Crystal structure of 3-(2-hy­droxy­eth­yl)-2-methyl­sulfanyl-6-nitro-3H-benzimidazol-1-ium chloride monohydrate

Abou, A.; Coulibali, S.; Kakou-Yao, R.; Zoueu, T.J.; Tenon, A.J.

doi:10.1107/S2056989016013657

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ISSN: 2056-9890

Volume 72| Part 9| September 2016| Pages 1356-1359

https://doi.org/10.1107/S2056989016013657

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Crystal structure of 3-(2-hydroxyethyl)-2-methylsulfanyl-6-nitro-3H-benzimidazol-1-ium chloride monohydrate

Akoun Abou,^a ^* Siomenan Coulibali,^b Rita Kakou-Yao,^c T. Jérémie Zoueu ^d and A. Jules Tenon ^c

^aUnité Mixte de Recherche et d'Innovation en Electronique et d'Electricité Appliquées (UMRI EEA), Equipe de Recherche: Instrumentation Image et Spectroscopie (L2IS), DFR–GEE, Institut National Polytechnique Félix Houphouët-Boigny (INP-HB), BP 1093, Yamoussoukro, Côte d'Ivoire, Laboratoire de Cristallographie et Physique Moléculaire, UFR SSMT, Université de Cocody 22 BP 582 Abidjan 22, Côte d'Ivoire, ^bLaboratoire de Chimie Organique, UFR SSMT, Université de Cocody 22 BP 582 Abidjan 22, Côte d'Ivoire, ^cLaboratoire de Cristallographie et Physique Moléculaire, UFR SSMT, Université de Cocody 22 BP 582 Abidjan 22, Côte d'Ivoire, and ^dUnité Mixte de Recherche et d'Innovation en Electronique et d'Electricité Appliquées (UMRI EEA)., Equipe de Recherche: Instrumentation Image et Spectroscopie (L2IS), DFR–GEE, Institut National Polytechnique Félix Houphouët-Boigny (INP-HB), BP 1093, Yamoussoukro, Côte d'Ivoire
^*Correspondence e-mail: abouakoun@gmail.com

Edited by J. Simpson, University of Otago, New Zealand (Received 18 August 2016; accepted 25 August 2016; online 31 August 2016)

In the cation of the title hydrated molecular salt, C₁₀H₁₂N₃O₃S⁺·Cl⁻·H₂O, the benzimidazolium ring system is almost planar (r.m.s. deviation = 0.006 Å) and the nitro group is inclined at an angle of 4.86 (9)° to this plane. In the crystal, C—H⋯O hydrogen bonds form centrosymmetric R₂²(20) dimers and these are further aggregated through N—H⋯O and O—H⋯Cl hydrogen bonds involving the water molecules and chloride anions. Aromatic π–π stacking interactions are also found between two parallel benzene rings or the benzene and imidazolium rings, with centroid–centroid distances of 3.5246 (9) and 3.7756 (9) Å, respectively. Analysis of the bond lengths and comparison with related compounds show that the nitro substituent is not involved in conjugation with the adjacent π-system and hence has no effect on the charge distribution of the heterocyclic ring.

Keywords: crystal structure; benzimidazole derivative; hydrogen bonding; π–π interactions.

CCDC reference: 1500918

1. Chemical context

Numerous compounds with benzimidazole ring systems display versatile pharmacological activities such as anti-viral, anti-helmintic, spasmolitic, anti-hypertensive and vasodilator properties (Akkurt et al., 2006 ). Many benzimidazole derivatives also have anti-microbial and anti-fungal activities (Küçükbay et al., 2003 , 2004 ; Puratchikody et al., 2008 ; Alasmary et al., 2015 ). The synthesis of new benzimidazole derivatives is therefore of considerable current interest. As part of our studies in this area, the title protonated benzimidazole compound (I) has been synthesized and its molecular structure is presented here.

