Salomón-Flores María K, Valdes-García Josue, Martínez-Otero Diego, Dorazco-González Alejandro
Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, Mexico, 04510, D.F., Mexico.
Centro Conjunto de Investigación en Química Sustentable, UAEM-UNAM, Instituto de Química, Universidad Nacional Autónoma de México, Carretera Toluca-Atlacomulco Km 14.5, CP 50200 Toluca, Estado de México, Mexico.
Acta Crystallogr E Crystallogr Commun. 2024 May 21;80(Pt 6):625-629. doi: 10.1107/S205698902400447X. eCollection 2024 May 1.
The synthesis, crystallization and characterization of a tri-fluoro-methane-sulfonate salt of 5,10,15,20-tetra-kis-(1-benzyl-pyridin-1-ium-4-yl)-21,23-por-phy-rin, CHN ·4CFSO ·4HO, ·OTf, are reported in this work. The reaction between 5,10,15,20-tetra-kis-(pyridin-4-yl)-21,23-porphyrin and benzyl bromide in the presence of 0.1 equiv. of Ca(OH) in CHCN under reflux with an N atmosphere and subsequent treatment with silver tri-fluoro-methane-sulfonate (AgOTf) salt produced a red-brown solution. This reaction mixture was filtered and the solvent was allowed to evaporate at room temperature for 3 d to give ·OTf. Crystal structure determination by single-crystal X-ray diffraction (SCXD) revealed that ·OTf crystallizes in the space group 2/. The asymmetric unit contains half a porphyrin mol-ecule, two tri-fluoro-methane-sulfonate anions and two water mol-ecules of crystallization. The macrocycle of tetra-pyrrole moieties is planar and unexpectedly it has coordinated Ca ions in occupational disorder. This Ca ion has only 10% occupancy (CHCaFNOS). The pyridinium rings bonded to methyl-ene groups from porphyrin are located in two different arrangements in almost orthogonal positions between the plane formed by the porphyrin and the pyridinium rings. The crystal structure features cation⋯π inter-actions between the Ca atom and the π-system of the phenyl ring of neighboring mol-ecules. Both tri-fluoro-methane-sulfonate anions are found at the periphery of , forming hydrogen bonds with water mol-ecules.
本文报道了5,10,15,20-四-（1-苄基吡啶-1-鎓-4-基）-21,23-卟啉三氟甲磺酸盐CHN·4CFSO·4HO，即·OTf的合成、结晶及表征。5,10,15,20-四-（吡啶-4-基）-21,23-卟啉与苄基溴在0.1当量Ca(OH)存在下于CHCN中在N气氛下回流反应，随后用三氟甲磺酸银（AgOTf）盐处理，得到红棕色溶液。将该反应混合物过滤，使溶剂在室温下蒸发3天得到·OTf。通过单晶X射线衍射（SCXD）确定晶体结构表明·OTf结晶于空间群2/。不对称单元包含半个卟啉分子、两个三氟甲磺酸盐阴离子和两个结晶水分子。四吡咯部分的大环是平面的，出乎意料的是它在职业性疾病中与钙离子配位。该钙离子占有率仅为10%（CHCaFNOS）。与卟啉亚甲基相连的吡啶鎓环位于卟啉和吡啶鎓环形成的平面之间几乎正交位置的两种不同排列中。晶体结构的特征是Ca原子与相邻分子苯环的π体系之间存在阳离子⋯π相互作用。两个三氟甲磺酸盐阴离子都位于的外围，与水分子形成氢键。
