1-Isobutyl-8,9-dimeth­oxy-3-phenyl-5,6-dihidro­imidazo[5,1-a]isoquinolin-2-ium chloride

Okmanov, R.Y.; Tukhtaev, D.B.; Saidov, A.S.; Tashkhodjaev, B.

doi:10.1107/S2414314619013907

organic compounds

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ISSN: 2414-3146

Volume 4| Part 10| October 2019| x191390

https://doi.org/10.1107/S2414314619013907

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1-Isobutyl-8,9-dimethoxy-3-phenyl-5,6-dihidroimidazo[5,1-a]isoquinolin-2-ium chloride

R. Ya. Okmanov,^a ^* D. B. Tukhtaev,^b A. Sh. Saidov ^b and B. Tashkhodjaev ^a

^aS. Yunusov Institute of the Chemistry of Plant Substances, Academy of Sciences of Uzbekistan, 100170, Mirzo Ulugbek Str. 77, Tashkent City, Uzbekistan, and ^bSamarkand State University, 140104, University blv. 15, Samarkand City, Samarkand region, Uzbekistan
^*Correspondence e-mail: raxul@mail.ru

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 8 October 2019; accepted 11 October 2019; online 22 October 2019)

The molecular salt, C₂₃H₂₆N₂O₂⁺·Cl⁻, was obtained from 1-isobutyl-8,9-dimethoxy-3-phenyl-5,6-dihydroimidazo[5,1-a]isoquinoline, which was synthesized by cyclocondensation of α-benzoylamino-γ-methyl-N-[2-(3,4-dimethoxyphenyl)ethyl]valeramide in the presence of phosphoryl chloride. The tetrahydropyridine ring adopts a twist–boat conformation. In the crystal structure, centrosymmetric dimers are formed by N—H⋯Cl and C—H⋯Cl hydrogen bonds.

Keywords: dihydroimidazo[5,1-a]isoquinoline; crystal structure; hydrogen bonding.

CCDC references: 1958696; 1958696

Structure description

The relevance of a wide range of potent biological activities of natural and synthetic isoquinoline alkaloids is interesting for the synthesis of new isoquinoline compounds. In nature, there are compounds that contain condensed imidazole and isoquinoline rings, for example, cribrostatin 6.

Cyclization of α-benzoylamino-γ-methyl-N-[2-(3,4-dimethoxyphenyl)ethyl]valeramide with phosphoryl chloride based on the Bischler–Napieralski reaction results in a heterocyclic compound containing condensed imidazole and isoquinoline rings (Seganish et al., 2012 ; Iaroshenko et al., 2015 ; Allin et al., 2005 ). In the reaction, phosphoryl chloride is used as a reagent and solvent (Fig. 1).

Figure 1
Reaction scheme for the preparation of the title compound.

However, from the obtained 1-isobutyl-8,9-dimethoxy-3-phenyl-5,6-dihydroimidazo[5,1-a]isoquinoline we could not get suitable single crystals for X-ray diffraction analysis. Good crystals of the title compound were obtained by slow evaporation of a solution of 1-isobutyl-8,9-dimethoxy-3-phenyl-5,6-dihydroimidazo[5,1-a]isoquinoline treated with hydrochloric acid.

The molecular structure of the title compound is shown in Fig. 2. The dihydropyridine ring occurs in a twist-boat conformation. The C6, C6A, C10A and C10B atoms of the dihydropyridine ring are almost coplanar (r.m.s. deviation = 0.095 Å). The C5 and N4 atoms deviate from this plane by 0.806 (5) and 0.413 (5) Å, respectively. The imidazole (C1/N2/C3/N4/C10B) and benzene (C17–C22) rings are essentially planar, the dihedral angle between the planes being 41.4 (1)°. In the crystal, N2—H1⋯Cl1 and C20—H20A⋯Cl1 hydrogen bonds are observed, resulting in the formation of a centrosymmetric dimer consisting of two anions and two cations (Fig. 3 and Table 1). These dimers are linked by C5—H5B⋯Cl1 hydrogen bonds into a chain directed along [011].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯Cl1	0.98 (3)	2.04 (3)	3.019 (2)	179
C20—H20A⋯Cl1ⁱ	0.93	2.89	3.650 (3)	140
C5—H5B⋯Cl1ⁱⁱ	0.97	2.83	3.707 (3)	152
Symmetry codes: (i) -x+1, -y+3, -z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The N—H⋯Cl hydrogen bond is shown as a dashed line.

Figure 3
Formation of a centrosymmetric dimer in the crystal structure of the title compound. N—H⋯Cl hydrogen bonds are shown as dashed lines.

Synthesis and crystallization

To a round-bottomed flask with 0.5 g (1.25 mmol) of α-benzoylamino-γ-methyl-N-[2-(3,4-dimethoxyphenyl)ethyl]valeramide was added dropwise 0.7 ml (7.64 mmol) of POCl₃. The reaction mixture was heated for 4 h in a boiling water bath. The course of the reaction was monitored using thin-layer chromatography (TLC). After heating, the reaction tube was filled with crushed ice, the pH of the solution was adjusted to 9 with 25% ammonium hydroxide solution. The solution was extracted with chloroform (30 ml) and the organic layer was washed with water and distilled. When acetone was added to the residue, a precipitate was formed. The precipitate was filtered off and dried and giving 0.33 g (yield 74%) of product; R_F = 0.61 (1:4 CH₃OH–CHCl₃ v/v); m.p. 433–436 K.

0.2 g of 1-isobutyl-8,9-dimethoxy-3-phenyl-5,6-dihydroimidazo[5,1-a]isoquinoline was dissolved in 25 ml of methanol and transferred to an acidic medium with 30% HCl (pH = 3). The methanol was distilled and a precipitate was obtained when acetone was added. The precipitate was filtered off, washed with acetone and dried in the open air. 0.18 g of 1-isobutyl-8,9-dimethoxy-3-phenyl-5,6-dihydroimidazo[5,1-a]isoquinoline hydrochloride was obtained (yield 82%); R_F = 0.32 (1:4 CH₃OH–CHCl₃ v/v); m.p. 475–477 K.

1-Isobutyl-8,9-dimethoxy-3-phenyl-5,6-dihydroimidazo[5,1-a]isoquinoline hydrochloride was dissolved in a 4:1 (v/v) acetone–methanol solvent mixture and allowed to evaporation at room temperature. Colourless crystals suitable for X-ray diffraction analysis were obtained.

¹H NMR [400 MHz, CD₃OD, δ (p.p.m.), J (Hz)]: 7.69 (2H, dt, J = 1.9; 6.0, H18 and H22); 7.62 (2H, dd, J = 1.7; 6.6, H19 and H21); 7.60 (1H, dt, J = 1.4; 6.0, H20), 7.18 (1H, s, H7); 6.97 (1H, s, H10); 4.26 (2H, t, J = 6.4, CH₂-5); 3.85 (3H, s, CH₃-12); 3.83 (3H, s, CH₃-11), 3.01 (2H, t, J = 6.4, CH₂-6); 2.86 (2H, t, J = 7.3, CH₂-13); 2.09 (1H, q, J = 6.8, H14); 1.02 (6H, d, J = 6.6, CH₃-15,16).

¹³C NMR [100 MHz, CD₃OD, δ (p.p.m.)]: 23.02 (C15, C16); 29.62 (C14); 30.61 (C6); 36.02 (C13); 44.52 (C5); 57.05 (C11); 57.27 (C12); 109.98 (C10); 113.96 (C7); 119.63 (C10A); 125.95 (C6A; C1), 128.73 (C18, C22); 131.06 (C19, C21); 131.42 (C20); 133.72 (C10B, C17); 144.77 (C3); 150.99 (C9); 152.16 (C8).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₃H₂₇N₂O₂⁺·Cl⁻
M_r	398.92
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	13.595 (3), 14.337 (3), 10.958 (2)
β (°)	92.23 (3)
V (Å³)	2134.1 (7)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	1.74
Crystal size (mm)	0.60 × 0.53 × 0.48

Data collection
Diffractometer	Rigaku Xcalibur Ruby
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.371, 0.434
No. of measured, independent and observed [I > 2σ(I)] reflections	9283, 4347, 2990
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.142, 1.01
No. of reflections	4347
No. of parameters	261
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.20
Computer programs: CrysAlis PRO (Rigaku OD, 2018 ), SHELXS7 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), XP (Bruker, 1998 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC references: 1958696; 1958696

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S2414314619013907/vm4042sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619013907/vm4042Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXS7 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP (Bruker, 1998); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

1-Isobutyl-8,9-dimethoxy-3-phenyl-5,6-dihydroimidazo[5,1-a]isoquinolin-2-ium chloride top

Crystal data top

C₂₃H₂₇N₂O₂⁺·Cl⁻	F(000) = 848
M_r = 398.92	D_x = 1.242 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 475(2) K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54184 Å
a = 13.595 (3) Å	Cell parameters from 2082 reflections
b = 14.337 (3) Å	θ = 4.5–75.8°
c = 10.958 (2) Å	µ = 1.74 mm⁻¹
β = 92.23 (3)°	T = 291 K
V = 2134.1 (7) Å³	Prizmatic, colorless
Z = 4	0.60 × 0.53 × 0.48 mm

Data collection top

Rigaku Xcalibur Ruby diffractometer	4347 independent reflections
Radiation source: fine-focus sealed tube	2990 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 10.2576 pixels mm^-1	θ_max = 76.0°, θ_min = 4.5°
ω scans	h = −16→17
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −18→16
T_min = 0.371, T_max = 0.434	l = −9→13
9283 measured reflections

Refinement top

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0678P)² + 0.2438P] where P = (F_o² + 2F_c²)/3
4347 reflections	(Δ/σ)_max = 0.001
261 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.20 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.

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 > 2sigma(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.

The H atoms bonded to C atoms were placed geometrically (with C—H distances of 0.98 Å for CH, 0.97 Å for CH₂, 0.96 Å for CH₃ and 0.93 Å for C_ar) and included in the refinement in a riding motion approximation, with U_iso(H) = 1.2U_eq(C) [U_iso(H) = 1.5U_eq(C) for methyl H atoms]. The H atom of N2 was located in a difference Fourier synthesis and refined with a N2—H1 distance = 0.79 (3) Å.

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

	x	y	z	U_iso*/U_eq
O1	0.85755 (14)	0.77486 (11)	0.41517 (17)	0.0640 (5)
O2	0.89458 (14)	0.91068 (12)	0.56498 (16)	0.0623 (5)
N2	0.66229 (14)	1.27667 (13)	0.26859 (17)	0.0478 (4)
N4	0.63568 (14)	1.13705 (12)	0.20336 (17)	0.0452 (4)
C1	0.72530 (17)	1.21988 (15)	0.3370 (2)	0.0457 (5)
C3	0.60827 (16)	1.22675 (15)	0.1889 (2)	0.0459 (5)
C5	0.5983 (2)	1.05567 (16)	0.1344 (2)	0.0569 (6)
H5A	0.5742	1.0748	0.0537	0.068*
H5B	0.5443	1.0273	0.1763	0.068*
C6	0.6813 (2)	0.98620 (19)	0.1235 (3)	0.0692 (8)
H6A	0.6550	0.9283	0.0901	0.083*
H6B	0.7283	1.0103	0.0670	0.083*
C6A	0.7336 (2)	0.96661 (16)	0.2439 (2)	0.0545 (6)
C7	0.7699 (2)	0.87809 (16)	0.2724 (2)	0.0589 (6)
H7A	0.7587	0.8298	0.2169	0.071*
C8	0.82169 (18)	0.85996 (15)	0.3799 (2)	0.0503 (5)
C9	0.83978 (17)	0.93362 (15)	0.4627 (2)	0.0474 (5)
C10	0.80171 (17)	1.02087 (15)	0.4369 (2)	0.0467 (5)
H10A	0.8115	1.0688	0.4932	0.056*
C10A	0.74883 (17)	1.03854 (14)	0.3279 (2)	0.0451 (5)
C10B	0.70861 (17)	1.13078 (15)	0.29649 (19)	0.0443 (5)
C11	0.8322 (2)	0.69713 (18)	0.3379 (3)	0.0744 (8)
H11A	0.8595	0.6411	0.3732	0.112*
H11B	0.8584	0.7067	0.2588	0.112*
H11C	0.7619	0.6915	0.3301	0.112*
C12	0.9174 (2)	0.98354 (18)	0.6494 (2)	0.0648 (7)
H12A	0.9622	0.9607	0.7123	0.097*
H12B	0.8580	1.0047	0.6853	0.097*
H12C	0.9472	1.0344	0.6076	0.097*
C13	0.79478 (19)	1.26228 (17)	0.4306 (2)	0.0551 (6)
H13A	0.8276	1.2126	0.4764	0.066*
H13B	0.7571	1.2983	0.4874	0.066*
C14	0.8726 (2)	1.32535 (19)	0.3772 (3)	0.0671 (7)
H14A	0.8384	1.3731	0.3277	0.080*
C15	0.9379 (3)	1.2716 (3)	0.2951 (4)	0.1234 (15)
H15A	0.8984	1.2425	0.2313	0.185*
H15B	0.9728	1.2246	0.3417	0.185*
H15C	0.9841	1.3133	0.2598	0.185*
C16	0.9321 (3)	1.3745 (3)	0.4774 (4)	0.1160 (15)
H16A	0.9796	1.4147	0.4418	0.174*
H16B	0.9654	1.3291	0.5284	0.174*
H16C	0.8889	1.4110	0.5257	0.174*
C17	0.53556 (17)	1.26476 (16)	0.1005 (2)	0.0479 (5)
C18	0.44587 (19)	1.22054 (18)	0.0757 (2)	0.0583 (6)
H18A	0.4311	1.1652	0.1153	0.070*
C19	0.3789 (2)	1.2590 (2)	−0.0080 (3)	0.0668 (7)
H19A	0.3185	1.2299	−0.0232	0.080*
C20	0.4007 (2)	1.34047 (19)	−0.0695 (2)	0.0653 (7)
H20A	0.3561	1.3651	−0.1273	0.078*
C21	0.4889 (2)	1.38447 (18)	−0.0442 (2)	0.0648 (7)
H21A	0.5035	1.4395	−0.0847	0.078*
C22	0.5564 (2)	1.34783 (17)	0.0408 (2)	0.0558 (6)
H22A	0.6155	1.3786	0.0580	0.067*
Cl1	0.65752 (5)	1.48541 (4)	0.30437 (6)	0.0602 (2)
H1	0.661 (2)	1.345 (2)	0.280 (3)	0.076 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0725 (11)	0.0376 (8)	0.0803 (12)	0.0105 (8)	−0.0194 (9)	−0.0055 (8)
O2	0.0825 (12)	0.0436 (9)	0.0588 (10)	0.0087 (8)	−0.0214 (9)	−0.0025 (8)
N2	0.0565 (11)	0.0344 (9)	0.0520 (11)	0.0013 (8)	−0.0040 (9)	−0.0001 (8)
N4	0.0521 (10)	0.0357 (9)	0.0472 (10)	−0.0002 (8)	−0.0038 (8)	0.0003 (8)
C1	0.0519 (12)	0.0374 (11)	0.0475 (12)	−0.0005 (9)	−0.0018 (10)	0.0013 (9)
C3	0.0508 (12)	0.0376 (11)	0.0492 (12)	0.0021 (9)	0.0012 (10)	0.0027 (9)
C5	0.0723 (16)	0.0405 (12)	0.0565 (14)	−0.0001 (11)	−0.0169 (12)	−0.0052 (11)
C6	0.095 (2)	0.0496 (14)	0.0608 (16)	0.0164 (14)	−0.0204 (15)	−0.0142 (12)
C6A	0.0677 (15)	0.0418 (12)	0.0532 (14)	0.0064 (11)	−0.0093 (12)	−0.0053 (10)
C7	0.0737 (16)	0.0394 (12)	0.0624 (15)	0.0062 (11)	−0.0145 (13)	−0.0113 (11)
C8	0.0542 (13)	0.0351 (11)	0.0612 (14)	0.0045 (9)	−0.0050 (11)	−0.0011 (10)
C9	0.0511 (12)	0.0400 (11)	0.0508 (12)	0.0007 (10)	−0.0030 (10)	0.0025 (10)
C10	0.0537 (12)	0.0376 (11)	0.0484 (12)	0.0001 (9)	−0.0040 (10)	−0.0032 (10)
C10A	0.0509 (12)	0.0360 (11)	0.0481 (12)	0.0006 (9)	−0.0017 (10)	−0.0006 (9)
C10B	0.0509 (12)	0.0389 (11)	0.0428 (11)	0.0002 (9)	−0.0018 (10)	−0.0008 (9)
C11	0.0809 (19)	0.0387 (13)	0.102 (2)	0.0087 (13)	−0.0182 (17)	−0.0127 (14)
C12	0.0815 (18)	0.0543 (14)	0.0567 (15)	0.0021 (13)	−0.0198 (13)	−0.0041 (12)
C13	0.0684 (15)	0.0421 (12)	0.0540 (13)	−0.0063 (11)	−0.0065 (11)	−0.0041 (11)
C14	0.0576 (15)	0.0552 (15)	0.087 (2)	−0.0029 (12)	−0.0157 (14)	0.0146 (14)
C15	0.092 (3)	0.142 (4)	0.139 (4)	−0.012 (3)	0.043 (3)	−0.017 (3)
C16	0.093 (3)	0.093 (3)	0.159 (4)	−0.036 (2)	−0.035 (3)	−0.009 (3)
C17	0.0572 (13)	0.0414 (12)	0.0449 (12)	0.0057 (10)	−0.0011 (10)	−0.0003 (9)
C18	0.0631 (15)	0.0484 (13)	0.0627 (15)	0.0028 (11)	−0.0067 (12)	0.0042 (11)
C19	0.0687 (16)	0.0615 (16)	0.0689 (17)	0.0069 (13)	−0.0158 (13)	−0.0083 (14)
C20	0.0848 (19)	0.0565 (15)	0.0534 (15)	0.0194 (14)	−0.0134 (14)	−0.0014 (12)
C21	0.097 (2)	0.0451 (13)	0.0514 (14)	0.0094 (14)	−0.0001 (14)	0.0068 (11)
C22	0.0710 (15)	0.0434 (12)	0.0531 (14)	0.0017 (11)	0.0012 (12)	0.0017 (11)
Cl1	0.0777 (4)	0.0391 (3)	0.0627 (4)	0.0086 (3)	−0.0097 (3)	−0.0026 (3)

Geometric parameters (Å, º) top

O1—C8	1.364 (3)	C11—H11B	0.9600
O1—C11	1.433 (3)	C11—H11C	0.9600
O2—C9	1.362 (3)	C12—H12A	0.9600
O2—C12	1.421 (3)	C12—H12B	0.9600
N2—C3	1.328 (3)	C12—H12C	0.9600
N2—C1	1.381 (3)	C13—C14	1.526 (4)
N2—H1	0.98 (3)	C13—H13A	0.9700
N4—C3	1.346 (3)	C13—H13B	0.9700
N4—C10B	1.398 (3)	C14—C15	1.501 (5)
N4—C5	1.470 (3)	C14—C16	1.512 (4)
C1—C10B	1.368 (3)	C14—H14A	0.9800
C1—C13	1.497 (3)	C15—H15A	0.9600
C3—C17	1.462 (3)	C15—H15B	0.9600
C5—C6	1.513 (4)	C15—H15C	0.9600
C5—H5A	0.9700	C16—H16A	0.9600
C5—H5B	0.9700	C16—H16B	0.9600
C6—C6A	1.500 (3)	C16—H16C	0.9600
C6—H6A	0.9700	C17—C18	1.392 (3)
C6—H6B	0.9700	C17—C22	1.393 (3)
C6A—C10A	1.393 (3)	C18—C19	1.381 (3)
C6A—C7	1.393 (3)	C18—H18A	0.9300
C7—C8	1.374 (3)	C19—C20	1.387 (4)
C7—H7A	0.9300	C19—H19A	0.9300
C8—C9	1.408 (3)	C20—C21	1.373 (4)
C9—C10	1.379 (3)	C20—H20A	0.9300
C10—C10A	1.393 (3)	C21—C22	1.385 (4)
C10—H10A	0.9300	C21—H21A	0.9300
C10A—C10B	1.467 (3)	C22—H22A	0.9300
C11—H11A	0.9600	Cl1—Cl1	0.0000 (19)

C8—O1—C11	116.95 (19)	H11A—C11—H11C	109.5
C9—O2—C12	117.16 (18)	H11B—C11—H11C	109.5
C3—N2—C1	110.75 (18)	O2—C12—H12A	109.5
C3—N2—H1	127.1 (16)	O2—C12—H12B	109.5
C1—N2—H1	122.1 (16)	H12A—C12—H12B	109.5
C3—N4—C10B	109.42 (18)	O2—C12—H12C	109.5
C3—N4—C5	127.51 (19)	H12A—C12—H12C	109.5
C10B—N4—C5	123.07 (18)	H12B—C12—H12C	109.5
C10B—C1—N2	106.43 (19)	C1—C13—C14	114.0 (2)
C10B—C1—C13	133.9 (2)	C1—C13—H13A	108.8
N2—C1—C13	119.61 (19)	C14—C13—H13A	108.8
N2—C3—N4	107.08 (19)	C1—C13—H13B	108.8
N2—C3—C17	125.23 (19)	C14—C13—H13B	108.8
N4—C3—C17	127.7 (2)	H13A—C13—H13B	107.7
N4—C5—C6	108.6 (2)	C15—C14—C16	111.3 (3)
N4—C5—H5A	110.0	C15—C14—C13	111.1 (3)
C6—C5—H5A	110.0	C16—C14—C13	110.9 (3)
N4—C5—H5B	110.0	C15—C14—H14A	107.8
C6—C5—H5B	110.0	C16—C14—H14A	107.8
H5A—C5—H5B	108.4	C13—C14—H14A	107.8
C6A—C6—C5	112.5 (2)	C14—C15—H15A	109.5
C6A—C6—H6A	109.1	C14—C15—H15B	109.5
C5—C6—H6A	109.1	H15A—C15—H15B	109.5
C6A—C6—H6B	109.1	C14—C15—H15C	109.5
C5—C6—H6B	109.1	H15A—C15—H15C	109.5
H6A—C6—H6B	107.8	H15B—C15—H15C	109.5
C10A—C6A—C7	118.9 (2)	C14—C16—H16A	109.5
C10A—C6A—C6	119.7 (2)	C14—C16—H16B	109.5
C7—C6A—C6	121.3 (2)	H16A—C16—H16B	109.5
C8—C7—C6A	122.0 (2)	C14—C16—H16C	109.5
C8—C7—H7A	119.0	H16A—C16—H16C	109.5
C6A—C7—H7A	119.0	H16B—C16—H16C	109.5
O1—C8—C7	125.3 (2)	C18—C17—C22	119.3 (2)
O1—C8—C9	115.9 (2)	C18—C17—C3	121.6 (2)
C7—C8—C9	118.8 (2)	C22—C17—C3	119.0 (2)
O2—C9—C10	125.2 (2)	C19—C18—C17	119.9 (2)
O2—C9—C8	115.19 (19)	C19—C18—H18A	120.1
C10—C9—C8	119.6 (2)	C17—C18—H18A	120.1
C9—C10—C10A	121.2 (2)	C18—C19—C20	120.7 (3)
C9—C10—H10A	119.4	C18—C19—H19A	119.7
C10A—C10—H10A	119.4	C20—C19—H19A	119.7
C10—C10A—C6A	119.4 (2)	C21—C20—C19	119.4 (2)
C10—C10A—C10B	122.7 (2)	C21—C20—H20A	120.3
C6A—C10A—C10B	117.9 (2)	C19—C20—H20A	120.3
C1—C10B—N4	106.30 (18)	C20—C21—C22	120.7 (3)
C1—C10B—C10A	135.2 (2)	C20—C21—H21A	119.6
N4—C10B—C10A	118.47 (19)	C22—C21—H21A	119.6
O1—C11—H11A	109.5	C21—C22—C17	119.9 (3)
O1—C11—H11B	109.5	C21—C22—H22A	120.0
H11A—C11—H11B	109.5	C17—C22—H22A	120.0
O1—C11—H11C	109.5

C3—N2—C1—C10B	0.0 (3)	C7—C6A—C10A—C10B	−179.1 (2)
C3—N2—C1—C13	178.6 (2)	C6—C6A—C10A—C10B	2.7 (4)
C1—N2—C3—N4	−0.5 (3)	N2—C1—C10B—N4	0.4 (3)
C1—N2—C3—C17	−178.7 (2)	C13—C1—C10B—N4	−177.8 (3)
C10B—N4—C3—N2	0.7 (3)	N2—C1—C10B—C10A	179.9 (3)
C5—N4—C3—N2	−178.7 (2)	C13—C1—C10B—C10A	1.7 (5)
C10B—N4—C3—C17	178.9 (2)	C3—N4—C10B—C1	−0.7 (3)
C5—N4—C3—C17	−0.6 (4)	C5—N4—C10B—C1	178.8 (2)
C3—N4—C5—C6	146.8 (2)	C3—N4—C10B—C10A	179.7 (2)
C10B—N4—C5—C6	−32.6 (3)	C5—N4—C10B—C10A	−0.8 (3)
N4—C5—C6—C6A	49.5 (3)	C10—C10A—C10B—C1	17.4 (4)
C5—C6—C6A—C10A	−37.4 (4)	C6A—C10A—C10B—C1	−162.0 (3)
C5—C6—C6A—C7	144.4 (3)	C10—C10A—C10B—N4	−163.1 (2)
C10A—C6A—C7—C8	−1.1 (4)	C6A—C10A—C10B—N4	17.4 (3)
C6—C6A—C7—C8	177.1 (3)	C10B—C1—C13—C14	112.9 (3)
C11—O1—C8—C7	−5.2 (4)	N2—C1—C13—C14	−65.2 (3)
C11—O1—C8—C9	174.3 (2)	C1—C13—C14—C15	−62.4 (3)
C6A—C7—C8—O1	178.5 (3)	C1—C13—C14—C16	173.2 (3)
C6A—C7—C8—C9	−1.0 (4)	N2—C3—C17—C18	−139.6 (3)
C12—O2—C9—C10	−2.6 (4)	N4—C3—C17—C18	42.6 (4)
C12—O2—C9—C8	178.1 (2)	N2—C3—C17—C22	39.8 (3)
O1—C8—C9—O2	2.7 (3)	N4—C3—C17—C22	−138.0 (3)
C7—C8—C9—O2	−177.7 (2)	C22—C17—C18—C19	0.3 (4)
O1—C8—C9—C10	−176.7 (2)	C3—C17—C18—C19	179.7 (2)
C7—C8—C9—C10	2.8 (4)	C17—C18—C19—C20	1.2 (4)
O2—C9—C10—C10A	178.1 (2)	C18—C19—C20—C21	−1.7 (4)
C8—C9—C10—C10A	−2.6 (4)	C19—C20—C21—C22	0.7 (4)
C9—C10—C10A—C6A	0.4 (4)	C20—C21—C22—C17	0.9 (4)
C9—C10—C10A—C10B	−179.0 (2)	C18—C17—C22—C21	−1.4 (4)
C7—C6A—C10A—C10	1.4 (4)	C3—C17—C22—C21	179.3 (2)
C6—C6A—C10A—C10	−176.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···Cl1	0.98 (3)	2.04 (3)	3.019 (2)	179
C20—H20A···Cl1ⁱ	0.93	2.89	3.650 (3)	140
C5—H5B···Cl1ⁱⁱ	0.97	2.83	3.707 (3)	152

Symmetry codes: (i) −x+1, −y+3, −z; (ii) −x+1, y−1/2, −z+1/2.

Funding information

Funding for this research was provided by the Academy of Sciences of the Republic of Uzbekistan (grant No. VA-FA-F-6–010).

References

Allin, S. M., Bowman, W. R., Elsegood, M. R. J., McKee, V., Karim, R. & Rahman, Sh. S. (2005). Tetrahedron, 61, 2689–2696. CSD CrossRef CAS Google Scholar
Bruker (1998). XP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2008). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Iaroshenko, V. O., Gevorgyan, A., Mkrtchyan, S., Arakelyan, K., Grigoryan, T., Yedoyan, J., Villinger, A. & Langer, P. (2015). J. Org. Chem. 80, 2103–2119. CSD CrossRef CAS PubMed Google Scholar
Rigaku OD (2018). CrysAlis PRO. Rigaku OD, Yarnton, England. Google Scholar
Seganish, W. M., Bercovici, A., Ho, G. D., Loozen, H. J. J., Timmers, C. M. & Tulshian, D. (2012). Tetrahedron Lett. 53, 903–905. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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