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

Kargar, H.; Kia, R.; Tahir, M.N.

doi:10.1107/S1600536811049920

organic compounds

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

Hadi Kargar,^a ^* Reza Kia ^b,^c and Muhammad Nawaz Tahir ^d ^*

^aDepartment of Chemistry, Payame Noor University, PO Box 19395-3697 Tehran, Iran, ^bX-ray Crystallography Laboratory, Plasma Physics Research Center, Science and Research Branch, Islamic Azad University, Tehran, Iran, ^cDepartment of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran, and ^dDepartment of Physics, University of Sargodha, Punjab, Pakistan
^*Correspondence e-mail: hkargar@pnu.ac.ir, dmntahir_uos@yahoo.com

(Received 13 November 2011; accepted 21 November 2011; online 25 November 2011)

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 R₂²(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, P 2₁ /c
a = 18.3690 (13) Å
b = 4.0016 (3) Å
c = 16.2877 (13) Å
β = 112.660 (4)°
V = 1104.82 (14) Å³
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[F² > 2σ(F²)] = 0.060
wR(F²) = 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

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) -x+2, -y, -z+1.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811049920/lh5379sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811049920/lh5379Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811049920/lh5379Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Structure description top

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).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	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.

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

Crystal data top

C₉H₆BrN₃OS₂	F(000) = 624
M_r = 316.20	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0412P)² + 3.7473P] where P = (F_o² + 2F_c²)/3
2734 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 1.25 e Å⁻³
0 restraints	Δρ_min = −0.71 e Å⁻³

Crystal data top

C₉H₆BrN₃OS₂	V = 1104.82 (14) Å³
M_r = 316.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.3690 (13) Å	µ = 4.08 mm⁻¹
b = 4.0016 (3) Å	T = 291 K
c = 16.2877 (13) Å	0.11 × 0.05 × 0.02 mm
β = 112.660 (4)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	10313 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1760 reflections with I > 2σ(I)
T_min = 0.663, T_max = 0.923	R_int = 0.071
2734 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.08	Δρ_max = 1.25 e Å⁻³
2734 reflections	Δρ_min = −0.71 e Å⁻³
147 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₉H₆BrN₃OS₂
M_r	316.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	18.3690 (13), 4.0016 (3), 16.2877 (13)
β (°)	112.660 (4)
V (Å³)	1104.82 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.08
Crystal size (mm)	0.11 × 0.05 × 0.02

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.663, 0.923
No. of measured, independent and observed [I > 2σ(I)] reflections	2734, 10313, 1760
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.140, 1.08
No. of reflections	2734
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.25, −0.71

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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) −x+2, −y, −z+1.

Acknowledgements

HK thanks PNU for financial support. RK thanks the Islamic Azad University. MNT thanks the GC University of Sargodha, Pakistan for research facilities.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bondi, A. (1964). J.Phys.Chem., 68, 441–451. CAS Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kargar, H., Kia, R. & Tahir, M. N. (2011). Acta Cryst. E67, o3311. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Zhang, Y.-X. (2003). Acta Cryst. E59, o581–o582. Web of Science CSD CrossRef IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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