The crystal structure of bis(cyclotetramethylene) diphosphine disulphide

Abstract

The crystal structure of bis(cyclotetramethylene)diphosphine disulphide,S has been determined from three-dimensional X-ray diffraction data. The unit cell is triclinic with space group PI (number 2), dimensions a = 7.65, b = 6.90, c = 5.88/~; e = 75 ° 30', p= 104 ° 15', ~, = 92 ° 36', and contains one molecule. The structure was refined by Fourier and full-matrix least-squares methods on 771 independent observed reflexions to R= 10"4%. The molecule possesses a centre of symmetry at the mid-point between the two phosphorus atoms and the two sulphur atoms are trans to each other. The environment of each phosphorus atom is that of a distorted tetrahedron; the inclusion of phosphorus in a ring system reduces the angle C-P-C from tetrahedral to 96"6 °. The ring system is saturated and consequently puckered.

Tetra-n-propyl-1,2-dithioxodi-λ5-phosphane

“…* Bond lengths, bond angles and selected torsion angles for the non-H atoms are given in Table 2. The distortion of the tetrahedral configuration around the P atom, and the p__pi, P--S, P--C bond lengths and bond angles are in good agreement with the structure of tetraethyldiphosphine disulfide (Dutta & Woolfson, 1961), bis(cyclotetramethylene)diphosphine disulfide (Lee & Goodacre, 1969) and bis-(cyclopentamethylene)diphosphine disulfide (Lee & Goodacre, 1970). 1 (McQuillan & Oxton, 1978).…”

Structures of tris(2-cyanoethyl)phosphine sulphide. P(CH2CH2CN)3S, and tris(2-cyanoethyl)phosphine selenide, P(CH2CH2CN)3Se

“…The P-S and P-Se bond lengths are comparable with those in other phosphine sulphides and selenides, insofar as such information (especially for the latter compounds) is available [see e.g. Cameron & Dahl6n (1975) ;Dreissig, Plieth & Z~iske (1972); Lee & Goodacre (1969; Wilkins, Hagen, Hedberg, Quang Shen & Hedberg (1975)]. The values obtained (P-S, 1.96; P-Se, 2.11 A) are very close to the calculated P=X double-bond distances (1.94 and 2.07/k respectively).…”

The crystal and molecular structure of 2,5-dithio-1-chloro-1-thiophosphorus(V)–cyclopentane

“…This is only about one standard deviation from the observed value. The P--S distances in a number of other compounds are appreciably longer than this [1.98 A in dimethyldiphenyldiphosphine disulphide (Wheatley, 1960), 1.94 A in tetraethyldiphosphine disulphide (Dutta & Woolfson, 1961), 1.95 A in bis(cyclotetramethylene)diphosphine disulphide (Lee & Goodacre, 1969), 1.95 A in bis(cyclopentamethylene)diphosphine disulphide (Lee & Goodacre, 1970b) and 1.95 and 1.97 A in tetramethyldiphosphine disulphide (Lee & Goodacre, 1971)]. It seems likely that the shortened P-S and P--S bonds arise because the high electronegativity of chlorine localizes the orbitals on the phosphorus atom and allows more effective overlap.…”