VanderWeide Andrew I, Staples Richard J, Biros Shannon M
Department of Chemistry, Grand Valley State University, 1 Campus Dr., Allendale, MI 49401, USA.
Center for Crystallographic Research, Department of Chemistry, Michigan State University, East Lansing, MI 48824, USA.
Acta Crystallogr E Crystallogr Commun. 2019 Jun 14;75(Pt 7):991-996. doi: 10.1107/S205698901900820X. eCollection 2019 Jul 1.
Two bis-carbamoyl-methyl-phosphine oxide compounds, namely {[(3-{[2-(di-phen-yl-phosphino-yl)ethanamido]-meth-yl}benz-yl)carbamo-yl]meth-yl}di-phenyl-phos-phine oxide, CHNOP, (I), and diethyl [({2-[2-(di-eth-oxy-phosphino-yl)ethanamido]-eth-yl}carbamo-yl)meth-yl]phospho-nate, CHNOP, (II), were synthesized nucleophilic acyl substitution reactions between an ester and a primary amine. Hydrogen-bonding inter-actions are present in both crystals, but these inter-actions are intra-molecular in the case of compound (I) and inter-molecular in compound (II). Intra-molecular π-π stacking inter-actions are also present in the crystal of compound (I) with a centroid-centroid distance of 3.9479 (12) Å and a dihedral angle of 9.56 (12)°. Inter-molecular C-H⋯π inter-actions [C⋯centroid distance of 3.622 (2) Å, C-H⋯centroid angle of 146°] give rise to supra-molecular sheets that lie in the plane. Key geometric features for compound (I) involve a nearly planar, amide group with a C-N-C-C torsion angle of 169.12 (17)°, and a torsion angle of -108.39 (15)° between the phosphine oxide phospho-rus atom and the amide nitro-gen atom. For compound (II), the electron density corresponding to the phosphoryl group was disordered, and was modeled as two parts with a 0.7387 (19):0.2613 (19) occupancy ratio. Compound (II) also boasts a -amide group that approaches planarity with a C-N-C-C torsion angle of -176.50 (16)°. The hydrogen bonds in this structure are inter-molecular, with a ⋯ distance of 2.883 (2) Å and a -H⋯ angle of 175.0 (18)° between the amide hydrogen atom and the P=O oxygen atom. These non-covalent inter-actions create ribbons that run along the -axis direction.
合成了两种双氨基甲酰甲基氧化膦化合物，即{[(3-{[2-(二苯基膦酰基)乙酰胺基]甲基}苄基)氨基甲酰基]甲基}二苯基氧化膦，CHNOP，(I)，以及二乙基[({2-[2-(二乙氧基膦酰基)乙酰胺基]乙基}氨基甲酰基)甲基]膦酸酯，CHNOP，(II)，通过酯与伯胺之间的亲核酰基取代反应合成。两种晶体中均存在氢键相互作用，但在化合物(I)中这些相互作用是分子内的，而在化合物(II)中是分子间的。化合物(I)的晶体中还存在分子内π-π堆积相互作用，质心间距为3.9479 (12) Å，二面角为9.56 (12)°。分子间C-H⋯π相互作用[C⋯质心距离为3.622 (2) Å，C-H⋯质心角为146°]形成了位于平面内的超分子片层。化合物(I)的关键几何特征包括一个近乎平面的酰胺基团，C-N-C-C扭转角为169.12 (17)°，以及氧化膦磷原子与酰胺氮原子之间的扭转角为-108.39 (15)°。对于化合物(II)，与磷酰基对应的电子密度是无序的，并被模拟为占有率比为0.7387 (19):0.2613 (19)的两部分。化合物(II)还拥有一个接近平面的酰胺基团，C-N-C-C扭转角为-176.50 (16)°。该结构中的氢键是分子间的，酰胺氢原子与P=O氧原子之间的⋯距离为2.883 (2) Å，-H⋯角为175.0 (18)°。这些非共价相互作用形成了沿-轴方向延伸的带状结构。
