Crystal structures of hibiscus acid and hibiscus acid dimethyl ester isolated from Hibiscus sabdariffa (Malvaceae)

The biologically active title compounds have been isolated from Hibiscus sabdariffa plants, hibiscus acid as a dimethyl sulfoxide monosolvate [systematic name: (2S,3R)-3-hy­droxy-5-oxo-2,3,4,5-tetra­hydro­furan-2,3-di­carb­oxy­lic acid dimethyl sulfoxide monosolvate], C₆H₆O₇·C₂H₆OS, (I), and hibiscus acid dimethyl ester [systematic name: dimethyl (2S,3R)-3-hy­droxy-5-oxo-2,3,4,5-tetra­hydro­furan-2,3-di­carboxyl­ate], C₈H₁₀O₇, (II). Compound (I) forms a layered structure with alternating layers of lactone and solvent mol­ecules, that include a two-dimensional hydrogen-bonding construct. Compound (II) has two crystallographically independent and conformationally similar mol­ecules per asymmetric unit and forms a one-dimensional hydrogen-bonding construct. The known absolute configuration for both compounds has been confirmed.

Key indicators

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C) = 0.007 Å
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.047
• wR factor = 0.113
• Data-to-parameter ratio = 11.0

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax < 18) ........       6.84 Note
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............      0.007 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          6 Report
PLAT915_ALERT_3_C No Flack x Check Done: Low Friedel Pair Coverage         68 %

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          6 Note
PLAT012_ALERT_1_G N.O.K. _shelx_res_checksum found in CIF ........     Please Check
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT398_ALERT_2_G Deviating  C-O-C  Angle from 120 Deg for O1           109.3 Degree
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          2 Note
              C2 H6 O S
PLAT791_ALERT_4_G The Model has Chirality at C1      (Chiral SPGR)          S Verify
PLAT791_ALERT_4_G The Model has Chirality at C2      (Chiral SPGR)          R Verify
PLAT850_ALERT_4_G Check Flack Parameter Exact Value 0.00 and s.u.        0.04 Check
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          4 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          7 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          3 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  11 ALERT level G = General information/check it is not something unexpected

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




Datablock: II


Alert level C
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax < 18) ........       7.26 Note
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0059 Ang.
PLAT915_ALERT_3_C No Flack x Check Done: Low Friedel Pair Coverage         83 %

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          4 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT432_ALERT_2_G Short Inter X...Y Contact  O3     ..  C6      ..       3.02 Ang.
PLAT791_ALERT_4_G The Model has Chirality at C3      (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G The Model has Chirality at C4      (Chiral SPGR)          S Verify
PLAT791_ALERT_4_G The Model has Chirality at C11     (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G The Model has Chirality at C12     (Chiral SPGR)          S Verify
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         38 Note
PLAT916_ALERT_2_G Hooft y and Flack x Parameter values differ by .       0.10 Check
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  11 ALERT level G = General information/check it is not something unexpected

   0 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
   4 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

For both structures, data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

(2S,3R)-3-Hydroxy-5-oxo-2,3,4,5-tetrahydrofuran-2,3-dicarboxylic acid dimethyl sulfoxide monosolvate (I)

Crystal data

C6H6O7·C2H6OS	F(000) = 280
Mr = 268.24	Dx = 1.608 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.5418 Å
a = 5.4258 (2) Å	Cell parameters from 2057 reflections
b = 8.9491 (3) Å	θ = 6.3–72.8°
c = 11.4365 (3) Å	µ = 2.94 mm^−1
β = 94.092 (3)°	T = 123 K
V = 553.90 (3) Å^3	Fragment from a square plate, colourless
Z = 2	0.30 × 0.15 × 0.05 mm

Data collection

Oxford Diffraction Gemini S CCD diffractometer	1640 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.054
ω scans	θmax = 72.8°, θmin = 3.9°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −6→6
Tmin = 0.554, Tmax = 1.000	k = −10→8
4397 measured reflections	l = −14→14
1854 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.047	w = 1/[σ^2(Fo^2) + (0.0678P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.113	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.44 e Å^−3
1854 reflections	Δρmin = −0.25 e Å^−3
169 parameters	Absolute structure: Flack x determined using 698 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
4 restraints	Absolute structure parameter: 0.00 (4)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component inversion twin

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

	x	y	z	Uiso*/Ueq
S1	0.90564 (19)	1.26444 (16)	0.85370 (9)	0.0235 (3)
O1	0.6239 (6)	0.7220 (4)	0.8066 (3)	0.0233 (9)
O2	1.0711 (6)	0.6125 (5)	0.7467 (3)	0.0285 (9)
O3	0.9028 (6)	0.5501 (5)	0.5682 (3)	0.0276 (8)
O4	0.8575 (6)	0.9112 (5)	0.6333 (3)	0.0232 (8)
O5	0.3551 (6)	0.7366 (5)	0.4714 (3)	0.0265 (9)
O6	0.6572 (6)	0.8844 (5)	0.4153 (3)	0.0254 (8)
O7	0.4156 (6)	0.8927 (5)	0.9015 (3)	0.0300 (9)
O8	0.8239 (7)	1.1798 (5)	0.7411 (3)	0.0295 (9)
C1	0.6534 (8)	0.6840 (7)	0.6856 (4)	0.0231 (11)
H1	0.5185	0.6149	0.6557	0.028*
C2	0.6288 (8)	0.8370 (6)	0.6206 (4)	0.0219 (11)
C3	0.4303 (8)	0.9097 (7)	0.6897 (4)	0.0236 (11)
H3A	0.4466	1.0198	0.6901	0.028*
H3B	0.2627	0.8823	0.6567	0.028*
C4	0.4814 (8)	0.8461 (7)	0.8109 (4)	0.0244 (11)
C5	0.9026 (8)	0.6125 (7)	0.6737 (4)	0.0221 (11)
C6	0.5504 (8)	0.8209 (6)	0.4898 (4)	0.0216 (10)
C7	1.2345 (8)	1.2784 (8)	0.8549 (4)	0.0273 (12)
H7A	1.2788	1.3417	0.7897	0.041*
H7B	1.3053	1.1786	0.8465	0.041*
H7C	1.2997	1.3227	0.9292	0.041*
C8	0.8906 (10)	1.1285 (8)	0.9679 (4)	0.0309 (13)
H8A	0.9898	1.0411	0.9498	0.046*
H8B	0.7184	1.0981	0.9739	0.046*
H8C	0.9552	1.1720	1.0425	0.046*
H2H	0.308 (11)	0.729 (8)	0.396 (3)	0.032 (17)*
H1H	1.043 (7)	0.509 (7)	0.555 (5)	0.026 (15)*
H3H	0.865 (17)	0.987 (7)	0.682 (6)	0.07 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0241 (5)	0.0207 (7)	0.0254 (5)	0.0013 (5)	0.0002 (4)	−0.0021 (5)
O1	0.0228 (14)	0.024 (3)	0.0232 (15)	0.0022 (13)	0.0016 (11)	0.0007 (13)
O2	0.0237 (16)	0.030 (3)	0.0320 (17)	0.0050 (15)	0.0000 (13)	0.0007 (16)
O3	0.0213 (14)	0.032 (3)	0.0299 (16)	0.0032 (15)	0.0023 (12)	−0.0049 (16)
O4	0.0187 (14)	0.021 (2)	0.0299 (17)	−0.0025 (14)	0.0029 (12)	−0.0026 (15)
O5	0.0248 (14)	0.030 (3)	0.0243 (14)	−0.0046 (15)	−0.0009 (11)	0.0008 (14)
O6	0.0258 (15)	0.024 (2)	0.0267 (15)	−0.0024 (15)	0.0046 (12)	0.0010 (15)
O7	0.0308 (16)	0.033 (3)	0.0274 (17)	0.0032 (16)	0.0073 (13)	−0.0037 (17)
O8	0.0329 (18)	0.025 (3)	0.0296 (17)	0.0006 (17)	−0.0058 (14)	0.0030 (17)
C1	0.019 (2)	0.027 (3)	0.024 (2)	0.000 (2)	0.0022 (16)	−0.001 (2)
C2	0.0178 (19)	0.018 (3)	0.030 (2)	−0.0008 (19)	0.0023 (16)	0.001 (2)
C3	0.0184 (19)	0.023 (3)	0.030 (2)	−0.0014 (19)	0.0027 (16)	−0.003 (2)
C4	0.019 (2)	0.024 (3)	0.030 (2)	−0.0040 (19)	0.0025 (16)	−0.002 (2)
C5	0.023 (2)	0.017 (3)	0.028 (2)	0.0014 (19)	0.0073 (18)	0.005 (2)
C6	0.019 (2)	0.019 (3)	0.027 (2)	0.0031 (18)	0.0028 (16)	−0.0004 (19)
C7	0.0204 (18)	0.031 (4)	0.030 (2)	−0.001 (2)	0.0012 (16)	0.001 (2)
C8	0.032 (2)	0.033 (4)	0.027 (2)	−0.004 (2)	0.0027 (18)	0.006 (2)

