Ouahrouch Abdelaaziz, Krim Jamal, Taourirte Moha, Lazrek Hassan B, Engels Joachim W, Bats Jan W
Laboratory of Bioorganic and Macromolecular Chemistry, Department of Chemistry, Faculty of Sciences and Technology Guéliz (FSTG), BP 549, Marrakech, Morocco.
Acta Crystallogr C. 2013 Oct;69(Pt 10):1157-63. doi: 10.1107/S0108270113022981. Epub 2013 Sep 6.
Crystal structures are reported for four related diethyl [(arylamino)(4-ethynylphenyl)lmethyl]phosphonate derivatives, namely diethyl [(4-bromoanilino)(4-ethynylphenyl)methyl]phosphonate, C19H21BrNO3P, (I), diethyl ((4-chloro-2-methylanilino){4-[2-(trimethylsilyl)ethynyl]phenyl}methyl)phosphonate, C23H31ClNO3PSi, (II), diethyl ((4-fluoroanilino){4-[2-(trimethylsilyl)ethynyl]phenyl}methyl)phosphonate, C22H29FNO3PSi, (III), and diethyl [(4-ethynylphenyl)(naphthalen-2-ylamino)methyl]phosphonate, C23H24NO3P, (IV). The conformation of the anilinobenzyl group is very similar in all four compounds. The P-C bond has an approximately staggered conformation, with the aniline and ethynylphenyl groups in gauche positions with respect to the P=O double bond. The two six-membered rings are almost perpendicular. The sums of the valence angles about the N atoms vary from 344 (2) to 351 (2)°. In the crystal structures, molecules of (I), (III) and (IV) are arranged as centrosymmetric or pseudocentrosymmetric dimers connected by two N-H···O=P hydrogen bonds. The molecules of (II) are arranged as centrosymmetric dimers connected by C(methyl)-H···O=P hydrogen bonds. The N-H bond of (II) is not involved in hydrogen bonding.
报道了四种相关的二乙基[(芳基氨基)(4-乙炔基苯基)甲基]膦酸酯衍生物的晶体结构，即二乙基[(4-溴苯胺基)(4-乙炔基苯基)甲基]膦酸酯，C19H21BrNO3P，(I)；二乙基((4-氯-2-甲基苯胺基){4-[2-(三甲基甲硅烷基)乙炔基]苯基}甲基)膦酸酯，C23H31ClNO3PSi，(II)；二乙基((4-氟苯胺基){4-[2-(三甲基甲硅烷基)乙炔基]苯基}甲基)膦酸酯，C22H29FNO3PSi，(III)；以及二乙基[(4-乙炔基苯基)(萘-2-基氨基)甲基]膦酸酯，C23H24NO3P，(IV)。在所有四种化合物中，苯胺苄基的构象非常相似。P-C键具有近似交错构象，苯胺基和乙炔基苯基相对于P=O双键处于 gauche 位置。两个六元环几乎垂直。N原子周围的价角总和在344 (2)°至351 (2)°之间变化。在晶体结构中，(I)、(III)和(IV)的分子排列成通过两个N-H···O=P氢键连接的中心对称或假中心对称二聚体。(II)的分子排列成通过C(甲基)-H···O=P氢键连接的中心对称二聚体。(II)的N-H键不参与氢键形成。
