Haezam Farah Natasha, Awang Normah, Kamaludin Nurul Farahana, Jotani Mukesh M, Tiekink Edward R T
Environmental Health and Industrial Safety Programme, Faculty of Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja Muda Abdul Aziz, 50300 Kuala Lumpur, Malaysia.
Department of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380001, India.
Acta Crystallogr E Crystallogr Commun. 2020 Jan 10;76(Pt 2):167-176. doi: 10.1107/S2056989020000122. eCollection 2020 Feb 1.
The crystal and mol-ecular structures of the title organotin di-thio-carbamate compounds, [Sn(CH)(CHNS)] (I) and [Sn(CH)(CHNS)] (II), present very distinct tin atom coordination geometries. In (I), the di-thio-carbamate ligand is asymmetrically coordinating with the resulting CS donor set defining a coordination geometry inter-mediate between square-pyramidal and trigonal-bipyramidal. In (II), two independent mol-ecules comprise the asymmetric unit, which differ in the conformations of the allyl substituents and in the relative orientations of the tin-bound phenyl rings. The di-thio-carbamate ligands in (II) coordinate in an asymmetric mode but the Sn-S bonds are more symmetric than observed in (I). The resulting CS donor set approximates an octa-hedral coordination geometry with a -disposition of the -carbon atoms and with the more tightly bound sulfur atoms approximately . The only directional inter-molecular contacts in the crystals of (I) and (II) are of the type phenyl-C-H⋯π(phen-yl) and vinyl-idene-C-H⋯π(phen-yl), respectively, with each leading to a supra-molecular chain propagating along the axis direction. The calculated Hirshfeld surfaces emphasize the importance of H⋯H contacts in the crystal of (I), . contributing 62.2% to the overall surface. The only other two significant contacts also involve hydrogen, . C⋯H/H⋯C (28.4%) and S⋯H/H⋯S (8.6%). Similar observations pertain to the individual mol-ecules of (II), which are clearly distinguishable in their surface contacts, with H⋯H being clearly dominant (59.9 and 64.9%, respectively) along with C⋯H/H⋯C (24.3 and 20.1%) and S⋯H/H⋯S (14.4 and 13.6%) contacts. The calculations of energies of inter-action suggest dispersive forces make a significant contribution to the stabilization of the crystals. The exception is for the C-H⋯π contacts in (II) where, in addition to the dispersive contribution, significant contributions are made by the electrostatic forces.
标题有机锡二硫代氨基甲酸盐化合物[Sn(CH)(CHNS)]（I）和[Sn(CH)(CHNS)]（II）的晶体结构和分子结构呈现出非常不同的锡原子配位几何形状。在（I）中，二硫代氨基甲酸盐配体以不对称方式配位，由此产生的CS供体集定义了一种介于四方锥和三角双锥之间的配位几何形状。在（II）中，两个独立的分子构成不对称单元，它们在烯丙基取代基的构象以及与锡相连的苯环的相对取向上有所不同。（II）中的二硫代氨基甲酸盐配体以不对称模式配位，但Sn-S键比在（I）中观察到的更对称。由此产生的CS供体集近似于八面体配位几何形状，其中碳原子呈 - 排列，且结合更紧密的硫原子近似于 。（I）和（II）晶体中唯一的定向分子间接触分别是苯基 - C - H⋯π（苯基）和亚乙烯基 - C - H⋯π（苯基）类型，每种接触都导致沿轴方向传播的超分子链。计算得到的Hirshfeld表面强调了H⋯H接触在（I）晶体中的重要性， 对总表面贡献了62.2%。另外两个唯一显著的接触也涉及氢， 即C⋯H/H⋯C（28.4%）和S⋯H/H⋯S（8.6%）。类似的观察结果适用于（II）的各个分子，它们在表面接触上明显可区分，其中H⋯H明显占主导（分别为59.9%和64.9%），同时还有C⋯H/H⋯C（24.3%和20.1%）以及S⋯H/H⋯S（14.4%和13.6%）接触。相互作用能的计算表明，色散力对晶体的稳定性有显著贡献。（II）中的C - H⋯π接触是个例外，除了色散贡献外，静电力也有显著贡献。
