5-Bromo-4-(3,4-dimeth-oxy-phen-yl)thia-zol-2-amine.

In the title compound, C(11)H(11)BrN(2)O(2)S, the thia-zole ring makes a dihedral angle of 53.16 (11)° with the adjacent benzene ring. The two meth-oxy groups are slightly twisted from the attached benzene ring with C-O-C-C torsion angles of -9.2 (3) and -5.5 (3)°. In the crystal, mol-ecules are linked by a pair of N-H⋯N hydrogen bonds into an inversion dimer with an R(2) (2)(8) ring motif. The dimers are further connected by N-H⋯O hydrogen bonds into a tape along [-110].

Related literature

For applications of the thia­zole ring system, see: Hargrave et al. (1983 ▶); Patt et al. (1992 ▶); Haviv et al. (1988 ▶); Jaen et al. (1990 ▶); Tsuji & Ishikawa (1994 ▶); Bell et al. (1995 ▶). For applications of amino­thia­zoles, see: Fink et al. (1999 ▶); Van Muijlwijk-Koezen et al. (2001 ▶); Metzger (1984 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the preparation, see: Das et al. (2006 ▶). For stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C11H11BrN2O2S

M = 315.19

Triclinic,

a = 7.4873 (2) Å

b = 8.0359 (2) Å

c = 10.6428 (3) Å

α = 86.571 (2)°

β = 77.633 (2)°

γ = 85.330 (2)°

V = 622.82 (3) Å3

Z = 2

Mo Kα radiation

μ = 3.46 mm−1

T = 100 K

0.45 × 0.20 × 0.09 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.305, T max = 0.737

10861 measured reflections

2121 independent reflections

1888 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.071

S = 1.12

2121 reflections

164 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.17 e Å−3

Δρmin = −0.73 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 datablock(s) global, I. DOI: 10.1107/S1600536812019320/is5132sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812019320/is5132Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812019320/is5132Isup3.cml

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

C11H11BrN2O2S	Z = 2
Mr = 315.19	F(000) = 316
Triclinic, P1	Dx = 1.681 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4873 (2) Å	Cell parameters from 7495 reflections
b = 8.0359 (2) Å	θ = 2.6–35.5°
c = 10.6428 (3) Å	µ = 3.46 mm−1
α = 86.571 (2)°	T = 100 K
β = 77.633 (2)°	Plate, brown
γ = 85.330 (2)°	0.45 × 0.20 × 0.09 mm
V = 622.82 (3) Å3

Bruker SMART APEXII CCD area-detector diffractometer	2121 independent reflections
Radiation source: fine-focus sealed tube	1888 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
Tmin = 0.305, Tmax = 0.737	k = −9→9
10861 measured reflections	l = −12→12

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.0446P)2 + 0.1359P] where P = (Fo2 + 2Fc2)/3
2121 reflections	(Δ/σ)max = 0.002
164 parameters	Δρmax = 1.17 e Å−3
0 restraints	Δρmin = −0.73 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
Br1	−0.16418 (3)	0.27703 (3)	1.04837 (2)	0.02360 (12)
S1	−0.30599 (8)	0.51061 (8)	0.84026 (6)	0.01865 (17)
O1	0.6319 (2)	−0.1031 (2)	0.74403 (16)	0.0203 (4)
O2	0.4088 (2)	−0.1521 (2)	0.60126 (16)	0.0213 (4)
N1	−0.0368 (3)	0.4074 (3)	0.6600 (2)	0.0187 (5)
N2	−0.2487 (4)	0.5970 (3)	0.5852 (2)	0.0237 (5)
C1	0.2811 (3)	0.2379 (3)	0.8495 (2)	0.0195 (6)
H1A	0.2539	0.3246	0.9090	0.023*
C2	0.4415 (3)	0.1345 (3)	0.8433 (2)	0.0193 (6)
H2A	0.5241	0.1524	0.8968	0.023*
C3	0.4794 (3)	0.0060 (3)	0.7588 (2)	0.0168 (5)
C4	0.3576 (3)	−0.0193 (3)	0.6795 (2)	0.0162 (5)
C5	0.2018 (3)	0.0867 (3)	0.6835 (2)	0.0166 (5)
H5A	0.1218	0.0719	0.6274	0.020*
C6	0.1613 (3)	0.2164 (3)	0.7706 (2)	0.0169 (5)
C7	−0.0059 (3)	0.3294 (3)	0.7743 (2)	0.0167 (5)
C8	−0.1867 (3)	0.5072 (3)	0.6792 (2)	0.0180 (6)
C9	−0.1366 (3)	0.3686 (3)	0.8796 (2)	0.0174 (5)
C10	0.7724 (3)	−0.0657 (3)	0.8075 (2)	0.0233 (6)
H10A	0.8799	−0.1439	0.7821	0.035*
H10B	0.7274	−0.0762	0.9010	0.035*
H10C	0.8065	0.0488	0.7831	0.035*
C11	0.2828 (4)	−0.1928 (4)	0.5250 (3)	0.0260 (6)
H11A	0.3359	−0.2877	0.4723	0.039*
H11B	0.2589	−0.0961	0.4689	0.039*
H11C	0.1675	−0.2225	0.5819	0.039*
H2N2	−0.324 (4)	0.669 (4)	0.602 (3)	0.028 (9)*
H1N2	−0.182 (4)	0.606 (4)	0.515 (3)	0.033 (9)*

	U11	U22	U33	U12	U13	U23
Br1	0.02354 (18)	0.02661 (19)	0.01783 (16)	0.00291 (11)	−0.00083 (11)	0.00253 (12)
S1	0.0173 (3)	0.0182 (4)	0.0182 (3)	0.0037 (3)	−0.0003 (3)	−0.0012 (3)
O1	0.0161 (9)	0.0188 (10)	0.0266 (9)	0.0041 (7)	−0.0071 (7)	−0.0039 (8)
O2	0.0207 (9)	0.0200 (10)	0.0238 (9)	0.0045 (8)	−0.0060 (8)	−0.0086 (8)
N1	0.0190 (11)	0.0185 (12)	0.0178 (10)	0.0028 (9)	−0.0033 (9)	−0.0020 (9)
N2	0.0244 (14)	0.0241 (15)	0.0187 (12)	0.0125 (11)	−0.0005 (10)	−0.0019 (11)
C1	0.0203 (14)	0.0167 (14)	0.0208 (12)	−0.0003 (11)	−0.0019 (10)	−0.0048 (11)
C2	0.0187 (13)	0.0199 (15)	0.0202 (13)	−0.0014 (11)	−0.0057 (10)	−0.0008 (11)
C3	0.0142 (13)	0.0132 (13)	0.0209 (12)	0.0013 (10)	−0.0003 (10)	0.0021 (10)
C4	0.0178 (13)	0.0135 (14)	0.0152 (11)	−0.0001 (10)	0.0006 (10)	−0.0003 (10)
C5	0.0172 (13)	0.0173 (14)	0.0149 (11)	−0.0009 (10)	−0.0029 (10)	0.0007 (10)
C6	0.0188 (13)	0.0137 (13)	0.0162 (11)	−0.0003 (10)	−0.0001 (10)	0.0030 (10)
C7	0.0175 (13)	0.0136 (13)	0.0190 (12)	−0.0011 (10)	−0.0039 (10)	−0.0008 (11)
C8	0.0193 (14)	0.0170 (14)	0.0171 (12)	0.0013 (11)	−0.0030 (10)	−0.0024 (11)
C9	0.0192 (13)	0.0136 (14)	0.0183 (12)	0.0021 (10)	−0.0035 (10)	0.0017 (11)
C10	0.0140 (13)	0.0262 (16)	0.0296 (14)	0.0026 (11)	−0.0050 (11)	−0.0034 (12)
C11	0.0263 (15)	0.0265 (16)	0.0270 (14)	0.0004 (12)	−0.0080 (12)	−0.0097 (12)

Br1—C9	1.876 (2)	C2—C3	1.382 (3)
S1—C9	1.738 (3)	C2—H2A	0.9500
S1—C8	1.755 (2)	C3—C4	1.402 (3)
O1—C3	1.369 (3)	C4—C5	1.382 (4)
O1—C10	1.426 (3)	C5—C6	1.407 (3)
O2—C4	1.372 (3)	C5—H5A	0.9500
O2—C11	1.437 (3)	C6—C7	1.480 (4)
N1—C8	1.312 (3)	C7—C9	1.355 (3)
N1—C7	1.390 (3)	C10—H10A	0.9800
N2—C8	1.340 (4)	C10—H10B	0.9800
N2—H2N2	0.78 (3)	C10—H10C	0.9800
N2—H1N2	0.80 (3)	C11—H11A	0.9800
C1—C6	1.380 (3)	C11—H11B	0.9800
C1—C2	1.395 (4)	C11—H11C	0.9800
C1—H1A	0.9500
C9—S1—C8	88.28 (12)	C1—C6—C7	121.1 (2)
C3—O1—C10	116.65 (19)	C5—C6—C7	119.8 (2)
C4—O2—C11	117.3 (2)	C9—C7—N1	114.3 (2)
C8—N1—C7	111.7 (2)	C9—C7—C6	126.9 (2)
C8—N2—H2N2	120 (2)	N1—C7—C6	118.7 (2)
C8—N2—H1N2	119 (2)	N1—C8—N2	123.9 (2)
H2N2—N2—H1N2	116 (3)	N1—C8—S1	114.24 (19)
C6—C1—C2	121.1 (2)	N2—C8—S1	121.9 (2)
C6—C1—H1A	119.4	C7—C9—S1	111.44 (19)
C2—C1—H1A	119.4	C7—C9—Br1	128.9 (2)
C3—C2—C1	119.6 (2)	S1—C9—Br1	119.41 (13)
C3—C2—H2A	120.2	O1—C10—H10A	109.5
C1—C2—H2A	120.2	O1—C10—H10B	109.5
O1—C3—C2	124.9 (2)	H10A—C10—H10B	109.5
O1—C3—C4	115.1 (2)	O1—C10—H10C	109.5
C2—C3—C4	120.0 (2)	H10A—C10—H10C	109.5
O2—C4—C5	125.4 (2)	H10B—C10—H10C	109.5
O2—C4—C3	114.6 (2)	O2—C11—H11A	109.5
C5—C4—C3	120.1 (2)	O2—C11—H11B	109.5
C4—C5—C6	120.1 (2)	H11A—C11—H11B	109.5
C4—C5—H5A	119.9	O2—C11—H11C	109.5
C6—C5—H5A	119.9	H11A—C11—H11C	109.5
C1—C6—C5	119.1 (2)	H11B—C11—H11C	109.5
C6—C1—C2—C3	−1.4 (4)	C8—N1—C7—C9	1.5 (3)
C10—O1—C3—C2	−9.2 (3)	C8—N1—C7—C6	−178.0 (2)
C10—O1—C3—C4	170.4 (2)	C1—C6—C7—C9	−52.8 (4)
C1—C2—C3—O1	179.9 (2)	C5—C6—C7—C9	128.5 (3)
C1—C2—C3—C4	0.3 (4)	C1—C6—C7—N1	126.6 (2)
C11—O2—C4—C5	−5.5 (3)	C5—C6—C7—N1	−52.1 (3)
C11—O2—C4—C3	175.2 (2)	C7—N1—C8—N2	−179.6 (2)
O1—C3—C4—O2	1.3 (3)	C7—N1—C8—S1	−1.3 (3)
C2—C3—C4—O2	−179.1 (2)	C9—S1—C8—N1	0.6 (2)
O1—C3—C4—C5	−178.0 (2)	C9—S1—C8—N2	179.0 (2)
C2—C3—C4—C5	1.6 (4)	N1—C7—C9—S1	−1.0 (3)
O2—C4—C5—C6	178.4 (2)	C6—C7—C9—S1	178.36 (19)
C3—C4—C5—C6	−2.4 (3)	N1—C7—C9—Br1	172.86 (17)
C2—C1—C6—C5	0.6 (4)	C6—C7—C9—Br1	−7.7 (4)
C2—C1—C6—C7	−178.1 (2)	C8—S1—C9—C7	0.28 (19)
C4—C5—C6—C1	1.3 (3)	C8—S1—C9—Br1	−174.28 (14)
C4—C5—C6—C7	−180.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N2···O1i	0.78 (3)	2.40 (3)	2.992 (3)	134 (3)
N2—H2N2···O2i	0.78 (3)	2.37 (3)	3.112 (3)	161 (3)
N2—H1N2···N1ii	0.81 (3)	2.20 (3)	2.998 (3)	168 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N2⋯O1i	0.78 (3)	2.40 (3)	2.992 (3)	134 (3)
N2—H2N2⋯O2i	0.78 (3)	2.37 (3)	3.112 (3)	161 (3)
N2—H1N2⋯N1ii	0.81 (3)	2.20 (3)	2.998 (3)	168 (3)

Symmetry codes: (i) ; (ii) .