1-Chloro-3,6-di­methoxy-2,5-di­methyl­benzene and 1-chloro-3,6-di­methoxy-2,4-di­methyl­benzene

The title compounds, 1-chloro-3,6-di­methoxy-2,5-di­methyl­benzene, (IIIa), and 1-­chloro-3,6-di­methoxy-2,4-di­methyl­benzene, (IIIb), both C₁₀H₁₃ClO₂, were obtained from 2,5- and 2,6-di­methyl-1,4-benzo­quinone, respectively, and are intermediates in the synthesis of ammonium quinone derivatives. The isomers have different substituents around the methoxy groups and crystallize in different space groups. In both mol­ecules, the methoxy groups each have different orientations with respect to the benzene ring. In both cases, one methoxy group lies in the plane of the ring and can participate in conjugation with the aromatic system, while the second is almost perpendicular to the plane of the aromatic ring. The C-O-C bond angles around these substituents are also different: 117.5 (4) and 118.2 (3)° in (IIIa) and (IIIb), respectively, when the methoxy groups lie in the plane of the ring, and 114.7 (3) and 113.6 (3)° in (IIIa) and (IIIb), respectively, when they are out of the plane of the ring.

S1. Comment

We have been engaged in the synthesis of ammonium quinone derivatives as electron acceptors for charge-transfer studies, and had occasion to prepare the two chlorodimethoxydimethylbenzene isomers, (IIIa) and (IIIb), as precursors to our targets. The chlorine substituents were introduced in order to prepare quinones with an electron-withdrawing group. These compounds were synthesized in a two-step sequence, namely treatment of a dimethylbenzoquinone with methanolic hydrogen chloride followed by O-methylation. For example, in the synthesis of (IIIa), 2,5-dimethyl-1,4-benzoquinone, (Ia), was treated with methanolic hydrogen chloride to give a quantitative yield of 2-chloro-3,6-dimethyl-4-methoxyphenol, (IIa). This latter species was then methylated under phase-transfer conditions with dimethyl sulfate to give a 96% yield of the diether (IIIa). The synthesis of (IIIb) was similar, but gave lower yields along with more side products in each step of this sequence, for reasons which are not clear. Starting with (IIIa) and (IIIb), we also synthesized unexpected dimers, using amidomethylation reactions (Wiedenfeld et al., 2004). \sch

Isomers (IIIa) and (IIIb) have different substituents around the methoxy groups on the adjacent atoms of the ring and crystallize in different space groups (Figs. 1 and 2). In both molecules, the methoxy groups each have different orientations with respect to the benzene ring. In both cases, one lies in the plane of the ring and can participate in conjugation with the aromatic system [torsion angles are C2—C3—O2—C9 − 179.4 (4)° in (IIIa) and C1—C6—O1—C7 − 179.9 (4)° in (IIIb)], and the second is almost perpendicular to the plane of the aromatic ring [torsion angles are C1—C6—O1—C7 86.9 (5)° in (IIIa) and C2—C3—O2—C9 94.0 (4)° in (IIIb)].

Such different orientations of the methoxy groups about the benzene ring in (IIIa) and (IIIb) account for the distortion of the bond angles. Thus, we found an increase in C3—O2—C9 to 117.5 (4)° in (IIIa) and in C6—O1—C7 to 118.2 (3)° in (IIIb), for the in-plane methoxy group. For the out-of-plane methoxy group, C6—O1—C7 and C3—O2—C9 are distinctly lower, at 114.7 (3)° in (IIIa) and 113.6 (3)° in (IIIb), respectively. We have previously found such effects in related compounds (Wiedenfeld et al., 2003, 2004). Such geometry is usual for compounds containing OCH₃ groups with different orientations about aromatic rings (Gallagher et al., 2001). Other bond lengths and angles in the title molecules have expected values (Allen et al., 1987).

Analysis of the crystal packing of compounds (IIIa) and (IIIb) shows that there are very weak intermolecular contacts [O1···H7B(x, y − 1, z) 2.54 Å in (IIIa) and O1···H8B(1 − x, 1/2 + y, 1 − z) 2.59 Å in (IIIb)], which can be considered to be weak hydrogen bonds that link molecules in the crystals with parameters O1···C7 3.461 (5) Å, C7—H7B 0.96 Å and C7—H7B···O1 161° in (IIIa), and O1···C8 3.524 (5) Å, C8—H8B 0.96 Å and O1···C8—H8B 164° in (IIIb).

In the crystal of (IIIb), the intermolecular distances Cl1···C5(-x, 1/2 + y, 1 − z) [3.587 (5) Å] and Cl1···C6(-x, 1/2 + y, 1 − z) [3.577 (5) Å] are slightly greater than the sum of their van der Waals radii (Rowland & Taylor, 1996) but shorter than in (IIIa), where the distance Cl1···C4(x − 1/2, 1/2 − y, z) is 3.613 (5) Å. Such weak intermolecular interactions could play a significant role in the stability of the crystal, especially in the case of (IIIb), which is more stable than (IIIa) under X-ray beams (see Experimental). The other intermolecular distances in both crystals are greater than the sum of the van der Waals radii of the atoms.

S2. Experimental

For the preparation of 2-chloro-3,6-dimethyl-4-methoxyphenol, (IIa), 2,5-dimethyl-1,4-benzoquinone, (Ia) (1.36 g, 10 mmole), was added to an ice-cold solution of MeOH (70 ml) containing AcCl (7 ml, 0.1 mol) and stirred overnight at room temperature. The solution was then concentrated on a rotary evaporator and vacuum dried, giving 1.86 g (100%) of (IIa) as a pink crystalline solid, pure by NMR. ¹H NMR (DMSO-d₆, δ, p.p.m.): 8.41 (s, 1H, OH), 6.72 (s, 1H, Ar—H), 3.71 (s, 3H, OCH₃), 2.19 (s, 3H, Ar—CH₃-3^*), 2.14 (s, 3H, Ar—CH₃-6^*); ¹³C NMR (DMSO-d₆, δ, p.p.m.): 150.4 (Ar—C4), 144.4 (Ar—C1), 123.7 (Ar—C3), 122.5 (Ar—C2), 121.4 (Ar—C6), 111.8 (Ar—C5), 56.0 (OCH₃), 16.9 (Ar—CH₃-6), 12.9 (Ar—CH₃-3). 3-Chloro-2,6-dimethyl-4-methoxyphenol, (IIb), was prepared analogously to (IIa), starting from 2,6-dimethyl-1,4-benzoquinone, (Ib). ¹H NMR (CDCl₃, δ, p.p.m.): 6.60 (s, 1H, Ar—H), 4.38 (br s, 1H, OH), 3.83 (s, 3H, OCH₃), 2.32 (s, 3H, Ar—CH₃-2^*), 2.24 (s, 3H, Ar—CH₃-6^*). Compound (IIIa) was prepared as follows. To a solution of (IIa) (1.86 g, 10 mmol) and (ⁿBu)₄NBr (0.97 g, 3 mmol, 0.3 equivalents) in CH₂Cl₂ (30 ml) was added a solution of KOH (1.98 g, 30 mmol, 3 equivalents at 85%) in H₂O (30 ml). To the vigorously stirred mixture was added Me₂SO₄ (2.85 ml, 30 mmol, 3 equivalents) in three portions over 6 h. After a further 3 h, 2 N aqueous NaOH (12 ml) was added and the mixture stirred overnight. Extractive workup with CH₂Cl₂ gave an orange oil which, after chromatography on silica gel using 25:1 hexanes:EtOAc as eluant, afforded 1.92 g (96%) of pure product as a colourless oil that crystallized slowly. After recrystallization from 10% EtOAc in hexane, the m.p. was 321–322 K. ¹H NMR (CDCl₃, δ, p.p.m.): 6.56 (s, 1H, Ar—H), 3.79 (s, 3H, OCH₃-6*), 3.76 (s, 3H, OCH₃-3*), 2.29 (s, 3H, Ar—CH₃-2^*), 2.24 (s, 3H, Ar—CH₃-5^*); ¹³C NMR (CDCl₃, δ, p.p.m.): 153.9 (Ar—C3), 148.0 (Ar—C6), 129.2 (Ar—C5,) 128.9 (Ar—C1), 123.6 (Ar—C2), 110.8 (Ar—C4), 60.1 (OCH₃-6), 55.9 (OCH₃-3), 16.4 (Ar—CH₃-5), 12.8 (Ar—CH₃-2). Compound (IIIb) was prepared as follows. O-Methylation of (IIb) was analogous to that for (IIa). After recrystallization from 10% EtOAc in hexane, the m.p. was 323–324 K. ¹H NMR (CDCl₃, δ, p.p.m.): 6.61 (s, 1H, Ar—H), 3.85 (s, 3H, OCH₃-6), 3.66 (s, 3H, OCH₃-3), 2.33 (s, 3H, Ar—CH₃-2), 2.28 (s, 3H, Ar—CH₃-4); ¹³C NMR (CDCl₃, δ, p.p.m.): 151.3 (Ar—C6), 150.9 (Ar—C3), 130.8 (Ar—C2), 129.3 (Ar—C4), 120.4 (Ar—C1), 111.3 (Ar—C5), 60.2 (OCH₃-3), 56.3 (OCH₃-6), 16.3 (Ar—CH₃-4), 13.6 (Ar—CH₃-2). For X-ray analysis, the crystals of both compounds were grown from 10% ethyl acetate in hexanes by slow evaporation at room temperature. X-ray investigations revealed that the crystals of these compounds exhibit different behaviour under an X-ray beam. Thus, the structure of compound (IIIa) was investigated several times, but the crystals decomposed during the experiments, while crystals of (IIIb) did not decay. For (IIIa), the crystal was coated with a two-component epoxy glue, which successfully protected the crystal and prevented further decay.

S3. Refinement

All H atoms were placed in geometrically calculated positions and refined using a riding model, with C—H distances of 0.93 Å for aromatic H and 0.96 Å for CH₃ groups, and with U_iso(H) = 1.2U_eq(C). Please check added text.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989) for (IIIa); CAD-4 Software (Enraf-Nonuis, 1989) for (IIIb). For both compounds, cell refinement: CAD-4 Software; data reduction: SHELXTL-Plus (Sheldrick, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the molecule of (IIIa), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the molecule of (IIIb), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

(IIIa) 1-chloro-3,6-dimethoxy-2,5-dimethylbenzene

Crystal data

C10H13ClO2	Dx = 1.316 Mg m^−3
Mr = 200.65	Melting point: 321 K
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 24 reflections
a = 14.490 (3) Å	θ = 11–12°
b = 4.1470 (8) Å	µ = 0.34 mm^−1
c = 16.848 (3) Å	T = 295 K
V = 1012.4 (3) Å^3	Prism, colourless
Z = 4	0.50 × 0.40 × 0.30 mm
F(000) = 424

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.098
Radiation source: fine-focus sealed tube	θmax = 30.0°, θmin = 2.8°
Graphite monochromator	h = −20→20
θ/2θ scans	k = −5→0
2961 measured reflections	l = 0→23
1507 independent reflections	3 standard reflections every 97 reflections
1010 reflections with I > 2σ(I)	intensity decay: 3%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.063	H-atom parameters constrained
wR(F^2) = 0.163	w = 1/[σ^2(Fo^2) + (0.09P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
1507 reflections	Δρmax = 0.60 e Å^−3
122 parameters	Δρmin = −0.47 e Å^−3
1 restraint	Absolute structure: Flack (1983), with xx Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.18 (14)

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. All H atoms were placed in geometrically calculated positions and refined using a riding model with C—H distances for (Ph)C—H of 0.93 Å and 0.96 Å for CH₃ groups.

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

	x	y	z	Uiso*/Ueq
Cl1	0.73848 (6)	0.1524 (2)	0.32326 (9)	0.0585 (3)
O1	0.8515 (2)	0.3172 (7)	0.18623 (16)	0.0500 (7)
O2	0.9963 (2)	0.6879 (8)	0.47511 (19)	0.0563 (8)
C1	0.8439 (2)	0.3514 (7)	0.3283 (3)	0.0391 (6)
C2	0.8798 (3)	0.4406 (10)	0.4012 (2)	0.0405 (8)
C3	0.9633 (3)	0.6035 (9)	0.4008 (2)	0.0419 (8)
C4	1.0082 (2)	0.6805 (8)	0.3308 (3)	0.0434 (7)
H4A	1.0633	0.7956	0.3324	0.052*
C5	0.9711 (3)	0.5859 (10)	0.2572 (2)	0.0411 (8)
C6	0.8878 (3)	0.4211 (9)	0.2562 (2)	0.0389 (8)
C7	0.7853 (3)	0.5273 (13)	0.1521 (3)	0.0631 (11)
H7A	0.7699	0.4536	0.0998	0.095*
H7B	0.8104	0.7412	0.1491	0.095*
H7C	0.7307	0.5295	0.1845	0.095*
C8	1.0208 (3)	0.6649 (11)	0.1820 (3)	0.0573 (11)
H8A	1.0103	0.4969	0.1438	0.086*
H8B	1.0857	0.6828	0.1924	0.086*
H8D	0.9982	0.8657	0.1613	0.086*
C9	1.0810 (4)	0.8581 (13)	0.4785 (3)	0.0638 (12)
H9A	1.0916	0.9312	0.5318	0.096*
H9D	1.0785	1.0403	0.4435	0.096*
H9B	1.1305	0.7181	0.4627	0.096*
C10	0.8348 (4)	0.3497 (13)	0.4788 (3)	0.0559 (11)
H10D	0.7700	0.3165	0.4705	0.084*
H10A	0.8437	0.5200	0.5166	0.084*
H10B	0.8621	0.1547	0.4986	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0523 (5)	0.0547 (5)	0.0686 (6)	−0.0131 (4)	0.0072 (6)	−0.0053 (6)
O1	0.0616 (16)	0.0432 (14)	0.0450 (13)	0.0063 (12)	−0.0054 (13)	−0.0073 (12)
O2	0.0634 (19)	0.061 (2)	0.0444 (15)	0.0006 (17)	−0.0070 (13)	−0.0038 (15)
C1	0.0373 (12)	0.0341 (12)	0.0459 (14)	0.0011 (12)	0.0061 (17)	0.0020 (18)
C2	0.0448 (19)	0.0360 (19)	0.0409 (16)	0.0039 (16)	0.0064 (13)	0.0046 (16)
C3	0.049 (2)	0.0371 (18)	0.0397 (17)	0.0061 (16)	−0.0048 (14)	0.0005 (17)
C4	0.0413 (13)	0.0433 (16)	0.0455 (16)	0.0015 (12)	−0.0041 (16)	0.005 (2)
C5	0.0407 (19)	0.044 (2)	0.0388 (16)	0.0030 (16)	0.0024 (13)	0.0040 (16)
C6	0.049 (2)	0.0310 (18)	0.0364 (15)	0.0064 (16)	0.0008 (13)	0.0011 (14)
C7	0.072 (3)	0.053 (2)	0.064 (2)	0.007 (2)	−0.023 (2)	−0.004 (2)
C8	0.064 (2)	0.066 (3)	0.0421 (19)	−0.008 (2)	0.0075 (18)	0.009 (2)
C9	0.068 (3)	0.062 (3)	0.061 (2)	0.003 (3)	−0.015 (2)	−0.015 (2)
C10	0.064 (3)	0.061 (3)	0.0419 (17)	0.000 (2)	0.0135 (17)	0.0074 (18)

Geometric parameters (Å, º)

Cl1—C1	1.738 (3)	C5—C8	1.494 (6)
O1—C6	1.362 (5)	C7—H7A	0.9600
O1—C7	1.418 (5)	C7—H7B	0.9600
O2—C3	1.385 (5)	C7—H7C	0.9600
O2—C9	1.417 (6)	C8—H8A	0.9600
C1—C2	1.384 (6)	C8—H8B	0.9600
C1—C6	1.402 (6)	C8—H8D	0.9600
C2—C3	1.386 (7)	C9—H9A	0.9600
C2—C10	1.509 (6)	C9—H9D	0.9600
C3—C4	1.385 (6)	C9—H9B	0.9600
C4—C5	1.406 (6)	C10—H10D	0.9600
C4—H4A	0.9300	C10—H10A	0.9600
C5—C6	1.387 (6)	C10—H10B	0.9600
C6—O1—C7	114.7 (3)	H7A—C7—H7B	109.5
C3—O2—C9	117.5 (4)	O1—C7—H7C	109.5
C2—C1—C6	122.9 (3)	H7A—C7—H7C	109.5
C2—C1—Cl1	120.1 (3)	H7B—C7—H7C	109.5
C6—C1—Cl1	117.0 (3)	C5—C8—H8A	109.5
C1—C2—C3	117.1 (4)	C5—C8—H8B	109.5
C1—C2—C10	122.6 (4)	H8A—C8—H8B	109.5
C3—C2—C10	120.2 (4)	C5—C8—H8D	109.5
C4—C3—O2	123.4 (4)	H8A—C8—H8D	109.5
C4—C3—C2	121.8 (4)	H8B—C8—H8D	109.5
O2—C3—C2	114.8 (4)	O2—C9—H9A	109.5
C3—C4—C5	120.4 (3)	O2—C9—H9D	109.5
C3—C4—H4A	119.8	H9A—C9—H9D	109.5
C5—C4—H4A	119.8	O2—C9—H9B	109.5
C6—C5—C4	118.7 (4)	H9A—C9—H9B	109.5
C6—C5—C8	121.1 (4)	H9D—C9—H9B	109.5
C4—C5—C8	120.2 (3)	C2—C10—H10D	109.5
O1—C6—C5	120.2 (4)	C2—C10—H10A	109.5
O1—C6—C1	120.6 (3)	H10D—C10—H10A	109.5
C5—C6—C1	119.1 (3)	C2—C10—H10B	109.5
O1—C7—H7A	109.5	H10D—C10—H10B	109.5
O1—C7—H7B	109.5	H10A—C10—H10B	109.5
C6—C1—C2—C3	−0.5 (5)	C3—C4—C5—C6	1.5 (5)
Cl1—C1—C2—C3	−178.9 (3)	C3—C4—C5—C8	−178.9 (4)
C6—C1—C2—C10	−176.7 (4)	C7—O1—C6—C5	−95.9 (5)
Cl1—C1—C2—C10	4.9 (5)	C7—O1—C6—C1	86.9 (5)
C9—O2—C3—C4	−0.8 (6)	C4—C5—C6—O1	−177.9 (3)
C9—O2—C3—C2	−179.4 (4)	C8—C5—C6—O1	2.5 (6)
C1—C2—C3—C4	1.3 (6)	C4—C5—C6—C1	−0.7 (6)
C10—C2—C3—C4	177.7 (4)	C8—C5—C6—C1	179.8 (4)
C1—C2—C3—O2	179.9 (3)	C2—C1—C6—O1	177.4 (4)
C10—C2—C3—O2	−3.8 (6)	Cl1—C1—C6—O1	−4.2 (4)
O2—C3—C4—C5	179.7 (4)	C2—C1—C6—C5	0.2 (5)
C2—C3—C4—C5	−1.9 (5)	Cl1—C1—C6—C5	178.6 (3)

(IIIb) 1-chloro-3,6-dimethoxy-2,4-dimethylbenzene

Crystal data

C10H13ClO2	F(000) = 212
Mr = 200.65	Dx = 1.307 Mg m^−3
Monoclinic, P21	Melting point: 323 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 6.0740 (12) Å	Cell parameters from 24 reflections
b = 9.1250 (18) Å	θ = 11–12°
c = 9.4450 (19) Å	µ = 0.34 mm^−1
β = 103.11 (3)°	T = 295 K
V = 509.85 (18) Å^3	Prism, colourless
Z = 2	0.45 × 0.35 × 0.25 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.056
Radiation source: fine-focus sealed tube	θmax = 30.0°, θmin = 2.2°
Graphite monochromator	h = 0→8
θ/2θ scans	k = 0→12
1688 measured reflections	l = −13→12
1559 independent reflections	3 standard reflections every 97 reflections
999 reflections with I > 2σ(I)	intensity decay: 3%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.155	w = 1/[σ^2(Fo^2) + (0.09P)^2 + 0.04P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
1559 reflections	Δρmax = 0.31 e Å^−3
122 parameters	Δρmin = −0.20 e Å^−3
1 restraint	Absolute structure: Flack (1983), with xx Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (13)

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. All H atoms were placed in geometrically calculated positions and refined using a riding model with C—H distances for (Ph)C—H of 0.93 Å and 0.96 Å for CH₃ groups.

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

	x	y	z	Uiso*/Ueq
Cl1	0.01454 (17)	0.57590 (14)	0.55551 (10)	0.0737 (4)
O1	0.4088 (5)	0.3990 (3)	0.6443 (3)	0.0661 (7)
O2	0.0608 (5)	0.3965 (4)	0.0534 (3)	0.0696 (8)
C1	0.1424 (6)	0.4760 (4)	0.4399 (4)	0.0519 (8)
C2	0.0481 (6)	0.4804 (4)	0.2909 (4)	0.0523 (8)
C3	0.1549 (6)	0.3989 (4)	0.2006 (3)	0.0539 (8)
C4	0.3471 (7)	0.3168 (4)	0.2552 (4)	0.0544 (9)
C5	0.4346 (7)	0.3163 (4)	0.4042 (4)	0.0548 (8)
H5A	0.5632	0.2612	0.4423	0.066*
C6	0.3348 (6)	0.3958 (4)	0.4975 (3)	0.0496 (7)
C7	0.6065 (8)	0.3182 (6)	0.7079 (4)	0.0725 (12)
H7A	0.6264	0.3175	0.8116	0.109*
H7B	0.7355	0.3632	0.6829	0.109*
H7C	0.5913	0.2195	0.6720	0.109*
C8	0.4604 (9)	0.2278 (6)	0.1589 (5)	0.0772 (12)
H8A	0.3507	0.1989	0.0734	0.116*
H8B	0.5270	0.1421	0.2102	0.116*
H8D	0.5760	0.2855	0.1312	0.116*
C9	0.1529 (10)	0.5040 (7)	−0.0264 (4)	0.0819 (13)
H9A	0.0944	0.4890	−0.1286	0.123*
H9D	0.3146	0.4953	−0.0044	0.123*
H9B	0.1116	0.6000	0.0001	0.123*
C10	−0.1605 (7)	0.5689 (8)	0.2295 (5)	0.0798 (12)
H10D	−0.2763	0.5448	0.2799	0.120*
H10A	−0.2130	0.5469	0.1280	0.120*
H10B	−0.1256	0.6714	0.2412	0.120*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0816 (6)	0.0788 (6)	0.0690 (5)	0.0149 (6)	0.0344 (4)	0.0000 (6)
O1	0.0833 (18)	0.0704 (17)	0.0438 (11)	0.0164 (15)	0.0126 (11)	−0.0011 (13)
O2	0.0820 (18)	0.0775 (19)	0.0449 (11)	−0.0243 (16)	0.0051 (11)	0.0045 (13)
C1	0.0601 (19)	0.0448 (16)	0.0567 (18)	−0.0053 (15)	0.0257 (15)	0.0018 (14)
C2	0.0535 (17)	0.0522 (17)	0.0527 (16)	−0.0067 (15)	0.0151 (13)	0.0107 (15)
C3	0.0621 (19)	0.0520 (17)	0.0479 (16)	−0.0153 (17)	0.0133 (14)	0.0044 (15)
C4	0.070 (2)	0.0464 (17)	0.0500 (17)	−0.0043 (18)	0.0197 (16)	−0.0037 (16)
C5	0.064 (2)	0.0494 (18)	0.0523 (16)	0.0062 (16)	0.0152 (15)	0.0046 (15)
C6	0.0601 (19)	0.0443 (16)	0.0449 (14)	−0.0027 (15)	0.0132 (14)	0.0036 (14)
C7	0.069 (3)	0.091 (3)	0.0546 (18)	0.007 (3)	0.0082 (19)	0.013 (2)
C8	0.108 (3)	0.074 (3)	0.055 (2)	0.012 (3)	0.028 (2)	−0.011 (2)
C9	0.099 (3)	0.092 (3)	0.0530 (19)	−0.019 (3)	0.014 (2)	0.017 (2)
C10	0.063 (2)	0.093 (3)	0.082 (3)	0.009 (3)	0.0127 (19)	0.018 (3)

Geometric parameters (Å, º)

Cl1—C1	1.735 (4)	C5—H5A	0.9300
O1—C6	1.358 (4)	C7—H7A	0.9600
O1—C7	1.421 (5)	C7—H7B	0.9600
O2—C3	1.378 (4)	C7—H7C	0.9600
O2—C9	1.426 (5)	C8—H8A	0.9600
C1—C6	1.381 (5)	C8—H8B	0.9600
C1—C2	1.394 (5)	C8—H8D	0.9600
C2—C3	1.398 (5)	C9—H9A	0.9600
C2—C10	1.503 (6)	C9—H9D	0.9600
C3—C4	1.385 (6)	C9—H9B	0.9600
C4—C5	1.387 (5)	C10—H10D	0.9600
C4—C8	1.498 (5)	C10—H10A	0.9600
C5—C6	1.383 (5)	C10—H10B	0.9600
C6—O1—C7	118.2 (3)	H7A—C7—H7B	109.5
C3—O2—C9	113.6 (3)	O1—C7—H7C	109.5
C6—C1—C2	122.0 (3)	H7A—C7—H7C	109.5
C6—C1—Cl1	119.3 (2)	H7B—C7—H7C	109.5
C2—C1—Cl1	118.7 (3)	C4—C8—H8A	109.5
C1—C2—C3	117.3 (3)	C4—C8—H8B	109.5
C1—C2—C10	121.5 (4)	H8A—C8—H8B	109.5
C3—C2—C10	121.1 (3)	C4—C8—H8D	109.5
O2—C3—C4	119.3 (3)	H8A—C8—H8D	109.5
O2—C3—C2	118.7 (3)	H8B—C8—H8D	109.5
C4—C3—C2	122.0 (3)	O2—C9—H9A	109.5
C3—C4—C5	118.5 (3)	O2—C9—H9D	109.5
C3—C4—C8	122.1 (3)	H9A—C9—H9D	109.5
C5—C4—C8	119.5 (4)	O2—C9—H9B	109.5
C6—C5—C4	121.5 (3)	H9A—C9—H9B	109.5
C6—C5—H5A	119.3	H9D—C9—H9B	109.5
C4—C5—H5A	119.3	C2—C10—H10D	109.5
O1—C6—C1	116.5 (3)	C2—C10—H10A	109.5
O1—C6—C5	124.8 (3)	H10D—C10—H10A	109.5
C1—C6—C5	118.8 (3)	C2—C10—H10B	109.5
O1—C7—H7A	109.5	H10D—C10—H10B	109.5
O1—C7—H7B	109.5	H10A—C10—H10B	109.5
C6—C1—C2—C3	0.6 (5)	O2—C3—C4—C8	1.6 (5)
Cl1—C1—C2—C3	180.0 (3)	C2—C3—C4—C8	179.2 (4)
C6—C1—C2—C10	−179.6 (4)	C3—C4—C5—C6	−0.3 (6)
Cl1—C1—C2—C10	−0.2 (5)	C8—C4—C5—C6	−179.5 (4)
C9—O2—C3—C4	−88.2 (5)	C7—O1—C6—C1	−179.9 (4)
C9—O2—C3—C2	94.0 (4)	C7—O1—C6—C5	1.7 (5)
C1—C2—C3—O2	177.5 (3)	C2—C1—C6—O1	−179.3 (3)
C10—C2—C3—O2	−2.3 (6)	Cl1—C1—C6—O1	1.3 (4)
C1—C2—C3—C4	−0.2 (5)	C2—C1—C6—C5	−0.9 (5)
C10—C2—C3—C4	−180.0 (4)	Cl1—C1—C6—C5	179.8 (3)
O2—C3—C4—C5	−177.7 (3)	C4—C5—C6—O1	179.0 (4)
C2—C3—C4—C5	0.0 (5)	C4—C5—C6—C1	0.7 (5)