3,3a-Dihydrocyclo­penta­[b]­chromen-1(2H)-ones from the reaction of salicylaldehyde and 2-cyclo­penten-1-one

The two title chromene compounds, 3,3a-dihydrocyclo­penta­[b]chromen-1(2H)-one, C₁₆H₁₂O₂, (I), and 2-(2-hydroxy­benzyl­idene)-3,3a-dihydrocyclo­penta­[b]chromen-1(2H)-one, C₁₉H₁₄O₃, (II), have been determined in the monoclinic space group P2₁/n. Compound (I) is mainly stabilized by C-H...[pi] inter­actions. Compound (II) is linked into infinite one-dimensional chains with a C(3) motif via inter­molecular O-H...O hydrogen bonds. The inter­molecular C-H...[pi] and [pi]-­[pi] inter­actions also play key roles in stabilizing the crystal packing. Two intra­molecular C-H...O hydrogen bonds with S(5) motifs were detected in (II).

S1. Comment

Chromenes (2H-1-benzopyrane derivatives) are frequently found in naturally occurring heterocycles, many of which exhibit biological activity (Bowers et al., 1976) and have been widely employed as important intermediates in the synthesis of many natural products and medicinal agents (Wang & Finn, 2000). Thus, various synthetic methods for the formation of these compounds have been reported (Kaye & Nocanda, 2000; Parker & Mindt, 2001).

Most recently, the reaction of 2-hydroxybenzaldehyde and cyclopent-2-enone, a typical Baylis–Hillman coupling, was suggested to occur through a domino oxa-Michael addition/aldol condesation pathway in the presence of DMAP (dimethylaminopyridine; Lee et al., 2003) or DABCO (diazabicyclo[2.2.2]octane; Bräse & Lesch, 2004) under aqueous conditions. We have also carried out the reactions with imidazole as a catalyst. Several crystal structures of chromene derivatives have been published (Huo et al., 2004a,b,c). In the present paper, another two crystal stuctures are reported.

In the five derivatives that we have studied [7a,8,9,10-tetrahydrobenzo[f]cyclopenta[b]chromen-10-one (Huo et al., 2004a), nitro/methoxy-2,3-dihydro-1H-cyclopenta[b]chromen-1-one (Huo et al., 2004b,c), 3,3a-dihydro-2H-cyclopenta[b]chromen-1-one and 5-benzylidene-3,3a-dihydro-2H-cyclopenta[b]chromen-1-one (the present work)], similarities in the geometry are observed and the pyran ring has the same configuration (half-chair). However, the crystal packings for the five compounds differ, partly because of the presence of different substituents.

Selected geometric parameters of (I) are listed in Table 1. The ellipsoid plot of the molecule is shown in Fig. 1. Single-crystal X-ray analysis of the good quality single crystals revealed a monoclinic crystal lattice with a P2₁/n space group. Atom C3 of the pyran ring in disordered over two sites, with a ratio of 0.59 (6):0.41 (6) for the major and minor components, respectively. All atoms, except atom C3, are coplanar within ±0.0611 (2) Å, while atom C3 deviates from the plane of the other atoms by 0.4784 (3) Å. The pyran ring adopts a half-chair conformation, the dihedral angle between the O2/C3/C2 and O2/C8/C7/C6 planes being 38.02 (2)°. The C1—C2—C3—O2 and C6—C2—C3—O2 torsion angles are −152.7 (2) and 40.2 (3)°, respectively. For the minor component, the C1—C2—C3A—O2 and C6—C2—C3A—O2 torsion angles are 156.0 (2) and −43.2 (3)°. The packing of the crystals indicates that the adjacent molecules show two C—H···π (edge-to-face) interactions, elucidated by PLATON (Spek, 2003), with the π system of the C7–C12 ring (with centroid Cg; Fig. 2). In the first of these interactions, the cyclopentene ring atom C5 interacts with Cg at (x, 1 + y, z) [C5···Cg = 3.776 (2) Å, H5A···Cg = 2.89 Å and C5—H5A···Cg = 153°]. In the second interaction, phenyl atom C10 interacts with Cg at (3/2 − x, −1/2 + y, 1/2 − z) [C10···Cg = 3.901 (2) Å, H10···Cg = 3.22 Å and C10—H10···Cg = 132°]. Selected geometric parameters of (II) are listed in Table 2. The ellipsoid plot of the molecule is shown in Fig. 3. Single-crystal X-ray analysis of the crystals of (II) revealed a monoclinic crystal lattice with a P2₁/n space group. The chromene fragment of the molecule is the same as that of (I). Except for atom C3, all atoms are coplanar within ±0.187 (2) Å, with atom C3 deviating by 0.4051 (2) Å. The dihedral angel between the O2/C3/C2 and O2/C8/C7/C6 planes is 35.51 (2)°. The The C1—C2—C3—O2 and C6—C2—C3—C4 torsion angles are 146.9 (2) and −151.0 (2)°, respectively. The C14–C19 phenyl ring and the chromene fragment are joined by atom C13. The C14—C13—C5—C4 and C5—C13—C14—C19 torsion angles are −5.6 (3) and −23.4 (3)°. A linear O—H···O intermolecular hydrogen bond of the hydroxy group was observed in the crystal structure of II (Fig. 4). The strong interaction links the molecules into an infinite one-dimensional chain-based vector [101], with a C(3) motif (Bernstein et al., 1995). The hydrogen-bonding parameters include an H1···O1 distance of 1.93 Å and an O3—H1···O1 angle of 178° (Table 3). Further detection indicates that the crystal has two intramolecular C—H···O hydrogen bonds (Table 3), with the sp² C13 atom acting as the only donor, and the carbonyl O atom and hydroxy O atom playing as acceptors. The O1···H13···O3 angle is 153.30°. Furthermore, the three intermolecular C—H···π interactions (Table 3; Cg₁ is the centroid of the C14–C19 ring, and Cg₂ the centroid of the C7–C12 ring) and π–π interactions are detected, which stabilize the crystal stacking. Fig. 5 shows the two C—H···π (edge-to-face) interactions related to the π electrons of the C14–C19 phenyl ring (with centroid Cg₁).

S2. Experimental

The title compounds were synthesized from Baylis–Hillman reactions. At room temperature, a clear solution of 2-hydroxybenzaldehyde (1 mmol), cyclopent-2-enone (2 mmol) and imidazole (1 mmol) in tetrahydrofuran (1.5 ml) was mixed with deionized water (1.5 ml). The mixture was stirred at ambient temperature for 48 h to finish the reaction. The mixture was diluted with water (10 ml) and extracted with ethyl acetate. The organic layer was concentrated under reduced pressure. After the usual work up, chromatography of the crude product on silica gel, using ethyl acetate and petroleum (1:4) as eluant, gave pure (I) with a yield of 53% and a little (II). Compound (I) (60 mg) was dissolved in CHCl₃ (2 ml). The solution was allowed to evaporate slowly at room temperature for several days. Yellow crystals suitable for X-ray crystallography were formed. Crystals of (II) were formed during the processes of chromatography.

S3. Refinement

All H atoms were placed in calculated positions and allowed to ride on their parent atoms, with U_iso(H) values set to 1.5U_eq(parent atom) for the Csp³-bound H atoms and the hydroxy-group O atom, and 1.2U_eq(parent atom) for Csp²-bound H atoms. The C—H distances were fixed in the range 0.93–0.98 Å and O—H distances were fixed at 0.82 Å.

Computing details

For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The suffix A denotes the 41% minor disorder component.
	Fig. 2. The packing of (I), viewed down the a axis. C5—H5A···Cg(x, 1 + y, z) and C10—H10···Cg(3/2 − x, −1/2 + y, 1/2 − z) interactions are indicated by dotted lines. The minor component of the disorder has been omitted for clarity.
	Fig. 3. A view of the molecular structure of (II). Displacement ellipsoids are shown at the 50% probability level.
	Fig. 4. The packing of (II). Infinite one-dimensional O—H···O^i hydrogen-bonding chains along the [101] orientation are indicated with dotted lines. The view is down the a axis. [Symmetry code: (i) −1/2 + x, 5/2 − y, −1/2 + z.]
	Fig. 5. C6—H6···Cg1^ii and C3—H3···Cg1^iii [symmetry codes: (ii) 2 − x, 2 − y, −z; (iii) 1 − x, 2 − y, −z; Cg1 is the centroid of the C14–C19 ring) interactions in the structure of (II). Selected atoms are labled. H atoms, except atoms H3 and H6, have been omitted for clarity.

(I) 3,3a-dihydro-2H-cyclopenta[b]chromen-1-one

Crystal data

C12H10O2	F(000) = 392
Mr = 186.20	Dx = 1.353 Mg m^−3
Monoclinic, P21/n	Melting point: 388 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 5.8015 (14) Å	Cell parameters from 5211 reflections
b = 7.6260 (19) Å	θ = 2.9–26.9°
c = 20.661 (5) Å	µ = 0.09 mm^−1
β = 91.254 (3)°	T = 298 K
V = 913.9 (4) Å^3	Block, yellow
Z = 4	0.73 × 0.25 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1579 independent reflections
Radiation source: fine-focus sealed tube	1324 reflections with I > 2 σ(I)
Graphite monochromator	Rint = 0.016
Detector resolution: 100x100 microns pixels mm^-1	θmax = 25.0°, θmin = 2.0°
ω scans	h = −6→5
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −8→9
Tmin = 0.723, Tmax = 0.978	l = −21→24
4188 measured reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0656P)^2 + 0.2252P] where P = (Fo^2 + 2Fc^2)/3
1579 reflections	(Δ/σ)max < 0.001
137 parameters	Δρmax = 0.24 e Å^−3
3 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	Occ. (<1)
O1	0.7229 (3)	1.2583 (2)	0.00041 (8)	0.0842 (5)
O2	1.1469 (2)	0.94154 (15)	0.15970 (6)	0.0564 (4)
C1	0.8706 (3)	1.2221 (2)	0.04004 (8)	0.0535 (5)
C2	0.8769 (3)	1.0640 (2)	0.08027 (9)	0.0555 (5)
C3	1.0474 (5)	1.0996 (3)	0.13654 (13)	0.0491 (10)	0.587 (6)
H3	0.9668	1.1578	0.1718	0.074*	0.587 (6)
C3A	1.1313 (5)	1.0401 (4)	0.10213 (15)	0.0514 (15)	0.413 (6)
H3A	1.2153	0.9797	0.0680	0.077*	0.413 (6)
C4	1.2154 (4)	1.2241 (3)	0.10787 (10)	0.0649 (5)
H4A	1.3400	1.1605	0.0879	0.097*	0.587 (6)
H4B	1.2805	1.3007	0.1410	0.097*	0.587 (6)
H4AA	1.3793	1.2298	0.0998	0.097*	0.413 (6)
H4AB	1.1887	1.2693	0.1509	0.097*	0.413 (6)
C5	1.0803 (4)	1.3303 (3)	0.05733 (9)	0.0617 (5)
H5A	1.0355	1.4428	0.0749	0.093*
H5B	1.1726	1.3502	0.0194	0.093*
C6	0.7411 (3)	0.9270 (2)	0.08357 (8)	0.0482 (4)
H6	0.6114	0.9184	0.0565	0.058*
C7	0.7943 (3)	0.7895 (2)	0.12959 (8)	0.0443 (4)
C8	1.0000 (3)	0.8026 (2)	0.16646 (7)	0.0433 (4)
C9	1.0582 (3)	0.6754 (2)	0.21136 (8)	0.0520 (5)
H9	1.1963	0.6835	0.2349	0.062*
C10	0.9125 (3)	0.5369 (2)	0.22138 (9)	0.0591 (5)
H10	0.9511	0.4524	0.2522	0.071*
C11	0.7090 (4)	0.5222 (3)	0.18601 (11)	0.0670 (6)
H11	0.6103	0.4285	0.1933	0.080*
C12	0.6519 (3)	0.6464 (3)	0.13994 (10)	0.0599 (5)
H12	0.5163	0.6342	0.1155	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0761 (10)	0.0796 (10)	0.0955 (11)	−0.0037 (8)	−0.0321 (9)	0.0362 (9)
O2	0.0506 (7)	0.0523 (7)	0.0652 (8)	−0.0044 (5)	−0.0207 (6)	0.0086 (6)
C1	0.0580 (11)	0.0511 (10)	0.0513 (10)	0.0050 (8)	−0.0017 (9)	0.0043 (8)
C2	0.0545 (10)	0.0550 (10)	0.0562 (10)	−0.0053 (8)	−0.0182 (8)	0.0086 (8)
C3	0.059 (2)	0.0443 (17)	0.0431 (18)	−0.0017 (13)	−0.0101 (14)	−0.0010 (13)
C3A	0.057 (3)	0.051 (3)	0.046 (3)	−0.003 (2)	−0.006 (2)	−0.0069 (19)
C4	0.0600 (11)	0.0590 (12)	0.0749 (13)	−0.0111 (9)	−0.0142 (9)	0.0077 (9)
C5	0.0728 (13)	0.0525 (10)	0.0594 (11)	−0.0081 (9)	−0.0044 (10)	0.0051 (9)
C6	0.0373 (9)	0.0559 (10)	0.0509 (9)	0.0024 (7)	−0.0081 (7)	0.0031 (8)
C7	0.0420 (9)	0.0470 (9)	0.0439 (9)	0.0017 (7)	−0.0017 (7)	−0.0007 (7)
C8	0.0431 (9)	0.0445 (9)	0.0422 (9)	0.0032 (7)	−0.0024 (7)	−0.0043 (7)
C9	0.0539 (10)	0.0549 (10)	0.0467 (9)	0.0085 (8)	−0.0084 (8)	0.0016 (8)
C10	0.0731 (12)	0.0549 (11)	0.0492 (10)	0.0062 (9)	0.0023 (9)	0.0095 (8)
C11	0.0682 (12)	0.0621 (12)	0.0707 (13)	−0.0133 (10)	0.0021 (10)	0.0157 (10)
C12	0.0504 (10)	0.0636 (11)	0.0651 (11)	−0.0105 (9)	−0.0076 (8)	0.0074 (9)

Geometric parameters (Å, º)

O1—C1	1.204 (2)	C4—H4AA	0.9700
O2—C8	1.369 (2)	C4—H4AB	0.9700
O2—C3A	1.408 (3)	C5—H5A	0.9700
O2—C3	1.415 (3)	C5—H5B	0.9700
C1—C2	1.464 (2)	C6—C7	1.444 (2)
C1—C5	1.506 (3)	C6—H6	0.9300
C2—C6	1.312 (2)	C7—C12	1.388 (2)
C2—C3	1.534 (3)	C7—C8	1.405 (2)
C2—C3A	1.544 (3)	C8—C9	1.379 (2)
C3—C4	1.493 (3)	C9—C10	1.371 (3)
C3—H3	0.9800	C9—H9	0.9300
C3A—C4	1.490 (3)	C10—C11	1.379 (3)
C3A—H3A	0.9800	C10—H10	0.9300
C4—C5	1.525 (3)	C11—C12	1.378 (3)
C4—H4A	0.9700	C11—H11	0.9300
C4—H4B	0.9700	C12—H12	0.9300
C8—O2—C3A	118.07 (15)	C5—C4—H4AA	110.4
C8—O2—C3	116.33 (15)	C3A—C4—H4AB	110.4
O1—C1—C2	125.69 (17)	C3—C4—H4AB	75.1
O1—C1—C5	126.48 (17)	C5—C4—H4AB	110.4
C2—C1—C5	107.83 (15)	H4A—C4—H4AB	134.8
C6—C2—C1	132.68 (16)	H4AA—C4—H4AB	108.6
C6—C2—C3	118.66 (16)	C1—C5—C4	105.79 (15)
C1—C2—C3	107.00 (16)	C1—C5—H5A	110.6
C6—C2—C3A	117.51 (17)	C4—C5—H5A	110.6
C1—C2—C3A	105.97 (17)	C1—C5—H5B	110.6
O2—C3—C4	114.26 (19)	C4—C5—H5B	110.6
O2—C3—C2	110.92 (17)	H5A—C5—H5B	108.7
C4—C3—C2	103.15 (17)	C2—C6—C7	119.51 (15)
O2—C3—H3	109.4	C2—C6—H6	120.2
C4—C3—H3	109.4	C7—C6—H6	120.2
C2—C3—H3	109.4	C12—C7—C8	118.27 (15)
O2—C3A—C4	114.9 (2)	C12—C7—C6	123.56 (15)
O2—C3A—C2	110.71 (19)	C8—C7—C6	118.16 (15)
C4—C3A—C2	102.78 (18)	O2—C8—C9	117.99 (15)
O2—C3A—H3A	109.4	O2—C8—C7	121.53 (14)
C4—C3A—H3A	109.4	C9—C8—C7	120.47 (16)
C2—C3A—H3A	109.4	C10—C9—C8	120.04 (17)
C3A—C4—C5	106.43 (17)	C10—C9—H9	120.0
C3—C4—C5	106.21 (17)	C8—C9—H9	120.0
C3A—C4—H4A	75.0	C9—C10—C11	120.39 (17)
C3—C4—H4A	110.5	C9—C10—H10	119.8
C5—C4—H4A	110.5	C11—C10—H10	119.8
C3A—C4—H4B	138.2	C12—C11—C10	120.02 (18)
C3—C4—H4B	110.5	C12—C11—H11	120.0
C5—C4—H4B	110.5	C10—C11—H11	120.0
H4A—C4—H4B	108.7	C11—C12—C7	120.78 (18)
C3A—C4—H4AA	110.4	C11—C12—H12	119.6
C3—C4—H4AA	138.4	C7—C12—H12	119.6
O1—C1—C2—C6	1.9 (4)	C2—C3A—C4—C5	−31.3 (2)
C5—C1—C2—C6	−178.3 (2)	O2—C3—C4—C3A	55.3 (2)
O1—C1—C2—C3	−162.7 (2)	C2—C3—C4—C3A	−65.24 (17)
C5—C1—C2—C3	17.1 (2)	O2—C3—C4—C5	151.43 (19)
O1—C1—C2—C3A	158.5 (2)	C2—C3—C4—C5	30.9 (2)
C5—C1—C2—C3A	−21.7 (2)	O1—C1—C5—C4	−178.0 (2)
C8—O2—C3—C4	−159.25 (17)	C2—C1—C5—C4	2.2 (2)
C3A—O2—C3—C4	−56.0 (2)	C3A—C4—C5—C1	18.9 (2)
C8—O2—C3—C2	−43.2 (2)	C3—C4—C5—C1	−21.2 (2)
C3A—O2—C3—C2	60.1 (2)	C1—C2—C6—C7	−179.77 (19)
C6—C2—C3—O2	40.2 (3)	C3—C2—C6—C7	−16.6 (3)
C1—C2—C3—O2	−152.68 (18)	C3A—C2—C6—C7	25.8 (3)
C3A—C2—C3—O2	−58.48 (19)	C2—C6—C7—C12	174.99 (18)
C6—C2—C3—C4	162.92 (18)	C2—C6—C7—C8	−4.1 (2)
C1—C2—C3—C4	−29.9 (2)	C3A—O2—C8—C9	160.18 (19)
C3A—C2—C3—C4	64.27 (17)	C3—O2—C8—C9	−153.84 (17)
C8—O2—C3A—C4	155.23 (18)	C3A—O2—C8—C7	−20.6 (2)
C3—O2—C3A—C4	56.6 (2)	C3—O2—C8—C7	25.4 (2)
C8—O2—C3A—C2	39.4 (3)	C12—C7—C8—O2	−178.85 (16)
C3—O2—C3A—C2	−59.3 (2)	C6—C7—C8—O2	0.3 (2)
C6—C2—C3A—O2	−43.2 (3)	C12—C7—C8—C9	0.4 (2)
C1—C2—C3A—O2	156.04 (19)	C6—C7—C8—C9	179.58 (15)
C3—C2—C3A—O2	58.8 (2)	O2—C8—C9—C10	177.77 (15)
C6—C2—C3A—C4	−166.34 (19)	C7—C8—C9—C10	−1.5 (3)
C1—C2—C3A—C4	32.9 (2)	C8—C9—C10—C11	1.1 (3)
C3—C2—C3A—C4	−64.32 (17)	C9—C10—C11—C12	0.5 (3)
O2—C3A—C4—C3	−56.1 (2)	C10—C11—C12—C7	−1.6 (3)
C2—C3A—C4—C3	64.24 (17)	C8—C7—C12—C11	1.2 (3)
O2—C3A—C4—C5	−151.6 (2)	C6—C7—C12—C11	−177.98 (18)

(II) 2-(2-hydroxybenzylidene)-3,3a-dihydro-2H-cyclopenta[b]chromen-1-one

Crystal data

C19H14O3	F(000) = 608
Mr = 290.30	Dx = 1.336 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8693 reflections
a = 8.8978 (9) Å	θ = 2.3–24.6°
b = 12.5893 (12) Å	µ = 0.09 mm^−1
c = 13.1797 (13) Å	T = 298 K
β = 102.157 (2)°	Block, orange
V = 1443.2 (2) Å^3	0.36 × 0.23 × 0.23 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2543 independent reflections
Radiation source: fine-focus sealed tube	1881 reflections with I > 2 σ(I)
Graphite monochromator	Rint = 0.056
Detector resolution: 100x100 microns pixels mm^-1	θmax = 25.0°, θmin = 2.3°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −13→14
Tmin = 0.733, Tmax = 0.980	l = −15→12
5951 measured reflections

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.135	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0745P)^2] where P = (Fo^2 + 2Fc^2)/3
2543 reflections	(Δ/σ)max < 0.001
200 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.17 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	1.00662 (17)	1.16604 (10)	0.09244 (10)	0.0488 (4)
O2	0.81915 (17)	0.85477 (11)	0.22844 (11)	0.0580 (4)
O3	0.64722 (19)	1.21752 (11)	−0.23748 (11)	0.0613 (5)
C1	0.9278 (2)	1.08728 (14)	0.10067 (14)	0.0384 (5)
C2	0.9320 (2)	1.02399 (15)	0.19441 (15)	0.0417 (5)
C3	0.7922 (2)	0.95434 (18)	0.17692 (16)	0.0536 (6)
C4	0.7471 (2)	0.94132 (16)	0.05991 (15)	0.0502 (5)
C5	0.8097 (2)	1.03955 (14)	0.01691 (15)	0.0383 (5)
C6	1.0387 (2)	1.01663 (15)	0.28121 (15)	0.0419 (5)
C7	1.0237 (2)	0.93498 (15)	0.35556 (15)	0.0423 (5)
C8	0.9087 (2)	0.85840 (16)	0.32677 (16)	0.0462 (5)
C9	0.8888 (3)	0.77979 (18)	0.39612 (18)	0.0608 (6)
C10	0.9832 (3)	0.7764 (2)	0.49356 (17)	0.0620 (7)
C11	1.0996 (3)	0.84881 (19)	0.52178 (17)	0.0593 (6)
C12	1.1191 (2)	0.92764 (18)	0.45361 (17)	0.0548 (6)
C13	0.7717 (2)	1.08290 (15)	−0.07750 (14)	0.0401 (5)
C14	0.6668 (2)	1.04355 (15)	−0.17031 (14)	0.0381 (5)
C15	0.6116 (2)	1.11356 (16)	−0.25240 (14)	0.0416 (5)
C16	0.5238 (2)	1.07604 (17)	−0.34508 (16)	0.0501 (5)
C17	0.4918 (3)	0.96939 (18)	−0.35754 (17)	0.0526 (6)
C18	0.5437 (2)	0.89901 (17)	−0.27783 (16)	0.0521 (6)
C19	0.6293 (2)	0.93556 (16)	−0.18566 (16)	0.0463 (5)
H1	0.6068	1.2513	−0.2892	0.092*
H3	0.7095	0.9914	0.2012	0.080*
H6	1.1216	1.0632	0.2940	0.050*
H9	0.8118	0.7292	0.3770	0.073*
H10	0.9677	0.7246	0.5406	0.074*
H11	1.1650	0.8446	0.5867	0.071*
H12	1.1975	0.9770	0.4734	0.066*
H13	0.8188	1.1474	−0.0852	0.048*
H17	0.4347	0.9445	−0.4204	0.063*
H18	0.5208	0.8271	−0.2865	0.063*
H19	0.6633	0.8877	−0.1320	0.056*
H16	0.4864	1.1231	−0.3989	0.060*
H4A	0.6362	0.9374	0.0370	0.075*
H4B	0.7924	0.8775	0.0379	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0648 (9)	0.0386 (8)	0.0391 (8)	−0.0113 (7)	0.0023 (7)	0.0000 (6)
O3	0.0900 (12)	0.0412 (9)	0.0442 (9)	0.0035 (8)	−0.0052 (8)	0.0038 (7)
O2	0.0702 (10)	0.0515 (9)	0.0480 (9)	−0.0175 (7)	0.0026 (8)	0.0095 (7)
C6	0.0423 (11)	0.0467 (12)	0.0360 (11)	−0.0040 (9)	0.0069 (9)	−0.0015 (9)
C13	0.0444 (11)	0.0347 (10)	0.0393 (12)	0.0035 (8)	0.0046 (9)	−0.0017 (8)
C14	0.0383 (10)	0.0401 (11)	0.0345 (11)	0.0039 (8)	0.0048 (8)	0.0004 (8)
C1	0.0436 (11)	0.0342 (10)	0.0361 (11)	0.0042 (8)	0.0055 (8)	−0.0019 (8)
C2	0.0457 (11)	0.0409 (11)	0.0380 (12)	−0.0031 (9)	0.0081 (9)	−0.0012 (9)
C5	0.0415 (10)	0.0354 (10)	0.0362 (11)	0.0020 (8)	0.0038 (8)	−0.0031 (8)
C7	0.0449 (11)	0.0449 (11)	0.0388 (12)	0.0039 (9)	0.0128 (9)	0.0039 (9)
C18	0.0576 (13)	0.0480 (13)	0.0477 (14)	−0.0072 (10)	0.0040 (10)	−0.0059 (10)
C8	0.0519 (12)	0.0475 (12)	0.0409 (12)	0.0038 (9)	0.0133 (10)	0.0047 (9)
C19	0.0520 (12)	0.0441 (12)	0.0401 (12)	−0.0011 (9)	0.0036 (9)	0.0023 (9)
C16	0.0553 (13)	0.0567 (14)	0.0345 (12)	0.0063 (10)	0.0010 (9)	0.0027 (10)
C4	0.0520 (12)	0.0528 (13)	0.0422 (12)	−0.0112 (10)	0.0015 (10)	−0.0009 (10)
C15	0.0463 (11)	0.0410 (12)	0.0365 (11)	0.0053 (9)	0.0065 (9)	−0.0017 (9)
C17	0.0503 (12)	0.0646 (15)	0.0383 (12)	−0.0063 (11)	−0.0013 (9)	−0.0080 (11)
C9	0.0690 (16)	0.0556 (14)	0.0603 (16)	−0.0072 (12)	0.0191 (12)	0.0114 (12)
C3	0.0557 (13)	0.0544 (13)	0.0492 (14)	−0.0073 (11)	0.0076 (10)	0.0049 (10)
C12	0.0512 (13)	0.0651 (14)	0.0453 (13)	0.0022 (11)	0.0038 (10)	0.0092 (11)
C11	0.0614 (14)	0.0733 (16)	0.0429 (13)	0.0160 (13)	0.0100 (11)	0.0165 (11)
C10	0.0749 (16)	0.0624 (15)	0.0524 (15)	0.0124 (13)	0.0221 (13)	0.0224 (12)

Geometric parameters (Å, º)

O1—C1	1.232 (2)	C18—C17	1.378 (3)
O3—C15	1.351 (2)	C18—H18	0.9300
O3—H1	0.8200	C8—C9	1.383 (3)
O2—C8	1.372 (2)	C19—H19	0.9300
O2—C3	1.422 (3)	C16—C17	1.375 (3)
C6—C2	1.327 (3)	C16—C15	1.387 (3)
C6—C7	1.446 (3)	C16—H16	0.9300
C6—H6	0.9300	C4—C3	1.518 (3)
C13—C5	1.335 (3)	C4—H4B	0.9700
C13—C14	1.460 (3)	C4—H4A	0.9700
C13—H13	0.9300	C17—H17	0.9300
C14—C15	1.402 (3)	C9—C10	1.379 (3)
C14—C19	1.404 (3)	C9—H9	0.9300
C1—C2	1.464 (3)	C3—H3	0.9800
C1—C5	1.482 (3)	C12—C11	1.374 (3)
C2—C3	1.499 (3)	C12—H12	0.9300
C5—C4	1.514 (3)	C11—C10	1.371 (3)
C7—C12	1.392 (3)	C11—H11	0.9300
C7—C8	1.399 (3)	C10—H10	0.9300
C18—C19	1.370 (3)
C15—O3—H1	109.5	C17—C16—H16	119.9
C8—O2—C3	115.33 (16)	C15—C16—H16	119.9
C2—C6—C7	118.87 (18)	C5—C4—C3	104.63 (16)
C2—C6—H6	120.6	C5—C4—H4B	110.8
C7—C6—H6	120.6	C3—C4—H4B	110.8
C5—C13—C14	129.32 (19)	C5—C4—H4A	110.8
C5—C13—H13	115.3	C3—C4—H4A	110.8
C14—C13—H13	115.3	H4B—C4—H4A	108.9
C15—C14—C19	117.62 (17)	O3—C15—C16	121.96 (18)
C15—C14—C13	119.44 (17)	O3—C15—C14	117.61 (17)
C19—C14—C13	122.67 (17)	C16—C15—C14	120.43 (19)
O1—C1—C2	126.76 (18)	C16—C17—C18	120.6 (2)
O1—C1—C5	126.03 (17)	C16—C17—H17	119.7
C2—C1—C5	107.21 (16)	C18—C17—H17	119.7
C6—C2—C1	130.69 (18)	C10—C9—C8	120.0 (2)
C6—C2—C3	120.75 (18)	C10—C9—H9	120.0
C1—C2—C3	108.40 (16)	C8—C9—H9	120.0
C13—C5—C1	121.93 (17)	O2—C3—C2	113.03 (17)
C13—C5—C4	129.92 (17)	O2—C3—C4	111.83 (18)
C1—C5—C4	108.14 (16)	C2—C3—C4	104.64 (16)
C12—C7—C8	118.31 (18)	O2—C3—H3	109.1
C12—C7—C6	123.47 (19)	C2—C3—H3	109.1
C8—C7—C6	118.21 (18)	C4—C3—H3	109.1
C19—C18—C17	119.6 (2)	C11—C12—C7	121.3 (2)
C19—C18—H18	120.2	C11—C12—H12	119.4
C17—C18—H18	120.2	C7—C12—H12	119.4
O2—C8—C9	118.09 (19)	C10—C11—C12	119.7 (2)
O2—C8—C7	121.68 (17)	C10—C11—H11	120.2
