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

Abstract

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 R ₂ ²(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,

• a = 5.4339 (11) Å

• b = 20.526 (4) Å

• c = 11.313 (2) Å

• β = 101.97 (3)°

• V = 1234.4 (4) ų

• 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[F ² > 2σ(F ²)] = 0.060

• wR(F ²) = 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

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.

Supplementary Material

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
N2—H2A⋯S1i	0.86	2.56	3.409 (5)	168

Symmetry code: (i) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H distances=0.97 Å, and with U_iso=1.2–1.5U_eq.

Figures

Fig. 1.

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

Crystal data

C10H11Cl2N3S	F(000) = 568
Mr = 276.18	Dx = 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

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

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.187	H-atom parameters constrained
S = 0.92	w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
2707 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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

Symmetry codes: (i) −x, −y+2, −z+2.