Tetra-kis(benzyl-amino)-phospho-nium chloride.

The title salt, [P(NHCH(2)C(6)H(5))(4)](+)·Cl(-), crystallizes with the P atom and Cl(-) anion lying on a twofold rotation axis. The P atom has a slightly distorted tetra-hedral geometry with two classes of N-P-N angles [101.15 (10) and 100.55 (11)° and 113.07 (9) and 114.83 (8)°] and the environments of sp(2)-hybridized N atoms are essentially planar (sum of angles = 359.9 and 360.1°). In the crystal, the phospho-nium ion inter-acts with each neighboring chloride ion via two approximately equal N-H⋯Cl inter-actions, forming parallel chains along the c axis.

Syntheses, spectroscopic study and X-ray crystallography of some new phosphoramidates and lanthanide(III) complexes of N-(4-nitrobenzoyl)-N',N''-bis(morpholino)phosphoric triamide.

New phosphoramidates with the formula RC(O)N(H)P(O)X(2), R = 2-NO(2)-C(6)H(4), 3-NO(2)-C(6)H(4) and 4-NO(2)-C(6)H(4), X = N(CH(2)CH(3)) (1)-(3), NC(4)H(8) (4)-(6), and NC(4)H(8)O (7)-(9) were synthesized and characterized by (1)H, (13)C, (31)P NMR and IR spectroscopy, and elemental analysis. The reaction of (9) with hydrated lanthanide(III) nitrate leads to ten- or nine-coordinated complexes, (10)-(13). The crystal structure has been determined for (3), (5), (9), (10) and (13). In contrast to all of the previously reported similar phosphoramidate compounds, the -C(O)-N(H)-P(O) skeleton in the free ligand (9) shows a cisoid conformation, with the C=O and P=O double bonds adopting a nearly syn conformation. Quantum chemical calculations were applied for clarifying this exceptional conformational behavior. The monodentate neutral ligand (9) is coordinated to the metal ions via the phosphoryl O atom, adopting the usual anti conformation between the C=O and P=O groups.

Synthesis, crystal structure and spectroscopic properties of a novel carbacylamidophosphate: N-(3-nitrobenzoyl)-N',N''-bis(tert-butyl)phosphoric triamide.

The new compound N-(3-nitrobenzoyl)-N',N''-bis(tert-butyl)phosphoric triamide was synthesized by reacting 3-nitrobenzoyl phosphoramidic dichloride and tert-butyl amine, and characterized by multinuclear ((1)H, (13)C and (31)P) NMR and FTIR spectroscopy techniques. Structural and conformational properties were analyzed using single-crystal X-ray diffraction, vibrational spectra and theoretical calculations. The crystal structure contains three symmetry-independent disordered molecules, connected via intermolecular N-H...O=P and N-H...O=C hydrogen bonds to form a centrosymmetric hexameric chain extended along the [2,1,1] direction. The disorder is mainly caused by rotation of the tert-butyl groups around the C-N bonds.