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

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

doi:10.1107/S1600536808033461

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2127

doi:10.1107/S1600536808033461

Open

access

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

Lu-Ping Lv,^a Xiao-Ming Ding,^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 13 October 2008; accepted 15 October 2008; online 18 October 2008)

The molecule of the title compound, C₁₃H₁₈N₂O₅, adopts a trans configuration with respect to the C=N bond. The dihedral angle between the benzene ring and the hydrazinecarboxylic acid plane is 49.75 (5)° and an intramolecular C—H⋯O interaction occurs. In the crystal structure, the molecules are linked into a chain along [010] by N—H⋯O hydrogen bonds, and a C—H⋯π contact further stabilizes the structure.

Related literature

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

Experimental

Crystal data

C₁₃H₁₈N₂O₅
M_r = 282.29
Monoclinic, P 2₁ /c
a = 22.037 (2) Å
b = 4.8782 (5) Å
c = 14.0212 (15) Å
β = 108.239 (4)°
V = 1431.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 273 (2) K
0.26 × 0.24 × 0.22 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.965, T_max = 0.968
14449 measured reflections
2520 independent reflections
2108 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.094
S = 1.03
2520 reflections
186 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C4–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O4ⁱ	0.86	1.98	2.8167 (17)	165
C2—H2A⋯O1	0.96	2.53	3.062 (2)	115
C1—H1C⋯Cg1ⁱ	0.96	2.92	3.755 (2)	146
Symmetry code: (i) x, y+1, z.

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/S1600536808033461/hb2820sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808033461/hb2820Isup2.hkl

checkCIF report

Comment top

Benzaldehydehydrazone derivatives are of interest due to their pharmacological activity (Parashar et al., 1988) and photochromic properties (Hadjoudis et al., 1987). As part of our studies of this type of derivatives, we report herein the crystal structure of the title compound (I).

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 C11/C12//N1/N2/O4/O5 plane is 49.75 (5)°. The bond lengths and angles agree with those observed for (E)-Methyl N'-(4-hydroxybenzylidene)hydrazinecarboxylate (Shang et al., 2007).

The molecules are linked into a chain along [010] by intermolecular and intramolecular N—H···O, C—H···O hydrogen bonds (Fig. 2, Table 1) and a C—H···π contact further stabilizes the structure.

Related literature top

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

Experimental top

3,4,5-trimethoxybenzaldehyde (1.96 g, 0.01 mol) and methyl hydrazinecarboxylate (1.04 g, 0.01 mol) were dissolved in stirred methanol (25 ml) and left for 3 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 90% yield. Colourless blocks of (I) were obtained by slow evaporation of a ethanol solution at room temperature (m.p. 452–454 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 (I), showing 40% probability displacement ellipsoids for the non-hydrogen atoms. The C—H···O interaction is shown as a dashed line.
	Fig. 2. Crystal packing of the title compound, viewed approximately down the a axis. Dashed lines indicate intermolecular hydrogen bonds.

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

Crystal data top

C₁₃H₁₈N₂O₅	F(000) = 600
M_r = 282.29	D_x = 1.310 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2520 reflections
a = 22.037 (2) Å	θ = 1.0–25.0°
b = 4.8782 (5) Å	µ = 0.10 mm⁻¹
c = 14.0212 (15) Å	T = 273 K
β = 108.239 (4)°	Block, colourless
V = 1431.5 (3) Å³	0.26 × 0.24 × 0.22 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2520 independent reflections
Radiation source: fine-focus sealed tube	2108 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 25.1°, θ_min = 1.0°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −24→25
T_min = 0.965, T_max = 0.968	k = −5→5
14449 measured reflections	l = −16→16

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)] = 0.035	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0431P)² + 0.3563P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2520 reflections	Δρ_max = 0.17 e Å⁻³
186 parameters	Δρ_min = −0.13 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: 0.0159 (15)

Crystal data top

C₁₃H₁₈N₂O₅	V = 1431.5 (3) Å³
M_r = 282.29	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 22.037 (2) Å	µ = 0.10 mm⁻¹
b = 4.8782 (5) Å	T = 273 K
c = 14.0212 (15) Å	0.26 × 0.24 × 0.22 mm
β = 108.239 (4)°

Data collection top

Bruker SMART CCD diffractometer	2520 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	2108 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.968	R_int = 0.029
14449 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.03	Δρ_max = 0.17 e Å⁻³
2520 reflections	Δρ_min = −0.13 e Å⁻³
186 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
C7	0.19238 (7)	0.8025 (3)	0.61046 (10)	0.0417 (3)
H7	0.1961	0.9206	0.6641	0.050*
C9	0.24447 (7)	0.6457 (3)	0.60759 (10)	0.0399 (3)
C4	0.13069 (7)	0.6200 (3)	0.44959 (10)	0.0407 (3)
C8	0.23981 (7)	0.4730 (3)	0.52645 (10)	0.0446 (4)
H8	0.2743	0.3643	0.5255	0.054*
C6	0.13492 (7)	0.7831 (3)	0.53350 (10)	0.0400 (3)
C11	0.44480 (7)	0.3407 (3)	0.82320 (10)	0.0423 (3)
C5	0.18340 (7)	0.4648 (3)	0.44715 (10)	0.0439 (4)
C10	0.30489 (7)	0.6728 (3)	0.68892 (10)	0.0424 (3)
H10	0.3141	0.8365	0.7245	0.051*
C3	0.08165 (8)	1.0795 (4)	0.61651 (12)	0.0587 (4)
H3A	0.0958	0.9706	0.6764	0.088*
H3B	0.0396	1.1488	0.6086	0.088*
H3C	0.1105	1.2300	0.6215	0.088*
C12	0.55019 (7)	0.2692 (4)	0.93180 (12)	0.0548 (4)
H12A	0.5554	0.1264	0.8869	0.066*
H12B	0.5409	0.1838	0.9881	0.066*
C2	0.03622 (8)	0.3905 (3)	0.35788 (13)	0.0584 (4)
H2A	0.0603	0.2298	0.3535	0.088*
H2B	0.0004	0.4072	0.2979	0.088*
H2C	0.0212	0.3755	0.4150	0.088*
C1	0.22489 (9)	0.1433 (4)	0.35569 (13)	0.0716 (6)
H1A	0.2618	0.2520	0.3588	0.107*
H1B	0.2117	0.0432	0.2936	0.107*
H1C	0.2353	0.0171	0.4110	0.107*
C13	0.60936 (8)	0.4386 (4)	0.96774 (14)	0.0681 (5)
H13A	0.6185	0.5183	0.9112	0.102*
H13B	0.6445	0.3248	1.0044	0.102*
H13C	0.6031	0.5816	1.0108	0.102*
O5	0.49926 (5)	0.4522 (2)	0.87979 (8)	0.0497 (3)
O2	0.07592 (5)	0.6268 (2)	0.36863 (7)	0.0485 (3)
O3	0.08020 (5)	0.9148 (2)	0.53188 (7)	0.0511 (3)
O1	0.17482 (5)	0.3161 (3)	0.36105 (8)	0.0617 (3)
O4	0.43507 (6)	0.0998 (2)	0.81180 (10)	0.0752 (4)
N2	0.40242 (6)	0.5408 (2)	0.78322 (9)	0.0447 (3)
H2	0.4111	0.7079	0.8021	0.054*
N1	0.34512 (6)	0.4774 (2)	0.71207 (8)	0.0425 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C7	0.0445 (8)	0.0412 (8)	0.0355 (7)	−0.0013 (6)	0.0070 (6)	−0.0019 (6)
C9	0.0396 (8)	0.0395 (8)	0.0365 (7)	−0.0036 (6)	0.0062 (6)	0.0028 (6)
C4	0.0411 (8)	0.0409 (8)	0.0333 (7)	0.0000 (6)	0.0020 (6)	0.0044 (6)
C8	0.0439 (8)	0.0452 (8)	0.0416 (8)	0.0037 (7)	0.0087 (7)	0.0005 (6)
C6	0.0402 (8)	0.0389 (8)	0.0390 (7)	0.0016 (6)	0.0093 (6)	0.0043 (6)
C11	0.0454 (9)	0.0363 (8)	0.0398 (7)	−0.0023 (6)	0.0055 (6)	−0.0018 (6)
C5	0.0495 (9)	0.0442 (8)	0.0338 (7)	0.0021 (7)	0.0071 (6)	−0.0012 (6)
C10	0.0418 (8)	0.0418 (8)	0.0402 (7)	−0.0041 (7)	0.0077 (6)	−0.0022 (6)
C3	0.0558 (10)	0.0653 (11)	0.0527 (9)	0.0110 (8)	0.0137 (8)	−0.0094 (8)
C12	0.0469 (9)	0.0577 (10)	0.0524 (9)	0.0147 (8)	0.0048 (7)	0.0007 (8)
C2	0.0537 (10)	0.0530 (10)	0.0546 (9)	−0.0050 (8)	−0.0031 (8)	0.0000 (8)
C1	0.0766 (13)	0.0769 (13)	0.0560 (10)	0.0208 (10)	0.0130 (9)	−0.0177 (9)
C13	0.0409 (9)	0.0941 (14)	0.0626 (10)	0.0069 (9)	0.0064 (8)	−0.0054 (10)
O5	0.0398 (6)	0.0418 (6)	0.0562 (6)	0.0018 (4)	−0.0014 (5)	−0.0038 (5)
O2	0.0477 (6)	0.0469 (6)	0.0386 (5)	0.0012 (5)	−0.0043 (4)	0.0037 (4)
O3	0.0443 (6)	0.0595 (7)	0.0434 (5)	0.0111 (5)	0.0048 (5)	−0.0053 (5)
O1	0.0615 (7)	0.0723 (8)	0.0408 (6)	0.0176 (6)	0.0010 (5)	−0.0162 (5)
O4	0.0734 (8)	0.0320 (6)	0.0930 (9)	−0.0032 (6)	−0.0131 (7)	−0.0022 (6)
N2	0.0404 (7)	0.0334 (6)	0.0491 (7)	−0.0041 (5)	−0.0020 (6)	−0.0040 (5)
N1	0.0397 (7)	0.0410 (7)	0.0396 (6)	−0.0060 (5)	0.0019 (5)	−0.0008 (5)

Geometric parameters (Å, º) top

C7—C6	1.3862 (19)	C3—H3B	0.9600
C7—C9	1.391 (2)	C3—H3C	0.9600
C7—H7	0.9300	C12—O5	1.4409 (17)
C9—C8	1.393 (2)	C12—C13	1.492 (2)
C9—C10	1.4630 (19)	C12—H12A	0.9700
C4—O2	1.3744 (16)	C12—H12B	0.9700
C4—C5	1.396 (2)	C2—O2	1.4264 (19)
C4—C6	1.399 (2)	C2—H2A	0.9600
C8—C5	1.385 (2)	C2—H2B	0.9600
C8—H8	0.9300	C2—H2C	0.9600
C6—O3	1.3602 (17)	C1—O1	1.409 (2)
C11—O4	1.1965 (18)	C1—H1A	0.9600
C11—O5	1.3303 (17)	C1—H1B	0.9600
C11—N2	1.3457 (18)	C1—H1C	0.9600
C5—O1	1.3697 (17)	C13—H13A	0.9600
C10—N1	1.2726 (18)	C13—H13B	0.9600
C10—H10	0.9300	C13—H13C	0.9600
C3—O3	1.4250 (18)	N2—N1	1.3772 (16)
C3—H3A	0.9600	N2—H2	0.8600

C6—C7—C9	120.07 (13)	O5—C12—H12A	110.4
C6—C7—H7	120.0	C13—C12—H12A	110.4
C9—C7—H7	120.0	O5—C12—H12B	110.4
C7—C9—C8	120.37 (13)	C13—C12—H12B	110.4
C7—C9—C10	119.07 (13)	H12A—C12—H12B	108.6
C8—C9—C10	120.51 (13)	O2—C2—H2A	109.5
O2—C4—C5	121.02 (12)	O2—C2—H2B	109.5
O2—C4—C6	119.39 (13)	H2A—C2—H2B	109.5
C5—C4—C6	119.49 (12)	O2—C2—H2C	109.5
C5—C8—C9	119.44 (14)	H2A—C2—H2C	109.5
C5—C8—H8	120.3	H2B—C2—H2C	109.5
C9—C8—H8	120.3	O1—C1—H1A	109.5
O3—C6—C7	124.73 (13)	O1—C1—H1B	109.5
O3—C6—C4	115.43 (12)	H1A—C1—H1B	109.5
C7—C6—C4	119.84 (13)	O1—C1—H1C	109.5
O4—C11—O5	124.87 (14)	H1A—C1—H1C	109.5
O4—C11—N2	125.79 (14)	H1B—C1—H1C	109.5
O5—C11—N2	109.33 (12)	C12—C13—H13A	109.5
O1—C5—C8	124.38 (14)	C12—C13—H13B	109.5
O1—C5—C4	114.98 (12)	H13A—C13—H13B	109.5
C8—C5—C4	120.61 (13)	C12—C13—H13C	109.5
N1—C10—C9	121.50 (13)	H13A—C13—H13C	109.5
N1—C10—H10	119.2	H13B—C13—H13C	109.5
C9—C10—H10	119.2	C11—O5—C12	117.58 (12)
O3—C3—H3A	109.5	C4—O2—C2	114.74 (11)
O3—C3—H3B	109.5	C6—O3—C3	117.63 (11)
H3A—C3—H3B	109.5	C5—O1—C1	117.99 (12)
O3—C3—H3C	109.5	C11—N2—N1	119.88 (12)
H3A—C3—H3C	109.5	C11—N2—H2	120.1
H3B—C3—H3C	109.5	N1—N2—H2	120.1
O5—C12—C13	106.72 (14)	C10—N1—N2	115.09 (12)

C6—C7—C9—C8	1.5 (2)	C7—C9—C10—N1	153.39 (14)
C6—C7—C9—C10	179.09 (13)	C8—C9—C10—N1	−29.0 (2)
C7—C9—C8—C5	1.9 (2)	O4—C11—O5—C12	−0.4 (2)
C10—C9—C8—C5	−175.66 (13)	N2—C11—O5—C12	178.13 (13)
C9—C7—C6—O3	175.98 (13)	C13—C12—O5—C11	166.29 (13)
C9—C7—C6—C4	−4.5 (2)	C5—C4—O2—C2	77.45 (18)
O2—C4—C6—O3	7.15 (19)	C6—C4—O2—C2	−106.16 (16)
C5—C4—C6—O3	−176.39 (13)	C7—C6—O3—C3	−1.6 (2)
O2—C4—C6—C7	−172.45 (13)	C4—C6—O3—C3	178.83 (14)
C5—C4—C6—C7	4.0 (2)	C8—C5—O1—C1	5.2 (2)
C9—C8—C5—O1	175.76 (14)	C4—C5—O1—C1	−176.66 (15)
C9—C8—C5—C4	−2.3 (2)	O4—C11—N2—N1	−9.3 (2)
O2—C4—C5—O1	−2.5 (2)	O5—C11—N2—N1	172.11 (11)
C6—C4—C5—O1	−178.86 (13)	C9—C10—N1—N2	173.88 (12)
O2—C4—C5—C8	175.78 (13)	C11—N2—N1—C10	170.86 (13)
C6—C4—C5—C8	−0.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4ⁱ	0.86	1.98	2.8167 (17)	165
C2—H2A···O1	0.96	2.53	3.062 (2)	115
C1—H1C···Cg1ⁱ	0.96	2.92	3.755 (2)	146

Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₈N₂O₅
M_r	282.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	22.037 (2), 4.8782 (5), 14.0212 (15)
β (°)	108.239 (4)
V (Å³)	1431.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.26 × 0.24 × 0.22

Data collection
Diffractometer	Bruker SMART CCD 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	14449, 2520, 2108
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.094, 1.03
No. of reflections	2520
No. of parameters	186
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.13

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	1.98	2.8167 (17)	165
C2—H2A···O1	0.96	2.53	3.062 (2)	115
C1—H1C···Cg1ⁱ	0.96	2.92	3.755 (2)	146

Symmetry code: (i) x, y+1, z.

Acknowledgements

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

References

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