(E)-Methyl N′-(3,4,5-trimethoxy­benzyl­idene)hydrazinecarboxyl­ate

Lv, L.-P.; Xie, J.-W.; Yu, W.-B.; Li, W.-W.; Hu, X.-C.

doi:10.1107/S1600536808031590

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2063

doi:10.1107/S1600536808031590

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(E)-Methyl N′-(3,4,5-trimethoxybenzylidene)hydrazinecarboxylate

Lu-Ping Lv,^a Jian-Wu Xie,^a Wen-Bo Yu,^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 30 September 2008; accepted 30 September 2008; online 4 October 2008)

The molecule of the title compound, C₁₂H₁₆N₂O₅, adopts a trans configuration with respect to the C=N double bond. The dihedral angle between the benzene and hydrazinecarboxylic acid methyl ester planes is 12.55 (7)°. The molecules are linked into a chain along [001] by intermolecular N—H⋯O hydrogen bonds, and the chains are cross-linked into a two-dimensional zigzag structure by C—H⋯O hydrogen bonds.

Related literature

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

Experimental

Crystal data

C₁₂H₁₆N₂O₅
M_r = 268.27
Monoclinic, P 2₁ /c
a = 8.554 (3) Å
b = 22.705 (7) Å
c = 7.813 (2) Å
β = 116.15 (1)°
V = 1362.1 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 273 (2) K
0.27 × 0.25 × 0.24 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.965, T_max = 0.968
7173 measured reflections
2394 independent reflections
1671 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.133
S = 1.03
2394 reflections
177 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O4ⁱ	0.86	2.16	3.000 (2)	166
C2—H2B⋯O2ⁱⁱ	0.96	2.57	3.498 (3)	161
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+2, -y, -z+3.

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/S1600536808031590/ci2687sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808031590/ci2687Isup2.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). They are important intermidiates of 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 bond. The hydrazine carboxylic acid methyl ester group is slightly twisted away from the attached ring. The dihedral angle between the benzene ring and the C10/C11//N1/N2/O4/O5 plane [r.m.s. deviation 0.051 Å] is 12.55 (7)°. The O1-C1 and O3-C3 methoxy groups are coplanar with the benzene ring [C8—C4—O1—C1 = -1.7 (3)° and C7—C6—O3—C3 = -1.9 (3)°] while the O2-C2 group is twisted almost perpendicular to the attached ring [C6—C5—O2—C2 = 91.6 (2)°]. The bond lengths and angles agree with those observed for N'-(4-methoxybenzylidene)methoxyformohydrazide (Shang et al., 2007).

The molecules are linked into a chain along the [001] by intermolecular N–H···O hydrogen bonds (Fig.2 and Table 1). The chains are cross-linked into a two-dimensional zigzag structure by C—H···O hydrogen bonds.

Related literature top

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

Experimental top

3,4,5-Trimethoxybenzaldehyde (1.96g, 0.01mol) and methyl hydrazinecarboxylate (0.9 g, 0.01 mol) were dissolved in stirred methanol (15 ml) and left for 3.2 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 94% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 472-474 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 molecular structure of the title compound, showing 40% probability displacement ellipsoids and the atomic numbering.
	Fig. 2. Crystal packing of the title compound, viewed approximately down the a axis. Dashed lines indicate hydrogen bonds.

(E)-Methyl N'-(3,4,5-trimethoxybenzylidene)hydrazinecarboxylate top

Crystal data top

C₁₂H₁₆N₂O₅	F(000) = 568
M_r = 268.27	D_x = 1.308 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2394 reflections
a = 8.554 (3) Å	θ = 1.8–25.0°
b = 22.705 (7) Å	µ = 0.10 mm⁻¹
c = 7.813 (2) Å	T = 273 K
β = 116.15 (1)°	Block, colourless
V = 1362.1 (7) Å³	0.27 × 0.25 × 0.24 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2394 independent reflections
Radiation source: fine-focus sealed tube	1671 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −10→10
T_min = 0.965, T_max = 0.968	k = −27→26
7173 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)] = 0.044	H-atom parameters constrained
wR(F²) = 0.133	w = 1/[σ²(F_o²) + (0.0696P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2394 reflections	Δρ_max = 0.18 e Å⁻³
177 parameters	Δρ_min = −0.19 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: 0.012 (3)

Crystal data top

C₁₂H₁₆N₂O₅	V = 1362.1 (7) Å³
M_r = 268.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.554 (3) Å	µ = 0.10 mm⁻¹
b = 22.705 (7) Å	T = 273 K
c = 7.813 (2) Å	0.27 × 0.25 × 0.24 mm
β = 116.15 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2394 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1671 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.968	R_int = 0.058
7173 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 1.04	Δρ_max = 0.18 e Å⁻³
2394 reflections	Δρ_min = −0.19 e Å⁻³
177 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
C11	0.1250 (2)	0.29913 (8)	0.4985 (2)	0.0442 (5)
C7	0.5205 (3)	0.07771 (8)	0.7843 (3)	0.0522 (5)
H7	0.4723	0.0607	0.6636	0.063*
C10	0.3534 (3)	0.16740 (8)	0.6404 (3)	0.0493 (5)
H10	0.3171	0.1508	0.5201	0.059*
C9	0.4743 (2)	0.13484 (8)	0.8080 (2)	0.0467 (5)
C6	0.6382 (3)	0.04596 (8)	0.9394 (3)	0.0508 (5)
C8	0.5451 (3)	0.16011 (9)	0.9895 (2)	0.0529 (5)
H8	0.5130	0.1980	1.0067	0.063*
C4	0.6637 (3)	0.12845 (9)	1.1436 (3)	0.0526 (5)
C5	0.7116 (2)	0.07116 (8)	1.1194 (3)	0.0499 (5)
C12	−0.0302 (4)	0.37985 (10)	0.3123 (3)	0.0850 (8)
H12A	−0.0984	0.3825	0.3820	0.127*
H12B	−0.1010	0.3900	0.1813	0.127*
H12C	0.0666	0.4065	0.3662	0.127*
C3	0.6171 (3)	−0.03833 (9)	0.7485 (3)	0.0677 (6)
H3A	0.4927	−0.0390	0.7001	0.102*
H3B	0.6600	−0.0779	0.7609	0.102*
H3C	0.6482	−0.0169	0.6620	0.102*
C1	0.7014 (4)	0.20690 (11)	1.3617 (3)	0.0986 (10)
H1A	0.7253	0.2340	1.2818	0.148*
H1B	0.7713	0.2169	1.4931	0.148*
H1C	0.5804	0.2092	1.3335	0.148*
C2	1.0022 (3)	0.04729 (13)	1.3133 (4)	0.0950 (9)
H2A	1.0190	0.0332	1.2067	0.143*
H2B	1.0752	0.0254	1.4253	0.143*
H2C	1.0323	0.0883	1.3335	0.143*
O5	0.03345 (18)	0.32059 (5)	0.32345 (16)	0.0574 (4)
O4	0.1466 (2)	0.32391 (5)	0.64414 (17)	0.0632 (5)
O2	0.82545 (17)	0.03987 (6)	1.27554 (19)	0.0608 (4)
O3	0.6917 (2)	−0.01046 (6)	0.9293 (2)	0.0670 (5)
O1	0.7416 (2)	0.14863 (6)	1.32715 (18)	0.0745 (5)
N1	0.29649 (19)	0.21810 (6)	0.65536 (19)	0.0442 (4)
N2	0.1871 (2)	0.24529 (6)	0.4883 (2)	0.0492 (4)
H2	0.1588	0.2285	0.3801	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C11	0.0513 (12)	0.0478 (10)	0.0312 (9)	0.0013 (9)	0.0160 (8)	−0.0003 (8)
C7	0.0572 (13)	0.0525 (11)	0.0440 (11)	0.0038 (9)	0.0198 (10)	0.0014 (8)
C10	0.0541 (13)	0.0511 (11)	0.0382 (10)	0.0028 (9)	0.0162 (9)	−0.0023 (8)
C9	0.0474 (11)	0.0509 (11)	0.0403 (10)	0.0040 (8)	0.0180 (9)	0.0054 (8)
C6	0.0510 (12)	0.0468 (11)	0.0576 (12)	0.0075 (9)	0.0268 (10)	0.0085 (9)
C8	0.0588 (13)	0.0498 (10)	0.0445 (11)	0.0071 (10)	0.0178 (10)	0.0048 (8)
C4	0.0564 (13)	0.0591 (12)	0.0382 (10)	0.0032 (10)	0.0171 (9)	0.0068 (8)
C5	0.0466 (11)	0.0554 (11)	0.0478 (11)	0.0073 (9)	0.0211 (9)	0.0165 (9)
C12	0.118 (2)	0.0590 (14)	0.0569 (14)	0.0348 (14)	0.0188 (14)	0.0078 (10)
C3	0.0801 (17)	0.0546 (12)	0.0745 (16)	0.0101 (11)	0.0395 (13)	0.0015 (10)
C1	0.134 (3)	0.0820 (17)	0.0484 (13)	0.0263 (17)	0.0111 (15)	−0.0086 (11)
C2	0.0506 (16)	0.118 (2)	0.101 (2)	0.0070 (14)	0.0191 (14)	0.0537 (17)
O5	0.0733 (10)	0.0556 (8)	0.0359 (7)	0.0213 (7)	0.0174 (7)	0.0050 (5)
O4	0.0951 (12)	0.0523 (8)	0.0379 (8)	0.0124 (7)	0.0253 (7)	−0.0012 (6)
O2	0.0523 (9)	0.0694 (9)	0.0573 (9)	0.0100 (7)	0.0211 (7)	0.0266 (7)
O3	0.0761 (10)	0.0544 (9)	0.0661 (10)	0.0191 (7)	0.0275 (8)	0.0098 (7)
O1	0.0913 (13)	0.0709 (10)	0.0415 (8)	0.0192 (8)	0.0111 (8)	0.0042 (7)
N1	0.0497 (10)	0.0482 (9)	0.0317 (8)	0.0036 (7)	0.0152 (7)	0.0034 (6)
N2	0.0616 (11)	0.0501 (9)	0.0296 (7)	0.0133 (8)	0.0145 (7)	0.0004 (6)

Geometric parameters (Å, º) top

C11—O4	1.209 (2)	C12—H12A	0.96
C11—O5	1.333 (2)	C12—H12B	0.96
C11—N2	1.349 (2)	C12—H12C	0.96
C7—C6	1.388 (2)	C3—O3	1.417 (2)
C7—C9	1.392 (3)	C3—H3A	0.96
C7—H7	0.93	C3—H3B	0.96
C10—N1	1.275 (2)	C3—H3C	0.96
C10—C9	1.462 (2)	C1—O1	1.422 (3)
C10—H10	0.93	C1—H1A	0.96
C9—C8	1.396 (2)	C1—H1B	0.96
C6—O3	1.374 (2)	C1—H1C	0.96
C6—C5	1.386 (3)	C2—O2	1.417 (3)
C8—C4	1.386 (2)	C2—H2A	0.96
C8—H8	0.93	C2—H2B	0.96
C4—O1	1.367 (2)	C2—H2C	0.96
C4—C5	1.401 (3)	N1—N2	1.3723 (19)
C5—O2	1.376 (2)	N2—H2	0.86
C12—O5	1.439 (2)

O4—C11—O5	124.93 (17)	H12A—C12—H12C	109.5
O4—C11—N2	125.21 (16)	H12B—C12—H12C	109.5
O5—C11—N2	109.85 (14)	O3—C3—H3A	109.5
C6—C7—C9	120.45 (17)	O3—C3—H3B	109.5
C6—C7—H7	119.8	H3A—C3—H3B	109.5
C9—C7—H7	119.8	O3—C3—H3C	109.5
N1—C10—C9	121.47 (17)	H3A—C3—H3C	109.5
N1—C10—H10	119.3	H3B—C3—H3C	109.5
C9—C10—H10	119.3	O1—C1—H1A	109.5
C7—C9—C8	119.77 (17)	O1—C1—H1B	109.5
C7—C9—C10	118.81 (16)	H1A—C1—H1B	109.5
C8—C9—C10	121.41 (17)	O1—C1—H1C	109.5
O3—C6—C5	115.43 (16)	H1A—C1—H1C	109.5
O3—C6—C7	124.47 (17)	H1B—C1—H1C	109.5
C5—C6—C7	120.11 (17)	O2—C2—H2A	109.5
C4—C8—C9	119.57 (18)	O2—C2—H2B	109.5
C4—C8—H8	120.2	H2A—C2—H2B	109.5
C9—C8—H8	120.2	O2—C2—H2C	109.5
O1—C4—C8	124.72 (18)	H2A—C2—H2C	109.5
O1—C4—C5	114.63 (16)	H2B—C2—H2C	109.5
C8—C4—C5	120.65 (17)	C11—O5—C12	116.06 (14)
O2—C5—C6	120.91 (17)	C5—O2—C2	113.36 (15)
O2—C5—C4	119.61 (17)	C6—O3—C3	117.27 (15)
C6—C5—C4	119.44 (16)	C4—O1—C1	117.67 (16)
O5—C12—H12A	109.5	C10—N1—N2	116.53 (14)
O5—C12—H12B	109.5	C11—N2—N1	118.23 (14)
H12A—C12—H12B	109.5	C11—N2—H2	120.9
O5—C12—H12C	109.5	N1—N2—H2	120.9

C6—C7—C9—C8	−0.7 (3)	C8—C4—C5—O2	−177.98 (18)
C6—C7—C9—C10	178.45 (18)	O1—C4—C5—C6	178.96 (17)
N1—C10—C9—C7	174.74 (18)	C8—C4—C5—C6	−0.5 (3)
N1—C10—C9—C8	−6.1 (3)	O4—C11—O5—C12	5.6 (3)
C9—C7—C6—O3	−179.79 (18)	N2—C11—O5—C12	−175.51 (18)
C9—C7—C6—C5	−0.5 (3)	C6—C5—O2—C2	91.6 (2)
C7—C9—C8—C4	1.3 (3)	C4—C5—O2—C2	−91.0 (2)
C10—C9—C8—C4	−177.86 (18)	C5—C6—O3—C3	178.74 (18)
C9—C8—C4—O1	179.89 (18)	C7—C6—O3—C3	−1.9 (3)
C9—C8—C4—C5	−0.7 (3)	C8—C4—O1—C1	−1.7 (3)
O3—C6—C5—O2	−2.1 (3)	C5—C4—O1—C1	178.9 (2)
C7—C6—C5—O2	178.52 (17)	C9—C10—N1—N2	178.42 (17)
O3—C6—C5—C4	−179.53 (17)	O4—C11—N2—N1	−6.2 (3)
C7—C6—C5—C4	1.1 (3)	O5—C11—N2—N1	174.90 (15)
O1—C4—C5—O2	1.5 (3)	C10—N1—N2—C11	−179.66 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4ⁱ	0.86	2.16	3.000 (2)	166
C2—H2B···O2ⁱⁱ	0.96	2.57	3.498 (3)	161

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆N₂O₅
M_r	268.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	8.554 (3), 22.705 (7), 7.813 (2)
β (°)	116.15 (1)
V (Å³)	1362.1 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.27 × 0.25 × 0.24

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.965, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	7173, 2394, 1671
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.133, 1.04
No. of reflections	2394
No. of parameters	177
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19

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···O4ⁱ	0.86	2.16	3.000 (2)	166
C2—H2B···O2ⁱⁱ	0.96	2.57	3.498 (3)	161

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

Acknowledgements

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

References

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