Ethyl 2-[(Z)-2-benzyl­hydrazin-1-yl­idene]-2-bromo­acetate

Yang, Q.-J.; Liu, D.; Zuo, J.; Hu, G.-D.; Zhao, L.-X.

doi:10.1107/S1600536810032071

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2334

https://doi.org/10.1107/S1600536810032071

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Ethyl 2-[(Z)-2-benzylhydrazin-1-ylidene]-2-bromoacetate

Qian-Jiao Yang,^a Dan Liu,^a Jian Zuo,^b Guo-Dong Hu ^a and Lin-Xiang Zhao ^a ^*

^aKey Laboratory of Original New Drug Design and Discovery of the Ministry of Education, College of Pharmaceutical Engineering, Shenyang Pharmaceutical University, Shenyang, Liaoning 110016, People's Republic of China, and ^bKey Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao, Shandong 266100, People's Republic of China
^*Correspondence e-mail: zhaolinxiang@syphu.edu.cn

(Received 28 July 2010; accepted 10 August 2010; online 18 August 2010)

In the title compound, C₁₁H₁₃BrN₂O₂, the dihedral angle between the phenyl ring and the almost planar (r.m.s. deviation = 0.011 Å) C—C(Br)=N—N(H)— fragment is 74.94 (16)°. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, which generate C(6) chains propagating in [010]. Weak aromatic π–π stacking [centroid–centroid separation = 3.784 (3) Å] may also help to consolidate the packing.

Related literature

For the use of the title compound in the preparation of heterocyclic compounds via the diploar cycloaddition of thiadiazole, see Feddouli et al. (2004 ); Abouricha et al. (2005 ); Hafez et al. (2008 ). For the synthesis of the title compound, see Bach et al. (1994 ).

Experimental

Crystal data

C₁₁H₁₃BrN₂O₂
M_r = 285.14
Monoclinic, P 2₁ /c
a = 9.046 (1) Å
b = 11.235 (1) Å
c = 12.326 (2) Å
β = 92.935 (4)°
V = 1251.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 3.27 mm⁻¹
T = 294 K
0.25 × 0.14 × 0.07 mm

Data collection

Siemens APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Siemens, 1996 ) T_min = 0.495, T_max = 0.803
4952 measured reflections
2188 independent reflections
1475 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.111
S = 1.02
2188 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.24	2.965 (4)	141
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); 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 I, global. DOI: https://doi.org/10.1107/S1600536810032071/hb5585sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810032071/hb5585Isup2.hkl

checkCIF report

Comment top

(Benzylhydrazono)acetate is a key intermediate in the preparation for pyrazoline compounds (Bach et al., 1994), which are selective for the NMDA receptors and show weak antagonists. In addition, it plays an important role in the synthesis of thiadiazole nucleus (Feddouli et al., 2004; Abouricha et al., 2005), which have been exhibited potential anti-inflammatory and analgesic activities (Hafez et al., 2008). Herein, the structure of ethyl 2-bromo-(Z)-2-(2-benzylhydrazono)acetate has been determined.

The crystal structure of the title compound is given in Fig. 1. In the crystal, the adjacent molecules are stabilized by N—H···O hydrogen bonding, with the distance of 2.965 (4) Å (Table 1). Molecules are linked into chain along the b axis by the above hydrogen bond (Fig. 2).

Related literature top

For the use of the title compound in the preparation of heterocyclic compounds via the diploar cycloaddition of thiadiazole, see Feddouli et al. (2004); Abouricha et al. (2005); Hafez et al. (2008). For the synthesis of the title compound, see Bach et al. (1994).

Experimental top

To a stirred solution of ethyl 2,2-diethoxyacetate (1 ml, 5.6 mmol) and acetyl chloride (0.8 ml, 11.2 mmol) was added iodine (3 mg, 0.01 mmol). After the mixture was stirred for overnight, excess acetyl chloride was removed in vacuo, the residue in 1,4-dioxane (25 ml) was treated with benzylhydrazine dihydrochloride (1.09 g, 5.6 mmol) in water (10 ml), then the mixture was adjusted to pH 4. After 1 h the mixture was neutralized to pH 8 with saturated NaOH and evaporated in vacuo. The residue was added water and extracted with CH2Cl2, the organic layer was dried over MgSO4, filtered and concentrated. The crude compound was dissolved in AcOEt (8 ml), which was reacted with NBS (1.1 g, 6.2 mmol) for 2 h. After evaporation of the solvent, the residue was dissolved in CH2Cl2 and filtered, the filtrate was concentrated and purified by column chromatography (eluent: PE/AcOEt = 28/1) to give the title compound (0.67 g, 2.35 mmol) as a white solid. Colorless blocks of (I) were grown in PE/AcOEt (14/0.5, V/V) solution by slow evaporation at room temperature.

Structure description top

For the use of the title compound in the preparation of heterocyclic compounds via the diploar cycloaddition of thiadiazole, see Feddouli et al. (2004); Abouricha et al. (2005); Hafez et al. (2008). For the synthesis of the title compound, see Bach et al. (1994).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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.
	Fig. 2. A view of the crystal structure of (I) showing chain to the b linked via N—H···O contact.

Ethyl 2-[(Z)-2-benzylhydrazin-1-ylidene]-2-bromoacetate top

Crystal data top

C₁₁H₁₃BrN₂O₂	F(000) = 576
M_r = 285.14	D_x = 1.514 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1479 reflections
a = 9.046 (1) Å	θ = 2.3–24.8°
b = 11.235 (1) Å	µ = 3.27 mm⁻¹
c = 12.326 (2) Å	T = 294 K
β = 92.935 (4)°	Block, colorless
V = 1251.1 (3) Å³	0.25 × 0.14 × 0.07 mm
Z = 4

Data collection top

Bruker APEX CCD diffractometer	2188 independent reflections
Radiation source: fine-focus sealed tube	1475 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
phi and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Siemens, 1996)	h = −10→10
T_min = 0.495, T_max = 0.803	k = −13→7
4952 measured reflections	l = −7→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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0656P)²] where P = (F_o² + 2F_c²)/3
2188 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.61 e Å⁻³

Crystal data top

C₁₁H₁₃BrN₂O₂	V = 1251.1 (3) Å³
M_r = 285.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.046 (1) Å	µ = 3.27 mm⁻¹
b = 11.235 (1) Å	T = 294 K
c = 12.326 (2) Å	0.25 × 0.14 × 0.07 mm
β = 92.935 (4)°

Data collection top

Bruker APEX CCD diffractometer	2188 independent reflections
Absorption correction: multi-scan (SADABS; Siemens, 1996)	1475 reflections with I > 2σ(I)
T_min = 0.495, T_max = 0.803	R_int = 0.019
4952 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.02	Δρ_max = 0.26 e Å⁻³
2188 reflections	Δρ_min = −0.61 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
Br1	0.44688 (4)	0.25237 (4)	0.31304 (3)	0.0668 (2)
O1	0.3161 (3)	0.0317 (2)	0.2073 (2)	0.0755 (8)
O2	0.3458 (2)	0.0749 (2)	0.03230 (18)	0.0534 (6)
N1	0.5769 (3)	0.3675 (3)	0.1176 (2)	0.0501 (7)
H1	0.5721	0.3973	0.1815	0.060*
N2	0.5071 (3)	0.2673 (2)	0.0922 (2)	0.0424 (7)
C1	0.8144 (3)	0.3760 (3)	0.0231 (3)	0.0436 (8)
C2	0.8605 (4)	0.3447 (4)	−0.0771 (3)	0.0726 (11)
H2	0.7946	0.3505	−0.1374	0.087*
C3	1.0035 (5)	0.3045 (4)	−0.0906 (4)	0.0852 (13)
H3	1.0321	0.2834	−0.1594	0.102*
C4	1.1013 (4)	0.2958 (4)	−0.0045 (4)	0.0696 (11)
H4	1.1976	0.2700	−0.0136	0.083*
C5	1.0569 (4)	0.3253 (4)	0.0954 (4)	0.0830 (13)
H5	1.1234	0.3182	0.1551	0.100*
C6	0.9142 (4)	0.3659 (4)	0.1105 (3)	0.0721 (11)
H6	0.8863	0.3862	0.1797	0.087*
C7	0.6617 (3)	0.4268 (3)	0.0367 (3)	0.0475 (8)
H7A	0.6717	0.5101	0.0563	0.057*
H7B	0.6064	0.4228	−0.0327	0.057*
C8	0.4424 (3)	0.2069 (3)	0.1640 (3)	0.0432 (7)
C9	0.3625 (3)	0.0958 (3)	0.1382 (3)	0.0508 (8)
C10	0.2617 (4)	−0.0317 (4)	0.0018 (3)	0.0722 (11)
H10A	0.1758	−0.0378	0.0454	0.087*
H10B	0.3226	−0.1017	0.0151	0.087*
C11	0.2142 (5)	−0.0254 (4)	−0.1139 (3)	0.0950 (15)
H11A	0.1489	0.0412	−0.1259	0.142*
H11B	0.1632	−0.0974	−0.1349	0.142*
H11C	0.2993	−0.0159	−0.1565	0.142*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0724 (3)	0.0882 (4)	0.0405 (3)	−0.00890 (18)	0.00985 (18)	−0.00325 (18)
O1	0.1002 (19)	0.0639 (19)	0.0630 (17)	−0.0140 (15)	0.0091 (14)	0.0199 (14)
O2	0.0622 (13)	0.0418 (15)	0.0561 (14)	−0.0035 (11)	0.0025 (11)	−0.0015 (11)
N1	0.0508 (14)	0.0531 (19)	0.0473 (16)	−0.0048 (13)	0.0106 (12)	−0.0090 (14)
N2	0.0409 (13)	0.0448 (19)	0.0414 (15)	0.0058 (12)	0.0014 (12)	−0.0029 (12)
C1	0.0470 (16)	0.0314 (19)	0.053 (2)	−0.0016 (13)	0.0059 (15)	0.0020 (16)
C2	0.063 (2)	0.099 (3)	0.056 (2)	0.012 (2)	0.0053 (18)	0.000 (2)
C3	0.080 (3)	0.104 (4)	0.074 (3)	0.021 (3)	0.024 (2)	−0.012 (3)
C4	0.055 (2)	0.057 (3)	0.099 (4)	0.0130 (18)	0.022 (2)	0.011 (2)
C5	0.059 (2)	0.110 (4)	0.079 (3)	0.022 (2)	−0.005 (2)	0.015 (3)
C6	0.061 (2)	0.099 (3)	0.056 (2)	0.013 (2)	0.0058 (19)	0.001 (2)
C7	0.0470 (17)	0.041 (2)	0.055 (2)	0.0042 (14)	0.0064 (15)	0.0036 (16)
C8	0.0423 (16)	0.048 (2)	0.0393 (18)	0.0079 (14)	0.0031 (14)	0.0039 (15)
C9	0.0520 (18)	0.049 (2)	0.051 (2)	0.0064 (15)	0.0036 (15)	0.0049 (18)
C10	0.090 (3)	0.046 (3)	0.080 (3)	−0.014 (2)	0.003 (2)	−0.009 (2)
C11	0.114 (4)	0.069 (3)	0.099 (4)	−0.014 (3)	−0.026 (3)	−0.008 (3)

Geometric parameters (Å, º) top

Br1—C8	1.906 (3)	C4—C5	1.355 (6)
O1—C9	1.207 (4)	C4—H4	0.9300
O2—C9	1.328 (4)	C5—C6	1.391 (5)
O2—C10	1.457 (4)	C5—H5	0.9300
N1—N2	1.320 (3)	C6—H6	0.9300
N1—C7	1.451 (4)	C7—H7A	0.9700
N1—H1	0.8600	C7—H7B	0.9700
N2—C8	1.280 (4)	C8—C9	1.468 (5)
C1—C2	1.370 (4)	C10—C11	1.470 (5)
C1—C6	1.374 (5)	C10—H10A	0.9700
C1—C7	1.512 (4)	C10—H10B	0.9700
C2—C3	1.388 (5)	C11—H11A	0.9600
C2—H2	0.9300	C11—H11B	0.9600
C3—C4	1.350 (6)	C11—H11C	0.9600
C3—H3	0.9300

C9—O2—C10	115.5 (3)	N1—C7—H7A	108.5
N2—N1—C7	119.5 (3)	C1—C7—H7A	108.5
N2—N1—H1	120.2	N1—C7—H7B	108.5
C7—N1—H1	120.2	C1—C7—H7B	108.5
C8—N2—N1	121.2 (3)	H7A—C7—H7B	107.5
C2—C1—C6	117.9 (3)	N2—C8—C9	122.6 (3)
C2—C1—C7	121.2 (3)	N2—C8—Br1	122.4 (3)
C6—C1—C7	120.7 (3)	C9—C8—Br1	115.0 (2)
C1—C2—C3	121.3 (4)	O1—C9—O2	124.2 (3)
C1—C2—H2	119.4	O1—C9—C8	122.7 (3)
C3—C2—H2	119.4	O2—C9—C8	113.1 (3)
C4—C3—C2	120.5 (4)	O2—C10—C11	109.5 (3)
C4—C3—H3	119.7	O2—C10—H10A	109.8
C2—C3—H3	119.7	C11—C10—H10A	109.8
C3—C4—C5	118.9 (4)	O2—C10—H10B	109.8
C3—C4—H4	120.6	C11—C10—H10B	109.8
C5—C4—H4	120.6	H10A—C10—H10B	108.2
C4—C5—C6	121.5 (4)	C10—C11—H11A	109.5
C4—C5—H5	119.3	C10—C11—H11B	109.5
C6—C5—H5	119.3	H11A—C11—H11B	109.5
C1—C6—C5	119.9 (4)	C10—C11—H11C	109.5
C1—C6—H6	120.1	H11A—C11—H11C	109.5
C5—C6—H6	120.1	H11B—C11—H11C	109.5
N1—C7—C1	114.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.24	2.965 (4)	141

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃BrN₂O₂
M_r	285.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	9.046 (1), 11.235 (1), 12.326 (2)
β (°)	92.935 (4)
V (Å³)	1251.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.27
Crystal size (mm)	0.25 × 0.14 × 0.07

Data collection
Diffractometer	Bruker APEX CCD
Absorption correction	Multi-scan (SADABS; Siemens, 1996)
T_min, T_max	0.495, 0.803
No. of measured, independent and observed [I > 2σ(I)] reflections	4952, 2188, 1475
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.111, 1.02
No. of reflections	2188
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.61

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), 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—H1···O1ⁱ	0.86	2.24	2.965 (4)	141

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Acknowledgements

This work was supported by the China International Science and Technology Cooperation Plan (2009DEA31200).

References

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