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Acta Cryst. (2010). E66, o2981    [ doi:10.1107/S1600536810043448 ]

5-Chloro-2-hydroxybenzaldehyde thiosemicarbazone

H. Kargar, R. Kia, M. Akkurt and O. Büyükgüngör

Abstract top

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 R22(8) motifs.

Comment top

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).

Related literature top

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

Experimental top

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 top

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).

Computing details top

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

Figures top
[Figure 1] Fig. 1. The title molecule with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
[Figure 2] 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.
5-Chloro-2-hydroxybenzaldehyde thiosemicarbazone top
Crystal data top
C8H8ClN3OSF(000) = 472
Mr = 229.69Dx = 1.503 Mg m−3
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 mm−1
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 top
Stoe IPDS II
diffractometer		1895 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 top
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 = 1.04 w = 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 Å−3
0 restraintsΔρmin = −0.36 e Å−3
Crystal data top
C8H8ClN3OSV = 1014.99 (12) Å3
Mr = 229.69Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.8303 (4) ŵ = 0.55 mm−1
b = 23.6579 (17) ÅT = 296 K
c = 7.5893 (5) Å0.52 × 0.33 × 0.08 mm
β = 104.164 (6)°
Data collection top
Stoe IPDS II
diffractometer		1895 independent reflections
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)		1524 reflections with I > 2σ(I)
Tmin = 0.763, Tmax = 0.957Rint = 0.051
4469 measured reflectionsθmax = 25.6°
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.120Δρmax = 0.20 e Å−3
S = 1.04Δρmin = −0.36 e Å−3
1895 reflectionsAbsolute structure: ?
128 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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) top
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.972.681 (3)144
N2—H2···S1i0.862.703.491 (2)153
N3—H3A···S1ii0.862.873.387 (2)120
N3—H3A···N10.862.362.693 (3)103
N3—H3B···S1iii0.862.553.390 (2)167
Symmetry codes: (i) −x, −y, −z+1; (ii) x+1, y, z; (iii) −x+1, −y, −z+2.
Acknowledgements top

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.

references
References top

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