The compound N,N',N"-tricyclohexylphosphorothioic triamide, C18H36N3PS or P(S)[NHC6H11]3, (I), crystallizes in the space group Pnma with the molecule lying across a mirror plane; one N atom lies on the mirror plane, whereas the bond-angle sum at the other N atom has a deviation of some 8° from the ideal value of 360° for a planar configuration. The orientation of the atoms attached to this nonplanar N atom corresponds to an anti orientation of the corresponding lone electron pair (LEP) with respect to the P═S group. The P═S bond length of 1.9785 (6) Å is within the expected range for compounds with a P(S)[N]3 skeleton; however, it is in the region of the longest bond lengths found for analogous structures. This may be due to the involvement of the P═S group in N—H…S═P hydrogen bonds. In O,O'-diethyl(2-phenylhydrazin-1-yl)thiophosphonate, C10H17N2O2PS or P(S)[OC2H5]2[NHNHC6H5], (II), the bond-angle sum at the N atom attached to the phenyl ring is 345.1°, whereas, for the N atom bonded to the P atom, a practically planar environment is observed, with a bond-angle sum of 359.1°. A Cambridge Structural Database [CSD; Allen (2002). Acta Cryst. B58, 380–388] analysis shows a shift of the maximum population of P═S bond lengths in compounds with a P(S)[O]2[N] skeleton to the shorter bond lengths relative to compounds with a P(S)[N]3 skeleton. The influence of this difference on the collective tendencies of N…S distances in N—H…S hydrogen bonds for structures with P(S)[N]3 and P(S)[O]2[N] segments were studied through a CSD analysis.

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