Ethyl (E)-2-(2-furyl­idene)hydrazine­carboxyl­ate

Lv, L.-P.; Li, W.-W.; Yu, T.-M.; Yu, W.-B.; Hu, X.-C.

doi:10.1107/S1600536809023654

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1678

doi:10.1107/S1600536809023654

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Ethyl (E)-2-(2-furylidene)hydrazinecarboxylate

Lu-Ping Lv,^a Wei-Wei Li,^a Tie-Ming Yu,^a Wen-Bo Yu ^a and Xian-Chao Hu ^b ^*

^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 14 June 2009; accepted 19 June 2009; online 24 June 2009)

In the title compound, C₈H₁₀N₂O₃, the hydrazinecarboxylate group is twisted from the furan ring by 6.98 (17)°. In the crystal, the molecules are linked into one-dimensional chains running along the c axis by N—H⋯O hydrogen bonds.

Related literature

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

Crystal data

C₈H₁₀N₂O₃
M_r = 182.18
Monoclinic, C c
a = 14.150 (6) Å
b = 9.285 (5) Å
c = 8.108 (4) Å
β = 118.540 (16)°
V = 935.8 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 223 K
0.24 × 0.22 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.975, T_max = 0.985
2344 measured reflections
816 independent reflections
733 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.071
S = 1.07
816 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.10 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2ⁱ	0.86	2.08	2.916 (3)	164
Symmetry code: (i) $[x, -y, z+{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023654/bg2272sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809023654/bg2272Isup2.hkl

checkCIF report

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).

In the title compound, C₈H₁₀N₂O₃ (I), the N1/N2/O2/O3/C6/C7 planes form dihedral angles of 6.98 (17)° with the O1/C1—C4 planes.The bond lengths and angles are comparable to those observed for methylN'-[(E)-4-methoxybenzylidene]hydrazinecarboxylate (Shang et al., 2007).

In the crystal structure, the molecules are linked into one-dimentional chains running along the c axis by N—H···O hydrogen bonds(Table 1,Fig.1).

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 Ethyl hydrazinecarboxylate (1.04 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 95% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 410–412 K).

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

	Fig. 1. The asymmetric unit of (I). Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. Crystal packing of (I), showing the formation of chains along c. Hydrogen bonds are shown as dashed lines.

Ethyl (E)-2-(2-furylidene)hydrazinecarboxylate top

Crystal data top

C₈H₁₀N₂O₃	F(000) = 384
M_r = 182.18	D_x = 1.293 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1451 reflections
a = 14.150 (6) Å	θ = 2.7–25.0°
b = 9.285 (5) Å	µ = 0.10 mm⁻¹
c = 8.108 (4) Å	T = 223 K
β = 118.540 (16)°	Block, colourless
V = 935.8 (8) Å³	0.24 × 0.22 × 0.17 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	816 independent reflections
Radiation source: fine-focus sealed tube	733 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −16→16
T_min = 0.975, T_max = 0.985	k = −10→10
2344 measured reflections	l = −8→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0384P)² + 0.0727P] where P = (F_o² + 2F_c²)/3
816 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.10 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₈H₁₀N₂O₃	V = 935.8 (8) Å³
M_r = 182.18	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 14.150 (6) Å	µ = 0.10 mm⁻¹
b = 9.285 (5) Å	T = 223 K
c = 8.108 (4) Å	0.24 × 0.22 × 0.17 mm
β = 118.540 (16)°

Data collection top

Bruker SMART CCD area-detector diffractometer	816 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	733 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.985	R_int = 0.024
2344 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.071	H-atom parameters constrained
S = 1.07	Δρ_max = 0.10 e Å⁻³
816 reflections	Δρ_min = −0.16 e Å⁻³
118 parameters

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

	x	y	z	U_iso*/U_eq
O3	−0.05924 (14)	−0.0975 (2)	0.4141 (2)	0.0686 (5)
N2	0.10734 (15)	−0.0174 (2)	0.5472 (3)	0.0561 (5)
H2	0.0934	0.0188	0.6309	0.067*
O1	0.41276 (15)	0.0404 (2)	0.6109 (3)	0.0754 (6)
O2	0.04565 (14)	−0.1545 (2)	0.2815 (2)	0.0654 (5)
N1	0.20660 (15)	0.0030 (2)	0.5573 (3)	0.0527 (5)
C3	0.4583 (2)	0.1980 (3)	0.8408 (4)	0.0702 (8)
H3	0.4555	0.2580	0.9302	0.084*
C5	0.27221 (19)	0.0837 (3)	0.6911 (3)	0.0541 (6)
H5	0.2503	0.1248	0.7719	0.065*
C6	0.03274 (18)	−0.0952 (3)	0.4038 (3)	0.0531 (6)
C4	0.37893 (19)	0.1127 (2)	0.7200 (3)	0.0533 (6)
C7	−0.1479 (2)	−0.1819 (4)	0.2726 (4)	0.0785 (8)
H7A	−0.1895	−0.2234	0.3273	0.094*
H7B	−0.1196	−0.2601	0.2299	0.094*
C1	0.5472 (2)	0.1804 (3)	0.8079 (4)	0.0745 (8)
H1	0.6138	0.2259	0.8705	0.089*
C2	0.5161 (2)	0.0859 (4)	0.6694 (5)	0.0822 (9)
H2A	0.5589	0.0544	0.6183	0.099*
C8	−0.2181 (3)	−0.0897 (5)	0.1115 (5)	0.1058 (12)
H8A	−0.2758	−0.1465	0.0190	0.159*
H8B	−0.1769	−0.0492	0.0571	0.159*
H8C	−0.2473	−0.0135	0.1537	0.159*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0582 (10)	0.0793 (13)	0.0731 (12)	−0.0042 (9)	0.0354 (9)	−0.0022 (10)
N2	0.0546 (12)	0.0655 (13)	0.0533 (11)	0.0001 (10)	0.0299 (9)	−0.0041 (10)
O1	0.0585 (10)	0.0904 (12)	0.0779 (12)	−0.0088 (10)	0.0329 (10)	−0.0277 (11)
O2	0.0669 (10)	0.0755 (11)	0.0593 (10)	−0.0093 (9)	0.0347 (9)	−0.0106 (9)
N1	0.0517 (11)	0.0574 (11)	0.0510 (11)	0.0013 (9)	0.0261 (9)	0.0025 (9)
C3	0.081 (2)	0.0659 (17)	0.0638 (16)	−0.0113 (15)	0.0347 (15)	−0.0160 (13)
C5	0.0610 (14)	0.0538 (14)	0.0474 (13)	0.0032 (13)	0.0259 (11)	0.0004 (12)
C6	0.0517 (13)	0.0586 (15)	0.0521 (14)	0.0045 (11)	0.0273 (11)	0.0110 (12)
C4	0.0594 (14)	0.0537 (13)	0.0451 (12)	0.0034 (11)	0.0236 (11)	−0.0002 (11)
C7	0.0616 (16)	0.082 (2)	0.092 (2)	−0.0168 (16)	0.0366 (16)	−0.0043 (17)
C1	0.0593 (14)	0.0745 (19)	0.0787 (19)	−0.0163 (14)	0.0241 (14)	−0.0068 (15)
C2	0.0567 (15)	0.099 (2)	0.095 (2)	−0.0099 (15)	0.0392 (15)	−0.0218 (19)
C8	0.0683 (19)	0.126 (3)	0.103 (3)	−0.012 (2)	0.0241 (19)	0.006 (2)

Geometric parameters (Å, º) top

O3—C6	1.344 (3)	C5—C4	1.438 (4)
O3—C7	1.459 (3)	C5—H5	0.9300
N2—C6	1.347 (3)	C7—C8	1.479 (5)
N2—N1	1.380 (2)	C7—H7A	0.9700
N2—H2	0.8600	C7—H7B	0.9700
O1—C2	1.371 (4)	C1—C2	1.324 (4)
O1—C4	1.366 (3)	C1—H1	0.9300
O2—C6	1.221 (3)	C2—H2A	0.9300
N1—C5	1.279 (3)	C8—H8A	0.9600
C3—C4	1.341 (4)	C8—H8B	0.9600
C3—C1	1.415 (4)	C8—H8C	0.9600
C3—H3	0.9300

C6—O3—C7	117.0 (2)	O3—C7—C8	110.2 (3)
C6—N2—N1	118.71 (18)	O3—C7—H7A	109.6
C6—N2—H2	120.6	C8—C7—H7A	109.6
N1—N2—H2	120.6	O3—C7—H7B	109.6
C2—O1—C4	105.7 (2)	C8—C7—H7B	109.6
C5—N1—N2	115.90 (18)	H7A—C7—H7B	108.1
C4—C3—C1	107.7 (2)	C2—C1—C3	105.7 (2)
C4—C3—H3	126.1	C2—C1—H1	127.1
C1—C3—H3	126.1	C3—C1—H1	127.1
N1—C5—C4	121.9 (2)	C1—C2—O1	111.5 (3)
N1—C5—H5	119.1	C1—C2—H2A	124.3
C4—C5—H5	119.1	O1—C2—H2A	124.3
O2—C6—O3	124.6 (2)	C7—C8—H8A	109.5
O2—C6—N2	125.6 (2)	C7—C8—H8B	109.5
O3—C6—N2	109.7 (2)	H8A—C8—H8B	109.5
C3—C4—O1	109.4 (2)	C7—C8—H8C	109.5
C3—C4—C5	132.7 (2)	H8A—C8—H8C	109.5
O1—C4—C5	117.9 (2)	H8B—C8—H8C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.86	2.08	2.916 (3)	164

Symmetry code: (i) x, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₁₀N₂O₃
M_r	182.18
Crystal system, space group	Monoclinic, Cc
Temperature (K)	223
a, b, c (Å)	14.150 (6), 9.285 (5), 8.108 (4)
β (°)	118.540 (16)
V (Å³)	935.8 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.24 × 0.22 × 0.17

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.975, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	2344, 816, 733
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.071, 1.07
No. of reflections	816
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.10, −0.16

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···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.86	2.08	2.916 (3)	164.0

Symmetry code: (i) x, −y, z+1/2.

Acknowledgements

The authors are grateful for financial suport from the Zhejiang University of Technology Foundation (grant No. 20080169) and the Analysis and Measurement Foundation of Zhejiang Province (grant No. 2008 F70003).

References

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