Crystal structure of ethyl 2-methyl-5,10-dioxo-4-phenyl-5,10-di­hydro-4H-11-thia-1,4a-di­aza­benzo[b]fluorene-3-carb­oxy­late

Yartsev, Y.; Lyubashov, P.; Povstyanoy, V.; Povstyaniy, M.; Lebedyeva, I.

doi:10.1107/S2056989018000117

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Volume 74| Part 2| February 2018| Pages 124-126

https://doi.org/10.1107/S2056989018000117

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Crystal structure of ethyl 2-methyl-5,10-dioxo-4-phenyl-5,10-dihydro-4H-11-thia-1,4a-diazabenzo[b]fluorene-3-carboxylate

Yegor Yartsev,^a ^* Pavel Lyubashov,^b Vyacheslav Povstyanoy,^b Mykhailo Povstyaniy ^b and Iryna Lebedyeva ^c

^aDepartment of Inorganic Chemistry, V. N. Karazin Kharkiv National University, 4, Svobody sq., Kharkiv 61077, Ukraine, ^bDepartment of Chemical Technology and Food Safety, Kherson National Technical, University, Berislavs'ke Highway 24, Kherson 73008, Ukraine, and ^cDepartment of Chemistry and Physics, Augusta University, 1120 15th Street, Augusta 30912, USA
^*Correspondence e-mail: yartsev.yegor@gmail.com

Edited by O. Blacque, University of Zürich, Switzerland (Received 17 December 2017; accepted 2 January 2018; online 9 January 2018)

The title compound, C₂₄H₁₈N₂O₄S, crystallizes in the orthorhombic P2₁2₁2₁ space group, indicating the existence of only one enantiomer with an S configuration of the chiral center in the crystal phase. The dihydropyrimidine ring adopts a twist-boat conformation while the quinone ring is slightly non-planar. In the crystal, molecules are linked by weak C—H⋯O and C—H⋯S hydrogen bonds and C—H⋯π interactions. In addition, a short intermolecular S⋯N contact of 3.250 (3) Å indicates an interaction between the S atom and the π-system of the thiazole ring.

Keywords: crystal structure; dihydropyrimidine; enantiomer; dihydropyrimidine; DHPM.

CCDC reference: 1814348

1. Chemical context

The three-component Biginelli reaction allows the assembly of a wide variety of dihydropyrimidine (DHPM) compounds that can be modified easily depending on the starting materials used during the reaction (Nagarajaiah et al., 2016 ). DHPMs exhibit antibacterial (Wani et al., 2017 ) and antifungal properties (Akhaja & Raval, 2012 ) and their thioanalogues such as monastrol are being used as inhibitors of mitotic kinesin Eg5 in the treatment of breast and ovarian tumors (Bobylev et al., 2017 ; Duan et al., 2015 ). In this work we investigated reactivity of thioDHPMs 1 in their reaction with the di-halogen-substituted nucleophile 2. It was expected that the reaction would proceed with substitution of one or both chlorine atoms and the formation of a thiazole ring in the product 3 (Fig. 1).

Figure 1
Synthesis of 3.

2. Structural commentary

Compound 3 crystallizes in the non-centrosymmetric chiral space group P2₁2₁2₁. This indicates the existence of only one enantiomer in the crystal with an S-configuration of the C12 chiral center according to the Flack parameter (Parsons et al., 2013 ). The quinone ring is slightly non-planar (Fig. 2). Its conformation can be described as a flattened asymmetric screw-boat with the C7 and C10 atoms deviating by 0.053 (3) and 0.082 (3) Å from the mean plane through the remaining ring atoms. This non-planarity may be caused by the formation of the weak intramolecular C12—H12⋯O2 hydrogen bond. Taking into account high conformational flexibility of the quinone ring (Shishkin, 1997 ; Kovalevsky et al., 1998 ), it could be suggested that the out-of plane deformation of the ring represents the easiest way for relaxation of its structure because of steric clashes.

Figure 2
The molecular structure of compound 3 with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

The dihydropyrimidine ring adopts a twist-boat conformation with puckering parameters (Zefirov et al., 1990 ) S = 0.34, Θ = 61.5° and ψ = 12.5°. The deviations of the C11 and N1 atoms from the mean plane through the remaining ring atoms are 0.307 (2) and 0.458 (2) Å, respectively. Such a conformation is common for 1,6-dihydroaromatic heterocycles (Shishkin, 1998 ). However, the presence of three vicinal substituents results in some twisting of the N2—C11 and C13—C14 endocyclic double bonds [the C14—N2—C11—N1 and C12—C13—C14—N2 torsion angles are −7.6 (4) and 4.5 (4)°] because of steric repulsion [the intramolecular O4⋯C24 contact is 2.739 (4) Å, shorter than the sum of the van der Waals radii (2.87 Å; Zefirov, 1997 ). The phenyl substituent has an axial orientation with respect to the dihydropyrimidine ring [C11—N1—C12—C15 = −98.7 (3)°] and is almost coplanar with the C12—H12 bond (C20—C15—C12—H12 = −8°) despite the shorten intramolecular H12⋯H20 contact of 2.30 Å (sum of van der Waals radii = 2.32 Å). The carbonyl group of the ester substituent is rotated slightly with respect to the C13—C14 bond [C14—C13—C21—O3 = 167.2 (2)°] probably as a result of the formation of the O3⋯H12 attractive intramolecular interaction (2.34 Å compared to the van der Waals radii sum of 2.45 Å). The ethoxyl group has an ap–ap conformation [C13—C21—O4—C22 and C21—O4—C22—C23 torsion angles are 175.1 (2) and −160.5 (3)°, respectively].

3. Supramolecular features

In the crystal, molecules are linked by weak C19—H19⋯O3 and C16—H16⋯S1 hydrogen bonds and C—H⋯π interactions (C3—H3⋯C16 and C22—H22A⋯C2 (see Table 1). In addition, a short intermolecular S1⋯N1(− $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, 2 − z) contact of 3.250 (3) Å (van der Waals radii sum is 3.32 Å) indicates an interaction between the S atom and the π-system of the thiazole ring (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O2	0.98	2.36	2.926 (4)	116
C19—H19⋯O3ⁱ	0.93	2.50	3.219 (5)	134
C16—H16⋯S1ⁱⁱ	0.93	3.07	3.810 (4)	138
C3—H3⋯C16ⁱⁱⁱ	0.93	2.84	3.542 (5)	133
C22—H22A⋯C2^iv	0.97	2.88	3.718 (5)	145
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, -z+2]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+2]$ ; (iii) $[-x+{\script{3\over 2}}, -y+2, z-{\script{1\over 2}}]$ ; (iv) $[-x+{\script{5\over 2}}, -y+2, z+{\script{1\over 2}}]$ .

Figure 3
The view of the S⋯N intermolecular interaction.

4. Database survey

A search of the Cambridge Structural Database (Version 5.37, update May 2016; Groom et al., 2016 ) did not reveal any compounds with a similar polycyclic fragment.

5. Synthesis and crystallization

Ethyl 6-methyl-4-phenyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate 1 (0.28 g, 1 mmol) was added to a solution of 2,3-dichloronaphthalene-1,4-dione (0.25 g, 1.1 mmol) in DMF (20 mL) and the mixture was kept under reflux for 3 h. After that, the reaction mixture was cooled, and the precipitated solid product was filtered off and purified via recrystallization from MeOH:DMF:H₂O (2:2:1) to give product 3 in the form of dark-red crystals in 78% yield (0.35 g), m.p. 520.3– 522.0 K.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were located in difference-Fourier maps and treated as riding (C—H = 0.93–0.97 Å) with U_iso(H) = nU_eq(C) (n = 1.5 for CH₃ and n = 1.2 for all other H atoms).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₄H₁₈N₂O₄S
M_r	430.46
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	8.1038 (3), 13.3915 (6), 18.7377 (9)
V (Å³)	2033.44 (15)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.19
Crystal size (mm)	0.14 × 0.14 × 0.12

Data collection
Diffractometer	Oxford Diffraction Xcalibur, Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$
T_min, T_max	0.991, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6202, 3574, 3160
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.087, 1.03
No. of reflections	3574
No. of parameters	282
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.14
Absolute structure	Flack x determined using 1207 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013).
Absolute structure parameter	0.00 (4)
Computer programs: (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ , SHELXT (Sheldrick, 2015a ), SHELXL2014/7 (Sheldrick, 2015b ), Mercury (Macrae et al., 2008 ), publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1814348

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018000117/zq2240sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018000117/zq2240Isup2.hkl

checkCIF report

Computing details top

Data collection: (CrysAlis PRO; Oxford Diffraction, 2010; cell refinement: (CrysAlis PRO; Oxford Diffraction, 2010; data reduction: (CrysAlis PRO; Oxford Diffraction, 2010; program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Ethyl 2-methyl-5,10-dioxo-4-phenyl-5,10-dihydro-4H-11-thia-1,4a-\ diazabenzo[b]fluorene-3-carboxylate top

Crystal data top

C₂₄H₁₈N₂O₄S	D_x = 1.406 Mg m⁻³
M_r = 430.46	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 3614 reflections
a = 8.1038 (3) Å	θ = 3.0–29.0°
b = 13.3915 (6) Å	µ = 0.19 mm⁻¹
c = 18.7377 (9) Å	T = 293 K
V = 2033.44 (15) Å³	Block, red
Z = 4	0.14 × 0.14 × 0.12 mm
F(000) = 896

Data collection top

Oxford Diffraction Xcalibur, Sapphire3 diffractometer	3574 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3160 reflections with I > 2σ(I)
Detector resolution: 16.1827 pixels mm^-1	R_int = 0.017
ω–scan	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: multi-scan (CrysAlisPro; Oxford Diffraction, 2010	h = −9→9
T_min = 0.991, T_max = 1.000	k = −13→15
6202 measured reflections	l = −22→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.087	w = 1/[σ²(F_o²) + (0.0436P)² + 0.1932P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3574 reflections	Δρ_max = 0.13 e Å⁻³
282 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Absolute structure: Flack x determined using 1207 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
Primary atom site location: difference Fourier map	Absolute structure parameter: 0.00 (4)

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
S1	0.70278 (10)	0.68425 (6)	0.96988 (5)	0.0577 (2)
O1	0.7487 (4)	0.6165 (2)	0.81545 (17)	0.0925 (9)
O2	1.0119 (3)	0.97193 (18)	0.87923 (13)	0.0727 (7)
O3	1.0162 (4)	1.08986 (18)	1.09805 (13)	0.0801 (8)
O4	0.9283 (2)	1.03242 (17)	1.20226 (11)	0.0561 (6)
N1	0.8225 (3)	0.86059 (16)	0.98532 (12)	0.0414 (5)
N2	0.7164 (3)	0.78761 (17)	1.09161 (14)	0.0499 (6)
C1	0.9415 (4)	0.8572 (3)	0.78826 (16)	0.0527 (8)
C2	1.0157 (4)	0.9143 (3)	0.73617 (18)	0.0670 (10)
H2	1.0638	0.9752	0.7478	0.080*
C3	1.0179 (5)	0.8804 (4)	0.6664 (2)	0.0827 (12)
H3	1.0673	0.9191	0.6311	0.099*
C4	0.9489 (5)	0.7914 (4)	0.6487 (2)	0.0890 (14)
H4	0.9493	0.7704	0.6014	0.107*
C5	0.8785 (5)	0.7318 (4)	0.7004 (2)	0.0766 (11)
H5	0.8338	0.6701	0.6881	0.092*
C6	0.8745 (4)	0.7644 (3)	0.77107 (18)	0.0589 (9)
C7	0.8000 (4)	0.7003 (3)	0.82700 (19)	0.0604 (8)
C8	0.7887 (4)	0.7446 (2)	0.89746 (17)	0.0497 (7)
C9	0.8483 (3)	0.8355 (2)	0.91469 (16)	0.0428 (7)
C10	0.9400 (4)	0.8963 (2)	0.86233 (17)	0.0499 (7)
C11	0.7472 (3)	0.7863 (2)	1.02436 (18)	0.0450 (7)
C12	0.8429 (3)	0.96026 (19)	1.01698 (15)	0.0415 (6)
H12	0.9494	0.9872	1.0014	0.050*
C13	0.8477 (3)	0.9481 (2)	1.09764 (15)	0.0415 (6)
C14	0.7823 (3)	0.8678 (2)	1.13005 (16)	0.0446 (7)
C15	0.7081 (4)	1.0300 (2)	0.99115 (14)	0.0438 (6)
C16	0.5438 (4)	1.0063 (3)	0.99771 (17)	0.0565 (8)
H16	0.5133	0.9456	1.0179	0.068*
C17	0.4239 (5)	1.0717 (3)	0.9747 (2)	0.0722 (10)
H17	0.3131	1.0548	0.9792	0.087*
C18	0.4674 (6)	1.1617 (3)	0.9451 (2)	0.0774 (11)
H18	0.3864	1.2060	0.9298	0.093*
C19	0.6310 (6)	1.1857 (3)	0.9383 (2)	0.0832 (12)
H19	0.6611	1.2466	0.9183	0.100*
C20	0.7504 (5)	1.1206 (2)	0.9608 (2)	0.0660 (9)
H20	0.8611	1.1374	0.9556	0.079*
C21	0.9387 (4)	1.0299 (2)	1.13135 (16)	0.0471 (7)
C22	1.0268 (4)	1.1067 (3)	1.23806 (18)	0.0609 (9)
H22B	0.9735	1.1714	1.2355	0.073*
H22A	1.1346	1.1117	1.2158	0.073*
C23	1.0436 (5)	1.0742 (3)	1.3141 (2)	0.0815 (12)
H23B	0.9359	1.0665	1.3348	0.122*
H23C	1.1043	1.1236	1.3403	0.122*
H23A	1.1012	1.0116	1.3160	0.122*
C24	0.7765 (4)	0.8499 (2)	1.20923 (17)	0.0594 (8)
H24C	0.8858	0.8554	1.2287	0.089*
H24A	0.7341	0.7842	1.2184	0.089*
H24B	0.7061	0.8986	1.2312	0.089*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0570 (4)	0.0437 (4)	0.0725 (5)	−0.0110 (4)	0.0073 (4)	−0.0060 (4)
O1	0.105 (2)	0.0743 (17)	0.098 (2)	−0.0213 (16)	0.0155 (17)	−0.0383 (17)
O2	0.0955 (17)	0.0606 (14)	0.0620 (14)	−0.0237 (14)	0.0224 (14)	−0.0034 (13)
O3	0.121 (2)	0.0638 (14)	0.0554 (13)	−0.0474 (16)	−0.0102 (15)	0.0097 (13)
O4	0.0569 (13)	0.0627 (13)	0.0486 (11)	−0.0122 (11)	−0.0002 (10)	−0.0033 (11)
N1	0.0428 (12)	0.0360 (12)	0.0452 (13)	−0.0025 (10)	0.0018 (11)	0.0033 (11)
N2	0.0532 (14)	0.0423 (13)	0.0542 (15)	−0.0095 (12)	0.0019 (13)	0.0078 (12)
C1	0.0458 (16)	0.064 (2)	0.0482 (17)	0.0134 (15)	−0.0009 (14)	−0.0004 (16)
C2	0.065 (2)	0.082 (3)	0.0540 (19)	0.0140 (19)	0.0023 (18)	0.007 (2)
C3	0.082 (3)	0.115 (4)	0.051 (2)	0.020 (3)	0.001 (2)	0.009 (2)
C4	0.080 (3)	0.140 (4)	0.047 (2)	0.022 (3)	−0.003 (2)	−0.012 (3)
C5	0.069 (2)	0.096 (3)	0.065 (2)	0.015 (2)	−0.008 (2)	−0.024 (2)
C6	0.0482 (17)	0.073 (2)	0.0555 (19)	0.0138 (16)	−0.0033 (16)	−0.0110 (18)
C7	0.0503 (16)	0.060 (2)	0.071 (2)	0.0030 (17)	0.0007 (17)	−0.0185 (18)
C8	0.0419 (15)	0.0473 (16)	0.0598 (18)	0.0009 (14)	0.0013 (15)	−0.0053 (15)
C9	0.0374 (13)	0.0410 (16)	0.0501 (16)	0.0042 (11)	−0.0016 (12)	−0.0006 (14)
C10	0.0487 (17)	0.0497 (18)	0.0514 (17)	0.0037 (15)	0.0036 (14)	0.0034 (15)
C11	0.0373 (14)	0.0371 (15)	0.0605 (19)	−0.0037 (11)	0.0011 (13)	0.0068 (15)
C12	0.0478 (15)	0.0309 (13)	0.0458 (15)	−0.0033 (11)	0.0024 (12)	0.0032 (13)
C13	0.0421 (14)	0.0383 (14)	0.0441 (15)	−0.0003 (12)	−0.0025 (12)	0.0044 (13)
C14	0.0417 (14)	0.0446 (15)	0.0475 (16)	−0.0003 (13)	0.0005 (14)	0.0079 (14)
C15	0.0537 (16)	0.0373 (15)	0.0405 (14)	0.0042 (13)	−0.0029 (13)	0.0013 (12)
C16	0.0561 (18)	0.0533 (17)	0.0600 (18)	0.0068 (15)	−0.0048 (15)	0.0014 (16)
C17	0.063 (2)	0.081 (3)	0.072 (2)	0.0174 (19)	−0.014 (2)	−0.007 (2)
C18	0.099 (3)	0.068 (2)	0.065 (2)	0.037 (2)	−0.022 (2)	−0.001 (2)
C19	0.107 (3)	0.056 (2)	0.087 (3)	0.019 (2)	−0.009 (3)	0.020 (2)
C20	0.074 (2)	0.0463 (18)	0.078 (2)	0.0044 (15)	−0.0003 (19)	0.0149 (18)
C21	0.0526 (16)	0.0405 (16)	0.0482 (16)	−0.0021 (14)	−0.0042 (14)	0.0065 (15)
C22	0.062 (2)	0.062 (2)	0.0587 (19)	−0.0050 (17)	−0.0081 (17)	−0.0109 (17)
C23	0.085 (3)	0.101 (3)	0.058 (2)	−0.009 (2)	−0.004 (2)	−0.010 (2)
C24	0.071 (2)	0.0556 (18)	0.0518 (18)	−0.0078 (16)	0.0021 (17)	0.0139 (16)

Geometric parameters (Å, º) top

S1—C8	1.726 (3)	C12—C15	1.517 (4)
S1—C11	1.743 (3)	C12—C13	1.521 (4)
O1—C7	1.216 (4)	C12—H12	0.9800
O2—C10	1.211 (4)	C13—C14	1.344 (4)
O3—C21	1.195 (3)	C13—C21	1.463 (4)
O4—C21	1.332 (4)	C14—C24	1.504 (4)
O4—C22	1.441 (4)	C15—C16	1.374 (4)
N1—C11	1.378 (3)	C15—C20	1.383 (4)
N1—C9	1.381 (4)	C16—C17	1.377 (4)
N1—C12	1.470 (4)	C16—H16	0.9300
N2—C11	1.285 (4)	C17—C18	1.373 (6)
N2—C14	1.399 (4)	C17—H17	0.9300
C1—C2	1.378 (5)	C18—C19	1.371 (6)
C1—C6	1.394 (5)	C18—H18	0.9300
C1—C10	1.484 (4)	C19—C20	1.369 (5)
C2—C3	1.384 (5)	C19—H19	0.9300
C2—H2	0.9300	C20—H20	0.9300
C3—C4	1.358 (6)	C22—C23	1.497 (5)
C3—H3	0.9300	C22—H22B	0.9700
C4—C5	1.378 (6)	C22—H22A	0.9700
C4—H4	0.9300	C23—H23B	0.9600
C5—C6	1.395 (5)	C23—H23C	0.9600
C5—H5	0.9300	C23—H23A	0.9600
C6—C7	1.483 (5)	C24—H24C	0.9600
C7—C8	1.451 (5)	C24—H24A	0.9600
C8—C9	1.348 (4)	C24—H24B	0.9600
C9—C10	1.476 (4)

C8—S1—C11	90.57 (14)	C14—C13—C21	127.1 (3)
C21—O4—C22	116.5 (2)	C14—C13—C12	121.6 (3)
C11—N1—C9	113.6 (2)	C21—C13—C12	111.2 (2)
C11—N1—C12	119.4 (2)	C13—C14—N2	122.2 (3)
C9—N1—C12	126.2 (2)	C13—C14—C24	125.9 (3)
C11—N2—C14	116.2 (2)	N2—C14—C24	111.9 (3)
C2—C1—C6	120.1 (3)	C16—C15—C20	118.7 (3)
C2—C1—C10	118.0 (3)	C16—C15—C12	121.8 (3)
C6—C1—C10	121.9 (3)	C20—C15—C12	119.5 (3)
C1—C2—C3	119.5 (4)	C15—C16—C17	120.6 (3)
C1—C2—H2	120.3	C15—C16—H16	119.7
C3—C2—H2	120.3	C17—C16—H16	119.7
C4—C3—C2	120.8 (4)	C18—C17—C16	120.2 (4)
C4—C3—H3	119.6	C18—C17—H17	119.9
C2—C3—H3	119.6	C16—C17—H17	119.9
C3—C4—C5	120.5 (4)	C19—C18—C17	119.5 (3)
C3—C4—H4	119.7	C19—C18—H18	120.3
C5—C4—H4	119.7	C17—C18—H18	120.3
C4—C5—C6	119.7 (4)	C20—C19—C18	120.4 (4)
C4—C5—H5	120.2	C20—C19—H19	119.8
C6—C5—H5	120.2	C18—C19—H19	119.8
C1—C6—C5	119.3 (4)	C19—C20—C15	120.7 (4)
C1—C6—C7	120.7 (3)	C19—C20—H20	119.7
C5—C6—C7	120.0 (4)	C15—C20—H20	119.7
O1—C7—C8	121.2 (3)	O3—C21—O4	122.5 (3)
O1—C7—C6	123.2 (3)	O3—C21—C13	122.8 (3)
C8—C7—C6	115.6 (3)	O4—C21—C13	114.7 (3)
C9—C8—C7	124.4 (3)	O4—C22—C23	107.0 (3)
C9—C8—S1	112.3 (2)	O4—C22—H22B	110.3
C7—C8—S1	123.3 (2)	C23—C22—H22B	110.3
C8—C9—N1	113.3 (3)	O4—C22—H22A	110.3
C8—C9—C10	121.3 (3)	C23—C22—H22A	110.3
N1—C9—C10	125.4 (3)	H22B—C22—H22A	108.6
O2—C10—C9	122.0 (3)	C22—C23—H23B	109.5
O2—C10—C1	122.4 (3)	C22—C23—H23C	109.5
C9—C10—C1	115.5 (3)	H23B—C23—H23C	109.5
N2—C11—N1	126.6 (3)	C22—C23—H23A	109.5
N2—C11—S1	123.1 (2)	H23B—C23—H23A	109.5
N1—C11—S1	110.3 (2)	H23C—C23—H23A	109.5
N1—C12—C15	110.4 (2)	C14—C24—H24C	109.5
N1—C12—C13	107.9 (2)	C14—C24—H24A	109.5
C15—C12—C13	113.7 (2)	H24C—C24—H24A	109.5
N1—C12—H12	108.2	C14—C24—H24B	109.5
C15—C12—H12	108.2	H24C—C24—H24B	109.5
C13—C12—H12	108.2	H24A—C24—H24B	109.5

C6—C1—C2—C3	2.3 (5)	C9—N1—C11—N2	176.2 (3)
C10—C1—C2—C3	−179.4 (3)	C12—N1—C11—N2	−13.3 (4)
C1—C2—C3—C4	−0.4 (6)	C9—N1—C11—S1	−1.8 (3)
C2—C3—C4—C5	−1.5 (6)	C12—N1—C11—S1	168.65 (19)
C3—C4—C5—C6	1.6 (6)	C8—S1—C11—N2	−177.5 (3)
C2—C1—C6—C5	−2.2 (5)	C8—S1—C11—N1	0.6 (2)
C10—C1—C6—C5	179.6 (3)	C11—N1—C12—C15	−98.7 (3)
C2—C1—C6—C7	177.6 (3)	C9—N1—C12—C15	70.4 (3)
C10—C1—C6—C7	−0.6 (4)	C11—N1—C12—C13	26.1 (3)
C4—C5—C6—C1	0.3 (5)	C9—N1—C12—C13	−164.8 (2)
C4—C5—C6—C7	−179.5 (3)	N1—C12—C13—C14	−22.3 (4)
C1—C6—C7—O1	−175.6 (3)	C15—C12—C13—C14	100.5 (3)
C5—C6—C7—O1	4.2 (5)	N1—C12—C13—C21	154.3 (2)
C1—C6—C7—C8	5.5 (4)	C15—C12—C13—C21	−82.9 (3)
C5—C6—C7—C8	−174.7 (3)	C21—C13—C14—N2	−171.5 (3)
O1—C7—C8—C9	177.5 (3)	C12—C13—C14—N2	4.5 (4)
C6—C7—C8—C9	−3.6 (5)	C21—C13—C14—C24	5.7 (5)
O1—C7—C8—S1	−0.2 (5)	C12—C13—C14—C24	−178.3 (3)
C6—C7—C8—S1	178.7 (2)	C11—N2—C14—C13	11.8 (4)
C11—S1—C8—C9	0.7 (2)	C11—N2—C14—C24	−165.7 (3)
C11—S1—C8—C7	178.6 (3)	N1—C12—C15—C16	54.1 (4)
C7—C8—C9—N1	−179.8 (3)	C13—C12—C15—C16	−67.3 (4)
S1—C8—C9—N1	−1.9 (3)	N1—C12—C15—C20	−126.6 (3)
C7—C8—C9—C10	−3.3 (4)	C13—C12—C15—C20	112.0 (3)
S1—C8—C9—C10	174.6 (2)	C20—C15—C16—C17	−0.2 (5)
C11—N1—C9—C8	2.4 (3)	C12—C15—C16—C17	179.1 (3)
C12—N1—C9—C8	−167.3 (3)	C15—C16—C17—C18	−0.2 (5)
C11—N1—C9—C10	−173.9 (2)	C16—C17—C18—C19	0.4 (6)
C12—N1—C9—C10	16.4 (4)	C17—C18—C19—C20	0.0 (7)
C8—C9—C10—O2	−170.5 (3)	C18—C19—C20—C15	−0.4 (6)
N1—C9—C10—O2	5.5 (5)	C16—C15—C20—C19	0.5 (5)
C8—C9—C10—C1	8.0 (4)	C12—C15—C20—C19	−178.8 (3)
N1—C9—C10—C1	−175.9 (3)	C22—O4—C21—O3	−5.1 (5)
C2—C1—C10—O2	−5.8 (5)	C22—O4—C21—C13	175.1 (2)
C6—C1—C10—O2	172.5 (3)	C14—C13—C21—O3	167.2 (3)
C2—C1—C10—C9	175.7 (3)	C12—C13—C21—O3	−9.1 (4)
C6—C1—C10—C9	−6.1 (4)	C14—C13—C21—O4	−12.9 (4)
C14—N2—C11—N1	−7.6 (4)	C12—C13—C21—O4	170.8 (2)
C14—N2—C11—S1	170.2 (2)	C21—O4—C22—C23	−160.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O2	0.98	2.36	2.926 (4)	116
C19—H19···O3ⁱ	0.93	2.50	3.219 (5)	134
C16—H16···S1ⁱⁱ	0.93	3.07	3.810 (4)	138
C3—H3···C16ⁱⁱⁱ	0.93	2.84	3.542 (5)	133
C22—H22A···C2^iv	0.97	2.88	3.718 (5)	145

Symmetry codes: (i) x−1/2, −y+5/2, −z+2; (ii) x−1/2, −y+3/2, −z+2; (iii) −x+3/2, −y+2, z−1/2; (iv) −x+5/2, −y+2, z+1/2.

Acknowledgements

The authors are thankful to the "Institute for Single Crystals", NAS of Ukraine, for providing equipment to conduct this work.

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