A new approach to alkaloid-like systems: synthesis and crystal structure of 1-(2-acetyl-11-meth­oxy-5,6-di­hydro­[1,3]dioxolo[4,5-g]pyrrolo­[2,1-a]isoquinolin-1-yl)propan-2-one

Anh, L.T.; Titov, A.A.; Samavati, R.; Voskressensky, L.G.; Varlamov, A.V.; Khrustalev, V.N.

doi:10.1107/S2056989017015110

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ISSN: 2056-9890

Volume 73| Part 11| November 2017| Pages 1732-1734

https://doi.org/10.1107/S2056989017015110

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A new approach to alkaloid-like systems: synthesis and crystal structure of 1-(2-acetyl-11-methoxy-5,6-dihydro[1,3]dioxolo[4,5-g]pyrrolo[2,1-a]isoquinolin-1-yl)propan-2-one

Le Tuan Anh,^a ^* Alexander A. Titov,^b Reza Samavati,^b Leonid G. Voskressensky,^b Alexey V. Varlamov ^b and Victor N. Khrustalev ^c

^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, and ^cInorganic 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 W. T. A. Harrison, University of Aberdeen, Scotland (Received 19 September 2017; accepted 17 October 2017; online 20 October 2017)

The title compound, C₁₉H₁₉NO₅, (I), is the product of a domino reaction between cotarnine chloride and acetylacetylene catalysed by copper(I) iodide. The molecule of (I) comprises a fused tetracyclic system containing two terminal five-membered rings (pyrrole and 1,3-dioxole) and two central six-membered rings (dihydropyridine and benzene). The five-membered 1,3-dioxole ring has an envelope conformation and the central six-membered dihydropyridine ring adopts a twist-boat conformation. The acyl substituent is almost coplanar with the pyrrole ring, whereas the methoxy substituent is twisted by 27.93 (16)° relative to the benzene ring. The 2-oxopropan-1-yl substituent is roughly perpendicular to the pyrrole ring. In the crystal, molecules are stacked along the a-axis direction; the stacks are linked by weak C—H⋯O hydrogen bonds into puckered layers lying parallel to (001).

Keywords: alkaloids; lamellarin; cotarnine; dihydropyrrolo[2,1-a]isoquinolines; domino reaction; crystal structure.

CCDC reference: 1580424

1. Chemical context

The 5,6-dihydropyrrolo[2,1-a]isoquinoline fragment is included in several natural products, for example in lamellarin I and K alkaloids, which possess a variety of biological properties, in particular, antitumor activity (Komatsubara et al., 2014 ; Imperatore et al., 2014 ).

The dihydropyrrolo[2,1-a]isoquinoline skeleton can be constructed in two different ways. The first way is annelation of a pyrrole ring to an isoquiniline fragment (Ma et al., 2014 ; Fujiya et al., 2016 ; Nekkanti et al., 2016 ). The second one, in contrast, is annelation of an isoquiniline fragment to pyrrole derivatives (Sun et al., 2012 ; Wiest et al., 2016 ). Previously, we developed synthetic approaches to substituted pyrrolo[2,1-a]isoquinolines via the interaction of 1-aroyl-3,4-dihydroisoquinilines or 1-ethynyl-1,2,3,4-tetrahydroisoquinolines with activated alkynes (Voskressensky, Titov et al., 2016 ; Voskressensky et al., 2017 ).

It is of fundamental importance for the preparation of 2,3-bifunctional substituted pyrrolo[2,1-a]isoquinolines to study the interaction of iminium salts with activated alkynes. In this work, we modified the approach to the synthesis of alkaloid-like compounds by the reaction of cotarnine chloride with activated alkynes in the presence of copper halogenides as a catalyst. The synthetic method proposed is new and original. This process includes the formation of the pyrrole ring and its functionalization, which is necessary for the chemical diversity of pyrroloisoquinoline systems.

The title compound (I) is a product of a new domino reaction between cotarnine chloride and acetylacetylene catalysed by copper(I) iodide. The reaction sequence starts with nucleophilic addition of copper(I) acetylide to cotarnine chloride followed by [2,3]-cycloaddition and aromatization of the pyrrole ring (Voskressensky, Borisova et al., 2016 ). The main speciality of the reaction is the conversion of the acetylethynyl fragment to acetylmethyl when the pyrrole ring is formed in an aprotic solvent. The structure of the product (I) was unambiguously established by an X-ray diffraction study.

2. Structural commentary

The molecule of (I), representing a new alkaloid-like skeleton, comprises a fused tetracyclic system containing two terminal five-membered rings (pyrrole and 1,3-dioxole) and two central six-membered rings (dihydropyridine and benzene) (Fig. 1). The five-membered 1,3-dioxole ring has its usual shallow envelope conformation, with the methylene group as the flap, and the central six-membered dihydropyridine ring adopts a twist-boat conformation. The dihedral angle between the pyrrole and benzene rings is 29.69 (3)°. The nitrogen N4 atom is essentially planar (sum of bond angles = 359.73°). The acyl substituent is almost coplanar with the pyrrole ring (r.m.s. deviation for non-hydrogen atoms = 0.012 Å), whereas the methoxy substituent is twisted by 27.93 (16)° relative to the benzene ring. The propan-2-one-1-yl substituent is roughly perpendicular to the pyrrole ring, the dihedral angle being 76.81 (5)°, because of steric reasons.

Figure 1
Molecular structure of (I)

. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radius.

3. Supramolecular features

The crystal packing of molecules of (I) involves stacking along the a-axis direction (Fig. 2), with molecules linked by weak C—H⋯O hydrogen bonds into puckered layers lying parallel to (001) (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O13ⁱ	0.95	2.44	3.2840 (14)	147
C9—H9A⋯O17ⁱⁱ	0.99	2.46	3.2207 (15)	133
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y, -z+1.

Figure 2
Crystal structure of (I)

illustrating the hydrogen-bonded layers parallel to (001). Dashed lines indicate the intermolecular C—H⋯O hydrogen bonds.

4. Synthesis and crystallization

Acetylacetylene (0.27 g, 3.9 mmol) was added to a stirred suspension of cotarnine chloride (0.10 g, 0.39 mmol) and CuI (0.011 g, 0.059 mmol) in CH₂Cl₂ (10 ml) under Ar at 256 K (Fig. 3). After stirring at 256 K for 1 h, triethylamine (0.059 g, 0.59 mmol) was added to the mixture under Ar at 256 K. The reaction mixture was stirred at 256 K for 30 min, and brought to room temperature and stirred for three days. The reaction progress was monitored by TLC (eluent EtOH). After the completion, the solvent was removed in vacuum, and the residue separated by column chromatography on silica gel (EtOAc–hexane, 1:1). After removing the solvent, the residue was recrystallized from an EtOAc–hexane solvent mixture to give 37 mg (28% yield) of yellow–orange crystals of the title compound, m.p. = 448–450 K (EtOAc–hexane).

Figure 3
Synthesis of (I)

using a domino reaction between cotarnine chloride and acetylacetylene catalysed by copper(I) iodide.

¹H NMR (CDCl₃, 600 MHz): δ = 2.29 (3H, s, COCH₃); 2.38 (3H, s, COCH₃); 2.85–2.87 (2H, m, 6-CH₂); 3.80 (3H, s, 11-OCH₃); 3.94–3.96 (2H, m, 5-CH₂); 4.00 (2H, s, CH₂COCH₃); 5.96 (2H, s, 9-CH₂); 6.49 (1H, s, H-7); 7.37 (1H, s, H-3); ¹³C NMR (CDCl₃, 150 MHz): δ = 27.4, 29.5, 31.5, 42.4, 44.9, 59.9, 101.0, 103.3, 115.4, 115.8, 123.0, 126.5, 127.5, 129.5, 136.5, 139.9, 147.8, 193.1, 207.4; m/z: 341 [M]⁺ (67), 299 (33), 298 (100), 284 (18), 283 (72), 282 (54), 268 (5), 256 (31), 255 (28), 254 (21), 241 (15), 240 (47), 212 (6), 182 (5), 168 (7), 167 (7), 154 (12), 127 (7), 43 (16). Analysis calculated for C₁₉H₁₉NO₅ (%): C 66.85, H 5.61, N 4.10; found (%): C 66.92, H 5.55, N 4.15.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were placed in calculated positions with C—H = 0.95–0.99 Å and refined using the riding model with fixed isotropic displacement parameters [U_iso(H) = 1.5U_eq(C) for the CH₃-groups and 1.2U_eq(C) for the other groups].

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₉NO₅
M_r	341.35
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	7.2782 (4), 14.0016 (7), 15.7852 (8)
β (°)	99.546 (1)
V (Å³)	1586.34 (14)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.15 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003 )
T_min, T_max	0.970, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	24316, 5762, 4535
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.758

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.133, 1.03
No. of reflections	5762
No. of parameters	229
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.38
Computer programs: APEX2 (Bruker, 2005 ), SAINT (Bruker, 2001 ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 1580424

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989017015110/hb7707sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017015110/hb7707Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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).

1-(2-Acetyl-11-methoxy-5,6-dihydro[1,3]dioxolo[4,5-g]pyrrolo[2,1-a]isoquinolin-1-yl)propan-2-one top

Crystal data top

C₁₉H₁₉NO₅	F(000) = 720
M_r = 341.35	D_x = 1.429 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.2782 (4) Å	Cell parameters from 5328 reflections
b = 14.0016 (7) Å	θ = 2.6–31.9°
c = 15.7852 (8) Å	µ = 0.10 mm⁻¹
β = 99.546 (1)°	T = 120 K
V = 1586.34 (14) Å³	Prism, orange
Z = 4	0.20 × 0.15 × 0.15 mm

Data collection top

Bruker APEXII CCD diffractometer	4535 reflections with I > 2σ(I)
Radiation source: fine-focus seales tube	R_int = 0.042
φ and ω scans	θ_max = 32.6°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −11→10
T_min = 0.970, T_max = 0.980	k = −20→21
24316 measured reflections	l = −23→23
5762 independent reflections

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.068P)² + 0.4867P] where P = (F_o² + 2F_c²)/3
5762 reflections	(Δ/σ)_max < 0.001
229 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

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

	x	y	z	U_iso*/U_eq
C1	0.20836 (15)	0.37136 (8)	0.45572 (7)	0.01256 (19)
C2	0.24234 (15)	0.46920 (8)	0.48054 (7)	0.0138 (2)
C3	0.28874 (16)	0.47143 (8)	0.56943 (7)	0.0147 (2)
H3	0.3177	0.5269	0.6036	0.018*
N4	0.28561 (14)	0.38096 (7)	0.59883 (6)	0.01391 (18)
C5	0.30680 (18)	0.35126 (8)	0.68855 (7)	0.0174 (2)
H5A	0.2856	0.4062	0.7252	0.021*
H5B	0.4344	0.3268	0.7081	0.021*
C6	0.16472 (17)	0.27329 (8)	0.69533 (7)	0.0165 (2)
H6A	0.1820	0.2487	0.7549	0.020*
H6B	0.0373	0.2999	0.6812	0.020*
C6A	0.18777 (15)	0.19242 (8)	0.63407 (7)	0.01320 (19)
C7	0.17044 (16)	0.09736 (8)	0.65958 (7)	0.0150 (2)
H7	0.1389	0.0818	0.7140	0.018*
C7A	0.20129 (16)	0.02752 (8)	0.60209 (7)	0.0147 (2)
O8	0.19904 (13)	−0.06993 (6)	0.61417 (6)	0.01939 (18)
C9	0.22878 (17)	−0.11078 (8)	0.53375 (8)	0.0169 (2)
H9A	0.3207	−0.1634	0.5441	0.020*
H9B	0.1105	−0.1367	0.5020	0.020*
O10	0.29712 (13)	−0.03606 (6)	0.48500 (6)	0.01822 (18)
C10A	0.25597 (15)	0.04791 (8)	0.52391 (7)	0.0137 (2)
C11	0.27333 (15)	0.14145 (8)	0.49713 (7)	0.01233 (19)
C11A	0.23175 (15)	0.21532 (8)	0.55265 (7)	0.01190 (19)
C11B	0.24022 (15)	0.31718 (8)	0.53044 (7)	0.01223 (19)
C12	0.13624 (15)	0.34137 (8)	0.36538 (7)	0.0141 (2)
H12A	0.0251	0.3802	0.3431	0.017*
H12B	0.0963	0.2738	0.3656	0.017*
C13	0.27738 (16)	0.35160 (8)	0.30483 (7)	0.0145 (2)
O13	0.44297 (12)	0.36125 (7)	0.33022 (6)	0.02009 (19)
C14	0.19984 (19)	0.34580 (11)	0.21036 (8)	0.0235 (3)
H14A	0.2926	0.3697	0.1771	0.035*
H14B	0.0867	0.3848	0.1979	0.035*
H14C	0.1698	0.2792	0.1946	0.035*
C15	0.23042 (17)	0.55343 (8)	0.42517 (8)	0.0165 (2)
O15	0.19111 (15)	0.54807 (7)	0.34639 (6)	0.0253 (2)
C16	0.26736 (18)	0.64920 (8)	0.46885 (8)	0.0196 (2)
H16A	0.2745	0.6986	0.4255	0.029*
H16B	0.3855	0.6467	0.5089	0.029*
H16C	0.1660	0.6644	0.5005	0.029*
O17	0.33691 (12)	0.16770 (6)	0.42396 (5)	0.01608 (17)
C17	0.31065 (19)	0.10236 (9)	0.35248 (8)	0.0206 (2)
H17A	0.3391	0.1348	0.3012	0.031*
H17B	0.1811	0.0803	0.3418	0.031*
H17C	0.3939	0.0474	0.3658	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0131 (4)	0.0129 (4)	0.0122 (4)	−0.0003 (4)	0.0034 (4)	−0.0007 (4)
C2	0.0154 (5)	0.0121 (5)	0.0143 (5)	0.0005 (4)	0.0036 (4)	0.0009 (4)
C3	0.0185 (5)	0.0114 (4)	0.0146 (5)	−0.0013 (4)	0.0035 (4)	−0.0010 (4)
N4	0.0184 (4)	0.0119 (4)	0.0113 (4)	−0.0009 (3)	0.0020 (3)	−0.0008 (3)
C5	0.0259 (6)	0.0148 (5)	0.0108 (4)	−0.0005 (4)	0.0007 (4)	−0.0013 (4)
C6	0.0242 (6)	0.0138 (5)	0.0126 (5)	0.0014 (4)	0.0064 (4)	−0.0008 (4)
C6A	0.0148 (5)	0.0129 (4)	0.0124 (4)	0.0006 (4)	0.0034 (4)	−0.0003 (4)
C7	0.0188 (5)	0.0133 (5)	0.0135 (5)	0.0010 (4)	0.0046 (4)	0.0016 (4)
C7A	0.0156 (5)	0.0117 (4)	0.0167 (5)	0.0002 (4)	0.0027 (4)	0.0013 (4)
O8	0.0291 (5)	0.0110 (4)	0.0192 (4)	0.0002 (3)	0.0077 (3)	0.0005 (3)
C9	0.0178 (5)	0.0121 (5)	0.0210 (5)	−0.0008 (4)	0.0039 (4)	−0.0017 (4)
O10	0.0249 (4)	0.0111 (4)	0.0204 (4)	−0.0003 (3)	0.0088 (3)	−0.0032 (3)
C10A	0.0146 (5)	0.0117 (4)	0.0152 (5)	−0.0001 (4)	0.0038 (4)	−0.0024 (4)
C11	0.0125 (4)	0.0135 (5)	0.0117 (4)	−0.0007 (4)	0.0040 (3)	−0.0010 (4)
C11A	0.0128 (4)	0.0115 (4)	0.0115 (4)	−0.0005 (3)	0.0020 (3)	−0.0009 (3)
C11B	0.0129 (4)	0.0122 (4)	0.0119 (4)	−0.0007 (3)	0.0031 (4)	−0.0012 (3)
C12	0.0140 (5)	0.0155 (5)	0.0124 (4)	−0.0014 (4)	0.0015 (4)	−0.0002 (4)
C13	0.0189 (5)	0.0121 (4)	0.0128 (4)	−0.0014 (4)	0.0040 (4)	−0.0004 (4)
O13	0.0177 (4)	0.0258 (5)	0.0173 (4)	−0.0038 (3)	0.0045 (3)	−0.0033 (3)
C14	0.0257 (6)	0.0330 (7)	0.0120 (5)	−0.0056 (5)	0.0035 (4)	−0.0004 (5)
C15	0.0181 (5)	0.0145 (5)	0.0174 (5)	0.0015 (4)	0.0046 (4)	0.0021 (4)
O15	0.0392 (6)	0.0209 (4)	0.0156 (4)	0.0024 (4)	0.0038 (4)	0.0038 (3)
C16	0.0235 (6)	0.0131 (5)	0.0224 (6)	0.0001 (4)	0.0041 (5)	0.0021 (4)
O17	0.0217 (4)	0.0151 (4)	0.0132 (4)	−0.0011 (3)	0.0081 (3)	−0.0022 (3)
C17	0.0281 (6)	0.0210 (6)	0.0138 (5)	0.0002 (5)	0.0061 (4)	−0.0049 (4)

Geometric parameters (Å, º) top

C1—C11B	1.3890 (15)	C9—H9B	0.9900
C1—C2	1.4350 (15)	O10—C10A	1.3820 (13)
C1—C12	1.4957 (15)	C10A—C11	1.3884 (15)
C2—C3	1.3880 (16)	C11—O17	1.3640 (13)
C2—C15	1.4620 (16)	C11—C11A	1.4204 (15)
C3—N4	1.3505 (14)	C11A—C11B	1.4723 (15)
C3—H3	0.9500	C12—C13	1.5215 (16)
N4—C11B	1.3977 (14)	C12—H12A	0.9900
N4—C5	1.4595 (14)	C12—H12B	0.9900
C5—C6	1.5197 (17)	C13—O13	1.2129 (14)
C5—H5A	0.9900	C13—C14	1.5066 (16)
C5—H5B	0.9900	C14—H14A	0.9800
C6—C6A	1.5162 (15)	C14—H14B	0.9800
C6—H6A	0.9900	C14—H14C	0.9800
C6—H6B	0.9900	C15—O15	1.2312 (15)
C6A—C7	1.4022 (16)	C15—C16	1.5114 (17)
C6A—C11A	1.4119 (15)	C16—H16A	0.9800
C7—C7A	1.3777 (16)	C16—H16B	0.9800
C7—H7	0.9500	C16—H16C	0.9800
C7A—O8	1.3783 (14)	O17—C17	1.4406 (14)
C7A—C10A	1.3877 (16)	C17—H17A	0.9800
O8—C9	1.4411 (14)	C17—H17B	0.9800
C9—O10	1.4355 (15)	C17—H17C	0.9800
C9—H9A	0.9900

C11B—C1—C2	107.01 (9)	O10—C10A—C11	129.04 (10)
C11B—C1—C12	129.72 (10)	C7A—C10A—C11	121.25 (10)
C2—C1—C12	123.07 (10)	O17—C11—C10A	124.94 (10)
C3—C2—C1	107.43 (10)	O17—C11—C11A	117.59 (9)
C3—C2—C15	124.52 (10)	C10A—C11—C11A	117.37 (10)
C1—C2—C15	128.05 (10)	C6A—C11A—C11	119.99 (10)
N4—C3—C2	108.12 (10)	C6A—C11A—C11B	117.49 (9)
N4—C3—H3	125.9	C11—C11A—C11B	122.47 (10)
C2—C3—H3	125.9	C1—C11B—N4	106.96 (9)
C3—N4—C11B	110.44 (9)	C1—C11B—C11A	136.34 (10)
C3—N4—C5	126.55 (9)	N4—C11B—C11A	116.67 (9)
C11B—N4—C5	122.74 (9)	C1—C12—C13	113.94 (9)
N4—C5—C6	108.02 (9)	C1—C12—H12A	108.8
N4—C5—H5A	110.1	C13—C12—H12A	108.8
C6—C5—H5A	110.1	C1—C12—H12B	108.8
N4—C5—H5B	110.1	C13—C12—H12B	108.8
C6—C5—H5B	110.1	H12A—C12—H12B	107.7
H5A—C5—H5B	108.4	O13—C13—C14	121.44 (11)
C6A—C6—C5	110.06 (9)	O13—C13—C12	122.70 (10)
C6A—C6—H6A	109.6	C14—C13—C12	115.83 (10)
C5—C6—H6A	109.6	C13—C14—H14A	109.5
C6A—C6—H6B	109.6	C13—C14—H14B	109.5
C5—C6—H6B	109.6	H14A—C14—H14B	109.5
H6A—C6—H6B	108.2	C13—C14—H14C	109.5
C7—C6A—C11A	121.45 (10)	H14A—C14—H14C	109.5
C7—C6A—C6	120.06 (10)	H14B—C14—H14C	109.5
C11A—C6A—C6	118.46 (10)	O15—C15—C2	122.38 (11)
C7A—C7—C6A	116.89 (10)	O15—C15—C16	120.58 (11)
C7A—C7—H7	121.6	C2—C15—C16	117.03 (10)
C6A—C7—H7	121.6	C15—C16—H16A	109.5
C7—C7A—O8	127.20 (10)	C15—C16—H16B	109.5
C7—C7A—C10A	122.82 (10)	H16A—C16—H16B	109.5
O8—C7A—C10A	109.78 (10)	C15—C16—H16C	109.5
C7A—O8—C9	105.31 (9)	H16A—C16—H16C	109.5
O10—C9—O8	107.40 (9)	H16B—C16—H16C	109.5
O10—C9—H9A	110.2	C11—O17—C17	118.20 (9)
O8—C9—H9A	110.2	O17—C17—H17A	109.5
O10—C9—H9B	110.2	O17—C17—H17B	109.5
O8—C9—H9B	110.2	H17A—C17—H17B	109.5
H9A—C9—H9B	108.5	O17—C17—H17C	109.5
C10A—O10—C9	105.18 (9)	H17A—C17—H17C	109.5
O10—C10A—C7A	109.60 (10)	H17B—C17—H17C	109.5

C11B—C1—C2—C3	−1.55 (13)	C7—C6A—C11A—C11	−4.76 (17)
C12—C1—C2—C3	173.73 (10)	C6—C6A—C11A—C11	173.48 (10)
C11B—C1—C2—C15	179.00 (11)	C7—C6A—C11A—C11B	177.82 (10)
C12—C1—C2—C15	−5.72 (18)	C6—C6A—C11A—C11B	−3.93 (15)
C1—C2—C3—N4	0.40 (13)	O17—C11—C11A—C6A	−172.16 (10)
C15—C2—C3—N4	179.88 (11)	C10A—C11—C11A—C6A	4.35 (16)
C2—C3—N4—C11B	0.91 (13)	O17—C11—C11A—C11B	5.12 (16)
C2—C3—N4—C5	−173.22 (11)	C10A—C11—C11A—C11B	−178.37 (10)
C3—N4—C5—C6	137.61 (11)	C2—C1—C11B—N4	2.06 (12)
C11B—N4—C5—C6	−35.84 (14)	C12—C1—C11B—N4	−172.80 (11)
N4—C5—C6—C6A	55.40 (12)	C2—C1—C11B—C11A	179.75 (12)
C5—C6—C6A—C7	140.24 (11)	C12—C1—C11B—C11A	4.9 (2)
C5—C6—C6A—C11A	−38.03 (14)	C3—N4—C11B—C1	−1.89 (13)
C11A—C6A—C7—C7A	1.02 (17)	C5—N4—C11B—C1	172.50 (10)
C6—C6A—C7—C7A	−177.19 (10)	C3—N4—C11B—C11A	179.90 (10)
C6A—C7—C7A—O8	177.40 (11)	C5—N4—C11B—C11A	−5.71 (16)
C6A—C7—C7A—C10A	3.08 (17)	C6A—C11A—C11B—C1	−150.28 (13)
C7—C7A—O8—C9	176.86 (12)	C11—C11A—C11B—C1	32.37 (19)
C10A—C7A—O8—C9	−8.22 (13)	C6A—C11A—C11B—N4	27.24 (15)
C7A—O8—C9—O10	15.32 (12)	C11—C11A—C11B—N4	−150.10 (10)
O8—C9—O10—C10A	−16.59 (12)	C11B—C1—C12—C13	−114.40 (13)
C9—O10—C10A—C7A	11.69 (12)	C2—C1—C12—C13	71.46 (14)
C9—O10—C10A—C11	−172.25 (11)	C1—C12—C13—O13	16.37 (16)
C7—C7A—C10A—O10	172.97 (11)	C1—C12—C13—C14	−165.56 (10)
O8—C7A—C10A—O10	−2.22 (13)	C3—C2—C15—O15	179.01 (12)
C7—C7A—C10A—C11	−3.45 (18)	C1—C2—C15—O15	−1.6 (2)
O8—C7A—C10A—C11	−178.64 (10)	C3—C2—C15—C16	−1.43 (17)
O10—C10A—C11—O17	0.16 (19)	C1—C2—C15—C16	177.94 (11)
C7A—C10A—C11—O17	175.81 (11)	C10A—C11—O17—C17	27.93 (16)
O10—C10A—C11—C11A	−176.06 (11)	C11A—C11—O17—C17	−155.86 (10)
C7A—C10A—C11—C11A	−0.40 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O13ⁱ	0.95	2.44	3.2840 (14)	147
C9—H9A···O17ⁱⁱ	0.99	2.46	3.2207 (15)	133

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1.

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.

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