Two polymorphs of 4-propyl-3,4-di­hydro-2H-naphtho[1,2-b]pyran-5,6-dione

Two polymorphs of the title compound, C₁₆H₁₆O₃, have been obtained from the same solution. One polymorph, (I_m), crystallizes in the monoclinic space group P2₁, while the other, (I_o), crystallizes in the ortho­rhom­bic space group P2₁2₁2₁. The cell constants of the two polymorphs are surprisingly similar. Whereas the a and b axes are equal in the two structures, the c axis in (I_o) is twice as long as that in (I_m). The monoclinic angle [beta] is 95.084 (9)° compared with 90° in the ortho­rhom­bic crystal system. The cell volume of (I_m) is almost exactly half of the cell volume of (I_o). The packing motifs are also very similar in the two structures. However, whereas the mol­ecules in (I_m) are related by a twofold screw axis just in the direction of the b axis, in (I_o) there are twofold screw axes along all three directions of the unit cell.

S1. Comment

β-Lapachone is a naturally occurring plant quinone primarily isolated from the Central and South American lapacho tree (Tabebuia avellanedae). Lapachone (2,2-dimethyl-3,4-dihydro-2H-naphtho[1,2-b]pyran-5,6-dione) and its derivatives exhibit a number of important pharmacological properties, such as antibacterial, antifungal, antitrypanosomal, antimalarial and antitumor activities (Guiraud et al., 1994; de Andrade-Neto et al., 2004; Ferreira et al., 2006). The title compound, (I), was synthesized from 2-hydroxy-1,4-naphthoquinone, α,β-unsaturated aldehyde and diarylprolinol catalyst, and recrystallized from CH₃OH/hexane/CH₂Cl₂ (Rueping et al., 2008). In the same reaction vessel, two different kinds of crystals were found, viz. yellow plates and yellow needles [both orange according to CIF]. Since the cell parameters of the two crystal types were different, for both types a full crystal structure determination was carried out. As a result, two polymorphs were encountered. The plates are an orthorhombic form, (I_o), whereas the needles are a monoclinic form, (I_m).

A perspective view of the two polymorphs of the title compound is shown in Figs. 1 and 2. Bond lengths and angles can be regarded as normal (Cambridge Structural Database; Version 5.28 of November 2006 plus two updates; Mogul; Version 1.1; Allen, 2002; Bruno et al., 2004). The 1,2-naphthoquinone unit is planar [the r.m.s. deviation for the ten C atoms is 0.014 and 0.016 Å for (I_m) and (I_o), respectively]. The 3,4,5,6-dihydro-2H-pyran ring adopts a half-chair conformation and exhibits local twofold rotational symmetry (Tables 2 and 3). The propyl chains adopt a trans conformation (Tables 2 and 3). The molecular conformation of both polymorphs is almost identical. A least-squares fit of all non-H atoms gives an r.m.s. deviation of 0.013 Å.

The packing patterns on the other hand show some interesting similarities and differences. Whereas the a and b axes are equal in both structures, the c axis in (I_o) is twice as long as in (I_m) and the monoclinic angle β of 95.084 (9) differs significantly from that of 90° in the orthorhombic crystal system. The cell volume of (I_m) is almost exactly half of the cell volume of (I_o). The packing motifs are also very similar in the two structures (Figs. 3 and 4). If only the central two columns of molecules in the packing of (I_o) are compared with only the right or left two columns in the packing of (I_m) the patterns seem to be the same, because the aromatic rings in two neighbouring molecules approach one another in the same manner. The reason for this similarity is that these molecules are related by a twofold screw axis running in the same direction in both structures, i.e. along b in (I_m) and along a in (I_o). However, the propyl chains of two neighbouring molecules approach each other in a completely different way. Whereas in (I_m) two molecules are again related by a twofold screw axis along b (in the plane of the paper), in (I_o) two molecules are related by a twofold screw axis along b (perpendicular to the plane of the paper). In other words, the propyl chains in (I_m) all point in the same direction (downwards in Fig. 3) whereas the propyl chains in (I_o) point upwards and downwards (Fig. 4). This difference is the reason for the appearance of two polymorphic forms of the title compound.

Related literature

For related literature, see: Allen (2002); Andrade-Neto et al. (2004); Bruno et al. (2004); Ferreira et al. (2006); Guiraud et al. (1994); Rueping et al. (2008).

S2. Experimental

Full experimenatal details are published elsewhere (Rueping et al., 2008).

S3. Refinement

Because of the absence of anomalous scatterers, Friedel pairs were merged prior to refinement. All H atoms could be located by difference Fourier synthesis. They were refined with fixed individual displacement parameters [U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C_methyl)] using a riding model, with C—H ranging from 0.95 to 1.00 Å.

Computing details

For both compounds, data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures

	Fig. 1. A perspective view of (Im), with the atom numbering; displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. A perspective view of (Io), with the atom numbering; displacement ellipsoids are shown at the 50% probability level.
	Fig. 3. The packing of (Im) with a view along the a axis; H atoms have been omitted for clarity.
	Fig. 4. The packing of (Io) with a view along the b axis; H atoms have been omitted for clarity.

(Im) 4-propyl-3,4-dihydro-2H-naphtho[1,2-b]pyran-5,6-dione

Crystal data

C16H16O3	F(000) = 272
Mr = 256.29	Dx = 1.314 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3913 reflections
a = 6.3201 (7) Å	θ = 2.2–25.5°
b = 5.2972 (8) Å	µ = 0.09 mm^−1
c = 19.429 (2) Å	T = 173 K
β = 95.084 (9)°	Needle, orange
V = 647.90 (14) Å^3	0.22 × 0.04 × 0.04 mm
Z = 2

Data collection

Stoe IPDSII two-circle diffractometer	1021 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.099
Graphite monochromator	θmax = 25.5°, θmin = 2.1°
ω scans	h = −7→7
6418 measured reflections	k = −6→6
1331 independent reflections	l = −23→23

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)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.087	w = 1/[σ^2(Fo^2) + (0.0396P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max < 0.001
1331 reflections	Δρmax = 0.16 e Å^−3
173 parameters	Δρmin = −0.18 e Å^−3
1 restraint	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.088 (9)

Special details

Experimental. ;

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	−0.0416 (4)	0.6319 (5)	0.10963 (12)	0.0454 (7)
O2	0.0959 (3)	0.9388 (4)	0.21703 (12)	0.0374 (6)
O3	0.7157 (3)	0.4375 (4)	0.25398 (11)	0.0333 (6)
C1	0.1312 (5)	0.5916 (6)	0.14041 (16)	0.0311 (7)
C2	0.2065 (5)	0.7573 (6)	0.20319 (16)	0.0304 (7)
C3	0.4053 (5)	0.6977 (6)	0.24317 (15)	0.0283 (7)
C4	0.5268 (5)	0.5070 (6)	0.22130 (15)	0.0279 (7)
C5	0.4705 (5)	0.3487 (6)	0.15938 (15)	0.0287 (7)
C6	0.2748 (5)	0.3874 (6)	0.12012 (15)	0.0300 (7)
C7	0.2169 (5)	0.2357 (6)	0.06332 (16)	0.0339 (8)
H7	0.0846	0.2620	0.0371	0.041*
C8	0.3508 (5)	0.0469 (7)	0.04473 (16)	0.0365 (8)
H8	0.3113	−0.0556	0.0056	0.044*
C9	0.5430 (5)	0.0069 (6)	0.08325 (16)	0.0351 (8)
H9	0.6336	−0.1251	0.0706	0.042*
C10	0.6052 (5)	0.1574 (6)	0.14025 (16)	0.0328 (8)
H10	0.7383	0.1300	0.1659	0.039*
C11	0.7659 (5)	0.5476 (7)	0.32131 (16)	0.0349 (7)
H11A	0.9189	0.5233	0.3355	0.042*
H11B	0.6842	0.4600	0.3553	0.042*
C12	0.7147 (5)	0.8257 (6)	0.32159 (17)	0.0332 (7)
H12A	0.7967	0.9142	0.2878	0.040*
H12B	0.7564	0.8968	0.3679	0.040*
C13	0.4775 (5)	0.8680 (6)	0.30309 (15)	0.0302 (7)
H13	0.4593	1.0460	0.2865	0.036*
C14	0.3442 (5)	0.8371 (7)	0.36480 (16)	0.0331 (8)
H14A	0.1937	0.8125	0.3473	0.040*
H14B	0.3915	0.6832	0.3907	0.040*
C15	0.3591 (6)	1.0598 (8)	0.4138 (2)	0.0500 (10)
H15A	0.3187	1.2147	0.3873	0.060*
H15B	0.5087	1.0792	0.4329	0.060*
C16	0.2199 (6)	1.0378 (10)	0.47349 (19)	0.0561 (11)
H16A	0.2389	1.1878	0.5029	0.084*
H16B	0.2605	0.8869	0.5007	0.084*
H16C	0.0707	1.0244	0.4553	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0328 (13)	0.0524 (17)	0.0488 (14)	0.0098 (12)	−0.0087 (11)	−0.0051 (12)
O2	0.0316 (12)	0.0377 (13)	0.0432 (14)	0.0085 (12)	0.0050 (10)	−0.0027 (12)
O3	0.0296 (12)	0.0356 (13)	0.0331 (12)	0.0034 (11)	−0.0066 (9)	−0.0002 (10)
C1	0.0270 (17)	0.0336 (18)	0.0326 (17)	−0.0011 (14)	0.0028 (14)	0.0033 (15)
C2	0.0291 (17)	0.0310 (18)	0.0317 (17)	0.0007 (15)	0.0068 (14)	0.0014 (14)
C3	0.0257 (16)	0.0305 (18)	0.0288 (17)	−0.0009 (14)	0.0028 (13)	0.0042 (14)
C4	0.0226 (15)	0.0303 (18)	0.0304 (16)	−0.0021 (14)	0.0010 (13)	0.0055 (14)
C5	0.0295 (16)	0.0288 (16)	0.0281 (15)	0.0006 (14)	0.0030 (13)	0.0067 (15)
C6	0.0301 (17)	0.0296 (18)	0.0300 (17)	0.0010 (13)	0.0008 (13)	0.0044 (14)
C7	0.0314 (18)	0.037 (2)	0.0322 (19)	−0.0024 (15)	−0.0026 (14)	0.0018 (15)
C8	0.044 (2)	0.0370 (18)	0.0280 (18)	−0.0014 (18)	0.0024 (14)	−0.0015 (16)
C9	0.0420 (19)	0.0300 (19)	0.0336 (18)	0.0048 (14)	0.0051 (14)	0.0031 (14)
C10	0.0330 (18)	0.0331 (18)	0.0326 (17)	0.0035 (15)	0.0044 (14)	0.0063 (16)
C11	0.0315 (17)	0.0382 (18)	0.0335 (17)	0.0003 (15)	−0.0056 (13)	0.0006 (16)
C12	0.0288 (17)	0.0347 (18)	0.0362 (18)	−0.0054 (14)	0.0033 (13)	−0.0032 (15)
C13	0.0310 (18)	0.0279 (17)	0.0318 (17)	−0.0021 (13)	0.0039 (13)	0.0010 (15)
C14	0.0329 (17)	0.0338 (18)	0.0325 (18)	−0.0059 (15)	0.0021 (13)	−0.0003 (15)
C15	0.053 (2)	0.048 (2)	0.051 (2)	−0.008 (2)	0.0132 (18)	−0.019 (2)
C16	0.057 (2)	0.069 (3)	0.044 (2)	−0.001 (2)	0.0089 (18)	−0.016 (2)

Geometric parameters (Å, º)

O1—C1	1.217 (4)	C10—H10	0.9500
O2—C2	1.232 (4)	C11—C12	1.509 (5)
O3—C4	1.353 (4)	C11—H11A	0.9900
O3—C11	1.442 (4)	C11—H11B	0.9900
C1—C6	1.487 (4)	C12—C13	1.527 (4)
C1—C2	1.543 (5)	C12—H12A	0.9900
C2—C3	1.452 (4)	C12—H12B	0.9900
C3—C4	1.359 (4)	C13—C14	1.534 (4)
C3—C13	1.511 (4)	C13—H13	1.0000
C4—C5	1.484 (4)	C14—C15	1.514 (5)
C5—C10	1.395 (4)	C14—H14A	0.9900
C5—C6	1.410 (4)	C14—H14B	0.9900
C6—C7	1.388 (4)	C15—C16	1.521 (5)
C7—C8	1.378 (5)	C15—H15A	0.9900
C7—H7	0.9500	C15—H15B	0.9900
C8—C9	1.385 (5)	C16—H16A	0.9800
C8—H8	0.9500	C16—H16B	0.9800
C9—C10	1.393 (5)	C16—H16C	0.9800
C9—H9	0.9500
C4—O3—C11	115.5 (2)	O3—C11—H11B	109.3
O1—C1—C6	122.6 (3)	C12—C11—H11B	109.3
O1—C1—C2	119.3 (3)	H11A—C11—H11B	108.0
C6—C1—C2	118.1 (3)	C11—C12—C13	110.4 (3)
O2—C2—C3	122.3 (3)	C11—C12—H12A	109.6
O2—C2—C1	118.4 (3)	C13—C12—H12A	109.6
C3—C2—C1	119.4 (3)	C11—C12—H12B	109.6
C4—C3—C2	118.7 (3)	C13—C12—H12B	109.6
C4—C3—C13	123.0 (3)	H12A—C12—H12B	108.1
C2—C3—C13	118.0 (3)	C3—C13—C12	108.5 (3)
O3—C4—C3	123.7 (3)	C3—C13—C14	112.9 (3)
O3—C4—C5	111.4 (3)	C12—C13—C14	113.3 (3)
C3—C4—C5	124.9 (3)	C3—C13—H13	107.3
C10—C5—C6	119.2 (3)	C12—C13—H13	107.3
C10—C5—C4	121.2 (3)	C14—C13—H13	107.3
C6—C5—C4	119.5 (3)	C15—C14—C13	113.6 (3)
C7—C6—C5	120.2 (3)	C15—C14—H14A	108.8
C7—C6—C1	120.5 (3)	C13—C14—H14A	108.8
C5—C6—C1	119.3 (3)	C15—C14—H14B	108.8
C8—C7—C6	120.3 (3)	C13—C14—H14B	108.8
C8—C7—H7	119.9	H14A—C14—H14B	107.7
C6—C7—H7	119.9	C14—C15—C16	114.3 (3)
C7—C8—C9	119.9 (3)	C14—C15—H15A	108.7
C7—C8—H8	120.0	C16—C15—H15A	108.7
C9—C8—H8	120.0	C14—C15—H15B	108.7
C8—C9—C10	120.9 (3)	C16—C15—H15B	108.7
C8—C9—H9	119.5	H15A—C15—H15B	107.6
C10—C9—H9	119.5	C15—C16—H16A	109.5
C9—C10—C5	119.5 (3)	C15—C16—H16B	109.5
C9—C10—H10	120.3	H16A—C16—H16B	109.5
C5—C10—H10	120.3	C15—C16—H16C	109.5
O3—C11—C12	111.6 (3)	H16A—C16—H16C	109.5
O3—C11—H11A	109.3	H16B—C16—H16C	109.5
C12—C11—H11A	109.3
O1—C1—C2—O2	−5.6 (4)	O1—C1—C6—C7	1.3 (5)
C6—C1—C2—O2	174.5 (3)	C2—C1—C6—C7	−178.8 (3)
O1—C1—C2—C3	175.4 (3)	O1—C1—C6—C5	−178.5 (3)
C6—C1—C2—C3	−4.5 (4)	C2—C1—C6—C5	1.4 (4)
O2—C2—C3—C4	−174.7 (3)	C5—C6—C7—C8	−0.3 (4)
C1—C2—C3—C4	4.3 (4)	C1—C6—C7—C8	179.9 (3)
O2—C2—C3—C13	−0.7 (4)	C6—C7—C8—C9	0.6 (5)
C1—C2—C3—C13	178.3 (3)	C7—C8—C9—C10	−0.9 (5)
C11—O3—C4—C3	10.8 (4)	C8—C9—C10—C5	1.0 (5)
C11—O3—C4—C5	−169.0 (3)	C6—C5—C10—C9	−0.6 (4)
C2—C3—C4—O3	179.2 (3)	C4—C5—C10—C9	177.6 (3)
C13—C3—C4—O3	5.5 (5)	C4—O3—C11—C12	−44.0 (4)
C2—C3—C4—C5	−1.1 (4)	O3—C11—C12—C13	61.5 (3)
C13—C3—C4—C5	−174.7 (3)	C4—C3—C13—C12	12.2 (4)
O3—C4—C5—C10	−0.6 (4)	C2—C3—C13—C12	−161.5 (3)
C3—C4—C5—C10	179.6 (3)	C4—C3—C13—C14	−114.3 (3)
O3—C4—C5—C6	177.6 (3)	C2—C3—C13—C14	72.0 (4)
C3—C4—C5—C6	−2.2 (4)	C11—C12—C13—C3	−43.4 (3)
C10—C5—C6—C7	0.3 (4)	C11—C12—C13—C14	82.9 (3)
C4—C5—C6—C7	−178.0 (3)	C3—C13—C14—C15	−159.7 (3)
C10—C5—C6—C1	−179.9 (3)	C12—C13—C14—C15	76.4 (4)
C4—C5—C6—C1	1.8 (4)	C13—C14—C15—C16	177.3 (3)

(Io) 4-propyl-3,4,5,6-tetrahydro-2H-naphtho[1,2-b]pyran-5,6-dione

Crystal data

C16H16O3	F(000) = 544
Mr = 256.29	Dx = 1.319 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3430 reflections
a = 5.2833 (7) Å	θ = 2.2–24.1°
b = 6.3043 (8) Å	µ = 0.09 mm^−1
c = 38.753 (6) Å	T = 173 K
V = 1290.8 (3) Å^3	Plate, orange
Z = 4	0.19 × 0.18 × 0.03 mm

Data collection

Stoe IPDSII two-circle diffractometer	738 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.083
Graphite monochromator	θmax = 24.8°, θmin = 2.1°
ω scans	h = −5→6
8057 measured reflections	k = −7→7
1399 independent reflections	l = −45→45

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) = 0.108	H-atom parameters constrained
S = 0.84	w = 1/[σ^2(Fo^2) + (0.056P)^2] where P = (Fo^2 + 2Fc^2)/3
1399 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.24 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	0.3409 (6)	0.1794 (5)	0.94506 (7)	0.0721 (9)
O2	0.6456 (6)	0.2881 (4)	0.89158 (7)	0.0642 (8)
O3	0.1459 (5)	0.8989 (4)	0.87354 (7)	0.0586 (7)
C1	0.2976 (8)	0.3442 (7)	0.92982 (11)	0.0575 (9)
C2	0.4634 (8)	0.4026 (6)	0.89841 (10)	0.0545 (9)
C3	0.4033 (7)	0.5906 (6)	0.87893 (10)	0.0526 (9)
C4	0.2114 (8)	0.7162 (6)	0.88969 (10)	0.0539 (9)
C5	0.0566 (8)	0.6794 (6)	0.92057 (10)	0.0511 (9)
C6	0.0949 (7)	0.4923 (6)	0.93991 (9)	0.0513 (9)
C7	−0.0561 (8)	0.4499 (6)	0.96839 (10)	0.0586 (11)
H7	−0.0272	0.3257	0.9817	0.070*
C8	−0.2491 (8)	0.5881 (8)	0.97754 (10)	0.0622 (11)
H8	−0.3548	0.5571	0.9967	0.075*
C9	−0.2870 (8)	0.7728 (7)	0.95843 (10)	0.0587 (10)
H9	−0.4170	0.8689	0.9649	0.070*
C10	−0.1373 (8)	0.8170 (7)	0.93017 (10)	0.0584 (10)
H10	−0.1666	0.9422	0.9172	0.070*
C11	0.2515 (9)	0.9309 (7)	0.83961 (10)	0.0597 (11)
H11A	0.2251	1.0800	0.8324	0.072*
H11B	0.1639	0.8380	0.8228	0.072*
C12	0.5325 (7)	0.8810 (7)	0.83959 (12)	0.0574 (10)
H12A	0.6202	0.9718	0.8567	0.069*
H12B	0.6046	0.9109	0.8165	0.069*
C13	0.5732 (8)	0.6480 (7)	0.84866 (9)	0.0553 (10)
H13	0.7520	0.6339	0.8568	0.066*
C14	0.5431 (8)	0.4985 (7)	0.81767 (10)	0.0583 (10)
H14A	0.5160	0.3524	0.8263	0.070*
H14B	0.3905	0.5405	0.8045	0.070*
C15	0.7692 (9)	0.4988 (8)	0.79350 (12)	0.0768 (12)
H15A	0.7947	0.6447	0.7847	0.092*
H15B	0.9220	0.4590	0.8068	0.092*
C16	0.7438 (11)	0.3498 (9)	0.76303 (12)	0.0885 (16)
H16A	0.8948	0.3608	0.7485	0.133*
H16B	0.5938	0.3883	0.7495	0.133*
H16C	0.7264	0.2038	0.7714	0.133*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.067 (2)	0.060 (2)	0.0894 (19)	0.0047 (17)	0.0040 (16)	0.0114 (16)
O2	0.0528 (17)	0.0569 (16)	0.0830 (18)	0.0107 (15)	−0.0020 (14)	−0.0022 (15)
O3	0.0531 (17)	0.0498 (16)	0.0730 (16)	0.0048 (14)	0.0008 (13)	0.0066 (14)
C1	0.056 (2)	0.044 (2)	0.072 (2)	0.000 (2)	−0.007 (2)	0.0021 (18)
C2	0.050 (2)	0.044 (2)	0.069 (2)	−0.001 (2)	−0.0087 (19)	−0.004 (2)
C3	0.044 (2)	0.046 (2)	0.067 (2)	0.0007 (17)	−0.0033 (18)	−0.0032 (18)
C4	0.053 (2)	0.0410 (19)	0.068 (2)	−0.0023 (19)	−0.0071 (18)	0.0005 (17)
C5	0.047 (2)	0.046 (2)	0.061 (2)	−0.001 (2)	−0.0093 (17)	0.0009 (17)
C6	0.042 (2)	0.047 (2)	0.065 (2)	0.0017 (17)	−0.0033 (19)	0.0026 (19)
C7	0.067 (3)	0.051 (3)	0.0573 (18)	0.003 (2)	−0.009 (2)	0.0070 (17)
C8	0.050 (2)	0.064 (3)	0.072 (2)	−0.005 (2)	−0.001 (2)	−0.0028 (18)
C9	0.050 (2)	0.062 (2)	0.063 (2)	0.009 (2)	−0.0041 (19)	−0.0051 (19)
C10	0.053 (2)	0.056 (3)	0.066 (2)	0.000 (2)	−0.003 (2)	−0.0003 (19)
C11	0.069 (3)	0.051 (3)	0.059 (2)	0.004 (2)	−0.002 (2)	0.0085 (16)
C12	0.0428 (16)	0.047 (2)	0.082 (2)	−0.008 (2)	0.002 (2)	0.003 (2)
C13	0.041 (2)	0.059 (3)	0.066 (2)	0.003 (2)	−0.0011 (16)	−0.0038 (19)
C14	0.050 (2)	0.060 (3)	0.065 (2)	−0.002 (2)	0.000 (2)	0.001 (2)
C15	0.066 (3)	0.080 (3)	0.084 (3)	−0.001 (3)	0.006 (3)	−0.008 (3)
C16	0.085 (4)	0.091 (4)	0.090 (3)	0.001 (3)	0.016 (3)	−0.019 (3)

Geometric parameters (Å, º)

O1—C1	1.217 (5)	C10—H10	0.9500
O2—C2	1.232 (5)	C11—C12	1.518 (6)
O3—C4	1.356 (4)	C11—H11A	0.9900
O3—C11	1.443 (5)	C11—H11B	0.9900
C1—C6	1.473 (5)	C12—C13	1.525 (6)
C1—C2	1.544 (6)	C12—H12A	0.9900
C2—C3	1.441 (5)	C12—H12B	0.9900
C3—C4	1.352 (5)	C13—C14	1.535 (5)
C3—C13	1.521 (5)	C13—H13	1.0000
C4—C5	1.467 (5)	C14—C15	1.518 (6)
C5—C10	1.393 (5)	C14—H14A	0.9900
C5—C6	1.412 (5)	C14—H14B	0.9900
C6—C7	1.388 (5)	C15—C16	1.515 (6)
C7—C8	1.387 (6)	C15—H15A	0.9900
C7—H7	0.9500	C15—H15B	0.9900
C8—C9	1.394 (6)	C16—H16A	0.9800
C8—H8	0.9500	C16—H16B	0.9800
C9—C10	1.380 (5)	C16—H16C	0.9800
C9—H9	0.9500
C4—O3—C11	116.2 (3)	O3—C11—H11B	109.6
O1—C1—C6	123.3 (4)	C12—C11—H11B	109.6
O1—C1—C2	118.6 (4)	H11A—C11—H11B	108.1
C6—C1—C2	118.0 (3)	C11—C12—C13	109.7 (4)
O2—C2—C3	122.8 (4)	C11—C12—H12A	109.7
O2—C2—C1	118.2 (4)	C13—C12—H12A	109.7
C3—C2—C1	119.0 (4)	C11—C12—H12B	109.7
C4—C3—C2	119.0 (4)	C13—C12—H12B	109.7
C4—C3—C13	122.8 (4)	H12A—C12—H12B	108.2
C2—C3—C13	118.0 (4)	C3—C13—C12	108.9 (3)
O3—C4—C3	123.1 (4)	C3—C13—C14	113.4 (3)
O3—C4—C5	111.6 (4)	C12—C13—C14	113.3 (3)
C3—C4—C5	125.2 (4)	C3—C13—H13	107.0
C10—C5—C6	118.9 (4)	C12—C13—H13	107.0
C10—C5—C4	122.0 (3)	C14—C13—H13	107.0
C6—C5—C4	119.0 (4)	C15—C14—C13	113.6 (4)
C7—C6—C5	120.0 (4)	C15—C14—H14A	108.8
C7—C6—C1	120.4 (4)	C13—C14—H14A	108.8
C5—C6—C1	119.5 (4)	C15—C14—H14B	108.8
C8—C7—C6	120.3 (4)	C13—C14—H14B	108.8
C8—C7—H7	119.8	H14A—C14—H14B	107.7
C6—C7—H7	119.8	C16—C15—C14	114.2 (4)
C7—C8—C9	119.6 (4)	C16—C15—H15A	108.7
C7—C8—H8	120.2	C14—C15—H15A	108.7
C9—C8—H8	120.2	C16—C15—H15B	108.7
C10—C9—C8	120.5 (4)	C14—C15—H15B	108.7
C10—C9—H9	119.7	H15A—C15—H15B	107.6
C8—C9—H9	119.7	C15—C16—H16A	109.5
C9—C10—C5	120.6 (4)	C15—C16—H16B	109.5
C9—C10—H10	119.7	H16A—C16—H16B	109.5
C5—C10—H10	119.7	C15—C16—H16C	109.5
O3—C11—C12	110.5 (4)	H16A—C16—H16C	109.5
O3—C11—H11A	109.6	H16B—C16—H16C	109.5
C12—C11—H11A	109.6
O1—C1—C2—O2	−5.5 (6)	O1—C1—C6—C7	1.1 (6)
C6—C1—C2—O2	174.3 (4)	C2—C1—C6—C7	−178.6 (3)
O1—C1—C2—C3	176.1 (4)	O1—C1—C6—C5	−179.5 (4)
C6—C1—C2—C3	−4.1 (5)	C2—C1—C6—C5	0.8 (5)
O2—C2—C3—C4	−175.1 (4)	C5—C6—C7—C8	1.5 (6)
C1—C2—C3—C4	3.2 (5)	C1—C6—C7—C8	−179.1 (4)
O2—C2—C3—C13	0.2 (6)	C6—C7—C8—C9	−1.5 (6)
C1—C2—C3—C13	178.5 (3)	C7—C8—C9—C10	1.2 (6)
C11—O3—C4—C3	13.8 (5)	C8—C9—C10—C5	−0.9 (6)
C11—O3—C4—C5	−168.7 (3)	C6—C5—C10—C9	1.0 (6)
C2—C3—C4—O3	178.2 (3)	C4—C5—C10—C9	177.0 (4)
C13—C3—C4—O3	3.2 (6)	C4—O3—C11—C12	−46.4 (5)
C2—C3—C4—C5	1.0 (6)	O3—C11—C12—C13	62.4 (5)
C13—C3—C4—C5	−174.0 (4)	C4—C3—C13—C12	13.6 (5)
O3—C4—C5—C10	2.1 (5)	C2—C3—C13—C12	−161.5 (3)
C3—C4—C5—C10	179.5 (4)	C4—C3—C13—C14	−113.5 (4)
O3—C4—C5—C6	178.1 (3)	C2—C3—C13—C14	71.4 (4)
C3—C4—C5—C6	−4.5 (6)	C11—C12—C13—C3	−44.3 (5)
C10—C5—C6—C7	−1.2 (5)	C11—C12—C13—C14	82.9 (5)
C4—C5—C6—C7	−177.4 (4)	C3—C13—C14—C15	−158.4 (4)
C10—C5—C6—C1	179.3 (3)	C12—C13—C14—C15	76.9 (5)
C4—C5—C6—C1	3.2 (5)	C13—C14—C15—C16	179.2 (4)