In the title mol-ecule, C24H20P2S, the P - P bond length is 2.2263 (5) Å. The two phenyl rings attached to the three- and five-coordinated P atoms, respectively, form dihedral angles of 56.22 (5) and 71.74 (5)°

Aluri, B.R.

Müller, B.H.

Peitz, S.

Peulecke, N.

Rosenthal, U.

Spannenberg, A.

Wöhl, A.

English

Repositorium für Naturwissenschaften und Technik

1,1,2,2-Tetraphenyl-1k5-diphosphane1-sulfideBhaskar R. Aluri,a* Stephan Peitz,a Anina Wöhl,b NormenPeulecke,a Bernd H. Müller,a Anke Spannenberga andUwe RosenthalaaLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse29a, 18059 Rostock, Germany, and bLinde AG, Linde Engineering Division,Dr.-Carl-von-Linde-Strasse 6–14, 82049 Pullach, GermanyCorrespondence e-mail: bhaskar-reddy.aluri@catalysis.deReceived 20 January 2009; accepted 23 January 2009Key indicators: single-crystal X-ray study; T = 200 K; mean (C–C) = 0.002 Å;R factor = 0.033; wR factor = 0.096; data-to-parameter ratio = 22.5.In the title molecule, C24H20P2S, the P—P bond length is2.2263 (5) Å. The two phenyl rings attached to the three- andfive-coordinated P atoms, respectively, form dihedral angles of56.22 (5) and 71.74 (5).Related literatureFor the literature on related compounds, see: Bhattacharyya etal. (1996); Gruber et al. (1990); Jones et al. (2002).ExperimentalCrystal dataC24H20P2SMr = 402.40Monoclinic, P21=ca = 9.32670 (19) Åb = 13.6496 (4) Åc = 16.0484 (4) Å = 91.7298 (17)V = 2042.12 (9) Å3Z = 4Mo K radiation = 0.32 mm1T = 200 (2) K0.45  0.30  0.28 mmData collectionStoe IPDS II diffractometerAbsorption correction: numerical(X-SHAPE; Stoe & Cie, 2005)Tmin = 0.892, Tmax = 0.96138972 measured reflections5499 independent reflections4493 reflections with I > 2(I)Rint = 0.027RefinementR[F 2 > 2(F 2)] = 0.033wR(F 2) = 0.096S = 1.085499 reflections244 parameters1 restraintH-atom parameters constrainedmax = 0.29 e Å3min = 0.28 e Å3Data collection: X-AREA (Stoe & Cie, 2005); cell refinement:X-AREA; data reduction: X-RED (Stoe & Cie, 2005); program(s)used to solve structure: SHELXS97 (Sheldrick, 2008); program(s)used to refine structure: SHELXL97 (Sheldrick, 2008); moleculargraphics: SHELXTL (Sheldrick, 2008); software used to preparematerial for publication: SHELXTL.This work was supported by the Leibniz-Institut fürKatalyse e. V. an der Universität Rostock.Supplementary data and figures for this paper are available from theIUCr electronic archives (Reference: CV2512).ReferencesBhattacharyya, P., Slawin, A. M. Z., Smith, M. B., Williams, D. J. & Woollins,J. D. (1996). J. Chem. Soc. Dalton Trans. pp. 3647–3651.Gruber, M., Jones, P. G. & Schmutzler, R. (1990). Chem. Ber. 123, 1313–1317.Jones, P. G., Fischer, A. K., Farkens, M. & Schmutzler, R. (2002). Acta Cryst.E58, m478–m479.Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Stoe & Cie (2005). X-SHAPE, X-RED and X-AREA. Stoe & Cie, Darmstadt,Germany.organic compoundso404 Aluri et al. doi:10.1107/S1600536809002955 Acta Cryst. (2009). E65, o404Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368supporting informationsup-1Acta Cryst. (2009). E65, o404    supporting informationActa Cryst. (2009). E65, o404    [doi:10.1107/S1600536809002955]1,1,2,2-Tetraphenyl-1λ5-diphosphane 1-sulfideBhaskar R. Aluri, Stephan Peitz, Anina Wöhl, Normen Peulecke, Bernd H. Müller, Anke Spannenberg and Uwe RosenthalS1. Comment Earlier, Gruber et al. (1990) reported that the only phosphorus-containing product formed from the reaction between Ph2PCl and thiourea was tetraphenyldiphosphane monosulfide. Bhattacharyya et al. (1996) reported this monosulfide formed as the by-product from the same reaction using different reaction conditions. In the present publication, we report the formation of tetraphenyldiphosphane monosulfide, which was observed as a major by-product in the reaction of Ph2P(S)CH2N(Li)Ph and ClPPh2. Its molecular structure (Fig. 1) shows the bond lengths and bond angles are within the normal ranges and are in accordance with the corresponding values in tetramethyldiphosphane monosulfide (Gruber et al., 1990). The molecular structure of pentacarbonyl(tetraphenyldiphosphinomonosulfide-P)chromium(0) was reported earlier by Jones et al. (2002).S2. Experimental BuLi (0.77 ml, 1.94 mmol, 2.5 M in n-hexane) was added dropwise to a solution of Ph2P(S)CH2N(H)Ph (660 mg, 2.03 mmol) in THF (5 ml) at -78°C and this reaction mixture was stirred for 4 h while slowly warming up to -40°C. The resultant yellow solution was added to ClPPh2 (0.38 ml, 2.03 mmol) at 0°C in small portions via a cannula over a period of 20 min and followed stirring at room temperature overnight. The major part of THF was removed from the reaction mixture and over-layered with n-hexane to get single crystals of the title compound, which were suitable for X-ray analysis. 31P NMR (THF-d8): -14.11 (d, 1J = 247.3 Hz), 44.11 (d, 1J = 247.3 Hz).S3. Refinement All H atoms were placed in idealized positions (C—H = 0.95 Å) and refined using a riding model with Uiso(H) fixed at 1.2 Ueq(C).supporting informationsup-2Acta Cryst. (2009). E65, o404    Figure 1The molecular structure of the title compound showing the atom-labelling scheme and 30% probability displacement ellipsoids. 1,1,2,2-Tetraphenyl-1λ5-diphosphane 1-sulfide Crystal data C24H20P2SMr = 402.40Monoclinic, P21/cHall symbol: -P 2ybca = 9.32670 (19) Åb = 13.6496 (4) Åc = 16.0484 (4) Åβ = 91.7298 (17)°V = 2042.12 (9) Å3Z = 4F(000) = 840Dx = 1.309 Mg m−3Mo Kα radiation, λ = 0.71073 ÅCell parameters from 32981 reflectionsθ = 2.0–29.6°µ = 0.32 mm−1T = 200 KPrism, colourless0.45 × 0.30 × 0.28 mmsupporting informationsup-3Acta Cryst. (2009). E65, o404    Data collection Stoe IPDS II diffractometerRadiation source: fine-focus sealed tubeGraphite monochromatorrotation method scansAbsorption correction: numerical (X-SHAPE; Stoe & Cie, 2005)Tmin = 0.892, Tmax = 0.96138972 measured reflections5499 independent reflections4493 reflections with I > 2σ(I)Rint = 0.027θmax = 29.1°, θmin = 2.0°h = −12→12k = −18→18l = −21→21Refinement Refinement on F2Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.033wR(F2) = 0.096S = 1.085499 reflections244 parameters1 restraintPrimary atom site location: structure-invariant direct methodsSecondary atom site location: difference Fourier mapHydrogen site location: inferred from neighbouring sitesH-atom parameters constrainedw = 1/[σ2(Fo2) + (0.0564P)2 + 0.1948P] where P = (Fo2 + 2Fc2)/3(Δ/σ)max = 0.001Δρmax = 0.29 e Å−3Δρmin = −0.28 e Å−3Special 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 (Å2) x y z Uiso*/UeqC1 0.58305 (14) 0.77663 (9) −0.01356 (8) 0.0323 (3)C2 0.58628 (15) 0.78402 (11) −0.10028 (8) 0.0380 (3)H2A 0.5640 0.7283 −0.1337 0.046*C3 0.62169 (16) 0.87176 (12) −0.13813 (10) 0.0450 (3)H3A 0.6232 0.8761 −0.1972 0.054*C4 0.65480 (16) 0.95274 (11) −0.08978 (11) 0.0469 (3)H4A 0.6797 1.0128 −0.1156 0.056*C5 0.65188 (16) 0.94677 (11) −0.00372 (10) 0.0439 (3)H5A 0.6751 1.0026 0.0293 0.053*C6 0.61519 (15) 0.85951 (10) 0.03445 (9) 0.0376 (3)H6A 0.6119 0.8561 0.0935 0.045*C7 0.66830 (14) 0.62119 (9) 0.10362 (7) 0.0309 (2)C8 0.78956 (15) 0.67684 (11) 0.12330 (9) 0.0399 (3)H8A 0.7999 0.7401 0.0996 0.048*C9 0.89570 (16) 0.64037 (12) 0.17754 (10) 0.0455 (3)H9A 0.9782 0.6789 0.1906 0.055*supporting informationsup-4Acta Cryst. (2009). E65, o404    C10 0.88200 (16) 0.54883 (12) 0.21250 (9) 0.0436 (3)H10A 0.9544 0.5244 0.2499 0.052*C11 0.76235 (17) 0.49268 (11) 0.19287 (9) 0.0420 (3)H11A 0.7528 0.4294 0.2167 0.050*C12 0.65601 (15) 0.52821 (10) 0.13849 (8) 0.0360 (3)H12A 0.5745 0.4889 0.1250 0.043*C13 0.22346 (14) 0.75419 (10) 0.03664 (9) 0.0352 (3)C14 0.21864 (17) 0.73376 (12) −0.04835 (10) 0.0461 (3)H14A 0.2841 0.6882 −0.0708 0.055*C15 0.11782 (19) 0.78017 (15) −0.10032 (11) 0.0589 (5)H15A 0.1161 0.7675 −0.1586 0.071*C16 0.02074 (18) 0.84419 (13) −0.06782 (10) 0.0609 (5)H16A −0.0496 0.8743 −0.1034 0.073*C17 0.02482 (17) 0.86493 (12) 0.01602 (12) 0.0557 (4)H17A −0.0422 0.9097 0.0380 0.067*C18 0.12649 (16) 0.82073 (11) 0.06868 (11) 0.0430 (3)H18A 0.1298 0.8359 0.1265 0.052*C19 0.28040 (15) 0.57847 (10) 0.13544 (9) 0.0379 (3)C20 0.21178 (18) 0.51924 (11) 0.07596 (10) 0.0459 (3)H20A 0.1989 0.5421 0.0203 0.055*C21 0.1620 (2) 0.42703 (13) 0.09741 (13) 0.0589 (5)H21A 0.1140 0.3873 0.0568 0.071*C22 0.1824 (2) 0.39341 (13) 0.17769 (15) 0.0642 (5)H22A 0.1500 0.3299 0.1922 0.077*C23 0.2495 (2) 0.45130 (16) 0.23683 (14) 0.0675 (6)H23A 0.2627 0.4275 0.2922 0.081*C24 0.29853 (18) 0.54423 (14) 0.21697 (11) 0.0532 (4)H24A 0.3439 0.5841 0.2585 0.064*P1 0.53134 (3) 0.65612 (2) 0.024981 (19) 0.03019 (9)P2 0.35427 (4) 0.69731 (2) 0.10811 (2) 0.03240 (9)S1 0.39983 (5) 0.77769 (3) 0.20569 (2) 0.04904 (11)Atomic displacement parameters (Å2) U11 U22 U33 U12 U13 U23C1 0.0296 (6) 0.0325 (6) 0.0344 (6) 0.0026 (5) −0.0032 (5) 0.0022 (5)C2 0.0367 (7) 0.0421 (7) 0.0350 (6) 0.0007 (6) −0.0036 (5) 0.0036 (5)C3 0.0396 (8) 0.0531 (8) 0.0423 (7) 0.0007 (6) 0.0002 (6) 0.0132 (6)C4 0.0374 (7) 0.0414 (8) 0.0619 (9) 0.0012 (6) 0.0019 (6) 0.0156 (7)C5 0.0371 (7) 0.0336 (7) 0.0608 (9) 0.0017 (6) −0.0018 (6) −0.0012 (6)C6 0.0363 (7) 0.0359 (7) 0.0404 (7) 0.0015 (5) −0.0020 (5) −0.0015 (5)C7 0.0305 (6) 0.0328 (6) 0.0294 (5) 0.0062 (5) −0.0001 (4) −0.0012 (4)C8 0.0347 (7) 0.0404 (7) 0.0441 (7) −0.0002 (5) −0.0050 (6) 0.0058 (6)C9 0.0317 (7) 0.0548 (9) 0.0494 (8) 0.0009 (6) −0.0065 (6) 0.0038 (7)C10 0.0391 (7) 0.0533 (8) 0.0383 (7) 0.0160 (6) −0.0034 (6) 0.0020 (6)C11 0.0511 (8) 0.0361 (7) 0.0390 (7) 0.0121 (6) 0.0018 (6) 0.0043 (5)C12 0.0392 (7) 0.0312 (6) 0.0373 (6) 0.0045 (5) −0.0005 (5) −0.0015 (5)C13 0.0304 (6) 0.0321 (6) 0.0430 (7) 0.0011 (5) −0.0030 (5) 0.0059 (5)supporting informationsup-5Acta Cryst. (2009). E65, o404    C14 0.0389 (7) 0.0547 (9) 0.0438 (7) 0.0065 (7) −0.0107 (6) 0.0024 (6)C15 0.0479 (9) 0.0735 (12) 0.0542 (9) 0.0031 (8) −0.0182 (8) 0.0125 (8)C16 0.0405 (8) 0.0593 (10) 0.0816 (13) 0.0032 (8) −0.0181 (8) 0.0254 (9)C17 