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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2981.
Published online 2010 October 30. doi:  10.1107/S1600536810043448
PMCID: PMC3009088

5-Chloro-2-hy­droxy­benzaldehyde thio­semicarbazone

Abstract

In the title compound, C8H8ClN3OS, the whole mol­ecule assumes a planar structure, with an r.m.s. deviation of 0.108 (2) Å, and an intra­molecular O—H(...)N hydrogen bond generates and S(6) and ring motif. In the crystal structure, each of two pairs of inter­molecular N—H(...)S hydrogen bonds connects two mol­ecules, forming inversion dimers with R 2 2(8) motifs.

Related literature

For the biological activities and pharmaceutical properties of thio­semicarbazones and their derivatives, see: Casas et al. (2000 [triangle]); Ferrari et al. (2000 [triangle]); Maccioni et al. (2003 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2981-scheme1.jpg

Experimental

Crystal data

  • C8H8ClN3OS
  • M r = 229.69
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2981-efi1.jpg
  • a = 5.8303 (4) Å
  • b = 23.6579 (17) Å
  • c = 7.5893 (5) Å
  • β = 104.164 (6)°
  • V = 1014.99 (12) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.55 mm−1
  • T = 296 K
  • 0.52 × 0.33 × 0.08 mm

Data collection

  • Stoe IPDS II diffractometer
  • Absorption correction: integration (X-RED32; Stoe & Cie, 2002 [triangle]) T min = 0.763, T max = 0.957
  • 4469 measured reflections
  • 1895 independent reflections
  • 1524 reflections with I > 2σ(I)
  • R int = 0.051

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.120
  • S = 1.04
  • 1895 reflections
  • 128 parameters
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.37 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 [triangle]); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 [triangle]); program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810043448/is2621sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810043448/is2621Isup2.hkl

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

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant F.279 of the University Research Fund). HK thanks Payame Noor University (PNU) for financial support of this work. RK thanks the Science and Research Branch of Islamic Azad University of Tehran.

supplementary crystallographic information

Comment

Thiosemicarbazones constitute an important class of N,S donor ligands due to their propensity to react with a wide range of metals (Casas et al., 2000). Thiosemicarbazones exhibit various biological activities and have therefore attracted considerable pharmaceutical interest (Maccioni et al., 2003; Ferrari et al., 2000). We here report the crystal structure of the title compound (I).

The title molecule (I) shown in Fig. 1 is planar with an r.m.s. deviation of 0.108 Å and all bond lengths agree with standard values (Allen et al., 1987). Intramolecular O—H···N and N—H···N hydrogen bonds (Table 1) generate the S(6) and S(5) ring motifs, respectively (Bernstein et al., 1995).

In the crystal structure, molecules are linked by N—H···S hydrogen bonds, forming R22(8) dimers (Table 1 and Fig. 2).

Experimental

A mixture of 5-chlorosalicylalehyde (0.01 mol) and hydrazinecarbothioamide (0.01 mol) in 20 ml of ethanol was refluxed for about 2 h. On cooling, the solid separated was filtered and recrystallized from ethanol. Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of ethanol.

Refinement

All H atoms were geometrically placed (C—H = 0.93 Å, N—H = 0.86 Å and O—H = 0.82 Å) and refined as riding with Uiso(H) = 1.2Ueq(C,N) and 1.5Ueq(O).

Figures

Fig. 1.
The title molecule with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
Fig. 2.
View of the packing and hydrogen bonding interactions of (I), showing dimer formation by R22(8) ring motif. All H atoms not involved in hydrogen bonding have been omitted for clarity.

Crystal data

C8H8ClN3OSF(000) = 472
Mr = 229.69Dx = 1.503 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8344 reflections
a = 5.8303 (4) Åθ = 1.7–26.2°
b = 23.6579 (17) ŵ = 0.55 mm1
c = 7.5893 (5) ÅT = 296 K
β = 104.164 (6)°Prism, colourless
V = 1014.99 (12) Å30.52 × 0.33 × 0.08 mm
Z = 4

Data collection

Stoe IPDS II diffractometer1895 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus1524 reflections with I > 2σ(I)
plane graphiteRint = 0.051
Detector resolution: 6.67 pixels mm-1θmax = 25.6°, θmin = 1.7°
ω scansh = −5→7
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)k = −28→26
Tmin = 0.763, Tmax = 0.957l = −9→9
4469 measured reflections

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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0681P)2 + 0.120P] where P = (Fo2 + 2Fc2)/3
1895 reflections(Δ/σ)max < 0.001
128 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = −0.36 e Å3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

xyzUiso*/Ueq
Cl10.36123 (17)0.20555 (4)−0.30970 (10)0.0868 (3)
S10.15507 (9)0.01021 (3)0.79551 (8)0.0559 (2)
O10.8537 (3)0.13549 (11)0.4272 (3)0.0750 (8)
N10.4525 (3)0.08332 (9)0.4467 (3)0.0489 (6)
N20.3002 (3)0.05468 (10)0.5260 (3)0.0523 (6)
N30.5874 (3)0.04298 (10)0.7883 (3)0.0524 (7)
C10.4996 (4)0.13306 (11)0.1830 (3)0.0493 (8)
C20.7333 (4)0.15067 (12)0.2573 (4)0.0573 (8)
C30.8480 (5)0.18395 (14)0.1559 (4)0.0687 (10)
C40.7368 (6)0.20095 (13)−0.0164 (4)0.0702 (10)
C50.5049 (5)0.18372 (12)−0.0912 (4)0.0604 (9)
C60.3886 (5)0.15099 (11)0.0062 (3)0.0542 (8)
C70.3665 (4)0.09979 (11)0.2818 (3)0.0507 (8)
C80.3636 (4)0.03756 (11)0.6999 (3)0.0454 (7)
H10.762700.120400.480000.1120*
H20.159600.047400.462600.0630*
H31.003500.195000.205500.0830*
H3A0.687900.057100.734400.0630*
H3B0.632800.032400.899800.0630*
H40.815200.22370−0.082600.0840*
H60.233100.14030−0.045100.0650*
H70.212100.089700.224300.0610*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.1118 (7)0.0820 (6)0.0700 (4)0.0054 (5)0.0287 (4)0.0188 (4)
S10.0349 (3)0.0795 (5)0.0526 (3)−0.0048 (3)0.0096 (2)0.0063 (3)
O10.0458 (10)0.0951 (17)0.0791 (12)−0.0077 (10)0.0058 (9)0.0132 (11)
N10.0379 (9)0.0554 (12)0.0544 (10)−0.0011 (8)0.0131 (8)0.0019 (9)
N20.0336 (9)0.0683 (14)0.0529 (10)−0.0059 (9)0.0065 (8)0.0074 (9)
N30.0334 (9)0.0742 (15)0.0485 (10)−0.0031 (9)0.0079 (7)0.0017 (9)
C10.0447 (12)0.0466 (14)0.0597 (13)0.0017 (10)0.0189 (10)−0.0007 (10)
C20.0453 (12)0.0558 (16)0.0729 (15)0.0009 (11)0.0186 (11)0.0020 (12)
C30.0489 (14)0.0623 (18)0.100 (2)−0.0044 (12)0.0281 (14)0.0079 (15)
C40.0725 (17)0.0577 (18)0.0926 (19)0.0020 (14)0.0438 (15)0.0108 (15)
C50.0729 (17)0.0490 (15)0.0653 (14)0.0056 (13)0.0283 (12)0.0030 (11)
C60.0540 (13)0.0505 (15)0.0595 (12)0.0029 (11)0.0168 (10)−0.0014 (11)
C70.0403 (12)0.0544 (15)0.0570 (12)0.0002 (10)0.0111 (10)0.0015 (11)
C80.0344 (10)0.0510 (14)0.0505 (11)0.0009 (9)0.0096 (9)−0.0029 (10)

Geometric parameters (Å, °)

Cl1—C51.743 (3)C1—C21.404 (4)
S1—C81.690 (2)C1—C61.405 (3)
O1—C21.357 (4)C1—C71.438 (3)
O1—H10.8200C2—C31.383 (4)
N1—N21.368 (3)C3—C41.370 (4)
N1—C71.289 (3)C4—C51.393 (5)
N2—C81.343 (3)C5—C61.361 (4)
N3—C81.319 (3)C3—H30.9300
N2—H20.8600C4—H40.9300
N3—H3A0.8600C6—H60.9300
N3—H3B0.8600C7—H70.9300
Cl1···C5i3.606 (3)C7···C8vi3.598 (4)
S1···N3ii3.387 (2)C7···N3vi3.440 (4)
S1···N2iii3.491 (2)C7···C3ii3.550 (4)
S1···N3iv3.390 (2)C8···C7vi3.598 (4)
S1···H3Aii2.8700C8···C6vii3.530 (3)
S1···H2iii2.7000C8···N1vi3.339 (3)
S1···H3Biv2.5500C3···H7v3.0300
S1···H7iii3.1700C3···H4viii2.9900
O1···N12.681 (3)C7···H3ii3.0500
O1···N2v3.168 (3)C7···H12.4800
O1···H2v2.7100H1···N11.9700
N1···O12.681 (3)H1···C72.4800
N1···N32.693 (3)H1···H3A2.5600
N1···C8vi3.339 (3)H2···O1ii2.7100
N2···O1ii3.168 (3)H2···H72.1500
N2···S1iii3.491 (2)H2···S1iii2.7000
N3···C6vii3.398 (3)H3···C7v3.0500
N3···S1iv3.390 (2)H3A···S1v2.8700
N3···S1v3.387 (2)H3A···N12.3600
N3···N12.693 (3)H3A···H12.5600
N3···C7vi3.440 (4)H3B···S1iv2.5500
N1···H11.9700H4···C3i2.9900
N1···H3A2.3600H6···H72.4000
C3···C7v3.550 (4)H7···C3ii3.0300
C5···Cl1viii3.606 (3)H7···H22.1500
C6···N3ix3.398 (3)H7···H62.4000
C6···C8ix3.530 (3)H7···S1iii3.1700
C2—O1—H1109.00Cl1—C5—C4119.6 (2)
N2—N1—C7115.9 (2)Cl1—C5—C6119.9 (2)
N1—N2—C8122.0 (2)C4—C5—C6120.5 (3)
C8—N2—H2119.00C1—C6—C5121.1 (3)
N1—N2—H2119.00N1—C7—C1122.7 (2)
H3A—N3—H3B120.00N2—C8—N3118.1 (2)
C8—N3—H3A120.00S1—C8—N2118.92 (18)
C8—N3—H3B120.00S1—C8—N3123.01 (18)
C2—C1—C6118.0 (2)C2—C3—H3119.00
C6—C1—C7118.8 (2)C4—C3—H3119.00
C2—C1—C7123.2 (2)C3—C4—H4120.00
O1—C2—C1121.9 (2)C5—C4—H4120.00
C1—C2—C3120.0 (3)C1—C6—H6119.00
O1—C2—C3118.1 (2)C5—C6—H6119.00
C2—C3—C4121.2 (3)N1—C7—H7119.00
C3—C4—C5119.2 (3)C1—C7—H7119.00
C7—N1—N2—C8−176.7 (2)C6—C1—C2—C3−0.9 (4)
N2—N1—C7—C1176.5 (2)C7—C1—C2—O12.5 (4)
N1—N2—C8—S1171.99 (18)O1—C2—C3—C4−179.8 (3)
N1—N2—C8—N3−8.0 (4)C1—C2—C3—C40.9 (5)
C7—C1—C2—C3−178.2 (3)C2—C3—C4—C5−0.8 (5)
C2—C1—C6—C51.0 (4)C3—C4—C5—Cl1179.5 (2)
C7—C1—C6—C5178.3 (3)C3—C4—C5—C60.8 (5)
C2—C1—C7—N1−0.3 (4)Cl1—C5—C6—C1−179.6 (2)
C6—C1—C7—N1−177.6 (2)C4—C5—C6—C1−0.9 (4)
C6—C1—C2—O1179.8 (2)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.972.681 (3)144
N2—H2···S1iii0.862.703.491 (2)153
N3—H3A···S1v0.862.873.387 (2)120
N3—H3A···N10.862.362.693 (3)103
N3—H3B···S1iv0.862.553.390 (2)167

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2621).

References

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  • Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst.32, 115–119.
  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Casas, J. S., Garcia-Tasende, M. S. & Sordo, J. (2000). Coord. Chem. Rev.209, 197–261.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Ferrari, M. B., Capacchi, S., Reffo, G., Pelosi, G., Tarasconi, P., Albertini, R., Pinelli, S. & Lunghi, P. (2000). J. Inorg. Biochem.81, 89–97. [PubMed]
  • Maccioni, E., Cardia, M. C., Distinto, S., Bonsignore, L. & De Logu, A. (2003). Il Farmaco, 58, 951–959. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Stoe & Cie (2002). X-AREA and X-RED32 Stoe & Cie, Darmstadt, Germany.

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