Literature DB >> 22589915

Diphenyl[2-(phenyl-sulfon-yl)propan-2-yl]-λ(5)-phosphane-thione.

Viktoria H Gessner1.   

Abstract

The title compound, C(21)H(21)O(2)PS(2), was obtained from the corresponding dilithio methandiide by treatment with iodo-methane. The bond lengths and angles deviate considerably from those in the dimetallated compound. These differences are most pronounced in the PCS backbone. While the title compound features C-P and C-S distances of 1.9082 (17) and 1.8348 (17) Å, respectively, the dianion showed C-P(av) distances shortened by 11% [1.710 (4) Å] and C-S distances shortened by 12% [1.614 (3) Å]. Additionally, the P-C-S angle experiences a contraction by methyl-ation of the dianion from 121.4 (2) to 111.96 (9)° in the title compound.

Entities:  

Year:  2012        PMID： 22589915      PMCID： PMC3344006          DOI： 10.1107/S1600536812010082

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For background to precursors for dilithio methandiides, see: Kasani et al. (1999 ▶); Ong & Stephan (1999 ▶); Cantat et al. (2006 ▶, 2008 ▶); Cavell et al. (2001 ▶); Harder (2011 ▶); Gessner (2011 ▶); Gessner & Schröter (2012 ▶); Cooper et al. (2010 ▶).

Experimental

Crystal data

C21H21O2PS2 M = 400.47 Orthorhombic, a = 8.2137 (7) Å b = 14.3714 (13) Å c = 16.6728 (15) Å V = 1968.1 (3) Å3 Z = 4 Mo Kα radiation μ = 0.37 mm−1 T = 173 K 0.26 × 0.2 × 0.16 mm

Data collection

Bruker APEX CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.973, T max = 0.980 30953 measured reflections 3457 independent reflections 3373 reflections with I > 2σ(I) R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.025 wR(F 2) = 0.068 S = 1.04 3457 reflections 237 parameters H-atom parameters constrained Δρmax = 0.27 e Å−3 Δρmin = −0.13 e Å−3 Absolute structure: Flack (1983 ▶), 1467 Friedel pairs Flack parameter: 0.03 (5) Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 1999 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97. Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812010082/bt5837sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812010082/bt5837Isup2.hkl Supplementary material file. DOI: 10.1107/S1600536812010082/bt5837Isup3.cml Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C21H21O2PS2Dx = 1.352 Mg m−3
Mr = 400.47Melting point: 410 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3457 reflections
a = 8.2137 (7) Åθ = 1.9–25°
b = 14.3714 (13) ŵ = 0.37 mm−1
c = 16.6728 (15) ÅT = 173 K
V = 1968.1 (3) Å3Block, colourless
Z = 40.26 × 0.2 × 0.16 mm
F(000) = 840
Bruker APEX CCD diffractometer3457 independent reflections
Radiation source: fine-focus sealed tube3373 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.040
ω scansθmax = 25°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 1999)h = −9→9
Tmin = 0.973, Tmax = 0.980k = −17→17
30953 measured reflectionsl = −19→19
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.068w = 1/[σ2(Fo2) + (0.0456P)2 + 0.2311P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.006
3457 reflectionsΔρmax = 0.27 e Å−3
237 parametersΔρmin = −0.13 e Å−3
0 restraintsAbsolute structure: Flack (1983), 1467 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.03 (5)
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.
xyzUiso*/Ueq
S20.17343 (5)0.02033 (3)0.10827 (2)0.03362 (11)
P10.00880 (5)−0.07757 (3)0.25295 (3)0.03106 (11)
S10.08167 (6)−0.16347 (4)0.33619 (3)0.04775 (14)
O10.01826 (15)0.06395 (9)0.09446 (8)0.0433 (3)
C12−0.2075 (2)0.07773 (11)0.24561 (11)0.0352 (4)
H12−0.17070.08820.19230.042*
O20.21542 (19)−0.06103 (9)0.06291 (8)0.0501 (4)
C130.1913 (2)−0.00806 (11)0.21520 (10)0.0337 (4)
C170.4808 (2)0.07625 (13)0.06696 (11)0.0396 (4)
H170.50250.01220.05770.048*
C210.2932 (2)0.19798 (12)0.10399 (13)0.0441 (4)
H210.18790.21720.12070.053*
C160.3273 (2)0.10474 (11)0.09172 (10)0.0334 (4)
C6−0.0079 (2)−0.21832 (12)0.14063 (12)0.0428 (4)
H60.0979−0.2340.15940.051*
C2−0.2416 (2)−0.12018 (13)0.14386 (12)0.0429 (4)
H2−0.2971−0.06720.16430.051*
C7−0.14183 (19)0.00496 (11)0.29077 (10)0.0326 (4)
C200.4151 (3)0.26272 (14)0.09151 (14)0.0558 (5)
H200.3930.3270.09910.067*
C11−0.3259 (2)0.13455 (13)0.27833 (12)0.0426 (4)
H11−0.37020.18390.24730.051*
C9−0.3160 (3)0.04939 (16)0.40124 (13)0.0542 (5)
H9−0.35340.03960.45450.065*
C180.6012 (2)0.14149 (15)0.05597 (12)0.0487 (5)
H180.70710.12240.040.058*
C3−0.3162 (3)−0.17589 (13)0.08735 (13)0.0510 (5)
H3−0.4232−0.16150.06960.061*
C4−0.2356 (3)−0.25289 (13)0.05628 (12)0.0463 (5)
H4−0.2864−0.29090.0170.056*
C150.2017 (2)0.08108 (14)0.26490 (11)0.0428 (4)
H15A0.19190.06570.3220.064*
H15B0.11320.12320.24940.064*
H15C0.30660.11150.25520.064*
C10−0.3803 (2)0.12028 (14)0.35551 (13)0.0499 (5)
H10−0.46240.15940.37730.06*
C8−0.1966 (2)−0.00755 (14)0.36918 (12)0.0452 (4)
H8−0.1514−0.05580.40110.054*
C5−0.0821 (3)−0.27321 (12)0.08296 (12)0.0463 (5)
H5−0.0259−0.32550.06170.056*
C140.3465 (2)−0.06516 (15)0.22535 (14)0.0509 (5)
H14A0.4401−0.02880.20670.076*
H14B0.3381−0.12250.19380.076*
H14C0.3611−0.08090.28210.076*
C1−0.0864 (2)−0.14097 (11)0.17107 (10)0.0317 (3)
C190.5685 (3)0.23456 (15)0.06813 (12)0.0523 (5)
H190.6520.27940.06040.063*
U11U22U33U12U13U23
S20.0321 (2)0.0363 (2)0.0325 (2)−0.00442 (18)0.00327 (17)−0.00215 (17)
P10.0248 (2)0.0357 (2)0.0327 (2)0.00245 (16)0.00071 (17)0.00384 (16)
S10.0398 (2)0.0565 (3)0.0469 (3)0.0057 (2)−0.0028 (2)0.0196 (2)
O10.0308 (6)0.0597 (8)0.0395 (7)−0.0048 (6)−0.0033 (5)0.0047 (6)
C120.0282 (8)0.0387 (8)0.0388 (9)−0.0012 (7)−0.0004 (7)−0.0033 (8)
O20.0647 (9)0.0389 (7)0.0468 (7)−0.0110 (6)0.0159 (7)−0.0096 (6)
C130.0262 (8)0.0406 (9)0.0343 (8)−0.0002 (7)0.0015 (7)0.0020 (7)
C170.0384 (10)0.0442 (9)0.0362 (9)0.0016 (8)0.0051 (8)0.0022 (8)
C210.0409 (10)0.0395 (9)0.0520 (11)0.0027 (8)−0.0034 (9)0.0023 (8)
C160.0301 (8)0.0363 (8)0.0336 (9)−0.0033 (7)−0.0003 (7)0.0019 (7)
C60.0393 (10)0.0383 (9)0.0507 (11)0.0063 (8)0.0059 (9)0.0019 (8)
C20.0367 (9)0.0391 (9)0.0528 (11)0.0073 (8)−0.0037 (9)−0.0119 (8)
C70.0262 (8)0.0381 (9)0.0334 (9)−0.0019 (6)0.0014 (6)−0.0044 (7)
C200.0681 (14)0.0369 (9)0.0625 (14)−0.0084 (10)−0.0144 (12)0.0073 (9)
C110.0316 (9)0.0410 (9)0.0551 (11)0.0013 (8)−0.0035 (8)−0.0105 (8)
C90.0466 (11)0.0731 (13)0.0428 (11)−0.0010 (10)0.0133 (10)−0.0128 (10)
C180.0327 (10)0.0758 (13)0.0376 (10)−0.0093 (10)0.0010 (8)0.0072 (9)
C30.0427 (10)0.0493 (10)0.0610 (12)−0.0003 (10)−0.0104 (10)−0.0145 (10)
C40.0602 (13)0.0377 (9)0.0410 (10)−0.0101 (9)0.0042 (9)−0.0057 (8)
C150.0343 (9)0.0573 (11)0.0369 (9)−0.0097 (8)−0.0008 (7)−0.0075 (8)
C100.0339 (10)0.0558 (11)0.0599 (13)0.0003 (9)0.0081 (9)−0.0244 (10)
C80.0415 (10)0.0577 (11)0.0366 (9)−0.0013 (9)0.0046 (8)0.0010 (8)
C50.0596 (12)0.0297 (8)0.0495 (11)0.0037 (9)0.0166 (10)−0.0038 (8)
C140.0277 (9)0.0625 (12)0.0623 (12)0.0066 (9)0.0042 (9)0.0142 (10)
C10.0296 (8)0.0291 (7)0.0363 (9)−0.0011 (7)0.0050 (7)0.0027 (6)
C190.0512 (12)0.0626 (13)0.0431 (11)−0.0239 (11)−0.0102 (10)0.0102 (9)
S2—O21.4347 (13)C7—C81.394 (3)
S2—O11.4389 (13)C20—C191.380 (3)
S2—C161.7734 (16)C20—H200.9500
S2—C131.8348 (17)C11—C101.378 (3)
P1—C11.8178 (17)C11—H110.9500
P1—C71.8263 (17)C9—C101.378 (3)
P1—C131.9082 (17)C9—C81.384 (3)
P1—S11.9515 (6)C9—H90.9500
C12—C111.382 (2)C18—C191.379 (3)
C12—C71.397 (2)C18—H180.9500
C12—H120.9500C3—C41.390 (3)
C13—C141.526 (2)C3—H30.9500
C13—C151.528 (2)C4—C51.368 (3)
C17—C181.375 (3)C4—H40.9500
C17—C161.388 (2)C15—H15A0.9800
C17—H170.9500C15—H15B0.9800
C21—C201.382 (3)C15—H15C0.9800
C21—C161.384 (2)C10—H100.9500
C21—H210.9500C8—H80.9500
C6—C11.382 (2)C5—H50.9500
C6—C51.385 (3)C14—H14A0.9800
C6—H60.9500C14—H14B0.9800
C2—C31.380 (3)C14—H14C0.9800
C2—C11.386 (3)C19—H190.9500
C2—H20.9500
O2—S2—O1118.92 (9)C10—C11—C12120.60 (18)
O2—S2—C16107.71 (8)C10—C11—H11119.7
O1—S2—C16107.96 (8)C12—C11—H11119.7
O2—S2—C13108.16 (8)C10—C9—C8119.67 (19)
O1—S2—C13108.87 (7)C10—C9—H9120.2
C16—S2—C13104.26 (8)C8—C9—H9120.2
C1—P1—C7107.07 (8)C17—C18—C19120.1 (2)
C1—P1—C13110.64 (8)C17—C18—H18119.9
C7—P1—C13107.83 (8)C19—C18—H18119.9
C1—P1—S1110.42 (6)C2—C3—C4120.36 (19)
C7—P1—S1111.90 (6)C2—C3—H3119.8
C13—P1—S1108.95 (6)C4—C3—H3119.8
C11—C12—C7120.08 (17)C5—C4—C3119.18 (19)
C11—C12—H12120.0C5—C4—H4120.4
C7—C12—H12120.0C3—C4—H4120.4
C14—C13—C15110.14 (16)C13—C15—H15A109.5
C14—C13—S2107.12 (13)C13—C15—H15B109.5
C15—C13—S2110.18 (12)H15A—C15—H15B109.5
C14—C13—P1109.78 (12)C13—C15—H15C109.5
C15—C13—P1107.68 (11)H15A—C15—H15C109.5
S2—C13—P1111.96 (9)H15B—C15—H15C109.5
C18—C17—C16119.45 (17)C9—C10—C11120.16 (18)
C18—C17—H17120.3C9—C10—H10119.9
C16—C17—H17120.3C11—C10—H10119.9
C20—C21—C16118.89 (19)C9—C8—C7120.96 (19)
C20—C21—H21120.6C9—C8—H8119.5
C16—C21—H21120.6C7—C8—H8119.5
C21—C16—C17120.86 (17)C4—C5—C6120.64 (18)
C21—C16—S2119.68 (14)C4—C5—H5119.7
C17—C16—S2119.46 (13)C6—C5—H5119.7
C1—C6—C5120.52 (18)C13—C14—H14A109.5
C1—C6—H6119.7C13—C14—H14B109.5
C5—C6—H6119.7H14A—C14—H14B109.5
C3—C2—C1120.44 (17)C13—C14—H14C109.5
C3—C2—H2119.8H14A—C14—H14C109.5
C1—C2—H2119.8H14B—C14—H14C109.5
C8—C7—C12118.51 (16)C6—C1—C2118.84 (17)
C8—C7—P1117.30 (14)C6—C1—P1118.59 (14)
C12—C7—P1124.17 (13)C2—C1—P1122.23 (13)
C19—C20—C21120.42 (19)C20—C19—C18120.23 (19)
C19—C20—H20119.8C20—C19—H19119.9
C21—C20—H20119.8C18—C19—H19119.9
Table 1

Selected bond lengths (Å)

S2—O21.4347 (13)
S2—O11.4389 (13)
S2—C161.7734 (16)
S2—C131.8348 (17)
P1—C11.8178 (17)
P1—C71.8263 (17)
P1—C131.9082 (17)
P1—S11.9515 (6)
  4 in total

1.  A monomeric dilithio methandiide with a distorted trans-planar four-coordinate carbon.

Authors:  Oliver J Cooper; Ashley J Wooles; Jonathan McMaster; William Lewis; Alexander J Blake; Stephen T Liddle
Journal:  Angew Chem Int Ed Engl       Date:  2010-07-26       Impact factor: 15.336

2.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

3.  Bis-phosphorus stabilised carbene complexes.

Authors:  Thibault Cantat; Nicolas Mézailles; Audrey Auffrant; Pascal Le Floch
Journal:  Dalton Trans       Date:  2008-01-22       Impact factor: 4.390

4.  [Ph2 P(NSiMe3 )]2 CLi2 : A Dilithium Dianionic Methanide Salt with an Unusual Li4 C2 Cluster Structure.

Authors:  Aparna Kasani; Ruppa P Kamalesh Babu; Robert McDonald; Ronald G Cavell
Journal:  Angew Chem Int Ed Engl       Date:  1999-05-17       Impact factor: 15.336
  4 in total
  1 in total

1.  Diphen-yl[(phenyl-sulfan-yl)meth-yl]-λ(5)-phosphane-thione.

Authors:  Viktoria H Gessner
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2014-02-28
  1 in total

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