de Melo Ana Paula Lopes, Bresolin Leandro, Tirloni Bárbara, de Farias Renan Lira, de Oliveira Adriano Bof
Escola de Química e Alimentos, Universidade Federal do Rio Grande, Av. Itália km 08, Campus Carreiros, 96203-900 Rio Grande-RS, Brazil.
Departamento de Química, Universidade Federal de Santa Maria, Av. Roraima 1000, Campus Universitário, 97105-900 Santa Maria-RS, Brazil.
Acta Crystallogr E Crystallogr Commun. 2023 Nov 16;79(Pt 12):1166-1172. doi: 10.1107/S2056989023009908. eCollection 2023 Dec 1.
The reaction between the (,)-fixolide 4-methyl-thio-semicarbazone and Pd chloride yielded the title compound, [Pd(CHNS)]·CHO {common name: -bis-[(,)-fixolide 4-methyl-thio-semicarbazonato-κ ]palladium(II) ethanol monosolvate}. The asymmetric unit of the title compound consists of one bis-thio-semicarbazonato Pd complex and one ethanol solvent mol-ecule. The thio-semicarbazononato ligands act as metal chelators with a configuration in a distorted square-planar geometry. A C-H⋯S intra-molecular inter-action, with graph-set motif (6), is observed and the coordination sphere resembles a hydrogen-bonded macrocyclic environment. Additionally, one C-H⋯Pd anagostic inter-action can be suggested. Each ligand is disordered over the aliphatic ring, which adopts a half-chair conformation, and two methyl groups [s.o.f. = 0.624 (2):0.376 (2)]. The disorder includes the chiral carbon atoms and, remarkably, one ligand has the ()-isomer with the highest s.o.f. value atoms, while the other one shows the opposite, the atoms with the highest s.o.f. value are associated with the ()-isomer. The N-N-C(=S)-N fragments of the ligands are approximately planar, with the maximum deviations from the mean plane through the selected atoms being 0.0567 (1) and -0.0307 (8) Å (r.m.s.d. = 0.0403 and 0.0269 Å) and the dihedral angle with the respective aromatic rings amount to 46.68 (5) and 50.66 (4)°. In the crystal, the complexes are linked pairs of N-H⋯S inter-actions, with graph-set motif (8), into centrosymmetric dimers. The dimers are further connected by centrosymmetric pairs of ethanol mol-ecules, building mono-periodic hydrogen-bonded ribbons along [011]. The Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are [atoms with highest/lowest s.o.f.s considered separately]: H⋯H (81.6/82.0%), H⋯C/C⋯H (6.5/6.4%), H⋯N/N⋯H (5.2/5.0%) and H⋯S/S⋯H (5.0/4.9%).
(,)-固甾醇4-甲基硫代氨基脲与氯化钯反应生成了标题化合物[Pd(CHNS)]·CHO {通用名称：-双-[(,)-固甾醇4-甲基硫代氨基脲合-κ ]钯(II)乙醇单溶剂合物}。标题化合物的不对称单元由一个双硫代氨基脲钯配合物和一个乙醇溶剂分子组成。硫代氨基脲配体作为金属螯合剂，在扭曲的平面正方形几何构型中呈 构型。观察到一个具有(6)图集模式的C-H⋯S分子内相互作用，并且配位球类似于氢键大环环境。此外，可以推测存在一个C-H⋯Pd次级相互作用。每个配体在脂肪环上无序排列，脂肪环呈半椅构象，两个甲基[占有率 = 0.624 (2):0.376 (2)]。这种无序包括手性碳原子，并且值得注意的是，一个配体中占有率最高的原子是()-异构体的原子，而另一个配体则相反，占有率最高的原子与()-异构体相关。配体的N-N-C(=S)-N片段近似平面，通过选定原子的平均平面的最大偏差分别为0.0567 (1)和 -0.0307 (8) Å（均方根偏差 = 0.0403和0.0269 Å），与各自芳香环的二面角分别为46.68 (5)和50.66 (4)°。在晶体中，配合物通过具有(8)图集模式的N-H⋯S相互作用对连接成中心对称二聚体。二聚体通过中心对称的乙醇分子对进一步连接，沿着[011]形成单周期氢键带。 Hirshfeld表面分析表明，晶体凝聚的主要贡献为[分别考虑占有率最高/最低的原子]：H⋯H (81.6/82.0%)、H⋯C/C⋯H (6.5/6.4%)、H⋯N/N⋯H (5.2/5.0%)和H⋯S/S⋯H (5.0/4.9%)。
