A comparison of the molecular structures of Dicyclohexyl(N-phenylthiocarbamoyl)-phosphine and Diphenyl(N-phenylthiocarbamoy1)phosphine as determined by X-ray crystallography

Abstract

The crystal and molecular structures of the title compounds, (C₆H₁₁)₂PC(S)N(H)C₆H₅(1) and (C₆H₅)₂PC(S)N(H)C₆H₅(2) have been determined by single-crystal three-dimensional X-ray diffraction techniques. Crystals of (1) are monoclinic, space group P2₁/c, with eight molecules in the unit cell of dimensions a 20.541(4), b 17.784(2), c 10.2564(9) Å and β 94.54(1)º; (2) crystallizes in the triclinic space group P1 with two molecules in the unit cell which has the dimensions a 9.242(2), b 9.994(3), c 10.373(3) Å, α 68.56(2), β 71.21(2) and γ 86.00(2)º. Both structures were refined by a least-squares procedure, applying anisotropic thermal parameters to all non-hydrogen atoms, with the use of 3119 and 2971 statistically significant reflections for (1) and (2) respectively; final R 0.055 for (1) and R 0.061 (R_w 0.062) for (2). The N, C(l), S moieties of both (1) and (2) display features consistent with the delocalization of π-electrons. There are notable differences in some of the bond angles between (I) and (2) which have been attributed to conformational effects arising from variations in steric pressures; this may account for the observed differences in reactivity between the two compounds.