5-Chloro-2-hy­droxy­benzaldehyde 4-ethyl­thio­semicarbazone

Lo, K.M.; Ng, S.W.

doi:10.1107/S160053681101796X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1453

doi:10.1107/S160053681101796X

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5-Chloro-2-hydroxybenzaldehyde 4-ethylthiosemicarbazone

Kong Mun Lo ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 9 May 2011; accepted 12 May 2011; online 20 May 2011)

In the title compound, C₁₀H₁₂ClN₃OS, the –C=N–N–C– chain bridging the ethylimino group and the benzene ring adopts an extended conformation with a C—N—N—C torsion angle of −171.98 (11)°. The imino H atom of the chain is a hydrogen-bond donor to the S atom of an inversion-related molecule, forming a supramolecular dimer. The hydroxy H atom is intramolecularly hydrogen bonded to the azomethine N atom.

Related literature

For the salicylaldehyde 4-methylthiosemicarbazone homolog, see: Vrdoljak et al. (2005 ).

Experimental

Crystal data

C₁₀H₁₂ClN₃OS
M_r = 257.74
Monoclinic, C 2/c
a = 21.7956 (3) Å
b = 11.8536 (2) Å
c = 9.4155 (1) Å
β = 101.6870 (9)°
V = 2382.12 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 100 K
0.40 × 0.40 × 0.40 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.832, T_max = 0.832
11204 measured reflections
2985 independent reflections
2582 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.085
S = 1.02
2985 reflections
157 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯N1	0.84 (1)	1.92 (1)	2.670 (2)	149 (2)
N2—H2n⋯S1ⁱ	0.87 (1)	2.48 (1)	3.308 (1)	159 (1)
Symmetry code: (i) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681101796X/xu5210sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681101796X/xu5210Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681101796X/xu5210Isup3.cml

checkCIF report

Comment top

Salicylaldehyde condenses with a large number of 4-alkyl/aryl-3-thiosemicarbazide to yield the corresponding thiosemicarbazone Schiff-bases. These compounds are used as chelating ligands to a range of metal ions. The semicarbazones, as exemplified by the salicylaldehyde 4-methyl-3-thiosemicarbazone homolog (Vrdoljak et al., 2005), feature an N–H···S hydrogen bond that connects two molecules into a hydrogen-bonded dimer. In C₁₀H₁₂ClN₃OS, the –C═N–N–C– chain separating the double-bond S atom and the benzene ring adopts an extended zigzag conformation (Fig.1). The amino H atom of the chain is hydrogen-bond donor to the S atom of an inversion-related molecule to form a dimer. The H atom of the hydroxy unit is hydrogen bond donor to the azomethine N atom. The other amino H atom is only weakly involved in hydrogen bonding (Table 1).

Related literature top

For the salicylaldehyde 4-methylthiosemicarbazone homolog, see: Vrdoljak et al. (2005).

Experimental top

5-Chloro-2-hydroxybenzaldehyde (3.1 g, 20 mol) and of 4-ethyl-3-thiosemicarbazide (2.4 g, 20 mmol) were heated in ethanol (100 ml) for an hour. The solution was filtered and colorless crystals were obtained upon slow evaporation of the solvent.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₀H₁₂ClN₃OS at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

5-Chloro-2-hydroxybenzaldehyde 4-ethylthiosemicarbazone top

Crystal data top

C₁₀H₁₂ClN₃OS	F(000) = 1072
M_r = 257.74	D_x = 1.437 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6011 reflections
a = 21.7956 (3) Å	θ = 2.8–28.3°
b = 11.8536 (2) Å	µ = 0.48 mm⁻¹
c = 9.4155 (1) Å	T = 100 K
β = 101.6870 (9)°	Block, colorless
V = 2382.12 (6) Å³	0.40 × 0.40 × 0.40 mm
Z = 8

Data collection top

Bruker SMART APEX diffractometer	2985 independent reflections
Radiation source: fine-focus sealed tube	2582 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 28.4°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −29→29
T_min = 0.832, T_max = 0.832	k = −15→15
11204 measured reflections	l = −12→12

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0483P)² + 1.7745P] where P = (F_o² + 2F_c²)/3
2985 reflections	(Δ/σ)_max = 0.001
157 parameters	Δρ_max = 0.33 e Å⁻³
3 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₀H₁₂ClN₃OS	V = 2382.12 (6) Å³
M_r = 257.74	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 21.7956 (3) Å	µ = 0.48 mm⁻¹
b = 11.8536 (2) Å	T = 100 K
c = 9.4155 (1) Å	0.40 × 0.40 × 0.40 mm
β = 101.6870 (9)°

Data collection top

Bruker SMART APEX diffractometer	2985 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2582 reflections with I > 2σ(I)
T_min = 0.832, T_max = 0.832	R_int = 0.022
11204 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	3 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.33 e Å⁻³
2985 reflections	Δρ_min = −0.28 e Å⁻³
157 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.485785 (16)	0.65980 (4)	0.51634 (4)	0.03990 (13)
S1	0.835591 (14)	0.65767 (3)	−0.01381 (3)	0.01821 (10)
O1	0.75861 (4)	0.62629 (8)	0.57947 (10)	0.01950 (19)
N1	0.73919 (5)	0.61554 (8)	0.29057 (11)	0.0159 (2)
N2	0.75536 (5)	0.63100 (9)	0.15711 (11)	0.0167 (2)
N3	0.85219 (5)	0.55435 (9)	0.24435 (11)	0.0169 (2)
C1	0.69537 (6)	0.62896 (10)	0.56025 (13)	0.0160 (2)
C2	0.66935 (6)	0.63906 (10)	0.68348 (14)	0.0189 (2)
H2	0.6959	0.6406	0.7769	0.023*
C3	0.60511 (6)	0.64685 (11)	0.67054 (14)	0.0215 (3)
H3	0.5875	0.6549	0.7544	0.026*
C4	0.56661 (6)	0.64280 (12)	0.53368 (15)	0.0230 (3)
C5	0.59099 (6)	0.63056 (11)	0.41045 (14)	0.0203 (3)
H5	0.5638	0.6262	0.3180	0.024*
C6	0.65605 (5)	0.62453 (10)	0.42189 (13)	0.0160 (2)
C7	0.68017 (5)	0.62429 (10)	0.28864 (13)	0.0166 (2)
H7	0.6517	0.6307	0.1982	0.020*
C8	0.81461 (5)	0.61070 (10)	0.14031 (12)	0.0152 (2)
C9	0.91574 (5)	0.51980 (11)	0.23606 (13)	0.0199 (2)
H9A	0.9414	0.5132	0.3353	0.024*
H9B	0.9350	0.5783	0.1840	0.024*
C10	0.91595 (6)	0.40780 (12)	0.15821 (14)	0.0235 (3)
H10A	0.9591	0.3872	0.1542	0.035*
H10B	0.8911	0.4144	0.0594	0.035*
H10C	0.8977	0.3494	0.2107	0.035*
H1O	0.7673 (10)	0.6201 (18)	0.4975 (14)	0.057 (6)*
H2N	0.7319 (6)	0.6770 (11)	0.0975 (14)	0.017 (4)*
H3N	0.8351 (7)	0.5207 (13)	0.3075 (15)	0.026 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01591 (17)	0.0783 (3)	0.0285 (2)	0.00085 (16)	0.01169 (14)	0.00069 (17)
S1	0.01839 (16)	0.02150 (16)	0.01680 (15)	0.00297 (10)	0.00847 (12)	0.00232 (11)
O1	0.0152 (4)	0.0239 (5)	0.0195 (4)	0.0018 (3)	0.0039 (3)	0.0007 (4)
N1	0.0165 (5)	0.0162 (5)	0.0165 (5)	0.0003 (4)	0.0072 (4)	0.0002 (4)
N2	0.0151 (5)	0.0210 (5)	0.0152 (5)	0.0030 (4)	0.0061 (4)	0.0030 (4)
N3	0.0144 (4)	0.0207 (5)	0.0166 (5)	0.0012 (4)	0.0055 (4)	0.0015 (4)
C1	0.0163 (5)	0.0135 (5)	0.0189 (5)	0.0006 (4)	0.0054 (4)	0.0010 (4)
C2	0.0218 (6)	0.0191 (6)	0.0163 (5)	−0.0002 (4)	0.0047 (5)	−0.0004 (4)
C3	0.0241 (6)	0.0238 (6)	0.0193 (6)	−0.0001 (5)	0.0106 (5)	0.0001 (5)
C4	0.0152 (6)	0.0318 (7)	0.0241 (6)	−0.0007 (5)	0.0092 (5)	0.0011 (5)
C5	0.0172 (6)	0.0263 (6)	0.0183 (6)	−0.0019 (5)	0.0053 (5)	0.0013 (5)
C6	0.0163 (5)	0.0162 (5)	0.0170 (5)	−0.0007 (4)	0.0070 (4)	0.0003 (4)
C7	0.0164 (5)	0.0175 (5)	0.0167 (5)	−0.0009 (4)	0.0053 (4)	0.0006 (4)
C8	0.0148 (5)	0.0157 (5)	0.0159 (5)	−0.0010 (4)	0.0047 (4)	−0.0031 (4)
C9	0.0127 (5)	0.0251 (6)	0.0217 (6)	0.0022 (4)	0.0031 (4)	0.0000 (5)
C10	0.0185 (6)	0.0273 (7)	0.0248 (6)	0.0043 (5)	0.0046 (5)	−0.0015 (5)

Geometric parameters (Å, º) top

Cl1—C4	1.7476 (13)	C2—H2	0.9500
S1—C8	1.7011 (12)	C3—C4	1.3889 (19)
O1—C1	1.3539 (14)	C3—H3	0.9500
O1—H1O	0.835 (9)	C4—C5	1.3782 (18)
N1—C7	1.2870 (15)	C5—C6	1.4020 (16)
N1—N2	1.3842 (13)	C5—H5	0.9500
N2—C8	1.3541 (14)	C6—C7	1.4552 (16)
N2—H2N	0.870 (9)	C7—H7	0.9500
N3—C8	1.3234 (15)	C9—C10	1.5169 (18)
N3—C9	1.4615 (14)	C9—H9A	0.9900
N3—H3N	0.860 (9)	C9—H9B	0.9900
C1—C2	1.3959 (17)	C10—H10A	0.9800
C1—C6	1.4078 (17)	C10—H10B	0.9800
C2—C3	1.3837 (17)	C10—H10C	0.9800

C1—O1—H1O	107.2 (15)	C6—C5—H5	120.1
C7—N1—N2	114.46 (10)	C5—C6—C1	119.07 (11)
C8—N2—N1	120.45 (10)	C5—C6—C7	118.05 (11)
C8—N2—H2N	119.1 (10)	C1—C6—C7	122.65 (11)
N1—N2—H2N	116.3 (10)	N1—C7—C6	121.50 (11)
C8—N3—C9	123.58 (10)	N1—C7—H7	119.2
C8—N3—H3N	117.1 (11)	C6—C7—H7	119.2
C9—N3—H3N	117.0 (11)	N3—C8—N2	117.72 (10)
O1—C1—C2	117.70 (11)	N3—C8—S1	124.30 (9)
O1—C1—C6	122.36 (11)	N2—C8—S1	117.97 (9)
C2—C1—C6	119.92 (11)	N3—C9—C10	111.51 (10)
C3—C2—C1	120.44 (12)	N3—C9—H9A	109.3
C3—C2—H2	119.8	C10—C9—H9A	109.3
C1—C2—H2	119.8	N3—C9—H9B	109.3
C2—C3—C4	119.33 (12)	C10—C9—H9B	109.3
C2—C3—H3	120.3	H9A—C9—H9B	108.0
C4—C3—H3	120.3	C9—C10—H10A	109.5
C5—C4—C3	121.41 (12)	C9—C10—H10B	109.5
C5—C4—Cl1	119.13 (10)	H10A—C10—H10B	109.5
C3—C4—Cl1	119.40 (10)	C9—C10—H10C	109.5
C4—C5—C6	119.81 (12)	H10A—C10—H10C	109.5
C4—C5—H5	120.1	H10B—C10—H10C	109.5

C7—N1—N2—C8	−171.98 (11)	C2—C1—C6—C5	0.09 (17)
O1—C1—C2—C3	177.38 (11)	O1—C1—C6—C7	−4.18 (17)
C6—C1—C2—C3	−1.19 (18)	C2—C1—C6—C7	174.32 (12)
C1—C2—C3—C4	0.97 (19)	N2—N1—C7—C6	−172.18 (10)
C2—C3—C4—C5	0.4 (2)	C5—C6—C7—N1	−177.90 (11)
C2—C3—C4—Cl1	−176.77 (10)	C1—C6—C7—N1	7.82 (18)
C3—C4—C5—C6	−1.5 (2)	C9—N3—C8—N2	175.63 (11)
Cl1—C4—C5—C6	175.68 (10)	C9—N3—C8—S1	−3.54 (17)
C4—C5—C6—C1	1.21 (18)	N1—N2—C8—N3	13.77 (17)
C4—C5—C6—C7	−173.28 (12)	N1—N2—C8—S1	−167.01 (8)
O1—C1—C6—C5	−178.40 (11)	C8—N3—C9—C10	−85.80 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N1	0.84 (1)	1.92 (1)	2.670 (2)	149 (2)
N2—H2n···S1ⁱ	0.87 (1)	2.48 (1)	3.308 (1)	159 (1)

Symmetry code: (i) −x+3/2, −y+3/2, −z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂ClN₃OS
M_r	257.74
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	21.7956 (3), 11.8536 (2), 9.4155 (1)
β (°)	101.6870 (9)
V (Å³)	2382.12 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.48
Crystal size (mm)	0.40 × 0.40 × 0.40

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.832, 0.832
No. of measured, independent and observed [I > 2σ(I)] reflections	11204, 2985, 2582
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.085, 1.02
No. of reflections	2985
No. of parameters	157
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.28

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N1	0.84 (1)	1.92 (1)	2.670 (2)	149 (2)
N2—H2n···S1ⁱ	0.87 (1)	2.48 (1)	3.308 (1)	159 (1)

Symmetry code: (i) −x+3/2, −y+3/2, −z.

Acknowledgements

We thank the University of Malaya (gant No. RG020/09AFR) for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vrdoljak, V., Cindrić, M., Milić, D., Matković-Čalogović, D., Novak, P. & Kamenar, B. (2005). Polyhedron, 24, 1717–1726. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar