4-Bromo-benzoic acid-6-(4-bromo-phen-yl)-3-methyl-1,2,4-triazolo[3,4-b][1,3,4]thia-diazole (1/1).

In the title 1:1 co-crystal, C(10)H(7)BrN(4)S·C(7)H(5)BrO(2), the triazolothia-diazole system is approximately planar [with a maximum deviation of 0.030 (4) Å] and forms a dihedral angle of 8.6 (1)° with the bromo-phenyl ring. In the carb-oxy-lic acid mol-ecule, the carboxyl group is rotated by 6.4 (3)° out of the benzene ring plane. The crystal structure features O-H⋯N and C-H⋯O hydrogen bonds, π-π stacking inter-actions [centroid-centroid distances = 3.713 (2), 3.670 (2) and 3.859 (3) Å] and short S⋯N [2.883 (4) Å] contacts.

Related literature

For the biological activity of triazole derivatives, thia­diazo­les and triazolothia­diazole compounds, see: Chaturvedi et al. (1988 ▶); Holla et al. (2003 ▶); Bhat et al. (2004 ▶); Bekircan & Bektas (2006 ▶); Shawali & Sayed (2006 ▶); Mathew et al. (2007 ▶); Karthikeyan et al. (2007 ▶); Zhou et al. (2007 ▶). For related structures, see: Dinçer et al. (2005 ▶); Arshad et al. (2009 ▶); Jia et al. (2011 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C10H7BrN4S·C7H5BrO2

M = 496.19

Triclinic,

a = 7.7592 (3) Å

b = 8.0634 (4) Å

c = 14.9076 (7) Å

α = 94.090 (4)°

β = 92.961 (3)°

γ = 99.326 (4)°

V = 916.13 (7) Å3

Z = 2

Mo Kα radiation

μ = 4.56 mm−1

T = 293 K

0.3 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2010 ▶) T min = 0.581, T max = 1.000

8264 measured reflections

3594 independent reflections

2254 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.116

S = 1.01

3594 reflections

236 parameters

H-atom parameters constrained

Δρmax = 0.43 e Å−3

Δρmin = −0.51 e Å−3

Data collection: CrysAlis PRO CCD (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO CCD; data reduction: CrysAlis PRO RED (Oxford Diffraction, 2010 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812012184/bh2421sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812012184/bh2421Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812012184/bh2421Isup3.cml

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

C10H7BrN4S·C7H5BrO2	Z = 2
Mr = 496.19	F(000) = 488
Triclinic, P1	Dx = 1.799 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7592 (3) Å	Cell parameters from 2731 reflections
b = 8.0634 (4) Å	θ = 3.4–28.9°
c = 14.9076 (7) Å	µ = 4.56 mm−1
α = 94.090 (4)°	T = 293 K
β = 92.961 (3)°	Block, white
γ = 99.326 (4)°	0.3 × 0.2 × 0.2 mm
V = 916.13 (7) Å3

Oxford Diffraction Xcalibur Sapphire3 diffractometer	3594 independent reflections
Radiation source: fine-focus sealed tube	2254 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Detector resolution: 16.1049 pixels mm-1	θmax = 26.0°, θmin = 3.4°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2010)	k = −9→9
Tmin = 0.581, Tmax = 1.000	l = −18→18
8264 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0424P)2 + 0.2229P] where P = (Fo2 + 2Fc2)/3
3594 reflections	(Δ/σ)max = 0.001
236 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.51 e Å−3
0 constraints

	x	y	z	Uiso*/Ueq
Br1	0.48693 (7)	0.65776 (8)	0.62657 (4)	0.0850 (3)
Br2	0.15874 (8)	0.27859 (8)	0.50571 (4)	0.0967 (3)
N1	−0.4623 (4)	0.3387 (4)	1.0195 (2)	0.0462 (9)
N2	−0.4261 (4)	0.1982 (4)	1.0619 (2)	0.0445 (9)
C3	−0.2777 (5)	0.1581 (5)	1.0362 (3)	0.0397 (10)
N4	−0.2150 (4)	0.2704 (4)	0.9772 (2)	0.0352 (8)
N5	−0.0694 (4)	0.2926 (4)	0.9277 (2)	0.0375 (8)
C6	−0.0778 (5)	0.4209 (5)	0.8811 (3)	0.0340 (9)
S7	−0.25764 (12)	0.52658 (14)	0.89676 (7)	0.0435 (3)
C8	−0.3311 (5)	0.3782 (5)	0.9699 (3)	0.0360 (9)
C9	−0.1926 (5)	0.0180 (5)	1.0658 (3)	0.0554 (13)
H9A	−0.2529	−0.0311	1.1146	0.083*
H9B	−0.0728	0.0603	1.0855	0.083*
H9C	−0.1970	−0.0661	1.0164	0.083*
C10	0.0567 (5)	0.4805 (5)	0.8205 (3)	0.0361 (9)
C11	0.2088 (5)	0.4096 (5)	0.8184 (3)	0.0440 (10)
H11	0.2251	0.3262	0.8565	0.053*
C12	0.3355 (5)	0.4618 (6)	0.7602 (3)	0.0527 (12)
H12	0.4359	0.4128	0.7583	0.063*
C13	0.3124 (5)	0.5858 (6)	0.7056 (3)	0.0480 (11)
C14	0.1622 (6)	0.6563 (6)	0.7054 (3)	0.0657 (14)
H14	0.1465	0.7390	0.6667	0.079*
C15	0.0365 (6)	0.6033 (6)	0.7628 (3)	0.0547 (12)
H15	−0.0648	0.6511	0.7629	0.066*
C16	−0.2498 (6)	0.0900 (5)	0.7076 (3)	0.0474 (11)
C17	−0.2908 (7)	0.1880 (7)	0.6397 (3)	0.0694 (15)
H17	−0.4023	0.2159	0.6342	0.083*
C18	−0.1704 (8)	0.2442 (7)	0.5808 (4)	0.0782 (16)
H18	−0.1989	0.3108	0.5357	0.094*
C19	−0.0075 (7)	0.2015 (6)	0.5886 (3)	0.0596 (13)
C20	0.0382 (6)	0.1051 (6)	0.6543 (3)	0.0614 (13)
H20	0.1500	0.0776	0.6590	0.074*
C21	−0.0852 (6)	0.0486 (6)	0.7140 (3)	0.0557 (12)
H21	−0.0560	−0.0181	0.7590	0.067*
C22	−0.3841 (6)	0.0335 (6)	0.7719 (3)	0.0541 (12)
O23	−0.5243 (5)	0.0796 (5)	0.7726 (3)	0.0950 (13)
O24	−0.3345 (4)	−0.0720 (4)	0.8274 (2)	0.0619 (9)
H24	−0.4124	−0.0992	0.8612	0.093*

	U11	U22	U33	U12	U13	U23
Br1	0.0729 (4)	0.1007 (5)	0.0763 (4)	−0.0147 (3)	0.0444 (3)	0.0090 (3)
Br2	0.1079 (5)	0.0963 (5)	0.0782 (5)	−0.0219 (4)	0.0536 (4)	0.0087 (3)
N1	0.0459 (19)	0.044 (2)	0.056 (2)	0.0171 (16)	0.0223 (17)	0.0206 (18)
N2	0.0456 (19)	0.044 (2)	0.049 (2)	0.0128 (16)	0.0183 (16)	0.0164 (17)
C3	0.044 (2)	0.041 (3)	0.039 (2)	0.0135 (19)	0.0142 (19)	0.0119 (19)
N4	0.0386 (17)	0.0350 (19)	0.0361 (19)	0.0122 (15)	0.0118 (14)	0.0096 (15)
N5	0.0347 (17)	0.041 (2)	0.041 (2)	0.0145 (15)	0.0147 (14)	0.0099 (16)
C6	0.036 (2)	0.033 (2)	0.034 (2)	0.0071 (17)	0.0065 (17)	0.0032 (18)
S7	0.0403 (5)	0.0434 (7)	0.0537 (7)	0.0157 (5)	0.0182 (5)	0.0205 (5)
C8	0.037 (2)	0.039 (2)	0.038 (2)	0.0161 (18)	0.0110 (18)	0.0093 (18)
C9	0.058 (3)	0.054 (3)	0.065 (3)	0.026 (2)	0.025 (2)	0.032 (2)
C10	0.034 (2)	0.039 (2)	0.036 (2)	0.0052 (17)	0.0076 (17)	0.0027 (18)
C11	0.043 (2)	0.046 (3)	0.048 (3)	0.011 (2)	0.0139 (19)	0.014 (2)
C12	0.038 (2)	0.065 (3)	0.058 (3)	0.009 (2)	0.014 (2)	0.008 (3)
C13	0.040 (2)	0.056 (3)	0.044 (3)	−0.008 (2)	0.020 (2)	0.000 (2)
C14	0.079 (3)	0.065 (4)	0.062 (3)	0.018 (3)	0.031 (3)	0.032 (3)
C15	0.061 (3)	0.059 (3)	0.054 (3)	0.024 (2)	0.023 (2)	0.026 (2)
C16	0.057 (3)	0.039 (3)	0.046 (3)	0.002 (2)	0.018 (2)	0.004 (2)
C17	0.075 (3)	0.075 (4)	0.068 (4)	0.022 (3)	0.024 (3)	0.034 (3)
C18	0.096 (4)	0.079 (4)	0.065 (4)	0.013 (3)	0.026 (3)	0.036 (3)
C19	0.068 (3)	0.055 (3)	0.050 (3)	−0.011 (3)	0.024 (2)	0.002 (2)
C20	0.058 (3)	0.062 (3)	0.063 (3)	0.002 (2)	0.014 (2)	0.009 (3)
C21	0.057 (3)	0.055 (3)	0.055 (3)	0.004 (2)	0.014 (2)	0.014 (2)
C22	0.059 (3)	0.049 (3)	0.056 (3)	0.006 (2)	0.025 (2)	0.015 (2)
O23	0.092 (3)	0.107 (3)	0.112 (3)	0.055 (2)	0.064 (2)	0.065 (3)
O24	0.0582 (18)	0.075 (2)	0.058 (2)	0.0100 (17)	0.0270 (15)	0.0309 (18)

Br1—C13	1.888 (4)	C12—C13	1.362 (6)
Br2—C19	1.895 (4)	C12—H12	0.9300
N1—C8	1.301 (5)	C13—C14	1.377 (6)
N1—N2	1.395 (4)	C14—C15	1.367 (6)
N2—C3	1.313 (5)	C14—H14	0.9300
C3—N4	1.359 (5)	C15—H15	0.9300
C3—C9	1.480 (5)	C16—C21	1.372 (6)
N4—C8	1.355 (4)	C16—C17	1.383 (6)
N4—N5	1.375 (4)	C16—C22	1.491 (6)
N5—C6	1.295 (5)	C17—C18	1.362 (7)
C6—C10	1.460 (5)	C17—H17	0.9300
C6—S7	1.766 (4)	C18—C19	1.364 (7)
S7—C8	1.724 (4)	C18—H18	0.9300
C9—H9A	0.9600	C19—C20	1.360 (7)
C9—H9B	0.9600	C20—C21	1.386 (6)
C9—H9C	0.9600	C20—H20	0.9300
C10—C15	1.380 (6)	C21—H21	0.9300
C10—C11	1.394 (5)	C22—O23	1.205 (5)
C11—C12	1.379 (5)	C22—O24	1.315 (5)
C11—H11	0.9300	O24—H24	0.8200
C8—N1—N2	104.9 (3)	C12—C13—C14	121.1 (4)
C3—N2—N1	110.0 (3)	C12—C13—Br1	119.3 (3)
N2—C3—N4	107.2 (4)	C14—C13—Br1	119.6 (4)
N2—C3—C9	126.9 (4)	C15—C14—C13	119.1 (4)
N4—C3—C9	125.9 (3)	C15—C14—H14	120.4
C8—N4—C3	106.8 (3)	C13—C14—H14	120.4
C8—N4—N5	118.7 (3)	C14—C15—C10	121.5 (4)
C3—N4—N5	134.5 (3)	C14—C15—H15	119.3
C6—N5—N4	107.6 (3)	C10—C15—H15	119.3
N5—C6—C10	122.4 (3)	C21—C16—C17	118.6 (4)
N5—C6—S7	116.7 (3)	C21—C16—C22	121.9 (4)
C10—C6—S7	120.9 (3)	C17—C16—C22	119.5 (4)
C8—S7—C6	87.70 (18)	C18—C17—C16	121.0 (5)
N1—C8—N4	111.2 (3)	C18—C17—H17	119.5
N1—C8—S7	139.6 (3)	C16—C17—H17	119.5
N4—C8—S7	109.2 (3)	C17—C18—C19	119.2 (5)
C3—C9—H9A	109.5	C17—C18—H18	120.4
C3—C9—H9B	109.5	C19—C18—H18	120.4
H9A—C9—H9B	109.5	C20—C19—C18	121.6 (4)
C3—C9—H9C	109.5	C20—C19—Br2	119.4 (4)
H9A—C9—H9C	109.5	C18—C19—Br2	119.0 (4)
H9B—C9—H9C	109.5	C19—C20—C21	118.7 (4)
C15—C10—C11	118.2 (4)	C19—C20—H20	120.6
C15—C10—C6	122.0 (4)	C21—C20—H20	120.6
C11—C10—C6	119.8 (4)	C16—C21—C20	120.7 (5)
C12—C11—C10	120.6 (4)	C16—C21—H21	119.6
C12—C11—H11	119.7	C20—C21—H21	119.6
C10—C11—H11	119.7	O23—C22—O24	123.5 (4)
C13—C12—C11	119.5 (4)	O23—C22—C16	123.2 (5)
C13—C12—H12	120.3	O24—C22—C16	113.2 (4)
C11—C12—H12	120.3	C22—O24—H24	109.5
C8—N1—N2—C3	−0.4 (5)	C15—C10—C11—C12	0.3 (6)
N1—N2—C3—N4	−0.1 (5)	C6—C10—C11—C12	178.6 (4)
N1—N2—C3—C9	179.6 (4)	C10—C11—C12—C13	1.1 (7)
N2—C3—N4—C8	0.5 (5)	C11—C12—C13—C14	−2.0 (7)
C9—C3—N4—C8	−179.2 (4)	C11—C12—C13—Br1	179.6 (3)
N2—C3—N4—N5	−179.2 (4)	C12—C13—C14—C15	1.6 (7)
C9—C3—N4—N5	1.1 (7)	Br1—C13—C14—C15	179.9 (4)
C8—N4—N5—C6	−0.6 (5)	C13—C14—C15—C10	−0.2 (8)
C3—N4—N5—C6	179.1 (4)	C11—C10—C15—C14	−0.7 (7)
N4—N5—C6—C10	180.0 (3)	C6—C10—C15—C14	−179.0 (4)
N4—N5—C6—S7	2.0 (4)	C21—C16—C17—C18	−0.7 (8)
N5—C6—S7—C8	−2.3 (3)	C22—C16—C17—C18	178.9 (5)
C10—C6—S7—C8	179.8 (3)	C16—C17—C18—C19	0.6 (9)
N2—N1—C8—N4	0.8 (5)	C17—C18—C19—C20	−0.4 (8)
N2—N1—C8—S7	−179.3 (4)	C17—C18—C19—Br2	179.5 (4)
C3—N4—C8—N1	−0.8 (5)	C18—C19—C20—C21	0.4 (8)
N5—N4—C8—N1	179.0 (3)	Br2—C19—C20—C21	−179.5 (4)
C3—N4—C8—S7	179.2 (3)	C17—C16—C21—C20	0.6 (7)
N5—N4—C8—S7	−1.0 (4)	C22—C16—C21—C20	−178.9 (4)
C6—S7—C8—N1	−178.3 (5)	C19—C20—C21—C16	−0.5 (7)
C6—S7—C8—N4	1.7 (3)	C21—C16—C22—O23	173.5 (5)
N5—C6—C10—C15	171.8 (4)	C17—C16—C22—O23	−6.0 (8)
S7—C6—C10—C15	−10.4 (6)	C21—C16—C22—O24	−6.7 (6)
N5—C6—C10—C11	−6.5 (6)	C17—C16—C22—O24	173.7 (4)
S7—C6—C10—C11	171.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O24—H24···N2i	0.82	1.87	2.674 (4)	169
C9—H9A···O23i	0.96	2.48	3.393 (6)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O24—H24⋯N2i	0.82	1.87	2.674 (4)	169
C9—H9A⋯O23i	0.96	2.48	3.393 (6)	159

Symmetry code: (i) .