Ep-oxy-cytochalasin H methanol solvate.

In the title solvate, C(30)H(39)NO(5)·CH(4)O {systematic name: 21-acet-oxy-18,21-dihy-droxy-5,6,16,18-tetra-methyl-10-phenyl-6,7-ep-oxy-[11]cytochalasa-13,19-dien-1-one methanol solvate}, the organic mol-ecule exhibits the tetra-cyclic terpenoid skeleton of cytochalasin, consisting of fused five-, six-, three- and 11-membered rings. The five-membered ring adopts an envelope conformation, while the six-membered ring is in a boat conformation. The ep-oxy O atom on the six-membered ring is pointing away from the five-membered ring. An inter-stitial methanol solvent mol-ecule is hydrogen bonded to the cytochalasin mol-ecules and inter-molecular O-H⋯O and N-H⋯O hydrogen bonds connect the mol-ecules into infinite chains along the (10) direction.

Related literature

For the isolation and structure elucidation of the title compound, see: Cole et al. (1982 ▶). For related structures, see: Buchi et al. (1973 ▶); Beno et al. (1977 ▶); Capasso et al. (1988 ▶); Edwards & Maitland et al. (1989 ▶); Chen et al. (1993 ▶); Feng et al. (2002 ▶); Evidente et al. (2002 ▶, 2003 ▶); Rochfort et al. (2008 ▶); Herath et al. (2005 ▶); Ding et al. (2006 ▶). For total syntheses of related compounds, see: Haidle & Myers et al. (2004 ▶). For the biological activity of related compounds, see: Hirose et al. (1990 ▶); Lingham et al. (1992 ▶); Burres et al. (1992 ▶); Meurer-Grimes et al. (2005 ▶)

Experimental

Crystal data

C30H39NO5·CH4O

M = 525.66

Triclinic,

a = 8.367 (2) Å

b = 8.5937 (18) Å

c = 10.917 (3) Å

α = 75.312 (9)°

β = 87.779 (10)°

γ = 68.150 (8)°

V = 703.4 (3) Å3

Z = 1

Mo Kα radiation

μ = 0.09 mm−1

T = 93 K

0.50 × 0.50 × 0.28 mm

Data collection

Rigaku SPIDER diffractometer

7075 measured reflections

3175 independent reflections

3015 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.070

S = 1.00

3175 reflections

361 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.16 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2004 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810029600/zl2284sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029600/zl2284Isup2.hkl

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

C30H39NO5·CH4O	F(000) = 284
Mr = 525.66	Dx = 1.241 Mg m−3
Triclinic, P1	Melting point: 398 K
a = 8.367 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.5937 (18) Å	Cell parameters from 2524 reflections
c = 10.917 (3) Å	θ = 3.2–27.5°
α = 75.312 (9)°	µ = 0.09 mm−1
β = 87.779 (10)°	T = 93 K
γ = 68.150 (8)°	Block, colorless
V = 703.4 (3) Å3	0.50 × 0.50 × 0.28 mm
Z = 1

Rigaku SPIDER diffractometer	3015 reflections with I > 2σ(I)
Radiation source: Rotating Anode	Rint = 0.022
graphite	θmax = 27.5°, θmin = 3.2°
ω scans	h = −10→10
7075 measured reflections	k = −11→10
3175 independent reflections	l = −14→14

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) = 0.070	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0338P)2 + 0.116P] where P = (Fo2 + 2Fc2)/3
3175 reflections	(Δ/σ)max < 0.001
361 parameters	Δρmax = 0.23 e Å−3
3 restraints	Δρmin = −0.16 e Å−3

Experimental. 13C NMR (150 MHz, CDCl3, δ, p.p.m.): 175.0(C1), 170.0(C29), 138.0(C14), 137.2(C31), 136.0(C20), 130.2(C24,28), 128.7(C25, 27), 127.6(C19), 127.1(C13), 125.5(C26), 76.0(C21), 74.1(C18), 62.9(C7), 57.0(C6), 53.8(C3), 53.7(C17), 53.5(C9), 51.1(C4), 45.7(C15), 45.0(C8), 43.1(C10), 36.6(C5), 30.1(C16), 28.6(C23), 26.4(C22), 20.6(C30), 19.5(C12), 13.0(C11). And they are in accordance with those reported by Cole (Cole et al. (1982)).

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.

	x	y	z	Uiso*/Ueq
O1	−0.26599 (18)	0.47464 (18)	0.27188 (13)	0.0196 (3)
O2	0.05816 (17)	0.57776 (17)	0.56786 (12)	0.0187 (3)
O3	0.80244 (17)	0.04100 (17)	0.57468 (13)	0.0173 (3)
O4	0.34749 (16)	0.40110 (17)	0.24838 (12)	0.0161 (3)
O5	0.40913 (18)	0.60342 (19)	0.09849 (13)	0.0233 (3)
N2	−0.0535 (2)	0.8235 (2)	0.40622 (15)	0.0155 (3)
C1	0.0353 (2)	0.6548 (2)	0.45346 (17)	0.0145 (4)
C3	−0.0527 (2)	0.8866 (2)	0.26910 (17)	0.0141 (4)
H3	−0.1731	0.9614	0.2336	0.017*
C4	0.0084 (2)	0.7177 (2)	0.22278 (16)	0.0134 (3)
H4	0.0976	0.7227	0.1598	0.016*
C5	−0.1383 (2)	0.6900 (2)	0.15966 (17)	0.0151 (4)
H5	−0.0812	0.5846	0.1273	0.018*
C6	−0.2551 (2)	0.6432 (2)	0.26100 (17)	0.0158 (4)
C7	−0.1616 (2)	0.4928 (2)	0.36551 (17)	0.0165 (4)
H7	−0.2082	0.4926	0.4513	0.020*
C8	0.0336 (2)	0.4143 (2)	0.36131 (17)	0.0148 (4)
H8	0.0586	0.3724	0.2825	0.018*
C9	0.0983 (2)	0.5674 (2)	0.34475 (17)	0.0134 (3)
C10	0.0622 (2)	0.9935 (2)	0.23827 (17)	0.0171 (4)
H10A	0.0325	1.0756	0.2925	0.021*
H10B	0.1837	0.9139	0.2611	0.021*
C11	−0.2324 (3)	0.8372 (3)	0.04402 (18)	0.0205 (4)
H11A	−0.3176	0.8074	0.0058	0.025*
H11B	−0.1488	0.8540	−0.0183	0.025*
H11C	−0.2910	0.9444	0.0704	0.025*
C12	−0.4211 (2)	0.7803 (3)	0.28126 (19)	0.0204 (4)
H12A	−0.5006	0.8201	0.2063	0.024*
H12B	−0.3978	0.8785	0.2950	0.024*
H12C	−0.4732	0.7318	0.3557	0.024*
C13	0.1132 (2)	0.2589 (2)	0.47220 (18)	0.0168 (4)
H13	0.0727	0.2658	0.5539	0.020*
C14	0.2369 (2)	0.1131 (2)	0.46122 (18)	0.0172 (4)
H14	0.2774	0.1110	0.3789	0.021*
C15	0.3193 (2)	−0.0482 (2)	0.56493 (18)	0.0186 (4)
H15A	0.3111	−0.1477	0.5393	0.022*
H15B	0.2547	−0.0368	0.6421	0.022*
C16	0.5108 (2)	−0.0869 (2)	0.59701 (18)	0.0183 (4)
H16	0.5685	−0.0715	0.5153	0.022*
C17	0.5316 (2)	0.0393 (3)	0.66833 (18)	0.0177 (4)
H17A	0.4150	0.1189	0.6813	0.021*
H17B	0.5883	−0.0291	0.7532	0.021*
C18	0.6351 (2)	0.1496 (2)	0.60366 (17)	0.0151 (4)
C19	0.5449 (2)	0.2644 (2)	0.47624 (17)	0.0152 (4)
H19	0.5953	0.2345	0.4018	0.018*
C20	0.4017 (2)	0.4024 (3)	0.46214 (17)	0.0169 (4)
H20	0.3600	0.4394	0.5362	0.020*
C21	0.2980 (2)	0.5068 (2)	0.33880 (17)	0.0143 (4)
H21	0.3281	0.6116	0.3058	0.017*
C22	0.5994 (3)	−0.2758 (3)	0.6732 (2)	0.0287 (5)
H22A	0.5433	−0.2951	0.7530	0.034*
H22B	0.7213	−0.3001	0.6915	0.034*
H22C	0.5903	−0.3531	0.6238	0.034*
C23	0.6591 (3)	0.2519 (3)	0.69262 (18)	0.0193 (4)
H23A	0.7233	0.1710	0.7710	0.023*
H23B	0.5459	0.3267	0.7127	0.023*
H23C	0.7235	0.3235	0.6512	0.023*
C24	0.1621 (3)	1.0297 (3)	0.0148 (2)	0.0231 (4)
H24	0.2495	0.9170	0.0403	0.028*
C25	0.1483 (3)	1.1291 (3)	−0.1103 (2)	0.0333 (5)
H25	0.2264	1.0832	−0.1693	0.040*
C26	0.0226 (4)	1.2931 (3)	−0.1488 (2)	0.0346 (6)
H26	0.0144	1.3602	−0.2338	0.042*
C27	−0.0913 (4)	1.3590 (3)	−0.0630 (2)	0.0331 (5)
H27	−0.1783	1.4719	−0.0890	0.040*
C28	−0.0791 (3)	1.2605 (3)	0.06136 (19)	0.0235 (4)
H28	−0.1586	1.3066	0.1196	0.028*
C29	0.4050 (2)	0.4611 (3)	0.13584 (17)	0.0180 (4)
C30	0.4606 (3)	0.3225 (3)	0.0651 (2)	0.0293 (5)
H30A	0.5033	0.3652	−0.0163	0.035*
H30B	0.3620	0.2928	0.0500	0.035*
H30C	0.5526	0.2191	0.1155	0.035*
C31	0.0484 (2)	1.0952 (2)	0.10157 (18)	0.0165 (4)
O6	1.0050 (2)	−0.2459 (2)	0.75153 (14)	0.0272 (3)
C32	1.1481 (3)	−0.3222 (3)	0.8413 (2)	0.0270 (5)
H32A	1.1523	−0.2359	0.8837	0.032*
H32B	1.2546	−0.3629	0.7979	0.032*
H32C	1.1363	−0.4205	0.9044	0.032*
H6O	1.023 (4)	−0.304 (4)	0.698 (3)	0.036 (8)*
H3O	0.856 (4)	−0.027 (4)	0.641 (3)	0.043 (8)*
H2N	−0.098 (3)	0.897 (3)	0.455 (2)	0.025 (6)*

