Methyl 5-chloro-4-hy­droxy-2,2-dioxo-1H-2λ6,1-benzo­thia­zine-3-carboxyl­ate: structure and Hirshfeld surface analysis

Shishkina, S.V.; Petrushova, L.A.; Burian, K.O.; Fedosov, A.I.; Ukrainets, I.V.

doi:10.1107/S2056989020012566

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ISSN: 2056-9890

Volume 76| Part 10| October 2020| Pages 1657-1660

https://doi.org/10.1107/S2056989020012566

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Methyl 5-chloro-4-hydroxy-2,2-dioxo-1H-2λ⁶,1-benzothiazine-3-carboxylate: structure and Hirshfeld surface analysis

Svitlana V. Shishkina,^a,^b ^* Lidiya A. Petrushova,^c Kateryna O. Burian,^c Andrii I. Fedosov ^c and Igor V. Ukrainets ^c

^aSSI Institute for Single Crystals' National Academy of Science of Ukraine, 60 Nauky ave., Kharkiv 61001, Ukraine, ^bDepartment of Inorganic Chemistry, V. N. Karazin Kharkiv National University, 4 Svobody Sq., Kharkiv 61077, Ukraine, and ^cNational University of Pharmacy, 4 Valentynivska St, Kharkiv 61168, Ukraine
^*Correspondence e-mail: sveta@xray.isc.kharkov.com

Edited by S. Parkin, University of Kentucky, USA (Received 11 August 2020; accepted 15 September 2020; online 18 September 2020)

The title compound, C₁₀H₈ClNO₅S, which has potential analgesic activity, crystallizes in space group P2₁/n. The benzothiazine ring system adopts an intermediate form between sofa and twist-boat conformations. The coplanarity of the ester substituent to the bicyclic fragment is stabilized by an O—H⋯O intramolecular hydrogen bond. In the crystal, hydrogen bonds of type N—H⋯O(SO₂) link the molecules into zigzag chains extending along the b-axis direction. Neighbouring chains are linked by both O—H⋯Cl and C—H⋯Cl interactions. A Hirshfeld surface analysis was used to compare different types of intermolecular interactions, giving contributions of O⋯H/H⋯O = 42.0%, C⋯H/H⋯C = 17.3%, Cl⋯H/H⋯Cl = 14.2%, H⋯H = 11.1%.

Keywords: benzothiazine derivative; molecular structure; crystal structure; Hirshfeld surface analysis.

CCDC reference: 2032151

1. Chemical context

Alkyl 4-hydroxy-2,2-dioxo-1H-2λ⁶,1-benzothiazine-3-carboxylates are known to be highly active analgesics (Ukrainets et al., 2013 ). The influence of substituents at the cyclic nitrogen atom on the biological properties of these substances has been studied in detail (Ukrainets et al., 2013, 2017 ). Continuing our research in this direction, we have synthesized and studied a new compound of this class with a substituent on the benzene part of the molecule. The biological properties of benzothiazine derivatives are known to depend on their molecular structure (Ukrainets et al., 2019a ,b ). In addition, such molecules can form polymorphic modifications possessing different biological activity, as was shown in our previous studies (Ukrainets et al., 2016a , 2018 ). Therefore, the molecular and crystal structure study as well as a Hirshfeld surface analysis were performed for the title compound, 1.

2. Structural commentary

The dihydrothiazine ring in molecule 1 adopts a conformation that is intermediate between a sofa and twist-boat (Fig. 1) with puckering parameters S = 0.53, Θ = 35.1°, Ψ = 11.3° (Zefirov et al., 1990 ). The S1 and C8 atoms deviate by 0.81 (1) and 0.22 (1) Å, respectively, from the mean-square plane of the remaining atoms in the ring. The Cremer–Pople ring puckering parameters for the dihydrothiazine ring are: Q = 0.457 (4) Å, Θ = 111.6 (5)°, Ψ = 192.1 (6)°. The ester substituent is essentially coplanar to the C7—C8 endocyclic double bond [the C7—C8—C9—O2 torsion angle is 3.0 (7)°] as a result of the stabilizing influence of the O1—H1O⋯O2 intramolecular hydrogen bond (Table 1). This hydrogen bond can be specified as S(6) in terms of graph-set theory since the six atoms comprise a intramolecular hydrogen-bonded motif. The formation of the O—H⋯O hydrogen bond causes some elongation of the C9—O2 and C7—C8 bonds as compared with typical values of 1.210 Å (Csp²=O bond) and 1.326 Å (Csp²—Csp² bond), respectively (Bürgi & Dunitz, 1994 ). The C7—O1 bond is shortened to 1.320 (6) Å (the typical length for a Csp²—O bond is 1.362 Å) for the same reason. The methyl group is located in an anti-periplanar position to the C8—C9 bond [the C10—O3—C9—C8 torsion angle is −178.4 (4)°]. The noticeable steric repulsion between chlorine and the hydroxyl group [the Cl1⋯O1 distance is 2.793 (4) Å as compared to the van der Waals radii sum (Zefirov, 1997 ) of 3.19 Å] results in twisting of the Cl1—C5—C6—C7 and C5—C6—C7—O1 torsion angles up to 14.7 (7) and 14.5 (7)°, respectively.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O2	0.84	1.76	2.509 (5)	148
N1—H1N⋯O4ⁱ	0.88	2.07	2.841 (5)	145
O1—H1O⋯Cl1ⁱⁱ	0.84	2.87	3.203 (4)	106
C10—H10C⋯Cl1ⁱⁱⁱ	0.98	2.84	3.399 (5)	117
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 1
The molecular structure of compound 1. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are shown as spheres of arbitrary radius.

3. Supramolecular features

In the crystal, molecules of 1 form zigzag chains in the [010] direction (Fig. 2) as a result of the formation of N1—H⋯O4ⁱ hydrogen bonds about the 2₁ screw axis parallel to b [symmetry code: (i) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; the N⋯O distance is 2.841 (5) Å, the N—H⋯O angle is 145.1° (Table 1)]. The crystal structure fragment formed by this hydrogen bond may be described as C(4) in terms of graph-set theory. Neighbouring zigzag chains are connected by weaker O—H⋯Clⁱⁱ interactions (Table 1) in the [001] direction [symmetry code: (ii) $[{3\over 2}]$ − x, y − $[{1\over 2}]$ , $[{3\over 2}]$ − z]. As a result, the hydrogen-bonded layers parallel to the bc plane may be considered as secondary structural motifs. There are weak C—H⋯Clⁱⁱⁱ interactions [symmetry code: (iii) x − $[{1\over 2}]$ , −y − $[{1\over 2}]$ , z − $[{1\over 2}]$ ] between molecules of neighbouring layers. In addition, stacking interactions between inversion-related (2 − x, 1 − y, 1 − z) benzene rings of molecules belonging to neighbouring layers are found. The distance between ring planes is 3.246 (2) Å. The stacking interactions are characterized by a centroid-to-centroid distance of 3.872 (2) Å, with a lateral shift of the benzene rings of 2.111 (2) Å.

Figure 2
A chain of molecules of 1 bound by N—H⋯O hydrogen bonds about the 2₁-screw axis parallel to the b axis.

4. Hirshfeld surface analysis

Hirshfeld surface analysis and 2D fingerprint plots are useful tools to investigate the different types of intra- and intermolecular interactions in a crystal (Turner et al., 2017 ). The Hirshfeld surface of the title compound was obtained using a standard (high) surface resolution, mapped over d_norm. The areas coloured red on the d_norm surfaces correspond to contacts that are shorter than the van der Waals radii sum of the closest atoms (Fig. 3). In this way, red spots on the Hirshfeld surface indicate atoms participating in hydrogen bonds or other short contacts. Such red spots are observed at the hydrogen atom of the NH group, one of the oxygen atoms of the SO₂ group, and the chlorine atom. Smaller red spots are also present at one of the hydrogen atoms of the methyl group.

Figure 3
Hirshfeld surface of a molecule of 1 mapped over d_norm, with transparency to show the conformation.

All of the hydrogen bonds and short contacts of the title compound are evident in the two-dimensional fingerprint plot presented in Fig. 4a. The pair of very sharp spikes indicates the presence of strong hydrogen bonds in the crystal of 1. The main contribution (42.0%) to these spikes is provided by O⋯H/H⋯O interactions (Fig. 4b). The contributions of C⋯H/H⋯C (17.3%) and Cl⋯H/H⋯Cl (14.2%) (Fig. 4c,d) interactions are similar, but the presence of sharp spikes in the fingerprint plot delineated Cl⋯H/H⋯Cl interactions suggests that these contacts are stronger. Surprisingly, the contribution of H⋯H interactions (11.1%) (Fig. 4e) is very small, which is unusual for molecular crystals.

Figure 4
Two-dimensional Hirshfeld fingerprint plot of (a) all contacts for compound 1 and those delineated into (b) O⋯H/ H⋯O (42.0%), (c) C⋯H/H⋯C (17.3%), (d) Cl⋯H/H⋯Cl (14.2%), (e) H⋯H (11.1%) contacts.

5. Database survey

A search of the Cambridge Structural Database (Version 5.41, update of November 2019; Groom et al., 2016 ) for the benzothiazine fragment revealed only ten hits [refcodes AKIJIP, AKIJIP01 (Ukrainets et al., 2016a), CABBEP (Lei et al., 2016 ), IJUJAA (Ukrainets et al., 2015b ), LANNUM (Ukrainets et al., 2016b ), LOGHEW (Ukrainets et al., 2014 ), MINJAW (Shishkina et al., 2013 ), NODGUK (Ukrainets et al., 2013), UWUCIA (Ukrainets et al., 2015a ) and XEKPUB (Ukrainets et al., 2017)]. In all these structures, the conformation of the benzothiazine rings as well as the redistribution of the electron density as a result of the formation of the O—H⋯O intramolecular hydrogen bond are similar.

The title compound may be considered as a structural analogue of methyl 4-hydroxy-2,2-dioxo-1-methyl-1H-2,1-benzothiazine-3-carboxylate (Ukrainets et al., 2013), which is substituted by chlorine on the benzene ring of the molecule and dealkylated at the cyclic nitrogen atom.

6. Synthesis and crystallization

Methyl (chlorosulfonyl)acetate (1.90 g, 0.011 mol) was added dropwise under stirring to a solution of methyl 6-chloroanthranilate (1.85 g, 0.010 mol) and triethylamine (1.54 mL, 0.011 mol) in CH₂Cl₂ (20 mL) and the mixture was cooled (268 to 273 K) (Fig. 5). After 10 h, water (50 mL) was added to the reaction mixture, which was acidified up to pH = 4 with 1 N HCl and mixed thoroughly. The organic layer was separated, dried over anhydrous CaCl₂, and distilled (at reduced pressure at the end). A solution of sodium methylate in anhydrous methanol [from metallic sodium (0.69 g, 0.030 mol) and absolute methanol (20 mL)] was added, the mixture was boiled and stored for 15 h at room temperature. The reaction mixture was diluted with cold water and acidified with 1 N HCl to pH = 4. The solid methyl 5-chloro-4-hydroxy-2,2-dioxo-1H-2λ⁶,1-benzothiazine-3-carboxylate was filtered, washed with water, and dried in air. Yield 2.43g (84%); colourless crystals; m.p. 464–466 K.

Figure 5
The synthesis of compound 1.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All of the hydrogen atoms were located in difference-Fourier maps. They were included in calculated positions and treated as riding with C—H = 0.96 Å, O—H = 0.84 Å, U_iso(H) = 1.5U_eq(C,O) for methyl and hydroxyl groups and with C—H = 0.93 Å, N—H = 0.88 Å, U_iso(H) = 1.2U_eq(C,N) for all other hydrogen atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₈ClNO₅S
M_r	289.68
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	11.153 (3), 6.8926 (15), 14.600 (3)
β (°)	97.528 (5)
V (Å³)	1112.6 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.54
Crystal size (mm)	0.30 × 0.10 × 0.05

Data collection
Diffractometer	Rigaku Oxford Diffraction Xcalibur, Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.428, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9166, 1957, 1343
R_int	0.111
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.145, 1.05
No. of reflections	1957
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.46
Computer programs: CrysAlis PRO (Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and Mercury (Macrae, 2020 ).

Supporting information

CCDC reference: 2032151

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020012566/pk2647sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020012566/pk2647Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989020012566/pk2647Isup3.cml

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: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: Mercury (Macrae, 2020).

Methyl 5-chloro-4-hydroxy-2,2-dioxo-1H-2λ⁶,1-benzothiazine-3-carboxylate top

Crystal data top

C₁₀H₈ClNO₅S	F(000) = 592
M_r = 289.68	D_x = 1.729 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.153 (3) Å	Cell parameters from 2736 reflections
b = 6.8926 (15) Å	θ = 3.3–34.2°
c = 14.600 (3) Å	µ = 0.54 mm⁻¹
β = 97.528 (5)°	T = 120 K
V = 1112.6 (4) Å³	Plate, colourless
Z = 4	0.30 × 0.10 × 0.05 mm

Data collection top

Rigaku Oxford Diffraction Xcalibur, Sapphire3 diffractometer	1957 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1343 reflections with I > 2σ(I)
Detector resolution: 16.1827 pixels mm^-1	R_int = 0.111
ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018)	h = −13→13
T_min = 0.428, T_max = 1.000	k = −8→8
9166 measured reflections	l = −17→17

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.063	H-atom parameters constrained
wR(F²) = 0.145	w = 1/[σ²(F_o²) + (0.0609P)² + 0.6529P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1957 reflections	Δρ_max = 0.38 e Å⁻³
165 parameters	Δρ_min = −0.46 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
Cl1	0.84549 (13)	0.2458 (2)	0.73322 (9)	0.0298 (4)
S1	0.76398 (12)	0.09884 (18)	0.35643 (9)	0.0158 (3)
O1	0.6753 (3)	0.0566 (5)	0.6066 (2)	0.0218 (9)
H1O	0.638729	−0.048715	0.594436	0.033*
O2	0.5710 (3)	−0.2111 (5)	0.5105 (2)	0.0232 (9)
O3	0.6006 (3)	−0.2377 (5)	0.3617 (2)	0.0212 (9)
O4	0.6887 (3)	0.0811 (5)	0.2691 (2)	0.0209 (8)
O5	0.8815 (3)	0.0129 (5)	0.3625 (2)	0.0213 (9)
N1	0.7714 (4)	0.3285 (6)	0.3778 (3)	0.0200 (10)
H1N	0.750045	0.409629	0.331963	0.024*
C1	0.8100 (4)	0.4052 (7)	0.4653 (3)	0.0150 (11)
C2	0.8599 (4)	0.5923 (7)	0.4729 (4)	0.0187 (12)
H2	0.867292	0.666061	0.418938	0.022*
C3	0.8974 (4)	0.6672 (8)	0.5574 (4)	0.0215 (12)
H3	0.928646	0.795566	0.562115	0.026*
C4	0.8914 (5)	0.5596 (8)	0.6383 (4)	0.0225 (13)
H4	0.921192	0.611991	0.697051	0.027*
C5	0.8413 (4)	0.3765 (8)	0.6308 (3)	0.0182 (12)
C6	0.7937 (4)	0.2947 (7)	0.5441 (3)	0.0156 (11)
C7	0.7202 (4)	0.1186 (7)	0.5325 (3)	0.0163 (11)
C8	0.6938 (4)	0.0228 (7)	0.4494 (3)	0.0152 (11)
C9	0.6170 (4)	−0.1515 (7)	0.4434 (3)	0.0180 (12)
C10	0.5228 (5)	−0.4067 (7)	0.3536 (4)	0.0247 (13)
H10C	0.528740	−0.471978	0.294700	0.037*
H10B	0.438987	−0.366365	0.355781	0.037*
H10A	0.548102	−0.495994	0.404669	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0396 (9)	0.0322 (8)	0.0162 (7)	0.0041 (7)	−0.0016 (6)	0.0010 (6)
S1	0.0175 (7)	0.0156 (7)	0.0151 (7)	−0.0009 (6)	0.0050 (5)	−0.0007 (6)
O1	0.030 (2)	0.020 (2)	0.0181 (19)	−0.0045 (17)	0.0113 (17)	0.0001 (16)
O2	0.022 (2)	0.023 (2)	0.028 (2)	−0.0011 (17)	0.0127 (17)	0.0031 (17)
O3	0.023 (2)	0.021 (2)	0.022 (2)	−0.0081 (17)	0.0110 (16)	−0.0049 (16)
O4	0.023 (2)	0.025 (2)	0.0143 (18)	0.0003 (17)	−0.0004 (15)	−0.0031 (16)
O5	0.020 (2)	0.019 (2)	0.028 (2)	0.0041 (16)	0.0107 (16)	0.0025 (16)
N1	0.029 (3)	0.014 (2)	0.017 (2)	0.003 (2)	0.004 (2)	0.0069 (18)
C1	0.009 (2)	0.017 (3)	0.019 (3)	0.002 (2)	0.001 (2)	−0.002 (2)
C2	0.017 (3)	0.013 (3)	0.027 (3)	−0.002 (2)	0.005 (2)	0.001 (2)
C3	0.011 (3)	0.018 (3)	0.036 (3)	0.002 (2)	0.005 (2)	−0.008 (2)
C4	0.015 (3)	0.028 (3)	0.024 (3)	0.005 (2)	−0.001 (2)	−0.008 (2)
C5	0.011 (3)	0.027 (3)	0.017 (3)	0.003 (2)	0.003 (2)	0.000 (2)
C6	0.010 (3)	0.018 (3)	0.019 (3)	0.006 (2)	0.002 (2)	0.000 (2)
C7	0.010 (3)	0.022 (3)	0.018 (3)	0.005 (2)	0.006 (2)	0.002 (2)
C8	0.013 (3)	0.014 (3)	0.019 (3)	0.002 (2)	0.007 (2)	0.001 (2)
C9	0.014 (3)	0.020 (3)	0.020 (3)	0.010 (2)	0.003 (2)	0.003 (2)
C10	0.020 (3)	0.021 (3)	0.034 (3)	−0.008 (3)	0.007 (2)	−0.009 (3)

Geometric parameters (Å, º) top

Cl1—C5	1.741 (5)	C1—C2	1.403 (7)
S1—O5	1.431 (4)	C1—C6	1.412 (7)
S1—O4	1.437 (3)	C2—C3	1.352 (7)
S1—N1	1.614 (4)	C3—C4	1.404 (7)
S1—C8	1.734 (5)	C4—C5	1.379 (7)
O1—C7	1.320 (6)	C5—C6	1.423 (7)
O2—C9	1.234 (6)	C6—C7	1.462 (7)
O3—C9	1.323 (6)	C7—C8	1.379 (7)
O3—C10	1.448 (6)	C8—C9	1.471 (7)
N1—C1	1.397 (6)

O5—S1—O4	116.3 (2)	C4—C5—Cl1	116.2 (4)
O5—S1—N1	111.8 (2)	C6—C5—Cl1	121.6 (4)
O4—S1—N1	105.3 (2)	C1—C6—C5	116.0 (5)
O5—S1—C8	109.3 (2)	C1—C6—C7	118.9 (4)
O4—S1—C8	113.4 (2)	C5—C6—C7	124.8 (4)
N1—S1—C8	99.3 (2)	O1—C7—C8	120.3 (5)
C9—O3—C10	116.5 (4)	O1—C7—C6	116.2 (4)
C1—N1—S1	123.3 (3)	C8—C7—C6	123.5 (4)
N1—C1—C2	119.5 (4)	C7—C8—C9	119.9 (4)
N1—C1—C6	119.0 (4)	C7—C8—S1	118.5 (4)
C2—C1—C6	121.5 (5)	C9—C8—S1	121.3 (4)
C3—C2—C1	119.7 (5)	O2—C9—O3	122.9 (5)
C2—C3—C4	121.5 (5)	O2—C9—C8	121.6 (5)
C5—C4—C3	118.8 (5)	O3—C9—C8	115.5 (4)
C4—C5—C6	122.2 (5)

O5—S1—N1—C1	−69.3 (4)	C5—C6—C7—O1	14.5 (7)
O4—S1—N1—C1	163.5 (4)	C1—C6—C7—C8	19.0 (7)
C8—S1—N1—C1	45.9 (4)	C5—C6—C7—C8	−167.7 (5)
S1—N1—C1—C2	154.5 (4)	O1—C7—C8—C9	−1.2 (7)
S1—N1—C1—C6	−27.8 (6)	C6—C7—C8—C9	−178.8 (4)
N1—C1—C2—C3	−180.0 (4)	O1—C7—C8—S1	−175.2 (3)
C6—C1—C2—C3	2.3 (7)	C6—C7—C8—S1	7.2 (7)
C1—C2—C3—C4	2.1 (7)	O5—S1—C8—C7	82.9 (4)
C2—C3—C4—C5	−2.7 (7)	O4—S1—C8—C7	−145.5 (4)
C3—C4—C5—C6	−1.2 (7)	N1—S1—C8—C7	−34.2 (4)
C3—C4—C5—Cl1	176.1 (4)	O5—S1—C8—C9	−91.1 (4)
N1—C1—C6—C5	176.5 (4)	O4—S1—C8—C9	40.5 (5)
C2—C1—C6—C5	−5.8 (7)	N1—S1—C8—C9	151.8 (4)
N1—C1—C6—C7	−9.7 (7)	C10—O3—C9—O2	1.1 (7)
C2—C1—C6—C7	168.0 (4)	C10—O3—C9—C8	−178.4 (4)
C4—C5—C6—C1	5.2 (7)	C7—C8—C9—O2	3.0 (7)
Cl1—C5—C6—C1	−171.9 (4)	S1—C8—C9—O2	176.9 (4)
C4—C5—C6—C7	−168.2 (5)	C7—C8—C9—O3	−177.5 (4)
Cl1—C5—C6—C7	14.7 (7)	S1—C8—C9—O3	−3.6 (6)
C1—C6—C7—O1	−158.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2	0.84	1.76	2.509 (5)	148
N1—H1N···O4ⁱ	0.88	2.07	2.841 (5)	145
O1—H1O···Cl1ⁱⁱ	0.84	2.87	3.203 (4)	106
C10—H10C···Cl1ⁱⁱⁱ	0.98	2.84	3.399 (5)	117

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

Acknowledgements

Any acknowledgements?

References

Bürgi, H.-B. & Dunitz, J. D. (1994). Structure Correlation, Vol. 2, pp. 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
Lei, K., Hua, X.-W., Tao, Y.-Y., Liu, Y., Liu, N., Ma, Y., Li, Y.-H., Xu, X.-H. & Kong, C.-H. (2016). Bioorg. Med. Chem. 24, 92–103. CSD CrossRef CAS PubMed Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shishkina, S. V., Ukrainets, I. V. & Petrushova, L. A. (2013). Acta Cryst. E69, o1698. CSD CrossRef IUCr Journals Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. https://hirshfeldsurface.net Google Scholar
Ukrainets, I. V., Burian, A. A., Baumer, V. N., Shishkina, S. V., Sidorenko, L. V., Tugaibei, I. A., Voloshchuk, N. I. & Bondarenko, P. S. (2018). Sci. Pharm. 86, 21, https://doi.org/10.3390/scipharm86020021 Google Scholar
Ukrainets, I. V., Burian, A. A., Hamza, G. M., Voloshchuk, N. I., Malchenko, O. V., Shishkina, S. V., Sidorenko, L. V., Burian, K. O. & Sim, G. (2019b). Sci. Pharm. 87, 12, https://doi.org/10.3390/scipharm87020012. Google Scholar
Ukrainets, I. V., Hamza, G. M., Burian, A. A., Voloshchuk, N. I., Malchenko, O. V., Shishkina, S. V., Danylova, I. A. & Sim, G. (2019a). Sci. Pharm. 87, 10, https://doi.org/10.3390/scipharm87020010. Google Scholar
Ukrainets, I. V., Petrushova, L. A. & Bereznyakova, N. L. (2015a). Pharm. Chem. J. 49, 519–522. CSD CrossRef CAS 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, 1, 114–122. Google Scholar
Ukrainets, I. V., Petrushova, L. A., Shishkina, S. V., Sidorenko, L. V., Sim, G. & Kryvanych, O. V. (2016b). Sci. Pharm. 84, 523–535. CSD CrossRef CAS PubMed Google Scholar
Ukrainets, I. V., Petrushova, L. A., Sim, G. & Bereznyakova, N. L. (2015b). Chem. Heterocycl. Compd, 51, 97–101. CrossRef CAS Google Scholar
Ukrainets, I. V., Petrushova, L. A., Sim, G. & Grinevich, L. A. (2017). Pharm. Chem. J. 51, 482–485. CSD CrossRef CAS Google Scholar
Ukrainets, I. V., Shishkina, S. V., Baumer, V. N., Gorokhova, O. V., Petrushova, L. A. & Sim, G. (2016a). Acta Cryst. C72, 411–415. Web of Science CSD CrossRef 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

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