Geometric parameters (Å, º)

S1—O8	1.532 (4)	C1—C5	1.511 (6)
S1—C7	1.788 (5)	C1—C2	1.559 (8)
S1—C8	1.791 (6)	C1—H1	1.0000
O1—C4	1.356 (7)	C2—C3	1.525 (6)
O1—C1	1.445 (6)	C2—C6	1.532 (6)
O2—C5	1.194 (6)	C3—C4	1.505 (7)
O3—C5	1.329 (6)	C3—H3A	0.9900
O3—H1H	0.87 (3)	C3—H3B	0.9900
O4—C2	1.406 (6)	C7—H7A	0.9800
O4—H3H	0.87 (3)	C7—H7B	0.9800
O5—C6	1.306 (6)	C7—H7C	0.9800
O5—H2H	0.89 (3)	C8—H8A	0.9800
O6—C6	1.206 (6)	C8—H8B	0.9800
O7—C4	1.195 (6)	C8—H8C	0.9800
O8—S1—C7	105.7 (2)	C2—C3—H3B	111.2
O8—S1—C8	104.6 (3)	H3A—C3—H3B	109.1
C7—S1—C8	98.0 (3)	O7—C4—O1	121.5 (5)
C4—O1—C1	109.3 (4)	O7—C4—C3	128.3 (5)
C5—O3—H1H	113 (4)	O1—C4—C3	110.1 (4)
C2—O4—H3H	116 (6)	O2—C5—O3	125.8 (5)
C6—O5—H2H	112 (4)	O2—C5—C1	125.6 (5)
O1—C1—C5	110.3 (4)	O3—C5—C1	108.6 (4)
O1—C1—C2	103.8 (4)	O6—C6—O5	125.7 (4)
C5—C1—C2	112.1 (4)	O6—C6—C2	122.1 (5)
O1—C1—H1	110.2	O5—C6—C2	112.1 (4)
C5—C1—H1	110.2	S1—C7—H7A	109.5
C2—C1—H1	110.2	S1—C7—H7B	109.5
O4—C2—C3	113.3 (4)	H7A—C7—H7B	109.5
O4—C2—C6	109.0 (4)	S1—C7—H7C	109.5
C3—C2—C6	112.9 (4)	H7A—C7—H7C	109.5
O4—C2—C1	108.7 (4)	H7B—C7—H7C	109.5
C3—C2—C1	99.6 (4)	S1—C8—H8A	109.5
C6—C2—C1	113.0 (5)	S1—C8—H8B	109.5
C4—C3—C2	103.0 (4)	H8A—C8—H8B	109.5
C4—C3—H3A	111.2	S1—C8—H8C	109.5
C2—C3—H3A	111.2	H8A—C8—H8C	109.5
C4—C3—H3B	111.2	H8B—C8—H8C	109.5
C4—O1—C1—C5	148.2 (4)	C2—C3—C4—O7	161.1 (5)
C4—O1—C1—C2	27.9 (5)	C2—C3—C4—O1	−17.9 (5)
O1—C1—C2—O4	82.0 (4)	O1—C1—C5—O2	−13.6 (8)
C5—C1—C2—O4	−37.1 (5)	C2—C1—C5—O2	101.5 (6)
O1—C1—C2—C3	−36.8 (4)	O1—C1—C5—O3	166.6 (4)
C5—C1—C2—C3	−155.9 (4)	C2—C1—C5—O3	−78.3 (6)
O1—C1—C2—C6	−156.8 (3)	O4—C2—C6—O6	−10.2 (7)
C5—C1—C2—C6	84.1 (5)	C3—C2—C6—O6	116.7 (5)
O4—C2—C3—C4	−83.0 (5)	C1—C2—C6—O6	−131.2 (5)
C6—C2—C3—C4	152.4 (5)	O4—C2—C6—O5	172.0 (4)
C1—C2—C3—C4	32.3 (5)	C3—C2—C6—O5	−61.2 (6)
C1—O1—C4—O7	174.3 (5)	C1—C2—C6—O5	50.9 (5)
C1—O1—C4—C3	−6.6 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1H···O4^i	0.87 (2)	2.42 (4)	2.996 (4)	124 (3)
O3—H1H···O6^i	0.87 (2)	1.98 (3)	2.805 (4)	158 (4)
O4—H3H···O8	0.87 (2)	1.87 (3)	2.714 (5)	160 (7)
O5—H2H···O8^ii	0.89 (2)	1.73 (2)	2.603 (4)	167 (5)

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

Dimethyl (2S,3R)-3-Hydroxy-5-oxo-2,3,4,5-tetrahydrofuran-2,3-dicarboxylate (II)

Crystal data

C8H10O7	F(000) = 456
Mr = 218.16	Dx = 1.519 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.5418 Å
a = 9.3057 (6) Å	Cell parameters from 3289 reflections
b = 7.6934 (6) Å	θ = 3.4–72.8°
c = 13.4012 (11) Å	µ = 1.20 mm^−1
β = 96.243 (7)°	T = 123 K
V = 953.74 (12) Å^3	Platey fragment, colourless
Z = 4	0.30 × 0.20 × 0.04 mm

Data collection

Oxford Diffraction Gemini S CCD diffractometer	2976 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.036
ω scans	θmax = 73.4°, θmin = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −11→11
Tmin = 0.747, Tmax = 1.000	k = −8→9
8046 measured reflections	l = −16→14
3506 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.044	w = 1/[σ^2(Fo^2) + (0.0568P)^2 + 0.1462P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.121	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 0.23 e Å^−3
3506 reflections	Δρmin = −0.22 e Å^−3
281 parameters	Absolute structure: Flack x determined using 1098 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
3 restraints	Absolute structure parameter: 0.08 (17)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
O1	0.0127 (3)	0.3894 (4)	0.4143 (2)	0.0393 (7)
O2	−0.0438 (4)	0.4647 (5)	0.2547 (2)	0.0502 (8)
O3	0.3364 (3)	0.3776 (4)	0.4119 (2)	0.0399 (7)
H1H	0.407 (4)	0.349 (7)	0.458 (3)	0.048*
O4	0.4351 (3)	0.0487 (4)	0.4527 (2)	0.0460 (8)
O5	0.2148 (3)	−0.0633 (4)	0.4061 (2)	0.0432 (7)
O6	0.1333 (3)	0.5084 (4)	0.5929 (2)	0.0460 (7)
O7	0.2626 (3)	0.2625 (4)	0.6205 (2)	0.0431 (7)
O8	0.5725 (3)	0.4161 (4)	−0.0594 (2)	0.0391 (7)
O9	0.6406 (3)	0.5063 (5)	−0.2045 (2)	0.0484 (8)
O10	0.8715 (3)	0.4023 (4)	0.0508 (2)	0.0388 (7)
H2H	0.904 (5)	0.376 (7)	0.1128 (16)	0.047*
O11	0.9307 (3)	0.0730 (4)	0.1173 (2)	0.0437 (7)
O12	0.7678 (3)	−0.0374 (4)	−0.0028 (3)	0.0467 (8)
O13	0.5379 (3)	0.5087 (4)	0.1312 (2)	0.0443 (7)
O14	0.6548 (3)	0.2682 (4)	0.1911 (2)	0.0414 (7)
C1	0.0312 (5)	0.3802 (6)	0.3161 (3)	0.0408 (9)
C2	0.1501 (5)	0.2555 (7)	0.3003 (3)	0.0424 (10)
H2A	0.2116	0.3012	0.2505	0.051*
H2B	0.1106	0.1412	0.2771	0.051*
C3	0.2350 (4)	0.2408 (6)	0.4034 (3)	0.0366 (9)
C4	0.1125 (4)	0.2751 (6)	0.4721 (3)	0.0377 (9)
H4	0.0637	0.1638	0.4870	0.045*
C5	0.3083 (5)	0.0651 (6)	0.4238 (3)	0.0389 (9)
C6	0.2722 (5)	−0.2380 (6)	0.4145 (4)	0.0477 (11)
H6A	0.3464	−0.2521	0.3685	0.072*
H6B	0.1940	−0.3216	0.3971	0.072*
H6C	0.3151	−0.2587	0.4835	0.072*
C7	0.1678 (4)	0.3672 (6)	0.5685 (3)	0.0378 (9)
C8	0.3289 (6)	0.3351 (8)	0.7144 (4)	0.0564 (13)
H8A	0.3960	0.4279	0.7003	0.085*
H8B	0.3819	0.2437	0.7538	0.085*
H8C	0.2537	0.3826	0.7524	0.085*
C9	0.6617 (5)	0.4150 (6)	−0.1329 (3)	0.0393 (9)
C10	0.7821 (4)	0.2878 (6)	−0.1067 (3)	0.0396 (9)
H10A	0.8750	0.3340	−0.1252	0.048*
H10B	0.7616	0.1755	−0.1414	0.048*
C11	0.7864 (4)	0.2667 (6)	0.0067 (3)	0.0352 (9)
C12	0.6230 (4)	0.2963 (6)	0.0191 (3)	0.0358 (9)
H12	0.5694	0.1840	0.0090	0.043*
C13	0.8388 (4)	0.0905 (6)	0.0475 (3)	0.0370 (9)
C14	0.8023 (5)	−0.2154 (7)	0.0250 (4)	0.0478 (11)
H14A	0.8702	−0.2623	−0.0192	0.072*
H14B	0.7137	−0.2851	0.0182	0.072*
H14C	0.8465	−0.2193	0.0947	0.072*
C15	0.5978 (4)	0.3732 (6)	0.1191 (3)	0.0365 (9)
C16	0.6380 (6)	0.3211 (7)	0.2932 (4)	0.0504 (12)
H16A	0.6857	0.4334	0.3071	0.076*
H16B	0.6820	0.2338	0.3402	0.076*
H16C	0.5349	0.3319	0.3012	0.076*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0391 (13)	0.0337 (18)	0.0436 (16)	0.0050 (13)	−0.0023 (11)	−0.0018 (13)
O2	0.0564 (18)	0.046 (2)	0.0456 (17)	0.0136 (15)	−0.0086 (14)	−0.0029 (14)
O3	0.0377 (14)	0.0332 (18)	0.0481 (16)	−0.0031 (13)	0.0012 (12)	0.0019 (13)
O4	0.0439 (16)	0.040 (2)	0.0519 (17)	0.0044 (14)	−0.0055 (13)	−0.0016 (13)
