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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o354.
Published online 2008 January 4. doi:  10.1107/S160053680706789X
PMCID: PMC2960455

Dichloro­diphenoxy­methane

Abstract

The title compound, C13H10Cl2O2, is a mixed derivative of orthocarbonic acid. The non-crystallographic symmetry of the mol­ecule is close to C 2v. The aromatic residues are oriented in a syn conformation with respect to the Cl atoms. The least-squares planes through the phenyl rings enclose an angle of 36.11 (10)°. The C—O bonds at the central carbon are relatively short, and the O—C—O and Cl—C—Cl angles are smaller than the tetra­hedral angle. These metrical peculiarities including a mol­ecular symmetry close to C 2v are also observed in density functional theory (DFT) calculations, thus ruling out the decisive influence of inter­molecular forces in the crystal structure. Accordingly, only few and weak inter­molecular inter­actions are found. At distances smaller than the sum of the van der Waals radii, only two attractive inter­actions are detected: a weak C—H(...)O and a weak C—H(...)Cl hydrogen bond to one of the two potential acceptor atoms each.

Related literature

For the synthesis of the title compound, see Bromley et al. (1996 [triangle]). For the crystal structure of related tetra­aryl­oxymethanes with slightly longer C—O bonds, see Narasimhamurthy et al. (1990 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o354-scheme1.jpg

Experimental

Crystal data

  • C13H10Cl2O2
  • M r = 269.11
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o354-efi1.jpg
  • a = 15.8380 (4) Å
  • b = 5.8973 (2) Å
  • c = 14.2517 (4) Å
  • β = 114.751 (2)°
  • V = 1208.85 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.52 mm−1
  • T = 200 (2) K
  • 0.22 × 0.20 × 0.15 mm

Data collection

  • Nonius KappaCCD diffractometer
  • Absorption correction: none
  • 9193 measured reflections
  • 2766 independent reflections
  • 2138 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.094
  • S = 1.07
  • 2766 reflections
  • 154 parameters
  • H-atom parameters constrained
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.29 e Å−3

Data collection: COLLECT (Nonius, 2004 [triangle]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 [triangle]); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680706789X/hg2358sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680706789X/hg2358Isup2.hkl

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

Acknowledgments

The authors thank Dr Peter Mayer for technical assistance.

supplementary crystallographic information

Comment

The title compound (I) was prepared as starting material for the synthesis of spirocyclic orthocarbonates.

In the molecule the two aromatic moieties are oriented syn with respect to the Cl atoms (Fig. 1). The bond lengths between the central C atom and the O atoms are slightly shorter than in related tetraaryloxymethanes (Narasimhamurthy et al., 1990). Unexpectedly, both the O—C—O and the Cl—C—Cl angles are smaller than the tetrahedral angle. The best planes through the phenyl moieties enclose an angle of 36.11 (10)°.

The molecular packing is shown in Figure 2. Below the limit of the sum of the van-der-Waals radii, one weak C—H···O and one weak C—H···Cl hydrogen bond were found in the asymmetric unit as well as an electrostatically repulsive C—H···H—C contact precisely at the vdW radii sum. No π stacking and no C—H···π contacts were observed within this cutoff criterion.

In agreement with the only weak intermolecular forces, the short bonds to the central carbon atom as well as the small bond angles mentioned above are corroborated by a DFT calculation on the B3LYP/6–311+G(2 d,p) level of theory.

Experimental

The title compound was prepared according to a published procedure (Bromley et al., 1996) upon chlorination of diphenylcarbonate with PCl5. Crystals suitable for X-ray analysis were obtained directly from the solid reaction product.

Refinement

H atoms were refined as riding on their parent atoms with Uiso as the 1.2-fold of the pilot atom's Ueq.

Figures

Fig. 1.
The molecular structure of (I), with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms.
Fig. 2.
The packing of (I) viewed along [0 1 0], C—H···O hydrogen bonds drawn as yellow bars.

Crystal data

C13H10Cl2O2F000 = 552
Mr = 269.11Dx = 1.479 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 12368 reflections
a = 15.8380 (4) Åθ = 3.1–27.5º
b = 5.8973 (2) ŵ = 0.52 mm1
c = 14.2517 (4) ÅT = 200 (2) K
β = 114.751 (2)ºBlock, colourless
V = 1208.85 (6) Å30.22 × 0.20 × 0.15 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer2138 reflections with I > 2σ(I)
Radiation source: rotating anodeRint = 0.034
Monochromator: MONTEL, graded multilayered X-ray opticsθmax = 27.5º
T = 200(2) Kθmin = 3.2º
CCD; rotation images; thick slices scansh = −20→20
Absorption correction: nonek = −7→7
9193 measured reflectionsl = −18→18
2766 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.094  w = 1/[σ2(Fo2) + (0.0387P)2 + 0.3721P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
2766 reflectionsΔρmax = 0.26 e Å3
154 parametersΔρmin = −0.29 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl10.22903 (3)0.81935 (8)−0.00008 (4)0.04218 (16)
Cl20.16437 (3)0.38393 (9)0.03397 (4)0.04247 (16)
O10.26019 (8)0.4390 (2)−0.07857 (9)0.0370 (3)
O20.34125 (8)0.4761 (2)0.08404 (9)0.0367 (3)
C10.25543 (12)0.5198 (3)0.00839 (13)0.0327 (4)
C20.18098 (12)0.4454 (3)−0.17458 (13)0.0323 (4)
C30.12316 (13)0.2594 (3)−0.20312 (14)0.0367 (4)
H30.13450.1336−0.15780.044*
C40.04817 (13)0.2588 (4)−0.29911 (14)0.0379 (4)
H40.00710.1327−0.31980.046*
C50.03320 (13)0.4419 (3)−0.36477 (14)0.0371 (4)
H5−0.01870.4424−0.43010.045*
C60.09367 (13)0.6242 (3)−0.33543 (14)0.0394 (5)
H60.08360.7484−0.38130.047*
C70.16881 (13)0.6273 (3)−0.23968 (14)0.0375 (4)
H70.21080.7516−0.21940.045*
C80.36336 (11)0.5446 (3)0.18686 (14)0.0332 (4)
C90.34856 (13)0.3947 (3)0.25296 (15)0.0404 (5)
H90.31950.25250.22860.048*
C100.37686 (13)0.4557 (4)0.35513 (16)0.0448 (5)
H100.36700.35470.40150.054*
C110.41948 (12)0.6623 (4)0.39062 (15)0.0418 (5)
H110.43820.70390.46090.050*
C120.43477 (13)0.8085 (3)0.32332 (15)0.0411 (5)
H120.46450.95000.34770.049*
C130.40687 (12)0.7493 (3)0.22053 (15)0.0377 (4)
H130.41770.84860.17420.045*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0470 (3)0.0337 (3)0.0407 (3)0.0093 (2)0.0133 (2)0.0033 (2)
Cl20.0378 (3)0.0472 (3)0.0451 (3)−0.0041 (2)0.0199 (2)−0.0028 (2)
O10.0306 (7)0.0447 (8)0.0353 (7)0.0066 (5)0.0134 (5)−0.0046 (6)
O20.0288 (6)0.0427 (8)0.0357 (7)0.0091 (5)0.0108 (5)0.0002 (6)
C10.0302 (9)0.0314 (10)0.0352 (10)0.0054 (7)0.0126 (8)0.0009 (8)
C20.0297 (9)0.0371 (10)0.0318 (9)0.0045 (7)0.0146 (7)−0.0024 (8)
C30.0459 (11)0.0300 (10)0.0354 (10)0.0030 (8)0.0182 (9)0.0028 (8)
C40.0406 (10)0.0394 (11)0.0361 (10)−0.0066 (8)0.0183 (8)−0.0059 (9)
C50.0385 (10)0.0471 (12)0.0277 (9)0.0000 (8)0.0157 (8)−0.0011 (9)
C60.0474 (11)0.0417 (11)0.0335 (10)−0.0002 (9)0.0213 (9)0.0068 (9)
C70.0411 (10)0.0368 (11)0.0398 (10)−0.0064 (8)0.0222 (9)−0.0028 (9)
C80.0253 (9)0.0366 (10)0.0341 (9)0.0071 (7)0.0090 (7)0.0029 (8)
C90.0337 (10)0.0350 (11)0.0450 (11)0.0009 (8)0.0092 (8)0.0085 (9)
C100.0366 (10)0.0520 (13)0.0420 (11)0.0004 (9)0.0128 (9)0.0154 (10)
C110.0320 (10)0.0557 (13)0.0347 (10)0.0041 (9)0.0108 (8)0.0024 (9)
C120.0319 (10)0.0413 (12)0.0428 (11)−0.0037 (8)0.0085 (8)−0.0018 (9)
C130.0318 (10)0.0407 (11)0.0394 (11)−0.0008 (8)0.0136 (8)0.0081 (9)

Geometric parameters (Å, °)

Cl1—C11.8078 (18)C6—C71.385 (3)
Cl2—C11.8154 (18)C6—H60.9500
O1—C11.359 (2)C7—H70.9500
O1—C21.418 (2)C8—C131.373 (3)
O2—C11.360 (2)C8—C91.381 (3)
O2—C81.415 (2)C9—C101.380 (3)
C2—C31.377 (3)C9—H90.9500
C2—C71.378 (3)C10—C111.382 (3)
C3—C41.386 (3)C10—H100.9500
C3—H30.9500C11—C121.384 (3)
C4—C51.383 (3)C11—H110.9500
C4—H40.9500C12—C131.386 (3)
C5—C61.383 (3)C12—H120.9500
C5—H50.9500C13—H130.9500
C1—O1—C2120.43 (13)C7—C6—H6119.7
C1—O2—C8119.92 (13)C2—C7—C6118.23 (18)
O1—C1—O2103.77 (13)C2—C7—H7120.9
O1—C1—Cl1112.41 (12)C6—C7—H7120.9
O2—C1—Cl1111.39 (13)C13—C8—C9121.85 (18)
O1—C1—Cl2112.36 (12)C13—C8—O2118.89 (16)
O2—C1—Cl2111.80 (12)C9—C8—O2118.98 (17)
Cl1—C1—Cl2105.29 (9)C10—C9—C8118.69 (19)
C3—C2—C7122.22 (17)C10—C9—H9120.7
C3—C2—O1118.32 (16)C8—C9—H9120.7
C7—C2—O1119.22 (16)C9—C10—C11120.60 (19)
C2—C3—C4118.85 (18)C9—C10—H10119.7
C2—C3—H3120.6C11—C10—H10119.7
C4—C3—H3120.6C10—C11—C12119.71 (19)
C5—C4—C3119.95 (18)C10—C11—H11120.1
C5—C4—H4120.0C12—C11—H11120.1
C3—C4—H4120.0C11—C12—C13120.33 (19)
C4—C5—C6120.11 (18)C11—C12—H12119.8
C4—C5—H5119.9C13—C12—H12119.8
C6—C5—H5119.9C8—C13—C12118.81 (18)
C5—C6—C7120.59 (18)C8—C13—H13120.6
C5—C6—H6119.7C12—C13—H13120.6
C2—O1—C1—O2177.16 (14)C3—C2—C7—C62.3 (3)
C2—O1—C1—Cl1−62.36 (19)O1—C2—C7—C6176.56 (16)
C2—O1—C1—Cl256.20 (19)C5—C6—C7—C2−0.6 (3)
C8—O2—C1—O1178.00 (15)C1—O2—C8—C13−94.4 (2)
C8—O2—C1—Cl156.83 (19)C1—O2—C8—C991.6 (2)
C8—O2—C1—Cl2−60.67 (19)C13—C8—C9—C101.3 (3)
C1—O1—C2—C3−91.8 (2)O2—C8—C9—C10175.07 (16)
C1—O1—C2—C793.7 (2)C8—C9—C10—C11−0.2 (3)
C7—C2—C3—C4−2.4 (3)C9—C10—C11—C12−0.7 (3)
O1—C2—C3—C4−176.73 (15)C10—C11—C12—C130.5 (3)
C2—C3—C4—C50.8 (3)C9—C8—C13—C12−1.4 (3)
C3—C4—C5—C60.9 (3)O2—C8—C13—C12−175.20 (16)
C4—C5—C6—C7−1.0 (3)C11—C12—C13—C80.5 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C3—H3···Cl1i0.952.813.723 (2)161
C10—H10···O1ii0.952.523.345 (3)145

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2358).

References

  • Bromley, M. K., Gason, S. J., Jhingran, A. C., Looney, M. G. & Solomon, D. H. (1996). Aust. J. Chem.49, 1261–1262.
  • Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.
  • Narasimhamurthy, N., Manohar, H., Samuelson, A. G. & Chandrasekhar, J. (1990). J. Am. Chem. Soc.112, 2937–2941.
  • Nonius (2004). COLLECT Nonius BV, Delft, The Netherlands.
  • Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography