(E)-3,4-Dihydroxy-benzaldehyde 4-methyl-thio-semicarbazone.

The title compound, C(9)H(11)N(3)O(2)S, adopts an E configuration with respect to the C=N bond. The mol-ecule is approximately planar, with an r.m.s. deviation from the mean plane through all 15 non-H atoms of 0.152 Å; the dihedral angle between the benzene ring plane and the least-squares plane through the thio-semicarbazone unit is 12.48 (7)°. A weak intra-molecular N-H⋯N inter-action contributes to the planarity of the semicarbazone unit. Centrosymmetric pairs of O-H⋯O and N-H⋯S hydrogen bonds form chains along c, generating R(2) (2)(10) and R(2) (2)(8) ring motifs, respectively. In the crystal structure, these chains are further linked by inter-molecular O-H⋯S and C-H⋯O inter-actions, forming stacks down the c axis.

Related literature

For the biological activity of thio­semicarbazones, see: de Sousa et al. (2007 ▶). For related structures, see: Kayed et al. (2008 ▶); Tan et al. (2008a ▶,b ▶). For hydrogen-bonding patterns, see: Bernstein et al. (1995 ▶). For reference structural data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C9H11N3O2S

M = 225.27

Monoclinic,

a = 6.8502 (9) Å

b = 14.911 (2) Å

c = 10.6299 (13) Å

β = 107.894 (6)°

V = 1033.3 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.30 mm−1

T = 92 (2) K

0.23 × 0.15 × 0.13 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T min = 0.799, T max = 0.962

17952 measured reflections

3696 independent reflections

2974 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.112

S = 1.07

3696 reflections

149 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.49 e Å−3

Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: APEX2 and SAINT (Bruker 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and TITAN (Hunter & Simpson, 1999 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ▶), PLATON (Spek, 2003 ▶) and publCIF (Westrip, 2008 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808034326/pv2112sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808034326/pv2112Isup2.hkl

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

C9H11N3O2S	F(000) = 472
Mr = 225.27	Dx = 1.448 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3847 reflections
a = 6.8502 (9) Å	θ = 2.4–29.8°
b = 14.911 (2) Å	µ = 0.30 mm−1
c = 10.6299 (13) Å	T = 92 K
β = 107.894 (6)°	Plate, colourless
V = 1033.3 (2) Å3	0.23 × 0.15 × 0.13 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	3696 independent reflections
Radiation source: fine-focus sealed tube	2974 reflections with I > 2σ(I)
graphite	Rint = 0.044
ω scans	θmax = 33.0°, θmin = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −10→10
Tmin = 0.799, Tmax = 0.962	k = −22→18
17952 measured reflections	l = −16→15

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0412P)2 + 0.5756P] where P = (Fo2 + 2Fc2)/3
3696 reflections	(Δ/σ)max < 0.001
149 parameters	Δρmax = 0.49 e Å−3
4 restraints	Δρmin = −0.32 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.2002 (2)	0.06919 (9)	−0.01216 (13)	0.0157 (2)
C2	0.2338 (2)	0.00229 (9)	−0.09567 (13)	0.0165 (2)
H2	0.3237	−0.0460	−0.0590	0.020*
C3	0.1378 (2)	0.00557 (9)	−0.23119 (13)	0.0160 (2)
O3	0.17512 (16)	−0.06151 (7)	−0.30786 (10)	0.0213 (2)
H3	0.110 (3)	−0.0532 (14)	−0.3876 (10)	0.032*
C4	0.0039 (2)	0.07616 (9)	−0.28381 (13)	0.0166 (2)
O4	−0.09897 (16)	0.07447 (7)	−0.41779 (10)	0.0206 (2)
H4	−0.2160 (18)	0.0940 (13)	−0.424 (2)	0.031*
C5	−0.0247 (2)	0.14471 (9)	−0.20207 (13)	0.0183 (3)
H5	−0.1111	0.1940	−0.2392	0.022*
C6	0.0727 (2)	0.14133 (10)	−0.06654 (14)	0.0180 (3)
H6	0.0523	0.1881	−0.0111	0.022*
C7	0.2988 (2)	0.05936 (9)	0.13036 (13)	0.0168 (2)
H7	0.3900	0.0107	0.1623	0.020*
N1	0.26441 (18)	0.11527 (8)	0.21297 (11)	0.0174 (2)
N2	0.36894 (18)	0.09854 (8)	0.34422 (11)	0.0182 (2)
H2N	0.456 (2)	0.0539 (9)	0.3669 (17)	0.022*
C8	0.3229 (2)	0.14654 (9)	0.43924 (13)	0.0163 (2)
S1	0.46023 (5)	0.12889 (2)	0.60055 (3)	0.01943 (10)
N3	0.17327 (18)	0.20621 (8)	0.39921 (12)	0.0188 (2)
H3N	0.107 (3)	0.2075 (12)	0.3142 (10)	0.023*
C9	0.1019 (2)	0.26414 (10)	0.48622 (16)	0.0259 (3)
H9A	0.0204	0.2289	0.5298	0.039*
H9B	0.0171	0.3123	0.4343	0.039*
H9C	0.2202	0.2902	0.5532	0.039*

	U11	U22	U33	U12	U13	U23
C1	0.0148 (5)	0.0165 (6)	0.0166 (5)	−0.0009 (5)	0.0061 (4)	−0.0004 (5)
C2	0.0158 (6)	0.0143 (6)	0.0202 (6)	0.0002 (5)	0.0067 (5)	0.0006 (5)
C3	0.0160 (6)	0.0148 (6)	0.0182 (6)	−0.0020 (5)	0.0067 (5)	−0.0019 (5)
O3	0.0239 (5)	0.0197 (5)	0.0194 (5)	0.0032 (4)	0.0055 (4)	−0.0040 (4)
C4	0.0149 (5)	0.0199 (6)	0.0153 (5)	−0.0006 (5)	0.0052 (4)	−0.0007 (5)
O4	0.0190 (5)	0.0258 (5)	0.0164 (4)	0.0032 (4)	0.0044 (4)	−0.0027 (4)
C5	0.0189 (6)	0.0172 (6)	0.0184 (6)	0.0031 (5)	0.0052 (5)	0.0000 (5)
C6	0.0172 (6)	0.0188 (6)	0.0182 (6)	0.0013 (5)	0.0058 (5)	−0.0009 (5)
C7	0.0157 (6)	0.0158 (6)	0.0187 (6)	0.0002 (5)	0.0050 (5)	0.0016 (5)
N1	0.0163 (5)	0.0198 (6)	0.0152 (5)	0.0012 (4)	0.0037 (4)	0.0011 (4)
N2	0.0200 (5)	0.0181 (6)	0.0160 (5)	0.0049 (4)	0.0050 (4)	0.0005 (4)
C8	0.0165 (6)	0.0141 (6)	0.0193 (6)	−0.0018 (5)	0.0072 (5)	−0.0010 (5)
S1	0.02201 (17)	0.01991 (18)	0.01649 (16)	0.00247 (12)	0.00609 (12)	−0.00049 (12)
N3	0.0184 (5)	0.0162 (5)	0.0214 (5)	0.0019 (4)	0.0056 (4)	−0.0010 (4)
C9	0.0277 (7)	0.0185 (7)	0.0348 (8)	0.0044 (6)	0.0148 (6)	−0.0034 (6)

C1—C6	1.3943 (19)	C6—H6	0.9500
C1—C2	1.4006 (18)	C7—N1	1.2841 (18)
C1—C7	1.4642 (18)	C7—H7	0.9500
C2—C3	1.3886 (18)	N1—N2	1.3812 (15)
C2—H2	0.9500	N2—C8	1.3518 (17)
C3—O3	1.3632 (16)	N2—H2N	0.876 (9)
C3—C4	1.3952 (19)	C8—N3	1.3251 (18)
O3—H3	0.837 (9)	C8—S1	1.7038 (14)
C4—O4	1.3815 (16)	N3—C9	1.4556 (18)
C4—C5	1.3937 (19)	N3—H3N	0.879 (9)
O4—H4	0.836 (9)	C9—H9A	0.9800
C5—C6	1.3901 (19)	C9—H9B	0.9800
C5—H5	0.9500	C9—H9C	0.9800
C6—C1—C2	119.39 (12)	N1—C7—C1	121.28 (12)
C6—C1—C7	122.50 (12)	N1—C7—H7	119.4
C2—C1—C7	118.10 (12)	C1—C7—H7	119.4
C3—C2—C1	120.98 (12)	C7—N1—N2	115.24 (12)
C3—C2—H2	119.5	C8—N2—N1	119.45 (11)
C1—C2—H2	119.5	C8—N2—H2N	119.4 (12)
O3—C3—C2	118.57 (12)	N1—N2—H2N	120.9 (12)
O3—C3—C4	122.33 (12)	N3—C8—N2	116.78 (12)
C2—C3—C4	119.08 (12)	N3—C8—S1	124.08 (11)
C3—O3—H3	111.0 (14)	N2—C8—S1	119.13 (10)
O4—C4—C5	122.08 (12)	C8—N3—C9	124.91 (13)
O4—C4—C3	117.63 (12)	C8—N3—H3N	116.8 (12)
C5—C4—C3	120.28 (12)	C9—N3—H3N	118.1 (12)
C4—O4—H4	104.4 (14)	N3—C9—H9A	109.5
C6—C5—C4	120.34 (13)	N3—C9—H9B	109.5
C6—C5—H5	119.8	H9A—C9—H9B	109.5
C4—C5—H5	119.8	N3—C9—H9C	109.5
C5—C6—C1	119.83 (13)	H9A—C9—H9C	109.5
C5—C6—H6	120.1	H9B—C9—H9C	109.5
C1—C6—H6	120.1

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N1	0.88 (1)	2.22 (2)	2.6282 (17)	108 (1)
O3—H3···O4i	0.84 (1)	2.07 (1)	2.8071 (14)	147 (2)
O4—H4···S1ii	0.84 (1)	2.37 (1)	3.1899 (11)	167 (2)
N2—H2N···S1iii	0.88 (1)	2.79 (1)	3.5766 (13)	151 (2)
C9—H9A···O4iv	0.98	2.56	3.435 (2)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯N1	0.879 (9)	2.220 (18)	2.6282 (17)	108.0 (14)
O3—H3⋯O4i	0.837 (9)	2.070 (14)	2.8071 (14)	146.5 (19)
O4—H4⋯S1ii	0.836 (9)	2.369 (10)	3.1899 (11)	167.1 (19)
N2—H2N⋯S1iii	0.876 (9)	2.785 (12)	3.5766 (13)	150.9 (15)
C9—H9A⋯O4iv	0.98	2.56	3.435 (2)	148

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .