Ethyl 2-[(Z)-2-benzyl-hydrazin-1-yl-idene]-2-bromo-acetate.

In the title compound, C(11)H(13)BrN(2)O(2), 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, mol-ecules 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 = 285.14

Monoclinic,

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[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 ▶); 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.

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

C11H13BrN2O2	F(000) = 576
Mr = 285.14	Dx = 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

Bruker APEX CCD diffractometer	2188 independent reflections
Radiation source: fine-focus sealed tube	1475 reflections with I > 2σ(I)
graphite	Rint = 0.019
phi and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Siemens, 1996)	h = −10→10
Tmin = 0.495, Tmax = 0.803	k = −13→7
4952 measured reflections	l = −7→14

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(Fo2) + (0.0656P)2] where P = (Fo2 + 2Fc2)/3
2188 reflections	(Δ/σ)max < 0.001
146 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.61 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) .