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4-[(E)-(2,4-二氟苯基)(羟基亚氨基)甲基]哌啶鎓苦味酸盐

4-[(E)-(2,4-Difluoro-phen-yl)(hydroxy-imino)meth-yl]piperidinium picrate.

作者信息

Jasinski Jerry P, Butcher Ray J, Yathirajan H S, Mallesha L, Mohana K N

出版信息

Acta Crystallogr Sect E Struct Rep Online. 2009 Sep 5;65(Pt 10):o2365-6. doi: 10.1107/S1600536809035363.

Abstract

The title compound, C(12)H(15)F(2)N(2)O(+)·C(6)H(2)N(3)O(7) (-), a picrate salt of 4-[(E)-(2,4-difluoro-phen-yl)(hydroxy-imino)meth-yl]piper-idine, crystallizes with two independent mol-ecules in a cation-anion pair in the asymmetric unit. In the cation, a methyl group is tris-ubstituted by hydroxy-imino, piperidin-4-yl and 2,4-difluoro-phenyl groups, the latter of which contains an F atom disordered over two positions in the ring [occupancy ratio 0.631 (4):0.369 (4)]. The mean plane of the hydr-oxy group is in a synclinical conformation nearly orthogonal [N-C-C-C = 72.44 (19)°] to the mean plane of the piperidine ring, which adopts a slightly distorted chair conformation. The dihedral angle between the mean plane of the 2,4-difluoro-phenyl and piperidin-4-yl groups is 60.2 (3)°. In the picrate anion, the mean planes of the two o-NO(2) and single p-NO(2) groups adopt twist angles of 5.7 (2), 25.3 (7) and 8.3 (6)°, respectively, with the attached planar benzene ring. The dihedral angle between the mean planes of the benzene ring in the picrate anion and those in the hydroxy-imino, piperidin-4-yl and 2,4-difluoro-phenyl groups in the cation are 84.9 (7), 78.9 (4) and 65.1 (1)°, respectively. Extensive hydrogen-bond inter-actions occur between the cation-anion pair, which help to establish the crystal packing in the unit cell. This includes dual three-center hydrogen bonds with the piperidin-4-yl group, the phenolate and o-NO(2) O atoms of the picrate anion at different positions in the unit cell, which form separate N-H⋯(O,O) bifurcated inter-molecular hydrogen-bond inter-actions. Also, the hydr-oxy group forms a separate hydrogen bond with a nearby piperidin-4-yl N atom, thus providing two groups of hydrogen bonds, which form an infinite two-dimensional network along (011).

摘要

标题化合物C(12)H(15)F(2)N(2)O(+)·C(6)H(2)N(3)O(7) (-),即4-[(E)-(2,4-二氟苯基)(羟基亚氨基)甲基]哌啶的苦味酸盐,在不对称单元中以阳离子 - 阴离子对的形式结晶,其中有两个独立的分子。在阳离子中,一个甲基被羟基亚氨基、哌啶-4-基和2,4-二氟苯基三取代,后者的一个F原子在环上的两个位置无序分布[占有率比为0.631 (4):0.369 (4)]。羟基的平均平面与哌啶环的平均平面呈近正交的顺叠构象[N-C-C-C = 72.44 (19)°],哌啶环呈轻微扭曲的椅式构象。2,4-二氟苯基与哌啶-4-基的平均平面之间的二面角为60.2 (3)°。在苦味酸根阴离子中,两个邻位硝基和单个对位硝基的平均平面与相连的平面苯环分别呈5.7 (2)°、25.3 (7)°和8.3 (6)°的扭转角。苦味酸根阴离子中苯环的平均平面与阳离子中羟基亚氨基、哌啶-4-基和2,4-二氟苯基的平均平面之间的二面角分别为84.9 (7)°、78.9 (4)°和65.1 (1)°。阳离子 - 阴离子对之间存在广泛的氢键相互作用,这有助于在晶胞中建立晶体堆积。这包括与哌啶-4-基、苦味酸根阴离子在晶胞中不同位置的酚盐和邻位硝基O原子形成的双三中心氢键,形成单独的N-H⋯(O,O)分叉分子间氢键相互作用。此外,羟基与附近的哌啶-4-基N原子形成单独的氢键,从而提供两组氢键,它们沿着(011)形成无限的二维网络。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/306b/2970333/2d361fa22c4c/e-65-o2365-fig1.jpg

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