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Acta Cryst. (2008). E64, o354    [ doi:10.1107/S160053680706789X ]

Dichlorodiphenoxymethane

R. Betz, P. Klüfers and M. M. Reichvilser

Abstract top

The title compound, C13H10Cl2O2, is a mixed derivative of orthocarbonic acid. The non-crystallographic symmetry of the molecule is close to C2v. 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 C2v 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.

Comment top

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.

Related literature top

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

Experimental top

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 top

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

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms.
[Figure 2] Fig. 2. The packing of (I) viewed along [0 1 0], C—H···O hydrogen bonds drawn as yellow bars.
Dichlorodiphenoxymethane top
Crystal data top
C13H10Cl2O2F000 = 552
Mr = 269.11Dx = 1.479 Mg m−3
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 mm−1
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 top
Nonius KappaCCD
diffractometer		2138 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 top
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 Å−3
154 parametersΔρmin = −0.29 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C13H10Cl2O2V = 1208.85 (6) Å3
Mr = 269.11Z = 4
Monoclinic, P21/cMo Kα
a = 15.8380 (4) ŵ = 0.52 mm−1
b = 5.8973 (2) ÅT = 200 (2) K
c = 14.2517 (4) Å0.22 × 0.20 × 0.15 mm
β = 114.751 (2)º
Data collection top
Nonius KappaCCD
diffractometer		2766 independent reflections
Absorption correction: none2138 reflections with I > 2σ(I)
9193 measured reflectionsRint = 0.034
Refinement top
R[F2 > 2σ(F2)] = 0.037154 parameters
wR(F2) = 0.094H-atom parameters constrained
S = 1.08Δρmax = 0.26 e Å−3
2766 reflectionsΔρmin = −0.29 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, °) top
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, °) top
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.
Table 1
Selected geometric parameters (Å, °) top
O1—C11.359 (2)O2—C11.360 (2)
O1—C1—O2103.77 (13)Cl1—C1—Cl2105.29 (9)
Table 2
Hydrogen-bond geometry (Å, °) top
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.
Acknowledgements top

The authors thank Dr Peter Mayer for technical assistance.

references
References top

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.