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

Goh, J.H.; Fun, H.-K.; Adhikari, A.; Kalluraya, B.

doi:10.1107/S1600536809050090

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages o3235-o3236

doi:10.1107/S1600536809050090

Open

access

(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 and B. Kalluraya ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India
^*Correspondence e-mail: hkfun@usm.my

(Received 18 November 2009; accepted 21 November 2009; online 28 November 2009)

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 R₂²(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 ).

Experimental

Crystal data

C₁₃H₁₁N₅OS·C₃H₇NO
M_r = 358.42
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.054
wR(F²) = 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

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
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) x, y, z-1; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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 ).

Supporting information

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

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

checkCIF report

Comment top

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].

Related literature top

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).

Experimental top

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.

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme. An intramolecular hydrogen bond is shown as dashed line.
	Fig. 2. Part of the crystal structure of the title compound, viewed along the a axis, showing dimers being linked into three-dimensional network. H atoms not involved in intermolecular interactions (dashed lines) have been omitted for clarity.

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

Crystal data top

C₁₃H₁₁N₅OS·C₃H₇NO	F(000) = 752
M_r = 358.42	D_x = 1.359 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5142 reflections
a = 7.2374 (1) Å	θ = 2.6–24.1°
b = 23.4970 (4) Å	µ = 0.21 mm⁻¹
c = 10.8214 (2) Å	T = 296 K
β = 107.820 (1)°	Block, orange
V = 1751.97 (5) Å³	0.45 × 0.27 × 0.19 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5088 independent reflections
Radiation source: fine-focus sealed tube	2909 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scans	θ_max = 30.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
T_min = 0.912, T_max = 0.962	k = −32→33
27543 measured reflections	l = −14→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0578P)² + 0.3261P] where P = (F_o² + 2F_c²)/3
5088 reflections	(Δ/σ)_max < 0.001
237 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₃H₁₁N₅OS·C₃H₇NO	V = 1751.97 (5) Å³
M_r = 358.42	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.2374 (1) Å	µ = 0.21 mm⁻¹
b = 23.4970 (4) Å	T = 296 K
c = 10.8214 (2) Å	0.45 × 0.27 × 0.19 mm
β = 107.820 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5088 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2909 reflections with I > 2σ(I)
T_min = 0.912, T_max = 0.962	R_int = 0.044
27543 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.23 e Å⁻³
5088 reflections	Δρ_min = −0.19 e Å⁻³
237 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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.62071 (9)	0.36346 (2)	0.02621 (6)	0.0699 (2)
O1	0.9054 (2)	0.46985 (6)	0.34539 (13)	0.0699 (4)
N1	1.0341 (2)	0.55794 (7)	0.39613 (17)	0.0555 (4)
N2	0.7262 (2)	0.50131 (6)	−0.03966 (15)	0.0485 (4)
N3	0.6254 (2)	0.45953 (6)	−0.12480 (14)	0.0452 (3)
N4	0.4855 (2)	0.38697 (7)	−0.22893 (17)	0.0554 (4)
N5	0.4700 (2)	0.42818 (7)	−0.32108 (16)	0.0586 (4)
C1	0.9416 (3)	0.51769 (8)	0.30855 (19)	0.0534 (5)
C2	1.0822 (3)	0.61175 (8)	0.36456 (19)	0.0510 (4)
C3	1.1770 (3)	0.65002 (9)	0.4618 (2)	0.0641 (5)
H3A	1.2079	0.6397	0.5488	0.077*
C4	1.2241 (3)	0.70310 (9)	0.4275 (2)	0.0698 (6)
H4A	1.2854	0.7290	0.4920	0.084*
C5	1.1817 (3)	0.71879 (9)	0.2983 (3)	0.0680 (6)
H5A	1.2162	0.7547	0.2769	0.082*
C6	1.0893 (3)	0.68142 (8)	0.2023 (2)	0.0617 (5)
H6A	1.0612	0.6922	0.1157	0.074*
C7	1.0366 (3)	0.62699 (8)	0.23332 (19)	0.0497 (4)
C8	0.9380 (3)	0.58604 (8)	0.13906 (19)	0.0505 (4)
H8A	0.9049	0.5956	0.0516	0.061*
C9	0.8906 (3)	0.53351 (7)	0.17255 (17)	0.0472 (4)
C10	0.7858 (3)	0.49056 (8)	0.07984 (19)	0.0526 (5)
H10A	0.7630	0.4549	0.1095	0.063*
C11	0.5783 (2)	0.40326 (7)	−0.10719 (19)	0.0485 (4)
C12	0.5562 (3)	0.47203 (8)	−0.25541 (19)	0.0516 (4)
C13	0.5759 (3)	0.52850 (9)	−0.3093 (2)	0.0685 (6)
H13A	0.5120	0.5284	−0.4012	0.103*
H13B	0.7109	0.5372	−0.2928	0.103*
H13C	0.5175	0.5567	−0.2690	0.103*
O2	0.3433 (2)	0.27901 (6)	0.71425 (18)	0.0801 (5)
N6	0.2576 (2)	0.19916 (7)	0.79911 (17)	0.0606 (4)
C14	0.3236 (3)	0.25191 (9)	0.8062 (2)	0.0645 (6)
H14A	0.3576	0.2697	0.8867	0.077*
C15	0.1949 (4)	0.17088 (10)	0.6743 (2)	0.0841 (7)
H15A	0.1598	0.1988	0.6065	0.126*
H15B	0.0847	0.1473	0.6696	0.126*
H15C	0.2987	0.1478	0.6643	0.126*
C16	0.2369 (5)	0.16951 (13)	0.9100 (3)	0.1056 (10)
H16A	0.2538	0.1957	0.9806	0.158*
H16B	0.3333	0.1401	0.9350	0.158*
H16C	0.1099	0.1528	0.8886	0.158*
H1N1	1.054 (3)	0.5478 (9)	0.482 (2)	0.063 (6)*
H1N4	0.436 (3)	0.3526 (10)	−0.249 (2)	0.070 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0962 (4)	0.0476 (3)	0.0632 (4)	−0.0040 (3)	0.0204 (3)	0.0050 (2)
O1	0.0986 (11)	0.0555 (8)	0.0482 (8)	−0.0161 (7)	0.0116 (8)	0.0012 (7)
N1	0.0672 (10)	0.0548 (10)	0.0410 (9)	−0.0070 (8)	0.0115 (8)	−0.0036 (8)
N2	0.0560 (9)	0.0419 (8)	0.0454 (9)	−0.0008 (6)	0.0122 (7)	−0.0048 (7)
N3	0.0482 (8)	0.0424 (8)	0.0445 (9)	0.0000 (6)	0.0133 (7)	−0.0046 (6)
N4	0.0597 (10)	0.0435 (9)	0.0593 (11)	−0.0032 (7)	0.0128 (8)	−0.0085 (8)
N5	0.0678 (10)	0.0497 (9)	0.0525 (10)	−0.0019 (7)	0.0098 (8)	−0.0063 (8)
C1	0.0603 (11)	0.0495 (11)	0.0479 (11)	−0.0028 (8)	0.0131 (9)	−0.0040 (9)
C2	0.0468 (10)	0.0499 (10)	0.0550 (12)	−0.0008 (8)	0.0137 (8)	−0.0072 (9)
C3	0.0641 (12)	0.0643 (13)	0.0594 (13)	−0.0034 (10)	0.0124 (10)	−0.0133 (10)
C4	0.0643 (13)	0.0584 (13)	0.0811 (17)	−0.0099 (10)	0.0139 (12)	−0.0210 (12)
C5	0.0706 (13)	0.0472 (11)	0.0881 (18)	−0.0082 (10)	0.0272 (12)	−0.0089 (11)
C6	0.0677 (12)	0.0519 (11)	0.0688 (14)	−0.0018 (9)	0.0258 (11)	−0.0025 (10)
C7	0.0486 (10)	0.0457 (10)	0.0561 (12)	0.0001 (7)	0.0181 (9)	−0.0043 (8)
C8	0.0568 (11)	0.0498 (10)	0.0458 (11)	0.0006 (8)	0.0169 (9)	−0.0025 (9)
C9	0.0509 (10)	0.0466 (10)	0.0433 (10)	0.0013 (8)	0.0135 (8)	−0.0030 (8)
C10	0.0622 (11)	0.0441 (10)	0.0509 (12)	−0.0029 (8)	0.0166 (9)	−0.0017 (8)
C11	0.0482 (9)	0.0399 (9)	0.0577 (12)	0.0024 (7)	0.0166 (9)	−0.0059 (8)
C12	0.0556 (10)	0.0506 (10)	0.0456 (11)	0.0018 (8)	0.0109 (8)	−0.0032 (9)
C13	0.0890 (15)	0.0562 (12)	0.0549 (13)	−0.0040 (11)	0.0137 (11)	0.0037 (10)
O2	0.0986 (12)	0.0576 (9)	0.0853 (12)	−0.0178 (8)	0.0299 (10)	−0.0067 (9)
N6	0.0706 (11)	0.0506 (9)	0.0597 (11)	−0.0023 (8)	0.0185 (9)	−0.0055 (8)
C14	0.0645 (13)	0.0587 (13)	0.0658 (15)	−0.0008 (10)	0.0131 (11)	−0.0148 (11)
C15	0.114 (2)	0.0615 (14)	0.0710 (16)	−0.0128 (13)	0.0200 (14)	−0.0153 (12)
C16	0.153 (3)	0.094 (2)	0.082 (2)	−0.0127 (19)	0.0536 (19)	0.0069 (16)

Geometric parameters (Å, º) top

S1—C11	1.668 (2)	C6—C7	1.405 (3)
O1—C1	1.247 (2)	C6—H6A	0.9300
N1—C1	1.361 (2)	C7—C8	1.425 (2)
N1—C2	1.382 (2)	C8—C9	1.359 (2)
N1—H1N1	0.93 (2)	C8—H8A	0.9300
N2—C10	1.257 (2)	C9—C10	1.461 (2)
N2—N3	1.3903 (19)	C10—H10A	0.9300
N3—C12	1.379 (2)	C12—C13	1.474 (3)
N3—C11	1.393 (2)	C13—H13A	0.9600
N4—C11	1.338 (2)	C13—H13B	0.9600
N4—N5	1.370 (2)	C13—H13C	0.9600
N4—H1N4	0.88 (2)	O2—C14	1.225 (3)
N5—C12	1.298 (2)	N6—C14	1.322 (3)
C1—C9	1.452 (3)	N6—C16	1.434 (3)
C2—C3	1.395 (3)	N6—C15	1.448 (3)
C2—C7	1.403 (3)	C14—H14A	0.9300
C3—C4	1.374 (3)	C15—H15A	0.9600
C3—H3A	0.9300	C15—H15B	0.9600
C4—C5	1.386 (3)	C15—H15C	0.9600
C4—H4A	0.9300	C16—H16A	0.9600
C5—C6	1.369 (3)	C16—H16B	0.9600
C5—H5A	0.9300	C16—H16C	0.9600

C1—N1—C2	124.83 (18)	C8—C9—C10	124.36 (17)
C1—N1—H1N1	114.3 (13)	C1—C9—C10	115.88 (16)
C2—N1—H1N1	120.6 (13)	N2—C10—C9	120.68 (17)
C10—N2—N3	119.03 (16)	N2—C10—H10A	119.7
C12—N3—N2	118.77 (15)	C9—C10—H10A	119.7
C12—N3—C11	108.36 (15)	N4—C11—N3	101.93 (16)
N2—N3—C11	132.85 (15)	N4—C11—S1	126.57 (14)
C11—N4—N5	114.79 (16)	N3—C11—S1	131.50 (14)
C11—N4—H1N4	123.0 (15)	N5—C12—N3	110.81 (17)
N5—N4—H1N4	122.2 (15)	N5—C12—C13	125.92 (18)
C12—N5—N4	104.12 (16)	N3—C12—C13	123.26 (17)
O1—C1—N1	120.69 (18)	C12—C13—H13A	109.5
O1—C1—C9	122.81 (17)	C12—C13—H13B	109.5
N1—C1—C9	116.50 (17)	H13A—C13—H13B	109.5
N1—C2—C3	120.42 (19)	C12—C13—H13C	109.5
N1—C2—C7	119.00 (17)	H13A—C13—H13C	109.5
C3—C2—C7	120.58 (18)	H13B—C13—H13C	109.5
C4—C3—C2	119.1 (2)	C14—N6—C16	122.4 (2)
C4—C3—H3A	120.4	C14—N6—C15	119.25 (19)
C2—C3—H3A	120.4	C16—N6—C15	118.30 (19)
C3—C4—C5	121.2 (2)	O2—C14—N6	124.8 (2)
C3—C4—H4A	119.4	O2—C14—H14A	117.6
C5—C4—H4A	119.4	N6—C14—H14A	117.6
C6—C5—C4	120.1 (2)	N6—C15—H15A	109.5
C6—C5—H5A	120.0	N6—C15—H15B	109.5
C4—C5—H5A	120.0	H15A—C15—H15B	109.5
C5—C6—C7	120.5 (2)	N6—C15—H15C	109.5
C5—C6—H6A	119.7	H15A—C15—H15C	109.5
C7—C6—H6A	119.7	H15B—C15—H15C	109.5
C2—C7—C6	118.54 (18)	N6—C16—H16A	109.5
C2—C7—C8	117.62 (17)	N6—C16—H16B	109.5
C6—C7—C8	123.84 (19)	H16A—C16—H16B	109.5
C9—C8—C7	122.29 (18)	N6—C16—H16C	109.5
C9—C8—H8A	118.9	H16A—C16—H16C	109.5
C7—C8—H8A	118.9	H16B—C16—H16C	109.5
C8—C9—C1	119.75 (17)

C10—N2—N3—C12	178.43 (17)	O1—C1—C9—C8	−178.68 (18)
C10—N2—N3—C11	−3.3 (3)	N1—C1—C9—C8	0.8 (3)
C11—N4—N5—C12	0.1 (2)	O1—C1—C9—C10	2.5 (3)
C2—N1—C1—O1	179.27 (18)	N1—C1—C9—C10	−178.08 (16)
C2—N1—C1—C9	−0.2 (3)	N3—N2—C10—C9	−179.39 (15)
C1—N1—C2—C3	179.90 (18)	C8—C9—C10—N2	−2.6 (3)
C1—N1—C2—C7	−0.9 (3)	C1—C9—C10—N2	176.18 (17)
N1—C2—C3—C4	179.58 (19)	N5—N4—C11—N3	−0.2 (2)
C7—C2—C3—C4	0.4 (3)	N5—N4—C11—S1	179.90 (13)
C2—C3—C4—C5	−1.0 (3)	C12—N3—C11—N4	0.18 (18)
C3—C4—C5—C6	0.8 (3)	N2—N3—C11—N4	−178.25 (16)
C4—C5—C6—C7	0.0 (3)	C12—N3—C11—S1	−179.91 (15)
N1—C2—C7—C6	−178.83 (17)	N2—N3—C11—S1	1.7 (3)
C3—C2—C7—C6	0.3 (3)	N4—N5—C12—N3	0.0 (2)
N1—C2—C7—C8	1.4 (3)	N4—N5—C12—C13	−178.53 (19)
C3—C2—C7—C8	−179.39 (16)	N2—N3—C12—N5	178.56 (15)
C5—C6—C7—C2	−0.5 (3)	C11—N3—C12—N5	−0.1 (2)
C5—C6—C7—C8	179.16 (18)	N2—N3—C12—C13	−2.9 (3)
C2—C7—C8—C9	−0.9 (3)	C11—N3—C12—C13	178.46 (18)
C6—C7—C8—C9	179.39 (18)	C16—N6—C14—O2	−179.8 (2)
C7—C8—C9—C1	−0.2 (3)	C15—N6—C14—O2	−2.8 (3)
C7—C8—C9—C10	178.53 (16)

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, y, z−1; (iii) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁N₅OS·C₃H₇NO
M_r	358.42
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.2374 (1), 23.4970 (4), 10.8214 (2)
β (°)	107.820 (1)
V (Å³)	1751.97 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.45 × 0.27 × 0.19

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.912, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	27543, 5088, 2909
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.144, 1.02
No. of reflections	5088
No. of parameters	237
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.19

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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	0.9300	2.4300	3.203 (2)	140.00
C16—H16A···O2ⁱⁱⁱ	0.9600	2.4800	3.368 (4)	153.00

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, y, z−1; (iii) x, −y+1/2, z+1/2.

Footnotes

‡Thomson Reuters ResearcherID: C-7576-2009.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

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.

References

Almasirad, A., Tabatabai, S. A., Faizi, M., Kebriaeezadeh, A., Mehrabi, N., Dalvandi, A. & Shafiee, A. (2004). Bioorg. Med. Chem. Lett. 14, 6057–6059. Web of Science CrossRef PubMed CAS Google Scholar
Al-Soud, Y. A., Al-Masoudi, N. A. & Ferwanah, A. E. S. (2003). Bioorg. Med. Chem. 11, 1701–1708. Web of Science CrossRef PubMed CAS Google Scholar
Amir, M. & Shikha, K. (2004). Eur. J. Med. Chem. 39, 535–545. Web of Science CrossRef PubMed CAS Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Demirbas, N., Karaoglu, S. A., Demirbas, A. & Sancak, K. (2004). Eur. J. Med. Chem. 39, 793–804. Web of Science CrossRef PubMed CAS Google Scholar
Dufresne, S., Bourque, A. N. & Skene, W. G. (2008). Acta Cryst. E64, o316. Web of Science CSD CrossRef IUCr Journals Google Scholar
Fun, H.-K., Goh, J. H., Vijesh, A. M., Padaki, M. & Isloor, A. M. (2009). Acta Cryst. E65, o1918–o1919. Web of Science CSD CrossRef IUCr Journals Google Scholar
Holla, B. S., Veerendra, B., Shivananda, M. K. & Poojary, B. (2003). Eur. J. Med. Chem. 38, 759–767. Web of Science CrossRef PubMed Google Scholar
Janardhana, N., Girisha, K. S., Shetty, N. S. & Kalluraya, B. (2008). Ind. J. Heterocycl. Chem. 17, 209–212. Google Scholar
Kalluraya, B. & Sreenivasa, S. (1998). Il Farmaco, 53, 399–404. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Song, J., Lin, Y. & Chan, W. L. (2008). Acta Cryst. E64, o934. Web of Science CSD CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sujith, K. V., Rao, J. N., Shetty, P. & Kalluraya, B. (2009). Eur. J. Med. Chem. 44, 3697–3702. Web of Science CrossRef PubMed CAS Google Scholar
Turan-Zitouni, G., Kaplancıklı, Z. A., Yıldız, M. T., Chevallet, P. & Kaya, D. (2005). Eur. J. Med. Chem. 40, 607–613. Web of Science CrossRef PubMed CAS Google Scholar
Walczak, K., Gondela, A. & Suwiński, J. (2004). Eur. J. Med. Chem. 39, 849–853. Web of Science CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.