research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

S-Benzyl 3-[1-(6-methyl­pyridin-2-yl)ethyl­­idene]di­thio­carbazate: crystal structure and Hirshfeld surface analysis

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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, School 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 20 January 2018; accepted 22 January 2018; online 31 January 2018)

In the title di­thio­carbazate ester, C16H17N3S2 (systematic name: (Z)-{[(benzyl­sulfan­yl)methane­thio­yl]amino}[1-(6-methyl­pyridin-2-yl)ethyl­idene]amine), the central methyl­idenehydrazinecarbodi­thio­ate (C2N2S2) core is almost planar (r.m.s. deviation = 0.0111 Å) and forms dihedral angles of 71.67 (3)° with the approximately orthogonally inclined thio­ester phenyl ring, and 7.16 (7)° with the approximately coplanar substituted pyridyl ring. The latter arrangement and the Z configuration about the imine-C=N bond allows for the formation of an intra­molecular hydrazine-N—H⋯N(pyrid­yl) hydrogen bond that closes an S(6) loop. In the crystal, phenyl-C—H⋯S(thione), methyl­ene-C—H⋯π(pyrid­yl), methyl­ene- and phenyl-C—H⋯π(phen­yl) contacts connect mol­ecules into supra­molecular layers propagating in the bc plane; the layers stack along the a axis with no directional inter­actions between them. The analysis of the Hirshfeld surface indicates the relative importance of an intra­layer phenyl-H⋯H(pyrid­yl) contact upon the mol­ecular packing.

1. Chemical context

Di­thio­carbaza­tes are compounds that contain both nitro­gen and sulfur donor atoms, which can react with ketones or aldehydes, via condensation, to yield Schiff bases. Different ligands can be obtained by introducing different organic substituents, which causes variation in their biological properties, although they may differ only slightly in their mol­ecular structures (Ali et al., 1977[Ali, M. A. & Tarafder, M. T. H. (1977). J. Inorg. Nucl. Chem. 39, 1785-1791.]; Tarafder et al., 2001[Tarafder, M. T. H., Kasbollah, A., Crouse, K. A., Ali, A. M., Yamin, B. M. & Fun, H.-K. (2001). Polyhedron, 20, 2363-2370.], 2002[Tarafder, M. T. H., Khoo, T., Crouse, K. A., Ali, A. M., Yamin, B. M. & Fun, H.-K. (2002). Polyhedron, 21, 2691-2698.]). Inter­est in this class of compound remains high as studies have shown that they possess anti-cancer (Mirza et al., 2014[Mirza, A. H., Hamid, M. H. S. A., Aripin, S., Karim, M. R., Arifuzzaman, Md., Ali, M. A. & Bernhardt, P. V. (2014). Polyhedron, 74, 16-23.]), anti-bacterial (Bhat et al., 2018[Bhat, R. A., Kumar, D., Malla, M. A., Bhat, S. U., Khan, Md. S., Manzoor, O., Srivastava, A., Naikoo, R. A., Mohsin, M. & Mir, M. A. (2018). J. Mol. Struct. 1156, 280-289.]), anti-fungal (Nithya et al., 2017[Nithya, P., Simpson, J. & Govindarajan, S. (2017). Inorg. Chim. Acta, 467, 180-193.]), anti-viral (Chew et al., 2004[Chew, K.-B., Tarafder, M. T. H., Crouse, K. A., Ali, A. M., Yamin, B. M. & Fun, H.-K. (2004). Polyhedron, 23, 1385-1392.]) and anti-inflammatory (Zangrando et al., 2015[Zangrando, E., Islam, M. T., Islam, M. A. A. A., Sheikh, M. C., Tarafder, M. T. H., Miyatake, R., Zahan, R. & Hossain, M. A. (2015). Inorg. Chim. Acta, 427, 278-284.]) properties. Pyridine derivatives have also been a subject of much inter­est since the 1930′s with the discovery of niacin for the treatment of dermatitis and dementia (Henry, 2004[Henry, G. D. (2004). Tetrahedron, 60, 6043-6061.]). 3-Amino­pyridine­carbaldehyde thio­semicarbazone is another pyridine-containing compound that has shown promising activity in advanced leukemia patients in a clinical phase I evaluation (Karp et al., 2008[Karp, J. E., Giles, F. J., Gojo, I., Morris, L., Greer, J., Johnson, B., Thein, M., Sznol, M. & Low, J. (2008). Leuk. Res. 32, 71-77.]). Although considerable work has been conducted on pyridine-derived Schiff bases and their biological activities, we report, as part of our research into the synthesis and characterization of pyridine-based Schiff bases and their metal complexes, the crystal structure and Hirshfeld surface analysis of a potentially tridentate Schiff base derived from the condensation of S-benzyl­dithio­carbazate with 2-acetyl-6-methyl pyridine.

[Scheme 1]

2. Structural commentary

The mol­ecular structure of (I)[link], Fig. 1[link], comprises three distinct almost planar residues with the central methyl­idenehydrazinecarbodi­thio­ate, C2N2S2, chromophore [r.m.s. deviation = 0.0111 Å] being flanked by the thio­ester-phenyl ring and the substituted pyridyl ring, forming dihedral angles of 71.67 (3) and 7.16 (7)°, respectively, indicating nearly orthogonal and co-planar dispositions, respectively; the dihedral angle between the outer rings is 65.79 (4)°. The configuration about the imine-C9=N2 bond [1.2924 (18) Å] is Z, resulting in the hydrazine-N1—H hydrogen atom being directed towards the pyridyl-N3 atom, enabling the formation of an inter­molecular amine-N1—H⋯N3(pyrid­yl) hydrogen bond that closes an S(6) loop, Table 1[link]. The pyridyl-methyl group is syn with the thione-S1 atom and at the same time is orientated to the opposite side of the mol­ecule to the imine-bound methyl group.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the (N3,C11–C15) and (C3—C8) rings, respectively.

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1N⋯N3 0.87 (1) 1.91 (2) 2.6123 (16) 138 (1)
C8—H8⋯S2i 0.95 2.90 3.6184 (16) 154
C2—H2ACg1ii 0.99 2.76 3.5325 (15) 135
C7—H7⋯Cg2iii 0.95 2.89 3.5760 (16) 130
C10—H10CCg2iv 0.98 2.68 3.5842 (15) 153
Symmetry codes: (i) x, y-1, z; (ii) [x, -y-{\script{1\over 2}}, z-{\script{3\over 2}}]; (iii) [-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iv) [x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}].
[Figure 1]
Figure 1
The mol­ecular structure of (I)[link], showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.

3. Supra­molecular features

The participation of the hydrazine-N1—H hydrogen and pyridyl-N3 atoms in the intra­molecular N—H⋯N hydrogen bond precludes their participation in inter­molecular inter­actions. The mol­ecular packing features weak phenyl-C8—H⋯S2(thione) inter­actions, leading to chains along the b-axis direction, and a number of C—H⋯π contacts, i.e. methyl­ene-C2—H⋯π(pyrid­yl), phenyl-C7—H⋯π(phen­yl) and methyl-C10—H⋯π(phen­yl), as detailed in Table 1[link]. The aforementioned contacts link mol­ecules into supra­molecular layers in the bc plane, Fig. 2[link]a. Layers stack along the a axis with no directional inter­actions between them, Fig. 2[link]b.

[Figure 2]
Figure 2
Mol­ecular packing in (I)[link], showing (a) a view of the supra­molecular layer sustained by C—H⋯S and C—H⋯π inter­actions and (b) a view of the unit-cell contents shown in projection down the b axis, highlighting the stacking of layers. The C—H⋯S and C—H⋯π inter­actions are shown as orange and purple dashed lines, respectively.

4. Analysis of the Hirshfeld surfaces

The Hirshfeld surfaces calculated for (I)[link] were performed in accord with recent studies on an organic mol­ecule (Tan et al., 2017[Tan, M. Y., Crouse, K. A., Ravoof, T. B. S. A., Jotani, M. M. & Tiekink, E. R. T. (2017). Acta Cryst. E73, o1001-o1008.]) and serve to provide insight into the influence of different inter­molecular inter­actions in the crystal. A very short (2.23 Å) intra-layer H⋯H contact between the phenyl-H4 and pyridyl-H15 atoms (Table 2[link]) is significant in the crystal of (I)[link] and is viewed as the bright-red spots near these atoms on the Hirshfeld surface mapped over dnorm in Fig. 3[link]a (labelled as `1'). The presence of the weak inter­molecular C—H⋯S contact involving the phenyl-C8 and thione-S2 atoms is evident from the diminutive red spots near these atoms in Fig. 3[link] (labelled as `2'). The faint-red spots near the phenyl-H7 and -C8 atoms in Fig. 3[link]b (labelled as `3') characterize the short surface C⋯H/H⋯C contacts and indicate the relative importance of this particular C—H⋯π contact compared with the other two C—H⋯π contacts summarized in Table 1[link]. The most prominent inter­layer contact appears to be a weak methyl-C16—H⋯S1(ester) inter­action (Table 2[link]). The donors and acceptors of inter­molecular inter­actions are also represented with blue and red regions, respectively, corresponding to positive and negative electrostatic potentials on the Hirshfeld surface mapped over electrostatic potential in Fig. 4[link]. The inter­molecular C—H⋯π contacts, involving donor atoms, and their reciprocal contacts, i.e. π⋯H—C, containing π-bond acceptors, on the Hirshfeld surface mapped with the shape-index property are illustrated in Fig. 5[link].

Table 2
Summary of short surface contacts (Å) in (I)

Contact Distance Symmetry operation
H4⋯H15 1.98 x, [{3\over 2}] − y, − [{1\over 2}] + z
H7⋯C8 2.74 -x, − [{1\over 2}] + y, [{1\over 2}] − z
H2A⋯C11 2.85 x, [{1\over 2}] − y, − [{1\over 2}] + z
H10C⋯ C3 2.86 x, [{1\over 2}] − y, [{1\over 2}] + z
H16C⋯S1 3.05 -x, −y, −z
[Figure 3]
Figure 3
Views of Hirshfeld surface mapped over dnorm for (I)[link]: (a) in the range −0.120 to +1.541 au highlighting short inter­atomic H⋯H contacts with yellow dashed lines and label `1' and (b) in the range −0.050 to +1.541 au highlighting short inter­atomic C⋯H/H⋯C contacts with black dashed lines and label `3'. Weak inter­molecular C—H⋯S/S⋯H—C contacts are indicated by sky-blue dashed lines and label `2' in both (a) and (b).
[Figure 4]
Figure 4
Two views of the Hirshfeld surface mapped over the electrostatic potential for (I)[link] in the range ±0.055 au. The red and blue regions represent negative and positive electrostatic potentials, respectively.
[Figure 5]
Figure 5
Two views of Hirshfeld surface mapped with shape-index properties for (I)[link] highlighting (a) C—H⋯π contacts and (b) their reciprocal i.e. π⋯H—C contacts, with red and blue dotted lines, respectively, and labels `1'–`3'.

The overall two-dimensional fingerprint plot for (I)[link], Fig. 6[link]a, and those delineated (McKinnon et al., 2007[McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814-3816.]) into H⋯H, C⋯H/H⋯C, S⋯H/H⋯S and N⋯H/H⋯N contacts are illustrated in Fig. 6[link]be; the percentage contributions from the different inter­atomic contacts to the Hirshfeld surface are summarized in Table 3[link]. The single tip at de + di ∼ 2.0 Å near the vertex of the cone-shaped distribution of points in the fingerprint plot delineated into H⋯H contacts (Fig. 6[link]b) indicate the significant influence of the short inter­atomic phenyl-H⋯H(pyrid­yl) contacts in the crystal mentioned above. The inter­molecular C—H⋯π inter­actions discussed earlier are characterized by short inter­atomic C⋯H/H⋯C contacts (Table 2[link]) and their presence are indicated by the distribution of points around a pair of peaks at de + di ∼ 2.8 Å in Fig. 6[link]c, and by the concave surfaces around the phenyl (C3–C8) and pyridyl (N3,C11–C15) rings on the Hirshfeld surface mapped over the electrostatic potential in Fig. 4[link]. The inter­molecular C8—H8⋯S2 contact in the crystal is characterized by the pair of forceps-like tips at de + di ∼ 2.8 Å in Fig. 6[link]d. The inter­atomic N⋯H/H⋯N contacts do not represent directional inter­actions as the inter­atomic separations are greater than sum of their van der Waals radii as evident from Fig. 6[link]e. Similarly, the other surface contacts summarized in Table 3[link] have negligible effect on the packing.

Table 3
Relative percentage contributions of close contacts to the Hirshfeld surface of (I)

H⋯H 45.1
C⋯H/H⋯C 25.6
S⋯H/H⋯S 16.8
N⋯H/H⋯N 8.8
C⋯S/S⋯C 2.1
S⋯N/N⋯S 0.9
C⋯C 0.7
[Figure 6]
Figure 6
(a) The full two-dimensional fingerprint plot for (I)[link] and fingerprint plots delineated into (b) H⋯H, (c) C⋯H/H⋯C, (d) S⋯H/H⋯S and (e) S⋯H/H⋯S contacts.

5. Database survey

As mentioned in the Chemical context, there is sustained inter­est in this class of compound and this is reflected by the observation there are four closely related structures available for comparison, varying in the S-bound group and substitution in the 2-pyridyl ring. In common with (I)[link], the derivative with the 4-methyl­benzyl ester and with a methyl group in the 5-position of the pyridyl ring, a Z-configuration is noted about the imine bond allowing for the formation of an intra­molecular hydrazine-N—H⋯N(pyrid­yl) hydrogen bond (Ravoof et al., 2015[Ravoof, T. B. S. A., Tiekink, E. R. T., Omar, S. A., Begum, S. Z. & Tahir, M. I. M. (2015). Acta Cryst. E71, o1071-o1072.]). By contrast, the three remaining analogues, i.e. the methyl ester with no substitution in the pyridyl ring (Basha et al., 2012[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.]), benzyl ester/4-methyl­pyridyl and 4-methyl­benzyl ester/4-methyl­pyridyl (Omar et al., 2014[Omar, S. A., Ravoof, T. B. S. A., Tahir, M. I. M. & Crouse, K. A. (2014). Transition Met. Chem. 39, 119-126.]), an E-configuration is found about the imine bond, a disposition that allows for the formation of inter­molecular thio­amide-N—H⋯S(thione) hydrogen bonds and eight-membered {⋯HNCS}2 synthons.

6. Synthesis and crystallization

All chemicals were of analytical grade and were used without any further purification. S-Benzyl­dithio­carbazate (SBDTC) was prepared according to the method published by Ali & Tarafder (1977[Ali, M. A. & Tarafder, M. T. H. (1977). J. Inorg. Nucl. Chem. 39, 1785-1791.]). Potassium hydroxide (11.4 g, 0.2 mol) was dissolved in absolute ethanol (70 ml) and to this solution hydrazine hydrate (10 g, 0.2 mol) was added. The mixture was then cooled in an ice bath followed by the dropwise addition of carbon di­sulfide (15.2 g, 0.2 mol) with constant stirring over 1 h. The two layers that formed were then separated using a separating funnel. The brown organic lower layer was dissolved in 40% ethanol. Benzyl chloride (25 ml, 0.2 mol) was then added dropwise into the mixture with vigorous stirring. The white product that formed was filtered off, washed with cold ethanol and dried in a desiccator over anhydrous silica gel. Pure SBDTC was obtained by recrystallization using absolute ethanol as the solvent. Yield: 75%, m.p. 397–399 K. SBDTC (1.98 g, 0.01 mol) was subsequently dissolved in hot aceto­nitrile (100 ml) and added to an equimolar solution of 2-acetyl-6-methyl pyridine (1.35 g, 0.01 mol) in ethanol (25 ml). The mixture was then heated on a water bath until the volume reduced to half. A yellow precipitate formed upon standing at room temperature for 1 h which was washed with cold ethanol. A small amount of product was dissolved in aceto­nitrile and left to stand for a week, after which yellow prisms suitable for single-crystal X-ray diffraction analysis formed. IR (cm−1): 2921 ν(N—H), 1560 ν(C=N), 1055 ν(N—N), 881 ν(CSS).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4[link]. 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 Uiso(H) set to 1.2–1.5Ueq(C). The nitro­gen-bound H atom was located in a difference Fourier map, but was refined with a distance restraint of N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.2Ueq(N).

Table 4
Experimental details

Crystal data
Chemical formula C16H17N3S2
Mr 315.44
Crystal system, space group Monoclinic, P21/c
Temperature (K) 100
a, b, c (Å) 17.0395 (3), 5.5354 (1), 16.4292 (2)
β (°) 91.355 (1)
V3) 1549.18 (4)
Z 4
Radiation type Cu Kα
μ (mm−1) 3.08
Crystal size (mm) 0.28 × 0.18 × 0.08
 
Data collection
Diffractometer Rigaku Oxford Diffraction Gemini E
Absorption correction Multi-scan (CrysAlis PRO; Agilent, 2011[Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England.])
Tmin, Tmax 0.561, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 29598, 3000, 2888
Rint 0.034
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.092, 1.04
No. of reflections 3000
No. of parameters 195
No. of restraints 1
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.40, −0.26
Computer programs: CrysAlis PRO (Agilent, 2011[Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]), DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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).

S-Benzyl 3-[1-(6-methylpyridin-2-yl)ethylidene]dithiocarbazate top
Crystal data top
C16H17N3S2F(000) = 664
Mr = 315.44Dx = 1.352 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.5418 Å
a = 17.0395 (3) ÅCell parameters from 16086 reflections
b = 5.5354 (1) Åθ = 3.7–71.4°
c = 16.4292 (2) ŵ = 3.08 mm1
β = 91.355 (1)°T = 100 K
V = 1549.18 (4) Å3Prism, yellow
Z = 40.28 × 0.18 × 0.08 mm
Data collection top
Rigaku Oxford Diffraction Gemini E
diffractometer
3000 independent reflections
Radiation source: Enhance X-ray source2888 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.034
Detector resolution: 16.1952 pixels mm-1θmax = 71.5°, θmin = 5.2°
ω scanh = 2020
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
k = 66
Tmin = 0.561, Tmax = 1.000l = 2020
29598 measured reflections
Refinement top
Refinement on F21 restraint
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.092 w = 1/[σ2(Fo2) + (0.0635P)2 + 0.6508P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
3000 reflectionsΔρmax = 0.40 e Å3
195 parametersΔρmin = 0.26 e Å3
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
xyzUiso*/Ueq
S10.36900 (2)0.02321 (6)0.35206 (2)0.01816 (12)
S20.20666 (2)0.21559 (6)0.30590 (2)0.01465 (12)
N10.29576 (7)0.3795 (2)0.42370 (7)0.0161 (3)
H1N0.3346 (8)0.396 (3)0.4582 (9)0.019*
N20.23272 (7)0.5327 (2)0.43063 (7)0.0156 (3)
N30.35999 (7)0.5890 (2)0.55123 (7)0.0151 (2)
C10.29438 (8)0.2120 (2)0.36453 (8)0.0144 (3)
C20.21915 (8)0.0396 (3)0.23758 (8)0.0168 (3)
H2A0.26090.00600.19820.020*
H2B0.23330.18720.26860.020*
C30.14062 (8)0.0702 (3)0.19410 (8)0.0141 (3)
C40.11330 (8)0.1021 (3)0.13811 (8)0.0166 (3)
H40.14560.23600.12530.020*
C50.03983 (8)0.0805 (3)0.10104 (8)0.0182 (3)
H50.02210.19920.06310.022*
C60.00811 (8)0.1147 (3)0.11931 (8)0.0178 (3)
H60.05860.12980.09400.021*
C70.01836 (9)0.2871 (3)0.17477 (9)0.0187 (3)
H70.01400.42110.18730.022*
C80.09226 (9)0.2646 (3)0.21221 (9)0.0166 (3)
H80.10970.38290.25040.020*
C90.23507 (8)0.6991 (2)0.48580 (8)0.0147 (3)
C100.16295 (8)0.8567 (3)0.48703 (8)0.0175 (3)
H10A0.12610.80580.44370.026*
H10B0.17801.02540.47830.026*
H10C0.13790.84110.53990.026*
C110.29926 (8)0.7469 (3)0.54680 (8)0.0146 (3)
C120.41782 (8)0.6242 (3)0.60655 (8)0.0167 (3)
C130.41666 (9)0.8185 (3)0.66067 (9)0.0203 (3)
H130.45800.83950.69990.024*
C140.35505 (9)0.9797 (3)0.65674 (9)0.0215 (3)
H140.35331.11260.69320.026*
C150.29548 (8)0.9452 (3)0.59868 (9)0.0192 (3)
H150.25281.05530.59450.023*
C160.48418 (9)0.4453 (3)0.60873 (10)0.0222 (3)
H16A0.47730.33030.56380.033*
H16B0.48440.35790.66060.033*
H16C0.53410.53090.60320.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0127 (2)0.0190 (2)0.0227 (2)0.00341 (12)0.00205 (14)0.00368 (13)
S20.01277 (19)0.0172 (2)0.01385 (19)0.00289 (12)0.00273 (13)0.00297 (12)
N10.0123 (6)0.0196 (6)0.0162 (6)0.0017 (5)0.0029 (4)0.0036 (5)
N20.0133 (6)0.0174 (6)0.0160 (6)0.0005 (5)0.0007 (4)0.0005 (4)
N30.0150 (6)0.0160 (6)0.0141 (5)0.0020 (5)0.0001 (4)0.0015 (4)
C10.0127 (7)0.0164 (7)0.0141 (6)0.0014 (5)0.0004 (5)0.0019 (5)
C20.0162 (7)0.0172 (7)0.0168 (6)0.0032 (5)0.0014 (5)0.0054 (5)
C30.0140 (6)0.0156 (6)0.0125 (6)0.0017 (5)0.0005 (5)0.0042 (5)
C40.0175 (7)0.0159 (7)0.0165 (6)0.0040 (5)0.0016 (5)0.0003 (5)
C50.0197 (7)0.0201 (7)0.0146 (6)0.0014 (6)0.0022 (5)0.0012 (5)
C60.0140 (7)0.0225 (7)0.0168 (6)0.0006 (5)0.0001 (5)0.0053 (6)
C70.0184 (7)0.0173 (7)0.0206 (7)0.0036 (5)0.0050 (6)0.0025 (5)
C80.0194 (7)0.0150 (7)0.0155 (6)0.0025 (5)0.0025 (5)0.0004 (5)
C90.0140 (7)0.0163 (7)0.0137 (6)0.0017 (5)0.0018 (5)0.0020 (5)
C100.0161 (7)0.0183 (7)0.0181 (6)0.0019 (6)0.0009 (5)0.0006 (5)
C110.0138 (7)0.0170 (7)0.0133 (6)0.0027 (5)0.0031 (5)0.0011 (5)
C120.0157 (7)0.0199 (7)0.0144 (6)0.0046 (5)0.0000 (5)0.0036 (5)
C130.0185 (7)0.0269 (8)0.0155 (7)0.0069 (6)0.0005 (5)0.0009 (6)
C140.0209 (8)0.0251 (8)0.0188 (7)0.0051 (6)0.0039 (6)0.0074 (6)
C150.0160 (7)0.0214 (7)0.0203 (7)0.0004 (6)0.0036 (5)0.0036 (6)
C160.0189 (7)0.0225 (8)0.0250 (7)0.0004 (6)0.0064 (6)0.0010 (6)
Geometric parameters (Å, º) top
S1—C11.6624 (14)C7—C81.394 (2)
S2—C11.7591 (14)C7—H70.9500
S2—C21.8199 (14)C8—H80.9500
N1—C11.3432 (18)C9—C111.4895 (19)
N1—N21.3754 (16)C9—C101.5074 (19)
N1—H1N0.865 (9)C10—H10A0.9800
N2—C91.2924 (18)C10—H10B0.9800
N3—C121.3390 (18)C10—H10C0.9800
N3—C111.3554 (18)C11—C151.392 (2)
C2—C31.5113 (19)C12—C131.396 (2)
C2—H2A0.9900C12—C161.503 (2)
C2—H2B0.9900C13—C141.378 (2)
C3—C81.392 (2)C13—H130.9500
C3—C41.397 (2)C14—C151.389 (2)
C4—C51.384 (2)C14—H140.9500
C4—H40.9500C15—H150.9500
C5—C61.392 (2)C16—H16A0.9800
C5—H50.9500C16—H16B0.9800
C6—C71.387 (2)C16—H16C0.9800
C6—H60.9500
C1—S2—C2102.63 (7)C7—C8—H8119.7
C1—N1—N2119.01 (11)N2—C9—C11127.48 (13)
C1—N1—H1N123.2 (12)N2—C9—C10114.20 (12)
N2—N1—H1N117.8 (12)C11—C9—C10118.31 (12)
C9—N2—N1119.09 (12)C9—C10—H10A109.5
C12—N3—C11119.42 (12)C9—C10—H10B109.5
N1—C1—S1121.52 (10)H10A—C10—H10B109.5
N1—C1—S2112.88 (10)C9—C10—H10C109.5
S1—C1—S2125.60 (8)H10A—C10—H10C109.5
C3—C2—S2105.26 (9)H10B—C10—H10C109.5
C3—C2—H2A110.7N3—C11—C15121.47 (13)
S2—C2—H2A110.7N3—C11—C9117.98 (12)
C3—C2—H2B110.7C15—C11—C9120.54 (13)
S2—C2—H2B110.7N3—C12—C13121.55 (14)
H2A—C2—H2B108.8N3—C12—C16117.48 (13)
C8—C3—C4118.60 (13)C13—C12—C16120.97 (13)
C8—C3—C2120.51 (13)C14—C13—C12119.43 (13)
C4—C3—C2120.81 (12)C14—C13—H13120.3
C5—C4—C3120.98 (13)C12—C13—H13120.3
C5—C4—H4119.5C13—C14—C15119.11 (14)
C3—C4—H4119.5C13—C14—H14120.4
C4—C5—C6120.09 (13)C15—C14—H14120.4
C4—C5—H5120.0C14—C15—C11119.02 (14)
C6—C5—H5120.0C14—C15—H15120.5
C7—C6—C5119.49 (13)C11—C15—H15120.5
C7—C6—H6120.3C12—C16—H16A109.5
C5—C6—H6120.3C12—C16—H16B109.5
C6—C7—C8120.32 (13)H16A—C16—H16B109.5
C6—C7—H7119.8C12—C16—H16C109.5
C8—C7—H7119.8H16A—C16—H16C109.5
C3—C8—C7120.53 (13)H16B—C16—H16C109.5
C3—C8—H8119.7
C1—N1—N2—C9177.73 (12)N1—N2—C9—C111.3 (2)
N2—N1—C1—S1179.30 (10)N1—N2—C9—C10179.55 (11)
N2—N1—C1—S21.64 (16)C12—N3—C11—C150.14 (19)
C2—S2—C1—N1175.99 (10)C12—N3—C11—C9178.65 (12)
C2—S2—C1—S13.02 (11)N2—C9—C11—N36.2 (2)
C1—S2—C2—C3171.62 (9)C10—C9—C11—N3172.96 (12)
S2—C2—C3—C8107.95 (12)N2—C9—C11—C15175.28 (14)
S2—C2—C3—C468.72 (14)C10—C9—C11—C155.57 (19)
C8—C3—C4—C50.2 (2)C11—N3—C12—C130.81 (19)
C2—C3—C4—C5176.92 (12)C11—N3—C12—C16179.56 (12)
C3—C4—C5—C60.0 (2)N3—C12—C13—C140.7 (2)
C4—C5—C6—C70.1 (2)C16—C12—C13—C14179.73 (13)
C5—C6—C7—C80.3 (2)C12—C13—C14—C150.2 (2)
C4—C3—C8—C70.4 (2)C13—C14—C15—C110.8 (2)
C2—C3—C8—C7177.14 (12)N3—C11—C15—C140.7 (2)
C6—C7—C8—C30.4 (2)C9—C11—C15—C14177.80 (13)
Hydrogen-bond geometry (Å, º) top
Cg1 and Cg2 are the centroids of the (N3,C11–C15) and (C3—C8) rings, respectively.
D—H···AD—HH···AD···AD—H···A
N1—H1N···N30.87 (1)1.91 (2)2.6123 (16)138 (1)
C8—H8···S2i0.952.903.6184 (16)154
C2—H2A···Cg1ii0.992.763.5325 (15)135
C7—H7···Cg2iii0.952.893.5760 (16)130
C10—H10C···Cg2iv0.982.683.5842 (15)153
Symmetry codes: (i) x, y1, z; (ii) x, y1/2, z3/2; (iii) x, y1/2, z+1/2; (iv) x, y1/2, z1/2.
Summary of short surface contacts (Å) in (I) top
ContactDistanceSymmetry operation
H4···H151.98x, 3/2 - y, - 1/2 + z
H7···C82.74-x, - 1/2 + y, 1/2 - z
H2A···C112.85x, 1/2 - y, - 1/2 + z
H10C··· C32.86x, 1/2 - y, 1/2 + z
H16C···S13.05-x, -y, -z
Relative percentage contributions of close contacts to the Hirshfeld surface of (I) top
H···H45.1
C···H/H···C25.6
S···H/H···S16.8
N···H/H···N8.8
C···S/S···C2.1
S···N/N···S0.9
C···C0.7
 

Footnotes

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

Acknowledgements

We thank the Department of Chemistry (Universiti Putra Malaysia; UPM) for access to facilities.

Funding information

This research was funded by UPM and the Malaysian Government under the Malaysian Fundamental Research Grant Scheme (FRGS No. 01-01-16-1833FR). CKC thanks the Malaysian government for the award of a MyBrain scholarship.

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