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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1646.
Published online 2008 July 31. doi:  10.1107/S1600536808023763
PMCID: PMC2962206

(E)-Ethyl N′-(4-bromo­benzyl­idene)hydrazinecarboxyl­ate

Abstract

The title compound, C10H11BrN2O2, crystallizes with two independent mol­ecules in the asymmetric unit, in which the dihedral angles between the benzene ring and the hydrazine carboxylic acid mean plane are 3.0 (4) and 45.3 (3)°. The mol­ecules are linked into a one-dimensional network by inter­molecular N—H(...)O hydrogen bonds.

Related literature

For general background, see: Parashar et al. (1988 [triangle]); Hadjoudis et al.(1987 [triangle]); Borg et al. (1999 [triangle]). For a related structure, see: Shang et al. (2007 [triangle]).

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Object name is e-64-o1646-scheme1.jpg

Experimental

Crystal data

  • C10H11BrN2O2
  • M r = 271.11
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1646-efi1.jpg
  • a = 16.499 (3) Å
  • b = 8.6052 (19) Å
  • c = 18.277 (4) Å
  • β = 116.279 (7)°
  • V = 2326.7 (8) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 3.52 mm−1
  • T = 123 (2) K
  • 0.30 × 0.26 × 0.25 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2002 [triangle]) T min = 0.419, T max = 0.474 (expected range = 0.367–0.415)
  • 24092 measured reflections
  • 4075 independent reflections
  • 1989 reflections with I > 2σ(I)
  • R int = 0.139

Refinement

  • R[F 2 > 2σ(F 2)] = 0.093
  • wR(F 2) = 0.259
  • S = 0.88
  • 4075 reflections
  • 273 parameters
  • H-atom parameters constrained
  • Δρmax = 1.35 e Å−3
  • Δρmin = −1.10 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [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/S1600536808023763/hb2762sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808023763/hb2762Isup2.hkl

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

Acknowledgments

The author acknowledges the financial support of Zhejiang Institute of Communications, China.

supplementary crystallographic information

Comment

Benzaldehydehydrazone derivatives have received considerable attention for a long time due to their pharmacological activity (Parashar et al., 1988) and their photochromic properties (Hadjoudis et al., 1987). They are important intermidiates for 1,3,4-oxadiazoles, which have been reported to be versatile compounds with many properties (Borg et al., 1999). As a further investigation of this type of derivatives, the crystal structure of the title compound, (I), is reported here (Fig. 1).

Compound (I) crystallizes with two independent but essentially identical molecules in the asymmetric unit. Each independent molecule adopts a trans configuration with respect to the C═N bond. In each molecule, the hydrazine carboxylic acid methyl ester group is twisted away from the attached ring. The dihedral angle between C1-C6 and N1/N2/O1/O2/C8-C10 planes is 3.0 (4)° and that between C11-C16 and N3/N4/O3/O4/C18 planes is 45.3 (3)°. The bond lengths and angles of each molecule in the asymmetric unit agree with those observed for methyl N'-[(E)-4-methoxybenzylidene]hydrazinecarboxylate (Shang et al., 2007).

In the crystal of (I), the molecules are linked into a one-dimensional network by intermolecular N—H···O hydrogen bonds (Table 1, Fig. 2).

Experimental

4-Bromobenzaldehyde (1.84 g, 0.01 mol) and ethyl hydrazinecarboxylate (1.04g, 0.01 mol) were dissolved in stirred methanol (20 ml) and left for 3 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 85% yield. Colourless blocks of (I) were obtained by slow evaporation of a methanol solution at room temperature (m.p. 433–435 K).

Refinement

The H atoms were positioned geometrically (N-H = 0.86 Å and C-H = 0.95-0.99Å) and refined as riding, with Uiso(H) = 1.2–1.5Ueq(carrier).

Figures

Fig. 1.
Molecular structure of (I), showing 30% probability displacement ellipsoids for the non-hydrogen atoms. The hydrogen bond is shown as a dashed line.
Fig. 2.
The crystal packing of (I). Hydrogen bonds are shown as dashed lines.

Crystal data

C10H11BrN2O2F000 = 1088
Mr = 271.11Dx = 1.548 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4075 reflections
a = 16.499 (3) Åθ = 1.4–25.0º
b = 8.6052 (19) ŵ = 3.52 mm1
c = 18.277 (4) ÅT = 123 (2) K
β = 116.279 (7)ºBlock, colourless
V = 2326.7 (8) Å30.30 × 0.26 × 0.25 mm
Z = 8

Data collection

Bruker SMART CCD diffractometer4075 independent reflections
Radiation source: fine-focus sealed tube1989 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.139
T = 123(2) Kθmax = 25.0º
ω scansθmin = 1.4º
Absorption correction: multi-scan(SADABS; Bruker, 2002)h = −19→18
Tmin = 0.419, Tmax = 0.474k = −9→10
24092 measured reflectionsl = −21→21

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.093H-atom parameters constrained
wR(F2) = 0.259  w = 1/[σ2(Fo2) + (0.1543P)2] where P = (Fo2 + 2Fc2)/3
S = 0.88(Δ/σ)max < 0.001
4075 reflectionsΔρmax = 1.35 e Å3
273 parametersΔρmin = −1.10 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Br1−0.38953 (6)0.41924 (14)0.35560 (6)0.1017 (5)
O10.1467 (3)0.9272 (6)0.6334 (3)0.0683 (15)
O20.2401 (3)0.9406 (6)0.5725 (3)0.0683 (14)
N10.0294 (4)0.7619 (7)0.4990 (3)0.0547 (14)
N20.1102 (4)0.8180 (7)0.5084 (3)0.0591 (16)
H2A0.12710.80160.47080.071*
C1−0.1496 (5)0.5277 (9)0.3484 (4)0.0614 (19)
H1−0.12260.50780.31300.074*
C2−0.2340 (6)0.4681 (9)0.3288 (4)0.068 (2)
H2−0.26570.41030.28010.082*
C3−0.2716 (5)0.4947 (10)0.3822 (5)0.069 (2)
C4−0.2254 (6)0.5766 (10)0.4538 (5)0.079 (2)
H4−0.25130.59280.49050.094*
C5−0.1413 (5)0.6341 (10)0.4709 (4)0.069 (2)
H5−0.10870.68820.52080.082*
C6−0.1020 (5)0.6165 (8)0.4185 (4)0.0540 (17)
C7−0.0147 (5)0.6797 (9)0.4356 (4)0.0566 (18)
H70.01060.65980.39880.068*
C80.1647 (5)0.8967 (9)0.5765 (4)0.0593 (19)
C90.3059 (5)1.0219 (11)0.6442 (4)0.075 (2)
H9A0.32530.95470.69300.090*
H9B0.27891.11780.65390.090*
C100.3843 (6)1.0610 (15)0.6288 (6)0.113 (4)
H10A0.42831.12080.67490.170*
H10B0.36391.12300.57880.170*
H10C0.41260.96500.62250.170*
Br2−0.40506 (7)0.72172 (16)0.13867 (7)0.1115 (5)
O30.2037 (4)0.7286 (7)0.4120 (3)0.0764 (16)
O40.2853 (3)0.6993 (6)0.3405 (3)0.0672 (14)
N30.0511 (4)0.7304 (7)0.2633 (3)0.0555 (15)
N40.1369 (4)0.7146 (7)0.2717 (3)0.0589 (15)
H4A0.14610.70480.22910.071*
C11−0.2224 (5)0.8208 (9)0.2063 (5)0.065 (2)
H11−0.24100.89500.23420.078*
C12−0.2835 (6)0.7232 (10)0.1526 (5)0.072 (2)
C13−0.2584 (6)0.6157 (10)0.1077 (4)0.074 (2)
H13−0.30170.54770.06930.089*
C14−0.1333 (5)0.8142 (9)0.2212 (4)0.063 (2)
H14−0.09040.88210.26010.075*
C15−0.1705 (5)0.6125 (9)0.1210 (4)0.064 (2)
H15−0.15320.54350.08980.076*
C16−0.1055 (5)0.7070 (8)0.1786 (4)0.0530 (17)
C17−0.0116 (5)0.6937 (8)0.1946 (4)0.0549 (18)
H170.00290.65690.15290.066*
C180.2083 (5)0.7143 (9)0.3472 (4)0.0604 (19)
C190.3667 (6)0.6862 (12)0.4155 (5)0.087 (3)
H19A0.36910.58390.44110.105*
H19B0.36890.76860.45410.105*
C200.4441 (7)0.7027 (18)0.3950 (8)0.134 (5)
H20A0.50090.69580.44510.201*
H20B0.44060.80380.36910.201*
H20C0.44180.61960.35750.201*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0722 (7)0.1265 (10)0.1016 (8)−0.0210 (5)0.0342 (6)−0.0047 (6)
O10.076 (4)0.094 (4)0.044 (3)−0.011 (3)0.035 (3)−0.005 (2)
O20.054 (3)0.110 (4)0.048 (3)−0.014 (3)0.029 (2)−0.005 (3)
N10.053 (4)0.068 (4)0.049 (3)0.001 (3)0.028 (3)0.004 (3)
N20.053 (4)0.091 (5)0.037 (3)−0.003 (3)0.024 (3)−0.005 (3)
C10.078 (6)0.063 (5)0.051 (4)−0.001 (4)0.036 (4)−0.001 (4)
C20.081 (6)0.073 (5)0.050 (4)0.008 (5)0.028 (4)−0.003 (4)
C30.065 (5)0.069 (5)0.065 (5)0.003 (4)0.022 (4)0.005 (4)
C40.076 (6)0.104 (7)0.068 (5)0.001 (5)0.043 (4)−0.009 (5)
C50.072 (5)0.088 (6)0.052 (4)−0.012 (5)0.033 (4)−0.011 (4)
C60.062 (5)0.058 (4)0.044 (4)0.007 (4)0.026 (3)0.004 (3)
C70.057 (4)0.073 (5)0.044 (4)0.006 (4)0.027 (4)−0.003 (4)
C80.052 (4)0.076 (5)0.048 (4)0.005 (4)0.020 (4)0.015 (4)
C90.063 (5)0.102 (6)0.056 (5)−0.016 (5)0.023 (4)0.001 (4)
C100.073 (7)0.173 (12)0.080 (6)−0.040 (7)0.021 (5)−0.003 (7)
Br20.0600 (7)0.1507 (11)0.1204 (9)−0.0002 (6)0.0369 (6)0.0102 (7)
O30.082 (4)0.108 (4)0.050 (3)0.009 (3)0.038 (3)−0.003 (3)
O40.054 (3)0.101 (4)0.052 (3)0.004 (3)0.028 (2)0.001 (3)
N30.058 (4)0.067 (4)0.055 (4)0.005 (3)0.037 (3)0.007 (3)
N40.062 (4)0.077 (4)0.046 (3)0.001 (3)0.032 (3)0.003 (3)
C110.063 (5)0.069 (5)0.072 (5)0.002 (4)0.037 (4)−0.012 (4)
C120.065 (5)0.085 (6)0.056 (4)−0.001 (4)0.020 (4)0.014 (4)
C130.083 (6)0.077 (6)0.050 (4)−0.015 (5)0.019 (4)−0.008 (4)
C140.073 (5)0.066 (5)0.054 (4)0.000 (4)0.032 (4)−0.007 (4)
C150.066 (5)0.076 (5)0.049 (4)0.004 (4)0.026 (4)−0.008 (4)
C160.069 (5)0.053 (4)0.041 (3)0.003 (4)0.027 (3)0.005 (3)
C170.065 (5)0.064 (5)0.041 (4)0.009 (4)0.029 (4)−0.001 (3)
C180.067 (5)0.064 (5)0.057 (5)−0.001 (4)0.033 (4)0.002 (4)
C190.079 (6)0.116 (8)0.063 (5)0.008 (5)0.027 (5)−0.001 (5)
C200.065 (7)0.215 (15)0.112 (8)−0.001 (7)0.030 (6)−0.005 (9)

Geometric parameters (Å, °)

Br1—C31.899 (8)Br2—C121.907 (8)
O1—C81.229 (8)O3—C181.226 (8)
O2—C81.333 (9)O4—C181.335 (9)
O2—C91.458 (9)O4—C191.437 (10)
N1—C71.275 (8)N3—C171.264 (8)
N1—N21.355 (8)N3—N41.360 (8)
N2—C81.352 (9)N4—C181.361 (9)
N2—H2A0.8600N4—H4A0.8601
C1—C21.374 (10)C11—C121.344 (11)
C1—C61.396 (10)C11—C141.372 (10)
C1—H10.9500C11—H110.9500
C2—C31.387 (10)C12—C131.415 (12)
C2—H20.9500C13—C151.360 (11)
C3—C41.381 (11)C13—H130.9500
C4—C51.373 (11)C14—C161.407 (10)
C4—H40.9500C14—H140.9500
C5—C61.382 (10)C15—C161.386 (10)
C5—H50.9500C15—H150.9500
C6—C71.439 (10)C16—C171.447 (10)
C7—H70.9500C17—H170.9500
C9—C101.478 (11)C19—C201.487 (14)
C9—H9A0.9900C19—H19A0.9900
C9—H9B0.9900C19—H19B0.9900
C10—H10A0.9800C20—H20A0.9800
C10—H10B0.9800C20—H20B0.9800
C10—H10C0.9800C20—H20C0.9800
C8—O2—C9115.4 (5)C18—O4—C19116.6 (5)
C7—N1—N2116.5 (5)C17—N3—N4116.1 (5)
C8—N2—N1120.8 (5)N3—N4—C18120.3 (5)
C8—N2—H2A119.9N3—N4—H4A120.0
N1—N2—H2A119.2C18—N4—H4A119.7
C2—C1—C6122.4 (7)C12—C11—C14120.7 (7)
C2—C1—H1118.8C12—C11—H11119.6
C6—C1—H1118.8C14—C11—H11119.6
C1—C2—C3118.2 (7)C11—C12—C13120.9 (8)
C1—C2—H2120.9C11—C12—Br2120.4 (7)
C3—C2—H2120.9C13—C12—Br2118.6 (7)
C4—C3—C2121.3 (8)C15—C13—C12118.2 (7)
C4—C3—Br1119.4 (6)C15—C13—H13120.9
C2—C3—Br1119.4 (6)C12—C13—H13120.9
C5—C4—C3118.6 (7)C11—C14—C16120.0 (7)
C5—C4—H4120.7C11—C14—H14120.0
C3—C4—H4120.7C16—C14—H14120.0
C4—C5—C6122.6 (7)C13—C15—C16121.9 (7)
C4—C5—H5118.7C13—C15—H15119.1
C6—C5—H5118.7C16—C15—H15119.1
C5—C6—C1116.8 (7)C15—C16—C14118.2 (7)
C5—C6—C7122.7 (7)C15—C16—C17120.3 (6)
C1—C6—C7120.5 (6)C14—C16—C17121.4 (7)
N1—C7—C6121.3 (6)N3—C17—C16120.9 (6)
N1—C7—H7119.3N3—C17—H17119.6
C6—C7—H7119.3C16—C17—H17119.6
O1—C8—O2124.6 (7)O3—C18—O4124.5 (7)
O1—C8—N2125.0 (7)O3—C18—N4125.6 (7)
O2—C8—N2110.4 (6)O4—C18—N4109.9 (6)
O2—C9—C10107.7 (7)O4—C19—C20107.3 (7)
O2—C9—H9A110.2O4—C19—H19A110.2
C10—C9—H9A110.2C20—C19—H19A110.2
O2—C9—H9B110.2O4—C19—H19B110.2
C10—C9—H9B110.2C20—C19—H19B110.2
H9A—C9—H9B108.5H19A—C19—H19B108.5
C9—C10—H10A109.5C19—C20—H20A109.5
C9—C10—H10B109.5C19—C20—H20B109.5
H10A—C10—H10B109.5H20A—C20—H20B109.5
C9—C10—H10C109.5C19—C20—H20C109.5
H10A—C10—H10C109.5H20A—C20—H20C109.5
H10B—C10—H10C109.5H20B—C20—H20C109.5
C7—N1—N2—C8−175.2 (7)C17—N3—N4—C18−164.0 (7)
C6—C1—C2—C3−1.6 (11)C14—C11—C12—C13−2.6 (12)
C1—C2—C3—C4−1.0 (12)C14—C11—C12—Br2175.0 (6)
C1—C2—C3—Br1178.2 (6)C11—C12—C13—C150.7 (12)
C2—C3—C4—C51.0 (12)Br2—C12—C13—C15−176.9 (6)
Br1—C3—C4—C5−178.2 (6)C12—C11—C14—C161.5 (11)
C3—C4—C5—C61.6 (13)C12—C13—C15—C162.2 (11)
C4—C5—C6—C1−4.0 (12)C13—C15—C16—C14−3.3 (11)
C4—C5—C6—C7178.6 (7)C13—C15—C16—C17176.2 (7)
C2—C1—C6—C54.0 (11)C11—C14—C16—C151.4 (10)
C2—C1—C6—C7−178.5 (7)C11—C14—C16—C17−178.1 (7)
N2—N1—C7—C6−178.9 (6)N4—N3—C17—C16−179.5 (6)
C5—C6—C7—N1−3.2 (11)C15—C16—C17—N3−153.1 (7)
C1—C6—C7—N1179.5 (7)C14—C16—C17—N326.4 (10)
C9—O2—C8—O13.9 (10)C19—O4—C18—O35.5 (11)
C9—O2—C8—N2−177.8 (6)C19—O4—C18—N4−175.8 (7)
N1—N2—C8—O1−1.6 (11)N3—N4—C18—O3−0.6 (11)
N1—N2—C8—O2−179.9 (6)N3—N4—C18—O4−179.3 (6)
C8—O2—C9—C10180.0 (8)C18—O4—C19—C20−168.8 (8)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O30.862.092.913 (7)161
N4—H4A···O1i0.862.092.875 (7)152

Symmetry codes: (i) x, −y+3/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2762).

References

  • Borg, S., Vollinga, R. C., Labarre, M., Payza, K., Terenius, L. & Luthman, K. (1999). J. Med. Chem.42, 4331–4342. [PubMed]
  • Bruker (2002). SADABS, SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345–1360.
  • Parashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim. Acta, 151, 201–208.
  • Shang, Z.-H., Zhang, H.-L. & Ding, Y. (2007). Acta Cryst. E63, o3394.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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