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The title compound, C11H26P2S2, displays crystallographic mirror symmetry. Key bond lengths (Å) are P1-C(methyl­ene) 1.8464 (18), P1-C(butyl) 1.8711 (13), P2-C(methyl­ene) 1.8266 (18), P2-C(methyl) 1.7948 (15), P1=S 1.9631 (8) and P2=S 1.9552 (8), where P1 is the di-tert-butyl­phosphino P atom and P2 is the di­methyl­phosphino P atom. The angle P-C-P [124.31 (10)°] is wide and S=P-C(methyl­ene) [108.91 (6)°] narrow. Steric pressure from the tert-butyl groups may cause some of the molecular dimensions to depart from normal values.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802014927/wn6117sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802014927/wn6117Isup2.hkl
Contains datablock I

CCDC reference: 197478

Key indicators

  • Single-crystal X-ray study
  • T = 143 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.027
  • wR factor = 0.072
  • Data-to-parameter ratio = 23.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry
Yellow Alert Alert Level C:
ABSTM_02 Alert C The ratio of Tmax/Tmin expected RT(exp) is > 1.10 Absorption corrections should be applied. Tmin and Tmax expected: 0.698 0.769 RT(exp) = 1.101
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

The title compound, (I), arose as an unexpected product during studies of triphosphines (Krill et al., 1993; see Experimental). The molecule, which is shown in Fig. 1, displays crystallographic mirror symmetry, with both P and S atoms and the central atom C1 lying in the mirror plane at y = 0.25. The configuration about the bond P1—C1 is that atoms S1 and P2 are exactly synperiplanar; in contrast, atoms S2 and P1 are exactly antiperiplanar about C1—P2. A search of the Cambridge Structural Database (Allen & Kennard, 1993; Version of April 2002) revealed only one other bis(dialkyl)phosphinomethane disulfide, namely the tetramethyl analogue, henceforth `Me4' (Karsch et al., 1992); this has no imposed symmetry (but twofold symmetry to a close approximation) and has S—P—C—P torsion angles of 48.4 and 48.7 (5)°.

Selected molecular dimensions for (I) are presented in Table 1. The PS and PC(methylene) bond lengths in (I) are comparable with those of Me4 [PS 1.958 (1) and 1.960 (1) Å, and P—C 1.822 (2) and 1.818 (2) Å], although P—C2 is slightly longer. This may be attributable to the steric pressure of the bulky tert-butyl group, as may the appreciably different bond lengths P1—C2 and P2—C6. The bond angle S1P1—C1 appears normal [cf. Me4; 115.5 (1) and 116.6 (1)°], but S2P2—C1 is unusually narrow at 108.91 (6)°. The angle at the methylene C atom is wide [cf. Me4 119.0 (1)°], which may also be caused by steric effects; comparable structures for a more detailed analysis are not available.

Experimental top

Attempts to recrystallize bis[(di-tert-butylphosphanyl)methyl]methylphosphane trisulfide (Krill et al., 1993) from diethyl ether–toluene led unexpectedly to crystals of the title compound.

Refinement top

The methylene H atoms were included using a riding model, while methyl H atoms were identified in difference syntheses and refined using idealized rigid methyl groups allowed to rotate but not tip. C—H bond lengths were fixed at 0.98 and 0.99 Å for methyl and methylene H atoms, respectively; Uiso(H) values were fixed at 1.2 times the Ueq values of the parent atom.

Computing details top

Data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecule of the title compound in the crystal. Ellipsoids represent 30% probability levels. H-atom radii are arbitrary. Only the asymmetric unit is numbered.
(Di-tert-butylphosphino)(dimethylphosphino)methane disulfide top
Crystal data top
C11H26P2S2Dx = 1.225 Mg m3
Mr = 284.38Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PnmaCell parameters from 52 reflections
a = 18.298 (5) Åθ = 10–11.5°
b = 12.792 (3) ŵ = 0.53 mm1
c = 6.586 (2) ÅT = 143 K
V = 1541.6 (7) Å3Tablet, colourless
Z = 40.7 × 0.6 × 0.5 mm
F(000) = 616
Data collection top
Stoe STADI-4
diffractometer
Rint = 0.020
Radiation source: fine-focus sealed tubeθmax = 27.5°, θmin = 3.2°
Graphite monochromatorh = 223
ω/θ scansk = 916
2346 measured reflectionsl = 88
1854 independent reflections3 standard reflections every 60 min
1712 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0363P)2 + 0.6264P]
where P = (Fo2 + 2Fc2)/3
1854 reflections(Δ/σ)max < 0.001
80 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
C11H26P2S2V = 1541.6 (7) Å3
Mr = 284.38Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 18.298 (5) ŵ = 0.53 mm1
b = 12.792 (3) ÅT = 143 K
c = 6.586 (2) Å0.7 × 0.6 × 0.5 mm
Data collection top
Stoe STADI-4
diffractometer
Rint = 0.020
2346 measured reflections3 standard reflections every 60 min
1854 independent reflections intensity decay: none
1712 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.072H-atom parameters constrained
S = 1.07Δρmax = 0.37 e Å3
1854 reflectionsΔρmin = 0.35 e Å3
80 parameters
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
P10.31790 (2)0.25000.54645 (7)0.01640 (12)
P20.14937 (2)0.25000.39177 (7)0.01930 (12)
S10.27809 (3)0.25000.82324 (7)0.02627 (13)
S20.09816 (2)0.25000.13121 (8)0.02721 (13)
C10.24776 (9)0.25000.3449 (3)0.0183 (3)
H1A0.25780.31200.25930.022*0.50
H1B0.25780.18800.25930.022*0.50
C20.37053 (7)0.12709 (10)0.4981 (2)0.0215 (3)
C30.31620 (8)0.03668 (11)0.5275 (3)0.0323 (3)
H3A0.29300.04290.66100.039*
H3B0.34230.03010.51900.039*
H3C0.27870.03960.42140.039*
C40.43156 (8)0.11512 (13)0.6569 (2)0.0332 (3)
H4A0.41150.12730.79280.040*
H4B0.47030.16610.62940.040*
H4C0.45180.04430.64970.040*
C50.40353 (7)0.12033 (11)0.2851 (2)0.0273 (3)
H5A0.36610.13760.18420.033*
H5B0.42150.04920.26100.033*
H5C0.44420.16990.27370.033*
C60.12750 (7)0.13849 (12)0.5456 (2)0.0305 (3)
H6A0.14150.07450.47380.037*
H6B0.07480.13740.57260.037*
H6C0.15420.14270.67430.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0162 (2)0.0201 (2)0.0128 (2)0.0000.00066 (15)0.000
P20.0150 (2)0.0220 (2)0.0209 (2)0.0000.00108 (17)0.000
S10.0276 (2)0.0375 (3)0.0138 (2)0.0000.00258 (17)0.000
S20.0181 (2)0.0360 (3)0.0276 (3)0.0000.00591 (18)0.000
C10.0155 (7)0.0239 (8)0.0154 (8)0.0000.0010 (6)0.000
C20.0215 (6)0.0211 (6)0.0217 (6)0.0031 (5)0.0024 (5)0.0002 (5)
C30.0327 (7)0.0212 (6)0.0429 (9)0.0007 (5)0.0020 (6)0.0034 (6)
C40.0297 (7)0.0388 (8)0.0310 (7)0.0103 (6)0.0084 (6)0.0015 (7)
C50.0256 (6)0.0297 (7)0.0266 (7)0.0054 (5)0.0027 (5)0.0052 (6)
C60.0251 (7)0.0332 (7)0.0331 (8)0.0059 (5)0.0039 (6)0.0082 (6)
Geometric parameters (Å, º) top
P1—C11.8464 (18)C3—H3B0.9800
P1—C21.8711 (13)C3—H3C0.9800
P1—S11.9631 (8)C4—H4A0.9800
P2—C61.7948 (15)C4—H4B0.9800
P2—C11.8266 (18)C4—H4C0.9800
P2—S21.9552 (8)C5—H5A0.9800
C1—H1A0.9900C5—H5B0.9800
C1—H1B0.9900C5—H5C0.9800
C2—C51.5296 (19)C6—H6A0.9800
C2—C31.5373 (19)C6—H6B0.9800
C2—C41.5377 (18)C6—H6C0.9800
C3—H3A0.9800
C1—P1—C2103.61 (5)H3A—C3—H3B109.5
C2—P1—C2i114.34 (8)C2—C3—H3C109.5
C1—P1—S1114.18 (6)H3A—C3—H3C109.5
C2—P1—S1110.43 (5)H3B—C3—H3C109.5
C6i—P2—C6105.27 (11)C2—C4—H4A109.5
C6—P2—C1108.37 (6)C2—C4—H4B109.5
C6—P2—S2112.87 (5)H4A—C4—H4B109.5
C1—P2—S2108.91 (6)C2—C4—H4C109.5
P2—C1—P1124.31 (10)H4A—C4—H4C109.5
P2—C1—H1A106.2H4B—C4—H4C109.5
P1—C1—H1A106.2C2—C5—H5A109.5
P2—C1—H1B106.2C2—C5—H5B109.5
P1—C1—H1B106.3H5A—C5—H5B109.5
H1A—C1—H1B106.4C2—C5—H5C109.5
C5—C2—C3109.18 (11)H5A—C5—H5C109.5
C5—C2—C4109.36 (11)H5B—C5—H5C109.5
C3—C2—C4107.99 (12)P2—C6—H6A109.5
C5—C2—P1114.00 (9)P2—C6—H6B109.5
C3—C2—P1106.13 (9)H6A—C6—H6B109.5
C4—C2—P1109.97 (10)P2—C6—H6C109.5
C2—C3—H3A109.5H6A—C6—H6C109.5
C2—C3—H3B109.5H6B—C6—H6C109.5
C6—P2—C1—P156.87 (6)C1—P1—C2—C362.98 (11)
S2—P2—C1—P1180.0C2i—P1—C2—C3175.03 (7)
C2—P1—C1—P2120.17 (5)S1—P1—C2—C359.71 (10)
S1—P1—C1—P20.0C1—P1—C2—C4179.55 (10)
C1—P1—C2—C557.22 (11)C2i—P1—C2—C468.40 (13)
C2i—P1—C2—C554.83 (13)S1—P1—C2—C456.86 (10)
S1—P1—C2—C5179.91 (8)
Symmetry code: (i) x, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC11H26P2S2
Mr284.38
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)143
a, b, c (Å)18.298 (5), 12.792 (3), 6.586 (2)
V3)1541.6 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.53
Crystal size (mm)0.7 × 0.6 × 0.5
Data collection
DiffractometerStoe STADI-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2346, 1854, 1712
Rint0.020
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.072, 1.07
No. of reflections1854
No. of parameters80
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.37, 0.35

Computer programs: DIF4 (Stoe & Cie, 1992), DIF4, REDU4 (Stoe & Cie, 1992), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.

Selected geometric parameters (Å, º) top
P1—C11.8464 (18)P2—C61.7948 (15)
P1—C21.8711 (13)P2—C11.8266 (18)
P1—S11.9631 (8)P2—S21.9552 (8)
C1—P1—C2103.61 (5)C6—P2—C1108.37 (6)
C2—P1—C2i114.34 (8)C6—P2—S2112.87 (5)
C1—P1—S1114.18 (6)C1—P2—S2108.91 (6)
C2—P1—S1110.43 (5)P2—C1—P1124.31 (10)
C6i—P2—C6105.27 (11)
S2—P2—C1—P1180.0S1—P1—C1—P20.0
C2—P1—C1—P2120.17 (5)C1—P1—C2—C4179.55 (10)
Symmetry code: (i) x, y+1/2, z.
 

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