5-Chloro-2-hy­droxy­benzaldehyde thio­semicarbazone

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

doi:10.1107/S1600536810043448

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2981

https://doi.org/10.1107/S1600536810043448

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5-Chloro-2-hydroxybenzaldehyde thiosemicarbazone

Hadi Kargar,^a Reza Kia,^b Mehmet Akkurt ^c ^* and Orhan Büyükgüngör ^d

^aDepartment of Chemistry, School of Science, Payame Noor University (PNU), Ardakan, Yazd, Iran, ^bDepartment of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran, ^cDepartment of Physics, Faculty of Arts and Sciences, Erciyes University, 38039 Kayseri, Turkey, and ^dDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Samsun, Turkey
^*Correspondence e-mail: akkurt@erciyes.edu.tr

(Received 24 October 2010; accepted 25 October 2010; online 30 October 2010)

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.

Related literature

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

Crystal data

C₈H₈ClN₃OS
M_r = 229.69
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.044
wR(F²) = 0.120
S = 1.04
1895 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1ⁱ	0.86	2.70	3.491 (2)	153
N3—H3A⋯S1ⁱⁱ	0.86	2.87	3.387 (2)	120
N3—H3A⋯N1	0.86	2.36	2.693 (3)	103
N3—H3B⋯S1ⁱⁱⁱ	0.86	2.55	3.390 (2)	167
Symmetry codes: (i) -x, -y, -z+1; (ii) x+1, y, z; (iii) -x+1, -y, -z+2.

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; 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 ).

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810043448/is2621Isup2.hkl

checkCIF report

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.

Structure description top

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

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).

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

	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.

5-Chloro-2-hydroxybenzaldehyde thiosemicarbazone top

Crystal data top

C₈H₈ClN₃OS	F(000) = 472
M_r = 229.69	D_x = 1.503 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8344 reflections
a = 5.8303 (4) Å	θ = 1.7–26.2°
b = 23.6579 (17) Å	µ = 0.55 mm⁻¹
c = 7.5893 (5) Å	T = 296 K
β = 104.164 (6)°	Prism, colourless
V = 1014.99 (12) Å³	0.52 × 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 focus	1524 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.051
Detector resolution: 6.67 pixels mm^-1	θ_max = 25.6°, θ_min = 1.7°
ω scans	h = −5→7
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −28→26
T_min = 0.763, T_max = 0.957	l = −9→9
4469 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0681P)² + 0.120P] where P = (F_o² + 2F_c²)/3
1895 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₈H₈ClN₃OS	V = 1014.99 (12) Å³
M_r = 229.69	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.8303 (4) Å	µ = 0.55 mm⁻¹
b = 23.6579 (17) Å	T = 296 K
c = 7.5893 (5) Å	0.52 × 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)
T_min = 0.763, T_max = 0.957	R_int = 0.051
4469 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.04	Δρ_max = 0.20 e Å⁻³
1895 reflections	Δρ_min = −0.37 e Å⁻³
128 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.36123 (17)	0.20555 (4)	−0.30970 (10)	0.0868 (3)
S1	0.15507 (9)	0.01021 (3)	0.79551 (8)	0.0559 (2)
O1	0.8537 (3)	0.13549 (11)	0.4272 (3)	0.0750 (8)
N1	0.4525 (3)	0.08332 (9)	0.4467 (3)	0.0489 (6)
N2	0.3002 (3)	0.05468 (10)	0.5260 (3)	0.0523 (6)
N3	0.5874 (3)	0.04298 (10)	0.7883 (3)	0.0524 (7)
C1	0.4996 (4)	0.13306 (11)	0.1830 (3)	0.0493 (8)
C2	0.7333 (4)	0.15067 (12)	0.2573 (4)	0.0573 (8)
C3	0.8480 (5)	0.18395 (14)	0.1559 (4)	0.0687 (10)
C4	0.7368 (6)	0.20095 (13)	−0.0164 (4)	0.0702 (10)
C5	0.5049 (5)	0.18372 (12)	−0.0912 (4)	0.0604 (9)
C6	0.3886 (5)	0.15099 (11)	0.0062 (3)	0.0542 (8)
C7	0.3665 (4)	0.09979 (11)	0.2818 (3)	0.0507 (8)
C8	0.3636 (4)	0.03756 (11)	0.6999 (3)	0.0454 (7)
H1	0.76270	0.12040	0.48000	0.1120*
H2	0.15960	0.04740	0.46260	0.0630*
H3	1.00350	0.19500	0.20550	0.0830*
H3A	0.68790	0.05710	0.73440	0.0630*
H3B	0.63280	0.03240	0.89980	0.0630*
H4	0.81520	0.22370	−0.08260	0.0840*
H6	0.23310	0.14030	−0.04510	0.0650*
H7	0.21210	0.08970	0.22430	0.0610*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1118 (7)	0.0820 (6)	0.0700 (4)	0.0054 (5)	0.0287 (4)	0.0188 (4)
S1	0.0349 (3)	0.0795 (5)	0.0526 (3)	−0.0048 (3)	0.0096 (2)	0.0063 (3)
O1	0.0458 (10)	0.0951 (17)	0.0791 (12)	−0.0077 (10)	0.0058 (9)	0.0132 (11)
N1	0.0379 (9)	0.0554 (12)	0.0544 (10)	−0.0011 (8)	0.0131 (8)	0.0019 (9)
N2	0.0336 (9)	0.0683 (14)	0.0529 (10)	−0.0059 (9)	0.0065 (8)	0.0074 (9)
N3	0.0334 (9)	0.0742 (15)	0.0485 (10)	−0.0031 (9)	0.0079 (7)	0.0017 (9)
C1	0.0447 (12)	0.0466 (14)	0.0597 (13)	0.0017 (10)	0.0189 (10)	−0.0007 (10)
C2	0.0453 (12)	0.0558 (16)	0.0729 (15)	0.0009 (11)	0.0186 (11)	0.0020 (12)
C3	0.0489 (14)	0.0623 (18)	0.100 (2)	−0.0044 (12)	0.0281 (14)	0.0079 (15)
C4	0.0725 (17)	0.0577 (18)	0.0926 (19)	0.0020 (14)	0.0438 (15)	0.0108 (15)
C5	0.0729 (17)	0.0490 (15)	0.0653 (14)	0.0056 (13)	0.0283 (12)	0.0030 (11)
C6	0.0540 (13)	0.0505 (15)	0.0595 (12)	0.0029 (11)	0.0168 (10)	−0.0014 (11)
C7	0.0403 (12)	0.0544 (15)	0.0570 (12)	0.0002 (10)	0.0111 (10)	0.0015 (11)
C8	0.0344 (10)	0.0510 (14)	0.0505 (11)	0.0009 (9)	0.0096 (9)	−0.0029 (10)

Geometric parameters (Å, º) top

Cl1—C5	1.743 (3)	C1—C2	1.404 (4)
S1—C8	1.690 (2)	C1—C6	1.405 (3)
O1—C2	1.357 (4)	C1—C7	1.438 (3)
O1—H1	0.8200	C2—C3	1.383 (4)
N1—N2	1.368 (3)	C3—C4	1.370 (4)
N1—C7	1.289 (3)	C4—C5	1.393 (5)
N2—C8	1.343 (3)	C5—C6	1.361 (4)
N3—C8	1.319 (3)	C3—H3	0.9300
N2—H2	0.8600	C4—H4	0.9300
N3—H3A	0.8600	C6—H6	0.9300
N3—H3B	0.8600	C7—H7	0.9300

Cl1···C5ⁱ	3.606 (3)	C7···C8^vi	3.598 (4)
S1···N3ⁱⁱ	3.387 (2)	C7···N3^vi	3.440 (4)
S1···N2ⁱⁱⁱ	3.491 (2)	C7···C3ⁱⁱ	3.550 (4)
S1···N3^iv	3.390 (2)	C8···C7^vi	3.598 (4)
S1···H3Aⁱⁱ	2.8700	C8···C6^vii	3.530 (3)
S1···H2ⁱⁱⁱ	2.7000	C8···N1^vi	3.339 (3)
S1···H3B^iv	2.5500	C3···H7^v	3.0300
S1···H7ⁱⁱⁱ	3.1700	C3···H4^viii	2.9900
O1···N1	2.681 (3)	C7···H3ⁱⁱ	3.0500
O1···N2^v	3.168 (3)	C7···H1	2.4800
O1···H2^v	2.7100	H1···N1	1.9700
N1···O1	2.681 (3)	H1···C7	2.4800
N1···N3	2.693 (3)	H1···H3A	2.5600
N1···C8^vi	3.339 (3)	H2···O1ⁱⁱ	2.7100
N2···O1ⁱⁱ	3.168 (3)	H2···H7	2.1500
N2···S1ⁱⁱⁱ	3.491 (2)	H2···S1ⁱⁱⁱ	2.7000
N3···C6^vii	3.398 (3)	H3···C7^v	3.0500
N3···S1^iv	3.390 (2)	H3A···S1^v	2.8700
N3···S1^v	3.387 (2)	H3A···N1	2.3600
N3···N1	2.693 (3)	H3A···H1	2.5600
N3···C7^vi	3.440 (4)	H3B···S1^iv	2.5500
N1···H1	1.9700	H4···C3ⁱ	2.9900
N1···H3A	2.3600	H6···H7	2.4000
C3···C7^v	3.550 (4)	H7···C3ⁱⁱ	3.0300
C5···Cl1^viii	3.606 (3)	H7···H2	2.1500
C6···N3^ix	3.398 (3)	H7···H6	2.4000
C6···C8^ix	3.530 (3)	H7···S1ⁱⁱⁱ	3.1700

C2—O1—H1	109.00	Cl1—C5—C4	119.6 (2)
N2—N1—C7	115.9 (2)	Cl1—C5—C6	119.9 (2)
N1—N2—C8	122.0 (2)	C4—C5—C6	120.5 (3)
C8—N2—H2	119.00	C1—C6—C5	121.1 (3)
N1—N2—H2	119.00	N1—C7—C1	122.7 (2)
H3A—N3—H3B	120.00	N2—C8—N3	118.1 (2)
C8—N3—H3A	120.00	S1—C8—N2	118.92 (18)
C8—N3—H3B	120.00	S1—C8—N3	123.01 (18)
C2—C1—C6	118.0 (2)	C2—C3—H3	119.00
C6—C1—C7	118.8 (2)	C4—C3—H3	119.00
C2—C1—C7	123.2 (2)	C3—C4—H4	120.00
O1—C2—C1	121.9 (2)	C5—C4—H4	120.00
C1—C2—C3	120.0 (3)	C1—C6—H6	119.00
O1—C2—C3	118.1 (2)	C5—C6—H6	119.00
C2—C3—C4	121.2 (3)	N1—C7—H7	119.00
C3—C4—C5	119.2 (3)	C1—C7—H7	119.00

C7—N1—N2—C8	−176.7 (2)	C6—C1—C2—C3	−0.9 (4)
N2—N1—C7—C1	176.5 (2)	C7—C1—C2—O1	2.5 (4)
N1—N2—C8—S1	171.99 (18)	O1—C2—C3—C4	−179.8 (3)
N1—N2—C8—N3	−8.0 (4)	C1—C2—C3—C4	0.9 (5)
C7—C1—C2—C3	−178.2 (3)	C2—C3—C4—C5	−0.8 (5)
C2—C1—C6—C5	1.0 (4)	C3—C4—C5—Cl1	179.5 (2)
C7—C1—C6—C5	178.3 (3)	C3—C4—C5—C6	0.8 (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—O1	179.8 (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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.97	2.681 (3)	144
N2—H2···S1ⁱⁱⁱ	0.86	2.70	3.491 (2)	153
N3—H3A···S1^v	0.86	2.87	3.387 (2)	120
N3—H3A···N1	0.86	2.36	2.693 (3)	103
N3—H3B···S1^iv	0.86	2.55	3.390 (2)	167

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

Experimental details

Crystal data
Chemical formula	C₈H₈ClN₃OS
M_r	229.69
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	5.8303 (4), 23.6579 (17), 7.5893 (5)
β (°)	104.164 (6)
V (Å³)	1014.99 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.55
Crystal size (mm)	0.52 × 0.33 × 0.08

Data collection
Diffractometer	Stoe IPDS II
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.763, 0.957
No. of measured, independent and observed [I > 2σ(I)] reflections	4469, 1895, 1524
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.120, 1.04
No. of reflections	1895
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.37

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.97	2.681 (3)	144
N2—H2···S1ⁱ	0.86	2.70	3.491 (2)	153
N3—H3A···S1ⁱⁱ	0.86	2.87	3.387 (2)	120
N3—H3A···N1	0.86	2.36	2.693 (3)	103
N3—H3B···S1ⁱⁱⁱ	0.86	2.55	3.390 (2)	167

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

Acknowledgements

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.

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