The O,O′-diacetyl (R,R)-hydrogentartrate ester of (S)-pantolactone

The synthesis of the title compound, (1R,2R)-1-carb­oxy-2-[(3S)-4,4-dimethyl-2-oxotetra­hydro­furan-3-yloxycarbonyl]ethane-1,2-diyl diacetate, C₁₄H₁₈O₁₀, from diacetyl­tartaric acid anhydride and pantolactone gave two enanti­omeric pairs and the crystal structure of the R,R,S enanti­omer is presented here. The mol­ecule consists of a hydrogen tartrate fragment in which the carboxyl group and the lactone ester group are in an anti conformation. In the crystal structure, mol­ecules are linked into C(10) chains by an inter­molecular O—H...O hydrogen bond and further by C—H...O inter­actions to form a layer structure with the second-level graph-set descriptor R₂²(8)[R₄⁴(26)].

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.035
• wR factor = 0.090
• Data-to-parameter ratio = 8.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.55 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.23 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C8     -   C9      ..       5.64 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C8
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.04
           From the CIF: _reflns_number_total               1784
           Count of symmetry unique reflns         1787
           Completeness (_total/calc)             99.83%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3     = .          R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C5     = .          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   6 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Four diastereomeric diacetyl hydrogentartrate esters of pantolactone representing two enantiomeric pairs have been obtained from diacetyltartaric acid anhydride and pantolactone. They may be exploited in the resolution of racemic pantolactone via diastereomeric ester formation (Beutel & Tishler, 1946). The esters posses unique structure, which combines two natural units: of tartaric acid and of pantolactone, what may be interesting in the synthesis of bioactive molecules from the chiral pool (Ghosh et al., 2001). Although application of such compounds is unknown it seems that they may be used, e.g. in the polymer chemistry. The structure of the (R,R,S) enantiomer (I) is presented here.

The molecule of (I) (Fig. 1) consists of the hydrogentartrate fragment in which the carboxyl group and the lactone ester group are in anti conformation with the torsion angle C1—C2—C3—C4 equal to 172.8 (2)°. The same conformation is observed in (S)-tetrahydrofurfuryl -O,O'-diacetyl-(R,R)-hydrogentartrate (Mravik et al., 1996) were the relevant torsion angle is 168.1 (5)°. Whereas in the second structurally characterized derivative, (S)-timolol-O,O'-diacetyl-(R,R)-hydrogentartrate (Kivikoski et al., 1993) the gauche conformation is observed and the corresponding torsion angle equals to 37.0 (5)°. The ester fragment consists of (S)-pantalactone heterocycle showing the open envelope conformation with the C8 atom displaced by 0.626 (3) Å out of the l.s. plane defined by C5, C6, O6 and C7 atoms.

The strong intermolecular hydrogen bonds are observed between the O1—H1 donor of carboxyl group and the carbonyl O5ⁱ atom of pantalactone [symmetry code: (i) 3/2 - x, 1 - y, 1/2 + z]. The molecules are arranged into infinite one-dimensional chain running along c axis with the assigned graph descriptor C(10) (Etter, 1990). The weak C—H···O intermolecular interactions are observed between C5—H5 chiral atom and the O2ⁱⁱ carbonyl oxygen of the carboxylic group [symmetry code: (ii) 1/2 - x, 1 - y, -1/2 + z]. This motif can be described as C(8) and it is also running along [001] direction. Together with the O1—H1···O5 motif they form a layer structure on (100) plane (Fig. 2) with the second level graph extended descriptor R²₂ (8)[R⁴₄(26)] (Bernstein et al., 1995). The remaining carbonyl oxygen O4, O8 and O10 atoms act as the acceptors to the methyl groups only and weakly join the adjacent layers into three-dimensional structure.

Related literature

The corresponding (R,R,R) diastereoisomer crysallizes as the monohydrate (Zachara et al., 2007; see the following paper). The molecular geometry is close to that of the (R,R,S) isomer but the molecules are O—H···O linked via water molecules to form a layer structure. There are only two other structurally characterized (R,R)-hydrogentartrate esters (Kivikoski et al., 1993; Mravik et al., 1996).

For related literature, see: Bernstein et al. (1995); Beutel & Tishler (1946); Etter (1990); Ghosh et al. (2001).

S2. Experimental

A (1:1 mol/mol) mixture of diacetyl-(R,R)-tartaric anhydride and (S)-pantolactone in toluene was heated up to boiling temperature in a nitrogen atmosphere under reflux for 18 h. The mixture was then cooled to the room temperature and filtered. The resulting white solid product was recrystallized from 2-propanol to give pure compound (I) with mp 183.8–185.5°C. [α]²⁵_D = +9.5% (c 2, ethyl acetate). IR (KBr): ν = 1088, 1212 cm^-1, (C—O), ν = 1760 cm^-1 (C=O), ν = 2946 cm^-1 (CH₃). Crystals suitable for single-crystal X-ray diffraction measurement were recrystallized from saturated ethyl acetate.

S3. Refinement

Due to the absence of significant anomalous scattering effects, the measured Friedel pairs have been merged. The absolute structure was assigned on the basis of the known configuration of the starting materials. H atoms were positioned geometrically and constrained to ride on their parent atoms, with C—H = 0.93–0.98 Å and U_iso(H) = 1.2 (1.5 for methyl groups) × U_eq(C). Two methyl groups (C12, C14) were modelled as idealized disordered rotating groups with refined occupancy factors, 0.69 (5) and 0.69 (4) for major conformers, respectively. The position of the H atom attached to O atom was freely refined with U_iso(H) = 1.5×U_eq(O).

Computing details

Data collection: P3/P4-PC Software (Siemens, 1991); cell refinement: P3/P4-PC Software; data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures

	Fig. 1. ORTEP plot of the molecural structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms not bonded to chiral carbons or the O atom are omitted for clarity.
	Fig. 2. An a axis projection showing layers of molecules linked by O—H···O (dashed lines) and C—H···O (dotted lines) H-bonds. Symmetry codes: (i) 3/2 - x, 1 - y, 1/2 + z; (ii) 1/2 - x, 1 - y, z - 1/2.

(1R,2R)-1-carboxy-2-[(3S)-4,4-dimethyl-2-oxotetrahydrofuran-3- yloxycarbonyl]ethane-1,2-diyl diacetate

Crystal data

C14H18O10	Dx = 1.319 Mg m^−3
Mr = 346.28	Melting point: 183.8 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 28 reflections
a = 7.946 (2) Å	θ = 15–24°
b = 13.067 (3) Å	µ = 0.11 mm^−1
c = 16.796 (3) Å	T = 293 K
V = 1743.9 (7) Å^3	Prism, white
Z = 4	0.60 × 0.54 × 0.50 mm
F(000) = 728

Data collection

Siemens P3 diffractometer	Rint = 0.017
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.4°
Graphite monochromator	h = −5→9
profile data from ω/2θ scans	k = −15→15
3184 measured reflections	l = −20→20
1784 independent reflections	2 standard reflections every 70 reflections
1420 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.090	w = 1/[σ^2(Fo^2) + (0.0483P)^2 + 0.1521P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
1784 reflections	Δρmax = 0.14 e Å^−3
223 parameters	Δρmin = −0.11 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0133 (17)

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 I > 2σ(I) is used only for calculating R-factors and is not relevant to the choice of reflections for refinement.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O2	0.3053 (3)	0.56229 (18)	0.66759 (13)	0.0712 (7)
O1	0.5720 (3)	0.6007 (2)	0.63717 (13)	0.0694 (7)
H1	0.591 (5)	0.586 (3)	0.692 (3)	0.104*
O3	0.5095 (3)	0.55520 (13)	0.37040 (10)	0.0507 (5)
O4	0.4240 (3)	0.39211 (15)	0.38236 (12)	0.0646 (7)
O5	0.7548 (4)	0.4649 (2)	0.26751 (13)	0.0772 (7)
O6	0.6492 (4)	0.56521 (18)	0.17255 (12)	0.0783 (8)
O7	0.2241 (2)	0.54728 (13)	0.51039 (12)	0.0485 (5)
O8	0.1568 (3)	0.71252 (15)	0.50821 (17)	0.0749 (7)
O9	0.4740 (2)	0.39796 (13)	0.54300 (10)	0.0434 (5)
O10	0.7233 (3)	0.34030 (19)	0.50182 (17)	0.0838 (8)
C1	0.4147 (4)	0.5780 (2)	0.62065 (17)	0.0469 (7)
C2	0.3928 (3)	0.5724 (2)	0.53104 (15)	0.0370 (6)
H2	0.4236	0.6382	0.5070	0.044*
C3	0.5048 (3)	0.48876 (18)	0.49835 (14)	0.0386 (6)
H3	0.6226	0.5089	0.5057	0.046*
C4	0.4737 (3)	0.4697 (2)	0.41073 (15)	0.0420 (7)
C5	0.4859 (4)	0.5518 (2)	0.28598 (15)	0.0493 (7)
H5	0.3951	0.5040	0.2728	0.059*
C6	0.6447 (5)	0.5206 (2)	0.24441 (18)	0.0603 (9)
C7	0.5031 (5)	0.6327 (2)	0.16463 (18)	0.0686 (10)
H7A	0.4133	0.5989	0.1357	0.082*
H7B	0.5332	0.6952	0.1368	0.082*
C8	0.4488 (5)	0.6560 (2)	0.25043 (18)	0.0600 (9)
C9	0.2646 (6)	0.6854 (3)	0.2554 (2)	0.0922 (13)
H9A	0.2487	0.7517	0.2321	0.138*
H9B	0.2303	0.6871	0.3102	0.138*
H9C	0.1982	0.6360	0.2272	0.138*
C10	0.5602 (7)	0.7381 (2)	0.2871 (2)	0.0944 (15)
H10A	0.5345	0.8031	0.2634	0.142*
H10B	0.6762	0.7216	0.2775	0.142*
H10C	0.5402	0.7413	0.3434	0.142*
C11	0.1167 (4)	0.6263 (2)	0.50047 (19)	0.0500 (7)
C12	−0.0534 (4)	0.5889 (3)	0.4791 (3)	0.0923 (14)
H12A	−0.1281	0.6460	0.4731	0.138*	0.69 (5)
H12B	−0.0944	0.5447	0.5205	0.138*	0.69 (5)
H12C	−0.0477	0.5516	0.4300	0.138*	0.69 (5)
H12D	−0.0520	0.5155	0.4759	0.138*	0.31 (5)
H12E	−0.0858	0.6168	0.4285	0.138*	0.31 (5)
H12F	−0.1325	0.6100	0.5191	0.138*	0.31 (5)
C13	0.5991 (4)	0.3268 (2)	0.53940 (19)	0.0537 (8)
C14	0.5592 (5)	0.2359 (2)	0.5890 (2)	0.0724 (10)
H14A	0.6507	0.1881	0.5865	0.109*	0.69 (4)
H14B	0.4585	0.2040	0.5695	0.109*	0.69 (4)
H14C	0.5424	0.2569	0.6432	0.109*	0.69 (4)
H14D	0.4504	0.2446	0.6130	0.109*	0.31 (4)
H14E	0.6426	0.2287	0.6300	0.109*	0.31 (4)
H14F	0.5587	0.1758	0.5562	0.109*	0.31 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0817 (17)	0.0784 (15)	0.0533 (12)	0.0062 (14)	0.0256 (13)	0.0025 (12)
O1	0.0672 (16)	0.0949 (17)	0.0462 (11)	−0.0177 (14)	−0.0139 (11)	−0.0016 (12)
O3	0.0744 (14)	0.0423 (10)	0.0352 (9)	−0.0148 (12)	0.0038 (10)	−0.0028 (8)
O4	0.0955 (18)	0.0464 (11)	0.0520 (11)	−0.0215 (13)	−0.0023 (12)	−0.0031 (10)
O5	0.0898 (18)	0.0856 (16)	0.0564 (13)	0.0162 (18)	0.0171 (13)	0.0121 (13)
O6	0.104 (2)	0.0833 (16)	0.0478 (12)	0.0046 (16)	0.0161 (13)	0.0164 (12)
O7	0.0340 (10)	0.0401 (10)	0.0713 (13)	0.0010 (9)	−0.0013 (10)	−0.0011 (9)
O8	0.0598 (14)	0.0443 (12)	0.121 (2)	0.0062 (12)	−0.0055 (15)	0.0025 (13)
O9	0.0411 (11)	0.0433 (10)	0.0459 (10)	0.0077 (9)	0.0020 (9)	0.0041 (8)
O10	0.0643 (16)	0.0783 (16)	0.109 (2)	0.0252 (14)	0.0259 (16)	0.0027 (15)
C1	0.056 (2)	0.0394 (14)	0.0456 (15)	0.0036 (14)	0.0067 (16)	0.0000 (13)
C2	0.0304 (14)	0.0380 (13)	0.0424 (13)	−0.0031 (12)	0.0012 (12)	−0.0006 (11)
C3	0.0341 (14)	0.0414 (13)	0.0404 (13)	−0.0030 (12)	0.0020 (13)	0.0023 (11)
C4	0.0430 (17)	0.0410 (14)	0.0420 (14)	−0.0033 (14)	0.0061 (13)	−0.0014 (12)
C5	0.069 (2)	0.0420 (14)	0.0366 (14)	−0.0108 (17)	−0.0009 (15)	−0.0061 (11)
C6	0.085 (3)	0.0526 (17)	0.0435 (17)	−0.0069 (19)	0.0091 (19)	0.0018 (15)
C7	0.102 (3)	0.0585 (18)	0.0455 (16)	−0.009 (2)	−0.008 (2)	0.0058 (15)
C8	0.090 (3)	0.0427 (15)	0.0477 (16)	−0.0034 (18)	−0.0056 (19)	−0.0014 (13)
C9	0.126 (4)	0.077 (2)	0.074 (3)	0.027 (3)	0.000 (3)	−0.004 (2)
C10	0.167 (4)	0.0466 (18)	0.069 (2)	−0.035 (3)	−0.021 (3)	0.0054 (16)
C11	0.0372 (16)	0.0461 (17)	0.0669 (18)	0.0045 (14)	0.0022 (15)	0.0040 (15)
C12	0.0417 (19)	0.073 (2)	0.162 (4)	0.0073 (18)	−0.015 (2)	0.001 (3)
C13	0.0474 (19)	0.0510 (17)	0.0627 (18)	0.0127 (16)	−0.0046 (17)	−0.0060 (15)
C14	0.067 (2)	0.0540 (18)	0.096 (3)	0.0116 (18)	−0.021 (2)	0.0115 (18)

