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Acta Cryst. (2008). E64, o2224    [ doi:10.1107/S1600536808033308 ]

2,4-Dihydroxybenzaldehyde 4-methylthiosemicarbazone

K. W. Tan, C. H. Ng, M. J. Maah and S. W. Ng

Abstract top

The approximately planar molecule of the title compound, C9H11N3O2S, is linked to adjacent molecules 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.

Comment top

In continuation of on-going studies into the structural chemistry of thiosemicarbazones (Tan et al., 2008), the title compound (I) was investigated. Molecule (I), Fig. 1, is essentially planar and is consolidated into a 2-D array by a combination of N-H···O and O-H···S hydrogen bonding contacts, Table 1.

Related literature top

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

Experimental top

4-Methylthiosemicarbazide (0.11 g, 1 mmol) and 2,4-dihydroxybenzaldehyde (0.14 g, 1 mmol) were heated in ethanol (10 ml) for 1 h. Slow evaporation of the solvent yielded yellow crystals.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with Uiso>(H) set to 1.2-1.5 Ueq(C). The hydroxy and amino H-atoms were located in a difference Fourier map, and were refined with distance retraints of O–H = 0.84±0.01 and N–H = 0.88±0.01 Å; their temperature factors were freely refined.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid (Barbour, 2001) plot of (I) drawn at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii.
2,4-Dihydroxybenzaldehyde 4-methylthiosemicarbazone top
Crystal data top
C9H11N3O2SF(000) = 472
Mr = 225.27Dx = 1.521 Mg m−3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 1090 reflections
a = 18.0046 (6) Åθ = 2.4–24.9°
b = 4.6436 (1) ŵ = 0.31 mm−1
c = 12.2842 (4) ÅT = 100 K
β = 106.695 (2)°Prims, yellow
V = 983.74 (5) Å30.09 × 0.06 × 0.03 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer		2128 independent reflections
Radiation source: fine-focus sealed tube1925 reflections with I > 2σ(I)
graphiteRint = 0.034
ω scansθmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −23→22
Tmin = 0.973, Tmax = 0.991k = −6→6
4390 measured reflectionsl = −15→15
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H 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 reflectionsΔρmax = 0.31 e Å−3
153 parametersΔρmin = −0.22 e Å−3
6 restraintsAbsolute structure: Flack (1983), 814 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.00 (1)
Crystal data top
C9H11N3O2SV = 983.74 (5) Å3
Mr = 225.27Z = 4
Monoclinic, CcMo Kα radiation
a = 18.0046 (6) ŵ = 0.31 mm−1
b = 4.6436 (1) ÅT = 100 K
c = 12.2842 (4) Å0.09 × 0.06 × 0.03 mm
β = 106.695 (2)°
Data collection top
Bruker SMART APEX
diffractometer		2128 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1925 reflections with I > 2σ(I)
Tmin = 0.973, Tmax = 0.991Rint = 0.034
4390 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109Δρmax = 0.31 e Å−3
S = 1.11Δρmin = −0.22 e Å−3
2128 reflectionsAbsolute structure: Flack (1983), 814 Friedel pairs
153 parametersFlack parameter: 0.00 (1)
6 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.50003 (5)0.63599 (16)0.50001 (6)0.01776 (19)
O10.65168 (12)−0.1181 (5)0.93136 (19)0.0174 (5)
O20.84529 (13)−0.8242 (5)1.05294 (19)0.0198 (5)
N10.63927 (15)0.1424 (5)0.7309 (2)0.0144 (5)
N20.60440 (15)0.2962 (6)0.6322 (2)0.0147 (5)
N30.53164 (15)0.5567 (6)0.7241 (2)0.0166 (6)
C10.73692 (17)−0.2114 (7)0.8141 (2)0.0128 (6)
C20.71210 (17)−0.2660 (7)0.9113 (2)0.0122 (6)
C30.74812 (18)−0.4725 (7)0.9891 (3)0.0141 (6)
H30.7300−0.51171.05300.017*
C40.81112 (16)−0.6232 (6)0.9739 (2)0.0142 (6)
C50.83798 (18)−0.5674 (7)0.8800 (3)0.0174 (7)
H50.8815−0.66880.87040.021*
C60.80096 (17)−0.3645 (7)0.8017 (3)0.0159 (7)
H60.8192−0.32740.73780.019*
C70.69685 (17)−0.0131 (7)0.7250 (2)0.0142 (6)
H70.71420.00200.65900.017*
C80.54711 (17)0.4887 (7)0.6279 (3)0.0149 (6)
C90.47552 (19)0.7743 (8)0.7317 (3)0.0206 (7)
H9A0.48790.84600.80990.031*
H9B0.42340.68990.71000.031*
H9C0.47730.93400.68040.031*
H1O0.633 (3)−0.017 (11)0.874 (3)0.08 (2)*
H2O0.8796 (19)−0.909 (8)1.032 (4)0.038 (13)*
H2N0.6097 (19)0.218 (7)0.5703 (17)0.011 (8)*
H3N0.5552 (19)0.476 (7)0.7898 (17)0.018 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0196 (4)0.0180 (4)0.0138 (3)0.0027 (4)0.0018 (3)0.0021 (4)
O10.0193 (13)0.0174 (12)0.0159 (11)0.0038 (9)0.0059 (9)0.0029 (10)
O20.0216 (12)0.0196 (13)0.0171 (12)0.0069 (10)0.0037 (9)0.0040 (9)
N10.0159 (13)0.0126 (13)0.0125 (12)−0.0018 (11)0.0008 (10)0.0013 (10)
N20.0176 (13)0.0163 (13)0.0097 (13)0.0024 (11)0.0030 (10)−0.0001 (11)
N30.0195 (14)0.0144 (13)0.0152 (13)0.0023 (11)0.0037 (10)0.0014 (10)
C10.0153 (14)0.0135 (15)0.0103 (14)−0.0029 (12)0.0048 (11)−0.0005 (12)
C20.0105 (14)0.0147 (15)0.0129 (15)−0.0017 (12)0.0056 (11)−0.0034 (12)
C30.0162 (15)0.0159 (16)0.0120 (15)−0.0032 (12)0.0069 (12)−0.0012 (11)
C40.0148 (16)0.0139 (14)0.0113 (14)−0.0007 (12)−0.0006 (12)0.0000 (12)
C50.0155 (16)0.0163 (16)0.0180 (17)0.0012 (12)0.0010 (12)−0.0031 (12)
C60.0121 (15)0.0214 (18)0.0134 (15)−0.0031 (14)0.0023 (12)−0.0033 (13)
C70.0157 (16)0.0164 (16)0.0117 (15)−0.0035 (13)0.0058 (12)−0.0016 (12)
C80.0154 (15)0.0127 (15)0.0175 (16)−0.0031 (12)0.0064 (12)0.0002 (12)
C90.0169 (16)0.0266 (19)0.0201 (17)0.0003 (13)0.0079 (13)−0.0038 (13)
Geometric parameters (Å, °) top
S1—C81.699 (3)C1—C21.413 (4)
O1—C21.367 (4)C1—C71.454 (4)
O1—H1O0.838 (10)C2—C31.378 (4)
O2—C41.360 (4)C3—C41.391 (4)
O2—H2O0.836 (10)C3—H30.9500
N1—C71.283 (4)C4—C51.397 (4)
N1—N21.392 (3)C5—C61.374 (4)
N2—C81.354 (4)C5—H50.9500
N2—H2N0.871 (10)C6—H60.9500
N3—C81.328 (4)C7—H70.9500
N3—C91.451 (4)C9—H9A0.9800
N3—H3N0.880 (10)C9—H9B0.9800
C1—C61.400 (4)C9—H9C0.9800
C2—O1—H1O106 (4)C3—C4—C5120.5 (3)
C4—O2—H2O109 (3)C6—C5—C4119.5 (3)
C7—N1—N2114.1 (3)C6—C5—H5120.3
C8—N2—N1121.4 (3)C4—C5—H5120.3
C8—N2—H2N121 (2)C5—C6—C1121.4 (3)
N1—N2—H2N114 (2)C5—C6—H6119.3
C8—N3—C9123.4 (3)C1—C6—H6119.3
C8—N3—H3N123 (3)N1—C7—C1123.2 (3)
C9—N3—H3N114 (3)N1—C7—H7118.4
C6—C1—C2118.1 (3)C1—C7—H7118.4
C6—C1—C7119.1 (3)N3—C8—N2118.3 (3)
C2—C1—C7122.8 (3)N3—C8—S1123.4 (2)
O1—C2—C3117.7 (3)N2—C8—S1118.3 (2)
O1—C2—C1121.6 (3)N3—C9—H9A109.5
C3—C2—C1120.8 (3)N3—C9—H9B109.5
C2—C3—C4119.8 (3)H9A—C9—H9B109.5
C2—C3—H3120.1N3—C9—H9C109.5
C4—C3—H3120.1H9A—C9—H9C109.5
O2—C4—C3117.9 (3)H9B—C9—H9C109.5
O2—C4—C5121.6 (3)
C7—N1—N2—C8−174.4 (3)C4—C5—C6—C10.2 (5)
C6—C1—C2—O1177.7 (3)C2—C1—C6—C51.4 (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—C3174.8 (3)C6—C1—C7—N1−177.7 (3)
O1—C2—C3—C4−178.3 (3)C2—C1—C7—N15.0 (5)
C1—C2—C3—C41.9 (5)C9—N3—C8—N2175.6 (3)
C2—C3—C4—O2179.7 (3)C9—N3—C8—S1−3.1 (4)
C2—C3—C4—C5−0.2 (5)N1—N2—C8—N38.8 (4)
O2—C4—C5—C6179.3 (3)N1—N2—C8—S1−172.5 (2)
C3—C4—C5—C6−0.9 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N10.84 (1)1.93 (3)2.694 (3)151 (6)
O2—H2O···S1i0.84 (1)2.54 (1)3.365 (2)170 (4)
N2—H2N···O1ii0.87 (1)2.11 (1)2.950 (4)162 (3)
Symmetry codes: (i) x+1/2, −y−1/2, z+1/2; (ii) x, −y, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N10.84 (1)1.93 (3)2.694 (3)151 (6)
O2—H2O···S1i0.84 (1)2.54 (1)3.365 (2)170 (4)
N2—H2N···O1ii0.87 (1)2.11 (1)2.950 (4)162 (3)
Symmetry codes: (i) x+1/2, −y−1/2, z+1/2; (ii) x, −y, z−1/2.
Acknowledgements top

We thank the University of Malaya (PJP FS316/2008 C) for supporting this study. KWT thanks the Ministry of Higher Education for a SLAI scholarship.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Tan, K. W., Ng, C. H., Maah, M. J. & Ng, S. W. (2008). Acta Cryst. E64, o1344.

Westrip, S. P. (2008). publCIF. In preparation.