5-[(E)-(5-Bromo-2-hy­droxy­benzyl­idene)amino]-1,3,4-thia­diazole-2(3H)-thione

Abstract

In the title mol­ecule, C₉H₆BrN₃OS₂, the dihedral angle between the benzene ring and the five-membered ring is 5.5 (3)°. An intra­molecular O—H⋯N hydrogen bond forms an S(6) ring motif. In the crystal, N—H⋯S hydrogen bonds link mol­ecules into centrosymmetric dimers creating R ₂ ²(8) ring motifs. In addition, there are inter­molecular S⋯S [3.430 (2) Å] contacts. The crystal used was a non-merohedral twin with a ratio of 0.113 (3):0.887 (3) for the components.

Related literature

For the biological versatility of thione ligands, see, for example: Kumar et al. (1988 ▶); Yadav et al. (1989 ▶). For related structures, see: Zhang (2003 ▶); Kargar et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For van der Waals radii, see: Bondi (1964 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

• C₉H₆BrN₃OS₂

• M _r = 316.20

• Monoclinic,

• a = 18.3690 (13) Å

• b = 4.0016 (3) Å

• c = 16.2877 (13) Å

• β = 112.660 (4)°

• V = 1104.82 (14) ų

• Z = 4

• Mo Kα radiation

• μ = 4.08 mm⁻¹

• T = 291 K

• 0.11 × 0.05 × 0.02 mm

Data collection

• Bruker SMART APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.663, T _max = 0.923

• 10313 measured reflections

• 2734 independent reflections

• 1760 reflections with I > 2σ(I)

• R _int = 0.071

Refinement

• R[F ² > 2σ(F ²)] = 0.060

• wR(F ²) = 0.140

• S = 1.08

• 2734 reflections

• 147 parameters

• H-atom parameters constrained

• Δρ_max = 1.25 e Å⁻³

• Δρ_min = −0.71 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811049920/lh5379Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.94	2.664 (7)	147
N3—H3⋯S2i	0.97	2.36	3.327 (5)	173

Symmetry code: (i) .

supplementary crystallographic information

Comment

The biological versatility of compounds incorporating a thiadiazole ring is well known (Kumar et al., 1988; Yadav et al., 1989). In continuation of our work on the crystal structure of thione-Schiff base ligands (Kargar et al., 2011), we have determined the crystal structure of the title compound.

The asymmetric unit of the title compound is shown in Fig. 1. The bond lengths (Allen et al., 1987) and angles are within the normal ranges and are comparable to related structures (Kargar et al., 2011; Zhang, 2003).

The dihedral angle between the benzene ring and the five-membered ring is 5.5 (3)°. An intramolecular O—H···N hydrogen bond forms an S(6) ring motif. Intermolecular N—H···S interactions link molecules into centrosymmetric dimers with R₂²(8) ring motifs (Bernstein et al.,1995). An interesting feature of the crystal structure is the short S1···S1ⁱ [3.430 (2)Å; (i) 2 - x, -1/2 + y, 1/2 - z] contact which is shorter than the sum of the Van der Waals radius of S [3.60Å] atoms (Bondi, 1964). The crystal was a non-merohedral twin with a refined BASF ratio of 0.113 (3)/0.887 (3).

Experimental

The title compound was synthesized by adding 5-bromo-salicylaldehyde (1 mmol) to a solution of 5-aminothiophene-2-thiol (1 mmol) in ethanol (30 ml). The mixture was refluxed with stirring for half an hour. The resultant solution was filtered. Yellow single crystals of the title compound suitable for X-ray structure determination were recrystallized from ethanol by slow evaporation of the solvent at room temperature over several days.

Refinement

All hydrogen atoms were positioned geometrically with C—H = 0.93 Å, N—H = 0.97 Å, O—H = 0.82 Å and included in a riding-model approximation with U_iso(H) = 1.2U_eq(C,N) and 1.5 U_eq(O). The crystal was a non-merohedral twin {Twin Law (1 0 0)[5 0 2]} which was treated TwinRotMat routine in PLATON (Spek, 2009) with a refined BASF ratio of 0.113 (3)/0.887 (3).

Figures

Fig. 1.

The molecular structure of the title compound, showing 40% probability displacement ellipsoids. The dashed line shows an intramolecular hydrogen bond.

Fig. 2.

A packing diagram of the title compound viewed along the b-axis showing short intermolecular S···S contacts and centrosymmetric dimers formed by intermolecular N—H···S hydrogen bonds. The dashed lines indicate the intermolecular interactions.

Crystal data

C9H6BrN3OS2	F(000) = 624
Mr = 316.20	Dx = 1.901 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2573 reflections
a = 18.3690 (13) Å	θ = 2.5–29.3°
b = 4.0016 (3) Å	µ = 4.08 mm−1
c = 16.2877 (13) Å	T = 291 K
β = 112.660 (4)°	Block, yellow
V = 1104.82 (14) Å3	0.11 × 0.05 × 0.02 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	10313 independent reflections
Radiation source: fine-focus sealed tube	1760 reflections with I > 2σ(I)
graphite	Rint = 0.071
φ and ω scans	θmax = 28.3°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −24→24
Tmin = 0.663, Tmax = 0.923	k = −5→5
2734 measured reflections	l = −21→21

Refinement

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0412P)2 + 3.7473P] where P = (Fo2 + 2Fc2)/3
2734 reflections	(Δ/σ)max < 0.001
147 parameters	Δρmax = 1.25 e Å−3
0 restraints	Δρmin = −0.71 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.65016 (4)	0.82937 (19)	−0.22477 (5)	0.0438 (2)
S1	0.92727 (8)	0.4125 (4)	0.25824 (11)	0.0306 (4)
S2	1.06396 (9)	0.3421 (4)	0.43539 (10)	0.0329 (4)
O1	0.6140 (2)	0.1515 (13)	0.0870 (3)	0.0439 (12)
H1	0.6563	0.1408	0.1296	0.066*
N1	0.7683 (3)	0.2398 (13)	0.1762 (3)	0.0314 (12)
N2	0.8404 (3)	0.0884 (14)	0.3226 (4)	0.0355 (13)
N3	0.9159 (3)	0.1150 (13)	0.3865 (3)	0.0347 (13)
H3	0.9211	−0.0002	0.4408	0.042*
C1	0.6244 (3)	0.3022 (18)	0.0192 (4)	0.0340 (15)
C2	0.6990 (3)	0.4180 (15)	0.0246 (4)	0.0286 (13)
C3	0.7065 (3)	0.5752 (15)	−0.0484 (4)	0.0315 (14)
H3A	0.7556	0.6477	−0.0453	0.038*
C4	0.6402 (3)	0.6216 (15)	−0.1255 (4)	0.0313 (14)
C5	0.5670 (4)	0.5144 (17)	−0.1308 (4)	0.0365 (15)
H5A	0.5229	0.5488	−0.1829	0.044*
C6	0.5587 (3)	0.3570 (17)	−0.0598 (4)	0.0367 (15)
H6A	0.5091	0.2864	−0.0642	0.044*
C7	0.7688 (3)	0.3839 (16)	0.1055 (4)	0.0339 (15)
H7A	0.8162	0.4697	0.1066	0.041*
C8	0.8377 (3)	0.2352 (15)	0.2507 (4)	0.0260 (13)
C9	0.9707 (3)	0.2737 (14)	0.3678 (4)	0.0261 (13)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.0511 (4)	0.0493 (4)	0.0304 (4)	0.0088 (3)	0.0152 (3)	0.0084 (3)
S1	0.0242 (7)	0.0387 (9)	0.0263 (8)	−0.0014 (6)	0.0067 (6)	0.0065 (7)
S2	0.0252 (7)	0.0429 (9)	0.0264 (9)	−0.0014 (7)	0.0055 (6)	−0.0007 (7)
O1	0.030 (2)	0.065 (3)	0.033 (3)	−0.009 (2)	0.008 (2)	0.008 (3)
N1	0.026 (3)	0.039 (3)	0.026 (3)	0.002 (2)	0.006 (2)	0.001 (2)
N2	0.024 (2)	0.051 (3)	0.029 (3)	−0.006 (2)	0.006 (2)	0.003 (3)
N3	0.033 (3)	0.047 (3)	0.024 (3)	−0.005 (2)	0.010 (2)	0.006 (3)
C1	0.029 (3)	0.053 (4)	0.024 (3)	−0.008 (3)	0.014 (3)	−0.004 (3)
C2	0.027 (3)	0.031 (3)	0.026 (3)	0.001 (2)	0.008 (3)	0.001 (3)
C3	0.024 (3)	0.041 (4)	0.028 (3)	0.002 (3)	0.008 (3)	0.000 (3)
C4	0.033 (3)	0.032 (3)	0.026 (3)	0.001 (3)	0.007 (3)	0.003 (3)
C5	0.033 (3)	0.044 (4)	0.025 (3)	0.003 (3)	0.003 (3)	−0.002 (3)
C6	0.024 (3)	0.045 (4)	0.037 (4)	−0.003 (3)	0.008 (3)	0.001 (3)
C7	0.023 (3)	0.042 (4)	0.034 (4)	0.002 (3)	0.007 (3)	−0.001 (3)
C8	0.021 (3)	0.033 (3)	0.023 (3)	0.003 (2)	0.007 (2)	0.003 (2)
C9	0.032 (3)	0.026 (3)	0.021 (3)	0.002 (2)	0.010 (3)	−0.003 (2)

Geometric parameters (Å, °)

Br1—C4	1.889 (6)	C1—C6	1.402 (8)
S1—C9	1.741 (6)	C1—C2	1.417 (8)
S1—C8	1.752 (6)	C2—C3	1.399 (8)
S2—C9	1.663 (6)	C2—C7	1.448 (8)
O1—C1	1.334 (7)	C3—C4	1.384 (8)
O1—H1	0.8200	C3—H3A	0.9300
N1—C7	1.292 (8)	C4—C5	1.382 (9)
N1—C8	1.381 (7)	C5—C6	1.377 (9)
N2—C8	1.293 (8)	C5—H5A	0.9300
N2—N3	1.381 (7)	C6—H6A	0.9300
N3—C9	1.322 (8)	C7—H7A	0.9300
N3—H3	0.9690
C9—S1—C8	89.4 (3)	C5—C4—Br1	119.7 (5)
C1—O1—H1	109.5	C3—C4—Br1	119.6 (5)
C7—N1—C8	117.9 (5)	C6—C5—C4	120.6 (6)
C8—N2—N3	108.9 (5)	C6—C5—H5A	119.7
C9—N3—N2	119.8 (5)	C4—C5—H5A	119.7
C9—N3—H3	128.5	C5—C6—C1	120.6 (6)
N2—N3—H3	111.7	C5—C6—H6A	119.7
O1—C1—C6	118.9 (5)	C1—C6—H6A	119.7
O1—C1—C2	122.7 (6)	N1—C7—C2	123.0 (6)
C6—C1—C2	118.4 (6)	N1—C7—H7A	118.5
C3—C2—C1	120.3 (6)	C2—C7—H7A	118.5
C3—C2—C7	118.2 (5)	N2—C8—N1	120.1 (5)
C1—C2—C7	121.5 (6)	N2—C8—S1	114.4 (4)
C4—C3—C2	119.4 (5)	N1—C8—S1	125.5 (5)
C4—C3—H3A	120.3	N3—C9—S2	127.4 (5)
C2—C3—H3A	120.3	N3—C9—S1	107.5 (4)
C5—C4—C3	120.8 (6)	S2—C9—S1	125.1 (4)
C8—N2—N3—C9	0.2 (8)	C8—N1—C7—C2	−177.1 (5)
O1—C1—C2—C3	−179.9 (6)	C3—C2—C7—N1	−179.2 (6)
C6—C1—C2—C3	−1.7 (10)	C1—C2—C7—N1	1.9 (10)
O1—C1—C2—C7	−1.1 (10)	N3—N2—C8—N1	179.3 (5)
C6—C1—C2—C7	177.1 (6)	N3—N2—C8—S1	−0.1 (7)
C1—C2—C3—C4	1.1 (9)	C7—N1—C8—N2	−178.7 (6)
C7—C2—C3—C4	−177.7 (6)	C7—N1—C8—S1	0.6 (8)
C2—C3—C4—C5	−0.1 (9)	C9—S1—C8—N2	0.0 (5)
C2—C3—C4—Br1	−179.3 (5)	C9—S1—C8—N1	−179.3 (5)
C3—C4—C5—C6	−0.4 (10)	N2—N3—C9—S2	178.3 (5)
Br1—C4—C5—C6	178.8 (5)	N2—N3—C9—S1	−0.2 (7)
C4—C5—C6—C1	−0.1 (10)	C8—S1—C9—N3	0.1 (5)
O1—C1—C6—C5	179.4 (6)	C8—S1—C9—S2	−178.4 (4)
C2—C1—C6—C5	1.2 (10)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.94	2.664 (7)	147
N3—H3···S2i	0.97	2.36	3.327 (5)	173

Symmetry codes: (i) −x+2, −y, −z+1.