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ISSN: 2056-9890

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

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aDepartment of Chemistry, Faculty of Science, Universiti Putra Malaysia, UPM, Serdang 43400, Malaysia, bDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380001, 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 8 January 2020; accepted 12 January 2020; online 17 January 2020)

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—Cm—Cm—Cm = −173.2 (3)° and Cm—Cm—Cm—Cme = 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.

1. Chemical context

The di­thio­carbazate dianion, NH2NHCS2−, and its esters such as S-benzyl­dithio­carbazate (Tian et al., 1996[Tian, Y.-P., Duan, C.-Y., Lu, Z.-L., You, X.-Z., Fun, H. K. & Sivakumar, K. (1996). Transition Met. Chem. 21, 254-257.]) and S-methyl­dithio­carbazate (Ali et al., 2008[Ali, M. A., Mirza, A. H., Hamid, M. H. S. A., Bernhardt, P. V., Atchade, O., Song, X., Eng, G. & May, L. (2008). Polyhedron, 27, 977-984.]), 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[Bera, P., Kim, C.-H. & Seok, S. I. (2009). Inorg. Chim. Acta, 362, 2603-2608.]; Ali et al., 2012[Ali, M. A., Tan, A. L., Mirza, A. H., Santos, J. H. & Abdullah, A. H. (2012). Transition Met. Chem. 37, 651-659.]; Begum et al., 2017[Begum, M. S., Zangrando, E., Sheikh, M. C., Miyatake, R., Howlader, M. B. H., Rahman, M. N. & Ghosh, A. (2017). Transit. Met. Chem. 42, 553-563.]). 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[Ali, M. A., Mirza, A. H., Nazimuddin, M., Ahmed, R., Gahan, L. R. & Bernhardt, P. V. (2003). Polyhedron 22, 1471-1479.]) while complexation via two sulfur atoms, resulting in the formation of a four-membered chelate ring, is also possible (Rakha & Bekheit, 2000[Rakha, T. H. & Bekheit, M. M. (2000). Chem. Pharm. Bull. 48, 914-919.]). It is also known that slight changes in mol­ecular structure can give rise to different coordination geometries (Chan et al., 2008[Chan, M. E., Crouse, K. A., Tahir, M. I. M., Rosli, R., Umar-Tsafe, N. & Cowley, A. R. (2008). Polyhedron, 27, 1141-1149.]). In a continuation of structural studies of S-alkyl di­thio­carbazate esters (Yusof et al., 2015[Yusof, E. N. S. A. Md, Ravoof, T. B. S. A., Tiekink, E. R. T., Veerakumarasivam, A., Crouse, K. A., Tahir, M. I. M. & Ahmad, H. (2015). Int. J. Mol. Sci. 16, 11034-11054.]; Low et al., 2016[Low, M. L., Maigre, L. M., Tahir, M. I. M. T., Tiekink, E. R. T., Dorlet, P., Guillot, R., Ravoof, T. B., Rosli, R., Pagès, J.-M., Policar, C., Delsuc, N. & Crouse, K. A. (2016). Eur. J. Med. Chem. 120, 1-12.]; Omar et al., 2018[Omar, S. A., Chah, C. K., Ravoof, T. B. S. A., Jotani, M. M. & Tiekink, E. R. T. (2018). Acta Cryst. E74, 261-266.]) and their complexation to metals with accompanying evaluation of biological potential (Low et al., 2016[Low, M. L., Maigre, L. M., Tahir, M. I. M. T., Tiekink, E. R. T., Dorlet, P., Guillot, R., Ravoof, T. B., Rosli, R., Pagès, J.-M., Policar, C., Delsuc, N. & Crouse, K. A. (2016). Eur. J. Med. Chem. 120, 1-12.]; Ravoof et al., 2017[Ravoof, T. B. S. A., Crouse, K. A., Tiekink, E. R. T., Tahir, M. I. M., Yusof, E. N. M. & Rosli, R. (2017). Polyhedron, 133, 383-392.]; Yusof et al., 2017[Yusof, E. N. M., Ravoof, T. B. S. A., Tahir, M. I. M., Jotani, M. M. & Tiekink, E. R. T. (2017). Acta Cryst. E73, 397-402.]), herein the crystal and mol­ecular structures of the title hydrazine carbodi­thio­ate ester, (I)[link], along with the calculated Hirshfeld surfaces and computational chemistry are described.

[Scheme 1]

2. Structural commentary

The mol­ecular structure of (I)[link], Fig. 1[link], 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]
Figure 1
The mol­ecular structure of (I)[link] showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level.

3. Supra­molecular features

With the exception of thio­amide-N—H⋯S(thio­amide) hydrogen bonding between centrosymmetrically related mol­ecules, Table 1[link], and which sustain a dimeric aggregate via an eight-membered {⋯HNCS}2 synthon, the mol­ecular packing is largely devoid of directional inter­actions (Spek, 2020[Spek, A. L. (2020). Acta Cryst. E76, 1-11.]). 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[link](a), being the only other identified supra­molecular association. Globally, chains pack without specific inter­actions between them, Fig. 2[link](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 DA D—H⋯A
N1—H1N⋯S1i 0.86 (1) 2.61 (2) 3.425 (3) 160 (3)
C9—H9CCg1ii 0.96 2.98 3.748 (4) 138
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x+1, y, z.
[Figure 2]
Figure 2
Mol­ecular packing in (I)[link]: (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.

4. Analysis of the Hirshfeld surfaces

The calculation of the Hirshfeld surfaces for (I)[link] were conducted as per a literature precedent (Tan et al., 2019[Tan, S. L., Jotani, M. M. & Tiekink, E. R. T. (2019). Acta Cryst. E75, 308-318.]) employing Crystal Explorer 17 (Turner et al., 2017[Turner, M. J., Mckinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). Crystal Explorer 17. The University of Western Australia.]). The presence of bright-red spots near the thio­amide-S1 and H1N atoms on the Hirshfeld surface mapped over dnorm shown in Fig. 3[link] 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[link]. The inter­molecular meth­oxy-C—H⋯π(meth­oxy­benzene) inter­action is also evident in Fig. 4[link], as the light-blue and light-red regions around the participating atoms. Fig. 5[link] 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]
Figure 3
A view of the Hirshfeld surface for (I)[link] mapped over dnorm in the range −0.299 to +1.278 arbitrary units.
[Figure 4]
Figure 4
A view of the Hirshfeld surface for (I)[link] mapped over the electrostatic potential in the range −0.056 to +0.104 atomic units.
[Figure 5]
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)[link] 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[link](a)–(e), respectively; the percentage contributions from the different inter­atomic contacts are summarized in Table 2[link]. In the fingerprint plot delineated into H⋯H contacts, Fig. 6[link](b), a short inter­atomic H⋯H contact involving methyl­ene-H10B with a symmetry-related mate (H10B⋯H10B = 2.26 Å; symmetry operationx, 1 − y, 2 − z) and occurring between supra­molecular chains aligned along the a axis, is observed as a single peak at de + di ∼ 2.2 Å. In the fingerprint delineated into S⋯H/H⋯S contacts, shown in Fig. 6[link](c), the pair of well-defined spikes at de + di ∼ 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[link](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[link], are merged within the plot. Although the points in the fingerprint plot delineated into C⋯H/H⋯C contacts in Fig. 6[link](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[link](e), also show a pair of forceps-like tips at de + di ∼ 2.8 Å, i.e. at van der Waals distances. The contribution from the other inter­atomic contacts summarized in Table 2[link] have negligible influence on the calculated Hirshfeld surface of (I)[link].

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
[Figure 6]
Figure 6
(a) The full two-dimensional fingerprint plot for (I)[link] 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.

5. Computational chemistry

The pairwise inter­action energies between mol­ecules in the crystal of (I)[link] were calculated by summing up four energy components, comprising electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) (Turner et al., 2017[Turner, M. J., Mckinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). Crystal Explorer 17. The University of Western Australia.]); 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[link]. As indicated in Table 3[link], 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[link] 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[link] 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 Eele, Edisp and Etot 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[link](a) and the thick green cylinders corresponding to the strong dispersive inter­actions provided by the methy­oxy-C—H⋯π(meth­oxy­benzene) inter­actions in Fig. 7[link](b).

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

Contact R (Å) Eele Epol Edis Erep Etot
N1—H1N⋯S1i 8.17 −59.2 −10.3 −17.1 66.6 −43.9
C9—H9CCg(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 ⋯H10Biv 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]
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)[link]. 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.

6. Database survey

Reflecting the inter­est in the chemistry of hydrazine carbodi­thio­ates related to (I)[link], 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[Fun, H.-K., Yip, B.-C., Tian, Y.-P., Duan, C.-Y., Lu, Z.-L. & You, X.-Z. (1996). Acta Cryst. C52, 87-89.]), n-hexyl (HUDJOH; Begum, Howlader et al., 2015[Begum, M. S., Howlader, M. B. H., Miyatake, R., Zangrando, E. & Sheikh, M. C. (2015). Acta Cryst. E71, o199.]), n-ocyl (XUFPAR; Begum, Zangrando et al., 2015[Begum, M. S., Zangrando, E., Sheikh, M. C., Miyatake, R. & Hossain, M. M. (2015). Acta Cryst. E71, o265-o266.]) and CH2Ph (YAHDAO; Fan et al., 2011[Fan, Z., Huang, Y.-L., Wang, Z., Guo, H.-Q. & Shan, S. (2011). Acta Cryst. E67, o3011.]) 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)[link].

7. 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)[link] 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)[link] 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-d6; 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-d6; 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.

8. 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 = 0.93–0.97 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2Ueq(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
Mr 282.41
Crystal system, space group Triclinic, P[\overline{1}]
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)
V3) 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[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England.])
Tmin, Tmax 0.868, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 9986, 3395, 2244
Rint 0.029
(sin θ/λ)max−1) 0.651
 
Refinement
R[F2 > 2σ(F2)], wR(F2), 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[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England.]), SHELXT2014 (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXL2014 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). 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, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

(E)-{[(Butylsulfanyl)methanethioyl]amino}(4-methoxybenzylidene)amine: top
Crystal data top
C13H18N2OS2Z = 2
Mr = 282.41F(000) = 300
Triclinic, P1Dx = 1.274 Mg m3
a = 4.7131 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.6998 (8) ÅCell parameters from 2643 reflections
c = 13.5696 (8) Åθ = 3.0–27.5°
α = 85.225 (5)°µ = 0.35 mm1
β = 81.139 (5)°T = 295 K
γ = 87.379 (5)°Block, colourless
V = 736.35 (8) Å30.30 × 0.25 × 0.20 mm
Data collection top
Agilent Technologies SuperNova Dual
diffractometer with Atlas detector
3395 independent reflections
Radiation source: SuperNova (Mo) X-ray Source2244 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.029
Detector resolution: 10.4041 pixels mm-1θmax = 27.6°, θmin = 3.1°
ω scanh = 65
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
k = 1515
Tmin = 0.868, Tmax = 1.000l = 1717
9986 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: mixed
wR(F2) = 0.174H 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 parametersΔρmax = 0.52 e Å3
1 restraintΔρmin = 0.45 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
S10.33083 (16)0.60524 (6)0.62361 (6)0.0687 (3)
S20.51025 (19)0.46574 (8)0.80444 (6)0.0813 (3)
O11.7337 (5)0.06363 (18)0.75096 (16)0.0786 (6)
N10.7095 (5)0.43553 (19)0.62083 (18)0.0561 (5)
H1N0.720 (7)0.443 (3)0.5569 (8)0.084 (11)*
N20.8729 (5)0.35129 (18)0.66505 (17)0.0565 (5)
C10.5246 (5)0.5021 (2)0.6764 (2)0.0542 (6)
C21.0604 (5)0.2985 (2)0.6052 (2)0.0548 (6)
H21.08050.31940.53690.066*
C31.2420 (5)0.2067 (2)0.64237 (19)0.0513 (6)
C41.4425 (5)0.1496 (2)0.5769 (2)0.0556 (6)
H41.46390.17270.50900.067*
C51.6119 (5)0.0592 (2)0.6098 (2)0.0564 (6)
H51.74460.02180.56430.068*
C61.5834 (6)0.0250 (2)0.7098 (2)0.0584 (6)
C71.3874 (7)0.0833 (3)0.7765 (2)0.0747 (9)
H71.37000.06150.84460.090*
C81.2198 (6)0.1720 (3)0.7436 (2)0.0679 (8)
H81.08900.20980.78940.081*
C91.9271 (7)0.1303 (3)0.6861 (3)0.0823 (9)
H9A1.82250.16660.64260.123*
H9B2.02230.18790.72510.123*
H9C2.06710.08150.64680.123*
C100.2533 (8)0.5676 (3)0.8614 (3)0.0891 (10)
H10A0.13710.59960.81200.107*
H10B0.12650.52770.91510.107*
C110.3805 (8)0.6607 (3)0.9014 (3)0.0946 (11)
H11A0.48930.70570.84630.114*
H11B0.51500.62820.94430.114*
C120.1686 (9)0.7410 (4)0.9608 (3)0.1070 (13)
H12A0.03410.77410.91810.128*
H12B0.05980.69641.01620.128*
C130.3015 (12)0.8331 (4)0.9999 (4)0.1316 (18)
H13A0.39180.80311.05580.197*
H13B0.15770.89031.02110.197*
H13C0.44330.86690.94860.197*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0716 (5)0.0568 (5)0.0760 (5)0.0258 (3)0.0129 (4)0.0078 (3)
S20.0890 (6)0.0890 (6)0.0667 (5)0.0326 (5)0.0197 (4)0.0151 (4)
O10.0860 (14)0.0684 (13)0.0780 (14)0.0319 (11)0.0154 (11)0.0007 (10)
N10.0550 (12)0.0495 (12)0.0640 (14)0.0135 (10)0.0122 (11)0.0076 (10)
N20.0542 (12)0.0460 (12)0.0711 (14)0.0134 (9)0.0180 (10)0.0076 (10)
C10.0493 (13)0.0468 (14)0.0676 (16)0.0048 (11)0.0119 (11)0.0089 (12)
C20.0512 (14)0.0495 (14)0.0649 (15)0.0073 (11)0.0123 (12)0.0088 (12)
C30.0483 (13)0.0432 (13)0.0643 (15)0.0080 (10)0.0135 (11)0.0109 (11)
C40.0558 (15)0.0514 (15)0.0588 (15)0.0078 (11)0.0084 (12)0.0061 (12)
C50.0498 (14)0.0497 (15)0.0685 (17)0.0104 (11)0.0036 (12)0.0130 (12)
C60.0574 (15)0.0506 (15)0.0675 (17)0.0120 (12)0.0141 (12)0.0055 (12)
C70.090 (2)0.075 (2)0.0570 (16)0.0288 (16)0.0126 (15)0.0091 (14)
C80.0734 (18)0.0662 (18)0.0621 (17)0.0249 (14)0.0063 (14)0.0151 (13)
C90.082 (2)0.070 (2)0.093 (2)0.0347 (17)0.0182 (18)0.0072 (17)
C100.079 (2)0.111 (3)0.076 (2)0.027 (2)0.0061 (17)0.0252 (19)
C110.079 (2)0.089 (3)0.118 (3)0.0138 (19)0.013 (2)0.032 (2)
C120.099 (3)0.115 (3)0.108 (3)0.029 (2)0.012 (2)0.040 (3)
C130.162 (5)0.099 (3)0.125 (4)0.004 (3)0.017 (3)0.033 (3)
Geometric parameters (Å, º) top
S1—C11.662 (3)C7—C81.363 (4)
S2—C11.745 (3)C7—H70.9300
S2—C101.793 (3)C8—H80.9300
O1—C61.359 (3)C9—H9A0.9600
O1—C91.420 (4)C9—H9B0.9600
N1—C11.330 (3)C9—H9C0.9600
N1—N21.378 (3)C10—C111.450 (5)
N1—H1N0.859 (10)C10—H10A0.9700
N2—C21.278 (3)C10—H10B0.9700
C2—C31.449 (3)C11—C121.524 (5)
C2—H20.9300C11—H11A0.9700
C3—C41.382 (3)C11—H11B0.9700
C3—C81.389 (4)C12—C131.446 (6)
C4—C51.382 (4)C12—H12A0.9700
C4—H40.9300C12—H12B0.9700
C5—C61.371 (4)C13—H13A0.9600
C5—H50.9300C13—H13B0.9600
C6—C71.387 (4)C13—H13C0.9600
C1—S2—C10103.87 (16)O1—C9—H9A109.5
C6—O1—C9118.4 (2)O1—C9—H9B109.5
C1—N1—N2120.6 (2)H9A—C9—H9B109.5
C1—N1—H1N119 (2)O1—C9—H9C109.5
N2—N1—H1N120 (2)H9A—C9—H9C109.5
C2—N2—N1115.6 (2)H9B—C9—H9C109.5
N1—C1—S1120.9 (2)C11—C10—S2114.0 (3)
N1—C1—S2112.76 (19)C11—C10—H10A108.7
S1—C1—S2126.35 (16)S2—C10—H10A108.7
N2—C2—C3120.9 (2)C11—C10—H10B108.7
N2—C2—H2119.6S2—C10—H10B108.7
C3—C2—H2119.6H10A—C10—H10B107.6
C4—C3—C8117.8 (2)C10—C11—C12115.3 (3)
C4—C3—C2120.4 (2)C10—C11—H11A108.4
C8—C3—C2121.8 (2)C12—C11—H11A108.4
C3—C4—C5121.7 (2)C10—C11—H11B108.4
C3—C4—H4119.1C12—C11—H11B108.4
C5—C4—H4119.1H11A—C11—H11B107.5
C6—C5—C4119.6 (2)C13—C12—C11114.1 (4)
C6—C5—H5120.2C13—C12—H12A108.7
C4—C5—H5120.2C11—C12—H12A108.7
O1—C6—C5125.1 (2)C13—C12—H12B108.7
O1—C6—C7115.7 (3)C11—C12—H12B108.7
C5—C6—C7119.1 (2)H12A—C12—H12B107.6
C8—C7—C6120.9 (3)C12—C13—H13A109.5
C8—C7—H7119.5C12—C13—H13B109.5
C6—C7—H7119.5H13A—C13—H13B109.5
C7—C8—C3120.8 (3)C12—C13—H13C109.5
C7—C8—H8119.6H13A—C13—H13C109.5
C3—C8—H8119.6H13B—C13—H13C109.5
C1—N1—N2—C2174.5 (2)C9—O1—C6—C7176.9 (3)
N2—N1—C1—S1178.96 (18)C4—C5—C6—O1178.8 (2)
N2—N1—C1—S22.2 (3)C4—C5—C6—C71.0 (4)
C10—S2—C1—N1179.3 (2)O1—C6—C7—C8178.5 (3)
C10—S2—C1—S11.9 (2)C5—C6—C7—C81.4 (5)
N1—N2—C2—C3178.8 (2)C6—C7—C8—C30.3 (5)
N2—C2—C3—C4179.5 (2)C4—C3—C8—C71.1 (4)
N2—C2—C3—C80.3 (4)C2—C3—C8—C7178.1 (3)
C8—C3—C4—C51.5 (4)C1—S2—C10—C11102.1 (3)
C2—C3—C4—C5177.8 (2)S2—C10—C11—C12173.2 (3)
C3—C4—C5—C60.4 (4)C10—C11—C12—C13180.0 (4)
C9—O1—C6—C53.0 (4)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the (C3–C8) ring.
D—H···AD—HH···AD···AD—H···A
N1—H1N···S1i0.86 (1)2.61 (2)3.425 (3)160 (3)
C9—H9C···Cg1ii0.962.983.748 (4)138
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z.
The percentage contributions of interatomic contacts to the Hirshfeld surface for (I) top
ContactPercentage contribution
H···H58.4
S···H/H···S17.1
C···H/H···C8.2
O···H/H···O4.9
C···N/N···C4.2
C···C3.0
S···N/N···S1.7
N···H/H···N0.9
C···O/O···C0.9
C···S/S···C0.7
A summary of interaction energies (kJ mol-1) calculated for (I) top
ContactR (Å)EeleEpolEdisErepEtot
N1—H1N···S1i8.17-59.2-10.3-17.166.6-43.9
C9—H9C···Cg(C3–C8)ii4.71-2.2-3.8-64.035.9-38.8
S1 ···H4iii6.85-15.6-5.2-19.319.6-25.1
H10B ···H10Biv10.74-1.0-0.3-11.35.7-7.5
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.
 

Footnotes

Additional correspondence author, e-mail: kacrouse@gmail.com.

Funding information

Financial support from the Ministry of Science, Technology and Innovation Malaysia and the Universiti Putra Malaysia (RUGS 05-01-11-1243RU and FRGS 01-13-11-986FR) as well as scholarships (MyBrain15 and Graduate Research Fellowship) for AFR are gratefully acknowledged. Crystallographic research at Sunway University is supported by Sunway University Sdn Bhd (grant No. STR-RCTR-RCCM-001-2019).

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