(Z)-1-[(2E)-3,4-Diphenyl-2,3-di-hydro-1,3-thia-zol-2-yl-idene]-2-[1-(4-hy-droxy-phen-yl)ethyl-idene]hydrazinium bromide including an unknown solvate.

In the title compound, C23H20N3OS(+)·Br(-), the di-hydro-thia-zole ring (r.m.s. deviation = 0.015 Å) is twisted with respect to each of the C- and N-bound phenyl rings and the hy-droxy-benzene ring, making dihedral angles of 76.0 (2), 71.2 (2) and 9.8 (2)°, respectively. In the crystal, inversion-related mol-ecules are linked by association of the bromide ions with the cations via N-H⋯Br and O-H⋯Br hydrogen-bonding inter-actions. These mol-ecules run in channels parallel to the a axis through face-to-face π-π stacking inter-actions between the hy-droxy-benzene rings [centroid-centroid distances = 3.785 (3) Å] which, in turn, are connected into layers parallel to (110) by weak C-H⋯π inter-actions. A small region of electron density well removed from the main mol-ecule and appearing disordered over a center of symmetry was removed with PLATON SQUEEZE [Spek (2009 ▶). Acta Cryst. D65, 148-15] following unsuccessful attempts to model it as plausible solvent molecule. The nature of the solvent was not known and hence, this is not taken into account when calculating M r and related data.

Related literature

For general medicinal and industrial applications of five-membered S,N-heterocycles thia­zolines, see: Abhinit et al. (2009 ▶). For chemical and diverse medicinal properties of thia­zoles, see: Sreedevi et al. (2013 ▶); Milne (2000 ▶); De Souza & De Almeida (2003 ▶); Lednicer et al. (1990 ▶); Rehman et al. (2005 ▶); Knadler et al. (1986 ▶). For a similar structure, see: Mague et al. (2014 ▶).

Experimental

Crystal data

C23H20N3OS+·Br−

M = 466.39

Triclinic,

a = 7.5987 (12) Å

b = 12.3017 (19) Å

c = 13.786 (2) Å

α = 68.0760 (17)°

β = 88.1540 (18)°

γ = 72.6540 (18)°

V = 1136.6 (3) Å3

Z = 2

Mo Kα radiation

μ = 1.92 mm−1

T = 220 K

0.17 × 0.17 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2013 ▶) T min = 0.56, T max = 0.80

11044 measured reflections

5146 independent reflections

3398 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.157

S = 1.01

5146 reflections

263 parameters

73 restraints

H-atom parameters constrained

Δρmax = 1.09 e Å−3

Δρmin = −0.48 e Å−3

Data collection: APEX2 (Bruker, 2013 ▶); cell refinement: SAINT (Bruker, 2013 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 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/S1600536814010125/tk5311sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814010125/tk5311Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814010125/tk5311Isup3.cml

CCDC reference: 1000895

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

C23H20N3OS+·Br−	Z = 2
Mr = 466.39	F(000) = 476
Triclinic, P1	Dx = 1.363 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5987 (12) Å	Cell parameters from 4151 reflections
b = 12.3017 (19) Å	θ = 2.8–26.7°
c = 13.786 (2) Å	µ = 1.92 mm−1
α = 68.0760 (17)°	T = 220 K
β = 88.1540 (18)°	Block, colourless
γ = 72.6540 (18)°	0.17 × 0.17 × 0.12 mm
V = 1136.6 (3) Å3

Bruker SMART APEX CCD diffractometer	5146 independent reflections
Radiation source: fine-focus sealed tube	3398 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 8.3660 pixels mm-1	θmax = 27.5°, θmin = 1.9°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −15→15
Tmin = 0.56, Tmax = 0.80	l = −17→17
11044 measured reflections

Refinement on F2	73 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.058	H-atom parameters constrained
wR(F2) = 0.157	w = 1/[σ2(Fo2) + (0.0867P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
5146 reflections	Δρmax = 1.09 e Å−3
263 parameters	Δρmin = −0.48 e Å−3

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 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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.98 Å) while those attached to nitrogen were placed in locations derived from a difference map and their coordinates adjusted to give N—H = 0.91 Å. That attached to oxygen was placed in an idealized position and the C—C—O—H torsion angle refined (AFIX 147)·All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. A small region of electron density well removed from the main molecule and appearing disordered over a center of symmetry was removed with PLATON SQUEEZE following unsuccessful attempts to model it as plausible lattice solvent (Spek, 2014).

	x	y	z	Uiso*/Ueq
S1	0.24831 (13)	0.51039 (10)	0.99502 (8)	0.0418 (3)
O1	−0.1920 (4)	1.0140 (3)	1.2638 (2)	0.0599 (11)
N1	0.1776 (4)	0.5582 (3)	0.8008 (2)	0.0376 (10)
N2	−0.0083 (4)	0.7072 (3)	0.8605 (2)	0.0427 (11)
N3	−0.0284 (5)	0.7434 (3)	0.9459 (2)	0.0434 (11)
C1	0.3784 (5)	0.4108 (4)	0.9384 (3)	0.0433 (12)
C2	0.3282 (5)	0.4476 (4)	0.8368 (3)	0.0399 (12)
C3	0.1253 (5)	0.6024 (4)	0.8761 (3)	0.0393 (12)
C4	0.4141 (5)	0.3930 (4)	0.7614 (3)	0.0398 (12)
C5	0.3820 (6)	0.2897 (4)	0.7589 (3)	0.0480 (16)
C6	0.4610 (6)	0.2396 (4)	0.6870 (4)	0.0510 (16)
C7	0.5711 (7)	0.2920 (5)	0.6183 (4)	0.0604 (17)
C8	0.6055 (8)	0.3930 (5)	0.6209 (5)	0.085 (3)
C9	0.5280 (7)	0.4447 (5)	0.6915 (4)	0.070 (2)
C10	0.0904 (5)	0.6216 (4)	0.6942 (3)	0.0389 (12)
C11	−0.0203 (6)	0.5700 (4)	0.6591 (4)	0.0543 (17)
C12	−0.1016 (7)	0.6310 (5)	0.5574 (4)	0.0689 (19)
C13	−0.0764 (6)	0.7396 (5)	0.4938 (4)	0.0608 (18)
C14	0.0333 (6)	0.7896 (5)	0.5299 (4)	0.0576 (17)
C15	0.1188 (6)	0.7291 (4)	0.6313 (3)	0.0495 (14)
C16	−0.1282 (5)	0.8544 (4)	0.9258 (3)	0.0380 (12)
C17	−0.2232 (6)	0.9401 (4)	0.8202 (3)	0.0478 (14)
C18	−0.1445 (5)	0.8977 (4)	1.0145 (3)	0.0388 (12)
C19	−0.0230 (6)	0.8316 (4)	1.1041 (3)	0.0443 (12)
C20	−0.0409 (6)	0.8719 (4)	1.1875 (3)	0.0480 (16)
C21	−0.1813 (6)	0.9791 (4)	1.1794 (3)	0.0446 (14)
C22	−0.2998 (6)	1.0452 (4)	1.0906 (3)	0.0470 (14)
C23	−0.2808 (6)	1.0045 (4)	1.0093 (3)	0.0451 (14)
Br1	0.46263 (6)	0.27288 (4)	0.21975 (3)	0.0504 (2)
H1	0.47420	0.33840	0.97570	0.0520*
H1O	−0.27870	1.07870	1.25100	0.0900*
H2	−0.09160	0.73360	0.80430	0.0510*
H5	0.30560	0.25280	0.80650	0.0570*
H6	0.43800	0.16900	0.68600	0.0620*
H7	0.62360	0.25870	0.56900	0.0730*
H8	0.68370	0.42830	0.57370	0.1020*
H9	0.55280	0.51490	0.69200	0.0830*
H11	−0.03950	0.49580	0.70320	0.0650*
H12	−0.17560	0.59700	0.53150	0.0830*
H13	−0.13440	0.78040	0.42500	0.0730*
H14	0.05050	0.86450	0.48600	0.0690*
H15	0.19550	0.76220	0.65630	0.0590*
H17A	−0.26820	1.02330	0.81860	0.0720*
H17B	−0.32660	0.91560	0.80600	0.0720*
H17C	−0.13670	0.93690	0.76730	0.0720*
H19	0.07160	0.75970	1.10900	0.0530*
H20	0.04110	0.82700	1.24860	0.0580*
H22	−0.39340	1.11780	1.08500	0.0570*
H23	−0.36270	1.05060	0.94830	0.0540*

	U11	U22	U33	U12	U13	U23
S1	0.0397 (6)	0.0478 (6)	0.0404 (5)	−0.0129 (5)	0.0012 (4)	−0.0197 (5)
O1	0.068 (2)	0.069 (2)	0.0568 (19)	−0.0195 (17)	0.0135 (15)	−0.0413 (17)
N1	0.0332 (17)	0.0438 (19)	0.0401 (17)	−0.0070 (14)	0.0016 (13)	−0.0244 (15)
N2	0.0413 (19)	0.050 (2)	0.0405 (18)	−0.0047 (15)	−0.0006 (14)	−0.0282 (16)
N3	0.050 (2)	0.050 (2)	0.0363 (17)	−0.0139 (17)	0.0061 (14)	−0.0244 (16)
C1	0.038 (2)	0.045 (2)	0.047 (2)	−0.0093 (18)	0.0020 (17)	−0.0202 (19)
C2	0.036 (2)	0.040 (2)	0.046 (2)	−0.0114 (17)	0.0024 (16)	−0.0192 (18)
C3	0.036 (2)	0.044 (2)	0.044 (2)	−0.0112 (17)	0.0021 (16)	−0.0243 (18)
C4	0.035 (2)	0.036 (2)	0.049 (2)	−0.0077 (17)	0.0045 (16)	−0.0193 (18)
C5	0.047 (2)	0.052 (3)	0.057 (3)	−0.026 (2)	0.0103 (19)	−0.026 (2)
C6	0.049 (3)	0.045 (2)	0.067 (3)	−0.009 (2)	−0.001 (2)	−0.034 (2)
C7	0.059 (3)	0.058 (3)	0.068 (3)	−0.008 (2)	0.018 (2)	−0.037 (3)
C8	0.092 (4)	0.073 (4)	0.114 (5)	−0.043 (3)	0.065 (4)	−0.054 (4)
C9	0.076 (4)	0.059 (3)	0.104 (4)	−0.038 (3)	0.050 (3)	−0.054 (3)
C10	0.033 (2)	0.046 (2)	0.042 (2)	−0.0056 (17)	0.0046 (16)	−0.0266 (18)
C11	0.052 (3)	0.060 (3)	0.055 (3)	−0.020 (2)	0.000 (2)	−0.024 (2)
C12	0.060 (3)	0.090 (4)	0.070 (3)	−0.024 (3)	−0.013 (2)	−0.043 (3)
C13	0.045 (3)	0.085 (4)	0.044 (2)	−0.006 (2)	−0.0011 (19)	−0.026 (2)
C14	0.049 (3)	0.062 (3)	0.050 (3)	−0.011 (2)	0.003 (2)	−0.013 (2)
C15	0.044 (2)	0.060 (3)	0.047 (2)	−0.020 (2)	0.0041 (18)	−0.020 (2)
C16	0.031 (2)	0.043 (2)	0.045 (2)	−0.0111 (17)	0.0097 (16)	−0.0230 (18)
C17	0.051 (3)	0.049 (2)	0.048 (2)	−0.016 (2)	0.0018 (18)	−0.023 (2)
C18	0.038 (2)	0.046 (2)	0.043 (2)	−0.0223 (18)	0.0144 (16)	−0.0223 (18)
C19	0.047 (2)	0.048 (2)	0.048 (2)	−0.0208 (19)	0.0112 (18)	−0.025 (2)
C20	0.050 (3)	0.055 (3)	0.044 (2)	−0.022 (2)	0.0069 (18)	−0.020 (2)
C21	0.049 (2)	0.053 (3)	0.050 (2)	−0.026 (2)	0.0232 (19)	−0.033 (2)
C22	0.043 (2)	0.055 (3)	0.052 (2)	−0.015 (2)	0.0135 (18)	−0.031 (2)
C23	0.041 (2)	0.052 (3)	0.051 (2)	−0.0170 (19)	0.0138 (18)	−0.028 (2)
Br1	0.0562 (3)	0.0514 (3)	0.0488 (3)	−0.0152 (2)	−0.0025 (2)	−0.0252 (2)

S1—C1	1.741 (5)	C16—C18	1.494 (6)
S1—C3	1.710 (4)	C18—C23	1.388 (7)
O1—C21	1.375 (5)	C18—C19	1.384 (6)
O1—H1O	0.8300	C19—C20	1.401 (6)
N1—C3	1.341 (5)	C20—C21	1.396 (7)
N1—C10	1.451 (5)	C21—C22	1.365 (6)
N1—C2	1.418 (6)	C22—C23	1.376 (6)
N2—C3	1.329 (6)	C1—H1	0.9400
N2—N3	1.395 (4)	C5—H5	0.9400
N3—C16	1.277 (6)	C6—H6	0.9400
N2—H2	0.9100	C7—H7	0.9400
C1—C2	1.331 (5)	C8—H8	0.9400
C2—C4	1.474 (6)	C9—H9	0.9400
C4—C9	1.378 (7)	C11—H11	0.9400
C4—C5	1.376 (7)	C12—H12	0.9400
C5—C6	1.386 (7)	C13—H13	0.9400
C6—C7	1.352 (7)	C14—H14	0.9400
C7—C8	1.357 (9)	C15—H15	0.9400
C8—C9	1.379 (9)	C17—H17A	0.9700
C10—C11	1.385 (7)	C17—H17B	0.9700
C10—C15	1.360 (6)	C17—H17C	0.9700
C11—C12	1.380 (7)	C19—H19	0.9400
C12—C13	1.363 (8)	C20—H20	0.9400
C13—C14	1.372 (8)	C22—H22	0.9400
C14—C15	1.387 (6)	C23—H23	0.9400
C16—C17	1.490 (6)
C1—S1—C3	89.3 (2)	O1—C21—C20	116.9 (4)
C21—O1—H1O	109.00	C20—C21—C22	120.5 (4)
C2—N1—C10	125.3 (3)	C21—C22—C23	119.3 (5)
C3—N1—C10	122.2 (4)	C18—C23—C22	122.1 (4)
C2—N1—C3	112.5 (3)	S1—C1—H1	124.00
N3—N2—C3	114.7 (3)	C2—C1—H1	123.00
N2—N3—C16	115.3 (3)	C4—C5—H5	120.00
C3—N2—H2	115.00	C6—C5—H5	120.00
N3—N2—H2	128.00	C5—C6—H6	120.00
S1—C1—C2	113.1 (4)	C7—C6—H6	120.00
N1—C2—C1	111.8 (4)	C6—C7—H7	120.00
N1—C2—C4	119.4 (3)	C8—C7—H7	120.00
C1—C2—C4	128.7 (4)	C7—C8—H8	119.00
S1—C3—N1	113.3 (3)	C9—C8—H8	119.00
N1—C3—N2	123.7 (3)	C4—C9—H9	120.00
S1—C3—N2	123.0 (3)	C8—C9—H9	120.00
C5—C4—C9	118.5 (4)	C10—C11—H11	121.00
C2—C4—C5	120.9 (4)	C12—C11—H11	121.00
C2—C4—C9	120.6 (5)	C11—C12—H12	119.00
C4—C5—C6	120.7 (4)	C13—C12—H12	119.00
C5—C6—C7	120.1 (5)	C12—C13—H13	120.00
C6—C7—C8	119.7 (5)	C14—C13—H13	120.00
C7—C8—C9	121.2 (6)	C13—C14—H14	120.00
C4—C9—C8	119.8 (6)	C15—C14—H14	120.00
C11—C10—C15	121.6 (4)	C10—C15—H15	120.00
N1—C10—C11	118.6 (4)	C14—C15—H15	120.00
N1—C10—C15	119.8 (4)	C16—C17—H17A	109.00
C10—C11—C12	117.9 (5)	C16—C17—H17B	109.00
C11—C12—C13	121.2 (5)	C16—C17—H17C	109.00
C12—C13—C14	120.1 (5)	H17A—C17—H17B	110.00
C13—C14—C15	119.8 (5)	H17A—C17—H17C	110.00
C10—C15—C14	119.4 (4)	H17B—C17—H17C	109.00
C17—C16—C18	120.0 (4)	C18—C19—H19	120.00
N3—C16—C18	116.5 (3)	C20—C19—H19	120.00
N3—C16—C17	123.5 (4)	C19—C20—H20	120.00
C16—C18—C19	120.4 (4)	C21—C20—H20	120.00
C16—C18—C23	121.1 (4)	C21—C22—H22	120.00
C19—C18—C23	118.5 (4)	C23—C22—H22	120.00
C18—C19—C20	120.0 (4)	C18—C23—H23	119.00
C19—C20—C21	119.6 (4)	C22—C23—H23	119.00
O1—C21—C22	122.6 (4)
C3—S1—C1—C2	0.0 (4)	C2—C4—C9—C8	−179.3 (5)
C1—S1—C3—N1	1.4 (3)	C5—C4—C9—C8	0.4 (7)
C1—S1—C3—N2	−178.5 (4)	C4—C5—C6—C7	0.1 (7)
C3—N1—C2—C1	2.3 (5)	C5—C6—C7—C8	0.7 (8)
C3—N1—C2—C4	−174.3 (4)	C6—C7—C8—C9	−1.0 (9)
C10—N1—C2—C1	−179.8 (4)	C7—C8—C9—C4	0.4 (9)
C10—N1—C2—C4	3.6 (6)	N1—C10—C11—C12	−179.7 (4)
C2—N1—C3—S1	−2.4 (4)	C15—C10—C11—C12	0.2 (7)
C2—N1—C3—N2	177.5 (4)	N1—C10—C15—C14	−179.4 (4)
C10—N1—C3—S1	179.6 (3)	C11—C10—C15—C14	0.8 (7)
C10—N1—C3—N2	−0.5 (6)	C10—C11—C12—C13	−1.0 (8)
C2—N1—C10—C11	72.5 (5)	C11—C12—C13—C14	0.9 (9)
C2—N1—C10—C15	−107.4 (5)	C12—C13—C14—C15	0.1 (8)
C3—N1—C10—C11	−109.8 (5)	C13—C14—C15—C10	−0.9 (8)
C3—N1—C10—C15	70.3 (5)	N3—C16—C18—C19	15.2 (6)
C3—N2—N3—C16	166.3 (4)	N3—C16—C18—C23	−164.8 (4)
N3—N2—C3—S1	6.3 (5)	C17—C16—C18—C19	−163.8 (4)
N3—N2—C3—N1	−173.6 (4)	C17—C16—C18—C23	16.2 (6)
N2—N3—C16—C17	1.9 (6)	C16—C18—C19—C20	−179.1 (4)
N2—N3—C16—C18	−177.1 (3)	C23—C18—C19—C20	0.9 (7)
S1—C1—C2—N1	−1.3 (5)	C16—C18—C23—C22	179.2 (4)
S1—C1—C2—C4	175.0 (4)	C19—C18—C23—C22	−0.9 (7)
N1—C2—C4—C5	−105.2 (5)	C18—C19—C20—C21	−0.2 (7)
N1—C2—C4—C9	74.5 (6)	C19—C20—C21—O1	180.0 (4)
C1—C2—C4—C5	78.8 (6)	C19—C20—C21—C22	−0.6 (7)
C1—C2—C4—C9	−101.5 (6)	O1—C21—C22—C23	−179.9 (4)
C2—C4—C5—C6	179.1 (4)	C20—C21—C22—C23	0.6 (7)
C9—C4—C5—C6	−0.6 (7)	C21—C22—C23—C18	0.1 (7)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···Br1i	0.83	2.50	3.328 (4)	178
N2—H2···Br1ii	0.91	2.88	3.570 (3)	134
C5—H5···Cg4iii	0.94	2.76	3.610 (5)	152

Table 1

Hydrogen-bond geometry (Å, °)

Cg4 is the centroid of the C18–C23 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯Br1i	0.83	2.50	3.328 (4)	178
N2—H2⋯Br1ii	0.91	2.88	3.570 (3)	134
C5—H5⋯Cg4iii	0.94	2.76	3.610 (5)	152

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