Predictable close-packing similarities between cis- and trans-2-hydroxy-1-cyclo­octanecarboxylic acids and trans-2-hydroxy-1-cyclooctanecarboxamide

In order to extend the experimental data already available on the close packing of cyclopentanes substituted with vicinal COX (X = OH, NH₂) and OH groups to the analogous cyclohexanes, cycloheptanes and cyclooctanes, (1R*,2S*)-cis-2-hydroxy-1-cyclooctanecarboxylic acid (8C), (1R*,2R*)-trans-2-hydroxy-1-cyclooctanecarboxylic acid (8T) and (1R*,2R*)-trans-2-hydroxy-1-cyclooctanecarboxamide (8T*) were subjected to X-ray crystal structure analysis. In 8T and 8T*, the hydrogen bonds form infinite ribbons of dimers joined by (12) rings with C_i symmetry. Two types of dimer alternate along each ribbon. The dimers differ in the donor and acceptor roles of the functional groups. This pattern was previously deduced topologically among the possible forms of association for heterochiral dimers [Kálmán et al. (2002). Acta Cryst. B58, 494-501]. As they have the same pattern of hydrogen bonds, 8T and 8T* are isostructural. The additional donor (i.e. the second hydrogen of the NH₂ group) present in 8T* links the adjacent ribbons so as to form smaller (8) rings between them. The crystals of the cis stereoisomer 8C are built up from antiparallel hydrogen-bonded helices. The topology and symmetry of this structure are the same as for the close packing of (1R*,2R*,4S*)-4-tert-butyl-2-hydroxy-1-cyclopentanecarboxamide [Kálmán et al. (2001). Acta Cryst. B57, 539-550]; only the hydrogen-bond donors and acceptors are interchanged, in the same way as in the two dimer types of 8T and 8T* ribbons. This analogy suggests that helices may originate as homochiral dimers with C₂ symmetry and polymerize into helices during crystal formation. The conformational characteristics of the heterochiral dimers observed in the title compounds and in closely related structures are discussed.

Computing details

For all compounds, data collection: CAD-4 EXPRESS; cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

Figures

(8T) (1R*,2R*)-trans-2-hydroxy-1-cyclooctanecarboxylic acid

Crystal data

C9H16O3	Z = 2
Mr = 172.22	F(000) = 188
Triclinic, P1	Dx = 1.268 Mg m^−3
a = 6.035 (1) Å	Mo Kα radiation, λ = 0.710730 Å
b = 8.390 (1) Å	Cell parameters from 25 reflections
c = 9.389 (2) Å	θ = 17.0–18.9°
α = 84.29 (1)°	µ = 0.09 mm^−1
β = 76.37 (1)°	T = 293 K
γ = 77.95 (1)°	Prism, colourless
V = 451.20 (13) Å^3	0.60 × 0.40 × 0.30 mm

Data collection

Enraf-Nonius CAD4 diffractometer	2585 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
Graphite monochromator	θmax = 35.0°, θmin = 2.5°
ω–2θ scans	h = −9→9
Absorption correction: ψ scan ?	k = −13→13
Tmin = 0.935, Tmax = 0.980	l = −15→15
8683 measured reflections	3 standard reflections every 60 min
3931 independent reflections	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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.142	Riding
S = 0.95	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
3931 reflections	(Δ/σ)max < 0.001
111 parameters	Δρmax = 0.33 e Å^−3
101 restraints	Δρmin = −0.20 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	0.24663 (10)	0.42030 (7)	0.17893 (7)	0.03759 (15)
H1	0.3888	0.3949	0.1606	0.049*
O2	0.27899 (11)	0.66197 (10)	−0.12937 (7)	0.05039 (19)
O3	−0.07127 (10)	0.68921 (8)	0.01809 (6)	0.04129 (16)
H3	−0.1044	0.6574	−0.0526	0.054*
C1	0.23780 (13)	0.71043 (9)	0.12595 (8)	0.03272 (15)
H1A	0.4072	0.6990	0.0995	0.043*
C2	0.17562 (13)	0.57618 (9)	0.24366 (8)	0.03178 (15)
H2	0.0059	0.5961	0.2756	0.041*
C3	0.27376 (17)	0.56596 (10)	0.38111 (9)	0.04166 (19)
H3A	0.4407	0.5577	0.3504	0.054*
H3B	0.2459	0.4659	0.4374	0.054*
C4	0.1765 (2)	0.70824 (12)	0.48309 (9)	0.0492 (2)
H4A	0.0278	0.7635	0.4635	0.064*
H4B	0.1480	0.6636	0.5836	0.064*
C5	0.3300 (2)	0.83474 (13)	0.47017 (11)	0.0539 (3)
H5A	0.2344	0.9321	0.5159	0.070*
H5B	0.4469	0.7924	0.5267	0.070*
C6	0.45338 (19)	0.88506 (16)	0.31697 (13)	0.0588 (3)
H6A	0.5449	0.7875	0.2696	0.076*
H6B	0.5606	0.9529	0.3262	0.076*
C7	0.2998 (3)	0.97648 (14)	0.21741 (12)	0.0593 (3)
H7A	0.3994	1.0105	0.1274	0.077*
H7B	0.2102	1.0747	0.2645	0.077*
C8	0.1307 (2)	0.88565 (10)	0.17615 (10)	0.0456 (2)
H8A	0.0667	0.9487	0.0978	0.059*
H8B	0.0030	0.8799	0.2603	0.059*
C9	0.15477 (13)	0.68416 (9)	−0.00872 (8)	0.03344 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0362 (3)	0.0354 (3)	0.0461 (3)	−0.0020 (2)	−0.0179 (2)	−0.0150 (2)
O2	0.0391 (3)	0.0799 (5)	0.0333 (3)	−0.0071 (3)	−0.0095 (2)	−0.0140 (3)
O3	0.0323 (3)	0.0551 (4)	0.0409 (3)	−0.0039 (2)	−0.0146 (2)	−0.0172 (3)
C1	0.0320 (3)	0.0380 (3)	0.0320 (3)	−0.0069 (3)	−0.0114 (3)	−0.0094 (2)
C2	0.0305 (3)	0.0339 (3)	0.0335 (3)	−0.0029 (2)	−0.0115 (2)	−0.0102 (2)
C3	0.0531 (5)	0.0400 (4)	0.0366 (4)	−0.0029 (3)	−0.0217 (3)	−0.0086 (3)
C4	0.0655 (6)	0.0506 (5)	0.0332 (4)	−0.0059 (4)	−0.0144 (4)	−0.0135 (3)
C5	0.0657 (6)	0.0526 (5)	0.0529 (5)	−0.0023 (4)	−0.0312 (5)	−0.0231 (4)
C6	0.0445 (5)	0.0724 (6)	0.0692 (6)	−0.0208 (5)	−0.0102 (4)	−0.0356 (5)
C7	0.0882 (8)	0.0534 (5)	0.0463 (5)	−0.0365 (6)	−0.0110 (5)	−0.0111 (4)
C8	0.0629 (6)	0.0344 (4)	0.0454 (4)	−0.0056 (4)	−0.0243 (4)	−0.0079 (3)
C9	0.0329 (3)	0.0358 (3)	0.0342 (3)	−0.0029 (3)	−0.0129 (3)	−0.0084 (3)

Geometric parameters (Å, º)

O1—C2	1.4369 (8)	C4—C5	1.5269 (15)
O1—H1	0.8200	C4—H4A	0.9700
O2—C9	1.2096 (10)	C4—H4B	0.9700
O3—C9	1.3199 (10)	C5—C6	1.5190 (17)
O3—H3	0.8200	C5—H5A	0.9700
C1—C9	1.5161 (10)	C5—H5B	0.9700
C1—C2	1.5376 (12)	C6—C7	1.513 (2)
C1—C8	1.5488 (12)	C6—H6A	0.9700
C1—H1A	0.9800	C6—H6B	0.9700
C2—C3	1.5299 (10)	C7—C8	1.5306 (15)
C2—H2	0.9800	C7—H7A	0.9700
C3—C4	1.5351 (11)	C7—H7B	0.9700
C3—H3A	0.9700	C8—H8A	0.9700
C3—H3B	0.9700	C8—H8B	0.9700
C2—O1—H1	109.5	C6—C5—H5A	108.0
C9—O3—H3	109.5	C4—C5—H5A	108.0
C9—C1—C2	108.18 (6)	C6—C5—H5B	108.0
C9—C1—C8	109.36 (6)	C4—C5—H5B	108.0
C2—C1—C8	113.69 (7)	H5A—C5—H5B	107.2
C9—C1—H1A	108.5	C5—C6—C7	116.26 (9)
C2—C1—H1A	108.5	C5—C6—H6A	108.2
C8—C1—H1A	108.5	C7—C6—H6A	108.2
O1—C2—C1	109.35 (6)	C5—C6—H6B	108.2
O1—C2—C3	108.70 (6)	C7—C6—H6B	108.2
C1—C2—C3	116.62 (7)	H6A—C6—H6B	107.4
O1—C2—H2	107.3	C6—C7—C8	117.19 (9)
C1—C2—H2	107.3	C6—C7—H7A	108.0
C3—C2—H2	107.3	C8—C7—H7A	108.0
C2—C3—C4	116.39 (7)	C6—C7—H7B	108.0
C2—C3—H3A	108.2	C8—C7—H7B	108.0
C4—C3—H3A	108.2	H7A—C7—H7B	107.2
C2—C3—H3B	108.2	C7—C8—C1	114.96 (9)
C4—C3—H3B	108.2	C7—C8—H8A	108.5
H3A—C3—H3B	107.3	C1—C8—H8A	108.5
C5—C4—C3	115.80 (9)	C7—C8—H8B	108.5
C5—C4—H4A	108.3	C1—C8—H8B	108.5
C3—C4—H4A	108.3	H8A—C8—H8B	107.5
C5—C4—H4B	108.3	O2—C9—O3	122.46 (7)
C3—C4—H4B	108.3	O2—C9—C1	124.59 (7)
H4A—C4—H4B	107.4	O3—C9—C1	112.94 (6)
C6—C5—C4	117.39 (7)
C9—C1—C2—O1	48.02 (8)	C5—C6—C7—C8	−63.33 (13)
C8—C1—C2—O1	169.70 (6)	C6—C7—C8—C1	−47.01 (13)
C9—C1—C2—C3	171.82 (6)	C9—C1—C8—C7	−135.91 (8)
C8—C1—C2—C3	−66.51 (9)	C2—C1—C8—C7	103.08 (9)
O1—C2—C3—C4	−167.79 (8)	C2—C1—C9—O2	−121.22 (9)
C1—C2—C3—C4	68.09 (10)	C8—C1—C9—O2	114.48 (10)
C2—C3—C4—C5	−101.20 (10)	C2—C1—C9—O3	59.34 (8)
C3—C4—C5—C6	40.99 (13)	C8—C1—C9—O3	−64.96 (9)
C4—C5—C6—C7	66.15 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.82	1.92	2.7386 (10)	177
O3—H3···O1^ii	0.82	1.85	2.6557 (8)	166

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z.

(8Tstar) (1R*,2R*)-trans-2-hydroxy-1-cyclooctanecarboxamide ?

Crystal data

C9H17NO2	Z = 2
Mr = 171.24	F(000) = 188
Triclinic, P1	Dx = 1.144 Mg m^−3
a = 6.760 (1) Å	Mo Kα radiation, λ = 0.710730 Å
b = 7.314 (1) Å	Cell parameters from 25 reflections
c = 11.217 (1) Å	θ = 12.0–14.4°
α = 79.22 (1)°	µ = 0.08 mm^−1
β = 74.12 (1)°	T = 293 K
γ = 69.45 (1)°	Prism, colourless
V = 496.93 (11) Å^3	0.30 × 0.25 × 0.02 mm

Data collection

Enraf-Nonius CAD4 diffractometer	989 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
Graphite monochromator	θmax = 26.0°, θmin = 3.0°
ω–2θ scans	h = −8→8
Absorption correction: ψ scan ?	k = −9→9
Tmin = 0.893, Tmax = 0.995	l = −13→13
4315 measured reflections	3 standard reflections every 60 min
1941 independent reflections	intensity decay: 2%

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.146	Riding
S = 0.84	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
1941 reflections	(Δ/σ)max < 0.001
110 parameters	Δρmax = 0.16 e Å^−3
146 restraints	Δρmin = −0.14 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	0.7699 (2)	0.3358 (2)	0.52719 (13)	0.0553 (4)
H1	0.6963	0.3068	0.4911	0.072*
O2	0.4304 (2)	0.79742 (19)	0.60322 (14)	0.0552 (4)
N1	0.7632 (3)	0.8183 (2)	0.52684 (17)	0.0550 (5)
H1B	0.7152	0.9264	0.4825	0.071*
H1C	0.8997	0.7686	0.5245	0.071*
C1	0.7208 (3)	0.5425 (3)	0.67721 (19)	0.0455 (5)
H1A	0.8794	0.5032	0.6519	0.059*
C2	0.6472 (3)	0.3823 (3)	0.65028 (19)	0.0497 (5)
H2	0.4946	0.4419	0.6459	0.065*
C3	0.6631 (4)	0.2002 (3)	0.7427 (2)	0.0630 (6)
H3A	0.5780	0.2422	0.8235	0.082*
H3B	0.5941	0.1215	0.7183	0.082*
C4	0.8849 (4)	0.0676 (3)	0.7595 (3)	0.0708 (7)
H4A	0.9677	0.0190	0.6800	0.092*
H4B	0.8660	−0.0447	0.8172	0.092*
C5	1.0213 (4)	0.1550 (4)	0.8062 (3)	0.0758 (8)
H5A	1.1439	0.0489	0.8286	0.099*
H5B	1.0784	0.2394	0.7383	0.099*
C6	0.9013 (5)	0.2732 (4)	0.9180 (3)	0.0872 (9)
H6A	0.9957	0.2398	0.9756	0.113*
H6B	0.7754	0.2327	0.9604	0.113*
C7	0.8258 (5)	0.4964 (4)	0.8882 (2)	0.0793 (8)
H7A	0.7742	0.5544	0.9665	0.103*
H7B	0.9518	0.5347	0.8425	0.103*
C8	0.6510 (4)	0.5874 (3)	0.8147 (2)	0.0638 (6)
H8A	0.6021	0.7286	0.8166	0.083*
H8B	0.5285	0.5415	0.8559	0.083*
C9	0.6286 (3)	0.7294 (3)	0.59782 (18)	0.0436 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0512 (8)	0.0545 (10)	0.0644 (10)	−0.0112 (7)	−0.0224 (7)	−0.0130 (7)
O2	0.0439 (8)	0.0441 (8)	0.0742 (10)	−0.0057 (6)	−0.0221 (7)	−0.0010 (7)
N1	0.0496 (10)	0.0415 (10)	0.0670 (12)	−0.0095 (8)	−0.0187 (9)	0.0093 (9)
C1	0.0469 (11)	0.0388 (11)	0.0511 (12)	−0.0100 (9)	−0.0177 (9)	−0.0023 (9)
C2	0.0432 (10)	0.0438 (11)	0.0594 (13)	−0.0078 (9)	−0.0167 (10)	−0.0033 (10)
C3	0.0656 (14)	0.0465 (13)	0.0777 (16)	−0.0201 (11)	−0.0193 (12)	0.0007 (11)
C4	0.0827 (16)	0.0475 (13)	0.0781 (17)	−0.0155 (12)	−0.0291 (14)	0.0095 (12)
C5	0.0811 (17)	0.0616 (16)	0.0823 (18)	−0.0118 (13)	−0.0406 (15)	0.0099 (14)
C6	0.117 (2)	0.0747 (19)	0.0737 (18)	−0.0218 (17)	−0.0511 (16)	0.0096 (15)
C7	0.112 (2)	0.0728 (18)	0.0606 (16)	−0.0252 (16)	−0.0388 (15)	−0.0034 (13)
C8	0.0838 (16)	0.0481 (13)	0.0564 (15)	−0.0152 (12)	−0.0179 (12)	−0.0059 (11)
C9	0.0489 (11)	0.0357 (10)	0.0473 (12)	−0.0070 (9)	−0.0183 (9)	−0.0081 (9)

Geometric parameters (Å, º)

O1—C2	1.436 (2)	C4—C5	1.529 (4)
O1—H1	0.8200	C4—H4A	0.9700
O2—C9	1.243 (2)	C4—H4B	0.9700
N1—C9	1.307 (3)	C5—C6	1.527 (4)
N1—H1B	0.8600	C5—H5A	0.9700
N1—H1C	0.8600	C5—H5B	0.9700
C1—C9	1.517 (3)	C6—C7	1.530 (4)
C1—C2	1.528 (3)	C6—H6A	0.9700
C1—C8	1.546 (3)	C6—H6B	0.9700
C1—H1A	0.9800	C7—C8	1.515 (3)
C2—C3	1.518 (3)	C7—H7A	0.9700
C2—H2	0.9800	C7—H7B	0.9700
C3—C4	1.513 (3)	C8—H8A	0.9700
C3—H3A	0.9700	C8—H8B	0.9700
C3—H3B	0.9700
C2—O1—H1	109.5	C6—C5—C4	115.2 (2)
C9—N1—H1B	120.0	C6—C5—H5A	108.5
C9—N1—H1C	120.0	C4—C5—H5A	108.5
H1B—N1—H1C	120.0	C6—C5—H5B	108.5
C9—C1—C2	107.95 (16)	C4—C5—H5B	108.5
C9—C1—C8	108.31 (16)	H5A—C5—H5B	107.5
C2—C1—C8	115.21 (18)	C5—C6—C7	115.7 (2)
C9—C1—H1A	108.4	C5—C6—H6A	108.4
C2—C1—H1A	108.4	C7—C6—H6A	108.4
C8—C1—H1A	108.4	C5—C6—H6B	108.4
O1—C2—C3	112.02 (18)	C7—C6—H6B	108.4
O1—C2—C1	104.85 (16)	H6A—C6—H6B	107.4
C3—C2—C1	117.76 (18)	C8—C7—C6	118.3 (2)
O1—C2—H2	107.2	C8—C7—H7A	107.7
C3—C2—H2	107.2	C6—C7—H7A	107.7
C1—C2—H2	107.2	C8—C7—H7B	107.7
C4—C3—C2	118.8 (2)	C6—C7—H7B	107.7
C4—C3—H3A	107.6	H7A—C7—H7B	107.1
C2—C3—H3A	107.6	C7—C8—C1	115.1 (2)
C4—C3—H3B	107.6	C7—C8—H8A	108.5
C2—C3—H3B	107.6	C1—C8—H8A	108.5
H3A—C3—H3B	107.1	C7—C8—H8B	108.5
C3—C4—C5	117.7 (2)	C1—C8—H8B	108.5
C3—C4—H4A	107.9	H8A—C8—H8B	107.5
C5—C4—H4A	107.9	O2—C9—N1	121.56 (17)
C3—C4—H4B	107.9	O2—C9—C1	120.54 (18)
C5—C4—H4B	107.9	N1—C9—C1	117.87 (16)
H4A—C4—H4B	107.2
C9—C1—C2—O1	71.69 (18)	C5—C6—C7—C8	66.8 (4)
C8—C1—C2—O1	−167.14 (16)	C6—C7—C8—C1	−68.7 (3)
C9—C1—C2—C3	−163.01 (18)	C9—C1—C8—C7	−138.0 (2)
C8—C1—C2—C3	−41.8 (3)	C2—C1—C8—C7	101.0 (2)
O1—C2—C3—C4	57.1 (3)	C2—C1—C9—O2	55.2 (2)
C1—C2—C3—C4	−64.6 (3)	C8—C1—C9—O2	−70.2 (2)
C2—C3—C4—C5	61.3 (3)	C2—C1—C9—N1	−126.63 (19)
C3—C4—C5—C6	46.7 (3)	C8—C1—C9—N1	108.0 (2)
C4—C5—C6—C7	−100.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.82	1.92	2.732 (2)	170
N1—H1B···O2^ii	0.86	2.09	2.945 (2)	172
N1—H1C···O1^iii	0.86	2.04	2.883 (2)	166

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

(8C) (1R*,2S*)-cis-2-hydroxy-1-cyclooctanecarboxylic acid

Crystal data

C9H16O3	F(000) = 376
Mr = 172.22	Dx = 1.215 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.710730 Å
a = 11.082 (1) Å	Cell parameters from 25 reflections
b = 7.618 (1) Å	θ = 16.2–17.8°
c = 11.579 (1) Å	µ = 0.09 mm^−1
β = 105.67 (1)°	T = 293 K
V = 941.20 (17) Å^3	Prism, colourless
Z = 4	0.50 × 0.40 × 0.25 mm

