2,5-Dihydroxy-benzaldehyde 4-methyl-thio-semicarbazone.

The planar mol-ecules of the title compound, C(9)H(11)N(3)O(2)S, are linked into a supra-molecualr chain via O-H⋯S hydrogen bonds. These chains are connected into a two-dimensional array via N-H⋯O hydrogen bonds; an intra-molecular O-H⋯N hydrogen bond is also present.

Related literature

For the medicinal activity of 2,5-dihydroxy­benzaldehyde thio­semicarbazone, see: Libermann et al. (1953 ▶); Taniyama & Tanaka (1965 ▶); Xue et al. (2007 ▶). For the structure of 2-hydroxy­benzaldehyde 4-methyl­thio­semicarbazone, see: Vrdoljak et al. (2005 ▶). For the structure of 3,4-dihydroxy­benzaldehyde 4-ethyl­thio­semicarbazone, see: Kayed et al. (2008 ▶).

Experimental

Crystal data

C9H11N3O2S

M = 225.27

Triclinic,

a = 5.9932 (4) Å

b = 8.5207 (6) Å

c = 10.3272 (6) Å

α = 78.552 (4)°

β = 74.181 (4)°

γ = 81.743 (4)°

V = 495.06 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.31 mm−1

T = 100 (2) K

0.24 × 0.16 × 0.02 mm

Data collection

Bruker SMART APEX diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.929, T max = 0.994

4189 measured reflections

2258 independent reflections

1580 reflections with I > 2σ(I)

R int = 0.050

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.123

S = 1.03

2258 reflections

153 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.47 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2008 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808018801/tk2278sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808018801/tk2278Isup2.hkl

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

C9H11N3O2S	Z = 2
Mr = 225.27	F000 = 236
Triclinic, P1	Dx = 1.511 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 5.9932 (4) Å	Cell parameters from 558 reflections
b = 8.5207 (6) Å	θ = 2.9–23.0º
c = 10.3272 (6) Å	µ = 0.31 mm−1
α = 78.552 (4)º	T = 100 (2) K
β = 74.181 (4)º	Plate, yellow
γ = 81.743 (4)º	0.24 × 0.16 × 0.02 mm
V = 495.06 (6) Å3

Bruker SMART APEX diffractometer	2258 independent reflections
Radiation source: fine-focus sealed tube	1580 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.050
T = 100(2) K	θmax = 27.5º
ω scans	θmin = 2.5º
Absorption correction: Multi-scan(SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.929, Tmax = 0.994	k = −11→8
4189 measured reflections	l = −13→13

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.123	w = 1/[σ2(Fo2) + (0.0471P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
2258 reflections	Δρmax = 0.32 e Å−3
153 parameters	Δρmin = −0.47 e Å−3
4 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

	x	y	z	Uiso*/Ueq
S1	0.44298 (12)	0.47335 (9)	0.72966 (7)	0.0189 (2)
O1	1.3132 (3)	0.8655 (2)	0.47568 (18)	0.0188 (4)
O2	1.2446 (3)	1.1893 (2)	−0.03406 (18)	0.0200 (5)
N1	0.8637 (4)	0.5405 (3)	0.7312 (2)	0.0147 (5)
N2	0.7415 (4)	0.6387 (3)	0.5359 (2)	0.0159 (5)
N3	0.9289 (4)	0.7298 (3)	0.4833 (2)	0.0145 (5)
C1	0.8391 (5)	0.4576 (3)	0.8709 (2)	0.0188 (6)
H1A	0.9802	0.4633	0.8996	0.028*
H1B	0.8160	0.3447	0.8763	0.028*
H1C	0.7044	0.5088	0.9310	0.028*
C2	0.7001 (4)	0.5552 (3)	0.6642 (2)	0.0134 (6)
C3	0.9368 (4)	0.8121 (3)	0.3637 (2)	0.0136 (6)
H3	0.8213	0.8018	0.3194	0.016*
C4	1.1147 (4)	0.9200 (3)	0.2937 (2)	0.0133 (6)
C5	1.2915 (4)	0.9450 (3)	0.3503 (2)	0.0140 (6)
C6	1.4505 (5)	1.0551 (3)	0.2796 (2)	0.0157 (6)
H6	1.5673	1.0745	0.3193	0.019*
C7	1.4389 (5)	1.1372 (3)	0.1504 (3)	0.0153 (6)
H7	1.5496	1.2111	0.1016	0.018*
C8	1.2669 (4)	1.1117 (3)	0.0929 (2)	0.0149 (6)
C9	1.1055 (4)	1.0049 (3)	0.1638 (2)	0.0146 (6)
H9	0.9866	0.9887	0.1243	0.018*
H1o	1.206 (4)	0.805 (3)	0.511 (3)	0.048 (12)*
H2o	1.352 (5)	1.245 (4)	−0.082 (3)	0.059 (13)*
H1n	0.988 (3)	0.581 (4)	0.689 (3)	0.032 (9)*
H2n	0.640 (4)	0.656 (4)	0.491 (3)	0.042 (10)*

	U11	U22	U33	U12	U13	U23
S1	0.0149 (4)	0.0241 (4)	0.0175 (3)	−0.0083 (3)	−0.0051 (3)	0.0033 (3)
O1	0.0222 (11)	0.0221 (12)	0.0140 (9)	−0.0081 (9)	−0.0089 (8)	0.0025 (8)
O2	0.0244 (11)	0.0202 (12)	0.0149 (9)	−0.0088 (9)	−0.0059 (8)	0.0047 (8)
N1	0.0114 (12)	0.0181 (13)	0.0148 (11)	−0.0035 (10)	−0.0038 (9)	−0.0007 (9)
N2	0.0153 (12)	0.0168 (13)	0.0158 (11)	−0.0060 (10)	−0.0056 (9)	0.0024 (9)
N3	0.0121 (11)	0.0136 (12)	0.0175 (11)	−0.0050 (9)	−0.0013 (9)	−0.0023 (9)
C1	0.0198 (15)	0.0231 (16)	0.0128 (12)	−0.0048 (12)	−0.0051 (11)	0.0015 (11)
C2	0.0137 (13)	0.0106 (14)	0.0155 (12)	−0.0011 (11)	−0.0032 (10)	−0.0022 (11)
C3	0.0136 (13)	0.0138 (14)	0.0147 (12)	−0.0019 (11)	−0.0053 (10)	−0.0025 (11)
C4	0.0134 (13)	0.0118 (14)	0.0153 (12)	−0.0008 (10)	−0.0034 (10)	−0.0038 (11)
C5	0.0137 (13)	0.0154 (15)	0.0133 (12)	0.0001 (11)	−0.0041 (10)	−0.0034 (11)
C6	0.0139 (13)	0.0162 (15)	0.0193 (13)	−0.0029 (11)	−0.0070 (10)	−0.0039 (11)
C7	0.0163 (14)	0.0102 (14)	0.0178 (13)	−0.0021 (11)	−0.0024 (10)	−0.0006 (11)
C8	0.0160 (14)	0.0144 (15)	0.0143 (12)	0.0006 (11)	−0.0050 (10)	−0.0023 (11)
C9	0.0158 (14)	0.0156 (15)	0.0140 (12)	−0.0021 (11)	−0.0059 (10)	−0.0031 (11)

S1—C2	1.695 (3)	C1—H1B	0.9800
O1—C5	1.367 (3)	C1—H1C	0.9800
O1—H1o	0.84 (3)	C3—C4	1.450 (4)
O2—C8	1.379 (3)	C3—H3	0.9500
O2—H2o	0.84 (3)	C4—C5	1.401 (4)
N1—C2	1.325 (3)	C4—C9	1.403 (3)
N1—C1	1.453 (3)	C5—C6	1.388 (4)
N1—H1n	0.84 (3)	C6—C7	1.393 (3)
N2—C2	1.349 (3)	C6—H6	0.9500
N2—N3	1.382 (3)	C7—C8	1.383 (4)
N2—H2n	0.84 (3)	C7—H7	0.9500
N3—C3	1.286 (3)	C8—C9	1.379 (4)
C1—H1A	0.9800	C9—H9	0.9500
C5—O1—H1O	110 (2)	C4—C3—H3	118.6
C8—O2—H2O	117 (3)	C5—C4—C9	118.9 (2)
C2—N1—C1	123.8 (2)	C5—C4—C3	123.2 (2)
C2—N1—H1N	117 (2)	C9—C4—C3	117.9 (2)
C1—N1—H1N	119 (2)	O1—C5—C6	117.7 (2)
C2—N2—N3	121.3 (2)	O1—C5—C4	122.3 (2)
C2—N2—H2N	122 (2)	C6—C5—C4	120.0 (2)
N3—N2—H2N	116 (2)	C5—C6—C7	120.1 (3)
C3—N3—N2	114.5 (2)	C5—C6—H6	120.0
N1—C1—H1A	109.5	C7—C6—H6	120.0
N1—C1—H1B	109.5	C8—C7—C6	120.3 (2)
H1A—C1—H1B	109.5	C8—C7—H7	119.9
N1—C1—H1C	109.5	C6—C7—H7	119.9
H1A—C1—H1C	109.5	O2—C8—C9	116.7 (2)
H1B—C1—H1C	109.5	O2—C8—C7	123.3 (2)
N1—C2—N2	118.2 (2)	C9—C8—C7	119.9 (2)
N1—C2—S1	123.80 (19)	C8—C9—C4	120.8 (2)
N2—C2—S1	118.0 (2)	C8—C9—H9	119.6
N3—C3—C4	122.7 (2)	C4—C9—H9	119.6
N3—C3—H3	118.6
C2—N2—N3—C3	−175.1 (2)	C3—C4—C5—C6	−177.4 (2)
C1—N1—C2—N2	178.3 (2)	O1—C5—C6—C7	178.8 (2)
C1—N1—C2—S1	−2.5 (4)	C4—C5—C6—C7	−2.0 (4)
N3—N2—C2—N1	−11.0 (4)	C5—C6—C7—C8	1.1 (4)
N3—N2—C2—S1	169.69 (19)	C6—C7—C8—O2	179.7 (2)
N2—N3—C3—C4	177.5 (2)	C6—C7—C8—C9	0.2 (4)
N3—C3—C4—C5	−0.6 (4)	O2—C8—C9—C4	179.8 (2)
N3—C3—C4—C9	−179.5 (2)	C7—C8—C9—C4	−0.7 (4)
C9—C4—C5—O1	−179.3 (2)	C5—C4—C9—C8	−0.2 (4)
C3—C4—C5—O1	1.8 (4)	C3—C4—C9—C8	178.8 (2)
C9—C4—C5—C6	1.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N3	0.84 (3)	1.97 (2)	2.698 (3)	144 (3)
O2—H2o···S1i	0.84 (3)	2.46 (2)	3.182 (2)	144 (3)
N2—H2n···O1ii	0.84 (3)	2.47 (3)	3.111 (3)	134 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯N3	0.84 (3)	1.97 (2)	2.698 (3)	144 (3)
O2—H2o⋯S1i	0.84 (3)	2.46 (2)	3.182 (2)	144 (3)
N2—H2n⋯O1ii	0.84 (3)	2.47 (3)	3.111 (3)	134 (3)

Symmetry codes: (i) ; (ii) .