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Structural diversity in coordination polymers with angular ditetrazole ligands
Inorganic Chemistry Communications 13 (2010) 1562–1565
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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
Structural diversity in coordination polymers with angular ditetrazole ligands Chun-Wei Yeh a, Keng-Han Chang a, Ann Chao a, Shuen-Bo Wang a, Chia-Jun Wu a, Jhy-Der Chen a,⁎, Ju-Chun Wang b a b
Department of Chemistry, Chung-Yuan Christian University, Chung-Li, Taiwan, ROC Department of Chemistry, Soochow University, Taipei, Taiwan, ROC
a r t i c l e
i n f o
Article history: Received 22 July 2010 Accepted 2 September 2010 Available online 16 September 2010 Keywords: Coordination polymer Copper Silver Tetrazole
a b s t r a c t Three new coordination polymers with angular bis(1-tetrazol)diphenyl ligands as bridges, {[Ag(L1)2](NO3)⋅2H2O}∞ [L1 =4,4'-bis(1-tetrazolyl)diphenyl methane], 1, [Ag(L2)2(NO3)]∞ [L2 =4,4'-bis(1-tetrazolyl)diphenyl sulfone], 2, and [CuBr(L3)0.5]∞ [L3 =4,4'-bis(1-tetrazolyl)diphenyl ether], 3, are reported, which show unique 2D structural types. Complex 1 forms 1D double-stranded helical chains where the cavities are threaded by linear hydrogen bondings formed by the co-crystallized water molecules and nitrate anions and complex 2 shows 2D grids involving M4L4 64-membered metallocycles composed of helical chains, while complex 3 exhibits a 2D pleated net comprising 1D channels linked by the double-chain CuBr ribbons. © 2010 Elsevier B.V. All rights reserved.
The design and synthesis of functional coordination polymers have been intensively studied during recent years [1,2]. These complexes thus synthesized not only show potential application in catalysis, magnet, semiconductor and optics but also interesting architectures and topologies. The range and variety of self-assembling inorganic structures that can be constructed relies on the presence of suitable metal–ligand interactions and supramolecular contacts, i.e., hydrogen bondings and other weak interactions [3]. The properties of a spacing ligand, such as rigidity, flexibility, length, size, and geometry also affect the structure. The ligands with 1-substituted ditetrazoles have been the subject of many studies by virtue of their flexible and bridging natures [4–6], and the angular dipyridyl ligands reported to form 1D looped chain structures [7] and interpenetrated frameworks with metal salts [7]. To prepare metal-organic frameworks with large cavities and to investigate the structural chemistry of coordination polymers with angular ditetrazolyl ligands, we have synthesized 4,4'-bis(1-tetrazolyl) diphenyl methane (L1) [8], 4,4'-bis(1-tetrazolyl)diphenyl sulfone (L2) [8] and 4,4'-bis(1-tetrazolyl)diphenyl ether (L3) [8], which were reacted with metal salts. The angular conformations in these ligands exerted by the CH2 (L1) and SO2 (L2) groups and O atom (L3) led to the formation of 2D coordination polymers with unique structural diversity, involving 1D double-stranded helical chain structure where the cavities are threaded by linear hydrogen-bonded chains, 2D grids with M4L4 metallocycles formed by helical chains and a 2D pleated net composed of 1D channel. We report here the synthesis and structural characterization of these complexes.
⁎ Corresponding author. Tel.: + 886 3 2653351; fax:+886 3 2653399. E-mail address: [email protected] (J.-D. Chen). 1387-7003/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2010.09.012
The reactions of AgNO3 with L1 in refluxing DMF and L2 in MeOH/ acetone at room temperature afforded the complexes {[Ag(L1)2] (NO3) ⋅ 2H2O}∞, 1, and [Ag(L2)2(NO3)]∞, 2, respectively, while the reaction of L3 with CuBr in MeOH/acetone at room temperature gave [Cu2Br2(L3)]∞, 3 [9]. Complexes 1–3 are stable in air at ambient temperature and almost insoluble in common solvents such as water, ethanol, methanol, THF, acetonitrile, chloroform and acetone. All the structures of 1–3 were solved in the space group C2/c with Z=4 [10]. Selected bond distances and angles (Table S1) are provided as supplementary materials. Fig. 1(a) shows the coordination environment of the Ag(I) metal center of 1. The distorted tetrahedral Ag(I) center lying on a two-fold axis is coordinated by four tetrazolyl nitrogen atoms belonging to different L1 ligands. Adjacent Ag(I) atoms are linked to each other through the L1 ligands to form 1D looped chains involving 32membered rings (size=14.63×13.34 Å2). The looped chains consist of two helical strands with shared silver atoms that are related by two-fold symmetry, Fig. 1(b). Each strand is formed by linking a pair of consecutive Ag(I) cations and one L1 ligands, which propagates in the direction of aaxis with a repeating unit of 25.862(2) Å. The unique structural feature is that the cavities of the double-stranded helical chains are threaded by the O–H–O [H–O=1.74(2)−2.61(4) Å, ∠O–H–O=116.5(8)−167.4(6)°] hydrogen-bonded chains, Fig. 1(c), composed of the uncoordinated
C.-W. Yeh et al. / Inorganic Chemistry Communications 13 (2010) 1562–1565
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with a repeating unit of 38.18 Å. The 2-D nets are interlinked through the C–H–O [H–O = 2.10 (1) Å and ∠C–H–O = 168.9 (4)°] hydrogen bonds and face to face π–π stacking interactions [3.581(2) Å]. Fig. 3(a) shows the coordination environment of the Cu(I) metal center of 3, while Fig. 3(b) shows its 2D pleated structure. The Cu(I) atoms in the CuBr double chains are 3-fold coordinated to Br, and all the Br atoms are bridged to three Cu(I) metal centers. Each L3 ligand is coordinated to two Cu(I) atoms through the nitrogen atoms which complete the fourth coordination of the metal center, resulting in a slightly distorted tetrahedral coordination geometry. The striking feature is that the 1D CuBr double chains are linked by the L3 ligands to form a 2D structure with 1D channels, Fig. 3(c), with the cavity size of 12.969 (2) × 15.677 (1) Å2. The structure of 3 is in marked to those of Cu2X2(bpy) (X = Cl, Br and bpy = 4,4'-bipyridine) [15] where simple 2D layered networks were observed. The structural
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Fig. 1. (a) Coordination environment of Ag(I) in 1. (b) 1D looped chains consisting of two helical strands with shared silver atoms. (c) The water molecules and nitrate anions are linked to each other in a linear way through O–H–O hydrogen bonds. (d) A schematic drawing showing the cavities threaded by the linear 1D hydrogen-bonded chains.
nitrate anions and the co-crystallized water molecules, to form a 2D structure, Fig. 1(d), which is supported by the C–H–O hydrogen bonds [H–O=2.50 (4)−2.68 (4) Å, ∠C–H–O=115.4 (3)−142.4 (4)°] among the phenyl hydrogen atoms of the L1 ligands and the oxygen atoms of the water molecules and nitrate anions. Fig. 2(a) shows the coordination environment of Ag(I) metal center of 2. The distorted trigonal bipyramidal Ag(I) center is coordinated by four tetrazolyl nitrogen atoms from four different L2 ligands and one nitrate oxygen atom with τ = 0.585 [14]. Fig. 2(b) shows a 2D structure of 2, depicting that Ag(I) atoms are linked to each other by the L2 ligands to form grids involving 64-membered [Ag 4 ( L 2 ) 4 ] rings (size = 19.09× 25.72 Å2). Most interestingly, the 2D grids are composed of helical chains with shared Ag(I) atoms, which show alternating opposite screw sense, Fig. 2(c), and propagate in the direction of b-axis
(c) Fig. 2. (a) Coordination environment of Ag(I) in 2. (b) A 2D layer of 3. (c) The 2D layer is composed of helical chains.
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Acknowledgments We are grateful to the National Science Council of the Republic of China for support. This research was also supported by the project of the specific research fields in Chung Yuan Christian University, Taiwan, ROC under grant CYCU-98-CR-CH. Appendix A. Supplementary material
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Supplementary data to this article can be found online at doi:10.1016/j.inoche.2010.09.012. References
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(c) Fig. 3. (a) Coordination environment of Cu(I) in 3. (b) A 2D pleated layer viewing down the b-axis. (c) A view looking down the c-axis, showing the 1D channels.
