Syntheses, spectroscopic characterization and crystal structures of some new phosphoramidates and an organotin(IV) complex of N-(4-fluorobenzoyl)-N′,N″-bis(piperidinyl)phosphoric triamide

Some new phosphoramidates with formula 4-F-C6H4C(O)N(H)P(O)X2, X = NC4H8 (1), NC5H10 (2), 4-CH3-NC5H9 (3), NC4H8O (4), NC6H12 (5), N(CH2CH3)2 (6), N(CH2CH2CH3)2 (7) were synthesized. The reaction of compound 2 with dimethyltin(IV) dichloride leads to an octahedral organotin(IV) complex, SnCl2(CH3)2[4-F-C6H4C(O)N(H)P(O)(NC5H10)2]2 (8) with equal ligands in trans positions. These compounds were characterized by IR, 1H, 13C, 31P, 119Sn NMR, mass spectroscopy and elemental analysis. The structures have been determined for compounds 1, 2, 4, 5 and 8. Compound 2 exists as four symmetrically independent molecules in the crystalline lattice. Compounds 1, 4 and 5 form dimmers via intermolecular –PO⋯H–N– hydrogen bonds that in 1 is centrosymmetric. In compound 2, two dimmers were formed; each of them was produced between two adjacent independent molecules. In compounds 1, 2, 3, 4 and 8, containing five- and six-membered ring amine groups, 3J(P,Caliphatic) > 2J(P,Caliphatic). Compound 5 with seven-membered ring amine, similar to compounds 6 and 7 with acyclic aliphatic amines, shows that 2J(P,Caliphatic) > 3J(P,Caliphatic). Mass spectra of these compounds indicate the 4-F-C6H4CO+ and 4-F-C6H4CN+ fragments.

Graphical abstractSome new phosphoramidates were synthesized. The reaction of 4-F-C6H4C(O)N(H)P(O)(NC5H10)2 (2) with SnCl2(CH3)2 leads to an octahedral organotin(IV) complex (8) with equal ligands in trans positions. Compound 2 exists as four symmetrically independent molecules in the crystalline lattice. Compounds 1, 2, 4, 5 and 8 form intermolecular –PO⋯H–N– hydrogen bonds in the crystals.Figure optionsDownload full-size imageDownload as PowerPoint slide