(E)-3-Methyl-4-[(2-oxidoquinolin-1-ium-3-yl)methyl­eneamino]-1H-1,2,4-triazole-5(4H)-thione N,N-dimethyl­formamide solvate

Jia Hao Goh; Hoong-Kun Fun; Adithya Adhikari; B Kalluraya

doi:10.1107/S1600536809050090

. 2009 Nov 28;65(Pt 12):o3235–o3236. doi: 10.1107/S1600536809050090

(E)-3-Methyl-4-[(2-oxidoquinolin-1-ium-3-yl)methyleneamino]-1H-1,2,4-triazole-5(4H)-thione N,N-dimethylformamide solvate

Jia Hao Goh ^a,^‡, Hoong-Kun Fun ^a,^*,^§, Adithya Adhikari ^b, B Kalluraya ^b

PMCID: PMC2972175 PMID: 21578940

Abstract

The title 1,2,4-triazole compound, C₁₃H₁₁N₅OS·C₃H₇NO, crystallizes as a 1:1 dimethylformamide (DMF) solvate. The main molecule exists in a trans configuration with respect to the acyclic C=N bond. An intramolecular C—H⋯S hydrogen bond generates an S(6) ring motif. In the synthesis, a proton is transferred from the O atom of a hydroxy group to the quinoline group N atom. The essentially planar triazole ring and quinoline ring system [maximum deviations of 0.001 (2) and 0.013 (2) Å, respectively] form a dihedral angle of 5.86 (9)°. In the crystal structure, molecules of (E)-4-[(2-hydroxy-3-quinolyl)methyleneamino]-3-methyl-1H-1,2,4-triazole-5(4H)-thione are linked into R ₂ ²(8) centrosymmteric dimers via N—H⋯O hydrogen bonds. These dimers are further linked into an extended three-dimensional structure by the DMF solvent molecules via intermolecular N—H⋯O and C—H⋯O hydrogen bonds. The crystal structure is consolidated by two different intermolecular π–π interactions [centroid–centroid distances = 3.6593 (12) and 3.6892 (12) Å].

Related literature

For general background to and applications of 1,2,4-triazole derivatives, see: Al-Soud et al. (2003 ▶); Almasirad et al. (2004 ▶); Amir & Shikha (2004 ▶); Holla et al. (2003 ▶); Turan-Zitouni et al. (2005 ▶); Walczak et al. (2004 ▶). For the pharmacological properties of quinoline derivatives, see: Janardhana et al. (2008 ▶); Kalluraya & Sreenivasa (1998 ▶). For general applications of Schiff base derivatives of 1,2,4-triazole-5-ones, see: Demirbas et al. (2004 ▶); Sujith et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For closely related structures, see: Dufresne et al. 2008 ▶; Fun et al. (2009 ▶); Song et al. (2008 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶). graphic file with name e-65-o3235-scheme1.jpg

Experimental

Crystal data

C₁₃H₁₁N₅OS·C₃H₇NO
M _r = 358.42
Monoclinic,
a = 7.2374 (1) Å
b = 23.4970 (4) Å
c = 10.8214 (2) Å
β = 107.820 (1)°
V = 1751.97 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 296 K
0.45 × 0.27 × 0.19 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.912, T _max = 0.962
27543 measured reflections
5088 independent reflections
2909 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.144
S = 1.02
5088 reflections
237 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809050090/lh2959sup1.cif

e-65-o3235-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809050090/lh2959Isup2.hkl

e-65-o3235-Isup2.hkl^{(249.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1ⁱ	0.93 (2)	1.85 (2)	2.774 (2)	178 (2)
N4—H1N4⋯O2ⁱⁱ	0.88 (2)	1.85 (2)	2.736 (2)	177.2 (14)
C10—H10A⋯S1	0.93	2.43	3.203 (2)	140
C16—H16A⋯O2ⁱⁱⁱ	0.96	2.48	3.368 (4)	153

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

HKF and JHG thank Universiti Sains Malaysia (USM) for the Research University Golden Goose grant (No. 1001/PFIZIK/811012). JHG also thanks USM for the award of a USM fellowship.

supplementary crystallographic information

Comment

A degree of respectability has been bestowed upon 1,2,4-triazole derivatives due to their anti-bacterial, anti-fungal (Turan-Zitouni et al., 2005), anti-tubercular (Walczak et al., 2004), anti-cancer (Holla et al., 2003), anti-tumor (Al-Soud et al., 2003), anti-convulsant (Almasirad et al., 2004), anti-inflammatory and analgesic (Amir & Shikha, 2004) properties. Similarly quinoline and its derivatives have been reported to be associated with interesting pharmacological properties (Janardhana et al., 2008; Kalluraya & Sreenivasa, 1998). They are found in numerous commercial products, including pharmaceuticals, frangrances and dyes. Schiff base derivatives of 1,2,4-triazol-5-ones are also found to possess anti-tumor (Demirbas et al., 2004) and anti-inflammatory (Sujith et al., 2009) activities. These observations prompted us to synthesize the title compound and to characterize it by single crystal XRD study.

The asymmetric unit of the title compound (Fig. 1) comprises of a 4-[(2-hydroxyquinolin-3-yl)methyleneamino]-3-methyl-1H-1,2,4-triazole- 5(4H)-thione molecule and a N,N-dimethylformamide solvent molecule. In the main molecule, exists in a trans configuration with respect to the acyclic C10═N2 bond. An intramolecular C10—H10A···S1 hydrogen bond (Table 1) generates a six-membered ring, producing an S(6) ring motif (Fig. 1, Berstein et al., 1995). A proton is transferred from atom O1 of the hydroxy group to atom N1. Comparing with the unprotonated structure (Dufresne et al., 2008), protonation of atom N1 has widened the C1—N1—C2 angle from 117.25 (14) to 124.83 (18)°. The 1,2,4-triazole ring and quinoline ring system are essentially planar, with maximum deviations of 0.001 (2) and 0.013 (2) Å, respectively, for atoms N3 and C6. These two ring systems are slightly inclined to one another at a dihedral angle of 5.86 (9)°. The bond lengths and angles are comparable to those related 1,2,4-triazole (Fun et al., 2009) and quinoline (Song et al., 2008) structures.

In the crystal structure (Fig. 2), the protonated N1 atom act as hydrogen bond donor to the O1 atom of an inversion-related molecule, producing an R₂²(8) hydrogen-bonded dimer through N1—H1N1···O1ⁱ hydrogen bond (see Table 1 for symmetry codes). The N,N-dimethylformamide solvent molecules further link these dimers via intermolecular N4—H1N4···O2ⁱⁱ and C16—H16A···O2ⁱⁱⁱ hydrogen bonds (Table 1), establishing connections within these dimers and thus creating a three dimensional network. The crystal structure is consolidated by two different weak intermolecular π–π interactions involving the 1,2,4-triazole (Cg1) and C1/N1/C2/C7-C9 pyridine (Cg2) rings [Cg1···Cg2^iv = 3.6593 (12) and Cg1···Cg2^v = 3.6892 (12) Å, respectively; (iv) 2-x, 1-y, -z and (v) 1-x, 1-y, -z].

Experimental

The title compound was obtained by refluxing 3-methyl-4-amino-1,2,4-triazole-5-thione (0.01 mol) and 2-hydroxy-3-formyl-quinoline (0.01 mol) in ethanol (30 ml) with the addition of three drops of concentrated sulphuric acid for 3 h. The solid product obtained was collected by filtration, washed with ethanol and dried. It was then recrystallized using ethanol. Single crystals suitable for X-ray analysis were obtained from a solution of the title compound in a mixture of ethanol and DMF by slow evaporation.