(E)-Methyl N′-(2,4,5-trimeth­oxy­benzyl­idene)hydrazinecarboxyl­ate

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

doi:10.1107/S1600536811026705

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2023

doi:10.1107/S1600536811026705

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(E)-Methyl N′-(2,4,5-trimethoxybenzylidene)hydrazinecarboxylate

Lu-Ping Lv,^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 22 June 2011; accepted 5 July 2011; online 13 July 2011)

The title molecule, C₁₂H₁₆N₂O₅, adopts a trans configuration with respect to the C=N bond. In the crystal, intermolecular N—H⋯O hydrogen bonds link the molecules into chains in [001], and weak intermolecular C—H⋯O interactions further link the chains into corrugated layers parallel to the bc plane.

Related literature

For applications of benzaldehydehydrazone derivatives, 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 = 9.9897 (15) Å
b = 17.606 (3) Å
c = 8.0801 (12) Å
β = 111.806 (4)°
V = 1319.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 223 K
0.18 × 0.15 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.971, T_max = 0.979
9747 measured reflections
2318 independent reflections
1836 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.112
S = 1.10
2318 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.19 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	2.09	2.8403 (18)	146
C8—H8A⋯O3ⁱⁱ	0.96	2.56	3.423 (2)	150
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+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/S1600536811026705/cv5126sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026705/cv5126Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811026705/cv5126Isup3.cml

checkCIF report

Comment top

Benzaldehydehydrazone derivatives have received considerable attentions due to their pharmacological activity (Parashar et al., 1988) and photochromic properties (Hadjoudis et al., 1987). They also serve as 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 compounds, we report herein the crystal structure of the title compound (I).

The title compound (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/C12//N1/N2/O4/O5 plane is 14.23 (5)°. The bond lengths and angles agree with those observed for (E)-methyl N'-(4-hydroxybenzylidene)hydrazinecarboxylate (Shang et al., 2007).

In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 1) link molecules into chains in [001], and weak intermolecular C—H···O interactions (Table 1) link further these chains into corrugated layers parallel to bc plane.

Related literature top

For applications of benzaldehydehydrazone derivatives, see: Parashar et al. (1988); Hadjoudis et al. (1987); Borg et al. (1999). For a related structure, see: Shang et al. (2007).

Experimental top

2,4,5-Trimethoxybenzaldehyde (1.96g, 0.01mol) and methyl hydrazinecarboxylate (0.9g, 0.01mol) were dissolved in stirred methanol (20ml) and left for 5.2h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 91% yield. Crystals suitable for X-ray analysis were obtained by slow evaporation of a ethanol solution at room temperature (m.p. 432-435 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 40% probability displacement ellipsoids and the atomic numbering.

(E)-Methyl N'-(2,4,5-trimethoxybenzylidene)hydrazinecarboxylate top

Crystal data top

C₁₂H₁₆N₂O₅	F(000) = 568
M_r = 268.27	D_x = 1.350 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2318 reflections
a = 9.9897 (15) Å	θ = 2.2–25.0°
b = 17.606 (3) Å	µ = 0.11 mm⁻¹
c = 8.0801 (12) Å	T = 223 K
β = 111.806 (4)°	Block, colourless
V = 1319.4 (3) Å³	0.18 × 0.15 × 0.12 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2318 independent reflections
Radiation source: fine-focus sealed tube	1836 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −11→11
T_min = 0.971, T_max = 0.979	k = −20→20
9747 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)] = 0.040	H-atom parameters constrained
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0529P)² + 0.1933P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
2318 reflections	Δρ_max = 0.19 e Å⁻³
173 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: 0.014 (2)

Crystal data top

C₁₂H₁₆N₂O₅	V = 1319.4 (3) Å³
M_r = 268.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.9897 (15) Å	µ = 0.11 mm⁻¹
b = 17.606 (3) Å	T = 223 K
c = 8.0801 (12) Å	0.18 × 0.15 × 0.12 mm
β = 111.806 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2318 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1836 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.979	R_int = 0.039
9747 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.10	Δρ_max = 0.19 e Å⁻³
2318 reflections	Δρ_min = −0.19 e Å⁻³
173 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
C1	0.0907 (2)	−0.07569 (10)	0.1659 (3)	0.0495 (5)
H1A	0.0345	−0.0999	0.0554	0.074*
H1B	0.0279	−0.0567	0.2218	0.074*
H1C	0.1565	−0.1118	0.2432	0.074*
C4	0.25538 (17)	0.02726 (9)	0.2728 (2)	0.0379 (4)
C5	0.31441 (18)	0.09331 (9)	0.2291 (2)	0.0393 (4)
C9	0.3154 (3)	0.17706 (12)	−0.0014 (3)	0.0740 (7)
H9A	0.2793	0.1803	−0.1291	0.111*
H9B	0.4188	0.1796	0.0445	0.111*
H9C	0.2780	0.2185	0.0455	0.111*
C6	0.40772 (18)	0.13694 (9)	0.3631 (2)	0.0375 (4)
H6	0.4482	0.1800	0.3339	0.045*
C3	0.28653 (17)	0.00903 (9)	0.4492 (2)	0.0374 (4)
H3	0.2450	−0.0338	0.4779	0.045*
C2	0.37954 (17)	0.05417 (9)	0.5844 (2)	0.0366 (4)
C8	0.3448 (2)	−0.02382 (11)	0.8084 (3)	0.0529 (5)
H8A	0.3788	−0.0283	0.9358	0.079*
H8B	0.3666	−0.0696	0.7588	0.079*
H8C	0.2424	−0.0158	0.7618	0.079*
C7	0.44350 (17)	0.11824 (9)	0.5432 (2)	0.0349 (4)
C10	0.54924 (18)	0.16166 (9)	0.6853 (2)	0.0381 (4)
H10	0.5663	0.1494	0.8034	0.046*
C11	0.81188 (18)	0.30059 (9)	0.7763 (2)	0.0360 (4)
C12	1.0210 (2)	0.37093 (12)	0.9307 (3)	0.0608 (6)
H12A	1.0813	0.3852	1.0498	0.091*
H12B	0.9823	0.4157	0.8618	0.091*
H12C	1.0771	0.3431	0.8769	0.091*
N1	0.61921 (14)	0.21635 (7)	0.65137 (17)	0.0357 (4)
N2	0.71776 (15)	0.25135 (8)	0.79917 (17)	0.0404 (4)
H2	0.7189	0.2418	0.9040	0.049*
O1	0.27162 (15)	0.10777 (7)	0.04985 (16)	0.0559 (4)
O2	0.16975 (13)	−0.01434 (7)	0.13198 (16)	0.0520 (4)
O3	0.41409 (14)	0.03895 (7)	0.76186 (16)	0.0501 (4)
O4	0.81346 (14)	0.32263 (7)	0.63555 (16)	0.0488 (4)
O5	0.90455 (14)	0.32388 (7)	0.93597 (16)	0.0530 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0485 (11)	0.0418 (10)	0.0529 (11)	−0.0116 (8)	0.0126 (9)	−0.0047 (8)
C4	0.0334 (9)	0.0372 (9)	0.0420 (10)	−0.0014 (7)	0.0128 (8)	−0.0043 (7)
C5	0.0406 (10)	0.0415 (9)	0.0363 (10)	−0.0020 (8)	0.0150 (8)	−0.0014 (7)
C9	0.1031 (19)	0.0639 (14)	0.0460 (12)	−0.0276 (13)	0.0170 (12)	0.0066 (10)
C6	0.0379 (9)	0.0362 (9)	0.0411 (10)	−0.0031 (7)	0.0178 (8)	−0.0002 (7)
C3	0.0343 (9)	0.0349 (9)	0.0460 (11)	−0.0018 (7)	0.0183 (8)	0.0003 (7)
C2	0.0339 (9)	0.0380 (9)	0.0391 (10)	0.0016 (7)	0.0150 (7)	0.0016 (7)
C8	0.0610 (13)	0.0518 (11)	0.0482 (11)	−0.0143 (9)	0.0230 (10)	0.0053 (9)
C7	0.0324 (8)	0.0345 (9)	0.0394 (10)	0.0011 (7)	0.0150 (7)	−0.0022 (7)
C10	0.0396 (9)	0.0404 (9)	0.0362 (9)	−0.0017 (8)	0.0164 (8)	−0.0006 (7)
C11	0.0407 (9)	0.0346 (9)	0.0348 (10)	−0.0027 (7)	0.0163 (8)	−0.0030 (7)
C12	0.0441 (11)	0.0646 (13)	0.0714 (15)	−0.0194 (10)	0.0187 (10)	−0.0095 (11)
N1	0.0356 (7)	0.0374 (7)	0.0337 (8)	−0.0032 (6)	0.0124 (6)	−0.0038 (6)
N2	0.0460 (8)	0.0475 (8)	0.0281 (8)	−0.0127 (7)	0.0141 (7)	−0.0033 (6)
O1	0.0700 (9)	0.0561 (8)	0.0372 (7)	−0.0229 (7)	0.0146 (6)	0.0005 (6)
O2	0.0565 (8)	0.0511 (8)	0.0439 (7)	−0.0195 (6)	0.0132 (6)	−0.0063 (6)
O3	0.0594 (8)	0.0510 (8)	0.0386 (7)	−0.0180 (6)	0.0168 (6)	0.0013 (5)
O4	0.0612 (8)	0.0506 (7)	0.0403 (8)	−0.0135 (6)	0.0255 (6)	−0.0020 (6)
O5	0.0510 (8)	0.0632 (8)	0.0408 (7)	−0.0249 (6)	0.0125 (6)	−0.0062 (6)

Geometric parameters (Å, º) top

C1—O2	1.423 (2)	C2—C7	1.396 (2)
C1—H1A	0.9600	C8—O3	1.426 (2)
C1—H1B	0.9600	C8—H8A	0.9600
C1—H1C	0.9600	C8—H8B	0.9600
C4—O2	1.3562 (19)	C8—H8C	0.9600
C4—C3	1.379 (2)	C7—C10	1.455 (2)
C4—C5	1.407 (2)	C10—N1	1.278 (2)
C5—C6	1.372 (2)	C10—H10	0.9300
C5—O1	1.3730 (19)	C11—O4	1.2072 (19)
C9—O1	1.409 (2)	C11—N2	1.341 (2)
C9—H9A	0.9600	C11—O5	1.343 (2)
C9—H9B	0.9600	C12—O5	1.442 (2)
C9—H9C	0.9600	C12—H12A	0.9600
C6—C7	1.403 (2)	C12—H12B	0.9600
C6—H6	0.9300	C12—H12C	0.9600
C3—C2	1.391 (2)	N1—N2	1.3790 (18)
C3—H3	0.9300	N2—H2	0.8600
C2—O3	1.371 (2)

O2—C1—H1A	109.5	O3—C8—H8B	109.5
O2—C1—H1B	109.5	H8A—C8—H8B	109.5
H1A—C1—H1B	109.5	O3—C8—H8C	109.5
O2—C1—H1C	109.5	H8A—C8—H8C	109.5
H1A—C1—H1C	109.5	H8B—C8—H8C	109.5
H1B—C1—H1C	109.5	C2—C7—C6	118.29 (15)
O2—C4—C3	124.82 (15)	C2—C7—C10	119.92 (15)
O2—C4—C5	115.38 (15)	C6—C7—C10	121.72 (15)
C3—C4—C5	119.79 (15)	N1—C10—C7	121.40 (15)
C6—C5—O1	125.66 (15)	N1—C10—H10	119.3
C6—C5—C4	119.35 (15)	C7—C10—H10	119.3
O1—C5—C4	114.99 (14)	O4—C11—N2	126.36 (16)
O1—C9—H9A	109.5	O4—C11—O5	124.16 (15)
O1—C9—H9B	109.5	N2—C11—O5	109.47 (14)
H9A—C9—H9B	109.5	O5—C12—H12A	109.5
O1—C9—H9C	109.5	O5—C12—H12B	109.5
H9A—C9—H9C	109.5	H12A—C12—H12B	109.5
H9B—C9—H9C	109.5	O5—C12—H12C	109.5
C5—C6—C7	121.62 (15)	H12A—C12—H12C	109.5
C5—C6—H6	119.2	H12B—C12—H12C	109.5
C7—C6—H6	119.2	C10—N1—N2	114.97 (13)
C4—C3—C2	120.49 (15)	C11—N2—N1	118.74 (13)
C4—C3—H3	119.8	C11—N2—H2	120.6
C2—C3—H3	119.8	N1—N2—H2	120.6
O3—C2—C3	123.04 (14)	C5—O1—C9	117.49 (14)
O3—C2—C7	116.58 (14)	C4—O2—C1	118.08 (14)
C3—C2—C7	120.38 (15)	C2—O3—C8	117.95 (13)
O3—C8—H8A	109.5	C11—O5—C12	115.01 (14)

O2—C4—C5—C6	−176.97 (14)	C5—C6—C7—C10	176.10 (15)
C3—C4—C5—C6	3.0 (2)	C2—C7—C10—N1	173.58 (15)
O2—C4—C5—O1	2.7 (2)	C6—C7—C10—N1	−3.6 (2)
C3—C4—C5—O1	−177.36 (15)	C7—C10—N1—N2	−178.78 (14)
O1—C5—C6—C7	178.98 (15)	O4—C11—N2—N1	6.0 (3)
C4—C5—C6—C7	−1.4 (3)	O5—C11—N2—N1	−175.46 (13)
O2—C4—C3—C2	177.90 (15)	C10—N1—N2—C11	169.23 (15)
C5—C4—C3—C2	−2.0 (2)	C6—C5—O1—C9	−6.7 (3)
C4—C3—C2—O3	179.82 (14)	C4—C5—O1—C9	173.66 (17)
C4—C3—C2—C7	−0.5 (2)	C3—C4—O2—C1	8.7 (2)
O3—C2—C7—C6	−178.24 (14)	C5—C4—O2—C1	−171.32 (15)
C3—C2—C7—C6	2.1 (2)	C3—C2—O3—C8	−3.5 (2)
O3—C2—C7—C10	4.5 (2)	C7—C2—O3—C8	176.82 (15)
C3—C2—C7—C10	−175.19 (14)	O4—C11—O5—C12	−7.7 (2)
C5—C6—C7—C2	−1.1 (2)	N2—C11—O5—C12	173.73 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4ⁱ	0.86	2.09	2.8403 (18)	146
C8—H8A···O3ⁱⁱ	0.96	2.56	3.423 (2)	150

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆N₂O₅
M_r	268.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	223
a, b, c (Å)	9.9897 (15), 17.606 (3), 8.0801 (12)
β (°)	111.806 (4)
V (Å³)	1319.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.18 × 0.15 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.971, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	9747, 2318, 1836
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.112, 1.10
No. of reflections	2318
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −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	2.09	2.8403 (18)	146
C8—H8A···O3ⁱⁱ	0.96	2.56	3.423 (2)	150

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

Acknowledgements

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

References

Borg, S., Vollinga, R. C., Labarre, M., Payza, K., Terenius, L. & Luthman, K. (1999). J. Med. Chem. 42, 4331–4342. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345–1360. CrossRef CAS Web of Science Google Scholar
Parashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim. Acta, 151, 201–208. CrossRef CAS Web of Science Google Scholar
Shang, Z.-H., Zhang, H.-L. & Ding, Y. (2007). Acta Cryst. E63, o3394. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar