2-[(1E)-({[(Benzyl­sulfan­yl)methane­thio­yl]amino}­imino)­meth­yl]-6-meth­oxy­phenol: crystal structure and Hirshfeld surface analysis

Yusof, E.N.M.; Jotani, M.M.; Tiekink, E.R.T.; Ravoof, T.B.S.A.

doi:10.1107/S2056989016004291

research communications

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ISSN: 2056-9890

Volume 72| Part 4| April 2016| Pages 516-521

https://doi.org/10.1107/S2056989016004291

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2-[(1E)-({[(Benzylsulfanyl)methanethioyl]amino}imino)methyl]-6-methoxyphenol: crystal structure and Hirshfeld surface analysis

Enis Nadia Md Yusof,^a Mukesh M. Jotani,^b Edward R. T. Tiekink ^c ^* and Thahira B. S. A. Ravoof ^a ‡

^aDepartment of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400, UPM Serdang, Selangor Darul Ehsan, Malaysia, ^bDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380 001, India, and ^cResearch Centre for Crystalline Materials, Faculty of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
^*Correspondence e-mail: edwardt@sunway.edu.my

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 11 March 2016; accepted 14 March 2016; online 18 March 2016)

The title dithiocarbazate ester, C₁₆H₁₆N₂O₂S₂, comprises two almost planar residues, i.e. the phenyl ring and the remaining 14 non-H atoms (r.m.s. deviation = 0.0410 Å). These are orientated perpendicularly, forming a dihedral angle of 82.72 (5)°. An intramolecular hydroxy-O—H⋯N(imine) hydrogen bond, leading to an S(6) loop, is noted. An analysis of the geometric parameters is consistent with the molecule existing as the thione tautomer, and the conformation about the C=N bond is E. The thione S and imine H atoms lie to the same side of the molecule, facilitating the formation of intermolecular N—H⋯S hydrogen bonds leading to eight-membered {⋯HNCS}₂ synthons in the crystal. These aggregates are connected by phenyl-C—H⋯O(hydroxy) interactions into a supramolecular layer in the bc plane; these stack with no directional interactions between them. An analysis of the Hirshfeld surface confirms the nature of the intermolecular interactions.

Keywords: crystal structure; hydrogen bonding; dithiocarbazate ester; Hirshfeld surface analysis.

CCDC reference: 1465209

1. Chemical context

Dithiocarbazate, NH₂NHC(=S)S⁻, and more specifically substituted derivatives, have attracted the attention of researchers for decades (Ali & Livingstone, 1974 ). While a common motivation for investigating transition metal complexes of these anions relates to potential biological activity (Basha et al., 2012 ; Vijayan et al., 2015 ), including our own recent work (Yusof, Ravoof, Jamsari et al., 2015 ; Yusof, Ravoof, Tiekink et al., 2015 ), other motivations exist. Thus, recent studies have described the photo-catalytic production of hydrogen mediated by a conjugated nickel(II) bis-dithiocarbazate complex (Wise et al., 2015 ). The use of a coumarin-based dithiocarbazate as a ratiometric and colormetric chemosensor for cobalt(II) is another recent development (Liu et al., 2015 ). In rationalizing the electronic structures of metal dithiocarbazates, a knowledge of the uncomplexed or `free ligand' structure is most useful. In keeping with this notion and as a part of an on-going study of the structural chemistry of metal dithiocarbazates and their ligands, the title compound was prepared and characterized both crystallographically and by a Hirshfeld surface analysis.

2. Structural commentary

The title compound, Fig. 1, comprises two almost planar regions, one being the phenyl ring, the other being the remaining 14 non-hydrogen atoms. The maximum deviations from the least-squares plane through the latter plane, with a r.m.s. deviation = 0.0410 Å, are 0.0715 (15) for the O1 atom and −0.0796 (18) for atom C16. To a first approximation, the molecule can be described as having mirror symmetry with the 1,4-atoms of the terminal ring being bisected by the plane. Substantiating this description is the dihedral angle between the planes of 82.72 (5)°, indicating a very close to perpendicular relationship. The observed planarity in the larger fragment may be ascribed, in part, to the presence of an intramolecular hydroxy-O—H⋯N(imine) hydrogen bond (Table 1), which leads to the formation of an S(6) loop. The molecule exists in the thione tautomeric form. Consistent with this assignment, the thione C1=S2 bond length, i.e. 1.670 (2) Å, is considerably shorter than the thiol C1—S1 and, especially, C2—S1 bonds of 1.749 (2) and 1.817 (2) Å, respectively. The conformation about the C=N bond is E, and the amine-N—H atom is flanked on either side by the thione-S and imine-H atoms.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯N2	0.84 (2)	1.90 (2)	2.639 (2)	146 (2)
N1—H1N⋯S2ⁱ	0.88 (2)	2.47 (2)	3.3351 (18)	168 (2)
C6—H6⋯O1ⁱⁱ	0.95	2.51	3.453 (3)	170
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 1
The molecular structure of the title compound, showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.

3. Supramolecular features

The most prominent feature of the packing of the title compound is the formation of centrosymmetric, eight-membered {⋯HNCS}₂ synthons through the agency of thioamide-N—H⋯S(thione) hydrogen bonds, Table 1. The dimeric aggregates are connected by phenyl-C—H⋯O(hydroxy) interactions to form a supramolecular layer in the bc-plane, Fig. 2a. The layers stack along the a axis with no directional interactions between them, Fig. 2b.

Figure 2
Molecular packing in the title compound: (a) a perspective view of the supramolecular layer sustained by thioamide-N—H⋯S(thione) and phenyl-C—H⋯O(hydroxy) interactions and, (b) a view of the unit-cell contents shown in projection down the b axis, highlighting one layer in space-filling mode. The N—H⋯S and C—H⋯O interactions are shown as blue and orange dashed lines, respectively. For (a), non-interacting H atoms have been omitted.

4. Analysis of the Hirshfeld surfaces

Crystal Explorer 3.1 (Wolff et al., 2012 ) was used to generate Hirshfeld surfaces mapped over d_norm, d_e, curvedness and electrostatic potential. The latter was calculated using TONTO (Spackman et al., 2008 ; Jayatilaka et al., 2005 ) which was integrated into Crystal Explorer; the experimental geometry was used as the input. Further, the electrostatic potentials were mapped on the Hirshfeld surface using the STO-3G basis set at the Hartree–Fock level of theory over the range ±0.1 au. The contact distances d_i and d_e from the Hirshfeld surface to the nearest atom inside and outside, respectively, enable the analysis of the intermolecular interactions through the mapping of d_norm. The combination of d_e and d_i in the form of a two-dimensional fingerprint plot (Rohl et al., 2008 ) provides a summary of the intermolecular contacts in the crystal.

From the view of the Hirshfeld surface mapped over d_norm, Fig. 3, the deep-red depressions at atoms H1N and S2 confirm their role as the N—H⋯S hydrogen-bond donor and acceptor, respectively. On the surface mapped over the electrostatic potential, Fig. 4, these atoms appear as the respective blue and red regions. The light-red spots near the phenyl-hydrogen atom, H6, and hydroxyl oxygen, O1, on the d_norm-mapped surface indicate the intermolecular C—H⋯O interaction between them. The immediate environment about the molecule within d_norm-mapped Hirshfeld surface mediated by the above interactions is illustrated in Fig. 5.

Figure 3
View of the Hirshfeld surface mapped over d_norm.

Figure 4
View of the Hirshfeld surface mapped over the electrostatic potential.

Figure 5
Hirshfeld surface mapped over d_norm showing hydrogen-bonding interactions with neighbouring molecules.

The overall two-dimensional fingerprint (FP) plot, Fig. 6a, and those delineated into H⋯H, O⋯H/H⋯O, S⋯H/H⋯S, C⋯H/H⋯C and C⋯C interactions are illustrated in Fig. 6b–f; the relative contributions are summarized in Table 2. The H⋯H contacts appear as the scattered points in nearly the entire plot, Fig. 6b, and make a significant contribution, i.e. 43.4%, to the Hirshfeld surface. The round single peak at d_e + d_i ∼ 2.3 Å results from a short interatomic H⋯H contact, Table 3. The FP delineated into O⋯H/H⋯O contacts show a pair of short spikes at d_e + d_i ∼ 2.5 Å and the small arcs linked to them are identified with labels 1 and 2 in Fig. 6c. These features correspond to a 10.3% contribution to the Hirshfeld surfaces and reflect the presence of intermolecular C—H⋯O interactions as well as interatomic O⋯H contacts only slightly shorter than their van der Waals separation, i.e. around d_e + d_i ∼ 2.7 Å, Table 3. The presence of intermolecular N—H⋯S hydrogen bonds in the crystal is evident from a prominent pair of sharp spikes in the outer region of the FP plot shown in Fig. 6d, i.e. at d_e + d_i ∼ 2.45 Å, with a 14.4% contribution to the Hirshfeld surface. The distinct pair of wings corresponding to C⋯H/H⋯C contacts, Fig. 6e, have `forceps-like' tips at d_e + d_i ∼ 2.8 Å due to short interatomic C⋯H/H⋯C contacts, Table 3, although C—H⋯π interactions are not evident in the structure within the sum of their van der Waals radii. The 2.5% contribution from C⋯C contacts to the Hirshfeld surface features two overlapping triangles, Fig. 6f, but the minimum (d_e + d_i) distance is greater than van der Waals separation, confirming the absence of π–π stacking interactions. This is also evident from the small segments delineated by blue outlines in the Hirshfeld surface mapped over curvedness, Fig. 7.

Table 2
Major percentage contribution of the different intermolecular interactions to the Hirshfeld surface of the title compound

Contact	%
H⋯H	43.4
O⋯H/H⋯O	10.3
S⋯H/H⋯S	14.4
C⋯H/H⋯C	21.3
N⋯H/H⋯N	0.8
C⋯C	2.5
S⋯S	0.4
C⋯N/N⋯C	2.9
S⋯O/O⋯S	1.4
S⋯N/N⋯S	1.4
C⋯S/S⋯C	0.9

Table 3
Additional short interatomic contacts (Å) for the title compound

Interaction	distance	symmetry operation
H8⋯H16C	2.25	− $[{1\over 2}]$ + x, $[{1\over 2}]$ + y, z
C6⋯H16B	2.86	$[{1\over 2}]$ − x, $[{3\over 2}]$ + y, $[{3\over 2}]$ − z
O1⋯H16A	2.70	x, 1 + y, z
C11⋯H16A	2.78	x, 1 + y, z
C12⋯H16A	2.89	x, 1 + y, z

Figure 6
The two-dimensional fingerprint plots for (a) all interactions, and delineated into (b) H⋯H, (c) O⋯H/H⋯O, (d) S⋯H/H⋯S, (e) C⋯H/H⋯C and (f) C⋯C interactions.

Figure 7
View of the Hirshfeld surface mapped over curvedness.

The enrichment ratio (ER), based on Hirshfeld surface analysis, gives further description of intermolecular interactions operating in a crystal (Jelsch et al., 2014 ). The ER values are summarized in Table 4. The ER value close to but slightly less than unity, i.e. 0.97, for H⋯H contacts is in accord with expectation (Jelsch et al., 2014). The sulfur atoms comprise 9.5% of Hirshfeld surface and the overall 14.4% contribution by S⋯H/H⋯S contacts results in an ER value of 1.14, which is in the expected range for N—H⋯S interactions, i.e. 1.0–1.5 (Jelsch et al., 2014). The ER value of 1.28 corresponding to O⋯H/H⋯O contacts show a high propensity to form even though the percentage relative contribution to the overall surface, i.e. 10.3%, is small as is the 6.0% exposure provided by hydroxyl- and methoxy-oxygen atoms. The low ER value of 1.09 corresponding to C⋯C contacts is consistent with a low propensity for π–π stacking interactions in the structure. The presence of short interatomic non-bonded C⋯H/H⋯C contacts result in an ER value close to unity, Table 4, as there is little influence of C—H⋯π interactions on the molecular packing. The other contributions to the surface i.e. N⋯H/H⋯N, S⋯S, S⋯O/O⋯S, C⋯S/S⋯C, etc. are very small and therefore, the ER values are not particularly informative although being > 1 for some interactions.

Table 4
Enrichment ratios (ER) for the title compound.

Interaction	ER
H⋯H	0.97
O⋯H/H⋯O	1.28
S⋯H/H⋯S	1.14
C⋯C	1.09
C⋯H/H⋯C	1.05
S⋯O/O⋯S	1.24
S⋯S	0.45
C⋯S/S⋯C	0.31

5. Database survey

Dithiocarbazate S-esters are well studied with many examples included in the Cambridge Structural Database (Groom & Allen, 2014 ).

There are three examples, II–IV, of derivatives with a hydroxy group in the 2-position of the ring connected to the imine-C atom (Madanhire et al., 2015 ; Sethuraman et al., 2002 ; Begum et al., 2016 ), with their chemical diagrams shown in Scheme 2. Interestingly, there are four virtually identical molecules comprising the asymmetric unit in IV (Begum et al., 2016). A common feature of each of I–IV, is the formation of an intramolecular hydroxy-O—H⋯N(imine) hydrogen bond. By contrast to I, each of the molecules in II–IV is effectively planar. Reflecting the interest in the structural chemistry of this class of compound, there are several structures of S-benzyl esters with methoxy-substituted terminal rings (Fan et al., 2011a ; Fan et al., 2011b ; Tan et al., 2015 ), see Scheme 2 for chemical structures. In each of V–VII, each methoxy group is co-planar with the benzene ring to which it is connected. To a first approximation, the molecules in V and VII adopt approximately the same conformation as in I, i.e. with all but the benzyl rings lying in a plane. The dihedral angles between the two residues are 85.23 (12)° in V and 63.01 (8)° in VII. By contrast, a somewhat twisted conformation is observed for each of the two independent molecules in VI.

6. Synthesis and crystallization

Following procedures adapted from the literature (Ali & Tarafder, 1977 ), S-benzyldithiocarbazate (SBDTC) (1.98 g, 0.01 mol) was dissolved in hot absolute ethanol (100 cm³) and added to an equimolar amount of 2-hydroxy-3-methoxybenzaldehyde (Merck, 1.52 g) in absolute ethanol (20 cm³). The mixture was heated with continuous stirring for about 30 min and was then allowed to stand overnight. The light-yellow crystals that formed were filtered and washed with absolute ethanol at room temperature. Yield: 70%. M.p.: 446–447 K. Analysis calculated for C₁₆H₁₆N₂O₂S₂: C, 57.81; H, 4.85; N, 8.43. Found: C, 58.21; H, 4.87; N, 8.28%. FT–IR (ATR, cm⁻¹): 3089, ν(N—H); 1598, ν(C=N); 1030, ν(N—N); 720, ν(C=S). ¹³C NMR (DMSO-d₆) δ (p.p.m.): 196.09 (C=S), 148.59 (C=N); 147.45–114.43 (aromatic-C), 56.43 (CH₃), 38.10 (CH₂). m/z calculated for C₁₆H₁₆N₂O₂S₂ 332.44, found 332.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. The carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2U_eq(C). The oxygen- and nitrogen-bound H-atoms were located in a difference Fourier map but were refined with distance restraints of O—H = 0.84±0.01 Å and N—H = 0.88±0.01 Å, and with U_iso(H) set to 1.5U_eq(O) and 1.2U_eq(N).

Table 5
Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₂O₂S₂
M_r	332.43
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	20.7896 (10), 4.6965 (2), 32.5217 (13)
β (°)	95.004 (4)
V (Å³)	3163.3 (2)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.35
Crystal size (mm)	0.25 × 0.15 × 0.07

Data collection
Diffractometer	Agilent Xcalibur Eos Gemini
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011 )
T_min, T_max	0.87, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections	6979, 3270, 2595
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.097, 1.06
No. of reflections	3270
No. of parameters	206
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)	0.33, −0.24
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg, 2006 ), publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1465209

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989016004291/hb7572sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016004291/hb7572Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016004291/hb7572Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

2-[(1E)-({[(Benzylsulfanyl)methanethioyl]amino}imino)methyl]-6-methoxyphenol top

Crystal data top

C₁₆H₁₆N₂O₂S₂	F(000) = 1392
M_r = 332.43	D_x = 1.396 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.7896 (10) Å	Cell parameters from 2185 reflections
b = 4.6965 (2) Å	θ = 2–29°
c = 32.5217 (13) Å	µ = 0.35 mm⁻¹
β = 95.004 (4)°	T = 100 K
V = 3163.3 (2) Å³	Plate, light-yellow
Z = 8	0.25 × 0.15 × 0.07 mm

Data collection top

Agilent Xcalibur Eos Gemini diffractometer	3270 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2595 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 16.1952 pixels mm^-1	θ_max = 26.5°, θ_min = 2.4°
ω scans	h = −25→26
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −5→5
T_min = 0.87, T_max = 0.98	l = −27→40
6979 measured reflections

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.041	w = 1/[σ²(F_o²) + (0.0382P)² + 1.7624P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.097	(Δ/σ)_max = 0.002
S = 1.06	Δρ_max = 0.33 e Å⁻³
3270 reflections	Δρ_min = −0.24 e Å⁻³
206 parameters

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	0.22247 (2)	0.46299 (12)	0.61684 (2)	0.02185 (15)
S2	0.17478 (3)	0.80851 (12)	0.54164 (2)	0.02258 (15)
O1	0.35672 (7)	−0.0373 (3)	0.63252 (4)	0.0239 (3)
H1O	0.3342 (10)	0.086 (4)	0.6194 (7)	0.036*
O2	0.43677 (8)	−0.4115 (3)	0.66547 (5)	0.0305 (4)
N1	0.27458 (8)	0.4630 (4)	0.54712 (5)	0.0203 (4)
H1N	0.2819 (10)	0.519 (5)	0.5223 (4)	0.024*
N2	0.31479 (8)	0.2682 (4)	0.56753 (5)	0.0194 (4)
C1	0.22604 (9)	0.5777 (4)	0.56594 (6)	0.0179 (4)
C2	0.15287 (10)	0.6579 (5)	0.63209 (6)	0.0237 (5)
H2A	0.1579	0.8639	0.6268	0.028*
H2B	0.1130	0.5907	0.6161	0.028*
C3	0.14873 (10)	0.6059 (5)	0.67741 (6)	0.0223 (5)
C4	0.18779 (13)	0.7499 (6)	0.70649 (8)	0.0395 (6)
H4	0.2181	0.8838	0.6979	0.047*
C5	0.18365 (13)	0.7029 (6)	0.74845 (8)	0.0432 (7)
H5	0.2108	0.8059	0.7682	0.052*
C6	0.14056 (12)	0.5086 (5)	0.76139 (7)	0.0356 (6)
H6	0.1381	0.4735	0.7900	0.043*
C7	0.10141 (14)	0.3670 (7)	0.73262 (8)	0.0502 (8)
H7	0.0708	0.2346	0.7413	0.060*
C8	0.10538 (13)	0.4127 (6)	0.69076 (8)	0.0404 (7)
H8	0.0779	0.3096	0.6712	0.048*
C9	0.35930 (10)	0.1553 (4)	0.54759 (6)	0.0192 (4)
H9	0.3635	0.2118	0.5199	0.023*
C10	0.40308 (9)	−0.0564 (4)	0.56664 (6)	0.0188 (4)
C11	0.40002 (9)	−0.1423 (4)	0.60766 (6)	0.0191 (4)
C12	0.44376 (10)	−0.3469 (5)	0.62508 (7)	0.0236 (5)
C13	0.48986 (10)	−0.4610 (5)	0.60167 (7)	0.0282 (5)
H13	0.5196	−0.5984	0.6134	0.034*
C14	0.49292 (11)	−0.3747 (5)	0.56070 (7)	0.0286 (5)
H14	0.5246	−0.4541	0.5448	0.034*
C15	0.45042 (10)	−0.1762 (5)	0.54345 (7)	0.0239 (5)
H15	0.4529	−0.1189	0.5156	0.029*
C16	0.47583 (12)	−0.6366 (5)	0.68359 (8)	0.0346 (6)
H16A	0.4679	−0.8109	0.6674	0.052*
H16B	0.4649	−0.6693	0.7119	0.052*
H16C	0.5215	−0.5840	0.6839	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0221 (3)	0.0271 (3)	0.0169 (3)	0.0071 (2)	0.0051 (2)	0.0040 (2)
S2	0.0225 (3)	0.0273 (3)	0.0180 (3)	0.0075 (2)	0.0024 (2)	0.0047 (2)
O1	0.0258 (8)	0.0281 (9)	0.0183 (7)	0.0072 (7)	0.0044 (6)	0.0034 (7)
O2	0.0399 (9)	0.0269 (9)	0.0238 (8)	0.0075 (7)	−0.0035 (7)	0.0064 (7)
N1	0.0206 (9)	0.0253 (10)	0.0154 (8)	0.0044 (8)	0.0040 (7)	0.0058 (8)
N2	0.0180 (8)	0.0208 (9)	0.0194 (9)	0.0039 (7)	0.0024 (7)	0.0026 (8)
C1	0.0181 (10)	0.0179 (10)	0.0176 (10)	−0.0018 (8)	0.0016 (8)	0.0000 (9)
C2	0.0239 (11)	0.0257 (12)	0.0222 (11)	0.0080 (9)	0.0061 (9)	0.0038 (10)
C3	0.0234 (11)	0.0231 (12)	0.0212 (11)	0.0093 (9)	0.0059 (9)	0.0005 (9)
C4	0.0430 (15)	0.0457 (16)	0.0293 (13)	−0.0093 (13)	0.0010 (12)	0.0040 (12)
C5	0.0523 (17)	0.0504 (17)	0.0258 (13)	−0.0002 (14)	−0.0034 (12)	−0.0029 (13)
C6	0.0411 (14)	0.0470 (16)	0.0200 (11)	0.0152 (12)	0.0103 (11)	0.0032 (12)
C7	0.0549 (18)	0.066 (2)	0.0310 (14)	−0.0188 (16)	0.0104 (13)	0.0078 (14)
C8	0.0493 (16)	0.0480 (16)	0.0244 (12)	−0.0172 (13)	0.0063 (12)	−0.0001 (12)
C9	0.0225 (10)	0.0203 (11)	0.0150 (10)	−0.0017 (9)	0.0028 (9)	0.0010 (9)
C10	0.0184 (10)	0.0170 (10)	0.0210 (10)	−0.0013 (9)	0.0015 (8)	−0.0030 (9)
C11	0.0185 (10)	0.0189 (11)	0.0197 (10)	−0.0013 (8)	0.0004 (9)	−0.0039 (9)
C12	0.0264 (11)	0.0194 (11)	0.0239 (11)	−0.0004 (9)	−0.0046 (9)	−0.0011 (9)
C13	0.0239 (11)	0.0238 (12)	0.0355 (13)	0.0068 (10)	−0.0067 (10)	−0.0046 (11)
C14	0.0228 (11)	0.0301 (13)	0.0331 (13)	0.0063 (10)	0.0035 (10)	−0.0077 (11)
C15	0.0223 (11)	0.0269 (12)	0.0228 (11)	0.0012 (9)	0.0041 (9)	−0.0030 (10)
C16	0.0411 (14)	0.0237 (13)	0.0363 (14)	−0.0008 (11)	−0.0129 (12)	0.0070 (11)

Geometric parameters (Å, º) top

S1—C1	1.749 (2)	C6—C7	1.359 (4)
S1—C2	1.817 (2)	C6—H6	0.9500
S2—C1	1.670 (2)	C7—C8	1.388 (3)
O1—C11	1.354 (2)	C7—H7	0.9500
O1—H1O	0.836 (10)	C8—H8	0.9500
O2—C12	1.368 (3)	C9—C10	1.450 (3)
O2—C16	1.429 (3)	C9—H9	0.9500
N1—C1	1.338 (2)	C10—C11	1.401 (3)
N1—N2	1.371 (2)	C10—C15	1.408 (3)
N1—H1N	0.874 (9)	C11—C12	1.408 (3)
N2—C9	1.290 (2)	C12—C13	1.383 (3)
C2—C3	1.504 (3)	C13—C14	1.400 (3)
C2—H2A	0.9900	C13—H13	0.9500
C2—H2B	0.9900	C14—C15	1.370 (3)
C3—C4	1.370 (3)	C14—H14	0.9500
C3—C8	1.376 (3)	C15—H15	0.9500
C4—C5	1.392 (3)	C16—H16A	0.9800
C4—H4	0.9500	C16—H16B	0.9800
C5—C6	1.370 (4)	C16—H16C	0.9800
C5—H5	0.9500

C1—S1—C2	101.75 (10)	C3—C8—C7	120.5 (2)
C11—O1—H1O	108.6 (16)	C3—C8—H8	119.7
C12—O2—C16	117.13 (17)	C7—C8—H8	119.7
C1—N1—N2	119.96 (16)	N2—C9—C10	121.21 (18)
C1—N1—H1N	120.0 (15)	N2—C9—H9	119.4
N2—N1—H1N	120.0 (15)	C10—C9—H9	119.4
C9—N2—N1	117.70 (17)	C11—C10—C15	119.1 (2)
N1—C1—S2	121.37 (15)	C11—C10—C9	121.72 (18)
N1—C1—S1	113.89 (15)	C15—C10—C9	119.15 (18)
S2—C1—S1	124.74 (11)	O1—C11—C10	123.47 (19)
C3—C2—S1	107.49 (14)	O1—C11—C12	116.60 (18)
C3—C2—H2A	110.2	C10—C11—C12	119.92 (18)
S1—C2—H2A	110.2	O2—C12—C13	125.4 (2)
C3—C2—H2B	110.2	O2—C12—C11	114.77 (18)
S1—C2—H2B	110.2	C13—C12—C11	119.8 (2)
H2A—C2—H2B	108.5	C12—C13—C14	120.2 (2)
C4—C3—C8	118.2 (2)	C12—C13—H13	119.9
C4—C3—C2	121.0 (2)	C14—C13—H13	119.9
C8—C3—C2	120.8 (2)	C15—C14—C13	120.4 (2)
C3—C4—C5	121.0 (2)	C15—C14—H14	119.8
C3—C4—H4	119.5	C13—C14—H14	119.8
C5—C4—H4	119.5	C14—C15—C10	120.6 (2)
C6—C5—C4	120.3 (3)	C14—C15—H15	119.7
C6—C5—H5	119.8	C10—C15—H15	119.7
C4—C5—H5	119.8	O2—C16—H16A	109.5
C7—C6—C5	118.8 (2)	O2—C16—H16B	109.5
C7—C6—H6	120.6	H16A—C16—H16B	109.5
C5—C6—H6	120.6	O2—C16—H16C	109.5
C6—C7—C8	121.1 (3)	H16A—C16—H16C	109.5
C6—C7—H7	119.4	H16B—C16—H16C	109.5
C8—C7—H7	119.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N2	0.84 (2)	1.90 (2)	2.639 (2)	146 (2)
N1—H1N···S2ⁱ	0.88 (2)	2.47 (2)	3.3351 (18)	168 (2)
C6—H6···O1ⁱⁱ	0.95	2.51	3.453 (3)	170

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

Major percentage contribution of the different intermolecular interactions to the Hirshfeld surface of the title compound top

Contact	%
H···H	43.4
O···H/H···O	10.3
S···H/H···S	14.4
C···H/H···C	21.3
N···H/H···N	0.8
C···C	2.5
S···S	0.4
C···N/N···C	2.9
S···O/O···S	1.4
S···N/N···S	1.4
C···S/S···C	0.9

Additional short interatomic contacts (Å) for the title compound top

Interaction	distance	symmetry operation
H8···H16C	2.25	-1/2 + x, 1/2 + y, z
C6···H16B	2.86	1/2 - x, 3/2 + y, 3/2 - z
O1···H16A	2.70	x, 1 + y, z
C11···H16A	2.78	x, 1 + y, z
C12···H16A	2.89	x, 1 + y, z

Enrichment ratios (ER) for the title compound. top

Interaction	ER
H···H	0.97
O···H/H···O	1.28
S···H/H···S	1.14
C···C	1.09
C···H/H···C	1.05
S···O/O···S	1.24
S···S	0.45
C···S/S···C	0.31

Footnotes

‡Additional correspondence author, e-mail: thahira@upm.edu.my.

Acknowledgements

We thank the Department of Chemistry, the Molecular Genetics Laboratory and the Department of Obstetrics and Gynaecology, Universiti Putra Malaysia, for access to facilities. This research was funded by Universiti Putra Malaysia (UPM) and the Malaysian Government under the Research University Grant Scheme (RUGS No. 9419400), the Malaysian Fundamental Research Grant Scheme (FRGS No. 01/02-13-1344FR) and the ScienceFund under the Ministry of Science, Technology and Innovation (MOSTI) (06-01-04-SF1810). ENMY also wishes to acknowledge the MyPhD Malaysian Government Scholarship (MyBrain15).

References

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Ali, M. A. & Livingstone, S. E. (1974). Coord. Chem. Rev. 13, 101–132. CrossRef CAS Google Scholar
Ali, M. A. & Tarafder, M. T. H. (1977). J. Inorg. Nucl. Chem. 39, 1785–1791. Google Scholar
Basha, M. T., Chartres, J. D., Pantarat, N., Ali, M. A., Mirza, A. H., Kalinowski, D. S., Richardson, D. R. & Bernhardt, P. V. (2012). Dalton Trans. 41, 6536–6548. CSD CrossRef CAS PubMed Google Scholar
Begum, M. S., Howlader, M. B. H., Sheikh, M. C., Miyatake, R. & Zangrando, E. (2016). Acta Cryst. E72, 290–292. CSD CrossRef IUCr Journals Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Fan, Z., Huang, Y.-L., Wang, Z., Guo, H.-Q. & Shan, S. (2011a). Acta Cryst. E67, o3011. CSD CrossRef IUCr Journals Google Scholar
Fan, Z., Huang, Y.-L., Wang, Z., Guo, H.-Q. & Shan, S. (2011b). Acta Cryst. E67, o3015. CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CSD CrossRef CAS Google Scholar
Jayatilaka, D., Grimwood, D. J., Lee, A., Lemay, A., Russel, A. J., Taylor, C., Wolff, S. K., Cassam-Chenai, P. & Whitton, A. (2005). TONTO. Available at: https://hirshfeldsurface.net/ Google Scholar
Jelsch, C., Ejsmont, K. & Huder, L. (2014). IUCrJ, 1, 119–128. Web of Science CrossRef CAS PubMed IUCr Journals Google Scholar
Liu, Z., Wang, W., Xu, H., Sheng, L., Chen, S., Huang, D. & Sun, F. (2015). Inorg. Chem. Commun. 62, 19–23. CSD CrossRef Google Scholar
Madanhire, T., Abrahams, A., Hosten, E. C. & Betz, R. (2015). Z. Kristallogr. New Cryst. Struct. 230, 13–14. CAS Google Scholar
Rohl, A. L., Moret, M., Kaminsky, W., Claborn, K., McKinnon, J. J. & Kahr, B. (2008). Cryst. Growth Des. 8, 4517–4525. Web of Science CSD CrossRef CAS Google Scholar
Sethuraman, G., Yamin, B. M., Shamsuddin, M., Usman, A., Razak, I. A. & Fun, H.-K. (2002). Acta Cryst. E58, o649–o651. 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
Spackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). CrystEngComm, 10, 377–388. CAS Google Scholar
Tan, Y.-F., Break, M. K. bin, Tahir, M. I. M. & Khoo, T.-J. (2015). Acta Cryst. E71, 238–240. Web of Science CSD CrossRef IUCr Journals Google Scholar
Vijayan, P., Viswanathamurthi, P., Sugumar, P., Ponnuswamy, M. N., Balakumaran, M. D., Kalaichelvan, P. T., Velmurugan, K., Nandhakumar, R. & Butcher, R. J. (2015). Inorg. Chem. Front. 2, 620–639. CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wise, C. F., Liu, D., Mayer, K. J., Crossland, P. M., Hartley, C. L. & McNamara, W. R. (2015). Dalton Trans. 44, 14265–14271. Web of Science CSD CrossRef CAS PubMed Google Scholar
Wolff, S. K., Grimwood, D. J., McKinnon, J. J., Turner, M. J., Jayatilaka, D. & Spackman, M. A. (2012). Crystal Explorer. The University of Western Australia. Google Scholar
Yusof, E. N. M., Ravoof, T. B. S. A., Jamsari, J., Tiekink, E. R. T., Veerakumarasivam, A., Crouse, K. A., Tahir, M. I. M. & Ahmad, H. (2015). Inorg. Chim. Acta, 438, 85–93. CSD CrossRef CAS Google Scholar
Yusof, E. N. M., Ravoof, T. B. S. A., Tiekink, E. R. T., Veerakumarasivam, A., Crouse, K. A., Tahir, M. I. M. & Ahmad, H. (2015). Int. J. Molec. Sci. 16, 11034–11054. CAS Google Scholar

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