Ji‐Jiang Wang

Crystal structure of catena-aquatris(1H-imidazole-N)(μ-sulfato)copper(II), Cu(H2O)(C3H4N2)3(SO4)

C9H14Q1N6O5S, monoclinic, P12i/nl (no. 14), a = 11.723(2) Ä, b = 8.651(2) A, c = 13.839(3) Ä, β = 91.703(4)°, V= 1402.8 A, Ζ = 4,R&(F) = 0.046, wRnffF) = 0.133, Τ = 296 Κ. Source of material The title complex was synthesized by mixed solution method. A solution of CuSC>4 · 5H2O (0.125 g, 0.5 mmol) in 10 ml methanol was added to a solution of Ι,Γ-carbonyl-diimidazole (0.081 g, 0.5 mmol) in 10 ml methanol. The reaction mixture was stirred for 2 h at room temperature and then filtered. The filtrate was diffused in ether. After two weeks, blue block-shaped crystals were obtained. Discussion Helical structures have received much attention in coordination chemistry and materials chemistry because helicity is an essential feature of life and also important in advanced materials such as optical devices and asymmetric catalysis [1,2]. Consequently, many single-, doubleand higher-order stranded helical complexes have been generated by self-assembly processes [3,4]. Herein, we report a novel ID helical chain coordination polymer [Cu(C3H4N2)3(H20XS04)]„. In the crystal structure of title compound (figure, top), the Cu(II) atoms are coordinated by three Ν atoms from three different imidazole ligands (d(Cu—Nl) = 1.998(3) Ä, d(Ca—N3) = 1.984(3) A, d(Cu—N5) = 1.997(4) Ä. Imidazole molecules resulted from Ι,Γ-carbonyl-diimidazole which was easily hydrolyzed in methanol solution. Furthermore, three Ο atoms from two sulfato groups (d(Cu—Ol) = 2.003(3) Ä, d(Cu—02A) = 2.534(4) Ä) and one water molecule (d(Cu—Ol) = 2.551(5) Ä) furnish a distorted octahedral environment. The cisoid and transoid bond angles around the Cu atoms fall in the regions of 85.6(2)° 92.1(2)° and 176.6(2)° -178.1(2)°, respectively. Each pair of adjacent Cu (Π) atoms are bridged by a bidentate sulfato group to form a ID single helical chain running along a crystallographic 2\ screw axis in b direction with a pitch of the lattice parameter (figure, bottom). Interestingly, the polymeric helical chains possess two types of intrachain hydrogen bonds. One type occurs between coordinating water and uncoordinated sulfato Ο atoms with </(0-0) = 2.714 Ä and ZO-H-O = 144.8°. The other type is between the uncoordinated -NH groups of the imidazole ligands and uncoordinated sulfato Ο atoms with </(N—0) = 2.850 Ä 2.873 Ä and ZN-H-O = 173° -175°. Therefore, the polymeric helical chains are further stabilized by these relatively strong intrachain hydrogen bonds. Through the interchain N-H—Ο and O-H—O hydrogen bonds, neighboring helical chains are interlinked to form the 3D framework. On the other hand, sulfato groups exhibit slight deviation from 7d symmetry {d{S—O) = 1.450(3) Ä 1.479(3) Ä, ZO-S-O = 108.6(2)° 110.9(2)°), due to the influence of sulfato groups joining in coordination. Table 1. Data collection and handling. Crystal: Wavelength: βDifEractometer, scan mode: 20jmxi N(hkl)mt*smi, N(hkl) uaique: Criterion for /oi», N(hkl)p: N(param)nGacA·. Programs: blue rod, size 0.06 χ 0.08 χ 0.22 mm Mo Κα radiation (0.71073 Ä) 17.41 cm -1 Broker SMART CCD, φ/ω 50.18° 6897,2495 /ohe > 2 a(Idx), 1631 199 SHELXS-97 [5], S H E L X I ^ [6] * Correspondence author (e-mail: lllnl832@sina.com) 1 % CU(H20XC3H4N2)3(S04) Tabk 2. Atomic coordinates and displacement parameters (in Ä). Tabk 2. Continued. Atom Site X y ζ i/iso Atom Site X y ζ l/iso H(2A) 4e 0.5787 0.1816 0.5876 0.057 H(3) 4c 0.3881 0.5427 0.6191 0.056 H(4A) 4c 0.6556 1.1432 0.9487 0.066 H(4) 4c 0.6105 1.0158 0.8024 0.066 H(6A) 4c 0.2988 0.9545 0.5952 0.064 H(5) 4c 0.6656 0.9609 1.0800 0.066 H(5A) 4c 0.515(5) 0.493(2) 0.936(4) 0.209 H(6) 4c 0.6316 0.7097 1.0087 0.059 H(5B) 4c 0.401(4) 0.518(6) 0.934(4) 0.209 H(7) 4c 0.4904 0.8747 0.6195 0.054 H(l) 4c 0.6714 0.3345 0.7072 0.052 H(8) 4c 0.1827 0.8613 0.7236 0.070 H(2) Ae 0.4019 0.2995 0.5309 0.063 H(9) 4c 0.3129 0.7167 0.8321 0.058 Tabk 3. Atomic coordinates and displacement parameters (in Ä). Atom Site X y ζ Un i/22 i/33 Ul2 Ul3 t/23 Cu(l) 4c 0.57914(5) 0.65540(7) 0.78070(5) 0.0468(4) 0.0273(4) 0.0538(4) 0.0093(3) -0.0122(3) -0.0129(3) S(l) 4c 0.7583(1) 0.4237(1) 0.89478(9) 0.0414(7) 0.0216(6) 0.0415(7) 0.0012(5) 0.0045(6) -0.0007(5) N(l) 4c 0.5413(3) 0.4833(5) 0.6890(3) 0.036(2) 0.035(2) 0.047(2) -0.002(2) 0.000(2) -0.007(2) N(2) 4c 0.5529(4) 0.2684(5) 0.6080(3) 0.065(3) 0.027(2) 0.051(3) 0.004(2) 0.004(2) -0.014(2) N(3) 4c 0.6126(3) 0.8189(4) 0.8780(3) 0.044(2) 0.024(2) 0.051(3) 0.003(2) -0.001(2) -0.005(2) N(4) 4c 0.6452(4) 1.0452(5) 0.9431(3) 0.063(3) 0.032(3) 0.069(3) -0.012(2) 0.009(2) -0.017(3) N(5) 4c 0.4393(3) 0.7708(5) 0.7372(3) 0.046(3) 0.029(2) 0.044(3) 0.007(2) -0.002(2) -0.008(2) N(6) 4c 0.3232(4) 0.8996(6) 0.6433(3) 0.053(3) 0.053(3) 0.053(3) 0.013(2) -0.003(2) 0.007(2) 0(1) 4c 0.7216(3) 0.5462(4) 0.8261(2) 0.041(2) 0.033(2) 0.045(2) 0.006(2) -0.007(2) -0.001(2) 0(2) 4c 0.8001(3) 0.2913(4) 0.8422(2) 0.048(2) 0.026(2) 0.050(2) 0.008(2) 0.004(2) -0.007(2) 0(3) 4c 0.6625(3) 0.3760(4) 0.9543(3) 0.074(3) 0.037(2) 0.099(3) 0.007(2) 0.054(2) 0.004(2) 0(4) 4c 0.8479(3) 0.4885(4) 0.9583(2) 0.076(2) 0.031(2) 0.047(2) -0.007(2) -0.018(2) 0.003(2) 0(5) 4c 0.4598(6) 0.5072(9) 0.9009(5) 0.134(6) 0.117(6) 0.169(6) -0.029(5) 0.053(5) -0.010(5) q i ) 4c 0.6028(4) 0.3574(6) 0.6748(4) 0.043(3) 0.031(3) 0.056(3) 0.004(2) -0.005(3) -0.011(3) C(2) 4c 0.4540(5) 0.3373(6) 0.5770(4) 0.052(3) 0.046(4) 0.059(4) -0.004(3) -0.010(3) -0.019(3) C(3) 4c 0.4466(4) 0.4707(6) 0.6260(4) 0.042(3) 0.042(3) 0.056(3) 0.002(3) -0.006(3) -0.010(3) C(4) 4c 0.6208(5) 0.9693(7) 0.8626(4) 0.076(4) 0.041(4) 0.049(3) -0.002(3) 0.009(3) 0.001(3) C(5) 4c 0.6510(5) 0.9406(7) 1.0148(4) 0.068(4) 0.042(4) 0.055(3) -0.005(3) -0.008(3) -0.006(3) C(6) 4c 0.6319(4) 0.8029(6) 0.9752(4) 0.061(4) 0.034(3) 0.051(3) -0.004(3) -0.005(3) -0.001(3) C(7) 4c 0.4301(4) 0.8521(6) 0.6593(4) 0.047(3) 0.040(3) 0.048(3) -0.007(3) 0.005(2) -0.005(3) C(8) 4c 0.2604(5) 0.8462(7) 0.7158(5) 0.045(3) 0.061(4) 0.069(4) 0.014(3) 0.008(3) -0.005(3) C(9) 4c 0.3323(4) 0.7662(7) 0.7753(4) 0.053(3) 0.047(4) 0.046(3) 0.007(3) 0.013(3) -0.008(3) Acknowledgment This project was supported by the Nature Scientific Research Foundation of Shaanxi Provincial Education Office of China (grant no. 05JK155).