(E)-3-Methyl-4-[(2-oxidoquinolin-1-ium-3-yl)methyl-eneamino]-1H-1,2,4-triazole-5(4H)-thione N,N-dimethyl-formamide solvate.

The title 1,2,4-triazole compound, C(13)H(11)N(5)OS·C(3)H(7)NO, crystallizes as a 1:1 dimethyl-formamide (DMF) solvate. The main mol-ecule exists in a trans configuration with respect to the acyclic C=N bond. An intra-molecular C-H⋯S hydrogen bond generates an S(6) ring motif. In the synthesis, a proton is transferred from the O atom of a hydr-oxy 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, mol-ecules of (E)-4-[(2-hydroxy-3--quinolyl)methyl-eneamino]-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 mol-ecules via inter-molecular N-H⋯O and C-H⋯O hydrogen bonds. The crystal structure is consolidated by two different inter-molecular π-π inter-actions [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 = 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 (; 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

Δρmax = 0.23 e Å−3

Δρmin = −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 ▶).

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

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

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

C13H11N5OS·C3H7NO	F(000) = 752
Mr = 358.42	Dx = 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

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

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(Fo2) + (0.0578P)2 + 0.3261P] where P = (Fo2 + 2Fc2)/3
5088 reflections	(Δ/σ)max < 0.001
237 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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

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) ; (ii) ; (iii) .