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Syntheses and crystal structures of two structurally diverse cobalt complexes constructed from 5-hydroxyl-1,3-benzenedicarboxylates
Journal of Molecular Structure 737 (2005) 97–101 www.elsevier.com/locate/molstruc
Syntheses and crystal structures of two structurally diverse cobalt complexes constructed from 5-hydroxyl-1,3-benzenedicarboxylates Hong-Yin Hea, Yi-Li Zhoua, Yan Honga, Long-Guan Zhub,* a Department of Chemical Engineering, Jiaxing College, Jiaxing 314001, People’s Republic of China Department of Chemistry, Zhejiang University, 38 Zheda Road, Hangzhou 310027, People’s Republic of China
b
Received 29 July 2004; revised 6 October 2004; accepted 12 October 2004 Available online 24 November 2004
Abstract Two structurally diverse compounds, {[Co(4,4 0 -bipy)(H2O)4](hmbdc)(H2O)}n (1) and {[Co(4,4 0 -bipy)(hmbdc)(H2O)2](4,4 0 bipy)(DMF)}n (2) (H2hmbdcZ5-hydroxyl-1,3-benzenedicarboxylic acid, 4,4 0 -bipyZ4,4 0 -bipyridine), were synthesized using different starting materials and solvents. Compound 1 possesses hydrogen-bonded 3D networks encapsulating 1D covalently bonded infinite [Co(4,4 0 bipy)(H2O)4]2C chain. Compound 2 shows a 2D architecture and free 4,4 0 -bipy and DMF molecules fill in the channels of the extended 3D hydrogen bonding network as guest molecules. q 2004 Elsevier B.V. All rights reserved. Keywords: Hydrogen bonding; Crystal structure; Cobalt complex; Diversity; Polymer
1. Introduction The crystal engineering in the field of supramolecular architectures based on metal and organic ligands has been extensively studied in recent years owing to their novel and diverse topologies and potential applications as functional materials [1–3]. In general, two different types of interactions (covalent bonds and noncovalent intermolecular forces) could be used to construct variable supramolecular architectures [4]. On this background, numerous compounds with the [M(4,4 0 -bipy)(H2O)4]2C building blocks have been prepared [5–8], such as [Zn(H2 O)4 (4,4 0 bipy)](NO3)2$2(4,4 0 -bipy), [Co(H2O)4(4,4 0 -bipy)](PF6)$3(3(bipy), and [Co(H2O)4(4,4 0 -bipy)](4-abs)2$H2O, which fabricate extended 2D or 3D architectures from 1D covalently bonded chains through hydrogen bonds. Here, we employed 4,4 0 -bipyridine and 5-hydroxyl-1,3-benzenedicarboxylic acid (H2hmbdc) as mixed organic building blocks to construct two supramolecular structures with uncoordinated hmbdc2K anion and coordinated * Corresponding author. Tel.: C86 571 8796 3867; fax: C86 571 8795 1895. E-mail address: [email protected] (L.-G. Zhu). 0022-2860/$ - see front matter q 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.molstruc.2004.10.006
hmbdc 2K ligand, namely {[Co(4,4 0 -bipy)(H 2O) 4](hmbdc)(H2O)}n (1) and {[Co(4,4 0 -bipy)(hmbdc)(H2O)2](DMF)(4,4 0 -bipy)}n (2).
2. Experimental 2.1. Synthesis and IR spectra {[Co(4,4 0 -bipy)(H2O)4](hmbdc)(H2O)}n (1). Crystals of 1 were grown by layer-method using three-layer solutions in a slender tube with a 0.8 cm diameter. The upper layer solution was 5 mL of C2H5OH/THF (v/v 2:1) containing 0.03 mol/L H2hmbdc and 0.06 mol/L 4,4 0 -bipyridine. The bottom layer solution was 5 mL of aqueous solution containing 0.03 mol/L Co(CH3COO)2$4H2O and the middle layer was 5 mL of C2H5OH/H2O (v/v 1:1) mixed solvent system. After standing for 2 months, purple rod crystals were obtained. They were collected by suction filtration. Anal. Calc. for C18H22CoN2O10: C, 44.55; H, 4.57; N, 5.77%. Found: C, 44.48; H, 4.62; N, 5.71%. IR (KBr pellet, cmK1): 3458(s), 3255(s), 1609(s), 1546(s), 1489(m), 1411(s), 1366(s), 1280(m), 1217(w), 1105(w), 1071(w), 983(w), 789(s), 729(m), 680(m), 634(m), 482(w).
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{[Co(4,4 0 -bipy)(hmbdc)(H2O)2](DMF)(4,4 0 -bipy)}n (2). Eight milliliters of DMF solution containing 4,4 0 -bipyridine (0.0468 g, 0.3 mmol) and H2hmbdc (0.0274 g, 0.15 mmol) was slowly added to a previously prepared aqueous solution (8 mL) of Co(NO3)2$6H2O (0.0438 g, 0.15 mmol). Then the mixed solution was slowly evaporated. After 5 months, red plate crystals were obtained. Anal. Calc. for C31H31CoN5O8: C, 56.37; H, 4.73; N, 10.60%. Found: C, 56.21; H, 4.75; N, 10.49%. IR (KBr pellet, cmK1): 3421(s), 1683(s), 1607(s), 1584(s), 1548(s), 1485(w), 1439(m), 1412(s), 1388(s), 1066(w), 815(w), 804(w), 782(m), 633(m), 606(w), 484(w). The IR spectra for compounds 1 and 2 show the characteristic vibration peaks of 4,4 0 -bipyridine and hmbdc2K. Compounds 1 and 2 exhibit OH stretching bands at 3458 and 3421 cmK1, respectively, indicating the presence of water molecules in both compounds. The well resolved peaks of aromatic rings in 1 and 2 could be clearly observed. The characteristic peaks of the carboxylate groups appear at 1584 and 1548 cmK1 for asymmetric vibrations and at 1412 and 1388 cmK1 for symmetric vibrations in 2. In general, the free hmbdc2K could not be distinguished from IR [9]. Therefore, corresponding peaks for asymmetric (1546 cmK1) and symmetric (1411 and 1366 cmK1) vibrations in 1 were observed due to strong hydrogen bonds between water molecules and hmbdc2K. 2.2. Single crystal structure determination X-ray diffraction data were collected for 1 and 2 using Bruker SMART CCD area detector diffractometer equipped
Fig. 1. ORTEP view of compound {[Co(4,4 0 -bipy)(H2O)4](hmbdc)(H2O)}n (1).
with graphite monochromated Mo Ka radiation (lZ ˚ ). An empirical absorption correction was applied 0.71073 A using the SADABS program [10]. The structures were solved by direct methods using SHELXS-97 [11] and refined by full matrix least-squares procedures on F2o using SHELXL97 [12] in the WinGX environment [13]. H atoms for OH and H2O in 1 and 2 were found in Fourier difference syntheses and aromatic hydrogen atoms were placed geometrically in calculated positions and thereafter refined using a riding model. DMF in 2 shows some disorder and atoms of DMF were refined with isotropic displacement parameters. Crystal data and structure refinements are given in Table 1.
Table 1 Crystal data and details of structural determination of compounds 1 and 2
3. Results and discussion Formula
C18H22CoN2O10
C31H31CoN5O8
Fw Crystal color, shape Crystal size (mm) Space group ˚) a (A ˚) b (A ˚) c (A a (8) b (8) g (8) ˚ 3) V (A Z D (Mg/cmK3) T (K) m (mmK1) Measured reflections Observed reflections R1 and wR2 (IO2s(I)) R1 and wR2 (all data) Number of variables Goodness of fit (GOF) Largest difference ˚ K3) peak and hole (e A
485.31 purple, rod 0.44!0.26!0.26 Orthorhombic/Pna21 13.4756(17) 12.7195(16) 11.3990(14) 90 90 90 1953.8(4) 4 1.650 293G2 0.941 10,991 3955 0.046, 0.065 0.073, 0.070 313 0.888 0.969, K0.556
660.54 red, plate 0.50!0.18!0.14 Orthorhombic/Pccn 14.078(8) 19.575(12) 22.714(13) 90 90 90 6259(6) 8 1.402 293G2 0.606 31,726 5883 0.057, 0.171 0.093, 0.188 402 0.962 0.876, K0.631
Compound 1 consists of 1D covalently bonded chains formed by 4,4 0 -bipyridine ligands connecting Co atoms, Table 2 ˚ ) and angles (8) for compound 1 Selected bond lengths (A Co1–O6 Co1–O8 Co1–N1 O1–C11 C11–C12 O4–C18 O5–C16 O6–Co1–O7 O6–Co1–O9 O6–Co1–N2* O7–Co1–O9 O7–Co1–N2* O8–Co1–N1 O9–Co1–N1 N1–Co1–N2* O3–C18–O4
2.075(3) 2.117(3) 2.140(6) 1.240(5) 1.499(6) 1.276(5) 1.356(6) 92.3(1) 91.1(1) 89.3(2) 176.6(1) 92.1(2) 95.1(2) 91.8 (2) 179.2(1) 123.9(5)
Symmetry code: (*) x, y, 1Kz.
Co1–O7 Co1–O9 Co1–N2* O2–C11 O3–C18 C14–C18
2.114(3) 2.129(3) 2.146(6) 1.277(5) 1.228(5) 1.510(6)
O6–Co1–O8 O6–Co1–N1 O7–Co1–O8 O7–Co1–N1 O8–Co1–O9 O8–Co1–N2* O9–Co1–N2* O1–C11–O2
173.0(2) 91.3(2) 90.8(1) 88.4(2) 85.9(1) 84.3(2) 87.7(2) 123.5(4)
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Fig. 2. ORTEP drawing of the 1D covalently bonded chain in 1 showing the coordination environment of the cobalt atom. The hydrogen atoms are omitted for clarity.
uncoordinated hmbdc2K anions, and coordinated and lattice water molecules. The CoII center exhibits slightly distorted octahedral coordination geometry, defined by four aqua ligands in the equatorial positions and two pyridyl nitrogen donors from two different 4,4 0 -bipy ligands in the apical positions (Fig. 1 and Table 2). These average Co–O ˚ , Co–NZ and Co–N distances [Co–OZ2.109(3) A ˚ ] in 1 are comparable to those observed for 2.143(6) A ˚, [Co(4,4 0 -bipy)(H2O)4](fum)(4H2O)] [Co–OZ2.096(2) A 0 ˚ Co–NZ2.146(2) A] [14], [Co(H2O)4(4,4 -bipy)](PF 6)$ ˚ , Co–NZ2.160(5) A ˚ ] [15], 3(4,4 0 -bipy) [Co–OZ2.099(3) A 0 and [Co(4,4 -bipy)(H 2O) 4](4-abs) 2$H 2O [Co–OZ ˚ , Co–NZ2.144(4) A ˚ ] [16]. The 4,4 0 -bipy ligands 2.100(5) A serve as bis-monodentate linkers and bridge adjacent Co ˚ into 1D centers with the Co/Co separation of 11.399(1) A infinite chain (Fig. 2). The two pyridyl rings in one 4,4 0 -bipy ligand are not coplanar and have a dihedral angle of 16.0(1)8. In compound 1, the uncoordinated hmbdc2K anions form a 1D chain through O5 and O3 (symmetry code: K xC1, KyC2, zK1/2), that is, the OH group of one hmbdc2K anion acts as a H-donor and interacts with the carboxylate oxygen atom O3 (symmetry code: KxC1, KyC2, zK1/2) from another hmbdc2K anion [O–H/O ˚ ]. Furthermore, these hydrogen bonding 1D 2.803(4) A chains are connected by the crystallization water molecules (O10) via hydrogen-bonding interactions
Fig. 3. View of 2D hydrogen bonding network among water molecules and hmbdc2K anions in 1.
˚ , O10–H/O5ii 2.754(5) A ˚ , sym[O10–H/O1i 2.762(5) A metry codes: (i) xC1/2, KyC1/2, z; (ii) KxC3/2, yK 1/2, zC1/2] and extended into a 2D layered network with large cavities (Fig. 3). The detail analysis shows that there are three kinds of hydrogen bonds in the extended 2D network between hydroxyl and carboxyl, hydroxyl and lattice water, and lattice water and carboxyl. In addition, the 2D layers are further linked by the coordinated water molecules (O6, O7, O8, and ˚; O9) through hydrogen bonds [O6–H/O4i, 2.710(5) A ii ˚ ˚ O6–H/O3 , 2.765(6) A; O7–H/O10, 2.681(7) A; O7– ˚ ; O8–H/O4iii, 2.769(5) A ˚ ; O9–H/ H/O2ii, 2.768(5) A iv ˚ ˚ O1, 2.773(5) A; O9–H/O2 , 2.778(5) A, symmetry codes: (i) xC1/2, KyC3/2, z; (ii) KxC3/2, yK1/2, zK1/2; (iii) x, yK1, z; (iv) KxC1, KyC1, zK1/2] into a 3D network with channels (Fig. 4). Although, 3D supramolecular networks can be expected for compounds with [Co(4,4 0 -bipy)(H2O)4]2C building blocks, 1D covalently bonded chains and cationic–anionic hydrogenbonding networks could be tuned by variable anions and lattice water molecules. For example, the dihedral angle of two pyridyl rings of one 4,4 0 -bipy in 1 is significantly larger than that of [Co(4,4 0 -bipy)(H2O)4](4abs)2$H2O [16]. ˚! Compound 2 is a 2D network with a grid of 9.844 A ˚ . The compound consists of 2D network, 4,4 0 11.357 A bipyridine, and DMF molecules. There are two cobalt atoms in an asymmetrical unit and both cobalt atoms have octahedral geometries completed by two water molecules,
Fig. 4. View of 3D hydrogen bonding network of 1.
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Fig. 6. View of 2D architecture for 2. Free ligands of 4,4 0 -bipyridine and DMF molecules are omitted for clarity.
Fig. 5. ORTEP view of compound {[Co(4,4 0 -bipy)(hmbdc)(H2O)2](4,4 0 bipy)(DMF)}n (2). Free ligand of 4,4 0 -bipy and DMF are omitted for clarity.
two carboxylate oxygen donors from two hmbdc2K, and two nitrogen atoms from two 4,4 0 -bipy ligands (Fig. 5). The average bond lengths of Co–O and Co–N are ˚ , respectively (Table 3). These 2.119(3) and 2.128(5) A bond lengths are similar to those in compound 1. The 4,4 0 bipy ligands form 1D chains with cobalt atoms. Two bipyridine ligands bonded to Co1 and Co2 have very different conformations. Two rings of the bipyridine bonded to Co1 have a dihedral angle of 16.2(2)8, which is similar to that of compound 1, while two rings of the bipyridine bonded to Co2 have a larger dihedral angle of 31.1(3)8. The proton of hydroxyl group on position 5 of the hmbdc2K
ligand is retained and the hydroxyl group is not coordinated to cobalt atom while the hydroxyl atom O5 can act as a donor of hydrogen bond. The hmbdc2K ligand has a bismonodentate mode acting as a bridging linker, which could extend 1D chains (4,4 0 -bipy-Co-4,4 0 -bipy-Co) into a 2D network (Fig. 6). The coordinated water molecules form intra-molecular hydrogen bonds with uncoordinated car˚ ; O7–H/ boxylate oxygen atoms [O6–H/O2, 2.663(4) A i ˚ O4 , 2.662(4) A, symmetry code: (i) KxC3/2, KyC5/2, z] and also form hydrogen bonds with DMF molecules [O6– ˚ ]. Moreover, hydrogen bonds are formed H/O8, 2.777(7) A between 2D layers via water molecule (O7), hydroxyl (O5), and uncoordinated carboxylate oxygen atoms (O2 and O4) [O7–H/O2i, 2.845(4); O5–H/O4ii, 2.704(4), symmetry codes: (i) KxC2, yC1/2, KzC1/2; (ii) xC1/2, KyC2, K zC1/2]. As expected, 3D hydrogen bonding network is
Table 3 ˚ ) and angles (8) for compound 2 Selected bond lengths (A Co1–O1 Co1–N1 Co2–O3 Co2–N3 O1–C1 C1–C2 O4–C8 O5–C4 O1–Co1–O6 O1–Co1–O6* O1–Co1–N2* O6–Co1–N1 N1–Co1–N2* O3–Co2–O3# O3–Co2–N3 O7–Co2–O7# O7–Co2–N4 O1–C1–O2
2.090(3) 2.122(5) 2.103(3) 2.126(5) 1.265(5) 1.491(5) 1.262(5) 1.370(5) 89.7(1) 90.3(1) 90.25(7) 87.57(8) 180.00(0) 176.1(1) 91.95(7) 179.4(2) 90.33(8) 125.0(4)
Co1–O6 Co1–N2* Co2–O7 Co2–N4# O2–C1 O3–C8 C6–C8 O1–Co1–O1* O1–Co1–N1 O6–Co1–O6* O6–Co1–N2* O3–Co2–O7 O3–Co2–O7# O3–Co2–N4# O7–Co2–N3 N3–Co2–N4# O3–C8–O4
2.138(3) 2.128(5) 2.144(3) 2.137(5) 1.260(5) 1.257(5) 1.501(5) 179.5(1) 89.75(7) 175.2(2) 92.43(8) 89.1(1) 91.0(1) 88.05(7) 89.67(8) 180.00(0) 123.9(4)
Symmetry code: (*) 1.5Kx, 1.5Ky, z; (#) 1.5Kx, 2.5Ky, z.
Fig. 7. View of the guest–host assembly for compound 2.
H.-Y. He et al. / Journal of Molecular Structure 737 (2005) 97–101
formed. The free ligands of 4,4 0 -bipy and DMF molecules act as guest molecules and fill in the channels of 3D hydrogen bonding network (Fig. 7). Interestingly, guest 4,4 0 -bipy molecules in channels stack each other as pairs ˚. and stacking distance is about 3.6 A Recently, numerous compounds with square nets constructed by [M(4,4 0 -bipy)2(H2O)2]2C building blocks have been extensively studied [17–20]. Square frameworks extended by [M(4,4 0 -bipy)2(H2O)2]2C are cationic species, while in compound 2 2D grid is a neutral network. These 2D grid frameworks have a common feature that they could form 3D supramolecular architectures through hydrogen bonds and guest molecules are included in channels of 3D supramolecular networks. In conclusion, two novel hydrogen-bonded 3D supramolecular architectures have been synthesized and structurally characterized. In these two compounds, the different coordination modes of hmbdc2K ligands create structurally diverse frameworks and topologies. These successful examples reveal that variable synthetic methods and solvents may provide multiple interactions such as covalent, hydrogen-bonding, and stacking interactions, which is of benefit to construct diverse functional materials.
4. Supplementary materials Crystallographic data (excluding structure factors) for the structural analysis have been deposited with the Cambridge Crystallographic Data Center as supplementary publication Nos. 246077 and 246078 for compounds 1 and 2, respectively. Copies of the data can be obtained free of charge via www.ccdc.ac.uk/conts/retrieving.html (or from The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK. Fax: C44 1223 336 033. E-mail: [email protected]. ac.uk).
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Acknowledgements The project was supported by the National Natural Science Foundation of China (50073019).
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Syntheses and crystal structures of two structurally diverse cobalt complexes constructed from 5-hydroxyl-1,3-benzenedicarboxylates Hong-Yin Hea, Yi-Li Zhoua, Yan Honga, Long-Guan Zhub,* a Department of Chemical Engineering, Jiaxing College, Jiaxing 314001, People’s Republic of China Department of Chemistry, Zhejiang University, 38 Zheda Road, Hangzhou 310027, People’s Republic of China
b
Received 29 July 2004; revised 6 October 2004; accepted 12 October 2004 Available online 24 November 2004
Abstract Two structurally diverse compounds, {[Co(4,4 0 -bipy)(H2O)4](hmbdc)(H2O)}n (1) and {[Co(4,4 0 -bipy)(hmbdc)(H2O)2](4,4 0 bipy)(DMF)}n (2) (H2hmbdcZ5-hydroxyl-1,3-benzenedicarboxylic acid, 4,4 0 -bipyZ4,4 0 -bipyridine), were synthesized using different starting materials and solvents. Compound 1 possesses hydrogen-bonded 3D networks encapsulating 1D covalently bonded infinite [Co(4,4 0 bipy)(H2O)4]2C chain. Compound 2 shows a 2D architecture and free 4,4 0 -bipy and DMF molecules fill in the channels of the extended 3D hydrogen bonding network as guest molecules. q 2004 Elsevier B.V. All rights reserved. Keywords: Hydrogen bonding; Crystal structure; Cobalt complex; Diversity; Polymer
1. Introduction The crystal engineering in the field of supramolecular architectures based on metal and organic ligands has been extensively studied in recent years owing to their novel and diverse topologies and potential applications as functional materials [1–3]. In general, two different types of interactions (covalent bonds and noncovalent intermolecular forces) could be used to construct variable supramolecular architectures [4]. On this background, numerous compounds with the [M(4,4 0 -bipy)(H2O)4]2C building blocks have been prepared [5–8], such as [Zn(H2 O)4 (4,4 0 bipy)](NO3)2$2(4,4 0 -bipy), [Co(H2O)4(4,4 0 -bipy)](PF6)$3(3(bipy), and [Co(H2O)4(4,4 0 -bipy)](4-abs)2$H2O, which fabricate extended 2D or 3D architectures from 1D covalently bonded chains through hydrogen bonds. Here, we employed 4,4 0 -bipyridine and 5-hydroxyl-1,3-benzenedicarboxylic acid (H2hmbdc) as mixed organic building blocks to construct two supramolecular structures with uncoordinated hmbdc2K anion and coordinated * Corresponding author. Tel.: C86 571 8796 3867; fax: C86 571 8795 1895. E-mail address: [email protected] (L.-G. Zhu). 0022-2860/$ - see front matter q 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.molstruc.2004.10.006
hmbdc 2K ligand, namely {[Co(4,4 0 -bipy)(H 2O) 4](hmbdc)(H2O)}n (1) and {[Co(4,4 0 -bipy)(hmbdc)(H2O)2](DMF)(4,4 0 -bipy)}n (2).
2. Experimental 2.1. Synthesis and IR spectra {[Co(4,4 0 -bipy)(H2O)4](hmbdc)(H2O)}n (1). Crystals of 1 were grown by layer-method using three-layer solutions in a slender tube with a 0.8 cm diameter. The upper layer solution was 5 mL of C2H5OH/THF (v/v 2:1) containing 0.03 mol/L H2hmbdc and 0.06 mol/L 4,4 0 -bipyridine. The bottom layer solution was 5 mL of aqueous solution containing 0.03 mol/L Co(CH3COO)2$4H2O and the middle layer was 5 mL of C2H5OH/H2O (v/v 1:1) mixed solvent system. After standing for 2 months, purple rod crystals were obtained. They were collected by suction filtration. Anal. Calc. for C18H22CoN2O10: C, 44.55; H, 4.57; N, 5.77%. Found: C, 44.48; H, 4.62; N, 5.71%. IR (KBr pellet, cmK1): 3458(s), 3255(s), 1609(s), 1546(s), 1489(m), 1411(s), 1366(s), 1280(m), 1217(w), 1105(w), 1071(w), 983(w), 789(s), 729(m), 680(m), 634(m), 482(w).
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{[Co(4,4 0 -bipy)(hmbdc)(H2O)2](DMF)(4,4 0 -bipy)}n (2). Eight milliliters of DMF solution containing 4,4 0 -bipyridine (0.0468 g, 0.3 mmol) and H2hmbdc (0.0274 g, 0.15 mmol) was slowly added to a previously prepared aqueous solution (8 mL) of Co(NO3)2$6H2O (0.0438 g, 0.15 mmol). Then the mixed solution was slowly evaporated. After 5 months, red plate crystals were obtained. Anal. Calc. for C31H31CoN5O8: C, 56.37; H, 4.73; N, 10.60%. Found: C, 56.21; H, 4.75; N, 10.49%. IR (KBr pellet, cmK1): 3421(s), 1683(s), 1607(s), 1584(s), 1548(s), 1485(w), 1439(m), 1412(s), 1388(s), 1066(w), 815(w), 804(w), 782(m), 633(m), 606(w), 484(w). The IR spectra for compounds 1 and 2 show the characteristic vibration peaks of 4,4 0 -bipyridine and hmbdc2K. Compounds 1 and 2 exhibit OH stretching bands at 3458 and 3421 cmK1, respectively, indicating the presence of water molecules in both compounds. The well resolved peaks of aromatic rings in 1 and 2 could be clearly observed. The characteristic peaks of the carboxylate groups appear at 1584 and 1548 cmK1 for asymmetric vibrations and at 1412 and 1388 cmK1 for symmetric vibrations in 2. In general, the free hmbdc2K could not be distinguished from IR [9]. Therefore, corresponding peaks for asymmetric (1546 cmK1) and symmetric (1411 and 1366 cmK1) vibrations in 1 were observed due to strong hydrogen bonds between water molecules and hmbdc2K. 2.2. Single crystal structure determination X-ray diffraction data were collected for 1 and 2 using Bruker SMART CCD area detector diffractometer equipped
Fig. 1. ORTEP view of compound {[Co(4,4 0 -bipy)(H2O)4](hmbdc)(H2O)}n (1).
with graphite monochromated Mo Ka radiation (lZ ˚ ). An empirical absorption correction was applied 0.71073 A using the SADABS program [10]. The structures were solved by direct methods using SHELXS-97 [11] and refined by full matrix least-squares procedures on F2o using SHELXL97 [12] in the WinGX environment [13]. H atoms for OH and H2O in 1 and 2 were found in Fourier difference syntheses and aromatic hydrogen atoms were placed geometrically in calculated positions and thereafter refined using a riding model. DMF in 2 shows some disorder and atoms of DMF were refined with isotropic displacement parameters. Crystal data and structure refinements are given in Table 1.
Table 1 Crystal data and details of structural determination of compounds 1 and 2
3. Results and discussion Formula
C18H22CoN2O10
C31H31CoN5O8
Fw Crystal color, shape Crystal size (mm) Space group ˚) a (A ˚) b (A ˚) c (A a (8) b (8) g (8) ˚ 3) V (A Z D (Mg/cmK3) T (K) m (mmK1) Measured reflections Observed reflections R1 and wR2 (IO2s(I)) R1 and wR2 (all data) Number of variables Goodness of fit (GOF) Largest difference ˚ K3) peak and hole (e A
485.31 purple, rod 0.44!0.26!0.26 Orthorhombic/Pna21 13.4756(17) 12.7195(16) 11.3990(14) 90 90 90 1953.8(4) 4 1.650 293G2 0.941 10,991 3955 0.046, 0.065 0.073, 0.070 313 0.888 0.969, K0.556
660.54 red, plate 0.50!0.18!0.14 Orthorhombic/Pccn 14.078(8) 19.575(12) 22.714(13) 90 90 90 6259(6) 8 1.402 293G2 0.606 31,726 5883 0.057, 0.171 0.093, 0.188 402 0.962 0.876, K0.631
Compound 1 consists of 1D covalently bonded chains formed by 4,4 0 -bipyridine ligands connecting Co atoms, Table 2 ˚ ) and angles (8) for compound 1 Selected bond lengths (A Co1–O6 Co1–O8 Co1–N1 O1–C11 C11–C12 O4–C18 O5–C16 O6–Co1–O7 O6–Co1–O9 O6–Co1–N2* O7–Co1–O9 O7–Co1–N2* O8–Co1–N1 O9–Co1–N1 N1–Co1–N2* O3–C18–O4
2.075(3) 2.117(3) 2.140(6) 1.240(5) 1.499(6) 1.276(5) 1.356(6) 92.3(1) 91.1(1) 89.3(2) 176.6(1) 92.1(2) 95.1(2) 91.8 (2) 179.2(1) 123.9(5)
Symmetry code: (*) x, y, 1Kz.
Co1–O7 Co1–O9 Co1–N2* O2–C11 O3–C18 C14–C18
2.114(3) 2.129(3) 2.146(6) 1.277(5) 1.228(5) 1.510(6)
O6–Co1–O8 O6–Co1–N1 O7–Co1–O8 O7–Co1–N1 O8–Co1–O9 O8–Co1–N2* O9–Co1–N2* O1–C11–O2
173.0(2) 91.3(2) 90.8(1) 88.4(2) 85.9(1) 84.3(2) 87.7(2) 123.5(4)
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Fig. 2. ORTEP drawing of the 1D covalently bonded chain in 1 showing the coordination environment of the cobalt atom. The hydrogen atoms are omitted for clarity.
uncoordinated hmbdc2K anions, and coordinated and lattice water molecules. The CoII center exhibits slightly distorted octahedral coordination geometry, defined by four aqua ligands in the equatorial positions and two pyridyl nitrogen donors from two different 4,4 0 -bipy ligands in the apical positions (Fig. 1 and Table 2). These average Co–O ˚ , Co–NZ and Co–N distances [Co–OZ2.109(3) A ˚ ] in 1 are comparable to those observed for 2.143(6) A ˚, [Co(4,4 0 -bipy)(H2O)4](fum)(4H2O)] [Co–OZ2.096(2) A 0 ˚ Co–NZ2.146(2) A] [14], [Co(H2O)4(4,4 -bipy)](PF 6)$ ˚ , Co–NZ2.160(5) A ˚ ] [15], 3(4,4 0 -bipy) [Co–OZ2.099(3) A 0 and [Co(4,4 -bipy)(H 2O) 4](4-abs) 2$H 2O [Co–OZ ˚ , Co–NZ2.144(4) A ˚ ] [16]. The 4,4 0 -bipy ligands 2.100(5) A serve as bis-monodentate linkers and bridge adjacent Co ˚ into 1D centers with the Co/Co separation of 11.399(1) A infinite chain (Fig. 2). The two pyridyl rings in one 4,4 0 -bipy ligand are not coplanar and have a dihedral angle of 16.0(1)8. In compound 1, the uncoordinated hmbdc2K anions form a 1D chain through O5 and O3 (symmetry code: K xC1, KyC2, zK1/2), that is, the OH group of one hmbdc2K anion acts as a H-donor and interacts with the carboxylate oxygen atom O3 (symmetry code: KxC1, KyC2, zK1/2) from another hmbdc2K anion [O–H/O ˚ ]. Furthermore, these hydrogen bonding 1D 2.803(4) A chains are connected by the crystallization water molecules (O10) via hydrogen-bonding interactions
Fig. 3. View of 2D hydrogen bonding network among water molecules and hmbdc2K anions in 1.
˚ , O10–H/O5ii 2.754(5) A ˚ , sym[O10–H/O1i 2.762(5) A metry codes: (i) xC1/2, KyC1/2, z; (ii) KxC3/2, yK 1/2, zC1/2] and extended into a 2D layered network with large cavities (Fig. 3). The detail analysis shows that there are three kinds of hydrogen bonds in the extended 2D network between hydroxyl and carboxyl, hydroxyl and lattice water, and lattice water and carboxyl. In addition, the 2D layers are further linked by the coordinated water molecules (O6, O7, O8, and ˚; O9) through hydrogen bonds [O6–H/O4i, 2.710(5) A ii ˚ ˚ O6–H/O3 , 2.765(6) A; O7–H/O10, 2.681(7) A; O7– ˚ ; O8–H/O4iii, 2.769(5) A ˚ ; O9–H/ H/O2ii, 2.768(5) A iv ˚ ˚ O1, 2.773(5) A; O9–H/O2 , 2.778(5) A, symmetry codes: (i) xC1/2, KyC3/2, z; (ii) KxC3/2, yK1/2, zK1/2; (iii) x, yK1, z; (iv) KxC1, KyC1, zK1/2] into a 3D network with channels (Fig. 4). Although, 3D supramolecular networks can be expected for compounds with [Co(4,4 0 -bipy)(H2O)4]2C building blocks, 1D covalently bonded chains and cationic–anionic hydrogenbonding networks could be tuned by variable anions and lattice water molecules. For example, the dihedral angle of two pyridyl rings of one 4,4 0 -bipy in 1 is significantly larger than that of [Co(4,4 0 -bipy)(H2O)4](4abs)2$H2O [16]. ˚! Compound 2 is a 2D network with a grid of 9.844 A ˚ . The compound consists of 2D network, 4,4 0 11.357 A bipyridine, and DMF molecules. There are two cobalt atoms in an asymmetrical unit and both cobalt atoms have octahedral geometries completed by two water molecules,
Fig. 4. View of 3D hydrogen bonding network of 1.
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Fig. 6. View of 2D architecture for 2. Free ligands of 4,4 0 -bipyridine and DMF molecules are omitted for clarity.
Fig. 5. ORTEP view of compound {[Co(4,4 0 -bipy)(hmbdc)(H2O)2](4,4 0 bipy)(DMF)}n (2). Free ligand of 4,4 0 -bipy and DMF are omitted for clarity.
two carboxylate oxygen donors from two hmbdc2K, and two nitrogen atoms from two 4,4 0 -bipy ligands (Fig. 5). The average bond lengths of Co–O and Co–N are ˚ , respectively (Table 3). These 2.119(3) and 2.128(5) A bond lengths are similar to those in compound 1. The 4,4 0 bipy ligands form 1D chains with cobalt atoms. Two bipyridine ligands bonded to Co1 and Co2 have very different conformations. Two rings of the bipyridine bonded to Co1 have a dihedral angle of 16.2(2)8, which is similar to that of compound 1, while two rings of the bipyridine bonded to Co2 have a larger dihedral angle of 31.1(3)8. The proton of hydroxyl group on position 5 of the hmbdc2K
ligand is retained and the hydroxyl group is not coordinated to cobalt atom while the hydroxyl atom O5 can act as a donor of hydrogen bond. The hmbdc2K ligand has a bismonodentate mode acting as a bridging linker, which could extend 1D chains (4,4 0 -bipy-Co-4,4 0 -bipy-Co) into a 2D network (Fig. 6). The coordinated water molecules form intra-molecular hydrogen bonds with uncoordinated car˚ ; O7–H/ boxylate oxygen atoms [O6–H/O2, 2.663(4) A i ˚ O4 , 2.662(4) A, symmetry code: (i) KxC3/2, KyC5/2, z] and also form hydrogen bonds with DMF molecules [O6– ˚ ]. Moreover, hydrogen bonds are formed H/O8, 2.777(7) A between 2D layers via water molecule (O7), hydroxyl (O5), and uncoordinated carboxylate oxygen atoms (O2 and O4) [O7–H/O2i, 2.845(4); O5–H/O4ii, 2.704(4), symmetry codes: (i) KxC2, yC1/2, KzC1/2; (ii) xC1/2, KyC2, K zC1/2]. As expected, 3D hydrogen bonding network is
Table 3 ˚ ) and angles (8) for compound 2 Selected bond lengths (A Co1–O1 Co1–N1 Co2–O3 Co2–N3 O1–C1 C1–C2 O4–C8 O5–C4 O1–Co1–O6 O1–Co1–O6* O1–Co1–N2* O6–Co1–N1 N1–Co1–N2* O3–Co2–O3# O3–Co2–N3 O7–Co2–O7# O7–Co2–N4 O1–C1–O2
2.090(3) 2.122(5) 2.103(3) 2.126(5) 1.265(5) 1.491(5) 1.262(5) 1.370(5) 89.7(1) 90.3(1) 90.25(7) 87.57(8) 180.00(0) 176.1(1) 91.95(7) 179.4(2) 90.33(8) 125.0(4)
Co1–O6 Co1–N2* Co2–O7 Co2–N4# O2–C1 O3–C8 C6–C8 O1–Co1–O1* O1–Co1–N1 O6–Co1–O6* O6–Co1–N2* O3–Co2–O7 O3–Co2–O7# O3–Co2–N4# O7–Co2–N3 N3–Co2–N4# O3–C8–O4
2.138(3) 2.128(5) 2.144(3) 2.137(5) 1.260(5) 1.257(5) 1.501(5) 179.5(1) 89.75(7) 175.2(2) 92.43(8) 89.1(1) 91.0(1) 88.05(7) 89.67(8) 180.00(0) 123.9(4)
Symmetry code: (*) 1.5Kx, 1.5Ky, z; (#) 1.5Kx, 2.5Ky, z.
Fig. 7. View of the guest–host assembly for compound 2.
H.-Y. He et al. / Journal of Molecular Structure 737 (2005) 97–101
formed. The free ligands of 4,4 0 -bipy and DMF molecules act as guest molecules and fill in the channels of 3D hydrogen bonding network (Fig. 7). Interestingly, guest 4,4 0 -bipy molecules in channels stack each other as pairs ˚. and stacking distance is about 3.6 A Recently, numerous compounds with square nets constructed by [M(4,4 0 -bipy)2(H2O)2]2C building blocks have been extensively studied [17–20]. Square frameworks extended by [M(4,4 0 -bipy)2(H2O)2]2C are cationic species, while in compound 2 2D grid is a neutral network. These 2D grid frameworks have a common feature that they could form 3D supramolecular architectures through hydrogen bonds and guest molecules are included in channels of 3D supramolecular networks. In conclusion, two novel hydrogen-bonded 3D supramolecular architectures have been synthesized and structurally characterized. In these two compounds, the different coordination modes of hmbdc2K ligands create structurally diverse frameworks and topologies. These successful examples reveal that variable synthetic methods and solvents may provide multiple interactions such as covalent, hydrogen-bonding, and stacking interactions, which is of benefit to construct diverse functional materials.
4. Supplementary materials Crystallographic data (excluding structure factors) for the structural analysis have been deposited with the Cambridge Crystallographic Data Center as supplementary publication Nos. 246077 and 246078 for compounds 1 and 2, respectively. Copies of the data can be obtained free of charge via www.ccdc.ac.uk/conts/retrieving.html (or from The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK. Fax: C44 1223 336 033. E-mail: [email protected]. ac.uk).
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Acknowledgements The project was supported by the National Natural Science Foundation of China (50073019).
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