(E)-{[(Butyl­sulfan­yl)methane­thio­yl]amino}(4-meth­oxy­benzyl­idene)amine: crystal structure and Hirshfeld surface analysis

The title hydrazine carbodi­thio­ate features an almost planar C₂N₂S₂ chromophore, which is close to co-planar with the terminal meth­oxy­benzene group; the n-butyl group has an extended, all-trans conformation. In the crystal, centrosymmetric, eight-membered {⋯HNCS}₂ synthons are formed by thio­amide-N—H⋯S(thio­amide) hydrogen bonds.

Abstract

The title hydrazine carbodi­thio­ate, C₁₃H₁₈N₂OS₂, is constructed about a central and almost planar C₂N₂S₂ chromophore (r.m.s. deviation = 0.0263 Å); the terminal meth­oxy­benzene group is close to coplanar with this plane [dihedral angle = 3.92 (11)°]. The n-butyl group has an extended all-trans conformation [torsion angles S—C_m—C_m—C_m = −173.2 (3)° and C_m—C_m—C_m—C_me = 180.0 (4)°; m = methyl­ene and me = meth­yl]. The most prominent feature of the mol­ecular packing is the formation of centrosymmetric eight-membered {⋯HNCS}₂ synthons, as a result of thio­amide-N—H⋯S(thio­amide) hydrogen bonds; these are linked via meth­oxy-C–H⋯π(meth­oxy­benzene) inter­actions to form a linear supra­molecular chain propagating along the a-axis direction. An analysis of the calculated Hirshfeld surfaces and two-dimensional fingerprint plots point to the significance of H⋯H (58.4%), S⋯H/H⋯S (17.1%), C⋯H/H⋯C (8.2%) and O⋯H/H⋯O (4.9%) contacts in the packing. The energies of the most significant inter­actions, i.e. the N—H⋯S and C—H⋯π inter­actions have their most significant contributions from electrostatic and dispersive components, respectively. The energies of two other identified close contacts at close to van der Waals distances, i.e. a thione–sulfur and meth­oxy­benzene–hydrogen contact (occurring within the chains along the a axis) and between methyl­ene-H atoms (occurring between chains to consolidate the three-dimensional architecture), are largely dispersive in nature.

Chemical context  

The di­thio­carbazate dianion, NH₂NHCS²⁻, and its esters such as S-benzyl­dithio­carbazate (Tian et al., 1996 ▸) and S-methyl­dithio­carbazate (Ali et al., 2008 ▸), are well-known to function as starting materials for the synthesis of a wide variety of Schiff bases containing both hard nitro­gen and soft sulfur donor atoms. Schiff bases derived from S-alkyl esters of di­thio­carbazate, NH₂NHC(=S)SR, and their metal complexes have been the subject of many studies because of their ability to act as multidentate ligands to metals and the subsequent enhanced bioactivity upon complexation (Bera et al., 2009 ▸; Ali et al., 2012 ▸; Begum et al., 2017 ▸). Schiff bases derived from the condensation of S-methyl- or S-benzyl­dithio­carbazate with heterocyclic aldehydes and ketones can complex metals to form five-membered chelate rings with the metal atoms bound to nitro­gen and sulfur atoms (Ali et al., 2003 ▸) while complexation via two sulfur atoms, resulting in the formation of a four-membered chelate ring, is also possible (Rakha & Bekheit, 2000 ▸). It is also known that slight changes in mol­ecular structure can give rise to different coordination geometries (Chan et al., 2008 ▸). In a continuation of structural studies of S-alkyl di­thio­carbazate esters (Yusof et al., 2015 ▸; Low et al., 2016 ▸; Omar et al., 2018 ▸) and their complexation to metals with accompanying evaluation of biological potential (Low et al., 2016 ▸; Ravoof et al., 2017 ▸; Yusof et al., 2017 ▸), herein the crystal and mol­ecular structures of the title hydrazine carbodi­thio­ate ester, (I), along with the calculated Hirshfeld surfaces and computational chemistry are described.

Structural commentary  

The mol­ecular structure of (I), Fig. 1 ▸, features a central C₂N₂S₂ residue which is close to planar, as seen in the r.m.s. deviation of 0.0263 Å for the fitted atoms. The maximum deviations to opposite sides of the plane occur for the N1 [0.0393 (18) Å] and C2 [0.0388 (14) Å] atoms with the appended C3 [0.033 (3) Å] and C10 [0.089 (4) Å] atoms lying to the same side of the central plane as the C2 atom. The meth­oxy­benzene ring forms a dihedral angle of 3.92 (11)° with the central residue indicating a close to co-planar relationship. The C9—O1—C6 —C7 dihedral angle of 176.9 (3)° indicates that the meth­oxy substituent lies almost in the plane of the benzene ring to which it is connected. The configuration about the C2=N2 imine bond [1.278 (3) Å] is E and this bond length is significantly shorter than the C1—N1 bond [1.330 (3) Å]; the N1—N2 bond length is 1.378 (3) Å. There is a large disparity in the C1—S1 [1.662 (3) Å] and C1—S2 [1.745 (3) Å] bond lengths, which correlate with significant double-bond character in the former; the C10—S2 bond length at 1.793 (3) Å is longer than each of these. The thione character of the C1—S1 bond is also reflected in the range of angles subtended at the C1 atom, which are systematically wider for those involving the thione-S1 atom, i.e. S1—C1—S2 [126.35 (16)°] and S1—C1—N1 [120.9 (2)°], cf. S2—C1—N1 [112.76 (19)°]. The thio­amide-N—H and thio­amide-S atoms have a syn disposition. Finally, the n-butyl group has an extended, all-trans conformation as seen in the S2—C10—C11—C12 [−173.2 (3)°] and C10—C11—C12—C13 [180.0 (4)°] torsion angles.

Figure 1.

The mol­ecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level.

Supra­molecular features  

With the exception of thio­amide-N—H⋯S(thio­amide) hydrogen bonding between centrosymmetrically related mol­ecules, Table 1 ▸, and which sustain a dimeric aggregate via an eight-membered {⋯HNCS}₂ synthon, the mol­ecular packing is largely devoid of directional inter­actions (Spek, 2020 ▸). The dimeric aggregates are connected into a linear supra­molecular chain along the a-axis direction via weak meth­oxy-C—H⋯π(meth­oxy­benzene) inter­actions, Fig. 2 ▸(a), being the only other identified supra­molecular association. Globally, chains pack without specific inter­actions between them, Fig. 2 ▸(b). An analysis of the weak non-covalent contacts within and connecting chains is given in the Analysis of the Hirshfeld surfaces.

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the (C3–C8) ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S1i	0.86 (1)	2.61 (2)	3.425 (3)	160 (3)
C9—H9C⋯Cg1ii	0.96	2.98	3.748 (4)	138

Symmetry codes: (i) ; (ii) .

Figure 2.

Mol­ecular packing in (I): (a) the linear supra­molecular chain whereby dimeric aggregates sustained by thio­amide-N—H⋯S(thio­amide) hydrogen bonding, shown by blue dashed lines, are connected by meth­oxy-C—H⋯π inter­actions (purple dashed lines) and (b) a view of the unit-cell contents shown in projection down the a axis highlighting the stacking of dimeric aggregates.

Analysis of the Hirshfeld surfaces  

The calculation of the Hirshfeld surfaces for (I) were conducted as per a literature precedent (Tan et al., 2019 ▸) employing Crystal Explorer 17 (Turner et al., 2017 ▸). The presence of bright-red spots near the thio­amide-S1 and H1N atoms on the Hirshfeld surface mapped over d _norm shown in Fig. 3 ▸ reflect the inter­molecular N—H⋯S hydrogen bonding. The donor and acceptor associated with this inter­action are also viewed as the blue and red regions, corresponding to positive and negative electrostatic potentials, respectively, on the Hirshfeld surface mapped over the calculated electrostatic potential in Fig. 4 ▸. The inter­molecular meth­oxy-C—H⋯π(meth­oxy­benzene) inter­action is also evident in Fig. 4 ▸, as the light-blue and light-red regions around the participating atoms. Fig. 5 ▸ also illustrates the donors and acceptors of this C—H⋯π contact through the dotted lines connecting the blue bump and red concave regions, respectively, on the Hirshfeld surface mapped with the shape-index property.

Figure 3.

A view of the Hirshfeld surface for (I) mapped over d _norm in the range −0.299 to +1.278 arbitrary units.

Figure 4.

A view of the Hirshfeld surface for (I) mapped over the electrostatic potential in the range −0.056 to +0.104 atomic units.

Figure 5.

A view of the Hirshfeld surface with the shape-index property highlighting the donors and acceptors of the C—H⋯π/π⋯H—C contacts by black dotted lines.

The overall two-dimensional fingerprint plot for (I) along with those delineated into the individual H⋯H, S⋯H/H⋯S, C⋯H/H⋯C and O⋯H/H⋯O contacts are illustrated in Fig. 6 ▸(a)–(e), respectively; the percentage contributions from the different inter­atomic contacts are summarized in Table 2 ▸. In the fingerprint plot delineated into H⋯H contacts, Fig. 6 ▸(b), a short inter­atomic H⋯H contact involving methyl­ene-H10B with a symmetry-related mate (H10B⋯H10B = 2.26 Å; symmetry operation −x, 1 − y, 2 − z) and occurring between supra­molecular chains aligned along the a axis, is observed as a single peak at d _e + d _i ∼ 2.2 Å. In the fingerprint delineated into S⋯H/H⋯S contacts, shown in Fig. 6 ▸(c), the pair of well-defined spikes at d _e + d _i ∼ 2.5 Å arise as a result of the prominent inter­molecular N—H⋯S inter­action. The points corresponding to S⋯H/H⋯S contacts involving the thione-S1 and meth­oxy­benzene-H4 atoms, occurring within the supra­molecular chain shown in Fig. 2 ▸(a), albeit at nearly van der Waals separations (S1⋯H4 = 3.02 Å for 2 − x, 1 − y, 1 − z), and reflected as an electrostatic inter­action in the Hirshfeld surface plotted over the electrostatic potential of Fig. 4 ▸, are merged within the plot. Although the points in the fingerprint plot delineated into C⋯H/H⋯C contacts in Fig. 6 ▸(d) are at distances equal to or greater than the sum of van der Waals radii, the presence of characteristic wings is the result of the inter­molecular methy­oxy-C—H⋯π(meth­oxy­benzene) contact. The points corresponding to inter­atomic O⋯H/H⋯O contacts illustrated in the corres­ponding fingerprint plot of Fig. 6 ▸(e), also show a pair of forceps-like tips at d _e + d _i ∼ 2.8 Å, i.e. at van der Waals distances. The contribution from the other inter­atomic contacts summarized in Table 2 ▸ have negligible influence on the calculated Hirshfeld surface of (I).

Figure 6.

(a) The full two-dimensional fingerprint plot for (I) and fingerprint plots delineated into (b) H⋯H, (c) S⋯H/H⋯S, (d) C⋯H/H⋯C and (e) O⋯H/H⋯O contacts.

Table 2. The percentage contributions of inter­atomic contacts to the Hirshfeld surface for (I).

Contact	Percentage contribution
H⋯H	58.4
S⋯H/H⋯S	17.1
C⋯H/H⋯C	8.2
O⋯H/H⋯O	4.9
C⋯N/N⋯C	4.2
C⋯C	3.0
S⋯N/N⋯S	1.7
N⋯H/H⋯N	0.9
C⋯O/O⋯C	0.9
C⋯S/S⋯C	0.7

Computational chemistry  

The pairwise inter­action energies between mol­ecules in the crystal of (I) were calculated by summing up four energy components, comprising electrostatic (E _ele), polarization (E _pol), dispersion (E _dis) and exchange-repulsion (E _rep) (Turner et al., 2017 ▸); the energies were calculated using the wave function calculated at the B3LYP/6-31G(d,p) level of theory. The nature and strength of the inter­molecular inter­actions in terms of their energies are qu­anti­tatively summarized in Table 3 ▸. As indicated in Table 3 ▸, the electrostatic energy component is most significant for the N—H⋯S hydrogen bond but also makes a significant contribution to the thione-S1 and meth­oxy­benzene-H4 contact, nearly as great as the dispersive component. The other two inter­molecular inter­actions listed in Table 3 ▸ show major contributions from dispersion to the energy. The most stabilizing inter­actions, in order, are those arising from the N—H⋯S and C—H⋯π contacts, compared to the short inter­atomic S⋯H/H⋯S and H⋯H contacts. The magnitudes of inter­molecular energies are also represented graphically in Fig. 7 ▸ by energy frameworks in order to view the supra­molecular architecture of the crystal through cylinders that connect the centroids of mol­ecular pairs. This is done using red, green and blue colour codes for the E _ele, E _disp and E _tot components, respectively; the radius of the cylinder is proportional to the magnitude of the inter­action energies. This is reflected in the relatively thick red cylinders corresponding to the electrostatic inter­actions via the N—H⋯S hydrogen bonding in Fig. 7 ▸(a) and the thick green cylinders corresponding to the strong dispersive inter­actions provided by the methy­oxy-C—H⋯π(meth­oxy­benzene) inter­actions in Fig. 7 ▸(b).

Table 3. A summary of inter­action energies (kJ mol⁻¹) calculated for (I).

Contact	R (Å)	E ele	E pol	E dis	E rep	E tot
N1—H1N⋯S1i	8.17	−59.2	−10.3	−17.1	66.6	−43.9
C9—H9C⋯Cg(C3–C8)ii	4.71	−2.2	−3.8	−64.0	35.9	−38.8
S1 ⋯H4iii	6.85	−15.6	−5.2	−19.3	19.6	−25.1
H10B ⋯H10B iv	10.74	−1.0	−0.3	−11.3	5.7	−7.5

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

Figure 7.

The calculated energy frameworks viewed down the a-axis direction comprising (a) electrostatic potential force, (b) dispersion force and (c) total energy for a cluster about a reference mol­ecule of (I). The energy frameworks were adjusted to the same scale factor of 50 with a cut-off value of 3 kJ mol⁻¹ within 4 × 4 × 4 unit cells.

Database survey  

Reflecting the inter­est in the chemistry of hydrazine carbodi­thio­ates related to (I), there are four crystal structures of literature precedents of the general formula, 4-MeOC₆H₄C(H)=NN(H)C(=S)SR. These are of the R = Me (CCDC refcode ZITZIL; Fun et al., 1996 ▸), n-hexyl (HUDJOH; Begum, Howlader et al., 2015 ▸), n-ocyl (XUFPAR; Begum, Zangrando et al., 2015 ▸) and CH₂Ph (YAHDAO; Fan et al., 2011 ▸) compounds. The common feature of all five structures is the E-configuration about the imine bond and the syn relationship between the thio­amide-N—H and thio­amide-S atoms in their mol­ecular structures. Further, the formation of centrosymmetric, eight-membered {⋯HNCS}₂ synthons is common in their crystals. For the n-hexyl and n-octyl compounds, extended, all-trans conformations are found for the alkyl chains, as for (I).

Synthesis and crystallization  

In an ice-bath, carbon di­sulfide (10.6 ml, 0.11 mol) was added dropwise to an absolute ethanol (35 ml) solution comprising KOH (6.2 g, 0.11 mol) and hydrazine hydrate (5.7 ml, 0.11 mol). After 30 min, 1-bromo­butane (20 ml, 0.11 mol) was added. The solution was stirred at 278 K for 1 h to form S-butyl­dithio­carbazate (SBuDTC). An ethano­lic solution (28 ml) of 4-meth­oxy­benzaldehyde (16.8 ml, 0.11 mol) was added directly to the SBuDTC in situ. This mixture was heated to 323 K with continuous stirring for 30 min. The yellow product (I) was filtered, washed with water and dried under vacuum. Colourless blocks suitable for the X-ray analysis were obtained from an ethanol solution of (I) by slow evaporation. Yield: 0.18 g, 65%. M.p. 375.7–376.3 K. Analysis calculated: C₁₃H₁₈N₂OS₂: C, 55.3; H, 6.4; N, 9.9; S, 22.7. Found: C, 55.9; H, 6.6; N, 9.8; S, 23.2. FT–IR (cm⁻¹): 3120 ν(NH), 2927 ν(CH), 1600 ν(C=N), 1248 and 1107 ν(COC), 1017 ν(NN), 861 ν(CSS). MS: calculated m/z = 282; Found m/z = 282. ¹H NMR (DMSO-d ₆; 500 MHz): δ 13.11 (1H, s, NH), 8.15 (1H, s, CH=N), 6.97, 7.02, 7.61, 7.78 (ArH), 3.76 (3H, s, OCH₃), 3.14 (2H, t, SCH₂), 1.58 (2H, q, CH₂), 1.36 (2H, sextet, CH₂), 0.86 (3H, t, CH₃). ¹³C{¹H} NMR (DMSO-d ₆; 125 MHz): δ 196.96 (C=S), 146.87 (C=N), 161.90, 129.65, 126.36, 115.00 (ArC), 55.86 (OCH₃), 33.19, 31.05, 22.10 (CH₂), 14.07 (CH₃). NMR data were measured on a JOEL ECX500 FT NMR spectrometer.

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 4 ▸. The carbon-bound H atoms were placed in calculated positions (C—H = 0.93–0.97 Å) and were included in the refinement in the riding model approximation, with U _iso(H) set to 1.2U _eq(C). The N-bound H atom was located in a difference-Fourier map but was refined with a N—H distance restraint of 0.86 (1) Å.

Table 4. Experimental details.

Crystal data
Chemical formula	C13H18N2OS2
M r	282.41
Crystal system, space group	Triclinic, P
Temperature (K)	295
a, b, c (Å)	4.7131 (3), 11.6998 (8), 13.5696 (8)
α, β, γ (°)	85.225 (5), 81.139 (5), 87.379 (5)
V (Å3)	736.35 (8)
Z	2
Radiation type	Mo Kα
μ (mm−1)	0.35
Crystal size (mm)	0.30 × 0.25 × 0.20
Data collection
Diffractometer	Agilent Technologies SuperNova Dual diffractometer with Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012 ▸)
T min, T max	0.868, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9986, 3395, 2244
R int	0.029
(sin θ/λ)max (Å−1)	0.651
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.055, 0.174, 1.03
No. of reflections	3395
No. of parameters	169
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.52, −0.46

Computer programs: CrysAlis PRO (Agilent, 2012 ▸), SHELXT2014 (Sheldrick, 2015a ▸), SHELXL2014 (Sheldrick, 2015b ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸), DIAMOND (Brandenburg, 2006 ▸) and publCIF (Westrip, 2010 ▸).

Supplementary Material

CCDC reference: 1977066

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Crystal data

C13H18N2OS2	Z = 2
Mr = 282.41	F(000) = 300
Triclinic, P1	Dx = 1.274 Mg m−3
a = 4.7131 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.6998 (8) Å	Cell parameters from 2643 reflections
c = 13.5696 (8) Å	θ = 3.0–27.5°
α = 85.225 (5)°	µ = 0.35 mm−1
β = 81.139 (5)°	T = 295 K
γ = 87.379 (5)°	Block, colourless
V = 736.35 (8) Å3	0.30 × 0.25 × 0.20 mm

Data collection

Agilent Technologies SuperNova Dual diffractometer with Atlas detector	3395 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2244 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.029
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 3.1°
ω scan	h = −6→5
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −15→15
Tmin = 0.868, Tmax = 1.000	l = −17→17
9986 measured reflections

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055	Hydrogen site location: mixed
wR(F2) = 0.174	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0724P)2 + 0.3095P] where P = (Fo2 + 2Fc2)/3
3395 reflections	(Δ/σ)max < 0.001
169 parameters	Δρmax = 0.52 e Å−3
1 restraint	Δρmin = −0.45 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.33083 (16)	0.60524 (6)	0.62361 (6)	0.0687 (3)
S2	0.51025 (19)	0.46574 (8)	0.80444 (6)	0.0813 (3)
O1	1.7337 (5)	−0.06363 (18)	0.75096 (16)	0.0786 (6)
N1	0.7095 (5)	0.43553 (19)	0.62083 (18)	0.0561 (5)
H1N	0.720 (7)	0.443 (3)	0.5569 (8)	0.084 (11)*
N2	0.8729 (5)	0.35129 (18)	0.66505 (17)	0.0565 (5)
C1	0.5246 (5)	0.5021 (2)	0.6764 (2)	0.0542 (6)
C2	1.0604 (5)	0.2985 (2)	0.6052 (2)	0.0548 (6)
H2	1.0805	0.3194	0.5369	0.066*
C3	1.2420 (5)	0.2067 (2)	0.64237 (19)	0.0513 (6)
C4	1.4425 (5)	0.1496 (2)	0.5769 (2)	0.0556 (6)
H4	1.4639	0.1727	0.5090	0.067*
C5	1.6119 (5)	0.0592 (2)	0.6098 (2)	0.0564 (6)
H5	1.7446	0.0218	0.5643	0.068*
C6	1.5834 (6)	0.0250 (2)	0.7098 (2)	0.0584 (6)
C7	1.3874 (7)	0.0833 (3)	0.7765 (2)	0.0747 (9)
H7	1.3700	0.0615	0.8446	0.090*
C8	1.2198 (6)	0.1720 (3)	0.7436 (2)	0.0679 (8)
H8	1.0890	0.2098	0.7894	0.081*
C9	1.9271 (7)	−0.1303 (3)	0.6861 (3)	0.0823 (9)
H9A	1.8225	−0.1666	0.6426	0.123*
H9B	2.0223	−0.1879	0.7251	0.123*
H9C	2.0671	−0.0815	0.6468	0.123*
C10	0.2533 (8)	0.5676 (3)	0.8614 (3)	0.0891 (10)
H10A	0.1371	0.5996	0.8120	0.107*
H10B	0.1265	0.5277	0.9151	0.107*
C11	0.3805 (8)	0.6607 (3)	0.9014 (3)	0.0946 (11)
H11A	0.4893	0.7057	0.8463	0.114*
H11B	0.5150	0.6282	0.9443	0.114*
C12	0.1686 (9)	0.7410 (4)	0.9608 (3)	0.1070 (13)
H12A	0.0341	0.7741	0.9181	0.128*
H12B	0.0598	0.6964	1.0162	0.128*
C13	0.3015 (12)	0.8331 (4)	0.9999 (4)	0.1316 (18)
H13A	0.3918	0.8031	1.0558	0.197*
H13B	0.1577	0.8903	1.0211	0.197*
H13C	0.4433	0.8669	0.9486	0.197*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0716 (5)	0.0568 (5)	0.0760 (5)	0.0258 (3)	−0.0129 (4)	−0.0078 (3)
S2	0.0890 (6)	0.0890 (6)	0.0667 (5)	0.0326 (5)	−0.0197 (4)	−0.0151 (4)
O1	0.0860 (14)	0.0684 (13)	0.0780 (14)	0.0319 (11)	−0.0154 (11)	0.0007 (10)
N1	0.0550 (12)	0.0495 (12)	0.0640 (14)	0.0135 (10)	−0.0122 (11)	−0.0076 (10)
N2	0.0542 (12)	0.0460 (12)	0.0711 (14)	0.0134 (9)	−0.0180 (10)	−0.0076 (10)
C1	0.0493 (13)	0.0468 (14)	0.0676 (16)	0.0048 (11)	−0.0119 (11)	−0.0089 (12)
C2	0.0512 (14)	0.0495 (14)	0.0649 (15)	0.0073 (11)	−0.0123 (12)	−0.0088 (12)
C3	0.0483 (13)	0.0432 (13)	0.0643 (15)	0.0080 (10)	−0.0135 (11)	−0.0109 (11)
C4	0.0558 (15)	0.0514 (15)	0.0588 (15)	0.0078 (11)	−0.0084 (12)	−0.0061 (12)
C5	0.0498 (14)	0.0497 (15)	0.0685 (17)	0.0104 (11)	−0.0036 (12)	−0.0130 (12)
C6	0.0574 (15)	0.0506 (15)	0.0675 (17)	0.0120 (12)	−0.0141 (12)	−0.0055 (12)
C7	0.090 (2)	0.075 (2)	0.0570 (16)	0.0288 (16)	−0.0126 (15)	−0.0091 (14)
C8	0.0734 (18)	0.0662 (18)	0.0621 (17)	0.0249 (14)	−0.0063 (14)	−0.0151 (13)
C9	0.082 (2)	0.070 (2)	0.093 (2)	0.0347 (17)	−0.0182 (18)	−0.0072 (17)
C10	0.079 (2)	0.111 (3)	0.076 (2)	0.027 (2)	−0.0061 (17)	−0.0252 (19)
C11	0.079 (2)	0.089 (3)	0.118 (3)	0.0138 (19)	−0.013 (2)	−0.032 (2)
C12	0.099 (3)	0.115 (3)	0.108 (3)	0.029 (2)	−0.012 (2)	−0.040 (3)
C13	0.162 (5)	0.099 (3)	0.125 (4)	0.004 (3)	0.017 (3)	−0.033 (3)

Geometric parameters (Å, º)

S1—C1	1.662 (3)	C7—C8	1.363 (4)
S2—C1	1.745 (3)	C7—H7	0.9300
S2—C10	1.793 (3)	C8—H8	0.9300
O1—C6	1.359 (3)	C9—H9A	0.9600
O1—C9	1.420 (4)	C9—H9B	0.9600
N1—C1	1.330 (3)	C9—H9C	0.9600
N1—N2	1.378 (3)	C10—C11	1.450 (5)
N1—H1N	0.859 (10)	C10—H10A	0.9700
N2—C2	1.278 (3)	C10—H10B	0.9700
C2—C3	1.449 (3)	C11—C12	1.524 (5)
C2—H2	0.9300	C11—H11A	0.9700
C3—C4	1.382 (3)	C11—H11B	0.9700
C3—C8	1.389 (4)	C12—C13	1.446 (6)
C4—C5	1.382 (4)	C12—H12A	0.9700
C4—H4	0.9300	C12—H12B	0.9700
C5—C6	1.371 (4)	C13—H13A	0.9600
C5—H5	0.9300	C13—H13B	0.9600
C6—C7	1.387 (4)	C13—H13C	0.9600
C1—S2—C10	103.87 (16)	O1—C9—H9A	109.5
C6—O1—C9	118.4 (2)	O1—C9—H9B	109.5
C1—N1—N2	120.6 (2)	H9A—C9—H9B	109.5
C1—N1—H1N	119 (2)	O1—C9—H9C	109.5
N2—N1—H1N	120 (2)	H9A—C9—H9C	109.5
C2—N2—N1	115.6 (2)	H9B—C9—H9C	109.5
N1—C1—S1	120.9 (2)	C11—C10—S2	114.0 (3)
N1—C1—S2	112.76 (19)	C11—C10—H10A	108.7
S1—C1—S2	126.35 (16)	S2—C10—H10A	108.7
N2—C2—C3	120.9 (2)	C11—C10—H10B	108.7
N2—C2—H2	119.6	S2—C10—H10B	108.7
C3—C2—H2	119.6	H10A—C10—H10B	107.6
C4—C3—C8	117.8 (2)	C10—C11—C12	115.3 (3)
C4—C3—C2	120.4 (2)	C10—C11—H11A	108.4
C8—C3—C2	121.8 (2)	C12—C11—H11A	108.4
C3—C4—C5	121.7 (2)	C10—C11—H11B	108.4
C3—C4—H4	119.1	C12—C11—H11B	108.4
C5—C4—H4	119.1	H11A—C11—H11B	107.5
C6—C5—C4	119.6 (2)	C13—C12—C11	114.1 (4)
C6—C5—H5	120.2	C13—C12—H12A	108.7
C4—C5—H5	120.2	C11—C12—H12A	108.7
O1—C6—C5	125.1 (2)	C13—C12—H12B	108.7
O1—C6—C7	115.7 (3)	C11—C12—H12B	108.7
C5—C6—C7	119.1 (2)	H12A—C12—H12B	107.6
C8—C7—C6	120.9 (3)	C12—C13—H13A	109.5
C8—C7—H7	119.5	C12—C13—H13B	109.5
C6—C7—H7	119.5	H13A—C13—H13B	109.5
C7—C8—C3	120.8 (3)	C12—C13—H13C	109.5
C7—C8—H8	119.6	H13A—C13—H13C	109.5
C3—C8—H8	119.6	H13B—C13—H13C	109.5
C1—N1—N2—C2	−174.5 (2)	C9—O1—C6—C7	176.9 (3)
N2—N1—C1—S1	178.96 (18)	C4—C5—C6—O1	178.8 (2)
N2—N1—C1—S2	−2.2 (3)	C4—C5—C6—C7	−1.0 (4)
C10—S2—C1—N1	179.3 (2)	O1—C6—C7—C8	−178.5 (3)
C10—S2—C1—S1	−1.9 (2)	C5—C6—C7—C8	1.4 (5)
N1—N2—C2—C3	−178.8 (2)	C6—C7—C8—C3	−0.3 (5)
N2—C2—C3—C4	179.5 (2)	C4—C3—C8—C7	−1.1 (4)
N2—C2—C3—C8	0.3 (4)	C2—C3—C8—C7	178.1 (3)
C8—C3—C4—C5	1.5 (4)	C1—S2—C10—C11	−102.1 (3)
C2—C3—C4—C5	−177.8 (2)	S2—C10—C11—C12	−173.2 (3)
C3—C4—C5—C6	−0.4 (4)	C10—C11—C12—C13	180.0 (4)
C9—O1—C6—C5	−3.0 (4)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the (C3–C8) ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1i	0.86 (1)	2.61 (2)	3.425 (3)	160 (3)
C9—H9C···Cg1ii	0.96	2.98	3.748 (4)	138

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

Funding Statement

This work was funded by Ministry of Science, Technology and Innovation Malaysia grant FRGS 01-13-11-986FR. Universiti Putra Malaysia grant RUGS 05-01-11-1243RU. Sunway University Sdn Bhd grant STR-RCTR-RCCM-001-2019.