Vassilyeva Olga Yu, Buvaylo Elena A, Kokozay Vladimir N, Goreshnik Evgeny A
Department of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska str. 64/13, 01601 Kyiv, Ukraine.
Department of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia.
Acta Crystallogr E Crystallogr Commun. 2024 Oct 4;80(Pt 11):1125-1129. doi: 10.1107/S2056989024009654. eCollection 2024 Oct 1.
The crystal structure of the title organic-inorganic hybrid salt, (CHN)[CdCl], (I), has been reported with four mol-ecules in the asymmetric unit in a monoclinic cell [Vassilyeva (2021 ▸). , , 7713-7722]. While using two different aldehydes in the oxidative cyclization-condensation involving CHNH·HCl to prepare a new monovalent cation with the imidazo[1,5-]pyridinium skeleton, a new polymorph was obtained for (I) in space group 1 and a unit cell with approximately half the volume of the monoclinic form. The structural configurations of the two crystallographically non-equivalent organic cations as well as the geometry of the moderately distorted tetra-hedral CdCl dianion show minor changes. In the crystal, identically stacked cations and tetra-chloro-cadmate anions form separate columns parallel to the axis. The loose packing of the anions leads to a minimal separation of approximately 9.53 Å between the metal atoms in the triclinic form 7.51 Å in the monoclinic one, indicating that the latter is packed slightly more densely. The two forms also differ by aromatic stacking motifs. Similar to the monoclinic polymorph, the triclinic one excited at 364 nm shows an intense unsymmetrical photoluminescent band with maximum at 403 nm and a full width at half maximum of 51 nm in the solid state.
标题有机-无机杂化盐(CHN)[CdCl]（I）的晶体结构已被报道，其不对称单元中有四个分子，属于单斜晶系[瓦西里耶娃（2021▸）。，，7713 - 7722]。在使用两种不同醛类进行涉及CHNH·HCl的氧化环化缩合反应以制备具有咪唑并[1,5 - ]吡啶鎓骨架的新型单价阳离子时，获得了（I）的一种新多晶型物，其空间群为1，晶胞体积约为单斜晶型的一半。两种晶体学上不等价的有机阳离子的结构构型以及中度扭曲的四面体CdCl二阴离子的几何形状显示出微小变化。在晶体中，相同堆积的阳离子和四氯镉酸盐阴离子形成平行于轴的单独柱体。阴离子的松散堆积导致三斜晶型中金属原子之间的最小间距约为9.53 Å，而单斜晶型中为7.51 Å，这表明后者堆积得稍密一些。这两种晶型在芳香堆积模式上也有所不同。与单斜多晶型物类似，在364 nm激发的三斜晶型在固态下显示出一个强烈的不对称光致发光带，最大发射波长为403 nm，半高宽为51 nm。
