2-((1E)-1-{2-[(2Z)-4-(4-Bromo-phen-yl)-3-phenyl-2,3-di-hydro-1,3-thia-zol-2-yl-idene]hydrazin-1-yl-idene}eth-yl)pyridin-1-ium bromide monohydrate.

In the title hydrated molecular salt, C22H18BrN4S(+)·Br(-)·H2O, the aromatic rings make dihedral angles of 14.20 (12), 34.29 (10) and 68.75 (11)° with the thia-zole ring. In the crystal, mol-ecules are linked into chains running parallel to the a axis by association of the bromide ions and the water mol-ecules of crystallization with the cations via N-H⋯O, O-H⋯Br, C-H⋯N and C-H⋯Br hydrogen-bonding inter-actions. C-H⋯π and C-Br⋯π [3.7426 (11) Å, 161.73 (7)°] inter-actions are also observed, forming infinite chains extending along the b-axis direction.

Related literature

For general background to thia­zole compounds, see: Siddiqui et al. (2009 ▶); Quiroga et al. (2002 ▶); Hutchinson et al. (2002 ▶). For the biological activity of thia­zoles, see: Sharma et al. (2009 ▶); Ergenc et al. (1999 ▶); Bell et al. (1995 ▶); Patt et al. (1992 ▶); Jaen et al. (1990 ▶); Badorc et al. (1997 ▶); Rudolph et al. (2001 ▶). For structures with C—Br⋯π inter­actions, see: Jasinski et al. (2010 ▶); Zukerman-Schpector et al. (2011 ▶).

Experimental

Crystal data

C22H18BrN4S+·Br−·H2O

M = 548.30

Triclinic,

a = 5.5768 (6) Å

b = 9.2288 (9) Å

c = 22.574 (2) Å

α = 85.974 (1)°

β = 84.438 (1)°

γ = 79.000 (1)°

V = 1133.51 (19) Å3

Z = 2

Mo Kα radiation

μ = 3.69 mm−1

T = 150 K

0.27 × 0.11 × 0.08 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: numerical (SADABS; Bruker, 2013 ▶) T min = 0.390, T max = 0.760

20898 measured reflections

5870 independent reflections

4807 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.095

S = 1.09

5870 reflections

272 parameters

H-atom parameters constrained

Δρmax = 0.94 e Å−3

Δρmin = −0.49 e Å−3

Data collection: APEX2 (Bruker, 2013 ▶); cell refinement: SAINT (Bruker, 2013 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg & Putz, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681400347X/qm2104sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681400347X/qm2104Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S160053681400347X/qm2104Isup3.cml

CCDC reference: 987315

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

C22H18BrN4S+·Br−·H2O	Z = 2
Mr = 548.30	F(000) = 548
Triclinic, P1	Dx = 1.598 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.5768 (6) Å	Cell parameters from 9919 reflections
b = 9.2288 (9) Å	θ = 2.4–29.1°
c = 22.574 (2) Å	µ = 3.69 mm−1
α = 85.974 (1)°	T = 150 K
β = 84.438 (1)°	Column, orange
γ = 79.000 (1)°	0.27 × 0.11 × 0.08 mm
V = 1133.51 (19) Å3

Bruker SMART APEX CCD diffractometer	5870 independent reflections
Radiation source: fine-focus sealed tube	4807 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
φ and ω scans	θmax = 29.3°, θmin = 1.8°
Absorption correction: numerical (SADABS; Bruker, 2013)	h = −7→7
Tmin = 0.390, Tmax = 0.760	k = −12→12
20898 measured reflections	l = −30→30

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)] = 0.035	H-atom parameters constrained
wR(F2) = 0.095	W = 1/[Σ2(FO2) + (0.0532P)2 + 0.0059P] WHERE P = (FO2 + 2FC2)/3
S = 1.09	(Δ/σ)max < 0.001
5870 reflections	Δρmax = 0.94 e Å−3
272 parameters	Δρmin = −0.49 e Å−3
0 restraints

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, colllected at φ = 0.00, 90.00 and 180.00° and 2 sets of 800 frames, each of width 0.45° in φ, collected at ω = -30.00 and 210.00°. The scan time was 8 sec/frame.

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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	−0.67572 (4)	0.25013 (3)	0.47615 (2)	0.0304 (1)
S1	0.27834 (11)	0.54280 (7)	0.18810 (2)	0.0295 (2)
N1	0.0981 (3)	0.6483 (2)	0.28912 (8)	0.0239 (5)
N2	0.3783 (4)	0.7847 (2)	0.23756 (8)	0.0277 (6)
N3	0.5417 (4)	0.7723 (2)	0.18707 (8)	0.0287 (6)
N4	0.8686 (4)	0.7361 (2)	0.09224 (8)	0.0289 (6)
C1	−0.1818 (4)	0.4718 (2)	0.33067 (10)	0.0244 (6)
C2	−0.1555 (4)	0.4784 (2)	0.39151 (10)	0.0246 (6)
C3	−0.3043 (4)	0.4146 (2)	0.43439 (10)	0.0254 (6)
C4	−0.4804 (4)	0.3437 (2)	0.41671 (10)	0.0245 (6)
C5	−0.5136 (4)	0.3367 (2)	0.35703 (10)	0.0276 (7)
C6	−0.3638 (4)	0.4001 (2)	0.31457 (10)	0.0266 (6)
C7	0.0640 (4)	0.4595 (3)	0.23186 (10)	0.0289 (7)
C8	−0.0151 (4)	0.5258 (2)	0.28337 (10)	0.0247 (6)
C9	0.2610 (4)	0.6731 (2)	0.24143 (9)	0.0253 (7)
C10	0.0341 (4)	0.7538 (2)	0.33465 (9)	0.0223 (6)
C11	0.2053 (4)	0.7667 (3)	0.37362 (10)	0.0265 (7)
C12	0.1458 (4)	0.8746 (3)	0.41508 (10)	0.0303 (7)
C13	−0.0796 (4)	0.9677 (3)	0.41774 (10)	0.0308 (7)
C14	−0.2523 (4)	0.9507 (3)	0.37950 (11)	0.0302 (7)
C15	−0.1951 (4)	0.8427 (2)	0.33767 (10)	0.0259 (6)
C16	0.6559 (5)	0.8811 (3)	0.17393 (10)	0.0288 (7)
C17	0.6171 (6)	1.0229 (3)	0.20592 (12)	0.0415 (9)
C18	0.8431 (5)	0.8590 (3)	0.12317 (10)	0.0287 (7)
C19	1.0414 (5)	0.7011 (3)	0.04748 (11)	0.0357 (8)
C20	1.2093 (5)	0.7923 (3)	0.03072 (11)	0.0395 (8)
C21	1.1876 (6)	0.9201 (3)	0.06046 (12)	0.0430 (9)
C22	1.0058 (5)	0.9543 (3)	0.10605 (11)	0.0374 (8)
Br2	0.27139 (5)	0.28139 (3)	0.09148 (2)	0.0383 (1)
O1	0.7203 (4)	0.4762 (2)	0.08156 (10)	0.0527 (8)
H2	−0.03430	0.52720	0.40350	0.0300*
H3	−0.28530	0.41960	0.47550	0.0310*
H4	0.77020	0.67170	0.09920	0.0350*
H5	−0.63730	0.28920	0.34550	0.0330*
H6	−0.38490	0.39500	0.27360	0.0320*
H7	0.00780	0.37530	0.22060	0.0350*
H11	0.36070	0.70280	0.37190	0.0320*
H12	0.26180	0.88460	0.44200	0.0360*
H13	−0.11680	1.04310	0.44560	0.0370*
H14	−0.40940	1.01290	0.38190	0.0360*
H15	−0.31250	0.83040	0.31150	0.0310*
H17A	0.48760	1.02160	0.23850	0.0620*
H17B	0.56860	1.10700	0.17790	0.0620*
H17C	0.76970	1.03220	0.22220	0.0620*
H19	1.04880	0.61340	0.02720	0.0430*
H20	1.33540	0.76760	−0.00030	0.0470*
H21	1.29900	0.98550	0.04950	0.0520*
H22	0.99180	1.04350	0.12580	0.0450*
H1A	0.59280	0.43750	0.08470	0.0630*
H1B	0.81640	0.42050	0.10420	0.0630*

	U11	U22	U33	U12	U13	U23
Br1	0.0262 (1)	0.0324 (1)	0.0331 (1)	−0.0090 (1)	0.0018 (1)	−0.0010 (1)
S1	0.0374 (3)	0.0343 (3)	0.0186 (3)	−0.0109 (2)	0.0009 (2)	−0.0075 (2)
N1	0.0252 (10)	0.0272 (9)	0.0205 (9)	−0.0067 (8)	−0.0009 (7)	−0.0059 (7)
N2	0.0317 (11)	0.0306 (10)	0.0216 (9)	−0.0085 (8)	0.0009 (8)	−0.0043 (7)
N3	0.0340 (11)	0.0329 (10)	0.0211 (9)	−0.0106 (8)	−0.0008 (8)	−0.0049 (8)
N4	0.0347 (11)	0.0322 (10)	0.0237 (9)	−0.0165 (9)	−0.0011 (8)	−0.0027 (8)
C1	0.0233 (11)	0.0221 (10)	0.0274 (11)	−0.0021 (8)	−0.0021 (9)	−0.0042 (8)
C2	0.0233 (11)	0.0263 (11)	0.0252 (11)	−0.0055 (9)	−0.0013 (9)	−0.0069 (8)
C3	0.0253 (11)	0.0281 (11)	0.0225 (10)	−0.0032 (9)	−0.0011 (9)	−0.0048 (8)
C4	0.0207 (10)	0.0230 (10)	0.0283 (11)	−0.0018 (8)	0.0015 (9)	−0.0021 (8)
C5	0.0251 (11)	0.0251 (11)	0.0345 (12)	−0.0064 (9)	−0.0066 (9)	−0.0041 (9)
C6	0.0253 (11)	0.0288 (11)	0.0258 (11)	−0.0029 (9)	−0.0035 (9)	−0.0055 (9)
C7	0.0359 (13)	0.0313 (12)	0.0227 (11)	−0.0132 (10)	−0.0028 (9)	−0.0051 (9)
C8	0.0260 (11)	0.0271 (11)	0.0227 (10)	−0.0060 (9)	−0.0056 (8)	−0.0047 (8)
C9	0.0269 (12)	0.0301 (12)	0.0194 (10)	−0.0044 (9)	−0.0038 (8)	−0.0039 (8)
C10	0.0243 (11)	0.0236 (10)	0.0194 (10)	−0.0058 (8)	0.0012 (8)	−0.0043 (8)
C11	0.0208 (11)	0.0348 (12)	0.0247 (11)	−0.0053 (9)	−0.0023 (9)	−0.0054 (9)
C12	0.0295 (12)	0.0401 (13)	0.0243 (11)	−0.0118 (10)	−0.0020 (9)	−0.0087 (10)
C13	0.0337 (13)	0.0337 (12)	0.0275 (12)	−0.0120 (10)	0.0034 (10)	−0.0112 (9)
C14	0.0260 (12)	0.0258 (12)	0.0378 (13)	−0.0025 (9)	0.0009 (10)	−0.0059 (9)
C15	0.0253 (11)	0.0282 (11)	0.0260 (11)	−0.0075 (9)	−0.0045 (9)	−0.0029 (9)
C16	0.0384 (13)	0.0280 (11)	0.0214 (10)	−0.0098 (10)	−0.0034 (9)	0.0000 (9)
C17	0.0620 (19)	0.0294 (13)	0.0329 (13)	−0.0115 (12)	0.0041 (12)	−0.0037 (10)
C18	0.0389 (13)	0.0281 (11)	0.0216 (10)	−0.0115 (10)	−0.0057 (9)	−0.0004 (9)
C19	0.0446 (15)	0.0396 (14)	0.0264 (12)	−0.0169 (12)	0.0025 (11)	−0.0094 (10)
C20	0.0468 (16)	0.0459 (15)	0.0293 (13)	−0.0221 (13)	0.0086 (11)	−0.0063 (11)
C21	0.0525 (17)	0.0473 (16)	0.0358 (14)	−0.0298 (13)	0.0055 (12)	−0.0051 (12)
C22	0.0535 (17)	0.0340 (13)	0.0296 (13)	−0.0224 (12)	0.0020 (11)	−0.0033 (10)
Br2	0.0409 (2)	0.0393 (2)	0.0399 (2)	−0.0198 (1)	0.0017 (1)	−0.0117 (1)
O1	0.0430 (12)	0.0436 (12)	0.0761 (15)	−0.0216 (9)	0.0117 (10)	−0.0213 (10)

Br1—C4	1.909 (2)	C13—C14	1.391 (3)
S1—C7	1.735 (2)	C14—C15	1.393 (3)
S1—C9	1.744 (2)	C16—C18	1.471 (4)
O1—H1A	0.8500	C16—C17	1.508 (4)
O1—H1B	0.8500	C18—C22	1.391 (4)
N1—C10	1.438 (3)	C19—C20	1.384 (4)
N1—C9	1.375 (3)	C20—C21	1.378 (4)
N1—C8	1.415 (3)	C21—C22	1.381 (4)
N2—C9	1.315 (3)	C2—H2	0.9500
N2—N3	1.386 (3)	C3—H3	0.9500
N3—C16	1.291 (3)	C5—H5	0.9500
N4—C19	1.339 (3)	C6—H6	0.9500
N4—C18	1.351 (3)	C7—H7	0.9500
N4—H4	0.8800	C11—H11	0.9500
C1—C2	1.402 (3)	C12—H12	0.9500
C1—C8	1.471 (3)	C13—H13	0.9500
C1—C6	1.401 (3)	C14—H14	0.9500
C2—C3	1.387 (3)	C15—H15	0.9500
C3—C4	1.382 (3)	C17—H17C	0.9800
C4—C5	1.385 (3)	C17—H17A	0.9800
C5—C6	1.383 (3)	C17—H17B	0.9800
C7—C8	1.349 (3)	C19—H19	0.9500
C10—C11	1.386 (3)	C20—H20	0.9500
C10—C15	1.379 (3)	C21—H21	0.9500
C11—C12	1.386 (4)	C22—H22	0.9500
C12—C13	1.379 (3)
C7—S1—C9	90.19 (11)	N4—C18—C22	116.9 (2)
H1A—O1—H1B	104.00	N4—C19—C20	120.2 (2)
C8—N1—C10	126.06 (18)	C19—C20—C21	117.8 (3)
C9—N1—C10	119.83 (17)	C20—C21—C22	120.7 (3)
C8—N1—C9	113.57 (17)	C18—C22—C21	120.4 (2)
N3—N2—C9	108.59 (17)	C3—C2—H2	120.00
N2—N3—C16	116.19 (19)	C1—C2—H2	120.00
C18—N4—C19	123.9 (2)	C2—C3—H3	120.00
C19—N4—H4	113.00	C4—C3—H3	120.00
C18—N4—H4	123.00	C6—C5—H5	121.00
C2—C1—C6	118.1 (2)	C4—C5—H5	121.00
C6—C1—C8	118.7 (2)	C5—C6—H6	119.00
C2—C1—C8	123.0 (2)	C1—C6—H6	119.00
C1—C2—C3	120.8 (2)	S1—C7—H7	123.00
C2—C3—C4	119.4 (2)	C8—C7—H7	123.00
C3—C4—C5	121.4 (2)	C10—C11—H11	121.00
Br1—C4—C5	119.76 (16)	C12—C11—H11	121.00
Br1—C4—C3	118.87 (17)	C13—C12—H12	120.00
C4—C5—C6	118.9 (2)	C11—C12—H12	120.00
C1—C6—C5	121.5 (2)	C12—C13—H13	120.00
S1—C7—C8	113.51 (19)	C14—C13—H13	120.00
N1—C8—C7	111.7 (2)	C15—C14—H14	120.00
N1—C8—C1	123.17 (18)	C13—C14—H14	120.00
C1—C8—C7	124.91 (19)	C10—C15—H15	120.00
N1—C9—N2	122.65 (18)	C14—C15—H15	120.00
S1—C9—N2	126.31 (16)	C16—C17—H17B	110.00
S1—C9—N1	111.01 (15)	C16—C17—H17C	109.00
C11—C10—C15	121.3 (2)	H17A—C17—H17B	109.00
N1—C10—C11	119.52 (19)	H17A—C17—H17C	109.00
N1—C10—C15	119.14 (19)	H17B—C17—H17C	109.00
C10—C11—C12	118.8 (2)	C16—C17—H17A	109.00
C11—C12—C13	120.8 (2)	N4—C19—H19	120.00
C12—C13—C14	119.7 (2)	C20—C19—H19	120.00
C13—C14—C15	120.1 (2)	C21—C20—H20	121.00
C10—C15—C14	119.2 (2)	C19—C20—H20	121.00
C17—C16—C18	118.8 (2)	C20—C21—H21	120.00
N3—C16—C18	114.8 (2)	C22—C21—H21	120.00
N3—C16—C17	126.3 (2)	C18—C22—H22	120.00
N4—C18—C16	119.0 (2)	C21—C22—H22	120.00
C16—C18—C22	124.0 (2)
C9—S1—C7—C8	−0.05 (19)	C2—C1—C8—C7	141.2 (2)
C7—S1—C9—N1	0.22 (17)	C6—C1—C8—N1	151.9 (2)
C7—S1—C9—N2	−177.7 (2)	C6—C1—C8—C7	−33.7 (3)
C9—N1—C8—C1	175.39 (19)	C1—C2—C3—C4	0.0 (3)
C9—N1—C8—C7	0.3 (3)	C2—C3—C4—Br1	177.72 (15)
C10—N1—C8—C1	−13.1 (3)	C2—C3—C4—C5	−0.9 (3)
C10—N1—C8—C7	171.8 (2)	Br1—C4—C5—C6	−177.46 (15)
C8—N1—C9—S1	−0.3 (2)	C3—C4—C5—C6	1.1 (3)
C8—N1—C9—N2	177.7 (2)	C4—C5—C6—C1	−0.5 (3)
C10—N1—C9—S1	−172.41 (15)	S1—C7—C8—N1	−0.1 (2)
C10—N1—C9—N2	5.6 (3)	S1—C7—C8—C1	−175.12 (18)
C8—N1—C10—C11	117.6 (2)	N1—C10—C11—C12	176.4 (2)
C8—N1—C10—C15	−63.9 (3)	C15—C10—C11—C12	−2.0 (3)
C9—N1—C10—C11	−71.4 (3)	N1—C10—C15—C14	−176.3 (2)
C9—N1—C10—C15	107.1 (2)	C11—C10—C15—C14	2.1 (3)
C9—N2—N3—C16	174.0 (2)	C10—C11—C12—C13	0.1 (4)
N3—N2—C9—S1	−7.0 (3)	C11—C12—C13—C14	1.8 (4)
N3—N2—C9—N1	175.30 (19)	C12—C13—C14—C15	−1.7 (4)
N2—N3—C16—C17	−4.0 (4)	C13—C14—C15—C10	−0.2 (3)
N2—N3—C16—C18	175.0 (2)	N3—C16—C18—N4	4.8 (4)
C19—N4—C18—C16	−176.2 (2)	N3—C16—C18—C22	−172.3 (2)
C19—N4—C18—C22	1.1 (4)	C17—C16—C18—N4	−176.2 (2)
C18—N4—C19—C20	0.6 (4)	C17—C16—C18—C22	6.8 (4)
C6—C1—C2—C3	0.5 (3)	N4—C18—C22—C21	−1.7 (4)
C8—C1—C2—C3	−174.40 (18)	C16—C18—C22—C21	175.4 (3)
C2—C1—C6—C5	−0.3 (3)	N4—C19—C20—C21	−1.6 (4)
C8—C1—C6—C5	174.87 (18)	C19—C20—C21—C22	0.9 (4)
C2—C1—C8—N1	−33.2 (3)	C20—C21—C22—C18	0.8 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Br2	0.85	2.49	3.332 (2)	170
O1—H1B···Br2i	0.85	2.61	3.271 (2)	135
N4—H4···O1	0.88	1.95	2.715 (3)	144
C15—H15···N2ii	0.95	2.62	3.571 (3)	177
C17—H17A···N2	0.98	2.38	2.798 (4)	105
C17—H17B···Br2iii	0.98	2.88	3.798 (3)	156
C19—H19···O1	0.95	2.59	3.006 (3)	107
C20—H20···Br2iv	0.95	2.85	3.798 (3)	175
C21—H21···Br2v	0.95	2.92	3.579 (3)	127
C11—H11···Cg3i	0.95	2.93	3.789 (3)	152

Table 1

Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯Br2	0.85	2.49	3.332 (2)	170
O1—H1B⋯Br2i	0.85	2.61	3.271 (2)	135
N4—H4⋯O1	0.88	1.95	2.715 (3)	144
C15—H15⋯N2ii	0.95	2.62	3.571 (3)	177
C17—H17B⋯Br2iii	0.98	2.88	3.798 (3)	156
C20—H20⋯Br2iv	0.95	2.85	3.798 (3)	175
C21—H21⋯Br2v	0.95	2.92	3.579 (3)	127
C11—H11⋯Cg3i	0.95	2.93	3.789 (3)	152

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .