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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 10| October 2015| Pages 1236-1241

Crystal structure of 1-(4-methyl­phen­yl)-3-(propan-2-yl­­idene­amino)­thio­urea

CROSSMARK_Color_square_no_text.svg

aDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380001, India, bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and cCentre for Chemical Crystallography, Faculty of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
*Correspondence e-mail: edward.tiekink@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 15 September 2015; accepted 20 September 2015; online 26 September 2015)

In the title thio­semicarbazone, C11H15N3S, the p-tolyl-N—H and imino-N—H groups are anti and syn, respectively, to the central thione-S atom. This allows for the formation of an intra­molecular p-tolyl-N—H⋯N(imino) hydrogen bond. The mol­ecule is twisted with the dihedral angle between the p-tolyl ring and the non-hydrogen atoms of the N=CMe2 residue being 29.27 (8)°. The crystal packing features supra­molecular layers lying in the bc plane whereby centrosymmetric aggregates sustained by eight-membered thio­amide {⋯HNCS}2 synthons are linked by further N—H⋯S hydrogen bonds. Layers are connected via methyl-C—H⋯π inter­actions. The supra­molecular aggregation was further investigated by an analysis of the Hirshfeld surface and comparison made to related structures.

1. Chemical context

The reaction between an alcohol or amine (primary or secondary) with N-alkyl- or N-aryl-iso­thio­cyanides usually results in the formation of thio­carbamides. For example, in the case of reactions involving a monofunctional alcohol, the reaction proceeds in the following manner: R—OH + R′N=C=S → ROC(=S)N(H)R′ (Ho et al., 2005[Ho, S. Y., Bettens, R. P. A., Dakternieks, D., Duthie, A. & Tiekink, E. R. T. (2005). CrystEngComm, 7, 682-689.]). Often, reactions are facilitated by initially employing an alkali metal hydroxide as the base and later adding an acid, e.g. HCl (Ho et al., 2005[Ho, S. Y., Bettens, R. P. A., Dakternieks, D., Duthie, A. & Tiekink, E. R. T. (2005). CrystEngComm, 7, 682-689.]). Such mol­ecules are of inter­est as when deprotonated, they can function as effective thiol­ate ligands for phosphanegold(I) derivatives, which display biological activity. For example, Ph3PAu[SC(O–alk­yl)=N(ar­yl)] com­pounds exhibit significant cytotoxicity against a variety of cancer cell lines and mechanistic studies show that they can kill cancer cells by initiating a variety of apoptotic pathways, both extrinsic and intrinsic (Yeo, Ooi et al., 2013[Yeo, C. I., Ooi, K. K., Akim, A. Md., Ang, K. P., Fairuz, Z. A., Halim, S. N. B. A., Ng, S. W., Seng, H.-L. & Tiekink, E. R. T. (2013). J. Inorg. Biochem. 127, 24-38.]; Ooi, Yeo et al., 2015[Ooi, K. K., Yeo, C. I., Ang, K.-P., Akim, A. Md., Cheah, Y.-K., Halim, S. N. A., Seng, H.-L. & Tiekink, E. R. T. (2015). J. Biol. Inorg. Chem. 20, 855-873.]). Related species, i.e. Ph3PAu[SC(O–alk­yl)=N(p-tol­yl)], exhibit potency against Gram-positive bacteria (Yeo, Sim et al., 2013[Yeo, C. I., Sim, J.-H., Khoo, C.-H., Goh, Z.-J., Ang, K.-P., Cheah, Y.-K., Fairuz, Z. A., Halim, S. N. B. A., Ng, S. W., Seng, H.-L. & Tiekink, E. R. T. (2013). Gold Bull. 46, 145-152.]). Over and above these considerations, systematic studies into the structural chemistry of these mol­ecules, which have proven relatively easy to crystallize, have been of some inter­est in crystal engineering endeavours (Ho et al., 2006[Ho, S. Y., Cheng, E. C.-C., Tiekink, E. R. T. & Yam, V. W.-W. (2006). Inorg. Chem. 45, 8165-8174.]; Kuan et al., 2008[Kuan, F. S., Yei Ho, S., Tadbuppa, P. P. & Tiekink, E. R. T. (2008). CrystEngComm, 10, 548-564.]). In the course of studies to increase the functionality of the thio­carbamide mol­ecules, bipodal {1,4-[MeOC(=S)N(H)]2C6H4} was successfully synthesized along with binuclear phosphanegold(I) complexes (Yeo, Khoo et al., 2015[Yeo, C. I., Khoo, C.-H., Chu, W.-C., Chen, B.-J., Chu, P.-L., Sim, J.-H., Cheah, Y.-K., Ahmad, J., Halim, S. N. A., Seng, H.-L., Ng, S., Otero-de-la-Roza, A. & Tiekink, E. R. T. (2015). RSC Adv. 5, 41401-41411.]). Recent attempts at expanding this chemistry by using thio­urea as an amine donor have been undertaken. As reported very recently, 1:2 reactions between thio­urea and R′N=C=S resulted in the isolation of salts containing 1,2,3-thia­zole-based cations resulting from 1:1 cyclizations (Yeo, Tan et al., 2015[Yeo, C. I., Tan, Y. S. & Tiekink, E. R. T. (2015). Acta Cryst. E71, 1159-1164.]). Herein, the product of an analogous reaction involving a bifunctional amine, i.e. H2NNH2 (hydrazine) with (p-tol­yl)N=C=S, conducted in acetone solution, is described, namely the thio­semicarbazone, (I)[link]. Mol­ecules related to (I)[link] and especially their metal complexes continue to attract attention owing to potential biological activity (Dilworth & Hueting, 2012[Dilworth, J. R. & Hueting, R. (2012). Inorg. Chim. Acta, 389, 3-15.]; Lukmantara et al., 2013[Lukmantara, A. Y., Kalinowski, D. S., Kumar, N. & Richardson, D. R. (2013). Org. Biomol. Chem. 11, 6414-6425.]; Su et al., 2013[Su, W., Qian, Q., Li, P., Lei, X., Xiao, Q., Huang, S., Huang, C. & Cui, J. (2013). Inorg. Chem. 52, 12440-12449.]).

