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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o325.
Published online 2007 December 21. doi:  10.1107/S160053680705739X
PMCID: PMC2915368

1,2-Bis(phenyl­phosphor­yl)ethane

Abstract

The geometric parameters of the mol­ecule of the title compound, C14H16O2P2, are in the usual ranges. It is a meso compound with the two chiral P atoms having opposite configurations. The P—CH2—CH2—P chain adopts a trans conformation [torsion angle −178.59 (17)°]. The P=O bonds are almost coplanar with the adjacent phenyl ring [torsion angles = 3.8 (3) and 0.3 (3)°]. Whereas one of them is synclinal [torsion angle = −59.0 (2)°] to the central C—C bond, the other is anti­clinal [torsion angle = 56.6 (2)°] to the central C—C bond. The dihedral angle between the two phenyl rings is 5.2 (3)°. The mol­ecules are linked by weak C—H(...)O hydrogen bonds. They crystallize in rows running along the c axis.

Related literature

For related literature, see: Dornhaus et al. (2007 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-64-0o325-scheme1.jpg

Experimental

Crystal data

  • C14H16O2P2
  • M r = 278.21
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o325-efi1.jpg
  • a = 10.2700 (10) Å
  • b = 5.1994 (5) Å
  • c = 26.241 (4) Å
  • V = 1401.2 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.30 mm−1
  • T = 173 (2) K
  • 0.31 × 0.24 × 0.08 mm

Data collection

  • Stoe IPDS II two-circle diffractometer
  • Absorption correction: multi-scan [MULABS (Spek, 2003 [triangle]; Blessing, 1995 [triangle])] T min = 0.912, T max = 0.966
  • 4658 measured reflections
  • 2482 independent reflections
  • 2157 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.093
  • S = 1.00
  • 2482 reflections
  • 163 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.72 e Å−3
  • Δρmin = −0.29 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1143 Friedel pairs
  • Flack parameter: 0.06 (14)

Data collection: X-AREA (Stoe & Cie, 2001 [triangle]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680705739X/at2477sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680705739X/at2477Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Very recently we have reported the syntheses of the diphospine PhHP—CH2—CH2—PHPh (Ph = C6H5) (Dornhaus et al., 2007). Oxidation of the diphosphine rac/meso PhHPH-CH2—CH2—PHPh with air provides facile access to the corresponding phosphine oxide rac/meso PhHPO—CH2—CH2—OPHPh. Single crystals of the pure diastereomer meso PhHPO—CH2—CH2—OPHPh have been obtained from diphospine PhHP—CH2—CH2—PHPh in air at room temperature.

The P—CH2—CH2—P chain adopts a trans conformation [torsion angle -178.59 (17)°]. The P?O bonds are almost coplanar with the adjacent phenyl ring [torsion angles 3.8 (3)° and 0.3 (3)°]. Whereas one of them is synclinal [torsion angle -59.0 (2)°] to the central C—C bond the other one is anticlinal [torsion angle 56.6 (2)°] to the central C—C bond. The dihedral angle between the two phenyl rings is 5.2 (3)°. The molecules are linked by weak C—H···O hydrogen bonds. They crystallize in rows running along the c axis.

Experimental

The diphospine PhHP—CH2—CH2—PHPh (0.29 g, 1.2 mmol) has been stored in air for 24 h at room temperature. Single crystals of the pure diastereomer meso PhHPO—CH2—CH2—OPHPh have been obtained in 5% yield.

Refinement

H atoms were refined with fixed individual displacement parameters [Uiso(H) = 1.2 Ueq(C,P)] using a riding model with P—H = 1.3 Å, Caromatic—H = 0.95 Å and Cmethylene—H = 0.99 Å

Figures

Fig. 1.
Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level.
Fig. 2.
Packing diagram of the title compound.

Crystal data

C14H16O2P2F000 = 584
Mr = 278.21Dx = 1.319 Mg m3
Orthorhombic, Pca21Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 5153 reflections
a = 10.2700 (10) Åθ = 3.9–25.8º
b = 5.1994 (5) ŵ = 0.30 mm1
c = 26.241 (4) ÅT = 173 (2) K
V = 1401.2 (3) Å3Plate, colourless
Z = 40.31 × 0.24 × 0.08 mm

Data collection

Stoe IPDS II two-circle diffractometer2482 independent reflections
Radiation source: fine-focus sealed tube2157 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
T = 173(2) Kθmax = 25.6º
ω scansθmin = 4.0º
Absorption correction: multi-scan[MULABS (Spek, 2003; Blessing, 1995)]h = −12→11
Tmin = 0.912, Tmax = 0.966k = −6→5
4658 measured reflectionsl = −31→30

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.038  w = 1/[σ2(Fo2) + (0.0613P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.093(Δ/σ)max < 0.001
S = 1.00Δρmax = 0.72 e Å3
2482 reflectionsΔρmin = −0.29 e Å3
163 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), with 1143 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.06 (14)
Secondary atom site location: difference Fourier map

Special 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)

xyzUiso*/Ueq
P10.75634 (7)0.09258 (15)0.55327 (3)0.01962 (18)
H10.7902−0.14730.55770.024*
O10.8765 (2)0.2475 (5)0.54496 (9)0.0332 (6)
C10.6354 (3)0.1150 (6)0.50342 (11)0.0184 (6)
H1A0.67250.04960.47110.022*
H1B0.55950.00640.51230.022*
C20.5901 (3)0.3960 (6)0.49600 (11)0.0185 (6)
H2A0.66550.50380.48620.022*
H2B0.55500.46290.52850.022*
P20.46596 (7)0.41704 (16)0.44712 (3)0.01884 (18)
H20.42790.65510.44420.023*
O20.3486 (2)0.2528 (5)0.45636 (9)0.0340 (6)
C110.6761 (3)0.1889 (7)0.61166 (11)0.0205 (7)
C120.5615 (3)0.0667 (8)0.62867 (12)0.0277 (7)
H120.5267−0.07460.61020.033*
C130.4993 (4)0.1532 (8)0.67257 (12)0.0377 (9)
H130.42280.06880.68420.045*
C140.5479 (5)0.3611 (10)0.69939 (12)0.0401 (11)
H140.50360.42130.72880.048*
C150.6626 (4)0.4834 (8)0.68326 (15)0.0404 (9)
H150.69660.62490.70190.048*
C160.7263 (4)0.3955 (8)0.63960 (12)0.0317 (8)
H160.80450.47670.62880.038*
C210.5436 (3)0.3326 (7)0.38734 (11)0.0228 (7)
C220.4890 (4)0.1358 (8)0.35768 (13)0.0348 (8)
H220.41260.04960.36890.042*
C230.5475 (5)0.0670 (9)0.31147 (15)0.0482 (11)
H230.5113−0.06760.29150.058*
C240.6574 (4)0.1937 (9)0.29480 (13)0.0427 (10)
H240.69600.14670.26320.051*
C250.7122 (4)0.3893 (9)0.32372 (13)0.0420 (10)
H250.78900.47310.31220.050*
C260.6548 (3)0.4630 (8)0.36958 (12)0.0310 (8)
H260.69050.60070.38880.037*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0143 (4)0.0230 (4)0.0216 (3)0.0010 (3)−0.0016 (3)0.0057 (4)
O10.0210 (12)0.0438 (16)0.0348 (14)−0.0042 (11)−0.0010 (10)0.0071 (11)
C10.0150 (13)0.0190 (17)0.0210 (13)0.0030 (13)−0.0019 (11)0.0008 (12)
C20.0140 (13)0.0201 (16)0.0215 (13)0.0016 (13)−0.0020 (10)0.0009 (12)
P20.0140 (3)0.0233 (4)0.0192 (3)0.0013 (3)−0.0012 (3)0.0027 (4)
O20.0217 (12)0.0443 (17)0.0360 (15)−0.0038 (11)−0.0010 (10)0.0018 (11)
C110.0195 (16)0.0225 (17)0.0194 (13)−0.0002 (14)−0.0045 (12)0.0033 (12)
C120.0236 (17)0.035 (2)0.0244 (15)−0.0017 (16)−0.0032 (12)0.0040 (14)
C130.033 (2)0.051 (3)0.0288 (17)0.0050 (19)0.0058 (14)0.0099 (15)
C140.054 (3)0.045 (3)0.0209 (17)0.015 (2)0.0010 (15)0.0014 (13)
C150.065 (3)0.033 (2)0.0230 (16)0.000 (2)−0.0038 (17)−0.0014 (15)
C160.042 (2)0.0276 (18)0.0253 (16)−0.0032 (17)−0.0053 (14)0.0039 (13)
C210.0222 (16)0.0247 (17)0.0215 (14)0.0031 (14)−0.0062 (12)0.0016 (13)
C220.043 (2)0.033 (2)0.0282 (17)−0.0124 (17)−0.0002 (15)−0.0011 (14)
C230.069 (3)0.044 (2)0.0324 (19)−0.012 (2)−0.0006 (18)−0.0133 (19)
C240.051 (2)0.053 (3)0.0241 (16)0.006 (2)0.0063 (16)−0.0064 (16)
C250.032 (2)0.066 (3)0.0276 (16)−0.009 (2)0.0071 (14)−0.0015 (18)
C260.0290 (18)0.043 (2)0.0211 (16)−0.0067 (17)−0.0003 (12)−0.0024 (14)

Geometric parameters (Å, °)

