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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1151.
Published online 2010 April 24. doi:  10.1107/S1600536810014078
PMCID: PMC2979131

1-(2,3,4-Trihydroxy­benzyl­idene)-4-ethyl­thio­semicarbazide

Abstract

In the title mol­ecule, C10H13N3O3S, the thio­semicarbazide =N—NH—C(=S)—NH– fragment is twisted with respect to the aromatic ring [dihedral angle = 20.5 (1)°]. A weak N—H(...)S hydrogen bond [3.480 (1) Å] links two mol­ecules about a center of inversion to generate a ring. The hydr­oxy groups are engaged in inter­molecular hydrogen bonding; the O—H(...)O and O—H(...)S hydrogen bonds generate a layer motif.

Related literature

For the crystal structures of 3,4-dihydroxy­benzaldehyde 4-ethyl­thio­semicarbazone and 2,4-dihydroxy­benzaldehyde 4-ethyl­thio­semicarbazone, see: Kayed et al. (2008 [triangle]); Tan et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1151-scheme1.jpg

Experimental

Crystal data

  • C10H13N3O3S
  • M r = 255.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1151-efi1.jpg
  • a = 7.5668 (5) Å
  • b = 14.6754 (10) Å
  • c = 10.8700 (7) Å
  • β = 104.711 (1)°
  • V = 1167.50 (13) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.28 mm−1
  • T = 100 K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.921, T max = 0.973
  • 10870 measured reflections
  • 2660 independent reflections
  • 2364 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.082
  • S = 1.04
  • 2660 reflections
  • 174 parameters
  • 5 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: APEX2 software (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [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, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810014078/pk2241sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810014078/pk2241Isup2.hkl

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

Acknowledgments

The authors thank the University of Malaya (grant No. PS354/2009) and MOHE (grant No. FRGS-FP001/2009) for supporting this study. HBS thanks the Libyan People’s Bureau in Malaysia for a scholarship.

supplementary crystallographic information

Experimental

2,3,4-Trihydroxybenzaldehyde (1.54 g, 10 mmol) and 4-ethylthiosemicarbazide (1.19 g, 1 mmol) were heated in ethanol (20 ml) for 2 hours; acetic acid (0.5 ml) was also added. A brown solid separated from the cool solution; this was recrystallized from methanol.

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 U(H) set to 1.2 or 1.5U(CMe).

The amino and hydroxy H-atoms were located in a difference Fourier map, and were refined with distance restraints of N–H 0.86±0.01 and O–H 0.84±0.01 Å; their temperature factors were freely refined.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of C10H13N3O3S at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C10H13N3O3SF(000) = 536
Mr = 255.29Dx = 1.452 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5730 reflections
a = 7.5668 (5) Åθ = 2.4–28.3°
b = 14.6754 (10) ŵ = 0.28 mm1
c = 10.8700 (7) ÅT = 100 K
β = 104.711 (1)°Prism, colorless
V = 1167.50 (13) Å30.30 × 0.20 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer2660 independent reflections
Radiation source: fine-focus sealed tube2364 reflections with I > 2σ(I)
graphiteRint = 0.026
ω scansθmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −9→9
Tmin = 0.921, Tmax = 0.973k = −19→19
10870 measured reflectionsl = −14→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082H atoms treated by a mixture of independent and constrained refinement
S = 1.04w = 1/[σ2(Fo2) + (0.0437P)2 + 0.4981P] where P = (Fo2 + 2Fc2)/3
2660 reflections(Δ/σ)max = 0.001
174 parametersΔρmax = 0.34 e Å3
5 restraintsΔρmin = −0.21 e Å3

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

xyzUiso*/Ueq
S10.70929 (4)0.59538 (2)0.58991 (3)0.01292 (10)
O10.50792 (13)0.28115 (6)0.03429 (8)0.0153 (2)
O20.54351 (14)0.26317 (6)−0.20701 (9)0.0176 (2)
O30.73079 (14)0.39064 (6)−0.30899 (9)0.0167 (2)
N10.73526 (15)0.49383 (7)0.26113 (10)0.0133 (2)
N20.69204 (15)0.50533 (7)0.37631 (10)0.0132 (2)
N30.91494 (16)0.61386 (8)0.42338 (11)0.0150 (2)
C10.66760 (17)0.42305 (8)0.05845 (12)0.0114 (2)
C20.59670 (17)0.34728 (8)−0.01603 (12)0.0114 (2)
C30.61719 (17)0.33861 (8)−0.13940 (12)0.0122 (2)
C40.71179 (18)0.40505 (8)−0.18813 (12)0.0123 (2)
C50.78291 (17)0.48082 (9)−0.11516 (12)0.0134 (3)
H50.84740.5261−0.14860.016*
C60.75918 (17)0.48975 (8)0.00612 (12)0.0127 (2)
H60.80590.54210.05500.015*
C70.64158 (17)0.43394 (8)0.18633 (12)0.0124 (2)
H70.55590.39690.21380.015*
C80.77826 (17)0.57177 (8)0.45530 (12)0.0118 (2)
C91.01416 (19)0.69298 (9)0.48851 (13)0.0168 (3)
H9A1.14560.68690.49170.020*
H9B1.00200.69510.57700.020*
C100.9416 (2)0.78045 (10)0.42107 (17)0.0283 (4)
H10A1.00800.83230.46780.042*
H10B0.81120.78630.41710.042*
H10C0.95840.77950.33460.042*
H1O0.472 (3)0.2409 (11)−0.0195 (16)0.039 (6)*
H2O0.554 (3)0.2673 (15)−0.2817 (11)0.045 (6)*
H3O0.731 (3)0.4420 (9)−0.343 (2)0.047 (6)*
H2N0.5992 (17)0.4785 (11)0.3933 (15)0.021 (4)*
H3N0.936 (2)0.5975 (11)0.3531 (11)0.023 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.01775 (18)0.01251 (16)0.00958 (16)−0.00113 (11)0.00547 (12)−0.00111 (10)
O10.0228 (5)0.0130 (4)0.0113 (4)−0.0065 (4)0.0064 (4)−0.0022 (3)
O20.0281 (5)0.0147 (5)0.0114 (5)−0.0064 (4)0.0078 (4)−0.0041 (4)
O30.0259 (5)0.0153 (5)0.0110 (5)0.0000 (4)0.0089 (4)0.0007 (3)
N10.0157 (5)0.0150 (5)0.0104 (5)−0.0001 (4)0.0056 (4)−0.0018 (4)
N20.0155 (5)0.0149 (5)0.0109 (5)−0.0040 (4)0.0063 (4)−0.0028 (4)
N30.0185 (6)0.0158 (5)0.0126 (5)−0.0046 (4)0.0075 (4)−0.0047 (4)
C10.0116 (6)0.0122 (5)0.0103 (6)0.0016 (4)0.0024 (4)0.0003 (4)
C20.0118 (6)0.0105 (5)0.0124 (6)0.0007 (4)0.0038 (5)0.0015 (4)
C30.0144 (6)0.0109 (6)0.0109 (6)0.0011 (5)0.0023 (5)−0.0012 (4)
C40.0137 (6)0.0144 (6)0.0096 (6)0.0034 (5)0.0042 (5)0.0009 (4)
C50.0132 (6)0.0129 (6)0.0144 (6)−0.0004 (5)0.0040 (5)0.0027 (5)
C60.0127 (6)0.0118 (6)0.0126 (6)−0.0003 (5)0.0016 (5)−0.0010 (5)
C70.0138 (6)0.0111 (6)0.0128 (6)0.0005 (5)0.0042 (5)0.0002 (4)
C80.0140 (6)0.0104 (5)0.0110 (6)0.0015 (5)0.0028 (5)0.0011 (4)
C90.0182 (7)0.0164 (6)0.0167 (6)−0.0067 (5)0.0060 (5)−0.0043 (5)
C100.0201 (8)0.0167 (7)0.0444 (10)−0.0032 (6)0.0012 (7)0.0005 (6)

Geometric parameters (Å, °)

S1—C81.7092 (13)C1—C61.4007 (17)
O1—C21.3707 (15)C1—C71.4613 (17)
O1—H1O0.827 (9)C2—C31.3944 (17)
O2—C31.3669 (15)C3—C41.3914 (17)
O2—H2O0.838 (9)C4—C51.3923 (17)
O3—C41.3738 (15)C5—C61.3811 (17)
O3—H3O0.841 (9)C5—H50.9500
N1—C71.2819 (16)C6—H60.9500
N1—N21.3824 (14)C7—H70.9500
N2—C81.3523 (16)C9—C101.511 (2)
N2—H2N0.866 (9)C9—H9A0.9900
N3—C81.3244 (17)C9—H9B0.9900
N3—C91.4639 (16)C10—H10A0.9800
N3—H3N0.853 (9)C10—H10B0.9800
C1—C21.3996 (17)C10—H10C0.9800
C2—O1—H1O109.3 (15)C6—C5—H5120.2
C3—O2—H2O109.6 (15)C4—C5—H5120.2
C4—O3—H3O107.5 (15)C5—C6—C1121.26 (11)
C7—N1—N2115.99 (11)C5—C6—H6119.4
C8—N2—N1118.43 (11)C1—C6—H6119.4
C8—N2—H2N118.7 (11)N1—C7—C1119.47 (11)
N1—N2—H2N122.0 (11)N1—C7—H7120.3
C8—N3—C9125.59 (11)C1—C7—H7120.3
C8—N3—H3N116.0 (12)N3—C8—N2116.93 (11)
C9—N3—H3N117.8 (12)N3—C8—S1123.94 (10)
C2—C1—C6118.47 (11)N2—C8—S1119.13 (10)
C2—C1—C7120.84 (11)N3—C9—C10111.14 (11)
C6—C1—C7120.66 (11)N3—C9—H9A109.4
O1—C2—C3120.30 (11)C10—C9—H9A109.4
O1—C2—C1119.11 (11)N3—C9—H9B109.4
C3—C2—C1120.59 (11)C10—C9—H9B109.4
O2—C3—C4122.81 (11)H9A—C9—H9B108.0
O2—C3—C2117.46 (11)C9—C10—H10A109.5
C4—C3—C2119.72 (11)C9—C10—H10B109.5
O3—C4—C3116.43 (11)H10A—C10—H10B109.5
O3—C4—C5123.27 (11)C9—C10—H10C109.5
C3—C4—C5120.30 (12)H10A—C10—H10C109.5
C6—C5—C4119.63 (12)H10B—C10—H10C109.5
C7—N1—N2—C8−175.71 (11)O3—C4—C5—C6−179.39 (12)
C6—C1—C2—O1179.53 (11)C3—C4—C5—C60.03 (19)
C7—C1—C2—O1−2.47 (18)C4—C5—C6—C11.21 (19)
C6—C1—C2—C30.05 (18)C2—C1—C6—C5−1.25 (19)
C7—C1—C2—C3178.06 (11)C7—C1—C6—C5−179.26 (12)
O1—C2—C3—O20.95 (18)N2—N1—C7—C1174.75 (11)
C1—C2—C3—O2−179.58 (11)C2—C1—C7—N1167.00 (12)
O1—C2—C3—C4−178.31 (11)C6—C1—C7—N1−15.04 (18)
C1—C2—C3—C41.16 (19)C9—N3—C8—N2173.77 (12)
O2—C3—C4—O3−0.96 (18)C9—N3—C8—S1−7.36 (19)
C2—C3—C4—O3178.26 (11)N1—N2—C8—N3−8.18 (17)
O2—C3—C4—C5179.58 (12)N1—N2—C8—S1172.89 (9)
C2—C3—C4—C5−1.20 (19)C8—N3—C9—C10−97.70 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1o···O20.83 (1)2.26 (2)2.717 (1)115 (2)
O1—H1o···S1i0.83 (1)2.55 (1)3.291 (1)150 (2)
O2—H2o···O30.84 (1)2.31 (2)2.745 (1)112 (2)
O2—H2o···O1ii0.84 (1)2.07 (1)2.832 (1)151 (2)
O3—H3o···S1iii0.84 (1)2.36 (1)3.189 (1)170 (2)
N2—H2N···S1iv0.872.623.480 (1)171

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) x, y, z−1; (iv) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2241).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2009). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Kayed, S. F., Farina, Y., Baba, I. & Simpson, J. (2008). Acta Cryst. E64, o824–o825. [PMC free article] [PubMed]
  • 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, o2123. [PMC free article] [PubMed]
  • Westrip, S. P. (2010). publCIF In preparation.

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