5-Chloro-2-hy­droxy­benzaldehyde 4-ethyl­thio­semicarbazone

Abstract

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,

• a = 21.7956 (3) Å

• b = 11.8536 (2) Å

• c = 9.4155 (1) Å

• β = 101.6870 (9)°

• V = 2382.12 (6) ų

• 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[F ² > 2σ(F ²)] = 0.029

• wR(F ²) = 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

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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S160053681101796X/xu5210Isup3.cml

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

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) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with U_iso(H) =1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for the others. The hydroxy and amino H atoms were located in a difference Fourier map, and were refined with distance restraints of O—H 0.84±0.01 and N—H 0.88±0.01 Å; their temperature factors were freely refined.

Figures

Fig. 1.

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

Crystal data

C10H12ClN3OS	F(000) = 1072
Mr = 257.74	Dx = 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

Bruker SMART APEX diffractometer	2985 independent reflections
Radiation source: fine-focus sealed tube	2582 reflections with I > 2σ(I)
graphite	Rint = 0.022
ω scans	θmax = 28.4°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −29→29
Tmin = 0.832, Tmax = 0.832	k = −15→15
11204 measured reflections	l = −12→12

Refinement

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(Fo2) + (0.0483P)2 + 1.7745P] where P = (Fo2 + 2Fc2)/3
2985 reflections	(Δ/σ)max = 0.001
157 parameters	Δρmax = 0.33 e Å−3
3 restraints	Δρmin = −0.28 e Å−3

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

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) −x+3/2, −y+3/2, −z.