O5	0.0441 (16)	0.0288 (17)	0.0561 (18)	−0.0004 (13)	0.0023 (13)	0.0014 (13)
O6	0.0513 (16)	0.0371 (19)	0.0477 (17)	0.0081 (14)	−0.0031 (14)	−0.0090 (14)
O7	0.0528 (16)	0.0314 (18)	0.0429 (16)	0.0050 (14)	−0.0048 (13)	0.0029 (13)
O8	0.0386 (14)	0.0344 (18)	0.0431 (15)	0.0009 (12)	−0.0014 (11)	0.0040 (12)
O9	0.0510 (17)	0.049 (2)	0.0441 (17)	−0.0017 (15)	0.0000 (14)	0.0089 (14)
O10	0.0405 (14)	0.0341 (19)	0.0404 (15)	−0.0032 (13)	−0.0021 (11)	−0.0002 (12)
O11	0.0484 (16)	0.0373 (18)	0.0439 (16)	0.0042 (14)	−0.0015 (13)	−0.0001 (13)
O12	0.0433 (16)	0.0281 (19)	0.066 (2)	0.0007 (13)	−0.0051 (14)	−0.0063 (14)
O13	0.0493 (16)	0.039 (2)	0.0428 (16)	0.0079 (14)	−0.0027 (13)	−0.0032 (14)
O14	0.0492 (15)	0.0353 (18)	0.0400 (15)	0.0056 (14)	0.0063 (12)	0.0045 (13)
C1	0.044 (2)	0.033 (3)	0.043 (2)	0.0020 (19)	−0.0042 (17)	−0.0038 (18)
C2	0.049 (2)	0.036 (3)	0.040 (2)	0.0044 (19)	−0.0029 (17)	−0.0028 (18)
C3	0.041 (2)	0.027 (2)	0.041 (2)	−0.0035 (17)	0.0022 (16)	−0.0005 (16)
C4	0.0380 (19)	0.031 (2)	0.043 (2)	−0.0024 (17)	−0.0014 (16)	0.0003 (18)
C5	0.043 (2)	0.037 (3)	0.036 (2)	0.0028 (18)	0.0024 (16)	−0.0034 (17)
C6	0.055 (3)	0.032 (3)	0.056 (3)	0.002 (2)	0.005 (2)	0.002 (2)
C7	0.0351 (18)	0.039 (3)	0.039 (2)	−0.0013 (17)	0.0045 (15)	0.0006 (18)
C8	0.069 (3)	0.050 (3)	0.046 (3)	0.004 (2)	−0.015 (2)	0.002 (2)
C9	0.045 (2)	0.036 (3)	0.037 (2)	−0.0065 (18)	−0.0001 (16)	−0.0026 (17)
C10	0.041 (2)	0.037 (3)	0.040 (2)	−0.0018 (18)	0.0036 (16)	−0.0003 (17)
C11	0.0377 (19)	0.029 (2)	0.039 (2)	0.0002 (16)	0.0020 (15)	−0.0029 (17)
C12	0.039 (2)	0.026 (2)	0.042 (2)	−0.0024 (17)	−0.0012 (16)	0.0026 (17)
C13	0.0368 (19)	0.031 (2)	0.043 (2)	−0.0014 (17)	0.0050 (17)	−0.0033 (17)
C14	0.042 (2)	0.036 (3)	0.065 (3)	0.000 (2)	0.007 (2)	−0.004 (2)
C15	0.0339 (17)	0.031 (2)	0.044 (2)	−0.0025 (17)	0.0017 (15)	0.0001 (17)
C16	0.060 (3)	0.048 (3)	0.043 (2)	0.005 (2)	0.006 (2)	0.008 (2)

