(E)-17β,19-Epoxy­methano-17,23,24-tridemethyl-4-nor-5β,18α-olean-3-one oxime

Froelich, A.; Kazakova, O.B.; Tolstikov, G.; Gzella, A.K.

doi:10.1107/S1600536809016675

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1262

doi:10.1107/S1600536809016675

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(E)-17β,19-Epoxymethano-17,23,24-tridemethyl-4-nor-5β,18α-olean-3-one oxime

Anna Froelich,^a Oxana B. Kazakova,^b Genrikh Tolstikov ^b and Andrzej K. Gzella ^a ^*

^aDepartment of Organic Chemistry, Poznan University of Medical Sciences, ul. Grunwaldzka 6, 60-780 Poznań, Poland, and ^bInstitute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences, 71, prosp. Oktyabrya, 450054 Ufa, Russian Federation
^*Correspondence e-mail: akgzella@ump.edu.pl

(Received 21 January 2009; accepted 4 May 2009; online 14 May 2009)

In the pentacyclic triterpenoide skeleton of the title molecule, C₂₇H₄₃NO₂ [systematic name: (3E,3aS,5aR,5bR,7aR,11R,11aR,11bR,13aR,13bR)-5a,5b,10,10,13b-pentamethylicosahydro-1H-11,7a-(epoxymethano)cyclopenta[a]chrysen-3-one oxime], the five-membered ring A has an envelope conformation, while the six-membered rings B–E adopt chair conformations. Rings A and B are cis-fused. The hydroximino group has an E configuration. Strong intermolecular O—H⋯O hydrogen bonds link the molecules into helical chains.

Related literature

For the syntheses of related compounds, see: Medvedeva et al. (2004 , 2006 ); Gzella et al. (1997 , 1998 ); Zaprutko (1995 , 1997 ). For a description of the Cambridge Structural Database, see: Allen (2002 ). For puckering parameters, see: Cremer & Pople (1975 ); Spek (2009 ).

Experimental

Crystal data

C₂₇H₄₃NO₂
M_r = 413.62
Orthorhombic, P 2₁ 2₁ 2₁
a = 12.5887 (16) Å
b = 13.2550 (11) Å
c = 14.5355 (12) Å
V = 2425.4 (4) Å³
Z = 4
Cu Kα radiation
μ = 0.53 mm⁻¹
T = 293 K
0.40 × 0.22 × 0.13 mm

Data collection

Kuma Diffraction KM-4 diffractometer
Absorption correction: none
4994 measured reflections
2610 independent reflections
2240 reflections with I > 2σ(I)
R_int = 0.037
3 standard reflections every 100 reflections intensity decay: 2.3%

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.094
S = 1.06
2610 reflections
281 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.87 (3)	1.93 (3)	2.782 (2)	164 (3)
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+2, z+{\script{1\over 2}}]$ .

Data collection: KM-4 Software (Kuma Diffraction, 1996 $[Kuma Diffraction (1996). KM-4 Software. Kuma Diffraction, Wrocław, Poland.]$ ); cell refinement: KM-4 Software; data reduction: KM-4 Software; 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: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809016675/fb2138sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016675/fb2138Isup2.hkl

checkCIF report

Comment top

One of the steps in our synthesis of the title compound, (E)-17β,19-epoxymethano-17,23,24-tridemethyl-4-nor-5β,18α-olean-3-one oxime (Scheme 1; Fig. 3 - (IV)), from allobetulin (Fig. 3 - (I)) involved ozonolysis of the intermediate δ-apoallobetulin, Fig. 3 - (II), to give 17β,19-epoxymethano-17,23,24-tridemethyl-4-nor-5β,18α-olean-3-one (Fig. 3 - (III)) as the transformation product with a cis-junction between the A/B rings. It should be mentioned that synthetic conversions to new derivatives with altered junction of A/B rings are rarely observed in triterpenoids of the oleanane group [Zaprutko (1995, 1997); Gzella et al. (1997); Gzella et al. (1998); Medvedeva et al. (2004)].

The X-ray structure determination of the title compound was carried out in order to confirm its spatial structure that had been proposed on the basis of spectroscopic data by Medvedeva et al. (2004).

The results obtained for the title compound confirm the cis-junction of A/B rings. The corresponding interplanar angle between the least-squares planes of the A/B rings is 71.85 (8)°. The H atom at the C5 asymmetric centre exhibits β-orientation and occupies a pseudo-axial position with respect to the A ring and an equatorial position to the B ring [the angles of the H5—C5 bond vector to the Cremer & Pople A and B ring plane normals are 9.60 (9) and 64.05 (7)°, respectively (Cremer & Pople, 1975; Spek, 2009)]. The torsion angle H5—C5—C10—C25 of 38° reveals a halfway conformation between synperiplanar and synclinal for bonds H5—C5 and C10—C25.

In the molecule the six-membered rings B–E of the pentacyclic ring system are trans-fused as in allobetuline. The dihedral angles between the least-squares planes of these rings are B/C 7.09 (10), C/D 0.80 (10), D/E 14.95 (9)°.

In the title structure, each of the six-membered rings B–E has a differently distorted chair conformation, whereas both five-membered rings, i.e. the carbocyclic ring A and the heterocyclic ring C17\C18\C19\O2\C28 including epoxymethylene group, assume envelope conformations. The respective puckering parameters (Cremer & Pople, 1975) are Q = 0.373 (2) Å, Φ = 147.1 (4)° and Q = 0.470 (2)Å, Φ = 253.2 (2)°.

The hydroximino function in C3 position has the E configuration. The value of the torsion angle O1—N1—C3—C5 is -179.80 (18)°.

The molecular packing is stabilized by O1—H···O2ⁱ hydrogen bonds (Tab. 1). The hydroxyl hydrogen is donated to the remote-ring epoxy O atom from the neighbour molecule. These hydrogen bonds link the molecules into helical chains which proceed in the c direction (Fig. 2).

Related literature top

For the syntheses of related compounds, see: Medvedeva et al. (2004, 2006); Zaprutko (1995, 1997). For related literature, see: Allen (2002); Cremer & Pople (1975); Gzella et al. (1997, 1998).

Experimental top

The title compound was obtained according to the procedure described by Medvedeva et al. (2004). Single colourless needle-crystals suitable for analysis were grown from ethanol by slow evaporation at room temperature.

Computing details top

Data collection: KM-4 Software (Kuma Diffraction, 1996); cell refinement: KM-4 Software (Kuma Diffraction, 1996); data reduction: KM-4 Software (Kuma Diffraction, 1996); 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: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The title molecule showing the atomic labeling scheme. The displacement ellipsoids are shown at the 30% probability level.
	Fig. 2. The hydrogen bonding (dashed lines) in the title structure. Symmetry code: (i) 0.5-x, 2-y, 1/2+z. The H atoms not involved in hydrogen bonds have been omitted for clarity.

(3E,3aS,5aR,5bR,7aR,11R,11aR, 11bR,13aR,13bR)-5a,5b,10,10,13b- pentamethylicosahydro-1H-11,7a- (epoxymethano)cyclopenta[a]chrysen-3-one oxime top

Crystal data top

C₂₇H₄₃NO₂	D_x = 1.133 Mg m⁻³
M_r = 413.62	Melting point = 468–470 K
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 54 reflections
a = 12.5887 (16) Å	θ = 14.5–28.5°
b = 13.2550 (11) Å	µ = 0.53 mm⁻¹
c = 14.5355 (12) Å	T = 293 K
V = 2425.4 (4) Å³	Needle, colourless
Z = 4	0.40 × 0.22 × 0.13 mm
F(000) = 912

Data collection top

Kuma Diffraction KM-4 diffractometer	R_int = 0.037
Radiation source: fine-focus sealed tube	θ_max = 70.1°, θ_min = 4.5°
Graphite monochromator	h = −15→15
ω/2θ scans	k = 0→16
4994 measured reflections	l = 0→17
2610 independent reflections	3 standard reflections every 100 reflections
2240 reflections with I > 2σ(I)	intensity decay: 2.3%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0523P)² + 0.1689P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2610 reflections	Δρ_max = 0.12 e Å⁻³
281 parameters	Δρ_min = −0.12 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
163 constraints	Extinction coefficient: 0.0011 (2)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₂₇H₄₃NO₂	V = 2425.4 (4) Å³
M_r = 413.62	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 12.5887 (16) Å	µ = 0.53 mm⁻¹
b = 13.2550 (11) Å	T = 293 K
c = 14.5355 (12) Å	0.40 × 0.22 × 0.13 mm

Data collection top

Kuma Diffraction KM-4 diffractometer	R_int = 0.037
4994 measured reflections	3 standard reflections every 100 reflections
2610 independent reflections	intensity decay: 2.3%
2240 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.12 e Å⁻³
2610 reflections	Δρ_min = −0.12 e Å⁻³
281 parameters

Special details top

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. 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.50319 (13)	0.77700 (17)	0.33765 (13)	0.0806 (5)
H1	0.491 (2)	0.762 (2)	0.395 (2)	0.100 (10)*
O2	0.06258 (10)	1.29692 (10)	0.00744 (9)	0.0561 (3)
N1	0.40209 (14)	0.75851 (15)	0.29992 (12)	0.0620 (5)
C1	0.43803 (18)	0.79829 (17)	0.05510 (15)	0.0631 (5)
H1A	0.4512	0.7343	0.0248	0.076*
H1B	0.4666	0.8519	0.0170	0.076*
C2	0.49002 (17)	0.7997 (2)	0.15037 (16)	0.0680 (6)
H2A	0.5484	0.7521	0.1537	0.082*
H2B	0.5162	0.8666	0.1654	0.082*
C3	0.40138 (16)	0.76952 (16)	0.21323 (14)	0.0561 (5)
C5	0.30026 (17)	0.75334 (15)	0.16039 (14)	0.0576 (5)
H5	0.2966	0.6817	0.1441	0.069*
C6	0.19970 (17)	0.77938 (18)	0.21268 (15)	0.0658 (6)
H6A	0.1384	0.7587	0.1769	0.079*
H6B	0.1985	0.7425	0.2703	0.079*
C7	0.19268 (16)	0.89107 (17)	0.23218 (13)	0.0591 (5)
H7A	0.2513	0.9103	0.2718	0.071*
H7B	0.1272	0.9046	0.2652	0.071*
C8	0.19556 (13)	0.95683 (15)	0.14448 (11)	0.0455 (4)
C9	0.29594 (14)	0.92829 (13)	0.08732 (11)	0.0427 (4)
H9	0.3562	0.9514	0.1245	0.051*
C10	0.31736 (16)	0.81371 (14)	0.07022 (13)	0.0526 (4)
C11	0.30140 (16)	0.99102 (13)	−0.00084 (11)	0.0475 (4)
H11A	0.3657	0.9740	−0.0341	0.057*
H11B	0.2413	0.9743	−0.0397	0.057*
C12	0.30058 (14)	1.10370 (13)	0.01892 (12)	0.0457 (4)
H12A	0.2966	1.1402	−0.0388	0.055*
H12B	0.3667	1.1221	0.0488	0.055*
C13	0.20788 (13)	1.13561 (13)	0.08002 (11)	0.0415 (4)
H13	0.1426	1.1200	0.0462	0.050*
C14	0.20485 (13)	1.07304 (15)	0.17054 (10)	0.0456 (4)
C15	0.10814 (16)	1.10874 (19)	0.22730 (13)	0.0629 (6)
H15A	0.0437	1.0922	0.1940	0.075*
H15B	0.1067	1.0722	0.2851	0.075*
C16	0.10920 (18)	1.2219 (2)	0.24743 (13)	0.0690 (6)
H16A	0.0434	1.2399	0.2781	0.083*
H16B	0.1671	1.2365	0.2894	0.083*
C17	0.12164 (15)	1.28729 (17)	0.16219 (13)	0.0558 (5)
C18	0.20859 (14)	1.24982 (14)	0.09614 (12)	0.0476 (4)
H18	0.2786	1.2714	0.1180	0.057*
C19	0.17728 (14)	1.31005 (14)	0.01104 (14)	0.0503 (4)
H19	0.2103	1.2809	−0.0439	0.060*
C20	0.20282 (19)	1.42351 (16)	0.01733 (18)	0.0691 (6)
C21	0.1451 (2)	1.46632 (19)	0.1015 (2)	0.0814 (8)
H21A	0.1774	1.5304	0.1177	0.098*
H21B	0.0718	1.4794	0.0849	0.098*
C22	0.14688 (19)	1.3980 (2)	0.18554 (18)	0.0773 (7)
H22A	0.0954	1.4224	0.2299	0.093*
H22B	0.2165	1.4016	0.2139	0.093*
C25	0.2534 (2)	0.76839 (18)	−0.00933 (16)	0.0742 (7)
H25A	0.2774	0.7008	−0.0209	0.111*
H25B	0.2634	0.8086	−0.0636	0.111*
H25C	0.1794	0.7673	0.0066	0.111*
C26	0.09170 (15)	0.93677 (17)	0.09073 (15)	0.0596 (5)
H26A	0.0862	0.8661	0.0770	0.089*
H26B	0.0924	0.9746	0.0344	0.089*
H26C	0.0320	0.9572	0.1274	0.089*
C27	0.30490 (15)	1.09487 (17)	0.22921 (12)	0.0561 (5)
H27A	0.3666	1.0694	0.1981	0.084*
H27B	0.2981	1.0624	0.2879	0.084*
H27C	0.3120	1.1663	0.2380	0.084*
C28	0.02439 (14)	1.28226 (19)	0.09950 (14)	0.0597 (5)
H28A	−0.0103	1.2172	0.1051	0.072*
H28B	−0.0261	1.3346	0.1157	0.072*
C29	0.3229 (2)	1.43864 (18)	0.0252 (2)	0.0896 (9)
H29A	0.3395	1.5088	0.0175	0.134*
H29B	0.3581	1.4000	−0.0216	0.134*
H29C	0.3465	1.4166	0.0847	0.134*
C30	0.1626 (2)	1.47527 (18)	−0.0701 (2)	0.0876 (8)
H30A	0.1719	1.5469	−0.0646	0.131*
H30B	0.0886	1.4603	−0.0784	0.131*
H30C	0.2020	1.4510	−0.1222	0.131*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0541 (8)	0.1201 (15)	0.0675 (10)	0.0019 (9)	−0.0063 (8)	0.0231 (10)
O2	0.0432 (6)	0.0761 (8)	0.0490 (7)	0.0101 (6)	−0.0029 (5)	−0.0061 (7)
N1	0.0510 (9)	0.0778 (12)	0.0573 (9)	0.0013 (8)	−0.0003 (8)	0.0150 (9)
C1	0.0741 (13)	0.0589 (11)	0.0564 (11)	0.0148 (11)	0.0171 (10)	0.0079 (9)
C2	0.0541 (11)	0.0841 (15)	0.0657 (13)	0.0125 (11)	0.0103 (10)	0.0207 (11)
C3	0.0550 (11)	0.0573 (11)	0.0558 (11)	0.0022 (9)	0.0036 (9)	0.0129 (9)
C5	0.0644 (11)	0.0537 (10)	0.0547 (10)	−0.0088 (9)	−0.0001 (10)	0.0128 (9)
C6	0.0531 (11)	0.0814 (14)	0.0629 (12)	−0.0158 (11)	0.0009 (10)	0.0286 (11)
C7	0.0456 (9)	0.0859 (14)	0.0458 (9)	0.0003 (10)	0.0111 (8)	0.0187 (9)
C8	0.0357 (8)	0.0656 (11)	0.0354 (8)	−0.0061 (8)	0.0018 (7)	0.0076 (7)
C9	0.0423 (8)	0.0524 (9)	0.0333 (7)	−0.0045 (7)	0.0039 (7)	0.0028 (7)
C10	0.0635 (11)	0.0504 (9)	0.0440 (9)	−0.0045 (9)	0.0029 (9)	0.0037 (8)
C11	0.0561 (10)	0.0525 (9)	0.0341 (8)	0.0009 (8)	0.0106 (8)	0.0016 (7)
C12	0.0455 (8)	0.0504 (9)	0.0413 (8)	0.0016 (8)	0.0123 (8)	0.0026 (7)
C13	0.0346 (7)	0.0561 (9)	0.0337 (7)	0.0005 (7)	0.0040 (7)	−0.0027 (7)
C14	0.0352 (8)	0.0693 (11)	0.0324 (7)	0.0020 (8)	0.0033 (7)	−0.0014 (7)
C15	0.0471 (10)	0.1020 (17)	0.0395 (9)	0.0119 (10)	0.0126 (8)	0.0045 (10)
C16	0.0566 (11)	0.1094 (18)	0.0408 (9)	0.0257 (12)	0.0037 (9)	−0.0167 (11)
C17	0.0433 (9)	0.0761 (13)	0.0481 (10)	0.0139 (9)	−0.0016 (8)	−0.0173 (10)
C18	0.0354 (8)	0.0603 (11)	0.0472 (9)	0.0046 (7)	0.0007 (8)	−0.0105 (8)
C19	0.0428 (9)	0.0542 (9)	0.0539 (10)	0.0089 (7)	0.0016 (8)	−0.0039 (8)
C20	0.0627 (12)	0.0550 (11)	0.0897 (15)	0.0113 (10)	0.0011 (13)	−0.0083 (11)
C21	0.0754 (15)	0.0661 (14)	0.103 (2)	0.0176 (12)	−0.0056 (14)	−0.0248 (14)
C22	0.0650 (13)	0.0908 (17)	0.0761 (15)	0.0210 (12)	−0.0096 (12)	−0.0400 (14)
C25	0.1048 (18)	0.0607 (14)	0.0572 (12)	−0.0073 (12)	−0.0101 (13)	−0.0062 (11)
C26	0.0426 (9)	0.0751 (13)	0.0609 (11)	−0.0125 (9)	−0.0076 (9)	0.0090 (11)
C27	0.0492 (10)	0.0764 (13)	0.0427 (9)	0.0034 (10)	−0.0086 (8)	−0.0082 (9)
C28	0.0413 (9)	0.0864 (14)	0.0514 (10)	0.0148 (10)	0.0010 (8)	−0.0128 (10)
C29	0.0691 (14)	0.0581 (12)	0.142 (3)	−0.0061 (11)	0.0053 (17)	−0.0063 (15)
C30	0.1021 (19)	0.0549 (12)	0.106 (2)	0.0156 (13)	−0.0037 (17)	0.0115 (13)

Geometric parameters (Å, º) top

O1—N1	1.407 (2)	C14—C27	1.548 (2)
O1—H1	0.88 (3)	C15—C16	1.529 (4)
O2—C28	1.435 (2)	C15—H15A	0.9700
O2—C19	1.455 (2)	C15—H15B	0.9700
N1—C3	1.268 (3)	C16—C17	1.520 (3)
C1—C2	1.532 (3)	C16—H16A	0.9700
C1—C10	1.548 (3)	C16—H16B	0.9700
C1—H1A	0.9700	C17—C28	1.528 (3)
C1—H1B	0.9700	C17—C18	1.538 (2)
C2—C3	1.497 (3)	C17—C22	1.540 (3)
C2—H2A	0.9700	C18—C19	1.524 (3)
C2—H2B	0.9700	C18—H18	0.9800
C3—C5	1.502 (3)	C19—C20	1.541 (3)
C5—C6	1.516 (3)	C19—H19	0.9800
C5—C10	1.551 (3)	C20—C29	1.529 (3)
C5—H5	0.9800	C20—C30	1.531 (4)
C6—C7	1.510 (3)	C20—C21	1.532 (3)
C6—H6A	0.9700	C21—C22	1.520 (4)
C6—H6B	0.9700	C21—H21A	0.9700
C7—C8	1.545 (2)	C21—H21B	0.9700
C7—H7A	0.9700	C22—H22A	0.9700
C7—H7B	0.9700	C22—H22B	0.9700
C8—C26	1.546 (2)	C25—H25A	0.9600
C8—C9	1.559 (2)	C25—H25B	0.9600
C8—C14	1.591 (3)	C25—H25C	0.9600
C9—C11	1.529 (2)	C26—H26A	0.9600
C9—C10	1.562 (3)	C26—H26B	0.9600
C9—H9	0.9800	C26—H26C	0.9600
C10—C25	1.532 (3)	C27—H27A	0.9600
C11—C12	1.521 (2)	C27—H27B	0.9600
C11—H11A	0.9700	C27—H27C	0.9600
C11—H11B	0.9700	C28—H28A	0.9700
C12—C13	1.526 (2)	C28—H28B	0.9700
C12—H12A	0.9700	C29—H29A	0.9600
C12—H12B	0.9700	C29—H29B	0.9600
C13—C18	1.532 (2)	C29—H29C	0.9600
C13—C14	1.556 (2)	C30—H30A	0.9600
C13—H13	0.9800	C30—H30B	0.9600
C14—C15	1.545 (2)	C30—H30C	0.9600

N1—O1—H1	100 (2)	C16—C15—H15B	108.9
C28—O2—C19	108.36 (14)	C14—C15—H15B	108.9
C3—N1—O1	111.93 (18)	H15A—C15—H15B	107.7
C2—C1—C10	106.80 (16)	C17—C16—C15	113.84 (16)
C2—C1—H1A	110.4	C17—C16—H16A	108.8
C10—C1—H1A	110.4	C15—C16—H16A	108.8
C2—C1—H1B	110.4	C17—C16—H16B	108.8
C10—C1—H1B	110.4	C15—C16—H16B	108.8
H1A—C1—H1B	108.6	H16A—C16—H16B	107.7
C3—C2—C1	103.30 (18)	C16—C17—C28	112.25 (19)
C3—C2—H2A	111.1	C16—C17—C18	113.46 (16)
C1—C2—H2A	111.1	C28—C17—C18	100.60 (14)
C3—C2—H2B	111.1	C16—C17—C22	112.64 (18)
C1—C2—H2B	111.1	C28—C17—C22	109.79 (18)
H2A—C2—H2B	109.1	C18—C17—C22	107.37 (18)
N1—C3—C2	129.2 (2)	C19—C18—C13	113.07 (14)
N1—C3—C5	119.83 (19)	C19—C18—C17	98.82 (14)
C2—C3—C5	110.97 (17)	C13—C18—C17	114.23 (16)
C3—C5—C6	114.75 (17)	C19—C18—H18	110.1
C3—C5—C10	103.94 (16)	C13—C18—H18	110.1
C6—C5—C10	114.97 (17)	C17—C18—H18	110.1
C3—C5—H5	107.6	O2—C19—C18	102.90 (15)
C6—C5—H5	107.6	O2—C19—C20	109.03 (15)
C10—C5—H5	107.6	C18—C19—C20	114.15 (17)
C7—C6—C5	111.48 (16)	O2—C19—H19	110.2
C7—C6—H6A	109.3	C18—C19—H19	110.2
C5—C6—H6A	109.3	C20—C19—H19	110.2
C7—C6—H6B	109.3	C29—C20—C30	109.3 (2)
C5—C6—H6B	109.3	C29—C20—C21	111.1 (2)
H6A—C6—H6B	108.0	C30—C20—C21	109.90 (19)
C6—C7—C8	113.39 (17)	C29—C20—C19	109.80 (17)
C6—C7—H7A	108.9	C30—C20—C19	108.6 (2)
C8—C7—H7A	108.9	C21—C20—C19	108.1 (2)
C6—C7—H7B	108.9	C22—C21—C20	114.47 (19)
C8—C7—H7B	108.9	C22—C21—H21A	108.6
H7A—C7—H7B	107.7	C20—C21—H21A	108.6
C7—C8—C26	107.47 (15)	C22—C21—H21B	108.6
C7—C8—C9	108.78 (15)	C20—C21—H21B	108.6
C26—C8—C9	111.99 (14)	H21A—C21—H21B	107.6
C7—C8—C14	110.59 (15)	C21—C22—C17	112.79 (19)
C26—C8—C14	110.43 (15)	C21—C22—H22A	109.0
C9—C8—C14	107.59 (14)	C17—C22—H22A	109.0
C11—C9—C8	110.56 (14)	C21—C22—H22B	109.0
C11—C9—C10	112.80 (14)	C17—C22—H22B	109.0
C8—C9—C10	117.42 (14)	H22A—C22—H22B	107.8
C11—C9—H9	104.9	C10—C25—H25A	109.5
C8—C9—H9	104.9	C10—C25—H25B	109.5
C10—C9—H9	104.9	H25A—C25—H25B	109.5
C25—C10—C1	110.89 (19)	C10—C25—H25C	109.5
C25—C10—C5	111.27 (16)	H25A—C25—H25C	109.5
C1—C10—C5	100.84 (16)	H25B—C25—H25C	109.5
C25—C10—C9	114.24 (17)	C8—C26—H26A	109.5
C1—C10—C9	108.67 (16)	C8—C26—H26B	109.5
C5—C10—C9	110.08 (15)	H26A—C26—H26B	109.5
C12—C11—C9	112.05 (14)	C8—C26—H26C	109.5
C12—C11—H11A	109.2	H26A—C26—H26C	109.5
C9—C11—H11A	109.2	H26B—C26—H26C	109.5
C12—C11—H11B	109.2	C14—C27—H27A	109.5
C9—C11—H11B	109.2	C14—C27—H27B	109.5
H11A—C11—H11B	107.9	H27A—C27—H27B	109.5
C11—C12—C13	112.78 (14)	C14—C27—H27C	109.5
C11—C12—H12A	109.0	H27A—C27—H27C	109.5
C13—C12—H12A	109.0	H27B—C27—H27C	109.5
C11—C12—H12B	109.0	O2—C28—C17	106.37 (15)
C13—C12—H12B	109.0	O2—C28—H28A	110.5
H12A—C12—H12B	107.8	C17—C28—H28A	110.5
C12—C13—C18	111.00 (14)	O2—C28—H28B	110.5
C12—C13—C14	111.29 (14)	C17—C28—H28B	110.5
C18—C13—C14	113.42 (14)	H28A—C28—H28B	108.6
C12—C13—H13	106.9	C20—C29—H29A	109.5
C18—C13—H13	106.9	C20—C29—H29B	109.5
C14—C13—H13	106.9	H29A—C29—H29B	109.5
C15—C14—C27	106.84 (14)	C20—C29—H29C	109.5
C15—C14—C13	107.91 (15)	H29A—C29—H29C	109.5
C27—C14—C13	110.26 (15)	H29B—C29—H29C	109.5
C15—C14—C8	111.46 (16)	C20—C30—H30A	109.5
C27—C14—C8	111.84 (15)	C20—C30—H30B	109.5
C13—C14—C8	108.46 (13)	H30A—C30—H30B	109.5
C16—C15—C14	113.33 (18)	C20—C30—H30C	109.5
C16—C15—H15A	108.9	H30A—C30—H30C	109.5
C14—C15—H15A	108.9	H30B—C30—H30C	109.5

C10—C1—C2—C3	24.3 (2)	C26—C8—C14—C15	57.27 (18)
O1—N1—C3—C2	−1.0 (4)	C9—C8—C14—C15	179.76 (13)
O1—N1—C3—C5	−179.80 (18)	C7—C8—C14—C27	57.97 (18)
C1—C2—C3—N1	179.6 (2)	C26—C8—C14—C27	176.80 (14)
C1—C2—C3—C5	−1.5 (2)	C9—C8—C14—C27	−60.70 (17)
N1—C3—C5—C6	31.2 (3)	C7—C8—C14—C13	179.78 (14)
C2—C3—C5—C6	−147.80 (19)	C26—C8—C14—C13	−61.40 (17)
N1—C3—C5—C10	157.6 (2)	C9—C8—C14—C13	61.10 (16)
C2—C3—C5—C10	−21.4 (2)	C27—C14—C15—C16	62.1 (2)
C3—C5—C6—C7	66.3 (2)	C13—C14—C15—C16	−56.4 (2)
C10—C5—C6—C7	−54.2 (2)	C8—C14—C15—C16	−175.40 (15)
C5—C6—C7—C8	58.2 (2)	C14—C15—C16—C17	53.3 (2)
C6—C7—C8—C26	67.6 (2)	C15—C16—C17—C28	68.0 (2)
C6—C7—C8—C9	−53.8 (2)	C15—C16—C17—C18	−45.2 (2)
C6—C7—C8—C14	−171.76 (16)	C15—C16—C17—C22	−167.46 (18)
C7—C8—C9—C11	179.45 (15)	C12—C13—C18—C19	71.70 (19)
C26—C8—C9—C11	60.81 (19)	C14—C13—C18—C19	−162.14 (14)
C14—C8—C9—C11	−60.72 (17)	C12—C13—C18—C17	−176.31 (14)
C7—C8—C9—C10	48.1 (2)	C14—C13—C18—C17	−50.1 (2)
C26—C8—C9—C10	−70.6 (2)	C16—C17—C18—C19	164.25 (17)
C14—C8—C9—C10	167.91 (14)	C28—C17—C18—C19	44.17 (19)
C2—C1—C10—C25	−154.75 (18)	C22—C17—C18—C19	−70.62 (18)
C2—C1—C10—C5	−36.8 (2)	C16—C17—C18—C13	43.9 (2)
C2—C1—C10—C9	78.9 (2)	C28—C17—C18—C13	−76.1 (2)
C3—C5—C10—C25	152.20 (18)	C22—C17—C18—C13	169.06 (16)
C6—C5—C10—C25	−81.5 (2)	C28—O2—C19—C18	28.72 (19)
C3—C5—C10—C1	34.5 (2)	C28—O2—C19—C20	−92.8 (2)
C6—C5—C10—C1	160.79 (18)	C13—C18—C19—O2	75.99 (17)
C3—C5—C10—C9	−80.1 (2)	C17—C18—C19—O2	−45.17 (17)
C6—C5—C10—C9	46.1 (2)	C13—C18—C19—C20	−166.02 (16)
C11—C9—C10—C25	−48.7 (2)	C17—C18—C19—C20	72.81 (19)
C8—C9—C10—C25	81.7 (2)	O2—C19—C20—C29	177.7 (2)
C11—C9—C10—C1	75.7 (2)	C18—C19—C20—C29	63.3 (3)
C8—C9—C10—C1	−153.95 (15)	O2—C19—C20—C30	−62.9 (2)
C11—C9—C10—C5	−174.71 (16)	C18—C19—C20—C30	−177.28 (18)
C8—C9—C10—C5	−44.4 (2)	O2—C19—C20—C21	56.3 (2)
C8—C9—C11—C12	56.7 (2)	C18—C19—C20—C21	−58.1 (2)
C10—C9—C11—C12	−169.56 (16)	C29—C20—C21—C22	−80.1 (3)
C9—C11—C12—C13	−52.8 (2)	C30—C20—C21—C22	158.8 (2)
C11—C12—C13—C18	−178.59 (15)	C19—C20—C21—C22	40.4 (3)
C11—C12—C13—C14	54.06 (19)	C20—C21—C22—C17	−45.1 (3)
C12—C13—C14—C15	−179.09 (15)	C16—C17—C22—C21	−172.49 (18)
C18—C13—C14—C15	54.9 (2)	C28—C17—C22—C21	−46.6 (2)
C12—C13—C14—C27	64.56 (18)	C18—C17—C22—C21	61.9 (2)
C18—C13—C14—C27	−61.45 (19)	C19—O2—C28—C17	0.2 (2)
C12—C13—C14—C8	−58.21 (17)	C16—C17—C28—O2	−149.50 (17)
C18—C13—C14—C8	175.78 (14)	C18—C17—C28—O2	−28.6 (2)
C7—C8—C14—C15	−61.56 (19)	C22—C17—C28—O2	84.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.87 (3)	1.93 (3)	2.782 (2)	164 (3)

Symmetry code: (i) −x+1/2, −y+2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₇H₄₃NO₂
M_r	413.62
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	12.5887 (16), 13.2550 (11), 14.5355 (12)
V (Å³)	2425.4 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.53
Crystal size (mm)	0.40 × 0.22 × 0.13

Data collection
Diffractometer	Kuma Diffraction KM-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4994, 2610, 2240
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.094, 1.06
No. of reflections	2610
No. of parameters	281
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.12

Computer programs: KM-4 Software (Kuma Diffraction, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.87 (3)	1.93 (3)	2.782 (2)	164 (3)

Symmetry code: (i) −x+1/2, −y+2, z+1/2.

References

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Medvedeva, N. I., Flekhter, O. B., Tretyakova, E. V., Galin, F. Z., Baltina, L. A., Spirikhin, L. V. & Tolstikov, G. A. (2004). Russ. J. Org. Chem. 40, 1092–1097. Web of Science CrossRef CAS Google Scholar
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