Mol­ecular and crystal structure of 5,9-dimethyl-5H-pyrano[3,2-c:5,6-c′]bis­[2,1-benzo­thia­zin]-7(9H)-one 6,6,8,8-tetroxide di­methyl­formamide monosolvate

Rybalka, A.; Shishkina, S.; Ukrainets, I.; Sidorenko, L.; Sim, G.

doi:10.1107/S2056989019008788

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 75| Part 7| July 2019| Pages 1076-1078

https://doi.org/10.1107/S2056989019008788

Open

access

Molecular and crystal structure of 5,9-dimethyl-5H-pyrano[3,2-c:5,6-c′]bis[2,1-benzothiazin]-7(9H)-one 6,6,8,8-tetroxide dimethylformamide monosolvate

Andrii Rybalka,^a ^* Svitlana Shishkina,^b Igor Ukrainets,^c Lyudmila Sidorenko ^c and Galina Sim ^d

^aV. N. Karazin Kharkiv National University, 4 Svobody sq., Kharkiv 61077, Ukraine, ^bSSI "Institute for Single Crystals", National Academy of Sciences of Ukraine, 60, Nauky Ave., Kharkiv 61001, Ukraine, ^cNational University of Pharmacy, 4 Valentynivska St., Kharkiv 61168, Ukraine, and ^dFar Eastern State Medical University, 35 Murav'eva-Amurskogo St., Khabarovsk, 680000, Russian Federation
^*Correspondence e-mail: rybalka19969@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 22 May 2019; accepted 20 June 2019; online 28 June 2019)

The title molecule crystallizes as a dimethylformamide monosolvate, C₁₉H₁₄N₂O₆S₂·C₃H₇NO. The molecule was expected to adopt mirror symmetry but slightly different conformational characteristics of the condensed benzothiazine ring lead to point group symmetry 1. In the crystal, molecules form two types of stacking dimers with distances of 3.464 (2) Å and 3.528 (2) Å between π-systems. As a result, columns extending parallel to [100] are formed, which are connected to intermediate dimethylformamide solvent molecules by C—H⋯O interactions.

Keywords: benzothiazine derivative; molecular structure; π-stacking dimer; crystal structure.

CCDC reference: 1935426

1. Chemical context

Alkyl 1-R-4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylates are highly reactive compounds (Ukrainets et al., 2007 ). They easily form the corresponding amides with primary and many secondary alkyl, aryl or hetarylamines and can be converted to 5,9-di-R-6,7,8-trioxodiquinolino [3,4-b; 3′,4′-e]-4H-pyrans in high yields through thermolysis (Ukrainets et al., 2000 ). The acylating ability is distinctly reduced in alkyl 1-R-4-hydroxy-2,2-dioxo-1H-2λ⁶,1-benzothiazine-3-carboxylates (Ukrainets et al., 2014 ). However, a similar heterocycle, 5,9-dimethyl-5H-pyrano [3,2-c:5,6-c′]bis[2,1]benzothiazin-7(9H)-one 6,6,8,8-tetroxide (I) was synthesized based on methyl 4-hydroxy-1-methyl-2,2-dioxo-1H-2λ⁶,1-benzothiazine-3-carboxylate (Ukrainets et al., 2013 ). The molecular and crystal structures of its dimethylformamide solvate are reported in the present communication.

2. Structural commentary

Both thiazine rings adopt a twist-boat conformation (Fig. 1) with slightly different characteristics despite the formally mirror-symmetric molecular structure of (I) in the gas phase. The puckering parameters (Zefirov et al., 1990 ) are: S = 0.51, θ = 44.8°, Ψ = 28.9° for the C1–C2–C3–C4–N1–S1 ring (1) and S = 0.48, θ = 50.0°, Ψ = 22.8° for the C5–C6–C7–C8–N2–S2 ring (2). The S1 and C1 atoms deviate by 0.669 (2) and 0.207 (2) Å, respectively, from the mean-square plane of the remaining atoms in ring (1). The corresponding deviations in ring (2) are 0.668 (2) and 0.270 (2) Å, respectively.

Figure 1
The structures of the molecular entities in solvated (I)

. Displacement ellipsoids are drawn at the 50% probability level.

The 4H-pyran-4-one ring (3) adopts a sofa conformation with puckering parameters S = 0.14, θ = 24.7°, Ψ = 22.6°. The deviation of C19 from the plane of the remaining atoms of (3) is 0.087 (2) Å. The C1=C2 and C5=C6 bonds [1.3571 (17) Å and 1.3529 (17) Å] are slightly elongated as compared to the mean value of 1.329 Å for a Csp²=Csp² bond (Bürgi & Dunitz, 1994 ).

The molecule also contains shortened contacts (the H⋯O van der Waals radii sum is 2.46 Å; Zefirov, 1997 ), which can be considered as attractive intramolecular interactions. However, the values of the corresponding C—H⋯O angles for the pairs C17⋯O3, C18⋯O5, C3A⋯O1A, C12⋯O1, C16⋯O1 (Table 1) are too small to allow them to be characterized as intramolecular hydrogen bonds.

Table 1
Hydrogen-bond geometry and short contacts (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17A⋯O3	0.96	2.40	2.885 (2)	111
C18—H18A⋯O5	0.96	2.41	2.895 (2)	111
C3A—H3AA⋯O1A	0.96	2.41	2.784 (3)	103
C12—H12⋯O1	0.93	2.39	2.7106 (17)	100
C16—H16⋯O1	0.93	2.39	2.7109 (17)	100
C9—H9⋯O1Aⁱ	0.93	2.41	3.324 (2)	169
C18—H18B⋯O1Aⁱⁱ	0.96	2.46	3.376 (3)	159
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

A further analysis of the molecular structure revealed the presence of other shortened intramolecular contacts: H9⋯H17C = 2.21 Å (expected 2.34 Å), H13⋯H18B = 2.28 Å (expected 2.34 Å), H13⋯H18C = 2.31 Å (expected 2.34 Å). These shortened contacts affect the very small pyramidalization of the nitrogen atoms; the sums of the bond angles centered at the N1 and N2 atoms are 354 and 356°, respectively.

3. Supramolecular features

In the crystal, molecules of (I) form columns extending parallel to [100] whereby centrosymmetric pairs of molecules within a column interact by π–π stacking interactions (Fig. 2). The plane-to-plane distances between the π-systems in the centrosymmetric dimers are 3.464 (2) and 3.528 (2) Å. The mean-square plane was calculated for O1 and all carbon atoms (with the exception of C19) of the polycyclic entity.

Figure 2
Two types of stacking dimers in the crystal structure of (I)

The dimethylformamide solvent molecules are situated between the columns (Fig. 3) and are bound by weak intermolecular hydrogen bonds including C9—H9⋯O1Aⁱ and C18—H18B⋯O1Aⁱⁱ (Table 2).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₄N₂O₆S₂·C₃H₇NO
M_r	503.54
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.2678 (2), 26.5667 (7), 11.3590 (3)
β (°)	90.498 (3)
V (Å³)	2193.13 (10)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.30
Crystal size (mm)	0.20 × 0.20 × 0.18

Data collection
Diffractometer	Agilent Xcalibur, Sapphire3
Absorption correction	Multi-scan (CrysAlis RED; Agilent, 2012 )
T_min, T_max	0.840, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	21958, 6370, 5409
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.111, 1.06
No. of reflections	6370
No. of parameters	311
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.35
Computer programs: CrysAlis CCD and CrysAlis RED (Agilent, 2012), SHELXS (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ), Mercury (Macrae et al., 2006 ) and publCIF (Westrip, 2010 ).

Figure 3
The packing of the molecular entities in the crystal structure of (I)

in a view along [100].

4. Database survey

A search of the Cambridge Structural Database (Version 5.38, update February 2019; Groom et al., 2016 ) for the benzothiazine skeleton revealed 34 hits. In all structures, the conformation of the benzothiazine fragment is similar.

The title compound may be considered as a structural analogue of 5,9-diethyl-6,7,8-trioxodiquinolino[3,4-b;3′,4′-e]-4H-pyran (Ukrainets et al., 2000) with the carbonyl groups being replaced by sulfonyl groups.

