Bis(2,5-dimethoxy-4-methylphenyl)methane and bis(2,5-dimethoxy-3,4,6-trimethylphenyl)methane

Bis(2,5-di­methoxy-4-methyl­phenyl)­methane, C₁₉H₂₄O₄, (IIa), was obtained and characterized as a minor product from the reaction of tolu­hydro­quinone di­methyl ether (1,4-dimethoxy-2-methylbenzene) with N-(hydroxy­methyl)­tri­fluoro­acet­amide. Similarly, bis(2,5-di­methoxy-3,4,6-tri­methyl­phenyl)­methane, C₂₃H₃₂O₄, (IIb), was prepared from the corresponding reaction of tri­methyl­hydro­quinone di­methyl ether (2,5-dimethoxy-1,3,4-trimethylbenzene). The mol­ecules of (IIa) and (IIb) each lie on a twofold axis passing through the methyl­ene group. The dihedral angle between the planar phenyl rings is 73.4 (1)° in (IIa) and 77.9 (1)° in (IIb). The external bond angles around the bridging methyl­ene group are 116.6 (2) and 117.3 (2)° for (IIa) and (IIb), respectively. In (IIa), the methoxy substituents lie in the plane of the ring and are conjugated with the aromatic system, whereas in (IIb), they are almost perpendicular to the phenyl ring and are positioned on opposite sides.

S1. Comment

In the course of the synthesis of ammonium quinone derivatives as potential electron acceptors for electron-transfer studies, the amidomethylation reactions of several dimethoxybenzene derivatives have been studied (Zaugg, 1970, 1984; Zaugg & Martin, 1965). The methodology involves reacting the aromatic derivative with N-(hydroxymethyl)trifluoroacetamide in solution in chloroform-trifluoroacetic acid. The major products in each of the reactions we have studied are the expected trifluoroacetamide adducts, (Ia) and (Ib). We will report, in due course, our studies to elaborate such adducts into ammonium quinones.

Interestingly, in the cases of trimethylhydroquinone dimethyl ether and toluylhydroquinone dimethyl ether, significant minor products were also obtained, namely the title bisarylmethane derivatives, (IIa) and (IIb). Such species are known products of other reaction sequences, but their formation has not previously been reported via the synthetic sequence used here and was unanticipated in these reactions. We report here the synthesis of both these bisarylmethane derivatives via this new reaction sequence, as well as their full characterization by X-ray analysis. \sch

In the crystals of both compounds, (IIa) and (IIb), the molecules lie on a twofold axis in space group C2/c (No. 15), which passes through the methylene group. The dihedral angles between the planar phenyl rings are 73.4 (1)° in (IIa) and 77.9 (1)° in (IIb). The external bond angles around the bridging methylene are 116.6 (2) and 117.3 (2)°, respectively, and significantly larger than the standard value. However, the C1—C7 bond lengths [1.514 (2) and 1.522 (2) Å, respectively] did not increase so dramatically relative to the standard value and are only slightly longer (Allen et al., 1987).

In (IIa), the methoxy substituents lie in the plane of the ring and are conjugated with the aromatic system. Methoxy-group conjugation with an aromatic ring has been observed in many systems, including arylidene dicyanovinyl derivatives (Antipin et al., 1997), trans-1-cyano-2-(2-methoxyphenyl)-1-nitroethylene (Nesterov et al., 2000) and [(2-methoxyanilino)methylene]malononitrile (Nesterov et al., 2003). In contrast, in (IIb) the methoxy groups are almost perpendicular to the phenyl ring [torsion angles C8—O1—C2—C1 93.3 (2) and C11—O2—C5—C4 − 93.3 (2)°] and they are positioned on opposite sides of the ring.

The presence in (IIb) of bulky substituents in both ortho-positions is apparently the cause of significant C_phenyl—O_methoxy bond stretching: the C2—O1 and C5—O2 bond lengths are 1.393 (2) and 1.389 (2) Å, respectively. In contrast, the corresponding bond lengths in (IIa), which does not have multiple ortho substitutions, are shorter than in (IIb), with values of 1.371 (2) and 1.372 (2) Å, respectively, comparable with the standard bond value (Allen et al., 1987).

The different orientations of the methoxy groups about the phenyl rings in (IIa) and (IIb) account for the distortion of the bond angles. Thus, we found an increase in the C2—O1—C8 and C5—O2—C10 angles [118.0 (2) and 117.3 (2)°, respectively] and in the C3—C2—O1 and C6—C5—O2 angles [124.2 (2) and 124.3 (2)°, respectively] in (IIa). The corresponding values in (IIb) are smaller [C—O—C angles 113.7 (1) and 113.7 (1)°], but the C—C—O values are approximately standard and within 1° of 120°. Such effects are usual for compounds containing OCH₃ groups and have been well explained previously (Gallagher et al., 2001). Other bond lengths and angles in (IIa) and (IIb) have the expected values (Allen et al., 1987).

There are no significant intermolecular interactions in either (IIa) or (IIb). However, in (IIb) there are some weak intramolecular contacts involving C9···O1 and C10/C12···O2 (all H···O > 2.30 Å, C···O > 2.80 Å, C—H···O ≈ 110°). Two other C7/C12···O1ⁱ contacts involve the symmetry-related parts of (IIb) [symmetry code: (i) =1 − x, y, 3/2 − z].

S2. Experimental

Bis(2,5-dimethoxy-4-methylphenyl)methane, (IIa), was prepared as follows. A mixture of methylhydroquinone dimethyl ether (1.31 g, 8.6 mmole), N-(hydroxymethyl)trifluoroacetamide (1.23 g, 8.6 mmole; Zaugg & Martin, 1965), CHCl₃ (18 ml) and trifluoroacetic acid (9 ml) was refluxed with stirring for 3 d under a drying tube filled with a 4 Å molecular sieve. The brown solution was cooled and the volatile components were removed on a rotary evaporator, leaving a yellowish-brown solid. Column chromatography on silica gel with 8:1 hexanes:ethyl acetate gave two fractions, both white crystalline solids. The diphenylmethane (0.15 g, 11%) was obtained as the first fraction; ¹H NMR and ¹³C NMR are in accordance with the literature (Rathore & Kochi, 1995). Crystallization from hexanes-ethyl acetate (Ratio?) gave X-ray quality crystals of (IIa) [m.p. 413–414 K; literature range (Rathore & Kochi, 1995; Hunt & Lindsey, 1962; Jacini & Bacchetti,1950): 420–421 K]. The second fraction, (Ia), was the expected amidomethylation product (yield 1.61 g, 68%). Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃, δ, p.p.m): 2.22 (s, 3H, Ar—CH₃), 3.78 (s, 3H, OCH₃), 3.83 (s, 3H, OCH₃), 4.48 (d, J = 5.9 Hz, 2H, Ar—CH₂), 6.73 (s, 1H, Ar—H), 6.75 (s, 1H, Ar—H), 6.94(br s, 1H, NH); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 16.3 (Ar—CH₃), 40.2 (Ar—CH₂), 55.9, 56.0 (2 × OCH₃), 116.0 (q, J = 287.7 Hz, CF₃), 112.6 (Ar—C6), 113.7 (Ar—C3), 121.4 (Ar—C4), 127.8 (Ar—C1), 151.2 (Ar—C2), 151.6 (Ar—C5), 156.7 (q, J = 36.7 Hz, CO). Minor peaks for the two possible regioisomers were also present in both spectra of this fraction. Bis(2,5-dimethoxy-3,4,6-trimethylphenyl)methane, (IIb), was prepared as follows. The above procedure was applied to trimethylhydroquinone dimethyl ether (Rathore et al., 1994a,b). In this case, the diphenylmethane was obtained in 40% yield, again as the first fraction. ¹H NMR and ¹³C NMR spectra were in accordance with the literature (Rathore & Kochi, 1995). Recrystallization from absolute ethanol gave X-ray quality crystals of (IIb) (m.p. 415–416 K; literature range (Rathore & Kochi, 1995): 415–416 K]. The second fraction, (Ib), was the expected amidomethylation product in 49% yield. Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 2.19 (s, 3H, Ar—CH₃), 2.21 (s, 3H, Ar—CH₃), 2.28 (s, 3H, Ar—CH₃); 3.65 (s, 3H, OCH₃), 3.71 (s, 3H, OCH₃), 4.56 (d, J = 5.5 Hz, 2H, Ar—CH₂), 6.67 (br s, 1H, NH); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 12.1, 12.8, 12.9 (3 × Ar—CH₃) 36.6 (Ar—CH₂), 60.2, 61.0 (2 × OCH₃), 115.9 (q, J = 287.7 Hz, CF₃), 125.4 (Ar—C6), 128.1 (Ar—C3 or Ar—C4), 128.5 (Ar—C4 or Ar—C3), 131.8 (Ar—C1), 153.4 (Ar—C5 or Ar—C2), 153.6 (Ar—C2 or Ar—C5), 156.7 (q, J = 36.7 Hz, CO).

S3. Refinement

Space group C2/c was assigned from the systematic absences, with subsequent solution and refinement for both (IIa) and (IIb) (as distinct from space group Cc). The H atom (H7A) of the methylene group was found from a difference Fourier map and refined isotropically, with C—H distances of 0.931 (17) and 0.960 (16) Å in (IIa) and (IIb), respectively. All other 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 atoms and 0.96 Å for CH₃ groups.

Computing details

For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1989); 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 (IIa) 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 (IIb) 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.

(IIa) Bis(2,5-dimethoxy-4-methylphenyl)methane

Crystal data

C19H24O4	F(000) = 680
Mr = 316.38	Dx = 1.226 Mg m^−3
Monoclinic, C2/c	Melting point = 413–414 K
Hall symbol: -C2yc	Mo Kα radiation, λ = 0.71073 Å
a = 23.282 (5) Å	Cell parameters from 24 reflections
b = 7.7280 (15) Å	θ = 11–12°
c = 9.6740 (19) Å	µ = 0.09 mm^−1
β = 100.10 (3)°	T = 295 K
V = 1713.6 (6) Å^3	Prism, colourless
Z = 4	0.45 × 0.35 × 0.25 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.044
Radiation source: fine-focus sealed tube	θmax = 27.0°, θmin = 1.8°
Graphite monochromator	h = 0→29
θ/2θ scans	k = 0→9
1900 measured reflections	l = −12→12
1856 independent reflections	3 standard reflections every 97 reflections
1130 reflections with I > 2σ(I)	intensity decay: 3%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: mixed
wR(F^2) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.07P)^2 + 0.8P] where P = (Fo^2 + 2Fc^2)/3
1856 reflections	(Δ/σ)max = 0.001
112 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.16 e Å^−3

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. The hydrogen atom of the methylene group was found from a difference Fourier map and refined isotropically. All the other 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 atoms and 0.96 Å for CH₃ groups.

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

	x	y	z	Uiso*/Ueq
O1	0.46047 (6)	0.25980 (17)	0.51486 (13)	0.0583 (4)
O2	0.32023 (6)	0.24188 (17)	0.91834 (15)	0.0609 (4)
C1	0.44388 (7)	0.1614 (2)	0.73346 (17)	0.0430 (4)
C2	0.42489 (8)	0.2601 (2)	0.61376 (18)	0.0455 (4)
C3	0.37184 (8)	0.3473 (2)	0.5983 (2)	0.0536 (5)
H3A	0.3596	0.4129	0.5179	0.064*
C4	0.33679 (8)	0.3385 (2)	0.7003 (2)	0.0525 (5)
C5	0.35617 (8)	0.2408 (2)	0.82005 (19)	0.0480 (4)
C6	0.40895 (7)	0.1536 (2)	0.83570 (18)	0.0452 (4)
H6A	0.4212	0.0885	0.9163	0.054*
C7	0.5000	0.0585 (3)	0.7500	0.0448 (6)
H7A	0.5009 (8)	−0.011 (2)	0.8291 (18)	0.053 (5)*
C8	0.44407 (12)	0.3620 (4)	0.3941 (2)	0.0868 (8)
H8A	0.4739	0.3563	0.3371	0.130*
H8B	0.4391	0.4798	0.4213	0.130*
H8C	0.4080	0.3196	0.3416	0.130*
C9	0.27885 (9)	0.4306 (3)	0.6798 (3)	0.0778 (7)
H9A	0.2738	0.4958	0.5940	0.117*
H9B	0.2778	0.5075	0.7572	0.117*
H9C	0.2480	0.3471	0.6750	0.117*
C10	0.33929 (10)	0.1496 (3)	1.0453 (2)	0.0707 (6)
H10A	0.3107	0.1604	1.1052	0.106*
H10B	0.3758	0.1963	1.0919	0.106*
H10C	0.3442	0.0296	1.0243	0.106*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0645 (9)	0.0590 (8)	0.0521 (7)	0.0143 (6)	0.0123 (6)	0.0095 (6)
O2	0.0531 (8)	0.0648 (9)	0.0670 (9)	0.0025 (6)	0.0165 (7)	0.0051 (7)
C1	0.0415 (9)	0.0361 (8)	0.0482 (9)	−0.0038 (7)	−0.0014 (7)	−0.0034 (7)
C2	0.0482 (10)	0.0396 (9)	0.0470 (9)	0.0004 (7)	0.0040 (8)	−0.0014 (7)
C3	0.0521 (10)	0.0472 (10)	0.0575 (11)	0.0048 (9)	−0.0016 (8)	0.0071 (9)
C4	0.0412 (9)	0.0448 (9)	0.0683 (12)	0.0020 (8)	0.0007 (8)	0.0008 (9)
C5	0.0441 (9)	0.0430 (9)	0.0553 (10)	−0.0058 (8)	0.0039 (8)	−0.0029 (8)
C6	0.0452 (9)	0.0397 (9)	0.0471 (9)	−0.0047 (7)	−0.0016 (7)	0.0007 (7)
C7	0.0459 (13)	0.0368 (12)	0.0499 (14)	0.000	0.0036 (11)	0.000
C8	0.117 (2)	0.0868 (17)	0.0636 (14)	0.0364 (15)	0.0348 (14)	0.0257 (13)
C9	0.0547 (12)	0.0782 (16)	0.0994 (18)	0.0183 (11)	0.0105 (12)	0.0219 (14)
C10	0.0701 (13)	0.0838 (16)	0.0614 (13)	0.0034 (12)	0.0205 (10)	0.0060 (12)

Geometric parameters (Å, º)

O1—C2	1.371 (2)	C3—H3A	0.9300
O1—C8	1.406 (2)	C6—H6A	0.9300
O2—C5	1.372 (2)	C7—H7A	0.931 (17)
O2—C10	1.422 (2)	C8—H8A	0.9600
C1—C2	1.392 (2)	C8—H8B	0.9600
C1—C6	1.388 (2)	C8—H8C	0.9600
C1—C7	1.514 (2)	C9—H9A	0.9600
C2—C3	1.392 (2)	C9—H9B	0.9600
C3—C4	1.388 (3)	C9—H9C	0.9600
C4—C5	1.390 (3)	C10—H10A	0.9600
C4—C9	1.507 (3)	C10—H10B	0.9600
C5—C6	1.386 (2)	C10—H10C	0.9600
C2—O1—C8	117.99 (16)	O2—C10—H10A	109.5
C5—O2—C10	117.34 (15)	O2—C10—H10B	109.5
O1—C2—C1	115.91 (15)	H10A—C10—H10B	109.5
O1—C2—C3	123.98 (16)	O2—C10—H10C	109.5
C1—C2—C3	120.08 (17)	H10A—C10—H10C	109.5
O2—C5—C4	115.21 (16)	H10B—C10—H10C	109.5
O2—C5—C6	124.32 (17)	C4—C9—H9A	109.5
C4—C5—C6	120.46 (18)	C4—C9—H9B	109.5
C2—C1—C6	118.46 (16)	H9A—C9—H9B	109.5
C2—C1—C7	121.19 (14)	C4—C9—H9C	109.5
C6—C1—C7	120.30 (14)	H9A—C9—H9C	109.5
C2—C3—C4	121.37 (17)	H9B—C9—H9C	109.5
C3—C4—C5	118.30 (17)	O1—C8—H8A	109.5
C3—C4—C9	120.46 (18)	O1—C8—H8B	109.5
C5—C4—C9	121.23 (19)	H8A—C8—H8B	109.5
C1—C6—C5	121.33 (17)	O1—C8—H8C	109.5
C4—C3—H3A	119.3	H8A—C8—H8C	109.5
C2—C3—H3A	119.3	H8B—C8—H8C	109.5
C5—C6—H6A	119.3	C1—C7—H7A	106.5 (11)
C1—C6—H6A	119.3
C8—O1—C2—C3	3.9 (3)	C10—O2—C5—C4	−177.51 (17)
C8—O1—C2—C1	−178.01 (19)	C3—C4—C5—O2	178.14 (16)
C6—C1—C2—O1	−178.50 (15)	C9—C4—C5—O2	−2.8 (3)
C7—C1—C2—O1	−1.0 (2)	C3—C4—C5—C6	−0.6 (3)
C6—C1—C2—C3	−0.3 (2)	C9—C4—C5—C6	178.46 (18)
C7—C1—C2—C3	177.12 (16)	O2—C5—C6—C1	−178.38 (16)
O1—C2—C3—C4	177.97 (17)	C4—C5—C6—C1	0.2 (3)
C1—C2—C3—C4	0.0 (3)	C2—C1—C6—C5	0.2 (2)
C2—C3—C4—C5	0.5 (3)	C7—C1—C6—C5	−177.23 (15)
C2—C3—C4—C9	−178.56 (18)	C6—C1—C7—C1^i	−114.85 (16)
C10—O2—C5—C6	1.2 (3)	C2—C1—C7—C1^i	67.74 (14)

Symmetry code: (i) −x+1, y, −z+3/2.

(IIb) Bis(2,5-dimethoxy-3,4,6-trimethylphenyl)methane

Crystal data

C23H32O4	F(000) = 808
Mr = 372.49	Dx = 1.190 Mg m^−3
Monoclinic, C2/c	Melting point = 415–416 K
Hall symbol: -C2yc	Mo Kα radiation, λ = 0.71073 Å
a = 24.321 (5) Å	Cell parameters from 24 reflections
b = 6.1410 (12) Å	θ = 12–13°
c = 15.042 (3) Å	µ = 0.08 mm^−1
β = 112.21 (3)°	T = 298 K
V = 2079.9 (8) Å^3	Prism, colourless
Z = 4	0.50 × 0.40 × 0.30 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.023
Radiation source: fine-focus sealed tube	θmax = 26.0°, θmin = 1.8°
Graphite monochromator	h = 0→29
θ/2θ scans	k = 0→7
2068 measured reflections	l = −18→17
2020 independent reflections	3 standard reflections every 97 reflections
1620 reflections with I > 2σ(I)	intensity decay: 3%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: mixed
wR(F^2) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.08P)^2 + 0.8P] where P = (Fo^2 + 2Fc^2)/3
2020 reflections	(Δ/σ)max = 0.001
132 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

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. The hydrogen atom of the methylene group was found from a difference Fourier map and refined isotropically. All the other H atoms were placed in geometrically calculated positions and refined using a riding model with C—H distances of 0.96 Å for CH₃ groups.

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

	x	y	z	Uiso*/Ueq
O1	0.40461 (4)	0.51521 (16)	0.81487 (7)	0.0455 (3)
O2	0.37015 (5)	−0.00163 (18)	0.49776 (7)	0.0545 (3)
C1	0.44291 (5)	0.3642 (2)	0.70225 (9)	0.0357 (3)
C2	0.39649 (5)	0.3842 (2)	0.73529 (9)	0.0379 (3)
C3	0.34282 (6)	0.2729 (2)	0.69306 (11)	0.0439 (4)
C4	0.33421 (6)	0.1388 (2)	0.61421 (10)	0.0451 (4)
C5	0.37998 (6)	0.1224 (2)	0.57958 (9)	0.0423 (3)
C6	0.43376 (6)	0.2321 (2)	0.62195 (9)	0.0390 (3)
C7	0.5000	0.4932 (3)	0.7500	0.0382 (4)
C8	0.38421 (8)	0.7345 (3)	0.79081 (13)	0.0621 (5)
H8A	0.3864	0.8104	0.8479	0.093*
H8B	0.3438	0.7329	0.7457	0.093*
H8C	0.4087	0.8070	0.7628	0.093*
C9	0.29550 (7)	0.2933 (3)	0.73482 (15)	0.0660 (5)
H9A	0.3093	0.3879	0.7897	0.099*
H9B	0.2871	0.1521	0.7540	0.099*
H9C	0.2600	0.3528	0.6873	0.099*
C10	0.27743 (7)	0.0124 (3)	0.56648 (14)	0.0641 (5)
H10A	0.2736	−0.0279	0.5028	0.096*
H10B	0.2442	0.1012	0.5632	0.096*
H10C	0.2783	−0.1165	0.6031	0.096*
C11	0.38963 (10)	−0.2231 (3)	0.51766 (14)	0.0729 (6)
H11A	0.3862	−0.2943	0.4590	0.109*
H11B	0.3654	−0.2974	0.5457	0.109*
H11C	0.4303	−0.2258	0.5616	0.109*
C12	0.47982 (7)	0.2156 (3)	0.57764 (11)	0.0550 (4)
H12A	0.4621	0.1546	0.5144	0.082*
H12B	0.5117	0.1235	0.6166	0.082*
H12C	0.4950	0.3580	0.5737	0.082*
H7A	0.5041 (7)	0.587 (3)	0.7019 (10)	0.047 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0480 (6)	0.0512 (6)	0.0414 (6)	0.0087 (4)	0.0214 (4)	−0.0021 (4)
O2	0.0656 (7)	0.0527 (6)	0.0373 (6)	−0.0044 (5)	0.0105 (5)	−0.0065 (4)
C1	0.0335 (6)	0.0377 (7)	0.0356 (6)	0.0024 (5)	0.0129 (5)	0.0025 (5)
C2	0.0383 (6)	0.0390 (7)	0.0377 (6)	0.0050 (5)	0.0160 (5)	0.0026 (5)
C3	0.0363 (7)	0.0453 (8)	0.0525 (8)	0.0030 (6)	0.0193 (6)	0.0073 (6)
C4	0.0378 (7)	0.0418 (8)	0.0505 (8)	−0.0012 (6)	0.0107 (6)	0.0069 (6)
C5	0.0462 (7)	0.0398 (7)	0.0362 (7)	0.0009 (6)	0.0103 (6)	0.0016 (6)
C6	0.0396 (7)	0.0418 (7)	0.0363 (7)	0.0031 (5)	0.0150 (5)	0.0015 (5)
C7	0.0373 (9)	0.0391 (10)	0.0379 (9)	0.000	0.0139 (8)	0.000
C8	0.0701 (11)	0.0551 (10)	0.0600 (10)	0.0158 (8)	0.0234 (8)	−0.0100 (8)
C9	0.0461 (9)	0.0780 (12)	0.0847 (12)	−0.0022 (8)	0.0371 (8)	−0.0029 (10)
C10	0.0477 (8)	0.0610 (10)	0.0722 (11)	−0.0134 (7)	0.0095 (8)	0.0028 (8)
C11	0.0977 (14)	0.0532 (10)	0.0614 (11)	0.0062 (10)	0.0228 (10)	−0.0155 (8)
C12	0.0514 (8)	0.0718 (10)	0.0478 (8)	−0.0024 (7)	0.0256 (7)	−0.0160 (8)

Geometric parameters (Å, º)

O1—C2	1.3930 (16)	C8—H8A	0.9600
O1—C8	1.4334 (19)	C8—H8B	0.9600
O2—C5	1.3892 (17)	C8—H8C	0.9600
O2—C11	1.434 (2)	C9—H9A	0.9600
C1—C2	1.4003 (17)	C9—H9B	0.9600
C1—C6	1.4013 (18)	C9—H9C	0.9600
C1—C7	1.5222 (16)	C10—H10A	0.9600
C2—C3	1.3956 (19)	C10—H10B	0.9600
C3—C4	1.393 (2)	C10—H10C	0.9600
C3—C9	1.510 (2)	C11—H11A	0.9600
C4—C5	1.400 (2)	C11—H11B	0.9600
C4—C10	1.509 (2)	C11—H11C	0.9600
C5—C6	1.393 (2)	C12—H12A	0.9600
C6—C12	1.5080 (19)	C12—H12B	0.9600
C7—H7A	0.960 (16)	C12—H12C	0.9600
C2—O1—C8	113.73 (11)	H8B—C8—H8C	109.5
C5—O2—C11	113.74 (12)	C3—C9—H9A	109.5
O1—C2—C1	118.95 (11)	C3—C9—H9B	109.5
O1—C2—C3	118.58 (11)	H9A—C9—H9B	109.5
C1—C2—C3	122.44 (12)	C3—C9—H9C	109.5
O2—C5—C4	118.33 (13)	H9A—C9—H9C	109.5
O2—C5—C6	119.20 (13)	H9B—C9—H9C	109.5
C4—C5—C6	122.43 (13)	C4—C10—H10A	109.5
C2—C1—C6	118.03 (12)	C4—C10—H10B	109.5
C2—C1—C7	120.07 (11)	H10A—C10—H10B	109.5
C6—C1—C7	121.82 (10)	C4—C10—H10C	109.5
C2—C3—C4	119.38 (12)	H10A—C10—H10C	109.5
C2—C3—C9	119.92 (14)	H10B—C10—H10C	109.5
C4—C3—C9	120.68 (13)	O2—C11—H11A	109.5
C3—C4—C5	118.34 (13)	O2—C11—H11B	109.5
C3—C4—C10	121.68 (15)	H11A—C11—H11B	109.5
C5—C4—C10	119.98 (15)	O2—C11—H11C	109.5
C1—C6—C5	119.34 (12)	H11A—C11—H11C	109.5
C1—C6—C12	121.17 (12)	H11B—C11—H11C	109.5
C5—C6—C12	119.42 (12)	C6—C12—H12A	109.5
C1—C7—H7A	107.1 (9)	C6—C12—H12B	109.5
O1—C8—H8A	109.5	H12A—C12—H12B	109.5
O1—C8—H8B	109.5	C6—C12—H12C	109.5
H8A—C8—H8B	109.5	H12A—C12—H12C	109.5
O1—C8—H8C	109.5	H12B—C12—H12C	109.5
H8A—C8—H8C	109.5
C8—O1—C2—C3	−88.41 (16)	C11—O2—C5—C4	−93.26 (18)
C8—O1—C2—C1	93.33 (15)	C3—C4—C5—O2	−176.49 (12)
C6—C1—C2—O1	−179.84 (11)	C10—C4—C5—O2	3.7 (2)
C7—C1—C2—O1	−3.01 (18)	C3—C4—C5—C6	1.0 (2)
C6—C1—C2—C3	2.0 (2)	C10—C4—C5—C6	−178.74 (13)
C7—C1—C2—C3	178.81 (12)	O2—C5—C6—C1	177.52 (11)
O1—C2—C3—C4	−179.14 (12)	C4—C5—C6—C1	0.0 (2)
C1—C2—C3—C4	−0.9 (2)	O2—C5—C6—C12	0.6 (2)
O1—C2—C3—C9	−1.0 (2)	C4—C5—C6—C12	−176.94 (13)
C1—C2—C3—C9	177.21 (14)	C2—C1—C6—C5	−1.47 (19)
C2—C3—C4—C5	−0.6 (2)	C7—C1—C6—C5	−178.25 (12)
C9—C3—C4—C5	−178.72 (14)	C2—C1—C6—C12	175.41 (13)
C2—C3—C4—C10	179.21 (13)	C7—C1—C6—C12	−1.4 (2)
C9—C3—C4—C10	1.1 (2)	C2—C1—C7—C1^i	118.12 (12)
C11—O2—C5—C6	89.12 (17)

Symmetry code: (i) −x+1, y, −z+3/2.