Novel Hydrogen-Bonded Three-Dimensional Networks Encapsulating One-Dimensional Covalent Chains: [M(4,4‘-bipy)(H₂O)₄](4-abs)₂·<i>n</i>H₂O (4,4‘-bipy = 4,4‘-Bipyridine; 4-abs = 4-Aminobenzenesulfonate) (M = Co, <i>n</i> = 1; M = Mn, <i>n</i> = 2)

Two novel compounds, [Co(4,4‘-bipy)(H2O)4](4-abs)2·H2O (1) and [Mn(4,4‘-bipy)(H2O)4](4-abs)2·2H2O (2) (4,4‘-bipy = 4,4‘-bipyridine; 4-abs = 4-aminobenzenesulfonate), have been synthesized in aqueous solution and characterized by single-crystal X-ray diffraction, elemental analyses, UV−vis and IR spectra, and TG analysis. X-ray structural analysis revealed that 1 and 2 both possess unusual hydrogen-bonded three-dimensional (3-D) networks encapsulating one-dimensional (1-D) covalently bonded infinite [M(4,4‘-bipy)(H2O)4]2+ (M = Co, Mn) chains. The 4-abs anions in 1 form 1-D zigzag chains through hydrogen bonds. These chains are further extended through crystallization water molecules into 3-D hydrogen-bonded networks with 1-D channels, in which the [Co(4,4‘-bipy)(H2O)4]2+ linear covalently bonded chains are located. Crystal data for 1: C22H30CoN4O11S2, monoclinic P21, a = 11.380(2) Å, b = 8.0274(16) Å, c = 15.670(3) Å, α = γ = 90°, β = 92.82(3)°, Z = 2. Compound 2 contains interesting two-dimensional (2-D) honeycomb-like networks formed by 4-abs anions and lattice water molecules via hydrogen bonding, which are extended through other crystallization water molecules into three dimensions with 1-D hexagonal channels. The [Mn(4,4‘-bipy)(H2O)4]2+ linear covalent chains exist in these channels. Crystal data for 2: C22H32MnN4O12S2, monoclinic P21/c, a = 15.0833(14) Å, b = 8.2887(4) Å, c = 23.2228(15) Å, α = γ = 90°, β = 95.186(3)°, Z = 4.本研究于水溶液中合成了两种新型配合物：[Co(4,4'-bipy)(H₂O)₄](4-abs)₂·H₂O（记为化合物1）与[Mn(4,4'-bipy)(H₂O)₄](4-abs)₂·2H₂O（记为化合物2），其中4,4'-联吡啶（4,4'-bipyridine，简称4,4'-bipy）、对氨基苯磺酸盐（4-aminobenzenesulfonate，简称4-abs）；并通过单晶X射线衍射、元素分析、紫外-可见（UV−vis）光谱、红外（IR）光谱以及热重（TG）分析对上述配合物进行了表征。X射线结构分析结果表明，化合物1与2均具备独特的氢键合三维（3-D）网络结构，该网络包封了一维（1-D）共价键合的无限[M(4,4'-bipy)(H₂O)₄]²⁺（M = Co, Mn）链。在化合物1中，4-abs阴离子通过氢键作用形成一维锯齿状链；此类链进一步通过结晶水分子扩展为带有一维通道的三维氢键网络，[Co(4,4'-bipy)(H₂O)₄]²⁺线性共价链即坐落于该通道之中。化合物1的晶体学参数为：化学式C₂₂H₃₀CoN₄O₁₁S₂，单斜晶系，空间群P2₁，晶胞参数a = 11.380(2) Å，b = 8.0274(16) Å，c = 15.670(3) Å，α = γ = 90°，β = 92.82(3)°，Z = 2。化合物2中，4-abs阴离子与晶格水分子通过氢键作用构筑出有趣的二维（2-D）蜂窝状网络；该网络通过其他结晶水分子进一步扩展为具有一维六方通道的三维结构，[Mn(4,4'-bipy)(H₂O)₄]²⁺线性共价链即存在于这些通道内。化合物2的晶体学参数为：化学式C₂₂H₃₂MnN₄O₁₂S₂，单斜晶系，空间群P2₁/c，晶胞参数a = 15.0833(14) Å，b = 8.2887(4) Å，c = 23.2228(15) Å，α = γ = 90°，β = 95.186(3)°，Z = 4。