Butcher Ray J, Purdy Andrew P, Brown Paul A, Gunlycke Daniel
Department of Chemistry, Howard University, 525 College Street NW, Washington DC 20059, USA.
Chemistry Division, Code 6123, Naval Research Laboratory, 4555 Overlook Av, SW, Washington DC 20375-5342, USA.
Acta Crystallogr E Crystallogr Commun. 2021 Jan 1;77(Pt 1):70-74. doi: 10.1107/S205698902001628X.
The title compound, -poly[[tetra-kis-(1-methyl-pyrrolidin-2-one-κ)calcium(II)]-μ-()-1,1'-dimethyl-2,2'-dioxo-1,1',2,2'-tetra-hydro-[3,3'-bipyrrolyl-idene]-5,5'-bis-(thiol-ato)-κ :'], [Ca(CHNOS)(CHNO)] , , crystallizes in the triclinic space group . The crystal studied was twinned by non-merohedry two different twofold operations, about the normals to (001) and (10), giving four twin domains with refined occupancies of 0.412 (4), 0.366 (4), 0.055 (1), 0.167 (4). The Ca atoms are located on centers of inversion. Each Ca is surrounded by four 1-methyl-pyrrolidin-2-one (NMP) ligands and coordinated through one of the two O atoms to two ()-1,1'-dimethyl-2,2'-dioxo-1,1',2,2'-tetra-hydro-[3,3'-bipyrrolyl-idene]-5,5'-bis-(thiol-ate), [CHNOS], dianions (abbreviation: DMTBT). This dianion thus facilitates the formation of a 1-D polymer, which propagates in the [011] direction. These ribbons are linked by inter-molecular C-H⋯S inter-actions. Each Ca atom is in an octa-hedral CaO six-coordinate environment with Ca-O bond lengths ranging from 2.308 (6) to 2.341 (6) Å, bond angles ranging from 88.2 (2) to 91.8 (2)° and the angles all 180° due to the Ca atoms being located on centers of inversion. Theoretical calculations were carried out using density functional theory (DFT) and the results showed that although the central DMTBT dianion is planar there is likely some resonance across the central bond between both aza-pentyl rings, but this is not sufficient to establish a ring current. The calculated UV-vis spectrum shows a peak at 625 nm, which accounts for the deep blue-purple color of solutions of the complex.
标题化合物，聚[[四-（1-甲基-吡咯烷-2-酮-κ）钙（II）]-μ-（）-1,1'-二甲基-2,2'-二氧代-1,1',2,2'-四氢-[3,3'-联吡咯亚基]-5,5'-双-（硫醇根）-κ：']，[Ca(CHNOS)(CHNO)] ， ，结晶于三斜空间群 。所研究的晶体通过非镜像孪晶形成，涉及两种不同的二次轴操作，分别关于（001）和（10）的法线，产生四个孪晶畴，其精细占有率分别为0.412 (4)、0.366 (4)、0.055 (1)、0.167 (4)。Ca原子位于对称中心上。每个Ca原子被四个1-甲基-吡咯烷-2-酮（NMP）配体包围，并通过两个O原子之一与两个（）-1,1'-二甲基-2,2'-二氧代-1,1',2,2'-四氢-[3,3'-联吡咯亚基]-5,5'-双-（硫醇根），[CHNOS]，二价阴离子（缩写：DMTBT）配位。因此，该二价阴离子促进了一维聚合物的形成，该聚合物沿[011]方向延伸。这些带通过分子间C-H⋯S相互作用相连。每个Ca原子处于八面体CaO六配位环境中，Ca-O键长范围为2.308 (6)至2.341 (6) Å，键角范围为88.2 (2)至91.8 (2)°，且由于Ca原子位于对称中心上， 角均为180°。使用密度泛函理论（DFT）进行了理论计算，结果表明，尽管中心DMTBT二价阴离子是平面的，但两个氮杂戊基环之间的中心键上可能存在一些共振，但这不足以建立环电流。计算得到的紫外可见光谱在625 nm处有一个峰，这解释了该配合物溶液的深蓝色-紫色。
