Synthesis and crystal structure of ((E)-{2-[(E)-(4-hy­droxynaphthalen-1-yl)methyl­idene]hydrazin-1-yl}(methyl­sulfan­yl)methyl­idene)azanium hydrogen sulfate monohydrate

Nehar, O.; Louhibi, S.; Boukli-Hacene, L.; Roisnel, T.

doi:10.1107/S2056989016013232

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 72| Part 9| September 2016| Pages 1326-1329

https://doi.org/10.1107/S2056989016013232

Open

access

Synthesis and crystal structure of ((E)-{2-[(E)-(4-hydroxynaphthalen-1-yl)methylidene]hydrazin-1-yl}(methylsulfanyl)methylidene)azanium hydrogen sulfate monohydrate

Oussama Nehar,^a Samira Louhibi,^a ^* Leila Boukli-Hacene ^b and Thierry Roisnel ^c

^aLaboratoire de Chimie Inorganique et Environnement, Université de Tlemcen, BP 119, 13000 Tlemcen, Algeria, ^bLaboratoire de Chimie Inorganique et Environnement, Universite de Tlemcen, BP 119, 13000 Tlemcen, Algeria, and ^cCentre de Diffractometrie X, UMR 6226 CNRS, Unité Sciences Chimiques de Rennes, Université de Rennes I, 263 Avenue du General Leclerc, 35042 Rennes, France
^*Correspondence e-mail: samhibi1@yahoo.fr

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 8 August 2016; accepted 17 August 2016; online 26 August 2016)

In the title hydrated molecular salt, C₁₃H₁₄N₃S⁺·HSO₄⁻·H₂O, the protonation of the azomethine N atom in sulfuric acid medium involves the formation of the bisulfate anion. The molecular structure of the cation is obtained from the thiol tautomer of thiosemicarbazone wherein the naphthalene moiety and the conjugation of the bonds contribute to the planarity of the molecular skeleton. In the crystal, the cation, anion and water molecule of crystallization are linked by a series of O—H⋯O and N—H⋯O hydrogen bonds, forming a three-dimensional network. Within this network, there are also C—H⋯π interactions present involving symmetry-related naphthalene rings.

Keywords: crystal structure; thiosemicarbazone; synthesis; hydrogen bonding.

CCDC reference: 1451398

1. Chemical context

Thiosemicarbazones and their metal complexes have been widely explored because of their pharmaceutical properties (Klayman et al., 1983 ). These compounds present a wide variety of biological activities, such as antitumoral, fungicidal and antiviral (Tarasconi et al., 2000 ), and bactericidal (Abram et al., 1998 ). The ability of thiosemicarbazone molecules to chelate with traces of metals in biological systems is believed to be a reason for their activity (Teoh et al., 1999 ). The nature of the aldehyde and ketone from which the thiosemicarbazone is obtained and the nature of the substituents attached at the ⁺NH₂ N atom influence the biological activity (Beraldo & Gambinob, 2004 ). Thiosemicarbazones can exist as E and Z isomers and they exhibit thione–thiol tautomerism, as illustrated for the title compound in Fig. 1. Complexation usually takes place via dissociation of the acidic proton, resulting in the formation of a five-membered chelate ring (Pal et al., 2002 ). The crystal structure of the title compound was determined in order to investigate the extent of electron delocalization, the ligand conformation and to explore its biological implications.

Figure 1
Thiosemicarbazones can exist as E and Z isomers and they exhibit thione–thiol tautomerism.

2. Structural commentary

The molecular structure of the title molecular salt is illustrated in Fig. 2. It is composed of three entities: a bisulfate anion, a thiosemicarbazone cation and a water molecule of crystallization. The cationic entity shows an E conformation with respect to the C12=N13 bond and is approximately planar, the maximum deviation from the mean plane through the 18 non-hydrogen atoms being 0.118 (2) Å for atom C12. This planarity is due to electron delocalization along the cationic entity backbone. Bond lengths and angles are close to those observed for similar (methylidene)hydrazinecarbothioamide derivatives (Gangadharan et al., 2015 ; Joseph et al., 2004 ; Houari et al., 2013 .)

Figure 2
A view of the molecular structure of the title molecular salt, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

In the crystal, there is an extensive hydrogen-bonding network present. The cation, anion and water molecule of crystallization are linked by a series of O—H⋯O and N—H⋯O hydrogen bonds, forming a three-dimensional network (Table 1 and Fig. 3). Within this network there are also C—H⋯π interactions present involving symmetry-related naphthalene rings (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of rings C1–C3/C5/C10/C11 and C5–C10, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O13ⁱ	0.89 (3)	1.96 (3)	2.791 (4)	155 (5)
O1W—H1WB⋯O13ⁱⁱ	0.86 (2)	1.88 (3)	2.732 (3)	172 (5)
O4—H4O⋯O11ⁱⁱⁱ	0.96 (6)	1.84 (6)	2.719 (3)	153 (6)
O12—H12O⋯O1W	0.94 (5)	1.61 (5)	2.543 (4)	168 (5)
N14—H14⋯O14	0.86 (2)	2.00 (2)	2.860 (3)	176 (4)
N16—H16A⋯O1W^iv	0.86 (2)	2.32 (3)	3.046 (4)	142 (4)
N16—H16B⋯O14^v	0.84 (2)	2.20 (3)	2.937 (3)	147 (4)
C6—H6⋯Cg2^vi	0.95	2.67	3.451 (3)	140
C7—H7⋯Cg1^vi	0.95	2.94	3.622 (3)	130
Symmetry codes: (i) x+1, y, z; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Figure 3
A view along the a axis of the crystal packing of the title molecular salt. The hydrogen bonds are drawn as dashed lines (see Table 1

) and the C-bound H atoms have been omitted for clarity.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.37, update May 2016; Groom et al., 2016 ) for the S-methyl (methylidene)thiosemicarbazidium cation substructure gave two hits, viz. S-methyl-N′-(pyrrolyl-2′-methylene)isothiosemicarbazidium iodide monohydrate (JIHZUV; Bourosh et al., 1990 ) and 8-quinolinealdehyde S-methylthiosemicarbazone hydrochloride dihydrate (RUJXOK; Botoshansky et al., 2009 ). Only the coordinates for the latter structure were available. The cation in RUJXOK, is relatively planar and the bond lengths and angles in the S-methyl (methylidene)thiosemicarbazidium moiety are similar to those observed for the title compound.

5. Synthesis and crystallization

The synthesis of the title molecular salt is illustrated in Fig. 4. An equimolar amount of thiosemicarbazide 10 mmol (0.91 g) and 3-hydroxy-2-naphthaldehyde 10 mmol (1.72 g) were dissolved in a mixture of methanol and water (30 ml, 50%) and refluxed for 5 h in the presence of a catalytic amount of glacial sulfuric acid. Brown crystals suitable for X-ray diffraction analysis were obtained after slow evaporation of the solution.

Figure 4
The synthesis of the title molecular salt.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydroxy H atom was located in a difference Fourier map and freely refined. The water and N-bound H atoms were located in difference Fourier maps and refined with distance restraints O—H = 0.84 (2) Å and N—H = 0.88 (2) Å. The C-bound H atoms were included in calculated positions and treated as riding atoms, with C—H = 0.95–0.98 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) otherwise.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₄N₃OS⁺·HO₄S⁻·H₂O
M_r	375.41
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	150
a, b, c (Å)	6.3726 (5), 14.2549 (11), 18.2817 (12)
V (Å³)	1660.7 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.36
Crystal size (mm)	0.42 × 0.33 × 0.19

Data collection
Diffractometer	Bruker D8 VENTURE
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.752, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	19123, 3786, 3586
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.103, 1.07
No. of reflections	3786
No. of parameters	247
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.33
Absolute structure	Flack x determined using 1477 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.03 (5)
Computer programs: APEX3 and SAINT (Bruker, 2015), SIR97 (Altomare et al., 1999 ), SHELXL2014 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1451398

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S2056989016013232/su5320sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016013232/su5320Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016013232/su5320Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

((E)-{2-[(E)-(4-Hydroxynaphthalen-1-yl)methylidene]hydrazin-1-yl}(methylsulfanyl)methylidene)azanium hydrogen sulfate monohydrate top

Crystal data top

C₁₃H₁₄N₃OS⁺·HO₄S⁻·H₂O	D_x = 1.501 Mg m⁻³
M_r = 375.41	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 9907 reflections
a = 6.3726 (5) Å	θ = 2.9–27.5°
b = 14.2549 (11) Å	µ = 0.36 mm⁻¹
c = 18.2817 (12) Å	T = 150 K
V = 1660.7 (2) Å³	Block, brown
Z = 4	0.42 × 0.33 × 0.19 mm
F(000) = 784

Data collection top

Bruker D8 VENTURE diffractometer	3586 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.073
rotation images scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −8→8
T_min = 0.752, T_max = 0.935	k = −18→18
19123 measured reflections	l = −23→23
3786 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.039	w = 1/[σ²(F_o²) + (0.0581P)² + 0.4752P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.103	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.36 e Å⁻³
3786 reflections	Δρ_min = −0.33 e Å⁻³
247 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
5 restraints	Extinction coefficient: 0.027 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack x determined using 1477 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.03 (5)

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	0.33252 (11)	0.30710 (5)	0.35547 (4)	0.0214 (2)
C1	0.6277 (5)	0.5080 (2)	0.06062 (17)	0.0274 (6)
H1	0.5211	0.5545	0.0624	0.033*
C2	0.8011 (5)	0.5215 (2)	0.01485 (18)	0.0302 (7)
H2	0.8125	0.5775	−0.0130	0.036*
C3	0.9553 (5)	0.4542 (2)	0.00993 (16)	0.0244 (6)
O4	1.1258 (4)	0.46247 (17)	−0.03340 (14)	0.0334 (6)
H4O	1.141 (10)	0.520 (5)	−0.059 (3)	0.09 (2)*
C5	0.9393 (5)	0.3697 (2)	0.05103 (15)	0.0210 (6)
C6	1.0925 (5)	0.2980 (2)	0.04354 (16)	0.0256 (6)
H6	1.2085	0.3069	0.0117	0.031*
C7	1.0739 (5)	0.2162 (2)	0.08197 (17)	0.0308 (7)
H7	1.1746	0.1678	0.0755	0.037*
C8	0.9071 (6)	0.2033 (2)	0.13084 (17)	0.0299 (7)
H8	0.8977	0.1467	0.1581	0.036*
C9	0.7567 (5)	0.2716 (2)	0.13989 (16)	0.0246 (6)
H9	0.6458	0.2620	0.1738	0.029*
C10	0.7656 (4)	0.3566 (2)	0.09897 (14)	0.0192 (5)
C11	0.6085 (5)	0.4279 (2)	0.10353 (16)	0.0215 (6)
C12	0.4268 (5)	0.4151 (2)	0.15100 (15)	0.0220 (6)
H12A	0.4066	0.3563	0.1744	0.026*
N13	0.2939 (4)	0.48088 (17)	0.16192 (12)	0.0205 (5)
N14	0.1329 (4)	0.45700 (16)	0.20919 (13)	0.0202 (5)
H14	0.144 (7)	0.406 (2)	0.234 (2)	0.040 (11)*
C15	−0.0120 (4)	0.5212 (2)	0.22410 (14)	0.0182 (5)
N16	−0.0075 (4)	0.60276 (18)	0.19085 (14)	0.0249 (5)
H16B	−0.103 (5)	0.641 (2)	0.199 (2)	0.032 (10)*
H16A	0.084 (5)	0.614 (3)	0.1575 (18)	0.036 (11)*
C17	−0.3802 (5)	0.5843 (2)	0.28398 (18)	0.0253 (6)
H17A	−0.4311	0.5911	0.2337	0.038*
H17B	−0.3101	0.6423	0.2992	0.038*
H17C	−0.4990	0.5718	0.3166	0.038*
S2	−0.19735 (11)	0.48825 (5)	0.28856 (4)	0.0245 (2)
O11	0.3992 (4)	0.40352 (16)	0.36112 (13)	0.0348 (6)
O12	0.5287 (4)	0.2471 (2)	0.33653 (15)	0.0442 (7)
H12O	0.631 (8)	0.246 (4)	0.374 (3)	0.059 (14)*
O13	0.2455 (5)	0.2712 (2)	0.42322 (13)	0.0433 (7)
O14	0.1937 (4)	0.29015 (14)	0.29348 (11)	0.0278 (5)
O1W	0.8206 (4)	0.2244 (2)	0.42969 (13)	0.0385 (6)
H1WA	0.939 (6)	0.256 (4)	0.426 (3)	0.060 (16)*
H1WB	0.784 (8)	0.225 (3)	0.4750 (15)	0.061 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0240 (3)	0.0184 (3)	0.0220 (3)	−0.0050 (3)	−0.0028 (3)	0.0010 (2)
C1	0.0309 (15)	0.0164 (14)	0.0349 (15)	0.0031 (12)	0.0053 (12)	0.0021 (11)
C2	0.0386 (17)	0.0186 (13)	0.0333 (15)	0.0000 (14)	0.0083 (14)	0.0045 (12)
C3	0.0286 (15)	0.0232 (14)	0.0215 (13)	−0.0062 (11)	0.0019 (12)	−0.0019 (11)
O4	0.0336 (13)	0.0323 (13)	0.0344 (12)	0.0011 (10)	0.0136 (10)	0.0079 (10)
C5	0.0226 (14)	0.0217 (14)	0.0186 (12)	−0.0016 (11)	−0.0032 (11)	−0.0032 (10)
C6	0.0250 (14)	0.0321 (17)	0.0196 (13)	0.0047 (13)	0.0002 (11)	−0.0013 (12)
C7	0.0324 (17)	0.0351 (18)	0.0248 (14)	0.0145 (14)	0.0001 (13)	0.0014 (13)
C8	0.0347 (16)	0.0299 (16)	0.0253 (14)	0.0108 (14)	0.0001 (13)	0.0084 (12)
C9	0.0254 (14)	0.0265 (14)	0.0218 (13)	0.0037 (11)	0.0008 (11)	0.0031 (11)
C10	0.0202 (13)	0.0207 (13)	0.0166 (12)	−0.0004 (10)	−0.0020 (10)	−0.0027 (10)
C11	0.0244 (14)	0.0176 (13)	0.0226 (13)	−0.0011 (11)	0.0024 (11)	−0.0026 (10)
C12	0.0234 (14)	0.0192 (13)	0.0233 (13)	−0.0003 (11)	−0.0012 (11)	−0.0009 (11)
N13	0.0204 (11)	0.0196 (11)	0.0215 (11)	0.0001 (10)	0.0021 (9)	−0.0011 (9)
N14	0.0212 (11)	0.0160 (11)	0.0233 (11)	0.0010 (8)	0.0028 (10)	0.0028 (9)
C15	0.0198 (12)	0.0182 (12)	0.0166 (11)	−0.0002 (10)	−0.0008 (9)	−0.0006 (10)
N16	0.0287 (13)	0.0187 (12)	0.0273 (12)	0.0058 (10)	0.0084 (11)	0.0056 (10)
C17	0.0218 (13)	0.0214 (13)	0.0326 (15)	0.0023 (11)	0.0030 (12)	−0.0007 (12)
S2	0.0264 (4)	0.0209 (3)	0.0263 (3)	0.0027 (3)	0.0080 (3)	0.0056 (3)
O11	0.0456 (14)	0.0215 (11)	0.0372 (12)	−0.0120 (10)	−0.0030 (11)	−0.0060 (10)
O12	0.0395 (14)	0.0493 (17)	0.0437 (14)	0.0146 (13)	−0.0118 (12)	−0.0185 (13)
O13	0.0443 (15)	0.0602 (17)	0.0254 (11)	−0.0204 (13)	−0.0057 (10)	0.0137 (11)
O14	0.0353 (12)	0.0209 (10)	0.0271 (10)	−0.0059 (9)	−0.0089 (10)	0.0040 (8)
O1W	0.0277 (12)	0.0604 (17)	0.0274 (11)	0.0027 (12)	0.0015 (10)	0.0012 (11)

Geometric parameters (Å, º) top

S1—O11	1.442 (2)	C9—C10	1.425 (4)
S1—O13	1.450 (2)	C9—H9	0.9500
S1—O14	1.458 (2)	C10—C11	1.429 (4)
S1—O12	1.554 (3)	C11—C12	1.459 (4)
C1—C11	1.391 (4)	C12—N13	1.279 (4)
C1—C2	1.399 (4)	C12—H12A	0.9500
C1—H1	0.9500	N13—N14	1.384 (3)
C2—C3	1.375 (4)	N14—C15	1.328 (4)
C2—H2	0.9500	N14—H14	0.86 (2)
C3—O4	1.350 (4)	C15—N16	1.313 (4)
C3—C5	1.424 (4)	C15—S2	1.733 (3)
O4—H4O	0.96 (6)	N16—H16B	0.84 (2)
C5—C6	1.420 (4)	N16—H16A	0.86 (2)
C5—C10	1.424 (4)	C17—S2	1.800 (3)
C6—C7	1.366 (5)	C17—H17A	0.9800
C6—H6	0.9500	C17—H17B	0.9800
C7—C8	1.400 (5)	C17—H17C	0.9800
C7—H7	0.9500	O12—H12O	0.94 (5)
C8—C9	1.376 (4)	O1W—H1WA	0.89 (3)
C8—H8	0.9500	O1W—H1WB	0.86 (2)

O11—S1—O13	112.83 (16)	C10—C9—H9	119.6
O11—S1—O14	113.10 (14)	C5—C10—C9	117.7 (3)
O13—S1—O14	111.92 (14)	C5—C10—C11	119.2 (3)
O11—S1—O12	107.66 (17)	C9—C10—C11	123.1 (3)
O13—S1—O12	107.67 (18)	C1—C11—C10	119.3 (3)
O14—S1—O12	102.94 (13)	C1—C11—C12	120.5 (3)
C11—C1—C2	121.3 (3)	C10—C11—C12	120.1 (3)
C11—C1—H1	119.4	N13—C12—C11	121.8 (3)
C2—C1—H1	119.4	N13—C12—H12A	119.1
C3—C2—C1	120.5 (3)	C11—C12—H12A	119.1
C3—C2—H2	119.7	C12—N13—N14	114.1 (2)
C1—C2—H2	119.7	C15—N14—N13	118.3 (2)
O4—C3—C2	123.5 (3)	C15—N14—H14	122 (3)
O4—C3—C5	116.2 (3)	N13—N14—H14	118 (3)
C2—C3—C5	120.3 (3)	N16—C15—N14	120.0 (3)
C3—O4—H4O	117 (4)	N16—C15—S2	124.7 (2)
C6—C5—C10	120.0 (3)	N14—C15—S2	115.3 (2)
C6—C5—C3	120.6 (3)	C15—N16—H16B	119 (3)
C10—C5—C3	119.4 (3)	C15—N16—H16A	120 (3)
C7—C6—C5	120.3 (3)	H16B—N16—H16A	120 (4)
C7—C6—H6	119.9	S2—C17—H17A	109.5
C5—C6—H6	119.9	S2—C17—H17B	109.5
C6—C7—C8	120.4 (3)	H17A—C17—H17B	109.5
C6—C7—H7	119.8	S2—C17—H17C	109.5
C8—C7—H7	119.8	H17A—C17—H17C	109.5
C9—C8—C7	120.8 (3)	H17B—C17—H17C	109.5
C9—C8—H8	119.6	C15—S2—C17	101.74 (14)
C7—C8—H8	119.6	S1—O12—H12O	114 (3)
C8—C9—C10	120.7 (3)	H1WA—O1W—H1WB	108 (5)
C8—C9—H9	119.6

C11—C1—C2—C3	1.5 (5)	C8—C9—C10—C5	−2.5 (4)
C1—C2—C3—O4	179.6 (3)	C8—C9—C10—C11	176.9 (3)
C1—C2—C3—C5	0.5 (5)	C2—C1—C11—C10	−2.0 (5)
O4—C3—C5—C6	−2.3 (4)	C2—C1—C11—C12	179.9 (3)
C2—C3—C5—C6	176.9 (3)	C5—C10—C11—C1	0.6 (4)
O4—C3—C5—C10	178.9 (3)	C9—C10—C11—C1	−178.9 (3)
C2—C3—C5—C10	−1.9 (4)	C5—C10—C11—C12	178.6 (3)
C10—C5—C6—C7	0.2 (4)	C9—C10—C11—C12	−0.8 (4)
C3—C5—C6—C7	−178.6 (3)	C1—C11—C12—N13	−8.9 (4)
C5—C6—C7—C8	−2.0 (5)	C10—C11—C12—N13	173.1 (3)
C6—C7—C8—C9	1.5 (5)	C11—C12—N13—N14	−179.2 (2)
C7—C8—C9—C10	0.9 (5)	C12—N13—N14—C15	179.6 (2)
C6—C5—C10—C9	2.0 (4)	N13—N14—C15—N16	4.2 (4)
C3—C5—C10—C9	−179.2 (3)	N13—N14—C15—S2	−175.70 (19)
C6—C5—C10—C11	−177.5 (3)	N16—C15—S2—C17	7.7 (3)
C3—C5—C10—C11	1.4 (4)	N14—C15—S2—C17	−172.4 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of rings C1–C3/C5/C10/C11 and C5–C10, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O13ⁱ	0.89 (3)	1.96 (3)	2.791 (4)	155 (5)
O1W—H1WB···O13ⁱⁱ	0.86 (2)	1.88 (3)	2.732 (3)	172 (5)
O4—H4O···O11ⁱⁱⁱ	0.96 (6)	1.84 (6)	2.719 (3)	153 (6)
O12—H12O···O1W	0.94 (5)	1.61 (5)	2.543 (4)	168 (5)
N14—H14···O14	0.86 (2)	2.00 (2)	2.860 (3)	176 (4)
N16—H16A···O1W^iv	0.86 (2)	2.32 (3)	3.046 (4)	142 (4)
N16—H16B···O14^v	0.84 (2)	2.20 (3)	2.937 (3)	147 (4)
C6—H6···Cg2^vi	0.95	2.67	3.451 (3)	140
C7—H7···Cg1^vi	0.95	2.94	3.622 (3)	130

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

Acknowledgements

The authors are grateful for the support provided by the Algerian Ministry for Education and Research.

References

Abram, S., Maichle-Mössmer, C. & Abram, U. (1998). Polyhedron, 17, 131–143. CSD CrossRef CAS Web of Science Google Scholar
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Beraldo, H. & Gambinob, D. (2004). Mini Rev. Med. Chem. 4, 159–165. Google Scholar
Botoshansky, M., Bourosh, P. N., Revenco, M. D., Korja, I. D., Simonov, Yu. A. & Panfilie, T. (2009). Zh. Strukt. Khim. 50, 188–191. Google Scholar
Bourosh, P. N., Jampolskaia, M. A., Dvorkin, A. A., Gerbeleu, N. V., Simonov, Yu. A. & Malinovskii, T. I. (1990). Dokl. Akad. Nauk SSSR, 311, 1119–1122. Google Scholar
Bruker (2015). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gangadharan, R., Haribabu, J., Karvembu, R. & Sethusankar, K. (2015). Acta Cryst. E71, 305–308. Web of Science CSD CrossRef IUCr Journals 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
Houari, B., Louhibi, S., Boukli-Hacene, L., Roisnel, T. & Taleb, M. (2013). Acta Cryst. E69, o1469. CSD CrossRef IUCr Journals Google Scholar
Joseph, M., Suni, V., Nayar, C. R., Kurup, M. R. P. & Fun, H.-K. (2004). J. Mol. Struct. 705, 63–70. Web of Science CSD CrossRef CAS Google Scholar
Klayman, D. L., Scovill, J. P., Bartosevich, J. F. & Bruce, J. J. (1983). J. Med. Chem. 26, 35–39. CrossRef CAS PubMed Google Scholar
Pal, I., Basuli, F. & Bhattacharya, S. (2002). J. Chem Sci 114, 255–268. CrossRef CAS Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. 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
Tarasconi, P., Capacchi, S., Pelosi, G., Cornia, M., Albertini, R., Bonati, A., Dall'Aglio, P. P., Lunghi, P. & Pinelli, S. (2000). Bioorg. Med. Chem. 8, 157–162. Web of Science CrossRef PubMed CAS Google Scholar
Teoh, S.-G., Ang, S.-H., Fun, H.-K. & Ong, C.-W. (1999). J. Organomet. Chem. 580, 17–21. CSD CrossRef 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.