1-(2,4-Dichloro­benzyl­idene)-4-ethyl­thio­semicarbazide

Li, Y.-F.

doi:10.1107/S1600536810035671

organic compounds

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Volume 66| Part 10| October 2010| Page o2550

doi:10.1107/S1600536810035671

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1-(2,4-Dichlorobenzylidene)-4-ethylthiosemicarbazide

Yu-Feng Li ^a ^*

^aMicroscale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: liyufeng8111@163.com

(Received 31 August 2010; accepted 6 September 2010; online 11 September 2010)

The title compound, C₁₀H₁₁Cl₂N₃S, was prepared by the reaction of 4-ethylthiosemicarbazide and 2,4-dichlorobenzaldehyde. It is approximately planar, the dihedral angle between the benzene ring and the thiourea unit being 8.43 (18)°. In the crystal, inversion dimers linked by pairs of N—H⋯S hydrogen bonds generate R₂²(8) loops.

Related literature

For background to Schiff bases, see: Casas et al. (2000 ). For a related structure, see: Li & Jian (2010 ).

Experimental

Crystal data

C₁₀H₁₁Cl₂N₃S
M_r = 276.18
Monoclinic, P 2₁ /n
a = 5.4339 (11) Å
b = 20.526 (4) Å
c = 11.313 (2) Å
β = 101.97 (3)°
V = 1234.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.67 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
10913 measured reflections
2707 independent reflections
1416 reflections with I > 2σ(I)
R_int = 0.109

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.187
S = 0.92
2707 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯S1ⁱ	0.86	2.56	3.409 (5)	168
Symmetry code: (i) -x, -y+2, -z+2.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810035671/hb5632sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810035671/hb5632Isup2.hkl

checkCIF report

Comment top

Schiff-base have attracted much attention because they can be utilized as effective ligands to be coordination compounds in coordination chemistry. (Casas et al., 2000). As part of our research for new Schiff-base compounds we synthesized the title compound (I), and describe its structure here. In the molecule structure, the dihedral angle between the benzene ring and the thiourea unit is [8.43 (18)°].

Bond lengths and angles agree with those observed in a related structure (Li & Jian, 2010).

Related literature top

For background to Schiff bases, see: Casas et al. (2000). For a related structure, see: Li & Jian (2010).

Experimental top

A mixture of 4-ethylthiosemicarbazide (0.1 mol) and 2,4-dichlorobenzaldehyde (0.1 mol) was stirred in refluxing ethanol (30 mL) for 2 h to afford the title compound (0.090 mol, yield 90%). Colourless blocks of (I) were obtained by recrystallization from ethanol at room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of (I) showing 30% probability displacement ellipsoids.

1-(2,4-Dichlorobenzylidene)-4-ethylthiosemicarbazide top

Crystal data top

C₁₀H₁₁Cl₂N₃S	F(000) = 568
M_r = 276.18	D_x = 1.486 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1416 reflections
a = 5.4339 (11) Å	θ = 3.5–27.5°
b = 20.526 (4) Å	µ = 0.67 mm⁻¹
c = 11.313 (2) Å	T = 293 K
β = 101.97 (3)°	Block, colorless
V = 1234.4 (4) Å³	0.22 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1416 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.109
Graphite monochromator	θ_max = 27.5°, θ_min = 3.5°
phi and ω scans	h = −6→6
10913 measured reflections	k = −26→26
2707 independent reflections	l = −14→14

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.187	H-atom parameters constrained
S = 0.92	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
2707 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₀H₁₁Cl₂N₃S	V = 1234.4 (4) Å³
M_r = 276.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.4339 (11) Å	µ = 0.67 mm⁻¹
b = 20.526 (4) Å	T = 293 K
c = 11.313 (2) Å	0.22 × 0.20 × 0.18 mm
β = 101.97 (3)°

Data collection top

Bruker SMART CCD diffractometer	1416 reflections with I > 2σ(I)
10913 measured reflections	R_int = 0.109
2707 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.187	H-atom parameters constrained
S = 0.92	Δρ_max = 0.37 e Å⁻³
2707 reflections	Δρ_min = −0.35 e Å⁻³
145 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) 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
S1	−0.1063 (2)	0.99987 (6)	0.79802 (13)	0.0434 (4)
Cl2	0.7303 (2)	0.85591 (6)	1.34950 (13)	0.0499 (4)
Cl1	1.4115 (2)	0.70212 (6)	1.20880 (15)	0.0558 (4)
N3	0.4756 (6)	0.90330 (15)	0.9707 (4)	0.0355 (9)
N2	0.2667 (7)	0.94274 (17)	0.9454 (4)	0.0390 (9)
H2A	0.2030	0.9583	1.0029	0.047*
N1	0.2795 (7)	0.93533 (18)	0.7450 (4)	0.0410 (10)
H1A	0.4117	0.9118	0.7681	0.049*
C5	0.7795 (7)	0.84768 (18)	1.1156 (4)	0.0317 (10)
C3	0.1623 (7)	0.95672 (19)	0.8288 (4)	0.0324 (10)
C8	1.1713 (8)	0.7596 (2)	1.1742 (5)	0.0381 (11)
C9	1.0643 (8)	0.78286 (19)	1.2644 (5)	0.0393 (12)
H9A	1.1209	0.7695	1.3440	0.047*
C4	0.5640 (8)	0.89200 (19)	1.0829 (5)	0.0373 (11)
H4A	0.4932	0.9114	1.1423	0.045*
C7	1.0936 (9)	0.7793 (2)	1.0562 (5)	0.0418 (12)
H7A	1.1715	0.7632	0.9964	0.050*
C10	0.8684 (8)	0.82717 (19)	1.2342 (4)	0.0332 (10)
C6	0.8994 (8)	0.8232 (2)	1.0276 (5)	0.0384 (11)
H6A	0.8471	0.8368	0.9480	0.046*
C2	0.2011 (10)	0.9487 (3)	0.6169 (5)	0.0492 (13)
H2B	0.2201	0.9949	0.6029	0.059*
H2C	0.0246	0.9377	0.5906	0.059*
C1	0.3510 (11)	0.9109 (3)	0.5440 (6)	0.0641 (16)
H1B	0.2935	0.9209	0.4599	0.096*
H1C	0.3306	0.8651	0.5567	0.096*
H1D	0.5255	0.9223	0.5686	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0362 (7)	0.0577 (7)	0.0350 (8)	0.0114 (4)	0.0044 (5)	0.0005 (5)
Cl2	0.0628 (8)	0.0614 (7)	0.0280 (8)	0.0123 (5)	0.0151 (6)	0.0009 (6)
Cl1	0.0561 (8)	0.0551 (7)	0.0546 (11)	0.0202 (5)	0.0078 (7)	0.0014 (6)
N3	0.037 (2)	0.0394 (19)	0.030 (3)	0.0028 (13)	0.0062 (17)	0.0035 (16)
N2	0.039 (2)	0.051 (2)	0.026 (3)	0.0122 (15)	0.0047 (17)	0.0013 (17)
N1	0.037 (2)	0.054 (2)	0.030 (3)	0.0091 (15)	0.0019 (18)	0.0029 (18)
C5	0.039 (2)	0.030 (2)	0.025 (3)	−0.0023 (15)	0.0038 (19)	0.0018 (17)
C3	0.031 (2)	0.040 (2)	0.026 (3)	−0.0020 (16)	0.0043 (19)	−0.0015 (18)
C8	0.040 (2)	0.038 (2)	0.034 (3)	0.0015 (17)	0.003 (2)	−0.0022 (19)
C9	0.045 (3)	0.041 (2)	0.029 (3)	0.0050 (17)	−0.001 (2)	0.0030 (19)
C4	0.038 (2)	0.042 (2)	0.030 (3)	0.0049 (17)	0.004 (2)	−0.0011 (19)
C7	0.045 (3)	0.047 (2)	0.035 (3)	0.0042 (18)	0.012 (2)	−0.007 (2)
C10	0.041 (2)	0.037 (2)	0.022 (3)	0.0003 (16)	0.0089 (19)	−0.0005 (18)
C6	0.045 (3)	0.047 (2)	0.023 (3)	0.0012 (18)	0.005 (2)	−0.003 (2)
C2	0.055 (3)	0.066 (3)	0.025 (3)	0.011 (2)	0.004 (2)	0.004 (2)
C1	0.057 (3)	0.099 (4)	0.038 (4)	0.015 (3)	0.013 (3)	−0.004 (3)

Geometric parameters (Å, º) top

S1—C3	1.681 (4)	C8—C7	1.376 (7)
Cl2—C10	1.738 (5)	C9—C10	1.388 (6)
Cl1—C8	1.743 (4)	C9—H9A	0.9300
N3—C4	1.282 (6)	C4—H4A	0.9300
N3—N2	1.375 (5)	C7—C6	1.373 (6)
N2—C3	1.354 (6)	C7—H7A	0.9300
N2—H2A	0.8600	C6—H6A	0.9300
N1—C3	1.322 (6)	C2—C1	1.491 (7)
N1—C2	1.449 (7)	C2—H2B	0.9700
N1—H1A	0.8600	C2—H2C	0.9700
C5—C6	1.392 (7)	C1—H1B	0.9600
C5—C10	1.393 (6)	C1—H1C	0.9600
C5—C4	1.468 (6)	C1—H1D	0.9600
C8—C9	1.362 (7)

C4—N3—N2	115.8 (4)	C6—C7—C8	119.2 (5)
C3—N2—N3	119.2 (4)	C6—C7—H7A	120.4
C3—N2—H2A	120.4	C8—C7—H7A	120.4
N3—N2—H2A	120.4	C9—C10—C5	122.1 (4)
C3—N1—C2	124.7 (4)	C9—C10—Cl2	117.8 (4)
C3—N1—H1A	117.7	C5—C10—Cl2	120.2 (3)
C2—N1—H1A	117.7	C7—C6—C5	121.3 (5)
C6—C5—C10	117.3 (4)	C7—C6—H6A	119.3
C6—C5—C4	120.7 (4)	C5—C6—H6A	119.3
C10—C5—C4	121.9 (4)	N1—C2—C1	111.9 (4)
N1—C3—N2	117.5 (4)	N1—C2—H2B	109.2
N1—C3—S1	123.6 (4)	C1—C2—H2B	109.2
N2—C3—S1	118.9 (4)	N1—C2—H2C	109.2
C9—C8—C7	122.1 (4)	C1—C2—H2C	109.2
C9—C8—Cl1	119.0 (4)	H2B—C2—H2C	107.9
C7—C8—Cl1	118.8 (4)	C2—C1—H1B	109.5
C8—C9—C10	118.0 (5)	C2—C1—H1C	109.5
C8—C9—H9A	121.0	H1B—C1—H1C	109.5
C10—C9—H9A	121.0	C2—C1—H1D	109.5
N3—C4—C5	118.5 (5)	H1B—C1—H1D	109.5
N3—C4—H4A	120.8	H1C—C1—H1D	109.5
C5—C4—H4A	120.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1ⁱ	0.86	2.56	3.409 (5)	168

Symmetry code: (i) −x, −y+2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁Cl₂N₃S
M_r	276.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	5.4339 (11), 20.526 (4), 11.313 (2)
β (°)	101.97 (3)
V (Å³)	1234.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.67
Crystal size (mm)	0.22 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10913, 2707, 1416
R_int	0.109
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.187, 0.92
No. of reflections	2707
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.35

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1ⁱ	0.86	2.56	3.409 (5)	168

Symmetry code: (i) −x, −y+2, −z+2.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Casas, J. S., Garcia-T, M. S. & Sordo, J. (2000). Coord. Chem. Rev. 209, 197–261. Web of Science CrossRef CAS Google Scholar
Li, Y.-F. & Jian, F.-F. (2010). Acta Cryst. E66, o1399. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2550

doi:10.1107/S1600536810035671

Open

access