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

Abstract

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.

Two Beta-Phosphorylamide Compounds as Ligands for Sm3+, Eu3+, and Tb3+: X-ray Crystallography and Luminescence Properties

“…Single crystals of both ligands 1 [ 25 ] and 2 have been isolated and analyzed by X-ray diffraction ( Figure 2 ). For the structure of compound 2 , the electron density corresponding to one of the phenyl rings was disordered and modeled as two orientations of the ring.…”

“…Ligand 1. This synthetic procedure represents an alternative to what was previously published by our group [ 25 ]. Ethylene diamine (1.0 mL, 0.015 mol) was dissolved in 8.3 mL methanol in a 25 mL round bottom flask.…”

“…IR: ν (cm −1 ): 3268 (N-H), 1666 (C=O), 1203 (P=O), 1016 (C-O), 963 (C-O); UV-VIS (1.0 mM, CH 3 CN): λ max 207 nm; 1 H NMR (300 MHz, CDCl 3 ): δ 7.73 (broad, 2H, -N H ), 4.14 (q, J = 7.0 Hz, 8H), 3.34 (d, J = 5.9 Hz, 4H), 2.85 (d, J P-H = 15.8 Hz, 4H), 1.33 (t, J = 7.0 Hz, 12H); 13 C NMR (75 MHz, CDCl 3 ): δ 165.4, 62.9, 35.8 (d, J P-C = 128 Hz), 16.5; 31 P NMR (121 MHz, CDCl 3 ): δ 24.5; HR-MS (ESI): expected for C 14 H 30 N 2 O 8 P 2 Na + : 439.1370; found: 439.1367. The X-ray crystal structure of this compound has been reported [ 25 ].…”

“… X-ray crystal structures of organic ligands 1 [ 25 ] and 2 . Thermal ellipsoids are depicted at the 50% probability level using standard CPK colors, and all hydrogen atoms bonded to carbon atoms have been omitted for clarity.…”