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

Lv, L.-P.; Yu, W.-P.; Yu, W.-B.; Zhou, X.-F.; Hu, X.-C.

doi:10.1107/S1600536808024264

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1676

doi:10.1107/S1600536808024264

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

Lu-Ping Lv,^a Wei-Ping Yu,^a Wen-Bo Yu,^a Xue-Feng Zhou ^b and Xian-Chao Hu ^c ^*

^aDepartment of Chemical Engineering, Hangzhou Vocational and Technical College, Hangzhou 310018, People's Republic of China, ^bZhejiang Xinan Chemical Industrial Group Co. Ltd, Jiande 311604, People's Republic of China, and ^cResearch Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: zgdhxc@126.com

(Received 27 July 2008; accepted 30 July 2008; online 6 August 2008)

The molecule of the title compound, C₁₁H₁₄N₂O₃, adopts a trans configuration with respect to the C=N bond. The dihedral angle between the benzene ring and the hydrazinecarboxylate plane is 12.06 (9)°. Molecules are linked into a one-dimensional network by N—H⋯O hydrogen bonds and C—H⋯π interactions. The benzene rings of inversion-related molecules are stacked with their centroids separated by 3.777 (1) Å, indicating π–π interactions.

Related literature

For general background, see: Parashar et al. (1988 ); Hadjoudis et al. (1987 ); Borg et al. (1999 ). For related structures, see: Shang et al. (2007 ).

Experimental

Crystal data

C₁₁H₁₄N₂O₃
M_r = 222.24
Monoclinic, P 2₁ /c
a = 12.416 (3) Å
b = 11.113 (3) Å
c = 8.073 (2) Å
β = 95.628 (3)°
V = 1108.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 273 (2) K
0.30 × 0.26 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.972, T_max = 0.978
7124 measured reflections
1952 independent reflections
1624 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.102
S = 1.07
1952 reflections
153 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2ⁱ	0.89 (2)	2.01 (2)	2.8864 (17)	169.0
C4—H4⋯Cg1ⁱⁱ	0.93	2.87	3.6488 (19)	142
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ . Cg1 is the centroid of the benzene ring.

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/S1600536808024264/zl2130sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024264/zl2130Isup2.hkl

checkCIF report

Comment top

Benzaldehydehydrazone derivatives have received considerable attention for a long time due to their pharmacological activity (Parashar et al., 1988) and their photochromic properties (Hadjoudis et al., 1987). Meanwhile, it's an important intermidiate of 1,3,4-oxadiazoles, which have been reported to be versatile compounds with many interesting properties (Borg et al., 1999). As a further investigation of this type of derivatives, the crystal structure of the title compound, C₁₁H₁₄N₂O₃ (Fig.1), is described here.

The title molecule (Fig.1) adopts a trans configuration with respect to the C═N bond. The N1/N2/O2/O3/C10/C11 plane of the hydrazine carboxylic acid methyl ester group is slightly twisted away from the attached ring. The dihedral angle between the C2—C7 ring and the N1/N2/O2/O3/C10/C11 plane is 12.06 (9)°. The bond lengths and angles agree with those observed for methyl N'-[(E)-4-methoxybenzylidene] hydrazinecarboxylate (Shang et al., 2007).

The molecules are linked into a one-dimensional network by N–H···O hydrogen bonds and C–H···π interactions (Table 1, Fig.2). The benzene rings of the inversion-related molecules are stacked with their centroids separated by a distance of 3.777 (1) Å, indicating π-π interactions.

Related literature top

For general background, see: Parashar et al. (1988); Hadjoudis et al. (1987); Borg et al., (1999). For related structures, see: Shang et al. (2007). Cg1 is the centroid of the benzene ring.

Experimental top

4-Methoxy-acetophenone (1.50 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90 g, 0.01 mol) were dissolved in stirred methanol (15 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 in 80% yield. Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 470–472 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. Molecular structure of (I), showing 50% probability displacement ellipsoids and the atomic numbering.
	Fig. 2. Crystal packing of the title compound, viewed approximately down the a axis. Dashed lines indicate intermolecular hydrogen bonds.

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

Crystal data top

C₁₁H₁₄N₂O₃	F(000) = 472
M_r = 222.24	D_x = 1.332 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1952 reflections
a = 12.416 (3) Å	θ = 1.6–25.0°
b = 11.113 (3) Å	µ = 0.10 mm⁻¹
c = 8.073 (2) Å	T = 273 K
β = 95.628 (3)°	Block, colourless
V = 1108.5 (5) Å³	0.30 × 0.26 × 0.25 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1952 independent reflections
Radiation source: fine-focus sealed tube	1624 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −14→14
T_min = 0.972, T_max = 0.978	k = −13→11
7124 measured reflections	l = −9→9

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)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0461P)² + 0.2826P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
1952 reflections	Δρ_max = 0.19 e Å⁻³
153 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: 0.042 (4)

Crystal data top

C₁₁H₁₄N₂O₃	V = 1108.5 (5) Å³
M_r = 222.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.416 (3) Å	µ = 0.10 mm⁻¹
b = 11.113 (3) Å	T = 273 K
c = 8.073 (2) Å	0.30 × 0.26 × 0.25 mm
β = 95.628 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1952 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1624 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.978	R_int = 0.030
7124 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.19 e Å⁻³
1952 reflections	Δρ_min = −0.14 e Å⁻³
153 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
H2A	0.6796 (14)	0.1822 (17)	0.308 (2)	0.059 (5)*
C7	0.96977 (11)	0.12453 (12)	0.16378 (16)	0.0297 (3)
C8	0.85779 (11)	0.12580 (12)	0.21369 (16)	0.0317 (3)
C10	0.62251 (11)	0.29834 (13)	0.14528 (18)	0.0348 (3)
C3	1.18244 (11)	0.12536 (13)	0.07457 (18)	0.0341 (3)
C5	1.04408 (11)	0.03686 (13)	0.22113 (17)	0.0351 (4)
H5	1.0223	−0.0236	0.2902	0.042*
C6	1.00522 (11)	0.21282 (12)	0.05809 (17)	0.0348 (4)
H6	0.9574	0.2727	0.0174	0.042*
C2	1.14990 (11)	0.03671 (13)	0.17850 (18)	0.0375 (4)
H2	1.1983	−0.0225	0.2196	0.045*
C4	1.10911 (11)	0.21306 (13)	0.01308 (18)	0.0364 (4)
H4	1.1305	0.2720	−0.0587	0.044*
C1	1.36336 (12)	0.05169 (17)	0.0921 (2)	0.0551 (5)
H1A	1.3691	0.0574	0.2113	0.083*
H1B	1.4320	0.0704	0.0531	0.083*
H1C	1.3425	−0.0286	0.0588	0.083*
C11	0.44286 (12)	0.36579 (16)	0.1528 (2)	0.0528 (5)
H11A	0.4628	0.4492	0.1589	0.079*
H11B	0.3810	0.3529	0.2132	0.079*
H11C	0.4254	0.3433	0.0385	0.079*
O1	1.28412 (8)	0.13431 (10)	0.02268 (14)	0.0460 (3)
O3	0.53202 (8)	0.29346 (10)	0.22464 (14)	0.0467 (3)
O2	0.63408 (8)	0.36576 (10)	0.03058 (13)	0.0432 (3)
N1	0.79718 (9)	0.21424 (11)	0.15959 (14)	0.0350 (3)
N2	0.69424 (10)	0.21707 (12)	0.21353 (17)	0.0391 (3)
C9	0.82244 (12)	0.02704 (14)	0.3229 (2)	0.0439 (4)
H9A	0.8329	0.0521	0.4372	0.066*
H9B	0.8646	−0.0439	0.3082	0.066*
H9C	0.7472	0.0098	0.2933	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C7	0.0318 (7)	0.0303 (7)	0.0271 (7)	−0.0005 (5)	0.0034 (5)	−0.0038 (5)
C8	0.0343 (7)	0.0334 (8)	0.0277 (7)	−0.0011 (6)	0.0052 (5)	−0.0037 (6)
C10	0.0317 (7)	0.0391 (8)	0.0346 (8)	0.0006 (6)	0.0082 (6)	−0.0059 (7)
C3	0.0301 (7)	0.0370 (8)	0.0357 (8)	0.0004 (6)	0.0048 (6)	−0.0050 (6)
C5	0.0388 (8)	0.0333 (8)	0.0336 (8)	0.0002 (6)	0.0058 (6)	0.0038 (6)
C6	0.0342 (7)	0.0328 (8)	0.0374 (8)	0.0051 (6)	0.0041 (6)	0.0021 (6)
C2	0.0362 (8)	0.0357 (8)	0.0403 (8)	0.0086 (6)	0.0021 (6)	0.0019 (6)
C4	0.0361 (8)	0.0354 (8)	0.0386 (8)	−0.0008 (6)	0.0079 (6)	0.0049 (6)
C1	0.0332 (8)	0.0649 (12)	0.0680 (12)	0.0125 (8)	0.0084 (8)	0.0035 (9)
C11	0.0314 (8)	0.0592 (11)	0.0684 (12)	0.0078 (7)	0.0075 (7)	0.0000 (9)
O1	0.0304 (5)	0.0522 (7)	0.0565 (7)	0.0053 (5)	0.0107 (5)	0.0060 (5)
O3	0.0316 (5)	0.0567 (7)	0.0539 (7)	0.0066 (5)	0.0153 (5)	0.0079 (5)
O2	0.0425 (6)	0.0493 (7)	0.0396 (6)	0.0093 (5)	0.0125 (5)	0.0054 (5)
N1	0.0308 (6)	0.0412 (7)	0.0345 (7)	0.0028 (5)	0.0097 (5)	0.0002 (5)
N2	0.0330 (6)	0.0467 (8)	0.0393 (7)	0.0047 (5)	0.0131 (5)	0.0059 (6)
C9	0.0379 (8)	0.0442 (9)	0.0516 (9)	0.0011 (7)	0.0144 (7)	0.0075 (7)

Geometric parameters (Å, º) top

C7—C5	1.3896 (19)	C2—H2	0.9300
C7—C6	1.399 (2)	C4—H4	0.9300
C7—C8	1.4850 (19)	C1—O1	1.4201 (19)
C8—N1	1.2878 (18)	C1—H1A	0.9600
C8—C9	1.500 (2)	C1—H1B	0.9600
C10—O2	1.2105 (17)	C1—H1C	0.9600
C10—N2	1.3476 (19)	C11—O3	1.4429 (19)
C10—O3	1.3479 (17)	C11—H11A	0.9600
C3—O1	1.3722 (17)	C11—H11B	0.9600
C3—C2	1.380 (2)	C11—H11C	0.9600
C3—C4	1.392 (2)	N1—N2	1.3905 (16)
C5—C2	1.390 (2)	N2—H2A	0.891 (19)
C5—H5	0.9300	C9—H9A	0.9600
C6—C4	1.3740 (19)	C9—H9B	0.9600
C6—H6	0.9300	C9—H9C	0.9600

C5—C7—C6	117.16 (13)	O1—C1—H1A	109.5
C5—C7—C8	121.66 (12)	O1—C1—H1B	109.5
C6—C7—C8	121.18 (12)	H1A—C1—H1B	109.5
N1—C8—C7	116.53 (12)	O1—C1—H1C	109.5
N1—C8—C9	124.24 (13)	H1A—C1—H1C	109.5
C7—C8—C9	119.23 (12)	H1B—C1—H1C	109.5
O2—C10—N2	127.18 (13)	O3—C11—H11A	109.5
O2—C10—O3	123.74 (13)	O3—C11—H11B	109.5
N2—C10—O3	109.08 (13)	H11A—C11—H11B	109.5
O1—C3—C2	124.78 (13)	O3—C11—H11C	109.5
O1—C3—C4	115.44 (13)	H11A—C11—H11C	109.5
C2—C3—C4	119.78 (13)	H11B—C11—H11C	109.5
C7—C5—C2	122.07 (13)	C3—O1—C1	117.08 (12)
C7—C5—H5	119.0	C10—O3—C11	115.40 (12)
C2—C5—H5	119.0	C8—N1—N2	115.82 (12)
C4—C6—C7	121.48 (13)	C10—N2—N1	118.55 (13)
C4—C6—H6	119.3	C10—N2—H2A	117.4 (12)
C7—C6—H6	119.3	N1—N2—H2A	122.0 (11)
C3—C2—C5	119.33 (13)	C8—C9—H9A	109.5
C3—C2—H2	120.3	C8—C9—H9B	109.5
C5—C2—H2	120.3	H9A—C9—H9B	109.5
C6—C4—C3	120.17 (13)	C8—C9—H9C	109.5
C6—C4—H4	119.9	H9A—C9—H9C	109.5
C3—C4—H4	119.9	H9B—C9—H9C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.89 (2)	2.01 (2)	2.8864 (17)	169.0
C4—H4···Cg1ⁱⁱ	0.93	2.87	3.6488 (19)	142

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N₂O₃
M_r	222.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	12.416 (3), 11.113 (3), 8.073 (2)
β (°)	95.628 (3)
V (Å³)	1108.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.26 × 0.25

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.972, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	7124, 1952, 1624
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.102, 1.07
No. of reflections	1952
No. of parameters	153
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
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	0.89 (2)	2.01 (2)	2.8864 (17)	169.0
C4—H4···Cg1ⁱⁱ	0.93	2.87	3.6488 (19)	142

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

Acknowledgements

The authors acknowledge financial support from Hangzhou Vocational and Technical College, China.

References

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