(+)-Methyl 3β-acet-oxy-13-carb-oxy-19-hy-droxy-11-oxo-C-norolean-18-en-30-oate γ-lactone.

The title compound, C(33)H(46)O(7), is an unusual oxydation product of the therapeutic agent glycyrrhetinic acid that has, in comparison to the latter, a distinctly altered triterpene structure with one five- and four six-membered carbocycles complemented by a γ-lactone ring with a spiro-junction and a ring double bond. The junction between the five-membered ring C, a cyclo-penta-none ring, and the six-membered ring D, previously in question, was found to be cis, confirming earlier structure assignments based solely on chemical transformations. In the solid state, the compound exhibits five intra- and four inter-molecular C-H⋯O inter-actions with H⋯O distances less than or equal to 2.70 Å and C-H⋯O greater than 100°.

Related literature

For the synthesis and structure elucidation of the title compound by chemical methods, see: Brownlie & Spring (1956 ▶); Jeger et al. (1944 ▶). For overviews of the therapeutic aspects of the parent compounds glycyrrhetinic acid and glycyrrhizin, see: Asl & Hosseinzadeh (2008 ▶); Baran et al. (1974 ▶); Kitagawa (2002 ▶). For recent research on the synthesis of new derivatives of glycyrrhetinic acid and their medicinal potency, see: Classen-Houben et al. (2009 ▶); Beseda et al. (2010 ▶); Amer et al. (2010 ▶).

Experimental

Crystal data

C33H46O7

M = 554.70

Orthorhombic,

a = 7.6310 (4) Å

b = 16.7922 (9) Å

c = 22.3822 (13) Å

V = 2868.1 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 100 K

0.56 × 0.44 × 0.32 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.88, T max = 0.97

41398 measured reflections

4654 independent reflections

4540 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.080

S = 1.05

4654 reflections

370 parameters

H-atom parameters constrained

Δρmax = 0.34 e Å−3

Δρmin = −0.19 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT, SADABS and XPREP (Bruker, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810036901/bt5349sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036901/bt5349Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C33H46O7	Dx = 1.285 Mg m−3
Mr = 554.70	Melting point: 565 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9893 reflections
a = 7.6310 (4) Å	θ = 2.6–30.5°
b = 16.7922 (9) Å	µ = 0.09 mm−1
c = 22.3822 (13) Å	T = 100 K
V = 2868.1 (3) Å3	Prism, colourless
Z = 4	0.56 × 0.44 × 0.32 mm
F(000) = 1200

Bruker Kappa APEXII CCD diffractometer	4654 independent reflections
Radiation source: fine-focus sealed tube	4540 reflections with I > 2σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 30.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −10→10
Tmin = 0.88, Tmax = 0.97	k = −23→22
41398 measured reflections	l = −30→31

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0571P)2 + 0.3708P] where P = (Fo2 + 2Fc2)/3
4654 reflections	(Δ/σ)max < 0.001
370 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

Geometry. All e.s.d.'s 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.

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.

	x	y	z	Uiso*/Ueq
O1	0.58647 (12)	0.36304 (5)	0.59280 (3)	0.01542 (16)
O2	0.21014 (12)	0.38578 (6)	0.30563 (4)	0.02061 (18)
O3	0.07765 (16)	0.16391 (6)	0.05217 (4)	0.0278 (2)
O4	0.02940 (13)	0.20027 (5)	0.14712 (4)	0.02104 (18)
O5	0.49099 (13)	0.23786 (5)	0.60940 (4)	0.02102 (18)
O6	0.51640 (14)	0.21478 (5)	0.28433 (4)	0.02095 (19)
O7	0.38773 (12)	0.22126 (5)	0.19472 (4)	0.01530 (16)
C1	0.38579 (15)	0.34494 (7)	0.43805 (5)	0.01347 (19)
H1A	0.2624	0.3473	0.4245	0.016*
H1B	0.4337	0.2923	0.4267	0.016*
C2	0.39189 (15)	0.35369 (7)	0.50625 (5)	0.0144 (2)
H2A	0.3375	0.4049	0.5180	0.017*
H2B	0.3242	0.3100	0.5250	0.017*
C3	0.57997 (15)	0.35113 (7)	0.52821 (5)	0.01303 (19)
H3	0.6294	0.2974	0.5190	0.016*
C4	0.70187 (15)	0.41476 (6)	0.50091 (5)	0.01278 (19)
C5	0.68261 (15)	0.40901 (6)	0.43176 (5)	0.01175 (19)
H5	0.7267	0.3546	0.4217	0.014*
C6	0.80504 (16)	0.46575 (7)	0.39755 (5)	0.0160 (2)
H6A	0.9228	0.4647	0.4161	0.019*
H6B	0.7594	0.5208	0.4005	0.019*
C7	0.82026 (15)	0.44215 (7)	0.33124 (5)	0.0155 (2)
H7A	0.8955	0.4812	0.3103	0.019*
H7B	0.8769	0.3893	0.3282	0.019*
C8	0.64014 (15)	0.43912 (6)	0.30072 (5)	0.01179 (18)
C9	0.51682 (14)	0.38750 (6)	0.34039 (4)	0.01017 (18)
H9	0.5757	0.3343	0.3420	0.012*
C10	0.49178 (14)	0.41083 (6)	0.40651 (5)	0.01149 (18)
C11	0.36470 (15)	0.37522 (6)	0.29852 (5)	0.01211 (19)
C12	0.46147 (16)	0.25521 (6)	0.24456 (5)	0.0144 (2)
C13	0.45088 (15)	0.34696 (6)	0.23907 (5)	0.01111 (18)
C14	0.63502 (14)	0.39140 (6)	0.23874 (5)	0.01162 (18)
C15	0.64754 (15)	0.44362 (7)	0.18159 (5)	0.0145 (2)
H15A	0.7407	0.4837	0.1881	0.017*
H15B	0.6864	0.4090	0.1483	0.017*
C16	0.48210 (16)	0.48775 (7)	0.16123 (5)	0.0156 (2)
H16A	0.5100	0.5191	0.1250	0.019*
H16B	0.4464	0.5256	0.1929	0.019*
C17	0.32639 (15)	0.43173 (6)	0.14723 (5)	0.01265 (19)
C18	0.35306 (14)	0.35531 (6)	0.18125 (5)	0.01168 (19)
C19	0.32842 (15)	0.28331 (6)	0.15797 (5)	0.01295 (19)
C20	0.27038 (16)	0.26123 (7)	0.09642 (5)	0.0144 (2)
C21	0.20702 (17)	0.33903 (7)	0.06549 (5)	0.0171 (2)
H21A	0.2051	0.3309	0.0217	0.021*
H21B	0.0859	0.3510	0.0786	0.021*
C22	0.32516 (17)	0.41004 (7)	0.08013 (5)	0.0157 (2)
H22A	0.2851	0.4568	0.0569	0.019*
H22B	0.4463	0.3976	0.0674	0.019*
C23	0.89158 (16)	0.39174 (7)	0.51797 (5)	0.0168 (2)
H23A	0.8966	0.3786	0.5606	0.025*
H23B	0.9701	0.4366	0.5097	0.025*
H23C	0.9283	0.3454	0.4944	0.025*
C24	0.66240 (17)	0.49816 (7)	0.52613 (5)	0.0168 (2)
H24A	0.6884	0.4991	0.5690	0.025*
H24B	0.5384	0.5108	0.5198	0.025*
H24C	0.7353	0.5377	0.5056	0.025*
C25	0.39079 (17)	0.48996 (7)	0.41380 (5)	0.0171 (2)
H25A	0.3027	0.4945	0.3821	0.026*
H25B	0.4729	0.5347	0.4110	0.026*
H25C	0.3327	0.4909	0.4528	0.026*
C26	0.57387 (17)	0.52513 (6)	0.29370 (5)	0.0169 (2)
H26A	0.5942	0.5545	0.3309	0.025*
H26B	0.4482	0.5246	0.2848	0.025*
H26C	0.6370	0.5511	0.2610	0.025*
C27	0.78590 (16)	0.33104 (7)	0.23470 (5)	0.0165 (2)
H27A	0.7713	0.2983	0.1988	0.025*
H27B	0.7849	0.2968	0.2702	0.025*
H27C	0.8978	0.3596	0.2326	0.025*
C28	0.15441 (17)	0.47305 (7)	0.16436 (6)	0.0181 (2)
H28A	0.1514	0.4816	0.2077	0.027*
H28B	0.0552	0.4395	0.1525	0.027*
H28C	0.1467	0.5245	0.1438	0.027*
C29	0.11726 (16)	0.20249 (7)	0.09537 (5)	0.0166 (2)
C30	0.42425 (19)	0.22355 (8)	0.06203 (6)	0.0219 (2)
H30A	0.4667	0.1767	0.0838	0.033*
H30B	0.5193	0.2625	0.0583	0.033*
H30C	0.3847	0.2075	0.0222	0.033*
C31	0.54224 (16)	0.30102 (7)	0.62791 (5)	0.0152 (2)
C32	0.5655 (2)	0.32204 (8)	0.69276 (5)	0.0236 (3)
H32A	0.5682	0.2732	0.7167	0.035*
H32B	0.4675	0.3555	0.7059	0.035*
H32C	0.6758	0.3511	0.6980	0.035*
C33	−0.11701 (18)	0.14577 (8)	0.14807 (7)	0.0252 (3)
H33A	−0.1760	0.1490	0.1869	0.038*
H33B	−0.0746	0.0914	0.1416	0.038*
H33C	−0.1998	0.1600	0.1163	0.038*

	U11	U22	U33	U12	U13	U23
O1	0.0208 (4)	0.0152 (3)	0.0103 (3)	−0.0016 (3)	−0.0006 (3)	−0.0002 (3)
O2	0.0112 (4)	0.0337 (5)	0.0169 (4)	0.0005 (4)	0.0006 (3)	0.0015 (4)
O3	0.0385 (6)	0.0258 (5)	0.0192 (4)	−0.0091 (5)	−0.0060 (4)	−0.0045 (3)
O4	0.0193 (4)	0.0213 (4)	0.0225 (4)	−0.0068 (4)	0.0010 (4)	−0.0053 (3)
O5	0.0262 (5)	0.0170 (4)	0.0199 (4)	−0.0032 (4)	−0.0017 (4)	0.0010 (3)
O6	0.0302 (5)	0.0131 (4)	0.0195 (4)	−0.0009 (4)	−0.0085 (4)	0.0036 (3)
O7	0.0206 (4)	0.0104 (3)	0.0149 (3)	0.0002 (3)	−0.0048 (3)	0.0009 (3)
C1	0.0123 (4)	0.0160 (5)	0.0121 (4)	−0.0032 (4)	0.0002 (4)	0.0012 (4)
C2	0.0129 (5)	0.0186 (5)	0.0118 (4)	−0.0017 (4)	0.0004 (4)	0.0005 (4)
C3	0.0150 (5)	0.0141 (4)	0.0100 (4)	−0.0010 (4)	−0.0005 (4)	−0.0011 (4)
C4	0.0131 (4)	0.0135 (4)	0.0117 (4)	−0.0007 (4)	−0.0003 (4)	−0.0024 (4)
C5	0.0106 (4)	0.0136 (4)	0.0111 (4)	−0.0010 (4)	−0.0003 (4)	−0.0015 (3)
C6	0.0156 (5)	0.0194 (5)	0.0131 (5)	−0.0073 (4)	0.0004 (4)	−0.0013 (4)
C7	0.0117 (4)	0.0210 (5)	0.0137 (4)	−0.0047 (4)	0.0007 (4)	−0.0005 (4)
C8	0.0115 (4)	0.0116 (4)	0.0122 (4)	−0.0015 (4)	0.0016 (4)	−0.0008 (3)
C9	0.0094 (4)	0.0107 (4)	0.0105 (4)	−0.0008 (4)	0.0005 (3)	0.0003 (3)
C10	0.0108 (4)	0.0126 (4)	0.0110 (4)	0.0000 (4)	0.0006 (4)	−0.0003 (4)
C11	0.0119 (4)	0.0129 (4)	0.0116 (4)	−0.0014 (4)	0.0002 (4)	0.0020 (3)
C12	0.0163 (5)	0.0116 (4)	0.0154 (5)	−0.0012 (4)	−0.0020 (4)	0.0004 (4)
C13	0.0122 (4)	0.0101 (4)	0.0110 (4)	−0.0009 (4)	−0.0010 (4)	0.0015 (3)
C14	0.0100 (4)	0.0128 (4)	0.0121 (4)	−0.0005 (4)	0.0008 (4)	0.0002 (3)
C15	0.0142 (5)	0.0162 (5)	0.0133 (4)	−0.0020 (4)	0.0018 (4)	0.0023 (4)
C16	0.0176 (5)	0.0133 (4)	0.0160 (5)	−0.0027 (4)	−0.0023 (4)	0.0038 (4)
C17	0.0130 (4)	0.0124 (4)	0.0126 (4)	0.0005 (4)	−0.0005 (4)	0.0028 (3)
C18	0.0111 (4)	0.0126 (4)	0.0113 (4)	0.0000 (4)	0.0001 (4)	0.0017 (3)
C19	0.0142 (5)	0.0124 (4)	0.0122 (4)	0.0004 (4)	−0.0013 (4)	0.0020 (3)
C20	0.0165 (5)	0.0143 (4)	0.0123 (4)	0.0001 (4)	−0.0011 (4)	−0.0006 (4)
C21	0.0215 (5)	0.0161 (5)	0.0138 (4)	−0.0008 (4)	−0.0046 (4)	0.0021 (4)
C22	0.0194 (5)	0.0156 (5)	0.0120 (4)	−0.0010 (4)	−0.0011 (4)	0.0032 (4)
C23	0.0138 (5)	0.0213 (5)	0.0153 (5)	0.0000 (4)	−0.0023 (4)	−0.0027 (4)
C24	0.0218 (5)	0.0138 (5)	0.0149 (4)	−0.0021 (4)	0.0002 (4)	−0.0037 (4)
C25	0.0190 (5)	0.0161 (5)	0.0162 (5)	0.0052 (4)	0.0020 (4)	0.0001 (4)
C26	0.0235 (6)	0.0110 (4)	0.0162 (5)	0.0004 (4)	0.0024 (4)	0.0007 (4)
C27	0.0136 (5)	0.0188 (5)	0.0171 (5)	0.0047 (4)	0.0013 (4)	−0.0020 (4)
C28	0.0169 (5)	0.0171 (5)	0.0202 (5)	0.0051 (4)	0.0010 (4)	0.0026 (4)
C29	0.0194 (5)	0.0136 (4)	0.0169 (5)	0.0005 (4)	−0.0046 (4)	0.0005 (4)
C30	0.0234 (6)	0.0229 (6)	0.0194 (5)	0.0027 (5)	0.0034 (5)	−0.0034 (4)
C31	0.0146 (5)	0.0167 (5)	0.0144 (5)	0.0019 (4)	−0.0008 (4)	0.0022 (4)
C32	0.0364 (7)	0.0214 (5)	0.0130 (5)	−0.0019 (5)	−0.0025 (5)	0.0018 (4)
C33	0.0185 (5)	0.0212 (5)	0.0359 (7)	−0.0065 (5)	−0.0001 (5)	−0.0029 (5)

O1—C31	1.3475 (13)	C15—H15B	0.9900
O1—C3	1.4603 (12)	C16—C17	1.5476 (16)
O2—C11	1.2033 (15)	C16—H16A	0.9900
O3—C29	1.2025 (15)	C16—H16B	0.9900
O4—C29	1.3389 (15)	C17—C18	1.5059 (14)
O4—C33	1.4444 (15)	C17—C28	1.5332 (16)
O5—C31	1.2039 (15)	C17—C22	1.5455 (15)
O6—C12	1.1953 (14)	C18—C19	1.3299 (15)
O7—C12	1.3735 (13)	C19—C20	1.4939 (15)
O7—C19	1.4024 (13)	C20—C29	1.5293 (17)
C1—C2	1.5342 (15)	C20—C30	1.5400 (17)
C1—C10	1.5416 (15)	C20—C21	1.5554 (16)
C1—H1A	0.9900	C21—C22	1.5304 (17)
C1—H1B	0.9900	C21—H21A	0.9900
C2—C3	1.5177 (16)	C21—H21B	0.9900
C2—H2A	0.9900	C22—H22A	0.9900
C2—H2B	0.9900	C22—H22B	0.9900
C3—C4	1.5428 (16)	C23—H23A	0.9800
C3—H3	1.0000	C23—H23B	0.9800
C4—C24	1.5397 (15)	C23—H23C	0.9800
C4—C23	1.5463 (16)	C24—H24A	0.9800
C4—C5	1.5575 (14)	C24—H24B	0.9800
C5—C6	1.5385 (15)	C24—H24C	0.9800
C5—C10	1.5624 (15)	C25—H25A	0.9800
C5—H5	1.0000	C25—H25B	0.9800
C6—C7	1.5407 (15)	C25—H25C	0.9800
C6—H6A	0.9900	C26—H26A	0.9800
C6—H6B	0.9900	C26—H26B	0.9800
C7—C8	1.5356 (16)	C26—H26C	0.9800
C7—H7A	0.9900	C27—H27A	0.9800
C7—H7B	0.9900	C27—H27B	0.9800
C8—C26	1.5382 (15)	C27—H27C	0.9800
C8—C9	1.5573 (14)	C28—H28A	0.9800
C8—C14	1.6026 (15)	C28—H28B	0.9800
C9—C11	1.5061 (15)	C28—H28C	0.9800
C9—C10	1.5429 (14)	C30—H30A	0.9800
C9—H9	1.0000	C30—H30B	0.9800
C10—C25	1.5448 (15)	C30—H30C	0.9800
C11—C13	1.5582 (15)	C31—C32	1.5044 (16)
C12—C13	1.5478 (15)	C32—H32A	0.9800
C13—C18	1.5006 (14)	C32—H32B	0.9800
C13—C14	1.5910 (15)	C32—H32C	0.9800
C14—C27	1.5366 (15)	C33—H33A	0.9800
C14—C15	1.5538 (15)	C33—H33B	0.9800
C15—C16	1.5332 (16)	C33—H33C	0.9800
C15—H15A	0.9900
C31—O1—C3	117.58 (9)	H16A—C16—H16B	107.7
C29—O4—C33	114.68 (10)	C18—C17—C28	112.02 (9)
C12—O7—C19	107.47 (8)	C18—C17—C22	106.94 (8)
C2—C1—C10	111.77 (9)	C28—C17—C22	110.15 (9)
C2—C1—H1A	109.3	C18—C17—C16	108.17 (9)
C10—C1—H1A	109.3	C28—C17—C16	109.36 (9)
C2—C1—H1B	109.3	C22—C17—C16	110.15 (9)
C10—C1—H1B	109.3	C19—C18—C13	108.86 (9)
H1A—C1—H1B	107.9	C19—C18—C17	123.89 (9)
C3—C2—C1	110.38 (9)	C13—C18—C17	125.65 (9)
C3—C2—H2A	109.6	C18—C19—O7	113.59 (9)
C1—C2—H2A	109.6	C18—C19—C20	128.96 (10)
C3—C2—H2B	109.6	O7—C19—C20	116.88 (9)
C1—C2—H2B	109.6	C19—C20—C29	113.62 (9)
H2A—C2—H2B	108.1	C19—C20—C30	109.68 (10)
O1—C3—C2	110.42 (9)	C29—C20—C30	108.05 (10)
O1—C3—C4	106.08 (8)	C19—C20—C21	107.11 (9)
C2—C3—C4	114.98 (9)	C29—C20—C21	107.30 (9)
O1—C3—H3	108.4	C30—C20—C21	111.08 (10)
C2—C3—H3	108.4	C22—C21—C20	112.09 (10)
C4—C3—H3	108.4	C22—C21—H21A	109.2
C24—C4—C3	111.51 (9)	C20—C21—H21A	109.2
C24—C4—C23	108.66 (9)	C22—C21—H21B	109.2
C3—C4—C23	107.07 (9)	C20—C21—H21B	109.2
C24—C4—C5	113.72 (9)	H21A—C21—H21B	107.9
C3—C4—C5	107.09 (9)	C21—C22—C17	113.28 (9)
C23—C4—C5	108.56 (9)	C21—C22—H22A	108.9
C6—C5—C4	113.51 (9)	C17—C22—H22A	108.9
C6—C5—C10	111.95 (9)	C21—C22—H22B	108.9
C4—C5—C10	116.50 (9)	C17—C22—H22B	108.9
C6—C5—H5	104.4	H22A—C22—H22B	107.7
C4—C5—H5	104.4	C4—C23—H23A	109.5
C10—C5—H5	104.4	C4—C23—H23B	109.5
C5—C6—C7	111.47 (9)	H23A—C23—H23B	109.5
C5—C6—H6A	109.3	C4—C23—H23C	109.5
C7—C6—H6A	109.3	H23A—C23—H23C	109.5
C5—C6—H6B	109.3	H23B—C23—H23C	109.5
C7—C6—H6B	109.3	C4—C24—H24A	109.5
H6A—C6—H6B	108.0	C4—C24—H24B	109.5
C8—C7—C6	111.68 (9)	H24A—C24—H24B	109.5
C8—C7—H7A	109.3	C4—C24—H24C	109.5
C6—C7—H7A	109.3	H24A—C24—H24C	109.5
C8—C7—H7B	109.3	H24B—C24—H24C	109.5
C6—C7—H7B	109.3	C10—C25—H25A	109.5
H7A—C7—H7B	107.9	C10—C25—H25B	109.5
C7—C8—C26	107.97 (9)	H25A—C25—H25B	109.5
C7—C8—C9	107.80 (8)	C10—C25—H25C	109.5
C26—C8—C9	112.47 (9)	H25A—C25—H25C	109.5
C7—C8—C14	115.05 (9)	H25B—C25—H25C	109.5
C26—C8—C14	111.90 (9)	C8—C26—H26A	109.5
C9—C8—C14	101.56 (8)	C8—C26—H26B	109.5
C11—C9—C10	122.43 (9)	H26A—C26—H26B	109.5
C11—C9—C8	100.79 (8)	C8—C26—H26C	109.5
C10—C9—C8	118.71 (9)	H26A—C26—H26C	109.5
C11—C9—H9	104.3	H26B—C26—H26C	109.5
C10—C9—H9	104.3	C14—C27—H27A	109.5
C8—C9—H9	104.3	C14—C27—H27B	109.5
C1—C10—C9	108.78 (8)	H27A—C27—H27B	109.5
C1—C10—C25	107.90 (9)	C14—C27—H27C	109.5
C9—C10—C25	112.43 (9)	H27A—C27—H27C	109.5
C1—C10—C5	108.02 (8)	H27B—C27—H27C	109.5
C9—C10—C5	103.10 (8)	C17—C28—H28A	109.5
C25—C10—C5	116.33 (9)	C17—C28—H28B	109.5
O2—C11—C9	130.77 (10)	H28A—C28—H28B	109.5
O2—C11—C13	124.86 (10)	C17—C28—H28C	109.5
C9—C11—C13	104.34 (9)	H28A—C28—H28C	109.5
O6—C12—O7	120.85 (10)	H28B—C28—H28C	109.5
O6—C12—C13	130.00 (10)	O3—C29—O4	123.70 (12)
O7—C12—C13	109.11 (9)	O3—C29—C20	123.50 (11)
C18—C13—C12	100.80 (9)	O4—C29—C20	112.78 (9)
C18—C13—C11	119.87 (9)	C20—C30—H30A	109.5
C12—C13—C11	104.91 (8)	C20—C30—H30B	109.5
C18—C13—C14	113.05 (8)	H30A—C30—H30B	109.5
C12—C13—C14	114.91 (9)	C20—C30—H30C	109.5
C11—C13—C14	103.52 (8)	H30A—C30—H30C	109.5
C27—C14—C15	106.12 (9)	H30B—C30—H30C	109.5
C27—C14—C13	110.65 (9)	O5—C31—O1	124.17 (10)
C15—C14—C13	108.83 (8)	O5—C31—C32	125.24 (11)
C27—C14—C8	111.26 (9)	O1—C31—C32	110.60 (10)
C15—C14—C8	115.40 (9)	C31—C32—H32A	109.5
C13—C14—C8	104.60 (8)	C31—C32—H32B	109.5
C16—C15—C14	117.84 (9)	H32A—C32—H32B	109.5
C16—C15—H15A	107.8	C31—C32—H32C	109.5
C14—C15—H15A	107.8	H32A—C32—H32C	109.5
C16—C15—H15B	107.8	H32B—C32—H32C	109.5
C14—C15—H15B	107.8	O4—C33—H33A	109.5
H15A—C15—H15B	107.2	O4—C33—H33B	109.5
C15—C16—C17	113.49 (9)	H33A—C33—H33B	109.5
C15—C16—H16A	108.9	O4—C33—H33C	109.5
C17—C16—H16A	108.9	H33A—C33—H33C	109.5
C15—C16—H16B	108.9	H33B—C33—H33C	109.5
C17—C16—H16B	108.9
C10—C1—C2—C3	−58.36 (12)	C11—C13—C14—C27	122.21 (9)
C31—O1—C3—C2	76.94 (12)	C18—C13—C14—C15	9.68 (12)
C31—O1—C3—C4	−157.87 (9)	C12—C13—C14—C15	124.65 (10)
C1—C2—C3—O1	177.46 (9)	C11—C13—C14—C15	−121.55 (9)
C1—C2—C3—C4	57.50 (12)	C18—C13—C14—C8	133.53 (9)
O1—C3—C4—C24	−49.35 (12)	C12—C13—C14—C8	−111.49 (10)
C2—C3—C4—C24	72.98 (12)	C11—C13—C14—C8	2.30 (10)
O1—C3—C4—C23	69.39 (11)	C7—C8—C14—C27	23.18 (12)
C2—C3—C4—C23	−168.28 (9)	C26—C8—C14—C27	146.90 (10)
O1—C3—C4—C5	−174.34 (9)	C9—C8—C14—C27	−92.92 (10)
C2—C3—C4—C5	−52.01 (12)	C7—C8—C14—C15	−97.78 (11)
C24—C4—C5—C6	59.79 (13)	C26—C8—C14—C15	25.93 (13)
C3—C4—C5—C6	−176.57 (9)	C9—C8—C14—C15	146.11 (9)
C23—C4—C5—C6	−61.28 (12)	C7—C8—C14—C13	142.69 (9)
C24—C4—C5—C10	−72.47 (12)	C26—C8—C14—C13	−93.60 (10)
C3—C4—C5—C10	51.18 (12)	C9—C8—C14—C13	26.58 (10)
C23—C4—C5—C10	166.46 (9)	C27—C14—C15—C16	158.17 (10)
C4—C5—C6—C7	163.94 (10)	C13—C14—C15—C16	39.06 (12)
C10—C5—C6—C7	−61.63 (12)	C8—C14—C15—C16	−78.12 (12)
C5—C6—C7—C8	56.45 (13)	C14—C15—C16—C17	−59.65 (13)
C6—C7—C8—C26	71.40 (11)	C15—C16—C17—C18	23.71 (13)
C6—C7—C8—C9	−50.35 (12)	C15—C16—C17—C28	145.97 (10)
C6—C7—C8—C14	−162.83 (9)	C15—C16—C17—C22	−92.85 (11)
C7—C8—C9—C11	−167.72 (9)	C12—C13—C18—C19	−4.12 (12)
C26—C8—C9—C11	73.36 (10)	C11—C13—C18—C19	−118.43 (11)
C14—C8—C9—C11	−46.42 (9)	C14—C13—C18—C19	119.06 (10)
C7—C8—C9—C10	55.67 (12)	C12—C13—C18—C17	−170.08 (10)
C26—C8—C9—C10	−63.26 (12)	C11—C13—C18—C17	75.61 (14)
C14—C8—C9—C10	176.96 (9)	C14—C13—C18—C17	−46.91 (14)
C2—C1—C10—C9	166.68 (9)	C28—C17—C18—C19	103.47 (13)
C2—C1—C10—C25	−71.10 (11)	C22—C17—C18—C19	−17.30 (15)
C2—C1—C10—C5	55.43 (12)	C16—C17—C18—C19	−135.92 (12)
C11—C9—C10—C1	60.76 (12)	C28—C17—C18—C13	−92.58 (13)
C8—C9—C10—C1	−172.31 (9)	C22—C17—C18—C13	146.65 (11)
C11—C9—C10—C25	−58.68 (13)	C16—C17—C18—C13	28.03 (14)
C8—C9—C10—C25	68.25 (12)	C13—C18—C19—O7	4.12 (14)
C11—C9—C10—C5	175.26 (9)	C17—C18—C19—O7	170.38 (10)
C8—C9—C10—C5	−57.82 (11)	C13—C18—C19—C20	−166.81 (11)
C6—C5—C10—C1	172.93 (9)	C17—C18—C19—C20	−0.55 (19)
C4—C5—C10—C1	−54.10 (12)	C12—O7—C19—C18	−2.10 (14)
C6—C5—C10—C9	57.89 (11)	C12—O7—C19—C20	170.00 (10)
C4—C5—C10—C9	−169.14 (9)	C18—C19—C20—C29	−129.02 (13)
C6—C5—C10—C25	−65.62 (11)	O7—C19—C20—C29	60.31 (14)
C4—C5—C10—C25	67.34 (12)	C18—C19—C20—C30	109.94 (14)
C10—C9—C11—O2	5.92 (19)	O7—C19—C20—C30	−60.74 (13)
C8—C9—C11—O2	−128.53 (13)	C18—C19—C20—C21	−10.71 (17)
C10—C9—C11—C13	−176.09 (9)	O7—C19—C20—C21	178.61 (10)
C8—C9—C11—C13	49.45 (9)	C19—C20—C21—C22	40.24 (13)
C19—O7—C12—O6	177.07 (12)	C29—C20—C21—C22	162.58 (10)
C19—O7—C12—C13	−0.79 (12)	C30—C20—C21—C22	−79.52 (12)
O6—C12—C13—C18	−174.68 (13)	C20—C21—C22—C17	−63.10 (13)
O7—C12—C13—C18	2.92 (12)	C18—C17—C22—C21	47.71 (13)
O6—C12—C13—C11	−49.55 (17)	C28—C17—C22—C21	−74.24 (12)
O7—C12—C13—C11	128.06 (9)	C16—C17—C22—C21	165.04 (10)
O6—C12—C13—C14	63.44 (17)	C33—O4—C29—O3	1.44 (18)
O7—C12—C13—C14	−118.96 (10)	C33—O4—C29—C20	179.73 (10)
O2—C11—C13—C18	19.22 (17)	C19—C20—C29—O3	−162.49 (12)
C9—C11—C13—C18	−158.92 (9)	C30—C20—C29—O3	−40.54 (16)
O2—C11—C13—C12	−92.91 (14)	C21—C20—C29—O3	79.32 (14)
C9—C11—C13—C12	88.95 (10)	C19—C20—C29—O4	19.21 (14)
O2—C11—C13—C14	146.27 (12)	C30—C20—C29—O4	141.16 (10)
C9—C11—C13—C14	−31.87 (10)	C21—C20—C29—O4	−98.98 (11)
C18—C13—C14—C27	−106.56 (10)	C3—O1—C31—O5	−3.23 (18)
C12—C13—C14—C27	8.41 (12)	C3—O1—C31—C32	176.93 (10)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O5	0.99	2.58	3.1121 (14)	114
C9—H9···O6	1.00	2.43	3.1601 (13)	129
C23—H23A···O1	0.98	2.49	2.9084 (15)	106
C25—H25A···O2	0.98	2.60	3.2898 (16)	127
C27—H27B···O6	0.98	2.49	3.0454 (16)	116
C1—H1A···O5i	0.99	2.63	3.4839 (15)	145
C5—H5···O5ii	1.00	2.64	3.5313 (14)	149
C7—H7B···O2iii	0.99	2.59	3.1743 (15)	118
C7—H7B···O5ii	0.99	2.70	3.5497 (15)	145

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯O5	0.99	2.58	3.1121 (14)	114
C9—H9⋯O6	1.00	2.43	3.1601 (13)	129
C23—H23A⋯O1	0.98	2.49	2.9084 (15)	106
C25—H25A⋯O2	0.98	2.60	3.2898 (16)	127
C27—H27B⋯O6	0.98	2.49	3.0454 (16)	116
C1—H1A⋯O5i	0.99	2.63	3.4839 (15)	145
C5—H5⋯O5ii	1.00	2.64	3.5313 (14)	149
C7—H7B⋯O2iii	0.99	2.59	3.1743 (15)	118
C7—H7B⋯O5ii	0.99	2.70	3.5497 (15)	145

Symmetry codes: (i) ; (ii) ; (iii) .