Triiso­propyl­phosphine sulfide

The title compound, C₉H₂₁PS, was sublimed to give crystals suitable for single-crystal X-ray diffraction studies and shows a single ³¹P {¹H} NMR signal in C₆D₆ and CD₃CN of 72.25 and 78.93 p.p.m., respectively, versus H₃PO₄.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.069
• wR factor = 0.218
• Data-to-parameter ratio = 20.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



SHFSU_01  Alert C The absolute value of parameter shift to su ratio > 0.05
          Absolute value of the parameter shift to su ratio given   0.052
          Additional refinement cycles may be required.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

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S1. Comment

The use of phosphines for the abstraction of sulfur from metal complexes has been used for years to promote favorable reaction chemistry (Liu et al., 1998). In our research, it was necessary to synthesize and characterize triisopropylphosphine sulfide to confirm its production in the reaction via ³¹P {¹H} NMR techniques (Osterloh et al., 2000). As part of this characterization, the X-ray crystal structure was carried out. Related phosphine sulfides which have been characterized by X-ray diffraction include triphenylphosphine sulfide (Codding & Kerr, 1978; Foces-Foces & Llamas-Saiz, 1998) and tricyclohexylphosphine sulfide (Kerr et al., 1977; Reibenspies et al., 1996).

S2. Experimental

Solid sulfur (0.05 g, 1.6 mmol) was slurried in 10 ml of tetrahydrofuran (THF) to which was added dropwise (36 µl, 1.6 mmol) triisopropylphosphine in 1 ml of THF. The sulfur dissolved rapidly yielding a pale yellow solution, which was filtered over celite. The nearly colorless solution was reduced in volume forming an oil. Sublimation at 273 K yielded 0.19 g (63%) of colorless block-shaped crystals. The compound was further characterized by ³¹P {¹H} NMR; (C₆D₆) d 72.25 (s), (CD₃CN) d 78.93 p.p.m (s).

Computing details

Data collection: ASTRO (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: CIFTAB in SHELXL97.

Figures

Fig. 1. Displacement ellipsoid plot (50% probability) of the title compound. H atoms have been drawn as spheres with arbitrary radii.

Triisopropylphosphine sulfide

Crystal data

C9H21PS	Dx = 1.069 Mg m^−3
Mr = 192.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Ibam	Cell parameters from 89 reflections
a = 13.573 (1) Å	θ = 2.5–18.8°
b = 13.8717 (9) Å	µ = 0.36 mm^−1
c = 12.688 (1) Å	T = 293 K
V = 2388.9 (3) Å^3	Block, colorless
Z = 8	0.15 × 0.10 × 0.10 mm
F(000) = 848

Data collection

Bruker CCD diffractometer	525 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.097
Graphite monochromator	θmax = 25.0°, θmin = 2.1°
0.3° ω scans	h = −16→14
6072 measured reflections	k = −16→15
1108 independent reflections	l = −15→9

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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.218	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0861P)^2 + 1.4788P] where P = (Fo^2 + 2Fc^2)/3
1108 reflections	(Δ/σ)max = 0.052
55 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

Experimental. Data was collected using a Bruker SMART CCD (charge coupled device) based diffractometer equipped with an LT-2 low-temperature apparatus operating at 213 K. A suitable crystal was chosen and mounted on a glass fiber using grease. Data were measured using omega scans of 0.3° per frame for 30 s, such that a hemisphere was collected. A total of 1271 frames were collected with a final resolution of 0.80 Å. The first 50 frames were recollected at the end of data collection to monitor for decay. Cell parameters were retrieved using SMART software and refined using SAINT on all observed reflections. Data reduction was performed using the SAINT software which corrects for Lp and decay. The structures are solved by the direct method using the SHELX90 program and refined by least squares method on F2 SHELXL97, incorporated in SHELXTL-PC V 5.10.

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
P1	0.18403 (12)	0.23903 (13)	0.0000	0.0658 (8)
S1	0.29883 (13)	0.32501 (15)	0.0000	0.1018 (11)
C4	0.0689 (5)	0.3047 (6)	0.0000	0.082 (3)
H4A	0.0158	0.2589	0.0000	0.098*
C1	0.1801 (4)	0.1698 (5)	0.1221 (7)	0.120 (3)
H1A	0.1754	0.2184	0.1780	0.144*
C5	0.0585 (4)	0.3666 (4)	0.1002 (7)	0.133 (3)
H5A	−0.0033	0.4001	0.0987	0.200*
H5B	0.1114	0.4125	0.1031	0.200*
H5C	0.0611	0.3257	0.1612	0.200*
C3	0.0872 (6)	0.1046 (6)	0.1374 (8)	0.215 (6)
H3A	0.0910	0.0726	0.2044	0.323*
H3B	0.0845	0.0575	0.0821	0.323*
H3C	0.0289	0.1439	0.1352	0.323*
C2	0.2698 (5)	0.1158 (5)	0.1464 (7)	0.143 (3)
H2A	0.2618	0.0830	0.2125	0.214*
H2B	0.3245	0.1595	0.1510	0.214*
H2C	0.2819	0.0695	0.0917	0.214*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0429 (10)	0.0582 (12)	0.0963 (17)	−0.0076 (8)	0.000	0.000
S1	0.0470 (11)	0.0755 (15)	0.183 (3)	−0.0175 (9)	0.000	0.000
C4	0.044 (4)	0.079 (5)	0.121 (8)	−0.017 (4)	0.000	0.000
C1	0.086 (5)	0.115 (5)	0.159 (7)	−0.012 (4)	−0.024 (5)	0.041 (5)
C5	0.084 (4)	0.131 (6)	0.185 (8)	−0.002 (4)	0.038 (5)	−0.061 (6)
C3	0.119 (6)	0.217 (9)	0.310 (15)	−0.056 (6)	−0.017 (7)	0.183 (10)
C2	0.143 (6)	0.105 (5)	0.181 (10)	0.018 (5)	−0.064 (6)	0.015 (6)

Geometric parameters (Å, º)

P1—C4	1.809 (8)	C4—C5	1.540 (7)
P1—C1^i	1.824 (8)	C4—C5^i	1.540 (7)
P1—C1	1.824 (8)	C1—C2	1.462 (8)
P1—S1	1.962 (2)	C1—C3	1.564 (8)
C4—P1—C1^i	103.9 (2)	C5—C4—C5^i	111.2 (7)
C4—P1—C1	103.9 (2)	C5—C4—P1	111.1 (4)
C1^i—P1—C1	116.3 (5)	C5^i—C4—P1	111.1 (4)
C4—P1—S1	112.3 (3)	C2—C1—C3	110.4 (6)
C1^i—P1—S1	110.1 (2)	C2—C1—P1	115.2 (6)
C1—P1—S1	110.1 (2)	C3—C1—P1	115.7 (6)
C1^i—P1—C4—C5	178.9 (5)	C4—P1—C1—C2	−174.9 (5)
C1—P1—C4—C5	56.8 (5)	C1^i—P1—C1—C2	71.7 (6)
S1—P1—C4—C5	−62.2 (4)	S1—P1—C1—C2	−54.4 (6)
C1^i—P1—C4—C5^i	−56.8 (5)	C4—P1—C1—C3	54.3 (7)
C1—P1—C4—C5^i	−178.9 (5)	C1^i—P1—C1—C3	−59.2 (8)
S1—P1—C4—C5^i	62.2 (4)	S1—P1—C1—C3	174.8 (5)

Symmetry code: (i) x, y, −z.