	U11	U22	U33	U12	U13	U23
O1	0.0189 (7)	0.0198 (7)	0.0219 (7)	−0.0094 (6)	−0.0008 (5)	−0.0053 (6)
O2	0.0231 (7)	0.0167 (7)	0.0131 (6)	−0.0052 (6)	0.0016 (5)	−0.0020 (5)
O3	0.0116 (6)	0.0165 (7)	0.0176 (7)	0.0010 (5)	−0.0018 (5)	−0.0032 (6)
O4	0.0153 (6)	0.0157 (7)	0.0150 (6)	−0.0027 (5)	0.0010 (5)	−0.0050 (5)
O5	0.0200 (7)	0.0246 (8)	0.0202 (7)	−0.0062 (6)	0.0026 (5)	−0.0004 (6)
N2	0.0172 (8)	0.0126 (8)	0.0142 (8)	−0.0023 (6)	0.0018 (6)	−0.0041 (6)
C1	0.0118 (8)	0.0153 (9)	0.0161 (9)	−0.0048 (7)	0.0012 (6)	−0.0042 (7)
C3	0.0139 (8)	0.0129 (9)	0.0129 (8)	−0.0027 (7)	0.0003 (6)	−0.0024 (7)
C4	0.0123 (8)	0.0134 (9)	0.0118 (8)	−0.0025 (7)	0.0003 (6)	−0.0023 (7)
C5	0.0143 (9)	0.0154 (9)	0.0139 (8)	−0.0038 (7)	−0.0006 (6)	−0.0035 (7)
C6	0.0137 (9)	0.0170 (10)	0.0179 (9)	−0.0062 (7)	−0.0011 (7)	−0.0055 (7)
C7	0.0153 (9)	0.0188 (10)	0.0168 (9)	−0.0084 (8)	0.0016 (7)	−0.0042 (7)
C8	0.0150 (9)	0.0136 (9)	0.0153 (9)	−0.0050 (7)	0.0005 (7)	−0.0034 (7)
C9	0.0130 (8)	0.0115 (9)	0.0134 (8)	−0.0027 (7)	−0.0001 (6)	−0.0017 (7)
C10	0.0192 (9)	0.0161 (10)	0.0165 (9)	−0.0073 (8)	−0.0021 (7)	−0.0034 (7)
C11	0.0208 (10)	0.0214 (11)	0.0162 (9)	−0.0049 (8)	−0.0036 (7)	−0.0037 (8)
C12	0.0147 (9)	0.0244 (11)	0.0220 (9)	−0.0064 (8)	0.0012 (7)	−0.0076 (8)
C13	0.0179 (9)	0.0166 (9)	0.0169 (9)	−0.0082 (8)	0.0002 (7)	−0.0029 (7)
C14	0.0193 (9)	0.0165 (10)	0.0171 (9)	−0.0096 (8)	−0.0019 (7)	−0.0018 (7)
C15	0.0191 (9)	0.0135 (10)	0.0230 (10)	−0.0066 (8)	−0.0017 (7)	−0.0030 (8)
C16	0.0165 (9)	0.0143 (9)	0.0221 (10)	−0.0041 (7)	−0.0015 (7)	−0.0033 (8)
C17	0.0179 (9)	0.0177 (10)	0.0162 (9)	−0.0066 (8)	0.0007 (7)	−0.0025 (7)
C18	0.0126 (8)	0.0142 (9)	0.0155 (9)	−0.0021 (7)	−0.0001 (6)	−0.0028 (7)
C19	0.0155 (9)	0.0154 (9)	0.0151 (9)	−0.0062 (7)	0.0020 (7)	−0.0041 (7)
C20	0.0164 (9)	0.0194 (10)	0.0145 (9)	−0.0053 (8)	0.0002 (7)	−0.0056 (7)
C21	0.0156 (8)	0.0121 (9)	0.0144 (8)	−0.0041 (7)	0.0017 (7)	−0.0038 (7)
C22	0.0228 (11)	0.0158 (10)	0.0417 (13)	−0.0042 (9)	−0.0060 (9)	−0.0009 (9)
C23	0.0213 (10)	0.0164 (10)	0.0192 (9)	−0.0054 (8)	−0.0020 (7)	−0.0048 (8)
C24	0.0233 (10)	0.0235 (11)	0.0259 (10)	−0.0114 (9)	0.0062 (8)	−0.0090 (9)
C25	0.0455 (14)	0.0428 (15)	0.0246 (11)	−0.0288 (12)	0.0159 (10)	−0.0140 (11)
C26	0.0605 (17)	0.0341 (13)	0.0178 (10)	−0.0319 (13)	0.0010 (10)	0.0006 (9)
C27	0.0493 (15)	0.0190 (11)	0.0265 (11)	−0.0121 (11)	−0.0105 (10)	0.0024 (9)
C28	0.0305 (11)	0.0186 (10)	0.0201 (10)	−0.0081 (9)	0.0004 (8)	−0.0040 (8)
C29	0.0129 (8)	0.0209 (10)	0.0144 (9)	−0.0011 (7)	−0.0004 (7)	−0.0027 (7)
C30	0.0300 (12)	0.0277 (12)	0.0203 (10)	0.0016 (9)	0.0032 (8)	−0.0086 (9)
C31	0.0197 (9)	0.0150 (9)	0.0185 (9)	−0.0107 (8)	0.0000 (7)	−0.0040 (7)
O6	0.0292 (8)	0.0218 (8)	0.0222 (8)	0.0026 (6)	−0.0077 (6)	−0.0086 (6)
C32	0.0262 (11)	0.0287 (12)	0.0241 (10)	−0.0094 (9)	−0.0045 (8)	−0.0037 (9)

O1—C7	1.444 (2)	C15—C16	1.545 (3)
O1—C6	1.460 (2)	C15—H15A	0.9900
O2—C1	1.241 (2)	C15—H15B	0.9900
O3—C18	1.440 (2)	C16—C22	1.531 (3)
O3—H3O	0.83 (3)	C16—C17	1.547 (3)
O4—C29	1.351 (2)	C16—H16	1.0000
O4—C21	1.454 (2)	C17—C18	1.540 (3)
O5—C29	1.200 (3)	C17—H17A	0.9900
N2—C1	1.330 (2)	C17—H17B	0.9900
N2—C3	1.458 (2)	C18—C19	1.519 (3)
N2—H2N	0.90 (3)	C18—C23	1.528 (3)
C1—C9	1.536 (2)	C19—C20	1.315 (3)
C3—C10	1.535 (3)	C19—H19	0.9500
C3—C4	1.557 (2)	C20—C21	1.506 (3)
C3—H3	1.0000	C20—H20	0.9500
C4—C5	1.551 (2)	C21—H21	1.0000
C4—C9	1.578 (2)	C22—H22A	0.9800
C4—H4	1.0000	C22—H22B	0.9800
C5—C6	1.524 (2)	C22—H22C	0.9800
C5—C11	1.530 (3)	C23—H23A	0.9800
C5—H5	1.0000	C23—H23B	0.9800
C6—C7	1.467 (3)	C23—H23C	0.9800
C6—C12	1.502 (3)	C24—C31	1.386 (3)
C7—C8	1.521 (3)	C24—C25	1.398 (3)
C7—H7	1.0000	C24—H24	0.9500
C8—C13	1.508 (3)	C25—C26	1.378 (4)
C8—C9	1.569 (2)	C25—H25	0.9500
C8—H8	1.0000	C26—C27	1.379 (4)
C9—C21	1.559 (2)	C26—H26	0.9500
C10—C31	1.510 (3)	C27—C28	1.390 (3)
C10—H10A	0.9900	C27—H27	0.9500
C10—H10B	0.9900	C28—C31	1.393 (3)
C11—H11A	0.9800	C28—H28	0.9500
C11—H11B	0.9800	C29—C30	1.502 (3)
C11—H11C	0.9800	C30—H30A	0.9800
C12—H12A	0.9800	C30—H30B	0.9800
C12—H12B	0.9800	C30—H30C	0.9800
C12—H12C	0.9800	O6—C32	1.416 (3)
C13—C14	1.325 (3)	O6—H6O	0.84 (3)
C13—H13	0.9500	C32—H32A	0.9800
C14—C15	1.494 (3)	C32—H32B	0.9800
C14—H14	0.9500	C32—H32C	0.9800
C7—O1—C6	60.70 (12)	C16—C15—H15B	108.9
C18—O3—H3O	109 (2)	H15A—C15—H15B	107.7
C29—O4—C21	119.78 (14)	C22—C16—C15	109.93 (16)
C1—N2—C3	115.28 (15)	C22—C16—C17	111.15 (17)
C1—N2—H2N	122.7 (16)	C15—C16—C17	112.02 (15)
C3—N2—H2N	121.5 (16)	C22—C16—H16	107.9
O2—C1—N2	125.31 (17)	C15—C16—H16	107.9
O2—C1—C9	124.87 (17)	C17—C16—H16	107.9
N2—C1—C9	109.76 (15)	C18—C17—C16	116.27 (15)
N2—C3—C10	109.65 (14)	C18—C17—H17A	108.2
N2—C3—C4	103.39 (14)	C16—C17—H17A	108.2
C10—C3—C4	115.66 (15)	C18—C17—H17B	108.2
N2—C3—H3	109.3	C16—C17—H17B	108.2
C10—C3—H3	109.3	H17A—C17—H17B	107.4
C4—C3—H3	109.3	O3—C18—C19	105.29 (14)
C5—C4—C3	113.89 (14)	O3—C18—C23	108.79 (15)
C5—C4—C9	112.81 (14)	C19—C18—C23	113.22 (15)
C3—C4—C9	104.64 (14)	O3—C18—C17	110.76 (15)
C5—C4—H4	108.4	C19—C18—C17	109.41 (15)
C3—C4—H4	108.4	C23—C18—C17	109.31 (15)
C9—C4—H4	108.4	C20—C19—C18	124.34 (16)
C6—C5—C11	114.86 (16)	C20—C19—H19	117.8
C6—C5—C4	109.27 (14)	C18—C19—H19	117.8
C11—C5—C4	113.97 (15)	C19—C20—C21	125.68 (17)
C6—C5—H5	106.0	C19—C20—H20	117.2
C11—C5—H5	106.0	C21—C20—H20	117.2
C4—C5—H5	106.0	O4—C21—C20	108.18 (15)
O1—C6—C7	59.09 (11)	O4—C21—C9	107.03 (14)
O1—C6—C12	114.16 (15)	C20—C21—C9	115.88 (15)
C7—C6—C12	120.90 (16)	O4—C21—H21	108.5
O1—C6—C5	114.31 (15)	C20—C21—H21	108.5
C7—C6—C5	113.23 (15)	C9—C21—H21	108.5
C12—C6—C5	120.09 (16)	C16—C22—H22A	109.5
O1—C7—C6	60.21 (12)	C16—C22—H22B	109.5
O1—C7—C8	118.13 (15)	H22A—C22—H22B	109.5
C6—C7—C8	116.79 (15)	C16—C22—H22C	109.5
O1—C7—H7	116.6	H22A—C22—H22C	109.5
C6—C7—H7	116.6	H22B—C22—H22C	109.5
C8—C7—H7	116.6	C18—C23—H23A	109.5
C13—C8—C7	111.45 (15)	C18—C23—H23B	109.5
C13—C8—C9	116.96 (15)	H23A—C23—H23B	109.5
C7—C8—C9	106.34 (14)	C18—C23—H23C	109.5
C13—C8—H8	107.2	H23A—C23—H23C	109.5
C7—C8—H8	107.2	H23B—C23—H23C	109.5
C9—C8—H8	107.2	C31—C24—C25	120.2 (2)
C1—C9—C21	111.33 (14)	C31—C24—H24	119.9
C1—C9—C8	108.67 (14)	C25—C24—H24	119.9
C21—C9—C8	112.47 (14)	C26—C25—C24	120.7 (2)
C1—C9—C4	103.13 (14)	C26—C25—H25	119.7
C21—C9—C4	109.56 (14)	C24—C25—H25	119.7
C8—C9—C4	111.29 (14)	C25—C26—C27	119.5 (2)
C31—C10—C3	115.31 (15)	C25—C26—H26	120.2
C31—C10—H10A	108.4	C27—C26—H26	120.2
C3—C10—H10A	108.4	C26—C27—C28	120.2 (2)
C31—C10—H10B	108.4	C26—C27—H27	119.9
C3—C10—H10B	108.4	C28—C27—H27	119.9
H10A—C10—H10B	107.5	C27—C28—C31	120.8 (2)
C5—C11—H11A	109.5	C27—C28—H28	119.6
C5—C11—H11B	109.5	C31—C28—H28	119.6
H11A—C11—H11B	109.5	O5—C29—O4	125.02 (18)
C5—C11—H11C	109.5	O5—C29—C30	125.77 (18)
H11A—C11—H11C	109.5	O4—C29—C30	109.20 (17)
H11B—C11—H11C	109.5	C29—C30—H30A	109.5
C6—C12—H12A	109.5	C29—C30—H30B	109.5
C6—C12—H12B	109.5	H30A—C30—H30B	109.5
H12A—C12—H12B	109.5	C29—C30—H30C	109.5
C6—C12—H12C	109.5	H30A—C30—H30C	109.5
H12A—C12—H12C	109.5	H30B—C30—H30C	109.5
H12B—C12—H12C	109.5	C24—C31—C28	118.69 (18)
C14—C13—C8	123.18 (17)	C24—C31—C10	121.66 (18)
C14—C13—H13	118.4	C28—C31—C10	119.63 (17)
C8—C13—H13	118.4	C32—O6—H6O	108 (2)
C13—C14—C15	126.72 (18)	O6—C32—H32A	109.5
C13—C14—H14	116.6	O6—C32—H32B	109.5
C15—C14—H14	116.6	H32A—C32—H32B	109.5
C14—C15—C16	113.25 (15)	O6—C32—H32C	109.5
C14—C15—H15A	108.9	H32A—C32—H32C	109.5
C16—C15—H15A	108.9	H32B—C32—H32C	109.5
C14—C15—H15B	108.9
C3—N2—C1—O2	176.02 (17)	C5—C4—C9—C21	132.78 (15)
C3—N2—C1—C9	−6.7 (2)	C3—C4—C9—C21	−102.89 (16)
C1—N2—C3—C10	−107.04 (18)	C5—C4—C9—C8	7.8 (2)
C1—N2—C3—C4	16.9 (2)	C3—C4—C9—C8	132.09 (15)
N2—C3—C4—C5	104.44 (16)	N2—C3—C10—C31	−168.78 (15)
C10—C3—C4—C5	−135.70 (16)	C4—C3—C10—C31	74.8 (2)
N2—C3—C4—C9	−19.19 (17)	C7—C8—C13—C14	136.71 (19)
C10—C3—C4—C9	100.67 (17)	C9—C8—C13—C14	−100.7 (2)
C3—C4—C5—C6	−71.29 (19)	C8—C13—C14—C15	−178.15 (17)
C9—C4—C5—C6	47.79 (19)	C13—C14—C15—C16	−112.7 (2)
C3—C4—C5—C11	58.7 (2)	C14—C15—C16—C22	−163.36 (17)
C9—C4—C5—C11	177.80 (15)	C14—C15—C16—C17	72.5 (2)
C7—O1—C6—C12	−112.79 (18)	C22—C16—C17—C18	116.22 (19)
C7—O1—C6—C5	103.53 (17)	C15—C16—C17—C18	−120.37 (18)
C11—C5—C6—O1	110.27 (17)	C16—C17—C18—O3	−54.2 (2)
C4—C5—C6—O1	−120.21 (16)	C16—C17—C18—C19	61.4 (2)
C11—C5—C6—C7	175.47 (15)	C16—C17—C18—C23	−174.07 (16)
C4—C5—C6—C7	−55.0 (2)	O3—C18—C19—C20	−167.40 (17)
C11—C5—C6—C12	−31.1 (2)	C23—C18—C19—C20	−48.7 (2)
C4—C5—C6—C12	98.44 (19)	C17—C18—C19—C20	73.5 (2)
C6—O1—C7—C8	−106.43 (18)	C18—C19—C20—C21	−172.52 (17)
C12—C6—C7—O1	101.40 (18)	C29—O4—C21—C20	−124.04 (17)
C5—C6—C7—O1	−105.38 (16)	C29—O4—C21—C9	110.43 (17)
O1—C6—C7—C8	108.64 (17)	C19—C20—C21—O4	18.5 (3)
C12—C6—C7—C8	−149.96 (17)	C19—C20—C21—C9	138.65 (19)
C5—C6—C7—C8	3.3 (2)	C1—C9—C21—O4	170.55 (14)
O1—C7—C8—C13	−109.94 (18)	C8—C9—C21—O4	48.30 (18)
C6—C7—C8—C13	−178.77 (15)	C4—C9—C21—O4	−76.03 (17)
O1—C7—C8—C9	121.54 (16)	C1—C9—C21—C20	49.8 (2)
C6—C7—C8—C9	52.7 (2)	C8—C9—C21—C20	−72.4 (2)
O2—C1—C9—C21	−71.7 (2)	C4—C9—C21—C20	163.22 (15)
N2—C1—C9—C21	110.94 (17)	C31—C24—C25—C26	0.2 (3)
O2—C1—C9—C8	52.7 (2)	C24—C25—C26—C27	−0.4 (4)
N2—C1—C9—C8	−124.65 (16)	C25—C26—C27—C28	0.0 (4)
O2—C1—C9—C4	170.86 (17)	C26—C27—C28—C31	0.5 (3)
N2—C1—C9—C4	−6.46 (18)	C21—O4—C29—O5	−5.2 (3)
C13—C8—C9—C1	−68.96 (19)	C21—O4—C29—C30	175.47 (16)
C7—C8—C9—C1	56.26 (18)	C25—C24—C31—C28	0.3 (3)
C13—C8—C9—C21	54.8 (2)	C25—C24—C31—C10	−178.39 (18)
C7—C8—C9—C21	179.99 (14)	C27—C28—C31—C24	−0.6 (3)
C13—C8—C9—C4	178.15 (15)	C27—C28—C31—C10	178.06 (19)
C7—C8—C9—C4	−56.64 (18)	C3—C10—C31—C24	−95.0 (2)
C5—C4—C9—C1	−108.57 (16)	C3—C10—C31—C28	86.4 (2)
C3—C4—C9—C1	15.75 (17)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O6	0.83 (3)	1.94 (3)	2.722 (2)	157 (3)
N2—H2N···O3i	0.90 (3)	1.97 (3)	2.867 (2)	175 (2)
O6—H6O···O2ii	0.84 (3)	1.90 (3)	2.736 (2)	176 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O6	0.83 (3)	1.94 (3)	2.722 (2)	157 (3)
N2—H2N⋯O3i	0.90 (3)	1.97 (3)	2.867 (2)	175 (2)
O6—H6O⋯O2ii	0.84 (3)	1.90 (3)	2.736 (2)	176 (3)

Symmetry codes: (i) ; (ii) .