rac-2-[(2-Chloro-phen-yl)(4-chloro-phen-yl)meth-yl]-1,3-dioxolane.

The title compound, C(16)H(14)Cl(2)O(2), is a chiral mitotane derivative that contains a dioxolane ring and crystallizes from methanol as a racemic mixture. It was obtained in high yield from mitotane and ethyl-eneglycol in alkaline medium, followed by neutralization with sulfuric acid and extraction with ethyl acetate. The mol-ecular structure is stabilized by an intra-molecular C- H⋯ O hydrogen bond. The dihedral angle between the aromatic rings is 80.1 (2)°. The dioxolane ring adopts a puckered envelope conformation with an O atom as the flap.

Related literature

For related dioxolane geometry, see: Bolte et al. (1997 ▶). For organochlorines, see: Smith & Bennett (1977 ▶); Canti­llana & Eriksson (2009 ▶); Jabbar et al. (2006 ▶). For dechlorination of organochlorine compounds, see: Grummitt et al. (1946 ▶). For their adrenolytic activity, see: Fassnacht et al. (2010 ▶); Berruti et al. (2005 ▶). For organochlorine as insecticide metabolites in bioremediation studies, see: Purnomo et al. (2011 ▶); Fuentes et al. (2010 ▶); Matsumoto et al. (2009 ▶). For the use of mitotane [systematic name: 2-(2-chloro­phen­yl)-2-(4-chloro­phen­yl)-1,1-dichloro­ethane] in adrenocortical carcinoma treatment, see: Maluf et al. (2011 ▶); Rosati et al. (2008) ▶; Terzolo et al. (2007 ▶). For structure–activity studies of mitotane derivatives, see: Bleiberg & Larson (1973 ▶); Schteingart et al. (1993 ▶).

Experimental

Crystal data

C16H14Cl2O2

M = 309.17

Triclinic,

a = 7.5728 (2) Å

b = 10.2268 (2) Å

c = 11.2858 (2) Å

α = 63.357 (1)°

β = 84.021 (1)°

γ = 71.194 (1)°

V = 738.68 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.44 mm−1

T = 296 K

0.59 × 0.56 × 0.29 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.783, T max = 0.883

24953 measured reflections

4556 independent reflections

3654 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.117

S = 1.05

4556 reflections

181 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.29 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812023781/bx2412sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023781/bx2412Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812023781/bx2412Isup3.cml

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

C16H14Cl2O2	Z = 2
Mr = 309.17	F(000) = 320
Triclinic, P1	Dx = 1.39 Mg m−3
a = 7.5728 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.2268 (2) Å	Cell parameters from 4556 reflections
c = 11.2858 (2) Å	θ = 4.2–57.4°
α = 63.357 (1)°	µ = 0.44 mm−1
β = 84.021 (1)°	T = 296 K
γ = 71.194 (1)°	Block, colourless
V = 738.68 (3) Å3	0.59 × 0.56 × 0.29 mm

Bruker SMART APEXII CCD diffractometer	4556 independent reflections
Radiation source: sealed tube	3654 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
phi & ω scans	θmax = 30.7°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.783, Tmax = 0.883	k = −14→14
24953 measured reflections	l = −16→16

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)] = 0.040	H-atom parameters constrained
wR(F2) = 0.117	w = 1/[σ2(Fo2) + (0.0556P)2 + 0.1712P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
4556 reflections	Δρmax = 0.37 e Å−3
181 parameters	Δρmin = −0.29 e Å−3
0 restraints

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

	x	y	z	Uiso*/Ueq
Cl1	0.77214 (6)	0.38255 (5)	0.01175 (4)	0.06217 (13)
Cl2	1.10734 (6)	−0.41352 (5)	0.31682 (5)	0.06334 (13)
C6	0.51390 (16)	0.19844 (14)	0.17862 (11)	0.0346 (2)
H6	0.5131	0.2544	0.0818	0.041*
C13	0.65594 (16)	0.04056 (14)	0.21569 (11)	0.0335 (2)
C15	0.86840 (19)	−0.19344 (15)	0.37708 (13)	0.0417 (3)
H15	0.9191	−0.2545	0.4634	0.05*
C14	0.73344 (18)	−0.05219 (15)	0.34448 (12)	0.0379 (2)
H14	0.6938	−0.0186	0.4098	0.046*
C7	0.57303 (16)	0.28987 (14)	0.23302 (13)	0.0377 (2)
C16	0.92668 (18)	−0.24239 (15)	0.27971 (14)	0.0414 (3)
C2	0.31576 (17)	0.19008 (16)	0.21133 (13)	0.0406 (3)
H2	0.2303	0.2932	0.1918	0.049*
C17	0.8485 (2)	−0.15571 (17)	0.15211 (14)	0.0479 (3)
H17	0.8857	−0.1914	0.088	0.058*
C18	0.7135 (2)	−0.01446 (16)	0.12117 (13)	0.0437 (3)
H18	0.6605	0.0446	0.0353	0.052*
C8	0.69189 (19)	0.37655 (15)	0.16361 (16)	0.0458 (3)
C9	0.7506 (2)	0.4593 (2)	0.2126 (2)	0.0655 (5)
H9	0.8287	0.5168	0.1639	0.079*
C5	0.1532 (2)	0.0332 (2)	0.34243 (16)	0.0560 (4)
H5A	0.033	0.1052	0.3428	0.067*
H5B	0.1653	−0.0658	0.4177	0.067*
C12	0.5178 (2)	0.28940 (17)	0.35447 (16)	0.0483 (3)
H12	0.4384	0.2333	0.4035	0.058*
C11	0.5776 (3)	0.3703 (2)	0.4049 (2)	0.0630 (4)
H11	0.5397	0.3666	0.4872	0.076*
C4	0.1763 (3)	0.0197 (2)	0.21519 (17)	0.0620 (4)
H4A	0.2555	−0.0822	0.2289	0.074*
H4B	0.0563	0.0397	0.1765	0.074*
C10	0.6927 (3)	0.4557 (2)	0.3333 (2)	0.0729 (5)
H10	0.7314	0.511	0.3664	0.088*
O1	0.30232 (14)	0.08905 (13)	0.34445 (9)	0.0480 (2)
O2	0.26110 (15)	0.13305 (14)	0.13264 (10)	0.0536 (3)

	U11	U22	U33	U12	U13	U23
Cl1	0.0564 (2)	0.0582 (2)	0.0640 (2)	−0.02759 (18)	0.01797 (18)	−0.01678 (18)
Cl2	0.0595 (2)	0.0481 (2)	0.0721 (3)	0.00034 (16)	−0.00404 (19)	−0.02775 (19)
C6	0.0336 (5)	0.0369 (6)	0.0318 (5)	−0.0132 (4)	0.0005 (4)	−0.0123 (4)
C13	0.0329 (5)	0.0370 (6)	0.0337 (5)	−0.0155 (4)	0.0016 (4)	−0.0151 (4)
C15	0.0460 (7)	0.0399 (6)	0.0344 (6)	−0.0138 (5)	−0.0027 (5)	−0.0109 (5)
C14	0.0439 (6)	0.0405 (6)	0.0315 (5)	−0.0151 (5)	0.0027 (4)	−0.0165 (5)
C7	0.0319 (5)	0.0330 (5)	0.0463 (6)	−0.0083 (4)	−0.0025 (5)	−0.0161 (5)
C16	0.0401 (6)	0.0364 (6)	0.0484 (7)	−0.0119 (5)	0.0004 (5)	−0.0188 (5)
C2	0.0348 (6)	0.0478 (7)	0.0385 (6)	−0.0163 (5)	−0.0002 (4)	−0.0157 (5)
C17	0.0540 (8)	0.0516 (8)	0.0451 (7)	−0.0119 (6)	−0.0003 (6)	−0.0297 (6)
C18	0.0487 (7)	0.0488 (7)	0.0348 (6)	−0.0119 (6)	−0.0042 (5)	−0.0205 (5)
C8	0.0371 (6)	0.0369 (6)	0.0601 (8)	−0.0121 (5)	0.0005 (5)	−0.0177 (6)
C9	0.0532 (9)	0.0539 (9)	0.1019 (14)	−0.0269 (7)	0.0039 (9)	−0.0379 (9)
C5	0.0488 (8)	0.0723 (10)	0.0500 (8)	−0.0347 (7)	0.0054 (6)	−0.0195 (7)
C12	0.0481 (7)	0.0489 (7)	0.0559 (8)	−0.0162 (6)	0.0048 (6)	−0.0295 (7)
C11	0.0651 (10)	0.0654 (10)	0.0756 (11)	−0.0147 (8)	−0.0005 (8)	−0.0483 (9)
C4	0.0702 (10)	0.0756 (11)	0.0547 (9)	−0.0449 (9)	0.0033 (7)	−0.0260 (8)
C10	0.0665 (11)	0.0683 (11)	0.1120 (16)	−0.0252 (9)	−0.0017 (10)	−0.0592 (12)
O1	0.0450 (5)	0.0713 (7)	0.0346 (4)	−0.0322 (5)	0.0057 (4)	−0.0203 (4)
O2	0.0545 (6)	0.0796 (7)	0.0372 (5)	−0.0400 (6)	−0.0004 (4)	−0.0209 (5)

Cl1—C8	1.7388 (16)	C17—C18	1.387 (2)
Cl2—C16	1.7402 (13)	C17—H17	0.93
C6—C7	1.5146 (17)	C18—H18	0.93
C6—C13	1.5189 (16)	C8—C9	1.390 (2)
C6—C2	1.5278 (17)	C9—C10	1.375 (3)
C6—H6	0.98	C9—H9	0.93
C13—C18	1.3885 (18)	C5—O1	1.4261 (17)
C13—C14	1.3926 (16)	C5—C4	1.491 (2)
C15—C16	1.3794 (19)	C5—H5A	0.97
C15—C14	1.3843 (19)	C5—H5B	0.97
C15—H15	0.93	C12—C11	1.390 (2)
C14—H14	0.93	C12—H12	0.93
C7—C12	1.389 (2)	C11—C10	1.373 (3)
C7—C8	1.3980 (18)	C11—H11	0.93
C16—C17	1.380 (2)	C4—O2	1.4181 (19)
C2—O1	1.4067 (16)	C4—H4A	0.97
C2—O2	1.4131 (17)	C4—H4B	0.97
C2—H2	0.98	C10—H10	0.93
C7—C6—C13	111.98 (9)	C17—C18—H18	119.3
C7—C6—C2	113.89 (10)	C13—C18—H18	119.3
C13—C6—C2	112.22 (10)	C9—C8—C7	121.93 (15)
C7—C6—H6	106	C9—C8—Cl1	117.88 (12)
C13—C6—H6	106	C7—C8—Cl1	120.19 (11)
C2—C6—H6	106	C10—C9—C8	119.73 (16)
C18—C13—C14	118.17 (12)	C10—C9—H9	120.1
C18—C13—C6	120.66 (11)	C8—C9—H9	120.1
C14—C13—C6	121.16 (11)	O1—C5—C4	102.77 (12)
C16—C15—C14	119.10 (12)	O1—C5—H5A	111.2
C16—C15—H15	120.5	C4—C5—H5A	111.2
C14—C15—H15	120.5	O1—C5—H5B	111.2
C15—C14—C13	121.18 (12)	C4—C5—H5B	111.2
C15—C14—H14	119.4	H5A—C5—H5B	109.1
C13—C14—H14	119.4	C7—C12—C11	121.95 (15)
C12—C7—C8	116.50 (12)	C7—C12—H12	119
C12—C7—C6	122.60 (11)	C11—C12—H12	119
C8—C7—C6	120.88 (12)	C10—C11—C12	119.98 (18)
C15—C16—C17	121.23 (12)	C10—C11—H11	120
C15—C16—Cl2	119.47 (10)	C12—C11—H11	120
C17—C16—Cl2	119.26 (11)	O2—C4—C5	104.37 (13)
O1—C2—O2	106.64 (11)	O2—C4—H4A	110.9
O1—C2—C6	112.75 (10)	C5—C4—H4A	110.9
O2—C2—C6	108.83 (11)	O2—C4—H4B	110.9
O1—C2—H2	109.5	C5—C4—H4B	110.9
O2—C2—H2	109.5	H4A—C4—H4B	108.9
C6—C2—H2	109.5	C11—C10—C9	119.91 (16)
C16—C17—C18	118.86 (12)	C11—C10—H10	120
C16—C17—H17	120.6	C9—C10—H10	120
C18—C17—H17	120.6	C2—O1—C5	104.87 (10)
C17—C18—C13	121.38 (12)	C2—O2—C4	108.24 (11)
C7—C6—C13—C18	−133.67 (12)	C14—C13—C18—C17	−1.9 (2)
C2—C6—C13—C18	96.78 (13)	C6—C13—C18—C17	177.41 (12)
C7—C6—C13—C14	45.63 (15)	C12—C7—C8—C9	−0.6 (2)
C2—C6—C13—C14	−83.91 (14)	C6—C7—C8—C9	−178.89 (13)
C16—C15—C14—C13	0.08 (19)	C12—C7—C8—Cl1	179.03 (10)
C18—C13—C14—C15	1.94 (18)	C6—C7—C8—Cl1	0.74 (17)
C6—C13—C14—C15	−177.38 (11)	C7—C8—C9—C10	0.6 (3)
C13—C6—C7—C12	−92.97 (14)	Cl1—C8—C9—C10	−179.00 (14)
C2—C6—C7—C12	35.70 (17)	C8—C7—C12—C11	−0.2 (2)
C13—C6—C7—C8	85.22 (14)	C6—C7—C12—C11	178.07 (13)
C2—C6—C7—C8	−146.12 (12)	C7—C12—C11—C10	0.9 (3)
C14—C15—C16—C17	−2.2 (2)	O1—C5—C4—O2	−28.32 (18)
C14—C15—C16—Cl2	175.65 (10)	C12—C11—C10—C9	−0.9 (3)
C7—C6—C2—O1	−74.72 (14)	C8—C9—C10—C11	0.1 (3)
C13—C6—C2—O1	53.83 (15)	O2—C2—O1—C5	−31.23 (15)
C7—C6—C2—O2	167.18 (10)	C6—C2—O1—C5	−150.62 (12)
C13—C6—C2—O2	−64.28 (13)	C4—C5—O1—C2	36.44 (17)
C15—C16—C17—C18	2.2 (2)	O1—C2—O2—C4	12.74 (16)
Cl2—C16—C17—C18	−175.63 (11)	C6—C2—O2—C4	134.64 (13)
C16—C17—C18—C13	−0.1 (2)	C5—C4—O2—C2	9.89 (18)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Cl1	0.98	2.57	3.0566 (13)	111
C12—H12···O1	0.93	2.38	3.046 (2)	128

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O1	0.93	2.38	3.046 (2)	128