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Four new coordination polymers of Cu(II) with 1,1′-(1,4-butanediyl)bis(imidazole)
Polyhedron 23 (2004) 553–559 www.elsevier.com/locate/poly
Four new coordination polymers of Cu(II) with 1,10 -(1,4-butanediyl)bis(imidazole) Jian-Fang Ma *, Jin Yang, Guo-Li Zheng, Li Li, Yong-Mei Zhang, Fang-Fang Li, Jing-Fu Liu Department of Chemistry, Northeast Normal University, No. 138 Renmin Street, Changchun 130024, PR China Received 31 July 2003; accepted 8 October 2003
Abstract Four new complexes, namely [CuL(IN)2 (H2 O)2 ] 4H2 O (1), [CuL2 (H2 O)]Cl2 5H2 O (2), [CuL2 (H2 O)](NO3 )2 H2 O (3) and [CuL2 ]SO4 8H2 O (4), where IN ¼ isonicotinate anion, were obtained from self-assembly of the corresponding copper(II) salts with 1,10 -(1,4-butanediyl)bis(imidazole) (L), and their structures were determined by X-ray diffraction method. In complex 1, each copper(II) cation is six-coordinated by two water molecules and four nitrogen atoms from two L molecules and two isonicotinate anions. Each L molecule coordinates to two copper(II) cations, acting as a bridging ligand. The copper(II) cations are bridged by L to form an infinite zigzag chain structure. In complexes 2 and 3, the copper(II) cation is five-coordinated by one water molecule and four nitrogen atoms from four L molecules. In 4 the copper(II) cation is four-coordinated by four nitrogen atoms from four L molecules. Copper(II) cations are bridged by L ligands to form infinite ð4; 4Þ networks that contain 44-membered rings in 2, 3 and 4. No interpenetration occurs in 2 and 3, while in 4 two ð4; 4Þ networks are interpenetrated in parallel fashion to form a layer. Ó 2003 Elsevier Ltd. All rights reserved. Keywords: Coordination polymer; Crystal structure; Hydrogen bonds; Copper(II)
1. Introduction The synthesis and characterization of coordination polymers with infinite two- and three-dimensional networks have been an area of rapid growth in recent years because of the potential of these polymers in various applications, such as catalysis, electrical conductivity, host– guest chemistry and magnetism [1–4]. Much of the work has so far been focused on coordination polymers with rigid ligands, such as 4,40 -bipyridine and pyrazine [5,6]. The linear and bifunctional ligand 4,40 -bipyridine and its analogs upon reaction with transition metals are known to form several types of coordination networks that include one-dimensional networks (ladders, linear chains and railroads) [7–12], two-dimensional networks (square and rectangular grids, brick-wall and bilayers) [13,14] and three-dimensional networks (octahedral and diamond-
*
Corresponding author. Tel.: +86-431-5268620; fax: +86-4315684009. E-mail address: [email protected] (J.-F. Ma). 0277-5387/$ - see front matter Ó 2003 Elsevier Ltd. All rights reserved. doi:10.1016/j.poly.2003.10.002
oid) [15]. Most of these structures have relatively large voids and potential interest for host–guest interaction and molecular recognition. Some transition metal complexes with flexible ligands have been investigated [16] and we are interested in coordination polymers containing flexible ligands. Based on its structure, 1,10 -(1,4-butanediyl)bis(imidazole) (L) can be used as a flexible divergent ligand to fabricate coordination polymer materials [17]. In this paper, we present the preparation and crystal structures of four coordination polymers of L with copper(II) salts, namely [CuL(IN)2 (H2 O)2 ] 4H2 O (1), [CuL2 (H2 O)]Cl2 5H2 O (2), [CuL2 (H2 O)](NO3 )2 H2 O (3) and [CuL2 ]SO4 8H2 O (4). 2. Experimental All materials were commercially available and used as received. The FT-IR spectra were recorded from KBr pellets in range 4000–400 cm1 on a Mattson AlphaCentauri spectrometer. Elemental analyses were carried out with a Carlo Erba 1106 elemental analyzer.
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2.1. Synthesis of 1,10 -(1,4-butanediyl)bis(imidazole) (L) A mixture of imidazole (3.4 g, 50 mmol) and NaOH (2.0 g, 50 mmol) in DMSO (10 ml) was stirred at 60 °C for 1 h, then 1,4-dichlorobutane (3.2 g, 25 mmol) was added. The mixture was cooled to room temperature after stirring at 60 °C for 2 h, then poured into 200 ml of water and a white solid formed immediately which weighted 4.1 g after drying in air. Anal. Calc. for C5 H7 N2 : C, 63.16; H, 7.37, N, 29.47. Found: C, 63.11; H, 7.42; N, 29.31%. 2.2. Synthesis of [CuL(IN)2 (H2 O)2 ] 4H2 O (1) A mixture of CuCl2 2H2 O (0.171 g, 1 mmol) and NaOH (0.08 g, 2 mmol) in water was stirring for 10 min at room temperature, then the Cu(OH)2 solid was filtered. Isonicotinic acid (0.246 g, 2 mmol) was added to the Cu(OH)2 suspension in water with constant stirring and give blue precipitation. Then L (0.380 g, 2 mmol) was added to the precipitation with stirring for 1 h and blue solution was obtained. Blue crystals were obtained from the filtrate after standing at room temperature for several days
(68% yield based on Cu). Anal. Calc. for C22 H34 CuN6 O10 : C, 43.56; H, 5.61; N, 13.86. Found: C, 43.67; H, 5.52; N, 13.93%. IR (cm1 , KBr): 3431(s), 3130(m), 2344(w), 1610(vs), 1551(s), 1450(m), 1382(vs), 1234(w), 1110(m), 1057(w), 951(w), 846(w), 779(w), 688(w), 669(m). 2.3. Synthesis of [CuL2 (H2 O)]Cl2 5H2 O (2) A mixture of CuCl2 2H2 O (0.171 g, 1 mmol) and L (0.380 g, 2 mmol) in water (20 ml) was refluxed for 30 min, then filtered whilst hot. Blue crystals were obtained from the filtrate after standing at room temperature for several days (73% yield based on Cu). Anal. Calc. for C20 H40 Cl2 CuN8 O6 : C, 38.52; H, 6.42; N, 17.98. Found: C, 38.67; H, 6.31; N, 18.08%. IR (cm1 , KBr): 3449(s), 3125(m), 2950(w), 1640(m), 1526(m), 1451(m), 1285(w), 1238(s), 1107(vs), 1099(vs), 948(w), 849(w), 771(w), 756(m), 664(s), 627(w). 2.4. Synthesis of [CuL2 (H2 O)](NO3 )2 H2 O (3) A mixture of Cu(NO3 )2 (0.126 g, 1 mmol) and L (0.380 g, 2 mmol) in water (20 ml) was refluxed for 30 min and blue precipitate was obtained. It was filtered
Table 1 Crystal data for compounds 1–4
Formula Formula weight Crystal size Crystal system Space group Unit cell dimensions a (A) b (A) c (A) a (°) b (°) c (°) 3 ) V (A Z Dc (g cm3 ) F ð000Þ l (mm1 ) Wavelength (A) Temperature (K) h Range for data collection (°) Index ranges
Rint GOF on F 2 Largest difference 3 ) peak and hole (e A Reflections collected Unique reflections Observed reflections ðI > 2rðIÞÞ R1 ðI > 2rðIÞÞ wR2 ðI > 2rðIÞÞ
1
2
3
4
C22 H34 CuN6 O10 606.09 0.288 0.214 0.179 monoclinic C2=c
C20 H40 Cl2 CuN8 O6 623.04 0.304 0.249 0.044 triclinic P 1
C20 H32 CuN10 O8 604.10 0.439 0.173 0.090 monoclinic C2=c
C20 H44 CuN8 O12 S 684.23 0.322 0.308 0.146 triclinic P 1
12.205(2) 13.448(3) 17.308(4) 90 106.93(3) 90 2717.7(9) 4 1.481 1268 0.868 0.71073 293(2) 2.31–27.48 0 < h < 15; 0 < k < 17; 22 < l < 21; 0.0360 0.962
10.919(2) 11.844(2) 12.724(3) 82.09(3) 68.51(3) 73.85(3) 1469.6(5) 2 1.408 654 0.972 0.71073 293(2) 1.72–27.48 0 < h < 14; 14 < k < 15; 15 < l < 16; 0.0288 0.968
20.509(4) 9.3405(19) 15.239(3) 90 101.27(3) 90 2863.0(10) 4 1.401 1260 0.822 0.71073 293(2) 2.02–27.40 0 < h < 26; 0 < k < 12; 19 < l < 19; 0.0287 1.006
8.1383(16) 11.648(2) 16.780(3) 73.49(3) 88.78(3) 82.06(3) 1510.1(5) 2 1.505 722 0.863 0.71073 293(2) 1.27–27.42 0 < h < 10; 14 < k < 15; 21 < l < 21 0.0228 1.047
0.317 and )0.446
1.351 and )0.627
0.798 and )0.463
1.089 and )0.455
12 396 3125 2393
13 631 6631 4883
13 530 3251 2540
14 122 6823 5143
0.0329 0.0811
0.0368 0.0940
0.0420 0.1213
0.0335 0.0917
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off, washed with water and dissolved in a minimum amount of ammonia (14 M). Blue single crystals were obtained by slow evaporation of the ammoniacal solution of the solid at room temperature (64% yield based on Cu). Anal. Calc. for C20 H32 CuN10 O8 : C, 39.73; H, 5.30; N, 23.17. Found: C, 39.81; H, 5.22; N, 23.21%. IR (cm1 , KBr): 3436(s), 3121(w), 2943(w), 2340(w), 1641(w), 1529(m), 1458(w), 1382(vs), 1240(w), 1103(s), 1038(w), 948(w), 837(w), 757(w), 622(m). 2.5. Synthesis of [CuL2 ]SO4 8H2 O (4) A mixture of CuSO4 5H2 O (0.250 g, 1 mmol) and L (0.380 g, 2 mmol) in water (20 ml) was refluxed for 30 min, then filtered whilst hot. Blue crystals were obtained from the filtrate after standing at room temperature for several days (77% yield based on Cu). Anal. Calc. for C20 H44 CuN8 O12 S: C, 35.08; H, 6.43; N, 16.37. Found: C, 35.11; H, 6.32; N, 16.53%. IR (cm1 , KBr): 3431(s), 3119(w), 2945(w),
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2342(w), 1631(m), 1524(w), 1452(s), 1384(w), 1239(m), 1114(vs), 949(w), 880(w), 753(w), 668(m), 622(m). 2.6. X-ray crystallography studies Experimental details of the X-ray analyses are provided in Table 1. Diffraction intensities for the compounds 1–4 were collected on a Rigaku RAXIS-RAPID image plate diffractometer using x scan technique with Absorption correcMo Ka radiation (k ¼ 0:71069 A). tions were applied using multi-scan technique [18]. The structures were solved with the direct method of S H E L X S -97 [19] and refined with full-matrix leastsquares techniques using the S H E L X L -97 program [20] within W I N G X [21]. Non-hydrogen atoms were refined anisotropically. Analytical expression of neutral-atom scattering factors were employed, and anomalous dispersion corrections incorporated [22]. Drawings were produced with S H E L X T L P L U S [23].
Table 2 and angles (°) for complexes 1–4 Selected bond distances (A) [CuL(IN)2 (H2 O)2 ] 4H2 O ð1Þ Bond distances Cu(1)–N(1) Cu(1)–Ow1 Bond angles N(1)–Cu(1)–Ow1 N(2)–Cu(1)–Ow1i N(2)–Cu(1)–Ow1 [CuL2 (H2 O)]Cl2 5H2 O ð2Þ Bond distances Cu(1)–N(11) Cu(1)–N(21) Cu(1)–N(14)i Bond angles N(21)–Cu(1)–N(11) N(11)–Cu(1)–N(31) N(14)i –Cu(1)–Ow1 N(21)–Cu(1)–N(31) N(11)–Cu(1)–Ow1 [CuL2 (H2 O)](NO3 )2 H2 O ð3Þ Bond distances Cu(1)–N(1) Cu(1)–Ow1 Bond angles N(1)i –Cu(1)–N(1) N(1)–Cu(1)–N(3)i N(1)–Cu(1)–Ow1 [CuL2 ]SO4 8H2 O ð4Þ Bond distances Cu(1)–N(11) Cu(2)–N(14) Bond angles N(11)–Cu(1)–N(21)ii N(14)–Cu(2)–N(24)i
2.0554(15) 2.4163(14) 92.63(6) 88.91(6) 91.09(6)
2.015(2) 2.014(2) 2.015(2) 88.72(8) 88.21(8) 90.53(9) 176.78(7) 92.67(9)
1.980(2) 2.210(3) 161.43(14) 91.47(9) 99.29(7)
2.00(2) 2.00(2) 88.8(7) 87.9(7)
Cu(1)–N(2)
N(1)–Cu(1)–Ow1 i N(2)–Cu(1)–N(1) N(2)–Cu(1)–N(1)i
Cu(1)–Ow1 Cu(1)–N(31)
N(11)–Cu(1)–N(14)i N(21)–Cu(1)–Ow1 N(21)–Cu(1)–N(14)i N(14)i –Cu(1)–N(31) N(31)–Cu(1)–Ow1
Cu(1)–N(3)
N(1)–Cu(1)–N(3) N(3)–Cu(1)–N(3)i N(3)–Cu(1)–Ow1
Cu(1)–N(21) Cu(2)–N(24)i N(11)–Cu(1)–N(21) N(14)–Cu(2)–N(24)iii
2.0067(15)
87.37(6) 90.11(6) 89.89(6)
2.393(2) 2.017(2)
176.80(8) 91.11(8) 91.08(7) 91.93(8) 90.01(8)
2.014(2)
87.55(9) 173.90(13) 93.05(7)
2.04(2) 2.00(2) 91.2(7) 92.1(7)
Symmetry codes for 1: i, x þ 1; y; z þ 1. Symmetry codes for 2: i, x; y; z 1. Symmetry codes for 3: i, x þ 2:5; y þ 0:5; z þ 2. Symmetry codes for 4: i, x; y; z þ 1; ii, x þ 2; y þ 1; z þ 2 and iii, x þ 4; y þ 1; z þ 2.
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3. Results and discussion Selected bond distances and angles for complexes 1–4 are listed in Table 2. Fig. 1(a) shows the coordination environments of the copper(II) cations in [CuL(IN)2 (H2 O)2 ] 4H2 O 1. The copper(II) cation lies at an inversion center. Each copper(II) cation is six-coordinated by two water molecules and four nitrogen atoms from two L molecules and two isonicotinate anions. The presence of an un-coordinated carboxylate group is somewhat unexpected because the carboxylate group of isonicotinate anion is a better coordinating group than water oxygen atom for copper(II) cation. In the related compound, {[Cu2 (IN)4 3H2 O] [Cu2 (IN)4 2H2 O]} 3H2 O [24], the carboxylate oxygen atom coordinated to the copper(II) cation. The Cu–N (isonicotinate) distance of is similar to that of copper(II) isonicotinate 2.0554(15) A complex [25]. The distance between the copper(II) cation and the nitrogen atom from L molecule is 2.0067(15) A. The Cu–O (water) distance of 2.4163(14) A is near to those of other copper(II) complexes [26,27]. Due to Jahn–Teller effects the axial Cu–O (water) distance is much longer than those of Cu–N (IN and L). The dis-
Fig. 1. (a) An O R T E P drawing of the local coordination of Cu(II) cation in complex 1. Atoms are shown 50% probability ellipsoids. (b) The infinite zigzag polymeric chain of 1 (The water molecules and isonicotinate anions are omitted for clarity). (c) The extended structure of 1 through H-bonds interactions between adjacent chains.