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. The nine-membered benzimidazolium ring system (N4/C11/N9/C13/C16/C7/C15/C18/C10) is essentially planar, the maximum deviation from planarity being 0.013 (1) Å for atom N4. In addition, atoms N12, C17 and S2 of the nitro, hydroxyethyl and methylsulfanyl substituents lie close to the benzimidazolium ring plane with a maximum deviation of −0.059 (1) Å for atom S2. The least-squares plane of the nitro group (C7/N12/O6/O8) lies close to the benzimidazolium ring system, making a dihedral angle of 4.86 (9)°. In the structure, the bond lengths and angles of the benzimidazolium ring are generally in good agreement with those observed in related structures (Morozov et al., 2004 ; Verdan et al., 2009 ; Chen et al., 2010 ; Yuasa et al., 2010 ; Gao et al., 2013 ; Samsonov et al., 2013 ; Liu et al., 2014 ). In addition, the C7—N12 bond length, 1.4667 (19) Å shows that the nitro group is not involved in conjugation with the adjacent π-system and hence has no effect on the charge distribution of the heterocyclic ring.

Figure 1
The molecular structure of (I)

, showing the atomic labelling scheme and displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.

3. Supramolecular features

In the crystal, C14—H14B⋯O8 hydrogen bonds (Table 1) link the organic fragments into centrosymmetric dimers with $[R_{2}^{2}]$ (20) ring motifs along the [100] direction (Fig. 2). These dimers are further connected along the [100] and [010] directions by N—H⋯O and O—H⋯Cl hydrogen bonds, respectively, generating R₄⁶(22) rings. In the latter ring motifs, both the water molecule and the oxygen atom of the hydroxyethyl substituent act as donors with the chloride anion as acceptor. The O3 atom of the water molecule serves as acceptor for the H9 atom of the imidazolium NH group (Fig. 3). The pattern formed by the water molecules connecting the chloride anions, and forming an R₂⁴(8) ring, is reminiscent of a parallelogram (Fig. 3). The supramolecular aggregation is completed by π–π stacking interactions between two parallel benzene rings and between the benzene and imidazolium rings: Cg2⋯Cg2(1 − x, −y, −z) = 3.5246 (9), Cg1⋯Cg2(1 − x, −y, −z) = 3.7756 (9) Å, slippage = 1.190 Å Cg1 and Cg2 are the centroids of the imidazolium and benzene rings respectively. The centroid–centroid separations are less than 3.8 Å, the maximum regarded as suitable for an effective π–π interaction (Janiak, 2000 ) (Fig. 4)).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯Cl1	0.82	2.40	3.1840 (15)	161
C17—H17B⋯S2	0.97	2.68	3.1514 (18)	110
O3—H3B⋯Cl1	0.83 (2)	2.28 (2)	3.1090 (14)	178 (2)
O3—H3A⋯Cl1ⁱ	0.79 (2)	2.37 (2)	3.1561 (14)	174 (2)
C14—H14B⋯O8ⁱⁱ	0.97	2.60	3.189 (2)	119
N9—H9⋯O3ⁱⁱⁱ	0.86	1.85	2.6949 (16)	165
Symmetry codes: (i) -x, -y, -z+1; (ii) -x, -y, -z; (iii) x+1, y, z.

Figure 2
The crystal packing of (I)

, showing the supramolecular aggregation resulting from the three-dimensional hydrogen-bonded network. Dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted for clarity.

Figure 3
The molecular packing of (I)

, showing the pattern formed by the water molecules hydrogen bonded to the chloride anions.

Figure 4
A view of the crystal packing, showing π–π stacking interactions (dashed lines). The brown dots are the centroids of the rings. H atoms have been omitted for clarity.

4. Database survey

A CSD search (Web CSD version 5.37; August 19, 2016; Groom et al., 2016 ) found eight benzimidazolium structures with substituents at the 1 and 2 positions of the imidazolium ring system (Morozov et al., 2004; Verdan et al., 2009; Chen et al., 2010; Yuasa et al., 2010; Gao et al., 2013; Samsonov et al., 2013; Liu et al., 2014; Kerimov et al., 2012 ). In these structures, the imidazolium rings generally show two long (in the range 1.36–1.40 Å) and two short (1.30–1.34 Å) C—N distances. This pattern is clearly repeated here with N4—C11 = 1.3492 (18) and N9—C11 = 1.3390 (17) Å while N4—C10 = 1.3898 (18) Å and N9—C13 = 1.3867 (16)Å. The sole exception to this pattern is the compound, 2-(4-chlorophenyl)-3-[(5-(3,5-dinitrophenyl)-1,3,4-oxadiazol-2-yl]methyl)-1H-benzimidazole (Kerimov et al., 2012), with an imidazolium ring, which reveals three long (1.37–1.39 Å) and one short ( 1.30 Å) C—N bonds, a pattern that is also displayed in benzimidazole structures (Abou et al., 2007 ; Yavo et al., 2007 ; Kakou-Yao et al., 2007 ; Akonan et al., 2010 ; Lokaj et al., 2009 ).

5. Synthesis and crystallization

2-Chloroethanol (1.3 ml, 19.2 mmol) and potassium carbonate (1.32 g, 9.6 mmol) were added to 2-methylthio-5-nitro-1H-benzimidazole (1.15 g, 4.8 mmol) in dimethyl sulfoxide (DMSO) (10 ml). The reaction mixture was agitated for 5 h at room temperature. 50 ml of water was then added to the reaction mixture, and the products were extracted with dichloromethane (3 × 50 ml). The combined organic extracts were washed with ammonium chloride solution (10 g of ammonium chloride in 100 ml of water), dried over Na₂SO₄, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel (elution: methanol/ethyl acetate, 20:80, v/v). The resulting powder was dissolved in dichloromethane and after three days, yellow crystals suitable for single-crystal X-ray diffraction analysis were obtained in 72% yield with a melting point of 425 K.

¹H NMR (DMSO, 300 MHz) δ(p.p.m.): 2.7 (s, 3H, CH₃); 3 (s, 2H, H₂O); 3.7 (m, 2H, CH₂O); 4.3 (m, 2H, CH₂N); 5 (t, 1H, OH); 7.5–8.5 (m, 3H, C₆H₃).

¹³C (DMSO, 75 MHz) δ (p.p.m.): 114.28 (CH₃); 47 (CH₂O); 59 (CH₂N); 106.56; 110.03; 112.87; 117.13; 136.38; 147.37; 155.52 (C4, C5, C6, C7, C8, C9); 162.23 (C=N).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The water H atoms were located in a difference Fourier map; their positional parameters and U_iso(H) were refined with O—H distances restrained to be 0.82 Å with a standard deviation of 0.02 Å. Other H atoms were placed in calculated positions [O—H = 0.82, N—H = 0.86, C—H = 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methylene)] and refined using a riding-model approximation with U_iso(H) constrained to 1.2 (amine, aromatic and methylene group) or 1.5 (hydroxyl, methyl group) times U_eq of the respective parent atom.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₃O₃S⁺·Cl⁻·H₂O
M_r	307.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	8.8587 (5), 22.1427 (8), 7.1657 (2)
β (°)	108.497 (3)
V (Å³)	1332.98 (10)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.46
Crystal size (mm)	0.30 × 0.15 × 0.10

Data collection
Diffractometer	Nonius KappaCCD
No. of measured, independent and observed [I > 2σ(I)] reflections	15850, 3856, 3030
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.110, 1.06
No. of reflections	3856
No. of parameters	183
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.24
Computer programs: COLLECT (Hooft, 1998 ), DENZO/SCALEPACK (Otwinowski & Minor, 1997 ), SIR94 (Burla et al., 2005 ), PLATON (Spek, 2009 ), SHELXL2014 (Sheldrick, 2015 ), publCIF (Westrip, 2010 ) and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1500918

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989016013657/sj5502sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016013657/sj5502Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016013657/sj5502Isup3.cml

checkCIF report

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR94 (Burla et al., 2005); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015), publCIF (Westrip, 2010) and WinGX (Farrugia, 2012).

3-(2-Hydroxyethyl)-2-methylsulfanyl-6-nitro-3H-benzimidazol-1-ium chloride monohydrate top

Crystal data top

C₁₀H₁₂N₃O₃S⁺·Cl⁻·H₂O	F(000) = 640
M_r = 307.75	D_x = 1.534 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 425 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.8587 (5) Å	Cell parameters from 15850 reflections
b = 22.1427 (8) Å	θ = 4.1–30.1°
c = 7.1657 (2) Å	µ = 0.46 mm⁻¹
β = 108.497 (3)°	T = 298 K
V = 1332.98 (10) Å³	Block, yellow
Z = 4	0.30 × 0.15 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	3030 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Graphite monochromator	θ_max = 30.1°, θ_min = 4.1°
f and ω scans	h = −12→12
15850 measured reflections	k = −31→31
3856 independent reflections	l = −9→9

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0512P)² + 0.4116P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3856 reflections	Δρ_max = 0.29 e Å⁻³
183 parameters	Δρ_min = −0.24 e Å⁻³
2 restraints	Extinction correction: SHELXL2014 (Sheldrick 2015, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
48 constraints	Extinction coefficient: 0.010 (3)
Primary atom site location: structure-invariant direct methods

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 > 2σ(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.

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

	x	y	z	U_iso*/U_eq
Cl1	0.13738 (5)	0.08560 (2)	0.42268 (6)	0.05068 (14)
S2	0.57871 (5)	0.21143 (2)	0.26622 (7)	0.04747 (14)
O3	−0.15176 (14)	0.05681 (6)	0.56505 (18)	0.0472 (3)
N4	0.36705 (14)	0.12789 (5)	0.06943 (17)	0.0345 (3)
O5	0.1477 (2)	0.20574 (6)	0.1828 (3)	0.0718 (4)
H5	0.1668	0.1773	0.2603	0.108*
O6	0.45778 (19)	−0.14042 (6)	0.3012 (2)	0.0634 (4)
C7	0.34801 (17)	−0.05387 (6)	0.1321 (2)	0.0342 (3)
O8	0.24519 (18)	−0.14988 (6)	0.0528 (2)	0.0679 (4)
N9	0.56755 (14)	0.08753 (5)	0.29958 (17)	0.0314 (2)
H9	0.6563	0.0838	0.3931	0.038*
C10	0.33709 (16)	0.06625 (6)	0.06760 (19)	0.0313 (3)
C11	0.50505 (17)	0.13941 (6)	0.2131 (2)	0.0333 (3)
N12	0.35085 (17)	−0.11931 (6)	0.1646 (2)	0.0430 (3)
C13	0.46514 (15)	0.04077 (6)	0.21301 (19)	0.0288 (3)
C14	0.1141 (2)	0.18374 (9)	−0.0101 (3)	0.0561 (5)
H14A	0.0477	0.2127	−0.1014	0.067*
H14B	0.0548	0.1463	−0.0229	0.067*
C15	0.21856 (18)	−0.02957 (7)	−0.0142 (2)	0.0395 (3)
H15	0.1372	−0.0546	−0.0881	0.047*
C16	0.47534 (16)	−0.02074 (6)	0.2500 (2)	0.0310 (3)
H16	0.5606	−0.0383	0.3459	0.037*
C17	0.26321 (19)	0.17270 (8)	−0.0631 (2)	0.0443 (4)
H17A	0.2347	0.1583	−0.1977	0.053*
H17B	0.3207	0.2104	−0.0550	0.053*
C18	0.21161 (17)	0.03179 (7)	−0.0491 (2)	0.0390 (3)
H18	0.1269	0.0493	−0.1461	0.047*
C19	0.7761 (2)	0.19682 (8)	0.4278 (3)	0.0560 (5)
H19A	0.7703	0.1756	0.5421	0.084*
H19B	0.8311	0.2344	0.4673	0.084*
H19C	0.8327	0.1727	0.3606	0.084*
H3B	−0.076 (2)	0.0647 (10)	0.524 (3)	0.060 (6)*
H3A	−0.152 (3)	0.0212 (7)	0.573 (4)	0.070 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0492 (2)	0.0521 (3)	0.0514 (2)	−0.00027 (17)	0.01683 (18)	0.00853 (17)
S2	0.0580 (3)	0.02568 (18)	0.0586 (3)	−0.00229 (15)	0.0185 (2)	−0.00067 (15)
O3	0.0382 (6)	0.0495 (7)	0.0520 (7)	0.0023 (5)	0.0116 (5)	0.0069 (5)
N4	0.0362 (6)	0.0320 (6)	0.0354 (6)	0.0051 (4)	0.0116 (5)	0.0048 (4)
O5	0.1054 (13)	0.0430 (7)	0.0891 (11)	0.0073 (7)	0.0620 (10)	0.0007 (7)
O6	0.0788 (10)	0.0336 (6)	0.0715 (9)	−0.0019 (6)	0.0152 (7)	0.0062 (6)
C7	0.0393 (7)	0.0307 (6)	0.0376 (7)	−0.0053 (5)	0.0193 (6)	−0.0049 (5)
O8	0.0661 (9)	0.0436 (7)	0.0917 (11)	−0.0218 (6)	0.0217 (8)	−0.0198 (7)
N9	0.0322 (6)	0.0264 (5)	0.0335 (6)	−0.0009 (4)	0.0075 (4)	−0.0016 (4)
C10	0.0325 (6)	0.0329 (6)	0.0299 (6)	0.0013 (5)	0.0119 (5)	0.0003 (5)
C11	0.0380 (7)	0.0283 (6)	0.0360 (7)	0.0018 (5)	0.0150 (5)	0.0011 (5)
N12	0.0507 (8)	0.0323 (6)	0.0540 (8)	−0.0091 (5)	0.0278 (6)	−0.0085 (6)
C13	0.0276 (6)	0.0301 (6)	0.0296 (6)	−0.0013 (5)	0.0103 (5)	−0.0019 (5)
C14	0.0517 (10)	0.0490 (10)	0.0725 (12)	0.0175 (8)	0.0269 (9)	0.0167 (9)
C15	0.0352 (7)	0.0463 (8)	0.0379 (7)	−0.0097 (6)	0.0129 (6)	−0.0094 (6)
C16	0.0330 (6)	0.0297 (6)	0.0322 (6)	−0.0002 (5)	0.0128 (5)	−0.0003 (5)
C17	0.0451 (8)	0.0437 (8)	0.0447 (8)	0.0122 (7)	0.0151 (7)	0.0151 (7)
C18	0.0317 (7)	0.0491 (8)	0.0335 (7)	0.0004 (6)	0.0066 (5)	−0.0011 (6)
C19	0.0531 (10)	0.0394 (8)	0.0723 (12)	−0.0149 (7)	0.0153 (9)	−0.0057 (8)

Geometric parameters (Å, º) top

S2—C11	1.7194 (14)	N9—H9	0.8600
S2—C19	1.794 (2)	C10—C18	1.388 (2)
O3—H3B	0.833 (16)	C10—C13	1.3932 (18)
O3—H3A	0.792 (16)	C13—C16	1.3849 (18)
N4—C11	1.3492 (18)	C14—C17	1.506 (2)
N4—C10	1.3898 (18)	C14—H14A	0.9700
N4—C17	1.4758 (18)	C14—H14B	0.9700
O5—C14	1.405 (3)	C15—C18	1.379 (2)
O5—H5	0.8200	C15—H15	0.9300
O6—N12	1.219 (2)	C16—H16	0.9300
C7—C16	1.3853 (19)	C17—H17A	0.9700
C7—C15	1.393 (2)	C17—H17B	0.9700
C7—N12	1.4667 (19)	C18—H18	0.9300
O8—N12	1.2251 (18)	C19—H19A	0.9600
N9—C11	1.3390 (17)	C19—H19B	0.9600
N9—C13	1.3867 (16)	C19—H19C	0.9600

C11—S2—C19	101.51 (8)	C17—C14—H14A	109.2
H3B—O3—H3A	105 (2)	O5—C14—H14B	109.2
C11—N4—C10	108.48 (11)	C17—C14—H14B	109.2
C11—N4—C17	126.35 (13)	H14A—C14—H14B	107.9
C10—N4—C17	125.16 (12)	C18—C15—C7	119.69 (13)
C14—O5—H5	109.5	C18—C15—H15	120.2
C16—C7—C15	124.82 (13)	C7—C15—H15	120.2
C16—C7—N12	117.17 (13)	C13—C16—C7	114.40 (12)
C15—C7—N12	118.01 (13)	C13—C16—H16	122.8
C11—N9—C13	108.53 (11)	C7—C16—H16	122.8
C11—N9—H9	125.7	N4—C17—C14	111.36 (13)
C13—N9—H9	125.7	N4—C17—H17A	109.4
C18—C10—N4	131.27 (13)	C14—C17—H17A	109.4
C18—C10—C13	122.29 (13)	N4—C17—H17B	109.4
N4—C10—C13	106.44 (11)	C14—C17—H17B	109.4
N9—C11—N4	109.42 (12)	H17A—C17—H17B	108.0
N9—C11—S2	128.39 (11)	C15—C18—C10	116.82 (13)
N4—C11—S2	122.18 (11)	C15—C18—H18	121.6
O6—N12—O8	123.47 (15)	C10—C18—H18	121.6
O6—N12—C7	118.44 (13)	S2—C19—H19A	109.5
O8—N12—C7	118.09 (15)	S2—C19—H19B	109.5
C16—C13—N9	130.92 (12)	H19A—C19—H19B	109.5
C16—C13—C10	121.98 (12)	S2—C19—H19C	109.5
N9—C13—C10	107.10 (11)	H19A—C19—H19C	109.5
O5—C14—C17	112.04 (17)	H19B—C19—H19C	109.5
O5—C14—H14A	109.2

C11—N4—C10—C18	179.32 (14)	C11—N9—C13—C10	0.53 (15)
C17—N4—C10—C18	−0.1 (2)	C18—C10—C13—C16	0.1 (2)
C11—N4—C10—C13	−1.53 (14)	N4—C10—C13—C16	−179.10 (12)
C17—N4—C10—C13	179.07 (13)	C18—C10—C13—N9	179.86 (12)
C13—N9—C11—N4	−1.51 (15)	N4—C10—C13—N9	0.61 (14)
C13—N9—C11—S2	178.15 (11)	C16—C7—C15—C18	−0.1 (2)
C10—N4—C11—N9	1.90 (15)	N12—C7—C15—C18	179.95 (13)
C17—N4—C11—N9	−178.70 (13)	N9—C13—C16—C7	179.86 (13)
C10—N4—C11—S2	−177.78 (10)	C10—C13—C16—C7	−0.51 (19)
C17—N4—C11—S2	1.6 (2)	C15—C7—C16—C13	0.5 (2)
C19—S2—C11—N9	11.50 (16)	N12—C7—C16—C13	−179.58 (12)
C19—S2—C11—N4	−168.88 (13)	C11—N4—C17—C14	−106.73 (18)
C16—C7—N12—O6	5.1 (2)	C10—N4—C17—C14	72.56 (19)
C15—C7—N12—O6	−174.94 (15)	O5—C14—C17—N4	60.0 (2)
C16—C7—N12—O8	−174.90 (14)	C7—C15—C18—C10	−0.2 (2)
C15—C7—N12—O8	5.0 (2)	N4—C10—C18—C15	179.29 (14)
C11—N9—C13—C16	−179.79 (14)	C13—C10—C18—C15	0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···Cl1	0.82	2.40	3.1840 (15)	161
C17—H17B···S2	0.97	2.68	3.1514 (18)	110
O3—H3B···Cl1	0.83 (2)	2.28 (2)	3.1090 (14)	178 (2)
O3—H3A···Cl1ⁱ	0.79 (2)	2.37 (2)	3.1561 (14)	174 (2)
C14—H14B···O8ⁱⁱ	0.97	2.60	3.189 (2)	119
N9—H9···O3ⁱⁱⁱ	0.86	1.85	2.6949 (16)	165

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

Acknowledgements

The authors are grateful to the Spectropôle Service of the Faculty of Sciences and Techniques of Saint Jérôme (France) for the use of the diffractometer.

References

Abou, A., Bany, G. E., Kakou-Yao, R., Seikou, T. & Ebby, N. D. (2007). Acta Cryst. E63, o4218. CrossRef IUCr Journals Google Scholar
Akkurt, M., Türktekin, S., Şireci, N., Küçükbay, H. & Büyükgüngör, O. (2006). Acta Cryst. E62, o185–o187. Web of Science CSD CrossRef IUCr Journals Google Scholar
Akonan, L., Molou, K. Y. G., Adohi-Krou, A., Abou, A. & Tenon, A. J. (2010). Acta Cryst. E66, o442. CrossRef IUCr Journals Google Scholar
Alasmary, F. A. S., Snelling, A. M., Zain, M. E., Alafeefy, A. M., Awaad, A. S. & Karodia, N. K. (2015). Molecules, 20, 15206–15223. CrossRef CAS PubMed Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Chen, S. H., Yang, F. R., Wang, M. T. & Wang, N. N. (2010). C. R. Chim. 13, 1391–1396. CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gao, X. J., Jin, S., Liang, S., Chen, W. & Wang, D. (2013). J. Mol. Struct. 1039, 144–152. CrossRef CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hooft, R. (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Janiak, J. (2000). J. Chem. Soc. Dalton Trans. pp. 3885–3896. Web of Science CrossRef Google Scholar
Kakou-Yao, R., Abou, A., Adjou, A., Bany, G. E. & Ebby, N. D. (2007). Acta Cryst. E63, o4463. CrossRef IUCr Journals Google Scholar
Kerimov, I., İlgar, , Ayhan-Kılcıgil, G., Özdamar, E. D., Can-Eke, B., Çoban, T., Özbey, S. & Kazak, C. (2012). Arch. Pharm. Pharm. Med. Chem. 345, 549–556. Google Scholar
Küçükbay, H., Durmaz, R., Okuyucu, N., Günal, S. & Kazaz, C. (2004). Arzneim.-Forsch. Drug. Res. 54, 64–68. Google Scholar
Küçükbay, H., Durmaz, R., Orhan, E. & Günal, S. (2003). Farmaco, 58, 431–437. PubMed CAS Google Scholar
Liu, J. & Pan, Q. (2014). Z. Kristallogr. New Cryst. Struct. 229, 111–112. CAS Google Scholar
Lokaj, J., Kettmann, V., Milata, V. & Solčan, T. (2009). Acta Cryst. E65, o1788. CrossRef IUCr Journals Google Scholar
Morozov, P. J., Kurbatov, S. V., Dolgushin, F. M., Antipin, M. Y. & Olekhnovich, L. P. (2004). Russ. Chem. Bull. 9, 1990–1994. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Puratchikody, A., Nagalakshmi, G. & Doble, M. (2008). Chem. Pharm. Bull. 56, 273–281. Web of Science CrossRef PubMed CAS Google Scholar
Samsonov, V. A., Gatilov, Y. V. & Savel'ev, V. A. (2013). Russ. J. Org. Chem. 49, 1208–1214. CrossRef CAS 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
Verdan, S., Melich, X., Bernardinelli, G. & Williams, A. F. (2009). CrystEngComm, 11, 1416–1426. CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yavo, E. A., Kakou-Yao, R., Coulibaly, S., Abou, A. & Tenon, A. J. (2007). Acta Cryst. E63, o4551. CrossRef IUCr Journals Google Scholar
Yuasa, J., Ogawa, T. & Kawai, T. (2010). Chem. Commun. 46, 3693–3695. CrossRef CAS Google Scholar

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