Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801004767/wn6010sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801004767/wn6010Isup2.hkl |
CCDC reference: 165659
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).
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.
Fig. 1. Displacement ellipsoid plot (50% probability) of the title compound. H atoms have been drawn as spheres with arbitrary radii. |
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) Å3 | Block, colorless |
Z = 8 | 0.15 × 0.10 × 0.10 mm |
F(000) = 848 |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.218 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0861P)2 + 1.4788P] where P = (Fo2 + 2Fc2)/3 |
1108 reflections | (Δ/σ)max = 0.052 |
55 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C9H21PS | V = 2388.9 (3) Å3 |
Mr = 192.29 | Z = 8 |
Orthorhombic, Ibam | Mo Kα radiation |
a = 13.573 (1) Å | µ = 0.36 mm−1 |
b = 13.8717 (9) Å | T = 293 K |
c = 12.688 (1) Å | 0.15 × 0.10 × 0.10 mm |
Bruker CCD diffractometer | 525 reflections with I > 2σ(I) |
6072 measured reflections | Rint = 0.097 |
1108 independent reflections |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.218 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.25 e Å−3 |
1108 reflections | Δρmin = −0.31 e Å−3 |
55 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
P1—C4 | 1.809 (8) | C4—C5 | 1.540 (7) |
P1—C1i | 1.824 (8) | C4—C5i | 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—C1i | 103.9 (2) | C5—C4—C5i | 111.2 (7) |
C4—P1—C1 | 103.9 (2) | C5—C4—P1 | 111.1 (4) |
C1i—P1—C1 | 116.3 (5) | C5i—C4—P1 | 111.1 (4) |
C4—P1—S1 | 112.3 (3) | C2—C1—C3 | 110.4 (6) |
C1i—P1—S1 | 110.1 (2) | C2—C1—P1 | 115.2 (6) |
C1—P1—S1 | 110.1 (2) | C3—C1—P1 | 115.7 (6) |
C1i—P1—C4—C5 | 178.9 (5) | C4—P1—C1—C2 | −174.9 (5) |
C1—P1—C4—C5 | 56.8 (5) | C1i—P1—C1—C2 | 71.7 (6) |
S1—P1—C4—C5 | −62.2 (4) | S1—P1—C1—C2 | −54.4 (6) |
C1i—P1—C4—C5i | −56.8 (5) | C4—P1—C1—C3 | 54.3 (7) |
C1—P1—C4—C5i | −178.9 (5) | C1i—P1—C1—C3 | −59.2 (8) |
S1—P1—C4—C5i | 62.2 (4) | S1—P1—C1—C3 | 174.8 (5) |
Symmetry code: (i) x, y, −z. |
Experimental details
Crystal data | |
Chemical formula | C9H21PS |
Mr | 192.29 |
Crystal system, space group | Orthorhombic, Ibam |
Temperature (K) | 293 |
a, b, c (Å) | 13.573 (1), 13.8717 (9), 12.688 (1) |
V (Å3) | 2388.9 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.36 |
Crystal size (mm) | 0.15 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6072, 1108, 525 |
Rint | 0.097 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.218, 1.14 |
No. of reflections | 1108 |
No. of parameters | 55 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.31 |
Computer programs: ASTRO (Bruker, 1997), SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), CIFTAB in SHELXL97.
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).