P1—O11.490 (2)C13—H130.9500
P1—C11.808 (3)C14—C151.404 (6)
P1—C111.811 (3)C14—H140.9500
P1—H11.3000C15—C161.396 (5)
C1—C21.546 (4)C15—H150.9500
C1—H1A0.9900C16—H160.9500
C1—H1B0.9900C21—C221.403 (5)
C2—P21.812 (3)C21—C261.407 (5)
C2—H2A0.9900C22—C231.400 (6)
C2—H2B0.9900C22—H220.9500
P2—O21.497 (3)C23—C241.378 (6)
P2—C211.814 (3)C23—H230.9500
P2—H21.3000C24—C251.388 (6)
C11—C161.399 (5)C24—H240.9500
C11—C121.410 (5)C25—C261.394 (5)
C12—C131.392 (5)C25—H250.9500
C12—H120.9500C26—H260.9500
C13—C141.383 (6)
O1—P1—C1115.39 (14)C14—C13—C12120.5 (4)
O1—P1—C11110.57 (16)C14—C13—H13119.7
C1—P1—C11106.35 (14)C12—C13—H13119.7
O1—P1—H1108.1C13—C14—C15120.2 (3)
C1—P1—H1108.1C13—C14—H14119.9
C11—P1—H1108.1C15—C14—H14119.9
C2—C1—P1111.03 (18)C16—C15—C14119.5 (4)
C2—C1—H1A109.4C16—C15—H15120.2
P1—C1—H1A109.4C14—C15—H15120.2
C2—C1—H1B109.4C15—C16—C11120.5 (4)
P1—C1—H1B109.4C15—C16—H16119.7
H1A—C1—H1B108.0C11—C16—H16119.7
C1—C2—P2110.98 (18)C22—C21—C26119.5 (3)
C1—C2—H2A109.4C22—C21—P2118.7 (3)
P2—C2—H2A109.4C26—C21—P2121.8 (3)
C1—C2—H2B109.4C23—C22—C21119.7 (4)
P2—C2—H2B109.4C23—C22—H22120.1
H2A—C2—H2B108.0C21—C22—H22120.1
O2—P2—C2114.67 (15)C24—C23—C22120.3 (4)
O2—P2—C21110.86 (16)C24—C23—H23119.9
C2—P2—C21106.76 (15)C22—C23—H23119.9
O2—P2—H2108.1C23—C24—C25120.6 (4)
C2—P2—H2108.1C23—C24—H24119.7
C21—P2—H2108.1C25—C24—H24119.7
C16—C11—C12119.2 (3)C24—C25—C26120.1 (4)
C16—C11—P1119.2 (3)C24—C25—H25120.0
C12—C11—P1121.6 (3)C26—C25—H25120.0
C13—C12—C11120.0 (4)C25—C26—C21119.8 (4)
C13—C12—H12120.0C25—C26—H26120.1
C11—C12—H12120.0C21—C26—H26120.1
O1—P1—C1—C2−59.0 (2)C12—C11—C16—C15−1.3 (5)
C11—P1—C1—C264.0 (2)P1—C11—C16—C15176.5 (3)
P1—C1—C2—P2−178.59 (17)O2—P2—C21—C220.3 (3)
C1—C2—P2—O256.6 (2)C2—P2—C21—C22125.8 (3)
C1—C2—P2—C21−66.6 (2)O2—P2—C21—C26178.8 (3)
O1—P1—C11—C163.8 (3)C2—P2—C21—C26−55.6 (3)
C1—P1—C11—C16−122.2 (3)C26—C21—C22—C231.6 (6)
O1—P1—C11—C12−178.5 (3)P2—C21—C22—C23−179.8 (3)
C1—P1—C11—C1255.5 (3)C21—C22—C23—C24−0.7 (6)
C16—C11—C12—C130.5 (5)C22—C23—C24—C250.6 (7)
P1—C11—C12—C13−177.2 (3)C23—C24—C25—C26−1.3 (7)
C11—C12—C13—C140.9 (5)C24—C25—C26—C212.2 (6)
C12—C13—C14—C15−1.5 (6)C22—C21—C26—C25−2.3 (5)
C13—C14—C15—C160.7 (6)P2—C21—C26—C25179.2 (3)
C14—C15—C16—C110.7 (6)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1A···O2i0.992.433.159 (4)130
C1—H1B···O1ii0.992.453.436 (4)173
C2—H2A···O2iii0.992.403.386 (4)176
C2—H2B···O1iv0.992.413.146 (4)131
C12—H12···O1ii0.952.473.332 (4)150
C26—H26···O2iii0.952.523.366 (4)148

Symmetry codes: (i) x+1/2, −y, z; (ii) x−1/2, −y, z; (iii) x+1/2, −y+1, z; (iv) x−1/2, −y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2477).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans, 2, pp. S1–19.
  • Blessing, R. H. (1995). Acta Cryst. A51, 33–38. [PubMed]
  • Dornhaus, F., Bolte, M., Lerner, H.-W. & Wagner, M. (2007). J. Organomet. Chem.692, 2949–2955.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Sheldrick, G. M. (1990). Acta Cryst. A46, 467–473.
  • Sheldrick, G. M. (1991). SHELXTL-Plus Release 4.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (1997). SHELXL97 University of Göttingen, Germany. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Stoe & Cie (2001). X-AREA Stoe & Cie, Darmstadt, Germany.

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