Ethyl 3-[1-(4-bromo­phen­yl)eth­ylidene]carbazate

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

doi:10.1107/S1600536809044614

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2938

https://doi.org/10.1107/S1600536809044614

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Ethyl 3-[1-(4-bromophenyl)ethylidene]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 26 October 2009; accepted 27 October 2009; online 31 October 2009)

In the crystal of the title compound, C₁₀H₁₁BrN₂O₂, the molecules are linked by N—H⋯O hydrogen bonds, forming S(4) chains propagating in [100]. A C—H⋯O interaction also occurs.

Related literature

For background to Schiff bases, see: Cimerman et al. (1997 ).

Experimental

Crystal data

C₁₀H₁₁BrN₂O₂
M_r = 271.11
Orthorhombic, P c a 2₁
a = 7.6810 (15) Å
b = 5.9520 (12) Å
c = 24.750 (5) Å
V = 1131.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 3.62 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.19 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
10040 measured reflections
2583 independent reflections
1675 reflections with I > 2σ(I)
R_int = 0.116

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.152
S = 1.02
2583 reflections
140 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.54 e Å⁻³
Absolute structure: Flack (1983 ), 1254 Friedel pairs
Flack parameter: −0.008 (16)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯O1ⁱ	0.76 (10)	2.26 (10)	2.929 (6)	148 (10)
C3—H3A⋯O1ⁱ	0.96	2.43	3.242 (8)	142
Symmetry code: (i) $[x-{\script{1\over 2}}, -y, z]$ .

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/S1600536809044614/hb5186sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809044614/hb5186Isup2.hkl

checkCIF report

Related literature top

For background to Schiff bases, see: Cimerman et al. (1997).

Experimental top

A mixture of 1-(4-bromophenyl)ethanone (0.1 mol), and methyl carbazate (0.1 mol) was stirred in refluxing ethanol (20 mL) for 4 h to afford the title compound (0.085 mol, yield 85%). Colourless blocks of (I) were obtained by recrystallization from ethanol at room temperature.

Structure description top

For background to Schiff bases, see: Cimerman et al. (1997).

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.

Ethyl 3-[1-(4-bromophenyl)ethylidene]carbazate top

Crystal data top

C₁₀H₁₁BrN₂O₂	D_x = 1.591 Mg m⁻³
M_r = 271.11	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca2₁	Cell parameters from 1982 reflections
a = 7.6810 (15) Å	θ = 3.6–27.5°
b = 5.9520 (12) Å	µ = 3.62 mm⁻¹
c = 24.750 (5) Å	T = 293 K
V = 1131.5 (4) Å³	Block, colourless
Z = 4	0.25 × 0.20 × 0.19 mm
F(000) = 544

Data collection top

Bruker SMART CCD diffractometer	1675 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.116
Graphite monochromator	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −9→8
10040 measured reflections	k = −7→7
2583 independent reflections	l = −31→32

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)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.152	w = 1/[σ²(F_o²) + (0.068P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.054
2583 reflections	Δρ_max = 0.45 e Å⁻³
140 parameters	Δρ_min = −0.54 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1254 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.008 (16)

Crystal data top

C₁₀H₁₁BrN₂O₂	V = 1131.5 (4) Å³
M_r = 271.11	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 7.6810 (15) Å	µ = 3.62 mm⁻¹
b = 5.9520 (12) Å	T = 293 K
c = 24.750 (5) Å	0.25 × 0.20 × 0.19 mm

Data collection top

Bruker SMART CCD diffractometer	1675 reflections with I > 2σ(I)
10040 measured reflections	R_int = 0.116
2583 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.152	Δρ_max = 0.45 e Å⁻³
S = 1.02	Δρ_min = −0.54 e Å⁻³
2583 reflections	Absolute structure: Flack (1983), 1254 Friedel pairs
140 parameters	Absolute structure parameter: −0.008 (16)
1 restraint

