research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 73| Part 11| November 2017| Pages 1770-1773
https://doi.org/10.1107/S2056989017014864

Unusual thermolysis of aza­cyclic allene under microwave conditions: crystal structure of (3RS,3aSR,8RS,8aRS)-methyl 5,6-dimeth­­oxy-3a,10-di­methyl-1-phenyl-3,3a,8,8a-tetra­hydro-3,8-(epimino­methano)­cyclo­penta­[a]indene-2-carboxyl­ate from synchrotron X-ray diffraction

CROSSMARK_Color_square_no_text.svg
Le Tuan Anh,a* Alexander A. Titov,b Maxim S. Kobzev,b Leonid G. Voskressensky,b Alexey V. Varlamov,b Pavel V. Dorovatovskiic and Victor N. Khrustalevd

aDepartment of Pharmaceutical Chemistry, Faculty of Chemistry, VNU University of Science, 19 Le Thanh Tong, Hoan Kiem, Hanoi 100000, Vietnam, bOrganic Chemistry Department, Peoples' Friendship University of Russia, (RUDN University), Miklukho-Maklay St., 6, Moscow 117198, Russian Federation, cNational Research Centre "Kurchatov Institute", 1 Acad. Kurchatov Sq., Moscow 123182, Russian Federation, and dInorganic Chemistry Department, Peoples' Friendship University of Russia, (RUDN University), Miklukho-Maklay St., 6, Moscow 117198, Russian Federation
*Correspondence e-mail: huschemical.lab@gmail.com

Edited by A. V. Yatsenko, Moscow State University, Russia (Received 5 October 2017; accepted 13 October 2017; online 24 October 2017)

The title compound, C25H27NO4 (I), the product of the unusual thermolysis of aza­cyclic allene methyl 10,11-dimeth­oxy-3,8-dimethyl-6-phenyl-3-aza­benzo[d]cyclo­deca-4,6,7-triene-5-carboxyl­ate, represents a bicyclic heterosystem and crystallizes in the monoclinic space group P21/c with three crystallographically independent mol­ecules in the unit cell. These independent mol­ecules adopt very similar geometries and differ only in the conformations of the two meth­oxy substituents on the benzene ring. In two of the three independent mol­ecules, both meth­oxy groups are almost coplanar with the benzene ring [the C—C—O—Me torsion angles are 10.8 (2), 12.3 (2), 9.1 (2) and 13.6 (3)°], whereas in the third mol­ecule, one of the meth­oxy groups is practically coplanar to and the other meth­oxy group is roughly perpendicular to the benzene ring, the C—C—O—Me torsion angles being 14.1 (2) and 76.5 (2)°. The mol­ecule of (I) comprises a fused tetra­cyclic system containing two five-membered rings (cyclo­pentenes) and two six-membered rings (piperidine and benzene). The five-membered rings have the usual envelope conformation, with the methyl-subsituted C atom as the flap in each molecule, and the six-membered piperidine ring has a chair conformation. The methyl substituent at the N atom occupies the sterically favourable equatorial position. The carboxyl­ate group lies almost within the basal plane of the parent cyclo­pentene ring [making dihedral angle of 11.68 (8), 18.94 (9) and 15.16 (9)° in the three independent mol­ecules], while the phenyl substituent is twisted by 48.26 (6), 42.04 (6) and 41.28 (6)° (for the three independent mol­ecules) relative to this plane. In the crystal, mol­ecules of (I) form stacks along the b-axis direction. The mol­ecules are arranged at van der Waals distances.

CCDC reference: 1579823

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1. Chemical context

The allene fragment is a part of some natural compounds – steroids, prostaglandins, amines acids, nucleosides. The vast majority of them contain a non-cyclic allene fragment. Ten-membered steroids with an allene fragment in bacteria have already been studied (Batzold & Robinson, 1975[Batzold, F. H. & Robinson, C. H. (1975). J. Am. Chem. Soc. 97, 2576-2578.], 1976[Batzold, F. H. & Robinson, C. H. (1976). J. Org. Chem. 41, 313-317.]; Batzold et al., 1977[Batzold, F. H., Covey, D. F. & Robinson, C. H. (1977). Cancer Treat. Rep. 61, 255-257.]). Bicyclic lactones comprising ten-membered sesquiterpene allenes have been isolated from the Vernonia plants of South America (Bohlmann et al., 1980[Bohlmann, F., Gupta, R. K., Jakupovic, J., King, R. M. & Robinson, H. (1980). Liebigs Ann. Chem. pp. 1904-1906.]; Jakupovic et al., 1985[Jakupovic, J., Schmeda-Hirschmann, G., Schuster, A., Zdero, C., Bohlmann, F., King, R. M., Robinson, H. & Pickardt, J. (1985). Phytochemistry, 25, 145-158.]; Warning et al., 1987[Warning, U., Jakupovic, J., Bohlmann, F. & Jones, S. B. (1987). Liebigs Ann. Chem. pp. 467-468.]). Natural functionalized allenes are inhibitors of enzymes that exhibit cytotoxic and anti­viral activity (Krause & Hoffmann-Röder, 2004[Krause, N. & Hoffmann-Röder, A. (2004). Modern Allene Chemistry, Vol. 2, edited by N. Krause & A. S. K. Hashmi, pp. 997-1032. Weinheim: Wiley-VCH Verlag GmbH & Co.]). However, heterocyclic allene systems are practically unexplored. Nitro­gen-containing nona­trienes-3,6,7 were obtained for the first time in 1984 with a yield of 8–10% (Sashida & Tsuchiya, 1984[Sashida, H. & Tsuchiya, T. (1984). Chem. Pharm. Bull. 32, 4600-4607.]). Further, the synthesis of 1-aza­deca­(undeca­)-4,5-dien-2-ones has been carried out (Perscheid et al., 2011[Perscheid, M., Schollmeyer, D. & Nubbemeyer, U. (2011). Eur. J. Org. Chem. pp. 5250-5253.]).

Recently, we proposed a relatively simple synthesis of benzo­aza­deca­trienes-4,6,7 from 1R-1-phenyl­ethynyl tetra­hydro­iso­quinolines and activated terminal alkynes in tri­fluoro­ethanol at 256 K (Voskressensky et al., 2017[Voskressensky, L. G., Titov, A. A., Dzhankaziev, M. S., Borisova, T. N., Kobzev, M. S., Dorovatovskii, P. V., Khrustalev, V. N., Aksenov, A. V. & Varlamov, A. V. (2017). New J. Chem. 41, 1902-1904.]). However, the thermal transformations of such strained systems have not yet been studied.

[Scheme 1]

In this work, the thermolysis of an aza­cyclic allene under microwave conditions was carried out by our research group. The structure of the product of this unusual reaction was established unambiguously by synchrotron X-ray diffraction study.

2. Structural commentary

The title compound crystallizes with three crystallographically independent mol­ecules (A, B and C, containing atoms N10, N32 and N54, respectively) in the unit cell (Fig. 1[link]). These independent mol­ecules adopt very similar geometries and differ only in the conformations of the two meth­oxy substituents at the benzene ring. In two of the three independent mol­ecules, both meth­oxy groups are almost coplanar to the benzene ring [the C—C—O—Me torsion angles are 10.8 (2) and 12.3 (2)° in mol­ecule A and 9.1 (2) and 13.6 (3)° in B], whereas in the third mol­ecule, C, one of the meth­oxy groups is practically coplanar with and the other meth­oxy group is roughly perpendicular to the benzene ring, the C—C—O—Me torsion angles being 14.1 (2) and 76.5 (2)°].

[Figure 1]
Figure 1
The mol­ecular structure of (I)[link] showing the three crystallographically independent mol­ecules. Displacement ellipsoids are shown at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.

The mol­ecule of (I)[link] comprises a fused tetra­cyclic system containing two five-membered rings (cyclo­pentenes) and two six-membered rings (piperidine and benzene) (Fig. 1[link]). The five-membered rings have the usual envelope conformation, with the methyl-subsituted C atom as the flap in each molecule, and the six-membered piperidine ring has a chair conformation. The methyl substituent at the nitro­gen atom occupies the sterically favourable equatorial position. The carboxyl­ate group lies almost within the basal plane of the parent cyclo­pentene ring, making dihedral angles of 11.68 (8), 18.94 (9) and 15.16 (9)°, respectively, in mol­ecules A, B and C, while the phenyl substituent is twisted by 48.26 (6), 42.04 (6) and 41.28 (6)° relative to this plane in mol­ecules A, B and C, respectively.

The title mol­ecule possesses four asymmetric centers at the C3, C3A, C8 and C8A carbon atoms and can have potentially numerous diastereomers. The crystal of (I)[link] is racemic and consists of enanti­omeric pairs with the following relative configuration of the centers: rac-3R*,3aS*,8R*,8aR*.

3. Supra­molecular features

The crystal packing motif of mol­ecules of (I)[link] is stacking along the crystallographic b axis (Fig. 2[link]). The mol­ecules are arranged at van der Waals distances.

[Figure 2]
Figure 2
Crystal structure of (I)[link] illustrating the stacks along [010]. For clarity, H atoms have been omitted.

4. Synthesis and crystallization

A stirred solution of cyclic allene (0.13 g, 0.32 mmol) in toluene (5 mL) was heated at 453 K for 1 h in a microwave reactor (Anton Paar Monowave 300) (Fig. 3[link]). The solvent was evaporated in vacuo, and the residue recrystallized from ether to give 60 mg of colourless crystals of (I)[link] in a yield of 50%, m.p. = 422–424 K (ether).

[Figure 3]
Figure 3
Thermolysis of aza­cyclic allene methyl 10,11-dimeth­oxy-3,8-dimethyl-6-phenyl-3-aza­benzo[d]cyclo­deca-4,6,7-triene-5-carboxyl­ate under microwave conditions.

1H NMR (CDCl3, 600 MHz): δ = 1.47 (3H, s, 3a-Me), 2.21 (3H, s, NMe), 2.47 (1H, dd, J = 2.5 Hz, J = 10.7 Hz, 9-CH), 2.65 (1H, dd, J = 2.5 Hz, J = 10.7 Hz, 9-CH), 3.09–3.10 (1H, m, 8-CH), 3.22 (1H, d, J = 5.0 Hz, 8a-CH), 3.67 (1H, d, J = 1.7 Hz, 3-CH), 3.69 (3H, s, OMe), 3.88 (3H, s, OMe), 3.91 (3H, s, OMe), 6.73 (1H, s, H7), 6.74 (1H, s, H4), 7.35–7.40 (3H, m, Ph), 7.47–7.48 (2H, m, Ph); 13C NMR (DMSO-d6, 150 MHz): δ = 18.3, 42.3, 42.6, 51.1, 51.2, 55.7, 55.8, 59.6, 67.9, 72.8, 106.9, 107.1, 124.9, 127.9 (2 C), 128.0 (2 C), 128.5, 135.1, 137.1, 137.3, 147.8, 148.3, 151.1, 166.3; m/z: 406 [M+H]+. Analysis calculated for C25H27NO4 (%): C 74.03, H 6.71, N 3.45; found (%): C 74.04, H 6.71, N 3.41.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1[link]. The X-ray diffraction study was carried out on the `Belok' beamline of the National Research Center `Kurchatov Institute' (Moscow, Russian Federation) using a Rayonix SX165 CCD detector. A total of 720 images were collected using an oscillation range of 1.0° (φ scan mode, two different crystal orientations) and corrected for absorption using the Scala program (Evans, 2006[Evans, P. (2006). Acta Cryst. D62, 72-82.]). The data were indexed, integrated and scaled using the utility iMOSFLM in CCP4 (Battye et al., 2011[Battye, T. G. G., Kontogiannis, L., Johnson, O., Powell, H. R. & Leslie, A. G. W. (2011). Acta Cryst. D67, 271-281.]).

Table 1
Experimental details

Crystal data
Chemical formula C25H27NO4
Mr 405.47
Crystal system, space group Monoclinic, P21/c
Temperature (K) 100
a, b, c (Å) 26.404 (5), 7.9303 (16), 30.720 (6)
β (°) 95.09 (3)
V (Å3) 6407 (2)
Z 12
Radiation type Synchrotron, λ = 0.96990 Å
μ (mm−1) 0.18
Crystal size (mm) 0.25 × 0.24 × 0.21
 
Data collection
Diffractometer Rayonix SX165 CCD
Absorption correction Multi-scan (SCALA; Evans, 2006[Evans, P. (2006). Acta Cryst. D62, 72-82.])
Tmin, Tmax 0.940, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections 74044, 13622, 10086
Rint 0.071
(sin θ/λ)max (Å−1) 0.659
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.146, 1.07
No. of reflections 13622
No. of parameters 827
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.46, −0.38
Computer programs: Marccd (Doyle, 2011[Doyle, R. A. (2011). Marccd software manual. Rayonix L. L. C., Evanston, IL 60201, USA.]), iMOSFLM (Battye et al., 2011[Battye, T. G. G., Kontogiannis, L., Johnson, O., Powell, H. R. & Leslie, A. G. W. (2011). Acta Cryst. D67, 271-281.]), SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXL2014 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]) and SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

Hydrogen atoms were placed in calculated positions with C—H = 0.95–1.00 Å and refined in the riding model with fixed isotropic displacement parameters [Uiso(H) = 1.5Ueq(C) for the CH3-groups and 1.2Ueq(C) for the other groups].

A rather large number of reflections have been omitted for the following reasons: (i) In order to achieve better Iσ statistics for high-angle reflections, we selected exposure times so as to admit a minor fraction of intensity overloads in the low-angle part of the detector. These low-angle reflections with imprecisely measured intensities were excluded from the final steps of the refinement. (ii) In the present setup of the synchrotron diffractometer, the low-temperature device eclipses a small region of the 2D detector near the high-angle limit. This small shadowed region was not masked during integration of the diffraction frames, which erroneously resulted in zero intensity for some reflections.

Supporting information

CCDC reference: 1579823

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989017014864/yk2110sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017014864/yk2110Isup2.hkl

checkCIF report


Computing details top

Data collection: Marccd (Doyle, 2011); cell refinement: iMOSFLM (Battye et al., 2011); data reduction: iMOSFLM (Battye et al., 2011); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(3RS,3aSR,8RS,8aRS)-Methyl 5,6-dimethoxy-3a,10-dimethyl-1-phenyl-3,3a,8,8a-tetrahydro-3,8-(epiminomethano)cyclopenta[a]indene-2-carboxylate top
Crystal data top
C25H27NO4F(000) = 2592
Mr = 405.47Dx = 1.261 Mg m−3
Monoclinic, P21/cSynchrotron radiation, λ = 0.96990 Å
a = 26.404 (5) ÅCell parameters from 600 reflections
b = 7.9303 (16) Åθ = 3.6–36.0°
c = 30.720 (6) ŵ = 0.18 mm−1
β = 95.09 (3)°T = 100 K
V = 6407 (2) Å3Prism, colourless
Z = 120.25 × 0.24 × 0.21 mm
Data collection top
Rayonix SX165 CCD
diffractometer		10086 reflections with I > 2σ(I)
/f scanRint = 0.071
Absorption correction: multi-scan
(Scala; Evans, 2006)		θmax = 39.7°, θmin = 3.5°
Tmin = 0.940, Tmax = 0.951h = −33→33
74044 measured reflectionsk = −8→10
13622 independent reflectionsl = −39→39
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.146 w = 1/[σ2(Fo2) + (0.0696P)2 + 0.8571P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
13622 reflectionsΔρmax = 0.46 e Å−3
827 parametersΔρmin = −0.38 e Å−3
0 restraintsExtinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: difference Fourier mapExtinction coefficient: 0.00120 (18)
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.27574 (4)0.67806 (16)0.64919 (4)0.0291 (3)
O20.19523 (4)0.75446 (16)0.65782 (4)0.0293 (3)
O30.30254 (4)0.29541 (15)0.38931 (4)0.0266 (3)
O40.26028 (4)0.55159 (15)0.35018 (3)0.0244 (3)
C10.16537 (6)0.6161 (2)0.57029 (5)0.0201 (3)
C20.21299 (6)0.6304 (2)0.59036 (5)0.0198 (3)
C30.25165 (6)0.5938 (2)0.55724 (5)0.0195 (3)
H30.28350.54320.57170.023*
C3A0.22152 (6)0.4638 (2)0.52660 (5)0.0195 (3)
C3B0.23500 (6)0.4674 (2)0.47966 (5)0.0197 (3)
C40.26706 (6)0.3619 (2)0.45845 (5)0.0210 (4)
H40.28420.27110.47360.025*
C50.27349 (6)0.3925 (2)0.41453 (5)0.0210 (4)
C60.24940 (6)0.5322 (2)0.39281 (5)0.0206 (4)
C70.21706 (6)0.6363 (2)0.41435 (5)0.0218 (4)
H70.20060.72970.39980.026*
C7A0.20952 (6)0.6002 (2)0.45771 (5)0.0196 (3)
C80.17978 (6)0.6978 (2)0.48975 (5)0.0205 (4)
H80.14780.74870.47560.025*
C8A0.16948 (6)0.5569 (2)0.52346 (5)0.0201 (3)
H8A0.14070.48170.51270.024*
C90.21579 (6)0.8298 (2)0.51258 (5)0.0207 (3)
H9A0.22470.91540.49110.025*
H9B0.19850.88780.53570.025*
N100.26251 (5)0.74768 (17)0.53217 (4)0.0200 (3)
C110.11459 (6)0.6438 (2)0.58631 (5)0.0205 (3)
C120.10117 (7)0.5756 (2)0.62547 (6)0.0291 (4)
H120.12550.51140.64310.035*
C130.05300 (7)0.5997 (2)0.63919 (6)0.0330 (4)
H130.04450.55060.66580.040*
C140.01719 (6)0.6951 (2)0.61416 (6)0.0294 (4)
H14−0.01560.71380.62370.035*
C150.03000 (6)0.7628 (2)0.57498 (6)0.0286 (4)
H150.00580.82860.55770.034*
C160.07783 (6)0.7357 (2)0.56054 (5)0.0248 (4)
H160.08560.77970.53310.030*
C170.23166 (6)0.6887 (2)0.63484 (5)0.0216 (4)
C180.21198 (7)0.8065 (3)0.70192 (5)0.0349 (5)
H18A0.24010.88680.70120.052*
H18B0.22350.70760.71920.052*
H18C0.18370.86020.71520.052*
C190.22182 (6)0.2883 (2)0.54690 (5)0.0243 (4)
H19A0.19900.21420.52870.036*
H19B0.21030.29540.57630.036*
H19C0.25640.24240.54870.036*
C200.24521 (7)0.7058 (2)0.32898 (5)0.0300 (4)
H20A0.25850.71000.30020.045*
H20B0.25880.80100.34670.045*
H20C0.20800.71240.32540.045*
C210.32021 (7)0.1375 (2)0.40771 (6)0.0308 (4)
H21A0.33900.07670.38650.046*
H21B0.29110.06970.41490.046*
H21C0.34270.15830.43430.046*
C220.29463 (6)0.8685 (2)0.55748 (5)0.0239 (4)
H22A0.27530.91990.57980.036*
H22B0.30570.95640.53800.036*
H22C0.32450.81030.57160.036*
O50.04526 (4)0.27952 (16)0.18932 (4)0.0306 (3)
O60.12346 (4)0.37557 (16)0.17935 (4)0.0302 (3)
O70.04963 (4)−0.16000 (15)0.44959 (4)0.0258 (3)
O80.11516 (4)0.06677 (16)0.48935 (3)0.0255 (3)
C230.16239 (6)0.1905 (2)0.25797 (5)0.0188 (3)
C240.11291 (6)0.2176 (2)0.24310 (5)0.0185 (3)
C250.07877 (6)0.1781 (2)0.27969 (5)0.0185 (3)
H250.04440.13820.26770.022*
C25A0.10949 (6)0.0350 (2)0.30487 (5)0.0193 (3)
C25B0.10346 (6)0.0281 (2)0.35363 (5)0.0192 (3)
C260.07316 (6)−0.0761 (2)0.37696 (5)0.0204 (3)
H260.0508−0.15540.36230.024*
C270.07641 (6)−0.0616 (2)0.42257 (5)0.0214 (4)
C280.10869 (6)0.0601 (2)0.44392 (5)0.0217 (4)
C290.13786 (6)0.1658 (2)0.42003 (5)0.0219 (4)
H290.15910.24930.43430.026*
C29A0.13541 (6)0.1474 (2)0.37498 (5)0.0205 (3)
C300.16122 (6)0.2481 (2)0.34132 (5)0.0204 (4)
H300.19580.28890.35260.025*
C30A0.16310 (6)0.1158 (2)0.30369 (5)0.0198 (3)
H30A0.19110.03180.30980.024*
C310.12553 (6)0.3929 (2)0.32492 (5)0.0210 (4)
H31A0.12170.47320.34910.025*
H31B0.14060.45450.30120.025*
N320.07522 (5)0.32672 (17)0.30861 (4)0.0199 (3)
C330.21087 (6)0.2266 (2)0.23888 (5)0.0201 (3)
C340.21906 (6)0.1952 (2)0.19520 (5)0.0259 (4)
H340.19260.14760.17610.031*
C350.26551 (7)0.2328 (2)0.17949 (6)0.0310 (4)
H350.27050.20980.14980.037*
C360.30473 (7)0.3035 (2)0.20663 (6)0.0293 (4)
H360.33620.33080.19560.035*
C370.29726 (6)0.3338 (2)0.25022 (6)0.0279 (4)
H370.32370.38290.26910.033*
C380.25138 (6)0.2928 (2)0.26632 (5)0.0235 (4)
H380.24730.30970.29640.028*
C390.09013 (6)0.2923 (2)0.20193 (5)0.0209 (4)
C400.10380 (8)0.4429 (3)0.13759 (6)0.0380 (5)
H40A0.08900.35150.11910.057*
H40B0.13150.49600.12330.057*
H40C0.07760.52720.14200.057*
C410.10082 (6)−0.1333 (2)0.28122 (5)0.0230 (4)
H41A0.1229−0.21930.29580.035*
H41B0.1088−0.12130.25080.035*
H41C0.0652−0.16720.28190.035*
C420.07612 (7)0.1543 (2)0.50948 (5)0.0289 (4)
H42A0.06960.26300.49490.043*
H42B0.08700.17340.54040.043*
H42C0.04490.08670.50700.043*
C430.02597 (7)−0.3088 (2)0.43054 (6)0.0338 (4)
H43A−0.0009−0.27630.40800.051*
H43B0.0112−0.37450.45330.051*
H43C0.0515−0.37710.41730.051*
C440.04325 (6)0.4598 (2)0.28805 (5)0.0245 (4)
H44A0.03790.54750.30960.037*
H44B0.01040.41220.27690.037*
H44C0.06000.50890.26380.037*
O90.38416 (4)0.20757 (16)0.51668 (4)0.0281 (3)
O100.46237 (4)0.31084 (16)0.50926 (4)0.0283 (3)
O110.36852 (5)−0.25476 (16)0.76825 (4)0.0337 (3)
O120.40905 (5)−0.00499 (16)0.81049 (4)0.0346 (3)
C450.49830 (6)0.1339 (2)0.59067 (5)0.0194 (3)
C460.44971 (6)0.1511 (2)0.57266 (5)0.0191 (3)
C470.41323 (6)0.0987 (2)0.60641 (5)0.0204 (4)
H470.38090.05100.59200.025*
C47A0.44527 (6)−0.0399 (2)0.63274 (5)0.0208 (4)
C47B0.43428 (6)−0.0539 (2)0.68019 (5)0.0217 (4)
C480.40304 (6)−0.1680 (2)0.70002 (5)0.0246 (4)
H480.3862−0.25620.68360.030*
C490.39714 (6)−0.1497 (2)0.74438 (5)0.0261 (4)
C500.42073 (7)−0.0153 (2)0.76786 (5)0.0274 (4)
C510.45268 (6)0.0966 (2)0.74807 (5)0.0263 (4)
H510.46910.18630.76420.032*
C51A0.45971 (6)0.0730 (2)0.70407 (5)0.0233 (4)
C520.48757 (6)0.1839 (2)0.67344 (5)0.0221 (4)
H520.51990.23180.68780.027*
C52A0.49672 (6)0.0566 (2)0.63598 (5)0.0206 (4)
H52A0.5263−0.01940.64390.025*
C530.45036 (6)0.3205 (2)0.65498 (5)0.0223 (4)
H53A0.44240.39800.67870.027*
H53B0.46620.38710.63260.027*
N540.40313 (5)0.24188 (18)0.63536 (4)0.0219 (3)
C550.54798 (6)0.1758 (2)0.57438 (5)0.0201 (3)
C560.55974 (6)0.1444 (2)0.53162 (5)0.0235 (4)
H560.53480.09560.51120.028*
C570.60753 (6)0.1839 (2)0.51869 (6)0.0273 (4)
H570.61510.16070.48960.033*
C580.64441 (6)0.2571 (2)0.54792 (5)0.0258 (4)
H580.67680.28550.53880.031*
C590.63324 (6)0.2882 (2)0.59062 (5)0.0253 (4)
H590.65810.33900.61080.030*
C600.58591 (6)0.2452 (2)0.60395 (5)0.0229 (4)
H600.57920.26300.63350.027*
C610.42839 (6)0.2241 (2)0.53060 (5)0.0212 (4)
C620.44417 (7)0.3744 (3)0.46658 (5)0.0337 (4)
H62A0.41330.44100.46890.050*
H62B0.43660.27960.44660.050*
H62C0.47040.44570.45530.050*
C630.44378 (7)−0.2058 (2)0.60785 (5)0.0260 (4)
H63A0.4673−0.28600.62310.039*
H63B0.4538−0.18640.57830.039*
H63C0.4092−0.25190.60610.039*
C640.42125 (8)0.1456 (3)0.83337 (6)0.0406 (5)
H64A0.40760.14150.86200.061*
H64B0.40640.24150.81670.061*
H64C0.45830.15860.83740.061*
C650.34943 (7)−0.4060 (2)0.74740 (6)0.0362 (5)
H65A0.3315−0.47250.76810.054*
H65B0.3778−0.47190.73780.054*
H65C0.3259−0.37700.72200.054*
C660.36905 (6)0.3679 (2)0.61390 (5)0.0253 (4)
H66A0.33860.31200.60010.038*
H66B0.38650.42700.59150.038*
H66C0.35920.44920.63560.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0238 (6)0.0403 (8)0.0228 (6)0.0006 (6)−0.0001 (5)−0.0031 (5)
O20.0268 (6)0.0402 (8)0.0210 (6)0.0067 (6)0.0022 (5)−0.0091 (5)
O30.0314 (7)0.0264 (7)0.0226 (6)0.0071 (5)0.0060 (5)−0.0020 (5)
O40.0300 (6)0.0262 (7)0.0170 (5)−0.0005 (5)0.0025 (5)0.0001 (5)
C10.0208 (8)0.0184 (9)0.0213 (8)0.0004 (7)0.0033 (6)0.0016 (7)
C20.0204 (8)0.0195 (9)0.0196 (8)−0.0001 (7)0.0027 (6)0.0007 (7)
C30.0189 (8)0.0208 (9)0.0186 (7)0.0017 (7)0.0013 (6)0.0009 (7)
C3A0.0195 (8)0.0193 (9)0.0198 (8)0.0003 (7)0.0024 (6)−0.0008 (7)
C3B0.0185 (8)0.0196 (9)0.0209 (8)−0.0015 (7)0.0012 (6)−0.0021 (7)
C40.0198 (8)0.0205 (9)0.0224 (8)−0.0007 (7)0.0002 (6)0.0004 (7)
C50.0191 (8)0.0224 (9)0.0216 (8)−0.0004 (7)0.0022 (6)−0.0044 (7)
C60.0208 (8)0.0242 (9)0.0165 (7)−0.0040 (7)−0.0002 (6)−0.0011 (7)
C70.0213 (8)0.0218 (9)0.0217 (8)−0.0008 (7)−0.0011 (6)0.0003 (7)
C7A0.0177 (8)0.0193 (9)0.0215 (8)−0.0021 (7)−0.0005 (6)−0.0023 (7)
C80.0203 (8)0.0228 (9)0.0181 (8)0.0033 (7)0.0007 (6)0.0005 (7)
C8A0.0174 (8)0.0209 (9)0.0218 (8)−0.0006 (7)0.0014 (6)−0.0018 (7)
C90.0211 (8)0.0197 (9)0.0214 (8)0.0022 (7)0.0028 (6)0.0015 (7)
N100.0186 (7)0.0199 (7)0.0214 (7)0.0002 (6)0.0011 (5)−0.0003 (6)
C110.0196 (8)0.0214 (9)0.0207 (8)−0.0027 (7)0.0025 (6)−0.0013 (7)
C120.0264 (9)0.0306 (10)0.0308 (9)0.0036 (8)0.0061 (7)0.0076 (8)
C130.0310 (10)0.0354 (11)0.0345 (10)−0.0002 (8)0.0146 (8)0.0077 (9)
C140.0212 (9)0.0313 (11)0.0367 (10)−0.0027 (8)0.0085 (7)−0.0046 (8)
C150.0205 (9)0.0378 (11)0.0271 (9)0.0037 (8)−0.0002 (7)−0.0032 (8)
C160.0222 (8)0.0329 (10)0.0191 (8)0.0027 (8)0.0010 (6)−0.0010 (7)
C170.0230 (9)0.0224 (9)0.0199 (8)0.0005 (7)0.0048 (6)0.0016 (7)
C180.0402 (11)0.0440 (12)0.0203 (9)0.0054 (9)0.0020 (7)−0.0089 (8)
C190.0274 (9)0.0227 (10)0.0227 (8)−0.0006 (7)0.0021 (7)−0.0007 (7)
C200.0361 (10)0.0325 (11)0.0211 (8)0.0020 (8)0.0006 (7)0.0061 (8)
C210.0351 (10)0.0272 (10)0.0308 (9)0.0084 (8)0.0067 (8)−0.0024 (8)
C220.0208 (8)0.0247 (10)0.0260 (8)−0.0038 (7)0.0022 (7)−0.0037 (7)
O50.0254 (6)0.0397 (8)0.0259 (6)−0.0022 (6)−0.0025 (5)0.0053 (6)
O60.0285 (7)0.0382 (8)0.0235 (6)−0.0069 (6)0.0000 (5)0.0125 (6)
O70.0278 (6)0.0281 (7)0.0222 (6)−0.0059 (5)0.0058 (5)0.0051 (5)
O80.0254 (6)0.0354 (7)0.0157 (5)0.0021 (5)0.0023 (4)0.0013 (5)
C230.0211 (8)0.0175 (9)0.0181 (7)−0.0006 (7)0.0031 (6)−0.0023 (6)
C240.0211 (8)0.0176 (9)0.0171 (7)−0.0017 (7)0.0027 (6)−0.0006 (6)
C250.0192 (8)0.0201 (9)0.0164 (7)−0.0016 (7)0.0027 (6)−0.0004 (6)
C25A0.0204 (8)0.0205 (9)0.0170 (7)−0.0011 (7)0.0011 (6)0.0007 (7)
C25B0.0173 (8)0.0200 (9)0.0203 (8)0.0006 (7)0.0008 (6)0.0011 (7)
C260.0194 (8)0.0201 (9)0.0213 (8)−0.0006 (7)0.0000 (6)0.0020 (7)
C270.0206 (8)0.0229 (9)0.0211 (8)0.0005 (7)0.0032 (6)0.0046 (7)
C280.0226 (8)0.0269 (10)0.0153 (7)0.0024 (7)0.0000 (6)0.0026 (7)
C290.0205 (8)0.0243 (9)0.0206 (8)−0.0027 (7)0.0001 (6)0.0004 (7)
C29A0.0194 (8)0.0227 (9)0.0191 (8)−0.0009 (7)0.0008 (6)0.0021 (7)
C300.0193 (8)0.0247 (9)0.0172 (7)−0.0050 (7)0.0014 (6)−0.0005 (7)
C30A0.0184 (8)0.0221 (9)0.0189 (8)0.0006 (7)0.0017 (6)0.0005 (7)
C310.0242 (8)0.0200 (9)0.0191 (8)−0.0040 (7)0.0045 (6)−0.0021 (7)
N320.0214 (7)0.0184 (7)0.0200 (7)−0.0005 (6)0.0026 (5)−0.0018 (6)
C330.0201 (8)0.0184 (9)0.0223 (8)0.0013 (7)0.0041 (6)0.0008 (7)
C340.0258 (9)0.0305 (10)0.0218 (8)−0.0028 (8)0.0046 (7)−0.0058 (7)
C350.0302 (10)0.0395 (12)0.0248 (9)−0.0016 (9)0.0109 (7)−0.0027 (8)
C360.0232 (9)0.0323 (11)0.0336 (10)0.0014 (8)0.0102 (7)0.0021 (8)
C370.0206 (9)0.0320 (11)0.0314 (9)−0.0012 (8)0.0038 (7)−0.0004 (8)
C380.0220 (8)0.0291 (10)0.0196 (8)0.0000 (7)0.0029 (6)−0.0003 (7)
C390.0223 (9)0.0212 (9)0.0196 (8)−0.0020 (7)0.0034 (6)−0.0019 (7)
C400.0441 (12)0.0455 (13)0.0230 (9)−0.0081 (10)−0.0040 (8)0.0134 (9)
C410.0272 (9)0.0196 (9)0.0218 (8)−0.0012 (7)−0.0005 (7)−0.0006 (7)
C420.0282 (9)0.0388 (11)0.0202 (8)0.0005 (8)0.0043 (7)−0.0016 (8)
C430.0391 (11)0.0301 (11)0.0335 (10)−0.0092 (9)0.0108 (8)0.0021 (8)
C440.0253 (9)0.0226 (9)0.0264 (8)0.0021 (7)0.0068 (7)0.0019 (7)
O90.0229 (6)0.0366 (8)0.0243 (6)−0.0016 (5)−0.0010 (5)0.0026 (5)
O100.0267 (6)0.0341 (7)0.0238 (6)−0.0040 (5)0.0006 (5)0.0099 (5)
O110.0405 (7)0.0343 (8)0.0281 (6)−0.0021 (6)0.0128 (5)0.0076 (6)
O120.0493 (8)0.0340 (8)0.0212 (6)−0.0002 (6)0.0071 (5)0.0008 (6)
C450.0222 (8)0.0170 (9)0.0194 (8)−0.0006 (7)0.0046 (6)−0.0021 (7)
C460.0197 (8)0.0188 (9)0.0189 (8)−0.0016 (7)0.0029 (6)−0.0015 (7)
C470.0184 (8)0.0237 (9)0.0193 (8)−0.0013 (7)0.0018 (6)0.0008 (7)
C47A0.0198 (8)0.0215 (9)0.0211 (8)−0.0003 (7)0.0021 (6)0.0016 (7)
C47B0.0193 (8)0.0239 (9)0.0222 (8)0.0020 (7)0.0030 (6)0.0035 (7)
C480.0236 (9)0.0256 (10)0.0248 (8)0.0019 (7)0.0027 (7)0.0046 (7)
C490.0271 (9)0.0263 (10)0.0256 (9)0.0031 (8)0.0063 (7)0.0072 (8)
C500.0324 (10)0.0320 (11)0.0184 (8)0.0078 (8)0.0056 (7)0.0069 (7)
C510.0293 (9)0.0275 (10)0.0218 (8)0.0036 (8)0.0008 (7)0.0009 (7)
C51A0.0227 (8)0.0268 (10)0.0203 (8)0.0040 (7)0.0011 (6)0.0039 (7)
C520.0227 (8)0.0256 (10)0.0181 (8)−0.0027 (7)0.0012 (6)−0.0017 (7)
C52A0.0179 (8)0.0216 (9)0.0225 (8)0.0013 (7)0.0021 (6)0.0016 (7)
C530.0246 (9)0.0217 (9)0.0207 (8)−0.0016 (7)0.0034 (6)−0.0013 (7)
N540.0204 (7)0.0236 (8)0.0219 (7)0.0017 (6)0.0033 (5)−0.0003 (6)
C550.0194 (8)0.0185 (9)0.0227 (8)0.0018 (7)0.0031 (6)0.0004 (7)
C560.0220 (8)0.0260 (10)0.0232 (8)−0.0024 (7)0.0046 (6)−0.0043 (7)
C570.0274 (9)0.0304 (10)0.0252 (9)0.0001 (8)0.0087 (7)−0.0013 (8)
C580.0208 (8)0.0274 (10)0.0303 (9)−0.0008 (7)0.0074 (7)0.0010 (8)
C590.0198 (8)0.0287 (10)0.0273 (9)−0.0023 (7)0.0009 (7)0.0020 (8)
C600.0226 (8)0.0253 (9)0.0211 (8)0.0010 (7)0.0031 (6)0.0004 (7)
C610.0232 (9)0.0209 (9)0.0199 (8)−0.0001 (7)0.0045 (6)−0.0018 (7)
C620.0393 (11)0.0379 (12)0.0235 (9)−0.0027 (9)0.0012 (8)0.0098 (8)
C630.0274 (9)0.0228 (10)0.0277 (9)−0.0012 (7)0.0018 (7)0.0016 (7)
C640.0562 (13)0.0413 (13)0.0230 (9)−0.0053 (10)−0.0031 (9)−0.0061 (9)
C650.0394 (11)0.0330 (11)0.0373 (11)−0.0078 (9)0.0088 (8)0.0058 (9)
C660.0251 (9)0.0247 (10)0.0267 (9)0.0044 (7)0.0057 (7)0.0026 (7)
Geometric parameters (Å, º) top
O1—C171.2105 (19)C31—N321.474 (2)
O2—C171.3477 (19)C31—H31A0.9900
O2—C181.447 (2)C31—H31B0.9900
O3—C51.3737 (19)N32—C441.459 (2)
O3—C211.435 (2)C33—C341.400 (2)
O4—C61.3741 (18)C33—C381.403 (2)
O4—C201.425 (2)C34—C351.390 (2)
C1—C21.355 (2)C34—H340.9500
C1—C111.485 (2)C35—C361.389 (3)
C1—C8A1.527 (2)C35—H350.9500
C2—C171.485 (2)C36—C371.392 (2)
C2—C31.532 (2)C36—H360.9500
C3—N101.485 (2)C37—C381.387 (2)
C3—C3A1.565 (2)C37—H370.9500
C3—H31.0000C38—H380.9500
C3A—C3B1.516 (2)C40—H40A0.9800
C3A—C191.525 (2)C40—H40B0.9800
C3A—C8A1.555 (2)C40—H40C0.9800
C3B—C7A1.391 (2)C41—H41A0.9800
C3B—C41.393 (2)C41—H41B0.9800
C4—C51.396 (2)C41—H41C0.9800
C4—H40.9500C42—H42A0.9800
C5—C61.415 (2)C42—H42B0.9800
C6—C71.396 (2)C42—H42C0.9800
C7—C7A1.394 (2)C43—H43A0.9800
C7—H70.9500C43—H43B0.9800
C7A—C81.524 (2)C43—H43C0.9800
C8—C91.541 (2)C44—H44A0.9800
C8—C8A1.563 (2)C44—H44B0.9800
C8—H81.0000C44—H44C0.9800
C8A—H8A1.0000O9—C611.2148 (19)
C9—N101.475 (2)O10—C611.346 (2)
C9—H9A0.9900O10—C621.446 (2)
C9—H9B0.9900O11—C491.379 (2)
N10—C221.458 (2)O11—C651.430 (2)
C11—C121.393 (2)O12—C501.3744 (19)
C11—C161.401 (2)O12—C641.409 (2)
C12—C131.388 (2)C45—C461.358 (2)
C12—H120.9500C45—C551.483 (2)
C13—C141.389 (3)C45—C52A1.525 (2)
C13—H130.9500C46—C611.481 (2)
C14—C151.387 (2)C46—C471.534 (2)
C14—H140.9500C47—N541.481 (2)
C15—C161.392 (2)C47—C47A1.567 (2)
C15—H150.9500C47—H471.0000
