Dichloro­diphenoxy­methane

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

doi:10.1107/S160053680706789X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o354

doi:10.1107/S160053680706789X

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Dichlorodiphenoxymethane

Richard Betz,^a Peter Klüfers ^a ^* and Moritz M. Reichvilser ^a

^aLudwig-Maximilians-Universität, Department Chemie und Biochemie, Butenandtstrasse 5–13, 81377 München, Germany
^*Correspondence e-mail: kluef@cup.uni-muenchen.de

(Received 28 November 2007; accepted 20 December 2007; online 4 January 2008)

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

Experimental

Crystal data

C₁₃H₁₀Cl₂O₂
M_r = 269.11
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.037
wR(F²) = 0.094
S = 1.07
2766 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

O1—C1	1.359 (2)
O2—C1	1.360 (2)

O1—C1—O2	103.77 (13)
Cl1—C1—Cl2	105.29 (9)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cl1ⁱ	0.95	2.81	3.723 (2)	161
C10—H10⋯O1ⁱⁱ	0.95	2.52	3.345 (3)	145
Symmetry codes: (i) x, y-1, z; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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.

Supporting information

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

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

checkCIF report

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.

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

	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.

Dichlorodiphenoxymethane top

Crystal data top

C₁₃H₁₀Cl₂O₂	F(000) = 552
M_r = 269.11	D_x = 1.479 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12368 reflections
a = 15.8380 (4) Å	θ = 3.1–27.5°
b = 5.8973 (2) Å	µ = 0.52 mm⁻¹
c = 14.2517 (4) Å	T = 200 K
β = 114.751 (2)°	Block, colourless
V = 1208.85 (6) Å³	0.22 × 0.20 × 0.15 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	2138 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.034
MONTEL, graded multilayered X-ray optics monochromator	θ_max = 27.5°, θ_min = 3.2°
CCD; rotation images; thick slices scans	h = −20→20
9193 measured reflections	k = −7→7
2766 independent reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0387P)² + 0.3721P] where P = (F_o² + 2F_c²)/3
2766 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₃H₁₀Cl₂O₂	V = 1208.85 (6) Å³
M_r = 269.11	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.8380 (4) Å	µ = 0.52 mm⁻¹
b = 5.8973 (2) Å	T = 200 K
c = 14.2517 (4) Å	0.22 × 0.20 × 0.15 mm
β = 114.751 (2)°

Data collection top

Nonius KappaCCD diffractometer	2138 reflections with I > 2σ(I)
9193 measured reflections	R_int = 0.034
2766 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.08	Δρ_max = 0.26 e Å⁻³
2766 reflections	Δρ_min = −0.29 e Å⁻³
154 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.22903 (3)	0.81935 (8)	−0.00008 (4)	0.04218 (16)
Cl2	0.16437 (3)	0.38393 (9)	0.03397 (4)	0.04247 (16)
O1	0.26019 (8)	0.4390 (2)	−0.07857 (9)	0.0370 (3)
O2	0.34125 (8)	0.4761 (2)	0.08404 (9)	0.0367 (3)
C1	0.25543 (12)	0.5198 (3)	0.00839 (13)	0.0327 (4)
C2	0.18098 (12)	0.4454 (3)	−0.17458 (13)	0.0323 (4)
C3	0.12316 (13)	0.2594 (3)	−0.20312 (14)	0.0367 (4)
H3	0.1345	0.1336	−0.1578	0.044*
C4	0.04817 (13)	0.2588 (4)	−0.29911 (14)	0.0379 (4)
H4	0.0071	0.1327	−0.3198	0.046*
C5	0.03320 (13)	0.4419 (3)	−0.36477 (14)	0.0371 (4)
H5	−0.0187	0.4424	−0.4301	0.045*
C6	0.09367 (13)	0.6242 (3)	−0.33543 (14)	0.0394 (5)
H6	0.0836	0.7484	−0.3813	0.047*
C7	0.16881 (13)	0.6273 (3)	−0.23968 (14)	0.0375 (4)
H7	0.2108	0.7516	−0.2194	0.045*
C8	0.36336 (11)	0.5446 (3)	0.18686 (14)	0.0332 (4)
C9	0.34856 (13)	0.3947 (3)	0.25296 (15)	0.0404 (5)
H9	0.3195	0.2525	0.2286	0.048*
C10	0.37686 (13)	0.4557 (4)	0.35513 (16)	0.0448 (5)
H10	0.3670	0.3547	0.4015	0.054*
C11	0.41948 (12)	0.6623 (4)	0.39062 (15)	0.0418 (5)
H11	0.4382	0.7039	0.4609	0.050*
C12	0.43477 (13)	0.8085 (3)	0.32332 (15)	0.0411 (5)
H12	0.4645	0.9500	0.3477	0.049*
C13	0.40687 (12)	0.7493 (3)	0.22053 (15)	0.0377 (4)
H13	0.4177	0.8486	0.1742	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0470 (3)	0.0337 (3)	0.0407 (3)	0.0093 (2)	0.0133 (2)	0.0033 (2)
Cl2	0.0378 (3)	0.0472 (3)	0.0451 (3)	−0.0041 (2)	0.0199 (2)	−0.0028 (2)
O1	0.0306 (7)	0.0447 (8)	0.0353 (7)	0.0066 (5)	0.0134 (5)	−0.0046 (6)
O2	0.0288 (6)	0.0427 (8)	0.0357 (7)	0.0091 (5)	0.0108 (5)	0.0002 (6)
C1	0.0302 (9)	0.0314 (10)	0.0352 (10)	0.0054 (7)	0.0126 (8)	0.0009 (8)
C2	0.0297 (9)	0.0371 (10)	0.0318 (9)	0.0045 (7)	0.0146 (7)	−0.0024 (8)
C3	0.0459 (11)	0.0300 (10)	0.0354 (10)	0.0030 (8)	0.0182 (9)	0.0028 (8)
C4	0.0406 (10)	0.0394 (11)	0.0361 (10)	−0.0066 (8)	0.0183 (8)	−0.0059 (9)
C5	0.0385 (10)	0.0471 (12)	0.0277 (9)	0.0000 (8)	0.0157 (8)	−0.0011 (9)
C6	0.0474 (11)	0.0417 (11)	0.0335 (10)	−0.0002 (9)	0.0213 (9)	0.0068 (9)
C7	0.0411 (10)	0.0368 (11)	0.0398 (10)	−0.0064 (8)	0.0222 (9)	−0.0028 (9)
C8	0.0253 (9)	0.0366 (10)	0.0341 (9)	0.0071 (7)	0.0090 (7)	0.0029 (8)
C9	0.0337 (10)	0.0350 (11)	0.0450 (11)	0.0009 (8)	0.0092 (8)	0.0085 (9)
C10	0.0366 (10)	0.0520 (13)	0.0420 (11)	0.0004 (9)	0.0128 (9)	0.0154 (10)
C11	0.0320 (10)	0.0557 (13)	0.0347 (10)	0.0041 (9)	0.0108 (8)	0.0024 (9)
C12	0.0319 (10)	0.0413 (12)	0.0428 (11)	−0.0037 (8)	0.0085 (8)	−0.0018 (9)
C13	0.0318 (10)	0.0407 (11)	0.0394 (11)	−0.0008 (8)	0.0136 (8)	0.0081 (9)

Geometric parameters (Å, º) top

Cl1—C1	1.8078 (18)	C6—C7	1.385 (3)
Cl2—C1	1.8154 (18)	C6—H6	0.9500
O1—C1	1.359 (2)	C7—H7	0.9500
O1—C2	1.418 (2)	C8—C13	1.373 (3)
O2—C1	1.360 (2)	C8—C9	1.381 (3)
O2—C8	1.415 (2)	C9—C10	1.380 (3)
C2—C3	1.377 (3)	C9—H9	0.9500
C2—C7	1.378 (3)	C10—C11	1.382 (3)
C3—C4	1.386 (3)	C10—H10	0.9500
C3—H3	0.9500	C11—C12	1.384 (3)
C4—C5	1.383 (3)	C11—H11	0.9500
C4—H4	0.9500	C12—C13	1.386 (3)
C5—C6	1.383 (3)	C12—H12	0.9500
C5—H5	0.9500	C13—H13	0.9500

C1—O1—C2	120.43 (13)	C7—C6—H6	119.7
C1—O2—C8	119.92 (13)	C2—C7—C6	118.23 (18)
O1—C1—O2	103.77 (13)	C2—C7—H7	120.9
O1—C1—Cl1	112.41 (12)	C6—C7—H7	120.9
O2—C1—Cl1	111.39 (13)	C13—C8—C9	121.85 (18)
O1—C1—Cl2	112.36 (12)	C13—C8—O2	118.89 (16)
O2—C1—Cl2	111.80 (12)	C9—C8—O2	118.98 (17)
Cl1—C1—Cl2	105.29 (9)	C10—C9—C8	118.69 (19)
C3—C2—C7	122.22 (17)	C10—C9—H9	120.7
C3—C2—O1	118.32 (16)	C8—C9—H9	120.7
C7—C2—O1	119.22 (16)	C9—C10—C11	120.60 (19)
C2—C3—C4	118.85 (18)	C9—C10—H10	119.7
C2—C3—H3	120.6	C11—C10—H10	119.7
C4—C3—H3	120.6	C10—C11—C12	119.71 (19)
C5—C4—C3	119.95 (18)	C10—C11—H11	120.1
C5—C4—H4	120.0	C12—C11—H11	120.1
C3—C4—H4	120.0	C11—C12—C13	120.33 (19)
C4—C5—C6	120.11 (18)	C11—C12—H12	119.8
C4—C5—H5	119.9	C13—C12—H12	119.8
C6—C5—H5	119.9	C8—C13—C12	118.81 (18)
C5—C6—C7	120.59 (18)	C8—C13—H13	120.6
C5—C6—H6	119.7	C12—C13—H13	120.6

C2—O1—C1—O2	177.16 (14)	C3—C2—C7—C6	2.3 (3)
C2—O1—C1—Cl1	−62.36 (19)	O1—C2—C7—C6	176.56 (16)
C2—O1—C1—Cl2	56.20 (19)	C5—C6—C7—C2	−0.6 (3)
C8—O2—C1—O1	178.00 (15)	C1—O2—C8—C13	−94.4 (2)
C8—O2—C1—Cl1	56.83 (19)	C1—O2—C8—C9	91.6 (2)
C8—O2—C1—Cl2	−60.67 (19)	C13—C8—C9—C10	1.3 (3)
C1—O1—C2—C3	−91.8 (2)	O2—C8—C9—C10	175.07 (16)
C1—O1—C2—C7	93.7 (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—C13	0.5 (3)
C2—C3—C4—C5	0.8 (3)	C9—C8—C13—C12	−1.4 (3)
C3—C4—C5—C6	0.9 (3)	O2—C8—C13—C12	−175.20 (16)
C4—C5—C6—C7	−1.0 (3)	C11—C12—C13—C8	0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl1ⁱ	0.95	2.81	3.723 (2)	161
C10—H10···O1ⁱⁱ	0.95	2.52	3.345 (3)	145

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀Cl₂O₂
M_r	269.11
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	15.8380 (4), 5.8973 (2), 14.2517 (4)
β (°)	114.751 (2)
V (Å³)	1208.85 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.52
Crystal size (mm)	0.22 × 0.20 × 0.15

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9193, 2766, 2138
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.094, 1.08
No. of reflections	2766
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.29

Computer programs: COLLECT (Nonius, 2004), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996).

Selected geometric parameters (Å, º) top

O1—C1	1.359 (2)	O2—C1	1.360 (2)

O1—C1—O2	103.77 (13)	Cl1—C1—Cl2	105.29 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl1ⁱ	0.95	2.81	3.723 (2)	161
C10—H10···O1ⁱⁱ	0.95	2.52	3.345 (3)	145

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

Acknowledgements

The authors thank Dr Peter Mayer for technical assistance.

References

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