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

Lv, L.-P.; Xie, J.-W.; Yu, W.-B.; Mao, Y.-H.; Hu, X.-C.

doi:10.1107/S1600536808031462

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2062

doi:10.1107/S1600536808031462

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

Lu-Ping Lv,^a Jian-Wu Xie,^a Wen-Bo Yu,^a Yu-Hui Mao ^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 26 September 2008; accepted 29 September 2008; online 4 October 2008)

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

Experimental

Crystal data

C₁₂H₁₆N₂O₃
M_r = 236.27
Orthorhombic, P b c a
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 ) 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[F² > 2σ(F²)] = 0.040
wR(F²) = 0.127
S = 1.07
2222 reflections
158 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2ⁱ	0.86	2.10	2.914 (2)	157
C12—H12C⋯O2ⁱ	0.96	2.52	3.250 (2)	133
C1—H1C⋯Cg1ⁱⁱ	0.96	2.76	3.637 (2)	153
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[x, -y-{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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/S1600536808031462/ci2686sup1.cif

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

checkCIF report

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 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.

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-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.

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 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.

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

Crystal data top

C₁₂H₁₆N₂O₃	F(000) = 1008
M_r = 236.27	D_x = 1.246 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2222 reflections
a = 12.1020 (11) Å	θ = 1.6–25.0°
b = 8.1727 (7) Å	µ = 0.09 mm⁻¹
c = 25.476 (2) Å	T = 123 K
V = 2519.8 (4) Å³	Block, colourless
Z = 8	0.27 × 0.23 × 0.22 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2222 independent reflections
Radiation source: fine-focus sealed tube	1845 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS, Bruker, 2002)	h = −12→14
T_min = 0.973, T_max = 0.981	k = −9→9
12848 measured reflections	l = −30→30

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.127	w = 1/[σ²(F_o²) + (0.0637P)² + 0.6384P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.002
2222 reflections	Δρ_max = 0.19 e Å⁻³
158 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0115 (13)

Crystal data top

C₁₂H₁₆N₂O₃	V = 2519.8 (4) Å³
M_r = 236.27	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.1020 (11) Å	µ = 0.09 mm⁻¹
b = 8.1727 (7) Å	T = 123 K
c = 25.476 (2) Å	0.27 × 0.23 × 0.22 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2222 independent reflections
Absorption correction: multi-scan (SADABS, Bruker, 2002)	1845 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.981	R_int = 0.026
12848 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.07	Δρ_max = 0.19 e Å⁻³
2222 reflections	Δρ_min = −0.14 e Å⁻³
158 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

	x	y	z	U_iso*/U_eq
C7	0.42346 (13)	0.5640 (2)	0.60487 (6)	0.0490 (4)
C8	0.43416 (13)	0.4210 (2)	0.56947 (6)	0.0501 (4)
C3	0.40760 (13)	0.8369 (2)	0.67166 (6)	0.0525 (4)
C2	0.37209 (14)	0.8477 (2)	0.62024 (7)	0.0570 (4)
H2	0.3430	0.9453	0.6075	0.068*
C9	0.59258 (14)	0.0586 (2)	0.56465 (7)	0.0542 (4)
C5	0.45905 (15)	0.5568 (2)	0.65717 (7)	0.0580 (5)
H5	0.4890	0.4600	0.6700	0.070*
C6	0.38006 (15)	0.7122 (2)	0.58781 (6)	0.0561 (4)
H6	0.3555	0.7207	0.5533	0.067*
C4	0.45058 (16)	0.6900 (2)	0.68974 (7)	0.0613 (5)
H4	0.4740	0.6816	0.7244	0.074*
C1	0.35816 (19)	1.1125 (2)	0.69025 (8)	0.0733 (6)
H1A	0.4039	1.1577	0.6631	0.110*
H1B	0.3550	1.1872	0.7193	0.110*
H1C	0.2850	1.0948	0.6769	0.110*
C11	0.7327 (2)	−0.0352 (3)	0.68377 (9)	0.0932 (7)
H11A	0.7656	0.0694	0.6908	0.140*
H11B	0.7815	−0.1204	0.6954	0.140*
H11C	0.6637	−0.0435	0.7021	0.140*
C10	0.7136 (2)	−0.0522 (3)	0.62760 (9)	0.0894 (8)
H10A	0.6803	−0.1576	0.6201	0.107*
H10B	0.7831	−0.0451	0.6087	0.107*
O3	0.63987 (11)	0.07917 (16)	0.61102 (5)	0.0677 (4)
O2	0.61004 (11)	−0.05717 (16)	0.53593 (5)	0.0701 (4)
O1	0.40315 (12)	0.96202 (16)	0.70721 (5)	0.0673 (4)
N2	0.52061 (12)	0.17888 (17)	0.55187 (5)	0.0571 (4)
H2A	0.4835	0.1713	0.5232	0.068*
N1	0.50534 (12)	0.31305 (17)	0.58366 (5)	0.0532 (4)
C12	0.36482 (15)	0.4117 (2)	0.52056 (7)	0.0621 (5)
H12A	0.4098	0.4361	0.4905	0.093*
H12B	0.3056	0.4896	0.5228	0.093*
H12C	0.3347	0.3036	0.5171	0.093*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C7	0.0429 (8)	0.0533 (9)	0.0509 (9)	−0.0002 (7)	0.0003 (7)	0.0052 (7)
C8	0.0451 (9)	0.0546 (10)	0.0505 (9)	−0.0011 (7)	0.0025 (7)	0.0067 (7)
C3	0.0468 (9)	0.0571 (10)	0.0536 (9)	−0.0019 (8)	0.0000 (7)	−0.0028 (7)
C2	0.0595 (10)	0.0542 (10)	0.0572 (9)	0.0087 (8)	−0.0028 (8)	0.0067 (8)
C9	0.0501 (9)	0.0571 (10)	0.0555 (9)	0.0012 (8)	−0.0014 (7)	−0.0050 (8)
C5	0.0597 (10)	0.0560 (10)	0.0584 (10)	0.0046 (8)	−0.0103 (8)	0.0079 (8)
C6	0.0606 (10)	0.0615 (11)	0.0461 (8)	0.0065 (8)	−0.0038 (7)	0.0049 (8)
C4	0.0642 (11)	0.0664 (11)	0.0532 (9)	0.0029 (9)	−0.0134 (8)	0.0029 (8)
C1	0.0867 (14)	0.0597 (12)	0.0736 (12)	0.0091 (10)	−0.0031 (10)	−0.0111 (10)
C11	0.1006 (18)	0.0890 (16)	0.0900 (15)	0.0101 (14)	−0.0275 (13)	0.0137 (13)
C10	0.0913 (17)	0.0877 (16)	0.0894 (15)	0.0396 (13)	−0.0261 (12)	−0.0145 (12)
O3	0.0734 (9)	0.0651 (8)	0.0646 (8)	0.0184 (6)	−0.0172 (6)	−0.0106 (6)
O2	0.0664 (8)	0.0722 (9)	0.0715 (8)	0.0159 (7)	−0.0101 (6)	−0.0200 (7)
O1	0.0760 (9)	0.0648 (8)	0.0611 (7)	0.0067 (6)	−0.0071 (6)	−0.0088 (6)
N2	0.0598 (8)	0.0592 (9)	0.0522 (8)	0.0075 (7)	−0.0079 (6)	−0.0035 (6)
N1	0.0563 (8)	0.0512 (8)	0.0520 (8)	0.0021 (6)	−0.0004 (6)	−0.0005 (6)
C12	0.0575 (10)	0.0676 (12)	0.0613 (10)	0.0027 (9)	−0.0066 (8)	−0.0046 (9)

Geometric parameters (Å, º) top

C7—C6	1.390 (2)	C1—O1	1.412 (2)
C7—C5	1.401 (2)	C1—H1A	0.96
C7—C8	1.482 (2)	C1—H1B	0.96
C8—N1	1.285 (2)	C1—H1C	0.96
C8—C12	1.504 (2)	C11—C10	1.456 (3)
C3—O1	1.367 (2)	C11—H11A	0.96
C3—C2	1.382 (2)	C11—H11B	0.96
C3—C4	1.387 (2)	C11—H11C	0.96
C2—C6	1.385 (2)	C10—O3	1.458 (2)
C2—H2	0.93	C10—H10A	0.97
C9—O2	1.215 (2)	C10—H10B	0.97
C9—O3	1.323 (2)	N2—N1	1.376 (2)
C9—N2	1.353 (2)	N2—H2A	0.86
C5—C4	1.372 (2)	C12—H12A	0.96
C5—H5	0.93	C12—H12B	0.96
C6—H6	0.93	C12—H12C	0.96
C4—H4	0.93

C6—C7—C5	116.71 (15)	O1—C1—H1C	109.5
C6—C7—C8	122.01 (14)	H1A—C1—H1C	109.5
C5—C7—C8	121.27 (15)	H1B—C1—H1C	109.5
N1—C8—C7	115.38 (14)	C10—C11—H11A	109.5
N1—C8—C12	124.94 (15)	C10—C11—H11B	109.5
C7—C8—C12	119.67 (14)	H11A—C11—H11B	109.5
O1—C3—C2	124.64 (16)	C10—C11—H11C	109.5
O1—C3—C4	116.25 (15)	H11A—C11—H11C	109.5
C2—C3—C4	119.11 (16)	H11B—C11—H11C	109.5
C3—C2—C6	119.53 (16)	C11—C10—O3	108.19 (18)
C3—C2—H2	120.2	C11—C10—H10A	110.1
C6—C2—H2	120.2	O3—C10—H10A	110.1
O2—C9—O3	124.14 (16)	C11—C10—H10B	110.1
O2—C9—N2	122.21 (16)	O3—C10—H10B	110.1
O3—C9—N2	113.64 (14)	H10A—C10—H10B	108.4
C4—C5—C7	121.26 (16)	C9—O3—C10	115.45 (14)
C4—C5—H5	119.4	C3—O1—C1	117.62 (14)
C7—C5—H5	119.4	C9—N2—N1	121.58 (14)
C2—C6—C7	122.46 (15)	C9—N2—H2A	119.2
C2—C6—H6	118.8	N1—N2—H2A	119.2
C7—C6—H6	118.8	C8—N1—N2	118.13 (14)
C5—C4—C3	120.91 (16)	C8—C12—H12A	109.5
C5—C4—H4	119.5	C8—C12—H12B	109.5
C3—C4—H4	119.5	H12A—C12—H12B	109.5
O1—C1—H1A	109.5	C8—C12—H12C	109.5
O1—C1—H1B	109.5	H12A—C12—H12C	109.5
H1A—C1—H1B	109.5	H12B—C12—H12C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.86	2.10	2.914 (2)	157
C12—H12C···O2ⁱ	0.96	2.52	3.250 (2)	133
C1—H1C···Cg1ⁱⁱ	0.96	2.76	3.637 (2)	153

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆N₂O₃
M_r	236.27
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	123
a, b, c (Å)	12.1020 (11), 8.1727 (7), 25.476 (2)
V (Å³)	2519.8 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.27 × 0.23 × 0.22

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS, Bruker, 2002)
T_min, T_max	0.973, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	12848, 2222, 1845
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.127, 1.07
No. of reflections	2222
No. of parameters	158
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.14

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—H2A···O2ⁱ	0.86	2.10	2.914 (2)	157
C12—H12C···O2ⁱ	0.96	2.52	3.250 (2)	133
C1—H1C···Cg1ⁱⁱ	0.96	2.76	3.637 (2)	153

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

Acknowledgements

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

References

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