[Scheme 1]

1.1. Structural commentary

The mol­ecular structure of (I)[link], Fig. 1[link], comprises three planar regions. The central NC(=S)N chromophore (the r.m.s. deviation of the fitted atoms is 0.0020 Å) has anti- and syn-dispositions of the N1- and N2-bound H atoms, respectively, with respect to the central thione-S1 atom. The N1-bound H atom is syn to the imino-N3 atom allowing for the formation of a five-membered loop via an N1—H⋯N3 hydrogen bond, Table 1[link]. The central plane forms dihedral angles of 23.49 (4)° with the propan-2-yl­idene­amino residue (N=CMe2; r.m.s. deviation for the C3N atoms = 0.0002 Å) and 43.30 (5)° with the p-tolyl ring. Overall, the mol­ecule is twisted as qu­anti­fied by the dihedral angle between the outer planes of 29.27 (8)°.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1N⋯N3 0.88 (1) 2.09 (2) 2.572 (2) 114 (1)
N1—H1N⋯S1i 0.88 (1) 2.87 (2) 3.5618 (17) 137 (2)
N2—H2N⋯S1ii 0.88 (2) 2.57 (2) 3.4373 (16) 169 (2)
C8—H8CCg1iii 0.98 2.81 3.716 (2) 154
Symmetry codes: (i) [x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]; (ii) -x, -y, -z+1; (iii) -x+1, -y, -z+1.
[Figure 1]
Figure 1
The mol­ecular structure of (I)[link] showing displacement ellipsoids at the 70% probability level.

Two P21/c polymorphs have been reported for the parent compound, i.e. having a phenyl rather than a p-tolyl substit­uent (Jian et al., 2005[Jian, F.-F., Bai, Z.-S., Xiao, H.-L. & Li, K. (2005). Acta Cryst. E61, o653-o654.]; Venkatraman et al., 2005[Venkatraman, R., Swesi, A. T. & Yamin, B. M. (2005). Acta Cryst. E61, o3914-o3916.]); the structure of (I)[link] also crystallizes in the P21/c space group. As revealed from the data collated in Table 2[link], there is a high degree of concordance in the key bond lengths and angles for the three mol­ecules, as might be expected. However, there are some notable differences in the torsion-angle data as well as in the dihedral angles between the three least-squares planes discussed above, Table 2[link]. From these and the overlay diagram shown in Fig. 2[link], it is apparent that the mol­ecular structure of (I)[link] more closely matches that observed in the polymorph reported by Venkatraman et al. (2005[Venkatraman, R., Swesi, A. T. & Yamin, B. M. (2005). Acta Cryst. E61, o3914-o3916.]) rather than that described by Jian et al. (2005[Jian, F.-F., Bai, Z.-S., Xiao, H.-L. & Li, K. (2005). Acta Cryst. E61, o653-o654.]). This conclusion is also vindicated in the unit cell data, i.e. a = 12.225 (3), b = 7.618 (2), c = 11.639 (3) Å, β = 102.660 (4)° reported for the former (Venkatraman et al., 2005[Venkatraman, R., Swesi, A. T. & Yamin, B. M. (2005). Acta Cryst. E61, o3914-o3916.]).

Table 2
Geometric data (Å, °) for (I)[link] and two polymorphs of (II)

Parameter (I) Form a of (II)a Form b of (II)b
N2—N3 1.397 (2) 1.386 (2) 1.392 (2)
C1—S1 1.6873 (18) 1.6816 (17) 1.6826 (17)
C1—N1 1.350 (2) 1.337 (2) 1.343 (2)
C1—N2 1.350 (2) 1.359 (2) 1.348 (2)
C2—N1 1.422 (2) 1.420 (2) 1.425 (2)
C9—N3 1.280 (2) 1.279 (2) 1.276 (2)
       
C1—N1—C2 127.79 (16) 129.98 (14) 127.97 (14)
C1—N2—N3 117.72 (15) 118.17 (14) 118.33 (14)
N2—N3—C9 117.91 (15) 118.85 (15) 117.73 (14)
S1—C1—N1 125.45 (14) 126.00 (13) 125.75 (13)
S1—C1—N2 120.00 (14) 119.37 (13) 119.50 (12)
N1—C1—N2 114.54 (16) 114.63 (15) 114.74 (15)
       
S1—C1—N2—N3 −169.57 (12) 177.46 (12) −170.56 (12)
C1—N1—C2—C3 132.2 (2) −153.87 (18) 131.10 (19)
C1—N2—N3—C9 −165.78 (16) 168.43 (16) −165.85 (15)
       
CN2S / C3N 23.49 (4) 13.19 (8) 22.42 (9)
CN2S / ar­yl 43.30 (5) 39.26 (6) 43.90 (6)
C3N / ar­yl 29.27 (8) 40.15 (8) 30.18 (8)
Notes: (a) Jian et al. (2005[Jian, F.-F., Bai, Z.-S., Xiao, H.-L. & Li, K. (2005). Acta Cryst. E61, o653-o654.]); (b) Venkatraman et al. (2005[Venkatraman, R., Swesi, A. T. & Yamin, B. M. (2005). Acta Cryst. E61, o3914-o3916.]).
[Figure 2]
Figure 2
Overlay diagram of the mol­ecules in (I)[link], red image, and (II), forms a (green) and b (blue). The mol­ecules have been overlapped so that the central NC(=S)N chromophores are coincident.

2. NMR invesitgations

The conformation of (I)[link] was also investigated in CDCl3 solution by NMR methods. Assignments were made with the aid of the inter­pretative program, Chemdraw Ultra (CambridgeSoft Corporation, 2002[CambridgeSoft Corporation (2002). CHEMDRAW Ultra. Cambridge, USA.]). On the basis of multiple 1H and 13C{1H} resonances for the methyl groups of the propan-2-yl­idene­amino residue, it appears that the (propan-2-yl­idene­amino)­thio­urea residue has a locked configuration, consistent with the persistence of the intra­molecular N1—H⋯N3 hydrogen bond in CDCl3 solution.

3. Supra­molecular features

In the crystal, N—H⋯S and C—H⋯π inter­actions provide identifiable points of contact between mol­ecules; these inter­actions are qu­anti­fied in Table 1[link]. Centrosymmetrically related mol­ecules are connected by pairs of amide-N2—H⋯S1 hydrogen bonds, forming eight-membered thio­amide {⋯HNCS}2 synthons. These are connected into supra­molecular layers in the bc plane by amide-N1—H⋯S1 hydrogen bonds so that the S1 atom accepts two hydrogen bonds, Fig. 3[link]. The p-tolyl groups protrude to either side of each layer and inter-digitate along the a axis with adjacent layers allowing for the formation of methyl-C8—H⋯π(C2–C7) inter­actions, thereby consolidating the three-dimensional architecture, Fig. 4[link].

[Figure 3]
Figure 3
Supra­molecular layer in the bc plane in the crystal packing of (I)[link]. Centrosymmetric aggregates mediated by eight-membered thio­amide {⋯HNCS}2 synthons (shown as orange dashed lines) are linked by additional amide-N—H⋯S hydrogen bonds, shown as blue dashed lines.
[Figure 4]
Figure 4
A view of the unit cell contents of (I)[link] shown in projection down the b axis. Supra­molecular layers, illustrated in Fig. 3[link], are linked via C—H⋯π inter­actions, shown as purple dashed lines, leading to a three-dimensional architecture.

4. Analysis of the Hirshfeld surfaces

The crystal packing was further investigated by an analysis of the Hirshfeld surface (Spackman & Jayatilaka, 2009[Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19-32.]) employing CrystalExplorer (Wolff et al., 2012[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.]). Fingerprint plots (Rohl et al., 2008[Rohl, A. L., Moret, M., Kaminsky, W., Claborn, K., McKinnon, J. J. & Kahr, B. (2008). Cryst. Growth Des. 8, 4517-4525.]) were calculated, as were the electrostatic potentials using TONTO (Spackman et al., 2008[Spackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). CrystEngComm, 10, 377-388.]; Jayatilaka et al., 2005[Jayatilaka, D., Grimwood, D. J., Lee, A., Lemay, A., Russel, A. J., Taylo, C., Wolff, S. K., Chenai, C. & Whitton, A. (2005). TONTO - A System for Computational Chemistry. Available at: https://hirshfeldsurface.net/]) integrated into CrystalExplorer; the electrostatic potentials were mapped on the Hirshfeld surfaces using the STO–3G basis set at the level of Hartree–Fock theory over a range of ±0.075 au.

Two views of the Hirshfeld surface mapped over dnorm are shown in Fig. 5[link]a and b. The deep-red depressions at the S1 and N2 atoms (Fig. 5[link]a) confirm their role as an acceptor and donor in the hydrogen-bonding scheme, respectively. This is also evident from the dark-red and blue regions, respectively, on the Hirshfeld surface mapped over the calculated electrostatic potential (Fig. 5[link]c). The diminutive red spots near S1 and N1 (Fig. 5[link]b) indicate their involvement in the inter­molecular N—H⋯S hydrogen bond.

[Figure 5]
Figure 5
Views of the Hirshfeld surface for (I)[link]: (a) and (b) mapped over dnorm, and (c) mapped over the calculated electrostatic potential.

The overall two-dimensional fingerprint plot (Fig. 6[link]a) and those delineated into H⋯H, S⋯H/H⋯S, N⋯H/H⋯N and C⋯H/H⋯C H⋯H (Fig. 6[link]bd, respectively) inter­actions operating in the crystal structure of (I)[link] are illustrated in Fig. 6[link]; the relative contributions are summarized in Table 3[link]. The prominent pair of sharp spikes of equal length (de + di = 2.45 Å; Fig. 6[link]b) with a 15.2% contribution due to S⋯H/H⋯S contacts to the Hirshfeld surfaces also suggest the presence of these inter­actions in the crystal packing. The light-red region near N3 (Fig. 5[link]a) and diminutive red spot near N1—H (Fig. 5[link]b) are consistent with relatively smaller contributions from N⋯H/H⋯N contacts, i.e. 2.5 and 3.0%, respectively, and are indicative of the weak intra­molecular hydrogen bond. The strength of such an inter­action can be visualized from the 2D fingerprint plot corresponding to N⋯H/ H⋯N contacts (Fig. 6[link]c). The bright-orange spot in the surface mapped with de (within a red circle in Fig. 7[link]) about the aryl ring and a light-blue region around the tolyl-hydrogen atom, H8C (Fig. 7[link]), suggest a contribution from the C—H⋯π inter­action (Table 1[link]). This is also evident through distinct pair of `wings' in the fingerprint plot corresponding to C⋯H/H⋯C contacts (Fig. 6[link]d). The wing at the top, left belongs to C—H donors, while that at the bottom, right corresponds to the surface around π-acceptors with 11.3 and 7.8% contribution from C⋯H and H⋯C contacts, respectively. The H⋯H contacts reflected in the middle of scattered points in Fig. 6[link]e provide the most significant contribution, i.e. 57.0%, to the Hirshfeld surface arising from a side-ways approach. The small, flat segments delineated by the blue outline in the surface mapped with curvedness (Fig. 8[link]) and the small (i.e. 0.7%) contribution from C⋯C contacts to the surface indicates the absence of ππ stacking inter­actions in the structure.

Table 3
Relative contribution (%) to inter­molecular inter­actions calculated from the Hirshfeld surface

Contact Contribution
H⋯H 57.0
S⋯H/H⋯S 15.2
N⋯H/H⋯N 5.5
C⋯H/H⋯C 19.1
C⋯C 0.7
N⋯N 1.4
C⋯N 0.8
C⋯S 0.2
others 0.1
[Figure 6]
Figure 6
2D Fingerprint plots for (I)[link]: (a) full, (b) delineated to show S⋯H/H⋯S, (c) N⋯H/H⋯N, (d) C⋯H/H⋯C, and (e) H⋯H inter­actions.
[Figure 7]
Figure 7
View of the Hirshfeld surface for (I)[link] mapped over de.
[Figure 8]
Figure 8
Hirshfeld surfaces for (I)[link] mapped over curvedness.

5. Database survey

According to a search of the Cambridge Structural Database (Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]), there are no direct analogues of (I)[link], either in the coordinated or uncoordinated form. As mentioned in the Structural commentary, the parent compound has been characterized in two polymorphic forms (Jian et al., 2005[Jian, F.-F., Bai, Z.-S., Xiao, H.-L. & Li, K. (2005). Acta Cryst. E61, o653-o654.]; Venkatraman et al., 2005[Venkatraman, R., Swesi, A. T. & Yamin, B. M. (2005). Acta Cryst. E61, o3914-o3916.]). The parent compound, LH, has also been observed to coordinate metal centres. Thus, monodentate coordination via the thione-S atom was observed in a neutral complex [ZnCl2(LH)2] (Bel'skii et al., 1987[Bel'skii, V. K., Prisyazhnyuk, A. I., Kolchinskii, E. V. & Koksharova, T. V. (1987). J. Struct. Chem. 27, 808-811.]). By contrast, a chelating mode via thione-S and imino-N atoms was observed in each of the charged complexes [CoBr(LH)2]Br (Dessy et al., 1978[Dessy, G., Fares, V., Scaramuzza, L., Tomlinson, A. A. B. & De Munno, G. (1978). J. Chem. Soc. Dalton Trans. pp. 1549-1554.]) and [(η6-p-cymene)RuCl(LH)]Cl (Su et al., 2013[Su, W., Qian, Q., Li, P., Lei, X., Xiao, Q., Huang, S., Huang, C. & Cui, J. (2013). Inorg. Chem. 52, 12440-12449.]). The most closely related structure having the p-tolyl substituent but variations at the imino-N atom is one where one methyl group has been substituted by a phenyl (Zhang et al., 2011[Zhang, Y.-L., Wu, C.-Z. & Zhang, F.-J. (2011). Acta Cryst. E67, o1547.]). This is also a twisted mol­ecule with the dihedral angle between the p-tolyl and NC3 residues being 65.44 (7)°.

6. Synthesis and crystallization

To p-tolyl iso­thio­cyanate (Sigma–Aldrich; 10 mmol, 1.49 g) in acetone (20 ml) was added hydrazine monohydrate (Sigma–Aldrich; 10 mmol, 0.76 ml). The resulting mixture was stirred for 4 h at room temperature. Both chloro­form (20 ml) and aceto­nitrile (20 ml) were then added, and the resulting mixture left for slow evaporation. Light-brown crystals were obtained after 2 weeks. Yield: 2.012 g (91%). M.p. 412–413 K. 1H NMR (400 MHz, CDCl3, 298 K): 9.19 (s, br, 1H, NH—N), 8.56 (s, br, 1H, NH), 7.49 (d, 2H, m-aryl, J = 8.28 Hz), 7.17 (d, 2H, o-aryl, J = 8.24 Hz), 2.34 (s, 3H, aryl-CH3), 2.05 (s, 3H, CH3), 1.94 (s, 3H, CH3). 13C NMR (400 MHz, CDCl3, 298 K): 176.4 [CS], 149.6 [C(CH3)2], 135.8 [Cipso], 135.4 [Cpara], 129.3 [Cmeta], 124.5 [Cortho], 25.3 [CH3], 21.0 [aryl-CH3], 16.9 [CH3, syn to N—H]. IR (cm−1): ν(N—H) 3240, 3168 (m), ν(C=N) 1514 (vs), ν(C—N) 1267 (s), ν(C=S) 1188 (vs).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4[link]. Carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2–1.5Ueq(C). The N-bound H atoms were located in a difference Fourier map but were 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 C11H15N3S
Mr 221.32
Crystal system, space group Monoclinic, P21/c
Temperature (K) 100
a, b, c (Å) 13.7289 (13), 7.4341 (7), 11.5757 (11)
β (°) 102.690 (1)
V3) 1152.58 (19)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.25
Crystal size (mm) 0.12 × 0.05 × 0.03
 
Data collection
Diffractometer Bruker SMART APEX CCD
Absorption correction Multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.])
Tmin, Tmax 0.970, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections 10739, 2646, 2052
Rint 0.050
(sin θ/λ)max−1) 0.650
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.098, 1.02
No. of reflections 2646
No. of parameters 147
No. of restraints 2
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.27, −0.27
Computer programs: APEX2 and SAINT (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014/7 (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.]), QMol (Gans & Shalloway, 2001[Gans, J. & Shalloway, D. (2001). J. Mol. Graphics Modell. 19, 557-559.]), 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