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
Br1	0.44214 (8)	0.19577 (12)	0.58046 (2)	0.0815 (3)
C8	0.3535 (7)	0.2162 (9)	0.5091 (2)	0.0584 (13)
C1	0.0415 (10)	−0.3211 (12)	0.1630 (3)	0.080 (2)
H1A	−0.0495	−0.3171	0.1364	0.120*
H1B	0.0344	−0.4590	0.1830	0.120*
H1C	0.1526	−0.3121	0.1454	0.120*
N1	0.1035 (6)	0.0551 (8)	0.27043 (18)	0.0548 (10)
C7	0.3861 (7)	0.0435 (10)	0.4736 (2)	0.0600 (12)
H7A	0.4517	−0.0798	0.4845	0.072*
C2	0.1408 (6)	−0.1185 (9)	0.23832 (19)	0.0515 (11)
O2	0.0223 (6)	−0.1363 (9)	0.19887 (18)	0.0724 (12)
C9	0.2600 (7)	0.4010 (9)	0.4932 (2)	0.0610 (12)
H9A	0.2385	0.5177	0.5172	0.073*
C4	0.1498 (6)	0.2404 (8)	0.3496 (2)	0.0463 (10)
C5	0.2249 (6)	0.2378 (8)	0.4043 (2)	0.0470 (10)
N2	0.1849 (5)	0.0686 (7)	0.31978 (17)	0.0509 (9)
C10	0.1984 (6)	0.4113 (9)	0.4408 (2)	0.0542 (11)
H10A	0.1374	0.5381	0.4297	0.065*
C6	0.3215 (7)	0.0544 (9)	0.4220 (2)	0.0552 (12)
H6A	0.3428	−0.0637	0.3983	0.066*
O1	0.2632 (5)	−0.2456 (6)	0.24299 (17)	0.0611 (9)
C3	0.0382 (7)	0.4343 (10)	0.3314 (3)	0.0633 (14)
H3A	0.0001	0.4090	0.2950	0.095*
H3B	0.1047	0.5707	0.3329	0.095*
H3C	−0.0613	0.4469	0.3547	0.095*
H1D	0.017 (13)	0.111 (17)	0.276 (4)	0.10 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1019 (5)	0.0934 (5)	0.0491 (3)	−0.0009 (3)	−0.0070 (4)	−0.0089 (4)
C8	0.057 (3)	0.067 (3)	0.051 (3)	−0.003 (2)	0.007 (2)	−0.008 (2)
C1	0.099 (5)	0.077 (5)	0.063 (4)	−0.003 (3)	−0.014 (3)	−0.023 (3)
N1	0.049 (2)	0.066 (3)	0.050 (2)	0.004 (2)	−0.0056 (19)	−0.007 (2)
C7	0.063 (3)	0.060 (3)	0.057 (3)	0.010 (2)	−0.006 (2)	−0.008 (2)
C2	0.050 (3)	0.059 (3)	0.045 (2)	−0.006 (2)	−0.003 (2)	−0.003 (2)
O2	0.070 (2)	0.085 (3)	0.062 (3)	0.011 (2)	−0.024 (2)	−0.020 (2)
C9	0.073 (3)	0.055 (3)	0.056 (3)	0.004 (3)	0.008 (2)	−0.015 (3)
C4	0.040 (2)	0.051 (2)	0.049 (3)	−0.0062 (19)	0.0064 (19)	−0.001 (2)
C5	0.039 (2)	0.047 (2)	0.055 (3)	−0.0015 (18)	0.0064 (19)	−0.004 (2)
N2	0.048 (2)	0.057 (2)	0.047 (2)	0.0031 (17)	0.0013 (16)	−0.002 (2)
C10	0.055 (3)	0.045 (3)	0.063 (3)	0.0062 (19)	0.003 (2)	−0.007 (2)
C6	0.058 (3)	0.057 (3)	0.051 (3)	0.009 (2)	0.003 (2)	−0.009 (2)
O1	0.055 (2)	0.064 (2)	0.065 (2)	0.0031 (18)	−0.0094 (16)	−0.0121 (18)
C3	0.061 (3)	0.058 (3)	0.070 (4)	0.008 (2)	−0.007 (2)	−0.002 (3)

Geometric parameters (Å, º) top

Br1—C8	1.896 (6)	C2—O2	1.339 (6)
C8—C9	1.372 (8)	C9—C10	1.380 (7)
C8—C7	1.376 (7)	C9—H9A	0.9300
C1—O2	1.421 (8)	C4—N2	1.289 (6)
C1—H1A	0.9600	C4—C5	1.473 (7)
C1—H1B	0.9600	C4—C3	1.507 (7)
C1—H1C	0.9600	C5—C10	1.387 (7)
N1—C2	1.335 (7)	C5—C6	1.391 (7)
N1—N2	1.374 (6)	C10—H10A	0.9300
N1—H1D	0.75 (10)	C6—H6A	0.9300
C7—C6	1.371 (7)	C3—H3A	0.9600
C7—H7A	0.9300	C3—H3B	0.9600
C2—O1	1.212 (6)	C3—H3C	0.9600

C9—C8—C7	120.7 (5)	C10—C9—H9A	120.5
C9—C8—Br1	120.5 (4)	N2—C4—C5	115.8 (4)
C7—C8—Br1	118.8 (4)	N2—C4—C3	123.8 (5)
O2—C1—H1A	109.5	C5—C4—C3	120.4 (4)
O2—C1—H1B	109.5	C10—C5—C6	117.2 (5)
H1A—C1—H1B	109.5	C10—C5—C4	122.3 (4)
O2—C1—H1C	109.5	C6—C5—C4	120.5 (4)
H1A—C1—H1C	109.5	C4—N2—N1	117.4 (4)
H1B—C1—H1C	109.5	C9—C10—C5	121.9 (5)
C2—N1—N2	118.5 (4)	C9—C10—H10A	119.1
C2—N1—H1D	129 (7)	C5—C10—H10A	119.1
N2—N1—H1D	103 (7)	C7—C6—C5	121.6 (5)
C8—C7—C6	119.6 (5)	C7—C6—H6A	119.2
C8—C7—H7A	120.2	C5—C6—H6A	119.2
C6—C7—H7A	120.2	C4—C3—H3A	109.5
O1—C2—N1	126.4 (5)	C4—C3—H3B	109.5
O1—C2—O2	123.2 (5)	H3A—C3—H3B	109.5
N1—C2—O2	110.4 (5)	C4—C3—H3C	109.5
C2—O2—C1	116.5 (5)	H3A—C3—H3C	109.5
C8—C9—C10	119.0 (5)	H3B—C3—H3C	109.5
C8—C9—H9A	120.5

C9—C8—C7—C6	−1.3 (8)	C3—C4—C5—C6	177.1 (5)
Br1—C8—C7—C6	179.3 (4)	C5—C4—N2—N1	173.9 (4)
N2—N1—C2—O1	−15.0 (8)	C3—C4—N2—N1	−5.5 (7)
N2—N1—C2—O2	164.9 (5)	C2—N1—N2—C4	178.4 (5)
O1—C2—O2—C1	2.8 (9)	C8—C9—C10—C5	1.5 (8)
N1—C2—O2—C1	−177.1 (6)	C6—C5—C10—C9	−2.0 (8)
C7—C8—C9—C10	0.2 (8)	C4—C5—C10—C9	175.8 (4)
Br1—C8—C9—C10	179.5 (4)	C8—C7—C6—C5	0.8 (8)
N2—C4—C5—C10	180.0 (4)	C10—C5—C6—C7	0.8 (7)
C3—C4—C5—C10	−0.6 (7)	C4—C5—C6—C7	−177.0 (5)
N2—C4—C5—C6	−2.3 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···O1ⁱ	0.76 (10)	2.26 (10)	2.929 (6)	148 (10)
C3—H3A···O1ⁱ	0.96	2.43	3.242 (8)	142

Symmetry code: (i) x−1/2, −y, z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁BrN₂O₂
M_r	271.11
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	293
a, b, c (Å)	7.6810 (15), 5.9520 (12), 24.750 (5)
V (Å³)	1131.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.62
Crystal size (mm)	0.25 × 0.20 × 0.19

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10040, 2583, 1675
R_int	0.116
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.152, 1.02
No. of reflections	2583
No. of parameters	140
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.54
Absolute structure	Flack (1983), 1254 Friedel pairs
Absolute structure parameter	−0.008 (16)

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—H1D···O1ⁱ	0.76 (10)	2.26 (10)	2.929 (6)	148 (10)
C3—H3A···O1ⁱ	0.96	2.43	3.242 (8)	142

Symmetry code: (i) x−1/2, −y, z.

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
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar