4-[(E)-2,6-Dichloro-benzyl-ideneamino]-3-{1-[4-(2-methyl-prop-yl)phen-yl]eth-yl}-1H-1,2,4-triazole-5(4H)-thione.

In the title Schiff base compound, C(21)H(22)Cl(2)N(4)S, the triazole ring makes dihedral angles of 2.15 (11) and 87.48 (11)° with the 2,6-dichloro-phenyl and methyl-propyl-phenyl rings, respectively. Weak intra-molecular C-H⋯S and C-H⋯Cl inter-actions generate S(6) and S(5) ring motifs, respectively. In the crystal structure, centrosymmetrically related mol-ecules are linked into dimers by N-H⋯S hydrogen bonds. These dimers are arranged into sheets parallel to the ab plane and are stacked along the c axis. C-H⋯π inter-actions involving the methyl-propyl-phenyl ring and π-π inter-actions involving the dichloro-phenyl ring [centroid-centroid distance = 3.5865 (3) Å] are also observed.

Related literature

For related literature on hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For related structures, see: Fun et al. (2008a ▶,b ▶). For background to the activities and applications of 1,2,4-triazole derivatives, see: Almasirad et al. (2004 ▶); Al-Soud et al. (2003 ▶); Amir & Shikha (2004 ▶); Holla et al. (2003 ▶); Kawashima et al. (1987 ▶); Palaska et al. (2002 ▶); Walczak et al. (2004 ▶); Zitouni et al. (2005 ▶).

Experimental

Crystal data

C21H22Cl2N4S

M = 433.40

Triclinic,

a = 8.6190 (2) Å

b = 9.4441 (2) Å

c = 14.4244 (4) Å

α = 104.669 (2)°

β = 95.492 (2)°

γ = 110.418 (1)°

V = 1042.33 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.43 mm−1

T = 100.0 (1) K

0.29 × 0.20 × 0.16 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.887, T max = 0.934

19865 measured reflections

6032 independent reflections

4139 reflections with I > 2σ(I)

R int = 0.050

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.136

S = 1.00

6032 reflections

256 parameters

H-atom parameters constrained

Δρmax = 0.59 e Å−3

Δρmin = −0.47 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); 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, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021272/ci2627sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021272/ci2627Isup2.hkl

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

C21H22Cl2N4S	Z = 2
Mr = 433.40	F000 = 452
Triclinic, P1	Dx = 1.381 Mg m−3
Hall symbol: -P 1	Melting point = 438–440 K
a = 8.6190 (2) Å	Mo Kα radiation λ = 0.71073 Å
b = 9.4441 (2) Å	Cell parameters from 6032 reflections
c = 14.4244 (4) Å	θ = 1.5–30.0º
α = 104.669 (2)º	µ = 0.43 mm−1
β = 95.492 (2)º	T = 100.0 (1) K
γ = 110.418 (1)º	Block, colourless
V = 1042.33 (5) Å3	0.29 × 0.20 × 0.16 mm

Bruker SMART APEXII CCD area-detector diffractometer	6032 independent reflections
Radiation source: fine-focus sealed tube	4139 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.050
Detector resolution: 8.33 pixels mm-1	θmax = 30.0º
T = 100.0(1) K	θmin = 1.5º
ω scans	h = −12→12
Absorption correction: multi-scan(SADABS; Bruker, 2005)	k = −13→13
Tmin = 0.887, Tmax = 0.935	l = −20→19
19865 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046	H-atom parameters constrained
wR(F2) = 0.136	w = 1/[σ2(Fo2) + (0.0746P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.001
6032 reflections	Δρmax = 0.59 e Å−3
256 parameters	Δρmin = −0.47 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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	0.79027 (6)	−0.43005 (6)	−0.06227 (3)	0.02335 (13)
Cl1	0.43164 (7)	−0.07928 (7)	0.21127 (4)	0.03523 (15)
Cl2	0.41695 (7)	−0.33808 (6)	−0.17537 (4)	0.03136 (14)
N1	0.9611 (2)	−0.3270 (2)	0.21761 (12)	0.0244 (4)
N2	0.9465 (2)	−0.3961 (2)	0.11923 (12)	0.0240 (4)
H2A	1.0037	−0.4511	0.0971	0.029*
N3	0.7738 (2)	−0.28053 (18)	0.12730 (11)	0.0192 (3)
N4	0.6602 (2)	−0.20834 (19)	0.11584 (12)	0.0229 (4)
C1	0.9409 (2)	0.0211 (2)	0.32320 (13)	0.0218 (4)
C2	1.1052 (3)	0.0657 (2)	0.30759 (15)	0.0259 (4)
H2B	1.1515	−0.0105	0.2915	0.031*
C3	1.2013 (3)	0.2223 (2)	0.31568 (15)	0.0266 (4)
H3A	1.3109	0.2492	0.3046	0.032*
C4	1.1366 (3)	0.3403 (2)	0.34015 (14)	0.0244 (4)
C5	0.9747 (3)	0.2957 (2)	0.35952 (14)	0.0262 (4)
H5A	0.9301	0.3726	0.3786	0.031*
C6	0.8779 (3)	0.1389 (2)	0.35107 (14)	0.0234 (4)
H6A	0.7696	0.1125	0.3642	0.028*
C7	0.8319 (3)	−0.1523 (2)	0.31079 (14)	0.0225 (4)
H7A	0.7131	−0.1651	0.3013	0.027*
C8	0.8563 (2)	−0.2560 (2)	0.22068 (14)	0.0217 (4)
C9	0.8351 (2)	−0.3702 (2)	0.06064 (14)	0.0206 (4)
C10	0.5498 (2)	−0.2695 (2)	0.03633 (14)	0.0223 (4)
H10A	0.5495	−0.3578	−0.0105	0.027*
C11	0.4228 (2)	−0.2036 (2)	0.01691 (14)	0.0215 (4)
C12	0.3619 (3)	−0.1177 (2)	0.08757 (15)	0.0239 (4)
C13	0.2388 (3)	−0.0628 (2)	0.06263 (16)	0.0270 (4)
H13A	0.2011	−0.0054	0.1112	0.032*
C14	0.1729 (3)	−0.0938 (2)	−0.03479 (16)	0.0278 (5)
H14A	0.0906	−0.0570	−0.0516	0.033*
C15	0.2278 (3)	−0.1792 (3)	−0.10761 (16)	0.0284 (5)
H15A	0.1829	−0.2003	−0.1732	0.034*
C16	0.3504 (3)	−0.2325 (2)	−0.08126 (14)	0.0246 (4)
C17	1.2359 (3)	0.5077 (2)	0.34117 (15)	0.0281 (5)
H17A	1.1787	0.5286	0.2881	0.034*
H17B	1.3462	0.5147	0.3281	0.034*
C18	1.2612 (3)	0.6380 (2)	0.43631 (15)	0.0248 (4)
H18A	1.1498	0.6274	0.4512	0.030*
C19	1.3448 (3)	0.8002 (2)	0.42311 (17)	0.0331 (5)
H19A	1.3584	0.8813	0.4826	0.050*
H19B	1.2752	0.8098	0.3709	0.050*
H19C	1.4535	0.8121	0.4075	0.050*
C20	1.3655 (3)	0.6216 (3)	0.52176 (15)	0.0307 (5)
H20A	1.3751	0.7017	0.5808	0.046*
H20B	1.4763	0.6345	0.5092	0.046*
H20C	1.3109	0.5185	0.5289	0.046*
C21	0.8713 (3)	−0.2028 (3)	0.39995 (15)	0.0315 (5)
H21A	0.8010	−0.3124	0.3882	0.047*
H21B	0.8496	−0.1387	0.4564	0.047*
H21C	0.9880	−0.1890	0.4113	0.047*

	U11	U22	U33	U12	U13	U23
S1	0.0258 (3)	0.0241 (2)	0.0194 (2)	0.0112 (2)	0.00672 (19)	0.00244 (18)
Cl1	0.0389 (3)	0.0551 (4)	0.0221 (3)	0.0310 (3)	0.0104 (2)	0.0093 (2)
Cl2	0.0362 (3)	0.0338 (3)	0.0213 (3)	0.0135 (2)	0.0063 (2)	0.0036 (2)
N1	0.0296 (9)	0.0241 (8)	0.0190 (8)	0.0132 (7)	0.0055 (7)	0.0016 (7)
N2	0.0272 (9)	0.0240 (8)	0.0228 (8)	0.0152 (7)	0.0061 (7)	0.0030 (7)
N3	0.0210 (8)	0.0184 (7)	0.0182 (8)	0.0081 (6)	0.0061 (6)	0.0043 (6)
N4	0.0241 (8)	0.0230 (8)	0.0247 (9)	0.0120 (7)	0.0080 (7)	0.0072 (7)
C1	0.0245 (10)	0.0248 (10)	0.0144 (9)	0.0095 (8)	0.0034 (7)	0.0036 (7)
C2	0.0280 (10)	0.0235 (10)	0.0270 (11)	0.0134 (8)	0.0080 (8)	0.0033 (8)
C3	0.0245 (10)	0.0280 (10)	0.0245 (10)	0.0090 (8)	0.0086 (8)	0.0037 (8)
C4	0.0299 (10)	0.0252 (10)	0.0159 (9)	0.0108 (8)	0.0050 (8)	0.0023 (8)
C5	0.0293 (10)	0.0250 (10)	0.0242 (10)	0.0140 (8)	0.0062 (8)	0.0020 (8)
C6	0.0245 (10)	0.0261 (10)	0.0205 (9)	0.0124 (8)	0.0072 (8)	0.0037 (8)
C7	0.0251 (10)	0.0229 (9)	0.0195 (9)	0.0103 (8)	0.0064 (8)	0.0042 (7)
C8	0.0249 (10)	0.0194 (9)	0.0199 (9)	0.0075 (8)	0.0069 (7)	0.0051 (7)
C9	0.0227 (9)	0.0165 (8)	0.0212 (9)	0.0067 (7)	0.0071 (7)	0.0039 (7)
C10	0.0216 (9)	0.0203 (9)	0.0237 (10)	0.0066 (8)	0.0081 (8)	0.0054 (7)
C11	0.0192 (9)	0.0203 (9)	0.0235 (10)	0.0049 (7)	0.0062 (8)	0.0072 (7)
C12	0.0228 (10)	0.0270 (10)	0.0223 (10)	0.0093 (8)	0.0068 (8)	0.0082 (8)
C13	0.0225 (10)	0.0300 (11)	0.0323 (11)	0.0125 (8)	0.0106 (8)	0.0113 (9)
C14	0.0219 (10)	0.0300 (11)	0.0356 (12)	0.0107 (9)	0.0062 (9)	0.0158 (9)
C15	0.0274 (10)	0.0296 (11)	0.0255 (11)	0.0074 (9)	0.0028 (8)	0.0103 (8)
C16	0.0246 (10)	0.0244 (10)	0.0226 (10)	0.0065 (8)	0.0079 (8)	0.0064 (8)
C17	0.0349 (12)	0.0259 (10)	0.0224 (10)	0.0104 (9)	0.0104 (9)	0.0060 (8)
C18	0.0267 (10)	0.0220 (10)	0.0241 (10)	0.0086 (8)	0.0062 (8)	0.0053 (8)
C19	0.0390 (13)	0.0245 (10)	0.0335 (12)	0.0102 (10)	0.0105 (10)	0.0070 (9)
C20	0.0353 (12)	0.0306 (11)	0.0264 (11)	0.0164 (9)	0.0049 (9)	0.0046 (9)
C21	0.0416 (13)	0.0319 (11)	0.0234 (11)	0.0159 (10)	0.0103 (9)	0.0088 (9)

S1—C9	1.6797 (19)	C10—C11	1.472 (3)
Cl1—C12	1.730 (2)	C10—H10A	0.93
Cl2—C16	1.740 (2)	C11—C12	1.398 (3)
N1—C8	1.297 (2)	C11—C16	1.409 (3)
N1—N2	1.377 (2)	C12—C13	1.389 (3)
N2—C9	1.345 (2)	C13—C14	1.381 (3)
N2—H2A	0.86	C13—H13A	0.93
N3—C8	1.384 (2)	C14—C15	1.382 (3)
N3—C9	1.385 (2)	C14—H14A	0.93
N3—N4	1.394 (2)	C15—C16	1.381 (3)
N4—C10	1.275 (2)	C15—H15A	0.93
C1—C2	1.388 (3)	C17—C18	1.531 (3)
C1—C6	1.390 (3)	C17—H17A	0.97
C1—C7	1.530 (3)	C17—H17B	0.97
C2—C3	1.388 (3)	C18—C19	1.519 (3)
C2—H2B	0.93	C18—C20	1.527 (3)
C3—C4	1.396 (3)	C18—H18A	0.98
C3—H3A	0.93	C19—H19A	0.96
C4—C5	1.388 (3)	C19—H19B	0.96
C4—C17	1.508 (3)	C19—H19C	0.96
C5—C6	1.389 (3)	C20—H20A	0.96
C5—H5A	0.93	C20—H20B	0.96
C6—H6A	0.93	C20—H20C	0.96
C7—C8	1.498 (3)	C21—H21A	0.96
C7—C21	1.529 (3)	C21—H21B	0.96
C7—H7A	0.98	C21—H21C	0.96
C8—N1—N2	104.17 (15)	C13—C12—Cl1	116.33 (16)
C9—N2—N1	114.24 (15)	C11—C12—Cl1	121.52 (16)
C9—N2—H2A	122.9	C14—C13—C12	119.57 (19)
N1—N2—H2A	122.9	C14—C13—H13A	120.2
C8—N3—C9	108.43 (15)	C12—C13—H13A	120.2
C8—N3—N4	119.01 (15)	C13—C14—C15	120.7 (2)
C9—N3—N4	132.41 (16)	C13—C14—H14A	119.6
C10—N4—N3	117.04 (16)	C15—C14—H14A	119.6
C2—C1—C6	117.99 (19)	C16—C15—C14	118.81 (19)
C2—C1—C7	121.30 (17)	C16—C15—H15A	120.6
C6—C1—C7	120.71 (18)	C14—C15—H15A	120.6
C1—C2—C3	121.00 (18)	C15—C16—C11	122.96 (19)
C1—C2—H2B	119.5	C15—C16—Cl2	117.26 (16)
C3—C2—H2B	119.5	C11—C16—Cl2	119.79 (16)
C2—C3—C4	121.3 (2)	C4—C17—C18	115.60 (17)
C2—C3—H3A	119.4	C4—C17—H17A	108.4
C4—C3—H3A	119.4	C18—C17—H17A	108.4
C5—C4—C3	117.32 (19)	C4—C17—H17B	108.4
C5—C4—C17	121.41 (18)	C18—C17—H17B	108.4
C3—C4—C17	121.22 (19)	H17A—C17—H17B	107.4
C4—C5—C6	121.51 (18)	C19—C18—C20	110.68 (17)
C4—C5—H5A	119.2	C19—C18—C17	109.89 (18)
C6—C5—H5A	119.2	C20—C18—C17	111.28 (17)
C5—C6—C1	120.83 (19)	C19—C18—H18A	108.3
C5—C6—H6A	119.6	C20—C18—H18A	108.3
C1—C6—H6A	119.6	C17—C18—H18A	108.3
C8—C7—C21	110.54 (16)	C18—C19—H19A	109.5
C8—C7—C1	108.88 (16)	C18—C19—H19B	109.5
C21—C7—C1	112.70 (16)	H19A—C19—H19B	109.5
C8—C7—H7A	108.2	C18—C19—H19C	109.5
C21—C7—H7A	108.2	H19A—C19—H19C	109.5
C1—C7—H7A	108.2	H19B—C19—H19C	109.5
N1—C8—N3	110.81 (16)	C18—C20—H20A	109.5
N1—C8—C7	126.05 (18)	C18—C20—H20B	109.5
N3—C8—C7	123.04 (17)	H20A—C20—H20B	109.5
N2—C9—N3	102.32 (15)	C18—C20—H20C	109.5
N2—C9—S1	127.33 (15)	H20A—C20—H20C	109.5
N3—C9—S1	130.33 (15)	H20B—C20—H20C	109.5
N4—C10—C11	121.60 (18)	C7—C21—H21A	109.5
N4—C10—H10A	119.2	C7—C21—H21B	109.5
C11—C10—H10A	119.2	H21A—C21—H21B	109.5
C12—C11—C16	115.84 (18)	C7—C21—H21C	109.5
C12—C11—C10	125.92 (18)	H21A—C21—H21C	109.5
C16—C11—C10	118.21 (17)	H21B—C21—H21C	109.5
C13—C12—C11	122.11 (19)
C8—N1—N2—C9	0.0 (2)	N1—N2—C9—N3	−1.0 (2)
C8—N3—N4—C10	−158.60 (18)	N1—N2—C9—S1	177.52 (14)
C9—N3—N4—C10	26.4 (3)	C8—N3—C9—N2	1.52 (19)
C6—C1—C2—C3	−2.6 (3)	N4—N3—C9—N2	176.87 (18)
C7—C1—C2—C3	177.75 (18)	C8—N3—C9—S1	−176.89 (16)
C1—C2—C3—C4	0.3 (3)	N4—N3—C9—S1	−1.5 (3)
C2—C3—C4—C5	2.3 (3)	N3—N4—C10—C11	179.51 (17)
C2—C3—C4—C17	−175.13 (19)	N4—C10—C11—C12	−26.3 (3)
C3—C4—C5—C6	−2.6 (3)	N4—C10—C11—C16	155.8 (2)
C17—C4—C5—C6	174.83 (19)	C16—C11—C12—C13	−0.6 (3)
C4—C5—C6—C1	0.3 (3)	C10—C11—C12—C13	−178.53 (19)
C2—C1—C6—C5	2.3 (3)	C16—C11—C12—Cl1	177.38 (15)
C7—C1—C6—C5	−178.04 (18)	C10—C11—C12—Cl1	−0.6 (3)
C2—C1—C7—C8	−42.3 (2)	C11—C12—C13—C14	0.3 (3)
C6—C1—C7—C8	138.03 (19)	Cl1—C12—C13—C14	−177.75 (16)
C2—C1—C7—C21	80.7 (2)	C12—C13—C14—C15	0.1 (3)
C6—C1—C7—C21	−98.9 (2)	C13—C14—C15—C16	−0.2 (3)
N2—N1—C8—N3	1.0 (2)	C14—C15—C16—C11	−0.1 (3)
N2—N1—C8—C7	−175.37 (18)	C14—C15—C16—Cl2	−179.50 (16)
C9—N3—C8—N1	−1.7 (2)	C12—C11—C16—C15	0.5 (3)
N4—N3—C8—N1	−177.76 (17)	C10—C11—C16—C15	178.60 (19)
C9—N3—C8—C7	174.84 (17)	C12—C11—C16—Cl2	179.88 (15)
N4—N3—C8—C7	−1.2 (3)	C10—C11—C16—Cl2	−2.0 (2)
C21—C7—C8—N1	−29.1 (3)	C5—C4—C17—C18	56.3 (3)
C1—C7—C8—N1	95.2 (2)	C3—C4—C17—C18	−126.4 (2)
C21—C7—C8—N3	154.92 (18)	C4—C17—C18—C19	−173.51 (18)
C1—C7—C8—N3	−80.8 (2)	C4—C17—C18—C20	63.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1i	0.86	2.44	3.2849 (19)	169
C10—H10A···Cl2	0.93	2.62	2.978 (2)	104
C10—H10A···S1	0.93	2.52	3.2066 (19)	131
C15—H15A···Cg1ii	0.93	2.94	3.793 (3)	154

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯S1i	0.86	2.44	3.2849 (19)	169
C10—H10A⋯Cl2	0.93	2.62	2.978 (2)	104
C10—H10A⋯S1	0.93	2.52	3.2066 (19)	131
C15—H15A⋯Cg1ii	0.93	2.94	3.793 (3)	154

Symmetry codes: (i) ; (ii) .