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水合二氯双[4,4,5,5-四甲基-2-(2-吡啶基)-4,5-二氢-1H-咪唑-1-氧基3-氧化物-κ(2)O(1),N(2)]镍(II)硝酸盐甲醇溶剂合物一水合物

Aquachlorobis[4,4,5,5-tetramethyl-2-(2-pyridyl)-4,5-dihydro-1H-imidazol-1-oxyl 3-oxide-kappa(2)O(1),N(2)]nickel(II) nitrate methanol disolvate monohydrate.

作者信息

Lewis Gareth R, Blake Alexander J

机构信息

School of Chemistry, University of Nottingham, Nottingham, NG7 2RD, England.

出版信息

Acta Crystallogr C. 2002 Jul;58(Pt 7):m398-400. doi: 10.1107/s0108270102008831. Epub 2002 Jun 20.

Abstract

The title complex, [NiCl(C(12)H(16)N(3)O(2))(2)(H(2)O)]NO(3) x 2CH(4)O x -H(2)O, was obtained from a methanolic solution of Ni(NO(3))(2) x 6H(2)O, 2-pyridyl nitronyl nitroxide (2-NITpy) and (NEt(4))(2)[CoCl(4)]. The equatorial coordination sites of the octahedral Ni(II) centre are occupied by two chelating radical ligands, with the axial positions occupied by the Cl(-) and water ligands. The H(2)O[bond]Ni[bond]Cl axis of the complex lies along a crystallographic twofold axis, so that only half the cation is present in the asymmetric unit. The Ni[bond]Cl bond length [2.3614 (17) A] is significantly shorter than distances typical of octahedral Ni(II) centres [2.441 (5) A]. However, with only one nitrate anion per formula unit, the oxidation state of the metal must be assigned as Ni(II). The 2-NITpy ligands bend away from the equatorial plane, forming a hydrophobic region around the Cl atoms. Conversely, the ligated water molecule forms moderately strong hydrogen bonds with the disordered methanol solvent molecules, which in turn form interactions with the water of crystallization and the disordered nitrate anion. These interactions combine to give hydrophilic regions throughout the crystal structure.

摘要

标题配合物[NiCl(C₁₂H₁₆N₃O₂)₂(H₂O)]NO₃·2CH₄O·H₂O是由Ni(NO₃)₂·6H₂O、2 - 吡啶基硝酰基氮氧化物(2 - NITpy)和(NEt₄)₂[CoCl₄]的甲醇溶液制得。八面体Ni(II)中心的赤道配位位点被两个螯合自由基配体占据,轴向位置被Cl⁻和水配体占据。配合物的H₂O—Ni—Cl轴沿着一个晶体学二重轴,因此不对称单元中仅存在半个阳离子。Ni—Cl键长[2.3614(17) Å]明显短于八面体Ni(II)中心的典型距离[2.441(5) Å]。然而,由于每个化学式单元仅有一个硝酸根阴离子,金属的氧化态必须指定为Ni(II)。2 - NITpy配体背离赤道平面弯曲,在Cl原子周围形成一个疏水区域。相反,配位水分子与无序的甲醇溶剂分子形成适度强的氢键,而这些甲醇溶剂分子又与结晶水和无序的硝酸根阴离子相互作用。这些相互作用共同在整个晶体结构中形成亲水区域。

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