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Acta Cryst. (2008). E64, o1035    [ doi:10.1107/S1600536808013287 ]

3,4-Dihydroxybenzaldehyde 4-phenylthiosemicarbazone

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

Abstract top

Molecules of the title compound, C14H13N3O2S, are linked by intermolecular O-H...O hydrogen bonds into centrosymmetric dimers forming R22(4) rings which are further linked by O-H...S hydrogen bonds and weaker N-H...S and N-H...O hydrogen bonds to form a three-dimensional network.

Comment top

A previous study of the Schiff bases derived by condensing substituted benzaldehydes with 4-phenylthiosemicarbazides reported the 2,3-dihydroxy compound, which crystallizes as a hemihydrate. The compound features extensive hydrogen bond (Swesi et al., 2006). In the title 3,4-dihydroxy isomer the 4-hydroxy group functions as hydrogen-bond donor to the 3-hydroxy group of a symmetry-related molecule forming R22(4) rings (Bernstein et al., 1995). In addition, the 3-hydroxy group is a donor to the sulfur atom of another molecule; the hydrogen bonding arrangement furnishes a three-dimensional network motif. The amino groups are involved in weaker hydrogen bond interactions.

Further work will investigate the formation of metal deratives of the ligand; some metal complexes have been reported by others but these have not characterized by crystallography yet (Zhu et al., 1997).

Related literature top

For the structure of 2,3-dihydroxybenzaldehyde thiosemicarbazone hemihydrate, see: Swesi et al. (2006). For metal derivatives of the title compound, see: Zhu et al. (1997). The graph-set notation is given by Bernstein et al. (1995).

Experimental top

4-Phenylthiosemicarbazide (0.17 g, 1 mmol) and 3,4-dihydroxybenzaldehyde (0.14 g, 1 mmol) were heated in ethanol (20 ml) for 3 h. Slow evaporation of the solvent yielded yellow crystals.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2 Ueq(C). The hydroxy and amino H-atoms were located in a difference Fourier map, and were refined with a distance retraint of O–H = N–H = 0.85±0.01 Å; their temperature factors were similarly tied.

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 C14H13N3O2S at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii.
3,4-Dihydroxybenzaldehyde 4-phenylthiosemicarbazone top
Crystal data top
C14H13N3O2SF000 = 600
Mr = 287.33Dx = 1.399 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2291 reflections
a = 9.7261 (2) Åθ = 2.5–23.4º
b = 13.1863 (3) ŵ = 0.24 mm−1
c = 10.7732 (3) ÅT = 100 (2) K
β = 99.055 (2)ºBlock, yellow
V = 1364.46 (6) Å30.40 × 0.30 × 0.20 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer		3132 independent reflections
Radiation source: fine-focus sealed tube2358 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.078
T = 100(2) Kθmax = 27.5º
ω scansθmin = 2.1º
Absorption correction: Multi-scan
(SADABS; Sheldrick, 1996)		h = −12→12
Tmin = 0.910, Tmax = 0.953k = −17→16
16724 measured reflectionsl = −13→13
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)] = 0.044H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.115  w = 1/[σ2(Fo2) + (0.0502P)2 + 0.2883P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
3132 reflectionsΔρmax = 0.40 e Å−3
197 parametersΔρmin = −0.32 e Å−3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C14H13N3O2SV = 1364.46 (6) Å3
Mr = 287.33Z = 4
Monoclinic, P21/cMo Kα
a = 9.7261 (2) ŵ = 0.24 mm−1
b = 13.1863 (3) ÅT = 100 (2) K
c = 10.7732 (3) Å0.40 × 0.30 × 0.20 mm
β = 99.055 (2)º
Data collection top
Bruker SMART APEX
diffractometer		3132 independent reflections
Absorption correction: Multi-scan
(SADABS; Sheldrick, 1996)		2358 reflections with I > 2σ(I)
Tmin = 0.910, Tmax = 0.953Rint = 0.078
16724 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0444 restraints
wR(F2) = 0.115H atoms treated by a mixture of
independent and constrained refinement
S = 1.04Δρmax = 0.40 e Å−3
3132 reflectionsΔρmin = −0.32 e Å−3
197 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S11.08441 (5)0.12769 (4)0.40212 (5)0.02006 (15)
O10.65919 (15)0.45705 (10)0.89678 (14)0.0221 (3)
O20.40955 (14)0.39195 (11)0.94986 (14)0.0231 (3)
N10.83208 (16)0.18905 (12)0.63925 (15)0.0187 (4)
N20.90695 (16)0.13520 (12)0.56294 (16)0.0185 (4)
N31.03542 (19)0.27810 (13)0.55853 (18)0.0258 (4)
C10.64419 (19)0.20682 (14)0.75172 (18)0.0172 (4)
C20.6914 (2)0.30261 (14)0.79586 (18)0.0177 (4)
H20.77980.32620.78140.021*
C30.61093 (19)0.36257 (14)0.85974 (18)0.0168 (4)
C40.48283 (19)0.32692 (15)0.88517 (18)0.0175 (4)
C50.4360 (2)0.23207 (15)0.84415 (19)0.0207 (4)
H50.34920.20770.86200.025*
C60.5160 (2)0.17194 (15)0.77643 (19)0.0204 (4)
H60.48310.10710.74710.024*
C70.72652 (19)0.14733 (15)0.67561 (19)0.0190 (4)
H70.70220.07920.65360.023*
C81.00702 (19)0.18502 (14)0.51400 (19)0.0177 (4)
C91.1227 (2)0.35150 (15)0.5122 (2)0.0212 (4)
C101.2393 (2)0.38550 (18)0.5909 (2)0.0304 (5)
H101.26510.35650.67190.037*
C111.3183 (3)0.4624 (2)0.5504 (2)0.0386 (6)
H111.39860.48630.60420.046*
C121.2821 (2)0.50451 (18)0.4336 (2)0.0339 (6)
H121.33660.55760.40700.041*
C131.1657 (2)0.46947 (18)0.3545 (2)0.0348 (6)
H131.14100.49770.27290.042*
C141.0858 (2)0.39327 (17)0.3946 (2)0.0287 (5)
H141.00530.36960.34100.034*
H1O0.602 (2)0.4875 (17)0.935 (2)0.035 (7)*
H2O0.3276 (14)0.3698 (18)0.950 (3)0.043 (8)*
H2N0.890 (2)0.0737 (9)0.542 (2)0.036 (7)*
H3N0.995 (2)0.2960 (17)0.6187 (16)0.027 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0175 (2)0.0195 (3)0.0249 (3)0.00003 (19)0.00859 (19)−0.0035 (2)
O10.0209 (7)0.0162 (7)0.0316 (9)−0.0015 (6)0.0116 (6)−0.0063 (6)
O20.0158 (7)0.0226 (8)0.0328 (9)−0.0011 (6)0.0093 (6)−0.0075 (6)
N10.0181 (8)0.0188 (9)0.0207 (9)0.0021 (7)0.0081 (7)−0.0017 (7)
N20.0173 (8)0.0148 (9)0.0250 (9)−0.0013 (7)0.0086 (7)−0.0043 (7)
N30.0313 (10)0.0202 (9)0.0310 (11)−0.0081 (8)0.0202 (8)−0.0076 (8)
C10.0159 (9)0.0187 (10)0.0178 (10)−0.0003 (7)0.0048 (8)−0.0011 (8)
C20.0146 (9)0.0178 (10)0.0216 (10)−0.0011 (7)0.0056 (8)−0.0001 (8)
C30.0169 (9)0.0148 (10)0.0184 (10)−0.0004 (7)0.0016 (7)0.0000 (7)
C40.0148 (9)0.0204 (10)0.0183 (10)0.0026 (7)0.0052 (7)−0.0008 (8)
C50.0141 (9)0.0206 (10)0.0285 (12)−0.0020 (8)0.0064 (8)−0.0007 (8)
C60.0199 (10)0.0175 (10)0.0246 (11)−0.0030 (8)0.0061 (8)−0.0026 (8)
C70.0185 (10)0.0168 (10)0.0223 (11)−0.0018 (8)0.0054 (8)−0.0027 (8)
C80.0145 (9)0.0167 (10)0.0224 (10)0.0011 (7)0.0046 (8)−0.0002 (8)
C90.0204 (10)0.0170 (10)0.0287 (12)−0.0037 (8)0.0114 (8)−0.0041 (8)
C100.0317 (12)0.0345 (13)0.0248 (12)−0.0058 (10)0.0034 (9)0.0012 (10)
C110.0328 (13)0.0442 (15)0.0381 (15)−0.0193 (11)0.0032 (11)−0.0047 (11)
C120.0323 (13)0.0250 (12)0.0474 (16)−0.0093 (10)0.0155 (11)0.0037 (11)
C130.0336 (13)0.0312 (13)0.0396 (15)0.0016 (10)0.0059 (11)0.0148 (11)
C140.0211 (10)0.0310 (12)0.0328 (13)−0.0033 (9)0.0011 (9)0.0030 (10)
Geometric parameters (Å, °) top
S1—C81.696 (2)C3—C41.398 (3)
O1—C31.368 (2)C4—C51.380 (3)
O1—H1O0.85 (1)C5—C61.395 (3)
O2—C41.373 (2)C5—H50.9500
O2—H2O0.85 (1)C6—H60.9500
N1—C71.279 (2)C7—H70.9500
N1—N21.378 (2)C9—C141.376 (3)
N2—C81.348 (2)C9—C101.380 (3)
N2—H2N0.85 (1)C10—C111.383 (3)
N3—C81.331 (3)C10—H100.9500
N3—C91.428 (3)C11—C121.370 (3)
N3—H3N0.84 (1)C11—H110.9500
C1—C61.393 (3)C12—C131.385 (3)
C1—C21.401 (3)C12—H120.9500
C1—C71.461 (3)C13—C141.381 (3)
C2—C31.372 (3)C13—H130.9500
C2—H20.9500C14—H140.9500
C3—O1—H1O110.7 (17)C5—C6—H6119.9
C4—O2—H2O110.6 (18)N1—C7—C1118.55 (17)
C7—N1—N2119.07 (16)N1—C7—H7120.7
C8—N2—N1117.64 (16)C1—C7—H7120.7
C8—N2—H2N119.3 (17)N3—C8—N2115.47 (17)
N1—N2—H2N123.0 (17)N3—C8—S1125.24 (15)
C8—N3—C9126.89 (17)N2—C8—S1119.28 (15)
C8—N3—H3N116.2 (16)C14—C9—C10120.35 (19)
C9—N3—H3N116.9 (16)C14—C9—N3120.67 (19)
C6—C1—C2119.21 (17)C10—C9—N3118.8 (2)
C6—C1—C7121.05 (18)C9—C10—C11119.2 (2)
C2—C1—C7119.68 (17)C9—C10—H10120.4
C3—C2—C1120.50 (17)C11—C10—H10120.4
C3—C2—H2119.7C12—C11—C10120.8 (2)
C1—C2—H2119.7C12—C11—H11119.6
O1—C3—C2118.33 (17)C10—C11—H11119.6
O1—C3—C4121.62 (17)C11—C12—C13119.8 (2)
C2—C3—C4120.06 (17)C11—C12—H12120.1
O2—C4—C5123.84 (17)C13—C12—H12120.1
O2—C4—C3116.05 (17)C14—C13—C12119.7 (2)
C5—C4—C3120.10 (18)C14—C13—H13120.1
C4—C5—C6119.95 (18)C12—C13—H13120.1
C4—C5—H5120.0C9—C14—C13120.1 (2)
C6—C5—H5120.0C9—C14—H14119.9
C1—C6—C5120.14 (18)C13—C14—H14119.9
C1—C6—H6119.9
C7—N1—N2—C8172.24 (18)C2—C1—C7—N1−7.8 (3)
C6—C1—C2—C3−1.7 (3)C9—N3—C8—N2−171.35 (19)
C7—C1—C2—C3175.33 (18)C9—N3—C8—S17.8 (3)
C1—C2—C3—O1−177.55 (17)N1—N2—C8—N38.7 (3)
C1—C2—C3—C42.2 (3)N1—N2—C8—S1−170.51 (13)
O1—C3—C4—O2−0.4 (3)C8—N3—C9—C1466.2 (3)
C2—C3—C4—O2179.82 (17)C8—N3—C9—C10−118.6 (2)
O1—C3—C4—C5178.64 (18)C14—C9—C10—C110.3 (3)
C2—C3—C4—C5−1.1 (3)N3—C9—C10—C11−174.9 (2)
O2—C4—C5—C6178.51 (18)C9—C10—C11—C12−0.2 (4)
C3—C4—C5—C6−0.5 (3)C10—C11—C12—C13−0.5 (4)
C2—C1—C6—C50.1 (3)C11—C12—C13—C141.0 (4)
C7—C1—C6—C5−176.89 (18)C10—C9—C14—C130.1 (3)
C4—C5—C6—C11.0 (3)N3—C9—C14—C13175.3 (2)
N2—N1—C7—C1−177.22 (16)C12—C13—C14—C9−0.8 (4)
C6—C1—C7—N1169.23 (19)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O2i0.85 (1)2.03 (2)2.737 (2)141 (2)
O2—H2O···S1ii0.85 (1)2.34 (1)3.134 (1)156 (2)
N2—H2N···S1iii0.85 (1)2.73 (1)3.487 (2)150 (2)
N2—H2N···O1iv0.85 (1)2.56 (2)3.022 (2)115 (2)
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1, −y+1/2, z+1/2; (iii) −x+2, −y, −z+1; (iv) x, −y+1/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O2i0.85 (1)2.03 (2)2.737 (2)141 (2)
O2—H2O···S1ii0.85 (1)2.34 (1)3.134 (1)156 (2)
N2—H2N···S1iii0.85 (1)2.73 (1)3.487 (2)150 (2)
N2—H2N···O1iv0.85 (1)2.56 (2)3.022 (2)115 (2)
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1, −y+1/2, z+1/2; (iii) −x+2, −y, −z+1; (iv) x, −y+1/2, z−1/2.
Acknowledgements top

We thank the University of Malaya (P0265/2007 A) for supporting this study; KWT thanks the Ministry of Higher Education for an SLAI scholarship in this research.

references
References top

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