difference is most probably due to the angular geometry of the L3 ligand. It is noted that the reaction of CuCl2 with L3 has been investigated but has not been structurally characterized by X-ray crystallography [8]. Based on the relative orientation of the C–H groups on the tetrazolyl rings, each ligand can adopt a syn or anti arrangement as shown in Figure S1 in supplementary materials. The L1–L3 ligand thus all adopt the syn conformation according to this descriptor. 1D looped chain with M2L2 rhombohedral metallocycles is the basic structural type for coordination polymers with angular dipyridyl ligands, which have been found for the ligands N,N′-bis(pyridylcarbonyl)4,4′-diaminodiphenyl ether [7], N,N'-(methylenedi-p-phenylene)bis(pyridine-4-carboxamide) (LB) [7] and N,N'-bis(4-pyridyl)isophthalamide [7]. Only a few complexes with 2D or 3D structure involving 1D looped chain were reported. In the complex Cu(LB)2(PF6)2 [7], the looped chains which are arranged in two directions are interlocked, leading to the formation of a 2D interwoven square-grid layer structure, while the complex [Co(LB)2(NO3)2] · 2(C2H5)2O · (CH3)2SO · H2O shows a 3D interpenetrating network with spacious nano-sized channels [7]. Obviously, the structural types of 1–3 which contain the angular bis (tetrazol-1-yl) ligands are in marked contrast to those containing the angular dipyridyl ligands. In summary, three first structurally characterized coordination polymers containing the angular bis(1-tetrazolyl)diphenyl ligands which show unique 2D structural types have been successfully accomplished. The unique structural types in 1–3 may be ascribed to the structural preference exerted by the CH2 (L1) and SO2 (L2) groups and the O atom (L3) of the spacer ligands. The donor ability of the tetrazolyl groups and the metal center geometries also play important roles. All the L1–L3 ligands in the three complexes adopt the same syn conformation which maximizes the intra- and intermolecular forces for the formation of 1–3.
[1] (a) J.M. Lehn, Supramolecular Chemistry, VCH, Weinheim, 1995; (b) R. Robson, B.E. Abrahams, S.R. Batten, R.W. Gable, B.F. Hoskins, J. Lieu, Supramolecular Architecture, ACS Publications, Washington, DC, 1992; (c) E.R.T. Tiekink, J.J. Vittal, Frontiers in Crystal Engineering, John Wiley and Sons Ltd, England, 2006. [2] (a) S. Kitagawa, S. Noro, T. Nakamura, Chem. Commun. (2006) 701; (b) O.M. Yaghi, H. Li, C. Davis, D. Richardson, T.L. Groy, Acc. Chem. Res. 31 (1998) 474; (c) H. Gudbjartson, K. Biradha, K.M. Poirier, M.J. Zaworotko, J. Am. Chem. Soc. 121 (1999) 2599; (d) C.B. Aakeröy, K.R. Seddon, Chem. Soc. Rev. (1993) 397; (e) M. Fujita, K. Ogura, Coord. Chem. Rev. 148 (1996) 249. [3] (a) T.R. Shattock, P. Vishweshwar, Z. Wang, M.J. Zaworotko, Cryst. Growth Des. 5 (2005) 2046; (b) J.C. Noveron, M.S. Lah, R.E.D. Sesto, A.M. Arif, J.S. Miller, P.J. Stang, J. Am. Chem. Soc. 124 (2002) 6613; (c) D.C. Sherrington, K.A. Taskinen, Chem. Soc. Rev. 30 (2001) 83; (d) D.S. Lawrence, T. Jiang, M. Levett, Chem. Rev. 95 (1995) 2229; (e) L.S. Reddy, S. Basavoja, V.R. Vangala, A. Nangia, Cryst. Growth Des. 6 (2006) 161. [4] (a) J. Schweifer, P. Weinberger, K. Mereiter, M. Boca, C. Reichl, G. Wiesinger, G. Hilscher, P.J. van Koningsbruggen, H. Kooijman, M. Grunert, W. Linert, Inorg. Chim. Acta 339 (2002) 297; (b) P.J. van Koningsbruggen, Y. Garcia, O. Kahn, L. Fournès, H. Kooijman, A.L. Spek, J.G. Haasnoot, J. Moscovici, K. Provost, A. Michalowicz, F. Renz, P. Gütlich, Inorg. Chem. 39 (2000) 1891; (c) M. Quesada, H. Kooijman, P. Gamez, J.S. Costa, P.J. van Koningsbruggen, P. Weinberger, M. Reissner, A.L. Spek, J.G. Haasnoot, J. Reedijk, Dalton Trans. (2007) 5434. [5] (a) J.-H. Yu, K. Mereiter, N. Hassan, C. Feldgitscher, W. Linert, Cryst. Growth Des. 8 (2008) 1535; (b) M. Quesada, F. Prins, O. Roubeau, P. Gamez, S.J. Teat, P.J. van Koningsbruggen, J.G. Haasnoot, J. Reedijk, Inorg. Chim. Acta 360 (2007) 3787. [6] (a) P.-P. Liu, P.-P. Liu, A.-L. Cheng, N. Liu, W.-W. Sun, E.-Q. Gao, Chem. Mater. 19 (2007) 2724; (b) P.-P. Liu, A.-L. Cheng, Q. Yue, N. Liu, W.-W. Sun, E.-Q. Gao, Cryst. Growth Des. 8 (2008) 1668. [7] (a) Y.-X. Li, Y.-H. Li, X.-R. Zeng, R.-G. Xiong, X.-Z. You, H.-K. Fun, Inorg. Chem. Commun. 6 (2003) 1144; (b) Y.W. Shin, T.H. Kim, K.Y. Lee, K.-M. Park, S.W. Han, S.S. Lee, J.S. Kim, J. Kim, Bull. Korean Chem. Soc. 26 (2005) 473; (c) C.-W. Yeh, J.-D. Chen, J.-C. Wang, Polyhedron 27 (2008) 3611; (d) Y.W. Shin, T.H. Kim, J. Seo, S.S. Lee, J. Kim, Bull. Korean Chem. Soc. 27 (2006) 1915; (e) Y.W. Shin, T.H. Kim, K.Y. Lee, K.-M. Park, S.S. Lee, J. Kim, Inorg. Chem. Commun. 7 (2004) 374; (f) N.N. Adarsh, D.K. Kumar, P. Dastidar, Cryst.Eng.Comm. 11 (2009) 796. [8] (a) M. Muttenthaler, M. Bartel, P. Weinberger, G. Hilscher, W. Linert, J. Mol. Struct. 741 (2005) 159; (b) P.N. Gaponik, S.V. Voitekhovich, A.S. Lyakhov, Chem. Heterocycl. Compd. 36 (2000) 326; (c) Y.V. Grigorév, I.I. Maruda, P.N. Gaponik, Vestsi Akad Navuk BSSR, Ser Khim Navuk 80 (1997); (d) P.N. Gaponik, S.V. Voitekhovich, I.I. Maruda, A.A. Kulak, O.A. Ivashkevich, Vestsi Akad Navuk BSSR, Ser Khim Navuk (2001) 62. [9] Preparation for 1: L1 (0.61 g, 2.0 mmol) was placed in a flask containing 30 mL DMF and AgNO3 (0.17 g, 1.0 mmol) was added. The mixture was then refluxed for 24 h to afford a yellow solution with some gray solid. The solution was filtered and then diethyl ether added to introduce precipitate. The precipitate was filtered and washed by diethyl ether (2× 10 ml) and then dried under vacuum to give the white product. Colorless crystals were obtained by slow diffusion of diethyl ether into the filtrate of the compound for several weeks. Yield: 0.37 g (48 % based on Ag). Anal Calcd for C30H24AgN17O3 (MW = 778.50), C, 46.29; H, 3.11; N, 30.59 %. Found: C, 45.97; H, 3.27; N, 30.23 %. IR data (cm− 1): 3416(w), 3100(br), 2925(w), 2855(m), 2669(w), 2403(m), 2061(w), 1924(s), 1760(w), 1657(s), 1513(s), 1396(w), 1207(s), 1092(s), 1043(s), 993(w), 966(m), 863(m), 797(s), 717(s), 636(w). Preparation for 2: Prepared as described for 1 except that L2 (0.71 g, 2.0 mmol) in MeOH/acetone was used. Yield: 0.44 g (50 % based on Ag). Anal. Calcd for C28H20AgN17O7S2
C.-W. Yeh et al. / Inorganic Chemistry Communications 13 (2010) 1562–1565 (MW= 878.60): C, 38.28; H, 2.29; N, 27.10. Found: C, 38.15; H, 2.59; N, 26.87 %. IR (cm− 1): 3421(w), 3112(s), 1884(m), 1663(m), 1595(w), 1508(m), 1387(m), 1282(s), 1243(w), 1168(m), 1080(s), 1042(m), 982(m), 872(m), 702(s), 656(s). Preparation of 3: Prepared as described for 1 except that L3 (0.31 g, 1.0 mmol) and CuBr (0.29 g, 2.0 mmol) were reacted in CH3OH/acetone (30 mL; 1 : 1). Yield: 0.44 g (74% based on Cu). Anal. Calcd for C14H10Cu2N8OBr2 (MW = 593.20): C, 28.35; H, 1.70; N, 18.89. Found: C, 28.15; H, 1.51; N, 18.67 %. IR (cm− 1): 3424(w), 3114(s), 1887(m), 1661(m), 1597(w), 1509(m), 1389(m), 1288(s), 1245(w), 1168(m), 1080(s), 1042(m), 992(m), 862(m), 702(s), 655(s). Brown crystals suitable for X-ray diffraction were grown by layering MeCN solution of CuBr with L3 in MeOH for several weeks. [10] Crystal data for 1: C30H28AgN17O5, Monoclinic, space group C2/c, Fw= 814.56, a = 31.229(3), b = 5.6630(5), c = 23.419(2) Å, β = 125.7640(10) o, V= 3360.7(5) , Z = 4, dcalc = 1.610 g cm− 3, μ = 0.669 mm− 1, F(000) = 1656. R1 = 0.0395 and wR2 = 0.1010, respectively, for I N 2σ(I). Crystal data for 2: C28H20AgN17O7S2, Monoclinic, space group C2/c, Fw = 878.60, a = 24.193(2), b = 19.0897(16), c = 7.1598(6) Å, β =100.712(2)o, V = 3249.0(5) , Z = 4, dcalc = 1.796 g cm− 3, μ = 0.827 mm− 1, F(000) = 1786. R1 = 0.0594, and wR2 = 0.1672, respectively, for I N 2σ(I). Crystal data for 3: C14H10Br2Cu2N8O, Monoclinic, space group C2/c, Fw= 593.20, a = 12.3339(6), b = 25.1322(12), c = 7.2905(3) Å, β = 93.907(3) o,
[11] [12] [13] [14] [15]
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V = 2254.64(18), Z = 4, dcalc = 1.748 g cm− 3, μ = 5.449 mm− 1, F(000) = 1144. R1 = 0.0349 and wR2 = 0.0885, respectively, for I N 2σ(I). Data reduction was carried by standard methods with use of well-established computational procedures [11]. The structure factors were obtained after Lorentz and polarization correction. The empirical absorption correction based on “multi-scan” was applied to the data for complexes 1–3. The positions of some of the heavier atoms, including the silver and copper atoms, were located by the direct method. The remaining atoms were found in a series of alternating difference Fourier maps and least-square refinements [12]. In 1, due to symmetry-imposed disorder, two orientations can be found for the NO-3 anion. Disordered solvent molecules, presumably to be diethyl ether and/or water molecules, are presented in 3, and PLATON/SQUEEZE tool was applied [13]. Large solvent void volume was observed for this structure and the relative percentage per unit cell is 24.5 % (552.1 out of 2254.6 Å3). Relevant geometric information for 3 is reported without disordered solvent contribution. SMART/SAINT/ASTRO, Release 4.03, Siemens Energy and Automation, Inc, Madison, Wisconsin, USA, 1995. G.M. Sheldrick, Acta Crystallogr. A64 (2008) 112. A.L. Spek, J. Appl. Cryst. 36 (2003) 7. T.N. Rao, A.W. Addison, J. Chem. Soc. Dalton Trans. (1984) 1349. J.Y. Lu, B.R. Cabrera, R.-J. Wang, J. Li, Inorg. Chem. 38 (1999) 4608.
Contents lists available at ScienceDirect
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
Structural diversity in coordination polymers with angular ditetrazole ligands Chun-Wei Yeh a, Keng-Han Chang a, Ann Chao a, Shuen-Bo Wang a, Chia-Jun Wu a, Jhy-Der Chen a,⁎, Ju-Chun Wang b a b
Department of Chemistry, Chung-Yuan Christian University, Chung-Li, Taiwan, ROC Department of Chemistry, Soochow University, Taipei, Taiwan, ROC
a r t i c l e
i n f o
Article history: Received 22 July 2010 Accepted 2 September 2010 Available online 16 September 2010 Keywords: Coordination polymer Copper Silver Tetrazole
a b s t r a c t Three new coordination polymers with angular bis(1-tetrazol)diphenyl ligands as bridges, {[Ag(L1)2](NO3)⋅2H2O}∞ [L1 =4,4'-bis(1-tetrazolyl)diphenyl methane], 1, [Ag(L2)2(NO3)]∞ [L2 =4,4'-bis(1-tetrazolyl)diphenyl sulfone], 2, and [CuBr(L3)0.5]∞ [L3 =4,4'-bis(1-tetrazolyl)diphenyl ether], 3, are reported, which show unique 2D structural types. Complex 1 forms 1D double-stranded helical chains where the cavities are threaded by linear hydrogen bondings formed by the co-crystallized water molecules and nitrate anions and complex 2 shows 2D grids involving M4L4 64-membered metallocycles composed of helical chains, while complex 3 exhibits a 2D pleated net comprising 1D channels linked by the double-chain CuBr ribbons. © 2010 Elsevier B.V. All rights reserved.