Geometric parameters (Å, º)

O2—C1	1.191 (3)	C7—H7A	0.9700
O1—C1	1.314 (4)	C7—H7B	0.9700
O1—H1	0.95 (4)	C8—C9	1.516 (6)
O3—C4	1.337 (3)	C8—C10	1.521 (5)
O3—C5	1.431 (3)	C9—H9A	0.9600
O4—C4	1.188 (3)	C9—H9B	0.9600
O5—C6	1.202 (4)	C9—H9C	0.9600
O6—C6	1.341 (4)	C10—H10A	0.9600
O6—C7	1.464 (5)	C10—H10B	0.9600
O7—C11	1.350 (3)	C10—H10C	0.9600
O7—C2	1.424 (3)	C11—C12	1.481 (5)
O8—C11	1.178 (3)	C12—H12A	0.9600
O9—C13	1.363 (3)	C12—H12B	0.9600
O9—C3	1.425 (3)	C12—H12C	0.9600
O10—C13	1.184 (4)	C12—H12D	0.9600
C1—C2	1.517 (4)	C12—H12E	0.9600
C2—C3	1.513 (4)	C12—H12F	0.9600
C2—H2	0.9800	C13—C14	1.486 (4)
C3—C4	1.513 (3)	C14—H14A	0.9600
C3—H3	0.9800	C14—H14B	0.9600
C5—C6	1.499 (5)	C14—H14C	0.9600
C5—C8	1.515 (4)	C14—H14D	0.9600
C5—H5	0.9800	C14—H14E	0.9600
C7—C8	1.535 (5)	C14—H14F	0.9600
C1—O1—H1	108 (3)	H10A—C10—H10B	109.5
C4—O3—C5	116.7 (2)	C8—C10—H10C	109.5
C6—O6—C7	108.8 (3)	H10A—C10—H10C	109.5
C11—O7—C2	116.7 (2)	H10B—C10—H10C	109.5
C13—O9—C3	114.8 (2)	O8—C11—O7	123.1 (3)
O2—C1—O1	126.4 (3)	O8—C11—C12	126.1 (3)
O2—C1—C2	124.4 (3)	O7—C11—C12	110.7 (3)
O1—C1—C2	109.2 (3)	C11—C12—H12A	109.5
O7—C2—C3	107.4 (2)	C11—C12—H12B	109.5
O7—C2—C1	111.1 (2)	H12A—C12—H12B	109.5
C3—C2—C1	109.1 (2)	C11—C12—H12C	109.5
O7—C2—H2	109.7	H12A—C12—H12C	109.5
C3—C2—H2	109.7	H12B—C12—H12C	109.5
C1—C2—H2	109.7	C11—C12—H12D	109.5
O9—C3—C2	108.03 (19)	H12A—C12—H12D	141.1
O9—C3—C4	110.3 (2)	H12B—C12—H12D	56.3
C2—C3—C4	112.1 (2)	H12C—C12—H12D	56.3
O9—C3—H3	108.8	C11—C12—H12E	109.5
C2—C3—H3	108.8	H12A—C12—H12E	56.3
C4—C3—H3	108.8	H12B—C12—H12E	141.1
O4—C4—O3	125.5 (2)	H12C—C12—H12E	56.3
O4—C4—C3	125.8 (2)	H12D—C12—H12E	109.5
O3—C4—C3	108.7 (2)	C11—C12—H12F	109.5
O3—C5—C6	111.1 (3)	H12A—C12—H12F	56.3
O3—C5—C8	112.9 (2)	H12B—C12—H12F	56.3
C6—C5—C8	103.0 (3)	H12C—C12—H12F	141.1
O3—C5—H5	109.9	H12D—C12—H12F	109.5
C6—C5—H5	109.9	H12E—C12—H12F	109.5
C8—C5—H5	109.9	O10—C13—O9	122.0 (3)
O5—C6—O6	122.3 (3)	O10—C13—C14	126.6 (3)
O5—C6—C5	128.8 (3)	O9—C13—C14	111.4 (3)
O6—C6—C5	108.8 (3)	C13—C14—H14A	109.5
O6—C7—C8	104.9 (3)	C13—C14—H14B	109.5
O6—C7—H7A	110.8	H14A—C14—H14B	109.5
C8—C7—H7A	110.8	C13—C14—H14C	109.5
O6—C7—H7B	110.8	H14A—C14—H14C	109.5
C8—C7—H7B	110.8	H14B—C14—H14C	109.5
H7A—C7—H7B	108.8	C13—C14—H14D	109.5
C5—C8—C9	113.2 (3)	H14A—C14—H14D	141.1
C5—C8—C10	111.2 (3)	H14B—C14—H14D	56.3
C9—C8—C10	111.1 (3)	H14C—C14—H14D	56.3
C5—C8—C7	97.9 (2)	C13—C14—H14E	109.5
C9—C8—C7	111.9 (3)	H14A—C14—H14E	56.3
C10—C8—C7	110.9 (3)	H14B—C14—H14E	141.1
C8—C9—H9A	109.5	H14C—C14—H14E	56.3
C8—C9—H9B	109.5	H14D—C14—H14E	109.5
H9A—C9—H9B	109.5	C13—C14—H14F	109.5
C8—C9—H9C	109.5	H14A—C14—H14F	56.3
H9A—C9—H9C	109.5	H14B—C14—H14F	56.3
H9B—C9—H9C	109.5	H14C—C14—H14F	141.1
C8—C10—H10A	109.5	H14D—C14—H14F	109.5
C8—C10—H10B	109.5	H14E—C14—H14F	109.5
C11—O7—C2—C3	−151.0 (2)	C7—O6—C6—O5	−176.5 (3)
C11—O7—C2—C1	89.7 (3)	C7—O6—C6—C5	3.9 (3)
O2—C1—C2—O7	0.8 (4)	O3—C5—C6—O5	31.1 (5)
O1—C1—C2—O7	179.6 (2)	C8—C5—C6—O5	152.2 (4)
O2—C1—C2—C3	−117.5 (3)	O3—C5—C6—O6	−149.3 (2)
O1—C1—C2—C3	61.4 (3)	C8—C5—C6—O6	−28.2 (3)
C13—O9—C3—C2	−159.5 (2)	C6—O6—C7—C8	21.8 (3)
C13—O9—C3—C4	77.7 (3)	O3—C5—C8—C9	−84.0 (3)
O7—C2—C3—O9	−69.4 (3)	C6—C5—C8—C9	156.2 (3)
C1—C2—C3—O9	51.1 (3)	O3—C5—C8—C10	42.0 (4)
O7—C2—C3—C4	52.3 (3)	C6—C5—C8—C10	−77.9 (3)
C1—C2—C3—C4	172.8 (2)	O3—C5—C8—C7	158.0 (3)
C5—O3—C4—O4	−0.2 (4)	C6—C5—C8—C7	38.2 (3)
C5—O3—C4—C3	−179.5 (2)	O6—C7—C8—C5	−36.8 (3)
O9—C3—C4—O4	2.9 (4)	O6—C7—C8—C9	−155.8 (3)
C2—C3—C4—O4	−117.5 (3)	O6—C7—C8—C10	79.5 (3)
O9—C3—C4—O3	−177.8 (2)	C2—O7—C11—O8	−0.1 (5)
C2—C3—C4—O3	61.8 (3)	C2—O7—C11—C12	179.9 (3)
C4—O3—C5—C6	−91.8 (3)	C3—O9—C13—O10	−0.1 (4)
C4—O3—C5—C8	153.1 (3)	C3—O9—C13—C14	178.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5^i	0.95 (5)	1.89 (4)	2.725 (3)	146 (4)
C5—H5···O2^ii	0.98	2.53	3.396 (4)	147
C12—H12A···O8^iii	0.96	2.54	3.476 (4)	166
C14—H14A···O4^iv	0.96	2.47	3.381 (4)	159
C14—H14B···O10^v	0.96	2.29	3.231 (5)	165

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