Crystal structures of two bis-carbamoylmethylphosphine oxide (CMPO) compounds

• Main Authors: Andrew I. VanderWeide, Richard J. Staples, Shannon M. Biros
• Format: Article
• Language: English
• Published: International Union of Crystallography 2019-07-01
• Series: Acta Crystallographica Section E: Crystallographic Communications
• Subjects: crystal structure; carbamoylmethylphosphine oxide; multidentate ligand; hydrogen bonds; C—H...π interactions; π–π stacking interactions
• Online Access: http://scripts.iucr.org/cgi-bin/paper?S205698901900820X

Two bis-carbamoylmethylphosphine oxide compounds, namely {[(3-{[2-(diphenylphosphinoyl)ethanamido]methyl}benzyl)carbamoyl]methyl}diphenylphosphine oxide, C36H34N2O4P2, (I), and diethyl [({2-[2-(diethoxyphosphinoyl)ethanamido]ethyl}carbamoyl)methyl]phosphonate, C14H30N2O8P2, (II), were synthesized via nucleophilic acyl substitution reactions between an ester and a primary amine. Hydrogen-bonding interactions are present in both crystals, but these interactions are intramolecular in the case of compound (I) and intermolecular in compound (II). Intramolecular π–π stacking interactions 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)°. Intermolecular C—H...π interactions [C...centroid distance of 3.622 (2) Å, C—H...centroid angle of 146°] give rise to supramolecular sheets that lie in the ab plane. Key geometric features for compound (I) involve a nearly planar, trans-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 phosphorus atom and the amide nitrogen 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 trans-amide group that approaches planarity with a C—N—C—C torsion angle of −176.50 (16)°. The hydrogen bonds in this structure are intermolecular, with a D...A distance of 2.883 (2) Å and a D—H...A angle of 175.0 (18)° between the amide hydrogen atom and the P=O oxygen atom. These non-covalent interactions create ribbons that run along the b-axis direction.