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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