5. Synthesis and crystallization

A mixture of methyl 4-hydroxy-1-methyl-2,2-dioxo-1H-2λ⁶,1-benzothiazine-3-carboxylate (2.69 g, 0.01 mol) and diphenyl oxide (10 ml) was maintained on a metal bath at 493 K for 3 h, then cooled and diluted with ethanol (Fig. 4). The precipitate was filtered off, washed with ethanol, and recrystallized from DMF. 1.86 g (37% yield) of a colourless substance were obtained, including yellowish crystals of the title solvate; m.p. 640–642 K (decomp.).

Figure 4
Synthesis scheme for compound (I)

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were located from difference-Fourier maps. They were included in calculated positions and treated as riding with C—H = 0.96 Å, U_iso(H) = 1.5U_eq(C) for methyl groups and with C—H = 0.93 Å, U_iso(H) = 1.2U_eq(C) for all other hydrogen atoms.

Supporting information

CCDC reference: 1935426

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019008788/wm5508sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019008788/wm5508Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Agilent, 2012); cell refinement: CrysAlis RED (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

5,9-Dimethyl-5H-pyrano[3,2-c:5,6-c']bis[2,1-benzothiazin]-7(9H)-one 6,6,8,8-tetroxide dimethylformamide monosolvate top

Crystal data top

C₁₉H₁₄N₂O₆S₂·C₃H₇NO	F(000) = 1048
M_r = 503.54	D_x = 1.525 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.2678 (2) Å	Cell parameters from 8803 reflections
b = 26.5667 (7) Å	θ = 3.3–32.1°
c = 11.3590 (3) Å	µ = 0.30 mm⁻¹
β = 90.498 (3)°	T = 293 K
V = 2193.13 (10) Å³	Block, colourless
Z = 4	0.20 × 0.20 × 0.18 mm

Data collection top

Agilent Xcalibur, Sapphire3 diffractometer	6370 independent reflections
Radiation source: Enhance (Mo) X-ray Source	5409 reflections with I > 2σ(I)
Detector resolution: 16.1827 pixels mm^-1	R_int = 0.022
ω scans	θ_max = 30.0°, θ_min = 3.2°
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012)	h = −9→10
T_min = 0.840, T_max = 1.000	k = −34→37
21958 measured reflections	l = −15→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.056P)² + 0.5564P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
6370 reflections	Δρ_max = 0.31 e Å⁻³
311 parameters	Δρ_min = −0.35 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
S1	0.27857 (5)	0.53088 (2)	0.78395 (3)	0.03522 (10)
S2	0.35468 (5)	0.68735 (2)	0.47772 (3)	0.03406 (9)
N1	0.31960 (18)	0.47039 (5)	0.76567 (10)	0.0355 (3)
N2	0.40095 (19)	0.68763 (4)	0.33637 (11)	0.0377 (3)
O1	0.27500 (14)	0.54076 (3)	0.43723 (8)	0.0300 (2)
O2	0.33446 (19)	0.63741 (4)	0.71036 (9)	0.0475 (3)
O3	0.4170 (2)	0.54940 (5)	0.86153 (10)	0.0556 (3)
O4	0.09057 (19)	0.53887 (5)	0.81476 (11)	0.0528 (3)
O5	0.50923 (18)	0.70840 (4)	0.53734 (11)	0.0511 (3)
O6	0.18001 (18)	0.70953 (5)	0.50021 (12)	0.0529 (3)
C1	0.30950 (19)	0.55350 (5)	0.64196 (11)	0.0294 (3)
C2	0.27719 (17)	0.52260 (5)	0.54891 (11)	0.0274 (2)
C3	0.23924 (18)	0.46944 (5)	0.55627 (12)	0.0287 (2)
C4	0.25669 (18)	0.44458 (5)	0.66557 (12)	0.0307 (3)
C5	0.33905 (18)	0.62303 (5)	0.50507 (11)	0.0288 (2)
C6	0.30000 (17)	0.59081 (5)	0.41606 (11)	0.0271 (2)
C7	0.27399 (18)	0.60439 (5)	0.29458 (11)	0.0293 (3)
C8	0.31990 (19)	0.65325 (5)	0.25751 (12)	0.0330 (3)
C9	0.2198 (2)	0.39295 (5)	0.67129 (15)	0.0388 (3)
H9	0.230327	0.375995	0.742662	0.047*
C10	0.1678 (2)	0.36734 (6)	0.57123 (16)	0.0447 (4)
H10	0.144752	0.332967	0.575848	0.054*
C11	0.1491 (2)	0.39142 (6)	0.46392 (16)	0.0445 (4)
H11	0.112482	0.373420	0.397521	0.053*
C12	0.1849 (2)	0.44209 (5)	0.45585 (13)	0.0366 (3)
H12	0.173175	0.458353	0.383672	0.044*
C13	0.2965 (2)	0.66588 (7)	0.13887 (14)	0.0450 (4)
H13	0.327636	0.697916	0.112718	0.054*
C14	0.2274 (2)	0.63092 (8)	0.06068 (14)	0.0489 (4)
H14	0.213819	0.639567	−0.018251	0.059*
C15	0.1778 (2)	0.58326 (7)	0.09716 (13)	0.0443 (4)
H15	0.128749	0.560360	0.043496	0.053*
C16	0.2012 (2)	0.56987 (6)	0.21301 (12)	0.0363 (3)
H16	0.168641	0.537724	0.237646	0.044*
C17	0.3401 (2)	0.44312 (7)	0.87830 (14)	0.0449 (4)
H17C	0.418161	0.414374	0.867349	0.067*
H17B	0.221431	0.432194	0.904561	0.067*
H17A	0.394062	0.465053	0.936211	0.067*
C18	0.4721 (3)	0.73589 (7)	0.29163 (18)	0.0593 (5)
H18C	0.371718	0.755881	0.262233	0.089*
H18B	0.557380	0.729589	0.229276	0.089*
H18A	0.533497	0.753615	0.354267	0.089*
C19	0.3323 (2)	0.60783 (5)	0.62857 (11)	0.0317 (3)
N1A	0.8356 (2)	0.81500 (6)	0.40202 (13)	0.0473 (3)
O1A	0.7557 (2)	0.81809 (6)	0.59460 (13)	0.0654 (4)
C1A	0.8365 (3)	0.79886 (7)	0.51263 (17)	0.0503 (4)
H1A	0.905307	0.770158	0.529054	0.060*
C2A	0.9428 (3)	0.79092 (10)	0.3113 (2)	0.0696 (6)
H2AC	1.005000	0.762143	0.343706	0.104*
H2AB	1.031860	0.814287	0.281574	0.104*
H2AA	0.862751	0.780360	0.248316	0.104*
C3A	0.7312 (4)	0.85925 (9)	0.3696 (2)	0.0769 (7)
H3AC	0.669591	0.853504	0.295690	0.115*
H3AB	0.812776	0.887473	0.362385	0.115*
H3AA	0.641725	0.866160	0.429150	0.115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0477 (2)	0.03408 (17)	0.02385 (16)	−0.00072 (14)	−0.00252 (13)	−0.00174 (12)
S2	0.04352 (19)	0.02353 (15)	0.03518 (18)	0.00017 (12)	0.00303 (14)	−0.00355 (12)
N1	0.0438 (7)	0.0324 (6)	0.0301 (6)	0.0006 (5)	−0.0039 (5)	0.0038 (5)
N2	0.0502 (7)	0.0283 (6)	0.0346 (6)	−0.0031 (5)	0.0049 (5)	0.0021 (5)
O1	0.0424 (5)	0.0251 (4)	0.0226 (4)	−0.0028 (4)	0.0001 (4)	−0.0031 (3)
O2	0.0785 (9)	0.0336 (5)	0.0304 (5)	0.0003 (5)	−0.0047 (5)	−0.0108 (4)
O3	0.0812 (9)	0.0509 (7)	0.0343 (6)	−0.0151 (6)	−0.0219 (6)	0.0006 (5)
O4	0.0595 (8)	0.0560 (7)	0.0431 (6)	0.0114 (6)	0.0164 (5)	0.0001 (5)
O5	0.0641 (8)	0.0393 (6)	0.0499 (7)	−0.0184 (5)	−0.0046 (6)	−0.0075 (5)
O6	0.0597 (8)	0.0381 (6)	0.0612 (8)	0.0165 (5)	0.0154 (6)	−0.0003 (5)
C1	0.0363 (6)	0.0282 (6)	0.0237 (6)	0.0000 (5)	−0.0018 (5)	−0.0020 (5)
C2	0.0298 (6)	0.0271 (6)	0.0252 (6)	0.0003 (5)	0.0001 (4)	−0.0020 (4)
C3	0.0291 (6)	0.0258 (6)	0.0313 (6)	0.0002 (4)	0.0005 (5)	−0.0028 (5)
C4	0.0280 (6)	0.0288 (6)	0.0352 (7)	0.0016 (5)	0.0024 (5)	−0.0003 (5)
C5	0.0336 (6)	0.0251 (5)	0.0276 (6)	0.0004 (5)	0.0001 (5)	−0.0025 (5)
C6	0.0296 (6)	0.0257 (6)	0.0261 (6)	−0.0006 (4)	0.0012 (4)	−0.0018 (4)
C7	0.0304 (6)	0.0332 (6)	0.0244 (6)	0.0023 (5)	0.0008 (5)	−0.0015 (5)
C8	0.0354 (7)	0.0326 (6)	0.0311 (6)	0.0048 (5)	0.0017 (5)	0.0021 (5)
C9	0.0379 (7)	0.0301 (7)	0.0483 (8)	0.0004 (5)	0.0049 (6)	0.0069 (6)
C10	0.0441 (8)	0.0268 (6)	0.0634 (10)	−0.0044 (6)	0.0050 (7)	−0.0016 (7)
C11	0.0494 (9)	0.0331 (7)	0.0508 (9)	−0.0058 (6)	−0.0023 (7)	−0.0128 (7)
C12	0.0425 (8)	0.0310 (7)	0.0363 (7)	−0.0025 (6)	−0.0033 (6)	−0.0065 (5)
C13	0.0552 (9)	0.0445 (8)	0.0352 (8)	0.0084 (7)	0.0007 (7)	0.0103 (6)
C14	0.0537 (10)	0.0648 (11)	0.0281 (7)	0.0108 (8)	−0.0033 (6)	0.0066 (7)
C15	0.0423 (8)	0.0628 (10)	0.0278 (7)	0.0007 (7)	−0.0038 (6)	−0.0071 (7)
C16	0.0382 (7)	0.0431 (8)	0.0277 (6)	−0.0032 (6)	0.0003 (5)	−0.0058 (6)
C17	0.0520 (9)	0.0474 (9)	0.0352 (8)	0.0035 (7)	−0.0022 (7)	0.0127 (7)
C18	0.0867 (14)	0.0381 (9)	0.0533 (11)	−0.0154 (9)	0.0146 (10)	0.0071 (8)
C19	0.0398 (7)	0.0281 (6)	0.0273 (6)	0.0003 (5)	−0.0030 (5)	−0.0042 (5)
N1A	0.0451 (7)	0.0465 (8)	0.0501 (8)	0.0034 (6)	−0.0014 (6)	0.0010 (6)
O1A	0.0776 (10)	0.0597 (8)	0.0593 (8)	−0.0037 (7)	0.0145 (7)	−0.0117 (7)
C1A	0.0513 (10)	0.0458 (9)	0.0539 (10)	0.0012 (7)	0.0039 (8)	0.0010 (8)
C2A	0.0693 (13)	0.0796 (15)	0.0602 (12)	0.0119 (11)	0.0173 (10)	0.0069 (11)
C3A	0.0933 (18)	0.0628 (13)	0.0744 (15)	0.0251 (12)	−0.0108 (13)	0.0045 (11)

Geometric parameters (Å, º) top

S1—O3	1.4197 (12)	C10—C11	1.382 (2)
S1—O4	1.4292 (14)	C10—H10	0.9300
S1—N1	1.6479 (13)	C11—C12	1.374 (2)
S1—C1	1.7375 (13)	C11—H11	0.9300
S2—O5	1.4212 (12)	C12—H12	0.9300
S2—O6	1.4247 (12)	C13—C14	1.377 (3)
S2—N2	1.6433 (13)	C13—H13	0.9300
S2—C5	1.7405 (13)	C14—C15	1.381 (3)
N1—C4	1.4012 (18)	C14—H14	0.9300
N1—C17	1.4767 (18)	C15—C16	1.372 (2)
N2—C8	1.4052 (18)	C15—H15	0.9300
N2—C18	1.474 (2)	C16—H16	0.9300
O1—C2	1.3571 (15)	C17—H17C	0.9600
O1—C6	1.3638 (15)	C17—H17B	0.9600
O2—C19	1.2168 (16)	C17—H17A	0.9600
C1—C2	1.3571 (17)	C18—H18C	0.9600
C1—C19	1.4610 (18)	C18—H18B	0.9600
C2—C3	1.4415 (17)	C18—H18A	0.9600
C3—C12	1.4062 (18)	N1A—C1A	1.328 (2)
C3—C4	1.4110 (19)	N1A—C3A	1.445 (3)
C4—C9	1.3992 (19)	N1A—C2A	1.446 (3)
C5—C6	1.3529 (17)	O1A—C1A	1.217 (2)
C5—C19	1.4611 (18)	C1A—H1A	0.9300
C6—C7	1.4371 (17)	C2A—H2AC	0.9600
C7—C16	1.4039 (19)	C2A—H2AB	0.9600
C7—C8	1.4055 (19)	C2A—H2AA	0.9600
C8—C13	1.398 (2)	C3A—H3AC	0.9600
C9—C10	1.375 (2)	C3A—H3AB	0.9600
C9—H9	0.9300	C3A—H3AA	0.9600

O3—S1—O4	118.06 (9)	C12—C11—H11	120.2
O3—S1—N1	106.74 (7)	C10—C11—H11	120.2
O4—S1—N1	110.49 (7)	C11—C12—C3	120.27 (14)
O3—S1—C1	111.08 (7)	C11—C12—H12	119.9
O4—S1—C1	107.92 (7)	C3—C12—H12	119.9
N1—S1—C1	101.26 (6)	C14—C13—C8	120.03 (16)
O5—S2—O6	116.97 (8)	C14—C13—H13	120.0
O5—S2—N2	107.23 (7)	C8—C13—H13	120.0
O6—S2—N2	111.32 (8)	C13—C14—C15	121.31 (14)
O5—S2—C5	110.72 (7)	C13—C14—H14	119.3
O6—S2—C5	108.33 (7)	C15—C14—H14	119.3
N2—S2—C5	101.13 (6)	C16—C15—C14	119.65 (15)
C4—N1—C17	119.52 (12)	C16—C15—H15	120.2
C4—N1—S1	121.43 (9)	C14—C15—H15	120.2
C17—N1—S1	112.73 (10)	C15—C16—C7	120.43 (15)
C8—N2—C18	119.46 (13)	C15—C16—H16	119.8
C8—N2—S2	122.12 (10)	C7—C16—H16	119.8
C18—N2—S2	114.59 (11)	N1—C17—H17C	109.5
C2—O1—C6	120.73 (10)	N1—C17—H17B	109.5
C2—C1—C19	122.37 (12)	H17C—C17—H17B	109.5
C2—C1—S1	119.40 (10)	N1—C17—H17A	109.5
C19—C1—S1	117.00 (9)	H17C—C17—H17A	109.5
C1—C2—O1	120.90 (12)	H17B—C17—H17A	109.5
C1—C2—C3	125.40 (12)	N2—C18—H18C	109.5
O1—C2—C3	113.69 (11)	N2—C18—H18B	109.5
C12—C3—C4	119.62 (12)	H18C—C18—H18B	109.5
C12—C3—C2	120.78 (12)	N2—C18—H18A	109.5
C4—C3—C2	119.60 (12)	H18C—C18—H18A	109.5
C9—C4—N1	120.23 (13)	H18B—C18—H18A	109.5
C9—C4—C3	118.95 (13)	O2—C19—C1	124.01 (13)
N1—C4—C3	120.73 (12)	O2—C19—C5	123.66 (13)
C6—C5—C19	122.28 (12)	C1—C19—C5	112.20 (11)
C6—C5—S2	120.08 (10)	C1A—N1A—C3A	120.13 (17)
C19—C5—S2	116.45 (9)	C1A—N1A—C2A	122.24 (17)
C5—C6—O1	120.83 (11)	C3A—N1A—C2A	117.58 (18)
C5—C6—C7	125.71 (12)	O1A—C1A—N1A	126.16 (19)
O1—C6—C7	113.42 (11)	O1A—C1A—H1A	116.9
C16—C7—C8	119.64 (12)	N1A—C1A—H1A	116.9
C16—C7—C6	121.02 (12)	N1A—C2A—H2AC	109.5
C8—C7—C6	119.33 (12)	N1A—C2A—H2AB	109.5
C13—C8—N2	120.35 (14)	H2AC—C2A—H2AB	109.5
C13—C8—C7	118.91 (13)	N1A—C2A—H2AA	109.5
N2—C8—C7	120.57 (12)	H2AC—C2A—H2AA	109.5
C10—C9—C4	119.88 (15)	H2AB—C2A—H2AA	109.5
C10—C9—H9	120.1	N1A—C3A—H3AC	109.5
C4—C9—H9	120.1	N1A—C3A—H3AB	109.5
C9—C10—C11	121.62 (14)	H3AC—C3A—H3AB	109.5
C9—C10—H10	119.2	N1A—C3A—H3AA	109.5
C11—C10—H10	119.2	H3AC—C3A—H3AA	109.5
C12—C11—C10	119.67 (14)	H3AB—C3A—H3AA	109.5

O3—S1—N1—C4	−156.20 (12)	C19—C5—C6—O1	−8.4 (2)
O4—S1—N1—C4	74.25 (13)	S2—C5—C6—O1	−175.54 (9)
C1—S1—N1—C4	−39.91 (13)	C19—C5—C6—C7	169.19 (13)
O3—S1—N1—C17	51.92 (13)	S2—C5—C6—C7	2.0 (2)
O4—S1—N1—C17	−77.63 (12)	C2—O1—C6—C5	4.20 (19)
C1—S1—N1—C17	168.21 (11)	C2—O1—C6—C7	−173.67 (11)
O5—S2—N2—C8	154.03 (12)	C5—C6—C7—C16	−168.18 (14)
O6—S2—N2—C8	−76.87 (13)	O1—C6—C7—C16	9.57 (18)
C5—S2—N2—C8	38.02 (13)	C5—C6—C7—C8	10.9 (2)
O5—S2—N2—C18	−48.17 (15)	O1—C6—C7—C8	−171.32 (12)
O6—S2—N2—C18	80.93 (15)	C18—N2—C8—C13	−3.9 (2)
C5—S2—N2—C18	−164.18 (13)	S2—N2—C8—C13	152.83 (12)
O3—S1—C1—C2	141.18 (12)	C18—N2—C8—C7	171.24 (15)
O4—S1—C1—C2	−87.94 (13)	S2—N2—C8—C7	−32.00 (19)
N1—S1—C1—C2	28.13 (13)	C16—C7—C8—C13	−1.8 (2)
O3—S1—C1—C19	−51.17 (13)	C6—C7—C8—C13	179.13 (13)
O4—S1—C1—C19	79.71 (12)	C16—C7—C8—N2	−176.99 (13)
N1—S1—C1—C19	−164.22 (11)	C6—C7—C8—N2	3.9 (2)
C19—C1—C2—O1	3.8 (2)	N1—C4—C9—C10	−176.42 (14)
S1—C1—C2—O1	170.77 (10)	C3—C4—C9—C10	0.1 (2)
C19—C1—C2—C3	−174.90 (13)	C4—C9—C10—C11	−0.6 (2)
S1—C1—C2—C3	−7.95 (19)	C9—C10—C11—C12	0.7 (3)
C6—O1—C2—C1	−1.91 (19)	C10—C11—C12—C3	−0.4 (2)
C6—O1—C2—C3	176.96 (11)	C4—C3—C12—C11	−0.1 (2)
C1—C2—C3—C12	171.94 (13)	C2—C3—C12—C11	179.99 (14)
O1—C2—C3—C12	−6.86 (18)	N2—C8—C13—C14	176.03 (15)
C1—C2—C3—C4	−8.0 (2)	C7—C8—C13—C14	0.8 (2)
O1—C2—C3—C4	173.18 (11)	C8—C13—C14—C15	0.8 (3)
C17—N1—C4—C9	−2.2 (2)	C13—C14—C15—C16	−1.4 (3)
S1—N1—C4—C9	−152.27 (12)	C14—C15—C16—C7	0.4 (2)
C17—N1—C4—C3	−178.74 (13)	C8—C7—C16—C15	1.2 (2)
S1—N1—C4—C3	31.23 (18)	C6—C7—C16—C15	−179.73 (14)
C12—C3—C4—C9	0.2 (2)	C2—C1—C19—O2	168.80 (15)
C2—C3—C4—C9	−179.87 (13)	S1—C1—C19—O2	1.6 (2)
C12—C3—C4—N1	176.72 (13)	C2—C1—C19—C5	−7.13 (19)
C2—C3—C4—N1	−3.32 (19)	S1—C1—C19—C5	−174.38 (10)
O5—S2—C5—C6	−136.55 (12)	C6—C5—C19—O2	−166.55 (15)
O6—S2—C5—C6	93.95 (13)	S2—C5—C19—O2	1.0 (2)
N2—S2—C5—C6	−23.15 (13)	C6—C5—C19—C1	9.40 (19)
O5—S2—C5—C19	55.58 (13)	S2—C5—C19—C1	176.98 (10)
O6—S2—C5—C19	−73.91 (12)	C3A—N1A—C1A—O1A	−0.3 (3)
N2—S2—C5—C19	168.99 (11)	C2A—N1A—C1A—O1A	177.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17A···O3	0.96	2.40	2.885 (2)	111
C18—H18A···O5	0.96	2.41	2.895 (2)	111
C3A—H3AA···O1A	0.96	2.41	2.784 (3)	103
C12—H12···O1	0.93	2.39	2.7106 (17)	100
C16—H16···O1	0.93	2.39	2.7109 (17)	100
C9—H9···O1Aⁱ	0.93	2.41	3.324 (2)	169
C18—H18B···O1Aⁱⁱ	0.96	2.46	3.376 (3)	159

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

Acknowledgements

Any acknowledgements?

References

Agilent (2012). CrysAlis CCD and CrysAlis RED. Agilent Technologies, Yarnton, England. Google Scholar
Bürgi, H.-B. & Dunitz, J. D. (1994). Structure Correlation, Vol. 2, 767–784. Weinheim: VCH. Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals 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
Ukrainets, I. V., Petrushova, L. A. & Dzyubenko, S. P. (2013). Chem. Heterocycl. Compd, 49, 1378–1383. CrossRef CAS Google Scholar
Ukrainets, I. V., Petrushova, L. A., Dzyubenko, S. P. & Sim, G. (2014). Chem. Heterocycl. Compd, 50, 103–110. CrossRef CAS Google Scholar
Ukrainets, I. V., Sidorenko, L. V., Svechnikova, E. N. & Shishkin, O. V. (2007). Chem. Heterocycl. Compd, 43, 1275–1279. CrossRef CAS Google Scholar
Ukrainets, I. V., Taran, E. A., Shishkin, O. V., Gorokhova, O. V., Taran, S. G., Jaradat, N. A. & Turov, A. V. (2000). Chem. Heterocycl. Compd. 36, 443–448. CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zefirov, N. S., Palyulin, V. A. & Dashevskaya, E. E. (1990). J. Phys. Org. Chem. 3, 147–158. CrossRef CAS Web of Science Google Scholar
Zefirov, Yu. V. (1997). Kristallografiya, 42, 936–958. CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.