The reaction of 2‐cyanopyridine with N‐phenylthiosemicarbazide afforded 2‐[amino(pyridin‐2‐yl)methylidene]‐N‐phenylhydrazine‐1‐carbothioamide (Ham4ph) and crystals of 4‐phenyl‐5‐(pyridin‐2‐yl)‐2,4‐dihydro‐3H‐1,2,4‐triazole‐3‐thione (pyph3NS, 1, C₁₃H₁₀N₄S). Crystals of methyl 2‐{[4‐phenyl‐5‐(pyridin‐2‐yl)‐4H‐1,2,4‐triazol‐3‐yl]sulfanyl}acetate (phpy2NS, 2, C₁₆H₁₄N₄O₂S), derived from 1, were obtained by the reaction of Ham4ph with chloroacetic acid, followed by the acid‐catalyzed esterification of the carboxylic acid with methyl alcohol. Crystals of bis(methanol‐κO)bis(methyl 2‐{[4‐phenyl‐5‐(pyridin‐2‐yl)‐4H‐1,2,4‐triazol‐3‐yl‐κ²N¹,N⁵]sulfanyl}acetato)zinc(II)/cadmium(II) hexabromidocadmate(II), [Zn_0.76Cd_0.24(C₁₆H₁₄N₄O₂S)₂(CH₃OH)₂][Cd₂Br₆] or [Zn_0.76Cd_0.24(phpy2NS)₂(MeOH)₂][Cd₂Br₆], 3, and dichlorido(methyl 2‐{[4‐phenyl‐5‐(pyridin‐2‐yl)‐4H‐1,2,4‐triazol‐3‐yl‐κ²N¹,N⁵]sulfanyl}acetato)mercury(II), [HgCl₂(C₁₆H₁₄N₄O₂S)] or [Hg(phpy2NS)Cl₂], 4, were synthesized using ligand 2 and CdBr₂ or HgCl₂, respectively. The molecular and supramolecular structures of the compounds were studied by X‐ray diffractometry. The asymmetric unit of 3 is formed from CdBr₃ and M(phpy2NS)(MeOH) units, where the metal centre M has a 76% occupancy of Zn^II and 24% of Cd^II. The M²⁺ centre of the cation, located on a crystallographic inversion centre, is hexacoordinated and appears as a slightly distorted octahedral [MN₄O₂]²⁺ cation. The Cd centre of the anion is coordinated by two terminal bromide ligands and two bridging bromide ligands that generate [Cd₂Br₆]²⁻ cadmium–bromide clusters. These clusters display crystallographic inversion symmetry forming two edge‐shared tetrahedra and serve as agents that direct the structure in the formation of supramolecular assemblies. In mononuclear complex 4, the coordination geometry around the Hg²⁺ ion is distorted tetrahedral and comprises two chloride ligands and two N‐atom donors from the phpy2NS ligand, viz. one pyridine N atom and the other from triazole. In the crystal packing, all four compounds exhibit weak intermolecular interactions, which facilitate the formation of three‐dimensional architectures. Along with the noncovalent interactions, the structural diversity in the complexes can be attributed to the metal centre and to the coordination geometry, as well as to its ionic or neutral character.

中文翻译：

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设计和合成2-{[4-苯基-5-（吡啶-2-基）-4H-1,2,4-三唑-3-基]硫烷基}乙酸甲酯（phpy2NS）作为基团配合物的配体12个要素：结构评估和氢键超分子组装分析。

2-氰基吡啶与N-苯基硫代氨基脲反应得到2- [氨基（吡啶-2-基）亚甲基] -N-苯基肼-1-碳硫酰胺（Ham4ph）和4-苯基-5-（吡啶-2-基）晶体）-2,4-二氢-3 H -1,2,4-三唑-3-硫酮（pyph3NS，1，C ₁₃ H ₁₀ N ₄ S）。2-{[[4-苯基-5-（吡啶-2-基）-甲基] -4 H -1,2,4-三唑-3-基]硫烷基}乙酸甲酯的晶体（phpy2NS，2，C ₁₆ H ₁₄ N ₄ O ₂ S），源自1可以通过Ham4ph与氯乙酸反应，然后将羧酸与甲醇进行酸催化酯化来获得。双晶（甲醇- κ ø）二（甲基2 - {[4-苯基-5-（吡啶-2-基）-4- ħ 1,2,4-三唑-3-基- κ ² Ñ ¹，N ⁵ ]硫烷基}乙酰基]锌（II）/镉（II）六溴代己二酸酯（II），[Zn _0.76 Cd _0.24（C ₁₆ H ₁₄ N ₄ O ₂ S）₂（CH ₃ OH）₂ ] [Cd ₂ Br ₆ ]或[Zn _0.76 Cd _0.24（phpy2NS）₂（MeOH）₂ ] [Cd ₂ Br ₆ ]，3和二氯基（甲基2-{[4-苯基-5-（吡啶-2-基）-4 - H -1,2,4-三唑） ‐-3-yl‐κ ² N ¹，N ⁵ [硫代基}乙酰）汞（II），[HgCl ₂（C ₁₆ H ₁₄ N ₄ O ₂ S）]或[Hg（phpy2NS）Cl ₂ ]，4分别为使用配体2和CdBr ₂或HgCl ₂合成， 分别。通过X射线衍射法研究了化合物的分子和超分子结构。3的不对称单元由CdBr ₃和M（phpy2NS）（MeOH）单元形成，其中金属中心M的Zn ^II占有率为76 ％，Cd ^II的占有率为24％。阳离子的M ²⁺中心位于晶体学反转中心，呈六配位形式，表现为略微扭曲的八面体[ M N ₄ O ₂ ] ²⁺阳离子。阴离子的Cd中心由两个末端溴化物配体和两个生成[Cd₂ Br ₆ ] ²⁻溴化镉簇。这些团簇显示出晶体学上的反转对称性，形成两个边缘共享的四面体，并充当在超分子组装体形成过程中指导结构的作用。在单核络合物4中，Hg ²⁺离子周围的配位几何是扭曲的四面体，包含两个氯化物配体和两个来自phpy2NS配体的N原子供体。一个吡啶N原子，另一个来自三唑。在晶体堆积中，所有四种化合物均显示出较弱的分子间相互作用，从而促进了三维结构的形成。除了非共价相互作用外，配合物中的结构多样性还可以归因于金属中心和配位几何，以及其离子或中性特征。