organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

(E)-Methyl N′-[1-(4-methyl­phen­yl)ethyl­­idene]hydrazine­carboxyl­ate

aDepartment of Chemical Engineering, Hangzhou Vocational and Technical College, Hangzhou 310018, People's Republic of China, and bResearch Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
*Correspondence e-mail: zgdhxc@126.com

(Received 1 October 2008; accepted 2 October 2008; online 4 October 2008)

The title mol­ecule, C11H14N2O2, adopts a trans configuration with respect to the C=N bond. The dihedral angle between the benzene ring and the hydrazinecarboxyl­ate plane is 7.61 (16)°. In the crystal structure, mol­ecules are linked into centrosymmetric dimers by N—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[Parashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim. Acta, 151, 201-208.]); Hadjoudis et al. (1987[Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345-1360.]); Borg et al. (1999[Borg, S., Vollinga, R. C., Labarre, M., Payza, K., Terenius, L. & Luthman, K. (1999). J. Med. Chem. 42, 4331-4342.]). For a related structure, see Lv et al. (2008[Lv, L.-P., Yu, W.-P., Yu, W.-B., Zhou, X.-F. & Hu, X.-C. (2008). Acta Cryst. E64, o1676.]).

[Scheme 1]

Experimental

Crystal data
  • C11H14N2O2

  • Mr = 206.24

  • Monoclinic, P 21 /c

  • a = 11.5197 (3) Å

  • b = 5.5734 (6) Å

  • c = 17.3281 (2) Å

  • β = 94.193 (14)°

  • V = 1109.55 (12) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 273 (2) K

  • 0.24 × 0.22 × 0.20 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2002[Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.978, Tmax = 0.980

  • 5502 measured reflections

  • 1951 independent reflections

  • 1209 reflections with I > 2σ(I)

  • Rint = 0.032

Refinement
  • R[F2 > 2σ(F2)] = 0.057

  • wR(F2) = 0.172

  • S = 1.03

  • 1951 reflections

  • 138 parameters

  • 3 restraints

  • H-atom parameters constrained

  • Δρmax = 0.28 e Å−3

  • Δρmin = −0.26 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2A⋯O1i 0.86 2.12 2.944 (3) 162
C2—H2⋯Cg1ii 0.93 2.83 3.538 (3) 134
Symmetry codes: (i) -x, -y, -z+1; (ii) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]. Cg1 is the centroid of the C2–C7 benzene ring.

Data collection: SMART (Bruker, 2002[Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2002[Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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 useful 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 CN 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). All atoms of O1/O2/N1/N2/C8-C11 are coplanar within ±-0.093 (2)Å. The dihedral angle between the benzene (C2-C7) and O1/O2/N1/N2/C8-C11 planes is 7.61 (16)°.

In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers (Fig. 2). A C—H···π contact (Table 1) between the benzene ring (centroid Cg1) and H atom of aromatic C2 further stabilizes the structure.

Related literature top

For general background, see: Parashar et al. (1988); Hadjoudis et al. (1987); Borg et al. (1999). For a related structure, see Lv et al. (2008).

Experimental top

4-Methyl-acetophenone (1.34 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90 g, 0.01 mol) were dissolved in stirred methanol (25 ml) and left for 5.5 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound (yield 93%, m.p. 453-455 K). Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Refinement top

H atoms were positioned geometrically, with N-H = 0.86 Å and C-H = 0.93 and 0.96 Å for aromatic 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.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level.
[Figure 2] Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
(E)-Methyl N'-[1-(4-methylphenyl)ethylidene]hydrazinecarboxylate top
Crystal data top
C11H14N2O2F(000) = 440
Mr = 206.24Dx = 1.235 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1951 reflections
a = 11.5197 (3) Åθ = 1.8–25.0°
b = 5.5734 (6) ŵ = 0.09 mm1
c = 17.3281 (2) ÅT = 273 K
β = 94.193 (14)°Block, colourless
V = 1109.55 (12) Å30.24 × 0.22 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
1951 independent reflections
Radiation source: fine-focus sealed tube1209 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
ϕ and ω scansθmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 1313
Tmin = 0.978, Tmax = 0.980k = 66
5502 measured reflectionsl = 1920
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.172H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.07P)2 + 0.5722P]
where P = (Fo2 + 2Fc2)/3
1951 reflections(Δ/σ)max < 0.001
138 parametersΔρmax = 0.28 e Å3
3 restraintsΔρmin = 0.26 e Å3
Crystal data top
C11H14N2O2V = 1109.55 (12) Å3
Mr = 206.24Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.5197 (3) ŵ = 0.09 mm1
b = 5.5734 (6) ÅT = 273 K
c = 17.3281 (2) Å0.24 × 0.22 × 0.20 mm
β = 94.193 (14)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1951 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
1209 reflections with I > 2σ(I)
Tmin = 0.978, Tmax = 0.980Rint = 0.032
5502 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0573 restraints
wR(F2) = 0.172H-atom parameters constrained
S = 1.03Δρmax = 0.28 e Å3
1951 reflectionsΔρmin = 0.26 e Å3
138 parameters
Special details top

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) top
xyzUiso*/Ueq
C60.4332 (2)0.0332 (5)0.39288 (14)0.0447 (6)
C50.5218 (2)0.2016 (5)0.40434 (17)0.0571 (8)
H50.51070.33400.43570.069*
C80.3200 (2)0.0595 (5)0.42808 (15)0.0472 (7)
C70.4558 (2)0.1643 (5)0.34621 (16)0.0520 (7)
H70.39940.28270.33790.062*
C30.6471 (2)0.0163 (5)0.32361 (16)0.0548 (7)
C20.5594 (2)0.1865 (5)0.31268 (16)0.0548 (7)
H20.57120.31930.28170.066*
C100.0517 (2)0.2495 (5)0.42066 (17)0.0562 (7)
C40.6258 (2)0.1771 (5)0.37036 (18)0.0632 (8)
H40.68300.29370.37920.076*
C10.7601 (3)0.0414 (7)0.28540 (19)0.0764 (10)
H1A0.75590.17860.25180.115*
H1B0.77320.10020.25570.115*
H1C0.82300.06180.32430.115*
C90.3016 (2)0.2711 (5)0.47910 (17)0.0602 (8)
H9A0.26980.21780.52580.063*
H9C0.37460.34990.49160.063*
H9B0.24840.38120.45260.063*
C110.0088 (3)0.5827 (6)0.3454 (2)0.0789 (10)
H11A0.07250.50480.31670.118*
H11B0.02350.70330.31370.118*
H11C0.03620.65640.39070.118*
N20.13765 (19)0.0920 (4)0.44132 (14)0.0613 (7)
H2A0.12570.01820.47460.074*
N10.24476 (18)0.1054 (4)0.40979 (13)0.0548 (6)
O20.07955 (17)0.4080 (4)0.36804 (12)0.0690 (7)
O10.04293 (16)0.2424 (4)0.44769 (13)0.0733 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C60.0480 (15)0.0439 (15)0.0421 (14)0.0020 (12)0.0018 (11)0.0030 (12)
C50.0586 (17)0.0476 (17)0.0660 (19)0.0056 (13)0.0102 (14)0.0060 (14)
C80.0514 (15)0.0426 (15)0.0478 (15)0.0001 (13)0.0055 (12)0.0006 (12)
C70.0509 (16)0.0495 (17)0.0559 (17)0.0076 (13)0.0054 (13)0.0025 (14)
C30.0485 (16)0.0588 (18)0.0572 (18)0.0005 (14)0.0052 (13)0.0077 (15)
C20.0564 (17)0.0573 (18)0.0515 (17)0.0049 (14)0.0089 (13)0.0058 (14)
C100.0485 (16)0.0579 (18)0.0631 (19)0.0015 (14)0.0098 (14)0.0062 (15)
C40.0537 (17)0.0569 (19)0.080 (2)0.0145 (14)0.0090 (15)0.0013 (16)
C10.0543 (18)0.095 (3)0.082 (2)0.0016 (18)0.0152 (16)0.004 (2)
C90.0566 (17)0.0590 (19)0.0662 (19)0.0039 (14)0.0116 (14)0.0098 (15)
C110.071 (2)0.070 (2)0.096 (3)0.0151 (18)0.0100 (18)0.0236 (19)
N20.0532 (14)0.0602 (16)0.0729 (16)0.0043 (12)0.0202 (12)0.0171 (13)
N10.0459 (13)0.0557 (15)0.0641 (15)0.0030 (11)0.0133 (11)0.0075 (12)
O20.0572 (12)0.0718 (15)0.0801 (15)0.0104 (11)0.0194 (11)0.0241 (12)
O10.0492 (12)0.0806 (16)0.0922 (16)0.0046 (11)0.0205 (11)0.0214 (13)
Geometric parameters (Å, º) top
C6—C51.390 (4)C10—N21.351 (4)
C6—C71.402 (4)C4—H40.9300
C6—C81.487 (3)C1—H1A0.9600
C5—C41.380 (4)C1—H1B0.9600
C5—H50.9300C1—H1C0.9600
C8—N11.286 (3)C9—H9A0.9600
C8—C91.498 (4)C9—H9C0.9600
C7—C21.370 (4)C9—H9B0.9600
C7—H70.9300C11—O21.442 (3)
C3—C41.381 (4)C11—H11A0.9600
C3—C21.389 (4)C11—H11B0.9600
C3—C11.509 (4)C11—H11C0.9600
C2—H20.9300N2—N11.388 (3)
C10—O11.218 (3)N2—H2A0.8600
C10—O21.326 (3)
C5—C6—C7116.5 (2)C3—C1—H1A109.5
C5—C6—C8122.1 (2)C3—C1—H1B109.5
C7—C6—C8121.3 (2)H1A—C1—H1B109.5
C4—C5—C6121.6 (3)C3—C1—H1C109.5
C4—C5—H5119.2H1A—C1—H1C109.5
C6—C5—H5119.2H1B—C1—H1C109.5
N1—C8—C6115.1 (2)C8—C9—H9A109.5
N1—C8—C9125.8 (2)C8—C9—H9C109.5
C6—C8—C9119.1 (2)H9A—C9—H9C109.5
C2—C7—C6121.3 (3)C8—C9—H9B109.5
C2—C7—H7119.3H9A—C9—H9B109.5
C6—C7—H7119.3H9C—C9—H9B109.5
C4—C3—C2117.0 (3)O2—C11—H11A109.5
C4—C3—C1121.7 (3)O2—C11—H11B109.5
C2—C3—C1121.3 (3)H11A—C11—H11B109.5
C7—C2—C3121.9 (3)O2—C11—H11C109.5
C7—C2—H2119.1H11A—C11—H11C109.5
C3—C2—H2119.1H11B—C11—H11C109.5
O1—C10—O2123.7 (3)C10—N2—N1121.1 (2)
O1—C10—N2122.4 (3)C10—N2—H2A119.5
O2—C10—N2113.9 (2)N1—N2—H2A119.5
C5—C4—C3121.6 (3)C8—N1—N2117.8 (2)
C5—C4—H4119.2C10—O2—C11115.8 (2)
C3—C4—H4119.2
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.862.122.944 (3)162
C2—H2···Cg1ii0.932.833.538 (3)134
Symmetry codes: (i) x, y, z+1; (ii) x+1, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC11H14N2O2
Mr206.24
Crystal system, space groupMonoclinic, P21/c
Temperature (K)273
a, b, c (Å)11.5197 (3), 5.5734 (6), 17.3281 (2)
β (°) 94.193 (14)
V3)1109.55 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.24 × 0.22 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.978, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections
5502, 1951, 1209
Rint0.032
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.172, 1.03
No. of reflections1951
No. of parameters138
No. of restraints3
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.26

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.862.122.944 (3)161.8
C2—H2···Cg1ii0.932.833.538 (3)134.0
Symmetry codes: (i) x, y, z+1; (ii) x+1, y+1/2, z+1/2.
 

Acknowledgements

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

References

First citationBorg, S., Vollinga, R. C., Labarre, M., Payza, K., Terenius, L. & Luthman, K. (1999). J. Med. Chem. 42, 4331–4342.  Web of Science CrossRef PubMed CAS Google Scholar
First citationBruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationHadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345–1360.  CrossRef CAS Web of Science Google Scholar
First citationLv, L.-P., Yu, W.-P., Yu, W.-B., Zhou, X.-F. & Hu, X.-C. (2008). Acta Cryst. E64, o1676.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationParashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim. Acta, 151, 201–208.  CrossRef CAS Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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