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异金属配合物二水合-1κ-二氯-2κ-(μ-2-甲酰基-6-甲氧基苯酚根-1κ,:2κ){μ-2-甲氧基-6-[(甲基亚氨基)甲基]苯酚根-1κ,:2κ}铅(II)镍(II)的全分子无序

Whole-mol-ecule disorder of the heterometallic complex di-aqua-1κ -di-chlorido-2κ -(μ-2-formyl-6-meth-oxy-phenolato-1κ , :2κ ){μ-2-meth-oxy-6-[(methyl-imino)-meth-yl]phenolato-1κ , :2κ }lead(II)nickel(II).

作者信息

Vassilyeva Olga Yu, Kokozay Vladimir N, Goreshnik Evgeny

机构信息

Department of Chemistry, Taras Shevchenko National University of Kyiv, 12, Hetman Pavlo Skoropadskyi str., 01601 Kyiv, Ukraine.

Department of Inorganic Chemistry and Technology, Jozef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia.

出版信息

Acta Crystallogr E Crystallogr Commun. 2025 Jul 1;81(Pt 8):667-671. doi: 10.1107/S2056989025005857. eCollection 2025 Aug 1.

Abstract

The new mol-ecular complex [NiPb(CHNO)(CHNO)Cl(HO)] with the Schiff base 2-meth-oxy-6-[(methyl-imino)-meth-yl]phenol and -vanillin ligands, both deprotonated, crystallizes in the monoclinic space group 2/ with one mol-ecule per asymmetric unit. The heterometallic mol-ecule exhibits a whole-mol-ecule orientational disorder [occupancy ratio 0.711 (6): 0.289 (6)] about a pseudo-twofold rotation axis that roughly bis-ects the mol-ecule along the Ni-Pb axis. The Ni centre coordination is distorted octa-hedral [Ni-N/O = 1.996 (8)-2.021 (7) Å, major component] with two water mol-ecules in the apexes [2.088 (6) and 2.090 (5) Å]. The Pb atom is six-coordinate in a highly distorted tetra-gonal-bipyramidal geometry. Two phenolato and two methoxo O atoms from the deprotonated ligand moieties are nearly coplanar with the metal centre [Pb-O 2.301 (8)-2.740 (10) Å, major component], while the two chlorides are located on opposite sides of the plane [Pb-Cl = 2.821 (5) and 2.868 (5) Å]. The Ni-Pb pair of metals is bridged by two phenolato O atoms enabling a metal-metal separation of 3.441 (3)/3.477 (7) Å. Two intra-molecular O-H⋯Cl hydrogen bonds between coordinated aqua and chloride ligands appear to be a reason for the Cl-Pb-Cl and O-Ni-O angles being far from 180°. In the solid state, the well-separated heterometallic mol-ecules are inter-linked by π-π stacking and weak O-H⋯Cl and C-H⋯Cl/O hydrogen bonds. The mol-ecules show no significant inter-molecular inter-actions: the minimal ⋯ distance in the crystal is about 7.65 Å (Ni⋯Pb).

摘要

新型分子配合物[NiPb(CHNO)(CHNO)Cl(HO)]与席夫碱2-甲氧基-6-[(甲基亚氨基)甲基]苯酚和香草醛配体(均去质子化),以单斜空间群2/结晶,每个不对称单元有一个分子。该异金属分子围绕一条大致沿Ni-Pb轴平分分子的伪二重旋转轴呈现全分子取向无序[占有率0.711 (6): 0.289 (6)]。Ni中心的配位为扭曲八面体[Ni-N/O = 1.996 (8)-2.021 (7) Å,主要成分],两个水分子位于顶点[2.088 (6)和2.090 (5) Å]。Pb原子以高度扭曲的四方双锥几何构型六配位。来自去质子化配体部分的两个酚氧基和两个甲氧基O原子与金属中心几乎共面[Pb-O 2.301 (8)-2.740 (10) Å,主要成分],而两个氯原子位于平面的相对两侧[Pb-Cl = 2.821 (5)和2.868 (5) Å]。Ni-Pb这对金属由两个酚氧基O原子桥连,金属-金属间距为3.441 (3)/3.477 (7) Å。配位水和氯配体之间的两个分子内O-H⋯Cl氢键似乎是Cl-Pb-Cl和O-Ni-O角远非180°的原因。在固态中,分离良好的异金属分子通过π-π堆积以及弱O-H⋯Cl和C-H⋯Cl/O氢键相互连接。分子间没有明显的相互作用:晶体中最小的⋯距离约为7.65 Å (Ni⋯Pb)。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb34/12326490/0e65cea42cfc/e-81-00667-fig1.jpg

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