7-(4-Chloro-benzyl-idene)-3-[(4-chloro-phen-oxy)meth-yl]-6-(4-nitro-thio-phen-2-yl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thia-diazine.

In the title compound, C(22)H(13)Cl(2)N(5)O(3)S(2), the thia-diazine ring adopts a half-chair conformation. The benzene rings of the chloro-phen-oxy and chloro-benzyl groups and the thio-phene ring form dihedral angles of 35.6 (1), 80.7 (1) and 14.2 (1)°, respectively, with the triazole ring. In the crystal, mol-ecules are connected into sheets parallel to ([Formula: see text]11) by inter-molecular C-H⋯N and C-H⋯Cl hydrogen bonds. In addition, π-π stacking inter-actions are observed between thio-phene and triazole rings, and between inversion-related triazole rings [centroid-centroid distances = 3.5975 (11) and 3.4324 (11) Å].

Related literature

For general background to and applications of 1,2,4-triazole derivatives, see: Shujuan et al. (2004 ▶); Clemons et al. (2004 ▶); Johnston (2002 ▶); Wei et al. (2007 ▶). For ring conformations and ring puckering analysis, see: Cremer & Pople (1975 ▶). For bond-length data, see: Allen et al. (1987 ▶); Jin et al. (2004 ▶). For related structures, see: Goh et al. (2010 ▶).

Experimental

Crystal data

C22H13Cl2N5O3S2

M = 530.39

Triclinic,

a = 8.5021 (2) Å

b = 10.0379 (2) Å

c = 14.3623 (3) Å

α = 94.434 (1)°

β = 97.981 (1)°

γ = 109.242 (1)°

V = 1136.07 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.51 mm−1

T = 296 K

0.39 × 0.32 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.827, T max = 0.946

19590 measured reflections

6548 independent reflections

5142 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.133

S = 1.04

6548 reflections

307 parameters

H-atom parameters constrained

Δρmax = 0.59 e Å−3

Δρmin = −0.46 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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/S1600536811015637/ci5185sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015637/ci5185Isup2.hkl

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

C22H13Cl2N5O3S2	Z = 2
Mr = 530.39	F(000) = 540
Triclinic, P1	Dx = 1.551 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5021 (2) Å	Cell parameters from 5767 reflections
b = 10.0379 (2) Å	θ = 2.7–32.0°
c = 14.3623 (3) Å	µ = 0.51 mm−1
α = 94.434 (1)°	T = 296 K
β = 97.981 (1)°	Plate, yellow
γ = 109.242 (1)°	0.39 × 0.32 × 0.11 mm
V = 1136.07 (4) Å3

Bruker SMART APEXII CCD area-detector diffractometer	6548 independent reflections
Radiation source: fine-focus sealed tube	5142 reflections with I > 2σ(I)
graphite	Rint = 0.031
φ and ω scans	θmax = 30.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.827, Tmax = 0.946	k = −14→14
19590 measured reflections	l = −20→20

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0647P)2 + 0.3979P] where P = (Fo2 + 2Fc2)/3
6548 reflections	(Δ/σ)max = 0.001
307 parameters	Δρmax = 0.59 e Å−3
0 restraints	Δρmin = −0.46 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	0.31310 (6)	0.39243 (5)	0.13806 (3)	0.03764 (12)
S2	0.65367 (7)	0.90408 (5)	0.02701 (4)	0.04462 (14)
Cl1	0.32206 (12)	1.05741 (9)	−0.46034 (7)	0.0906 (3)
Cl2	0.17004 (8)	0.36669 (8)	0.58962 (4)	0.06035 (17)
N1	0.0052 (2)	0.34827 (18)	−0.09684 (11)	0.0418 (4)
N2	0.0543 (2)	0.29741 (17)	−0.01333 (11)	0.0391 (3)
N3	0.23458 (18)	0.51207 (16)	−0.01635 (10)	0.0316 (3)
N4	0.37735 (19)	0.63329 (16)	0.00403 (10)	0.0349 (3)
N5	1.0471 (2)	0.9832 (2)	0.22741 (17)	0.0602 (5)
O1	0.25195 (18)	0.62527 (17)	−0.20276 (10)	0.0451 (3)
O2	1.1570 (3)	1.0856 (3)	0.2079 (2)	0.0994 (8)
O3	1.0661 (3)	0.9215 (3)	0.29489 (15)	0.0825 (6)
C1	0.1175 (3)	0.7481 (2)	−0.31056 (13)	0.0416 (4)
H1A	0.0097	0.6926	−0.3027	0.050*
C2	0.1376 (3)	0.8504 (2)	−0.37127 (14)	0.0455 (5)
H2A	0.0436	0.8644	−0.4045	0.055*
C3	0.2982 (3)	0.9316 (2)	−0.38211 (16)	0.0486 (5)
C4	0.4404 (3)	0.9153 (3)	−0.33232 (18)	0.0540 (5)
H4A	0.5479	0.9717	−0.3399	0.065*
C5	0.4199 (3)	0.8139 (2)	−0.27120 (15)	0.0464 (5)
H5A	0.5145	0.8028	−0.2364	0.056*
C6	0.2593 (2)	0.7284 (2)	−0.26134 (12)	0.0367 (4)
C7	0.0975 (3)	0.5693 (2)	−0.16998 (14)	0.0433 (4)
H7A	0.0089	0.5158	−0.2227	0.052*
H7B	0.0664	0.6464	−0.1426	0.052*
C8	0.1140 (2)	0.4746 (2)	−0.09737 (12)	0.0355 (4)
C9	0.1912 (2)	0.39706 (18)	0.03185 (12)	0.0321 (3)
C10	0.4010 (2)	0.57962 (18)	0.16945 (12)	0.0314 (3)
C11	0.4557 (2)	0.66196 (18)	0.09118 (12)	0.0317 (3)
C12	0.6138 (2)	0.78458 (19)	0.10904 (12)	0.0336 (3)
C13	0.7497 (2)	0.8140 (2)	0.17988 (13)	0.0379 (4)
H13A	0.7535	0.7623	0.2307	0.045*
C14	0.8840 (2)	0.9339 (2)	0.16526 (15)	0.0416 (4)
C15	0.8518 (3)	0.9942 (2)	0.08699 (16)	0.0456 (5)
H15A	0.9278	1.0739	0.0687	0.055*
C16	0.4132 (2)	0.64263 (19)	0.25710 (12)	0.0351 (4)
H16A	0.4627	0.7413	0.2673	0.042*
C17	0.3573 (2)	0.57331 (19)	0.33897 (12)	0.0336 (3)
C18	0.2834 (3)	0.6385 (2)	0.40089 (13)	0.0405 (4)
H18A	0.2732	0.7258	0.3906	0.049*
C19	0.2251 (3)	0.5746 (2)	0.47743 (13)	0.0435 (4)
H19A	0.1746	0.6180	0.5179	0.052*
C20	0.2426 (2)	0.4462 (2)	0.49313 (12)	0.0392 (4)
C21	0.3189 (3)	0.3808 (2)	0.43452 (13)	0.0411 (4)
H21A	0.3314	0.2947	0.4463	0.049*
C22	0.3765 (2)	0.4453 (2)	0.35809 (12)	0.0377 (4)
H22A	0.4290	0.4021	0.3188	0.045*

	U11	U22	U33	U12	U13	U23
S1	0.0452 (3)	0.0336 (2)	0.0311 (2)	0.01036 (19)	0.00304 (18)	0.00748 (16)
S2	0.0439 (3)	0.0399 (3)	0.0487 (3)	0.0095 (2)	0.0095 (2)	0.0183 (2)
Cl1	0.1026 (6)	0.0671 (4)	0.1053 (6)	0.0239 (4)	0.0179 (5)	0.0532 (4)
Cl2	0.0592 (4)	0.0895 (4)	0.0412 (3)	0.0276 (3)	0.0205 (2)	0.0311 (3)
N1	0.0374 (9)	0.0467 (9)	0.0348 (8)	0.0072 (7)	0.0040 (6)	0.0042 (7)
N2	0.0395 (9)	0.0373 (8)	0.0343 (8)	0.0054 (7)	0.0059 (6)	0.0041 (6)
N3	0.0280 (7)	0.0361 (7)	0.0276 (6)	0.0057 (6)	0.0063 (5)	0.0072 (5)
N4	0.0309 (7)	0.0381 (8)	0.0310 (7)	0.0043 (6)	0.0068 (6)	0.0083 (6)
N5	0.0348 (10)	0.0588 (12)	0.0699 (14)	0.0003 (9)	0.0002 (9)	−0.0045 (10)
O1	0.0376 (7)	0.0657 (9)	0.0394 (7)	0.0221 (7)	0.0121 (6)	0.0219 (6)
O2	0.0397 (10)	0.0808 (15)	0.144 (2)	−0.0193 (10)	−0.0013 (12)	0.0271 (14)
O3	0.0505 (11)	0.1096 (17)	0.0642 (12)	0.0057 (11)	−0.0134 (9)	0.0150 (11)
C1	0.0357 (10)	0.0531 (11)	0.0356 (9)	0.0142 (9)	0.0050 (7)	0.0100 (8)
C2	0.0512 (12)	0.0492 (11)	0.0379 (10)	0.0227 (10)	0.0005 (8)	0.0052 (8)
C3	0.0614 (14)	0.0369 (10)	0.0472 (11)	0.0146 (9)	0.0109 (10)	0.0109 (8)
C4	0.0462 (12)	0.0482 (12)	0.0640 (14)	0.0089 (10)	0.0117 (10)	0.0162 (10)
C5	0.0370 (10)	0.0531 (12)	0.0483 (11)	0.0151 (9)	0.0045 (8)	0.0099 (9)
C6	0.0361 (9)	0.0473 (10)	0.0274 (8)	0.0153 (8)	0.0051 (7)	0.0060 (7)
C7	0.0338 (10)	0.0613 (12)	0.0345 (9)	0.0139 (9)	0.0063 (7)	0.0156 (8)
C8	0.0308 (9)	0.0439 (10)	0.0287 (8)	0.0090 (7)	0.0048 (6)	0.0046 (7)
C9	0.0328 (8)	0.0338 (8)	0.0285 (7)	0.0086 (7)	0.0076 (6)	0.0050 (6)
C10	0.0283 (8)	0.0348 (8)	0.0291 (8)	0.0071 (7)	0.0062 (6)	0.0073 (6)
C11	0.0302 (8)	0.0349 (8)	0.0295 (8)	0.0083 (7)	0.0086 (6)	0.0075 (6)
C12	0.0316 (9)	0.0332 (8)	0.0328 (8)	0.0049 (7)	0.0087 (7)	0.0074 (6)
C13	0.0331 (9)	0.0427 (10)	0.0329 (8)	0.0063 (8)	0.0058 (7)	0.0053 (7)
C14	0.0309 (9)	0.0404 (10)	0.0457 (10)	0.0031 (8)	0.0069 (8)	0.0002 (8)
C15	0.0408 (11)	0.0304 (9)	0.0591 (12)	0.0004 (8)	0.0172 (9)	0.0059 (8)
C16	0.0346 (9)	0.0352 (9)	0.0315 (8)	0.0056 (7)	0.0082 (7)	0.0046 (7)
C17	0.0302 (8)	0.0395 (9)	0.0274 (8)	0.0073 (7)	0.0052 (6)	0.0037 (6)
C18	0.0448 (11)	0.0387 (9)	0.0372 (9)	0.0115 (8)	0.0118 (8)	0.0053 (7)
C19	0.0466 (11)	0.0532 (12)	0.0327 (9)	0.0178 (9)	0.0138 (8)	0.0031 (8)
C20	0.0331 (9)	0.0540 (11)	0.0263 (8)	0.0086 (8)	0.0047 (7)	0.0089 (7)
C21	0.0434 (11)	0.0495 (11)	0.0341 (9)	0.0201 (9)	0.0051 (8)	0.0118 (8)
C22	0.0389 (10)	0.0496 (10)	0.0278 (8)	0.0192 (8)	0.0060 (7)	0.0055 (7)

S1—C9	1.7342 (18)	C5—C6	1.386 (3)
S1—C10	1.7727 (18)	C5—H5A	0.93
S2—C15	1.694 (2)	C7—C8	1.486 (3)
S2—C12	1.7330 (17)	C7—H7A	0.97
Cl1—C3	1.736 (2)	C7—H7B	0.97
Cl2—C20	1.7386 (18)	C10—C16	1.339 (2)
N1—C8	1.302 (2)	C10—C11	1.483 (2)
N1—N2	1.403 (2)	C11—C12	1.467 (2)
N2—C9	1.303 (2)	C12—C13	1.364 (3)
N3—C9	1.364 (2)	C13—C14	1.413 (3)
N3—C8	1.376 (2)	C13—H13A	0.93
N3—N4	1.383 (2)	C14—C15	1.354 (3)
N4—C11	1.296 (2)	C15—H15A	0.93
N5—O3	1.210 (3)	C16—C17	1.468 (2)
N5—O2	1.221 (3)	C16—H16A	0.93
N5—C14	1.449 (3)	C17—C22	1.391 (3)
O1—C6	1.375 (2)	C17—C18	1.397 (3)
O1—C7	1.410 (2)	C18—C19	1.384 (3)
C1—C2	1.382 (3)	C18—H18A	0.93
C1—C6	1.391 (3)	C19—C20	1.377 (3)
C1—H1A	0.93	C19—H19A	0.93
C2—C3	1.378 (3)	C20—C21	1.381 (3)
C2—H2A	0.93	C21—C22	1.383 (3)
C3—C4	1.381 (3)	C21—H21A	0.93
C4—C5	1.378 (3)	C22—H22A	0.93
C4—H4A	0.93
C9—S1—C10	95.62 (8)	N3—C9—S1	121.40 (13)
C15—S2—C12	92.18 (10)	C16—C10—C11	122.26 (16)
C8—N1—N2	107.87 (15)	C16—C10—S1	122.39 (13)
C9—N2—N1	106.29 (15)	C11—C10—S1	115.32 (12)
C9—N3—C8	104.63 (14)	N4—C11—C12	114.57 (15)
C9—N3—N4	128.75 (14)	N4—C11—C10	125.55 (16)
C8—N3—N4	126.23 (14)	C12—C11—C10	119.85 (15)
C11—N4—N3	115.80 (14)	C13—C12—C11	128.47 (16)
O3—N5—O2	124.2 (2)	C13—C12—S2	111.57 (14)
O3—N5—C14	118.5 (2)	C11—C12—S2	119.62 (13)
O2—N5—C14	117.2 (2)	C12—C13—C14	110.48 (17)
C6—O1—C7	115.44 (15)	C12—C13—H13A	124.8
C2—C1—C6	119.61 (19)	C14—C13—H13A	124.8
C2—C1—H1A	120.2	C15—C14—C13	115.29 (18)
C6—C1—H1A	120.2	C15—C14—N5	122.83 (19)
C3—C2—C1	119.4 (2)	C13—C14—N5	121.8 (2)
C3—C2—H2A	120.3	C14—C15—S2	110.47 (15)
C1—C2—H2A	120.3	C14—C15—H15A	124.8
C2—C3—C4	121.7 (2)	S2—C15—H15A	124.8
C2—C3—Cl1	119.05 (18)	C10—C16—C17	127.24 (17)
C4—C3—Cl1	119.29 (18)	C10—C16—H16A	116.4
C5—C4—C3	118.8 (2)	C17—C16—H16A	116.4
C5—C4—H4A	120.6	C22—C17—C18	118.34 (16)
C3—C4—H4A	120.6	C22—C17—C16	122.56 (16)
C4—C5—C6	120.4 (2)	C18—C17—C16	119.10 (17)
C4—C5—H5A	119.8	C19—C18—C17	120.80 (18)
C6—C5—H5A	119.8	C19—C18—H18A	119.6
O1—C6—C5	116.08 (17)	C17—C18—H18A	119.6
O1—C6—C1	123.84 (17)	C20—C19—C18	119.36 (18)
C5—C6—C1	120.07 (18)	C20—C19—H19A	120.3
O1—C7—C8	109.98 (16)	C18—C19—H19A	120.3
O1—C7—H7A	109.7	C19—C20—C21	121.20 (17)
C8—C7—H7A	109.7	C19—C20—Cl2	119.24 (15)
O1—C7—H7B	109.7	C21—C20—Cl2	119.55 (16)
C8—C7—H7B	109.7	C20—C21—C22	119.05 (18)
H7A—C7—H7B	108.2	C20—C21—H21A	120.5
N1—C8—N3	109.93 (16)	C22—C21—H21A	120.5
N1—C8—C7	124.21 (17)	C21—C22—C17	121.21 (17)
N3—C8—C7	125.52 (17)	C21—C22—H22A	119.4
N2—C9—N3	111.26 (15)	C17—C22—H22A	119.4
N2—C9—S1	127.32 (14)
C8—N1—N2—C9	−0.1 (2)	C16—C10—C11—N4	−140.1 (2)
C9—N3—N4—C11	−21.5 (3)	S1—C10—C11—N4	38.2 (2)
C8—N3—N4—C11	166.81 (17)	C16—C10—C11—C12	42.0 (3)
C6—C1—C2—C3	0.0 (3)	S1—C10—C11—C12	−139.59 (14)
C1—C2—C3—C4	−1.3 (3)	N4—C11—C12—C13	−156.04 (19)
C1—C2—C3—Cl1	178.71 (16)	C10—C11—C12—C13	22.0 (3)
C2—C3—C4—C5	0.8 (4)	N4—C11—C12—S2	16.7 (2)
Cl1—C3—C4—C5	−179.26 (18)	C10—C11—C12—S2	−165.26 (13)
C3—C4—C5—C6	1.1 (4)	C15—S2—C12—C13	−0.15 (16)
C7—O1—C6—C5	161.28 (18)	C15—S2—C12—C11	−174.03 (15)
C7—O1—C6—C1	−19.9 (3)	C11—C12—C13—C14	173.10 (18)
C4—C5—C6—O1	176.5 (2)	S2—C12—C13—C14	−0.1 (2)
C4—C5—C6—C1	−2.4 (3)	C12—C13—C14—C15	0.4 (3)
C2—C1—C6—O1	−176.98 (18)	C12—C13—C14—N5	−176.46 (18)
C2—C1—C6—C5	1.8 (3)	O3—N5—C14—C15	−178.6 (2)
C6—O1—C7—C8	−172.11 (16)	O2—N5—C14—C15	1.6 (4)
N2—N1—C8—N3	−0.7 (2)	O3—N5—C14—C13	−2.0 (3)
N2—N1—C8—C7	−174.39 (17)	O2—N5—C14—C13	178.2 (2)
C9—N3—C8—N1	1.1 (2)	C13—C14—C15—S2	−0.5 (2)
N4—N3—C8—N1	174.43 (16)	N5—C14—C15—S2	176.31 (17)
C9—N3—C8—C7	174.73 (17)	C12—S2—C15—C14	0.37 (16)
N4—N3—C8—C7	−12.0 (3)	C11—C10—C16—C17	177.31 (17)
O1—C7—C8—N1	−132.7 (2)	S1—C10—C16—C17	−0.9 (3)
O1—C7—C8—N3	54.6 (3)	C10—C16—C17—C22	39.3 (3)
N1—N2—C9—N3	0.8 (2)	C10—C16—C17—C18	−141.3 (2)
N1—N2—C9—S1	−177.89 (13)	C22—C17—C18—C19	−2.3 (3)
C8—N3—C9—N2	−1.18 (19)	C16—C17—C18—C19	178.31 (18)
N4—N3—C9—N2	−174.25 (16)	C17—C18—C19—C20	0.9 (3)
C8—N3—C9—S1	177.59 (13)	C18—C19—C20—C21	0.7 (3)
N4—N3—C9—S1	4.5 (2)	C18—C19—C20—Cl2	179.75 (16)
C10—S1—C9—N2	−155.83 (17)	C19—C20—C21—C22	−0.8 (3)
C10—S1—C9—N3	25.61 (15)	Cl2—C20—C21—C22	−179.87 (15)
C9—S1—C10—C16	135.40 (16)	C20—C21—C22—C17	−0.6 (3)
C9—S1—C10—C11	−42.97 (14)	C18—C17—C22—C21	2.2 (3)
N3—N4—C11—C12	175.41 (15)	C16—C17—C22—C21	−178.45 (18)
N3—N4—C11—C10	−2.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15A···N2i	0.93	2.60	3.495 (3)	162
C21—H21A···Cl1ii	0.93	2.81	3.691 (2)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15A⋯N2i	0.93	2.60	3.495 (3)	162
C21—H21A⋯Cl1ii	0.93	2.81	3.691 (2)	159

Symmetry codes: (i) ; (ii) .