research communications
of 1-(4-methylphenyl)-3-(propan-2-ylideneamino)thiourea
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
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.
Keywords: crystal structure; hydrogen bonding; thiourea derivative; thiosemicarbazone; Hirshfeld surface analysis.
CCDC reference: 1425975
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). 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′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). 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). 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).
1.1. Structural commentary
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 (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)°.
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 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 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).
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2. NMR invesitgations
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.
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. 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.
4. Analysis of the Hirshfeld surfaces
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 Fig. 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 H⋯H (Fig. 6b–d, respectively) interactions operating in the 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. 6e 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) and the small (i.e. 0.7%) contribution from C⋯C contacts to the surface indicates the absence of π–π stacking interactions in the structure.
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5. Database survey
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)°.
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 . Carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the 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).
details are summarized in Table 4
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Supporting information
CCDC reference: 1425975
10.1107/S2056989015017624/hb7507sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015017624/hb7507Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015017624/hb7507Isup3.cml
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). 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'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). 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). 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).
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 (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)°.
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 β = 102.660 (4)° reported for the former (Venkatraman et al., 2005).
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 data, i.e. a = 12.225 (3), b = 7.618 (2), c = 11.639 (3) Å,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.
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.
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 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 π–π stacking interactions in the 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···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)°.
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).
Crystal data, data collection and structure
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 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).Data collection: APEX2 (Bruker, 2008); cell
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).Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 70% probability level. | |
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. | |
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. | |
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. | |
Fig. 5. Views of the Hirshfeld surface for (I): (a) and (b) mapped over dnorm, and (c) mapped over the calculated electrostatic potential. | |
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. | |
