5-[(2-Hydro­xy­phenyl)­methyl­ene­amino]-1,3,4-thia­diazo­le-2(3H)-thione

The title compound, C₉H₇N₃OS₂, is essentially planar and features an intramolecular O—H...N interaction. Centrosymmetrically related mol­ecules associate via N—H...S contacts.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.034
• wR factor = 0.085
• Data-to-parameter ratio = 13.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

The biological versatility of compounds incorporating a thiadiazole ring is well known (Kumar et al., 1988; Yadav et al., 1989). In this connection, it was thought of interest to combine a Schiff base with a thiadiazole ring system. Thus, the synthesis and structure of a new compound, namely 5-[(2-hydroxyphenyl)methyleneamino]-1,3,4-thiadiazole-2(3H)-thione, (I), is reported.

The molecular structure of (I) (Fig. 1 and Table 1) has two approximately parallel fragments linked by an Schiff base, with the dihedral angle between the aromatic and thiadiazole rings being 1.0 (1)°. The C9—S2 bond length of 1.662 (3) Å is approximately 0.08 Å shorter than the C9—S1 bond length, confirming the presence of the thione. There is an O1—H···N1 intramolecular hydrogen-bonding interaction, so that the O···N separation is 2.614 (3) Å, with an O—H···N angle of 146°. Centrosymmetrically related molecules associate via N—H···Sⁱ contacts [H···S2ⁱ = 2.44° and N3···S2ⁱ = 3.291 (2) Å; symmetry code: (i) −1 − x, 1 − y, 1 − z]. There is also a C7—H···O1ⁱⁱ interaction with a C···Oⁱⁱ separation of 3.391 (3) Å [symmetry code: (ii) x, 1/2 − y, 1/2 + z].

Further work investigating the biological profile of (I) is in progress.

S2. Experimental

(I) was prepared using a procedure similar to a reported method (Wang et al., 1999). Yellow single crystals were obtained by recrystallization from a hot ethanol solution of the compound. IR (KBr): 3390 (s), 3260 (s), 1615 (s) cm^{−1. 1}H NMR (DMSO-d₆): δ 14.58 (1H, m), 8.89 (1H, m), 11.15 (1H, s), 7.02–7.98 (4H, s). Calculated for C₉H₇N₃OS₂: C 45.23, H2.68, N 17.50%; found: C 45.53, H 2.97, N 17.74%.

S3. Refinement

The H atoms were included in the riding-model approximation.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. View of (I), showing displacement ellipsoids at the 30% probability level.

5-[(2-Hydroxyphenyl)methleneamino]-1,3,4-thiadiazole-2(3H)-thione

Crystal data

C9H7N3OS2	F(000) = 488
Mr = 237.30	Dx = 1.502 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.587 (3) Å	Cell parameters from 662 reflections
b = 13.723 (5) Å	θ = 3.1–26.0°
c = 11.758 (5) Å	µ = 0.48 mm^−1
β = 99.183 (6)°	T = 293 K
V = 1049.2 (7) Å^3	Block, yellow
Z = 4	0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1822 independent reflections
Radiation source: fine-focus sealed tube	1440 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
ϕ and ω scans	θmax = 25.1°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Blessing, 1995; Sheldrick, 1996)	h = −4→7
Tmin = 0.841, Tmax = 0.890	k = −14→16
2862 measured reflections	l = −12→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0363P)^2 + 0.2779P] where P = (Fo^2 + 2Fc^2)/3
1822 reflections	(Δ/σ)max < 0.001
137 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
S1	0.02404 (9)	0.41301 (5)	0.69266 (5)	0.0463 (2)
S2	−0.37268 (10)	0.52545 (5)	0.68937 (5)	0.0553 (2)
N2	−0.1020 (3)	0.36578 (15)	0.48081 (15)	0.0490 (5)
N1	0.2126 (3)	0.29468 (14)	0.54584 (15)	0.0451 (5)
N3	−0.2447 (3)	0.42387 (14)	0.51818 (15)	0.0467 (5)
H3A	−0.3548	0.4395	0.4721	0.056*
C6	0.5334 (3)	0.21686 (16)	0.61021 (17)	0.0389 (5)
C5	0.6984 (4)	0.20360 (16)	0.70044 (19)	0.0445 (6)
H5	0.6946	0.2334	0.7711	0.053*
C7	0.3638 (3)	0.27793 (16)	0.62733 (18)	0.0413 (5)
H7	0.3632	0.3061	0.6992	0.050*
C8	0.0505 (4)	0.35235 (16)	0.56372 (17)	0.0418 (6)
C9	−0.2142 (3)	0.45686 (16)	0.62677 (18)	0.0422 (5)
C1	0.5415 (4)	0.16994 (19)	0.50441 (19)	0.0512 (6)
C4	0.8644 (4)	0.14782 (18)	0.6865 (2)	0.0528 (6)
H4	0.9729	0.1402	0.7469	0.063*
O1	0.3886 (3)	0.17983 (17)	0.41334 (14)	0.0781 (6)
H1	0.2950	0.2121	0.4326	0.117*
C3	0.8696 (5)	0.10311 (19)	0.5824 (2)	0.0627 (8)
H3	0.9835	0.0658	0.5727	0.075*
C2	0.7088 (5)	0.1126 (2)	0.4918 (2)	0.0665 (8)
H2	0.7134	0.0804	0.4226	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0449 (4)	0.0553 (4)	0.0351 (3)	0.0079 (3)	−0.0048 (2)	−0.0032 (3)
S2	0.0478 (4)	0.0715 (5)	0.0436 (3)	0.0128 (3)	−0.0018 (3)	−0.0044 (3)
N2	0.0479 (12)	0.0623 (13)	0.0345 (10)	0.0063 (10)	−0.0005 (9)	0.0006 (9)
N1	0.0472 (12)	0.0529 (12)	0.0340 (10)	0.0069 (10)	0.0025 (9)	0.0004 (8)
N3	0.0418 (11)	0.0608 (12)	0.0342 (10)	0.0058 (10)	−0.0040 (8)	0.0020 (9)
C6	0.0442 (13)	0.0413 (12)	0.0315 (11)	0.0006 (10)	0.0066 (10)	0.0035 (9)
C5	0.0513 (14)	0.0470 (13)	0.0339 (11)	0.0025 (12)	0.0032 (10)	0.0028 (10)
C7	0.0473 (14)	0.0471 (13)	0.0296 (11)	−0.0016 (11)	0.0063 (10)	0.0011 (9)
C8	0.0460 (14)	0.0476 (13)	0.0304 (11)	−0.0014 (11)	0.0017 (10)	0.0029 (10)
C9	0.0411 (13)	0.0455 (13)	0.0377 (12)	−0.0039 (11)	−0.0011 (10)	0.0044 (10)
C1	0.0621 (17)	0.0565 (15)	0.0335 (12)	0.0081 (13)	0.0030 (11)	0.0002 (11)
C4	0.0528 (15)	0.0550 (15)	0.0479 (14)	0.0107 (13)	−0.0001 (11)	0.0057 (12)
O1	0.0837 (15)	0.1076 (16)	0.0364 (9)	0.0337 (13)	−0.0111 (9)	−0.0168 (10)
C3	0.0703 (19)	0.0609 (17)	0.0582 (16)	0.0254 (15)	0.0145 (14)	0.0017 (13)
C2	0.086 (2)	0.0679 (18)	0.0450 (14)	0.0236 (16)	0.0093 (14)	−0.0100 (13)

Geometric parameters (Å, º)

S1—C9	1.743 (2)	C5—C4	1.366 (3)
S1—C8	1.762 (2)	C5—H5	0.9300
S2—C9	1.662 (3)	C7—H7	0.9300
N2—C8	1.296 (3)	C1—O1	1.354 (3)
N2—N3	1.358 (3)	C1—C2	1.382 (4)
N1—C7	1.288 (3)	C4—C3	1.375 (3)
N1—C8	1.372 (3)	C4—H4	0.9300
N3—C9	1.339 (3)	O1—H1	0.8200
N3—H3A	0.8600	C3—C2	1.383 (4)
C6—C5	1.404 (3)	C3—H3	0.9300
C6—C1	1.409 (3)	C2—H2	0.9300
C6—C7	1.436 (3)
C9—S1—C8	89.22 (11)	N1—C8—S1	126.19 (16)
C8—N2—N3	109.48 (19)	N3—C9—S2	127.19 (17)
C7—N1—C8	121.16 (19)	N3—C9—S1	107.13 (17)
C9—N3—N2	120.04 (18)	S2—C9—S1	125.68 (13)
C9—N3—H3A	120.0	O1—C1—C2	118.5 (2)
N2—N3—H3A	120.0	O1—C1—C6	121.6 (2)
C5—C6—C1	118.3 (2)	C2—C1—C6	119.9 (2)
C5—C6—C7	119.69 (19)	C5—C4—C3	119.4 (2)
C1—C6—C7	122.0 (2)	C5—C4—H4	120.3
C4—C5—C6	121.3 (2)	C3—C4—H4	120.3
C4—C5—H5	119.3	C1—O1—H1	109.5
C6—C5—H5	119.3	C4—C3—C2	121.3 (3)
N1—C7—C6	121.8 (2)	C4—C3—H3	119.4
N1—C7—H7	119.1	C2—C3—H3	119.4
C6—C7—H7	119.1	C1—C2—C3	119.8 (2)
N2—C8—N1	119.7 (2)	C1—C2—H2	120.1
N2—C8—S1	114.12 (18)	C3—C2—H2	120.1
C8—N2—N3—C9	−0.4 (3)	N2—N3—C9—S1	1.2 (3)
C1—C6—C5—C4	0.8 (3)	C8—S1—C9—N3	−1.20 (17)
C7—C6—C5—C4	−178.5 (2)	C8—S1—C9—S2	178.05 (17)
C8—N1—C7—C6	179.3 (2)	C5—C6—C1—O1	−179.6 (2)
C5—C6—C7—N1	177.7 (2)	C7—C6—C1—O1	−0.3 (4)
C1—C6—C7—N1	−1.6 (3)	C5—C6—C1—C2	0.1 (4)
N3—N2—C8—N1	179.24 (19)	C7—C6—C1—C2	179.4 (2)
N3—N2—C8—S1	−0.6 (3)	C6—C5—C4—C3	−0.5 (4)
C7—N1—C8—N2	−178.2 (2)	C5—C4—C3—C2	−0.8 (4)
C7—N1—C8—S1	1.6 (3)	O1—C1—C2—C3	178.4 (3)
C9—S1—C8—N2	1.12 (19)	C6—C1—C2—C3	−1.3 (4)
C9—S1—C8—N1	−178.8 (2)	C4—C3—C2—C1	1.7 (5)
N2—N3—C9—S2	−178.03 (17)