(3β,18β,20β)-N-Eth-oxy-carbonyl-methyl-3-nitrato-11-oxoolean-12-ene-29-carboxamide methanol monosolvate.

The title compound, C(34)H(52)N(2)O(7)·CH(4)O, is the methanol solvate of a difunctionalized derivative of the therapeutic agent 18β-glycyrrhetinic acid, a penta-cyclic triterpene. The five six-membered rings of the glycyrrhetinic acid moiety show normal geometries, with four rings in chair conformations and the unsaturated ring in a half-chair conformation. This moiety is substituted by a nitrate ester group and an O-ethyl-glycine group. In the crystal, the nonsolvent mol-ecules are packed parallel to (010) in a herringbone fashion with the nitrato, ethyl-glycine and methanol-O atom being proximate. The methanol solvent mol-ecule is anchored via a donated O-H⋯O(ac-yl) and an accepted N-H⋯O hydrogen bond, giving rise to infinite zigzag chains of hydrogen bonds parallel to [100]. Two weak intermolecular C-H⋯O interactions to the methanol and to an acyl oxygen establish links along [100] and [010], respectively.

Related literature

For overviews on the therapeutic aspects of glycyrrhetinic acid, see: Baran et al. (1974 ▶); Asl & Hosseinzadeh (2008 ▶). For the synthesis of new derivatives of 18β-glycyrrhetinic acid and their effect on 11β-hy­droxy­steroid dehydrogenase, see: Su et al. (2004 ▶); Beseda et al. (2010 ▶); Amer et al. (2010 ▶). For the crystal structure of 18β-glycyrrhetinic acid, see: Campsteyn et al. (1977 ▶); Alvarez-Larena et al. (2007 ▶). For the crystal structures of derivatives of 18β-glycyrrhetinic acid, see: Beseda et al. (2010 ▶); Amer et al. (2010 ▶); Czollner et al. (2011 ▶).

Experimental

Crystal data

C34H52N2O7·CH4O

M = 632.82

Orthorhombic,

a = 10.1598 (8) Å

b = 11.1275 (9) Å

c = 30.387 (2) Å

V = 3435.3 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 100 K

0.55 × 0.53 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.88, T max = 1.00

49017 measured reflections

5565 independent reflections

5044 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.122

S = 1.10

5565 reflections

416 parameters

H-atom parameters constrained

Δρmax = 0.68 e Å−3

Δρmin = −0.38 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: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812012561/xu5490sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812012561/xu5490Isup2.hkl

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

C34H52N2O7·CH4O	F(000) = 1376
Mr = 632.82	Dx = 1.224 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9832 reflections
a = 10.1598 (8) Å	θ = 2.4–30.4°
b = 11.1275 (9) Å	µ = 0.09 mm−1
c = 30.387 (2) Å	T = 100 K
V = 3435.3 (5) Å3	Plate, colourless
Z = 4	0.55 × 0.53 × 0.15 mm

Bruker Kappa APEXII CCD diffractometer	5565 independent reflections
Radiation source: fine-focus sealed tube	5044 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
φ and ω scans	θmax = 30.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→14
Tmin = 0.88, Tmax = 1.00	k = −15→15
49017 measured reflections	l = −42→42

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0659P)2 + 1.0649P] where P = (Fo2 + 2Fc2)/3
5565 reflections	(Δ/σ)max < 0.001
416 parameters	Δρmax = 0.68 e Å−3
0 restraints	Δρmin = −0.38 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	1.24049 (15)	0.35130 (14)	0.11927 (4)	0.0235 (3)
O2	1.36996 (17)	0.22076 (15)	0.15496 (6)	0.0312 (4)
O3	1.43774 (19)	0.3126 (2)	0.09603 (6)	0.0416 (5)
O4	0.97494 (15)	0.54091 (15)	0.30766 (5)	0.0278 (3)
O5	0.43899 (16)	0.36705 (16)	0.49446 (6)	0.0332 (4)
O6	0.7628 (3)	0.6180 (2)	0.45042 (6)	0.0531 (6)
O7	0.7763 (2)	0.66683 (18)	0.52248 (6)	0.0458 (5)
N1	1.35858 (19)	0.28882 (17)	0.12425 (6)	0.0266 (4)
N2	0.64623 (18)	0.40002 (17)	0.47119 (6)	0.0259 (4)
H2N	0.7079	0.3830	0.4518	0.031*
C1	1.09373 (18)	0.41293 (17)	0.23173 (6)	0.0171 (3)
H1A	1.1245	0.4667	0.2556	0.021*
H1B	1.0903	0.3302	0.2437	0.021*
C2	1.19274 (18)	0.41682 (17)	0.19389 (6)	0.0181 (3)
H2A	1.2026	0.5006	0.1835	0.022*
H2B	1.2796	0.3888	0.2045	0.022*
C3	1.14771 (19)	0.33810 (17)	0.15614 (6)	0.0179 (3)
H3	1.1464	0.2523	0.1659	0.021*
C4	1.01167 (19)	0.37181 (18)	0.13737 (6)	0.0192 (3)
C5	0.91408 (18)	0.37368 (16)	0.17714 (6)	0.0162 (3)
H5	0.9131	0.2891	0.1883	0.019*
C6	0.77159 (19)	0.39889 (18)	0.16342 (6)	0.0208 (4)
H6A	0.7604	0.4858	0.1575	0.025*
H6B	0.7510	0.3544	0.1360	0.025*
C7	0.67731 (19)	0.35989 (18)	0.20001 (6)	0.0210 (4)
H7A	0.6826	0.2715	0.2033	0.025*
H7B	0.5863	0.3800	0.1910	0.025*
C8	0.70534 (17)	0.41850 (16)	0.24500 (6)	0.0152 (3)
C9	0.85615 (17)	0.41574 (16)	0.25560 (6)	0.0145 (3)
H9	0.8759	0.3294	0.2618	0.017*
C10	0.95365 (18)	0.45125 (15)	0.21774 (5)	0.0146 (3)
C11	0.87786 (18)	0.47971 (17)	0.29951 (6)	0.0180 (3)
C12	0.77583 (18)	0.46438 (17)	0.33337 (6)	0.0178 (3)
H12	0.7923	0.4972	0.3617	0.021*
C13	0.66101 (17)	0.40716 (16)	0.32705 (6)	0.0160 (3)
C14	0.63076 (18)	0.34767 (16)	0.28289 (6)	0.0159 (3)
C15	0.48044 (18)	0.34403 (18)	0.27359 (6)	0.0197 (4)
H15A	0.4530	0.4229	0.2616	0.024*
H15B	0.4631	0.2828	0.2507	0.024*
C16	0.39605 (19)	0.31545 (18)	0.31388 (7)	0.0217 (4)
H16A	0.4151	0.2324	0.3237	0.026*
H16B	0.3020	0.3192	0.3055	0.026*
C17	0.42072 (18)	0.40218 (18)	0.35212 (7)	0.0200 (4)
C18	0.56722 (18)	0.39382 (17)	0.36569 (6)	0.0178 (3)
H18	0.5851	0.4618	0.3863	0.021*
C19	0.5989 (2)	0.27590 (18)	0.39060 (6)	0.0212 (4)
H19A	0.5889	0.2075	0.3700	0.025*
H19B	0.6921	0.2781	0.4001	0.025*
C20	0.5117 (2)	0.25336 (19)	0.43106 (7)	0.0242 (4)
C21	0.3676 (2)	0.2538 (2)	0.41571 (8)	0.0278 (4)
H21A	0.3525	0.1853	0.3956	0.033*
H21B	0.3090	0.2437	0.4415	0.033*
C22	0.3332 (2)	0.3711 (2)	0.39203 (7)	0.0262 (4)
H22A	0.3390	0.4378	0.4135	0.031*
H22B	0.2407	0.3664	0.3820	0.031*
C23	0.9709 (2)	0.2695 (2)	0.10587 (7)	0.0273 (4)
H23A	1.0442	0.2508	0.0861	0.041*
H23B	0.8944	0.2949	0.0885	0.041*
H23C	0.9481	0.1979	0.1230	0.041*
C24	1.0178 (2)	0.4897 (2)	0.11115 (7)	0.0269 (4)
H24A	1.0641	0.5508	0.1285	0.040*
H24B	0.9282	0.5174	0.1048	0.040*
H24C	1.0649	0.4761	0.0835	0.040*
C25	0.9541 (2)	0.58783 (17)	0.20873 (6)	0.0210 (4)
H25A	0.9410	0.6313	0.2364	0.032*
H25B	0.8829	0.6078	0.1882	0.032*
H25C	1.0388	0.6111	0.1958	0.032*
C26	0.6570 (2)	0.54965 (17)	0.24300 (7)	0.0209 (4)
H26A	0.6996	0.5909	0.2183	0.031*
H26B	0.6793	0.5906	0.2706	0.031*
H26C	0.5614	0.5508	0.2389	0.031*
C27	0.6788 (2)	0.21528 (16)	0.28652 (7)	0.0207 (4)
H27A	0.7626	0.2129	0.3025	0.031*
H27B	0.6910	0.1819	0.2569	0.031*
H27C	0.6131	0.1676	0.3024	0.031*
C28	0.3869 (2)	0.53116 (18)	0.33834 (7)	0.0234 (4)
H28A	0.3980	0.5851	0.3636	0.035*
H28B	0.2955	0.5344	0.3281	0.035*
H28C	0.4457	0.5564	0.3145	0.035*
C29	0.5290 (2)	0.34592 (19)	0.46787 (7)	0.0241 (4)
C30	0.5474 (2)	0.1303 (2)	0.45119 (8)	0.0312 (5)
H30A	0.4898	0.1139	0.4763	0.047*
H30B	0.6393	0.1314	0.4610	0.047*
H30C	0.5359	0.0673	0.4290	0.047*
C31	0.6742 (2)	0.4853 (2)	0.50557 (7)	0.0288 (4)
H31A	0.7311	0.4468	0.5279	0.035*
H31B	0.5908	0.5086	0.5201	0.035*
C32	0.7418 (3)	0.5969 (2)	0.48836 (8)	0.0343 (5)
C33	0.8405 (4)	0.7825 (3)	0.51337 (11)	0.0540 (8)
H33A	0.8960	0.7756	0.4867	0.065*
H33B	0.8976	0.8052	0.5384	0.065*
C34	0.7380 (4)	0.8759 (3)	0.50655 (12)	0.0644 (10)
H34A	0.6815	0.8527	0.4818	0.097*
H34B	0.7803	0.9530	0.5001	0.097*
H34C	0.6846	0.8835	0.5333	0.097*
O8	0.38763 (16)	0.1963 (2)	0.55652 (6)	0.0416 (5)
H8	0.4016	0.2506	0.5379	0.062*
C35	0.5070 (2)	0.1671 (3)	0.57816 (8)	0.0371 (5)
H35A	0.5336	0.2342	0.5970	0.056*
H35B	0.5757	0.1518	0.5562	0.056*
H35C	0.4941	0.0950	0.5962	0.056*

	U11	U22	U33	U12	U13	U23
O1	0.0232 (7)	0.0269 (7)	0.0203 (6)	0.0070 (6)	0.0020 (5)	0.0015 (5)
O2	0.0276 (8)	0.0276 (7)	0.0384 (8)	0.0093 (7)	0.0014 (7)	0.0064 (7)
O3	0.0313 (9)	0.0535 (12)	0.0399 (9)	0.0083 (9)	0.0150 (8)	0.0041 (9)
O4	0.0220 (7)	0.0355 (8)	0.0259 (7)	−0.0126 (7)	0.0030 (6)	−0.0124 (6)
O5	0.0256 (7)	0.0384 (9)	0.0356 (8)	0.0058 (7)	0.0138 (7)	0.0080 (7)
O6	0.0758 (15)	0.0490 (11)	0.0345 (9)	−0.0191 (12)	0.0162 (10)	0.0097 (8)
O7	0.0582 (13)	0.0365 (9)	0.0427 (10)	−0.0103 (9)	0.0196 (9)	−0.0067 (8)
N1	0.0239 (8)	0.0255 (8)	0.0305 (9)	0.0041 (7)	0.0031 (7)	−0.0032 (7)
N2	0.0236 (8)	0.0304 (9)	0.0238 (8)	0.0012 (7)	0.0078 (7)	0.0030 (7)
C1	0.0158 (7)	0.0190 (8)	0.0166 (7)	−0.0007 (7)	−0.0027 (6)	0.0005 (6)
C2	0.0171 (8)	0.0192 (8)	0.0181 (7)	−0.0003 (7)	−0.0011 (6)	−0.0013 (6)
C3	0.0190 (8)	0.0178 (7)	0.0169 (7)	0.0040 (7)	−0.0012 (7)	−0.0005 (6)
C4	0.0205 (8)	0.0216 (8)	0.0156 (7)	0.0025 (7)	−0.0044 (7)	−0.0018 (6)
C5	0.0180 (8)	0.0153 (7)	0.0153 (7)	0.0008 (6)	−0.0040 (6)	−0.0027 (6)
C6	0.0185 (8)	0.0246 (9)	0.0192 (8)	0.0032 (7)	−0.0056 (7)	−0.0002 (7)
C7	0.0174 (8)	0.0230 (9)	0.0226 (8)	−0.0012 (7)	−0.0072 (7)	−0.0036 (7)
C8	0.0131 (7)	0.0136 (7)	0.0188 (7)	0.0003 (6)	−0.0042 (6)	−0.0010 (6)
C9	0.0135 (7)	0.0136 (7)	0.0164 (7)	−0.0016 (6)	−0.0027 (6)	−0.0010 (6)
C10	0.0163 (7)	0.0121 (7)	0.0153 (7)	−0.0001 (6)	−0.0026 (6)	−0.0003 (6)
C11	0.0161 (8)	0.0189 (8)	0.0192 (8)	−0.0019 (7)	−0.0014 (6)	−0.0027 (6)
C12	0.0161 (8)	0.0187 (8)	0.0184 (7)	−0.0010 (7)	−0.0017 (6)	−0.0007 (6)
C13	0.0132 (7)	0.0136 (7)	0.0213 (8)	0.0013 (6)	−0.0020 (6)	0.0025 (6)
C14	0.0132 (7)	0.0123 (7)	0.0221 (8)	−0.0003 (6)	−0.0034 (6)	0.0003 (6)
C15	0.0138 (8)	0.0183 (8)	0.0270 (9)	−0.0022 (7)	−0.0068 (7)	−0.0003 (7)
C16	0.0136 (8)	0.0190 (8)	0.0324 (10)	−0.0016 (7)	−0.0039 (7)	0.0018 (7)
C17	0.0128 (7)	0.0185 (8)	0.0286 (9)	−0.0001 (6)	−0.0002 (7)	0.0041 (7)
C18	0.0127 (7)	0.0181 (8)	0.0224 (8)	0.0001 (6)	−0.0007 (6)	0.0029 (7)
C19	0.0171 (8)	0.0215 (8)	0.0251 (9)	0.0029 (7)	0.0010 (7)	0.0056 (7)
C20	0.0204 (9)	0.0222 (9)	0.0300 (10)	0.0016 (8)	0.0051 (8)	0.0098 (8)
C21	0.0189 (9)	0.0272 (10)	0.0374 (11)	−0.0037 (8)	0.0045 (8)	0.0112 (9)
C22	0.0146 (8)	0.0294 (10)	0.0346 (10)	0.0004 (8)	0.0036 (8)	0.0086 (9)
C23	0.0278 (10)	0.0332 (11)	0.0209 (8)	0.0019 (9)	−0.0054 (8)	−0.0098 (8)
C24	0.0278 (10)	0.0320 (10)	0.0208 (9)	0.0063 (9)	−0.0019 (8)	0.0072 (8)
C25	0.0241 (9)	0.0130 (7)	0.0260 (9)	−0.0010 (7)	0.0022 (7)	−0.0001 (7)
C26	0.0195 (8)	0.0165 (8)	0.0268 (9)	0.0050 (7)	−0.0015 (7)	0.0041 (7)
C27	0.0185 (8)	0.0131 (7)	0.0306 (9)	0.0001 (7)	−0.0015 (7)	0.0015 (7)
C28	0.0178 (8)	0.0200 (8)	0.0323 (10)	0.0023 (7)	−0.0011 (8)	0.0037 (7)
C29	0.0208 (9)	0.0240 (9)	0.0273 (9)	0.0051 (8)	0.0054 (8)	0.0114 (8)
C30	0.0324 (11)	0.0251 (10)	0.0362 (11)	0.0044 (9)	0.0045 (10)	0.0124 (9)
C31	0.0334 (11)	0.0295 (10)	0.0233 (9)	0.0013 (9)	0.0068 (9)	0.0064 (8)
C32	0.0373 (12)	0.0313 (11)	0.0343 (11)	−0.0010 (10)	0.0121 (10)	0.0040 (9)
C33	0.0566 (19)	0.0508 (17)	0.0546 (17)	−0.0206 (16)	0.0115 (15)	−0.0036 (14)
C34	0.079 (2)	0.0497 (18)	0.064 (2)	−0.0230 (19)	−0.014 (2)	0.0164 (16)
O8	0.0170 (7)	0.0702 (14)	0.0375 (9)	−0.0064 (8)	−0.0026 (7)	0.0239 (9)
C35	0.0225 (10)	0.0544 (15)	0.0344 (11)	−0.0013 (11)	−0.0057 (9)	0.0076 (11)

O1—N1	1.395 (2)	C16—H16B	0.9900
O1—C3	1.472 (2)	C17—C28	1.534 (3)
O2—N1	1.207 (2)	C17—C22	1.543 (3)
O3—N1	1.205 (3)	C17—C18	1.547 (3)
O4—C11	1.224 (2)	C18—C19	1.549 (3)
O5—C29	1.243 (3)	C18—H18	1.0000
O6—C32	1.196 (3)	C19—C20	1.536 (3)
O7—C32	1.343 (3)	C19—H19A	0.9900
O7—C33	1.469 (4)	C19—H19B	0.9900
N2—C29	1.338 (3)	C20—C29	1.531 (3)
N2—C31	1.440 (3)	C20—C21	1.537 (3)
N2—H2N	0.8800	C20—C30	1.543 (3)
C1—C2	1.528 (3)	C21—C22	1.531 (3)
C1—C10	1.545 (3)	C21—H21A	0.9900
C1—H1A	0.9900	C21—H21B	0.9900
C1—H1B	0.9900	C22—H22A	0.9900
C2—C3	1.514 (3)	C22—H22B	0.9900
C2—H2A	0.9900	C23—H23A	0.9800
C2—H2B	0.9900	C23—H23B	0.9800
C3—C4	1.542 (3)	C23—H23C	0.9800
C3—H3	1.0000	C24—H24A	0.9800
C4—C24	1.536 (3)	C24—H24B	0.9800
C4—C23	1.544 (3)	C24—H24C	0.9800
C4—C5	1.563 (3)	C25—H25A	0.9800
C5—C6	1.532 (3)	C25—H25B	0.9800
C5—C10	1.559 (2)	C25—H25C	0.9800
C5—H5	1.0000	C26—H26A	0.9800
C6—C7	1.530 (3)	C26—H26B	0.9800
C6—H6A	0.9900	C26—H26C	0.9800
C6—H6B	0.9900	C27—H27A	0.9800
C7—C8	1.541 (2)	C27—H27B	0.9800
C7—H7A	0.9900	C27—H27C	0.9800
C7—H7B	0.9900	C28—H28A	0.9800
C8—C26	1.541 (3)	C28—H28B	0.9800
C8—C9	1.566 (2)	C28—H28C	0.9800
C8—C14	1.588 (3)	C30—H30A	0.9800
C9—C11	1.528 (2)	C30—H30B	0.9800
C9—C10	1.569 (2)	C30—H30C	0.9800
C9—H9	1.0000	C31—C32	1.513 (3)
C10—C25	1.544 (2)	C31—H31A	0.9900
C11—C12	1.470 (3)	C31—H31B	0.9900
C12—C13	1.343 (2)	C33—C34	1.486 (6)
C12—H12	0.9500	C33—H33A	0.9900
C13—C18	1.519 (3)	C33—H33B	0.9900
C13—C14	1.527 (3)	C34—H34A	0.9800
C14—C15	1.554 (3)	C34—H34B	0.9800
C14—C27	1.556 (2)	C34—H34C	0.9800
C15—C16	1.528 (3)	O8—C35	1.417 (3)
C15—H15A	0.9900	O8—H8	0.8400
C15—H15B	0.9900	C35—H35A	0.9800
C16—C17	1.531 (3)	C35—H35B	0.9800
C16—H16A	0.9900	C35—H35C	0.9800
N1—O1—C3	114.75 (14)	C13—C18—C19	109.26 (15)
C32—O7—C33	118.6 (2)	C17—C18—C19	112.42 (15)
O3—N1—O2	128.6 (2)	C13—C18—H18	107.3
O3—N1—O1	112.79 (18)	C17—C18—H18	107.3
O2—N1—O1	118.61 (17)	C19—C18—H18	107.3
C29—N2—C31	121.79 (18)	C20—C19—C18	114.16 (16)
C29—N2—H2N	119.1	C20—C19—H19A	108.7
C31—N2—H2N	119.1	C18—C19—H19A	108.7
C2—C1—C10	113.04 (14)	C20—C19—H19B	108.7
C2—C1—H1A	109.0	C18—C19—H19B	108.7
C10—C1—H1A	109.0	H19A—C19—H19B	107.6
C2—C1—H1B	109.0	C29—C20—C19	114.11 (17)
C10—C1—H1B	109.0	C29—C20—C21	109.22 (18)
H1A—C1—H1B	107.8	C19—C20—C21	107.84 (17)
C3—C2—C1	110.78 (15)	C29—C20—C30	106.28 (17)
C3—C2—H2A	109.5	C19—C20—C30	109.05 (18)
C1—C2—H2A	109.5	C21—C20—C30	110.33 (18)
C3—C2—H2B	109.5	C22—C21—C20	111.27 (17)
C1—C2—H2B	109.5	C22—C21—H21A	109.4
H2A—C2—H2B	108.1	C20—C21—H21A	109.4
O1—C3—C2	108.99 (15)	C22—C21—H21B	109.4
O1—C3—C4	105.56 (14)	C20—C21—H21B	109.4
C2—C3—C4	114.24 (15)	H21A—C21—H21B	108.0
O1—C3—H3	109.3	C21—C22—C17	115.40 (18)
C2—C3—H3	109.3	C21—C22—H22A	108.4
C4—C3—H3	109.3	C17—C22—H22A	108.4
C24—C4—C3	111.32 (17)	C21—C22—H22B	108.4
C24—C4—C23	108.59 (16)	C17—C22—H22B	108.4
C3—C4—C23	106.91 (16)	H22A—C22—H22B	107.5
C24—C4—C5	114.53 (16)	C4—C23—H23A	109.5
C3—C4—C5	106.60 (14)	C4—C23—H23B	109.5
C23—C4—C5	108.59 (16)	H23A—C23—H23B	109.5
C6—C5—C10	110.96 (15)	C4—C23—H23C	109.5
C6—C5—C4	113.04 (14)	H23A—C23—H23C	109.5
C10—C5—C4	117.11 (15)	H23B—C23—H23C	109.5
C6—C5—H5	104.8	C4—C24—H24A	109.5
C10—C5—H5	104.8	C4—C24—H24B	109.5
C4—C5—H5	104.8	H24A—C24—H24B	109.5
C7—C6—C5	109.99 (15)	C4—C24—H24C	109.5
C7—C6—H6A	109.7	H24A—C24—H24C	109.5
C5—C6—H6A	109.7	H24B—C24—H24C	109.5
C7—C6—H6B	109.7	C10—C25—H25A	109.5
C5—C6—H6B	109.7	C10—C25—H25B	109.5
H6A—C6—H6B	108.2	H25A—C25—H25B	109.5
C6—C7—C8	114.13 (16)	C10—C25—H25C	109.5
C6—C7—H7A	108.7	H25A—C25—H25C	109.5
C8—C7—H7A	108.7	H25B—C25—H25C	109.5
C6—C7—H7B	108.7	C8—C26—H26A	109.5
C8—C7—H7B	108.7	C8—C26—H26B	109.5
H7A—C7—H7B	107.6	H26A—C26—H26B	109.5
C26—C8—C7	107.86 (15)	C8—C26—H26C	109.5
C26—C8—C9	109.78 (15)	H26A—C26—H26C	109.5
C7—C8—C9	110.79 (15)	H26B—C26—H26C	109.5
C26—C8—C14	110.28 (14)	C14—C27—H27A	109.5
C7—C8—C14	110.18 (14)	C14—C27—H27B	109.5
C9—C8—C14	107.95 (14)	H27A—C27—H27B	109.5
C11—C9—C8	108.15 (14)	C14—C27—H27C	109.5
C11—C9—C10	115.58 (14)	H27A—C27—H27C	109.5
C8—C9—C10	117.53 (14)	H27B—C27—H27C	109.5
C11—C9—H9	104.7	C17—C28—H28A	109.5
C8—C9—H9	104.7	C17—C28—H28B	109.5
C10—C9—H9	104.7	H28A—C28—H28B	109.5
C25—C10—C1	108.51 (15)	C17—C28—H28C	109.5
C25—C10—C5	113.92 (14)	H28A—C28—H28C	109.5
C1—C10—C5	107.61 (14)	H28B—C28—H28C	109.5
C25—C10—C9	112.32 (15)	O5—C29—N2	121.4 (2)
C1—C10—C9	108.08 (13)	O5—C29—C20	121.2 (2)
C5—C10—C9	106.15 (14)	N2—C29—C20	117.40 (18)
O4—C11—C12	119.42 (17)	C20—C30—H30A	109.5
O4—C11—C9	123.50 (17)	C20—C30—H30B	109.5
C12—C11—C9	117.08 (15)	H30A—C30—H30B	109.5
C13—C12—C11	124.57 (17)	C20—C30—H30C	109.5
C13—C12—H12	117.7	H30A—C30—H30C	109.5
C11—C12—H12	117.7	H30B—C30—H30C	109.5
C12—C13—C18	118.73 (16)	N2—C31—C32	112.32 (18)
C12—C13—C14	120.39 (16)	N2—C31—H31A	109.1
C18—C13—C14	120.69 (15)	C32—C31—H31A	109.1
C13—C14—C15	111.65 (15)	N2—C31—H31B	109.1
C13—C14—C27	106.56 (15)	C32—C31—H31B	109.1
C15—C14—C27	107.25 (15)	H31A—C31—H31B	107.9
C13—C14—C8	109.02 (14)	O6—C32—O7	125.7 (2)
C15—C14—C8	110.50 (15)	O6—C32—C31	125.2 (2)
C27—C14—C8	111.82 (15)	O7—C32—C31	109.10 (19)
C16—C15—C14	114.29 (16)	O7—C33—C34	109.2 (3)
C16—C15—H15A	108.7	O7—C33—H33A	109.8
C14—C15—H15A	108.7	C34—C33—H33A	109.8
C16—C15—H15B	108.7	O7—C33—H33B	109.8
C14—C15—H15B	108.7	C34—C33—H33B	109.8
H15A—C15—H15B	107.6	H33A—C33—H33B	108.3
C15—C16—C17	112.65 (16)	C33—C34—H34A	109.5
C15—C16—H16A	109.1	C33—C34—H34B	109.5
C17—C16—H16A	109.1	H34A—C34—H34B	109.5
C15—C16—H16B	109.1	C33—C34—H34C	109.5
C17—C16—H16B	109.1	H34A—C34—H34C	109.5
H16A—C16—H16B	107.8	H34B—C34—H34C	109.5
C16—C17—C28	110.23 (16)	C35—O8—H8	109.5
C16—C17—C22	111.17 (16)	O8—C35—H35A	109.5
C28—C17—C22	107.16 (17)	O8—C35—H35B	109.5
C16—C17—C18	108.77 (16)	H35A—C35—H35B	109.5
C28—C17—C18	110.14 (16)	O8—C35—H35C	109.5
C22—C17—C18	109.36 (16)	H35A—C35—H35C	109.5
C13—C18—C17	113.05 (15)	H35B—C35—H35C	109.5
C3—O1—N1—O3	−171.98 (18)	C12—C13—C14—C27	91.53 (19)
C3—O1—N1—O2	7.6 (3)	C18—C13—C14—C27	−83.32 (19)
C10—C1—C2—C3	−57.2 (2)	C12—C13—C14—C8	−29.3 (2)
N1—O1—C3—C2	77.22 (19)	C18—C13—C14—C8	155.85 (15)
N1—O1—C3—C4	−159.65 (15)	C26—C8—C14—C13	−61.40 (18)
C1—C2—C3—O1	175.89 (14)	C7—C8—C14—C13	179.64 (15)
C1—C2—C3—C4	58.1 (2)	C9—C8—C14—C13	58.54 (18)
O1—C3—C4—C24	−47.73 (19)	C26—C8—C14—C15	61.66 (19)
C2—C3—C4—C24	72.0 (2)	C7—C8—C14—C15	−57.31 (19)
O1—C3—C4—C23	70.72 (19)	C9—C8—C14—C15	−178.41 (15)
C2—C3—C4—C23	−169.56 (16)	C26—C8—C14—C27	−178.96 (15)
O1—C3—C4—C5	−173.29 (14)	C7—C8—C14—C27	62.08 (18)
C2—C3—C4—C5	−53.6 (2)	C9—C8—C14—C27	−59.02 (18)
C24—C4—C5—C6	59.7 (2)	C13—C14—C15—C16	−39.6 (2)
C3—C4—C5—C6	−176.67 (16)	C27—C14—C15—C16	76.7 (2)
C23—C4—C5—C6	−61.8 (2)	C8—C14—C15—C16	−161.15 (15)
C24—C4—C5—C10	−71.1 (2)	C14—C15—C16—C17	55.7 (2)
C3—C4—C5—C10	52.5 (2)	C15—C16—C17—C28	60.9 (2)
C23—C4—C5—C10	167.32 (16)	C15—C16—C17—C22	179.60 (16)
C10—C5—C6—C7	−64.4 (2)	C15—C16—C17—C18	−59.9 (2)
C4—C5—C6—C7	161.69 (16)	C12—C13—C18—C17	144.52 (17)
C5—C6—C7—C8	56.1 (2)	C14—C13—C18—C17	−40.5 (2)
C6—C7—C8—C26	75.1 (2)	C12—C13—C18—C19	−89.5 (2)
C6—C7—C8—C9	−45.1 (2)	C14—C13—C18—C19	85.45 (19)
C6—C7—C8—C14	−164.45 (15)	C16—C17—C18—C13	51.0 (2)
C26—C8—C9—C11	58.58 (18)	C28—C17—C18—C13	−69.9 (2)
C7—C8—C9—C11	177.61 (14)	C22—C17—C18—C13	172.58 (16)
C14—C8—C9—C11	−61.66 (18)	C16—C17—C18—C19	−73.29 (19)
C26—C8—C9—C10	−74.52 (19)	C28—C17—C18—C19	165.80 (16)
C7—C8—C9—C10	44.5 (2)	C22—C17—C18—C19	48.3 (2)
C14—C8—C9—C10	165.23 (14)	C13—C18—C19—C20	179.00 (16)
C2—C1—C10—C25	−70.77 (19)	C17—C18—C19—C20	−54.6 (2)
C2—C1—C10—C5	52.94 (19)	C18—C19—C20—C29	−64.7 (2)
C2—C1—C10—C9	167.18 (14)	C18—C19—C20—C21	56.9 (2)
C6—C5—C10—C25	−64.3 (2)	C18—C19—C20—C30	176.67 (18)
C4—C5—C10—C25	67.5 (2)	C29—C20—C21—C22	68.4 (2)
C6—C5—C10—C1	175.38 (15)	C19—C20—C21—C22	−56.1 (2)
C4—C5—C10—C1	−52.79 (19)	C30—C20—C21—C22	−175.09 (19)
C6—C5—C10—C9	59.85 (18)	C20—C21—C22—C17	56.4 (3)
C4—C5—C10—C9	−168.32 (15)	C16—C17—C22—C21	69.3 (2)
C11—C9—C10—C25	−55.9 (2)	C28—C17—C22—C21	−170.23 (18)
C8—C9—C10—C25	73.8 (2)	C18—C17—C22—C21	−50.9 (2)
C11—C9—C10—C1	63.80 (19)	C31—N2—C29—O5	0.0 (3)
C8—C9—C10—C1	−166.48 (15)	C31—N2—C29—C20	−177.81 (18)
C11—C9—C10—C5	179.00 (15)	C19—C20—C29—O5	154.10 (19)
C8—C9—C10—C5	−51.27 (19)	C21—C20—C29—O5	33.3 (2)
C8—C9—C11—O4	−144.77 (19)	C30—C20—C29—O5	−85.7 (2)
C10—C9—C11—O4	−10.6 (3)	C19—C20—C29—N2	−28.1 (3)
C8—C9—C11—C12	35.9 (2)	C21—C20—C29—N2	−148.88 (18)
C10—C9—C11—C12	170.02 (16)	C30—C20—C29—N2	92.1 (2)
O4—C11—C12—C13	174.69 (19)	C29—N2—C31—C32	−134.1 (2)
C9—C11—C12—C13	−5.9 (3)	C33—O7—C32—O6	2.8 (4)
C11—C12—C13—C18	177.53 (17)	C33—O7—C32—C31	−178.3 (3)
C11—C12—C13—C14	2.6 (3)	N2—C31—C32—O6	4.9 (4)
C12—C13—C14—C15	−151.67 (17)	N2—C31—C32—O7	−174.1 (2)
C18—C13—C14—C15	33.5 (2)	C32—O7—C33—C34	87.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O8i	0.88	2.04	2.806 (3)	144
O8—H8···O5	0.84	1.89	2.728 (2)	177
C1—H1A···O4	0.99	2.34	2.968 (2)	120
C19—H19B···O8i	0.99	2.40	3.359 (3)	163
C25—H25A···O4	0.98	2.41	3.058 (3)	123
C34—H34B···O5ii	0.98	2.58	3.515 (4)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O8i	0.88	2.04	2.806 (3)	144
O8—H8⋯O5	0.84	1.89	2.728 (2)	177
C1—H1A⋯O4	0.99	2.34	2.968 (2)	120
C19—H19B⋯O8i	0.99	2.40	3.359 (3)	163
C25—H25A⋯O4	0.98	2.41	3.058 (3)	123
C34—H34B⋯O5ii	0.98	2.58	3.515 (4)	160

Symmetry codes: (i) ; (ii) .