C9—C8—C7	120.1 (2)	C12—C11—H11	120.2
C18—C19—C14	121.58 (19)	C11—C10—C9	120.6 (2)
C18—C19—H19	119.2	C11—C10—H10	119.7
C14—C19—H19	119.2	C9—C10—H10	119.7
C17—C16—C15	120.1 (2)
C5—C13—C14—C15	162.77 (19)	C13—C5—C4—C3	−160.9 (2)
C5—C13—C14—C19	−23.4 (3)	C1—C5—C4—C3	18.2 (2)
C7—C6—C2—C1	−170.40 (19)	C17—C16—C15—O3	179.13 (19)
C7—C6—C2—C3	4.5 (3)	C17—C16—C15—C14	−0.9 (3)
O1—C1—C2—C6	−18.8 (3)	C19—C14—C15—O3	179.75 (17)
C5—C1—C2—C6	161.6 (2)	C13—C14—C15—O3	−6.1 (3)
O1—C1—C2—C3	165.79 (19)	C19—C14—C15—C16	−0.3 (3)
C5—C1—C2—C3	−13.7 (2)	C13—C14—C15—C16	173.86 (18)
C14—C13—C5—C1	175.45 (17)	C15—C16—C17—C18	1.4 (3)
C14—C13—C5—C4	−5.6 (3)	C19—C18—C17—C16	−0.7 (3)
O1—C1—C5—C13	−3.4 (3)	O2—C8—C9—C10	175.76 (19)
C2—C1—C5—C13	176.08 (17)	C7—C8—C9—C10	−0.4 (3)
O1—C1—C5—C4	177.37 (19)	C8—O2—C3—C2	40.8 (2)
C2—C1—C5—C4	−3.1 (2)	C8—O2—C3—C4	158.55 (16)
C2—C6—C7—C12	−172.63 (19)	C6—C2—C3—O2	−29.1 (3)
C2—C6—C7—C8	8.3 (3)	C1—C2—C3—O2	146.85 (17)
C3—O2—C8—C9	153.34 (19)	C6—C2—C3—C4	−151.0 (2)
C3—O2—C8—C7	−30.5 (3)	C1—C2—C3—C4	24.9 (2)
C12—C7—C8—O2	−174.15 (18)	C5—C4—C3—O2	−148.59 (17)
C6—C7—C8—O2	4.9 (3)	C5—C4—C3—C2	−25.9 (2)
C12—C7—C8—C9	1.9 (3)	C8—C7—C12—C11	−1.4 (3)
C6—C7—C8—C9	−179.01 (18)	C6—C7—C12—C11	179.62 (19)
C17—C18—C19—C14	−0.5 (3)	C7—C12—C11—C10	−0.7 (3)
C15—C14—C19—C18	0.9 (3)	C12—C11—C10—C9	2.2 (4)
C13—C14—C19—C18	−172.99 (19)	C8—C9—C10—C11	−1.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O3	0.93	2.42	2.750 (2)	101
C13—H13···O1	0.93	2.59	2.917 (2)	102
O3—H1···O1^i	0.82	1.93	2.749 (2)	178
C3—H3···Cg1^ii	0.98	2.85	3.746 (2)	152
C6—H6···Cg1^iii	0.93	2.92	3.476 (2)	120
C12—H12···Cg2^iv	0.93	3.25	3.471 (2)	96

Symmetry codes: (i) x−1/2, −y+5/2, z−1/2; (ii) −x+1, −y+2, −z; (iii) −x+2, −y+2, −z; (iv) −x+2, −y+2, −z+1.