(E)-2-(2-Hy­droxy-3-methyl­benzyl­idene)-N-methyl­hydrazine-1-carbo­thio­amide: supra­molecular assemblies in two-dimensions mediated by N—H⋯S and C—H⋯π inter­actions

Arafath, M.A.; Kwong, H.C.; Adam, F.

doi:10.1107/S2056989019004444

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 75| Part 5| May 2019| Pages 571-575

https://doi.org/10.1107/S2056989019004444

Open

access

(E)-2-(2-Hydroxy-3-methylbenzylidene)-N-methylhydrazine-1-carbothioamide: supramolecular assemblies in two-dimensions mediated by N—H⋯S and C—H⋯π interactions

Md. Azharul Arafath,^a ^* Huey Chong Kwong ^b and Farook Adam ^b ^*

^aDepartment of Chemistry, Shahjalal University of Science and Technology, Sylhet 3114, Bangladesh, and ^bSchool of Chemical Sciences, Universiti Sains Malaysia, Penang 11800 USM, Malaysia
^*Correspondence e-mail: arafath.usm@gmail.com, farook@usm.my

Edited by M. Nieger, University of Helsinki, Finland (Received 4 March 2019; accepted 1 April 2019; online 5 April 2019)

In the title compound, C₁₀H₁₃N₃OS, the azomethine C=N double bond has an E configuration. The phenyl ring and methylhydrazine carbothioamide moiety [maximum deviation = 0.008 (2) Å] are twisted slightly with a dihedral angle of 14.88 (10)°. In the crystal, molecules are linked into sheets parallel to the ab plane via N—H⋯S hydrogen bonds and C—H⋯π interactions.

Keywords: crystal structure; hydrazine carbothioamide; Schiff base; intermolecular interaction.

CCDC reference: 1485713

1. Chemical context

Schiff base compounds are very important and can be used for multidisciplinary applications. They are widely used in the food and dye industries and exhibit many types of biological activity (Gaur, 2000 ) such as antibacterial, antifungal, and antimalarial (Annapoorani & Krishnan, 2013 ). The azomethine C=N group of Schiff bases plays an important role in the biological activity. Metal complexes of thiosemicarbazones have also received much attention. The metal chelation typically improves the lipophilicity of the ligand and facilitates the penetration of the complexes into bacterial membranes (Lobana et al., 2009 ; Rogolino et al., 2017 ). Thiosemicarbazones have multi-donor characteristics because of the presence of nitrogen and sulfur atoms in their molecular backbone. This results in a variety of coordination modes and many different physiochemical properties (Sharma et al., 2016 ). As part of our ongoing studies on thiosemicarbazone Schiff bases (Arafath et al., 2018a ), we report herein the synthesis and structural determination of the title compound.

2. Structural commentary

The title compound (I) crystallizes in the non-centrosymmetric orthorhombic space group Iba2 and exhibits an E configuration with respect to the azomethine C=N double bond (Fig. 1). The C8=N1 and C9=S1 bond lengths of 1.288 (3) and 1.689 (2) Å, respectively, confirm the presence of the double bonds while the C6—C8, N2—C9 and C9—N3 bond lengths of 1.452 (3), 1.354 (3) and 1.321 (3) Å, respectively, confirm their single-bond character. The C6—C8—N1 and N2—C9—N3 angles are 122.5 (2) and 117.8 (2)°, respectively, and are consistent with an sp²-hybridized character for atom C8 and C9 (Arafath et al., 2018b ; Khalaji et al., 2012 ). The unique molecular conformation of (I) can be characterized by four torsion angles, viz. τ₁ (C5—C6—C8—N1), τ₂ (C8—N1—N2—C9), τ₃ (N1—N2—C9—N3) and τ₄ (N2—C9—N3—C10), respectively (Fig. 2). The torsion angles τ₃ and τ₄ are 0.4 (3) and 179.9 (2)°, signifying the planarity of the methylhydrazine carbothioamide moiety [N1—N2—(C9=S1)—N3—C10; mean deviation σ = 0.002 Å, maximum deviation = 0.008 (2) Å for atom C9]. τ₁ and τ₂ are slightly twisted [τ₁ = −4.2 (3) and τ₂ = 170.4 (2)°, respectively], and the C1–C6 phenyl ring and the methylhydrazine carbothioamide moiety subtend a dihedral angle of 14.88 (10)°. In the molecule, the hydroxy group acts as a hydrogen-bond donor for the adjacent hydrazine group, forming a intramolecular hydrogen bond with an S(6) ring motif (Fig. 1, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯N1	0.84 (4)	1.94 (4)	2.681 (3)	147 (4)
N2—H1N2⋯S1ⁱ	0.89 (3)	2.51 (3)	3.387 (2)	173 (3)
C10—H10A⋯Cg1ⁱⁱ	0.96	2.70	3.577 (4)	152
Symmetry codes: (i) -x+1, -y+1, z; (ii) $[-x, y+2, z+{\script{1\over 2}}]$ .

Figure 1
The atom labelling scheme and displacement ellipsoids of the molecular structure at the 50% probability level.

Figure 2
General chemical diagram showing torsion angles, τ₁, τ₂, τ₃ and τ₄ in the title compound.

3. Supramolecular features

In the crystal, molecules are linked into dimers with an R₂²(8) ring motif via N2—H1N2⋯S1 hydrogen bonds (Fig. 3a, Table 1). The dimers are connected into sheets parallel to the ab plane through C—H⋯π interactions (Fig. 3b, Table 1).

Figure 3
(a) A view of a dimer of C₁₀H₁₃N₃OS with N2—H1N2⋯S1 hydrogen bonds shown as cyan dotted lines. (b) A view of a dimeric sheet with C10—H10A⋯Cg1 interactions shown as green dotted lines. Hydrogen atoms not involved in with these interactions are omitted for clarity.

4. Database survey

A search of the Cambridge Structural Database (CSD version 5.39, last update February 2018; Groom et al., 2016 ) using (E)-2-(2-hydroxybenzylidene)-N-(λ¹-methyl)hydrazine-1-carbothioamide as reference moiety found 44 structures containing the 2-(2-hydroxybenzylidene)hydrazinecarbothioamide moiety with different substituents. The basic structural motif (E)-2-(2-hydroxybenzylidene)-N-(λ¹-methyl)hydrazine-1-carbothioamide is shown in Fig. 2 and the different substituents (R₁ and R₂) together with the torsion angles of the C—CH=N—NH—C(=S)—NH—C backbone are summarized in Table 2. In these structures, the torsion angle τ₁ exists in either the syn-periplanar (range from 0 to 12°) or anti-periplanar (range from 167 to 179°) conformation. As for the torsion angle τ₂, all structures adopt an anti-periplanar conformation (169–179°). Similar to the title compound, torsion angles τ₃ and τ₄ for most of the structures are syn-periplanar (0–16°) and anti-periplanar (171-180°), respectively. However, there are two outliers (YOCJOR and YOCJUX; (Chumakov et al., 2014 )) where the 2-(2-hydroxybenzylidene) hydrazinecarbothioamide is substituted with a pyridine ring. In contrast to most of the structures, torsion angles τ₃ and τ₄ for YOCJOR and YOCJUX are anti-periplanar (178 and 177°, respectively) and syn-periplanar (1 and 3°, respectively).

Table 2
Torsion angles τ₁, τ₂, τ₃ and τ₄ (°)

Compound	R₁	R₂	τ₁	τ₂	τ₃	τ₄
(I)	2-hydroxy-3-methylbenzylidenyl	methyl	4	170	0	180
AWAZOP (Hussein & Guan, 2015 )	5-bromo-2-hydroxybenzylidenyl	methyl	1	175	12	179
AWEBEL (Hussein & Guan, 2015)	3-ethoxy-2-hydroxybenzylidenyl	methyl	176	174	4	180
CIVZAK (Hussein et al., 2014b )	5-(tert-butyl)-2-hydroxybenzylidenyl	ethyl	2	174	15	180
CIWBAN (Hussein et al., 2014b)	5-allyl-3-ethyl-2-hydroxybenzylidenyl	methyl	169	173	5	178
DAGVOZ (Arafath et al., 2017b )	2-hydroxy-5-methoxy-3-nitrobenzylidenyl	methyl	177	176	7	179
EFUPAX (Rubčić et al., 2008 )	2-hydroxy-4-methoxybenzylidenyl	phenyl	2	173	4	174
EROVIR (Lo & Ng, 2011 )	5-chloro-2-hydroxybenzylidenyl	ethyl	8	172	14	176
GOZQIX (Hussein et al., 2015a )	2-hydroxy-5-methoxybenzylidenyl	methyl	3	175	14	180
GOZQIX01 (Salam et al., 2016 )	2-hydroxy-5-methoxybenzylidenyl	methyl	3	175	15	180
GOZQIX02 (Subhashree et al., 2017 )	2-hydroxy-5-methoxybenzylidenyl	methyl	2	175	13	180
HABDEW (Hussein et al., 2015c )	3-ethoxy-2-hydroxybenzylidenyl	ethyl	177	176	5	180
HABFEY (Hussein et al., 2015c)	5-allyl-2-hydroxy-3-methoxybenzylidenyl	ethyl	173, 173	176, 179	6, 8	178, 177
HAXROO (Vrdoljak et al., 2005 )	2-hydroxybenzylidenyl	methyl	1	176	11	178
HAXROO01 (Liu, 2015 )	2-hydroxybenzylidenyl	methyl	2	175	11	178
HAXSAB (Vrdoljak et al., 2005)	2-hydroxy-3-methoxybenzylidenyl	methyl	177	174	5	178
IBAZUJ (Haque et al., 2015 )	2,3-dihydroxybenzyliden	methyl	1	170	1	175
IBEDOL (Haque et al., 2015)	2-hydroxy-5-methylbenzylidenyl	methyl	3, 2	175, 173	16, 16	175, 175
IFUXEN (Tan et al., 2008b )	2,4-dihydroxybenzylidenyl	ethyl	2	179	0	176
IFUXEN01 (Hussein et al., 2014b)	2,4-dihydroxybenzylidenyl	ethyl	2	179	0	176
IFUXEN02 (Ramaiyer & Frank, 2015 )	2,4-dihydroxybenzylidenyl	ethyl	1	175	4	179
IFUXEN03 (Ramaiyer & Frank, 2015)	2,4-dihydroxybenzylidenyl	ethyl	5	171	6	178
IGALUY (Tan et al., 2008c )	2,4-dihydroxybenzylidenyl	methyl	5	174	9	176
IGALUY01 (Salam et al., 2015 )	2,4-dihydroxybenzylidenyl	methyl	2	177	16	178
IMAFIN (El-Asmy et al., 2016 )	2-hydroxybenzylidenyl	ethyl	1	177	13	177
JAJHUA (Li et al., 2016 )	5-bromo-2-hydroxybenzylidenyl	methyl	1	175	12	179
JOFHIW (Tan et al., 2008a )	2,5-dihydroxybenzyliden	methyl	1	175	11	178
KOCLIY (Đilović et al., 2008 )	4-(diethylamino)-2-hydroxybenzylidenyl	phenyl	2	172	12	174
LAQCIR (Jacob & Kurup, 2012 )	5-bromo-2-hydroxy-3-methoxybenzylidenyl	cyclohexyl	172	177	4	179
NUQNAP (Shawish et al., 2010 )	2,3,4-trihydroxybenzylidenyl	ethyl	167	176	8	174
OBOLOJ (Arafath et al., 2017a )	5-chloro-2-hydroxybenzylidenyl	cyclohexyl	175	176	6	177
PAXCAU (Jacob et al., 2012 )	5-bromo-2-hydroxy-3-methoxybenzylidenyl	phenyl	177	180	6	177
RIVFAE (Seena et al., 2008 )	2-hydroxybenzylidenyl	phenyl	2, 5, 2	179, 175, 178	12, 9, 2	171, 177, 180
RIVFAE01 (Rubcic et al., 2008)	2-hydroxybenzylidenyl	phenyl	11, 3	177, 171	2, 2	175, 170
SUKQOG (Hussein et al., 2015d )	5-allyl-2-hydroxy-3-methoxybenzylidenyl	phenyl	168	172	4	179
WEXDAG (Orysyk et al., 2013 )	2-hydroxybenzylidenyl	allyl	4	170	7	173
XOTPED (Hussein et al., 2015b )	2-hydroxy-3-methylbenzylidenyl	ethyl	2	179	7	179
YOCJOR (Chumakov et al., 2014)	5-bromo-2-hydroxybenzylidenyl	pyridin-2-yl	0	179	178	1
YOCJUX (Chumakov et al., 2014)	2-hydroxy-3-methoxybenzylidenyl	pyridin-2-yl	3	178	177	3
YOPHUI (Hussein et al., 2014a )	3-(tert-butyl)-2-hydroxybenzylidenyl	ethyl	4, 8	171, 169	4, 18	179, 180
YOPLIA (Hussein et al., 2014a)	2-hydroxy-5-methylbenzylidenyl	ethyl	4	171	10	180
YUKYOU (Salam & Haque, 2015 )	3,5-dichloro-2-hydroxybenzylidenyl	ethyl	179	180	2	178
YUXJOS (Arafath et al., 2018a)	3-(tert-butyl)-2-hydroxybenzylidenyl	cyclohexyl	12	170	12	176
ZIJKIO (Li & Sato, 2013 )	5-bromo-2-hydroxybenzylidenyl	ethyl	6	172	12	176
ZIJKIO02 (Hussein et al., 2015b)	5-bromo-2-hydroxybenzylidenyl	ethyl	7	173	13	177
Note: there is more than one torsion angle for compounds HABFEY, IBEDOL, RIVFAE, RIVFAE01 and YOPHUI because there are more than one independent molecules in their asymmetric units.

5. Synthesis and crystallization

2-Hydroxy-3-methylbenzaldehyde (0.68 g, 5.00 mmol) was dissolved in 20.0 mL of methanol. 0.20 mL of glacial acetic acid was added and the mixture was refluxed for 30 minutes. A solution of 0.52 g (5.00 mmol) of N-methyl hydrazinecarbothioamide in 20.0 mL of methanol was added dropwise with stirring to the aldehyde solution (Fig. 4). The resulting colourless solution was heated under reflux for 4 h with stirring. The crude product was washed with 5.0 mL of n-hexane. The recovered product was dissolved in DMSO for purification and recrystallization. Light-yellow single crystals (m.p. 454–455 K; yield 94%) suitable for X-ray diffraction were obtained by slow evaporation of the solvent.

Figure 4
Reaction scheme for the synthesis of C₁₀H₁₃N₃OS.

Analysis calculated for C₁₀H₁₃N₃OS (FW: 223.29 g mol⁻¹); C, 53.74; H, 5.83; N, 18.81; found: C, 53.71; H, 5.79; N, 18.83%. ¹H NMR (500 MHz, DMSO-d₆, Me₄Si ppm): δ 11.38 (s, N—NH), δ 9.39 (s, OH), δ 8.34 (s, HC=N), δ 8.44 (q, CS–NH), δ 7.42–6.81 (multiplet, aromatic), δ 3.00 (d, J = 4.5 Hz, N—CH₃), δ 2.20 (s, Ph—CH₃). ¹³C NMR (DMSO-d₆, Me₄Si ppm): δ 177.48 (C=S), δ 154.24 (C=N), δ 143.64–119.10 (C-aromatic), δ 31.05 (N—CH₃), δ 15.91(Ph—CH₃) ppm. IR (KBr pellets υ_max/cm⁻¹): 3418 υ(NH), 3133 υ(OH), 2983(NC—H₃, sp³), 1618 υ(C=N), 1553 υ(C=C, aromatic), 1270 υ(C=S), 1251 υ(CH, bend., aromatic), 1085 υ(C—O). 1043 υ(C—N).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. C-bound H atoms were positioned geometrically (C—H = 0.93–0.96 Å) and refined using a riding model with U_iso(H) = 1.2 or 1.5 U_eq(C). All N- and O-bound H atoms were located from a difference-Fourier map and freely refined.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₃OS
M_r	223.29
Crystal system, space group	Orthorhombic, Iba2
Temperature (K)	296
a, b, c (Å)	14.6474 (14), 17.522 (2), 8.9048 (8)
V (Å³)	2285.4 (4)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.26
Crystal size (mm)	0.46 × 0.26 × 0.16

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.853, 0.879
No. of measured, independent and observed [I > 2σ(I)] reflections	14825, 3359, 2949
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.094, 1.06
No. of reflections	3359
No. of parameters	150
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.16
Absolute structure	Flack parameter determined using 1222 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.04 (3)
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015 ), Mercury (Macrae et al., 2006 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1485713

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019004444/nr2074sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019004444/nr2074Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019004444/nr2074Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXL2013 (Sheldrick, 2015) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015) and PLATON (Spek, 2009).

(E)-2-(2-Hydroxy-3-methylbenzylidene)-N-methylhydrazine-1-carbothioamide top

Crystal data top

C₁₀H₁₃N₃OS	D_x = 1.298 Mg m⁻³
M_r = 223.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Iba2	Cell parameters from 5563 reflections
a = 14.6474 (14) Å	θ = 2.3–29.5°
b = 17.522 (2) Å	µ = 0.26 mm⁻¹
c = 8.9048 (8) Å	T = 296 K
V = 2285.4 (4) Å³	Block, yellow
Z = 8	0.46 × 0.26 × 0.16 mm
F(000) = 944

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	3359 independent reflections
Radiation source: fine-focus sealed tube	2949 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
φ and ω scans	θ_max = 30.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −20→20
T_min = 0.853, T_max = 0.879	k = −23→24
14825 measured reflections	l = −12→12

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)] = 0.033	w = 1/[σ²(F_o²) + (0.0497P)² + 0.3888P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.094	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 0.17 e Å⁻³
3359 reflections	Δρ_min = −0.15 e Å⁻³
150 parameters	Absolute structure: Flack parameter determined using 1222 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.04 (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	0.35594 (4)	0.50006 (3)	0.20442 (10)	0.05018 (16)
O1	0.45729 (12)	0.77741 (11)	0.6162 (3)	0.0621 (6)
N1	0.48391 (12)	0.65142 (9)	0.4511 (3)	0.0414 (4)
N2	0.46275 (13)	0.59332 (10)	0.3526 (2)	0.0436 (4)
N3	0.31035 (13)	0.60707 (11)	0.4029 (2)	0.0459 (4)
C1	0.69785 (15)	0.72085 (14)	0.6081 (2)	0.0443 (5)
H1A	0.735599	0.683585	0.567182	0.053*
C2	0.73506 (15)	0.77658 (13)	0.6987 (3)	0.0493 (5)
H2A	0.797160	0.776261	0.720393	0.059*
C3	0.67936 (16)	0.83287 (14)	0.7568 (3)	0.0492 (5)
H3A	0.704945	0.871242	0.815398	0.059*
C4	0.58596 (16)	0.83349 (12)	0.7297 (3)	0.0479 (5)
C5	0.54896 (14)	0.77591 (12)	0.6405 (3)	0.0424 (4)
C6	0.60427 (14)	0.71939 (12)	0.5768 (2)	0.0380 (4)
C7	0.5255 (2)	0.89533 (18)	0.7931 (5)	0.0783 (10)
H7A	0.491901	0.918970	0.713173	0.117*
H7B	0.562565	0.932944	0.842504	0.117*
H7C	0.483746	0.873420	0.864103	0.117*
C8	0.56962 (15)	0.65960 (11)	0.4793 (3)	0.0410 (4)
H8A	0.610876	0.625925	0.435625	0.049*
C9	0.37548 (14)	0.57095 (11)	0.3289 (2)	0.0397 (4)
C10	0.21430 (16)	0.58990 (19)	0.3892 (4)	0.0647 (7)
H10A	0.179253	0.629791	0.435460	0.097*
H10B	0.201496	0.542285	0.438227	0.097*
H10C	0.198298	0.586205	0.284940	0.097*
H1N2	0.5065 (18)	0.5680 (16)	0.307 (4)	0.056 (8)*
H1N3	0.3243 (19)	0.6428 (16)	0.471 (4)	0.054 (7)*
H1O1	0.444 (3)	0.7429 (19)	0.555 (5)	0.076 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0523 (3)	0.0455 (3)	0.0527 (3)	−0.0030 (2)	−0.0095 (3)	−0.0097 (2)
O1	0.0328 (8)	0.0601 (11)	0.0936 (16)	−0.0015 (7)	−0.0014 (8)	−0.0230 (10)
N1	0.0439 (9)	0.0367 (7)	0.0436 (8)	−0.0042 (6)	−0.0024 (9)	0.0006 (9)
N2	0.0412 (9)	0.0404 (9)	0.0491 (10)	0.0001 (7)	−0.0030 (8)	−0.0060 (8)
N3	0.0409 (9)	0.0495 (10)	0.0475 (9)	0.0000 (8)	−0.0055 (7)	−0.0078 (8)
C1	0.0380 (10)	0.0490 (12)	0.0460 (11)	0.0012 (9)	0.0008 (9)	0.0009 (9)
C2	0.0379 (9)	0.0576 (12)	0.0525 (11)	−0.0059 (9)	−0.0058 (10)	0.0016 (12)
C3	0.0478 (12)	0.0485 (11)	0.0513 (11)	−0.0119 (10)	−0.0057 (10)	−0.0017 (9)
C4	0.0446 (11)	0.0416 (10)	0.0575 (15)	−0.0049 (9)	0.0020 (9)	−0.0064 (9)
C5	0.0327 (10)	0.0401 (10)	0.0544 (12)	−0.0048 (8)	0.0031 (8)	0.0002 (9)
C6	0.0357 (9)	0.0380 (10)	0.0401 (10)	−0.0037 (8)	0.0010 (8)	0.0033 (8)
C7	0.0642 (17)	0.0641 (17)	0.107 (3)	0.0081 (14)	−0.0021 (18)	−0.0325 (17)
C8	0.0413 (10)	0.0387 (9)	0.0428 (11)	−0.0008 (8)	−0.0006 (8)	0.0020 (8)
C9	0.0439 (10)	0.0365 (9)	0.0387 (9)	−0.0016 (8)	−0.0064 (8)	0.0033 (8)
C10	0.0403 (12)	0.0802 (18)	0.0736 (17)	−0.0043 (12)	−0.0015 (12)	−0.0148 (15)

Geometric parameters (Å, º) top

S1—C9	1.689 (2)	C2—H2A	0.9300
O1—C5	1.360 (3)	C3—C4	1.389 (3)
O1—H1O1	0.84 (4)	C3—H3A	0.9300
N1—C8	1.288 (3)	C4—C5	1.393 (3)
N1—N2	1.379 (3)	C4—C7	1.509 (4)
N2—C9	1.354 (3)	C5—C6	1.400 (3)
N2—H1N2	0.88 (3)	C6—C8	1.452 (3)
N3—C9	1.321 (3)	C7—H7A	0.9600
N3—C10	1.444 (3)	C7—H7B	0.9600
N3—H1N3	0.90 (3)	C7—H7C	0.9600
C1—C2	1.379 (3)	C8—H8A	0.9300
C1—C6	1.399 (3)	C10—H10A	0.9600
C1—H1A	0.9300	C10—H10B	0.9600
C2—C3	1.381 (4)	C10—H10C	0.9600

C5—O1—H1O1	108 (3)	C4—C5—C6	121.21 (19)
C8—N1—N2	115.18 (18)	C1—C6—C5	118.25 (19)
C9—N2—N1	121.68 (18)	C1—C6—C8	118.35 (19)
C9—N2—H1N2	118.0 (19)	C5—C6—C8	123.40 (18)
N1—N2—H1N2	120.2 (19)	C4—C7—H7A	109.5
C9—N3—C10	124.2 (2)	C4—C7—H7B	109.5
C9—N3—H1N3	120.5 (18)	H7A—C7—H7B	109.5
C10—N3—H1N3	115.1 (18)	C4—C7—H7C	109.5
C2—C1—C6	121.1 (2)	H7A—C7—H7C	109.5
C2—C1—H1A	119.4	H7B—C7—H7C	109.5
C6—C1—H1A	119.4	N1—C8—C6	122.5 (2)
C1—C2—C3	119.4 (2)	N1—C8—H8A	118.7
C1—C2—H2A	120.3	C6—C8—H8A	118.7
C3—C2—H2A	120.3	N3—C9—N2	117.8 (2)
C2—C3—C4	121.5 (2)	N3—C9—S1	123.86 (17)
C2—C3—H3A	119.3	N2—C9—S1	118.37 (16)
C4—C3—H3A	119.3	N3—C10—H10A	109.5
C3—C4—C5	118.4 (2)	N3—C10—H10B	109.5
C3—C4—C7	121.2 (2)	H10A—C10—H10B	109.5
C5—C4—C7	120.3 (2)	N3—C10—H10C	109.5
O1—C5—C4	117.4 (2)	H10A—C10—H10C	109.5
O1—C5—C6	121.4 (2)	H10B—C10—H10C	109.5

C8—N1—N2—C9	170.4 (2)	O1—C5—C6—C1	−179.2 (2)
C6—C1—C2—C3	−1.4 (4)	C4—C5—C6—C1	1.7 (3)
C1—C2—C3—C4	1.9 (4)	O1—C5—C6—C8	1.1 (3)
C2—C3—C4—C5	−0.6 (3)	C4—C5—C6—C8	−178.0 (2)
C2—C3—C4—C7	−179.8 (3)	N2—N1—C8—C6	178.06 (19)
C3—C4—C5—O1	179.6 (2)	C1—C6—C8—N1	176.1 (2)
C7—C4—C5—O1	−1.1 (4)	C5—C6—C8—N1	−4.2 (3)
C3—C4—C5—C6	−1.2 (3)	C10—N3—C9—N2	179.9 (2)
C7—C4—C5—C6	178.0 (3)	C10—N3—C9—S1	1.2 (3)
C2—C1—C6—C5	−0.3 (3)	N1—N2—C9—N3	0.4 (3)
C2—C1—C6—C8	179.4 (2)	N1—N2—C9—S1	179.17 (16)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N1	0.84 (4)	1.94 (4)	2.681 (3)	147 (4)
N2—H1N2···S1ⁱ	0.89 (3)	2.51 (3)	3.387 (2)	173 (3)
C10—H10A···Cg1ⁱⁱ	0.96	2.70	3.577 (4)	152

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

Torsion angles τ₁, τ₂, τ₃ and τ₄ (°) top

Compound	R₁	R₂	τ₁	τ₂	τ₃	τ₄
(I)	2-hydroxy-3-methylbenzylidenyl	methyl	4	170	0	180
AWAZOP (Hussein & Guan, 2015)	5-bromo-2-hydroxybenzylidenyl	methyl	1	175	12	179
AWEBEL (Hussein & Guan, 2015)	3-ethoxy-2-hydroxybenzylidenyl	methyl	176	174	4	180
CIVZAK (Hussein et al., 2014b)	5-(tert-butyl)-2-hydroxybenzylidenyl	ethyl	2	174	15	180
CIWBAN (Hussein et al., 2014b)	5-allyl-3-ethyl-2-hydroxybenzylidenyl	methyl	169	173	5	178
DAGVOZ (Arafath et al., 2017b)	2-hydroxy-5-methoxy-3-nitrobenzylidenyl	methyl	177	176	7	179
EFUPAX (Rubcic et al., 2008)	2-hydroxy-4-methoxybenzylidenyl	phenyl	2	173	4	174
EROVIR (Lo & Ng, 2011)	5-chloro-2-hydroxybenzylidenyl	ethyl	8	172	14	176
GOZQIX (Hussein et al., 2015a)	2-hydroxy-5-methoxybenzylidenyl	methyl	3	175	14	180
GOZQIX01 (Salam et al., 2016)	2-hydroxy-5-methoxybenzylidenyl	methyl	3	175	15	180
GOZQIX02 (Subhashree et al., 2017)	2-hydroxy-5-methoxybenzylidenyl	methyl	2	175	13	180
HABDEW (Hussein et al., 2015c)	3-ethoxy-2-hydroxybenzylidenyl	ethyl	177	176	5	180
HABFEY (Hussein et al., 2015c)	5-allyl-2-hydroxy-3-methoxybenzylidenyl	ethyl	173, 173	176, 179	6, 8	178, 177
HAXROO (Vrdoljak et al., 2005)	2-hydroxybenzylidenyl	methyl	1	176	11	178
HAXROO01 (Liu, 2015)	2-hydroxybenzylidenyl	methyl	2	175	11	178
HAXSAB (Vrdoljak et al., 2005)	2-hydroxy-3-methoxybenzylidenyl	methyl	177	174	5	178
IBAZUJ (Haque et al., 2015)	2,3-dihydroxybenzyliden	methyl	1	170	1	175
IBEDOL (Haque et al., 2015)	2-hydroxy-5-methylbenzylidenyl	methyl	3, 2	175, 173	16, 16	175, 175
IFUXEN (Tan et al., 2008b)	2,4-dihydroxybenzylidenyl	ethyl	2	179	0	176
IFUXEN01 (Hussein et al., 2014b)	2,4-dihydroxybenzylidenyl	ethyl	2	179	0	176
IFUXEN02 (Ramaiyer & Frank, 2015)	2,4-dihydroxybenzylidenyl	ethyl	1	175	4	179
IFUXEN03 (Ramaiyer & Frank, 2015)	2,4-dihydroxybenzylidenyl	ethyl	5	171	6	178
IGALUY (Tan et al., 2008c)	2,4-dihydroxybenzylidenyl	methyl	5	174	9	176
IGALUY01 (Salam et al., 2015)	2,4-dihydroxybenzylidenyl	methyl	2	177	16	178
IMAFIN (El-Asmy et al., 2016)	2-hydroxybenzylidenyl	ethyl	1	177	13	177
JAJHUA (Li et al., 2016)	5-bromo-2-hydroxybenzylidenyl	methyl	1	175	12	179
JOFHIW (Tan et al., 2008a)	2,5-dihydroxybenzyliden	methyl	1	175	11	178
KOCLIY (Đilović et al., 2008)	4-(diethylamino)-2-hydroxybenzylidenyl	phenyl	2	172	12	174
LAQCIR (Jacob & Kurup, 2012)	5-bromo-2-hydroxy-3-methoxybenzylidenyl	cyclohexyl	172	177	4	179
NUQNAP (Shawish et al., 2010)	2,3,4-trihydroxybenzylidenyl	ethyl	167	176	8	174
OBOLOJ (Arafath et al., 2017a)	5-chloro-2-hydroxybenzylidenyl	cyclohexyl	175	176	6	177
PAXCAU (Jacob et al., 2012)	5-bromo-2-hydroxy-3-methoxybenzylidenyl	phenyl	177	180	6	177
RIVFAE (Seena et al., 2008)	2-hydroxybenzylidenyl	phenyl	2, 5, 2	179, 175, 178	12, 9, 2	171, 177, 180
RIVFAE01 (Rubcic et al., 2008)	2-hydroxybenzylidenyl	phenyl	11, 3	177, 171	2, 2	175, 170
SUKQOG (Hussein et al., 2015d)	5-allyl-2-hydroxy-3-methoxybenzylidenyl	phenyl	168	172	4	179
WEXDAG (Orysyk et al., 2013)	2-hydroxybenzylidenyl	allyl	4	170	7	173
XOTPED (Hussein et al., 2015b)	2-hydroxy-3-methylbenzylidenyl	ethyl	2	179	7	179
YOCJOR (Chumakov et al., 2014)	5-bromo-2-hydroxybenzylidenyl	pyridin-2-yl	0	179	178	1
YOCJUX (Chumakov et al., 2014)	2-hydroxy-3-methoxybenzylidenyl	pyridin-2-yl	3	178	177	3
YOPHUI (Hussein et al., 2014a)	3-(tert-butyl)-2-hydroxybenzylidenyl	ethyl	4, 8	171, 169	4, 18	179, 180
YOPLIA (Hussein et al., 2014a)	2-hydroxy-5-methylbenzylidenyl	ethyl	4	171	10	180
YUKYOU (Salam & Haque, 2015)	3,5-dichloro-2-hydroxybenzylidenyl	ethyl	179	180	2	178
YUXJOS (Arafath et al., 2018a)	3-(tert-butyl)-2-hydroxybenzylidenyl	cyclohexyl	12	170	12	176
ZIJKIO (Li & Sato, 2013)	5-bromo-2-hydroxybenzylidenyl	ethyl	6	172	12	176
ZIJKIO02 (Hussein et al., 2015b)	5-bromo-2-hydroxybenzylidenyl	ethyl	7	173	13	177

Note: there is more than one torsion angle for compounds HABFEY, IBEDOL, RIVFAE, RIVFAE01 and YOPHUI because there are more than one independent molecules in their asymmetric units.

Funding information

This research was supported financially by the RU grant No. 1001/PKIMIA/811269 from Universiti Sains Malaysia. The authors wish to thank Universiti Sains Malaysia and The World Academy of Science for a USM–TWAS fellowship to MdAA. HCK would like to thank the Malaysian Government for a MyBrain15 scholarship.

References

Annapoorani, S. & Krishnan, C. (2013). Synthesis, 5, 180–185. CAS Google Scholar
Arafath, M. A., Adam, F. & Razali, M. R. (2017a). IUCrData, 2, x161997. Google Scholar
Arafath, M. A., Adam, F., Razali, M. R., Ahmed Hassan, L. E., Ahamed, M. B. K. & Majid, A. M. S. A. (2017b). J. Mol. Struct. 1130, 791–798. Web of Science CSD CrossRef CAS Google Scholar
Arafath, M. A., Kwong, H. C., Adam, F. & Razali, M. R. (2018a). Acta Cryst. E74, 687–690. Web of Science CSD CrossRef IUCr Journals Google Scholar
Arafath, M. A., Kwong, H. C., Adam, F. & Razali, M. R. (2018b). Acta Cryst. E74, 1460–1462. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2012). Bruker AXS Inc., Madison. Wisconsin, USA. Google Scholar
Chumakov, Y. M., Petrenko, P. A., Codita, T. B., Tsapkov, V. I., Poirier, D. & Gulea, A. P. (2014). Crystallogr. Rep. 59, 207–212. Web of Science CSD CrossRef CAS Google Scholar
Đilović, I., Rubčić, M., Vrdoljak, V., Pavelić, S. K., Kralj, M., Piantanida, I. & Cindrić, M. (2008). Bioorg. Med. Chem. 16, 5189–5198. PubMed Google Scholar
El-Asmy, A. A., Jeragh, B. & Ali, M. S. (2016). Private communication (Refcode CCDC 1478956. CCDC, Cambridge, England. Google Scholar
Gaur, S. (2000). Asian J. Chem. 43, 250–254. 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
Haque, R. A., Salam, M. A. & Arafath, M. A. (2015). J. Coord. Chem. 68, 2953–2967. Web of Science CSD CrossRef CAS Google Scholar
Hussein, M. A. & Guan, T. S. (2015). Eur. J. Chem. 6, 451–460. CSD CrossRef CAS Google Scholar
Hussein, M. A., Guan, T. S., Haque, R. A., Ahamed, M. B. K. & Majid, A. M. S. A. (2015a). Polyhedron, 85, 93–103. Web of Science CSD CrossRef CAS Google Scholar
Hussein, M. A., Guan, T. S., Haque, R. A., Khadeer Ahamed, M. B. & Abdul Majid, A. M. S. (2014a). Inorg. Chim. Acta, 421, 270–283. Web of Science CSD CrossRef CAS Google Scholar
Hussein, M. A., Guan, T. S., Haque, R. A., Khadeer Ahamed, M. B. & Abdul Majid, A. M. S. (2015b). Spectrochim. Acta A, 136, 1335–1348. Web of Science CSD CrossRef CAS Google Scholar
Hussein, M. A., Iqbal, M. A., Asif, M., Haque, R. A., Ahamed, M. B. K., Majid, A. M. S. A. & Guan, T. S. (2015c). Phosphorus Sulfur Silicon, 190, 1498–1508. Web of Science CSD CrossRef CAS Google Scholar
Hussein, M. A., Iqbal, M. A., Umar, M. I., Haque, R. A. & Guan, T. S. (2015d). Arab. J. Chem. In the Press. Google Scholar
Hussein, M. A., Guan, T. S., Haque, R. A., Ahamed, M. B. K. & Majid, A. M. S. A. (2014b). J. Coord. Chem. 67, 714–727. Web of Science CSD CrossRef CAS Google Scholar
Jacob, J. M. & Kurup, M. R. P. (2012). Acta Cryst. E68, o836–o837. CSD CrossRef CAS IUCr Journals Google Scholar
Jacob, J. M., Sithambaresan, M. & Kurup, M. R. P. (2012). Acta Cryst. E68, o1871–o1872. CSD CrossRef IUCr Journals Google Scholar
Khalaji, A. D., Fejfarova, K. & Dusek, M. (2012). J. Chem. Crystallogr. 42, 263–266. Web of Science CSD CrossRef CAS Google Scholar
Li, Z. & Sato, O. (2013). Acta Cryst. E69, o762. CSD CrossRef IUCr Journals Google Scholar
Li, Z.-Y., Ohtsu, H., Kojima, T., Dai, J.-W., Yoshida, T., Breedlove, B. K., Zhang, W.-X., Iguchi, H., Sato, O., Kawano, M. & Yamashita, M. (2016). Angew. Chem. Int. Ed. 55, 5184–5189. Web of Science CSD CrossRef CAS Google Scholar
Liu, Z.-X. (2015). J. Struct. Chem. 56, 1420–1425. Web of Science CSD CrossRef CAS Google Scholar
Lo, K. M. & Ng, S. W. (2011). Acta Cryst. E67, o1453. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lobana, T. S., Sharma, R., Bawa, G. & Khanna, S. (2009). Coord. Chem. Rev. 253, 977–1055. Web of Science CrossRef CAS 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
Orysyk, S. I., Bon, V. V., Zholob, O. O., Pekhnyo, V. I., Orysyk, V. V., Zborovskii, Y. L. & Vovk, M. V. (2013). Polyhedron, 51, 211–221. Web of Science CSD 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
Ramaiyer, V. & Frank, R. (2015). Private communication (Refcode CCDC 1058555. CCDC, Cambridge, England. Google Scholar
Rogolino, D., Gatti, A., Carcelli, M., Pelosi, G., Bisceglie, F., Restivo, F. M., Degola, F., Buschini, A., Montalbano, S., Feretti, D. & Zani, C. (2017). Sci. Rep. 7, 11214. Web of Science CSD CrossRef PubMed Google Scholar
Rubčić, M., Đilović, I., Cindrić, M. & Matković-Čalogović, D. (2008). Acta Cryst. C64, o570–o573. Web of Science CSD CrossRef IUCr Journals Google Scholar
Salam, M. A. & Haque, R. A. (2015). Inorg. Chim. Acta, 435, 103–108. Web of Science CSD CrossRef CAS Google Scholar
Salam, M. A., Hussein, M. A., Ramli, I. & Islam, M. S. (2016). J. Organomet. Chem. 813, 71–77. Web of Science CSD CrossRef CAS Google Scholar
Salam, M. A., Hussein, M. A. & Tiekink, E. R. T. (2015). Acta Cryst. E71, 58–61. Web of Science CSD CrossRef IUCr Journals Google Scholar
Seena, E. B., Prathapachandra Kurup, M. R. & Suresh, E. (2008). J. Chem. Crystallogr. 38, 93–96. Web of Science CSD CrossRef CAS Google Scholar
Sharma, R., Lobana, T. S., Kaur, M., Thathai, N., Hundal, G., Jasinski, J. P. & Butcher, R. J. (2016). J. Chem. Sci. 128, 1103–1112. Web of Science CSD CrossRef CAS Google Scholar
Shawish, H. B., Maah, M. J. & Ng, S. W. (2010). Acta Cryst. E66, o1151. Web of Science CSD CrossRef 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
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Subhashree, G. R., Haribabu, J., Saranya, S., Yuvaraj, P., Anantha Krishnan, D., Karvembu, R. & Gayathri, D. (2017). J. Mol. Struct. 1145, 160–169. Web of Science CSD CrossRef CAS Google Scholar
Tan, K. W., Ng, C. H., Maah, M. J. & Ng, S. W. (2008a). Acta Cryst. E64, o1344. Web of Science CSD CrossRef IUCr Journals Google Scholar
Tan, K. W., Ng, C. H., Maah, M. J. & Ng, S. W. (2008b). Acta Cryst. E64, o2123. Web of Science CSD CrossRef IUCr Journals Google Scholar
Tan, K. W., Ng, C. H., Maah, M. J. & Ng, S. W. (2008c). Acta Cryst. E64, o2224. Web of Science CSD CrossRef IUCr Journals Google Scholar
Vrdoljak, V., Cindrić, M., Milić, D., Matković-Čalogović, D., Novak, P. & Kamenar, B. (2005). Polyhedron, 24, 1717–1726. Web of Science 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.