Chemical characterization, absolute configuration and optical purity of (1S)-(+)- and (1R)-(–)-10-camphorsulfonic acid

Comprehensive chemical characterization for two isomers of camphorsulfonic acid (CSA), occasionally used in the manufacture of active pharmaceutical ingredients (APIs), was performed by nuclear magnetic resonance (NMR) spec­troscopy, high-resolution mass spectroscopy in negative electrospray ionization mode and gas chromatography/mass spectrometry (GC/MS) in electron ionization mode. Electronic circular dichroism (ECD) spectra together with quantum chemical calculations using time-dependent density functional theory (TD-DFT) were used to assign the stereochemistry for CSA for the first time and these assignments were then confirmed by single-crystal X-ray dif­­frac­tion. As crystals were grown under the same conditions of high supersaturation using a mixed solvent without water removal, the crystal structures of the two enanti­omers contained one ordered mol­ecule of water in the asymmetric unit. The crystals of the (+)-enanti­omer have a 1S,4R con­figuration and the H atom of the sulfonic acid group combines with the water mol­ecule to form a hydro­nium ion, namely, hydro­nium (1S,4R)-(7,7-dimethyl-2-oxobi­cyclo­[2.2.1]heptan-1-yl)methane­sul­fon­ate, H₃O⁺·C₁₀H₁₅O₄S⁻. The crystals of the (−)-enanti­omer have a 1R,4S configuration. The determination of the optical purity of CSA using NMR spectroscopy with a chiral solvating agent, (1R,2R)-1,2-di­phenyl­ethane-1,2-di­amine, and GC/MS with a chiral column has been well explored. The results showed that the examined samples of these two isomers of CSA proved to be enanti­omerically pure. In particular, for (1R)-(−)-10-camphorsulfonic acid, this is, to our knowledge, the first description on its spectral characterization in a scientific context.

Computing details

For both structures, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Hydronium (1S,4R)-(7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonate (20220428_1)

Crystal data

H3O^+·C10H15O4S^−	Dx = 1.416 Mg m^−3
Mr = 250.30	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 11038 reflections
a = 6.72815 (4) Å	θ = 2.8–73.8°
b = 11.24661 (6) Å	µ = 2.52 mm^−1
c = 15.51195 (8) Å	T = 100 K
V = 1173.77 (1) Å^3	Block, clear colourless
Z = 4	0.5 × 0.35 × 0.3 mm
F(000) = 536

Data collection

Rigaku XtaLAB0 PRO MM007HF (rotating anode) diffractometer equipped with a PILATUS200K CCD plate detector	2349 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source	2349 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω scans	θmax = 74.0°, θmin = 4.9°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −8→8
Tmin = 0.628, Tmax = 1.000	k = −13→13
11811 measured reflections	l = −19→19

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.028P)^2 + 0.3955P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.022	(Δ/σ)max = 0.001
wR(F^2) = 0.057	Δρmax = 0.25 e Å^−3
S = 1.14	Δρmin = −0.30 e Å^−3
2349 reflections	Extinction correction: SHELXL2019 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
159 parameters	Extinction coefficient: 0.0195 (9)
3 restraints	Absolute structure: Flack x determined using 956 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: dual	Absolute structure parameter: 0.011 (6)
Hydrogen site location: mixed

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. The single crystals of the (1S)-(+)- and (1R)-(-)-CSA enantiomers, colourless block, 0.5*0.35*0.3 and 0.35*0.2*0.05 mm³ respectively, were mounted on a Rigaku XtaLAB0 PRO MM007HF (rotating anode) diffractometer equipped with a PILATUS200K CCD plate detector, and data were collected using Cu Kα radiation (λ = 1.54184 Å) at 100 K with the ω-scans method. Data collection, reduction, and absorption correction (multi-scan) were performed by the CrysAlis PRO program (1.171.39.28b, Rigaku Oxford Diffraction, 2015). Using OLEX2 GUI, the structure was solved with the ShelXT program and refined by the SHELXL program with full-matrix least-squares calculations based on F².

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

	x	y	z	Uiso*/Ueq
S01	0.73068 (6)	0.55683 (3)	0.45697 (3)	0.00982 (13)
O1	1.1574 (2)	0.38541 (13)	0.39267 (9)	0.0183 (3)
O2	0.89723 (19)	0.52350 (12)	0.51232 (8)	0.0138 (3)
O3	0.7234 (2)	0.68416 (11)	0.43850 (8)	0.0161 (3)
O4	0.54364 (19)	0.51152 (12)	0.49180 (9)	0.0142 (3)
C1	0.8074 (3)	0.35855 (15)	0.35138 (11)	0.0102 (3)
C2	1.0244 (3)	0.32339 (16)	0.36582 (11)	0.0124 (4)
C3	1.0442 (3)	0.19582 (17)	0.33283 (13)	0.0165 (4)
H3A	1.072040	0.140894	0.379517	0.020*
H3B	1.147860	0.189331	0.289609	0.020*
C4	0.8375 (3)	0.17337 (16)	0.29367 (12)	0.0148 (4)
H4	0.834221	0.111168	0.249455	0.018*
C5	0.6960 (3)	0.15229 (16)	0.36964 (13)	0.0180 (4)
H5A	0.749484	0.093795	0.409306	0.022*
H5B	0.566423	0.126072	0.349869	0.022*
C6	0.6838 (3)	0.27721 (16)	0.41234 (12)	0.0141 (4)
H6A	0.740537	0.275911	0.469824	0.017*
H6B	0.547177	0.304227	0.415927	0.017*
C7	0.7760 (3)	0.29880 (15)	0.26101 (11)	0.0129 (4)
C8	0.9131 (3)	0.34879 (18)	0.19078 (12)	0.0185 (4)
H8A	1.046681	0.352807	0.212298	0.028*
H8B	0.869281	0.427038	0.174930	0.028*
H8C	0.909020	0.297823	0.141170	0.028*
C9	0.5615 (3)	0.30553 (19)	0.22873 (14)	0.0205 (4)
H9A	0.534716	0.384243	0.207793	0.031*
H9B	0.472289	0.287334	0.275200	0.031*
H9C	0.542780	0.249226	0.182922	0.031*
C10	0.7668 (3)	0.49132 (14)	0.35389 (10)	0.0116 (3)
H10A	0.649314	0.506833	0.319452	0.014*
H10B	0.877245	0.531550	0.326228	0.014*
O5	1.22234 (19)	0.62434 (11)	0.47241 (9)	0.0150 (3)
H5C	1.119 (2)	0.5855 (19)	0.4853 (16)	0.018*
H5D	1.329 (3)	0.586 (3)	0.478 (2)	0.047 (9)*
H5E	1.222 (5)	0.6880 (15)	0.5008 (16)	0.041 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S01	0.0086 (2)	0.0096 (2)	0.0113 (2)	0.00077 (15)	−0.00064 (15)	−0.00114 (14)
O1	0.0112 (6)	0.0197 (7)	0.0239 (7)	−0.0005 (5)	−0.0021 (5)	−0.0060 (6)
O2	0.0109 (6)	0.0168 (6)	0.0138 (6)	0.0009 (5)	−0.0020 (5)	0.0001 (5)
O3	0.0208 (7)	0.0089 (6)	0.0186 (6)	0.0018 (5)	−0.0010 (5)	−0.0012 (5)
O4	0.0097 (6)	0.0161 (6)	0.0168 (6)	0.0008 (5)	0.0015 (5)	−0.0019 (5)
C1	0.0105 (8)	0.0096 (7)	0.0103 (8)	−0.0002 (6)	0.0008 (6)	−0.0007 (6)
C2	0.0123 (9)	0.0139 (8)	0.0109 (8)	0.0008 (7)	0.0006 (7)	−0.0003 (7)
C3	0.0161 (10)	0.0128 (9)	0.0205 (9)	0.0030 (8)	0.0007 (7)	−0.0029 (7)
C4	0.0173 (9)	0.0102 (9)	0.0170 (8)	−0.0012 (7)	0.0017 (7)	−0.0034 (7)
C5	0.0200 (9)	0.0117 (8)	0.0224 (9)	−0.0033 (7)	0.0043 (8)	0.0006 (7)
C6	0.0142 (9)	0.0121 (8)	0.0161 (8)	−0.0015 (7)	0.0045 (7)	0.0007 (7)
C7	0.0151 (9)	0.0117 (8)	0.0120 (8)	−0.0012 (7)	−0.0005 (7)	−0.0021 (6)
C8	0.0260 (10)	0.0177 (9)	0.0119 (8)	−0.0036 (8)	0.0039 (8)	−0.0027 (7)
C9	0.0206 (10)	0.0206 (10)	0.0204 (9)	−0.0014 (8)	−0.0063 (8)	−0.0035 (8)
C10	0.0145 (9)	0.0108 (8)	0.0097 (7)	0.0016 (7)	−0.0003 (7)	0.0006 (6)
O5	0.0114 (6)	0.0116 (6)	0.0220 (7)	−0.0001 (5)	−0.0004 (6)	−0.0025 (5)

Geometric parameters (Å, º)

S01—O2	1.4606 (13)	C5—H5B	0.9700
S01—O3	1.4612 (12)	C5—C6	1.555 (2)
S01—O4	1.4613 (13)	C6—H6A	0.9700
S01—C10	1.7773 (17)	C6—H6B	0.9700
O1—C2	1.209 (2)	C7—C8	1.534 (3)
C1—C2	1.529 (2)	C7—C9	1.530 (3)
C1—C6	1.556 (2)	C8—H8A	0.9600
C1—C7	1.569 (2)	C8—H8B	0.9600
C1—C10	1.519 (2)	C8—H8C	0.9600
C2—C3	1.529 (3)	C9—H9A	0.9600
C3—H3A	0.9700	C9—H9B	0.9600
C3—H3B	0.9700	C9—H9C	0.9600
C3—C4	1.539 (3)	C10—H10A	0.9700
C4—H4	0.9800	C10—H10B	0.9700
C4—C5	1.533 (3)	O5—H5C	0.844 (7)
C4—C7	1.555 (2)	O5—H5D	0.841 (7)
C5—H5A	0.9700	O5—H5E	0.841 (7)
O2—S01—O3	113.12 (8)	C1—C6—H6A	110.9
O2—S01—O4	110.72 (8)	C1—C6—H6B	110.9
O2—S01—C10	108.51 (8)	C5—C6—C1	104.13 (14)
O3—S01—C10	103.56 (7)	C5—C6—H6A	110.9
O4—S01—O3	112.66 (8)	C5—C6—H6B	110.9
O4—S01—C10	107.81 (8)	H6A—C6—H6B	108.9
C2—C1—C6	105.61 (14)	C4—C7—C1	93.53 (13)
C2—C1—C7	98.57 (14)	C8—C7—C1	113.35 (15)
C6—C1—C7	102.65 (14)	C8—C7—C4	113.82 (16)
C10—C1—C2	114.99 (15)	C9—C7—C1	113.50 (15)
C10—C1—C6	117.78 (14)	C9—C7—C4	113.75 (16)
C10—C1—C7	114.83 (14)	C9—C7—C8	108.46 (16)
O1—C2—C1	127.46 (17)	C7—C8—H8A	109.5
O1—C2—C3	126.32 (17)	C7—C8—H8B	109.5
C1—C2—C3	106.07 (15)	C7—C8—H8C	109.5
C2—C3—H3A	111.4	H8A—C8—H8B	109.5
C2—C3—H3B	111.4	H8A—C8—H8C	109.5
C2—C3—C4	101.96 (15)	H8B—C8—H8C	109.5
H3A—C3—H3B	109.2	C7—C9—H9A	109.5
C4—C3—H3A	111.4	C7—C9—H9B	109.5
C4—C3—H3B	111.4	C7—C9—H9C	109.5
C3—C4—H4	114.4	H9A—C9—H9B	109.5
C3—C4—C7	102.73 (15)	H9A—C9—H9C	109.5
C5—C4—C3	106.46 (16)	H9B—C9—H9C	109.5
C5—C4—H4	114.4	S01—C10—H10A	108.0
C5—C4—C7	103.03 (15)	S01—C10—H10B	108.0
C7—C4—H4	114.4	C1—C10—S01	117.09 (12)
C4—C5—H5A	111.2	C1—C10—H10A	108.0
C4—C5—H5B	111.2	C1—C10—H10B	108.0
C4—C5—C6	102.72 (14)	H10A—C10—H10B	107.3
H5A—C5—H5B	109.1	H5C—O5—H5D	114 (3)
C6—C5—H5A	111.2	H5C—O5—H5E	108 (3)
C6—C5—H5B	111.2	H5D—O5—H5E	112 (3)
O1—C2—C3—C4	−170.45 (18)	C5—C4—C7—C9	−62.10 (18)
O2—S01—C10—C1	51.98 (16)	C6—C1—C2—O1	−118.24 (19)
O3—S01—C10—C1	172.43 (14)	C6—C1—C2—C3	66.02 (17)
O4—S01—C10—C1	−67.99 (16)	C6—C1—C7—C4	−51.79 (16)
C1—C2—C3—C4	5.36 (18)	C6—C1—C7—C8	−169.65 (16)
C2—C1—C6—C5	−72.10 (17)	C6—C1—C7—C9	66.04 (18)
C2—C1—C7—C4	56.44 (15)	C6—C1—C10—S01	41.7 (2)
C2—C1—C7—C8	−61.42 (18)	C7—C1—C2—O1	135.98 (19)
C2—C1—C7—C9	174.26 (16)	C7—C1—C2—C3	−39.77 (16)
C2—C1—C10—S01	−83.86 (17)	C7—C1—C6—C5	30.68 (18)
C2—C3—C4—C5	−76.13 (18)	C7—C1—C10—S01	162.77 (13)
C2—C3—C4—C7	31.79 (16)	C7—C4—C5—C6	−38.44 (18)
C3—C4—C5—C6	69.27 (18)	C10—C1—C2—O1	13.4 (3)
C3—C4—C7—C1	−54.99 (16)	C10—C1—C2—C3	−162.36 (14)
C3—C4—C7—C8	62.48 (18)	C10—C1—C6—C5	157.89 (16)
C3—C4—C7—C9	−172.61 (15)	C10—C1—C7—C4	179.15 (15)
C4—C5—C6—C1	4.32 (19)	C10—C1—C7—C8	61.3 (2)
C5—C4—C7—C1	55.52 (16)	C10—C1—C7—C9	−63.0 (2)
C5—C4—C7—C8	172.99 (16)

Hydronium (1R,4S)-(7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonate (20220502_2)

Crystal data

H3O^+·C10H15O4S^−	Dx = 1.418 Mg m^−3
Mr = 250.30	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 12507 reflections
a = 6.72595 (5) Å	θ = 2.8–73.7°
b = 11.23408 (8) Å	µ = 2.52 mm^−1
c = 15.51954 (11) Å	T = 100 K
V = 1172.65 (1) Å^3	Plate, clear colourless
Z = 4	0.35 × 0.2 × 0.05 mm
F(000) = 536

Data collection

Rigaku XtaLAB0 PRO MM007HF (rotating anode) diffractometer equipped with a PILATUS200K CCD plate detector	2348 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source	2338 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω scans	θmax = 73.9°, θmin = 4.9°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −8→8
Tmin = 0.464, Tmax = 1.000	k = −13→13
14186 measured reflections	l = −19→18

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0276P)^2 + 0.3833P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.022	(Δ/σ)max < 0.001
wR(F^2) = 0.059	Δρmax = 0.26 e Å^−3
S = 1.14	Δρmin = −0.27 e Å^−3
2348 reflections	Extinction correction: SHELXL2019 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
155 parameters	Extinction coefficient: 0.0049 (5)
0 restraints	Absolute structure: Flack x determined using 954 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: dual	Absolute structure parameter: 0.011 (6)
Hydrogen site location: mixed

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. The single crystals of the (1S)-(+)- and (1R)-(-)-CSA enantiomers, colourless block, 0.5*0.35*0.3 and 0.35*0.2*0.05 mm³ respectively, were mounted on a Rigaku XtaLAB0 PRO MM007HF (rotating anode) diffractometer equipped with a PILATUS200K CCD plate detector, and data were collected using Cu Kα radiation (λ = 1.54184 Å) at 100 K with the ω-scans method. Data collection, reduction, and absorption correction (multi-scan) were performed by the CrysAlis PRO program (1.171.39.28b, Rigaku Oxford Diffraction, 2015). Using OLEX2 GUI, the structure was solved with the ShelXT program and refined by the SHELXL program with full-matrix least-squares calculations based on F².

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

	x	y	z	Uiso*/Ueq
S001	0.73026 (6)	0.44327 (4)	0.45694 (3)	0.01226 (13)
O1	0.8968 (2)	0.47675 (13)	0.51223 (9)	0.0162 (3)
O5	1.2218 (2)	0.37552 (12)	0.47227 (9)	0.0172 (3)
H5C	1.324740	0.418174	0.479688	0.026*
H5D	1.125531	0.420540	0.486331	0.026*
O4	1.1571 (2)	0.61471 (13)	0.39265 (10)	0.0209 (3)
O3	0.54319 (19)	0.48870 (12)	0.49178 (9)	0.0166 (3)
O2	0.7229 (2)	0.31577 (11)	0.43857 (8)	0.0186 (3)
C2	1.0243 (3)	0.67676 (17)	0.36579 (12)	0.0148 (4)
C1	0.8073 (3)	0.64163 (16)	0.35133 (12)	0.0125 (4)
C9	0.9131 (3)	0.65116 (19)	0.19098 (13)	0.0211 (4)
H9A	1.046900	0.647939	0.212393	0.032*
H9B	0.908236	0.701607	0.141097	0.032*
H9C	0.870132	0.572474	0.175642	0.032*
C4	0.8372 (3)	0.82699 (17)	0.29350 (13)	0.0173 (4)
H4	0.834001	0.889243	0.249291	0.021*
C7	0.7758 (3)	0.70141 (16)	0.26097 (11)	0.0153 (4)
C10	0.7665 (3)	0.50878 (15)	0.35395 (11)	0.0140 (4)
H10A	0.876849	0.468420	0.326305	0.017*
H10B	0.648888	0.493282	0.319539	0.017*
C5	0.6958 (3)	0.84804 (17)	0.36943 (14)	0.0206 (4)
H5A	0.566145	0.874177	0.349690	0.025*
H5B	0.749289	0.906684	0.409023	0.025*
C6	0.6839 (3)	0.72320 (17)	0.41217 (13)	0.0164 (4)
H6A	0.547243	0.696143	0.415872	0.020*
H6B	0.740819	0.724626	0.469592	0.020*
C8	0.5615 (3)	0.6946 (2)	0.22872 (14)	0.0231 (4)
H8A	0.534697	0.615728	0.207975	0.035*
H8B	0.542924	0.750779	0.182795	0.035*
H8C	0.472280	0.713073	0.275105	0.035*
C3	1.0442 (3)	0.80432 (18)	0.33270 (13)	0.0189 (4)
H3A	1.147848	0.810660	0.289480	0.023*
H3B	1.072163	0.859368	0.379301	0.023*
H5E	1.225 (5)	0.309 (3)	0.5014 (18)	0.037 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S001	0.0101 (2)	0.0126 (2)	0.0141 (2)	−0.00077 (15)	−0.00059 (16)	0.00111 (15)
O1	0.0117 (6)	0.0201 (7)	0.0168 (6)	−0.0010 (5)	−0.0022 (5)	−0.0004 (5)
O5	0.0131 (6)	0.0141 (6)	0.0244 (7)	0.0002 (5)	−0.0007 (6)	0.0022 (5)
O4	0.0131 (7)	0.0228 (7)	0.0269 (8)	0.0004 (6)	−0.0018 (6)	0.0057 (6)
O3	0.0112 (6)	0.0190 (7)	0.0197 (7)	−0.0007 (5)	0.0022 (5)	0.0017 (6)
O2	0.0222 (7)	0.0124 (6)	0.0212 (6)	−0.0016 (6)	−0.0011 (6)	0.0018 (5)
C2	0.0144 (9)	0.0165 (9)	0.0134 (8)	−0.0001 (7)	0.0006 (7)	0.0001 (8)
C1	0.0113 (8)	0.0130 (8)	0.0130 (8)	0.0002 (7)	0.0007 (7)	0.0007 (7)
C9	0.0283 (11)	0.0206 (10)	0.0144 (9)	0.0037 (9)	0.0035 (8)	0.0024 (8)
C4	0.0186 (10)	0.0134 (9)	0.0200 (9)	0.0022 (7)	0.0020 (7)	0.0033 (7)
C7	0.0164 (9)	0.0143 (8)	0.0152 (8)	0.0019 (7)	−0.0004 (7)	0.0018 (7)
C10	0.0160 (9)	0.0138 (8)	0.0123 (8)	−0.0015 (8)	−0.0003 (7)	−0.0007 (6)
C5	0.0217 (10)	0.0149 (9)	0.0252 (10)	0.0029 (8)	0.0043 (8)	−0.0007 (8)
C6	0.0168 (10)	0.0141 (9)	0.0183 (9)	0.0012 (7)	0.0045 (8)	−0.0009 (7)
C8	0.0224 (11)	0.0240 (11)	0.0230 (10)	0.0013 (9)	−0.0070 (8)	0.0032 (9)
C3	0.0173 (10)	0.0156 (9)	0.0237 (10)	−0.0027 (8)	0.0007 (8)	0.0029 (8)

Geometric parameters (Å, º)

S001—O1	1.4604 (14)	C4—H4	0.9800
S001—O3	1.4615 (14)	C4—C7	1.554 (3)
S001—O2	1.4613 (13)	C4—C5	1.533 (3)
S001—C10	1.7764 (18)	C4—C3	1.540 (3)
O5—H5C	0.8499	C7—C8	1.527 (3)
O5—H5D	0.8500	C10—H10A	0.9700
O5—H5E	0.87 (3)	C10—H10B	0.9700
O4—C2	1.207 (2)	C5—H5A	0.9700
C2—C1	1.528 (3)	C5—H5B	0.9700
C2—C3	1.528 (3)	C5—C6	1.553 (3)
C1—C7	1.569 (2)	C6—H6A	0.9700
C1—C10	1.518 (2)	C6—H6B	0.9700
C1—C6	1.555 (3)	C8—H8A	0.9600
C9—H9A	0.9600	C8—H8B	0.9600
C9—H9B	0.9600	C8—H8C	0.9600
C9—H9C	0.9600	C3—H3A	0.9700
C9—C7	1.533 (3)	C3—H3B	0.9700
O1—S001—O3	110.67 (8)	C8—C7—C1	113.51 (16)
O1—S001—O2	113.15 (8)	C8—C7—C9	108.53 (17)
O1—S001—C10	108.47 (9)	C8—C7—C4	113.75 (17)
O3—S001—C10	107.84 (9)	S001—C10—H10A	108.0
O2—S001—O3	112.65 (8)	S001—C10—H10B	108.0
O2—S001—C10	103.61 (8)	C1—C10—S001	117.14 (12)
H5C—O5—H5D	104.5	C1—C10—H10A	108.0
H5C—O5—H5E	112.9	C1—C10—H10B	108.0
H5D—O5—H5E	113.3	H10A—C10—H10B	107.3
O4—C2—C1	127.47 (18)	C4—C5—H5A	111.2
O4—C2—C3	126.33 (18)	C4—C5—H5B	111.2
C3—C2—C1	106.05 (15)	C4—C5—C6	102.76 (15)
C2—C1—C7	98.61 (15)	H5A—C5—H5B	109.1
C2—C1—C6	105.55 (15)	C6—C5—H5A	111.2
C10—C1—C2	115.00 (16)	C6—C5—H5B	111.2
C10—C1—C7	114.85 (15)	C1—C6—H6A	110.9
C10—C1—C6	117.80 (15)	C1—C6—H6B	110.9
C6—C1—C7	102.61 (14)	C5—C6—C1	104.19 (15)
H9A—C9—H9B	109.5	C5—C6—H6A	110.9
H9A—C9—H9C	109.5	C5—C6—H6B	110.9
H9B—C9—H9C	109.5	H6A—C6—H6B	108.9
C7—C9—H9A	109.5	C7—C8—H8A	109.5
C7—C9—H9B	109.5	C7—C8—H8B	109.5
C7—C9—H9C	109.5	C7—C8—H8C	109.5
C7—C4—H4	114.5	H8A—C8—H8B	109.5
C5—C4—H4	114.5	H8A—C8—H8C	109.5
C5—C4—C7	102.99 (15)	H8B—C8—H8C	109.5
C5—C4—C3	106.42 (16)	C2—C3—C4	102.03 (15)
C3—C4—H4	114.5	C2—C3—H3A	111.4
C3—C4—C7	102.62 (15)	C2—C3—H3B	111.4
C9—C7—C1	113.21 (15)	C4—C3—H3A	111.4
C9—C7—C4	113.83 (16)	C4—C3—H3B	111.4
C4—C7—C1	93.57 (13)	H3A—C3—H3B	109.2
O1—S001—C10—C1	−51.90 (17)	C10—C1—C7—C4	−179.23 (15)
O4—C2—C1—C7	−136.0 (2)	C10—C1—C7—C8	62.9 (2)
O4—C2—C1—C10	−13.3 (3)	C10—C1—C6—C5	−157.79 (16)
O4—C2—C1—C6	118.3 (2)	C5—C4—C7—C1	−55.47 (17)
O4—C2—C3—C4	170.45 (19)	C5—C4—C7—C9	−172.80 (16)
O3—S001—C10—C1	68.00 (16)	C5—C4—C7—C8	62.18 (19)
O2—S001—C10—C1	−172.39 (14)	C5—C4—C3—C2	76.00 (19)
C2—C1—C7—C9	61.39 (19)	C6—C1—C7—C9	169.56 (16)
C2—C1—C7—C4	−56.46 (15)	C6—C1—C7—C4	51.71 (16)
C2—C1—C7—C8	−174.31 (17)	C6—C1—C7—C8	−66.14 (19)
C2—C1—C10—S001	83.80 (18)	C6—C1—C10—S001	−41.7 (2)
C2—C1—C6—C5	72.21 (18)	C3—C2—C1—C7	39.69 (17)
C1—C2—C3—C4	−5.29 (19)	C3—C2—C1—C10	162.34 (15)
C4—C5—C6—C1	−4.4 (2)	C3—C2—C1—C6	−66.05 (18)
C7—C1—C10—S001	−162.74 (13)	C3—C4—C7—C1	54.95 (16)
C7—C1—C6—C5	−30.59 (19)	C3—C4—C7—C9	−62.38 (19)
C7—C4—C5—C6	38.47 (19)	C3—C4—C7—C8	172.60 (16)
C7—C4—C3—C2	−31.83 (17)	C3—C4—C5—C6	−69.10 (19)
C10—C1—C7—C9	−61.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5C···O3^i	0.85	1.68	2.5261 (18)	174
O5—H5D···O1	0.85	1.71	2.5408 (19)	165
O5—H5E···O2^ii	0.87 (3)	1.68 (3)	2.5559 (18)	177 (3)

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