Geometric parameters (Å, º)

O1—C1	1.347 (5)	C2—H2B	0.9900
O1—C4	1.442 (5)	C3—C5	1.526 (6)
O2—C1	1.210 (5)	C3—C4	1.562 (6)
O3—C3	1.410 (5)	C4—C7	1.514 (6)
O3—H1H	0.880 (14)	C4—H4	1.0000
O4—C5	1.208 (5)	C6—H6A	0.9800
O5—C5	1.320 (5)	C6—H6B	0.9800
O5—C6	1.446 (6)	C6—H6C	0.9800
O6—C7	1.189 (6)	C8—H8A	0.9800
O7—C7	1.334 (5)	C8—H8B	0.9800
O7—C8	1.451 (6)	C8—H8C	0.9800
O8—C9	1.355 (5)	C9—C10	1.501 (6)
O8—C12	1.439 (5)	C10—C11	1.524 (6)
O9—C9	1.188 (5)	C10—H10A	0.9900
O10—C11	1.401 (5)	C10—H10B	0.9900
O10—H2H	0.876 (14)	C11—C13	1.522 (6)
O11—C13	1.204 (5)	C11—C12	1.565 (5)
O12—C13	1.328 (5)	C12—C15	1.506 (6)
O12—C14	1.446 (6)	C12—H12	1.0000
O13—C15	1.202 (5)	C14—H14A	0.9800
O14—C15	1.324 (5)	C14—H14B	0.9800
O14—C16	1.452 (6)	C14—H14C	0.9800
C1—C2	1.497 (6)	C16—H16A	0.9800
C2—C3	1.519 (6)	C16—H16B	0.9800
C2—H2A	0.9900	C16—H16C	0.9800
C1—O1—C4	110.4 (3)	H8A—C8—H8B	109.5
C3—O3—H1H	108 (4)	O7—C8—H8C	109.5
C5—O5—C6	116.8 (3)	H8A—C8—H8C	109.5
C7—O7—C8	114.6 (4)	H8B—C8—H8C	109.5
C9—O8—C12	110.5 (3)	O9—C9—O8	121.5 (4)
C11—O10—H2H	110 (4)	O9—C9—C10	128.9 (4)
C13—O12—C14	119.2 (4)	O8—C9—C10	109.6 (4)
C15—O14—C16	116.1 (4)	C9—C10—C11	103.9 (3)
O2—C1—O1	120.7 (4)	C9—C10—H10A	111.0
O2—C1—C2	129.0 (4)	C11—C10—H10A	111.0
O1—C1—C2	110.3 (4)	C9—C10—H10B	111.0
C1—C2—C3	103.7 (3)	C11—C10—H10B	111.0
C1—C2—H2A	111.0	H10A—C10—H10B	109.0
C3—C2—H2A	111.0	O10—C11—C13	111.5 (3)
C1—C2—H2B	111.0	O10—C11—C10	107.1 (3)
C3—C2—H2B	111.0	C13—C11—C10	115.2 (4)
H2A—C2—H2B	109.0	O10—C11—C12	111.0 (3)
O3—C3—C2	107.1 (3)	C13—C11—C12	111.6 (3)
O3—C3—C5	111.4 (3)	C10—C11—C12	99.8 (3)
C2—C3—C5	114.0 (4)	O8—C12—C15	109.2 (3)
O3—C3—C4	110.6 (4)	O8—C12—C11	105.0 (3)
C2—C3—C4	100.6 (3)	C15—C12—C11	113.5 (3)
C5—C3—C4	112.6 (4)	O8—C12—H12	109.6
O1—C4—C7	108.2 (3)	C15—C12—H12	109.6
O1—C4—C3	104.8 (3)	C11—C12—H12	109.6
C7—C4—C3	112.3 (3)	O11—C13—O12	125.7 (4)
O1—C4—H4	110.5	O11—C13—C11	123.5 (4)
C7—C4—H4	110.5	O12—C13—C11	110.8 (3)
C3—C4—H4	110.5	O12—C14—H14A	109.5
O4—C5—O5	125.5 (4)	O12—C14—H14B	109.5
O4—C5—C3	123.5 (4)	H14A—C14—H14B	109.5
O5—C5—C3	111.0 (3)	O12—C14—H14C	109.5
O5—C6—H6A	109.5	H14A—C14—H14C	109.5
O5—C6—H6B	109.5	H14B—C14—H14C	109.5
H6A—C6—H6B	109.5	O13—C15—O14	125.9 (4)
O5—C6—H6C	109.5	O13—C15—C12	125.4 (4)
H6A—C6—H6C	109.5	O14—C15—C12	108.6 (4)
H6B—C6—H6C	109.5	O14—C16—H16A	109.5
O6—C7—O7	126.2 (4)	O14—C16—H16B	109.5
O6—C7—C4	125.9 (4)	H16A—C16—H16B	109.5
O7—C7—C4	107.9 (4)	O14—C16—H16C	109.5
O7—C8—H8A	109.5	H16A—C16—H16C	109.5
O7—C8—H8B	109.5	H16B—C16—H16C	109.5
C4—O1—C1—O2	179.0 (4)	C12—O8—C9—O9	−179.1 (4)
C4—O1—C1—C2	−0.5 (5)	C12—O8—C9—C10	0.3 (5)
O2—C1—C2—C3	160.9 (5)	O9—C9—C10—C11	158.1 (5)
O1—C1—C2—C3	−19.7 (5)	O8—C9—C10—C11	−21.2 (5)
C1—C2—C3—O3	−86.2 (4)	C9—C10—C11—O10	−84.8 (4)
C1—C2—C3—C5	150.1 (4)	C9—C10—C11—C13	150.5 (4)
C1—C2—C3—C4	29.3 (5)	C9—C10—C11—C12	30.9 (4)
C1—O1—C4—C7	139.9 (4)	C9—O8—C12—C15	142.4 (3)
C1—O1—C4—C3	19.9 (4)	C9—O8—C12—C11	20.3 (4)
O3—C3—C4—O1	82.7 (4)	O10—C11—C12—O8	81.3 (4)
C2—C3—C4—O1	−30.2 (4)	C13—C11—C12—O8	−153.6 (3)
C5—C3—C4—O1	−152.0 (3)	C10—C11—C12—O8	−31.4 (4)
O3—C3—C4—C7	−34.5 (5)	O10—C11—C12—C15	−37.9 (5)
C2—C3—C4—C7	−147.5 (4)	C13—C11—C12—C15	87.1 (4)
C5—C3—C4—C7	90.8 (4)	C10—C11—C12—C15	−150.6 (4)
C6—O5—C5—O4	−5.2 (6)	C14—O12—C13—O11	−1.2 (7)
C6—O5—C5—C3	175.1 (4)	C14—O12—C13—C11	180.0 (4)
O3—C3—C5—O4	6.5 (6)	O10—C11—C13—O11	8.2 (6)
C2—C3—C5—O4	127.9 (5)	C10—C11—C13—O11	130.5 (4)
C4—C3—C5—O4	−118.4 (5)	C12—C11—C13—O11	−116.6 (4)
O3—C3—C5—O5	−173.8 (3)	O10—C11—C13—O12	−173.0 (3)
C2—C3—C5—O5	−52.4 (5)	C10—C11—C13—O12	−50.6 (5)
C4—C3—C5—O5	61.3 (5)	C12—C11—C13—O12	62.3 (4)
C8—O7—C7—O6	−1.3 (6)	C16—O14—C15—O13	2.1 (6)
C8—O7—C7—C4	178.3 (4)	C16—O14—C15—C12	−178.9 (4)
O1—C4—C7—O6	1.0 (6)	O8—C12—C15—O13	3.7 (5)
C3—C4—C7—O6	116.1 (5)	C11—C12—C15—O13	120.6 (5)
O1—C4—C7—O7	−178.6 (3)	O8—C12—C15—O14	−175.2 (3)
C3—C4—C7—O7	−63.4 (4)	C11—C12—C15—O14	−58.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1H···O4^i	0.88 (1)	2.36 (5)	2.951 (4)	125 (4)
O10—H2H···O2^ii	0.88 (1)	2.03 (3)	2.802 (4)	147 (5)

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