The design and synthesis of functional coordination polymers have been intensively studied during recent years [1,2]. These complexes thus synthesized not only show potential application in catalysis, magnet, semiconductor and optics but also interesting architectures and topologies. The range and variety of self-assembling inorganic structures that can be constructed relies on the presence of suitable metal–ligand interactions and supramolecular contacts, i.e., hydrogen bondings and other weak interactions [3]. The properties of a spacing ligand, such as rigidity, flexibility, length, size, and geometry also affect the structure. The ligands with 1-substituted ditetrazoles have been the subject of many studies by virtue of their flexible and bridging natures [4–6], and the angular dipyridyl ligands reported to form 1D looped chain structures [7] and interpenetrated frameworks with metal salts [7]. To prepare metal-organic frameworks with large cavities and to investigate the structural chemistry of coordination polymers with angular ditetrazolyl ligands, we have synthesized 4,4'-bis(1-tetrazolyl) diphenyl methane (L1) [8], 4,4'-bis(1-tetrazolyl)diphenyl sulfone (L2) [8] and 4,4'-bis(1-tetrazolyl)diphenyl ether (L3) [8], which were reacted with metal salts. The angular conformations in these ligands exerted by the CH2 (L1) and SO2 (L2) groups and O atom (L3) led to the formation of 2D coordination polymers with unique structural diversity, involving 1D double-stranded helical chain structure where the cavities are threaded by linear hydrogen-bonded chains, 2D grids with M4L4 metallocycles formed by helical chains and a 2D pleated net composed of 1D channel. We report here the synthesis and structural characterization of these complexes.
⁎ Corresponding author. Tel.: + 886 3 2653351; fax:+886 3 2653399. E-mail address: [email protected] (J.-D. Chen). 1387-7003/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2010.09.012
The reactions of AgNO3 with L1 in refluxing DMF and L2 in MeOH/ acetone at room temperature afforded the complexes {[Ag(L1)2] (NO3) ⋅ 2H2O}∞, 1, and [Ag(L2)2(NO3)]∞, 2, respectively, while the reaction of L3 with CuBr in MeOH/acetone at room temperature gave [Cu2Br2(L3)]∞, 3 [9]. Complexes 1–3 are stable in air at ambient temperature and almost insoluble in common solvents such as water, ethanol, methanol, THF, acetonitrile, chloroform and acetone. All the structures of 1–3 were solved in the space group C2/c with Z=4 [10]. Selected bond distances and angles (Table S1) are provided as supplementary materials. Fig. 1(a) shows the coordination environment of the Ag(I) metal center of 1. The distorted tetrahedral Ag(I) center lying on a two-fold axis is coordinated by four tetrazolyl nitrogen atoms belonging to different L1 ligands. Adjacent Ag(I) atoms are linked to each other through the L1 ligands to form 1D looped chains involving 32membered rings (size=14.63×13.34 Å2). The looped chains consist of two helical strands with shared silver atoms that are related by two-fold symmetry, Fig. 1(b). Each strand is formed by linking a pair of consecutive Ag(I) cations and one L1 ligands, which propagates in the direction of aaxis with a repeating unit of 25.862(2) Å. The unique structural feature is that the cavities of the double-stranded helical chains are threaded by the O–H–O [H–O=1.74(2)−2.61(4) Å, ∠O–H–O=116.5(8)−167.4(6)°] hydrogen-bonded chains, Fig. 1(c), composed of the uncoordinated
C.-W. Yeh et al. / Inorganic Chemistry Communications 13 (2010) 1562–1565
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with a repeating unit of 38.18 Å. The 2-D nets are interlinked through the C–H–O [H–O = 2.10 (1) Å and ∠C–H–O = 168.9 (4)°] hydrogen bonds and face to face π–π stacking interactions [3.581(2) Å]. Fig. 3(a) shows the coordination environment of the Cu(I) metal center of 3, while Fig. 3(b) shows its 2D pleated structure. The Cu(I) atoms in the CuBr double chains are 3-fold coordinated to Br, and all the Br atoms are bridged to three Cu(I) metal centers. Each L3 ligand is coordinated to two Cu(I) atoms through the nitrogen atoms which complete the fourth coordination of the metal center, resulting in a slightly distorted tetrahedral coordination geometry. The striking feature is that the 1D CuBr double chains are linked by the L3 ligands to form a 2D structure with 1D channels, Fig. 3(c), with the cavity size of 12.969 (2) × 15.677 (1) Å2. The structure of 3 is in marked to those of Cu2X2(bpy) (X = Cl, Br and bpy = 4,4'-bipyridine) [15] where simple 2D layered networks were observed. The structural
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Fig. 1. (a) Coordination environment of Ag(I) in 1. (b) 1D looped chains consisting of two helical strands with shared silver atoms. (c) The water molecules and nitrate anions are linked to each other in a linear way through O–H–O hydrogen bonds. (d) A schematic drawing showing the cavities threaded by the linear 1D hydrogen-bonded chains.
nitrate anions and the co-crystallized water molecules, to form a 2D structure, Fig. 1(d), which is supported by the C–H–O hydrogen bonds [H–O=2.50 (4)−2.68 (4) Å, ∠C–H–O=115.4 (3)−142.4 (4)°] among the phenyl hydrogen atoms of the L1 ligands and the oxygen atoms of the water molecules and nitrate anions. Fig. 2(a) shows the coordination environment of Ag(I) metal center of 2. The distorted trigonal bipyramidal Ag(I) center is coordinated by four tetrazolyl nitrogen atoms from four different L2 ligands and one nitrate oxygen atom with τ = 0.585 [14]. Fig. 2(b) shows a 2D structure of 2, depicting that Ag(I) atoms are linked to each other by the L2 ligands to form grids involving 64-membered [Ag 4 ( L 2 ) 4 ] rings (size = 19.09× 25.72 Å2). Most interestingly, the 2D grids are composed of helical chains with shared Ag(I) atoms, which show alternating opposite screw sense, Fig. 2(c), and propagate in the direction of b-axis
(c) Fig. 2. (a) Coordination environment of Ag(I) in 2. (b) A 2D layer of 3. (c) The 2D layer is composed of helical chains.
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Acknowledgments We are grateful to the National Science Council of the Republic of China for support. This research was also supported by the project of the specific research fields in Chung Yuan Christian University, Taiwan, ROC under grant CYCU-98-CR-CH. Appendix A. Supplementary material
(a)
Supplementary data to this article can be found online at doi:10.1016/j.inoche.2010.09.012. References
(b)
(c) Fig. 3. (a) Coordination environment of Cu(I) in 3. (b) A 2D pleated layer viewing down the b-axis. (c) A view looking down the c-axis, showing the 1D channels.
difference is most probably due to the angular geometry of the L3 ligand. It is noted that the reaction of CuCl2 with L3 has been investigated but has not been structurally characterized by X-ray crystallography [8]. Based on the relative orientation of the C–H groups on the tetrazolyl rings, each ligand can adopt a syn or anti arrangement as shown in Figure S1 in supplementary materials. The L1–L3 ligand thus all adopt the syn conformation according to this descriptor. 1D looped chain with M2L2 rhombohedral metallocycles is the basic structural type for coordination polymers with angular dipyridyl ligands, which have been found for the ligands N,N′-bis(pyridylcarbonyl)4,4′-diaminodiphenyl ether [7], N,N'-(methylenedi-p-phenylene)bis(pyridine-4-carboxamide) (LB) [7] and N,N'-bis(4-pyridyl)isophthalamide [7]. Only a few complexes with 2D or 3D structure involving 1D looped chain were reported. In the complex Cu(LB)2(PF6)2 [7], the looped chains which are arranged in two directions are interlocked, leading to the formation of a 2D interwoven square-grid layer structure, while the complex [Co(LB)2(NO3)2] · 2(C2H5)2O · (CH3)2SO · H2O shows a 3D interpenetrating network with spacious nano-sized channels [7]. Obviously, the structural types of 1–3 which contain the angular bis (tetrazol-1-yl) ligands are in marked contrast to those containing the angular dipyridyl ligands. In summary, three first structurally characterized coordination polymers containing the angular bis(1-tetrazolyl)diphenyl ligands which show unique 2D structural types have been successfully accomplished. The unique structural types in 1–3 may be ascribed to the structural preference exerted by the CH2 (L1) and SO2 (L2) groups and the O atom (L3) of the spacer ligands. The donor ability of the tetrazolyl groups and the metal center geometries also play important roles. All the L1–L3 ligands in the three complexes adopt the same syn conformation which maximizes the intra- and intermolecular forces for the formation of 1–3.
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C.-W. Yeh et al. / Inorganic Chemistry Communications 13 (2010) 1562–1565 (MW= 878.60): C, 38.28; H, 2.29; N, 27.10. Found: C, 38.15; H, 2.59; N, 26.87 %. IR (cm− 1): 3421(w), 3112(s), 1884(m), 1663(m), 1595(w), 1508(m), 1387(m), 1282(s), 1243(w), 1168(m), 1080(s), 1042(m), 982(m), 872(m), 702(s), 656(s). Preparation of 3: Prepared as described for 1 except that L3 (0.31 g, 1.0 mmol) and CuBr (0.29 g, 2.0 mmol) were reacted in CH3OH/acetone (30 mL; 1 : 1). Yield: 0.44 g (74% based on Cu). Anal. Calcd for C14H10Cu2N8OBr2 (MW = 593.20): C, 28.35; H, 1.70; N, 18.89. Found: C, 28.15; H, 1.51; N, 18.67 %. IR (cm− 1): 3424(w), 3114(s), 1887(m), 1661(m), 1597(w), 1509(m), 1389(m), 1288(s), 1245(w), 1168(m), 1080(s), 1042(m), 992(m), 862(m), 702(s), 655(s). Brown crystals suitable for X-ray diffraction were grown by layering MeCN solution of CuBr with L3 in MeOH for several weeks. [10] Crystal data for 1: C30H28AgN17O5, Monoclinic, space group C2/c, Fw= 814.56, a = 31.229(3), b = 5.6630(5), c = 23.419(2) Å, β = 125.7640(10) o, V= 3360.7(5) , Z = 4, dcalc = 1.610 g cm− 3, μ = 0.669 mm− 1, F(000) = 1656. R1 = 0.0395 and wR2 = 0.1010, respectively, for I N 2σ(I). Crystal data for 2: C28H20AgN17O7S2, Monoclinic, space group C2/c, Fw = 878.60, a = 24.193(2), b = 19.0897(16), c = 7.1598(6) Å, β =100.712(2)o, V = 3249.0(5) , Z = 4, dcalc = 1.796 g cm− 3, μ = 0.827 mm− 1, F(000) = 1786. R1 = 0.0594, and wR2 = 0.1672, respectively, for I N 2σ(I). Crystal data for 3: C14H10Br2Cu2N8O, Monoclinic, space group C2/c, Fw= 593.20, a = 12.3339(6), b = 25.1322(12), c = 7.2905(3) Å, β = 93.907(3) o,
[11] [12] [13] [14] [15]
1565
V = 2254.64(18), Z = 4, dcalc = 1.748 g cm− 3, μ = 5.449 mm− 1, F(000) = 1144. R1 = 0.0349 and wR2 = 0.0885, respectively, for I N 2σ(I). Data reduction was carried by standard methods with use of well-established computational procedures [11]. The structure factors were obtained after Lorentz and polarization correction. The empirical absorption correction based on “multi-scan” was applied to the data for complexes 1–3. The positions of some of the heavier atoms, including the silver and copper atoms, were located by the direct method. The remaining atoms were found in a series of alternating difference Fourier maps and least-square refinements [12]. In 1, due to symmetry-imposed disorder, two orientations can be found for the NO-3 anion. Disordered solvent molecules, presumably to be diethyl ether and/or water molecules, are presented in 3, and PLATON/SQUEEZE tool was applied [13]. Large solvent void volume was observed for this structure and the relative percentage per unit cell is 24.5 % (552.1 out of 2254.6 Å3). Relevant geometric information for 3 is reported without disordered solvent contribution. SMART/SAINT/ASTRO, Release 4.03, Siemens Energy and Automation, Inc, Madison, Wisconsin, USA, 1995. G.M. Sheldrick, Acta Crystallogr. A64 (2008) 112. A.L. Spek, J. Appl. Cryst. 36 (2003) 7. T.N. Rao, A.W. Addison, J. Chem. Soc. Dalton Trans. (1984) 1349. J.Y. Lu, B.R. Cabrera, R.-J. Wang, J. Li, Inorg. Chem. 38 (1999) 4608.