0.0359 (8) 0.0426 (8) 0.0887 (13) 0.0083 (6) 0.0001 (8) 0.0139 (8)C18 0.0343 (7) 0.0352 (7) 0.0595 (9) 0.0035 (5) 0.0032 (6) 0.0068 (6)C19 0.0321 (6) 0.0387 (7) 0.0432 (7) 0.0083 (5) 0.0062 (5) 0.0076 (5)C20 0.0526 (9) 0.0380 (7) 0.0481 (8) 0.0001 (6) 0.0162 (7) −0.0033 (6)C21 0.0642 (11) 0.0407 (8) 0.0733 (11) −0.0032 (8) 0.0278 (9) −0.0076 (8)C22 0.0558 (11) 0.0419 (9) 0.0963 (15) 0.0086 (8) 0.0248 (10) 0.0192 (9)C23 0.0510 (10) 0.0739 (13) 0.0776 (12) 0.0079 (9) 0.0020 (9) 0.0428 (11)C24 0.0423 (8) 0.0632 (10) 0.0538 (9) 0.0029 (7) −0.0049 (7) 0.0224 (8)P1 0.03128 (16) 0.03040 (16) 0.02864 (15) 0.00166 (12) −0.00294 (12) −0.00140 (11)P2 0.03193 (17) 0.03396 (17) 0.03117 (16) 0.00544 (13) −0.00136 (12) 0.00023 (12)S1 0.0586 (2) 0.0524 (2) 0.03591 (18) 0.00869 (18) −0.00217 (16) −0.01034 (15)Geometric parameters (Å, º) C1—C6 1.3962 (18) C13—C14 1.392 (2)C1—C2 1.3966 (18) C13—P2 1.8228 (13)C1—P1 1.8273 (13) C14—C15 1.391 (2)C2—C3 1.387 (2) C14—H14A 0.9500C2—H2A 0.9500 C15—C16 1.3727 (19)C3—C4 1.380 (2) C15—H15A 0.9500C3—H3A 0.9500 C16—C17 1.3743 (19)C4—C5 1.385 (2) C16—H16A 0.9500C4—H4A 0.9500 C17—C18 1.389 (2)C5—C6 1.387 (2) C17—H17A 0.9500C5—H5A 0.9500 C18—H18A 0.9500C6—H6A 0.9500 C19—C20 1.392 (2)C7—C8 1.3907 (19) C19—C24 1.395 (2)C7—C12 1.3931 (18) C19—P2 1.8210 (15)C7—P1 1.8316 (12) C20—C21 1.388 (2)C8—C9 1.3905 (19) C20—H20A 0.9500C8—H8A 0.9500 C21—C22 1.375 (3)C9—C10 1.377 (2) C21—H21A 0.9500C9—H9A 0.9500 C22—C23 1.372 (3)C10—C11 1.382 (2) C22—H22A 0.9500C10—H10A 0.9500 C23—C24 1.389 (3)C11—C12 1.3887 (19) C23—H23A 0.9500C11—H11A 0.9500 C24—H24A 0.9500C12—H12A 0.9500 P1—P2 2.2263 (5)C13—C18 1.391 (2) P2—S1 1.9486 (5)C6—C1—C2 118.73 (13) C13—C14—H14A 120.1C6—C1—P1 126.67 (10) C16—C15—C14 120.26 (16)C2—C1—P1 114.59 (10) C16—C15—H15A 119.9C3—C2—C1 120.75 (14) C14—C15—H15A 119.9C3—C2—H2A 119.6 C15—C16—C17 120.27 (15)supporting informationsup-6Acta Cryst. (2009). E65, o404    C1—C2—H2A 119.6 C15—C16—H16A 119.9C4—C3—C2 119.83 (14) C17—C16—H16A 119.9C4—C3—H3A 120.1 C16—C17—C18 120.30 (15)C2—C3—H3A 120.1 C16—C17—H17A 119.9C3—C4—C5 120.19 (14) C18—C17—H17A 119.9C3—C4—H4A 119.9 C17—C18—C13 119.88 (16)C5—C4—H4A 119.9 C17—C18—H18A 120.1C4—C5—C6 120.24 (14) C13—C18—H18A 120.1C4—C5—H5A 119.9 C20—C19—C24 119.26 (14)C6—C5—H5A 119.9 C20—C19—P2 121.44 (11)C5—C6—C1 120.26 (13) C24—C19—P2 119.23 (12)C5—C6—H6A 119.9 C21—C20—C19 120.44 (16)C1—C6—H6A 119.9 C21—C20—H20A 119.8C8—C7—C12 118.85 (12) C19—C20—H20A 119.8C8—C7—P1 124.04 (10) C22—C21—C20 119.80 (19)C12—C7—P1 116.73 (10) C22—C21—H21A 120.1C9—C8—C7 120.35 (14) C20—C21—H21A 120.1C9—C8—H8A 119.8 C23—C22—C21 120.22 (17)C7—C8—H8A 119.8 C23—C22—H22A 119.9C10—C9—C8 120.45 (14) C21—C22—H22A 119.9C10—C9—H9A 119.8 C22—C23—C24 120.92 (17)C8—C9—H9A 119.8 C22—C23—H23A 119.5C9—C10—C11 119.63 (13) C24—C23—H23A 119.5C9—C10—H10A 120.2 C23—C24—C19 119.34 (18)C11—C10—H10A 120.2 C23—C24—H24A 120.3C10—C11—C12 120.40 (13) C19—C24—H24A 120.3C10—C11—H11A 119.8 C1—P1—C7 106.37 (6)C12—C11—H11A 119.8 C1—P1—P2 100.58 (5)C11—C12—C7 120.31 (13) C7—P1—P2 99.63 (4)C11—C12—H12A 119.8 C19—P2—C13 106.26 (6)C7—C12—H12A 119.8 C19—P2—S1 112.51 (5)C18—C13—C14 119.41 (13) C13—P2—S1 113.05 (5)C18—C13—P2 118.41 (11) C19—P2—P1 102.26 (5)C14—C13—P2 122.18 (11) C13—P2—P1 103.00 (5)C15—C14—C13 119.85 (16) S1—P2—P1 118.43 (2)C15—C14—H14A 120.1C6—C1—C2—C3 0.4 (2) C22—C23—C24—C19 −0.7 (3)P1—C1—C2—C3 179.04 (11) C20—C19—C24—C23 0.9 (2)C1—C2—C3—C4 0.3 (2) P2—C19—C24—C23 −176.34 (14)C2—C3—C4—C5 −0.4 (2) C6—C1—P1—C7 −52.24 (13)C3—C4—C5—C6 −0.2 (2) C2—C1—P1—C7 129.30 (10)C4—C5—C6—C1 1.0 (2) C6—C1—P1—P2 51.19 (12)C2—C1—C6—C5 −1.1 (2) C2—C1—P1—P2 −127.26 (10)P1—C1—C6—C5 −179.48 (11) C8—C7—P1—C1 −3.34 (14)C12—C7—C8—C9 −0.6 (2) C12—C7—P1—C1 −176.18 (10)P1—C7—C8—C9 −173.34 (12) C8—C7—P1—P2 −107.46 (12)C7—C8—C9—C10 −0.1 (2) C12—C7—P1—P2 79.70 (10)supporting informationsup-7Acta Cryst. (2009). E65, o404    C8—C9—C10—C11 0.5 (2) C20—C19—P2—C13 41.29 (14)C9—C10—C11—C12 −0.3 (2) C24—C19—P2—C13 −141.56 (12)C10—C11—C12—C7 −0.5 (2) C20—C19—P2—S1 165.51 (11)C8—C7—C12—C11 0.9 (2) C24—C19—P2—S1 −17.34 (14)P1—C7—C12—C11 174.15 (11) C20—C19—P2—P1 −66.36 (12)C18—C13—C14—C15 0.3 (2) C24—C19—P2—P1 110.79 (12)P2—C13—C14—C15 −179.17 (13) C18—C13—P2—C19 97.09 (12)C13—C14—C15—C16 −1.6 (3) C14—C13—P2—C19 −83.43 (14)C14—C15—C16—C17 1.7 (3) C18—C13—P2—S1 −26.79 (13)C15—C16—C17—C18 −0.5 (3) C14—C13—P2—S1 152.68 (11)C16—C17—C18—C13 −0.8 (2) C18—C13—P2—P1 −155.79 (10)C14—C13—C18—C17 0.9 (2) C14—C13—P2—P1 23.68 (13)P2—C13—C18—C17 −179.60 (12) C1—P1—P2—C19 171.48 (6)C24—C19—C20—C21 −0.1 (2) C7—P1—P2—C19 −79.70 (6)P2—C19—C20—C21 177.07 (13) C1—P1—P2—C13 61.35 (6)C19—C20—C21—C22 −0.9 (3) C7—P1—P2—C13 170.16 (6)C20—C21—C22—C23 1.1 (3) C1—P1—P2—S1 −64.24 (5)C21—C22—C23—C24 −0.3 (3) C7—P1—P2—S1 44.58 (5)

1,1,2,2-Tetra-phenyl-15-diphosphane 1-sulfide

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1,1,2,2-Tetra-phenyl-15-diphosphane 1-sulfide

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