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

Abstract

In the title compound, C₁₀H₉N₃O₂S₂, the dihedral angle between the benzene ring and the five-membered ring is 1.54 (13)°. An intra­molecular O—H⋯N hydrogen bond makes an S(6) ring. In the crystal, mol­ecules are linked together through bifurcated N—H⋯(O,O) hydrogen bonds having R ₁ ²(5) ring motifs, forming chains along the b axis. The crystal structure also features π–π inter­actions, with centroid–centroid distances of 3.699 (3)–3.767 (3) Å.

Related literature

For standard bond lengths, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). 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 ▶, 2011a ▶, 2011b ▶).

Experimental

Crystal data

• C₁₀H₉N₃O₂S₂

• M _r = 267.32

• Monoclinic,

• a = 7.432 (5) Å

• b = 14.993 (5) Å

• c = 10.853 (5) Å

• β = 101.738 (5)°

• V = 1184.0 (10) ų

• Z = 4

• Mo Kα radiation

• μ = 0.44 mm⁻¹

• T = 291 K

• 0.25 × 0.21 × 0.11 mm

Data collection

• Stoe IPDS 2T Image Plate diffractometer

• Absorption correction: multi-scan [MULABS (Blessing, 1995 ▶) in PLATON (Spek, 2009 ▶)] T _min = 0.898, T _max = 1.000

• 9012 measured reflections

• 3147 independent reflections

• 1530 reflections with I > 2σ(I)

• R _int = 0.075

Refinement

• R[F ² > 2σ(F ²)] = 0.057

• wR(F ²) = 0.079

• S = 0.92

• 3147 reflections

• 155 parameters

• H-atom parameters constrained

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.22 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2009 ▶); cell refinement: X-AREA; data reduction: X-AREA; 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/S1600536811050902/fj2484Isup3.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	0.76	1.97	2.633 (3)	146
N3—H3⋯O1i	0.86	2.23	2.919 (3)	138
N3—H3⋯O2i	0.86	2.29	3.034 (3)	146

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).

The asymmetric unit of the title compound, Fig. 1, comprises a thione-Schiff base ligand. The bond lengths (Allen et al., 1987) and angles are within the normal ranges and are comparable to the related structure (Zhang, 2003; Kargar et al., 2011a,b; Kargar & Kia, 2011).

The dihedral angle between the benzene ring and the five-membered ring is 1.54 (13)°. The intramolecular O—H···N hydrogen bond makes S(6) ring motif (Bernstein et al., 1995). In the crystal packing molecules are linked together through bifurctaed N—H···O hydrogen bonds with R²₁(5) ring motifs (Bernstein et al., 1995), forming one-dimensional extended chains along the b axis. The crystal structure is further stabilized by the intermolecular π-π interactions [[Cg1···Cg2ⁱ = 3.767 (3)Å, (i) -x, 1 - y, 1 -z; Cg1···Cg2ⁱⁱ = 3.699 (3)Å, (ii) 1 - x, 1 - y, 1 - z; Cg1 and Cg2 are centroids of S(1)/C(8)/N(2)/N(3)/C(9) and C1–C6 rings, respectively].

Experimental

The title compound was synthesized by adding 3-methoxy-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 solvents at room temperature over several days.

Refinement

All hydrogen atoms were positioned geometrically with C—H = 0.93-0.96 Å and included in a riding model approximation with U_iso (H) = 1.2 or 1.5 U_eq (C). A rotating group model was applied to the methyl group.

Figures

Fig. 1.

The ORTEP plot of the title compound, showing 40% probability displacement ellipsoids and the atomic numbering. The dashed lines show the intermolecular interaction.

Fig. 2.

The packing diagram of the title compound viewed down the c-axis showing linkning of molecules through the intermolecular N—H···O intearctions R21(5) ring motifs, forming one-dimensional extended chains along the b-axis. Only the H atoms involved the hydrogen bonds are shown. The dashed lines show the intermolecular interactions.

Crystal data

C10H9N3O2S2	F(000) = 552
Mr = 267.32	Dx = 1.500 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 2780 reflections
a = 7.432 (5) Å	θ = 2.5–27.4°
b = 14.993 (5) Å	µ = 0.44 mm−1
c = 10.853 (5) Å	T = 291 K
β = 101.738 (5)°	Block, yellow
V = 1184.0 (10) Å3	0.25 × 0.21 × 0.11 mm
Z = 4

Data collection

Stoe IPDS 2T Image Plate diffractometer	3147 independent reflections
Radiation source: fine-focus sealed tube	1530 reflections with I > 2σ(I)
graphite	Rint = 0.075
Detector resolution: 0.15 mm pixels mm-1	θmax = 29.0°, θmin = 2.4°
ω scans	h = −9→10
Absorption correction: multi-scan [MULABS (Blessing, 1995) in PLATON (Spek, 2009)]	k = −20→19
Tmin = 0.898, Tmax = 1.000	l = −14→14
9012 measured reflections

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079	H-atom parameters constrained
S = 0.92	w = 1/[σ2(Fo2) + (0.0235P)2] where P = (Fo2 + 2Fc2)/3
3147 reflections	(Δ/σ)max = 0.001
155 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.22 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
S1	0.21750 (10)	0.70390 (4)	0.52967 (6)	0.04780 (19)
S2	0.26803 (11)	0.88098 (5)	0.66246 (8)	0.0669 (3)
O1	0.3794 (2)	0.35277 (10)	0.59426 (14)	0.0493 (5)
H1	0.3815	0.4009	0.6167	0.074*
O2	0.3399 (3)	0.19524 (12)	0.50192 (17)	0.0610 (5)
N1	0.3081 (3)	0.52471 (12)	0.57179 (17)	0.0366 (5)
N2	0.4094 (3)	0.63027 (13)	0.72724 (18)	0.0436 (5)
N3	0.3970 (3)	0.72004 (13)	0.74725 (18)	0.0471 (6)
H3	0.4552	0.7361	0.8202	0.056*
C1	0.2778 (3)	0.34679 (16)	0.4758 (2)	0.0380 (6)
C2	0.2551 (4)	0.26105 (18)	0.4235 (2)	0.0437 (7)
C3	0.1578 (4)	0.2506 (2)	0.3031 (3)	0.0561 (8)
H3A	0.1432	0.1940	0.2674	0.067*
C4	0.0809 (4)	0.3235 (2)	0.2342 (3)	0.0604 (8)
H4A	0.0156	0.3155	0.1523	0.073*
C5	0.0996 (4)	0.40713 (18)	0.2846 (2)	0.0528 (7)
H5A	0.0462	0.4556	0.2375	0.063*
C6	0.1990 (3)	0.41983 (17)	0.4071 (2)	0.0365 (6)
C7	0.2189 (3)	0.50812 (16)	0.4597 (2)	0.0395 (6)
H7A	0.1647	0.5555	0.4103	0.047*
C8	0.3194 (3)	0.61176 (16)	0.6153 (2)	0.0351 (6)
C9	0.3028 (4)	0.77222 (16)	0.6575 (2)	0.0438 (6)
C10	0.2996 (5)	0.10417 (18)	0.4652 (3)	0.0769 (10)
H10A	0.3550	0.0653	0.5326	0.115*
H10B	0.3481	0.0910	0.3917	0.115*
H10C	0.1690	0.0953	0.4468	0.115*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0536 (5)	0.0348 (4)	0.0529 (4)	0.0065 (3)	0.0058 (3)	0.0043 (3)
S2	0.0708 (6)	0.0335 (4)	0.0980 (6)	0.0065 (4)	0.0208 (5)	−0.0043 (4)
O1	0.0629 (13)	0.0321 (10)	0.0487 (11)	0.0050 (9)	0.0013 (9)	0.0003 (7)
O2	0.0684 (14)	0.0303 (11)	0.0841 (14)	0.0019 (10)	0.0148 (11)	−0.0055 (9)
N1	0.0394 (13)	0.0303 (12)	0.0397 (12)	0.0015 (10)	0.0071 (10)	−0.0017 (9)
N2	0.0455 (14)	0.0333 (13)	0.0497 (13)	0.0026 (10)	0.0041 (11)	−0.0036 (10)
N3	0.0482 (14)	0.0407 (14)	0.0499 (13)	−0.0017 (11)	0.0044 (11)	−0.0094 (11)
C1	0.0352 (15)	0.0415 (15)	0.0389 (13)	−0.0042 (12)	0.0112 (12)	−0.0040 (12)
C2	0.0428 (17)	0.0374 (16)	0.0540 (17)	−0.0030 (13)	0.0175 (14)	−0.0048 (13)
C3	0.062 (2)	0.0465 (19)	0.0655 (19)	−0.0168 (15)	0.0269 (16)	−0.0203 (15)
C4	0.067 (2)	0.064 (2)	0.0484 (16)	−0.0238 (18)	0.0068 (15)	−0.0136 (16)
C5	0.0549 (19)	0.0518 (19)	0.0478 (17)	−0.0114 (15)	0.0013 (14)	0.0021 (13)
C6	0.0338 (15)	0.0358 (15)	0.0399 (14)	−0.0044 (12)	0.0074 (12)	0.0008 (11)
C7	0.0374 (16)	0.0366 (16)	0.0449 (15)	0.0006 (12)	0.0094 (13)	0.0077 (12)
C8	0.0344 (14)	0.0309 (14)	0.0414 (14)	0.0033 (11)	0.0108 (12)	0.0054 (11)
C9	0.0390 (15)	0.0376 (15)	0.0578 (16)	−0.0019 (13)	0.0167 (13)	−0.0025 (13)
C10	0.083 (3)	0.0348 (18)	0.115 (3)	−0.0048 (17)	0.026 (2)	−0.0109 (18)

Geometric parameters (Å, °)

S1—C9	1.737 (3)	C1—C2	1.401 (3)
S1—C8	1.749 (2)	C2—C3	1.369 (3)
S2—C9	1.654 (3)	C3—C4	1.381 (4)
O1—C1	1.355 (3)	C3—H3A	0.9300
O1—H1	0.7607	C4—C5	1.364 (3)
O2—C2	1.370 (3)	C4—H4A	0.9300
O2—C10	1.437 (3)	C5—C6	1.397 (3)
N1—C7	1.286 (3)	C5—H5A	0.9300
N1—C8	1.385 (3)	C6—C7	1.437 (3)
N2—C8	1.292 (3)	C7—H7A	0.9300
N2—N3	1.369 (3)	C10—H10A	0.9600
N3—C9	1.332 (3)	C10—H10B	0.9600
N3—H3	0.8561	C10—H10C	0.9600
C1—C6	1.386 (3)
C9—S1—C8	89.62 (13)	C4—C5—H5A	120.1
C1—O1—H1	109.8	C6—C5—H5A	120.1
C2—O2—C10	118.0 (2)	C1—C6—C5	119.2 (2)
C7—N1—C8	119.3 (2)	C1—C6—C7	121.1 (2)
C8—N2—N3	108.7 (2)	C5—C6—C7	119.7 (2)
C9—N3—N2	120.2 (2)	N1—C7—C6	123.0 (2)
C9—N3—H3	127.1	N1—C7—H7A	118.5
N2—N3—H3	112.7	C6—C7—H7A	118.5
O1—C1—C6	123.5 (2)	N2—C8—N1	120.5 (2)
O1—C1—C2	116.3 (2)	N2—C8—S1	114.54 (18)
C6—C1—C2	120.3 (2)	N1—C8—S1	125.01 (18)
C3—C2—O2	126.7 (3)	N3—C9—S2	128.1 (2)
C3—C2—C1	119.3 (3)	N3—C9—S1	106.85 (18)
O2—C2—C1	114.0 (2)	S2—C9—S1	125.01 (17)
C2—C3—C4	120.4 (3)	O2—C10—H10A	109.5
C2—C3—H3A	119.8	O2—C10—H10B	109.5
C4—C3—H3A	119.8	H10A—C10—H10B	109.5
C5—C4—C3	120.9 (3)	O2—C10—H10C	109.5
C5—C4—H4A	119.5	H10A—C10—H10C	109.5
C3—C4—H4A	119.5	H10B—C10—H10C	109.5
C4—C5—C6	119.9 (3)
C8—N2—N3—C9	0.0 (3)	C4—C5—C6—C1	0.1 (4)
C10—O2—C2—C3	−11.4 (4)	C4—C5—C6—C7	179.8 (2)
C10—O2—C2—C1	169.9 (2)	C8—N1—C7—C6	−179.6 (2)
O1—C1—C2—C3	−178.4 (2)	C1—C6—C7—N1	−0.5 (4)
C6—C1—C2—C3	1.3 (4)	C5—C6—C7—N1	179.8 (2)
O1—C1—C2—O2	0.4 (3)	N3—N2—C8—N1	−179.1 (2)
C6—C1—C2—O2	−179.9 (2)	N3—N2—C8—S1	0.5 (2)
O2—C2—C3—C4	−179.3 (3)	C7—N1—C8—N2	−179.5 (2)
C1—C2—C3—C4	−0.7 (4)	C7—N1—C8—S1	1.0 (3)
C2—C3—C4—C5	−0.3 (4)	C9—S1—C8—N2	−0.61 (19)
C3—C4—C5—C6	0.6 (4)	C9—S1—C8—N1	178.9 (2)
O1—C1—C6—C5	178.7 (2)	N2—N3—C9—S2	179.02 (18)
C2—C1—C6—C5	−1.0 (4)	N2—N3—C9—S1	−0.4 (3)
O1—C1—C6—C7	−1.0 (4)	C8—S1—C9—N3	0.53 (18)
C2—C1—C6—C7	179.3 (2)	C8—S1—C9—S2	−178.93 (18)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.76	1.97	2.633 (3)	146.
N3—H3···O1i	0.86	2.23	2.919 (3)	138.
N3—H3···O2i	0.86	2.29	3.034 (3)	146.

Symmetry codes: (i) −x+1, y+1/2, −z+3/2.