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

The approximately planar mol-ecule of the title compound, C(9)H(11)N(3)O(2)S, is linked to adjacent mol-ecules by O-H⋯S hydrogen bonds to form a zigzag chain. Adjacent chains are consolidated by N-H⋯O hydrogen bonds into a two-dimensional array. An intramolecular O-H⋯N link is also present.

Related literature

For the structure of isomeric 2,5-dihydroxy­benzaldehyde 4-methyl­thio­semicarbazone, see: Tan et al. (2008 ▶).

Experimental

Crystal data

C9H11N3O2S

M = 225.27

Monoclinic,

a = 18.0046 (6) Å

b = 4.6436 (1) Å

c = 12.2842 (4) Å

β = 106.695 (2)°

V = 983.74 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.31 mm−1

T = 100 (2) K

0.09 × 0.06 × 0.03 mm

Data collection

Bruker SMART APEX diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.973, T max = 0.991

4390 measured reflections

2128 independent reflections

1925 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.109

S = 1.11

2128 reflections

153 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.22 e Å−3

Absolute structure: Flack (1983 ▶), with 814 Friedel pairs

Flack parameter: 0.00 (1)

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/S1600536808033308/tk2316sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808033308/tk2316Isup2.hkl

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

C9H11N3O2S	F(000) = 472
Mr = 225.27	Dx = 1.521 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1090 reflections
a = 18.0046 (6) Å	θ = 2.4–24.9°
b = 4.6436 (1) Å	µ = 0.31 mm−1
c = 12.2842 (4) Å	T = 100 K
β = 106.695 (2)°	Prims, yellow
V = 983.74 (5) Å3	0.09 × 0.06 × 0.03 mm
Z = 4

Bruker SMART APEX diffractometer	2128 independent reflections
Radiation source: fine-focus sealed tube	1925 reflections with I > 2σ(I)
graphite	Rint = 0.034
ω scans	θmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→22
Tmin = 0.973, Tmax = 0.991	k = −6→6
4390 measured reflections	l = −15→15

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)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109	w = 1/[σ2(Fo2) + (0.0598P)2] where P = (Fo2 + 2Fc2)/3
S = 1.11	(Δ/σ)max = 0.001
2128 reflections	Δρmax = 0.31 e Å−3
153 parameters	Δρmin = −0.22 e Å−3
6 restraints	Absolute structure: Flack (1983), 814 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.00 (1)

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.

	x	y	z	Uiso*/Ueq
S1	0.50003 (5)	0.63599 (16)	0.50001 (6)	0.01776 (19)
O1	0.65168 (12)	−0.1181 (5)	0.93136 (19)	0.0174 (5)
O2	0.84529 (13)	−0.8242 (5)	1.05294 (19)	0.0198 (5)
N1	0.63927 (15)	0.1424 (5)	0.7309 (2)	0.0144 (5)
N2	0.60440 (15)	0.2962 (6)	0.6322 (2)	0.0147 (5)
N3	0.53164 (15)	0.5567 (6)	0.7241 (2)	0.0166 (6)
C1	0.73692 (17)	−0.2114 (7)	0.8141 (2)	0.0128 (6)
C2	0.71210 (17)	−0.2660 (7)	0.9113 (2)	0.0122 (6)
C3	0.74812 (18)	−0.4725 (7)	0.9891 (3)	0.0141 (6)
H3	0.7300	−0.5117	1.0530	0.017*
C4	0.81112 (16)	−0.6232 (6)	0.9739 (2)	0.0142 (6)
C5	0.83798 (18)	−0.5674 (7)	0.8800 (3)	0.0174 (7)
H5	0.8815	−0.6688	0.8704	0.021*
C6	0.80096 (17)	−0.3645 (7)	0.8017 (3)	0.0159 (7)
H6	0.8192	−0.3274	0.7378	0.019*
C7	0.69685 (17)	−0.0131 (7)	0.7250 (2)	0.0142 (6)
H7	0.7142	0.0020	0.6590	0.017*
C8	0.54711 (17)	0.4887 (7)	0.6279 (3)	0.0149 (6)
C9	0.47552 (19)	0.7743 (8)	0.7317 (3)	0.0206 (7)
H9A	0.4879	0.8460	0.8099	0.031*
H9B	0.4234	0.6899	0.7100	0.031*
H9C	0.4773	0.9340	0.6804	0.031*
H1O	0.633 (3)	−0.017 (11)	0.874 (3)	0.08 (2)*
H2O	0.8796 (19)	−0.909 (8)	1.032 (4)	0.038 (13)*
H2N	0.6097 (19)	0.218 (7)	0.5703 (17)	0.011 (8)*
H3N	0.5552 (19)	0.476 (7)	0.7898 (17)	0.018 (9)*

	U11	U22	U33	U12	U13	U23
S1	0.0196 (4)	0.0180 (4)	0.0138 (3)	0.0027 (4)	0.0018 (3)	0.0021 (4)
O1	0.0193 (13)	0.0174 (12)	0.0159 (11)	0.0038 (9)	0.0059 (9)	0.0029 (10)
O2	0.0216 (12)	0.0196 (13)	0.0171 (12)	0.0069 (10)	0.0037 (9)	0.0040 (9)
N1	0.0159 (13)	0.0126 (13)	0.0125 (12)	−0.0018 (11)	0.0008 (10)	0.0013 (10)
N2	0.0176 (13)	0.0163 (13)	0.0097 (13)	0.0024 (11)	0.0030 (10)	−0.0001 (11)
N3	0.0195 (14)	0.0144 (13)	0.0152 (13)	0.0023 (11)	0.0037 (10)	0.0014 (10)
C1	0.0153 (14)	0.0135 (15)	0.0103 (14)	−0.0029 (12)	0.0048 (11)	−0.0005 (12)
C2	0.0105 (14)	0.0147 (15)	0.0129 (15)	−0.0017 (12)	0.0056 (11)	−0.0034 (12)
C3	0.0162 (15)	0.0159 (16)	0.0120 (15)	−0.0032 (12)	0.0069 (12)	−0.0012 (11)
C4	0.0148 (16)	0.0139 (14)	0.0113 (14)	−0.0007 (12)	−0.0006 (12)	0.0000 (12)
C5	0.0155 (16)	0.0163 (16)	0.0180 (17)	0.0012 (12)	0.0010 (12)	−0.0031 (12)
C6	0.0121 (15)	0.0214 (18)	0.0134 (15)	−0.0031 (14)	0.0023 (12)	−0.0033 (13)
C7	0.0157 (16)	0.0164 (16)	0.0117 (15)	−0.0035 (13)	0.0058 (12)	−0.0016 (12)
C8	0.0154 (15)	0.0127 (15)	0.0175 (16)	−0.0031 (12)	0.0064 (12)	0.0002 (12)
C9	0.0169 (16)	0.0266 (19)	0.0201 (17)	0.0003 (13)	0.0079 (13)	−0.0038 (13)

S1—C8	1.699 (3)	C1—C2	1.413 (4)
O1—C2	1.367 (4)	C1—C7	1.454 (4)
O1—H1O	0.838 (10)	C2—C3	1.378 (4)
O2—C4	1.360 (4)	C3—C4	1.391 (4)
O2—H2O	0.836 (10)	C3—H3	0.9500
N1—C7	1.283 (4)	C4—C5	1.397 (4)
N1—N2	1.392 (3)	C5—C6	1.374 (4)
N2—C8	1.354 (4)	C5—H5	0.9500
N2—H2N	0.871 (10)	C6—H6	0.9500
N3—C8	1.328 (4)	C7—H7	0.9500
N3—C9	1.451 (4)	C9—H9A	0.9800
N3—H3N	0.880 (10)	C9—H9B	0.9800
C1—C6	1.400 (4)	C9—H9C	0.9800
C2—O1—H1O	106 (4)	C3—C4—C5	120.5 (3)
C4—O2—H2O	109 (3)	C6—C5—C4	119.5 (3)
C7—N1—N2	114.1 (3)	C6—C5—H5	120.3
C8—N2—N1	121.4 (3)	C4—C5—H5	120.3
C8—N2—H2N	121 (2)	C5—C6—C1	121.4 (3)
N1—N2—H2N	114 (2)	C5—C6—H6	119.3
C8—N3—C9	123.4 (3)	C1—C6—H6	119.3
C8—N3—H3N	123 (3)	N1—C7—C1	123.2 (3)
C9—N3—H3N	114 (3)	N1—C7—H7	118.4
C6—C1—C2	118.1 (3)	C1—C7—H7	118.4
C6—C1—C7	119.1 (3)	N3—C8—N2	118.3 (3)
C2—C1—C7	122.8 (3)	N3—C8—S1	123.4 (2)
O1—C2—C3	117.7 (3)	N2—C8—S1	118.3 (2)
O1—C2—C1	121.6 (3)	N3—C9—H9A	109.5
C3—C2—C1	120.8 (3)	N3—C9—H9B	109.5
C2—C3—C4	119.8 (3)	H9A—C9—H9B	109.5
C2—C3—H3	120.1	N3—C9—H9C	109.5
C4—C3—H3	120.1	H9A—C9—H9C	109.5
O2—C4—C3	117.9 (3)	H9B—C9—H9C	109.5
O2—C4—C5	121.6 (3)
C7—N1—N2—C8	−174.4 (3)	C4—C5—C6—C1	0.2 (5)
C6—C1—C2—O1	177.7 (3)	C2—C1—C6—C5	1.4 (4)
C7—C1—C2—O1	−4.9 (4)	C7—C1—C6—C5	−176.0 (3)
C6—C1—C2—C3	−2.5 (4)	N2—N1—C7—C1	−174.0 (3)
C7—C1—C2—C3	174.8 (3)	C6—C1—C7—N1	−177.7 (3)
O1—C2—C3—C4	−178.3 (3)	C2—C1—C7—N1	5.0 (5)
C1—C2—C3—C4	1.9 (5)	C9—N3—C8—N2	175.6 (3)
C2—C3—C4—O2	179.7 (3)	C9—N3—C8—S1	−3.1 (4)
C2—C3—C4—C5	−0.2 (5)	N1—N2—C8—N3	8.8 (4)
O2—C4—C5—C6	179.3 (3)	N1—N2—C8—S1	−172.5 (2)
C3—C4—C5—C6	−0.9 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1	0.84 (1)	1.93 (3)	2.694 (3)	151 (6)
O2—H2O···S1i	0.84 (1)	2.54 (1)	3.365 (2)	170 (4)
N2—H2N···O1ii	0.87 (1)	2.11 (1)	2.950 (4)	162 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯N1	0.84 (1)	1.93 (3)	2.694 (3)	151 (6)
O2—H2O⋯S1i	0.84 (1)	2.54 (1)	3.365 (2)	170 (4)
N2—H2N⋯O1ii	0.87 (1)	2.11 (1)	2.950 (4)	162 (3)

Symmetry codes: (i) ; (ii) .