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Acta Cryst. (2008). E64, o2146    [ doi:10.1107/S1600536808033825 ]

(E)-Methyl N'-(2-furylmethylene)hydrazinecarboxylate

L.-P. Lv, Y.-Z. Zhang, X.-M. Ding, W.-B. Yu and X.-C. Hu

Abstract top

The title compound, C7H8N2O3, 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. The hydrazinecarboxylate group is twisted from the furan ring by 7.78 (13)° in one molecule and by 7.01 (17)° in the other. In the crystal structure, molecules are linked into chains running along [010] by bifurcated N-H...(N,O) and N-H...O hydrogen bonds. In addition, weak C-H...O interactions and an O...C short contact [2.896 (3) Å] are observed.

Comment top

Benzaldehydehydrazone derivatives have attracted much attention due to their pharmacological activity (Parashar et al., 1988) and their photochromic properties (Hadjoudis et al., 1987). They are important intermidiates of 1,3,4-oxadiazoles, which have been reported to be versatile compounds with many interesting properties (Borg et al., 1999). Metal complexes based on Schiff bases have received considerable attention because they can be utilized as model compounds of active centres in various proteins and enzymes (Kahwa et al., 1986; Santos et al., 2001). We report here the crystal structure of the title compound (Fig. 1).

The title compound contains two independent, but essentially identical molecules in the asymmetric unit. Each independent molecule adopts a trans configuration with respect to the C═N bond. The N1/N2/O2/O3/C6/C7 and N3/N4/O5/O6/C13/C14 planes form dihedral angles of 7.78 (13) and 7.01 (17)°, respectively, with the O1/C1–C4 and O4/C8–C11 planes. The dihedral angle between the two independent furan rings is 85.17 (11)°. The bond lengths and angles are comparable to those observed for methyl N'-[(E)-4-methoxybenzylidene]hydrazinecarboxylate (Shang et al., 2007).

In the crystal structure, the molecules are linked into chains running along the [010] by N—H···O and N—H···N hydrogen bonds (Table 1 and Fig.2). In addition, weak C—H···O interactions and an O4···C5 short contact [2.896 (3) Å] are also observed.

Related literature top

For general background, see: Parashar et al. (1988); Hadjoudis et al. (1987); Borg et al. (1999); Kahwa et al. (1986); Santos et al. (2001). For a related structure, see: Shang et al. (2007).

Experimental top

Furfuraldehyde (0.96 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90 g, 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. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 408–413 K).

Refinement top

H atoms were positioned geometrically (N—H = 0.86 Å and C—H = 0.93 or 0.96 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(C,N) and 1.5Ueq(Cmethyl). In the absence of significant anomalous scattering effects, Friedel pairs were averaged.

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 asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 2] Fig. 2. Crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.
(E)-Methyl N'-(2-furylmethylene)hydrazinecarboxylate top
Crystal data top
C7H8N2O3F(000) = 704
Mr = 168.15Dx = 1.313 Mg m−3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2yCell parameters from 1601 reflections
a = 14.9185 (17) Åθ = 1.4–25.0°
b = 7.8124 (9) ŵ = 0.10 mm−1
c = 15.1299 (19) ÅT = 193 K
β = 105.251 (7)°Block, colourless
V = 1701.3 (4) Å30.19 × 0.17 × 0.16 mm
Z = 8
Data collection top
Bruker SMART CCD area-detector
diffractometer		1601 independent reflections
Radiation source: fine-focus sealed tube1399 reflections with I > 2σ(I)
graphiteRint = 0.020
φ and ω scansθmax = 25.0°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		h = −17→17
Tmin = 0.978, Tmax = 0.982k = −9→8
4679 measured reflectionsl = −17→16
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.085 w = 1/[σ2(Fo2) + (0.0464P)2 + 0.2178P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
1601 reflectionsΔρmax = 0.10 e Å−3
218 parametersΔρmin = −0.09 e Å−3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0051 (9)
Crystal data top
C7H8N2O3V = 1701.3 (4) Å3
Mr = 168.15Z = 8
Monoclinic, C2Mo Kα radiation
a = 14.9185 (17) ŵ = 0.10 mm−1
b = 7.8124 (9) ÅT = 193 K
c = 15.1299 (19) Å0.19 × 0.17 × 0.16 mm
β = 105.251 (7)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		1601 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		1399 reflections with I > 2σ(I)
Tmin = 0.978, Tmax = 0.982Rint = 0.020
4679 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.085Δρmax = 0.10 e Å−3
S = 1.07Δρmin = −0.09 e Å−3
1601 reflectionsAbsolute structure: ?
218 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Special details top

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) top
xyzUiso*/Ueq
C10.6802 (2)0.5242 (5)−0.0094 (2)0.0834 (9)
H10.69850.4241−0.03300.100*
C20.6239 (2)0.6570 (6)−0.0595 (2)0.0971 (12)
H20.59690.6590−0.12230.117*
C30.6170 (2)0.7771 (6)0.0000 (2)0.1020 (12)
H30.58500.8797−0.01520.122*
C40.70165 (17)0.5730 (4)0.07936 (17)0.0617 (7)
C50.75360 (16)0.4883 (3)0.16066 (17)0.0583 (6)
H50.77690.37920.15610.070*
C60.83278 (17)0.5270 (4)0.39638 (18)0.0600 (6)
C70.8972 (3)0.4683 (6)0.5526 (2)0.1191 (15)
H7A0.92690.37730.59220.179*
H7B0.84110.50100.56810.179*
H7C0.93830.56480.56000.179*
C80.5302 (2)0.2842 (6)0.1389 (3)0.1233 (17)
H80.51390.38840.10930.148*
C90.4711 (2)0.1714 (5)0.1540 (3)0.0977 (11)
H90.40670.18010.13680.117*
C100.52379 (19)0.0344 (5)0.2012 (2)0.0786 (8)
H100.5006−0.06420.22160.094*
C110.61376 (17)0.0724 (3)0.21148 (18)0.0615 (7)
C120.69799 (17)−0.0134 (3)0.25482 (16)0.0586 (6)
H120.6952−0.12480.27560.070*
C130.93793 (17)0.0282 (4)0.32608 (17)0.0609 (6)
C141.0967 (2)−0.0296 (6)0.3959 (3)0.1240 (16)
H14A1.1351−0.11780.43070.186*
H14B1.10470.07430.43110.186*
H14C1.1143−0.01050.34000.186*
N10.76861 (13)0.5587 (3)0.23906 (14)0.0552 (5)
N20.81642 (15)0.4606 (3)0.31122 (14)0.0652 (6)
H2A0.83550.35970.30250.078*
N30.77726 (14)0.0577 (3)0.26606 (14)0.0596 (5)
N40.85235 (15)−0.0392 (3)0.31071 (16)0.0692 (6)
H40.8447−0.14140.32860.083*
O10.66343 (14)0.7290 (3)0.08659 (13)0.0860 (7)
O20.81342 (12)0.6698 (2)0.41521 (12)0.0673 (5)
O30.87484 (17)0.4105 (3)0.45826 (13)0.0932 (7)
O40.61942 (13)0.2275 (3)0.17282 (18)0.1027 (8)
O50.95630 (12)0.1665 (2)0.30007 (12)0.0699 (5)
O60.99994 (13)−0.0822 (3)0.37459 (16)0.0895 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0933 (19)0.090 (2)0.0653 (18)−0.024 (2)0.0181 (15)−0.0164 (18)
C20.090 (2)0.131 (3)0.0597 (19)−0.034 (2)0.0009 (16)0.004 (2)
C30.097 (2)0.118 (3)0.080 (2)0.012 (2)0.0033 (18)0.024 (2)
C40.0599 (13)0.0630 (19)0.0627 (17)−0.0120 (13)0.0170 (11)−0.0070 (14)
C50.0606 (12)0.0503 (16)0.0669 (16)−0.0080 (11)0.0217 (11)−0.0033 (13)
C60.0688 (14)0.0525 (16)0.0598 (16)0.0034 (12)0.0191 (11)0.0131 (13)
C70.186 (4)0.101 (3)0.063 (2)0.045 (3)0.021 (2)0.022 (2)
C80.0559 (16)0.103 (3)0.200 (4)0.0057 (19)0.014 (2)0.072 (3)
C90.0562 (15)0.102 (3)0.129 (3)−0.0063 (18)0.0139 (16)0.034 (3)
C100.0716 (16)0.0723 (18)0.088 (2)−0.0234 (16)0.0139 (14)0.0125 (16)
C110.0673 (15)0.0484 (16)0.0684 (16)−0.0082 (12)0.0168 (12)0.0072 (13)
C120.0711 (15)0.0428 (14)0.0618 (15)−0.0042 (12)0.0172 (11)0.0016 (11)
C130.0668 (15)0.0493 (15)0.0629 (15)0.0061 (13)0.0108 (11)0.0055 (13)
C140.0683 (19)0.096 (3)0.185 (4)0.0045 (19)−0.007 (2)0.036 (3)
N10.0628 (11)0.0452 (12)0.0577 (13)−0.0017 (9)0.0159 (9)0.0039 (10)
N20.0882 (15)0.0433 (11)0.0659 (14)0.0111 (11)0.0237 (11)0.0071 (11)
N30.0637 (12)0.0448 (12)0.0693 (13)0.0024 (10)0.0158 (10)0.0078 (10)
N40.0663 (12)0.0437 (11)0.0940 (16)0.0038 (10)0.0148 (11)0.0182 (12)
O10.0971 (14)0.0878 (16)0.0700 (13)0.0182 (12)0.0162 (10)0.0062 (11)
O20.0868 (12)0.0485 (11)0.0639 (11)0.0061 (10)0.0154 (9)0.0031 (9)
O30.1460 (19)0.0685 (15)0.0641 (12)0.0357 (14)0.0256 (12)0.0230 (11)
O40.0575 (10)0.0748 (14)0.171 (2)−0.0016 (10)0.0218 (12)0.0520 (15)
O50.0733 (10)0.0521 (11)0.0783 (12)−0.0049 (10)0.0092 (9)0.0131 (10)
O60.0698 (11)0.0645 (14)0.1240 (17)0.0081 (10)0.0075 (11)0.0283 (13)
Geometric parameters (Å, °) top
C1—C41.351 (4)C8—H80.93
C1—C21.421 (6)C9—C101.406 (5)
C1—H10.93C9—H90.93
C2—C31.322 (6)C10—C111.343 (4)
C2—H20.93C10—H100.93
C3—O11.364 (4)C11—O41.357 (3)
C3—H30.93C11—C121.423 (3)
C4—O11.362 (4)C12—N31.277 (3)
C4—C51.432 (4)C12—H120.93
C5—N11.273 (3)C13—O51.206 (3)
C5—H50.93C13—O61.334 (3)
C6—O21.206 (4)C13—N41.344 (3)
C6—O31.337 (3)C14—O61.454 (4)
C6—N21.350 (3)C14—H14A0.96
C7—O31.450 (4)C14—H14B0.96
C7—H7A0.96C14—H14C0.96
C7—H7B0.96N1—N21.370 (3)
C7—H7C0.96N2—H2A0.86
C8—C91.309 (5)N3—N41.373 (3)
C8—O41.368 (4)N4—H40.86
C4—C1—C2106.0 (3)C11—C10—C9107.4 (3)
C4—C1—H1127.0C11—C10—H10126.3
C2—C1—H1127.0C9—C10—H10126.3
C3—C2—C1107.2 (3)C10—C11—O4108.7 (3)
C3—C2—H2126.4C10—C11—C12133.1 (3)
C1—C2—H2126.4O4—C11—C12118.1 (2)
C2—C3—O1110.3 (4)N3—C12—C11122.1 (2)
C2—C3—H3124.8N3—C12—H12119.0
O1—C3—H3124.8C11—C12—H12119.0
C1—C4—O1109.7 (3)O5—C13—O6125.1 (2)
C1—C4—C5131.0 (3)O5—C13—N4125.6 (2)
O1—C4—C5119.2 (2)O6—C13—N4109.4 (2)
N1—C5—C4121.6 (2)O6—C14—H14A109.5
N1—C5—H5119.2O6—C14—H14B109.5
C4—C5—H5119.2H14A—C14—H14B109.5
O2—C6—O3124.2 (3)O6—C14—H14C109.5
O2—C6—N2125.9 (2)H14A—C14—H14C109.5
O3—C6—N2109.9 (3)H14B—C14—H14C109.5
O3—C7—H7A109.5C5—N1—N2115.3 (2)
O3—C7—H7B109.5C6—N2—N1118.1 (2)
H7A—C7—H7B109.5C6—N2—H2A120.9
O3—C7—H7C109.5N1—N2—H2A120.9
H7A—C7—H7C109.5C12—N3—N4115.6 (2)
H7B—C7—H7C109.5C13—N4—N3118.9 (2)
C9—C8—O4110.5 (3)C13—N4—H4120.5
C9—C8—H8124.8N3—N4—H4120.5
O4—C8—H8124.8C4—O1—C3106.7 (3)
C8—C9—C10106.8 (3)C6—O3—C7114.9 (3)
C8—C9—H9126.6C11—O4—C8106.6 (2)
C10—C9—H9126.6C13—O6—C14116.3 (2)
C4—C1—C2—C31.7 (4)C5—N1—N2—C6−178.6 (2)
C1—C2—C3—O1−1.6 (4)C11—C12—N3—N4178.7 (2)
C2—C1—C4—O1−1.1 (3)O5—C13—N4—N3−3.8 (4)
C2—C1—C4—C5177.6 (3)O6—C13—N4—N3176.4 (2)
C1—C4—C5—N1178.0 (3)C12—N3—N4—C13−179.1 (2)
O1—C4—C5—N1−3.3 (3)C1—C4—O1—C30.2 (3)
O4—C8—C9—C100.8 (6)C5—C4—O1—C3−178.8 (2)
C8—C9—C10—C11−0.6 (5)C2—C3—O1—C40.9 (4)
C9—C10—C11—O40.1 (4)O2—C6—O3—C7−0.4 (4)
C9—C10—C11—C12178.3 (3)N2—C6—O3—C7179.2 (3)
C10—C11—C12—N3−171.0 (3)C10—C11—O4—C80.3 (4)
O4—C11—C12—N37.0 (4)C12—C11—O4—C8−178.1 (3)
C4—C5—N1—N2177.8 (2)C9—C8—O4—C11−0.7 (5)
O2—C6—N2—N1−4.2 (4)O5—C13—O6—C14−0.8 (5)
O3—C6—N2—N1176.2 (2)N4—C13—O6—C14179.0 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O50.862.363.138 (3)151
N2—H2A···N30.862.523.242 (3)141
N4—H4···O2i0.862.112.913 (3)156
C2—H2···O5ii0.932.603.521 (4)172
C10—H10···O5iii0.932.593.508 (4)171
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y+1/2, −z; (iii) x−1/2, y−1/2, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O50.862.363.138 (3)151
N2—H2A···N30.862.523.242 (3)141
N4—H4···O2i0.862.112.913 (3)156
C2—H2···O5ii0.932.603.521 (4)172
C10—H10···O5iii0.932.593.508 (4)171
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y+1/2, −z; (iii) x−1/2, y−1/2, z.
Acknowledgements top

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

references
References top

Borg, S., Vollinga, R. C., Labarre, M., Payza, K., Terenius, L. & Luthman, K. (1999). J. Med. Chem. 42, 4331–4342.

Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345–1360.

Kahwa, I. A., Selbin, J., Hsieh, T. Y. & Laine, R. A. (1986). Inorg. Chim. Acta, 151, 201–208.

Parashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim. Acta, 151, 201–208.

Santos, M. L. P., Bagatin, I. A., Pereira, E. M. & Ferreira, A. M. D. C. (2001). J. Chem. Soc. Dalton Trans. pp. 838–844.

Shang, Z.-H., Zhang, H.-L. & Ding, Y. (2007). Acta Cryst. E63, o3394.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.