Benzene-1,3,5-triyl triacetate

Haines, A.H.; Hughes, D.L.

doi:10.1107/S1600536809050016

organic compounds

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Volume 65| Part 12| December 2009| Page o3279

doi:10.1107/S1600536809050016

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Benzene-1,3,5-triyl triacetate

Alan H. Haines ^a and David L. Hughes ^a ^*

^aSchool of Chemistry, University of East Anglia, Norwich NR4 7TJ, England
^*Correspondence e-mail: d.l.hughes@uea.ac.uk

(Received 23 October 2009; accepted 20 November 2009; online 28 November 2009)

The asymmetric unit of the title compound, C₁₂H₁₂O₆, contains two essentially identical molecules related by a pseudo-inversion centre. The three acetoxy groups in each molecule are essentially planar and are tilted, in a regular propeller-style arrangement, with their normals oriented between 56.72 (12) and 76.35 (9)° from the normal to the mean plane of the central C₆ ring; in each molecule the three carbonyl O atoms are on the same side of the C₆ ring, with the C_ring—O—C—Me bonds in a trans conformation. The principal intermolecular contacts appear to be C—H⋯π-ring interactions; each C₆ ring has such a contact to both faces of the ring; in addition, each molecule has two intermolecular C—H⋯O contacts with H⋯O distances less than 2.55 Å.

Related literature

For our previous studies in this area, see: Haines & Hughes (2007 ); Haines et al. (2008 , 2009 ). For a related structure, see: Haines & Hughes (2009 ).

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Experimental

Crystal data

C₁₂H₁₂O₆
M_r = 252.22
Monoclinic, P 2₁ /n
a = 6.20290 (16) Å
b = 24.6643 (6) Å
c = 15.3862 (4) Å
β = 95.297 (2)°
V = 2343.88 (11) Å³
Z = 8
Mo- Kα radiation
μ = 0.12 mm⁻¹
T = 140 K
0.38 × 0.18 × 0.17 mm

Data collection

Oxford Diffraction Xcalibur 3/CCD diffractometer
Absorption correction: multi-scan (CrysAlisPro RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlisPro CCD and CrysAlisPro RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.931, T_max = 1.041
40881 measured reflections
4128 independent reflections
2769 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.196
S = 1.08
4128 reflections
331 parameters
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C52—H52A⋯O31ⁱ	0.96	2.53	3.363 (4)	145
C52—H52C⋯O11ⁱ	0.96	2.31	3.242 (4)	163
C932—H93A⋯O911ⁱⁱ	0.96	2.51	3.292 (4)	139
C952—H95C⋯O951ⁱⁱⁱ	0.96	2.54	3.474 (4)	165
C4—H4⋯Cg2^iv	0.93	2.68	3.460 (3)	141
C12—H12C⋯Cg1^v	0.96	2.86	3.604 (4)	135
C912—H91B⋯Cg2^vi	0.96	2.84	3.658 (4)	143
C94—H94⋯Cg1^vii	0.93	2.67	3.435 (3)	140
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) -x, -y+1, -z; (iv) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) x-1, y, z; (vi) x+1, y, z; (vii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg1 and Cg2 are the centroids of the C1–C6 and C91–C96 rings, respectively.

Data collection: CrysAlisPro CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlisPro CCD and CrysAlisPro RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlisPro RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlisPro CCD and CrysAlisPro RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlisPro RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050016/hb5176sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809050016/hb5176Isup2.hkl

checkCIF report

Comment top

Structural factors which enhance the solubility of organic compounds in liquid carbon dioxide are difficult to identify, but a knowledge of these is important in view of the possibility of using liquid carbon dioxide as an environmentally acceptable, cheap, safe and readily available alternative to replace organic-based solvents in the development of so-called "green chemistry". Previous studies (Haines et al., 2008) have shown that certain types of acyl group promote the solubilities of per-acylated D-glucopyranose derivatives in liquid carbon dioxide; in particular trimethylacetyl groups promoted solubility, their effect being comparable to acetyl groups and superior to dimethylacetyl groups. In searching for an explanation for solubility differences in this series based on differing intermolecular forces in the solid state, we conducted crystal structure studies on the compounds (Haines & Hughes, 2007), but the results indicated no substantial difference in such intermolecular forces.

Measurement of solubilities in liquid carbon dioxide of the series of 1,3,5-triacetoxybenzene (1) and substituted derivatives, viz 1,3,5-tris-(dimethylacetoxy)benzene (2) and 1,3,5-tris-(trimethylacetoxy)benzene (3), chosen in an attempt to separate the effects on solubility of the number and structure of peripheral substituents in compounds of similar overall molecular dimensions to the carbohydrate derivatives, showed no major differences (Haines, et al., 2009, unpublished results) and prompted an investigation of their crystal structures in order to compare intermolecular interactions in these compounds.

The stucture of the first compound of the series, (1) is shown in Figure 1; other compounds of the series are described in the accompanying paper (Haines and Hughes, 2009). Dimensions are available in the archived CIFs.

Compound (1) was prepared by the acylation of 1,3,5-trihydroxybenzene with acetic anhydride and formed crystals having two essentially identical molecules with very similar orientations in the cell, related by a pseudo inversion centre. The three acetoxy groups in each molecule are essentially planar and are tilted, in a regular propeller-style arrangement, with their normals at 56.72 (12), 76.35 (9) and 60.73 (12)° from the normal to the mean-plane of the central C₆ ring in one molecule and 58.44 (11), 75.11 (13) and 63.76 (11) ° in the second molecule. In each molecule the three carbonyl O-atoms are on the same side of the C₆ ring, with the C_ring—O—C—Me bonds in a trans conformation. The principal intermolecular contacts appear to be C—H···π-ring interactions: each C₆ ring has such a contact to both faces of the ring – the ring C(1–6) has H(12C^a) and H(94^b) on opposite sides of the ring at 3.25 and 2.63 Å from the ring mean-plane, and the ring of C(91–96) is bounded by H(4^c) and H(91B^d) at 2.65 and 3.14 Å from the ring mean-plane (the superscripts a–d indicate symmetry operations). Also, each molecule makes two intermolecular C—H···O contacts with H···O distances in the range 2.31–2.54 Å.

Related literature top

For our previous studies in this area, see: Haines & Hughes (2007); Haines et al. (2008, 2009). For further synthetic details, see: Hegetschweiler et al. (1990). For a related structure, see: Haines & Hughes (2009).

Experimental top

The title compound was prepared by the conventional acylation of the parent 1,3,5-trihydroxybenzene and has been described previously (Hegetschweiler et al., 1990); the physical data (m.p., ¹H and ¹³C NMR spectra) of our product agreed with those reported.

To a solution of anhydrous 1,3,5-trihydroxybenzene (phloroglucinol) (1.26 g) in pyridine (6 ml) was added acetic anhydride (5.6 ml) and after 12 h the solution was poured into iced water which led to formation of a white precipitate. After stirring for 2 h, the solid was collected by filtration, and recrystallized from ethanol to give compound 1 (1.67 g, 66%), m.p. 106–107 °C (lit. {Hegetschweiler et al., 1990} 106 °C); δ_H(CDCl₃) 6.84, (s, 3H), 2.27 (s, 9H); δ_C(CDCl₃) 168.65, 151.19, 112.76, 20.91. The NMR data are in full agreement with the reported literature values (Hegetschweiler et al., 1990).

Computing details top

Data collection: CrysAlis PRO CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis PRO RED (Oxford Diffraction, 2008); data reduction: CrysAlis PRO RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. View of the two independent molecules in (I), related by a pseudo-inversion centre at ca 0, 1/4, 1/2. Displacement ellipsoids are drawn at the 50% probability level.

Benzene-1,3,5-triyl triacetate top

Crystal data top

C₁₂H₁₂O₆	Z = 8
M_r = 252.22	F(000) = 1056
Monoclinic, P2₁/n	D_x = 1.429 Mg m⁻³
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 6.20290 (16) Å	µ = 0.12 mm⁻¹
b = 24.6643 (6) Å	T = 140 K
c = 15.3862 (4) Å	Prism, colourless
β = 95.297 (2)°	0.38 × 0.18 × 0.17 mm
V = 2343.88 (11) Å³

Data collection top

Oxford Diffraction Xcalibur 3/CCD diffractometer	4128 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2769 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
Detector resolution: 16.0050 pixels mm^-1	θ_max = 25.0°, θ_min = 3.1°
Thin–slice ϕ and ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2008)	k = −29→29
T_min = 0.931, T_max = 1.041	l = −18→18
40881 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.196	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.1157P)² + 0.643P] where P = (F_o² + 2F_c²)/3
4128 reflections	(Δ/σ)_max = 0.001
331 parameters	Δρ_max = 0.65 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₂H₁₂O₆	V = 2343.88 (11) Å³
M_r = 252.22	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.20290 (16) Å	µ = 0.12 mm⁻¹
b = 24.6643 (6) Å	T = 140 K
c = 15.3862 (4) Å	0.38 × 0.18 × 0.17 mm
β = 95.297 (2)°

Data collection top

Oxford Diffraction Xcalibur 3/CCD diffractometer	4128 independent reflections
Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2008)	2769 reflections with I > 2σ(I)
T_min = 0.931, T_max = 1.041	R_int = 0.054
40881 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.196	H-atom parameters constrained
S = 1.08	Δρ_max = 0.65 e Å⁻³
4128 reflections	Δρ_min = −0.26 e Å⁻³
331 parameters

Special details top

Experimental. CrysAlisPro RED, Oxford Diffraction Ltd., Version 1.171.32.24 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.1644 (5)	0.22484 (12)	0.2555 (2)	0.0171 (7)
C2	0.2182 (5)	0.21091 (12)	0.17203 (19)	0.0171 (7)
H2	0.1296	0.2200	0.1221	0.020*
C3	0.4090 (5)	0.18306 (12)	0.16789 (19)	0.0188 (7)
C4	0.5456 (5)	0.16979 (12)	0.24048 (19)	0.0177 (7)
H4	0.6756	0.1518	0.2353	0.021*
C5	0.4830 (5)	0.18408 (13)	0.32137 (19)	0.0191 (7)
C6	0.2907 (5)	0.21159 (12)	0.33028 (19)	0.0176 (7)
H6	0.2493	0.2207	0.3850	0.021*
O1	−0.0344 (3)	0.24931 (9)	0.26764 (13)	0.0208 (5)
C11	−0.0865 (5)	0.29755 (13)	0.2254 (2)	0.0216 (7)
O11	0.0352 (4)	0.32021 (9)	0.18212 (16)	0.0330 (6)
C12	−0.3065 (5)	0.31541 (14)	0.2446 (2)	0.0255 (8)
H12A	−0.3271	0.3527	0.2281	0.038*
H12B	−0.3206	0.3115	0.3059	0.038*
H12C	−0.4137	0.2935	0.2122	0.038*
O3	0.4578 (3)	0.16404 (8)	0.08570 (13)	0.0210 (5)
C31	0.6135 (5)	0.19045 (13)	0.0455 (2)	0.0211 (7)
O31	0.7100 (4)	0.22877 (10)	0.07680 (15)	0.0301 (6)
C32	0.6401 (5)	0.16603 (14)	−0.04125 (19)	0.0255 (8)
H32A	0.5192	0.1759	−0.0816	0.038*
H32B	0.6469	0.1273	−0.0359	0.038*
H32C	0.7714	0.1792	−0.0622	0.038*
O5	0.6130 (3)	0.16564 (9)	0.39428 (13)	0.0233 (5)
C51	0.7090 (5)	0.20210 (14)	0.4523 (2)	0.0222 (7)
O51	0.6831 (4)	0.25004 (10)	0.44501 (15)	0.0325 (6)
C52	0.8440 (5)	0.17336 (15)	0.5235 (2)	0.0265 (8)
H52A	0.9872	0.1885	0.5292	0.040*
H52B	0.8518	0.1355	0.5096	0.040*
H52C	0.7797	0.1776	0.5775	0.040*
C91	0.8316 (5)	0.52607 (12)	0.23650 (19)	0.0169 (7)
C92	0.7795 (5)	0.53882 (12)	0.32051 (19)	0.0155 (7)
H92	0.8699	0.5293	0.3697	0.019*
C93	0.5880 (5)	0.56608 (12)	0.32707 (19)	0.0177 (7)
C94	0.4486 (5)	0.58031 (12)	0.25507 (19)	0.0181 (7)
H94	0.3188	0.5981	0.2614	0.022*
C95	0.5094 (5)	0.56707 (12)	0.17385 (18)	0.0170 (7)
C96	0.7021 (5)	0.54049 (11)	0.16326 (19)	0.0162 (7)
H96	0.7423	0.5327	0.1079	0.019*
O91	1.0296 (3)	0.50177 (9)	0.22335 (13)	0.0189 (5)
C911	1.0768 (5)	0.45224 (13)	0.26152 (19)	0.0184 (7)
O911	0.9526 (4)	0.42894 (9)	0.30330 (16)	0.0317 (6)
C912	1.2938 (6)	0.43354 (14)	0.2422 (2)	0.0240 (7)
H91A	1.3171	0.3972	0.2635	0.036*
H91B	1.4021	0.4571	0.2703	0.036*
H91C	1.3030	0.4342	0.1803	0.036*
O93	0.5437 (3)	0.58395 (9)	0.41005 (13)	0.0224 (5)
C931	0.3854 (5)	0.55818 (14)	0.4494 (2)	0.0211 (7)
O931	0.2877 (4)	0.52004 (11)	0.41682 (15)	0.0315 (6)
C932	0.3602 (6)	0.58228 (15)	0.5361 (2)	0.0290 (9)
H93A	0.2355	0.5669	0.5594	0.043*
H93B	0.3420	0.6208	0.5302	0.043*
H93C	0.4870	0.5747	0.5749	0.043*
O95	0.3780 (3)	0.58607 (9)	0.10101 (13)	0.0217 (5)
C951	0.2842 (5)	0.54966 (13)	0.04289 (19)	0.0196 (7)
O951	0.3003 (3)	0.50160 (9)	0.05213 (13)	0.0241 (5)
C952	0.1636 (5)	0.57803 (15)	−0.0327 (2)	0.0273 (8)
H95A	0.2478	0.5771	−0.0819	0.041*
H95B	0.1380	0.6150	−0.0171	0.041*
H95C	0.0277	0.5601	−0.0474	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0166 (16)	0.0130 (15)	0.0220 (16)	−0.0003 (13)	0.0030 (12)	0.0001 (12)
C2	0.0153 (16)	0.0180 (17)	0.0176 (15)	−0.0033 (14)	−0.0001 (12)	0.0030 (13)
C3	0.0249 (17)	0.0158 (16)	0.0158 (15)	−0.0062 (14)	0.0019 (13)	−0.0008 (12)
C4	0.0195 (16)	0.0127 (16)	0.0208 (16)	−0.0002 (13)	0.0012 (13)	−0.0017 (12)
C5	0.0215 (16)	0.0151 (16)	0.0195 (16)	−0.0029 (13)	−0.0047 (13)	0.0001 (12)
C6	0.0208 (17)	0.0176 (17)	0.0150 (15)	−0.0015 (14)	0.0051 (12)	−0.0013 (13)
O1	0.0186 (11)	0.0217 (12)	0.0225 (12)	0.0032 (9)	0.0034 (9)	0.0036 (9)
C11	0.0286 (18)	0.0173 (17)	0.0186 (16)	−0.0003 (14)	0.0005 (14)	−0.0033 (13)
O11	0.0367 (14)	0.0195 (13)	0.0459 (15)	0.0016 (11)	0.0193 (12)	0.0053 (11)
C12	0.0261 (17)	0.0234 (19)	0.0261 (18)	0.0035 (17)	−0.0022 (14)	−0.0001 (14)
O3	0.0263 (12)	0.0209 (12)	0.0159 (11)	−0.0037 (10)	0.0025 (9)	−0.0021 (9)
C31	0.0166 (16)	0.0240 (18)	0.0227 (17)	0.0027 (14)	0.0020 (13)	0.0025 (14)
O31	0.0279 (13)	0.0334 (14)	0.0294 (13)	−0.0088 (11)	0.0052 (10)	−0.0059 (11)
C32	0.0285 (18)	0.033 (2)	0.0159 (16)	0.0031 (15)	0.0049 (14)	0.0009 (14)
O5	0.0276 (12)	0.0208 (12)	0.0203 (11)	0.0033 (10)	−0.0051 (9)	−0.0036 (9)
C51	0.0174 (16)	0.0282 (19)	0.0214 (17)	0.0000 (14)	0.0050 (13)	−0.0055 (14)
O51	0.0434 (15)	0.0262 (14)	0.0262 (13)	−0.0040 (12)	−0.0056 (11)	−0.0018 (11)
C52	0.0247 (18)	0.036 (2)	0.0184 (16)	0.0039 (16)	−0.0025 (14)	−0.0049 (14)
C91	0.0150 (16)	0.0148 (15)	0.0210 (16)	−0.0036 (13)	0.0019 (13)	0.0006 (12)
C92	0.0179 (16)	0.0137 (16)	0.0144 (15)	−0.0037 (13)	−0.0010 (12)	0.0004 (12)
C93	0.0224 (16)	0.0153 (16)	0.0158 (15)	−0.0030 (13)	0.0031 (12)	−0.0027 (12)
C94	0.0200 (16)	0.0148 (16)	0.0199 (16)	−0.0029 (13)	0.0035 (13)	−0.0016 (12)
C95	0.0185 (15)	0.0162 (16)	0.0157 (15)	−0.0002 (13)	−0.0018 (12)	0.0031 (12)
C96	0.0241 (17)	0.0114 (16)	0.0139 (14)	−0.0019 (13)	0.0053 (12)	−0.0021 (12)
O91	0.0177 (11)	0.0205 (12)	0.0190 (11)	0.0034 (9)	0.0045 (9)	0.0034 (9)
C911	0.0241 (17)	0.0168 (16)	0.0142 (15)	−0.0007 (14)	0.0008 (13)	−0.0021 (12)
O911	0.0407 (14)	0.0178 (12)	0.0398 (14)	0.0016 (11)	0.0209 (12)	0.0034 (11)
C912	0.0276 (17)	0.0188 (18)	0.0255 (17)	0.0052 (16)	0.0015 (13)	0.0004 (14)
O93	0.0275 (12)	0.0262 (13)	0.0143 (11)	−0.0010 (10)	0.0061 (9)	−0.0055 (9)
C931	0.0170 (16)	0.0264 (19)	0.0203 (16)	0.0076 (14)	0.0039 (13)	0.0062 (14)
O931	0.0282 (13)	0.0416 (16)	0.0249 (13)	−0.0075 (12)	0.0036 (10)	−0.0011 (11)
C932	0.0313 (19)	0.039 (2)	0.0177 (17)	0.0069 (17)	0.0072 (14)	0.0040 (14)
O95	0.0251 (12)	0.0194 (12)	0.0192 (11)	0.0044 (9)	−0.0050 (9)	−0.0028 (9)
C951	0.0176 (16)	0.0255 (18)	0.0160 (16)	−0.0011 (14)	0.0040 (12)	−0.0044 (14)
O951	0.0297 (13)	0.0219 (13)	0.0205 (12)	−0.0041 (10)	0.0012 (9)	−0.0015 (9)
C952	0.0292 (19)	0.030 (2)	0.0210 (17)	0.0029 (16)	−0.0061 (14)	0.0004 (14)

Geometric parameters (Å, º) top

C1—C6	1.370 (4)	C91—C96	1.369 (4)
C1—C2	1.399 (4)	C91—C92	1.397 (4)
C1—O1	1.401 (3)	C91—O91	1.398 (3)
C2—C3	1.375 (4)	C92—C93	1.376 (4)
C2—H2	0.9300	C92—H92	0.9300
C3—C4	1.378 (4)	C93—C94	1.386 (4)
C3—O3	1.408 (4)	C93—O93	1.402 (3)
C4—C5	1.383 (4)	C94—C95	1.377 (4)
C4—H4	0.9300	C94—H94	0.9300
C5—C6	1.390 (4)	C95—C96	1.386 (4)
C5—O5	1.396 (3)	C95—O95	1.404 (3)
C6—H6	0.9300	C96—H96	0.9300
O1—C11	1.380 (4)	O91—C911	1.375 (4)
C11—O11	1.191 (4)	C911—O911	1.195 (4)
C11—C12	1.489 (4)	C911—C912	1.479 (4)
C12—H12A	0.9600	C912—H91A	0.9600
C12—H12B	0.9600	C912—H91B	0.9600
C12—H12C	0.9600	C912—H91C	0.9600
O3—C31	1.360 (4)	O93—C931	1.359 (4)
C31—O31	1.196 (4)	C931—O931	1.203 (4)
C31—C32	1.488 (4)	C931—C932	1.481 (4)
C32—H32A	0.9600	C932—H93A	0.9600
C32—H32B	0.9600	C932—H93B	0.9600
C32—H32C	0.9600	C932—H93C	0.9600
O5—C51	1.365 (4)	O95—C951	1.359 (4)
C51—O51	1.197 (4)	C951—O951	1.197 (4)
C51—C52	1.495 (4)	C951—C952	1.496 (4)
C52—H52A	0.9600	C952—H95A	0.9600
C52—H52B	0.9600	C952—H95B	0.9600
C52—H52C	0.9600	C952—H95C	0.9600

C6—C1—C2	123.1 (3)	C96—C91—C92	122.3 (3)
C6—C1—O1	115.7 (3)	C96—C91—O91	116.7 (3)
C2—C1—O1	121.0 (3)	C92—C91—O91	120.8 (3)
C3—C2—C1	116.4 (3)	C93—C92—C91	116.9 (3)
C3—C2—H2	121.8	C93—C92—H92	121.5
C1—C2—H2	121.8	C91—C92—H92	121.5
C2—C3—C4	123.3 (3)	C92—C93—C94	122.9 (3)
C2—C3—O3	117.7 (3)	C92—C93—O93	117.6 (3)
C4—C3—O3	118.8 (3)	C94—C93—O93	119.2 (3)
C3—C4—C5	117.8 (3)	C95—C94—C93	117.5 (3)
C3—C4—H4	121.1	C95—C94—H94	121.2
C5—C4—H4	121.1	C93—C94—H94	121.2
C4—C5—C6	121.9 (3)	C94—C95—C96	122.0 (3)
C4—C5—O5	116.8 (3)	C94—C95—O95	117.2 (3)
C6—C5—O5	121.1 (3)	C96—C95—O95	120.5 (3)
C1—C6—C5	117.6 (3)	C91—C96—C95	118.2 (3)
C1—C6—H6	121.2	C91—C96—H96	120.9
C5—C6—H6	121.2	C95—C96—H96	120.9
C11—O1—C1	118.7 (2)	C911—O91—C91	118.3 (2)
O11—C11—O1	122.3 (3)	O911—C911—O91	122.3 (3)
O11—C11—C12	127.7 (3)	O911—C911—C912	127.0 (3)
O1—C11—C12	109.9 (3)	O91—C911—C912	110.7 (3)
C11—C12—H12A	109.5	C911—C912—H91A	109.5
C11—C12—H12B	109.5	C911—C912—H91B	109.5
H12A—C12—H12B	109.5	H91A—C912—H91B	109.5
C11—C12—H12C	109.5	C911—C912—H91C	109.5
H12A—C12—H12C	109.5	H91A—C912—H91C	109.5
H12B—C12—H12C	109.5	H91B—C912—H91C	109.5
C31—O3—C3	118.0 (2)	C931—O93—C93	118.0 (2)
O31—C31—O3	123.1 (3)	O931—C931—O93	122.5 (3)
O31—C31—C32	126.0 (3)	O931—C931—C932	126.8 (3)
O3—C31—C32	110.9 (3)	O93—C931—C932	110.7 (3)
C31—C32—H32A	109.5	C931—C932—H93A	109.5
C31—C32—H32B	109.5	C931—C932—H93B	109.5
H32A—C32—H32B	109.5	H93A—C932—H93B	109.5
C31—C32—H32C	109.5	C931—C932—H93C	109.5
H32A—C32—H32C	109.5	H93A—C932—H93C	109.5
H32B—C32—H32C	109.5	H93B—C932—H93C	109.5
C51—O5—C5	119.7 (2)	C951—O95—C95	119.1 (2)
O51—C51—O5	122.9 (3)	O951—C951—O95	123.4 (3)
O51—C51—C52	126.8 (3)	O951—C951—C952	125.8 (3)
O5—C51—C52	110.4 (3)	O95—C951—C952	110.8 (3)
C51—C52—H52A	109.5	C951—C952—H95A	109.5
C51—C52—H52B	109.5	C951—C952—H95B	109.5
H52A—C52—H52B	109.5	H95A—C952—H95B	109.5
C51—C52—H52C	109.5	C951—C952—H95C	109.5
H52A—C52—H52C	109.5	H95A—C952—H95C	109.5
H52B—C52—H52C	109.5	H95B—C952—H95C	109.5

C6—C1—C2—C3	−0.6 (5)	C96—C91—C92—C93	1.1 (4)
O1—C1—C2—C3	−174.8 (3)	O91—C91—C92—C93	175.6 (3)
C1—C2—C3—C4	−1.1 (4)	C91—C92—C93—C94	0.7 (4)
C1—C2—C3—O3	174.2 (2)	C91—C92—C93—O93	−173.7 (2)
C2—C3—C4—C5	1.9 (5)	C92—C93—C94—C95	−1.2 (5)
O3—C3—C4—C5	−173.4 (3)	O93—C93—C94—C95	173.1 (3)
C3—C4—C5—C6	−0.9 (5)	C93—C94—C95—C96	0.0 (5)
C3—C4—C5—O5	173.9 (3)	C93—C94—C95—O95	−174.1 (3)
C2—C1—C6—C5	1.5 (5)	C92—C91—C96—C95	−2.2 (4)
O1—C1—C6—C5	175.9 (3)	O91—C91—C96—C95	−176.9 (3)
C4—C5—C6—C1	−0.7 (5)	C94—C95—C96—C91	1.6 (5)
O5—C5—C6—C1	−175.3 (3)	O95—C95—C96—C91	175.6 (3)
C6—C1—O1—C11	127.7 (3)	C96—C91—O91—C911	−125.3 (3)
C2—C1—O1—C11	−57.7 (4)	C92—C91—O91—C911	59.9 (4)
C1—O1—C11—O11	−3.2 (4)	C91—O91—C911—O911	1.9 (4)
C1—O1—C11—C12	178.0 (2)	C91—O91—C911—C912	−178.7 (2)
C2—C3—O3—C31	105.9 (3)	C92—C93—O93—C931	−108.7 (3)
C4—C3—O3—C31	−78.6 (3)	C94—C93—O93—C931	76.7 (4)
C3—O3—C31—O31	0.1 (4)	C93—O93—C931—O931	2.1 (4)
C3—O3—C31—C32	−178.5 (3)	C93—O93—C931—C932	−179.9 (3)
C4—C5—O5—C51	120.3 (3)	C94—C95—O95—C951	−120.5 (3)
C6—C5—O5—C51	−64.9 (4)	C96—C95—O95—C951	65.3 (4)
C5—O5—C51—O51	1.9 (4)	C95—O95—C951—O951	3.1 (4)
C5—O5—C51—C52	−178.6 (3)	C95—O95—C951—C952	−176.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C52—H52A···O31ⁱ	0.96	2.53	3.363 (4)	145
C52—H52C···O11ⁱ	0.96	2.31	3.242 (4)	163
C932—H93A···O911ⁱⁱ	0.96	2.51	3.292 (4)	139
C952—H95C···O951ⁱⁱⁱ	0.96	2.54	3.474 (4)	165
C4—H4···Cg2^iv	0.93	2.68	3.460 (3)	141
C12—H12C···Cg1^v	0.96	2.86	3.604 (4)	135
C912—H91B···Cg2^vi	0.96	2.84	3.658 (4)	143
C94—H94···Cg1^vii	0.93	2.67	3.435 (3)	140

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z; (iv) −x+3/2, y−1/2, −z+1/2; (v) x−1, y, z; (vi) x+1, y, z; (vii) −x+1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂O₆
M_r	252.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	140
a, b, c (Å)	6.20290 (16), 24.6643 (6), 15.3862 (4)
β (°)	95.297 (2)
V (Å³)	2343.88 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.38 × 0.18 × 0.17

Data collection
Diffractometer	Oxford Diffraction Xcalibur 3/CCD diffractometer
Absorption correction	Multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2008)
T_min, T_max	0.931, 1.041
No. of measured, independent and observed [I > 2σ(I)] reflections	40881, 4128, 2769
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.196, 1.08
No. of reflections	4128
No. of parameters	331
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.26

Computer programs: CrysAlis PRO CCD (Oxford Diffraction, 2008), CrysAlis PRO RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C52—H52A···O31ⁱ	0.96	2.53	3.363 (4)	145
C52—H52C···O11ⁱ	0.96	2.31	3.242 (4)	163
C932—H93A···O911ⁱⁱ	0.96	2.51	3.292 (4)	139
C952—H95C···O951ⁱⁱⁱ	0.96	2.54	3.474 (4)	165
C4—H4···Cg2^iv	0.93	2.68	3.460 (3)	141
C12—H12C···Cg1^v	0.96	2.86	3.604 (4)	135
C912—H91B···Cg2^vi	0.96	2.84	3.658 (4)	143
C94—H94···Cg1^vii	0.93	2.67	3.435 (3)	140

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z; (iv) −x+3/2, y−1/2, −z+1/2; (v) x−1, y, z; (vi) x+1, y, z; (vii) −x+1/2, y+1/2, −z+1/2.

References

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Haines, A. H. & Hughes, D. L. (2007). Carbohydr. Res. 342, 2264–2269. Web of Science CSD CrossRef PubMed CAS Google Scholar
Haines, A. H. & Hughes, D. L. (2009). Acta Cryst. E65, o3280. CrossRef IUCr Journals Google Scholar
Haines, A. H., Steytler, D. C. & Rivett, C. (2008). J. Supercrit. Fluids, 44, 21–24. Web of Science CrossRef CAS Google Scholar
Haines, A. H., Steytler, D. C. & Rivett, C. (2009). Unpublished data. Google Scholar
Oxford Diffraction (2008). CrysAlisPro CCD and CrysAlisPro RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 65| Part 12| December 2009| Page o3279

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