Vassilyeva Olga Yu, Kokozay Vladimir N, Petrusenko Svitlana, Sobolev Alexandre N
Department of Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrska Street, Kyiv 01601, Ukraine.
School of Molecular Sciences, M310, University of Western Australia, 35 Stirling Highway, Perth, 6009, W.A., Australia.
Acta Crystallogr E Crystallogr Commun. 2021 Sep 21;77(Pt 10):1033-1036. doi: 10.1107/S2056989021009580. eCollection 2021 Oct 1.
The title compound, [Fe(CHNO)][CdCl], crystallizes in the trigonal space group and is assembled from discrete [Fe(DMF)] cations (DMF = ,-di-methyl-formamide) and [CdCl] anions. In the cation, the iron(III) atom, located on a special position of site symmetry, is coordinated by six oxygen atoms from DMF ligands with all Fe-O distances being equal [2.0072 (16) Å]. A slight distortion of the octa-hedral environment of the metal comes from the O-Fe-O angles deviating from the ideal value of 90° [86.85 (7) and 93.16 (7)°] whilst all the angles are strictly 180°. The central Cl atom of the [CdCl] anion is also located on a special position of site symmetry and bridges two corner sharing, tetra-hedrally coordinated Cd atoms. The two Cd atoms and the central Cl atom are colinear. The two sets of terminal chloride ligands on either side of the dumbbell-like anion are rotated relative to each other by 30°. In the crystal, the cations and anions, stacked one above the other along the -axis direction, are held in place principally by electrostatic inter-actions. There are also C-H⋯Cl and C-H⋯O inter-actions, but these are rather weak. Of the six crystal structures reported to date for ionic salts of [Fe(DMF)] cations ( = 2, 3), five contain Fe ions. The title compound is the second example of a stable compound containing the [Fe(DMF)] cation. The existence of both [Fe(DMF)] and [Fe(DMF)] cations shows that the DMF ligand coordination sphere can accommodate changes in the charge and spin states of the metal centre.
标题化合物[Fe(CHNO)][CdCl]结晶于三方空间群，由离散的[Fe(DMF)]阳离子（DMF = N,N - 二甲基甲酰胺）和[CdCl]阴离子组装而成。在阳离子中，位于具有特殊位置对称性位点的铁(III)原子由来自DMF配体的六个氧原子配位，所有Fe - O距离相等[2.0072 (16) Å]。金属八面体环境的轻微扭曲源于O - Fe - O角偏离理想值90°[86.85 (7)和93.16 (7)°]，而所有的 角严格为180°。[CdCl]阴离子的中心Cl原子也位于具有特殊位置对称性的位点上，并桥连两个共角、四面体配位的Cd原子。两个Cd原子和中心Cl原子共线。哑铃状阴离子两侧的两组末端氯配体彼此相对旋转30°。在晶体中，阳离子和阴离子沿z轴方向一个叠在另一个之上堆积，主要通过静电相互作用保持在位。也存在C - H⋯Cl和C - H⋯O相互作用，但这些作用相当弱。在迄今为止报道的[Fe(DMF)]阳离子（n = 2, 3）的离子盐的六个晶体结构中，五个含有Fe离子。标题化合物是含有[Fe(DMF)]阳离子的稳定化合物的第二个例子。[Fe(DMF)]和[Fe(DMF)]阳离子的存在表明DMF配体配位球可以适应金属中心电荷和自旋状态的变化。
