Ardan Bohdan, Kinzhybalo Vasyl, Slyvka Yurii, Shyyka Olga, Luk Yanov Mykhaylo, Lis Tadeusz, Mys Kiv Marian
Faculty of Chemistry, Ivan Franko National University, Kyryla i Mefodia Str. 6, 79005 L'viv, Ukraine.
Institute of Low Temperature and Structure Research, Okolna 2, 50-422 Wroclaw, Poland.
Acta Crystallogr C Struct Chem. 2017 Jan 1;73(Pt 1):36-46. doi: 10.1107/S2053229616018751.
As an important class of heterocyclic compounds, 1,3,4-thiadiazoles have a broad range of potential applications in medicine, agriculture and materials chemistry, and were found to be excellent precursors for the crystal engineering of organometallic materials. The coordinating behaviour of allyl derivatives of 1,3,4-thiadiazoles with respect to transition metal ions has been little studied. Five new crystalline copper(I) π-complexes have been obtained by means of an alternating current electrochemical technique and have been characterized by single-crystal X-ray diffraction and IR spectroscopy. The compounds are bis[μ-5-methyl-N-(prop-2-en-1-yl)-1,3,4-thiadiazol-2-amine]bis[nitratocopper(I)], [Cu(NO)(CHNS)], (1), bis[μ-5-methyl-N-(prop-2-en-1-yl)-1,3,4-thiadiazol-2-amine]bis[(tetrafluoroborato)copper(I)], [Cu(BF)(CHNS)], (2), μ-aqua-bis{μ-5-[(prop-2-en-1-yl)sulfanyl]-1,3,4-thiadiazol-2-amine}bis[nitratocopper(I)], [Cu(NO)(CHNS)(HO)], (3), μ-aqua-(hexafluorosilicato)bis{μ-5-[(prop-2-en-1-yl)sulfanyl]-1,3,4-thiadiazol-2-amine}dicopper(I)-acetonitrile-water (2/1/4), [Cu(SiF)(CHNS)(HO)]·0.5CHCN·2HO, (4), and μ-benzenesulfonato-bis{μ-5-[(prop-2-en-1-yl)sulfanyl]-1,3,4-thiadiazol-2-amine}dicopper(I) benzenesulfonate-methanol-water (1/1/1), Cu(CHOS)(CHNS)·CHOH·HO, (5). The structure of the ligand 5-methyl-N-(prop-2-en-1-yl)-1,3,4-thiadiazol-2-amine (Mepeta), CHNS, was also structurally characterized. Both Mepeta and 5-[(prop-2-en-1-yl)sulfanyl]-1,3,4-thiadiazol-2-amine (Pesta) (denoted L) reveal a strong tendency to form dimeric {CuL} fragments, being attached to the metal atom in a chelating-bridging mode via two thiadiazole N atoms and an allylic C=C bond. Flexibility of the {Cu(Pesta)} unit allows the Cu atom site to be split into two positions with different metal-coordination environments, thus enabling the competitive participation of different molecules in bonding to the metal centre. The Pesta ligand in (4) allows the Cu atom to vary between water O-atom and hexafluorosilicate F-atom coordination, resulting in the rare case of a direct Cu...FSiF interaction. Extensive three-dimensional hydrogen-bonding patterns are formed in the reported crystal structures. Complex (5) should be considered as the first known example of a Cu(CHSO) coordination compound. To determine the hydrogen-bond interactions in the structures of (1) and (2), a Hirshfeld surface analysis has been performed.
作为一类重要的杂环化合物，1,3,4 - 噻二唑在医药、农业和材料化学领域有着广泛的潜在应用，并且被发现是有机金属材料晶体工程的优良前体。1,3,4 - 噻二唑烯丙基衍生物与过渡金属离子的配位行为研究较少。通过交流电化学技术获得了五种新型结晶铜（I）π - 配合物，并通过单晶X射线衍射和红外光谱对其进行了表征。这些化合物分别是双[μ - 5 - 甲基 - N - （丙 - 2 - 烯 - 1 - 基） - 1,3,4 - 噻二唑 - 2 - 胺]双[硝酸铜（I）]，[Cu(NO)(CHNS)]，（1）；双[μ - 5 - 甲基 - N - （丙 - 2 - 烯 - 1 - 基） - 1,3,4 - 噻二唑 - 2 - 胺]双[（四氟硼酸根）铜（I）]，[Cu(BF)(CHNS)]，（2）；μ - 水合 - 双{μ - 5 - [（丙 - 2 - 烯 - 1 - 基）硫烷基] - 1,3,4 - 噻二唑 - 2 - 胺}双[硝酸铜（I）]，[Cu(NO)(CHNS)(HO)]，（3）；μ - 水合 - （六氟硅酸根）双{μ - 5 - [（丙 - 2 - 烯 - 1 - 基）硫烷基] - 1,3,4 - 噻二唑 - 2 - 胺}二铜（I） - 乙腈 - 水（2/1/4），[Cu(SiF)(CHNS)(HO)]·0.5CHCN·2HO，（4）；以及μ - 苯磺酸根 - 双{μ - 5 - [（丙 - 2 - 烯 - 1 - 基）硫烷基] - 1,3,4 - 噻二唑 - 2 - 胺}二铜（I）苯磺酸盐 - 甲醇 - 水（1/1/1），Cu(CHOS)(CHNS)·CHOH·HO，（5）。还对配体5 - 甲基 - N - （丙 - 2 - 烯 - 1 - 基） - 1,3,4 - 噻二唑 - 2 - 胺（Mepeta），CHNS的结构进行了表征。Mepeta和5 - [（丙 - 2 - 烯 - 1 - 基）硫烷基] - 1,3,4 - 噻二唑 - 2 - 胺（Pesta）（表示为L）均显示出形成二聚体{CuL}片段的强烈倾向，通过两个噻二唑N原子和一个烯丙基C = C键以螯合 - 桥连模式连接到金属原子上。{Cu(Pesta)}单元的灵活性使Cu原子位点分裂为两个具有不同金属配位环境的位置，从而使不同分子能够竞争性地参与与金属中心的键合。（4）中的Pesta配体使Cu原子在水O原子和六氟硅酸盐F原子配位之间变化，导致罕见的直接Cu...FSiF相互作用情况。在所报道的晶体结构中形成了广泛的三维氢键模式。配合物（5）应被视为第一个已知的Cu(CHSO)配位化合物的例子。为了确定（1）和（2）结构中的氢键相互作用，进行了 Hirshfeld表面分析。