Chemical context top

The reaction between an alcohol or amine (primary or secondary) with N-alkyl- or N-aryl-iso­thio­cyanides usually results in the formation of thio­carbamides. For example, in the case of reactions involving a monofunctional alcohol, the reaction proceeds in the following manner: R—OH + R'NCS ROC( S)N(H)R' (Ho et al., 2005). Often, reactions are facilitated by initially employing an alkali metal hydroxide as the base and later adding an acid, e.g. HCl (Ho et al., 2005). Such molecules are of inter­est as when deprotonated, they can function as effective thiol­ate ligands for phosphanegold(I) derivatives, which display biological activity. For example, Ph3PAu[SC(O–alkyl)N(aryl)] compounds exhibit significant cytotoxicity against a variety of cancer cell lines and mechanistic studies show that they can kill cancer cells by initiating a variety of apoptotic pathways, both extrinsic and intrinsic (Yeo, Ooi et al., 2013; Ooi, Yeo et al., 2015). Related species, i.e. Ph3PAu[SC(O–alkyl) N(p-tolyl)], exhibit potency against Gram-positive bacteria (Yeo, Sim et al., 2013). Over and above these considerations, systematic studies into the structural chemistry of these molecules, which have proven relatively easy to crystallize, have been of some inter­est in crystal engineering endeavours (Ho et al., 2006; Kuan et al., 2008). In the course of studies to increase the functionality of the thio­carbamide molecules, bipodal {1,4-[MeOC(S)N(H)]2C6H4} was successfully synthesized along with binuclear phosphanegold(I) complexes (Yeo, Khoo et al., 2015). Recent attempts at expanding this chemistry by using thio­urea as an amine donor have been undertaken. As reported very recently, 1:2 reactions between thio­urea and R'NCS resulted in the isolation of salts containing 1,2,3-thia­zole-based cations resulting from 1:1 cyclizations (Yeo, Tan et al., 2015). Herein, the product of an analogous reaction involving a bifunctional amine, i.e. H2NNH2 (hydrazine) with (p-tolyl)NCS, conducted in acetone solution, is described, namely the thio­semicarbazone, (I). Molecules related to (I) and especially their metal complexes continue to attract attention owing to potential biological activity (Dilworth & Hueting, 2012; Lukmantara et al., 2013; Su et al., 2013).

Structural commentary top

The molecular structure of (I), Fig. 1, comprises three planar regions. The central NC(S)N chromophore (the r.m.s. deviation of the fitted atoms is 0.0020 Å) has anti- and syn-dispositions of the N1- and N2-bound H atoms, respectively, with respect to the central thione-S1 atom. The N1-bound H atom is syn to the imino-N3 atom allowing for the formation of a five-membered loop via an N1—H···N3 hydrogen bond, Table 1. The central plane forms dihedral angles of 23.49 (4)° with the propan-2-yl­idene­amino residue (NCMe2; r.m.s. deviation for the C3N atoms = 0.0002 Å) and 43.30 (5)° with the p-tolyl ring. Overall, the molecule is twisted as qu­anti­fied by the dihedral angle between the outer planes of 29.27 (8)°.

Two P21/c polymorphs have been reported for the parent compound, i.e. having a phenyl rather than a p-tolyl substituent (Jian et al., 2005; Venkatraman et al., 2005); the structure of (I) also crystallizes in the P21/c space group. As revealed from the data collated in Table 2, there is a high degree of concordance in the key bond lengths and angles for the three molecules, as might be expected. However, there are some notable differences in the torsion-angle data as well as in the dihedral angles between the three least-squares planes discussed above, Table 2. From these and the overlay diagram shown in Fig. 2, it is apparent that the molecular structure of (I) more closely matches that observed in the polymorph reported by Venkatraman et al. (2005) rather than that described by Jian et al. (2005). This conclusion is also vindicated in the unit cell data, i.e. a = 12.225 (3), b = 7.618 (2), c = 11.639 (3) Å, β = 102.660 (4)° reported for the former (Venkatraman et al., 2005).

NMR invesitgations top

The conformation of (I) was also investigated in CDCl3 solution by NMR methods. Assignments were made with the aid of the inter­pretative program, Chemdraw Ultra (CambridgeSoft Corporation, 2002). On the basis of multiple 1H and 13C{1H} resonances for the methyl groups of the propan-2-yl­idene­amino residue, it appears that the (propan-2-yl­idene­amino)­thio­urea residue has a locked configuration, consistent with the persistence of the intra­molecular N1—H···N3 hydrogen bond in CDCl3 solution.

Supra­molecular features top

In the crystal, N—H···S and C—H···π inter­actions provide identifiable points of contact between molecules; these inter­actions are qu­anti­fied in Table 1. Centrosymmetrically related molecules are connected by pairs of amide-N2—H···S1 hydrogen bonds, forming eight-membered thio­amide {···HNCS}2 synthons. These are connected into supra­molecular layers in the bc plane by amide-N1—H···S1 hydrogen bonds so that the S1 atom accepts two hydrogen bonds, Fig. 3. The p-tolyl groups protrude to either side of each layer and inter-digitate along the a axis with adjacent layers allowing for the formation of methyl-C8—H···π(C2–C7) inter­actions, thereby consolidating the three-dimensional architecture, Fig. 4.

Analysis of the Hirshfeld surfaces top

The crystal packing was further investigated by an analysis of the Hirshfeld surface (Spackman & Jayatilaka, 2009) employing CrystalExplorer (Wolff et al., 2012). Fingerprint plots (Rohl et al., 2008) were calculated, as were the electrostatic potentials using TONTO (Spackman et al., 2008; Jayatilaka et al., 2005) integrated into CrystalExplorer; the electrostatic potentials were mapped on the Hirshfeld surfaces using the STO–3G basis set at the level of Hartree–Fock theory over a range of ±0.075 au.

Two views of the Hirshfeld surface mapped over dnorm are shown in Figs 5a and b. The deep-red depressions at the S1 and N2 atoms (Fig. 5a) confirm their role as an acceptor and donor in the hydrogen-bonding scheme, respectively. This is also evident from the dark-red and blue regions, respectively, on the Hirshfeld surface mapped over the calculated electrostatic potential (Fig. 5c). The diminutive red spots near S1 and N1 (Fig. 5b) indicate their involvement in the inter­molecular N—H···S hydrogen bond.

The overall two-dimensional fingerprint plot (Fig. 6a) and those delineated into H···H, S···H/H···S, N···H/H···N and C···H/H···C (Figs 6b--d, respectively) inter­actions operating in the crystal structure of (I) are illustrated in Fig. 6; the relative contributions are summarized in Table 3. The prominent pair of sharp spikes of equal length (de + di = 2.45 Å; Fig. 6b) with a 15.2% contribution due to S···H/H···S contacts to the Hirshfeld surfaces also suggest the presence of these inter­actions in the crystal packing. The light-red region near N3 (Fig. 5a) and diminutive red spot near N1—H (Fig. 5b) are consistent with relatively smaller contributions from N···H/H···N contacts, i.e. 2.5 and 3.0 %, respectively, and are indicative of the weak intra­molecular hydrogen bond. The strength of such an inter­action can be visualized from the 2D fingerprint plot corresponding to N···H/ H···N contacts (Fig. 6c). The bright-orange spot in the surface mapped with de (within a red circle in Fig. 7) about the aryl ring and a light-blue region around the tolyl-hydrogen atom, H8C (Fig. 7), suggest a contribution from the C—H···π inter­action (Table 1). This is also evident through distinct pair of `wings' in the fingerprint plot corresponding to C···H/H···C contacts (Fig. 6d). The wing at the top, left belongs to C—H donors, while that at the bottom, right corresponds to the surface around π-acceptors with 11.3 and 7.8% contribution from C···H and H···C contacts, respectively. The H···H contacts reflected in the middle of scattered points in Fig. 6d provide the most significant contribution, i.e. 57.0%, to the Hirshfeld surface arising from a side-ways approach. The small, flat segments delineated by blue outline in the surface mapped with curvedness (Fig. 8) and the small (i.e. 0.7%) contribution from C···C contacts to the surface indicates the absence of ππ stacking inter­actions in the structure.

Database survey top

According to a search of the Cambridge Structural Database (Groom & Allen, 2014), there are no direct analogues of (I), either in the coordinated or uncoordinated form. As mentioned in the Structural commentary, the parent compound has been characterized in two polymorphic forms (Jian et al., 2005; Venkatraman et al., 2005). The parent compound, LH, has also been observed to coordinate metal centres. Thus, monodentate coordination via the thione-S atom was observed in a neutral complex [ZnCl2(LH)2] (Bel'skii et al., 1987). By contrast, a chelating mode via thione-S and imino-N atoms was observed in each of the charged complexes [CoBr(LH)2]Br (Dessy et al., 1978) and [(η6-p-cymene)RuCl(LH)]Cl (Su et al., 2013). The most closely related structure having the p-tolyl substituent but variations at the imino-N atom is one where one methyl group has been substituted by a phenyl (Zhang et al., 2011). This is also a twisted molecule with the dihedral angle between the p-tolyl and NC3 residues being 65.44 (7)°.

Synthesis and crystallization top

To p-tolyl iso­thio­cyanate (Sigma–Aldrich; 10 mmol, 1.49 g) in acetone (20 ml) was added hydrazine monohydrate (Sigma–Aldrich; 10 mmol, 0.76 ml). The resulting mixture was stirred for 4 h at room temperature. Both chloro­form (20 ml) and aceto­nitrile (20 ml) were then added, and the resulting mixture left for slow evaporation. Light-brown crystals were obtained after 2 weeks. Yield: 2.012 g (91%). M.p. 412–413 K. 1H NMR (400 MHz, CDCl3, 298 K): 9.19 (s, br, 1H, NH—N), 8.56 (s, br, 1H, NH), 7.49 (d, 2H, m-aryl, J = 8.28 Hz), 7.17 (d, 2H, o-aryl, J = 8.24 Hz), 2.34 (s, 3H, aryl-CH3), 2.05 (s, 3H, CH3), 1.94 (s, 3H, CH3). 13C NMR (400 MHz, CDCl3, 298 K): 176.4 [CS], 149.6 [C(CH3)2], 135.8 [Cipso], 135.4 [Cpara], 129.3 [Cmeta], 124.5 [Cortho], 25.3 [CH3], 21.0 [aryl-CH3], 16.9 [CH3, syn to N—H]. IR (cm-1): ν(N—H) 3240, 3168 (m), ν(CN) 1514 (vs), ν(C—N) 1267 (s), ν(CS) 1188 (vs).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 4. For (I), carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2–1.5Ueq(C). The N-bound H-atoms were located in a difference Fourier map but were refined with a distance restraint of N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.2Ueq(N).

Related literature top

For related literature, see:

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001), DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 70% probability level.
[Figure 2] Fig. 2. Overlay diagram of the molecules in (I), red image, and (II), forms a (green) and b (blue). The molecules have been overlapped so that the central NC(S)N chromophores are coincident.
[Figure 3] Fig. 3. Supramolecular layer in the bc plane in the crystal packing of (I). Centrosymmetric aggregates mediated by eight-membered thioamide {···HNCS}2 synthons (shown as orange dashed lines) are linked by additional amide-N—H···S hydrogen bonds, shown as blue dashed lines.
[Figure 4] Fig. 4. A view of the unit cell contents of (I) shown in projection down the b axis. Supramolecular layers, illustrated in Fig. 3, are linked via C—H···π interactions, shown as purple dashed lines, leading to a three-dimensional architecture.
[Figure 5] Fig. 5. Views of the Hirshfeld surface for (I): (a) and (b) mapped over dnorm, and (c) mapped over the calculated electrostatic potential.
[Figure 6] Fig. 6. 2D Fingerprint plots for (I): (a) full, (b) delineated to show S···H/H···S, (c) N···H/H···N, (d) C···H/H···C, and (e) H···H interactions.
[Figure 7] Fig. 7. View of the Hirshfeld surface for (I) mapped over de.
[Figure 8] Fig. 8. Hirshfeld surfaces for (I) mapped over curvedness.
1-(4-Methylphenyl)-3-(propan-2-ylideneamino)thiourea top
Crystal data top
C11H15N3SF(000) = 472
Mr = 221.32Dx = 1.275 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 13.7289 (13) ÅCell parameters from 1590 reflections
b = 7.4341 (7) Åθ = 3.0–25.5°
c = 11.5757 (11) ŵ = 0.25 mm1
β = 102.690 (1)°T = 100 K
V = 1152.58 (19) Å3Prism, light-brown
Z = 40.12 × 0.05 × 0.03 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
2646 independent reflections
Radiation source: fine-focus sealed tube2052 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
φ and ω scansθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1717
Tmin = 0.970, Tmax = 0.993k = 99
10739 measured reflectionsl = 1315
Refinement top
Refinement on F22 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.098 w = 1/[σ2(Fo2) + (0.0332P)2 + 0.7356P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
2646 reflectionsΔρmax = 0.27 e Å3
147 parametersΔρmin = 0.27 e Å3
Crystal data top
C11H15N3SV = 1152.58 (19) Å3
Mr = 221.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.7289 (13) ŵ = 0.25 mm1
b = 7.4341 (7) ÅT = 100 K
c = 11.5757 (11) Å0.12 × 0.05 × 0.03 mm
β = 102.690 (1)°
Data collection top
Bruker SMART APEX CCD
diffractometer
2646 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2052 reflections with I > 2σ(I)
Tmin = 0.970, Tmax = 0.993Rint = 0.050
10739 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0412 restraints
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.27 e Å3
2646 reflectionsΔρmin = 0.27 e Å3
147 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
xyzUiso*/Ueq
S10.14991 (3)0.10760 (6)0.53754 (4)0.01865 (13)
N10.17657 (11)0.1754 (2)0.31707 (14)0.0179 (3)
H1N0.1468 (14)0.175 (3)0.2419 (9)0.023 (6)*
N20.01790 (11)0.1178 (2)0.33437 (14)0.0174 (3)
H2N0.0236 (13)0.073 (3)0.3744 (17)0.032 (6)*
N30.00516 (11)0.1118 (2)0.21071 (13)0.0177 (3)
C10.11491 (13)0.1348 (2)0.38949 (16)0.0158 (4)
C20.28274 (13)0.1793 (2)0.34532 (16)0.0174 (4)
C30.33249 (14)0.0928 (3)0.26883 (17)0.0218 (4)
H30.29550.03130.20130.026*
C40.43587 (14)0.0956 (3)0.29054 (17)0.0240 (4)
H40.46880.03570.23740.029*
C50.49234 (14)0.1841 (3)0.38822 (17)0.0218 (4)
C60.44118 (15)0.2713 (3)0.46362 (18)0.0240 (4)
H60.47810.33290.53110.029*
C70.33772 (14)0.2703 (3)0.44266 (17)0.0221 (4)
H70.30460.33190.49490.027*
C80.60488 (15)0.1844 (3)0.4134 (2)0.0316 (5)
H8A0.62990.30060.44750.047*
H8B0.62710.16500.33950.047*
H8C0.63070.08800.46950.047*
C90.09645 (13)0.1333 (2)0.15732 (16)0.0163 (4)
C100.18214 (14)0.1717 (3)0.21420 (17)0.0220 (4)
H10A0.15710.22600.29220.033*
H10B0.21690.05920.22330.033*
H10C0.22850.25490.16430.033*
C110.11855 (14)0.1185 (3)0.02523 (16)0.0201 (4)
H11A0.05610.12620.00240.030*
H11B0.16310.21660.00960.030*
H11C0.15090.00280.00110.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0168 (2)0.0218 (2)0.0167 (2)0.00133 (19)0.00219 (18)0.00207 (18)
N10.0133 (8)0.0252 (8)0.0149 (8)0.0017 (6)0.0020 (6)0.0013 (7)
N20.0148 (8)0.0226 (8)0.0149 (8)0.0018 (6)0.0033 (6)0.0014 (6)
N30.0182 (8)0.0196 (8)0.0152 (8)0.0022 (6)0.0037 (6)0.0000 (6)
C10.0149 (9)0.0129 (8)0.0196 (9)0.0003 (7)0.0041 (7)0.0007 (7)
C20.0151 (9)0.0177 (8)0.0194 (9)0.0003 (7)0.0040 (7)0.0046 (7)
C30.0200 (10)0.0272 (10)0.0181 (10)0.0009 (8)0.0043 (8)0.0008 (8)
C40.0194 (10)0.0308 (11)0.0239 (11)0.0016 (8)0.0092 (8)0.0014 (8)
C50.0171 (10)0.0233 (9)0.0247 (10)0.0006 (8)0.0038 (8)0.0080 (8)
C60.0203 (10)0.0258 (10)0.0245 (11)0.0051 (8)0.0018 (8)0.0010 (8)
C70.0206 (10)0.0224 (9)0.0251 (11)0.0026 (8)0.0087 (8)0.0040 (8)
C80.0172 (10)0.0364 (12)0.0408 (13)0.0008 (9)0.0053 (9)0.0085 (10)
C90.0182 (9)0.0121 (8)0.0186 (9)0.0004 (7)0.0041 (7)0.0009 (7)
C100.0178 (10)0.0288 (10)0.0179 (10)0.0056 (8)0.0009 (8)0.0009 (8)
C110.0199 (10)0.0228 (9)0.0167 (9)0.0008 (8)0.0020 (8)0.0004 (7)
Geometric parameters (Å, º) top
S1—C11.6873 (18)C5—C81.508 (3)
N1—C11.350 (2)C6—C71.387 (3)
N1—C21.422 (2)C6—H60.9500
N1—H1N0.876 (9)C7—H70.9500
N2—C11.350 (2)C8—H8A0.9800
N2—N31.397 (2)C8—H8B0.9800
N2—H2N0.875 (9)C8—H8C0.9800
N3—C91.280 (2)C9—C111.496 (2)
C2—C71.387 (3)C9—C101.496 (3)
C2—C31.389 (3)C10—H10A0.9800
C3—C41.386 (3)C10—H10B0.9800
C3—H30.9500C10—H10C0.9800
C4—C51.388 (3)C11—H11A0.9800
C4—H40.9500C11—H11B0.9800
C5—C61.395 (3)C11—H11C0.9800
C1—N1—C2127.79 (16)C2—C7—C6119.87 (18)
C1—N1—H1N113.3 (14)C2—C7—H7120.1
C2—N1—H1N117.3 (14)C6—C7—H7120.1
C1—N2—N3117.72 (15)C5—C8—H8A109.5
C1—N2—H2N118.4 (15)C5—C8—H8B109.5
N3—N2—H2N120.2 (15)H8A—C8—H8B109.5
C9—N3—N2117.91 (15)C5—C8—H8C109.5
N1—C1—N2114.54 (16)H8A—C8—H8C109.5
N1—C1—S1125.45 (14)H8B—C8—H8C109.5
N2—C1—S1120.00 (14)N3—C9—C11116.21 (16)
C7—C2—C3119.20 (17)N3—C9—C10126.34 (17)
C7—C2—N1122.98 (17)C11—C9—C10117.46 (16)
C3—C2—N1117.79 (17)C9—C10—H10A109.5
C4—C3—C2120.30 (18)C9—C10—H10B109.5
C4—C3—H3119.9H10A—C10—H10B109.5
C2—C3—H3119.9C9—C10—H10C109.5
C3—C4—C5121.42 (18)H10A—C10—H10C109.5
C3—C4—H4119.3H10B—C10—H10C109.5
C5—C4—H4119.3C9—C11—H11A109.5
C4—C5—C6117.52 (17)C9—C11—H11B109.5
C4—C5—C8121.55 (18)H11A—C11—H11B109.5
C6—C5—C8120.92 (18)C9—C11—H11C109.5
C7—C6—C5121.69 (18)H11A—C11—H11C109.5
C7—C6—H6119.2H11B—C11—H11C109.5
C5—C6—H6119.2
C1—N2—N3—C9165.78 (16)C3—C4—C5—C60.4 (3)
C2—N1—C1—N2171.29 (17)C3—C4—C5—C8178.82 (19)
C2—N1—C1—S19.3 (3)C4—C5—C6—C70.0 (3)
N3—N2—C1—N111.0 (2)C8—C5—C6—C7179.16 (18)
N3—N2—C1—S1169.57 (12)C3—C2—C7—C61.1 (3)
C1—N1—C2—C750.1 (3)N1—C2—C7—C6178.81 (17)
C1—N1—C2—C3132.2 (2)C5—C6—C7—C20.7 (3)
C7—C2—C3—C40.8 (3)N2—N3—C9—C11177.62 (15)
N1—C2—C3—C4178.60 (17)N2—N3—C9—C102.4 (3)
C2—C3—C4—C50.0 (3)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C2–C7 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1N···N30.88 (1)2.09 (2)2.572 (2)114 (1)
N1—H1N···S1i0.88 (1)2.87 (2)3.5618 (17)137 (2)
N2—H2N···S1ii0.88 (2)2.57 (2)3.4373 (16)169 (2)
C8—H8C···Cg1iii0.982.813.716 (2)154
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y, z+1; (iii) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C2–C7 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1N···N30.876 (11)2.091 (19)2.572 (2)113.7 (14)
N1—H1N···S1i0.876 (11)2.873 (15)3.5618 (17)136.7 (17)
N2—H2N···S1ii0.875 (19)2.57 (2)3.4373 (16)169.0 (19)
C8—H8C···Cg1iii0.982.813.716 (2)154
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y, z+1; (iii) x+1, y, z+1.
Geometric data (Å, °) for (I) and two polymorphs of (II) top
Parameter(I)Form a of (II)aForm b of (II)b
N2—N31.397 (2)1.386 (2)1.392 (2)
C1—S11.6873 (18)1.6816 (17)1.6826 (17)
C1—N11.350 (2)1.337 (2)1.343 (2)
C1—N21.350 (2)1.359 (2)1.348 (2)
C2—N11.422 (2)1.420 (2)1.425 (2)
C9—N31.280 (2)1.279 (2)1.276 (2)
C1—N1—C2127.79 (16)129.98 (14)127.97 (14)
C1—N2—N3117.72 (15)118.17 (14)118.33 (14)
N2—N3—C9117.91 (15)118.85 (15)117.73 (14)
S1—C1—N1125.45 (14)126.00 (13)125.75 (13)
S1—C1—N2120.00 (14)119.37 (13)119.50 (12)
N1—C1—N2114.54 (16)114.63 (15)114.74 (15)
S1—C1—N2—N3-169.57 (12)177.46 (12)-170.56 (12)
C1—N1—C2—C3132.2 (2)-153.87 (18)131.10 (19)
C1—N2—N3—C9-165.78 (16)168.43 (16)-165.85 (15)
CN2S / C3N23.49 (4)13.19 (8)22.42 (9)
CN2S / aryl43.30 (5)39.26 (6)43.90 (6)
C3N / aryl29.27 (8)40.15 (8)30.18 (8)
Notes: (a) Jian et al. (2005); (b) Venkatraman et al. (2005).
Relative contribution (%) to intermolecular interactions calculated from the Hirshfeld surface top
ContactContribution
H···H57.0
S···H/H···S15.2
N···H/H···N5.5
C···H/H···C19.1
C···C0.7
N···N1.4
C···N0.8
C···S0.2
others0.1

Experimental details

Crystal data
Chemical formulaC11H15N3S
Mr221.32
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)13.7289 (13), 7.4341 (7), 11.5757 (11)
β (°) 102.690 (1)
V3)1152.58 (19)
Z4
Radiation typeMo Kα
µ (mm1)0.25
Crystal size (mm)0.12 × 0.05 × 0.03
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.970, 0.993
No. of measured, independent and
observed [I > 2σ(I)] reflections
10739, 2646, 2052
Rint0.050
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.098, 1.02
No. of reflections2646
No. of parameters147
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.27, 0.27

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL2014/7 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

 

Footnotes

Additional correspondence author, e-mail: mmjotani@rediffmail.com.

Acknowledgements

This research was supported by the Trans-disciplinary Research Grant Scheme (TR002-2014A) provided by the Ministry of Education, Malaysia. The intensity data set was provided by the University of Malaya Crystallographic Laboratory.

References

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Volume 71| Part 10| October 2015| Pages 1236-1241
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