tance between the neighboring copper(II) cations is Each L molecule coordinates to two copper(II) 8.654 A. cations, acting as a bridging ligand to form an infinite zigzag chain structure [Fig. 1(b)]. In 1, one carboxylate oxygen atom H-bonds to one lattice water molecule and one coordinated water molecule of the neighboring Cu(II) cation within the same polymeric chain while the other carboxylate oxygen atom H-bonds to one lattice water molecule and one coordinated water molecule from adjacent polymeric chain. The extended structure was formed through H-bonds interactions between adjacent chains as illustrated in Fig. 1(c). Part of the structure of [CuL2 (H2 O)]Cl2 5H2 O (2) and [CuL2 (H2 O)](NO3 )2 H2 O (3) are shown in Figs. 2(a) and 3(a), respectively. The coordination geometries of the copper(II) cation are all completed by four nitrogen atoms from four L molecules and by one water molecule. Both the chloride anions and nitrate anions only play a role of un-coordinating counter-anions. In 2, there exist inversion centers at the mid-points of the C24 –C24 * and C34 –C34 # bonds. In 3, Cu1 cation and Ow1 lie on a twofold axis, and there are inversion centers at the midpoints of C15 –C15 * and C25 –C25 # bonds. The average Cu–N distance and the Cu–O (water) distance in 2 and 3 are quite near to those of 1. Each L molecule coordinates to two copper(II) cations, bridging the copper(II) cations to form infinite ð4; 4Þ networks [Figs. 2(b) and (c), 3(b) and (c)]. In 2, chloride ions and some lattice water molecules are encapsulated in the 44-membered rings of the ð4; 4Þ network, one chloride ion H-bonds to one coordinated water molecule and three lattice water molecules while the other chloride ion H-bonds to three lattice water molecules. The adjacent ð4; 4Þ networks are interconnected through hydrogen bonds as shown in Fig. 2(d). In 3, nitrate ions are encapsulated in the 44membered rings of the ð4; 4Þ network, and each nitrate ion H-bonds to one coordinated water molecule from the adjacent ð4; 4Þ networks as shown in Fig. 3(d). The uncoordinating counter-anions and water molecules filled in the networks may be the main reason for the non-interpenetrating structures of 2 and 3. As shown in Fig. 4(a), 4 consists of two crystallographically unique Cu(II) ions in the asymmetric unit. Both of them lie at the inversion center and have the similar coordination environment. The copper(II) cation of 4 is coordinated by four nitrogen atoms from four L molecules. In the related compound, [ZnL1:5 (H2 O) (SO4 )] 6H2 O complex with infinite ð6; 3Þ networks, the sulfate anion coordinates to the central zinc(II) cation [17a]. But in the present complex the sulfate anions play a role of counter-anion. The Cu–N (L) distances of are similar to those in complex 1, 2 2.00(2) and 2.04(2) A and 3. In complex 4, copper(II) ions are bridged by L to form infinite ð4; 4Þ networks [Fig. 4(b)], and two ð4; 4Þ networks are interpenetrated in parallel mode to form a layer [Fig. 4(c)]. The sulfate anions and water molecules
J.-F. Ma et al. / Polyhedron 23 (2004) 553–559
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Fig. 2. (a) An O R T E P drawing of the local coordination of Cu(II) cation in complex 2. Atoms are shown 50% probability ellipsoids. (b) The large ring of the ð4; 4Þ network in 2. (c) Extended structure of 2 (water and chloride anions are omitted for clarity). (d) The H-bonds interactions between adjacent layers.
Fig. 3. (a) An O R T E P drawing of the local coordination of Cu(II) cation in complex 3. Atoms are shown 50% probability ellipsoids. (b) The large ring of the ð4; 4Þ network in 3. (c) Extended structure of 3 (water and nitrate anions are omitted for clarity). (d) The H-bonds interactions between adjacent layers.
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Fig. 4. (a) An O R T E P drawing of the local coordination of Cu(II) in complex 4. Atoms are shown 50% probability ellipsoids. (b) The large ring of the ð4; 4Þ network in 4. (c) Schematic representation of the mode of interpenetration. (d) The alternative H-bonding layers and [CuL2 ]2þ layers.
are intercalated into the layers, and each sulfate ion Hbonds to six lattice water molecules. The extended structure was formed by stacking the layer of hydrogenbonded water molecules and sulfate ions and the layer of polymeric [CuL2 ]2þ alternatively [Fig. 4(d)]. The number of different ways two ð4; 4Þ nets could theoretically interpenetrate in the parallel fashion may be given by systematic study of the topology of interpenetration [28]. The interpenetrating structures of related complexes, [MnL3 (BF4 )2 ] [29] and [ZnL1:5 (H2 O)(SO4 )] 6H2 O [17a] have been reported. The reported [MnL3 (BF4 )2 ] complexes are composed of two equivalent, mutually interpenetrating three-dimensional networks, while in complex [ZnL1:5 (H2 O)(SO4 )] 6H2 O, the networks are interpenetrated in an inclined mode by symmetry related, identical networks to give an interlocked three-dimensional structure. In complexes 1, 2, 3 and 4 each L molecule coordinates to two copper(II) cations through its two aromatic nitrogen atoms acting as a bridging bidentate ligand. Copper(II) cations are bridged by L molecules to form one-dimensional chain in 1, ð4; 4Þ networks in 2, 3 and 4. The networks contain square grids (44-membered) with a copper(II) cation at each corner and a molecule of L at each edge connecting two copper(II) cations. The lengths of the opposite edges are equal in 2, 3 and 4. The for 2, 11.886 and edge lengths are 12.317 and 12.724 A for 3, 11.812 and 11.564 A for 4. 14.225 A The structures of these complexes imply a role of counter-anions in the fabrication of the framework.
Since isonicotinate anion is a better ligand for Cu(II) than other three anions, isonicotinate anions are coordinated to copper(II) ion in 1 while in other complexes the anions are non-coordinating. In each compound the anions are connected to water molecules through Hbonding interactions, and it can be seen that the polymeric networks can be tailored by using different anions.
4. Supplementary material CCDC-198614 (for 1), 198615 (for 2), 198616 (for 3) and 198617 (for 4) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK (fax: +44-1223-336-033; E-mail: [email protected] or http://www.ccdc.cam.ac.uk).
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Four new coordination polymers of Cu(II) with 1,10 -(1,4-butanediyl)bis(imidazole) Jian-Fang Ma *, Jin Yang, Guo-Li Zheng, Li Li, Yong-Mei Zhang, Fang-Fang Li, Jing-Fu Liu Department of Chemistry, Northeast Normal University, No. 138 Renmin Street, Changchun 130024, PR China Received 31 July 2003; accepted 8 October 2003
Abstract Four new complexes, namely [CuL(IN)2 (H2 O)2 ] 4H2 O (1), [CuL2 (H2 O)]Cl2 5H2 O (2), [CuL2 (H2 O)](NO3 )2 H2 O (3) and [CuL2 ]SO4 8H2 O (4), where IN ¼ isonicotinate anion, were obtained from self-assembly of the corresponding copper(II) salts with 1,10 -(1,4-butanediyl)bis(imidazole) (L), and their structures were determined by X-ray diffraction method. In complex 1, each copper(II) cation is six-coordinated by two water molecules and four nitrogen atoms from two L molecules and two isonicotinate anions. Each L molecule coordinates to two copper(II) cations, acting as a bridging ligand. The copper(II) cations are bridged by L to form an infinite zigzag chain structure. In complexes 2 and 3, the copper(II) cation is five-coordinated by one water molecule and four nitrogen atoms from four L molecules. In 4 the copper(II) cation is four-coordinated by four nitrogen atoms from four L molecules. Copper(II) cations are bridged by L ligands to form infinite ð4; 4Þ networks that contain 44-membered rings in 2, 3 and 4. No interpenetration occurs in 2 and 3, while in 4 two ð4; 4Þ networks are interpenetrated in parallel fashion to form a layer. Ó 2003 Elsevier Ltd. All rights reserved. Keywords: Coordination polymer; Crystal structure; Hydrogen bonds; Copper(II)
1. Introduction The synthesis and characterization of coordination polymers with infinite two- and three-dimensional networks have been an area of rapid growth in recent years because of the potential of these polymers in various applications, such as catalysis, electrical conductivity, host– guest chemistry and magnetism [1–4]. Much of the work has so far been focused on coordination polymers with rigid ligands, such as 4,40 -bipyridine and pyrazine [5,6]. The linear and bifunctional ligand 4,40 -bipyridine and its analogs upon reaction with transition metals are known to form several types of coordination networks that include one-dimensional networks (ladders, linear chains and railroads) [7–12], two-dimensional networks (square and rectangular grids, brick-wall and bilayers) [13,14] and three-dimensional networks (octahedral and diamond-
*
Corresponding author. Tel.: +86-431-5268620; fax: +86-4315684009. E-mail address: [email protected] (J.-F. Ma). 0277-5387/$ - see front matter Ó 2003 Elsevier Ltd. All rights reserved. doi:10.1016/j.poly.2003.10.002
oid) [15]. Most of these structures have relatively large voids and potential interest for host–guest interaction and molecular recognition. Some transition metal complexes with flexible ligands have been investigated [16] and we are interested in coordination polymers containing flexible ligands. Based on its structure, 1,10 -(1,4-butanediyl)bis(imidazole) (L) can be used as a flexible divergent ligand to fabricate coordination polymer materials [17]. In this paper, we present the preparation and crystal structures of four coordination polymers of L with copper(II) salts, namely [CuL(IN)2 (H2 O)2 ] 4H2 O (1), [CuL2 (H2 O)]Cl2 5H2 O (2), [CuL2 (H2 O)](NO3 )2 H2 O (3) and [CuL2 ]SO4 8H2 O (4). 2. Experimental All materials were commercially available and used as received. The FT-IR spectra were recorded from KBr pellets in range 4000–400 cm1 on a Mattson AlphaCentauri spectrometer. Elemental analyses were carried out with a Carlo Erba 1106 elemental analyzer.
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2.1. Synthesis of 1,10 -(1,4-butanediyl)bis(imidazole) (L) A mixture of imidazole (3.4 g, 50 mmol) and NaOH (2.0 g, 50 mmol) in DMSO (10 ml) was stirred at 60 °C for 1 h, then 1,4-dichlorobutane (3.2 g, 25 mmol) was added. The mixture was cooled to room temperature after stirring at 60 °C for 2 h, then poured into 200 ml of water and a white solid formed immediately which weighted 4.1 g after drying in air. Anal. Calc. for C5 H7 N2 : C, 63.16; H, 7.37, N, 29.47. Found: C, 63.11; H, 7.42; N, 29.31%. 2.2. Synthesis of [CuL(IN)2 (H2 O)2 ] 4H2 O (1) A mixture of CuCl2 2H2 O (0.171 g, 1 mmol) and NaOH (0.08 g, 2 mmol) in water was stirring for 10 min at room temperature, then the Cu(OH)2 solid was filtered. Isonicotinic acid (0.246 g, 2 mmol) was added to the Cu(OH)2 suspension in water with constant stirring and give blue precipitation. Then L (0.380 g, 2 mmol) was added to the precipitation with stirring for 1 h and blue solution was obtained. Blue crystals were obtained from the filtrate after standing at room temperature for several days
(68% yield based on Cu). Anal. Calc. for C22 H34 CuN6 O10 : C, 43.56; H, 5.61; N, 13.86. Found: C, 43.67; H, 5.52; N, 13.93%. IR (cm1 , KBr): 3431(s), 3130(m), 2344(w), 1610(vs), 1551(s), 1450(m), 1382(vs), 1234(w), 1110(m), 1057(w), 951(w), 846(w), 779(w), 688(w), 669(m). 2.3. Synthesis of [CuL2 (H2 O)]Cl2 5H2 O (2) A mixture of CuCl2 2H2 O (0.171 g, 1 mmol) and L (0.380 g, 2 mmol) in water (20 ml) was refluxed for 30 min, then filtered whilst hot. Blue crystals were obtained from the filtrate after standing at room temperature for several days (73% yield based on Cu). Anal. Calc. for C20 H40 Cl2 CuN8 O6 : C, 38.52; H, 6.42; N, 17.98. Found: C, 38.67; H, 6.31; N, 18.08%. IR (cm1 , KBr): 3449(s), 3125(m), 2950(w), 1640(m), 1526(m), 1451(m), 1285(w), 1238(s), 1107(vs), 1099(vs), 948(w), 849(w), 771(w), 756(m), 664(s), 627(w). 2.4. Synthesis of [CuL2 (H2 O)](NO3 )2 H2 O (3) A mixture of Cu(NO3 )2 (0.126 g, 1 mmol) and L (0.380 g, 2 mmol) in water (20 ml) was refluxed for 30 min and blue precipitate was obtained. It was filtered
Table 1 Crystal data for compounds 1–4
Formula Formula weight Crystal size Crystal system Space group Unit cell dimensions a (A) b (A) c (A) a (°) b (°) c (°) 3 ) V (A Z Dc (g cm3 ) F ð000Þ l (mm1 ) Wavelength (A) Temperature (K) h Range for data collection (°) Index ranges
Rint GOF on F 2 Largest difference 3 ) peak and hole (e A Reflections collected Unique reflections Observed reflections ðI > 2rðIÞÞ R1 ðI > 2rðIÞÞ wR2 ðI > 2rðIÞÞ
1
2
3
4
C22 H34 CuN6 O10 606.09 0.288 0.214 0.179 monoclinic C2=c
C20 H40 Cl2 CuN8 O6 623.04 0.304 0.249 0.044 triclinic P 1
C20 H32 CuN10 O8 604.10 0.439 0.173 0.090 monoclinic C2=c
C20 H44 CuN8 O12 S 684.23 0.322 0.308 0.146 triclinic P 1
12.205(2) 13.448(3) 17.308(4) 90 106.93(3) 90 2717.7(9) 4 1.481 1268 0.868 0.71073 293(2) 2.31–27.48 0 < h < 15; 0 < k < 17; 22 < l < 21; 0.0360 0.962
10.919(2) 11.844(2) 12.724(3) 82.09(3) 68.51(3) 73.85(3) 1469.6(5) 2 1.408 654 0.972 0.71073 293(2) 1.72–27.48 0 < h < 14; 14 < k < 15; 15 < l < 16; 0.0288 0.968
20.509(4) 9.3405(19) 15.239(3) 90 101.27(3) 90 2863.0(10) 4 1.401 1260 0.822 0.71073 293(2) 2.02–27.40 0 < h < 26; 0 < k < 12; 19 < l < 19; 0.0287 1.006
8.1383(16) 11.648(2) 16.780(3) 73.49(3) 88.78(3) 82.06(3) 1510.1(5) 2 1.505 722 0.863 0.71073 293(2) 1.27–27.42 0 < h < 10; 14 < k < 15; 21 < l < 21 0.0228 1.047
0.317 and )0.446
1.351 and )0.627
0.798 and )0.463
1.089 and )0.455
12 396 3125 2393
13 631 6631 4883
13 530 3251 2540
14 122 6823 5143
0.0329 0.0811
0.0368 0.0940
0.0420 0.1213
0.0335 0.0917
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off, washed with water and dissolved in a minimum amount of ammonia (14 M). Blue single crystals were obtained by slow evaporation of the ammoniacal solution of the solid at room temperature (64% yield based on Cu). Anal. Calc. for C20 H32 CuN10 O8 : C, 39.73; H, 5.30; N, 23.17. Found: C, 39.81; H, 5.22; N, 23.21%. IR (cm1 , KBr): 3436(s), 3121(w), 2943(w), 2340(w), 1641(w), 1529(m), 1458(w), 1382(vs), 1240(w), 1103(s), 1038(w), 948(w), 837(w), 757(w), 622(m). 2.5. Synthesis of [CuL2 ]SO4 8H2 O (4) A mixture of CuSO4 5H2 O (0.250 g, 1 mmol) and L (0.380 g, 2 mmol) in water (20 ml) was refluxed for 30 min, then filtered whilst hot. Blue crystals were obtained from the filtrate after standing at room temperature for several days (77% yield based on Cu). Anal. Calc. for C20 H44 CuN8 O12 S: C, 35.08; H, 6.43; N, 16.37. Found: C, 35.11; H, 6.32; N, 16.53%. IR (cm1 , KBr): 3431(s), 3119(w), 2945(w),
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2342(w), 1631(m), 1524(w), 1452(s), 1384(w), 1239(m), 1114(vs), 949(w), 880(w), 753(w), 668(m), 622(m). 2.6. X-ray crystallography studies Experimental details of the X-ray analyses are provided in Table 1. Diffraction intensities for the compounds 1–4 were collected on a Rigaku RAXIS-RAPID image plate diffractometer using x scan technique with Absorption correcMo Ka radiation (k ¼ 0:71069 A). tions were applied using multi-scan technique [18]. The structures were solved with the direct method of S H E L X S -97 [19] and refined with full-matrix leastsquares techniques using the S H E L X L -97 program [20] within W I N G X [21]. Non-hydrogen atoms were refined anisotropically. Analytical expression of neutral-atom scattering factors were employed, and anomalous dispersion corrections incorporated [22]. Drawings were produced with S H E L X T L P L U S [23].
Table 2 and angles (°) for complexes 1–4 Selected bond distances (A) [CuL(IN)2 (H2 O)2 ] 4H2 O ð1Þ Bond distances Cu(1)–N(1) Cu(1)–Ow1 Bond angles N(1)–Cu(1)–Ow1 N(2)–Cu(1)–Ow1i N(2)–Cu(1)–Ow1 [CuL2 (H2 O)]Cl2 5H2 O ð2Þ Bond distances Cu(1)–N(11) Cu(1)–N(21) Cu(1)–N(14)i Bond angles N(21)–Cu(1)–N(11) N(11)–Cu(1)–N(31) N(14)i –Cu(1)–Ow1 N(21)–Cu(1)–N(31) N(11)–Cu(1)–Ow1 [CuL2 (H2 O)](NO3 )2 H2 O ð3Þ Bond distances Cu(1)–N(1) Cu(1)–Ow1 Bond angles N(1)i –Cu(1)–N(1) N(1)–Cu(1)–N(3)i N(1)–Cu(1)–Ow1 [CuL2 ]SO4 8H2 O ð4Þ Bond distances Cu(1)–N(11) Cu(2)–N(14) Bond angles N(11)–Cu(1)–N(21)ii N(14)–Cu(2)–N(24)i
2.0554(15) 2.4163(14) 92.63(6) 88.91(6) 91.09(6)
2.015(2) 2.014(2) 2.015(2) 88.72(8) 88.21(8) 90.53(9) 176.78(7) 92.67(9)
1.980(2) 2.210(3) 161.43(14) 91.47(9) 99.29(7)
2.00(2) 2.00(2) 88.8(7) 87.9(7)
Cu(1)–N(2)
N(1)–Cu(1)–Ow1 i N(2)–Cu(1)–N(1) N(2)–Cu(1)–N(1)i
Cu(1)–Ow1 Cu(1)–N(31)
N(11)–Cu(1)–N(14)i N(21)–Cu(1)–Ow1 N(21)–Cu(1)–N(14)i N(14)i –Cu(1)–N(31) N(31)–Cu(1)–Ow1
Cu(1)–N(3)
N(1)–Cu(1)–N(3) N(3)–Cu(1)–N(3)i N(3)–Cu(1)–Ow1
Cu(1)–N(21) Cu(2)–N(24)i N(11)–Cu(1)–N(21) N(14)–Cu(2)–N(24)iii
2.0067(15)
87.37(6) 90.11(6) 89.89(6)
2.393(2) 2.017(2)
176.80(8) 91.11(8) 91.08(7) 91.93(8) 90.01(8)
2.014(2)
87.55(9) 173.90(13) 93.05(7)
2.04(2) 2.00(2) 91.2(7) 92.1(7)
Symmetry codes for 1: i, x þ 1; y; z þ 1. Symmetry codes for 2: i, x; y; z 1. Symmetry codes for 3: i, x þ 2:5; y þ 0:5; z þ 2. Symmetry codes for 4: i, x; y; z þ 1; ii, x þ 2; y þ 1; z þ 2 and iii, x þ 4; y þ 1; z þ 2.
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3. Results and discussion Selected bond distances and angles for complexes 1–4 are listed in Table 2. Fig. 1(a) shows the coordination environments of the copper(II) cations in [CuL(IN)2 (H2 O)2 ] 4H2 O 1. The copper(II) cation lies at an inversion center. Each copper(II) cation is six-coordinated by two water molecules and four nitrogen atoms from two L molecules and two isonicotinate anions. The presence of an un-coordinated carboxylate group is somewhat unexpected because the carboxylate group of isonicotinate anion is a better coordinating group than water oxygen atom for copper(II) cation. In the related compound, {[Cu2 (IN)4 3H2 O] [Cu2 (IN)4 2H2 O]} 3H2 O [24], the carboxylate oxygen atom coordinated to the copper(II) cation. The Cu–N (isonicotinate) distance of is similar to that of copper(II) isonicotinate 2.0554(15) A complex [25]. The distance between the copper(II) cation and the nitrogen atom from L molecule is 2.0067(15) A. The Cu–O (water) distance of 2.4163(14) A is near to those of other copper(II) complexes [26,27]. Due to Jahn–Teller effects the axial Cu–O (water) distance is much longer than those of Cu–N (IN and L). The dis-
Fig. 1. (a) An O R T E P drawing of the local coordination of Cu(II) cation in complex 1. Atoms are shown 50% probability ellipsoids. (b) The infinite zigzag polymeric chain of 1 (The water molecules and isonicotinate anions are omitted for clarity). (c) The extended structure of 1 through H-bonds interactions between adjacent chains.
tance between the neighboring copper(II) cations is Each L molecule coordinates to two copper(II) 8.654 A. cations, acting as a bridging ligand to form an infinite zigzag chain structure [Fig. 1(b)]. In 1, one carboxylate oxygen atom H-bonds to one lattice water molecule and one coordinated water molecule of the neighboring Cu(II) cation within the same polymeric chain while the other carboxylate oxygen atom H-bonds to one lattice water molecule and one coordinated water molecule from adjacent polymeric chain. The extended structure was formed through H-bonds interactions between adjacent chains as illustrated in Fig. 1(c). Part of the structure of [CuL2 (H2 O)]Cl2 5H2 O (2) and [CuL2 (H2 O)](NO3 )2 H2 O (3) are shown in Figs. 2(a) and 3(a), respectively. The coordination geometries of the copper(II) cation are all completed by four nitrogen atoms from four L molecules and by one water molecule. Both the chloride anions and nitrate anions only play a role of un-coordinating counter-anions. In 2, there exist inversion centers at the mid-points of the C24 –C24 * and C34 –C34 # bonds. In 3, Cu1 cation and Ow1 lie on a twofold axis, and there are inversion centers at the midpoints of C15 –C15 * and C25 –C25 # bonds. The average Cu–N distance and the Cu–O (water) distance in 2 and 3 are quite near to those of 1. Each L molecule coordinates to two copper(II) cations, bridging the copper(II) cations to form infinite ð4; 4Þ networks [Figs. 2(b) and (c), 3(b) and (c)]. In 2, chloride ions and some lattice water molecules are encapsulated in the 44-membered rings of the ð4; 4Þ network, one chloride ion H-bonds to one coordinated water molecule and three lattice water molecules while the other chloride ion H-bonds to three lattice water molecules. The adjacent ð4; 4Þ networks are interconnected through hydrogen bonds as shown in Fig. 2(d). In 3, nitrate ions are encapsulated in the 44membered rings of the ð4; 4Þ network, and each nitrate ion H-bonds to one coordinated water molecule from the adjacent ð4; 4Þ networks as shown in Fig. 3(d). The uncoordinating counter-anions and water molecules filled in the networks may be the main reason for the non-interpenetrating structures of 2 and 3. As shown in Fig. 4(a), 4 consists of two crystallographically unique Cu(II) ions in the asymmetric unit. Both of them lie at the inversion center and have the similar coordination environment. The copper(II) cation of 4 is coordinated by four nitrogen atoms from four L molecules. In the related compound, [ZnL1:5 (H2 O) (SO4 )] 6H2 O complex with infinite ð6; 3Þ networks, the sulfate anion coordinates to the central zinc(II) cation [17a]. But in the present complex the sulfate anions play a role of counter-anion. The Cu–N (L) distances of are similar to those in complex 1, 2 2.00(2) and 2.04(2) A and 3. In complex 4, copper(II) ions are bridged by L to form infinite ð4; 4Þ networks [Fig. 4(b)], and two ð4; 4Þ networks are interpenetrated in parallel mode to form a layer [Fig. 4(c)]. The sulfate anions and water molecules
J.-F. Ma et al. / Polyhedron 23 (2004) 553–559
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Fig. 2. (a) An O R T E P drawing of the local coordination of Cu(II) cation in complex 2. Atoms are shown 50% probability ellipsoids. (b) The large ring of the ð4; 4Þ network in 2. (c) Extended structure of 2 (water and chloride anions are omitted for clarity). (d) The H-bonds interactions between adjacent layers.
Fig. 3. (a) An O R T E P drawing of the local coordination of Cu(II) cation in complex 3. Atoms are shown 50% probability ellipsoids. (b) The large ring of the ð4; 4Þ network in 3. (c) Extended structure of 3 (water and nitrate anions are omitted for clarity). (d) The H-bonds interactions between adjacent layers.
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Fig. 4. (a) An O R T E P drawing of the local coordination of Cu(II) in complex 4. Atoms are shown 50% probability ellipsoids. (b) The large ring of the ð4; 4Þ network in 4. (c) Schematic representation of the mode of interpenetration. (d) The alternative H-bonding layers and [CuL2 ]2þ layers.
are intercalated into the layers, and each sulfate ion Hbonds to six lattice water molecules. The extended structure was formed by stacking the layer of hydrogenbonded water molecules and sulfate ions and the layer of polymeric [CuL2 ]2þ alternatively [Fig. 4(d)]. The number of different ways two ð4; 4Þ nets could theoretically interpenetrate in the parallel fashion may be given by systematic study of the topology of interpenetration [28]. The interpenetrating structures of related complexes, [MnL3 (BF4 )2 ] [29] and [ZnL1:5 (H2 O)(SO4 )] 6H2 O [17a] have been reported. The reported [MnL3 (BF4 )2 ] complexes are composed of two equivalent, mutually interpenetrating three-dimensional networks, while in complex [ZnL1:5 (H2 O)(SO4 )] 6H2 O, the networks are interpenetrated in an inclined mode by symmetry related, identical networks to give an interlocked three-dimensional structure. In complexes 1, 2, 3 and 4 each L molecule coordinates to two copper(II) cations through its two aromatic nitrogen atoms acting as a bridging bidentate ligand. Copper(II) cations are bridged by L molecules to form one-dimensional chain in 1, ð4; 4Þ networks in 2, 3 and 4. The networks contain square grids (44-membered) with a copper(II) cation at each corner and a molecule of L at each edge connecting two copper(II) cations. The lengths of the opposite edges are equal in 2, 3 and 4. The for 2, 11.886 and edge lengths are 12.317 and 12.724 A for 3, 11.812 and 11.564 A for 4. 14.225 A The structures of these complexes imply a role of counter-anions in the fabrication of the framework.
Since isonicotinate anion is a better ligand for Cu(II) than other three anions, isonicotinate anions are coordinated to copper(II) ion in 1 while in other complexes the anions are non-coordinating. In each compound the anions are connected to water molecules through Hbonding interactions, and it can be seen that the polymeric networks can be tailored by using different anions.
4. Supplementary material CCDC-198614 (for 1), 198615 (for 2), 198616 (for 3) and 198617 (for 4) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK (fax: +44-1223-336-033; E-mail: [email protected] or http://www.ccdc.cam.ac.uk).
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