PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2334.
Published online 2010 August 18. doi:  10.1107/S1600536810032071
PMCID: PMC3007982

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

Abstract

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 [triangle]); Abouricha et al. (2005 [triangle]); Hafez et al. (2008 [triangle]). For the synthesis of the title compound, see Bach et al. (1994 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2334-scheme1.jpg

Experimental

Crystal data

  • C11H13BrN2O2
  • M r = 285.14
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2334-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.111
  • S = 1.02
  • 2188 reflections
  • 146 parameters
  • H-atom parameters constrained
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.61 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810032071/hb5585sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032071/hb5585Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

(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).

Experimental

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.

Refinement

All H-atoms were positioned geometrically and refined using a riding model, with C—H = 0.96 Å (methyl), 0.97 Å (methenyl), 0.93 Å (aromatic), and Uiso(H) =1.2Ueq(C).

Figures

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.

Crystal data

C11H13BrN2O2F(000) = 576
Mr = 285.14Dx = 1.514 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1479 reflections
a = 9.046 (1) Åθ = 2.3–24.8°
b = 11.235 (1) ŵ = 3.27 mm1
c = 12.326 (2) ÅT = 294 K
β = 92.935 (4)°Block, colorless
V = 1251.1 (3) Å30.25 × 0.14 × 0.07 mm
Z = 4

Data collection

Bruker APEX CCD diffractometer2188 independent reflections
Radiation source: fine-focus sealed tube1475 reflections with I > 2σ(I)
graphiteRint = 0.019
phi and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Siemens, 1996)h = −10→10
Tmin = 0.495, Tmax = 0.803k = −13→7
4952 measured reflectionsl = −7→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0656P)2] where P = (Fo2 + 2Fc2)/3
2188 reflections(Δ/σ)max < 0.001
146 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = −0.61 e Å3

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 (Å2)

xyzUiso*/Ueq
Br10.44688 (4)0.25237 (4)0.31304 (3)0.0668 (2)
O10.3161 (3)0.0317 (2)0.2073 (2)0.0755 (8)
O20.3458 (2)0.0749 (2)0.03230 (18)0.0534 (6)
N10.5769 (3)0.3675 (3)0.1176 (2)0.0501 (7)
H10.57210.39730.18150.060*
N20.5071 (3)0.2673 (2)0.0922 (2)0.0424 (7)
C10.8144 (3)0.3760 (3)0.0231 (3)0.0436 (8)
C20.8605 (4)0.3447 (4)−0.0771 (3)0.0726 (11)
H20.79460.3505−0.13740.087*
C31.0035 (5)0.3045 (4)−0.0906 (4)0.0852 (13)
H31.03210.2834−0.15940.102*
C41.1013 (4)0.2958 (4)−0.0045 (4)0.0696 (11)
H41.19760.2700−0.01360.083*
C51.0569 (4)0.3253 (4)0.0954 (4)0.0830 (13)
H51.12340.31820.15510.100*
C60.9142 (4)0.3659 (4)0.1105 (3)0.0721 (11)
H60.88630.38620.17970.087*
C70.6617 (3)0.4268 (3)0.0367 (3)0.0475 (8)
H7A0.67170.51010.05630.057*
H7B0.60640.4228−0.03270.057*
C80.4424 (3)0.2069 (3)0.1640 (3)0.0432 (7)
C90.3625 (3)0.0958 (3)0.1382 (3)0.0508 (8)
C100.2617 (4)−0.0317 (4)0.0018 (3)0.0722 (11)
H10A0.1758−0.03780.04540.087*
H10B0.3226−0.10170.01510.087*
C110.2142 (5)−0.0254 (4)−0.1139 (3)0.0950 (15)
H11A0.14890.0412−0.12590.142*
H11B0.1632−0.0974−0.13490.142*
H11C0.2993−0.0159−0.15650.142*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0724 (3)0.0882 (4)0.0405 (3)−0.00890 (18)0.00985 (18)−0.00325 (18)
O10.1002 (19)0.0639 (19)0.0630 (17)−0.0140 (15)0.0091 (14)0.0199 (14)
O20.0622 (13)0.0418 (15)0.0561 (14)−0.0035 (11)0.0025 (11)−0.0015 (11)
N10.0508 (14)0.0531 (19)0.0473 (16)−0.0048 (13)0.0106 (12)−0.0090 (14)
N20.0409 (13)0.0448 (19)0.0414 (15)0.0058 (12)0.0014 (12)−0.0029 (12)
C10.0470 (16)0.0314 (19)0.053 (2)−0.0016 (13)0.0059 (15)0.0020 (16)
C20.063 (2)0.099 (3)0.056 (2)0.012 (2)0.0053 (18)0.000 (2)
C30.080 (3)0.104 (4)0.074 (3)0.021 (3)0.024 (2)−0.012 (3)
C40.055 (2)0.057 (3)0.099 (4)0.0130 (18)0.022 (2)0.011 (2)
C50.059 (2)0.110 (4)0.079 (3)0.022 (2)−0.005 (2)0.015 (3)
C60.061 (2)0.099 (3)0.056 (2)0.013 (2)0.0058 (19)0.001 (2)
C70.0470 (17)0.041 (2)0.055 (2)0.0042 (14)0.0064 (15)0.0036 (16)
C80.0423 (16)0.048 (2)0.0393 (18)0.0079 (14)0.0031 (14)0.0039 (15)
C90.0520 (18)0.049 (2)0.051 (2)0.0064 (15)0.0036 (15)0.0049 (18)
C100.090 (3)0.046 (3)0.080 (3)−0.014 (2)0.003 (2)−0.009 (2)
C110.114 (4)0.069 (3)0.099 (4)−0.014 (3)−0.026 (3)−0.008 (3)

Geometric parameters (Å, °)

Br1—C81.906 (3)C4—C51.355 (6)
O1—C91.207 (4)C4—H40.9300
O2—C91.328 (4)C5—C61.391 (5)
O2—C101.457 (4)C5—H50.9300
N1—N21.320 (3)C6—H60.9300
N1—C71.451 (4)C7—H7A0.9700
N1—H10.8600C7—H7B0.9700
N2—C81.280 (4)C8—C91.468 (5)
C1—C21.370 (4)C10—C111.470 (5)
C1—C61.374 (5)C10—H10A0.9700
C1—C71.512 (4)C10—H10B0.9700
C2—C31.388 (5)C11—H11A0.9600
C2—H20.9300C11—H11B0.9600
C3—C41.350 (6)C11—H11C0.9600
C3—H30.9300
C9—O2—C10115.5 (3)N1—C7—H7A108.5
N2—N1—C7119.5 (3)C1—C7—H7A108.5
N2—N1—H1120.2N1—C7—H7B108.5
C7—N1—H1120.2C1—C7—H7B108.5
C8—N2—N1121.2 (3)H7A—C7—H7B107.5
C2—C1—C6117.9 (3)N2—C8—C9122.6 (3)
C2—C1—C7121.2 (3)N2—C8—Br1122.4 (3)
C6—C1—C7120.7 (3)C9—C8—Br1115.0 (2)
C1—C2—C3121.3 (4)O1—C9—O2124.2 (3)
C1—C2—H2119.4O1—C9—C8122.7 (3)
C3—C2—H2119.4O2—C9—C8113.1 (3)
C4—C3—C2120.5 (4)O2—C10—C11109.5 (3)
C4—C3—H3119.7O2—C10—H10A109.8
C2—C3—H3119.7C11—C10—H10A109.8
C3—C4—C5118.9 (4)O2—C10—H10B109.8
C3—C4—H4120.6C11—C10—H10B109.8
C5—C4—H4120.6H10A—C10—H10B108.2
C4—C5—C6121.5 (4)C10—C11—H11A109.5
C4—C5—H5119.3C10—C11—H11B109.5
C6—C5—H5119.3H11A—C11—H11B109.5
C1—C6—C5119.9 (4)C10—C11—H11C109.5
C1—C6—H6120.1H11A—C11—H11C109.5
C5—C6—H6120.1H11B—C11—H11C109.5
N1—C7—C1114.9 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.242.965 (4)141

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5585).

References

  • Abouricha, S., Rakib, E., Benchat, N., Alaoui, M., Allouchi, H. & EI-Bali, B. (2005). Synth. Commun.35, 2213–2221.
  • Bach, K. K., El-Seedi, H. R., Jensen, H. M., Nielsen, H. B., Thomsen, I. & Torssell, K. B. G. (1994). Tetrahedron, 50, 7543–7556.
  • Feddouli, A., Itto, M. Y. A., Hasnaoui, A., Villemin, D., Jaffrs, P. A., Santos, J. S. D. O., Riahi, A., Huet, F. & Daran, J. C. (2004). J. Heterocycl. Chem.41, 731–735.
  • Hafez, H. N., Hegab, M. I., Ahmed-Farag, I. S. & EI-Gazzar, A. B. A. (2008). Bioorg. Med. Chem. Lett.18, 4538–4543. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siemens (1996). SMART, SAINT and SADABS Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography