Anaya-Avila Odalys, Muñoz-Granados Oscar, Andrade-López Noemí, Alvarado-Rodríguez José G, Martínez-Otero Diego
Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria, Carretera Pachuca-Tulancingo, km 4.5 Colonia Carboneras, Mineral de la Reforma, Hidalgo 42184, Mexico.
Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, km 14.5 Carretera Toluca-Atlacomulco, Toluca 50200, Mexico.
Acta Crystallogr C Struct Chem. 2024 Nov 1;80(Pt 11):698-706. doi: 10.1107/S205322962400946X. Epub 2024 Oct 4.
Three dinuclear zinc(II) acetate complexes of the general formula [Zn{L}(AcO)], namely, di-μ-acetato-κO:O'-bis[({2-[(pyridin-2-ylmethylidene)amino]phenyl}sulfanido-κN,N',S)zinc(II)], [Zn(CHNS)(CHO)] (n = 1), 4, μ-acetato-1:2κO:O'-acetato-2κO-[μ-(2-{[1-(pyridin-2-yl)ethylidene]amino}phenyl)sulfanido-1κS:2κN,N',S][(2-{[1-(pyridin-2-yl)ethylidene]amino}phenyl)sulfanido-1κN,N',S]dizinc(II), [Zn(CHNS)(CHO)] (n = 2), 5, and μ-acetato-1:2κO:O'-acetato-2κO-[μ-(2-{[phenyl(pyridin-2-yl)methylidene]amino}phenyl)sulfanido-1κS:2κN,N',S][(2-{[phenyl(pyridin-2-yl)methylidene]amino}phenyl)sulfanido-1κN,N',S]dizinc(II)-bis(2-aminophenyl) disulfide (2/1), [Zn(CHNS)(CHO)]·0.5CHNS (n = 3), 6·0.5(2-APS), were obtained from the reaction of 2-R-(pyridin-2-yl)benzothiazoline precursors (R = H, 1; R = Me, 2; R = Ph, 3) with zinc acetate dihydrate in a 1:1 ratio. All the complexes crystallized as dinuclear species and complex 6 cocrystallized with one molecule of bis(2-aminophenyl) disulfide (2-APS). The anionic Schiff base ligands {L} displayed a κN,κS-tridentate coordination mode with the formation of two five-membered chelate rings. In 4, 5 and 6·0.5(2-APS), both Zn ions are pentacoordinated and the coordination sphere of 4 was different with respect to those in 5 and 6·0.5(2-APS). For 4, the X-ray diffraction study showed a dinuclear complex containing two bridging acetate ligands linked to both Zn ions. For 5 and 6·0.5(2-APS), the dinuclear complexes displayed one bridging acetate ligand linked to both Zn ions, where the first Zn ion includes a dative bond with one S atom from an adjacent anionic Schiff base {L}, while the second Zn ion is coordinated to one terminal acetate ligand. In each dinuclear complex, the geometry is the same for both Zn metal centres. The local geometry of the Zn cation in 4 is halfway between trigonal bipyramidal and square pyramidal local geometries; in 5 and 6, the local geometries are described as distorted square pyramidal. Hirshfeld surface analysis of 5 and 6 showed the predominance of H...H interactions, as well as the contribution of C-H...C, C-H...O and C-H...S noncovalent interactions to the cohesion of the crystalline network of the Zn complexes.
通式为[Zn{L}(AcO)]的三种双核乙酸锌（II）配合物，即二-μ-乙酸根-κO:O'-双[({2-[(吡啶-2-基亚甲基)氨基]苯基}硫代-κN,N',S)锌（II）]，[Zn(CHNS)(CHO)]（n = 1），4，μ-乙酸根-1:2κO:O'-乙酸根-2κO-[μ-(2-{[1-(吡啶-2-基)亚乙基]氨基}苯基)硫代-1κS:2κN,N',S][(2-{[1-(吡啶-2-基)亚乙基]氨基}苯基)硫代-1κN,N',S]二锌（II），[Zn(CHNS)(CHO)]（n = 2），5，以及μ-乙酸根-1:2κO:O'-乙酸根-2κO-[μ-(2-{[苯基(吡啶-2-基)亚甲基]氨基}苯基)硫代-1κS:2κN,N',S][(2-{[苯基(吡啶-2-基)亚甲基]氨基}苯基)硫代-1κN,N',S]二锌（II）-双（2-氨基苯基）二硫化物（2/1），[Zn(CHNS)(CHO)]·0.5CHNS（n = 3），6·0.5(2-APS)，是由2-R-（吡啶-2-基）苯并噻唑啉前体（R = H，1；R = Me，2；R = Ph，3）与二水合乙酸锌以1:1的比例反应得到的。所有配合物均以双核物种形式结晶，配合物6与一分子双（2-氨基苯基）二硫化物（2-APS）共结晶。阴离子席夫碱配体{L}呈现κN,κS-三齿配位模式，形成两个五元螯合环。在4、5和6·0.5(2-APS)中，两个锌离子均为五配位，且4的配位环境与5和6·0.5(2-APS)中的不同。对于4，X射线衍射研究表明其为一种双核配合物，含有两个与两个锌离子相连的桥连乙酸根配体。对于5和6·0.5(2-APS)，双核配合物呈现一个与两个锌离子相连的桥连乙酸根配体，其中第一个锌离子与相邻阴离子席夫碱{L}中的一个硫原子形成一个配位键，而第二个锌离子与一个末端乙酸根配体配位。在每个双核配合物中，两个锌金属中心的几何构型相同。4中锌阳离子的局部几何构型介于三角双锥和四方锥局部几何构型之间；在5和6中，局部几何构型被描述为扭曲的四方锥。对5和6的 Hirshfeld 表面分析表明，H...H相互作用占主导，以及C-H...C、C-H...O和C-H...S非共价相互作用对锌配合物晶体网络的凝聚有贡献。