Data collection

Enraf-Nonius CAD4 diffractometer	2100 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.016
Graphite monochromator	θmax = 35.0°, θmin = 3.2°
ω–2θ scans	h = −17→17
Absorption correction: ψ scan ?	k = −12→0
Tmin = 0.958, Tmax = 0.988	l = 0→18
4372 measured reflections	3 standard reflections every 60 min
4074 independent reflections	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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.154	Riding
S = 0.85	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
4074 reflections	(Δ/σ)max < 0.001
111 parameters	Δρmax = 0.31 e Å^−3
99 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	0.00245 (6)	0.22080 (10)	0.11454 (7)	0.03749 (19)
H1	−0.0107	0.1985	0.0429	0.049*
O2	0.07036 (8)	−0.17111 (10)	0.13317 (7)	0.0418 (2)
O3	0.14942 (8)	−0.06238 (11)	0.31595 (7)	0.0475 (2)
H3	0.1048	−0.1382	0.3333	0.062*
C1	0.20784 (9)	0.08228 (13)	0.15978 (8)	0.03058 (19)
H1A	0.2892	0.0920	0.2195	0.040*
C2	0.13409 (10)	0.25314 (13)	0.16540 (9)	0.0339 (2)
H2	0.1465	0.2825	0.2502	0.044*
C3	0.17177 (13)	0.41215 (15)	0.10455 (13)	0.0490 (3)
H3A	0.1116	0.5047	0.1042	0.064*
H3B	0.1643	0.3816	0.0216	0.064*
C4	0.30256 (15)	0.4869 (2)	0.15783 (16)	0.0659 (4)
H4A	0.3075	0.5981	0.1186	0.086*
H4B	0.3111	0.5121	0.2418	0.086*
C5	0.41537 (15)	0.3764 (3)	0.15052 (16)	0.0709 (4)
H5A	0.4314	0.2906	0.2148	0.092*
H5B	0.4880	0.4528	0.1653	0.092*
C6	0.40454 (14)	0.2802 (2)	0.03419 (15)	0.0679 (4)
H6A	0.3448	0.3425	−0.0293	0.088*
H6B	0.4851	0.2857	0.0165	0.088*
C7	0.36447 (12)	0.0883 (2)	0.03002 (13)	0.0558 (3)
H7A	0.4235	0.0279	0.0951	0.073*
H7B	0.3739	0.0387	−0.0442	0.073*
C8	0.23276 (10)	0.04339 (15)	0.03808 (10)	0.0389 (2)
H8A	0.2178	−0.0805	0.0205	0.051*
H8B	0.1728	0.1087	−0.0234	0.051*
C9	0.13589 (9)	−0.06453 (13)	0.19924 (9)	0.0317 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0377 (4)	0.0430 (4)	0.0329 (4)	0.0057 (3)	0.0116 (3)	−0.0072 (3)
O2	0.0545 (5)	0.0348 (4)	0.0360 (4)	−0.0087 (3)	0.0123 (3)	−0.0054 (3)
O3	0.0591 (5)	0.0547 (5)	0.0298 (4)	−0.0231 (4)	0.0142 (3)	−0.0013 (3)
C1	0.0319 (4)	0.0335 (4)	0.0272 (4)	−0.0001 (4)	0.0094 (3)	0.0011 (3)
C2	0.0404 (5)	0.0325 (5)	0.0282 (4)	0.0006 (4)	0.0084 (4)	−0.0035 (4)
C3	0.0580 (7)	0.0342 (5)	0.0534 (7)	−0.0001 (5)	0.0123 (6)	0.0077 (5)
C4	0.0755 (10)	0.0462 (7)	0.0744 (10)	−0.0216 (7)	0.0175 (8)	−0.0033 (7)
C5	0.0572 (8)	0.0814 (10)	0.0695 (10)	−0.0275 (8)	0.0091 (7)	0.0028 (8)
C6	0.0537 (8)	0.0890 (11)	0.0685 (9)	−0.0161 (8)	0.0292 (7)	0.0076 (8)
C7	0.0439 (6)	0.0772 (9)	0.0537 (7)	0.0001 (6)	0.0258 (6)	−0.0004 (7)
C8	0.0401 (5)	0.0469 (6)	0.0341 (5)	0.0010 (4)	0.0177 (4)	−0.0025 (4)
C9	0.0353 (4)	0.0314 (4)	0.0291 (4)	0.0016 (4)	0.0100 (3)	0.0007 (3)

Geometric parameters (Å, º)

O1—C2	1.4393 (12)	C4—C5	1.528 (3)
O1—H1	0.8200	C4—H4A	0.9700
O2—C9	1.2131 (12)	C4—H4B	0.9700
O3—C9	1.3189 (12)	C5—C6	1.509 (2)
O3—H3	0.8200	C5—H5A	0.9700
C1—C9	1.5140 (14)	C5—H5B	0.9700
C1—C8	1.5363 (13)	C6—C7	1.525 (2)
C1—C2	1.5476 (14)	C6—H6A	0.9700
C1—H1A	0.9800	C6—H6B	0.9700
C2—C3	1.5157 (16)	C7—C8	1.5263 (16)
C2—H2	0.9800	C7—H7A	0.9700
C3—C4	1.5239 (19)	C7—H7B	0.9700
C3—H3A	0.9700	C8—H8A	0.9700
C3—H3B	0.9700	C8—H8B	0.9700
C2—O1—H1	109.5	C4—C5—H5A	108.1
C9—O3—H3	109.5	C6—C5—H5A	108.1
C9—C1—C8	111.98 (8)	C4—C5—H5B	108.1
C9—C1—C2	106.34 (8)	C6—C5—H5B	108.1
C8—C1—C2	115.38 (8)	H5A—C5—H5B	107.3
C9—C1—H1A	107.6	C7—C6—C5	116.50 (13)
C8—C1—H1A	107.6	C7—C6—H6A	108.2
C2—C1—H1A	107.6	C5—C6—H6A	108.2
O1—C2—C3	108.82 (9)	C7—C6—H6B	108.2
O1—C2—C1	109.10 (8)	C5—C6—H6B	108.2
C3—C2—C1	115.96 (9)	H6A—C6—H6B	107.3
O1—C2—H2	107.5	C6—C7—C8	119.21 (12)
C3—C2—H2	107.5	C6—C7—H7A	107.5
C1—C2—H2	107.5	C8—C7—H7A	107.5
C2—C3—C4	117.49 (11)	C6—C7—H7B	107.5
C2—C3—H3A	107.9	C8—C7—H7B	107.5
C4—C3—H3A	107.9	H7A—C7—H7B	107.0
C2—C3—H3B	107.9	C7—C8—C1	115.13 (10)
C4—C3—H3B	107.9	C7—C8—H8A	108.5
H3A—C3—H3B	107.2	C1—C8—H8A	108.5
C5—C4—C3	118.33 (13)	C7—C8—H8B	108.5
C5—C4—H4A	107.7	C1—C8—H8B	108.5
C3—C4—H4A	107.7	H8A—C8—H8B	107.5
C5—C4—H4B	107.7	O2—C9—O3	122.51 (9)
C3—C4—H4B	107.7	O2—C9—C1	125.34 (9)
H4A—C4—H4B	107.1	O3—C9—C1	112.13 (8)
C4—C5—C6	116.60 (14)
C9—C1—C2—O1	−43.91 (11)	C5—C6—C7—C8	66.10 (19)
C8—C1—C2—O1	80.90 (11)	C6—C7—C8—C1	−67.83 (17)
C9—C1—C2—C3	−167.16 (9)	C9—C1—C8—C7	−137.14 (11)
C8—C1—C2—C3	−42.36 (13)	C2—C1—C8—C7	101.04 (12)
O1—C2—C3—C4	170.74 (11)	C8—C1—C9—O2	−22.54 (14)
C1—C2—C3—C4	−65.86 (14)	C2—C1—C9—O2	104.33 (11)
C2—C3—C4—C5	67.30 (18)	C8—C1—C9—O3	159.09 (9)
C3—C4—C5—C6	41.1 (2)	C2—C1—C9—O3	−74.04 (10)
C4—C5—C6—C7	−96.78 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.82	1.98	2.7876 (11)	170
O3—H3···O1^ii	0.82	1.82	2.6344 (11)	171

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