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

Abstract

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,

• a = 9.9897 (15) Å

• b = 17.606 (3) Å

• c = 8.0801 (12) Å

• β = 111.806 (4)°

• V = 1319.4 (3) ų

• 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[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811026705/cv5126Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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).

Refinement

H atoms were geometrically positioned (C—H 0.93 - 0.96 Å; N—H 0.86 Å), and refined using a riding model, with U_iso(H) = 1.2-1.5 U_eq(C, N).

Figures

Fig. 1.

Molecular structure of (I), showing 40% probability displacement ellipsoids and the atomic numbering.

Crystal data

C12H16N2O5	F(000) = 568
Mr = 268.27	Dx = 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

Bruker SMART CCD area-detector diffractometer	2318 independent reflections
Radiation source: fine-focus sealed tube	1836 reflections with I > 2σ(I)
graphite	Rint = 0.039
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −11→11
Tmin = 0.971, Tmax = 0.979	k = −20→20
9747 measured reflections	l = −9→9

Refinement

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(Fo2) + (0.0529P)2 + 0.1933P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
2318 reflections	Δρmax = 0.19 e Å−3
173 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.