Fig. 7. View of the Hirshfeld surface for (I) mapped over de. | |
Fig. 8. Hirshfeld surfaces for (I) mapped over curvedness. |
C11H15N3S | F(000) = 472 |
Mr = 221.32 | Dx = 1.275 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.7289 (13) Å | Cell parameters from 1590 reflections |
b = 7.4341 (7) Å | θ = 3.0–25.5° |
c = 11.5757 (11) Å | µ = 0.25 mm−1 |
β = 102.690 (1)° | T = 100 K |
V = 1152.58 (19) Å3 | Prism, light-brown |
Z = 4 | 0.12 × 0.05 × 0.03 mm |
Bruker SMART APEX CCD diffractometer | 2646 independent reflections |
Radiation source: fine-focus sealed tube | 2052 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
φ and ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −17→17 |
Tmin = 0.970, Tmax = 0.993 | k = −9→9 |
10739 measured reflections | l = −13→15 |
Refinement on F2 | 2 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.041 | H 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 reflections | Δρmax = 0.27 e Å−3 |
147 parameters | Δρmin = −0.27 e Å−3 |
C11H15N3S | V = 1152.58 (19) Å3 |
Mr = 221.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.7289 (13) Å | µ = 0.25 mm−1 |
b = 7.4341 (7) Å | T = 100 K |
c = 11.5757 (11) Å | 0.12 × 0.05 × 0.03 mm |
β = 102.690 (1)° |
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 = 0.993 | Rint = 0.050 |
10739 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 2 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.27 e Å−3 |
2646 reflections | Δρmin = −0.27 e Å−3 |
147 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.14991 (3) | 0.10760 (6) | 0.53754 (4) | 0.01865 (13) | |
N1 | 0.17657 (11) | 0.1754 (2) | 0.31707 (14) | 0.0179 (3) | |
H1N | 0.1468 (14) | 0.175 (3) | 0.2419 (9) | 0.023 (6)* | |
N2 | 0.01790 (11) | 0.1178 (2) | 0.33437 (14) | 0.0174 (3) | |
H2N | −0.0236 (13) | 0.073 (3) | 0.3744 (17) | 0.032 (6)* | |
N3 | −0.00516 (11) | 0.1118 (2) | 0.21071 (13) | 0.0177 (3) | |
C1 | 0.11491 (13) | 0.1348 (2) | 0.38949 (16) | 0.0158 (4) | |
C2 | 0.28274 (13) | 0.1793 (2) | 0.34532 (16) | 0.0174 (4) | |
C3 | 0.33249 (14) | 0.0928 (3) | 0.26883 (17) | 0.0218 (4) | |
H3 | 0.2955 | 0.0313 | 0.2013 | 0.026* | |
C4 | 0.43587 (14) | 0.0956 (3) | 0.29054 (17) | 0.0240 (4) | |
H4 | 0.4688 | 0.0357 | 0.2374 | 0.029* | |
C5 | 0.49234 (14) | 0.1841 (3) | 0.38822 (17) | 0.0218 (4) | |
C6 | 0.44118 (15) | 0.2713 (3) | 0.46362 (18) | 0.0240 (4) | |
H6 | 0.4781 | 0.3329 | 0.5311 | 0.029* | |
C7 | 0.33772 (14) | 0.2703 (3) | 0.44266 (17) | 0.0221 (4) | |
H7 | 0.3046 | 0.3319 | 0.4949 | 0.027* | |
C8 | 0.60488 (15) | 0.1844 (3) | 0.4134 (2) | 0.0316 (5) | |
H8A | 0.6299 | 0.3006 | 0.4475 | 0.047* | |
H8B | 0.6271 | 0.1650 | 0.3395 | 0.047* | |
H8C | 0.6307 | 0.0880 | 0.4695 | 0.047* | |
C9 | −0.09645 (13) | 0.1333 (2) | 0.15732 (16) | 0.0163 (4) | |
C10 | −0.18214 (14) | 0.1717 (3) | 0.21420 (17) | 0.0220 (4) | |
H10A | −0.1571 | 0.2260 | 0.2922 | 0.033* | |
H10B | −0.2169 | 0.0592 | 0.2233 | 0.033* | |
H10C | −0.2285 | 0.2549 | 0.1643 | 0.033* | |
C11 | −0.11855 (14) | 0.1185 (3) | 0.02523 (16) | 0.0201 (4) | |
H11A | −0.0561 | 0.1262 | −0.0024 | 0.030* | |
H11B | −0.1631 | 0.2166 | −0.0096 | 0.030* | |
H11C | −0.1509 | 0.0028 | 0.0011 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0168 (2) | 0.0218 (2) | 0.0167 (2) | −0.00133 (19) | 0.00219 (18) | 0.00207 (18) |
N1 | 0.0133 (8) | 0.0252 (8) | 0.0149 (8) | −0.0017 (6) | 0.0020 (6) | 0.0013 (7) |
N2 | 0.0148 (8) | 0.0226 (8) | 0.0149 (8) | −0.0018 (6) | 0.0033 (6) | 0.0014 (6) |
N3 | 0.0182 (8) | 0.0196 (8) | 0.0152 (8) | −0.0022 (6) | 0.0037 (6) | 0.0000 (6) |
C1 | 0.0149 (9) | 0.0129 (8) | 0.0196 (9) | 0.0003 (7) | 0.0041 (7) | 0.0007 (7) |
C2 | 0.0151 (9) | 0.0177 (8) | 0.0194 (9) | −0.0003 (7) | 0.0040 (7) | 0.0046 (7) |
C3 | 0.0200 (10) | 0.0272 (10) | 0.0181 (10) | −0.0009 (8) | 0.0043 (8) | 0.0008 (8) |
C4 | 0.0194 (10) | 0.0308 (11) | 0.0239 (11) | 0.0016 (8) | 0.0092 (8) | 0.0014 (8) |
C5 | 0.0171 (10) | 0.0233 (9) | 0.0247 (10) | −0.0006 (8) | 0.0038 (8) | 0.0080 (8) |
C6 | 0.0203 (10) | 0.0258 (10) | 0.0245 (11) | −0.0051 (8) | 0.0018 (8) | −0.0010 (8) |
C7 | 0.0206 (10) | 0.0224 (9) | 0.0251 (11) | −0.0026 (8) | 0.0087 (8) | −0.0040 (8) |
C8 | 0.0172 (10) | 0.0364 (12) | 0.0408 (13) | −0.0008 (9) | 0.0053 (9) | 0.0085 (10) |
C9 | 0.0182 (9) | 0.0121 (8) | 0.0186 (9) | −0.0004 (7) | 0.0041 (7) | 0.0009 (7) |
C10 | 0.0178 (10) | 0.0288 (10) | 0.0179 (10) | 0.0056 (8) | 0.0009 (8) | 0.0009 (8) |
C11 | 0.0199 (10) | 0.0228 (9) | 0.0167 (9) | −0.0008 (8) | 0.0020 (8) | 0.0004 (7) |
S1—C1 | 1.6873 (18) | C5—C8 | 1.508 (3) |
N1—C1 | 1.350 (2) | C6—C7 | 1.387 (3) |
N1—C2 | 1.422 (2) | C6—H6 | 0.9500 |
N1—H1N | 0.876 (9) | C7—H7 | 0.9500 |
N2—C1 | 1.350 (2) | C8—H8A | 0.9800 |
N2—N3 | 1.397 (2) | C8—H8B | 0.9800 |
N2—H2N | 0.875 (9) | C8—H8C | 0.9800 |
N3—C9 | 1.280 (2) | C9—C11 | 1.496 (2) |
C2—C7 | 1.387 (3) | C9—C10 | 1.496 (3) |
C2—C3 | 1.389 (3) | C10—H10A | 0.9800 |
C3—C4 | 1.386 (3) | C10—H10B | 0.9800 |
C3—H3 | 0.9500 | C10—H10C | 0.9800 |
C4—C5 | 1.388 (3) | C11—H11A | 0.9800 |
C4—H4 | 0.9500 | C11—H11B | 0.9800 |
C5—C6 | 1.395 (3) | C11—H11C | 0.9800 |
C1—N1—C2 | 127.79 (16) | C2—C7—C6 | 119.87 (18) |
C1—N1—H1N | 113.3 (14) | C2—C7—H7 | 120.1 |
C2—N1—H1N | 117.3 (14) | C6—C7—H7 | 120.1 |
C1—N2—N3 | 117.72 (15) | C5—C8—H8A | 109.5 |
C1—N2—H2N | 118.4 (15) | C5—C8—H8B | 109.5 |
N3—N2—H2N | 120.2 (15) | H8A—C8—H8B | 109.5 |
C9—N3—N2 | 117.91 (15) | C5—C8—H8C | 109.5 |
N1—C1—N2 | 114.54 (16) | H8A—C8—H8C | 109.5 |
N1—C1—S1 | 125.45 (14) | H8B—C8—H8C | 109.5 |
N2—C1—S1 | 120.00 (14) | N3—C9—C11 | 116.21 (16) |
C7—C2—C3 | 119.20 (17) | N3—C9—C10 | 126.34 (17) |
C7—C2—N1 | 122.98 (17) | C11—C9—C10 | 117.46 (16) |
C3—C2—N1 | 117.79 (17) | C9—C10—H10A | 109.5 |
C4—C3—C2 | 120.30 (18) | C9—C10—H10B | 109.5 |
C4—C3—H3 | 119.9 | H10A—C10—H10B | 109.5 |
C2—C3—H3 | 119.9 | C9—C10—H10C | 109.5 |
C3—C4—C5 | 121.42 (18) | H10A—C10—H10C | 109.5 |
C3—C4—H4 | 119.3 | H10B—C10—H10C | 109.5 |
C5—C4—H4 | 119.3 | C9—C11—H11A | 109.5 |
C4—C5—C6 | 117.52 (17) | C9—C11—H11B | 109.5 |
C4—C5—C8 | 121.55 (18) | H11A—C11—H11B | 109.5 |
C6—C5—C8 | 120.92 (18) | C9—C11—H11C | 109.5 |
C7—C6—C5 | 121.69 (18) | H11A—C11—H11C | 109.5 |
C7—C6—H6 | 119.2 | H11B—C11—H11C | 109.5 |
C5—C6—H6 | 119.2 | ||
C1—N2—N3—C9 | −165.78 (16) | C3—C4—C5—C6 | −0.4 (3) |
C2—N1—C1—N2 | −171.29 (17) | C3—C4—C5—C8 | 178.82 (19) |
C2—N1—C1—S1 | 9.3 (3) | C4—C5—C6—C7 | 0.0 (3) |
N3—N2—C1—N1 | 11.0 (2) | C8—C5—C6—C7 | −179.16 (18) |
N3—N2—C1—S1 | −169.57 (12) | C3—C2—C7—C6 | −1.1 (3) |
C1—N1—C2—C7 | −50.1 (3) | N1—C2—C7—C6 | −178.81 (17) |
C1—N1—C2—C3 | 132.2 (2) | C5—C6—C7—C2 | 0.7 (3) |
C7—C2—C3—C4 | 0.8 (3) | N2—N3—C9—C11 | −177.62 (15) |
N1—C2—C3—C4 | 178.60 (17) | N2—N3—C9—C10 | 2.4 (3) |
C2—C3—C4—C5 | 0.0 (3) |
Cg1 is the centroid of the C2–C7 ring. |
D—H···A | D—H | H···A | D···A | 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—H8C···Cg1iii | 0.98 | 2.81 | 3.716 (2) | 154 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, −y, −z+1; (iii) −x+1, −y, −z+1. |
Cg1 is the centroid of the C2–C7 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N3 | 0.876 (11) | 2.091 (19) | 2.572 (2) | 113.7 (14) |
N1—H1N···S1i | 0.876 (11) | 2.873 (15) | 3.5618 (17) | 136.7 (17) |
N2—H2N···S1ii | 0.875 (19) | 2.57 (2) | 3.4373 (16) | 169.0 (19) |
C8—H8C···Cg1iii | 0.98 | 2.81 | 3.716 (2) | 154 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, −y, −z+1; (iii) −x+1, −y, −z+1. |
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); (b) Venkatraman et al. (2005). |
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 |
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) |
V (Å3) | 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 diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
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 (Å−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 (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.
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