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

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

doi:10.1107/S160053680803184X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2071

doi:10.1107/S160053680803184X

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

Lu-Ping Lv,^a Wen-Bo Yu,^a Feng Wang,^a Wei-Wei Li ^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 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 ); Hadjoudis et al. (1987 ); Borg et al. (1999 ). For a related structure, see Lv et al. (2008 ).

Experimental

Crystal data

C₁₁H₁₄N₂O₂
M_r = 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 ) T_min = 0.978, T_max = 0.980
5502 measured reflections
1951 independent reflections
1209 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); 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/S160053680803184X/cv2459sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680803184X/cv2459Isup2.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 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 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). 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.

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 40% probability level.
	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

C₁₁H₁₄N₂O₂	F(000) = 440
M_r = 206.24	D_x = 1.235 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1951 reflections
a = 11.5197 (3) Å	θ = 1.8–25.0°
b = 5.5734 (6) Å	µ = 0.09 mm⁻¹
c = 17.3281 (2) Å	T = 273 K
β = 94.193 (14)°	Block, colourless
V = 1109.55 (12) Å³	0.24 × 0.22 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1951 independent reflections
Radiation source: fine-focus sealed tube	1209 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −13→13
T_min = 0.978, T_max = 0.980	k = −6→6
5502 measured reflections	l = −19→20

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.07P)² + 0.5722P] where P = (F_o² + 2F_c²)/3
1951 reflections	(Δ/σ)_max < 0.001
138 parameters	Δρ_max = 0.28 e Å⁻³
3 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₁H₁₄N₂O₂	V = 1109.55 (12) Å³
M_r = 206.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.5197 (3) Å	µ = 0.09 mm⁻¹
b = 5.5734 (6) Å	T = 273 K
c = 17.3281 (2) Å	0.24 × 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)
T_min = 0.978, T_max = 0.980	R_int = 0.032
5502 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	3 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.03	Δρ_max = 0.28 e Å⁻³
1951 reflections	Δρ_min = −0.26 e Å⁻³
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

	x	y	z	U_iso*/U_eq
C6	0.4332 (2)	−0.0332 (5)	0.39288 (14)	0.0447 (6)
C5	0.5218 (2)	−0.2016 (5)	0.40434 (17)	0.0571 (8)
H5	0.5107	−0.3340	0.4357	0.069*
C8	0.3200 (2)	−0.0595 (5)	0.42808 (15)	0.0472 (7)
C7	0.4558 (2)	0.1643 (5)	0.34621 (16)	0.0520 (7)
H7	0.3994	0.2827	0.3379	0.062*
C3	0.6471 (2)	0.0163 (5)	0.32361 (16)	0.0548 (7)
C2	0.5594 (2)	0.1865 (5)	0.31268 (16)	0.0548 (7)
H2	0.5712	0.3193	0.2817	0.066*
C10	0.0517 (2)	0.2495 (5)	0.42066 (17)	0.0562 (7)
C4	0.6258 (2)	−0.1771 (5)	0.37036 (18)	0.0632 (8)
H4	0.6830	−0.2937	0.3792	0.076*
C1	0.7601 (3)	0.0414 (7)	0.28540 (19)	0.0764 (10)
H1A	0.7559	0.1786	0.2518	0.115*
H1B	0.7732	−0.1002	0.2557	0.115*
H1C	0.8230	0.0618	0.3243	0.115*
C9	0.3016 (2)	−0.2711 (5)	0.47910 (17)	0.0602 (8)
H9A	0.2698	−0.2178	0.5258	0.063*
H9C	0.3746	−0.3499	0.4916	0.063*
H9B	0.2484	−0.3812	0.4526	0.063*
C11	−0.0088 (3)	0.5827 (6)	0.3454 (2)	0.0789 (10)
H11A	−0.0725	0.5048	0.3167	0.118*
H11B	0.0235	0.7033	0.3137	0.118*
H11C	−0.0362	0.6564	0.3907	0.118*
N2	0.13765 (19)	0.0920 (4)	0.44132 (14)	0.0613 (7)
H2A	0.1257	−0.0182	0.4746	0.074*
N1	0.24476 (18)	0.1054 (4)	0.40979 (13)	0.0548 (6)
O2	0.07955 (17)	0.4080 (4)	0.36804 (12)	0.0690 (7)
O1	−0.04293 (16)	0.2424 (4)	0.44769 (13)	0.0733 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C6	0.0480 (15)	0.0439 (15)	0.0421 (14)	0.0020 (12)	0.0018 (11)	−0.0030 (12)
C5	0.0586 (17)	0.0476 (17)	0.0660 (19)	0.0056 (13)	0.0102 (14)	0.0060 (14)
C8	0.0514 (15)	0.0426 (15)	0.0478 (15)	0.0001 (13)	0.0055 (12)	0.0006 (12)
C7	0.0509 (16)	0.0495 (17)	0.0559 (17)	0.0076 (13)	0.0054 (13)	0.0025 (14)
C3	0.0485 (16)	0.0588 (18)	0.0572 (18)	−0.0005 (14)	0.0052 (13)	−0.0077 (15)
C2	0.0564 (17)	0.0573 (18)	0.0515 (17)	−0.0049 (14)	0.0089 (13)	0.0058 (14)
C10	0.0485 (16)	0.0579 (18)	0.0631 (19)	−0.0015 (14)	0.0098 (14)	0.0062 (15)
C4	0.0537 (17)	0.0569 (19)	0.080 (2)	0.0145 (14)	0.0090 (15)	0.0013 (16)
C1	0.0543 (18)	0.095 (3)	0.082 (2)	−0.0016 (18)	0.0152 (16)	−0.004 (2)
C9	0.0566 (17)	0.0590 (19)	0.0662 (19)	0.0039 (14)	0.0116 (14)	0.0098 (15)
C11	0.071 (2)	0.070 (2)	0.096 (3)	0.0151 (18)	0.0100 (18)	0.0236 (19)
N2	0.0532 (14)	0.0602 (16)	0.0729 (16)	0.0043 (12)	0.0202 (12)	0.0171 (13)
N1	0.0459 (13)	0.0557 (15)	0.0641 (15)	0.0030 (11)	0.0133 (11)	0.0075 (12)
O2	0.0572 (12)	0.0718 (15)	0.0801 (15)	0.0104 (11)	0.0194 (11)	0.0241 (12)
O1	0.0492 (12)	0.0806 (16)	0.0922 (16)	0.0046 (11)	0.0205 (11)	0.0214 (13)

Geometric parameters (Å, º) top

C6—C5	1.390 (4)	C10—N2	1.351 (4)
C6—C7	1.402 (4)	C4—H4	0.9300
C6—C8	1.487 (3)	C1—H1A	0.9600
C5—C4	1.380 (4)	C1—H1B	0.9600
C5—H5	0.9300	C1—H1C	0.9600
C8—N1	1.286 (3)	C9—H9A	0.9600
C8—C9	1.498 (4)	C9—H9C	0.9600
C7—C2	1.370 (4)	C9—H9B	0.9600
C7—H7	0.9300	C11—O2	1.442 (3)
C3—C4	1.381 (4)	C11—H11A	0.9600
C3—C2	1.389 (4)	C11—H11B	0.9600
C3—C1	1.509 (4)	C11—H11C	0.9600
C2—H2	0.9300	N2—N1	1.388 (3)
C10—O1	1.218 (3)	N2—H2A	0.8600
C10—O2	1.326 (3)

C5—C6—C7	116.5 (2)	C3—C1—H1A	109.5
C5—C6—C8	122.1 (2)	C3—C1—H1B	109.5
C7—C6—C8	121.3 (2)	H1A—C1—H1B	109.5
C4—C5—C6	121.6 (3)	C3—C1—H1C	109.5
C4—C5—H5	119.2	H1A—C1—H1C	109.5
C6—C5—H5	119.2	H1B—C1—H1C	109.5
N1—C8—C6	115.1 (2)	C8—C9—H9A	109.5
N1—C8—C9	125.8 (2)	C8—C9—H9C	109.5
C6—C8—C9	119.1 (2)	H9A—C9—H9C	109.5
C2—C7—C6	121.3 (3)	C8—C9—H9B	109.5
C2—C7—H7	119.3	H9A—C9—H9B	109.5
C6—C7—H7	119.3	H9C—C9—H9B	109.5
C4—C3—C2	117.0 (3)	O2—C11—H11A	109.5
C4—C3—C1	121.7 (3)	O2—C11—H11B	109.5
C2—C3—C1	121.3 (3)	H11A—C11—H11B	109.5
C7—C2—C3	121.9 (3)	O2—C11—H11C	109.5
C7—C2—H2	119.1	H11A—C11—H11C	109.5
C3—C2—H2	119.1	H11B—C11—H11C	109.5
O1—C10—O2	123.7 (3)	C10—N2—N1	121.1 (2)
O1—C10—N2	122.4 (3)	C10—N2—H2A	119.5
O2—C10—N2	113.9 (2)	N1—N2—H2A	119.5
C5—C4—C3	121.6 (3)	C8—N1—N2	117.8 (2)
C5—C4—H4	119.2	C10—O2—C11	115.8 (2)
C3—C4—H4	119.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N₂O₂
M_r	206.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	11.5197 (3), 5.5734 (6), 17.3281 (2)
β (°)	94.193 (14)
V (Å³)	1109.55 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.24 × 0.22 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.978, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	5502, 1951, 1209
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.172, 1.03
No. of reflections	1951
No. of parameters	138
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.86	2.12	2.944 (3)	161.8
C2—H2···Cg1ⁱⁱ	0.93	2.83	3.538 (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

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