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Four coordination polymers derived from 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole and copper sulfate
Inorganic Chemistry Communications 13 (2010) 976–980
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Inorganic Chemistry Communications j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i n o c h e
Four coordination polymers derived from 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole and copper sulfate Kui Liu, Xia Zhu, Ju Wang, Baolong Li ⁎, Yong Zhang Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry and Chemical Engineering and Material Science, Soochow University, Suzhou 215123, PR China
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Article history: Received 16 March 2010 Accepted 20 May 2010 Available online 26 May 2010 Keywords: Copper sulfate complex Solvent-controlled assembly Coordination polymer 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole
a b s t r a c t The reaction of 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-bpt) with copper sulfate in EtOH/H2O solvent yields four coordination polymers [Cu(3-bpt)(H2O)4](SO4)·H2O (1), [Cu(3-bpt)(H2O)4][Cu(3-bpt)(H2O)3 (SO4)](SO4)·7H2O (2), [Cu(3-bpt)(H2O)3(SO4)]·2H2O (3) and [Cu(3-bpt)(H2O)(SO4)] (4), showing onedimensional undulated chain, zigzag chain and two-dimensional network. The formations of compounds 1, 2 and 3 are controlled by the EtOH/H2O ratio. The synthesis of compound 4 may be controlled by the EtOH/H2O ratio and the temperature because it is prepared under solvothermal condition. The thermal properties have been investigated. © 2010 Elsevier B.V. All rights reserved.
The current interest in the crystal engineering of coordination polymer frameworks stems not only from their potential applications as functional materials for gas storage, separation, microelectronics, nonlinear optics and catalysis, but also from their intriguing variety of topologies [1–7]. Designing effective ligands and selecting metal centers are the key points to construct of novel metal-organic frameworks. 4-Amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-bpt), an angular dipyridyl ligand, may show three typical conformations under appropriate surrounds and it can construct novel metal-organic frameworks [8–13]. The design of coordination polymers is highly influenced by several factors such as the geometric preference of metal ions, the size and shapes of the organic building blocks, the metal–ligand ratio, templates, the solvent systems and the counterions [14–19]. Among these the solvent media used in the assembling processes may significantly influence the structures of the resulting coordination polymers [8,20–30]. On the other hand, the simple anion SO2− 4 , can play an important role in the assembly of coordination frameworks [31–35]. Water molecules are terminal ligands and competitive with the sulfate groups in bonding the metal cations. However the roles of water solvent and SO2− ion on the structural assemblies of metal-organic 4 frameworks has still not been well-understood. To further explore this attractive topic, we report here a study of the solvent effect on metalorganic frameworks by employing H2O and EtOH/H2O solvents, and organic ligand 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-bpt) and copper sulfate. Four coordination polymers [Cu(3-bpt)(H2O)4]
⁎ Corresponding author. Tel.: +86 512 65880324; fax: +86 512 65880089. E-mail address: [email protected] (B. Li). 1387-7003/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2010.05.011
(SO 4 )·H 2 O (1), [Cu(3-bpt)(H 2 O) 4 ][Cu(3-bpt)(H 2 O) 3 (SO 4 )] (SO4)·7H2O (2), [Cu(3-bpt)(H2O)3(SO4)]·2H2O (3) and [Cu(3-bpt) (H2O)(SO4)] (4) were synthesized and structurally characterized. Scheme 1 shows the syntheses of compounds 1–4 [36]. The design of coordination polymers is highly influenced by the solvent systems [8,20–30]. The direct reaction of ligand 4-amino-3,5-bis(3-pyridyl)1,2,4-triazole (3-bpt) and copper sulfate in an aqueous solution gives [Cu(3-bpt)(H2O)4](SO4)·H2O (1). When an EtOH/H2O solution (2 mL EtOH and 10 mL H2O) is used, the direct reaction of 3-bpt and copper sulfate gives [Cu(3-bpt)(H2O)4][Cu(3-bpt)(H2O)3(SO4)](SO4)·7H2O (2). However the precipitates are formed immediately when more EtOH is used in the synthesis. [Cu(3-bpt)(H2O)3(SO4)]·2H2O (3) is obtained when an EtOH solution of 3-bpt diffuses into an aqueous solution of copper sulfate. The hydrothermal reaction of 3-bpt and copper sulfate in a solution of 6 mL EtOH and 10 mL H2O produces [Cu (3-bpt)(H2O)(SO4)] (4). The formations of compounds 1, 2 and 3 are controlled by the EtOH/H2O ratio. The more EtOH is used, the less water coordinate to Cu(II) atom, and the more competitive
Scheme 1. The syntheses of compounds 1 to 4.
K. Liu et al. / Inorganic Chemistry Communications 13 (2010) 976–980
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Fig. 1. The one-dimensional undulated cationic chain of compound 1.
coordination ability the sulfate exhibits. The synthesis of compound 4 may be controlled by the EtOH/H2O ratio and the temperature because it is prepared under solvothermal condition. Compound 1 is comprised of the [Cu(3-bpt)(H2O)4]2n+ cationic n chain, SO2− anions, and lattice water molecules [37]. In the cationic 4 chain, each Cu(II) atom displays a distorted octahedral coordination geometry {CuN2O4}, coordinated by four oxygen atoms from four water, and two pyridine nitrogen atoms from two 3-bpt ligands (Fig. 1, Table S1). The Cu–O (2.034(2)–2.243(2) Å) and Cu–N bond lengths (2.026(2)–2.032(2) Å) are in the typical ranges. Each Cu(II) center connects two 3-bpt ligands. Each 3-bpt ligand exhibits the cisoid-I conformation. The 3-bpt ligands link the Cu(II) atoms to form a one-dimensional undulated chain with the Cu…Cu distance of 9.642 (2)Å. There are versatile hydrogen bonding interactions (Table S2, Supporting Information) between the coordination water and the lattice water (O(1)…O(9)), and the oxygen atoms of SO2− 4 anion (O(1) … O(3), O(2)…O(5), O(3)…O(6), O(4)…O(8), O(4)…O(6), O(4)…O(7)), and the triazole nitrogen atoms (O(2)…N(3), O(3)…N(4)), between … the lattice water and the oxygen atoms of SO2− 4 anion (O(9) O(5), O … (9) O(8)), between the amino hydrogen atom of 3-bpt and the … oxygen atom of SO2− 4 anion (N(6) O(7)). These hydrogen bonding interactions further stabilize the crystal of compound 1 (Fig. S1, Supporting Information). Compound 2 is made of the [Cu2(3-bpt)2(H2O)7(SO4)]2n+ cationic n chain (Fig. 2), SO2− 4 anions, and lattice water molecules. In the cationic chain, there are three independent Cu(II) atoms. Cu(1) displays an elongated-octahedral coordination geometry {CuN2O4}, coordinated by two oxygen atoms from two water (Cu(1)–O(1) 2.004(2) Å; Cu (1)–O(2) 1.987(2) Å) and two pyridine nitrogen atoms (Cu(1)–N(1) 2.020(2) Å; Cu(1)–N(7) 2.025(2) Å) from two 3-bpt ligands in the cispositions in the equatorial plane, and two oxygen atoms from one water (Cu(1)–O(3) 2.430(2) Å) and one sulfate anion (Cu(1)–O(8) 2.326(2) Å) in the apical positions (Fig. 2). Cu(2) and Cu(3) atoms
display an elongated-octahedral coordination geometry {CuN2O4}, coordinated by two oxygen atoms from two water molecules (Cu(2)– O(4) 1.963(2) Å; Cu(3)–O(6) 1.956(2) Å) and two pyridine nitrogen atoms (Cu(2)–N(2) 2.072(2) Å; Cu(3)–N(8) 2.051(2) Å) from two 3bpt ligands in the trans-positions in the equatorial plane, and two oxygen atoms from two water molecules (Cu(2)–O(5) 2.403(2) Å; Cu (3)–O(7) 2.492(2) Å) in the apical positions. Each 3-bpt ligand exhibits the cisoid-I conformation. The 3-bpt ligands link the Cu(II) atoms to form a one-dimensional zigzag chain with the Cu(1)…Cu(2) distance of 10.083(2) Å and the Cu(1)…Cu(3) distance of 9.386(2) Å. There are two independent sulfate anions. One sulfate [S(1)O(8)O(9)O(10)O(11)] shows a monodentate coordination mode. The other sulfate [S(2)O(12)O(13)O(14)O(15)] is free anion in 2. There are versatile hydrogen bonding interactions (Table S3, Supporting Information) between the coordination water and the lattice water (O(2)…O(18), O(2)…O(22), O(3)…O(17), O(5)…O(16), O (7)…O(21), O(16)…O(9), O(18)…O(7), O(22)…O(9), and the coordi… … … nation SO2− 4 anions (O(1) O(10), O(1) O(11), O(3) O(10)), and the free sulfate anions (O(4)…O(13), O(5)…O(15), O(6)…O(12), O(7)…O (14)), and the triazole nitrogen atoms (O(4)…N(3), O(6)…N(9)), between the lattice water and triazole nitrogen atoms (O(16)…N(4), O(21)…N(10)), and the coordination SO2− anion (O(19)…O(11), O 4 … (21) O(11)), and the free sulfate anion (O(20)…O(14)), between lattice water (O(17)…O(15), O(17)…O(20), O(20)…O(20), O(22)…O (19)), between the amino hydrogen atom of 3-bpt and the coordination SO2− anion (N(6)…O(12), N(6)…O(15), N(12)…O(14)). 4 These hydrogen bonding interactions further stabilize the crystal of compound 2 (Fig. S2, Supporting Information). Compound 3 consists of the [Cu(3-bpt)(H2O)3(SO4)]n neutral chain (Fig. 3), and lattice water molecule. Each Cu(II) atom displays an elongated-octahedral coordination geometry {CuN2O4}, coordinated by two oxygen atoms from two water (Cu(1)–O(5) 2.004(3) Å; Cu (1)–O(6) 1.988(3) Å) and two pyridine nitrogen atoms (Cu(1)–N(1)
Fig. 2. The one-dimensional zigzag cationic chain of compound 2.
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Fig. 3. The one-dimensional zigzag chain of compound 3.
2.028(3) Å; Cu(1)–N(2A) 2.037(3) Å) from two 3-bpt ligands in the trans-positions in the equatorial plane, and two oxygen atoms from one water (Cu(1)–O(7) 2.212(3) Å) and one sulfate anion (Cu(1)–O (1) 2.643(3) Å) in the apical positions. Each 3-bpt ligand exhibits the transoid conformation. The 3-bpt ligands link the Cu(II) atoms to form a one-dimensional zigzag chain with the Cu…Cu distance of 12.459(2) Å. There are inter-chain hydrogen bonding interactions (Table S4, Supporting Information) between the coordination water and the … … … … coordination SO2− 4 anion [O(5) O(3), O(5) O(2), O(6) O(3), O(7) O(2), O(7)…O(1)]. Through these hydrogen bonding interactions compound 3 forms a two-dimensional hydrogen bonding network [Cu(H2O)3(SO4)]n. The two-dimensional hydrogen bonding networks [Cu(H2O)3(SO4)]n are connected by 3-bpt to construct a three-
dimensional hydrogen bonding network (Fig. 4). There are also hydrogen bonding interactions between the coordination water and the triazole nitrogen atom [O(6)…N(3)], between the lattice water and the triazole nitrogen atom [O(8)…N(4)], between the lattice and coordination water [O(8)…O(4)]. These hydrogen bonding interactions further stabilize the three-dimensional network in 3. The structure of compound 4 is a two-dimensional network. Each Cu(II) atom shows a distorted trigonal–bipyramidal geometry (Fig. 5), coordinated with the sulfate oxygen atom [Cu(1)–O(3B) 2.194(3) Å], two pyridine atoms [Cu(1)–N(1) 2.003(3) Å, Cu(1)–N(2A) 2.005(3) Å] in the trigonal plane, one water [Cu(1)–O(1) 1.983(3) Å] and one sulfate oxygen atom [Cu(1)–O(2) 1.935(2) Å] in the pyramidal positions. The Cu–O (1.935(2)–2.005(3) Å) and Cu–N (2.003(3)– 2.005(3) Å) bond lengths are in the typical ranges. The bond angles at
Fig. 4. The hydrogen bonding network of compound 3.
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Fig. 5. The coordination environment of the copper(II) atom of compound 4.
the trigonal plane are in the range of 101.45(12) to 155.14(12)°. The bond angles between the coordination atom of the trigonal plane and the pyramidal positions are in the range of 86.15(13) to 96.15(11)°. Each sulfate anion displays a bisdentate bridging mode in 4. Two oxygen atoms of a sulfate anion bond two different Cu(II) ions, thus bridging the metal centers to form a one-dimensional inorganic chain [Cu(H2O)(SO4)]n (Fig. 6) in which the distance between two neighbouring Cu(II) atoms is 5.450(1) Å. Each 3-bpt ligand exhibits the transoid conformation. The 3-bpt ligands further link the [Cu(H2O) (SO4)]n chains to construct a two-dimensional network with the Cu… Cu distance of 12.204(3) Å. There are intra-chain hydrogen bonding interactions (Table S5, Supporting Information) between the coordination water and the sulfate oxygen atom [O(1)…O(5)] in 4. There are intra-sheet hydrogen bonding interactions between amino hydrogen atom and the sulfate
oxygen atom [N(6)…O(4)], between the coordination water and the triazole nitrogen atom [O(1)…N(3)]. The two-dimensional sheets parallel stack (Fig. S3, Supporting Information). The interlayer distance is approximately 7.0 Å. Thermal analysis (Fig. S4) shows that the lattice water and coordination water molecules are lost from 50 to 106 °C (observed. 3.84%, calculated: 3.69%) and from 106 to 150 °C (observed. 14.46%, calculated: 14.77%) for compound 1 and from 45 to 102 °C (observed. 7.62%, calculated: 7.38%) and from 102 to 154 °C (observed. 10.72%, calculated: 11.08%) for compound 3, respectively. The lattice water and coordination water molecules are lost in a continuous fashion from 30 to 160 °C (observed. 23.67%, calculated: 24.07%) for compound 2. The coordination water molecule is lost from 118 to 180 °C (observed. 4.21%, calculated: 4.33%) for compound 4. Then the anhydrous substances continuously discompose above 256, 255, 256
Fig. 6. The two-dimensional network of compound 4.
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and 258 °C for compounds 1, 2, 3 and 4, respectively. The residue substances are 57.19%, 53.86%, 56.42% and 66.12% weight upon heated to 500 °C for compounds 1, 2, 3 and 4, respectively. No reasonable fragments can be assigned corresponding to the weight loss processes of compounds 1, 2, 3 and 4. In summary, four coordination polymers 1–4 from one-dimensional undulated chain, zigzag chain, to a two-dimensional network were synthesized by the reaction of 4-amino-3,5-bis(3-pyridyl)1,2,4-triazole (3-bpt) and copper sulfate. Compounds 1 and 3 are isomers with the same formula. Four water molecules coordinate to a Cu(II) atom and the sulfate shows the free anion in 1. Three water molecules and a monodentate sulfate bond to a Cu(II) atom in 3. Compound 2 exhibits two coordination mode as the combination of compounds 1 and 3. However one water and a bisdentate bridging sulfate coordinate to a Cu(II) atom in compound 4. The formations of compounds 1, 2 and 3 are controlled by the EtOH/H2O ratio. The synthesis of compound 4 may be controlled by the EtOH/H2O ratio and the temperature because it is prepared under solvothermal condition. Further investigation of the role of water solvent on the structural assemblies of metal-organic frameworks of metal sulfates is underway in our laboratory. Acknowledgment This work was supported by the Natural Science Foundation of China (No. 20671066), the Jiangsu Province (No. BK2006049), and the Funds of Key Laboratory of Organic Synthesis of Jiangsu Province. Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.inoche.2010.05.011. References [1] P.J. Hagrman, Z. Hagrmam, J. Zubieta, Angew. Chem. Int. Ed. 38 (1999) 2638–2684. [2] M. Eddaoudi, D.B. Moler, H.L. Li, B.L. Chen, T.M. Reineke, M. O'Keeffe, O.M. Yaghi, Acc. Chem. Res. 34 (2001) 319–330. [3] M.J. Zaworotko, Chem. Commun. (2001) 1–9. [4] S.R. Batten, Curr. Opin. Solid State Mater. Sci. 5 (2001) 107–114. [5] S. Kitagawa, R. Kitaura, S.I. Noro, Angew. Chem. Int. Ed. 43 (2004) 2334–2375. [6] T.G. Stamatatos, S.J. Teat, W. Wernsdorfer, G. Christou, Angew. Chem. Int. Ed. 48 (2009) 521–524. [7] D.Y. Wu, O. Sato, Y. Einaga, C.Y. Duan, Angew. Chem. Int. Ed. 48 (2009) 1475–1478. [8] M.A. Withersby, A.J. Blake, N.R. Champness, P.A. Cooke, P. Hubberstey, W.S. Li, M. Schroder, Inorg. Chem. 38 (1999) 2259–2266. [9] Y.B. Dong, J.Y. Cheng, H.Y. Wang, R.Q. Huang, B. Tang, Chem. Mater. 15 (2003) 2593–2604. [10] Y.B. Dong, P. Wang, J.P. Ma, X.X. Zhao, H.Y. Wang, B. Tang, R.Q. Huang, J. Am. Chem. Soc. 129 (2007) 4872–4873. [11] P. Wang, J.P. Ma, Y.B. Dong, R.Q. Huang, J. Am. Chem. Soc. 129 (2007) 10620–10621. [12] M. Du, Z.H. Zhang, Y.P. You, X.J. Zhao, Cryst. Eng. Comm. 10 (2008) 306–321. [13] J.J. Liu, X. He, M. Shao, M.X. Li, J. Mol. Struct. 891 (2008) 50–57. [14] A. Galet, M.C. Munoz, J.A. Real, J. Am. Chem. Soc. 125 (2003) 14224–14225. [15] B.Q. Ma, H.L. Sun, S. Gao, Chem. Commun. (2003) 2164–2165.
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Inorganic Chemistry Communications j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i n o c h e
Four coordination polymers derived from 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole and copper sulfate Kui Liu, Xia Zhu, Ju Wang, Baolong Li ⁎, Yong Zhang Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry and Chemical Engineering and Material Science, Soochow University, Suzhou 215123, PR China
a r t i c l e
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Article history: Received 16 March 2010 Accepted 20 May 2010 Available online 26 May 2010 Keywords: Copper sulfate complex Solvent-controlled assembly Coordination polymer 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole
a b s t r a c t The reaction of 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-bpt) with copper sulfate in EtOH/H2O solvent yields four coordination polymers [Cu(3-bpt)(H2O)4](SO4)·H2O (1), [Cu(3-bpt)(H2O)4][Cu(3-bpt)(H2O)3 (SO4)](SO4)·7H2O (2), [Cu(3-bpt)(H2O)3(SO4)]·2H2O (3) and [Cu(3-bpt)(H2O)(SO4)] (4), showing onedimensional undulated chain, zigzag chain and two-dimensional network. The formations of compounds 1, 2 and 3 are controlled by the EtOH/H2O ratio. The synthesis of compound 4 may be controlled by the EtOH/H2O ratio and the temperature because it is prepared under solvothermal condition. The thermal properties have been investigated. © 2010 Elsevier B.V. All rights reserved.
The current interest in the crystal engineering of coordination polymer frameworks stems not only from their potential applications as functional materials for gas storage, separation, microelectronics, nonlinear optics and catalysis, but also from their intriguing variety of topologies [1–7]. Designing effective ligands and selecting metal centers are the key points to construct of novel metal-organic frameworks. 4-Amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-bpt), an angular dipyridyl ligand, may show three typical conformations under appropriate surrounds and it can construct novel metal-organic frameworks [8–13]. The design of coordination polymers is highly influenced by several factors such as the geometric preference of metal ions, the size and shapes of the organic building blocks, the metal–ligand ratio, templates, the solvent systems and the counterions [14–19]. Among these the solvent media used in the assembling processes may significantly influence the structures of the resulting coordination polymers [8,20–30]. On the other hand, the simple anion SO2− 4 , can play an important role in the assembly of coordination frameworks [31–35]. Water molecules are terminal ligands and competitive with the sulfate groups in bonding the metal cations. However the roles of water solvent and SO2− ion on the structural assemblies of metal-organic 4 frameworks has still not been well-understood. To further explore this attractive topic, we report here a study of the solvent effect on metalorganic frameworks by employing H2O and EtOH/H2O solvents, and organic ligand 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-bpt) and copper sulfate. Four coordination polymers [Cu(3-bpt)(H2O)4]
⁎ Corresponding author. Tel.: +86 512 65880324; fax: +86 512 65880089. E-mail address: [email protected] (B. Li). 1387-7003/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2010.05.011
(SO 4 )·H 2 O (1), [Cu(3-bpt)(H 2 O) 4 ][Cu(3-bpt)(H 2 O) 3 (SO 4 )] (SO4)·7H2O (2), [Cu(3-bpt)(H2O)3(SO4)]·2H2O (3) and [Cu(3-bpt) (H2O)(SO4)] (4) were synthesized and structurally characterized. Scheme 1 shows the syntheses of compounds 1–4 [36]. The design of coordination polymers is highly influenced by the solvent systems [8,20–30]. The direct reaction of ligand 4-amino-3,5-bis(3-pyridyl)1,2,4-triazole (3-bpt) and copper sulfate in an aqueous solution gives [Cu(3-bpt)(H2O)4](SO4)·H2O (1). When an EtOH/H2O solution (2 mL EtOH and 10 mL H2O) is used, the direct reaction of 3-bpt and copper sulfate gives [Cu(3-bpt)(H2O)4][Cu(3-bpt)(H2O)3(SO4)](SO4)·7H2O (2). However the precipitates are formed immediately when more EtOH is used in the synthesis. [Cu(3-bpt)(H2O)3(SO4)]·2H2O (3) is obtained when an EtOH solution of 3-bpt diffuses into an aqueous solution of copper sulfate. The hydrothermal reaction of 3-bpt and copper sulfate in a solution of 6 mL EtOH and 10 mL H2O produces [Cu (3-bpt)(H2O)(SO4)] (4). The formations of compounds 1, 2 and 3 are controlled by the EtOH/H2O ratio. The more EtOH is used, the less water coordinate to Cu(II) atom, and the more competitive
Scheme 1. The syntheses of compounds 1 to 4.
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Fig. 1. The one-dimensional undulated cationic chain of compound 1.
coordination ability the sulfate exhibits. The synthesis of compound 4 may be controlled by the EtOH/H2O ratio and the temperature because it is prepared under solvothermal condition. Compound 1 is comprised of the [Cu(3-bpt)(H2O)4]2n+ cationic n chain, SO2− anions, and lattice water molecules [37]. In the cationic 4 chain, each Cu(II) atom displays a distorted octahedral coordination geometry {CuN2O4}, coordinated by four oxygen atoms from four water, and two pyridine nitrogen atoms from two 3-bpt ligands (Fig. 1, Table S1). The Cu–O (2.034(2)–2.243(2) Å) and Cu–N bond lengths (2.026(2)–2.032(2) Å) are in the typical ranges. Each Cu(II) center connects two 3-bpt ligands. Each 3-bpt ligand exhibits the cisoid-I conformation. The 3-bpt ligands link the Cu(II) atoms to form a one-dimensional undulated chain with the Cu…Cu distance of 9.642 (2)Å. There are versatile hydrogen bonding interactions (Table S2, Supporting Information) between the coordination water and the lattice water (O(1)…O(9)), and the oxygen atoms of SO2− 4 anion (O(1) … O(3), O(2)…O(5), O(3)…O(6), O(4)…O(8), O(4)…O(6), O(4)…O(7)), and the triazole nitrogen atoms (O(2)…N(3), O(3)…N(4)), between … the lattice water and the oxygen atoms of SO2− 4 anion (O(9) O(5), O … (9) O(8)), between the amino hydrogen atom of 3-bpt and the … oxygen atom of SO2− 4 anion (N(6) O(7)). These hydrogen bonding interactions further stabilize the crystal of compound 1 (Fig. S1, Supporting Information). Compound 2 is made of the [Cu2(3-bpt)2(H2O)7(SO4)]2n+ cationic n chain (Fig. 2), SO2− 4 anions, and lattice water molecules. In the cationic chain, there are three independent Cu(II) atoms. Cu(1) displays an elongated-octahedral coordination geometry {CuN2O4}, coordinated by two oxygen atoms from two water (Cu(1)–O(1) 2.004(2) Å; Cu (1)–O(2) 1.987(2) Å) and two pyridine nitrogen atoms (Cu(1)–N(1) 2.020(2) Å; Cu(1)–N(7) 2.025(2) Å) from two 3-bpt ligands in the cispositions in the equatorial plane, and two oxygen atoms from one water (Cu(1)–O(3) 2.430(2) Å) and one sulfate anion (Cu(1)–O(8) 2.326(2) Å) in the apical positions (Fig. 2). Cu(2) and Cu(3) atoms
display an elongated-octahedral coordination geometry {CuN2O4}, coordinated by two oxygen atoms from two water molecules (Cu(2)– O(4) 1.963(2) Å; Cu(3)–O(6) 1.956(2) Å) and two pyridine nitrogen atoms (Cu(2)–N(2) 2.072(2) Å; Cu(3)–N(8) 2.051(2) Å) from two 3bpt ligands in the trans-positions in the equatorial plane, and two oxygen atoms from two water molecules (Cu(2)–O(5) 2.403(2) Å; Cu (3)–O(7) 2.492(2) Å) in the apical positions. Each 3-bpt ligand exhibits the cisoid-I conformation. The 3-bpt ligands link the Cu(II) atoms to form a one-dimensional zigzag chain with the Cu(1)…Cu(2) distance of 10.083(2) Å and the Cu(1)…Cu(3) distance of 9.386(2) Å. There are two independent sulfate anions. One sulfate [S(1)O(8)O(9)O(10)O(11)] shows a monodentate coordination mode. The other sulfate [S(2)O(12)O(13)O(14)O(15)] is free anion in 2. There are versatile hydrogen bonding interactions (Table S3, Supporting Information) between the coordination water and the lattice water (O(2)…O(18), O(2)…O(22), O(3)…O(17), O(5)…O(16), O (7)…O(21), O(16)…O(9), O(18)…O(7), O(22)…O(9), and the coordi… … … nation SO2− 4 anions (O(1) O(10), O(1) O(11), O(3) O(10)), and the free sulfate anions (O(4)…O(13), O(5)…O(15), O(6)…O(12), O(7)…O (14)), and the triazole nitrogen atoms (O(4)…N(3), O(6)…N(9)), between the lattice water and triazole nitrogen atoms (O(16)…N(4), O(21)…N(10)), and the coordination SO2− anion (O(19)…O(11), O 4 … (21) O(11)), and the free sulfate anion (O(20)…O(14)), between lattice water (O(17)…O(15), O(17)…O(20), O(20)…O(20), O(22)…O (19)), between the amino hydrogen atom of 3-bpt and the coordination SO2− anion (N(6)…O(12), N(6)…O(15), N(12)…O(14)). 4 These hydrogen bonding interactions further stabilize the crystal of compound 2 (Fig. S2, Supporting Information). Compound 3 consists of the [Cu(3-bpt)(H2O)3(SO4)]n neutral chain (Fig. 3), and lattice water molecule. Each Cu(II) atom displays an elongated-octahedral coordination geometry {CuN2O4}, coordinated by two oxygen atoms from two water (Cu(1)–O(5) 2.004(3) Å; Cu (1)–O(6) 1.988(3) Å) and two pyridine nitrogen atoms (Cu(1)–N(1)
Fig. 2. The one-dimensional zigzag cationic chain of compound 2.
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Fig. 3. The one-dimensional zigzag chain of compound 3.
2.028(3) Å; Cu(1)–N(2A) 2.037(3) Å) from two 3-bpt ligands in the trans-positions in the equatorial plane, and two oxygen atoms from one water (Cu(1)–O(7) 2.212(3) Å) and one sulfate anion (Cu(1)–O (1) 2.643(3) Å) in the apical positions. Each 3-bpt ligand exhibits the transoid conformation. The 3-bpt ligands link the Cu(II) atoms to form a one-dimensional zigzag chain with the Cu…Cu distance of 12.459(2) Å. There are inter-chain hydrogen bonding interactions (Table S4, Supporting Information) between the coordination water and the … … … … coordination SO2− 4 anion [O(5) O(3), O(5) O(2), O(6) O(3), O(7) O(2), O(7)…O(1)]. Through these hydrogen bonding interactions compound 3 forms a two-dimensional hydrogen bonding network [Cu(H2O)3(SO4)]n. The two-dimensional hydrogen bonding networks [Cu(H2O)3(SO4)]n are connected by 3-bpt to construct a three-
dimensional hydrogen bonding network (Fig. 4). There are also hydrogen bonding interactions between the coordination water and the triazole nitrogen atom [O(6)…N(3)], between the lattice water and the triazole nitrogen atom [O(8)…N(4)], between the lattice and coordination water [O(8)…O(4)]. These hydrogen bonding interactions further stabilize the three-dimensional network in 3. The structure of compound 4 is a two-dimensional network. Each Cu(II) atom shows a distorted trigonal–bipyramidal geometry (Fig. 5), coordinated with the sulfate oxygen atom [Cu(1)–O(3B) 2.194(3) Å], two pyridine atoms [Cu(1)–N(1) 2.003(3) Å, Cu(1)–N(2A) 2.005(3) Å] in the trigonal plane, one water [Cu(1)–O(1) 1.983(3) Å] and one sulfate oxygen atom [Cu(1)–O(2) 1.935(2) Å] in the pyramidal positions. The Cu–O (1.935(2)–2.005(3) Å) and Cu–N (2.003(3)– 2.005(3) Å) bond lengths are in the typical ranges. The bond angles at
Fig. 4. The hydrogen bonding network of compound 3.
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Fig. 5. The coordination environment of the copper(II) atom of compound 4.
the trigonal plane are in the range of 101.45(12) to 155.14(12)°. The bond angles between the coordination atom of the trigonal plane and the pyramidal positions are in the range of 86.15(13) to 96.15(11)°. Each sulfate anion displays a bisdentate bridging mode in 4. Two oxygen atoms of a sulfate anion bond two different Cu(II) ions, thus bridging the metal centers to form a one-dimensional inorganic chain [Cu(H2O)(SO4)]n (Fig. 6) in which the distance between two neighbouring Cu(II) atoms is 5.450(1) Å. Each 3-bpt ligand exhibits the transoid conformation. The 3-bpt ligands further link the [Cu(H2O) (SO4)]n chains to construct a two-dimensional network with the Cu… Cu distance of 12.204(3) Å. There are intra-chain hydrogen bonding interactions (Table S5, Supporting Information) between the coordination water and the sulfate oxygen atom [O(1)…O(5)] in 4. There are intra-sheet hydrogen bonding interactions between amino hydrogen atom and the sulfate
oxygen atom [N(6)…O(4)], between the coordination water and the triazole nitrogen atom [O(1)…N(3)]. The two-dimensional sheets parallel stack (Fig. S3, Supporting Information). The interlayer distance is approximately 7.0 Å. Thermal analysis (Fig. S4) shows that the lattice water and coordination water molecules are lost from 50 to 106 °C (observed. 3.84%, calculated: 3.69%) and from 106 to 150 °C (observed. 14.46%, calculated: 14.77%) for compound 1 and from 45 to 102 °C (observed. 7.62%, calculated: 7.38%) and from 102 to 154 °C (observed. 10.72%, calculated: 11.08%) for compound 3, respectively. The lattice water and coordination water molecules are lost in a continuous fashion from 30 to 160 °C (observed. 23.67%, calculated: 24.07%) for compound 2. The coordination water molecule is lost from 118 to 180 °C (observed. 4.21%, calculated: 4.33%) for compound 4. Then the anhydrous substances continuously discompose above 256, 255, 256
Fig. 6. The two-dimensional network of compound 4.
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and 258 °C for compounds 1, 2, 3 and 4, respectively. The residue substances are 57.19%, 53.86%, 56.42% and 66.12% weight upon heated to 500 °C for compounds 1, 2, 3 and 4, respectively. No reasonable fragments can be assigned corresponding to the weight loss processes of compounds 1, 2, 3 and 4. In summary, four coordination polymers 1–4 from one-dimensional undulated chain, zigzag chain, to a two-dimensional network were synthesized by the reaction of 4-amino-3,5-bis(3-pyridyl)1,2,4-triazole (3-bpt) and copper sulfate. Compounds 1 and 3 are isomers with the same formula. Four water molecules coordinate to a Cu(II) atom and the sulfate shows the free anion in 1. Three water molecules and a monodentate sulfate bond to a Cu(II) atom in 3. Compound 2 exhibits two coordination mode as the combination of compounds 1 and 3. However one water and a bisdentate bridging sulfate coordinate to a Cu(II) atom in compound 4. The formations of compounds 1, 2 and 3 are controlled by the EtOH/H2O ratio. The synthesis of compound 4 may be controlled by the EtOH/H2O ratio and the temperature because it is prepared under solvothermal condition. Further investigation of the role of water solvent on the structural assemblies of metal-organic frameworks of metal sulfates is underway in our laboratory. Acknowledgment This work was supported by the Natural Science Foundation of China (No. 20671066), the Jiangsu Province (No. BK2006049), and the Funds of Key Laboratory of Organic Synthesis of Jiangsu Province. Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.inoche.2010.05.011. References [1] P.J. Hagrman, Z. Hagrmam, J. Zubieta, Angew. Chem. Int. Ed. 38 (1999) 2638–2684. [2] M. Eddaoudi, D.B. Moler, H.L. Li, B.L. Chen, T.M. Reineke, M. O'Keeffe, O.M. Yaghi, Acc. Chem. Res. 34 (2001) 319–330. [3] M.J. Zaworotko, Chem. Commun. (2001) 1–9. [4] S.R. Batten, Curr. Opin. Solid State Mater. Sci. 5 (2001) 107–114. [5] S. Kitagawa, R. Kitaura, S.I. Noro, Angew. Chem. Int. Ed. 43 (2004) 2334–2375. [6] T.G. Stamatatos, S.J. Teat, W. Wernsdorfer, G. Christou, Angew. Chem. Int. Ed. 48 (2009) 521–524. [7] D.Y. Wu, O. Sato, Y. Einaga, C.Y. Duan, Angew. Chem. Int. Ed. 48 (2009) 1475–1478. [8] M.A. Withersby, A.J. Blake, N.R. Champness, P.A. Cooke, P. Hubberstey, W.S. Li, M. Schroder, Inorg. Chem. 38 (1999) 2259–2266. [9] Y.B. Dong, J.Y. Cheng, H.Y. Wang, R.Q. Huang, B. Tang, Chem. Mater. 15 (2003) 2593–2604. [10] Y.B. Dong, P. Wang, J.P. Ma, X.X. Zhao, H.Y. Wang, B. Tang, R.Q. Huang, J. Am. Chem. Soc. 129 (2007) 4872–4873. [11] P. Wang, J.P. Ma, Y.B. Dong, R.Q. Huang, J. Am. Chem. Soc. 129 (2007) 10620–10621. [12] M. Du, Z.H. Zhang, Y.P. You, X.J. Zhao, Cryst. Eng. Comm. 10 (2008) 306–321. [13] J.J. Liu, X. He, M. Shao, M.X. Li, J. Mol. Struct. 891 (2008) 50–57. [14] A. Galet, M.C. Munoz, J.A. Real, J. Am. Chem. Soc. 125 (2003) 14224–14225. [15] B.Q. Ma, H.L. Sun, S. Gao, Chem. Commun. (2003) 2164–2165.
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