Naturally occurring 1,2,8-trimethoxyxanthone and biphenyl ether intermediates leading to 1,2-dimethoxyxanthone

In order to study structure-activity relationships, a series of mono-, di- and trioxy­genated xanthones has been synthesized and the structures of methyl 2-(3,4-di­methoxy­phenoxy)­benzoate, C₁₆H₁₆O₅, 2-(3,4-di­methoxy­phenoxy)­benzoic acid, C₁₅H₁₄O₅, 1,2-di­methoxy-9H-xanthen-9-one, C₁₅H₁₂O₄, and 1,2,8-tri­methoxy-9H-xanthen-9-one, C₁₆H₁₄O₅, have been determined. The first two compounds both assume skew conformations, the dihedral angles between the two phenyl rings being 80.04 (8) and 83.0 (1)°, respectively. The latter two compounds are essentially planar and their methoxy substituents assume orientations consistent with minimum steric interactions.

S1. Comment

Xanthones are major secondary metabolites of the plants of the family Guttiferae (Bennett & Lee, 1989). Both synthetic and naturally occurring xanthones have been reported to mediate various biological effects, such as hepatoprotection (Fernandes et al., 1995) and reversible monoamine oxidase A inhibitors (Thull et al., 1993; Fujimoto et al., 1998). As part of our ongoing research concerning the variety of biological properties of this class of compounds, we have investigated the xanthone constituents of Calophyllum teysmanii var. inophylloide and studied their immunomodulatory activity (Gonzalez et al., 1999).

Among the xanthones tested, 2-hydroxy-1-methoxyxanthone has been shown to exhibit the highest inhibitory activity on T-cell proliferation. Further examination of the extract of Calophyllum teysmanii var. inophylloide has led to an isolation of, among many known xanthones, the new xanthones 1,2,8-trimethoxy-9H-xanthen-9-one, (IV), and 1,3,5,7-tetramethoxyxanthone (Kijjoa et al., 2000). However, the biological activities of these xanthones have not yet been evaluated. Taking into account the variety of biological properties of xanthones, we have planned the synthesis of a series of 1,2-dioxygenated xanthones to evaluate their antitumour and immunomodulatory activities. The syntheses of some 1,2-dioxygenated xanthones have been reported previously: 1,2-dimethoxy-9H-xanthen-9-one, (III), was obtained in a very low yield by a multi-step synthesis of its intermediate 1-formyl-2-hydroxyxanthone (Golberg & Wragg, 1958). More recently, 1-hydroxy-2-methoxyxanthone has been prepared by an LDA-induced regiospecific route from diaryl ether 2-carbohexamines (Familoni et al., 1997). Please define LDA. In contrast, we have succeeded in preparing (III) by a facile one-step conversion of the diaryl intermediate 2-(3,4-dimethoxyphenoxy)benzoic acid, (II), into the corresponding xanthone. In this paper, we report the structures of the intermediate compounds, methyl 2-(3,4-dimethoxyphenoxy)benzoate, (I), and 2-(3,4-dimethoxyphenoxy)benzoic acid, (II), obtained during the synthesis of (III), as well as the structure of this xanthone compared with (IV), which is very similar and was isolated from a plant. \sch

Compounds (I) and (II) (Figs. 1 and 2) differ only in the substituent at C2, which is a methyl ester in (I) and a carboxylic acid group in (II). They both assume a skew conformation, the angle between the phenyl rings being 80.04 (8)° for (I) and 83.0 (1)° for (II). These angles are in close agreement with the value of 84.8 (1)° observed in another open-ring intermediate for the synthesis of xanthones (Damas et al., 1997).

In (I), the plane defined by C1, O1 and C1' makes an angle of 4.8 (1)° with the C1—C6 phenyl ring plane and 76.5 (2)° with the other ring, C1'-C6'. The methyl ester group is nearly coplanar with the phenyl ring, as shown by the r.m.s. deviations from the ring plane: C7 0.039 (3), O2 0.173 (4), O3 - 0.079 (4) and C10 - 0.029 (6) Å. Furthermore, the bond angles between the methyl ester group and the phenyl ring C atoms adjacent to C2 are 126.3 (2)° for C1—C2—C7 and 115.8 (2)° for C3—C2—C7. The difference between these angles (10.4°) is probably due to a requirement of minimum steric interaction of the methyl ester group with the other phenyl ring.

The two methoxy substituents do not diverge significantly from the ring plane, as shown by the torsion angles C3'-C4'-O5—C9 [177.8 (2)°] and C4'-C3'-O4—C8 [176.9 (2)°]. Again, the orientation of the two methoxy substituents appears to have been determined by the requirement of minimum steric interaction between them.

In (II), the C1—C6 phenyl ring is nearly coplanar with the C1/O1/C1' plane, the relevant angle being 1.4 (2)°. The angle between the other ring, C1'-C6', and the C1/O1/C1' plane is 84.3 (2)°. The carboxylic acid group is nearly coplanar with the phenyl ring, the r.m.s. deviations from the ring plane being 0.036 (3), 0.132 (4) and -0.034 (4) Å for C7, O2 and O3, respectively. The C1—C2—C7 angle of 124.1 (2)° is 6.2° wider than the C3—C2—C7 angle [117.9 (2)°]; this difference is smaller than observed for (I), probably because the substituent in (I) is larger. The two methoxy substituents are in the plane of the phenyl ring [C3'-C4'-O5—C9 179.2 (2)° and C4'-C3'-O4—C8 179.8 (2)°], as in (I). Compound (II) also shows two intermolecular hydrogen bonds: O3···O2ⁱ 2.612 (3) and O3···O3ⁱ 3.449 (4) Å [symmetry code: (i) 1 - x, -y, 3 - z]. Further details of these are given in Table 3.

The 1,2-dimethoxy-9H-xanthen-9-one molecule in (III) is nearly planar (Fig. 3); the three rings define a plane with an r.m.s. deviation for the fitted atoms of 0.0297 Å. The maximum deviation of the O atoms, which were not included in the calculation of the least squares plane, is 0.14 Å for O13. Of the two methoxy substituents on the phenyl ring, one methyl group lies much further out of the ring plane than does the other [C2—C1—O11—C11 - 102.5 (3), compared with C1—C2—O12—C12 179.1 (3)°]. Atom C11 is probably forced out of the phenyl plane due to the proximity of atoms O13 and O12. Adoption of these orientations of the phenyl rings with multiple methoxy substituents has been observed previously and is consistent with minimum steric interactions (Hibbs et al., 1995; Kijjoa et al., 1998).

In the 1,2,8-trimethoxy-9H-xanthen-9-one compound, (IV), isolated from the wood of Callophyllum teysmanii var. inophylloide, two of the methyl groups of the three methoxy substituents are much closer to the plane of the molecule than the other (Fig. 4), as shown by the torsion angles C1—C2—O12—C12 [-162.0 (2)°], C2—C1—O11—C11 [79.6 (3)°] and C7—C8—O13—C13 [3.9 (4)°]. As in (III), atom C11 lies out of the ring plane, probably to minimize the steric interactions due to the presence of atoms O12 and O14 on either side of the methoxy group.

Papers describing the biological activity of these four compounds are in preparation. Comparison of the three-dimensional structure of molecules (III) and (IV) with those of the xanthone constituents of Calophyllum teysmanii var. inophylloide, whose activity has been studied, will reveal details of the relationship between structure and activity for this class of compounds.

Related literature

For related literature, see: Bennett & Lee (1989); Damas et al. (1997); Familoni et al. (1997); Fernandes et al. (1995); Fujimoto et al. (1998); Golberg & Wragg (1958); Gonzalez et al. (1999); Hibbs et al. (1995); Kijjoa et al. (1998, 2000); Thull et al. (1993).

S2. Experimental

The synthesis of (I) [step (1) in the Scheme] was carried out according to the method of Fernandes et al. (1995). A mixture of 2-bromobenzoic acid methyl ester (16.2 g, 75 mmol), 3,4-dimethoxyphenol (11.9 g, 77 mmol), copper bronze (9.8 g, 155 mmol) and Na₂CO₃ (21.3 g, 154 mmol) in dry pyridine (240 ml) was thoroughly degassed with nitrogen and refluxed for 26 h. The mixture was then cooled to room temperature, filtered and concentrated, furnishing a dark-brown oily liquid which was dissolved in methylene chloride and then washed with 0.5 N NaOH. The organic layer was dried over Na₂SO₄, filtered and concentrated under reduced presssure to provide an oily brown liquid (18.2 g). This was purified by column chromatography [petroleum ether (313–333 K boiling fraction)/diethyl ether (5:5)]. Evaporation of the solvent under reduced pressure furnished a solid product, (I) (9.0 g, 41%), which was crystallized from a mixture of diethyl ether/n-hexane.

The synthesis of (II) [step (2) in the Scheme] was carried out according to the method of Fernandes et al. (1995). Compound (I) (8.2 g, 28 mmol) was dissolved in methanol/tetrahydrofuran (1:1) and treated with aqueous 5 N NaOH solution (12 ml) at room temperature for 96 h. The crude product was washed with ether, and the aqueous layer was separated, washed with methylene chloride, acidified with 5 N HCl and extracted with methylene chloride. The organic phase was dried over Na₂SO₄, filtered and concentrated under reduced pressure, furnishing a white solid, (II) (7.6 g, 98%), which was crystallized from methylene chloride.

The synthesis of (III) [step (3) in the Scheme] was carried out according to the method of Fernandes et al. (1995). To a 2M solution of LDA (please define LDA) in tetrahydrofuran/heptane/ethylbenzene (2.5 ml, 5 mmol, ratio of solvents?), a solution of (II) (2.688 mg, 2.5 mmol) in dry tetrahydrofuran (25 ml) was added dropwise over 1 h at 273 K under a nitrogen atmosphere. The reaction mixture was allowed to reach room temperature over 1 h. The reaction was quenched by addition of 5% HCl and then extracted with methylene chloride. The organic phase was washed with 5% Na₂CO₃, dried over Na₂SO₄, filtered and concentrated under reduced pressure, to furnish an oily brown liquid. This crude product was purified by column chromatography [chloroform/n-hexane (7:3)]. After evaporation of the solvent, the solid, (III) (476.3 mg, 74%), was crystallized from a mixture of methylene chloride/n-hexane.

Compound (IV) was isolated from the wood of Callophyllum teysmanii var. inophylloide, using the method of Kijjoa et al. (2000).

S3. Refinement

All H atoms in (I), H5 and H6 in (II), H4 and H8 in (III) and the aromatic H atoms in (IV) were located from difference Fourier maps and refined freely with isotropic displacement parameters. The remaining H atoms could not be clearly located from the difference maps, and were placed geometrically and refined riding on their parent C atoms at distances of 0.93 Å (aromatic) and 0.96 Å (methyl), with U_iso(H) = xU_eq(C), where x = 1.2 and 1.5, respectively. A degree of racemic twinning was indicated for compound (IV) and a twin correction with two equal components was applied. This improved the refinement marginally.

Computing details

For all compounds, data collection: IPDS (Stoe & Cie, 1994); cell refinement: IPDS; data reduction: IPDS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and ORTEP-3.

Figures

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular structure of (II) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The molecular structure of (III) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. The molecular structure of (IV) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Atom C12 wholly obscures one of the attached H atoms.

(I) Methyl 2-(3,4-dimethoxyphenoxy)benzoate

Crystal data

C16H16O5	Dx = 1.322 Mg m^−3
Mr = 288.29	Melting point = 335–336 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
a = 15.306 (7) Å	Cell parameters from 1232 reflections
b = 7.788 (4) Å	θ = 5.0–28.1°
c = 16.426 (7) Å	µ = 0.10 mm^−1
β = 132.31 (3)°	T = 293 K
V = 1448.0 (12) Å^3	Square prism, colourless
Z = 4	0.30 × 0.25 × 0.20 mm
F(000) = 608

Data collection

Stoe IPDS diffractometer	2221 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.068
Graphite monochromator	θmax = 28.1°, θmin = 5.0°
Image Plate scans	h = −20→19
13194 measured reflections	k = −10→10
3439 independent reflections	l = −21→21

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.165	All H-atom parameters refined
S = 1.05	w = 1/[σ^2(Fo^2) + (0.068P)^2 + 0.376P] where P = (Fo^2 + 2Fc^2)/3
3439 reflections	(Δ/σ)max < 0.001
254 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.22 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.

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

	x	y	z	Uiso*/Ueq
O1	0.24922 (13)	0.95469 (19)	0.36254 (10)	0.0701 (5)
O2	0.52741 (18)	1.1418 (3)	0.67270 (13)	0.1062 (8)
O3	0.43905 (15)	0.9146 (2)	0.56698 (12)	0.0799 (5)
O4	0.08949 (12)	0.7792 (2)	0.00103 (11)	0.0648 (4)
O5	−0.10491 (12)	0.6765 (2)	−0.05112 (10)	0.0647 (4)
C1	0.27071 (16)	1.1278 (3)	0.37561 (14)	0.0511 (4)
C2	0.36879 (16)	1.1880 (3)	0.48176 (15)	0.0532 (4)
C3	0.3895 (2)	1.3644 (3)	0.49603 (19)	0.0668 (6)
C4	0.3174 (2)	1.4790 (3)	0.4103 (2)	0.0730 (6)
C5	0.2212 (2)	1.4168 (3)	0.30683 (19)	0.0649 (5)
C6	0.19786 (18)	1.2434 (3)	0.28934 (16)	0.0563 (5)
C1'	0.15623 (18)	0.8911 (3)	0.25623 (14)	0.0586 (5)
C2'	0.17351 (18)	0.8712 (3)	0.18365 (15)	0.0575 (5)
C3'	0.08389 (16)	0.8010 (2)	0.08024 (14)	0.0522 (4)
C4'	−0.02158 (16)	0.7463 (3)	0.05170 (14)	0.0534 (5)
C5'	−0.03561 (19)	0.7676 (3)	0.12593 (16)	0.0616 (5)
C6'	0.0536 (2)	0.8416 (3)	0.22907 (16)	0.0636 (5)
C7	0.45267 (17)	1.0809 (3)	0.58277 (15)	0.0580 (5)
C8	0.1928 (3)	0.8416 (4)	0.0255 (3)	0.0776 (7)
C9	−0.2103 (2)	0.6147 (4)	−0.0804 (2)	0.0687 (6)
C10	0.5178 (3)	0.8075 (5)	0.6633 (2)	0.0852 (8)
H3	0.460 (2)	1.401 (3)	0.572 (2)	0.079 (7)*
H4	0.336 (2)	1.602 (4)	0.424 (2)	0.088 (8)*
H5	0.167 (2)	1.495 (3)	0.246 (2)	0.075 (7)*
H6	0.134 (2)	1.201 (3)	0.2192 (19)	0.067 (6)*
H2'	0.244 (2)	0.902 (3)	0.2046 (18)	0.066 (6)*
H5'	−0.108 (2)	0.731 (3)	0.105 (2)	0.073 (7)*
H6'	0.044 (2)	0.854 (3)	0.2804 (19)	0.072 (6)*
H8A	−0.252 (2)	0.556 (3)	−0.151 (2)	0.086 (8)*
H8B	−0.254 (2)	0.715 (4)	−0.084 (2)	0.079 (7)*
H8C	−0.190 (2)	0.531 (3)	−0.025 (2)	0.074 (7)*
H9A	0.181 (3)	0.818 (4)	−0.040 (3)	0.110 (10)*
H9B	0.262 (3)	0.777 (4)	0.091 (2)	0.092 (9)*
H9C	0.205 (3)	0.969 (4)	0.042 (2)	0.096 (9)*
H10A	0.505 (4)	0.841 (6)	0.710 (3)	0.153 (16)*
H10B	0.594 (4)	0.830 (5)	0.699 (3)	0.133 (13)*
H10C	0.494 (4)	0.694 (6)	0.640 (3)	0.156 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0700 (9)	0.0592 (9)	0.0393 (7)	−0.0049 (7)	0.0198 (7)	−0.0001 (6)
O2	0.0953 (14)	0.0945 (14)	0.0488 (9)	0.0103 (10)	0.0160 (9)	−0.0106 (8)
O3	0.0726 (10)	0.0693 (10)	0.0459 (7)	0.0002 (8)	0.0188 (7)	0.0077 (7)
O4	0.0586 (8)	0.0822 (10)	0.0578 (8)	−0.0099 (7)	0.0409 (7)	−0.0071 (7)
O5	0.0508 (7)	0.0875 (10)	0.0450 (7)	−0.0137 (7)	0.0279 (6)	−0.0088 (7)
C1	0.0484 (9)	0.0586 (11)	0.0441 (9)	0.0014 (8)	0.0302 (8)	−0.0011 (8)
C2	0.0470 (9)	0.0632 (11)	0.0480 (9)	0.0010 (8)	0.0315 (8)	−0.0019 (8)
C3	0.0608 (12)	0.0680 (13)	0.0596 (12)	−0.0046 (10)	0.0356 (10)	−0.0085 (10)
C4	0.0787 (15)	0.0574 (13)	0.0778 (15)	−0.0022 (11)	0.0505 (13)	−0.0036 (11)
C5	0.0685 (13)	0.0639 (13)	0.0645 (12)	0.0128 (10)	0.0457 (11)	0.0107 (10)
C6	0.0533 (10)	0.0653 (12)	0.0465 (10)	0.0054 (9)	0.0320 (9)	0.0041 (8)
C1'	0.0565 (11)	0.0567 (11)	0.0392 (9)	0.0012 (8)	0.0227 (8)	0.0024 (7)
C2'	0.0466 (10)	0.0581 (11)	0.0510 (10)	−0.0022 (8)	0.0260 (8)	0.0031 (8)
C3'	0.0499 (9)	0.0553 (10)	0.0441 (9)	0.0015 (8)	0.0286 (8)	0.0021 (7)
C4'	0.0468 (9)	0.0608 (11)	0.0409 (9)	−0.0004 (8)	0.0248 (8)	0.0015 (8)
C5'	0.0514 (11)	0.0782 (14)	0.0503 (10)	−0.0023 (10)	0.0323 (9)	0.0017 (9)
C6'	0.0650 (12)	0.0744 (14)	0.0472 (10)	0.0019 (10)	0.0361 (10)	0.0020 (9)
C7	0.0469 (9)	0.0748 (13)	0.0436 (9)	0.0021 (9)	0.0269 (8)	−0.0064 (9)
C8	0.0762 (16)	0.0856 (19)	0.0892 (18)	−0.0148 (14)	0.0630 (15)	−0.0064 (15)
C9	0.0535 (11)	0.0801 (16)	0.0600 (13)	−0.0126 (11)	0.0331 (10)	−0.0059 (12)
C10	0.0695 (16)	0.088 (2)	0.0566 (13)	0.0065 (14)	0.0256 (12)	0.0197 (13)

Geometric parameters (Å, º)

O1—C1	1.370 (3)	C1—C2	1.411 (3)
O1—C1'	1.405 (2)	C2—C3	1.394 (3)
O4—C3'	1.371 (2)	C2—C7	1.493 (3)
O4—C8	1.429 (3)	C3—C4	1.380 (3)
O5—C4'	1.369 (2)	C3—H3	1.00 (3)
O5—C9	1.422 (3)	C4—C5	1.387 (3)
O2—C7	1.200 (2)	C4—H4	0.98 (3)
O3—C7	1.310 (3)	C5—C6	1.377 (3)
O3—C10	1.444 (3)	C5—H5	0.97 (3)
C1'—C6'	1.368 (3)	C6—H6	0.93 (2)
C1'—C2'	1.393 (3)	C8—H9A	0.98 (3)
C2'—C3'	1.389 (3)	C8—H9B	1.00 (3)
C2'—H2'	0.92 (2)	C8—H9C	1.02 (3)
C3'—C4'	1.410 (3)	C9—H8A	0.99 (3)
C4'—C5'	1.383 (3)	C9—H8B	1.00 (3)
C5'—C6'	1.397 (3)	C9—H8C	0.98 (3)
C5'—H5'	0.96 (3)	C10—H10A	0.94 (4)
C6'—H6'	0.96 (3)	C10—H10B	0.90 (4)
C1—C6	1.391 (3)	C10—H10C	0.93 (5)
C1—O1—C1'	118.49 (15)	C3—C4—C5	119.0 (2)
C3'—O4—C8	117.06 (18)	C3—C4—H4	119.0 (16)
C4'—O5—C9	117.00 (17)	C5—C4—H4	122.0 (16)
C7—O3—C10	116.7 (2)	C6—C5—C4	120.7 (2)
C6'—C1'—C2'	121.82 (18)	C6—C5—H5	118.6 (15)
C6'—C1'—O1	119.00 (19)	C4—C5—H5	120.7 (15)
C2'—C1'—O1	119.07 (19)	C5—C6—C1	120.3 (2)
C3'—C2'—C1'	119.4 (2)	C5—C6—H6	120.7 (14)
C3'—C2'—H2'	120.3 (14)	C1—C6—H6	119.0 (14)
C1'—C2'—H2'	120.3 (14)	O4—C8—H9A	106.1 (19)
O4—C3'—C2'	124.63 (18)	O4—C8—H9B	107.9 (17)
O4—C3'—C4'	115.85 (16)	H9A—C8—H9B	111 (2)
C2'—C3'—C4'	119.52 (18)	O4—C8—H9C	112.0 (17)
O5—C4'—C5'	124.52 (18)	H9A—C8—H9C	110 (2)
O5—C4'—C3'	115.94 (17)	H9B—C8—H9C	109 (2)
C5'—C4'—C3'	119.54 (18)	O5—C9—H8A	104.1 (16)
C4'—C5'—C6'	120.9 (2)	O5—C9—H8B	108.6 (15)
C4'—C5'—H5'	118.5 (14)	H8A—C9—H8B	114 (2)
C6'—C5'—H5'	120.6 (14)	O5—C9—H8C	109.6 (15)
C1'—C6'—C5'	118.8 (2)	H8A—C9—H8C	110 (2)
C1'—C6'—H6'	120.8 (14)	H8B—C9—H8C	110 (2)
C5'—C6'—H6'	120.3 (14)	O2—C7—O3	121.8 (2)
O1—C1—C6	122.28 (17)	O2—C7—C2	122.8 (2)
O1—C1—C2	117.67 (16)	O3—C7—C2	115.42 (16)
C6—C1—C2	120.03 (19)	O3—C10—H10A	105 (3)
C3—C2—C1	117.90 (18)	O3—C10—H10B	111 (2)
C3—C2—C7	115.82 (18)	H10A—C10—H10B	107 (4)
C1—C2—C7	126.26 (19)	O3—C10—H10C	107 (3)
C4—C3—C2	122.0 (2)	H10A—C10—H10C	111 (4)
C4—C3—H3	122.7 (15)	H10B—C10—H10C	115 (4)
C2—C3—H3	115.3 (15)

(II) 2-(3,4-Dimethoxyphenoxy)benzoic acid

Crystal data

C15H14O5	F(000) = 288
Mr = 274.26	Dx = 1.356 Mg m^−3
Triclinic, P1	Melting point = 420–422 K
a = 7.920 (4) Å	Mo Kα radiation, λ = 0.71069 Å
b = 8.550 (5) Å	Cell parameters from 854 reflections
c = 11.360 (7) Å	θ = 4.7–24.2°
α = 76.02 (7)°	µ = 0.10 mm^−1
β = 82.46 (7)°	T = 293 K
γ = 64.20 (6)°	Rectangular prism, colourless
V = 671.8 (7) Å^3	0.7 × 0.4 × 0.3 mm
Z = 2

Data collection

Stoe IPDS diffractometer	1618 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.047
Graphite monochromator	θmax = 24.1°, θmin = 4.7°
Image Plate scans	h = −9→8
4584 measured reflections	k = −9→9
1923 independent reflections	l = −12→12

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.098P)^2 + 0.065P] where P = (Fo^2 + 2Fc^2)/3
1923 reflections	(Δ/σ)max = 0.001
189 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.15 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.

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

	x	y	z	Uiso*/Ueq
O1	0.25935 (19)	0.52786 (18)	0.28297 (15)	0.0871 (5)
O2	0.4304 (2)	0.2115 (2)	0.41975 (16)	0.0960 (6)
O3	0.2642 (2)	0.05641 (19)	0.49096 (16)	0.0931 (6)
H3	0.3679	−0.0181	0.5146	0.140*
O4	0.2559 (2)	0.91095 (18)	−0.10998 (11)	0.0805 (5)
O5	0.2565 (2)	1.14851 (18)	−0.00850 (13)	0.0818 (5)
C1	0.0937 (3)	0.5098 (2)	0.31241 (16)	0.0662 (5)
C2	0.1019 (3)	0.3482 (2)	0.38412 (15)	0.0633 (5)
C3	−0.0656 (3)	0.3280 (3)	0.41072 (17)	0.0736 (6)
H3A	−0.0624	0.2209	0.4569	0.088*
C4	−0.2344 (3)	0.4611 (3)	0.3708 (2)	0.0801 (6)
H4	−0.3443	0.4449	0.3898	0.096*
C5	−0.2392 (3)	0.6200 (3)	0.3017 (2)	0.0786 (6)
H5	−0.354 (4)	0.709 (3)	0.270 (2)	0.089 (6)*
C6	−0.0778 (3)	0.6457 (3)	0.27240 (18)	0.0739 (6)
H6	−0.082 (3)	0.755 (3)	0.223 (2)	0.079 (6)*
C1'	0.2517 (3)	0.6894 (3)	0.21153 (19)	0.0718 (6)
C2'	0.2543 (3)	0.7141 (2)	0.08560 (18)	0.0704 (6)
H2'	0.2557	0.6265	0.0498	0.085*
C3'	0.2548 (3)	0.8701 (2)	0.01435 (16)	0.0645 (5)
C4'	0.2555 (3)	1.0000 (2)	0.06998 (17)	0.0644 (5)
C5'	0.2544 (3)	0.9711 (3)	0.19456 (18)	0.0731 (6)
H5'	0.2548	1.0572	0.2312	0.088*
C6'	0.2527 (3)	0.8147 (3)	0.26675 (17)	0.0757 (6)
H6'	0.2522	0.7958	0.3509	0.091*
C7	0.2768 (3)	0.1981 (2)	0.43362 (15)	0.0662 (5)
C8	0.2560 (3)	0.7846 (3)	−0.1720 (2)	0.0867 (7)
H8A	0.2564	0.8300	−0.2579	0.130*
H8B	0.1459	0.7631	−0.1479	0.130*
H8C	0.3659	0.6755	−0.1518	0.130*
C9	0.2548 (4)	1.2853 (3)	0.0412 (2)	0.0920 (7)
H9A	0.2560	1.3810	−0.0233	0.138*
H9B	0.3636	1.2402	0.0892	0.138*
H9C	0.1437	1.3277	0.0913	0.138*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0685 (8)	0.0683 (9)	0.1013 (10)	−0.0262 (7)	−0.0054 (7)	0.0201 (7)
O2	0.0748 (9)	0.0744 (10)	0.1130 (12)	−0.0262 (7)	−0.0031 (8)	0.0168 (8)
O3	0.0889 (10)	0.0682 (9)	0.1075 (12)	−0.0331 (7)	−0.0163 (8)	0.0155 (8)
O4	0.1120 (11)	0.0721 (8)	0.0622 (8)	−0.0446 (8)	0.0002 (7)	−0.0121 (6)
O5	0.1122 (11)	0.0623 (8)	0.0762 (9)	−0.0453 (7)	−0.0060 (7)	−0.0049 (6)
C1	0.0688 (11)	0.0651 (10)	0.0585 (10)	−0.0270 (9)	0.0032 (8)	−0.0066 (8)
C2	0.0727 (11)	0.0606 (10)	0.0512 (9)	−0.0260 (8)	0.0031 (7)	−0.0085 (7)
C3	0.0829 (13)	0.0700 (12)	0.0662 (11)	−0.0347 (10)	0.0049 (9)	−0.0098 (9)
C4	0.0702 (12)	0.0863 (14)	0.0822 (13)	−0.0343 (10)	0.0029 (10)	−0.0146 (11)
C5	0.0685 (12)	0.0785 (13)	0.0776 (12)	−0.0235 (10)	−0.0064 (9)	−0.0084 (10)
C6	0.0738 (12)	0.0655 (11)	0.0705 (11)	−0.0242 (9)	−0.0048 (9)	−0.0012 (9)
C1'	0.0612 (10)	0.0615 (10)	0.0773 (12)	−0.0229 (8)	−0.0021 (8)	0.0076 (9)
C2'	0.0740 (11)	0.0551 (10)	0.0777 (12)	−0.0262 (8)	0.0001 (9)	−0.0085 (8)
C3'	0.0680 (10)	0.0577 (10)	0.0615 (10)	−0.0242 (8)	0.0016 (8)	−0.0075 (8)
C4'	0.0682 (10)	0.0552 (9)	0.0660 (10)	−0.0256 (8)	−0.0005 (8)	−0.0069 (8)
C5'	0.0785 (12)	0.0719 (12)	0.0687 (11)	−0.0310 (10)	−0.0014 (9)	−0.0157 (9)
C6'	0.0753 (12)	0.0817 (13)	0.0608 (10)	−0.0300 (10)	−0.0016 (9)	−0.0039 (9)
C7	0.0777 (12)	0.0599 (10)	0.0545 (9)	−0.0278 (9)	0.0041 (8)	−0.0053 (8)
C8	0.0982 (15)	0.0931 (15)	0.0790 (13)	−0.0444 (12)	0.0063 (11)	−0.0323 (11)
C9	0.1114 (17)	0.0695 (13)	0.1067 (17)	−0.0490 (12)	−0.0016 (13)	−0.0180 (12)

Geometric parameters (Å, º)

O1—C1	1.376 (2)	C2'—C1'	1.393 (3)
O1—C1'	1.403 (2)	C2'—H2'	0.9300
O2—C7	1.257 (3)	C1'—C6'	1.369 (3)
O3—C7	1.268 (2)	C5—C4	1.382 (3)
O3—H3	0.8200	C5—H5	0.94 (3)
O4—C3'	1.370 (2)	C5'—C6'	1.394 (3)
O4—C8	1.425 (3)	C5'—H5'	0.9300
O5—C4'	1.366 (2)	C6'—H6'	0.9300
O5—C9	1.410 (3)	C3—C4	1.369 (3)
C4'—C5'	1.376 (3)	C3—H3A	0.9300
C4'—C3'	1.407 (3)	C4—H4	0.9300
C1—C6	1.391 (3)	C8—H8A	0.9600
C1—C2	1.403 (3)	C8—H8B	0.9600
C2—C3	1.397 (3)	C8—H8C	0.9600
C2—C7	1.480 (3)	C9—H9A	0.9600
C3'—C2'	1.384 (3)	C9—H9B	0.9600
C6—C5	1.375 (3)	C9—H9C	0.9600
C6—H6	0.96 (2)
C3'—O4—C8	118.16 (17)	O2—C7—O3	121.77 (18)
C7—O3—H3	109.5	O2—C7—C2	121.20 (17)
C1—O1—C1'	118.16 (15)	O3—C7—C2	117.04 (19)
C4'—O5—C9	117.90 (17)	C4'—C5'—C6'	121.0 (2)
O5—C4'—C5'	125.47 (19)	C4'—C5'—H5'	119.5
O5—C4'—C3'	114.88 (16)	C6'—C5'—H5'	119.5
C5'—C4'—C3'	119.65 (18)	C1'—C6'—C5'	118.81 (18)
O1—C1—C6	121.75 (17)	C1'—C6'—H6'	120.6
O1—C1—C2	117.97 (16)	C5'—C6'—H6'	120.6
C6—C1—C2	120.27 (19)	C4—C3—C2	121.93 (19)
C3—C2—C1	117.91 (17)	C4—C3—H3A	119.0
C3—C2—C7	117.95 (17)	C2—C3—H3A	119.0
C1—C2—C7	124.14 (18)	C3—C4—C5	119.1 (2)
O4—C3'—C2'	125.06 (19)	C3—C4—H4	120.5
O4—C3'—C4'	115.35 (16)	C5—C4—H4	120.5
C2'—C3'—C4'	119.59 (18)	O4—C8—H8A	109.5
C5—C6—C1	119.70 (19)	O4—C8—H8B	109.5
C5—C6—H6	120.7 (13)	H8A—C8—H8B	109.5
C1—C6—H6	119.6 (13)	O4—C8—H8C	109.5
C3'—C2'—C1'	119.4 (2)	H8A—C8—H8C	109.5
C3'—C2'—H2'	120.3	H8B—C8—H8C	109.5
C1'—C2'—H2'	120.3	O5—C9—H9A	109.5
C6'—C1'—C2'	121.58 (18)	O5—C9—H9B	109.5
C6'—C1'—O1	119.29 (19)	H9A—C9—H9B	109.5
C2'—C1'—O1	119.0 (2)	O5—C9—H9C	109.5
C6—C5—C4	121.1 (2)	H9A—C9—H9C	109.5
C6—C5—H5	119.8 (15)	H9B—C9—H9C	109.5
C4—C5—H5	119.0 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2^i	0.82	1.81	2.612 (3)	168
O3—H3···O3^i	0.82	2.78	3.449 (4)	140

Symmetry code: (i) −x+1, −y, −z+1.

(III) 1,2-Dimethoxy-9H-xanthen-9-one

Crystal data

C15H12O4	Dx = 1.407 Mg m^−3
Mr = 256.25	Melting point = 406–408 K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
a = 4.953 (2) Å	Cell parameters from 1542 reflections
b = 13.930 (6) Å	θ = 3.7–24.1°
c = 17.670 (8) Å	µ = 0.10 mm^−1
β = 97.23 (6)°	T = 293 K
V = 1209.5 (9) Å^3	Rectangular prism, yellow
Z = 4	0.60 × 0.25 × 0.20 mm
F(000) = 536

Data collection

Stoe IPDS diffractometer	1225 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.056
Graphite monochromator	θmax = 24.1°, θmin = 3.7°
Image Plate scans	h = −5→5
7542 measured reflections	k = −15→15
1807 independent reflections	l = −20→20

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.168	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.08P)^2 + 0.422P] where P = (Fo^2 + 2Fc^2)/3
1807 reflections	(Δ/σ)max = 0.001
180 parameters	Δρmax = 0.17 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.

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

	x	y	z	Uiso*/Ueq
O10	0.1782 (4)	0.04584 (12)	0.12661 (11)	0.0671 (6)
O11	0.6932 (4)	0.25908 (13)	0.31078 (12)	0.0722 (6)
O12	0.9964 (5)	0.11133 (14)	0.36272 (12)	0.0788 (7)
O13	0.2837 (5)	0.32503 (13)	0.20306 (12)	0.0824 (7)
C1	0.6361 (6)	0.17037 (18)	0.27668 (16)	0.0614 (7)
C2	0.8009 (6)	0.0927 (2)	0.30233 (16)	0.0634 (7)
C3	0.7572 (6)	0.00285 (19)	0.26745 (17)	0.0661 (8)
H3	0.8704	−0.0484	0.2836	0.079*
C4	0.5477 (6)	−0.0101 (2)	0.20938 (16)	0.0644 (8)
H4	0.502 (6)	−0.076 (2)	0.1884 (16)	0.074 (8)*
C5	−0.2023 (7)	0.0912 (2)	0.04099 (17)	0.0735 (8)
H5	−0.2205	0.0277	0.0249	0.088*
C6	−0.3784 (7)	0.1603 (3)	0.00908 (18)	0.0820 (9)
H6	−0.5162	0.1432	−0.0293	0.098*
C7	−0.3548 (7)	0.2560 (2)	0.03311 (19)	0.0795 (9)
H7	−0.4756	0.3021	0.0109	0.095*
C8	−0.1530 (7)	0.2813 (2)	0.08945 (18)	0.0739 (9)
H8	−0.131 (6)	0.347 (2)	0.1089 (17)	0.081 (9)*
C9	0.2513 (6)	0.23974 (19)	0.18346 (16)	0.0643 (8)
C11	0.5135 (7)	0.2855 (2)	0.36529 (19)	0.0802 (9)
H11A	0.5650	0.3473	0.3864	0.120*
H11B	0.5259	0.2387	0.4054	0.120*
H11C	0.3299	0.2882	0.3404	0.120*
C12	1.1668 (8)	0.0336 (2)	0.3915 (2)	0.0874 (10)
H12A	1.2944	0.0557	0.4333	0.131*
H12B	1.2637	0.0094	0.3518	0.131*
H12C	1.0569	−0.0166	0.4088	0.131*
C4a	0.3821 (6)	0.06718 (18)	0.18490 (15)	0.0595 (7)
C8a	0.0339 (6)	0.21248 (19)	0.12325 (15)	0.0616 (7)
C9a	0.4242 (6)	0.15965 (17)	0.21638 (15)	0.0590 (7)
C10a	0.0032 (6)	0.1177 (2)	0.09776 (15)	0.0637 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O10	0.0663 (14)	0.0570 (11)	0.0760 (12)	0.0006 (9)	0.0010 (10)	−0.0071 (9)
O11	0.0668 (15)	0.0565 (11)	0.0931 (14)	−0.0060 (9)	0.0087 (10)	−0.0137 (10)
O12	0.0740 (15)	0.0685 (12)	0.0886 (14)	0.0055 (10)	−0.0094 (11)	−0.0082 (10)
O13	0.0887 (18)	0.0516 (12)	0.1030 (16)	0.0015 (10)	−0.0036 (12)	−0.0062 (10)
C1	0.0600 (19)	0.0510 (15)	0.0737 (17)	−0.0050 (12)	0.0099 (13)	−0.0052 (12)
C2	0.0582 (19)	0.0609 (16)	0.0698 (16)	−0.0010 (12)	0.0028 (13)	−0.0038 (12)
C3	0.068 (2)	0.0551 (16)	0.0750 (17)	0.0035 (12)	0.0107 (14)	0.0009 (13)
C4	0.068 (2)	0.0502 (15)	0.0755 (18)	−0.0007 (13)	0.0092 (14)	−0.0043 (12)
C5	0.068 (2)	0.0779 (19)	0.0739 (19)	−0.0058 (15)	0.0058 (15)	−0.0072 (15)
C6	0.073 (2)	0.095 (2)	0.0761 (19)	0.0000 (18)	0.0013 (16)	0.0039 (17)
C7	0.072 (2)	0.082 (2)	0.084 (2)	0.0077 (16)	0.0042 (17)	0.0097 (17)
C8	0.073 (2)	0.0691 (19)	0.080 (2)	0.0038 (15)	0.0115 (16)	0.0060 (15)
C9	0.064 (2)	0.0543 (16)	0.0757 (17)	0.0002 (13)	0.0128 (14)	0.0000 (13)
C11	0.081 (2)	0.0732 (19)	0.086 (2)	0.0033 (16)	0.0103 (17)	−0.0193 (16)
C12	0.082 (3)	0.081 (2)	0.094 (2)	0.0100 (17)	−0.0081 (18)	0.0014 (17)
C4a	0.0576 (19)	0.0537 (15)	0.0671 (16)	−0.0026 (12)	0.0067 (13)	−0.0025 (12)
C8a	0.0592 (19)	0.0591 (16)	0.0668 (16)	−0.0001 (12)	0.0087 (13)	0.0021 (12)
C9a	0.0580 (19)	0.0480 (14)	0.0714 (16)	−0.0024 (11)	0.0100 (13)	−0.0029 (11)
C10a	0.062 (2)	0.0618 (16)	0.0681 (16)	0.0017 (13)	0.0112 (13)	0.0001 (13)

Geometric parameters (Å, º)

O10—C10a	1.379 (3)	C5—C6	1.372 (5)
O10—C4a	1.381 (3)	C5—H5	0.9300
O11—C1	1.388 (3)	C11—H11A	0.9600
O11—C11	1.439 (4)	C11—H11B	0.9600
O12—C2	1.373 (3)	C11—H11C	0.9600
O12—C12	1.426 (4)	C8—C7	1.365 (5)
O13—C9	1.242 (3)	C8—H8	0.98 (3)
C2—C1	1.396 (4)	C7—C6	1.400 (5)
C2—C3	1.400 (4)	C7—H7	0.9300
C9a—C1	1.406 (4)	C3—C4	1.376 (4)
C9a—C4a	1.408 (4)	C3—H3	0.9300
C9a—C9	1.480 (4)	C4—H4	1.00 (3)
C8a—C10a	1.397 (4)	C6—H6	0.9300
C8a—C8	1.412 (4)	C12—H12A	0.9600
C8a—C9	1.465 (4)	C12—H12B	0.9600
C4a—C4	1.389 (4)	C12—H12C	0.9600
C10a—C5	1.387 (4)
C10a—O10—C4a	119.1 (2)	O11—C11—H11C	109.5
C1—O11—C11	114.1 (2)	H11A—C11—H11C	109.5
C2—O12—C12	117.5 (2)	H11B—C11—H11C	109.5
O12—C2—C1	115.6 (2)	C7—C8—C8a	121.0 (3)
O12—C2—C3	124.5 (3)	C7—C8—H8	122.3 (18)
C1—C2—C3	119.9 (3)	C8a—C8—H8	116.7 (18)
C1—C9a—C4a	117.1 (2)	C8—C7—C6	119.5 (3)
C1—C9a—C9	123.9 (2)	C8—C7—H7	120.3
C4a—C9a—C9	119.0 (2)	C6—C7—H7	120.3
C10a—C8a—C8	117.8 (3)	C4—C3—C2	120.4 (3)
C10a—C8a—C9	121.3 (3)	C4—C3—H3	119.8
C8—C8a—C9	120.9 (3)	C2—C3—H3	119.8
O10—C4a—C4	114.4 (2)	C3—C4—C4a	119.4 (3)
O10—C4a—C9a	123.3 (2)	C3—C4—H4	120.7 (17)
C4—C4a—C9a	122.3 (3)	C4a—C4—H4	119.7 (17)
O10—C10a—C5	116.3 (3)	O13—C9—C8a	120.5 (3)
O10—C10a—C8a	121.9 (3)	O13—C9—C9a	124.3 (3)
C5—C10a—C8a	121.7 (3)	C8a—C9—C9a	115.2 (2)
O11—C1—C2	118.0 (3)	C5—C6—C7	121.3 (3)
O11—C1—C9a	121.0 (2)	C5—C6—H6	119.4
C2—C1—C9a	120.9 (2)	C7—C6—H6	119.4
C6—C5—C10a	118.8 (3)	O12—C12—H12A	109.5
C6—C5—H5	120.6	O12—C12—H12B	109.5
C10a—C5—H5	120.6	H12A—C12—H12B	109.5
O11—C11—H11A	109.5	O12—C12—H12C	109.5
O11—C11—H11B	109.5	H12A—C12—H12C	109.5
H11A—C11—H11B	109.5	H12B—C12—H12C	109.5

(IV) 1,2,8-Trimethoxy-9H-xanthen-9-one

Crystal data

C16H14O5	Dx = 1.411 Mg m^−3
Mr = 286.27	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 1345 reflections
a = 5.273 (1) Å	θ = 4.1–24.2°
b = 15.443 (4) Å	µ = 0.11 mm^−1
c = 16.550 (6) Å	T = 293 K
V = 1347.7 (7) Å^3	Rectangular prism, colourless
Z = 4	0.8 × 0.5 × 0.3 mm
F(000) = 600

Data collection

Stoe IPDS diffractometer	1887 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 24.2°, θmin = 4.1°
Image Plate scans	h = −5→5
8453 measured reflections	k = −17→17
2068 independent reflections	l = −18→18

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)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.108	w = 1/[σ^2(Fo^2) + (0.046P)^2 + 0.426P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
2068 reflections	Δρmax = 0.14 e Å^−3
210 parameters	Δρmin = −0.11 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: not reliably determined

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.

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

	x	y	z	Uiso*/Ueq
O10	0.1263 (4)	0.98200 (11)	0.76476 (10)	0.0659 (5)
O11	−0.1765 (4)	1.02405 (12)	0.49169 (9)	0.0650 (5)
O12	−0.4768 (4)	0.88684 (14)	0.50771 (12)	0.0889 (7)
O13	0.4716 (4)	1.23093 (12)	0.63195 (11)	0.0751 (6)
O14	0.0708 (4)	1.15012 (12)	0.57548 (11)	0.0767 (6)
C1	−0.1870 (5)	0.98420 (16)	0.56569 (14)	0.0578 (6)
C2	−0.3372 (5)	0.91028 (18)	0.57463 (16)	0.0656 (7)
C3	−0.3319 (6)	0.8639 (2)	0.64644 (18)	0.0732 (8)
H3	−0.450 (7)	0.811 (2)	0.651 (2)	0.100 (11)*
C4	−0.1762 (7)	0.88916 (18)	0.70914 (19)	0.0707 (7)
H4	−0.170 (7)	0.857 (2)	0.7581 (18)	0.086 (9)*
C5	0.4639 (6)	1.05602 (18)	0.82292 (16)	0.0665 (7)
H5	0.455 (6)	1.015 (2)	0.8658 (18)	0.083 (9)*
C6	0.6424 (6)	1.12058 (19)	0.82110 (18)	0.0703 (8)
H6	0.767 (6)	1.1247 (18)	0.8633 (18)	0.079 (9)*
C7	0.6530 (6)	1.17989 (19)	0.75761 (16)	0.0665 (7)
H7	0.773 (6)	1.2248 (18)	0.7577 (16)	0.070 (8)*
C8	0.4804 (6)	1.17423 (15)	0.69478 (14)	0.0591 (6)
C9	0.1117 (5)	1.09513 (16)	0.62757 (14)	0.0573 (6)
C11	−0.3865 (6)	1.0794 (2)	0.47141 (19)	0.0817 (9)
H11A	−0.3601	1.1037	0.4187	0.123*
H11B	−0.3991	1.1251	0.5105	0.123*
H11C	−0.5404	1.0462	0.4715	0.123*
C12	−0.6838 (6)	0.8298 (2)	0.5180 (2)	0.0866 (9)
H12A	−0.7649	0.8203	0.4669	0.130*
H12B	−0.8032	0.8548	0.5551	0.130*
H12C	−0.6240	0.7756	0.5391	0.130*
C13	0.6603 (7)	1.29780 (18)	0.62707 (19)	0.0792 (8)
H13A	0.6317	1.3321	0.5795	0.119*
H13B	0.8257	1.2720	0.6243	0.119*
H13C	0.6497	1.3340	0.6741	0.119*
C4a	−0.0259 (5)	0.96225 (15)	0.69987 (14)	0.0581 (6)
C8a	0.2966 (5)	1.10672 (15)	0.69314 (14)	0.0536 (6)
C9a	−0.0338 (5)	1.01263 (15)	0.62985 (13)	0.0536 (6)
C10a	0.2972 (6)	1.04926 (16)	0.75881 (14)	0.0586 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O10	0.0733 (12)	0.0665 (10)	0.0580 (9)	−0.0065 (9)	−0.0047 (9)	0.0109 (8)
O11	0.0660 (11)	0.0795 (11)	0.0495 (9)	0.0052 (10)	0.0019 (9)	0.0011 (8)
O12	0.0872 (15)	0.1058 (15)	0.0738 (13)	−0.0327 (13)	−0.0056 (12)	−0.0122 (11)
O13	0.0863 (14)	0.0677 (11)	0.0712 (11)	−0.0177 (11)	−0.0085 (11)	0.0100 (9)
O14	0.0875 (14)	0.0716 (11)	0.0710 (11)	−0.0105 (10)	−0.0148 (11)	0.0216 (9)
C1	0.0582 (14)	0.0638 (14)	0.0515 (13)	0.0020 (13)	0.0025 (11)	−0.0015 (11)
C2	0.0640 (16)	0.0696 (16)	0.0632 (15)	−0.0068 (14)	0.0046 (14)	−0.0106 (12)
C3	0.076 (2)	0.0709 (18)	0.0730 (18)	−0.0128 (16)	0.0078 (16)	0.0005 (14)
C4	0.0772 (19)	0.0676 (16)	0.0672 (16)	−0.0063 (16)	0.0039 (16)	0.0091 (13)
C5	0.0768 (19)	0.0679 (15)	0.0548 (14)	0.0044 (15)	−0.0082 (14)	0.0050 (13)
C6	0.073 (2)	0.0738 (17)	0.0641 (16)	0.0087 (15)	−0.0126 (15)	−0.0097 (14)
C7	0.0680 (18)	0.0666 (16)	0.0648 (16)	−0.0032 (14)	−0.0056 (14)	−0.0091 (13)
C8	0.0685 (16)	0.0548 (13)	0.0542 (13)	−0.0002 (13)	0.0021 (12)	−0.0013 (11)
C9	0.0615 (15)	0.0580 (13)	0.0523 (13)	0.0056 (11)	0.0031 (12)	0.0048 (11)
C11	0.075 (2)	0.094 (2)	0.0765 (18)	0.0180 (17)	−0.0089 (16)	0.0082 (16)
C12	0.0642 (19)	0.087 (2)	0.109 (2)	−0.0118 (17)	−0.0058 (18)	−0.0153 (19)
C13	0.084 (2)	0.0636 (16)	0.090 (2)	−0.0209 (15)	0.0031 (19)	0.0065 (14)
C4a	0.0590 (15)	0.0597 (13)	0.0554 (14)	0.0006 (12)	0.0013 (12)	0.0004 (11)
C8a	0.0602 (15)	0.0504 (12)	0.0502 (12)	0.0031 (11)	0.0004 (11)	0.0015 (9)
C9a	0.0553 (14)	0.0553 (12)	0.0503 (12)	0.0015 (11)	0.0039 (11)	0.0018 (10)
C10a	0.0662 (17)	0.0576 (13)	0.0521 (13)	0.0037 (12)	0.0023 (12)	0.0001 (10)

Geometric parameters (Å, º)

O10—C4a	1.375 (3)	C7—H7	0.94 (3)
O10—C10a	1.379 (3)	C9a—C1	1.404 (3)
O11—C1	1.372 (3)	C9a—C9	1.488 (3)
O11—C11	1.438 (3)	C4—C3	1.379 (4)
O12—C2	1.378 (3)	C4—H4	0.95 (3)
O12—C12	1.413 (4)	C13—H13A	0.9600
O13—C8	1.360 (3)	C13—H13B	0.9600
O13—C13	1.436 (3)	C13—H13C	0.9600
O14—C9	1.229 (3)	C12—H12A	0.9600
C8a—C10a	1.403 (3)	C12—H12B	0.9600
C8a—C8	1.424 (4)	C12—H12C	0.9600
C8a—C9	1.470 (3)	C1—C2	1.398 (4)
C5—C6	1.371 (4)	C2—C3	1.387 (4)
C5—C10a	1.382 (4)	C6—H6	0.96 (3)
C5—H5	0.95 (3)	C3—H3	1.03 (4)
C8—C7	1.385 (4)	C11—H11A	0.9600
C4a—C4	1.388 (4)	C11—H11B	0.9600
C4a—C9a	1.396 (3)	C11—H11C	0.9600
C7—C6	1.395 (4)
C4a—O10—C10a	119.53 (19)	O13—C13—H13A	109.5
C1—O11—C11	116.4 (2)	O13—C13—H13B	109.5
C8—O13—C13	118.8 (2)	H13A—C13—H13B	109.5
C10a—C8a—C8	116.5 (2)	O13—C13—H13C	109.5
C10a—C8a—C9	119.8 (2)	H13A—C13—H13C	109.5
C8—C8a—C9	123.7 (2)	H13B—C13—H13C	109.5
C6—C5—C10a	118.3 (3)	O12—C12—H12A	109.5
C6—C5—H5	122.3 (19)	O12—C12—H12B	109.5
C10a—C5—H5	119.3 (19)	H12A—C12—H12B	109.5
O13—C8—C7	123.8 (2)	O12—C12—H12C	109.5
O13—C8—C8a	115.7 (2)	H12A—C12—H12C	109.5
C7—C8—C8a	120.5 (2)	H12B—C12—H12C	109.5
O10—C10a—C5	114.7 (2)	O11—C1—C2	118.9 (2)
O10—C10a—C8a	122.0 (2)	O11—C1—C9a	120.8 (2)
C5—C10a—C8a	123.3 (3)	C2—C1—C9a	120.1 (2)
O10—C4a—C4	115.3 (2)	O12—C2—C3	124.3 (3)
O10—C4a—C9a	122.8 (2)	O12—C2—C1	115.6 (2)
C4—C4a—C9a	121.9 (2)	C3—C2—C1	120.0 (3)
C8—C7—C6	119.9 (3)	C5—C6—C7	121.4 (3)
C8—C7—H7	119.4 (17)	C5—C6—H6	120.0 (18)
C6—C7—H7	120.7 (17)	C7—C6—H6	118.5 (18)
C4a—C9a—C1	118.1 (2)	C4—C3—C2	120.7 (3)
C4a—C9a—C9	118.9 (2)	C4—C3—H3	121.5 (19)
C1—C9a—C9	123.0 (2)	C2—C3—H3	117.8 (19)
C2—O12—C12	118.6 (2)	O11—C11—H11A	109.5
O14—C9—C8a	123.4 (2)	O11—C11—H11B	109.5
O14—C9—C9a	121.3 (2)	H11A—C11—H11B	109.5
C8a—C9—C9a	115.3 (2)	O11—C11—H11C	109.5
C3—C4—C4a	119.1 (3)	H11A—C11—H11C	109.5
C3—C4—H4	121 (2)	H11B—C11—H11C	109.5
C4a—C4—H4	120 (2)