4-Iso­propyl-5,5-di­methyl-2-sulfanyl-1,3,2-dioxaphosphinane 2-sulfide

The title compound, C₈H₁₇O₂PS₂, displays a distorted tetra­hedral geometry around the P atom. The P atom is part of a six-membered ring with an isopropyl group in the equatorial position. The mol­ecules are linked by S—H⋯S hydrogen bonds in the crystal packing.

Related literature

For dithio­phospho­ric acid ligands that form metal complexes, see: Srivastava et al. (2010). For applications as lubricating oil additives and load-carrying capacitors, see: Jiang et al. (1996); Haire et al. (2008); Plaza et al. (2001). For a related structure, see: Li et al. (2007).

Experimental

Crystal data

• C₈H₁₇O₂PS₂

• M_r = 240.31

• Monoclinic, P 2₁ /c

• a = 8.2831 (2) Å

• b = 13.1532 (4) Å

• c = 11.5255 (3) Å

• β = 104.128 (3)°

• V = 1217.72 (6) ų

• Z = 4

• Mo Kα radiation

• μ = 0.54 mm⁻¹

• T = 123 K

• 0.65 × 0.2 × 0.1 mm

Data collection

• Agilent Xcalibur Ruby Gemini diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) T_min = 0.872, T_max = 1.000

• 10444 measured reflections

• 4979 independent reflections

• 3999 reflections with I > 2σ(I)

• R_int = 0.024

Refinement

• R[F² > 2σ(F²)] = 0.038

• wR(F²) = 0.094

• S = 1.09

• 4979 reflections

• 123 parameters

• H-atom parameters constrained

• Δρ_max = 0.45 e Å⁻³

• Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
S1—H1S⋯S2^i	1.20	2.76	3.9456 (5)	170
Symmetry code: (i) .

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

S1. Comment

Organo-phosphorus compounds with sulfur donors have recently drawn more attention due to their adjustable coordination ability and interesting applications as high viscosity lubricant additives(Jiang et al., 1996; Haire et al., 2008) and load carrying capacity (Plaza et al., 2001). As part of our investigation on the organotin dithio complexes (Srivastava et al., 2010), we herein report the synthesis and structure of I.

The crystal structure of I is illustrated in Fig.1. The conformation of the molecule with respect to P is distorted tetrahedral as reflected by torsion angles O2—P—O1—C1, S2—P—O2—C5 and S1—P—O1—C1 of 41.57 (10), -165.77 (7) and -74.71 (9)° respectively. The phosphorus atom is coordinated by both sulfur and oxygen atoms with the formation of a six-membered ring. The isopropyl group is in equatorial position as indicated by bond angles C5—C6—C8 [108.83 (11)°], C5—C6—C7 [115.18 (11)°] and C7—C6—C8 [110.12 (12)°]. The P—S1, P—S2 and mean P—O distances are 2.0723 (5), 1.9216 (4) and 1.5794 (9) Å, respectively, which are comparable to reported values (Li et al., 2007). The molecules are stabilized by S—H···S intermolecular hydrogen bonds in the crystal packing (Table 1; Fig.2).

Related literature

For dithiophosphoric acid ligands that form metal complexes, see: Srivastava et al. (2010). For applications as lubricating oil additives and load-carrying capacitors, see: Jiang et al. (1996); Haire et al. (2008); Plaza et al. (2001). For a related structure, see: Li et al. (2007).

S2. Experimental

4-Isopropyl-2-mercapto-5,5-dimethyl-1,3,2-dioxaphosphinane 2-sulfide was prepared by the reaction of P₄S₁₀ (4.44 g, 0.01 mol) with O.O'-2,2,4-trimethyl-1,3- pentanediol(0.02 g, 0.02 mol) with stirring. The reaction was carried out in moisture free anhydrous condition and in presence of dry nitrogen. The P₄S₁₀ was slowly dissolved in glycol solution (in dry benzene) with evolution of H₂S.The reaction mixture was warmed gently on water bath (60 - 80 °C) in order to complete the reaction. After cooling, an yellow viscous liquid was obtained which crystallizes in deep freezer overnight. White crystal suitable for X-ray analysis was obtained in 60% yield. (M.P.: 336 K). Anal. Calc. for C₈H₁₇O₂PS₂ (%): C,39.98; H, 7.13. Found: C 39.84; H, 7.05.

S3. Refinement

All H atoms were located by a Fourier map. Nevertheless, they were placed in their calculated positions and then refined using the riding model with atom—H lengths of 1.00 Å (CH),0.99 Å (CH₂) or 0.98 Å (CH₃). Isotropic displacement parameters for these atoms were set to 1.2 (CH or CH₂) or 1.5 (CH₃) times U_eq of the parent atom. The torsions angles O-P-S-H of the S-H group and C-C-C-H for the methyl groups were refined.

Computing details

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. Molecular structure of the title compound showing the atom labeling scheme and 30% probability displacement ellipsoids.
	Fig. 2. Crystal packing for (I) viewed along b axis. Dashed lines indicate an intermolecular S—H···S hydrogen bonds.

4-Isopropyl-5,5-dimethyl-2-sulfanyl-1,3,2-dioxaphosphinane 2-sulfide

Crystal data

C8H17O2PS2	F(000) = 512
Mr = 240.31	Dx = 1.311 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3599 reflections
a = 8.2831 (2) Å	θ = 3.1–35.0°
b = 13.1532 (4) Å	µ = 0.54 mm^−1
c = 11.5255 (3) Å	T = 123 K
β = 104.128 (3)°	Long plate, colorless
V = 1217.72 (6) Å^3	0.65 × 0.2 × 0.1 mm
Z = 4

Data collection

Agilent Xcalibur Ruby Gemini diffractometer	4979 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3999 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 10.5081 pixels mm^-1	θmax = 35.0°, θmin = 3.1°
ω scans	h = −13→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −17→21
Tmin = 0.872, Tmax = 1.000	l = −18→17
10444 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0372P)^2 + 0.2639P] where P = (Fo^2 + 2Fc^2)/3
4979 reflections	(Δ/σ)max = 0.001
123 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.38 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
P	0.80019 (4)	0.22223 (2)	0.26248 (3)	0.01693 (7)
S1	0.89229 (5)	0.16081 (3)	0.43126 (3)	0.02970 (9)
H1S	0.8790	0.2219	0.5057	0.036*
S2	0.81069 (4)	0.12077 (3)	0.14460 (3)	0.02277 (8)
O1	0.90574 (11)	0.31992 (7)	0.24915 (9)	0.02352 (19)
O2	0.61912 (10)	0.26399 (7)	0.25326 (8)	0.01907 (17)
C1	0.87839 (16)	0.41289 (10)	0.31086 (13)	0.0249 (3)
H1A	0.9469	0.4682	0.2895	0.030*
H1B	0.9153	0.4019	0.3983	0.030*
C2	0.69484 (16)	0.44550 (10)	0.27866 (12)	0.0207 (2)
C3	0.6409 (2)	0.47148 (12)	0.14512 (13)	0.0303 (3)
H3A	0.7253	0.5148	0.1235	0.046*
H3B	0.5342	0.5076	0.1284	0.046*
H3C	0.6287	0.4087	0.0980	0.046*
C4	0.68450 (19)	0.54015 (11)	0.35475 (13)	0.0288 (3)
H4A	0.7635	0.5915	0.3409	0.043*
H4B	0.7121	0.5214	0.4396	0.043*
H4C	0.5713	0.5679	0.3322	0.043*
C5	0.59607 (15)	0.35802 (9)	0.31797 (11)	0.0182 (2)
H5A	0.6488	0.3453	0.4045	0.022*
C6	0.40844 (16)	0.36803 (11)	0.30692 (12)	0.0231 (3)
H6A	0.3888	0.4362	0.3394	0.028*
C7	0.29883 (18)	0.36110 (15)	0.17915 (14)	0.0349 (3)
H7A	0.1813	0.3621	0.1814	0.052*
H7B	0.3230	0.2977	0.1421	0.052*
H7C	0.3220	0.4191	0.1323	0.052*
C8	0.35565 (18)	0.28763 (13)	0.38615 (14)	0.0317 (3)
H8A	0.2379	0.2970	0.3849	0.048*
H8B	0.4232	0.2946	0.4684	0.048*
H8C	0.3720	0.2197	0.3559	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P	0.01539 (13)	0.01640 (14)	0.01950 (14)	0.00176 (11)	0.00521 (11)	0.00062 (11)
S1	0.03645 (18)	0.03029 (19)	0.02098 (15)	0.00996 (15)	0.00431 (14)	0.00425 (13)
S2	0.02690 (15)	0.02011 (15)	0.02217 (15)	0.00522 (12)	0.00769 (12)	−0.00132 (12)
O1	0.0191 (4)	0.0197 (4)	0.0342 (5)	−0.0022 (3)	0.0112 (4)	−0.0017 (4)
O2	0.0157 (3)	0.0167 (4)	0.0256 (4)	0.0003 (3)	0.0065 (3)	−0.0032 (3)
C1	0.0226 (5)	0.0190 (6)	0.0339 (7)	−0.0054 (5)	0.0084 (5)	−0.0030 (5)
C2	0.0238 (5)	0.0150 (5)	0.0236 (5)	−0.0003 (4)	0.0065 (5)	−0.0002 (5)
C3	0.0390 (8)	0.0260 (7)	0.0273 (6)	0.0021 (6)	0.0106 (6)	0.0053 (6)
C4	0.0352 (7)	0.0171 (6)	0.0344 (7)	−0.0012 (5)	0.0092 (6)	−0.0038 (5)
C5	0.0186 (5)	0.0160 (5)	0.0204 (5)	0.0010 (4)	0.0055 (4)	−0.0015 (4)
C6	0.0186 (5)	0.0234 (6)	0.0282 (6)	0.0027 (5)	0.0074 (5)	−0.0043 (5)
C7	0.0197 (6)	0.0500 (10)	0.0332 (7)	0.0035 (6)	0.0027 (5)	0.0027 (7)
C8	0.0263 (6)	0.0393 (8)	0.0332 (7)	−0.0052 (6)	0.0141 (6)	−0.0030 (6)

Geometric parameters (Å, º)

P—O2	1.5762 (9)	C3—H3C	0.9800
P—O1	1.5826 (10)	C4—H4A	0.9800
P—S2	1.9216 (5)	C4—H4B	0.9800
P—S1	2.0723 (5)	C4—H4C	0.9800
S1—H1S	1.2000	C5—C6	1.5337 (17)
O1—C1	1.4599 (17)	C5—H5A	1.0000
O2—C5	1.4804 (15)	C6—C8	1.529 (2)
C1—C2	1.5355 (18)	C6—C7	1.533 (2)
C1—H1A	0.9900	C6—H6A	1.0000
C1—H1B	0.9900	C7—H7A	0.9800
C2—C3	1.5328 (19)	C7—H7B	0.9800
C2—C4	1.5372 (18)	C7—H7C	0.9800
C2—C5	1.5426 (18)	C8—H8A	0.9800
C3—H3A	0.9800	C8—H8B	0.9800
C3—H3B	0.9800	C8—H8C	0.9800
O2—P—O1	104.46 (5)	H4A—C4—H4B	109.5
O2—P—S2	113.64 (4)	C2—C4—H4C	109.5
O1—P—S2	111.95 (4)	H4A—C4—H4C	109.5
O2—P—S1	108.99 (4)	H4B—C4—H4C	109.5
O1—P—S1	108.79 (4)	O2—C5—C6	106.41 (10)
S2—P—S1	108.85 (2)	O2—C5—C2	109.41 (10)
P—S1—H1S	109.5	C6—C5—C2	120.72 (11)
C1—O1—P	118.53 (8)	O2—C5—H5A	106.5
C5—O2—P	119.65 (7)	C6—C5—H5A	106.5
O1—C1—C2	112.24 (10)	C2—C5—H5A	106.5
O1—C1—H1A	109.2	C8—C6—C7	110.12 (12)
C2—C1—H1A	109.2	C8—C6—C5	108.83 (11)
O1—C1—H1B	109.2	C7—C6—C5	115.18 (11)
C2—C1—H1B	109.2	C8—C6—H6A	107.5
H1A—C1—H1B	107.9	C7—C6—H6A	107.5
C3—C2—C1	109.50 (11)	C5—C6—H6A	107.5
C3—C2—C4	110.43 (11)	C6—C7—H7A	109.5
C1—C2—C4	106.15 (11)	C6—C7—H7B	109.5
C3—C2—C5	114.56 (11)	H7A—C7—H7B	109.5
C1—C2—C5	106.59 (10)	C6—C7—H7C	109.5
C4—C2—C5	109.22 (11)	H7A—C7—H7C	109.5
C2—C3—H3A	109.5	H7B—C7—H7C	109.5
C2—C3—H3B	109.5	C6—C8—H8A	109.5
H3A—C3—H3B	109.5	C6—C8—H8B	109.5
C2—C3—H3C	109.5	H8A—C8—H8B	109.5
H3A—C3—H3C	109.5	C6—C8—H8C	109.5
H3B—C3—H3C	109.5	H8A—C8—H8C	109.5
C2—C4—H4A	109.5	H8B—C8—H8C	109.5
C2—C4—H4B	109.5
O2—P—O1—C1	41.56 (10)	P—O2—C5—C2	56.81 (12)
S2—P—O1—C1	164.95 (8)	C3—C2—C5—O2	61.00 (14)
S1—P—O1—C1	−74.71 (9)	C1—C2—C5—O2	−60.27 (13)
O1—P—O2—C5	−43.49 (10)	C4—C2—C5—O2	−174.55 (10)
S2—P—O2—C5	−165.77 (7)	C3—C2—C5—C6	−62.90 (16)
S1—P—O2—C5	72.65 (9)	C1—C2—C5—C6	175.83 (11)
P—O1—C1—C2	−54.83 (14)	C4—C2—C5—C6	61.55 (15)
O1—C1—C2—C3	−63.68 (14)	O2—C5—C6—C8	72.23 (13)
O1—C1—C2—C4	177.11 (11)	C2—C5—C6—C8	−162.46 (12)
O1—C1—C2—C5	60.77 (14)	O2—C5—C6—C7	−51.96 (15)
P—O2—C5—C6	−171.25 (8)	C2—C5—C6—C7	73.35 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
S1—H1S···S2^i	1.20	2.76	3.9456 (5)	170

Symmetry code: (i) x, −y+1/2, z+1/2.