PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): o2062.
Published online 2008 October 4. doi:  10.1107/S1600536808031462
PMCID: PMC2959676

(E)-Ethyl N′-[1-(4-methoxy­phen­yl)ethyl­idene]hydrazinecarboxyl­ate

Abstract

The mol­ecule of the title compound, C12H16N2O3, adopts a trans configuration with respect to the C=N bond. The dihedral angle between the benzene ring and the hydrazinecarboxyl­ate plane is 13.82 (6)°. In the crystal structure, mol­ecules are linked into centrosymmetric dimers by N—H(...)O and C—H(...)O hydrogen bonds, and the dimers are linked together by C—H(...)π inter­actions.

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: Lv et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2062-scheme1.jpg

Experimental

Crystal data

  • C12H16N2O3
  • M r = 236.27
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2062-efi1.jpg
  • a = 12.1020 (11) Å
  • b = 8.1727 (7) Å
  • c = 25.476 (2) Å
  • V = 2519.8 (4) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 123 (2) K
  • 0.27 × 0.23 × 0.22 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS, Bruker, 2002 [triangle]) T min = 0.973, T max = 0.981
  • 12848 measured reflections
  • 2222 independent reflections
  • 1845 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.127
  • S = 1.07
  • 2222 reflections
  • 158 parameters
  • H-atom parameters constrained
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.14 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/S1600536808031462/ci2686sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808031462/ci2686Isup2.hkl

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

Acknowledgments

The authors thank Hangzhou Vocational and Technical College, China, for financial support.

supplementary crystallographic information

Comment

Benzaldehydehydrazone derivatives have received considerable attention for a long time, due to their pharmacological activities (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, we report herein the crystal structure of the title compound.

The title molecule (Fig. 1) adopts a trans configuration with respect to the C═N double bond. The bond lengths and angles are comparable to those observed for (E)-methyl N'-[1-(4-methoxyphenyl)ethylidene]hydrazinecarboxylate (Lv et al., 2008). Atoms C11 and C12 deviate from the O2/O3/N1/N2/C7-C10 plane by 0.406 (2) and 0.175 (2) Å, respectively. The dihedral angle between benzene (C2-C7) and O2/O3/N1/N2/C7-C10 planes is 13.82 (6)°.

In the crystal structure, intermolecular N—H···O and C–H···O hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers (Fig. 2). A C—H···π contact (Table 1) between benzene ring (centroid Cg1) and C1-methyl group further stabilizes the structure.

Experimental

4-Methoxy-acetophenone (1.50 g, 0.01 mol) and ethyl hydrazinecarboxylate (1.04 g, 0.01 mol) were dissolved in stirred methanol (25 ml) and left for 3.5 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound (yield 83%, m.p. 465-468 K). Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Refinement

H atoms were positioned geometrically, with N-H = 0.86 Å and C-H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H and x = 1.2 for all other H atoms. A rotating group model was used for the methyl groups.

Figures

Fig. 1.
The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
The crystal packing of the title compound, viewed approximately down the c axis. Hydrogen bonds are shown as dashed lines.

Crystal data

C12H16N2O3F(000) = 1008
Mr = 236.27Dx = 1.246 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2222 reflections
a = 12.1020 (11) Åθ = 1.6–25.0°
b = 8.1727 (7) ŵ = 0.09 mm1
c = 25.476 (2) ÅT = 123 K
V = 2519.8 (4) Å3Block, colourless
Z = 80.27 × 0.23 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer2222 independent reflections
Radiation source: fine-focus sealed tube1845 reflections with I > 2σ(I)
graphiteRint = 0.026
[var phi] and ω scansθmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS, Bruker, 2002)h = −12→14
Tmin = 0.973, Tmax = 0.981k = −9→9
12848 measured reflectionsl = −30→30

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.127w = 1/[σ2(Fo2) + (0.0637P)2 + 0.6384P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.002
2222 reflectionsΔρmax = 0.19 e Å3
158 parametersΔρmin = −0.14 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0115 (13)

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
C70.42346 (13)0.5640 (2)0.60487 (6)0.0490 (4)
C80.43416 (13)0.4210 (2)0.56947 (6)0.0501 (4)
C30.40760 (13)0.8369 (2)0.67166 (6)0.0525 (4)
C20.37209 (14)0.8477 (2)0.62024 (7)0.0570 (4)
H20.34300.94530.60750.068*
C90.59258 (14)0.0586 (2)0.56465 (7)0.0542 (4)
C50.45905 (15)0.5568 (2)0.65717 (7)0.0580 (5)
H50.48900.46000.67000.070*
C60.38006 (15)0.7122 (2)0.58781 (6)0.0561 (4)
H60.35550.72070.55330.067*
C40.45058 (16)0.6900 (2)0.68974 (7)0.0613 (5)
H40.47400.68160.72440.074*
C10.35816 (19)1.1125 (2)0.69025 (8)0.0733 (6)
H1A0.40391.15770.66310.110*
H1B0.35501.18720.71930.110*
H1C0.28501.09480.67690.110*
C110.7327 (2)−0.0352 (3)0.68377 (9)0.0932 (7)
H11A0.76560.06940.69080.140*
H11B0.7815−0.12040.69540.140*
H11C0.6637−0.04350.70210.140*
C100.7136 (2)−0.0522 (3)0.62760 (9)0.0894 (8)
H10A0.6803−0.15760.62010.107*
H10B0.7831−0.04510.60870.107*
O30.63987 (11)0.07917 (16)0.61102 (5)0.0677 (4)
O20.61004 (11)−0.05717 (16)0.53593 (5)0.0701 (4)
O10.40315 (12)0.96202 (16)0.70721 (5)0.0673 (4)
N20.52061 (12)0.17888 (17)0.55187 (5)0.0571 (4)
H2A0.48350.17130.52320.068*
N10.50534 (12)0.31305 (17)0.58366 (5)0.0532 (4)
C120.36482 (15)0.4117 (2)0.52056 (7)0.0621 (5)
H12A0.40980.43610.49050.093*
H12B0.30560.48960.52280.093*
H12C0.33470.30360.51710.093*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C70.0429 (8)0.0533 (9)0.0509 (9)−0.0002 (7)0.0003 (7)0.0052 (7)
C80.0451 (9)0.0546 (10)0.0505 (9)−0.0011 (7)0.0025 (7)0.0067 (7)
C30.0468 (9)0.0571 (10)0.0536 (9)−0.0019 (8)0.0000 (7)−0.0028 (7)
C20.0595 (10)0.0542 (10)0.0572 (9)0.0087 (8)−0.0028 (8)0.0067 (8)
C90.0501 (9)0.0571 (10)0.0555 (9)0.0012 (8)−0.0014 (7)−0.0050 (8)
C50.0597 (10)0.0560 (10)0.0584 (10)0.0046 (8)−0.0103 (8)0.0079 (8)
C60.0606 (10)0.0615 (11)0.0461 (8)0.0065 (8)−0.0038 (7)0.0049 (8)
C40.0642 (11)0.0664 (11)0.0532 (9)0.0029 (9)−0.0134 (8)0.0029 (8)
C10.0867 (14)0.0597 (12)0.0736 (12)0.0091 (10)−0.0031 (10)−0.0111 (10)
C110.1006 (18)0.0890 (16)0.0900 (15)0.0101 (14)−0.0275 (13)0.0137 (13)
C100.0913 (17)0.0877 (16)0.0894 (15)0.0396 (13)−0.0261 (12)−0.0145 (12)
O30.0734 (9)0.0651 (8)0.0646 (8)0.0184 (6)−0.0172 (6)−0.0106 (6)
O20.0664 (8)0.0722 (9)0.0715 (8)0.0159 (7)−0.0101 (6)−0.0200 (7)
O10.0760 (9)0.0648 (8)0.0611 (7)0.0067 (6)−0.0071 (6)−0.0088 (6)
N20.0598 (8)0.0592 (9)0.0522 (8)0.0075 (7)−0.0079 (6)−0.0035 (6)
N10.0563 (8)0.0512 (8)0.0520 (8)0.0021 (6)−0.0004 (6)−0.0005 (6)
C120.0575 (10)0.0676 (12)0.0613 (10)0.0027 (9)−0.0066 (8)−0.0046 (9)

Geometric parameters (Å, °)

C7—C61.390 (2)C1—O11.412 (2)
C7—C51.401 (2)C1—H1A0.96
C7—C81.482 (2)C1—H1B0.96
C8—N11.285 (2)C1—H1C0.96
C8—C121.504 (2)C11—C101.456 (3)
C3—O11.367 (2)C11—H11A0.96
C3—C21.382 (2)C11—H11B0.96
C3—C41.387 (2)C11—H11C0.96
C2—C61.385 (2)C10—O31.458 (2)
C2—H20.93C10—H10A0.97
C9—O21.215 (2)C10—H10B0.97
C9—O31.323 (2)N2—N11.376 (2)
C9—N21.353 (2)N2—H2A0.86
C5—C41.372 (2)C12—H12A0.96
C5—H50.93C12—H12B0.96
C6—H60.93C12—H12C0.96
C4—H40.93
C6—C7—C5116.71 (15)O1—C1—H1C109.5
C6—C7—C8122.01 (14)H1A—C1—H1C109.5
C5—C7—C8121.27 (15)H1B—C1—H1C109.5
N1—C8—C7115.38 (14)C10—C11—H11A109.5
N1—C8—C12124.94 (15)C10—C11—H11B109.5
C7—C8—C12119.67 (14)H11A—C11—H11B109.5
O1—C3—C2124.64 (16)C10—C11—H11C109.5
O1—C3—C4116.25 (15)H11A—C11—H11C109.5
C2—C3—C4119.11 (16)H11B—C11—H11C109.5
C3—C2—C6119.53 (16)C11—C10—O3108.19 (18)
C3—C2—H2120.2C11—C10—H10A110.1
C6—C2—H2120.2O3—C10—H10A110.1
O2—C9—O3124.14 (16)C11—C10—H10B110.1
O2—C9—N2122.21 (16)O3—C10—H10B110.1
O3—C9—N2113.64 (14)H10A—C10—H10B108.4
C4—C5—C7121.26 (16)C9—O3—C10115.45 (14)
C4—C5—H5119.4C3—O1—C1117.62 (14)
C7—C5—H5119.4C9—N2—N1121.58 (14)
C2—C6—C7122.46 (15)C9—N2—H2A119.2
C2—C6—H6118.8N1—N2—H2A119.2
C7—C6—H6118.8C8—N1—N2118.13 (14)
C5—C4—C3120.91 (16)C8—C12—H12A109.5
C5—C4—H4119.5C8—C12—H12B109.5
C3—C4—H4119.5H12A—C12—H12B109.5
O1—C1—H1A109.5C8—C12—H12C109.5
O1—C1—H1B109.5H12A—C12—H12C109.5
H1A—C1—H1B109.5H12B—C12—H12C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O2i0.862.102.914 (2)157
C12—H12C···O2i0.962.523.250 (2)133
C1—H1C···Cg1ii0.962.763.637 (2)153

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2686).

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.
  • Lv, L.-P., Yu, W.-P., Yu, W.-B., Zhou, X.-F. & Hu, X.-C. (2008). Acta Cryst. E64, o1676. [PMC free article] [PubMed]
  • 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]

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