N-(1,3-Thia-zol-2-yl)-N'-[(thio-phen-2-yl)carbon-yl]thio-urea hemihydrate.

The title compound, C9H7N3OS3·0.5H2O, crystallizes with two independent but similar mol-ecules in the asymmetric unit, both of which are linked by a water mol-ecule through O-H⋯N hydrogen bonds. In addition the water O atom is further linked by N-H⋯O hydrogen bonds to two additional main mol-ecules, forming a tetra-meric unit. These tetra-meric units then form infinite ribbons parallel to the ac plane.The dihedral angle between the thio-phenoyl and thia-zolyl rings is 12.15 (10) and 21.69 (11)° in mol-ecules A and B, respectively. The central thio-urea core makes dihedral angles of 5.77 (11) and 8.61 (9)°, respectively, with the thio--phen-oyl and thia-zolyl rings in mol-ecule A and 8.41 (10) and 13.43 (12)° in mol-ecule B. Each mol-ecule adopts a trans-cis geometry with respect to the position of thio-phenoyl and thia-zole groups relative to the S atom across the thio-urea C-N bonds. This geometry is stabilized by intra-molecular N-H⋯O hydrogen bonds.

Related literature

For general background to aroyl­thio­urea and its derivatives, see: Aly et al. (2007 ▶). For related structures, see: Koch (2001 ▶); Pérez et al. (2008 ▶). For their biological activity, see: Saeed et al. (2008 ▶); Gu et al. (2007 ▶); Xu et al. (2004 ▶); Yan & Xue (2008 ▶).

Experimental

Crystal data

C9H7N3OS3·0.5H2O

M = 278.37

Triclinic,

a = 7.4489 (4) Å

b = 11.1060 (6) Å

c = 14.7935 (7) Å

α = 93.559 (4)°

β = 99.813 (4)°

γ = 107.789 (5)°

V = 1139.74 (11) Å3

Z = 4

Cu Kα radiation

μ = 5.86 mm−1

T = 123 K

0.35 × 0.25 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur (Ruby, Gemini CCD) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.441, T max = 1.000

7828 measured reflections

4566 independent reflections

3906 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.110

S = 1.08

4566 reflections

304 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.30 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681204500X/zs2240sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681204500X/zs2240Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S160053681204500X/zs2240Isup3.cml

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

C9H7N3OS3·0.5H2O	Z = 4
Mr = 278.37	F(000) = 572
Triclinic, P1	Dx = 1.622 Mg m−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.4489 (4) Å	Cell parameters from 3735 reflections
b = 11.1060 (6) Å	θ = 3.1–75.6°
c = 14.7935 (7) Å	µ = 5.86 mm−1
α = 93.559 (4)°	T = 123 K
β = 99.813 (4)°	Block, colorless
γ = 107.789 (5)°	0.35 × 0.25 × 0.18 mm
V = 1139.74 (11) Å3

Oxford Diffraction Xcalibur (Ruby, Gemini CCD) diffractometer	4566 independent reflections
Radiation source: Enhance (Cu) X-ray Source	3906 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 10.5081 pixels mm-1	θmax = 75.8°, θmin = 3.1°
ω scans	h = −9→6
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −13→13
Tmin = 0.441, Tmax = 1.000	l = −12→18
7828 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0566P)2 + 0.1264P] where P = (Fo2 + 2Fc2)/3
4566 reflections	(Δ/σ)max = 0.001
304 parameters	Δρmax = 0.43 e Å−3
3 restraints	Δρmin = −0.30 e Å−3

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
S1A	0.17373 (9)	0.25490 (5)	0.47025 (4)	0.02167 (15)
S1B	0.26874 (10)	−0.44204 (6)	0.98233 (4)	0.02371 (15)
S2A	0.29573 (10)	−0.30344 (6)	0.38262 (4)	0.02567 (16)
S2B	0.22859 (9)	0.13688 (5)	1.07688 (4)	0.01906 (14)
S3A	0.32482 (9)	−0.42492 (5)	0.56122 (4)	0.02351 (15)
S3B	0.14624 (9)	0.23871 (5)	0.89130 (4)	0.02046 (15)
O1A	0.2481 (3)	0.03651 (16)	0.55080 (11)	0.0221 (4)
O1B	0.2523 (3)	−0.20849 (16)	0.90756 (12)	0.0243 (4)
O1W	0.5774 (2)	0.02421 (15)	0.75431 (12)	0.0196 (4)
N1A	0.2661 (3)	−0.07508 (18)	0.41864 (13)	0.0171 (4)
H1AA	0.2675	−0.0709	0.3609	0.021*
N1B	0.2789 (3)	−0.08541 (17)	1.04263 (13)	0.0149 (4)
H1BA	0.3020	−0.0830	1.1018	0.018*
N2A	0.3233 (3)	−0.17714 (18)	0.54658 (13)	0.0172 (4)
H2AA	0.3276	−0.1065	0.5757	0.021*
N2B	0.2633 (3)	0.02718 (18)	0.91718 (13)	0.0158 (4)
H2BA	0.2896	−0.0347	0.8907	0.019*
N3A	0.3823 (3)	−0.24320 (18)	0.69077 (14)	0.0198 (4)
N3B	0.2608 (3)	0.10852 (18)	0.77715 (13)	0.0187 (4)
C1A	0.1092 (4)	0.3120 (2)	0.36934 (18)	0.0230 (5)
H1A	0.0858	0.3894	0.3665	0.028*
C1B	0.2768 (4)	−0.5164 (2)	1.07967 (18)	0.0253 (5)
H1B	0.2776	−0.5999	1.0804	0.030*
C2A	0.0959 (4)	0.2312 (2)	0.29353 (18)	0.0235 (5)
H2A	0.0615	0.2470	0.2331	0.028*
C2B	0.2821 (4)	−0.4394 (2)	1.15643 (17)	0.0228 (5)
H2B	0.2863	−0.4647	1.2153	0.027*
C3A	0.1405 (3)	0.1203 (2)	0.31700 (17)	0.0196 (5)
H3A	0.1388	0.0553	0.2738	0.024*
C3B	0.2803 (3)	−0.3171 (2)	1.13637 (16)	0.0188 (5)
H3B	0.2834	−0.2528	1.1805	0.023*
C4A	0.1863 (3)	0.1199 (2)	0.41070 (16)	0.0163 (5)
C4B	0.2735 (3)	−0.3040 (2)	1.04436 (16)	0.0164 (5)
C5A	0.2352 (3)	0.0259 (2)	0.46643 (16)	0.0161 (5)
C5B	0.2672 (3)	−0.1975 (2)	0.99201 (16)	0.0161 (5)
C6A	0.2953 (3)	−0.1828 (2)	0.45404 (16)	0.0170 (5)
C6B	0.2569 (3)	0.0239 (2)	1.00755 (16)	0.0152 (4)
C7A	0.3461 (3)	−0.2706 (2)	0.60104 (17)	0.0167 (5)
C7B	0.2328 (3)	0.1179 (2)	0.86155 (16)	0.0149 (4)
C8A	0.3920 (4)	−0.3491 (2)	0.73281 (18)	0.0226 (5)
H8A	0.4158	−0.3481	0.7967	0.027*
C8B	0.2079 (4)	0.2002 (2)	0.73046 (17)	0.0210 (5)
H8B	0.2173	0.2082	0.6691	0.025*
C9A	0.3645 (4)	−0.4542 (2)	0.67459 (18)	0.0254 (6)
H9A	0.3667	−0.5323	0.6932	0.030*
C9B	0.1420 (4)	0.2768 (2)	0.77978 (17)	0.0219 (5)
H9B	0.0998	0.3417	0.7570	0.026*
H1W	0.486 (3)	0.052 (3)	0.750 (3)	0.050*
H2W	0.531 (4)	−0.0536 (3)	0.744 (2)	0.050*

	U11	U22	U33	U12	U13	U23
S1A	0.0280 (3)	0.0159 (3)	0.0215 (3)	0.0091 (2)	0.0033 (2)	−0.0003 (2)
S1B	0.0384 (4)	0.0153 (3)	0.0203 (3)	0.0137 (3)	0.0053 (2)	−0.0009 (2)
S2A	0.0424 (4)	0.0177 (3)	0.0177 (3)	0.0141 (3)	0.0017 (3)	−0.0029 (2)
S2B	0.0280 (3)	0.0126 (3)	0.0167 (3)	0.0081 (2)	0.0033 (2)	−0.0014 (2)
S3A	0.0336 (3)	0.0113 (3)	0.0234 (3)	0.0059 (2)	0.0030 (2)	−0.0002 (2)
S3B	0.0286 (3)	0.0172 (3)	0.0218 (3)	0.0133 (2)	0.0095 (2)	0.0050 (2)
O1A	0.0312 (10)	0.0176 (8)	0.0176 (9)	0.0089 (7)	0.0043 (7)	−0.0004 (6)
O1B	0.0396 (11)	0.0183 (8)	0.0183 (9)	0.0139 (8)	0.0064 (8)	0.0011 (7)
O1W	0.0232 (9)	0.0117 (8)	0.0228 (9)	0.0067 (7)	0.0012 (7)	−0.0014 (7)
N1A	0.0231 (10)	0.0127 (9)	0.0151 (9)	0.0065 (8)	0.0015 (8)	0.0000 (7)
N1B	0.0183 (9)	0.0120 (9)	0.0145 (9)	0.0060 (7)	0.0019 (7)	0.0006 (7)
N2A	0.0217 (10)	0.0104 (9)	0.0175 (10)	0.0043 (7)	0.0018 (8)	−0.0020 (7)
N2B	0.0189 (9)	0.0123 (9)	0.0181 (10)	0.0079 (7)	0.0046 (8)	−0.0001 (7)
N3A	0.0210 (10)	0.0154 (10)	0.0204 (10)	0.0035 (8)	0.0015 (8)	0.0019 (8)
N3B	0.0229 (10)	0.0139 (9)	0.0192 (10)	0.0061 (8)	0.0042 (8)	0.0007 (8)
C1A	0.0238 (12)	0.0190 (12)	0.0285 (13)	0.0101 (10)	0.0045 (10)	0.0058 (10)
C1B	0.0376 (15)	0.0148 (11)	0.0254 (13)	0.0125 (10)	0.0030 (11)	0.0042 (10)
C2A	0.0228 (12)	0.0283 (13)	0.0220 (12)	0.0117 (10)	0.0037 (10)	0.0058 (10)
C2B	0.0313 (13)	0.0177 (12)	0.0184 (12)	0.0090 (10)	0.0006 (10)	0.0026 (9)
C3A	0.0189 (11)	0.0183 (11)	0.0220 (12)	0.0066 (9)	0.0043 (9)	0.0014 (9)
C3B	0.0210 (12)	0.0130 (11)	0.0202 (12)	0.0059 (9)	−0.0009 (9)	−0.0031 (9)
C4A	0.0141 (10)	0.0137 (10)	0.0195 (11)	0.0031 (8)	0.0023 (9)	−0.0008 (9)
C4B	0.0153 (10)	0.0117 (10)	0.0218 (12)	0.0055 (8)	0.0020 (9)	−0.0031 (9)
C5A	0.0139 (10)	0.0120 (10)	0.0199 (12)	0.0018 (8)	0.0022 (9)	−0.0015 (9)
C5B	0.0139 (10)	0.0124 (10)	0.0212 (12)	0.0045 (8)	0.0024 (9)	−0.0010 (9)
C6A	0.0164 (11)	0.0137 (10)	0.0182 (11)	0.0030 (8)	0.0002 (9)	0.0009 (8)
C6B	0.0132 (10)	0.0100 (10)	0.0201 (11)	0.0022 (8)	0.0009 (8)	0.0003 (8)
C7A	0.0150 (11)	0.0107 (10)	0.0219 (12)	0.0016 (8)	0.0026 (9)	−0.0003 (8)
C7B	0.0137 (10)	0.0109 (10)	0.0194 (11)	0.0042 (8)	0.0015 (8)	−0.0006 (8)
C8A	0.0228 (12)	0.0218 (12)	0.0217 (12)	0.0054 (10)	0.0026 (10)	0.0062 (10)
C8B	0.0245 (12)	0.0181 (11)	0.0196 (12)	0.0059 (10)	0.0029 (9)	0.0042 (9)
C9A	0.0304 (14)	0.0169 (12)	0.0269 (14)	0.0048 (10)	0.0036 (11)	0.0082 (10)
C9B	0.0268 (13)	0.0195 (12)	0.0219 (12)	0.0102 (10)	0.0042 (10)	0.0088 (10)

S1A—C1A	1.709 (3)	N2B—H2BA	0.8600
S1A—C4A	1.727 (2)	N3A—C7A	1.306 (3)
S1B—C1B	1.705 (3)	N3A—C8A	1.379 (3)
S1B—C4B	1.725 (2)	N3B—C7B	1.303 (3)
S2A—C6A	1.655 (2)	N3B—C8B	1.382 (3)
S2B—C6B	1.657 (2)	C1A—C2A	1.362 (4)
S3A—C9A	1.721 (3)	C1A—H1A	0.9300
S3A—C7A	1.728 (2)	C1B—C2B	1.366 (4)
S3B—C7B	1.721 (2)	C1B—H1B	0.9300
S3B—C9B	1.726 (2)	C2A—C3A	1.418 (3)
O1A—C5A	1.231 (3)	C2A—H2A	0.9300
O1B—C5B	1.230 (3)	C2B—C3B	1.411 (3)
O1W—H1W	0.8199 (10)	C2B—H2B	0.9300
O1W—H2W	0.8199 (11)	C3A—C4A	1.370 (3)
N1A—C5A	1.387 (3)	C3A—H3A	0.9300
N1A—C6A	1.396 (3)	C3B—C4B	1.372 (3)
N1A—H1AA	0.8600	C3B—H3B	0.9300
N1B—C5B	1.383 (3)	C4A—C5A	1.463 (3)
N1B—C6B	1.393 (3)	C4B—C5B	1.461 (3)
N1B—H1BA	0.8600	C8A—C9A	1.347 (4)
N2A—C6A	1.344 (3)	C8A—H8A	0.9300
N2A—C7A	1.385 (3)	C8B—C9B	1.340 (4)
N2A—H2AA	0.8600	C8B—H8B	0.9300
N2B—C6B	1.348 (3)	C9A—H9A	0.9300
N2B—C7B	1.387 (3)	C9B—H9B	0.9300
C1A—S1A—C4A	91.39 (12)	C3A—C4A—C5A	131.8 (2)
C1B—S1B—C4B	91.37 (12)	C3A—C4A—S1A	111.53 (18)
C9A—S3A—C7A	88.14 (12)	C5A—C4A—S1A	116.61 (17)
C7B—S3B—C9B	88.16 (11)	C3B—C4B—C5B	131.9 (2)
H1W—O1W—H2W	106 (2)	C3B—C4B—S1B	111.50 (17)
C5A—N1A—C6A	127.1 (2)	C5B—C4B—S1B	116.60 (18)
C5A—N1A—H1AA	116.4	O1A—C5A—N1A	122.3 (2)
C6A—N1A—H1AA	116.4	O1A—C5A—C4A	121.5 (2)
C5B—N1B—C6B	126.7 (2)	N1A—C5A—C4A	116.1 (2)
C5B—N1B—H1BA	116.7	O1B—C5B—N1B	122.6 (2)
C6B—N1B—H1BA	116.7	O1B—C5B—C4B	121.1 (2)
C6A—N2A—C7A	128.3 (2)	N1B—C5B—C4B	116.3 (2)
C6A—N2A—H2AA	115.9	N2A—C6A—N1A	114.9 (2)
C7A—N2A—H2AA	115.9	N2A—C6A—S2A	125.44 (18)
C6B—N2B—C7B	128.1 (2)	N1A—C6A—S2A	119.68 (17)
C6B—N2B—H2BA	116.0	N2B—C6B—N1B	114.6 (2)
C7B—N2B—H2BA	116.0	N2B—C6B—S2B	125.81 (17)
C7A—N3A—C8A	110.1 (2)	N1B—C6B—S2B	119.57 (17)
C7B—N3B—C8B	109.9 (2)	N3A—C7A—N2A	118.5 (2)
C2A—C1A—S1A	112.31 (19)	N3A—C7A—S3A	115.58 (18)
C2A—C1A—H1A	123.8	N2A—C7A—S3A	125.85 (18)
S1A—C1A—H1A	123.8	N3B—C7B—N2B	118.3 (2)
C2B—C1B—S1B	112.34 (19)	N3B—C7B—S3B	115.79 (17)
C2B—C1B—H1B	123.8	N2B—C7B—S3B	125.78 (18)
S1B—C1B—H1B	123.8	C9A—C8A—N3A	115.1 (2)
C1A—C2A—C3A	112.5 (2)	C9A—C8A—H8A	122.4
C1A—C2A—H2A	123.7	N3A—C8A—H8A	122.4
C3A—C2A—H2A	123.7	C9B—C8B—N3B	115.3 (2)
C1B—C2B—C3B	112.4 (2)	C9B—C8B—H8B	122.3
C1B—C2B—H2B	123.8	N3B—C8B—H8B	122.3
C3B—C2B—H2B	123.8	C8A—C9A—S3A	111.08 (19)
C4A—C3A—C2A	112.3 (2)	C8A—C9A—H9A	124.5
C4A—C3A—H3A	123.9	S3A—C9A—H9A	124.5
C2A—C3A—H3A	123.9	C8B—C9B—S3B	110.83 (18)
C4B—C3B—C2B	112.4 (2)	C8B—C9B—H9B	124.6
C4B—C3B—H3B	123.8	S3B—C9B—H9B	124.6
C2B—C3B—H3B	123.8
C4A—S1A—C1A—C2A	0.6 (2)	C7A—N2A—C6A—N1A	176.5 (2)
C4B—S1B—C1B—C2B	0.3 (2)	C7A—N2A—C6A—S2A	−4.3 (4)
S1A—C1A—C2A—C3A	−0.5 (3)	C5A—N1A—C6A—N2A	−10.2 (3)
S1B—C1B—C2B—C3B	−0.3 (3)	C5A—N1A—C6A—S2A	170.44 (18)
C1A—C2A—C3A—C4A	0.1 (3)	C7B—N2B—C6B—N1B	175.1 (2)
C1B—C2B—C3B—C4B	0.1 (3)	C7B—N2B—C6B—S2B	−5.7 (4)
C2A—C3A—C4A—C5A	177.8 (2)	C5B—N1B—C6B—N2B	−13.9 (3)
C2A—C3A—C4A—S1A	0.3 (3)	C5B—N1B—C6B—S2B	166.76 (18)
C1A—S1A—C4A—C3A	−0.49 (19)	C8A—N3A—C7A—N2A	177.4 (2)
C1A—S1A—C4A—C5A	−178.44 (19)	C8A—N3A—C7A—S3A	−0.9 (3)
C2B—C3B—C4B—C5B	179.2 (2)	C6A—N2A—C7A—N3A	176.3 (2)
C2B—C3B—C4B—S1B	0.1 (3)	C6A—N2A—C7A—S3A	−5.5 (4)
C1B—S1B—C4B—C3B	−0.2 (2)	C9A—S3A—C7A—N3A	0.9 (2)
C1B—S1B—C4B—C5B	−179.44 (19)	C9A—S3A—C7A—N2A	−177.3 (2)
C6A—N1A—C5A—O1A	7.0 (4)	C8B—N3B—C7B—N2B	174.97 (19)
C6A—N1A—C5A—C4A	−173.1 (2)	C8B—N3B—C7B—S3B	−1.3 (3)
C3A—C4A—C5A—O1A	−170.5 (2)	C6B—N2B—C7B—N3B	174.7 (2)
S1A—C4A—C5A—O1A	6.9 (3)	C6B—N2B—C7B—S3B	−9.5 (3)
C3A—C4A—C5A—N1A	9.6 (4)	C9B—S3B—C7B—N3B	1.54 (19)
S1A—C4A—C5A—N1A	−173.01 (16)	C9B—S3B—C7B—N2B	−174.4 (2)
C6B—N1B—C5B—O1B	6.8 (4)	C7A—N3A—C8A—C9A	0.5 (3)
C6B—N1B—C5B—C4B	−173.2 (2)	C7B—N3B—C8B—C9B	0.2 (3)
C3B—C4B—C5B—O1B	−176.5 (2)	N3A—C8A—C9A—S3A	0.2 (3)
S1B—C4B—C5B—O1B	2.5 (3)	C7A—S3A—C9A—C8A	−0.6 (2)
C3B—C4B—C5B—N1B	3.5 (4)	N3B—C8B—C9B—S3B	0.9 (3)
S1B—C4B—C5B—N1B	−177.49 (16)	C7B—S3B—C9B—C8B	−1.32 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1AA···O1Wi	0.86	2.22	3.003 (3)	152
N1B—H1BA···O1Wii	0.86	2.14	2.973 (3)	163
N2A—H2AA···O1A	0.86	1.89	2.599 (3)	138
N2B—H2BA···O1B	0.86	1.90	2.588 (3)	136
O1W—H1W···N3B	0.82 (1)	2.06 (1)	2.852 (3)	163 (4)
O1W—H2W···N3A	0.82 (1)	2.09 (1)	2.892 (3)	167 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1AA⋯O1W i	0.86	2.22	3.003 (3)	152
N1B—H1BA⋯O1W ii	0.86	2.14	2.973 (3)	163
N2A—H2AA⋯O1A	0.86	1.89	2.599 (3)	138
N2B—H2BA⋯O1B	0.86	1.90	2.588 (3)	136
O1W—H1W⋯N3B	0.82 (1)	2.06 (1)	2.852 (3)	163 (4)
O1W—H2W⋯N3A	0.82 (1)	2.09 (1)	2.892 (3)	167 (3)

Symmetry codes: (i) ; (ii) .