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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): o2224.
Published online 2008 October 31. doi:  10.1107/S1600536808033308
PMCID: PMC2959547

2,4-Dihydroxy­benzaldehyde 4-methyl­thio­semicarbazone

Abstract

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.

Related literature

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

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Object name is e-64-o2224-scheme1.jpg

Experimental

Crystal data

  • C9H11N3O2S
  • M r = 225.27
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2224-efi1.jpg
  • 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 [triangle]) 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 [triangle]), with 814 Friedel pairs
  • Flack parameter: 0.00 (1)

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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

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.

Figures

Fig. 1.
Thermal ellipsoid (Barbour, 2001) plot of (I) drawn at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii.

Crystal data

C9H11N3O2SF(000) = 472
Mr = 225.27Dx = 1.521 Mg m3
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 mm1
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

Bruker SMART APEX diffractometer2128 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

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) = 0.109w = 1/[σ2(Fo2) + (0.0598P)2] where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.001
2128 reflectionsΔρmax = 0.31 e Å3
153 parametersΔρmin = −0.22 e Å3
6 restraintsAbsolute structure: Flack (1983), 814 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.00 (1)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2316).

References

  • 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. [PubMed]
  • Tan, K. W., Ng, C. H., Maah, M. J. & Ng, S. W. (2008). Acta Cryst. E64, o1344. [PMC free article] [PubMed]
  • Westrip, S. P. (2008). publCIF In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography