Xiang Hao (Institute of Chemistry, Chinese Academy of Sciences), for invaluable assistance with the Xray crystallography. The authors also thank Prof. Nanyan Fu (Fuzhou University) for her constructive opinion. Appendix A. Supplementary data Supplementary data related to this article can be found at http:// dx.doi.org/10.1016/j.molstruc.2016.01.005. Appendix B Crystallographic data, excluding structure factors, have been
[1] B. Gyurcsik, L. Nagy, Coord. Chem. Rev. 203 (2000) 81e148. [2] C.G. Hartinger, A.A. Nazarov, S.M. Ashraf, P.J. Dyson, B.K. Keppler, Curr. Med. Chem. 15 (2008) 2574e2591. [3] C. Vetter, P. Pornsuriyasak, J. Schmidt, N.P. Rath, T. Ruffer, A.V. Demchenko, D. Steinborn, Dalton Trans. 39 (2010) 6327e6338. [4] G.H. Li, A. Badkar, H. Kalluri, A.K. Banga, J. Pharm. Sci. 99 (2010) 1931e1941. [5] T. Storr, M. Merkel, G.X. Song-Zhao, L.E. Scott, D.E. Green, M.L. Bowen, K.H. Thompson, B.O. Patrick, H.J. Schugar, C. Orvig, J. Am. Chem. Soc. 129 (2007) 7453e7463. [6] N. Taccardi, D. Assenbaum, M.E.M. Berger, A. Bosmann, F. Enzenberger, R. Wolfel, S. Neuendorf, V. Goeke, N. Schodel, H.-J. Maass, H. Kistenmacher, P. Wasserscheid, Green Chem. 12 (2010) 1150e1156. [7] M. Gottschaldt, U.S. Schubert, Chem. Eur. J. 15 (2009) 1548e1557. [8] I. Garcia, M. Marradi, S. Penades, Nanomedicine 5 (2010) 777e792. [9] V. Oliveri, G.I. Grasso, F. Bellia, F. Attanasio, M. Viale, G. Vecchio, Inorg. Chem. 54 (2015) 2591e2602. [10] S.J. Angyal, D.C. Craig, Carbohydr. Res. 241 (1993) 1e8. [11] W.J. Cook, C.E. Bugg, Structures of calcium-carbohydrate complexes, in: B. Pullman, N. Goldblum (Eds.), Metal-ligand Interactions in Organic Chemistry and Biochemistry, Part 2, 1977, pp. 231e256. [12] L.M. Yang, X.H. Hua, J.H. Xue, Q.H. Pan, L. Yu, W.H. Li, Y.Z. Xu, G.Z. Zhao, L.M. Liu, K.X. Liu, J.E. Chen, J.G. Wu, Inorg. Chem. 51 (2012) 499e510. [13] Y.E. Alekseev, A.D. Garnovskii, Y.A. Zhdanov, Uspekhi Khimii 67 (1998) 723e744. [14] T. Allscher, X. Kaestele, G. Kettenbach, P. Kluefers, T. Kunte, Chem. Asian. J. 2 (2007) 1037e1045. [15] S. Yano, M. Otsuka, Sugar-metal ion interactions, in: H. Sigel (Ed.), Metal Ions in Biological Systems, vol. 32, 1996, pp. 27e60. [16] N. Buzas, T. Gajda, L. Nagy, E. Kuzmann, A. Vertes, K. Burger, Inorg. Chim. Acta 274 (1998) 167e176. [17] L.M. Yang, Y.Z. Xu, Y.L. Wang, S.W. Zhang, S.F. Weng, K. Zhao, J.G. Wu, Carbohydr. Res. 340 (2005) 2773e2781. [18] B. Hu, D. Yu, K. Huang, S.J. Yu, Chin. J. Struct. Chem. 34 (2015) 764e770. [19] C.A. Accorsi, V. Bertolasi, V. Ferretti, G. Gilli, Carbohydr. Res. 191 (1989) 91e104. [20] C.A. Accorsi, F. Bellucci, V. Bertolasi, V. Ferretti, G. Gilli, Carbohydr. Res. 191 (1989) 105e116. [21] Z. Peralta-Inga, G.P. Johnson, M.K. Dowd, J.A. Rendleman, E.D. Stevens, A.D. French, Carbohydr. Res. 337 (2002) 851e861. [22] C.E. Bugg, J. Am. Chem. Soc. 95 (1973) 908e913. [23] C.E. Bugg, W.J. Cook, J. Chem. Soc.-Chem. Commun. 12 (1972) 727e729. [24] K. Geetha, M.S.S. Raghavan, S.K. Kulshreshtha, R. Sasikala, C.P. Rao, Carbohydr. Res. 271 (1995) 163e175. [25] A. Mukhopadhyay, E. Kolehmainen, C.P. Rao, Carbohydr. Res. 324 (2000) 30e37. [26] A. Mukhopadhyay, E. Kolehmainen, C.P. Rao, Carbohydr. Res. 328 (2000) 103e113. [27] P.K. Banipal, V. Singh, T.S. Banipal, J. Chem. Thermodyn. 42 (2010) 90e103. [28] P.K. Banipal, T.S. Banipal, J.C. Ahluwalia, B.S. Lark, J. Chem. Thermodyn. 34 (2002) 1825e1846. [29] M.L. Swartz, R.A. Bernhard, T.A. Nickerson, J. Food Sci. 43 (1978) 93e97. [30] Vishnu, V.S. Mishra, Carbohydr. Res. 89 (1981) 55e63. [31] R. Palani, S. Balakrishnan, J. Indian Chem. Soc. 88 (2011) 431e436. [32] A. Terzis, Cryst. Struct. Comm. 7 (1978) 95e99. [33] P. Klufers, T. Kunte, Chem. Eur. J. 9 (2003) 2013e2018. [34] H.A. Tajmir-Riahi, Biophys. Chem. 25 (1986) 271e276. [35] H.A. Tajmir-Riahi, J. Inorg. Biochem. 27 (1986) 65e74. [36] H.A. Tajmir-Riahi, Carbohydr. Res. 127 (1984) 1e8. [37] H.A. Tajmir-Riahi, J. Inorg. Biochem. 22 (1984) 55e64. [38] H.A. Tajmir-Riahi, Monatsh. Chem. 118 (1987) 245e254. [39] A.L. Heaton, P.B. Armentrout, J. Phys. Chem. A 112 (2008) 10156e10167. [40] K.L. Zhuo, J.J. Wang, H.H. Zheng, X.P. Xuan, Y. Zhao, J. Solut. Chem. 34 (2005) 155e170. [41] J. Parada, S. Bunel, E. Moraga, C. Ibarra, N.D. Gillitt, C.A. Bunton, Polyhedron 20 (2001) 2223e2230. [42] P.A.M. Williams, S.B. Etcheverry, E.J. Baran, Carbohydr. Res. 6 (2000) 41e47. [43] O.V. Dolomanov, L.J. Bourhis, R.J. Gildea, J.A.K. Howard, H. Puschmann, J. Appl. Cryst. 42 (2009) 339e341. [44] G.M. Sheldrick, Acta Crystallogr. Sect. A Found. Crystallogr. 64 (2008) 112e122. [45] Y. Hu, X.H. Wang, L.T. Guo, C.L. Zhang, H.B. Liu, X.C. Zhang, Acta Phys. Sin. 54 (2005) 4124e4128. [46] J.H. Smith, S.E. Dann, M.R.J. Elsegood, S.H. Dale, C.G. Blatchford, Acta Cryst. E61 (2005) o2499eo2501.
Y. Jiang et al. / Journal of Molecular Structure 1109 (2016) 179e191 [47] A. Hordvik, Acta Chem. Scand. 15 (1961) 16e30. [48] H.J. Hu, J.H. Xue, X.D. Wen, W.H. Li, C. Zhang, L.M. Yang, Y.Z. Xu, G.Z. Zhao, X.X. Bu, K.X. Liu, J.E. Chen, J.G. Wu, Inorg. Chem. 52 (2013) 13132e13145. [49] Y. Sun, R.D. Soloway, Y.Z. Han, G.D. Yang, X.Z. Wang, Z.J. Liu, Z.L. Yang, Y.Z. Xu, J.G. Wu, Steroids 67 (2002) 385e392. [50] J.G. Wu, Modern Fourier Transform Spectroscopic Techniques and its Applications, Science and Technology References Press, Beijing, 1994. [51] S.F. Weng, Fourier Transform Infrared Spectrometer, Chemical Industry Press, Beijing, 2005. [52] J. De Gelder, K. De Gussem, P. Vandenabeele, L. Moens, J. Raman Spectrosc. 38 (2007) 1133e1147. [53] M. Kacurakova, M. Mathlouthi, Carbohydr. Res. 284 (1996) 145e157. [54] L.Q. Yang, J.G. Wu, Q. Zhou, J. Bian, Y.M. Yang, D.F. Xu, G.X. Xu, Mikrochim. Acta 14 (1997) 251e252. [55] L.M. Yang, G.Z. Zhao, W.H. Li, Y.F. Liu, X.X. Shi, X.F. Jia, K. Zhao, X.Y. Lu, Y.Z. Xu, D.T. Xie, J.G. Wu, J.E. Chen, Spectrochim. Acta A 73 (2009) 884e891. [56] R.J. Falconer, A.G. Markelz, J. Infrared Milli Terahz Waves 33 (2012) 973e988. [57] D.G. Allis, A.M. Fedor, T.M. Korter, J.E. Bjarnason, E.R. Brown, Chem. Phys. Lett. 440 (2007) 203e209.
191
[58] B.B. Jin, Z.X. Chen, Z. Li, J.L. Ma, R. Fu, C.H. Zhang, J. Chen, P.H. Wu, in: 34th International Conference on Infrared, Millimeter, and Terahertz Waves, 1 & 2, 2009, pp. 362e363. [59] S. Yamauchi, Y. Imai, H. Yokota, M. Tonouchi, in: Proc. SPIE 8011, 22nd Congress of the International Commission for Optics: Light for the Development of the World, 2011, p. 80118L. [60] X.J. Ma, H.W. Zhao, G.F. Liu, T. Ji, Z.Y. Zhang, B. Dai, Spectrosc. Spect. Anal. 29 (2009) 2885e2888. [61] E. Jung, J. Kim, Y. Han, K. Moon, M. Lim, H. Han, Biochip J. 2 (2008) 296e299. [62] J.E. Bjarnason, E.R. Brown, T.M. Korter, Terahertz for military and security applications V, in: Proceedings of the Society of Photo-optical Instrumentation Engineers (SPIE), vol. 6549, 2007. L5490eL5490. [63] E.R. Brown, J.E. Bjarnason, A.M. Fedor, T.M. Korter, Appl. Phys. Lett. 90 (2007) 061908. [64] S. Saito, T.M. Inerbaev, H. Mizuseki, N. Igarashi, R. Note, Y. Kawazoe, Jpn. J. Appl. Phys. 45 (2006) L1156eL1158. [65] M. Ge, H.W. Zhao, T. Ji, X.H. Yu, W.F. Wang, W.X. Li, Sci. China-Chem. 35 (2005) 441e445.
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Sugar-metal ion interactions: The coordination behavior of cesium ion with lactose, D-arabinose and L-arabinose Ye Jiang a, c, Junhui Xue d, Xiaodong Wen a, Yanjun Zhai c, Limin Yang a, *, Yizhuang Xu b, **, Guozhong Zhao e, Kuan Kou e, Kexin Liu a, Jia'er Chen a, Jinguang Wu b a
State Key Laboratory of Nuclear Physics and Technology, Institute of Heavy Ion Physics, School of Physics, Peking University, Beijing, 100871, China Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China c College of Pharmacy, Liaoning University of Traditional Chinese Medicine, Dalian, 116600, China d Department of Chemistry, Renmin University of China, Beijing, 100872, China e Department of Physics, Capital Normal University, Beijing, 100037, China b
a r t i c l e i n f o
a b s t r a c t
Article history: Received 25 September 2015 Received in revised form 23 December 2015 Accepted 4 January 2016 Available online 7 January 2016
The novel cesium chlorideelactose complex (CsCl$C12H22O10 (Cs-Lac), cesium chloride-D-arabinose and Larabinose complexes (CsCl$C5H10O5, Cs-D-Ara and Cs-L-Ara) have been synthesized and characterized using X-ray diffraction, FTIR, FIR, THz and Raman spectroscopies. Csþ is 9-coordinated to two chloride ions and seven hydroxyl groups from five lactose molecules in Cs-Lac. In the structures of CsCl-D-arabinose and CsCl-L-arabinose complexes, two kinds of Csþ ions coexist in the structures. Cs1 is 10coordinated with two chloride ions and eight hydroxyl groups from five arabinose molecule; Cs2 is 9coordinated to three chloride ions and six hydroxyl groups from five arabinose molecules. Two coordination modes of arabinose coexist in the structures. a-D-arabinopyranose and a-L-arabinopyranose appear in the structures of Cs-D-Ara and Cs-L-Ara complexes. FTIR and Raman results indicate variations of hydrogen bonds and the conformation of the ligands after complexation. FIR and THz spectra also confirm the formation of Cs-complexes. Crystal structure, FTIR, FIR, THz and Raman spectra provide detailed information on the structure and coordination of hydroxyl groups to metal ions in the cesium chlorideelactose, cesium chloride-D- and L-arabinose complexes. © 2016 Elsevier B.V. All rights reserved.
Keywords: Cesium Lactose Arabinose Complexation Crystal structure THz
1. Introduction The interactions between metal ions and carbohydrates may be involved in many important biochemical processes, such as the transport and storage of metal ions, stabilization of membrane structures, binding of glycoproteins to cell surfaces, toxic metal metabolism, binding of protein to sugar, and so on [1e3]. It has also been exploited in metal-catalyzed enantioselective synthesis, therapeutic agents, catalysts and diagnostic tracers, etc. [4e9]. A series of crystal structures of metal-sugar complexes have been reported, most of them are related to calcium and lanthanide complexes [10e15]. The coordination structures of metalsaccharides complexes are complicated, even metal-promoted
* Corresponding author. ** Corresponding author. E-mail addresses: [email protected] (L. Yang), [email protected] (Y. Xu). http://dx.doi.org/10.1016/j.molstruc.2016.01.005 0022-2860/© 2016 Elsevier B.V. All rights reserved.
deprotonation of alcoholic OH groups in aqueous solutions of low pH can be observed [16e18]. Na and K ions are the most important metal ions in vivo. Sodium-potassium pump is an important process in life. Transport is related to the binding of Na, K with biological molecules. No crystal structure of K with carbohydrates is available at present. The crystal structures of Na-carbohydrate complexes are limited [19e21], which is not enough to serve as references of the structures of K with saccharides. In the periodic table of the elements, K is located between Na and Cs. K with saccharide may demonstrate properties between Na-saccharide and Cs-saccharide. Thus, the structures of Cs-saccharides complexes are helpful in understanding the physiological nature of Ksaccharide interactions. Here CsCl-lactose, CsCl-D-arabinose and CsCl-L-arabinose complexes are investigated to simulate the interactions between K and carbohydrates. Lactose (C12H22O11) is a disaccharide consisting of D-glucose and D-galactose moieties joined by a b-1-4-glycosidic linkage. The crystal structures of CaBr2-lactose (C12H22O11$CaBr2$7H2O) and
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CaCl2-lactose (C12H22O11$CaCl2$7H2O) have been reported [11,22,23]. Rao group has reported the synthesis and characterization of Fe(III)-lactose [24], Ce-lactose [25], Pr and Nd-lactose and arabinose complexes under alkaline conditions by various spectral and analytical techniques, and appropriate structures are assigned [26]. The interactions of lactose with metal ions in water solution have been studied by employing conductance measurements, ultrasonic velocity, density and viscosity, volumetric parameters, etc. [27e31]. The single crystal structures of CaCl2-b-L-arabinose (C5H10O5$CaCl2$4H2O), CaCl2-a-L -arabinose (C5H10O5$CaCl2$4H2O) prepared in neutral condition, [(en)2Pd2(b-D-Arap1,2,3,4 H4)] under alkaline conditions, and bis(4-dehydro-L-arabinose) calcium methanol bishydrate (Ca(C5H9O5)2$CH3OH$2H2O) have been reported [18,32e34]. The reactions between L-arabinose and Mg2þ, Sr2þ, Ba2þ, Zn2þ, Cd2þ, Hg2þ and UO2þ have been studied in 2 aqueous solution and adducts by means of FTIR, 1H NMR spectroscopy, molar conductivity and X-ray powder diffraction measurements [35e39]. Experimental and theoretical studies of sodium cation interactions with D-arabinose, xylose, glucose, and galactose suggest the possible coordination structures [40]. Interactions of D- or L-arabinose with metal ions in aqueous solution have been investigated by volumetric parameters, 1H NMR and circular dichroism spectra, etc. [41e43]. Crystal structures provide definite information about coordination structures, bond lengths and bond angles of metal-sugar complexes. Here novel structures of cesium chlorideelactose (denoted as Cs-Lac), cesium chloride-D-arabinose (denoted as Cs-DAra) and cesium chloride-L-arabinose (denoted as Cs-L-Ara) are observed. The single crystals of metal-sugar complexes are difficult to prepare. For the compounds that are surely coordination compounds but which cannot form a single crystal for the X-ray analysis, IR, Raman, FIR and THz spectra are effective methods to deduce the unknown structures, so here the relationship between these spectra and crystal structure results is also discussed. The complexity of Cs binding with carbohydrate may be a reference for understanding the mechanism of sodium-potassium pump. 2. Experimental section 2.1. Materials and methods CsCl, lactose, D- and L-arabinose were purchased from J&K company in China, and were used without further purification. 2.2. Synthesis of Cs-Lac, Cs-D-Ara and Cs-L-Ara complex The procedures of preparation of the cesium chlorideelactose complex (Cs-Lac) was as follows: 1.010 g CsCl and 1.027 g lactose were dissolved in 4 ml H2O/6 ml ethanol and heated on a water bath at about 80 C. Small aliquots of EtOH (Analytical Reagent) were periodically added to the solution during the heating process to prolong the reaction time, leading to the formation of the complexes. The total reaction time was about 120 h and about 38 ml H2O/ethanol were used. Then the concentrated solutions were cooled down for crystallization. The Cs-Lac complex is stable, and the percentage yield of the product was about 50%. The same method was applied for the preparation of cesium chloride-D-arabinose (Cs-D-Ara) and cesium chloride-L-arabinose (Cs-L-Ara). For Cs-D-Ara, 0.253 g CsCl and 0.168 g D-arabinose were dissolved in 4 ml H2O/6 ml ethanol and heated on a water bath at about 80 C. The total reaction time was about 120 h and about 60 ml H2O/ethanol were used. The Cs-D-Ara complex is stable, and the percentage yield was about 40%. For Cs-L-Ara, 0.758 g CsCl and 0.451 g L-arabinose were used.
The total reaction time was about 200 h and about 60 ml H2O/ ethanol were used. The Cs-D-Ara complex is stable, and the percentage yield was about 40%. Anal. Calcd for Cs-Lac (CsCl$C12H21O11): C, 28.28; H, 4.15. Found: C, 28.05; H, 4.21. Anal. Calcd for Cs-D-Ara (CsCl$C5H10O5): C, 18.86; H, 3.16. Found: C, 18.12; H, 3.01. Anal. Calcd for Cs-L-Ara (CsCl$C5H10O5): C, 18.86; H, 3.16. Found: C, 18.69; H, 3.07. The characteristic IR bands are as follows: for Cs-Lac, 3422, 3357, 3286, 2979, 2936, 2890, 2866, 1462, 1440, 1420, 1369, 1321, 1283, 1264, 1198, 1166, 1150, 1119, 1094, 1063, 1033, 1018, 987, 916, 903, 876, 846, 786, 771, 722, 688 and 661 cm1. For Cs-D-Ara, 3346, 2940, 2903, 2874, 1460, 1438, 1408, 1389, 1375, 1343, 1300, 1257, 1210, 1139, 1122, 1104, 1079, 1058, 1000, 946, 932, 891, 871, 840, 782 and 696 cm1. For Cs-L-Ara, 3354, 2973, 2940, 2905, 2863, 2825, 1467, 1436, 1390, 1376, 1343, 1302, 1275, 1256, 1214, 1139, 1122, 1104, 1079, 1060, 1034, 1001, 945, 928, 891, 871, 840, 781 and 694 cm1. 2.3. Physical measurements Data for the metal complexes were collected on a Xcalibur, Eos, Gemini diffractometer using fine-focus sealed tube (l ¼ 0.71073 Å) at 105(2) K. Using Olex2, the structures of three metal complexes were solved with the XS structure solution program using direct method and refined with the XL refinement package using least squares minimization. Anisotropic thermal parameters were used for the non-hydrogen atoms and isotropic parameters for the hydrogen atoms. Hydrogen atoms were added geometrically and refined using a riding model [44]. The mid-IR spectra in the 4000600 cm1 region were measured on a Nicolet Magna IN10 spectrometer using micro-IR method at 4 cm1 resolution and 64 scans. The variable temperature FTIR spectra of the metal complexes were measured on a Bruker VERTEX 80v FTIR spectrometer with variable temperature attachment at 4 cm1 resolution and 32 scans. The Elemental analyses were carried out on an Elementar Vario EL spectrometer. The THz absorption spectra in the 0.2e2.6 THz region were recorded on the THz time-domain device of Capital Normal University of China. The experimental apparatus for terahertz transmission measurements was discussed in detail elsewhere [45]. The far-IR spectra of the molecules in the 65050 cm1 region were measured using polyethylene pellet method and were taken on a Bruker VERTEX 80v FTIR spectrometer at room temperature and at 4 cm1 resolution and 32 scans. The Raman spectra were recorded on a Nicolet 6700 FTIR NXR FT-Raman module at 4 cm1 resolution and 256 scans. 3. Results and discussion 3.1. Crystal structures of cesium chlorideelactose complex and cesium chloride-D-, and L-arabinose complexes The crystal structures of cesium chlorideelactose and cesium chloride-D-, and L-arabinose complexes are shown in Fig. 1. All H atoms are not shown here for clarity. The crystal data and structure refinements of Cs-Lac, Cs-D-Ara and Cs-L-Ara complexes are listed in Table 1. The selected bond lengths and bond angles for Cs-Lac, CsD-Ara and Cs-L-Ara complexes are listed in Table S1. The symmetry space group of Cs-Lac is P21, which is the same with a-lactose itself. Csþ is 9-coordinated to two chloride ions, O50 , O60 from one lactose molecule, two O20 atoms from two lactose molecules, O3 and O4 from the fourth lactose molecule and O3 from the fifth lactose in Cs-Lac, so one Csþ is connecting with five lactose molecules. For one lactose molecule, its O50 (the oxygen atom in the ring) and O60 is coordinated to the first cesium ion, O20
Y. Jiang et al. / Journal of Molecular Structure 1109 (2016) 179e191
Fig. 1. The crystal structures of the metal complexes (a) Cs-Lac, (b) Cs-D-Ara, (c) Cs-L-Ara.
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Table 1 Crystal data and structure refinement for Cs-Lac, Cs-D-Ara and Cs-L-Ara complexes. Compound
Cs-Lac
Cs-D-Ara
Cs-L-Ara
Empirical formula CCDC No. Formula weight T(K) Crystal system, space group Unit cell dimensions V (Å3) Reflections collected/ unique Rint Z, Calculated density (Mg/ m3) Absorption coefficient (mm1) F(000) Crystal size (mm3) q range for data collection Limiting indices Completeness to qmax Data/restraints/ parameters Goodness-of-fit on F2 Final R indices [I > 2s (I)] R indices (all data) Largest diff. peak and hole, e$Å3 Flack parameter
CsCl$C12H22O11
CsCl$C5H10O5
CsCl$C5H10O5
1003812 510.66 102.1 Monoclinic, P21
1003813 318.49 97.5 Triclinic, P1
1005408 318.49 102.0 Triclinic, P1
a ¼ 4.85591(13) Å, b ¼ 23.9725(6) Å, c ¼ 7.7387(2) Å a ¼ g ¼ 90 b ¼ 104.664(3) 871.50(4) 6302/3395
a ¼ 5.438(7) Å b ¼ 7.584(2) Å c ¼ 11.7194(18) Å, a ¼ 96.322(17), b ¼ 102.86(5), g ¼ 91.64(5) 467.6(6) 6095/3675
a ¼ 5.4456(3) Å b ¼ 7.5810(4) Å c ¼ 11.7202(7) Å, a ¼ 96.323(5) b ¼ 102.859(5), g ¼ 91.684(4) 468.12(4) 6173/3680
0.0214 2, 1.946
0.0260 2, 2.262
0.0258 2, 2.260
2.333
4.228
4.223
508 0.40 0.30 0.30
304 0.17 0.10 0.08
304 0.40 0.30 0.05
3.21e26.00
3.06e26.00
3.06e25.99
5 h 5, 29 k 29, 9 l 9 99.8%
6 h 6, 9 k 9, 14 l 14 99.9%
6 h 6, 9 k 9, 14 l 14 99.8%
3395/1/230
3675/3/217
3680/3/220
1.108
1.012
1.061
R1 ¼ 0.0228, wR2 ¼ 0.0463
R1 ¼ 0.0242, wR2 ¼ 0.0493
R1 ¼ 0.0280, wR2 ¼ 0.0694
R1 ¼ 0.0233, wR2 ¼ 0.0465
R1 ¼ 0.0250, wR2 ¼ 0.0498
R1 ¼ 0.0283, wR2 ¼ 0.0699
0.49/0.66
0.40/0.54
1.23/0.89
0.007(12)
0.014(16)
0.017(19)
atom is coordinated to the second and the third cesium ions, O3 and O4 are coordinated to the fourth Csþ and O3 is also coordinated to the fifth Csþ, so its O3, O4, O20 , O50 and O60 are involved in the coordination. One chloride ion is connected with two cesium ions. CsO distances are from 3.110 to 3.513 Å; the average CseO distance is 3.240 Å. CsCl distances are 3.5578(10) and 3.6317(9) Å. The CeC bond lengths are 1.496(6), 1.509(5), 1.518(5), 1.519(5), 1.522(5), 1.523(5), 1.525(5) and 1.527(5) Å, CeO bond lengths are 1.388(4), 1.399(4), 1.410(4), 1.422(4), 1.423(4), 1.426(4), 1.427(4), 1.436(4), 1.440(4), 1.443(4) and 1.449(4) Å. The OeCeC bond angles are 106.3(3), 106.7(3), 107.3(3), 107.7(3), 108.9(3), 109.0(3), 109.1(3), 109.2(3), 109.7(3), 109.8(3), 110.1(3), 110.7(3), 111.2(3), 111.6(3), 111.9(3), 112.0(3), 112.1(3), 112.7(3), 112.8(3) and 114.1(3) , CeCeC bond angles are 108.1(3), 108.7(3), 108.8(3), 109.3(3), 110.1(3), 111.6(3), 111.9(3) and 113.7(3) and the bond angle of CeOeC is 112.3(3), 113.6(3) and 116.8(3) for Cs-Lac complex. Here lactose coordinates to five metal ions in Cs-Lac. In the corresponding calciumelactose complexes (CaCl2$C12H22O11$7H2O and CaBr2$C12H22O11$7H2O), O3 and O4 of galactose part, O20 and O30 of glucose part of lactose, and 4 water molecules are coordinated with Ca2þ, so Ca2þ is 8-coordinated, Cl or Br ions are hydrogen bonded [11]. Therefore, lactose has different coordination modes to Csþ and Ca2þ, which may be related to large ion radii of Csþ. Comparison of the stereochemistry of the galactose and glucose moieties in Cs-Lac with that in the crystal structure of a-lactose monohydrate indicates that the Csþ interactions are responsible for
small conformational changes at the Csþ binding sites, which is similar to Ca2þ in Ca-lactose. For example, the bond angle of C1eO1eC40 is 116.8(3) in Cs-Lac, which is similar to 116.88(17) in a-Lactose monohydrate itself [46]. The torsion angles related to coordinated hydroxyl groups have small changes (from 1.5 to 5.9 ): the torsion angles of O5eC50 eC60 eO60 , O10 eC10 eC20 eO20 , O50 eC10 eC20 eO20 , C40 eC30 eC20 eO20 , O30 eC30 eC20 eO20 , O20 eC20 e C10 eO50 , O20 eC20 eC10 eO10 are 62.8(4), 63.4(4), 173.3(3), 178.8(3), 56.3(4), 173.3(3) and 63.4(4) (64.3(2), 57.8(3), 179.21(18), 175.98(19), 62.2(3), 179.21(18) and 57.8(3) in a-Lactose monohydrate) [46]. For D- and L-arabinose, their coordination structures with Csþ are different with the reported crystal structures of Ca-arabinose complexes. D- and L-arabinose complexes have the same coordination structures, so here only CsCl-L-arabinose complex is discussed in detail. Two kinds of Csþ ions coexist in the structure of CsL-Ara. Cs1 is 10-coordinated with five arabinose molecule: O1 and O2 of the first arabinose molecule; O6, O9 and O10 of the second arabinose molecule, O2 from the third arabinose molecule, O8 from the fourth arabinose molecule, O10 from the fifth arabinose molecule, and two chloride ions. Cs2 is 9-coordinated to five arabinose molecules: O3, O5, O6 and O7 from four arabinose molecules, respectively, O3 and O4 from the fifth arabinose molecule, and three chloride ions. The two a-L-arabinopyranose have different coordination manners. For example, the ring oxygen atoms (O5 and O10), O5 is coordinated to Cs210 (the bond length of
Y. Jiang et al. / Journal of Molecular Structure 1109 (2016) 179e191
O5eCs210 is 3.042(4) Å), O10 is coordinated to Cs1 and Cs11 (the bond lengths of O10eCs1 and O10eCs11 are 3.250(4) and 3.398(4) Å). For the two arabinose molecules, all of the hydroxyl groups are involved in the coordination, O1, O4, O5, O7, O8 and O9 are coordinated to one Csþ, O2, O3, O6 and O10 are coordinated to two metal ions. Correspondingly, two kinds of chloride ions exist in the structure of Cs-L-Ara, one is coordinated to two metal ions and the other is connecting with three metal ions. The coordination structures of Cs-D-Ara and Cs-L-Ara are different with Ca-L -arabinose complex (CaCl2,C5H10O5,4H2O), in which Ca2þ is bound to two symmetry related arabinose molecules (through O3 and O4 in one and through O1 and O5 in the other as well as four water molecules) and two chloride ions are hydrogenbonded [31], or bis(4-dehydro-L-arabinose) calcium methanol bishydrate (Ca(C5H9O5)2$CH3OH$2H2O), in which Ca2þ is bound to O1, O2 of two sugar molecules as well as O3, O4 of the other two sugar molecules, and the ligand is 4-dehydro-L-arabinose [18]. On 2þ 2þ the basis of spectral similarities, Mg2þ, Sr2þ, Ba2þ, UO2þ 2 , Zn , Cd 2þ and Hg were found to be six-coordinated or eight-coordinated in the corresponding sugar complexes, binding to two moieties in a similar fashion to that of the Ca(II) ion and the two or four water molecules [35e39]. But here Csþ has different structure compared to other reported metal-arabinose complexes as shown in Fig. 1, each Cs ion is coordinated to five arabinose molecules, chloride ions are also coordinated to Csþ and no water appears in the structure of Cs-L-Ara complex. For Cs-L-Ara complex, the CseO distances are 3.042(4), 3.062(4), 3.132(4), 3.162(4), 3.250(4), 3.268(4), 3.295(4), 3.365(4), 3.398(4), 3.422(4), 3.531(4), 3.545(4), 3.630(4) and 3.652(4) Å (CaeO distances are from 2.328 to 2.703 Å in Ca-L-Ara), CseCl distances are 3.3828(13), 3.5054(14), 3.5862(14), 3.6207(14) and 3.9303(14) Å. The CeC bond lengths are 1.501(8), 1.510(7), 1.516(8), 1.517(8), 1.519(7), 1.521(7), 1.525(7) and 1.528(8) Å, CeO bond lengths are 1.389(6), 1.407(7), 1.425(7), 1.427(7), 1.428(7), 1.434(6), 1.435(6), 1.435(7), 1.436(7) and 1.440(7) Å, CeOeC bond angles are 111.4(4) and 111.9(4) (113.9 for Ca-L-Ara), OeCeO bond angles are 107.0(4) and 107.2(4) (103.4 for Ca-L-Ara). OeCeC bond angles are 107.0(4), 107.0(5), 107.2(5), 107.7(4), 107.8(4), 107.9(4), 108.1(4), 109.6(4), 109.9(4), 110.2(4), 110.4(4), 110.5(4), 110.8(4), 110.9(5), 111.6(4) and 112.2(4) . CeCeC bond angles are 108.4(5), 108.7(5), 111.0(4), 111.5(5), 111.7(4) and 112.1(5) in Cs-L-Ara, respectively. The metal hydroxyl interactions produce small conformational changes in the sugar at the metal-binding sites. For example, the bond angles of CeOeC are 111.4(4) and 111.9(4) in Cs-L-Ara (112.7(6) for arabinose itself, 113.9 for Ca-L-Ara), which show small deviation from the ligand [47], Csþ and Ca2þ introduce different changes of conformation of ligands. a-D-Arabinopyranose and a-L-Arabinopyranose appear in the structures of Cs-D-Ara and Cs-L-Ara complexes. For Cs-L-Ara, the hydrogen bonds data show that ring oxygen atoms (O5 and O10) do not form hydrogen bonds. The only OeH … O hydrogen bond is O7eH7 … O4 [x, y, z1] (171.84 , 2.770 Å). Other hydrogen bonds are OeH … Cl hydrogen bonds: O3eH3 … Cl1 [x1, y, z] (147.46 , 3.117 Å); O9eH9 … Cl1 [x, yþ1, z] (166.10 , 3.159 Å); O2eH1 … Cl1 (155.56 , 3.117 Å); O8eH8 … Cl2 (149.01, 3.100 Å); O6eH6 … Cl2 [xþ1, y1, z] (155.57, 3.033 Å); O1eH1B … Cl1 [x, yþ1, z] (174.61, 3.112 Å); O4eH4A … Cl2 [x, y1, zþ1] (167.22 , 3.142 Å). These OeH … Cl hydrogen bonds are related to the bands at 3352, 3334, 3331, 3328, 3320, 3318 and 3316 cm1 in the second derivative results. The only OeH … O hydrogen bond is related to 3204 cm1 in the IR spectrum. The coordination modes of lactose and arabinose with Ca2þ and þ Cs are shown in Fig. 2 and Table 2, which indicate that lactose and arabinose have different coordination structures with Ca2þ and Csþ. Here lactose, D-arabinose and L-arabinose have novel coordination
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modes in Csþ-complexes, they are coordinated to five cesium ions, even two coordination modes of arabinose coexist to form complicated coordination structures. Chloride ions are coordinated to metal ions and no water molecule exists in the three structures. The structures of cesium with lactose, D-arabinose and L-arabinose are different with calcium ion. For example, for Ca-L-arabinose, Ca2þ is bound to two symmetry related arabinose molecules (through O3 and O4 in one and through O1 and O5 in the other) as well as four water molecules. The observed coordination number is 9 or 10 for Csþ-complexes, but Ca2þ is usually 8-coordinated. The various coordination structures and coordination number difference for Ca2þ and Csþ are related to large ion radii of Csþ. Chloride ion coordinates to Csþ and water molecules are absent in the known Cs-saccharide complexes, but they are coordinated or hydrogen-bonded for some Ca-saccharide complexes. Csþ is inclined to coordinate to several saccharide molecules and one saccharide is coordinated with several Csþ. Cesium complexes with other ligands also can have structures different with other metal ions. For example, cesium chloride-D-ribose, myo-inositol and cholic acid complexes have different coordination structures compared to calcium and lanthanide ions [48,49]. 3.2. FTIR spectra of cesium chlorideelactose complex and cesium chloride-D- and L-arabinose complexes The FTIR spectra of lactose, CsCl-lactose complex, D-arabinose, CsCl-D-arabinose complex, L-arabinose and CsCl-L-arabinose complex are shown in Fig. 3. Compared to the IR spectrum of lactose, the changes in the IR spectrum of Cs-Lac indicate the formation of cesium chlorideelactose complex. For the spectrum of Cs-Lac, in the 3600e2600 cm1 region, 3422, 3357 and 3286 cm1 bands are observed (3524, 3378, 3337 and 3275 cm1 bands for lactose), which are related to the hydrogen bonds after complexation. For investigation of the hydrogen bonds, the variable temperature FTIR spectra of Cs-Lac have been measured and shown in Fig. 4. The variable temperature FTIR spectra and micro-IR spectrum are measured on different spectrometers and using different methods. Absorption water exists for KBr pellet method, so the two FTIR spectra at room temperature have some differences. The weak band at 3521 cm1 can be observed, 3417, 3376, 3355, 3321 and 3286 cm1 bands are identified using KBr pellet on the Bruker FTIR spectrometer (3422, 3357 and 3286 cm1 for micro-IR spectrum). At low temperature (184 C) the bands at 3331 and 3251 cm1 are emphasized, and the peak positions have shifts compared to the spectrum at room temperature (3520, 3447, 3413, 3370, 3348, 3331, 3314, 3281, 3251 cm1 and a weak band at 3389 cm1 for the spectrum at 184 C, but 3521, 3417, 3376, 3355, 3321 and 3286 cm1 for the spectrum at room temperature). At high temperature (200 C) the bands are not so obvious. The hydrogen bond data show that there are 9 hydrogen bonds, including OeH … O and OeH … Cl hydrogen bonds in Cs-Lac. To compare the nOH and the hydrogen bonds data, 10 bands can be observed at 184 C, maybe the bands can be assigned to the hydrogen bonds according to the hydrogen bond distances, i.e., 3520 cm1 is the influence of absorption water, 3447 cm1 (O4eH4 … Cl1 [xþ1, y1/2, -zþ3] (169.99 , 3.111 Å); 3413 cm1 (O10 H10 … Cl1 [xþ1, y, z1], 160.80 , 3.103 Å); 3389 cm1 (O3eH3 … Cl1 [-x, y1/2, -zþ2] (126.74 , 3.055 Å); 3370 cm1 (O3eH3 … O2 (117.33 , 2.868 Å); 3348 cm1 (O6eH6 … O2 [xþ1, y, zþ1] (153.64 , 2.797 Å); 3331 cm1 (O30 H30 … O5 (159.31, 2.735 Å); 3314 cm1 (O2eH2A … O6 [x, y, z1] (160.52 , 2.711 Å); 3281 cm1 (O20 H20 … O60 [xþ1, y, zþ1] (169.39 , 2.702 Å) and 3251 cm1 (O60 H60 … O30 [ x, y, z1] (173.57, 2.702 Å), respectively. The relatively weak bands at 2979, 2945, 2936, 2912, 2890 and 2866 cm1 for Cs-Lac (2985, 2978, 2945, 2933, 2918, 2900 and
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Fig. 2. The coordination modes of lactose and arabinose with metal ions (a) Ca-lactose (b) Cs-lactose; (c) Ca-a-L-arabinose; (d) Ca-b-L-arabinose, (e) bis(4-dehydro-L-arabinose) calcium methanol bishydrate (f) Cs-arabinose; (g) Cs-arabinose. Table 2 The coordination modes of the metal-lactose and arabinose complexes11,18,31. Stoichiometry
C. N.
Space group
OH
Coordination mode
Coordinated H2O
C12H22O11$CaBr2$7H2O C12H22O11$CaCl2$7H2O CsCl$C12H22O11 CaCl2$C5H10O5$4H2O(a-L-arabinose) CaCl2$C5H10O5$4H2O (b-L-arabinose) Ca(C5H9O5)2$CH3OH$2H2O(b-L-arabinose) CsCl$C5H10O5(a-D-arabinose) CsCl$C5H10O5(a-L-arabinose)
8 8 9 8 8 8 10 and 9 10 and 9
P212121 P212121 P21 C2 C2 P43212 P1 P1
4 4 7 4 4 8 8 or 6 8 or 6
2(a) 2(a) 2(b) 2(c) 2(d) 2(e) 2(f) (g) 2(f) (g)
4 4
Cl
2 4 4 2 or 3 2 or 3
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Fig. 3. FTIR spectra of lactose, Cs-Lac, D-arabinose, Cs-D-Ara, L-arabinose and Cs-L-Ara in the 36002600 and 1700650 cm1 region.
2887 cm1 bands for lactose) are related to nCH. The band shifts and the changes of relative intensities indicate the formation of metal complexes and rearrangement of CH chain. No band can be observed in the 1700e1600 cm1 region, which indicate that no water exists in the structure of Cs-Lac. The peak positions and relative intensities of the bands in the 1500600 cm1 region for Cs-Lac are changed compared to lactose.
dCH2 has shifted from 1469 to 1455 cm1 in lactose to 1462 cm1 in Cs-Lac. The nCO, nCC and dCOH localized at 1168, 1143, 1116, 1095,
1084, 1073, 1059, 1037 and 1020 cm1 in the lactose spectrum are shifted to 1166, 1150, 1119, 1094, 1080, 1063, 1033 and 1018 cm1 in the Cs-Lac spectrum, which indicate the coordination of hydroxyl groups to Csþ ion [50e53]. The bands in the 950e800 cm1 region related to dCOH, dCCH and dOCH are located at 846, 876, 903 and
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Fig. 4. The variable temperature FTIR spectra of Cs-Lac, Cs-D-Ara and Cs-L-Ara complexes in the 3600e3000 cm1 region.
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Fig. 5. FIR spectra of lactose, Cs-Lac, D-arabinose, Cs-D-Ara, L-arabinose and Cs-L-Ara in the 650e50 cm1 region.
916 cm1 in the Cs-Lac spectrum (876, 899 and 916 cm1 bands for lactose). The shifts are not obvious, so maybe only small conformation changes occur after complexation.
The FTIR spectra of D-arabinose, L-arabinose and their cesium chloride complexes shown in Fig. 3 indicate the formation of cesium chloride-D-arabinose and cesium chloride-L-arabinose
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complexes. The IR spectra of D-arabinose and L-arabinose are similar, and the IR spectra of Cs-D-Ara and Cs-L-Ara are also similar, which indicate that their cesium chloride complexes have similar structures. The nOH vibrations are located at 3530 and 3334 cm1 for D-arabinose (3535 and 3331 cm1 for L-arabinose), and the bands are shifted to 3346 cm1 in Cs-D-Ara (3354 cm1 for Cs-LAra), which indicate the changes of hydrogen bonds after complexation. The nCH vibrations are located at 2998, 2969, 2956, 2939, 2895 and 2863 cm1 in D-arabinose (2997, 2968, 2955, 2939, 2894 and 2867 cm1 in L-arabinose), and the bands are shifted to 2973, 2940, 2903, 2874 and 2833 cm1 in Cs-D-Ara (2973, 2940, 2905, 2863 and 2825 cm1 in Cs-L-Ara), which indicate the changes of CH chain of D-arabinose and L-arabinose after complexation. There is no band at ~1640 cm1, which show that no water exists in the structures of Cs-D-Ara and Cs-L-Ara. The dCH2 band at 1474 cm1 in D-arabinose (1473 cm1 in Larabinose) is shifted to 1460 cm1 in Cs-D-Ara (1467 cm1 in Cs-LAra), which also indicate the changes of CH chain. The bands in the fingerprint region also show fine structures after complexation, which indicate the formation of the metal complexes. For example, the bands at 1372, 1354, 1316, 1257 and 1232 cm1 in D-arabinose (1371, 1354, 1315, 1257 and 1231 cm1 in L-arabinose) related to d(CCH), d(OCH) and d(COH), etc. [38,50,51] are shifted to 1389, 1375, 1343, 1300, 1257 and 1210 cm1 in Cs-D-Ara (1390, 1376, 1343, 1302, 1275, 1256 and 1214 cm1 in Cs-L-Ara), which indicate the conformation changes of the ligands. The bands at 1134, 1104, 1092, 1066 and 1053 cm1 in D-arabinose (1132, 1103, 1090, 1065 and 1051 cm1 in L-arabinose) mainly related to n(CO) and n(CC) are corresponding to 1139, 1122, 1104, 1096, 1079, 1058 and 1036 cm1 in Cs-D-Ara (1139, 1122, 1104, 1079, 1060 and 1034 cm1 in Cs-LAra), which indicate the coordination of hydroxyl groups of the ligands. The bands at 998 and 994 cm1 are related to n(CO) and d(CCO) in L-arabinose, which are shifted to 1001 cm1 in Cs-L-Ara. The band at 893 cm1 in D-arabinose (892 cm1 in L-arabinose) related to n(CC) and d(CH), is shifted to 891 and 871 cm1 in Cs-DAra and Cs-L-Ara. The bands at 785 and 679 cm1 in D-arabinose (784 and 678 cm1 in L-arabinose) are related to t (CO) and d(CCO), which are shifted to 782 and 696 cm1 in Cs-D-Ara (781 and 694 cm1 in Cs-L-Ara). The results show the formation of the metal complexes and the similarity of the structures of CsCl-D- and Larabinose complexes. The variable temperature FTIR spectra of Cs-D-Ara and Cs-L-Ara shown in Fig. 4 indicate the changes of the hydrogen bonds after complexation. In the 3600e3000 cm1 region, the bands at 3507, 3319 and 3204 cm1 at low temperature are observed in Cs-L-Ara, among them the band at 3204 cm1 is a new band. Second derivative results indicate that the 3319 cm1 band has child bands located at 3352, 3334, 3331, 3328, 3320, 3318 and 3316 cm1. At high temperature the peak positions are shifted to higher frequencies (3527 and 3344 cm1). For Cs-D-Ara, the bands are located at 3525 and 3342 cm1 at 187 C, and 3535 and 3347 cm1 at 200 C. No new band appears at low temperature for Cs-D-Ara. The bands at ~3520 cm1 may be related to absorption water.
196 and 175 cm1 are belonging to MO vibrations, 148 and 131 cm1 bands may be related to CseCl vibrations. The bands may be also related to MOeH, MOeC, OMO deformation or out of plane vibrations, etc. The peak positions and relative intensities of the bands in Cs-Lac are changed compared to lactose, which confirm the formation of metal complex. The FIR spectra of D-, L-arabinose and their cesium chloride complexes also indicate the formation of the metal complex. The changes in peak positions and relative intensities are evident after complexation, for example, the bands in the 400e100 cm1 region related to nMeO and nMeCl are shifted from 402, 370, 317, 278, 228, 162, 148 and 115 cm1 in D-arabinose (400, 371, 317, 275, 228, 161, 147 and 113 cm1 in L-arabinose) to 400, 374, 332, 294, 230, 205 and 146 cm1 in Cs-D-Ara (400, 374, 331, 319, 293, 231, 205 and 145 cm1 in Cs-L-Ara), which reflect the changes of the conformation of D- and L-arabinose and the formation of MO and MCl bonds. THz bands are mainly related to lattice vibrations and hydrogen bonds, etc. [55] The THz spectrum of lactose is extensively investigated and the bands at ~0.53, 1.23, 1.42 and 1.86 THz are observed [57e64]. The THz absorption bands of cesium chlorideelactose complex shown in Fig. 6 are located at 0.50, 1.05, 1.52, 1.95, 2.19 and 2.46 THz (17, 35, 51, 65, 73 and 82 cm1) for Cs-Lac. The FIR and THz spectra confirm the formation of the metal complex and the changes of hydrogen bonds. D- and L-arabinose also have similar THz spectra. The bands are located at 1.48, 2.16 and 2.36 THz (49, 72 and 79 cm1) for Darabinose (1.49, 2.16 and 2.34 THz, 50, 72 and 78 cm1 for L-arabinose) [65]. After complexation, the bands are shifted to 1.32, 1.66 and 2.23 THz (44, 55 and 74 cm1) for Cs-D-Ara, 1.31, 1.62 and 2.15 THz (44, 54 and 72 cm1, but the bands are not obvious) for CsL-Ara. The band positions are similar for Cs-D-Ara and Cs-L-Ara, which also indicate that they have the same coordination structures.
3.3. FIR and THz spectra of lactose, cesium chlorideelactose complex, D-, L-arabinose and their cesium chloride complexes FIR and THz are effective methods to determine the formation of metal-ligand complexes [54e56]. The FIR spectra of lactose, D- and L-arabinose and their cesium chloride complexes are shown in Fig. 5. In the 65050 cm1 region the bands of Cs-Lac are located at 614, 557, 480, 444, 433, 423, 390, 357, 293, 256, 196, 175, 148, 131 and 73 cm1. The bands near 200 cm1 are usually assigned as MO vibrations for metal-sugar complexes [54], so the bands at 293, 256,
Fig. 6. THz absorption spectra of Cs-Lac, Cs-L-Ara.
D-arabinose,
Cs-D-Ara, L-arabinose and
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Fig. 7. Raman spectra of lactose, Cs-Lac, L-arabinose and Cs-L-Ara in the 3500e2700 and 1500e100 cm1 region.
3.4. Raman spectra of lactose, L-arabinose and their cesium chloride complexes The Raman spectra of lactose, L-arabinose and their cesium chloride complexes are shown in Fig. 7. The Raman spectra of Darabinose and CsCl-D-Arabinose complex are not shown here because the quality of their Raman spectra is not good for the reason of luminescence effect. For lactose and Cs-Lac, the intensities of nOH are decreased in Raman spectra compared to corresponding IR spectra and the bands are shifted from 3385, 3349, 3296 and 3224 cm1 in lactose to 3427, 3408, 3364 and 3300 cm1 in Cs-Lac. nCH are located at 2980, 2947, 2936, 2918 and 2890 cm1 in lactose, the bands are shifted to 2982, 2947, 2939, 2918 and 2892 cm1 in Cs-Lac. Many bands appear in the fingerprint region, which are related to nCO, nCC, dCCO and dCOC, etc. dCH2 is shifted from 1471 to 1456e1464 cm1; uCH2 is shifted from 1347 to 1335 to 1340 and 1324 cm1, tCH2 is shifted from 1264 to 1273 cm1 [49e52]. nCO, nCC and dCOH located at 1140, 1121, 1088, 1055, 1041 and 1021 cm1 are shifted to 1147, 1119, 1089, 1063, 1039 and 1015 cm1 after complexation, which reflect the coordination of hydroxyl groups of lactose. The bands at 359, 317, 260, 178 and 139 cm1 related to nCseO and nCseCl in Cs-Lac. These bands have different shifts
compared to the spectrum of lactose, which indicate the formation of cesiumelactose complex. The main bands are similar for the IR and Raman spectra of Cs-Lac, for example, the bands related to nCO, nCC and dCOH are located at 1147, 1119, 1089, 1063, 1039 and 1015 cm1 in the Raman spectrum, and 1150, 1119, 1094, 1063, 1033 and 1018 cm1 in the IR spectrum. The Raman spectra of L-arabinose and cesium chloride-Larabinose complex also indicate the formation of metal complex. The weak nOH are located at 3388 cm1 in Cs-L-Ara (3338 cm1 in L-arabinose), and the nCH vibrations are at 2978, 2941, 2907, 2876 and 2853 cm1 (3002, 2958, 2940 and 2891 cm1 for Larabinose), which show the changes of CH chain. The bands at 1379, 1358, 1314 and 1260 cm1 in L-Ara mainly related to dCOH, dCCH and dOCH are shifted to 1376, 1351 and 1260 cm1 in Cs-LAra. The nCC and nCO vibrations mainly located at 1138, 1095 and 1054 cm1 in L-Ara are shifted to 1140, 1081 and 1061 cm1 in Cs-L-Ara. The band at 995 cm1 related to nCO and dCCO is shifted to 1003 cm1 in Cs-L-Ara. The strong band at 844 cm1 in L-Ara has small shift to 843 cm1 in Cs-L-Ara. The bands at 333, 280, 233 and 148 cm1 in Cs-L-Ara mainly related to nMO and nMCl confirms the formation of metal complex. Compared the IR and Raman spectra of Cs-L-Ara, some of the bands are similar, for example, 1376 (1376), 1351 (1343), 1260 (1256), 1140 (1139),
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1081 (1079), 1061 (1060), 1003 (1001), 947 (945), 933 (928), 894 (891), 873 (871), 843 (840), 784 (781) and 699 (694) cm1 in Raman (IR). Raman is sensitive to the nonpolar group, such as CH chain structure, but IR is more clearly show the bind of Csþ with the polar group of carbohydrate. The results confirm the formation of Cs-L-Ara complex.
deposited with the Cambridge Crystallographic Data Centre as supplementary publication with CCDC Nos. 1003812, 1003813 and 1005408. Copies of the data can be obtained free of charge on application with the Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax þ44-1223-336-033; e-mail: [email protected]).
4. Conclusions
References
CsCl-lactose, CsCl-D-arabinose and CsCl-L-arabinose complexes have been obtained and characterized. For CsCl-lactose complex, Cs-Lac, the single crystal structure results show that Csþ is 9coordinated to two chloride ions, O50 , O60 from the first lactose molecule, O20 from the second lactose molecule, O20 from the third lactose molecule, O3 and O4 from the fourth lactose molecule and O3 from the fifth lactose, so one Csþ is connecting with five lactose molecules. For one lactose molecule, its O50 (the oxygen atom in the ring) and O60 is coordinated to one cesium ion, O20 atom is coordinated to two cesium ions, O3 and O4 are coordinated to the fourth Csþ and O3 is also coordinated to the fifth Csþ, so its O3, O4, O20 , O50 and O60 are involved in the coordination. One chloride ion is connecting with two cesium ions. For CsCl-L-arabinose complex, two kinds of Csþ ions coexist in the structures. Cs1 is 10-coordinated with five arabinose molecule: O1 and O2 of the first arabinose molecule; O6, O9 and O10 of the second arabinose molecule, O2 from the third arabinose molecule, O8 from the fourth arabinose molecule, O10 from the fifth arabinose molecule, and two chloride ions. Cs2 is 9-coordinated to O3 of the first arabinose molecule, O5 of the second arabinose molecule, O6 of the third arabinose molecule, O7 of the fourth arabinose molecules, O3 and O4 from the fifth arabinose molecule, and three chloride ions. The two a-L-arabinopyranose molecules have different coordination manners in Cs-L-Ara. CsCl-D-arabinose complex has similar structure with CsCl-L-arabinose. Compared to other metal ions, Csþ often has more complicated coordination structures. Here it can coordinate to five sugar molecules to form novel structures. FTIR, variable temperature FTIR spectra, FIR, THz and Raman spectra confirm the formation of the metal complex and the changes of hydrogen bonds. The crystal structures and spectroscopic results provide detailed information of metalsaccharides interactions. Acknowledgments Financial support from National Natural Science Foundation of China for the grants (21001009 and 50973003), the State Key Project for Fundamental Research of MOST (2011CB808304) and National High-tech R&D Program of China (863 Program) of MOST (2010AA03A406) and the Scientific Research Project of Beijing Municipal Commission of Education and Beijing Natural Science Foundation (Grant No. KZ201310028032) are gratefully acknowledged. The authors thank Prof. Jian Hao (Beijing University of Chemical Technology) and Prof. Xiang Hao (Institute of Chemistry, Chinese Academy of Sciences), for invaluable assistance with the Xray crystallography. The authors also thank Prof. Nanyan Fu (Fuzhou University) for her constructive opinion. Appendix A. Supplementary data Supplementary data related to this article can be found at http:// dx.doi.org/10.1016/j.molstruc.2016.01.005. Appendix B Crystallographic data, excluding structure factors, have been
[1] B. Gyurcsik, L. Nagy, Coord. Chem. Rev. 203 (2000) 81e148. [2] C.G. Hartinger, A.A. Nazarov, S.M. Ashraf, P.J. Dyson, B.K. Keppler, Curr. Med. Chem. 15 (2008) 2574e2591. [3] C. Vetter, P. Pornsuriyasak, J. Schmidt, N.P. Rath, T. Ruffer, A.V. Demchenko, D. Steinborn, Dalton Trans. 39 (2010) 6327e6338. [4] G.H. Li, A. Badkar, H. Kalluri, A.K. Banga, J. Pharm. Sci. 99 (2010) 1931e1941. [5] T. Storr, M. Merkel, G.X. Song-Zhao, L.E. Scott, D.E. Green, M.L. Bowen, K.H. Thompson, B.O. Patrick, H.J. Schugar, C. Orvig, J. Am. Chem. Soc. 129 (2007) 7453e7463. [6] N. Taccardi, D. Assenbaum, M.E.M. Berger, A. Bosmann, F. Enzenberger, R. Wolfel, S. Neuendorf, V. Goeke, N. Schodel, H.-J. Maass, H. Kistenmacher, P. Wasserscheid, Green Chem. 12 (2010) 1150e1156. [7] M. Gottschaldt, U.S. Schubert, Chem. Eur. J. 15 (2009) 1548e1557. [8] I. Garcia, M. Marradi, S. Penades, Nanomedicine 5 (2010) 777e792. [9] V. Oliveri, G.I. Grasso, F. Bellia, F. Attanasio, M. Viale, G. Vecchio, Inorg. Chem. 54 (2015) 2591e2602. [10] S.J. Angyal, D.C. Craig, Carbohydr. Res. 241 (1993) 1e8. [11] W.J. Cook, C.E. Bugg, Structures of calcium-carbohydrate complexes, in: B. Pullman, N. Goldblum (Eds.), Metal-ligand Interactions in Organic Chemistry and Biochemistry, Part 2, 1977, pp. 231e256. [12] L.M. Yang, X.H. Hua, J.H. Xue, Q.H. Pan, L. Yu, W.H. Li, Y.Z. Xu, G.Z. Zhao, L.M. Liu, K.X. Liu, J.E. Chen, J.G. Wu, Inorg. Chem. 51 (2012) 499e510. [13] Y.E. Alekseev, A.D. Garnovskii, Y.A. Zhdanov, Uspekhi Khimii 67 (1998) 723e744. [14] T. Allscher, X. Kaestele, G. Kettenbach, P. Kluefers, T. Kunte, Chem. Asian. J. 2 (2007) 1037e1045. [15] S. Yano, M. Otsuka, Sugar-metal ion interactions, in: H. Sigel (Ed.), Metal Ions in Biological Systems, vol. 32, 1996, pp. 27e60. [16] N. Buzas, T. Gajda, L. Nagy, E. Kuzmann, A. Vertes, K. Burger, Inorg. Chim. Acta 274 (1998) 167e176. [17] L.M. Yang, Y.Z. Xu, Y.L. Wang, S.W. Zhang, S.F. Weng, K. Zhao, J.G. Wu, Carbohydr. Res. 340 (2005) 2773e2781. [18] B. Hu, D. Yu, K. Huang, S.J. Yu, Chin. J. Struct. Chem. 34 (2015) 764e770. [19] C.A. Accorsi, V. Bertolasi, V. Ferretti, G. Gilli, Carbohydr. Res. 191 (1989) 91e104. [20] C.A. Accorsi, F. Bellucci, V. Bertolasi, V. Ferretti, G. Gilli, Carbohydr. Res. 191 (1989) 105e116. [21] Z. Peralta-Inga, G.P. Johnson, M.K. Dowd, J.A. Rendleman, E.D. Stevens, A.D. French, Carbohydr. Res. 337 (2002) 851e861. [22] C.E. Bugg, J. Am. Chem. Soc. 95 (1973) 908e913. [23] C.E. Bugg, W.J. Cook, J. Chem. Soc.-Chem. Commun. 12 (1972) 727e729. [24] K. Geetha, M.S.S. Raghavan, S.K. Kulshreshtha, R. Sasikala, C.P. Rao, Carbohydr. Res. 271 (1995) 163e175. [25] A. Mukhopadhyay, E. Kolehmainen, C.P. Rao, Carbohydr. Res. 324 (2000) 30e37. [26] A. Mukhopadhyay, E. Kolehmainen, C.P. Rao, Carbohydr. Res. 328 (2000) 103e113. [27] P.K. Banipal, V. Singh, T.S. Banipal, J. Chem. Thermodyn. 42 (2010) 90e103. [28] P.K. Banipal, T.S. Banipal, J.C. Ahluwalia, B.S. Lark, J. Chem. Thermodyn. 34 (2002) 1825e1846. [29] M.L. Swartz, R.A. Bernhard, T.A. Nickerson, J. Food Sci. 43 (1978) 93e97. [30] Vishnu, V.S. Mishra, Carbohydr. Res. 89 (1981) 55e63. [31] R. Palani, S. Balakrishnan, J. Indian Chem. Soc. 88 (2011) 431e436. [32] A. Terzis, Cryst. Struct. Comm. 7 (1978) 95e99. [33] P. Klufers, T. Kunte, Chem. Eur. J. 9 (2003) 2013e2018. [34] H.A. Tajmir-Riahi, Biophys. Chem. 25 (1986) 271e276. [35] H.A. Tajmir-Riahi, J. Inorg. Biochem. 27 (1986) 65e74. [36] H.A. Tajmir-Riahi, Carbohydr. Res. 127 (1984) 1e8. [37] H.A. Tajmir-Riahi, J. Inorg. Biochem. 22 (1984) 55e64. [38] H.A. Tajmir-Riahi, Monatsh. Chem. 118 (1987) 245e254. [39] A.L. Heaton, P.B. Armentrout, J. Phys. Chem. A 112 (2008) 10156e10167. [40] K.L. Zhuo, J.J. Wang, H.H. Zheng, X.P. Xuan, Y. Zhao, J. Solut. Chem. 34 (2005) 155e170. [41] J. Parada, S. Bunel, E. Moraga, C. Ibarra, N.D. Gillitt, C.A. Bunton, Polyhedron 20 (2001) 2223e2230. [42] P.A.M. Williams, S.B. Etcheverry, E.J. Baran, Carbohydr. Res. 6 (2000) 41e47. [43] O.V. Dolomanov, L.J. Bourhis, R.J. Gildea, J.A.K. Howard, H. Puschmann, J. Appl. Cryst. 42 (2009) 339e341. [44] G.M. Sheldrick, Acta Crystallogr. Sect. A Found. Crystallogr. 64 (2008) 112e122. [45] Y. Hu, X.H. Wang, L.T. Guo, C.L. Zhang, H.B. Liu, X.C. Zhang, Acta Phys. Sin. 54 (2005) 4124e4128. [46] J.H. Smith, S.E. Dann, M.R.J. Elsegood, S.H. Dale, C.G. Blatchford, Acta Cryst. E61 (2005) o2499eo2501.
Y. Jiang et al. / Journal of Molecular Structure 1109 (2016) 179e191 [47] A. Hordvik, Acta Chem. Scand. 15 (1961) 16e30. [48] H.J. Hu, J.H. Xue, X.D. Wen, W.H. Li, C. Zhang, L.M. Yang, Y.Z. Xu, G.Z. Zhao, X.X. Bu, K.X. Liu, J.E. Chen, J.G. Wu, Inorg. Chem. 52 (2013) 13132e13145. [49] Y. Sun, R.D. Soloway, Y.Z. Han, G.D. Yang, X.Z. Wang, Z.J. Liu, Z.L. Yang, Y.Z. Xu, J.G. Wu, Steroids 67 (2002) 385e392. [50] J.G. Wu, Modern Fourier Transform Spectroscopic Techniques and its Applications, Science and Technology References Press, Beijing, 1994. [51] S.F. Weng, Fourier Transform Infrared Spectrometer, Chemical Industry Press, Beijing, 2005. [52] J. De Gelder, K. De Gussem, P. Vandenabeele, L. Moens, J. Raman Spectrosc. 38 (2007) 1133e1147. [53] M. Kacurakova, M. Mathlouthi, Carbohydr. Res. 284 (1996) 145e157. [54] L.Q. Yang, J.G. Wu, Q. Zhou, J. Bian, Y.M. Yang, D.F. Xu, G.X. Xu, Mikrochim. Acta 14 (1997) 251e252. [55] L.M. Yang, G.Z. Zhao, W.H. Li, Y.F. Liu, X.X. Shi, X.F. Jia, K. Zhao, X.Y. Lu, Y.Z. Xu, D.T. Xie, J.G. Wu, J.E. Chen, Spectrochim. Acta A 73 (2009) 884e891. [56] R.J. Falconer, A.G. Markelz, J. Infrared Milli Terahz Waves 33 (2012) 973e988. [57] D.G. Allis, A.M. Fedor, T.M. Korter, J.E. Bjarnason, E.R. Brown, Chem. Phys. Lett. 440 (2007) 203e209.
191
[58] B.B. Jin, Z.X. Chen, Z. Li, J.L. Ma, R. Fu, C.H. Zhang, J. Chen, P.H. Wu, in: 34th International Conference on Infrared, Millimeter, and Terahertz Waves, 1 & 2, 2009, pp. 362e363. [59] S. Yamauchi, Y. Imai, H. Yokota, M. Tonouchi, in: Proc. SPIE 8011, 22nd Congress of the International Commission for Optics: Light for the Development of the World, 2011, p. 80118L. [60] X.J. Ma, H.W. Zhao, G.F. Liu, T. Ji, Z.Y. Zhang, B. Dai, Spectrosc. Spect. Anal. 29 (2009) 2885e2888. [61] E. Jung, J. Kim, Y. Han, K. Moon, M. Lim, H. Han, Biochip J. 2 (2008) 296e299. [62] J.E. Bjarnason, E.R. Brown, T.M. Korter, Terahertz for military and security applications V, in: Proceedings of the Society of Photo-optical Instrumentation Engineers (SPIE), vol. 6549, 2007. L5490eL5490. [63] E.R. Brown, J.E. Bjarnason, A.M. Fedor, T.M. Korter, Appl. Phys. Lett. 90 (2007) 061908. [64] S. Saito, T.M. Inerbaev, H. Mizuseki, N. Igarashi, R. Note, Y. Kawazoe, Jpn. J. Appl. Phys. 45 (2006) L1156eL1158. [65] M. Ge, H.W. Zhao, T. Ji, X.H. Yu, W.F. Wang, W.X. Li, Sci. China-Chem. 35 (2005) 441e445.