Department of Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
Molecules. 2021 Jan 21;26(3):551. doi: 10.3390/molecules26030551.
The crystal structures of two azobenzene derivative Schiff base metal complexes (new CHCuNO of -1 and known CHMnNO of 2/c abbreviated as Cu and Mn, respectively) were (re-)determined experimentally using conventional X-ray analysis to obtain electron density using a PLATON program. Cu affords a four-coordinated square planar geometry, while Mn affords a hexa-coordinated distorted octahedral geometry whose apical sites are occupied by an acetate ion and water ligands, which are associated with hydrogen bonds. The π-π or CH-π and hydrogen bonding intermolecular interactions were found in both crystals, which were also analyzed using a Hirshfeld surface analysis program. To compare these results with experimental results, a density functional theory (DFT) calculation was also carried out based on the crystal structures to obtain calculated electron density using a conventional Gaussian program. These results revealed that the axial Mn-O coordination bonds of Mn were relatively weaker than the in-plane M-N or M-O coordination bonds.
实验采用常规 X 射线分析重新确定了两种偶氮苯衍生物席夫碱金属配合物（新的 CHCuNO-1 和已知的 CHMnNO-2/c，分别缩写为 Cu 和 Mn）的晶体结构，使用 PLATON 程序获得电子密度。Cu 呈现出四配位的平面正方形几何形状，而 Mn 呈现出六配位的扭曲八面体几何形状，其顶点位置被醋酸根离子和水分子配体占据，这些配体与氢键有关。在两个晶体中都发现了π-π 或 CH-π 和氢键的分子间相互作用，这些相互作用也使用 Hirshfeld 表面分析程序进行了分析。为了将这些结果与实验结果进行比较，还基于晶体结构进行了密度泛函理论（DFT）计算，使用常规高斯程序获得计算电子密度。这些结果表明，轴向 Mn-O 配位键的 Mn 相对较弱，而平面内的 M-N 或 M-O 配位键较强。
