Bis(diphenyl­phospho­rothio­yl) tris­ulfide

Monika Kulcsar; Anca Silvestru; Marius Vonas

doi:10.1107/S1600536808024070

. 2008 Aug 6;64(Pt 9):o1683–o1684. doi: 10.1107/S1600536808024070

Bis(diphenylphosphorothioyl) trisulfide

Monika Kulcsar ^a, Anca Silvestru ^a,^*, Marius Vonas ^a

PMCID: PMC2960680 PMID: 21201673

Abstract

In the title compound, C₂₄H₂₀P₂S₅, the P atoms are arranged trans with respect to the S₃ group and the S=P—S—S systems have cisoid geometry, with an average S—P—S—S torsion angle of −56.7°. The dihedral angles between the two phenyl rings attached to the P atoms are 87.33 (12) and 75.67 (10)°. In the crystal structure, the molecules are linked into chains running parallel to the a axis by weak intermolecular C—H⋯S hydrogen bonds. Centrosymmetrically related chains are further connected by π–π stacking interactions, with a centroid-to-centroid distance of 3.795 (5) Å.

Related literature

For related literature. see: Deleanu et al. (2002 ▶); Drake et al. (2001a ▶,b ▶); Gallacher & Pinkerton (1992a ▶,b ▶, 1993 ▶); Kulcsar et al. (2005 ▶); Newton et al. (1993 ▶); Silvestru et al. (1994a ▶,b ▶); Buranda et al. (1991 ▶); Fest & Schmidt (1982 ▶); Knopik et al. (1993 ▶); Lawton (1970 ▶); McCleverty et al. (1983 ▶); Molyneux (1967 ▶); Perlikowska et al. (2004 ▶); Potrzebowski et al. (1991 ▶, 1994 ▶); Tiekink (2001 ▶); Tkachev et al. (1976 ▶); Zhang et al. (2004 ▶); Emsley (1994 ▶); Yadav et al. (1989 ▶).

Experimental

Crystal data

C₂₄H₂₀P₂S₅
M _r = 530.64
Triclinic,
a = 9.2287 (8) Å
b = 11.5476 (10) Å
c = 12.9728 (12) Å
α = 92.690 (2)°
β = 105.287 (2)°
γ = 106.124 (2)°
V = 1270.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 297 (2) K
0.35 × 0.27 × 0.21 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.819, T _max = 0.885
13712 measured reflections
5178 independent reflections
4536 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.106
S = 1.13
5178 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808024070/rz2237sup1.cif

e-64-o1683-sup1.cif^{(21.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808024070/rz2237Isup2.hkl

e-64-o1683-Isup2.hkl^{(253.5KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯S5ⁱ	0.93	2.94	3.737 (3)	145

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Romanian Ministry of Education and Research (CNCSIS grant No. 12/1456/2007). We thank the National Center for X-ray Diffraction (Babes-Bolyai University, Cluj-Napoca) for support in the solid-state structure determination.

supplementary crystallographic information

Comment

Our interest was focused for long time on studies concerning reactions between bis(diorganothiophosphoryl)disulfides and diorganodichalcogenides of type R₂E₂ (E = Se, Te) in order to obtain new organochalcogen compounds with diorganodithiophosphorus ligands (Newton et al., 1993; Silvestru et al., 1994a,b; Drake et al., 2001a,b; Kulcsar et al., 2005; Deleanu et al., 2002). Bis(diorganothiophosphoryl)disulfides attracted much interest also due to their potential applications as pesticides (Fest & Schmidt, 1982), additives in motor oils (Molyneux, 1967) and in the rubber vulcanization (McCleverty et al., 1983). Both alkyl and aryl substituted derivatives of type [R₂P(S)S]₂ were already structurally characterized, e.g. R = OPr-i (Lawton, 1970; Tkachev et al., 1976; Tiekink, 2001; Zhang et al., 2004), R = OMe, OBu-t (Potrzebowski et al., 1991), cyclohexyl (Buranda et al., 1991), Me, Pr-i (Gallacher & Pinkerton, 1992b), Ph (Gallacher & Pinkerton, 1993), OPh (Gallacher & Pinkerton, 1993; Knopik et al., 1993), menthoxy (Perlikowska et al., 2004), R₂ = OCMe₂—CMe₂O (Yadav et al., 1989), OCMe₂—CH₂O (Potrzebowski et al., 1994). A search of the Cambridge Structure Database revealed that only for one trisulfide, [Et₂P(S)S]₂S, the X-ray crystal structure was determined (Gallacher & Pinkerton, 1992a). Here we report about the phenyl substituted analog, [Ph₂P(S)S]₂S.

The chalcogen atoms S2 and S3 are doubly bonded to phosphorus [S2═P1 = 1.9351 (9); S3═P2 = 1.9303 (9) Å], while the P1—S1 [2.1171 (9) Å] and P2—S4 [2.1282 (9) Å] distances correspond to single P—S bonds (cf. [Ph₂P(S)S]₂: P═S = 1.930 (1), P—S = 2.139 (1) Å; Gallacher & Pinkerton, 1993). The sulfur–sulfur distances within the S₃ group are not significantly different [S5—S4 = 2.0407 (10), S5—S1 = 2.0440 (10) Å], corresponding to a S—S single bond. These values are similar to those found in bis(diorganothiophosphoryl)disulfides or in [Et₂P(S)S]₂S. The SPS₃PS skeleton of the title compound adopts a twisted zigzag chain structure (Fig. 1), with the torsion angles S2—P1—S1—S5 = -56.30 (5)°, P1—S1—S5—S4 = 96.84 (4)°, S1—S5—S4—P2 = 87.42 (5)° and S5—S4—P2—S3 = -57.13 (5)°. Although apparently the conformation of the SPS₃PS skeleton is similar to that of the previously reported ethyl derivative, some differences should be noted. In the title compound the phosphorus atoms are trans with respect of the central S₃ group [P1—S1···S5—P2 = 171.4°], as are in the related [Et₂P(S)S]₂S compound (the torsion angle between corresponding atoms is 159.8°). In both cases the central S atom and the terminal S atoms, respectively, are placed on opposite sides of the best plane described by the remaining atoms of the skeleton. However, the S═P···P═S torsion angle is 138.8°, but only -89.4° in the ethyl derivative. Moreover, the S═P—S—S system has a cisoid geometry [S2—P1—S1—S5 = -56.30 (5)°, S5—S4—P2—S3 = -57.13 (5)°], while it has a transoid geometry in [Et₂P(S)S]₂S (average S═P—S—S torsion angle 179.6°; Gallacher & Pinkerton, 1992a). The S—P—S angles [S2—P1—S1 = 113.77 (4)° and S3—P2—S4 = 114.34 (4)°] are consistent with a cisoid geometry, similar with that found for [Ph₂P(S)S]₂ [114.44 (4)°; Gallacher & Pinkerton, 1993], but much larger than in the transoid derivatives [(PhO)₂P(S)S]₂ [108.39 (7)°; Gallacher & Pinkerton, 1993] and [Et₂P(S)S]₂S [av. 103.7°; Gallacher & Pinkerton, 1992a]. The dihedral angles formed by the plane of the phenyl rings attached to the P1 and P2 atoms are 87.33 (12) 75.67 (10)° respectively. The crystal structure is stabilized by weak intermolecular hydrogen bonding interactions (Emsley, 1994) between the central sulfur atom and an aromatic proton of a neighbouring molecule (Table 1) forming chains parellel to the a axis (Fig. 2). Weak intermolecular S···H contacts were observed in [(PhO)₂P(S)S]₂ [2.954 (1) Å], but they are absent in [Et₂P(S)S]₂S or [Ph₂P(S)S]₂. Centrosymmetrically related chains are further connected by π–π stacking interactions involving the C13–C18 phenyl rings, with centroid-to-centroid distance of 3.795 (5) Å.

Experimental

The title compound was isolated as a by-product during recrystallization of PhSeS₂PPh₂ obtained in the reaction between [Ph₂P(S)S]₂ and Ph₂Se₂.