Crystal and molecular structures of P,P-diphenyl-N-methyl-phosphinylthioformamide and P,P-diphenyl-N-phenyl-selenophosphinylthioformamide

George Siasios and Edward R. T. Tiekink


The crystal structures of the title compounds P,P-diphenyl-N-methyl-phosphinylthioformamide, [Ph2P(O)C(S)N(H)Me], and P,P-diphenyl-N-phenyl-selenophosphinylthioformamide, [Ph2P(Se)C(S)N(H)Ph], have been determined at room temperature. The pale-yellow crystals of [Ph2P(O)C(S)N(H)Me] are monoclinic, space group P21/c with unit cell dimensions a = 9.663(1), b = 14.073(2), c = 10.775(1) Å, β = 105.78(1)°, Z = 4 and Dx = 1.297 Mg m−3. The green crystals of [Ph2P(Se)C(S)N(H)Ph] are orthorhombic, crystallizing in the Pbca space group with dimensions a = 11.978(1), b = 8.772(5), c = 34.241(4) Å, Z = 8 and Dx = 1.477 Mg m−3. The structures were solved by direct-methods and Patterson methods, respectively and each refined by a full-matrix least-squares procedure to final R = 0.041 using 1474 reflections for [Ph2P(O)C(S)N(H)Me] and R = 0.046 using 1371 reflections for [Ph2P(Se)C(S)N(H)Ph]. The conformation about the C–N bond in [Ph2P(O)C(S)N(H)Me] is Z with important parameters: P = O 1.485(2), P–C 1.843(3), C = S 1.653(3) and C–N 1.313(4) Å. Centrosymmetric molecules associate in the lattice via hydrogen bonding contacts. A similar Z conformation is found in [Ph2P(Se)C(S)N(H)Ph] with important parameters: P = Se 2.108(2), P–C 1.871(7), C = S 1.634(8) and C–N 1.317(9) Å. The analysis of the geometric parameters defining the central chromophore indicate that the P–C bonds are comparatively weak in these phosphorus(V) compounds.

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Zeitschrift für Kristallographie – Crystalline Materials offers a place for researchers to present results of their crystallographic studies. The journal includes theoretical as well as experimental research. It publishes Original Papers, Letters and Review Articles in manifold areas of crystallography.