Crystal structure of 4-[(E)-(4-chloro-benzyl-idene)amino]-3-(2-methyl-benz-yl)-1H-1,2,4-triazole-5(4H)-thione.

In the title mol-ecule, C17H15ClN4S, the benzene rings form dihedral angles of 16.6 (1) and 77.2 (1)° with the triazole ring. The dihedral angle between the benzene rings is 86.6 (1)°. In the crystal, pairs of N-H⋯S hydrogen bonds form inversion dimers with graph-set notation R 2 (2)(8). Weak C-H⋯S hydrogen bonds link these dimers into layers parallel to (100). Weak intra-molecular C-H⋯S and C-H⋯N contacts are observed.

Related literature

For the chemistry of Schiff base compounds, see: Dubey & Vaid (1991 ▶); Yadav et al. (1994 ▶); Reddy & Lirgappa (1994 ▶); Wyrzykiewicz & Prukah (1998 ▶); Galic et al. (2001 ▶). For the biological activity of 1,2,4-triazole derivatives, see: Jones et al. (1965 ▶); Kane et al. (1988 ▶); Mullican et al. (1993 ▶); Cansiz et al. (2001 ▶). For the biological activity of sulfur- and nitro­gen-containing compounds, see: Malik et al. (2011 ▶); Wei & Bell (1982 ▶). For related structures, see: Ding et al. (2009 ▶); Vinduvahini et al. (2011 ▶); Almutairi et al. (2012 ▶); Sarojini et al. (2013 ▶, 2014a ▶,b ▶). For standard bond-lengths, see: Allen et al. (1987 ▶). For hydrogen-bond graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C17H15ClN4S

M = 342.84

Monoclinic,

a = 13.4821 (9) Å

b = 6.8479 (4) Å

c = 18.4895 (12) Å

β = 100.443 (6)°

V = 1678.75 (18) Å3

Z = 4

Mo Kα radiation

μ = 0.36 mm−1

T = 293 K

0.30 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur, Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.858, T max = 1.000

6947 measured reflections

3306 independent reflections

2252 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.115

S = 1.04

3306 reflections

213 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.24 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814018352/lh5724sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814018352/lh5724Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814018352/lh5724Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814018352/lh5724fig1.tif

The mol­ecular structure with ellipsoids drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii.

Click here for additional data file.

. DOI: 10.1107/S1600536814018352/lh5724fig2.tif

A pair mol­ecules of the title compound. Dashed lines indicate N—H⋯S hydrogen bonds forming (8) graph set motifs linking the mol­ecules into dimers.

Click here for additional data file.

b . DOI: 10.1107/S1600536814018352/lh5724fig3.tif

The packing arrangement of mol­ecules viewed along the b axis. Hydrogen bonds are shown as dashed lines.

CCDC reference: 1018973

Additional supporting information: crystallographic information; 3D view; checkCIF report

C17H15ClN4S	F(000) = 712
Mr = 342.84	Dx = 1.356 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1855 reflections
a = 13.4821 (9) Å	θ = 3.6–26.5°
b = 6.8479 (4) Å	µ = 0.36 mm−1
c = 18.4895 (12) Å	T = 293 K
β = 100.443 (6)°	Block, white
V = 1678.75 (18) Å3	0.30 × 0.20 × 0.20 mm
Z = 4

Oxford Diffraction Xcalibur, Sapphire3 diffractometer	3306 independent reflections
Radiation source: fine-focus sealed tube	2252 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 16.1049 pixels mm-1	θmax = 26.0°, θmin = 3.6°
ω scans	h = −16→12
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −8→5
Tmin = 0.858, Tmax = 1.000	l = −22→18
6947 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0402P)2 + 0.2834P] where P = (Fo2 + 2Fc2)/3
3306 reflections	(Δ/σ)max < 0.001
213 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

Experimental. CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010 CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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	0.07980 (5)	0.72738 (9)	0.46649 (4)	0.0604 (2)
Cl1	0.43301 (6)	−0.35687 (10)	0.54977 (5)	0.0791 (3)
N2	0.11694 (13)	0.6086 (2)	0.61288 (11)	0.0416 (5)
N1	0.17171 (13)	0.4355 (2)	0.61469 (11)	0.0444 (5)
C6	0.27146 (17)	0.0685 (3)	0.61625 (13)	0.0454 (6)
H6	0.2424	0.0961	0.6570	0.055*
C9	0.09068 (17)	0.6762 (3)	0.67729 (13)	0.0450 (6)
C1	0.25988 (17)	0.1987 (3)	0.55810 (13)	0.0468 (6)
N4	0.03338 (15)	0.8286 (3)	0.66436 (12)	0.0576 (6)
C7	0.20400 (19)	0.3820 (3)	0.55848 (15)	0.0550 (7)
H7	0.1924	0.4596	0.5165	0.066*
C4	0.36590 (18)	−0.1416 (3)	0.55312 (14)	0.0491 (6)
C5	0.32542 (17)	−0.1010 (3)	0.61443 (14)	0.0474 (6)
H5	0.3344	−0.1868	0.6541	0.057*
N3	0.02267 (16)	0.8556 (3)	0.59013 (13)	0.0569 (6)
C11	0.23908 (18)	0.6491 (3)	0.77823 (12)	0.0459 (6)
C10	0.12992 (18)	0.5931 (3)	0.75064 (14)	0.0516 (6)
H10A	0.1244	0.4520	0.7481	0.062*
H10B	0.0890	0.6391	0.7853	0.062*
C12	0.31449 (19)	0.5143 (4)	0.77442 (14)	0.0549 (7)
H12	0.2972	0.3899	0.7562	0.066*
C8	0.07340 (16)	0.7288 (3)	0.55585 (14)	0.0456 (6)
C3	0.3549 (2)	−0.0174 (4)	0.49465 (15)	0.0663 (8)
H3	0.3826	−0.0473	0.4534	0.080*
C16	0.2652 (2)	0.8359 (4)	0.80624 (13)	0.0554 (7)
C14	0.4396 (2)	0.7446 (5)	0.82462 (17)	0.0775 (9)
H14	0.5069	0.7777	0.8407	0.093*
C2	0.3021 (2)	0.1532 (4)	0.49789 (15)	0.0699 (8)
H2	0.2948	0.2397	0.4585	0.084*
C17	0.1871 (2)	0.9886 (4)	0.81350 (16)	0.0759 (9)
H17A	0.2199	1.1030	0.8366	0.114*
H17B	0.1412	0.9382	0.8430	0.114*
H17C	0.1506	1.0221	0.7656	0.114*
C15	0.3658 (3)	0.8780 (4)	0.82831 (16)	0.0738 (9)
H15	0.3842	1.0020	0.8464	0.089*
C13	0.4148 (2)	0.5614 (5)	0.79722 (15)	0.0720 (8)
H13	0.4649	0.4701	0.7941	0.086*
H3'	−0.0073 (19)	0.954 (4)	0.5690 (14)	0.064 (8)*

	U11	U22	U33	U12	U13	U23
S1	0.0735 (5)	0.0570 (4)	0.0470 (4)	0.0249 (3)	0.0007 (3)	−0.0027 (3)
Cl1	0.0901 (6)	0.0569 (4)	0.0945 (6)	0.0351 (4)	0.0281 (5)	0.0062 (4)
N2	0.0369 (10)	0.0382 (10)	0.0481 (12)	0.0069 (8)	0.0032 (9)	−0.0019 (9)
N1	0.0408 (11)	0.0388 (10)	0.0514 (13)	0.0099 (8)	0.0023 (10)	−0.0040 (9)
C6	0.0512 (14)	0.0440 (13)	0.0430 (15)	0.0035 (11)	0.0138 (12)	0.0008 (11)
C9	0.0403 (13)	0.0465 (13)	0.0502 (16)	0.0032 (10)	0.0135 (11)	−0.0024 (11)
C1	0.0506 (14)	0.0438 (13)	0.0451 (15)	0.0129 (10)	0.0062 (12)	0.0019 (11)
N4	0.0574 (13)	0.0605 (13)	0.0577 (15)	0.0195 (10)	0.0177 (11)	0.0014 (11)
C7	0.0651 (17)	0.0471 (14)	0.0531 (17)	0.0207 (12)	0.0120 (14)	0.0080 (12)
C4	0.0500 (14)	0.0422 (13)	0.0553 (16)	0.0108 (11)	0.0101 (12)	−0.0024 (12)
C5	0.0526 (15)	0.0406 (12)	0.0486 (15)	0.0067 (11)	0.0079 (12)	0.0093 (11)
N3	0.0616 (14)	0.0550 (13)	0.0536 (15)	0.0255 (11)	0.0095 (11)	0.0014 (11)
C11	0.0556 (15)	0.0528 (14)	0.0308 (13)	−0.0013 (11)	0.0119 (11)	0.0091 (11)
C10	0.0585 (16)	0.0488 (13)	0.0522 (16)	−0.0001 (12)	0.0223 (13)	0.0064 (12)
C12	0.0590 (17)	0.0611 (15)	0.0430 (16)	0.0058 (13)	0.0051 (13)	0.0030 (12)
C8	0.0397 (13)	0.0430 (12)	0.0517 (15)	0.0075 (10)	0.0021 (11)	−0.0046 (11)
C3	0.090 (2)	0.0651 (17)	0.0493 (17)	0.0296 (15)	0.0280 (15)	0.0052 (14)
C16	0.0769 (19)	0.0574 (15)	0.0338 (14)	−0.0077 (14)	0.0151 (13)	0.0048 (12)
C14	0.063 (2)	0.108 (3)	0.057 (2)	−0.0215 (19)	−0.0024 (16)	0.0029 (18)
C2	0.101 (2)	0.0657 (17)	0.0464 (17)	0.0376 (16)	0.0231 (16)	0.0186 (14)
C17	0.115 (3)	0.0588 (17)	0.059 (2)	0.0044 (16)	0.0285 (18)	−0.0072 (14)
C15	0.092 (2)	0.076 (2)	0.0499 (18)	−0.0228 (18)	0.0031 (17)	−0.0016 (15)
C13	0.0611 (19)	0.103 (2)	0.0496 (18)	0.0169 (17)	0.0025 (15)	0.0046 (16)

S1—C8	1.670 (3)	C11—C12	1.384 (3)
Cl1—C4	1.736 (2)	C11—C16	1.401 (3)
N2—C8	1.382 (3)	C11—C10	1.517 (3)
N2—C9	1.382 (3)	C10—H10A	0.9700
N2—N1	1.394 (2)	C10—H10B	0.9700
N1—C7	1.252 (3)	C12—C13	1.380 (4)
C6—C5	1.374 (3)	C12—H12	0.9300
C6—C1	1.383 (3)	C3—C2	1.375 (3)
C6—H6	0.9300	C3—H3	0.9300
C9—N4	1.295 (3)	C16—C15	1.375 (4)
C9—C10	1.477 (3)	C16—C17	1.507 (4)
C1—C2	1.375 (3)	C14—C15	1.362 (4)
C1—C7	1.465 (3)	C14—C13	1.371 (4)
N4—N3	1.366 (3)	C14—H14	0.9300
C7—H7	0.9300	C2—H2	0.9300
C4—C3	1.363 (3)	C17—H17A	0.9600
C4—C5	1.373 (3)	C17—H17B	0.9600
C5—H5	0.9300	C17—H17C	0.9600
N3—C8	1.335 (3)	C15—H15	0.9300
N3—H3'	0.85 (2)	C13—H13	0.9300
C8—N2—C9	108.55 (18)	C11—C10—H10B	109.2
C8—N2—N1	132.44 (19)	H10A—C10—H10B	107.9
C9—N2—N1	118.78 (19)	C13—C12—C11	121.1 (3)
C7—N1—N2	119.4 (2)	C13—C12—H12	119.4
C5—C6—C1	120.7 (2)	C11—C12—H12	119.4
C5—C6—H6	119.6	N3—C8—N2	102.0 (2)
C1—C6—H6	119.6	N3—C8—S1	126.62 (18)
N4—C9—N2	110.4 (2)	N2—C8—S1	131.34 (17)
N4—C9—C10	125.6 (2)	C4—C3—C2	118.6 (2)
N2—C9—C10	123.8 (2)	C4—C3—H3	120.7
C2—C1—C6	118.6 (2)	C2—C3—H3	120.7
C2—C1—C7	119.1 (2)	C15—C16—C11	118.0 (3)
C6—C1—C7	122.3 (2)	C15—C16—C17	119.7 (3)
C9—N4—N3	104.2 (2)	C11—C16—C17	122.3 (3)
N1—C7—C1	120.7 (2)	C15—C14—C13	120.1 (3)
N1—C7—H7	119.6	C15—C14—H14	120.0
C1—C7—H7	119.6	C13—C14—H14	120.0
C3—C4—C5	121.8 (2)	C3—C2—C1	121.4 (2)
C3—C4—Cl1	119.0 (2)	C3—C2—H2	119.3
C5—C4—Cl1	119.28 (19)	C1—C2—H2	119.3
C4—C5—C6	118.9 (2)	C16—C17—H17A	109.5
C4—C5—H5	120.6	C16—C17—H17B	109.5
C6—C5—H5	120.6	H17A—C17—H17B	109.5
C8—N3—N4	114.8 (2)	C16—C17—H17C	109.5
C8—N3—H3'	123.0 (18)	H17A—C17—H17C	109.5
N4—N3—H3'	121.7 (18)	H17B—C17—H17C	109.5
C12—C11—C16	119.3 (2)	C14—C15—C16	122.4 (3)
C12—C11—C10	119.4 (2)	C14—C15—H15	118.8
C16—C11—C10	121.2 (2)	C16—C15—H15	118.8
C9—C10—C11	112.06 (19)	C14—C13—C12	119.1 (3)
C9—C10—H10A	109.2	C14—C13—H13	120.4
C11—C10—H10A	109.2	C12—C13—H13	120.4
C9—C10—H10B	109.2
C8—N2—N1—C7	12.7 (3)	C10—C11—C12—C13	178.3 (2)
C9—N2—N1—C7	−173.4 (2)	N4—N3—C8—N2	2.0 (3)
C8—N2—C9—N4	0.5 (3)	N4—N3—C8—S1	−177.43 (18)
N1—N2—C9—N4	−174.75 (18)	C9—N2—C8—N3	−1.4 (2)
C8—N2—C9—C10	−175.1 (2)	N1—N2—C8—N3	172.9 (2)
N1—N2—C9—C10	9.7 (3)	C9—N2—C8—S1	177.92 (18)
C5—C6—C1—C2	1.1 (4)	N1—N2—C8—S1	−7.7 (4)
C5—C6—C1—C7	−179.2 (2)	C5—C4—C3—C2	0.3 (4)
N2—C9—N4—N3	0.7 (3)	Cl1—C4—C3—C2	−179.7 (2)
C10—C9—N4—N3	176.2 (2)	C12—C11—C16—C15	0.6 (3)
N2—N1—C7—C1	−178.63 (19)	C10—C11—C16—C15	−178.2 (2)
C2—C1—C7—N1	−174.1 (3)	C12—C11—C16—C17	−178.7 (2)
C6—C1—C7—N1	6.1 (4)	C10—C11—C16—C17	2.5 (3)
C3—C4—C5—C6	0.8 (4)	C4—C3—C2—C1	−0.7 (5)
Cl1—C4—C5—C6	−179.26 (18)	C6—C1—C2—C3	0.0 (4)
C1—C6—C5—C4	−1.5 (4)	C7—C1—C2—C3	−179.7 (3)
C9—N4—N3—C8	−1.7 (3)	C13—C14—C15—C16	0.9 (5)
N4—C9—C10—C11	−101.5 (3)	C11—C16—C15—C14	−0.8 (4)
N2—C9—C10—C11	73.5 (3)	C17—C16—C15—C14	178.5 (3)
C12—C11—C10—C9	−102.1 (2)	C15—C14—C13—C12	−0.7 (5)
C16—C11—C10—C9	76.6 (3)	C11—C12—C13—C14	0.5 (4)
C16—C11—C12—C13	−0.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3′···S1i	0.84 (3)	2.43 (3)	3.261 (2)	167 (2)
C17—H17B···S1ii	0.96	2.81	3.710 (3)	157
C17—H17C···N4	0.96	2.59	3.321 (4)	134
C7—H7···S1	0.93	2.45	3.203 (2)	138

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3′⋯S1i	0.84 (3)	2.43 (3)	3.261 (2)	167 (2)
C17—H17B⋯S1ii	0.96	2.81	3.710 (3)	157
C17—H17C⋯N4	0.96	2.59	3.321 (4)	134
C7—H7⋯S1	0.93	2.45	3.203 (2)	138

Symmetry codes: (i) ; (ii) .