C16—H160.9500C47A—C47B1.515 (2)
C18—H18A0.9800C47A—C631.520 (2)
C18—H18B0.9800C47A—C52A1.555 (2)
C18—H18C0.9800C47B—C51A1.383 (2)
C19—H19A0.9800C47B—C481.400 (2)
C19—H19B0.9800C48—C491.393 (2)
C19—H19C0.9800C48—H480.9500
C20—H20A0.9800C49—C501.402 (3)
C20—H20B0.9800C50—C511.400 (3)
C20—H20C0.9800C51—C51A1.393 (2)
C21—H21A0.9800C51—H510.9500
C21—H21B0.9800C51A—C521.524 (2)
C21—H21C0.9800C52—C531.537 (2)
C22—H22A0.9800C52—C52A1.566 (2)
C22—H22B0.9800C52—H521.0000
C22—H22C0.9800C52A—H52A1.0000
O5—C391.2177 (19)C53—N541.474 (2)
O6—C391.3414 (19)C53—H53A0.9900
O6—C401.443 (2)C53—H53B0.9900
O7—C271.3789 (19)N54—C661.462 (2)
O7—C431.435 (2)C55—C561.399 (2)
O8—C281.3919 (18)C55—C601.403 (2)
O8—C421.428 (2)C56—C571.392 (2)
C23—C241.362 (2)C56—H560.9500
C23—C331.483 (2)C57—C581.391 (2)
C23—C30A1.523 (2)C57—H570.9500
C24—C391.476 (2)C58—C591.392 (2)
C24—C251.534 (2)C58—H580.9500
C25—N321.484 (2)C59—C601.392 (2)
C25—C25A1.560 (2)C59—H590.9500
C25—H251.0000C60—H600.9500
C25A—C25B1.521 (2)C62—H62A0.9800
C25A—C411.527 (2)C62—H62B0.9800
C25A—C30A1.557 (2)C62—H62C0.9800
C25B—C261.392 (2)C63—H63A0.9800
C25B—C29A1.393 (2)C63—H63B0.9800
C26—C271.401 (2)C63—H63C0.9800
C26—H260.9500C64—H64A0.9800
C27—C281.410 (2)C64—H64B0.9800
C28—C291.391 (2)C64—H64C0.9800
C29—C29A1.387 (2)C65—H65A0.9800
C29—H290.9500C65—H65B0.9800
C29A—C301.515 (2)C65—H65C0.9800
C30—C311.541 (2)C66—H66A0.9800
C30—C30A1.566 (2)C66—H66B0.9800
C30—H301.0000C66—H66C0.9800
C30A—H30A1.0000
C17—O2—C18115.32 (13)H31A—C31—H31B108.1
C5—O3—C21116.44 (13)C44—N32—C31111.03 (13)
C6—O4—C20117.24 (13)C44—N32—C25112.34 (12)
C2—C1—C11131.73 (15)C31—N32—C25112.55 (12)
C2—C1—C8A108.29 (13)C34—C33—C38117.90 (15)
C11—C1—C8A119.97 (13)C34—C33—C23123.82 (15)
C1—C2—C17131.57 (15)C38—C33—C23118.26 (14)
C1—C2—C3109.17 (13)C35—C34—C33120.70 (16)
C17—C2—C3118.94 (13)C35—C34—H34119.6
N10—C3—C2111.07 (13)C33—C34—H34119.6
N10—C3—C3A109.91 (12)C36—C35—C34120.82 (16)
C2—C3—C3A101.02 (12)C36—C35—H35119.6
N10—C3—H3111.5C34—C35—H35119.6
C2—C3—H3111.5C35—C36—C37119.05 (16)
C3A—C3—H3111.5C35—C36—H36120.5
C3B—C3A—C19114.39 (13)C37—C36—H36120.5
C3B—C3A—C8A102.28 (12)C38—C37—C36120.35 (16)
C19—C3A—C8A115.55 (13)C38—C37—H37119.8
C3B—C3A—C3114.21 (13)C36—C37—H37119.8
C19—C3A—C3111.78 (13)C37—C38—C33121.11 (15)
C8A—C3A—C397.13 (12)C37—C38—H38119.4
C7A—C3B—C4121.05 (14)C33—C38—H38119.4
C7A—C3B—C3A109.34 (14)O5—C39—O6122.77 (15)
C4—C3B—C3A129.61 (15)O5—C39—C24123.36 (15)
C3B—C4—C5118.62 (15)O6—C39—C24113.86 (13)
C3B—C4—H4120.7O6—C40—H40A109.5
C5—C4—H4120.7O6—C40—H40B109.5
O3—C5—C4124.74 (15)H40A—C40—H40B109.5
O3—C5—C6115.02 (14)O6—C40—H40C109.5
C4—C5—C6120.24 (15)H40A—C40—H40C109.5
O4—C6—C7125.03 (15)H40B—C40—H40C109.5
O4—C6—C5114.44 (14)C25A—C41—H41A109.5
C7—C6—C5120.52 (14)C25A—C41—H41B109.5
C7A—C7—C6118.45 (15)H41A—C41—H41B109.5
C7A—C7—H7120.8C25A—C41—H41C109.5
C6—C7—H7120.8H41A—C41—H41C109.5
C3B—C7A—C7121.01 (15)H41B—C41—H41C109.5
C3B—C7A—C8109.04 (13)O8—C42—H42A109.5
C7—C7A—C8129.64 (15)O8—C42—H42B109.5
C7A—C8—C9107.86 (13)H42A—C42—H42B109.5
C7A—C8—C8A101.22 (13)O8—C42—H42C109.5
C9—C8—C8A108.69 (12)H42A—C42—H42C109.5
C7A—C8—H8112.8H42B—C42—H42C109.5
C9—C8—H8112.8O7—C43—H43A109.5
C8A—C8—H8112.8O7—C43—H43B109.5
C1—C8A—C3A102.94 (12)H43A—C43—H43B109.5
C1—C8A—C8115.81 (14)O7—C43—H43C109.5
C3A—C8A—C8100.12 (12)H43A—C43—H43C109.5
C1—C8A—H8A112.3H43B—C43—H43C109.5
C3A—C8A—H8A112.3N32—C44—H44A109.5
C8—C8A—H8A112.3N32—C44—H44B109.5
N10—C9—C8110.22 (13)H44A—C44—H44B109.5
N10—C9—H9A109.6N32—C44—H44C109.5
C8—C9—H9A109.6H44A—C44—H44C109.5
N10—C9—H9B109.6H44B—C44—H44C109.5
C8—C9—H9B109.6C61—O10—C62115.94 (13)
H9A—C9—H9B108.1C49—O11—C65117.15 (14)
C22—N10—C9110.70 (13)C50—O12—C64117.71 (15)
C22—N10—C3113.17 (12)C46—C45—C55132.22 (15)
C9—N10—C3112.43 (12)C46—C45—C52A108.11 (13)
C12—C11—C16118.24 (15)C55—C45—C52A119.67 (14)
C12—C11—C1122.36 (15)C45—C46—C61131.83 (14)
C16—C11—C1119.36 (14)C45—C46—C47108.93 (13)
C13—C12—C11121.27 (17)C61—C46—C47118.88 (13)
C13—C12—H12119.4N54—C47—C46110.80 (13)
C11—C12—H12119.4N54—C47—C47A110.20 (12)
C12—C13—C14120.25 (16)C46—C47—C47A101.34 (12)
C12—C13—H13119.9N54—C47—H47111.4
C14—C13—H13119.9C46—C47—H47111.4
C15—C14—C13119.00 (16)C47A—C47—H47111.4
C15—C14—H14120.5C47B—C47A—C63114.94 (14)
C13—C14—H14120.5C47B—C47A—C52A102.44 (13)
C14—C15—C16120.99 (17)C63—C47A—C52A116.19 (14)
C14—C15—H15119.5C47B—C47A—C47114.04 (13)
C16—C15—H15119.5C63—C47A—C47111.00 (13)
C15—C16—C11120.19 (15)C52A—C47A—C4796.70 (13)
C15—C16—H16119.9C51A—C47B—C48121.09 (15)
C11—C16—H16119.9C51A—C47B—C47A109.35 (14)
O1—C17—O2122.95 (15)C48—C47B—C47A129.54 (15)
O1—C17—C2122.93 (14)C49—C48—C47B118.67 (16)
O2—C17—C2114.11 (14)C49—C48—H48120.7
O2—C18—H18A109.5C47B—C48—H48120.7
O2—C18—H18B109.5O11—C49—C48124.86 (16)
H18A—C18—H18B109.5O11—C49—C50115.17 (14)
O2—C18—H18C109.5C48—C49—C50119.96 (16)
H18A—C18—H18C109.5O12—C50—C51124.83 (17)
H18B—C18—H18C109.5O12—C50—C49114.11 (15)
C3A—C19—H19A109.5C51—C50—C49121.06 (15)
C3A—C19—H19B109.5C51A—C51—C50118.25 (17)
H19A—C19—H19B109.5C51A—C51—H51120.9
C3A—C19—H19C109.5C50—C51—H51120.9
H19A—C19—H19C109.5C47B—C51A—C51120.81 (16)
H19B—C19—H19C109.5C47B—C51A—C52109.30 (14)
O4—C20—H20A109.5C51—C51A—C52129.37 (16)
O4—C20—H20B109.5C51A—C52—C53107.87 (13)
H20A—C20—H20B109.5C51A—C52—C52A101.29 (13)
O4—C20—H20C109.5C53—C52—C52A108.58 (13)
H20A—C20—H20C109.5C51A—C52—H52112.8
H20B—C20—H20C109.5C53—C52—H52112.8
O3—C21—H21A109.5C52A—C52—H52112.8
O3—C21—H21B109.5C45—C52A—C47A103.53 (12)
H21A—C21—H21B109.5C45—C52A—C52115.48 (14)
O3—C21—H21C109.5C47A—C52A—C5299.98 (12)
H21A—C21—H21C109.5C45—C52A—H52A112.3
H21B—C21—H21C109.5C47A—C52A—H52A112.3
N10—C22—H22A109.5C52—C52A—H52A112.3
N10—C22—H22B109.5N54—C53—C52110.03 (14)
H22A—C22—H22B109.5N54—C53—H53A109.7
N10—C22—H22C109.5C52—C53—H53A109.7
H22A—C22—H22C109.5N54—C53—H53B109.7
H22B—C22—H22C109.5C52—C53—H53B109.7
C39—O6—C40116.17 (13)H53A—C53—H53B108.2
C27—O7—C43116.59 (13)C66—N54—C53111.07 (13)
C28—O8—C42115.06 (12)C66—N54—C47112.94 (13)
C24—C23—C33132.29 (14)C53—N54—C47112.27 (12)
C24—C23—C30A107.67 (13)C56—C55—C60118.20 (15)
C33—C23—C30A119.97 (13)C56—C55—C45123.61 (15)
C23—C24—C39131.03 (15)C60—C55—C45118.14 (14)
C23—C24—C25109.29 (13)C57—C56—C55120.68 (16)
C39—C24—C25119.26 (13)C57—C56—H56119.7
N32—C25—C24110.41 (13)C55—C56—H56119.7
N32—C25—C25A109.79 (12)C58—C57—C56120.66 (15)
C24—C25—C25A101.45 (12)C58—C57—H57119.7
N32—C25—H25111.6C56—C57—H57119.7
C24—C25—H25111.6C57—C58—C59119.18 (15)
C25A—C25—H25111.6C57—C58—H58120.4
C25B—C25A—C41114.38 (13)C59—C58—H58120.4
C25B—C25A—C30A102.27 (12)C60—C59—C58120.32 (16)
C41—C25A—C30A116.53 (13)C60—C59—H59119.8
C25B—C25A—C25114.79 (13)C58—C59—H59119.8
C41—C25A—C25110.51 (12)C59—C60—C55120.90 (15)
C30A—C25A—C2597.07 (12)C59—C60—H60119.5
C26—C25B—C29A120.83 (14)C55—C60—H60119.5
C26—C25B—C25A130.04 (14)O9—C61—O10123.04 (15)
C29A—C25B—C25A109.12 (13)O9—C61—C46122.97 (15)
C25B—C26—C27118.64 (15)O10—C61—C46113.99 (14)
C25B—C26—H26120.7O10—C62—H62A109.5
C27—C26—H26120.7O10—C62—H62B109.5
O7—C27—C26124.50 (15)H62A—C62—H62B109.5
O7—C27—C28115.37 (14)O10—C62—H62C109.5
C26—C27—C28120.13 (14)H62A—C62—H62C109.5
C29—C28—O8118.79 (14)H62B—C62—H62C109.5
C29—C28—C27120.49 (14)C47A—C63—H63A109.5
O8—C28—C27120.50 (14)C47A—C63—H63B109.5
C29A—C29—C28118.94 (15)H63A—C63—H63B109.5
C29A—C29—H29120.5C47A—C63—H63C109.5
C28—C29—H29120.5H63A—C63—H63C109.5
C29—C29A—C25B120.93 (15)H63B—C63—H63C109.5
C29—C29A—C30129.89 (15)O12—C64—H64A109.5
C25B—C29A—C30109.08 (13)O12—C64—H64B109.5
C29A—C30—C31108.47 (13)H64A—C64—H64B109.5
C29A—C30—C30A101.31 (13)O12—C64—H64C109.5
C31—C30—C30A108.45 (12)H64A—C64—H64C109.5
C29A—C30—H30112.6H64B—C64—H64C109.5
C31—C30—H30112.6O11—C65—H65A109.5
C30A—C30—H30112.6O11—C65—H65B109.5
C23—C30A—C25A104.16 (12)H65A—C65—H65B109.5
C23—C30A—C30114.93 (13)O11—C65—H65C109.5
C25A—C30A—C3099.80 (12)H65A—C65—H65C109.5
C23—C30A—H30A112.3H65B—C65—H65C109.5
C25A—C30A—H30A112.3N54—C66—H66A109.5
C30—C30A—H30A112.3N54—C66—H66B109.5
N32—C31—C30110.63 (13)H66A—C66—H66B109.5
N32—C31—H31A109.5N54—C66—H66C109.5
C30—C31—H31A109.5H66A—C66—H66C109.5
N32—C31—H31B109.5H66B—C66—H66C109.5
C30—C31—H31B109.5
C11—C1—C2—C17−4.3 (3)C29—C29A—C30—C30A154.58 (17)
C8A—C1—C2—C17177.21 (17)C25B—C29A—C30—C30A−29.07 (16)
C11—C1—C2—C3−177.48 (16)C24—C23—C30A—C25A23.32 (17)
C8A—C1—C2—C33.99 (18)C33—C23—C30A—C25A−159.21 (14)
C1—C2—C3—N1085.35 (16)C24—C23—C30A—C30−84.78 (16)
C17—C2—C3—N10−88.86 (17)C33—C23—C30A—C3092.68 (17)
C1—C2—C3—C3A−31.19 (17)C25B—C25A—C30A—C23−157.64 (12)
C17—C2—C3—C3A154.60 (14)C41—C25A—C30A—C2376.86 (16)
N10—C3—C3A—C3B32.76 (18)C25—C25A—C30A—C23−40.30 (14)
C2—C3—C3A—C3B150.15 (13)C25B—C25A—C30A—C30−38.65 (15)
N10—C3—C3A—C19164.63 (13)C41—C25A—C30A—C30−164.14 (13)
C2—C3—C3A—C19−77.98 (15)C25—C25A—C30A—C3078.70 (13)
N10—C3—C3A—C8A−74.17 (14)C29A—C30—C30A—C23151.59 (13)
C2—C3—C3A—C8A43.22 (14)C31—C30—C30A—C2337.56 (17)
C19—C3A—C3B—C7A149.06 (14)C29A—C30—C30A—C25A40.86 (14)
C8A—C3A—C3B—C7A23.36 (17)C31—C30—C30A—C25A−73.17 (14)
C3—C3A—C3B—C7A−80.35 (16)C29A—C30—C31—N32−54.65 (16)
C19—C3A—C3B—C4−30.9 (2)C30A—C30—C31—N3254.58 (16)
C8A—C3A—C3B—C4−156.63 (16)C30—C31—N32—C44−172.92 (12)
C3—C3A—C3B—C499.7 (2)C30—C31—N32—C25−46.02 (16)
C7A—C3B—C4—C50.4 (2)C24—C25—N32—C4473.76 (16)
C3A—C3B—C4—C5−179.63 (15)C25A—C25—N32—C44−175.20 (12)
C21—O3—C5—C410.8 (2)C24—C25—N32—C31−52.44 (16)
C21—O3—C5—C6−169.50 (14)C25A—C25—N32—C3158.60 (16)
C3B—C4—C5—O3−177.74 (15)C24—C23—C33—C34−43.9 (3)
C3B—C4—C5—C62.6 (2)C30A—C23—C33—C34139.35 (17)
C20—O4—C6—C712.3 (2)C24—C23—C33—C38137.56 (19)
C20—O4—C6—C5−168.59 (14)C30A—C23—C33—C38−39.2 (2)
O3—C5—C6—O4−2.0 (2)C38—C33—C34—C35−1.7 (3)
C4—C5—C6—O4177.74 (14)C23—C33—C34—C35179.80 (17)
O3—C5—C6—C7177.21 (14)C33—C34—C35—C36−0.5 (3)
C4—C5—C6—C7−3.1 (2)C34—C35—C36—C371.1 (3)
O4—C6—C7—C7A179.67 (14)C35—C36—C37—C380.4 (3)
C5—C6—C7—C7A0.6 (2)C36—C37—C38—C33−2.7 (3)
C4—C3B—C7A—C7−2.9 (2)C34—C33—C38—C373.2 (3)
C3A—C3B—C7A—C7177.10 (14)C23—C33—C38—C37−178.16 (16)
C4—C3B—C7A—C8−177.06 (14)C40—O6—C39—O5−3.2 (2)
C3A—C3B—C7A—C82.94 (18)C40—O6—C39—C24176.56 (15)
C6—C7—C7A—C3B2.4 (2)C23—C24—C39—O5165.36 (17)
C6—C7—C7A—C8175.21 (15)C25—C24—C39—O5−22.9 (2)
C3B—C7A—C8—C986.25 (16)C23—C24—C39—O6−14.4 (3)
C7—C7A—C8—C9−87.25 (19)C25—C24—C39—O6157.40 (14)
C3B—C7A—C8—C8A−27.78 (16)C55—C45—C46—C61−2.5 (3)
C7—C7A—C8—C8A158.72 (16)C52A—C45—C46—C61177.20 (16)
C2—C1—C8A—C3A25.11 (17)C55—C45—C46—C47−175.48 (16)
C11—C1—C8A—C3A−153.63 (14)C52A—C45—C46—C474.22 (18)
C2—C1—C8A—C8−83.04 (17)C45—C46—C47—N5485.56 (16)
C11—C1—C8A—C898.23 (17)C61—C46—C47—N54−88.48 (17)
C3B—C3A—C8A—C1−158.40 (13)C45—C46—C47—C47A−31.37 (17)
C19—C3A—C8A—C176.66 (16)C61—C46—C47—C47A154.60 (14)
C3—C3A—C8A—C1−41.65 (14)N54—C47—C47A—C47B32.61 (18)
C3B—C3A—C8A—C8−38.74 (14)C46—C47—C47A—C47B149.97 (13)
C19—C3A—C8A—C8−163.67 (13)N54—C47—C47A—C63164.35 (13)
C3—C3A—C8A—C878.01 (13)C46—C47—C47A—C63−78.29 (15)
C7A—C8—C8A—C1149.93 (13)N54—C47—C47A—C52A−74.25 (14)
C9—C8—C8A—C136.53 (18)C46—C47—C47A—C52A43.12 (14)
C7A—C8—C8A—C3A40.12 (14)C63—C47A—C47B—C51A150.67 (14)
C9—C8—C8A—C3A−73.29 (15)C52A—C47A—C47B—C51A23.74 (17)
C7A—C8—C9—N10−53.83 (16)C47—C47A—C47B—C51A−79.52 (17)
C8A—C8—C9—N1055.13 (16)C63—C47A—C47B—C48−31.1 (2)
C8—C9—N10—C22−174.44 (12)C52A—C47A—C47B—C48−158.03 (17)
C8—C9—N10—C3−46.77 (16)C47—C47A—C47B—C4898.7 (2)
C2—C3—N10—C2274.47 (16)C51A—C47B—C48—C491.2 (2)
C3A—C3—N10—C22−174.60 (12)C47A—C47B—C48—C49−176.84 (16)
C2—C3—N10—C9−51.88 (17)C65—O11—C49—C489.1 (2)
C3A—C3—N10—C959.06 (16)C65—O11—C49—C50−171.75 (15)
C2—C1—C11—C12−48.2 (3)C47B—C48—C49—O11−178.54 (15)
C8A—C1—C11—C12130.16 (17)C47B—C48—C49—C502.4 (2)
C2—C1—C11—C16134.47 (19)C64—O12—C50—C5113.6 (3)
C8A—C1—C11—C16−47.1 (2)C64—O12—C50—C49−165.73 (16)
C16—C11—C12—C13−1.0 (3)O11—C49—C50—O12−3.4 (2)
C1—C11—C12—C13−178.31 (17)C48—C49—C50—O12175.73 (15)
C11—C12—C13—C14−0.9 (3)O11—C49—C50—C51177.20 (15)
C12—C13—C14—C151.3 (3)C48—C49—C50—C51−3.6 (3)
C13—C14—C15—C160.2 (3)O12—C50—C51—C51A−178.05 (15)
C14—C15—C16—C11−2.2 (3)C49—C50—C51—C51A1.2 (3)
C12—C11—C16—C152.5 (3)C48—C47B—C51A—C51−3.6 (3)
C1—C11—C16—C15179.93 (16)C47A—C47B—C51A—C51174.76 (15)
C18—O2—C17—O1−2.2 (2)C48—C47B—C51A—C52−176.13 (15)
C18—O2—C17—C2177.75 (15)C47A—C47B—C51A—C522.28 (18)
C1—C2—C17—O1172.56 (18)C50—C51—C51A—C47B2.4 (2)
C3—C2—C17—O1−14.8 (2)C50—C51—C51A—C52173.18 (16)
C1—C2—C17—O2−7.4 (3)C47B—C51A—C52—C5386.89 (16)
C3—C2—C17—O2165.25 (14)C51—C51A—C52—C53−84.8 (2)
C33—C23—C24—C390.6 (3)C47B—C51A—C52—C52A−27.06 (17)
C30A—C23—C24—C39177.66 (16)C51—C51A—C52—C52A161.30 (17)
C33—C23—C24—C25−171.75 (16)C46—C45—C52A—C47A24.97 (17)
C30A—C23—C24—C255.29 (18)C55—C45—C52A—C47A−155.29 (14)
C23—C24—C25—N3284.75 (16)C46—C45—C52A—C52−83.22 (17)
C39—C24—C25—N32−88.66 (17)C55—C45—C52A—C5296.52 (17)
C23—C24—C25—C25A−31.61 (16)C47B—C47A—C52A—C45−157.99 (13)
C39—C24—C25—C25A154.98 (14)C63—C47A—C52A—C4575.88 (17)
N32—C25—C25A—C25B32.49 (18)C47—C47A—C52A—C45−41.51 (14)
C24—C25—C25A—C25B149.30 (13)C47B—C47A—C52A—C52−38.55 (15)
N32—C25—C25A—C41163.65 (12)C63—C47A—C52A—C52−164.68 (13)
C24—C25—C25A—C41−79.54 (15)C47—C47A—C52A—C5277.94 (13)
N32—C25—C25A—C30A−74.56 (14)C51A—C52—C52A—C45149.79 (13)
C24—C25—C25A—C30A42.26 (13)C53—C52—C52A—C4536.38 (18)
C41—C25A—C25B—C26−29.3 (2)C51A—C52—C52A—C47A39.48 (15)
C30A—C25A—C25B—C26−156.20 (16)C53—C52—C52A—C47A−73.93 (15)
C25—C25A—C25B—C26100.0 (2)C51A—C52—C53—N54−53.32 (16)
C41—C25A—C25B—C29A149.53 (14)C52A—C52—C53—N5455.67 (16)
C30A—C25A—C25B—C29A22.64 (17)C52—C53—N54—C66−174.61 (12)
C25—C25A—C25B—C29A−81.20 (17)C52—C53—N54—C47−47.09 (17)
C29A—C25B—C26—C27−1.6 (2)C46—C47—N54—C6674.48 (16)
C25A—C25B—C26—C27177.10 (15)C47A—C47—N54—C66−174.19 (13)
C43—O7—C27—C2614.1 (2)C46—C47—N54—C53−52.04 (17)
C43—O7—C27—C28−165.90 (15)C47A—C47—N54—C5359.29 (16)
C25B—C26—C27—O7−178.15 (15)C46—C45—C55—C56−42.3 (3)
C25B—C26—C27—C281.9 (2)C52A—C45—C55—C56138.03 (17)
C42—O8—C28—C29103.54 (18)C46—C45—C55—C60140.13 (19)
C42—O8—C28—C27−81.8 (2)C52A—C45—C55—C60−39.5 (2)
O7—C27—C28—C29179.56 (15)C60—C55—C56—C57−1.1 (3)
C26—C27—C28—C29−0.5 (2)C45—C55—C56—C57−178.70 (16)
O7—C27—C28—O85.0 (2)C55—C56—C57—C58−0.7 (3)
C26—C27—C28—O8−175.00 (14)C56—C57—C58—C591.0 (3)
O8—C28—C29—C29A173.37 (14)C57—C58—C59—C600.5 (3)
C27—C28—C29—C29A−1.2 (2)C58—C59—C60—C55−2.4 (3)
C28—C29—C29A—C25B1.5 (2)C56—C55—C60—C592.7 (2)
C28—C29—C29A—C30177.52 (16)C45—C55—C60—C59−179.63 (15)
C26—C25B—C29A—C29−0.1 (2)C62—O10—C61—O9−4.4 (2)
C25A—C25B—C29A—C29−179.06 (15)C62—O10—C61—C46175.83 (14)
C26—C25B—C29A—C30−176.84 (14)C45—C46—C61—O9168.95 (17)
C25A—C25B—C29A—C304.20 (18)C47—C46—C61—O9−18.6 (2)
C29—C29A—C30—C31−91.4 (2)C45—C46—C61—O10−11.3 (3)
C25B—C29A—C30—C3184.96 (16)C47—C46—C61—O10161.13 (14)
 

Funding information

The publication was prepared with the support of the RUDN University Program `5–100' and by the Russian Foundation for Basic Research (project No. 17-53-540001-Viet-a). This research is funded by the Vietnam National Foundation for Science and Technology Development (NAFOSTED) under grant No. 104.01–2015.27. Synchrotron radiation measurements were performed at the unique scientific facility Kurchatov Synchrotron Radiation Source supported by the Ministry of Education and Science of the Russian Federation (project code RFMEFI61917X0007).

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ISSN: 2056-9890
Volume 73| Part 11| November 2017| Pages 1770-1773
https://doi.org/10.1107/S2056989017014864
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