Ethyl 3-(2,4-dichloro­benzyl­idene)carbazate

Li, Y.-F.; Liu, H.-X.; Jian, F.-F.

doi:10.1107/S1600536809044420

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2919

https://doi.org/10.1107/S1600536809044420

Open

access

Ethyl 3-(2,4-dichlorobenzylidene)carbazate

Yu-Feng Li,^a Hai-Xing Liu ^a and Fang-Fang Jian ^b ^*

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

(Received 13 October 2009; accepted 26 October 2009; online 31 October 2009)

The title compound, C₁₀H₁₀Cl₂N₂O₂, was prepared by the reaction of ethyl carbazate and 2,4-dichlorobenzaldehyde. In the crystal structure, molecules are linked by intermolecular N—H⋯O hydrogen bonds, forming extended chains along [001].

Related literature

For applications of Schiff base compounds, see: Cimerman et al. (1997 ). For the C=N double-bond length in a related structure, see: Girgis (2006 ).

Experimental

Crystal data

C₁₀H₁₀Cl₂N₂O₂
M_r = 261.10
Tetragonal, I 4₁ /a
a = 18.021 (3) Å
c = 14.983 (3) Å
V = 4865.8 (14) Å³
Z = 16
Mo Kα radiation
μ = 0.52 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.492, T_max = 0.729
21376 measured reflections
2789 independent reflections
2409 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.121
S = 1.09
2789 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86	2.12	2.927 (2)	156
Symmetry code: (i) $[-y+{\script{3\over 4}}, x+{\script{1\over 4}}, z+{\script{1\over 4}}]$ .

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: https://doi.org/10.1107/S1600536809044420/lh2929sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809044420/lh2929Isup2.hkl

checkCIF report

Comment top

Schiff bases have received considerable attention in the literature and have potential analytical applications (Cimerman et al., 1997). As part of our search for new schiff base compounds we synthesized the title compound (I), and its crystal structure is determined herein.

The molcular structure of (I) is shown in Fig. 1. The C8—N1 bond length of 1.271 (2)Å is comparable with C—N double bond [1.281 (2) Å] reported in a related structure (Girgis, 2006). In the crystal structure, molecules are linked by intermolecular N-H···O hydrogen bonds to form extended chains along [001].

Related literature top

For applications of Schiff base compounds, see: Cimerman et al. (1997). For the C═N double-bond length in a related structure, see: Girgis (2006).

Experimental top

A mixture of the 2,4-dichlorobenzaldehyde (0.1 mol), and Ethyl carbazate (0.1 mol) was stirred in refluxing ethanol (20 mL) for 4 h to afford the title compound (0.080 mol, yield 80%). Single crystals suitable for X-ray measurements were obtained by recrystallization of a solution of (I) in ethanol at room temperature.

Structure description top

For applications of Schiff base compounds, see: Cimerman et al. (1997). For the C═N double-bond length in a related structure, see: Girgis (2006).

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 molecular structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.

Ethyl 3-(2,4-dichlorobenzylidene)carbazate top

Crystal data top

C₁₀H₁₀Cl₂N₂O₂	D_x = 1.426 Mg m⁻³
M_r = 261.10	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/a	Cell parameters from 1977 reflections
Hall symbol: -I 4ad	θ = 3.5–27.4°
a = 18.021 (3) Å	µ = 0.52 mm⁻¹
c = 14.983 (3) Å	T = 293 K
V = 4865.8 (14) Å³	Block, colorless
Z = 16	0.25 × 0.20 × 0.18 mm
F(000) = 2144

Data collection top

Bruker SMART CCD diffractometer	2789 independent reflections
Radiation source: fine-focus sealed tube	2409 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
φ and ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→23
T_min = 0.492, T_max = 0.729	k = −23→23
21376 measured reflections	l = −19→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.0645P)² + 2.5907P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
2789 reflections	Δρ_max = 0.37 e Å⁻³
146 parameters	Δρ_min = −0.50 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0030 (4)

Crystal data top

C₁₀H₁₀Cl₂N₂O₂	Z = 16
M_r = 261.10	Mo Kα radiation
Tetragonal, I4₁/a	µ = 0.52 mm⁻¹
a = 18.021 (3) Å	T = 293 K
c = 14.983 (3) Å	0.25 × 0.20 × 0.18 mm
V = 4865.8 (14) Å³

Data collection top

Bruker SMART CCD diffractometer	2789 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2409 reflections with I > 2σ(I)
T_min = 0.492, T_max = 0.729	R_int = 0.045
21376 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 1.09	Δρ_max = 0.37 e Å⁻³
2789 reflections	Δρ_min = −0.50 e Å⁻³
146 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
Cl1	0.22311 (4)	0.76326 (3)	0.01502 (4)	0.0730 (2)
Cl2	0.09897 (3)	0.79872 (3)	−0.30581 (4)	0.0661 (2)
N2	0.28329 (7)	0.54137 (8)	−0.06890 (9)	0.0376 (3)
O2	0.39424 (7)	0.41332 (7)	0.04214 (8)	0.0474 (3)
N1	0.32058 (8)	0.50259 (8)	−0.00379 (9)	0.0416 (3)
H1A	0.3228	0.5189	0.0501	0.050*
O1	0.34815 (8)	0.40718 (7)	−0.09813 (8)	0.0500 (3)
C8	0.35371 (9)	0.43809 (9)	−0.02677 (10)	0.0362 (3)
C7	0.26094 (9)	0.60548 (10)	−0.04588 (11)	0.0411 (4)
H7A	0.2695	0.6224	0.0119	0.049*
C4	0.22188 (8)	0.65273 (9)	−0.10968 (10)	0.0371 (3)
C2	0.16741 (10)	0.67119 (10)	−0.25620 (11)	0.0440 (4)
H2B	0.1568	0.6534	−0.3130	0.053*
C5	0.20078 (10)	0.72492 (10)	−0.08829 (11)	0.0441 (4)
C3	0.20456 (10)	0.62758 (9)	−0.19537 (11)	0.0414 (4)
H3A	0.2186	0.5798	−0.2119	0.050*
C1	0.14623 (10)	0.74200 (10)	−0.23128 (12)	0.0445 (4)
C6	0.16227 (11)	0.76940 (10)	−0.14764 (13)	0.0498 (4)
H6A	0.1475	0.8170	−0.1314	0.060*
C9	0.44238 (11)	0.35079 (11)	0.02348 (14)	0.0538 (5)
H9A	0.4173	0.3167	−0.0166	0.065*
H9B	0.4529	0.3246	0.0786	0.065*
C10	0.51290 (15)	0.37543 (18)	−0.0177 (2)	0.0908 (9)
H10A	0.5436	0.3330	−0.0297	0.136*
H10B	0.5383	0.4083	0.0225	0.136*
H10C	0.5025	0.4010	−0.0725	0.136*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1010 (5)	0.0595 (3)	0.0586 (3)	0.0176 (3)	−0.0303 (3)	−0.0252 (2)
Cl2	0.0726 (4)	0.0565 (3)	0.0693 (4)	0.0135 (2)	−0.0261 (3)	0.0084 (2)
N2	0.0396 (7)	0.0420 (7)	0.0312 (6)	0.0035 (6)	−0.0042 (5)	0.0013 (5)
O2	0.0540 (7)	0.0566 (7)	0.0316 (6)	0.0170 (6)	−0.0047 (5)	0.0045 (5)
N1	0.0505 (8)	0.0476 (8)	0.0266 (6)	0.0112 (6)	−0.0060 (5)	−0.0019 (5)
O1	0.0713 (8)	0.0455 (6)	0.0332 (6)	0.0116 (6)	−0.0084 (6)	−0.0044 (5)
C8	0.0401 (8)	0.0411 (8)	0.0275 (7)	0.0010 (6)	−0.0002 (6)	0.0048 (6)
C7	0.0445 (8)	0.0457 (9)	0.0332 (7)	0.0056 (7)	−0.0035 (6)	−0.0033 (7)
C4	0.0351 (7)	0.0399 (8)	0.0361 (8)	0.0016 (6)	−0.0014 (6)	−0.0019 (6)
C2	0.0458 (9)	0.0494 (9)	0.0367 (8)	0.0031 (7)	−0.0066 (7)	−0.0039 (7)
C5	0.0477 (9)	0.0423 (8)	0.0423 (9)	0.0029 (7)	−0.0076 (7)	−0.0086 (7)
C3	0.0451 (9)	0.0403 (8)	0.0388 (8)	0.0063 (7)	−0.0026 (7)	−0.0048 (7)
C1	0.0418 (9)	0.0437 (9)	0.0481 (9)	0.0038 (7)	−0.0090 (7)	0.0051 (7)
C6	0.0548 (10)	0.0383 (8)	0.0562 (11)	0.0077 (7)	−0.0096 (9)	−0.0067 (8)
C9	0.0595 (11)	0.0533 (10)	0.0484 (10)	0.0185 (9)	0.0017 (9)	0.0126 (8)
C10	0.0688 (15)	0.106 (2)	0.098 (2)	0.0277 (14)	0.0305 (14)	0.0353 (17)

Geometric parameters (Å, º) top

Cl1—C5	1.7421 (17)	C2—C3	1.377 (2)
Cl2—C1	1.7370 (17)	C2—C1	1.383 (2)
N2—C7	1.271 (2)	C2—H2B	0.9300
N2—N1	1.3755 (18)	C5—C6	1.384 (2)
O2—C8	1.3412 (19)	C3—H3A	0.9300
O2—C9	1.449 (2)	C1—C6	1.378 (3)
N1—C8	1.351 (2)	C6—H6A	0.9300
N1—H1A	0.8600	C9—C10	1.481 (3)
O1—C8	1.2097 (19)	C9—H9A	0.9700
C7—C4	1.461 (2)	C9—H9B	0.9700
C7—H7A	0.9300	C10—H10A	0.9600
C4—C5	1.393 (2)	C10—H10B	0.9600
C4—C3	1.397 (2)	C10—H10C	0.9600

C7—N2—N1	115.10 (13)	C2—C3—H3A	118.9
C8—O2—C9	115.87 (14)	C4—C3—H3A	118.9
C8—N1—N2	118.18 (13)	C6—C1—C2	121.22 (16)
C8—N1—H1A	120.9	C6—C1—Cl2	118.48 (13)
N2—N1—H1A	120.9	C2—C1—Cl2	120.30 (14)
O1—C8—O2	124.90 (15)	C1—C6—C5	118.83 (16)
O1—C8—N1	125.78 (15)	C1—C6—H6A	120.6
O2—C8—N1	109.31 (13)	C5—C6—H6A	120.6
N2—C7—C4	120.32 (14)	O2—C9—C10	111.15 (19)
N2—C7—H7A	119.8	O2—C9—H9A	109.4
C4—C7—H7A	119.8	C10—C9—H9A	109.4
C5—C4—C3	116.98 (15)	O2—C9—H9B	109.4
C5—C4—C7	121.69 (14)	C10—C9—H9B	109.4
C3—C4—C7	121.33 (14)	H9A—C9—H9B	108.0
C3—C2—C1	118.81 (16)	C9—C10—H10A	109.5
C3—C2—H2B	120.6	C9—C10—H10B	109.5
C1—C2—H2B	120.6	H10A—C10—H10B	109.5
C6—C5—C4	122.01 (15)	C9—C10—H10C	109.5
C6—C5—Cl1	117.20 (13)	H10A—C10—H10C	109.5
C4—C5—Cl1	120.79 (13)	H10B—C10—H10C	109.5
C2—C3—C4	122.12 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.12	2.927 (2)	156

Symmetry code: (i) −y+3/4, x+1/4, z+1/4.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀Cl₂N₂O₂
M_r	261.10
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	293
a, c (Å)	18.021 (3), 14.983 (3)
V (Å³)	4865.8 (14)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.52
Crystal size (mm)	0.25 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.492, 0.729
No. of measured, independent and observed [I > 2σ(I)] reflections	21376, 2789, 2409
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.121, 1.09
No. of reflections	2789
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.50

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
N1—H1A···O1ⁱ	0.86	2.12	2.927 (2)	156

Symmetry code: (i) −y+3/4, x+1/4, z+1/4.

Acknowledgements

The authors would like to thank the Science Foundation of WeiFang University (No. 2009Z24).

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cimerman, Z., Galic, N. & Bosner, B. (1997). Anal. Chim. Acta, 343, 145–153. CrossRef CAS Web of Science Google Scholar
Girgis, A. S. (2006). J. Chem. Res. 2, 81–83. CrossRef 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