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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1544.
Published online 2008 July 19. doi:  10.1107/S1600536808021983
PMCID: PMC2962168

(E)-Methyl N′-(4-bromo­benzyl­idene)­hydrazinecarboxyl­ate at 123 K

Abstract

The title compound, C9H9BrN2O2, crystallizes with two independent but essentially identical mol­ecules in the asymmetric unit. Each mol­ecule adopts a trans configuration with respect to the C=N bond. In one of the mol­ecules, the dihedral angle between the benzene ring and the hydrazinecarboxylic acid plane is 24.9 (2)°, and that in the other mol­ecule is 16.1 (2)°. The mol­ecules are linked into a three-dimensional network via inter­molecular N—H(...)O, C—H(...)O, C—H(...)N and C—H(...)Br hydrogen bonds. An intramolecular N—H(...)O hydrogen bond is also present.

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: Cheng (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1544-scheme1.jpg

Experimental

Crystal data

  • C9H9BrN2O2
  • M r = 257.09
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1544-efi1.jpg
  • a = 13.8585 (10) Å
  • b = 9.5257 (7) Å
  • c = 15.5871 (11) Å
  • β = 95.967 (3)°
  • V = 2046.5 (3) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 3.99 mm−1
  • T = 123 (2) K
  • 0.30 × 0.26 × 0.25 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2002 [triangle]) T min = 0.320, T max = 0.367
  • 20978 measured reflections
  • 3610 independent reflections
  • 2615 reflections with I > 2σ(I)
  • R int = 0.056

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.099
  • S = 1.05
  • 3610 reflections
  • 254 parameters
  • H-atom parameters constrained
  • Δρmax = 0.76 e Å−3
  • Δρmin = −0.49 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/S1600536808021983/ci2632sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021983/ci2632Isup2.hkl

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

Acknowledgments

The authors acknowledge financial support from Zhejiang Police College, 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 is reported here.

The title molecule (Fig.1) 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/C7-C9 planes is 24.9 (2)° and that between C10-C15 and N3/N4/O3/O4/C16-C18 planes is 14.8 (2)°. The bond lengths and angles of each molecule in the asymmetric unit agree with those observed for ethyl N'-[(E)-4-hydroxybenzylidene]hydrazinecarboxylate (Cheng, 2008). The independent molecules are linked through N4-H4A···O1 hydrogen bond.

The molecules are linked into a three-dimensional network by intermolecular N—H···O, C—H···O, C—H···N and C—H···Br hydrogen bonds (Fig.2).

Experimental

4-Bromobenzaldehyde (1.84 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90 g, 0.01 mol) were dissolved in stirred methanol (25 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 75% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution at room temperature (m.p. 459–462 K).

Refinement

H atoms were positioned geometrically (N-H = 0.88 Å and C-H = 0.95 or 0.98 Å) and refined using a riding model, with Uiso(H) = 1.2–1.5Ueq(C).

Figures

Fig. 1.
Molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atomic numbering.
Fig. 2.
The crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C9H9BrN2O2F000 = 1024
Mr = 257.09Dx = 1.669 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3610 reflections
a = 13.8585 (10) Åθ = 1.5–25.0º
b = 9.5257 (7) ŵ = 3.99 mm1
c = 15.5871 (11) ÅT = 123 (2) K
β = 95.967 (3)ºBlock, colourless
V = 2046.5 (3) Å30.30 × 0.26 × 0.25 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer3610 independent reflections
Radiation source: fine-focus sealed tube2615 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.056
T = 123(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 1.5º
Absorption correction: multi-scan(SADABS; Bruker, 2002)h = −16→16
Tmin = 0.320, Tmax = 0.368k = −11→9
20978 measured reflectionsl = −18→18

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.036  w = 1/[σ2(Fo2) + (0.048P)2 + 0.8965P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.099(Δ/σ)max = 0.001
S = 1.05Δρmax = 0.76 e Å3
3610 reflectionsΔρmin = −0.49 e Å3
254 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0078 (6)
Secondary atom site location: difference Fourier map

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
Br20.54645 (3)0.79291 (5)0.97542 (3)0.07171 (19)
Br10.53903 (3)0.13944 (5)0.80455 (3)0.0767 (2)
O2−0.13460 (16)0.5200 (3)0.56109 (14)0.0519 (6)
O1−0.05639 (17)0.5733 (3)0.69189 (14)0.0545 (6)
O3−0.01087 (16)0.2800 (3)0.95955 (15)0.0562 (6)
O4−0.12520 (16)0.3158 (3)0.84755 (15)0.0558 (6)
N2−0.00584 (19)0.3978 (3)0.60735 (17)0.0473 (7)
H2A−0.02240.34310.56280.057*
N40.0057 (2)0.4480 (3)0.85778 (17)0.0484 (7)
H4A−0.02230.49150.81200.058*
N30.09646 (19)0.4870 (3)0.89337 (16)0.0473 (7)
N10.07984 (19)0.3755 (3)0.65906 (16)0.0447 (7)
C8−0.0638 (2)0.5048 (4)0.6263 (2)0.0423 (7)
C60.2240 (2)0.2373 (3)0.6832 (2)0.0420 (7)
C70.1282 (2)0.2684 (4)0.6391 (2)0.0443 (8)
H70.10120.20750.59460.053*
C160.1337 (2)0.5923 (4)0.8575 (2)0.0473 (8)
H160.09770.63920.81090.057*
C140.2665 (3)0.7650 (4)0.8564 (2)0.0527 (9)
H140.22650.81830.81540.063*
C30.2686 (3)0.1104 (4)0.6674 (2)0.0519 (9)
H30.23500.04340.63040.062*
C17−0.0398 (2)0.3416 (4)0.8945 (2)0.0435 (8)
C150.2313 (2)0.6402 (3)0.8879 (2)0.0449 (8)
C18−0.1841 (3)0.2064 (4)0.8805 (3)0.0655 (10)
H18A−0.24420.19550.84210.098*
H18B−0.19980.23210.93840.098*
H18C−0.14810.11770.88350.098*
C40.3665 (2)0.3015 (4)0.7766 (2)0.0519 (9)
H40.40040.36640.81500.062*
C20.3607 (3)0.0802 (4)0.7048 (2)0.0566 (9)
H20.3904−0.00690.69370.068*
C50.2746 (3)0.3315 (4)0.7396 (2)0.0508 (9)
H50.24500.41780.75260.061*
C130.2918 (3)0.5639 (4)0.9480 (2)0.0552 (9)
H130.26910.47850.97030.066*
C100.3585 (3)0.8122 (4)0.8839 (2)0.0562 (9)
H100.38150.89790.86250.067*
C110.4167 (2)0.7338 (4)0.9426 (2)0.0521 (9)
C10.4090 (2)0.1767 (4)0.7578 (2)0.0484 (8)
C9−0.2049 (3)0.6282 (4)0.5732 (3)0.0651 (10)
H9A−0.25340.63140.52280.098*
H9B−0.17210.71920.58020.098*
H9C−0.23710.60730.62480.098*
C120.3837 (3)0.6103 (4)0.9756 (2)0.0575 (9)
H120.42410.55781.01680.069*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br20.0498 (2)0.0817 (3)0.0820 (3)−0.0070 (2)−0.00095 (19)−0.0060 (2)
Br10.0418 (2)0.1006 (4)0.0865 (3)0.0154 (2)0.00182 (18)0.0141 (2)
O20.0420 (12)0.0612 (15)0.0504 (13)0.0084 (11)−0.0059 (10)−0.0043 (11)
O10.0605 (15)0.0590 (15)0.0427 (13)0.0140 (12)−0.0011 (11)−0.0030 (12)
O30.0524 (14)0.0644 (17)0.0493 (14)0.0002 (12)−0.0066 (11)0.0131 (12)
O40.0439 (13)0.0578 (15)0.0625 (14)−0.0003 (11)−0.0102 (11)0.0068 (12)
N20.0409 (15)0.0501 (17)0.0487 (15)0.0057 (13)−0.0060 (12)−0.0100 (13)
N40.0487 (16)0.0476 (18)0.0459 (15)0.0009 (13)−0.0096 (12)0.0090 (13)
N30.0452 (16)0.0499 (18)0.0453 (15)0.0034 (13)−0.0025 (12)−0.0006 (13)
N10.0415 (15)0.0497 (18)0.0420 (14)0.0004 (13)−0.0005 (11)0.0008 (12)
C80.0357 (16)0.049 (2)0.0417 (18)−0.0013 (15)0.0014 (13)0.0047 (16)
C60.0416 (17)0.0395 (19)0.0449 (17)0.0017 (15)0.0045 (13)0.0022 (14)
C70.0448 (18)0.040 (2)0.0470 (18)−0.0026 (15)0.0012 (14)−0.0019 (15)
C160.052 (2)0.045 (2)0.0430 (18)0.0084 (16)0.0009 (15)−0.0022 (16)
C140.057 (2)0.048 (2)0.052 (2)0.0085 (17)−0.0007 (16)0.0052 (17)
C30.055 (2)0.043 (2)0.057 (2)−0.0030 (17)0.0008 (16)−0.0047 (16)
C170.0405 (17)0.045 (2)0.0437 (18)0.0097 (15)−0.0005 (14)−0.0026 (15)
C150.0474 (18)0.043 (2)0.0436 (17)0.0068 (16)0.0022 (14)−0.0030 (15)
C180.048 (2)0.070 (3)0.078 (3)−0.005 (2)−0.0002 (18)0.001 (2)
C40.0491 (19)0.048 (2)0.056 (2)−0.0009 (17)−0.0036 (16)−0.0030 (16)
C20.055 (2)0.049 (2)0.068 (2)0.0130 (18)0.0124 (18)0.0032 (18)
C50.053 (2)0.043 (2)0.055 (2)0.0035 (16)−0.0003 (16)−0.0064 (16)
C130.061 (2)0.045 (2)0.058 (2)0.0010 (18)0.0006 (17)0.0061 (17)
C100.059 (2)0.052 (2)0.058 (2)−0.0010 (18)0.0059 (17)0.0058 (17)
C110.0416 (18)0.057 (2)0.057 (2)0.0005 (17)0.0024 (15)−0.0102 (17)
C10.0379 (17)0.054 (2)0.0537 (19)0.0032 (16)0.0041 (15)0.0096 (17)
C90.0423 (19)0.072 (3)0.078 (3)0.0148 (19)−0.0051 (18)0.004 (2)
C120.054 (2)0.053 (2)0.062 (2)0.0061 (18)−0.0060 (17)0.0071 (18)

Geometric parameters (Å, °)

Br2—C111.903 (3)C14—C151.394 (5)
Br1—C11.906 (3)C14—H140.95
O2—C81.345 (4)C3—C21.377 (5)
O2—C91.445 (4)C3—H30.95
O1—C81.208 (4)C15—C131.394 (5)
O3—C171.204 (4)C18—H18A0.98
O4—C171.348 (4)C18—H18B0.98
O4—C181.450 (5)C18—H18C0.98
N2—C81.349 (4)C4—C11.371 (5)
N2—N11.380 (3)C4—C51.374 (5)
N2—H2A0.88C4—H40.95
N4—C171.352 (4)C2—C11.364 (5)
N4—N31.372 (4)C2—H20.95
N4—H4A0.88C5—H50.95
N3—C161.283 (4)C13—C121.375 (5)
N1—C71.277 (4)C13—H130.95
C6—C51.393 (4)C10—C111.376 (5)
C6—C31.392 (5)C10—H100.95
C6—C71.460 (4)C11—C121.380 (5)
C7—H70.95C9—H9A0.98
C16—C151.458 (5)C9—H9B0.98
C16—H160.95C9—H9C0.98
C14—C101.377 (5)C12—H120.95
C8—O2—C9115.3 (3)O4—C18—H18B109.5
C17—O4—C18115.7 (3)H18A—C18—H18B109.5
C8—N2—N1118.9 (3)O4—C18—H18C109.5
C8—N2—H2A120.5H18A—C18—H18C109.5
N1—N2—H2A120.5H18B—C18—H18C109.5
C17—N4—N3118.7 (3)C1—C4—C5119.4 (3)
C17—N4—H4A120.7C1—C4—H4120.3
N3—N4—H4A120.7C5—C4—H4120.3
C16—N3—N4115.4 (3)C1—C2—C3119.4 (3)
C7—N1—N2115.0 (3)C1—C2—H2120.3
O1—C8—O2124.9 (3)C3—C2—H2120.3
O1—C8—N2126.4 (3)C4—C5—C6121.0 (3)
O2—C8—N2108.6 (3)C4—C5—H5119.5
C5—C6—C3117.9 (3)C6—C5—H5119.5
C5—C6—C7122.7 (3)C12—C13—C15121.0 (3)
C3—C6—C7119.5 (3)C12—C13—H13119.5
N1—C7—C6121.4 (3)C15—C13—H13119.5
N1—C7—H7119.3C14—C10—C11119.3 (3)
C6—C7—H7119.3C14—C10—H10120.4
N3—C16—C15120.3 (3)C11—C10—H10120.4
N3—C16—H16119.9C10—C11—C12121.1 (3)
C15—C16—H16119.9C10—C11—Br2119.3 (3)
C10—C14—C15121.1 (3)C12—C11—Br2119.5 (3)
C10—C14—H14119.5C2—C1—C4121.3 (3)
C15—C14—H14119.5C2—C1—Br1119.4 (3)
C2—C3—C6121.1 (3)C4—C1—Br1119.3 (3)
C2—C3—H3119.5O2—C9—H9A109.5
C6—C3—H3119.5O2—C9—H9B109.5
O3—C17—O4124.4 (3)H9A—C9—H9B109.5
O3—C17—N4126.4 (3)O2—C9—H9C109.5
O4—C17—N4109.2 (3)H9A—C9—H9C109.5
C13—C15—C14118.2 (3)H9B—C9—H9C109.5
C13—C15—C16121.8 (3)C13—C12—C11119.3 (3)
C14—C15—C16120.0 (3)C13—C12—H12120.3
O4—C18—H18A109.5C11—C12—H12120.3
C17—N4—N3—C16−177.3 (3)N3—C16—C15—C138.7 (5)
C8—N2—N1—C7176.9 (3)N3—C16—C15—C14−171.7 (3)
C9—O2—C8—O10.5 (5)C6—C3—C2—C1−0.2 (5)
C9—O2—C8—N2178.0 (3)C1—C4—C5—C60.0 (5)
N1—N2—C8—O1−11.7 (5)C3—C6—C5—C41.7 (5)
N1—N2—C8—O2170.8 (3)C7—C6—C5—C4−176.8 (3)
N2—N1—C7—C6174.9 (3)C14—C15—C13—C120.0 (5)
C5—C6—C7—N1−9.9 (5)C16—C15—C13—C12179.6 (3)
C3—C6—C7—N1171.6 (3)C15—C14—C10—C110.7 (5)
N4—N3—C16—C15−177.9 (3)C14—C10—C11—C12−1.2 (6)
C5—C6—C3—C2−1.6 (5)C14—C10—C11—Br2176.3 (3)
C7—C6—C3—C2177.0 (3)C3—C2—C1—C42.0 (5)
C18—O4—C17—O30.5 (5)C3—C2—C1—Br1−176.7 (3)
C18—O4—C17—N4−178.2 (3)C5—C4—C1—C2−1.8 (5)
N3—N4—C17—O34.3 (5)C5—C4—C1—Br1176.8 (3)
N3—N4—C17—O4−177.0 (3)C15—C13—C12—C11−0.5 (6)
C10—C14—C15—C13−0.1 (5)C10—C11—C12—C131.1 (6)
C10—C14—C15—C16−179.7 (3)Br2—C11—C12—C13−176.4 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O3i0.882.012.854 (4)160
N4—H4A···O10.882.042.896 (3)165
C7—H7···O3i0.952.493.261 (4)139
C9—H9A···Br2ii0.982.893.697 (3)141
C18—H18C···N1iii0.982.603.548 (5)162

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x−1, −y+3/2, z−1/2; (iii) −x, y−1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2632).

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.
  • Cheng, X.-W. (2008). Acta Cryst. E64, o1396. [PMC free article] [PubMed]
  • 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.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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