(E)-3-(3,5-Dimethoxy­phen­yl)acrylo­hydrazide

Abstract

In the title compound, C₁₁H₁₄N₂O₃, the planar hydrazide group is oriented with respect to the benzene ring at a dihedral angle of 48.00 (3)°. In the crystal structure, inter­molecular N—H⋯O hydrogen bonds link the mol­ecules.

Related literature

For related literature, see: Zheng et al. (2003 ▶); Al-Talib et al. (1990 ▶); Yousif et al. (1986 ▶); Ahmad et al. (2001 ▶); Al-Soud et al. (2004 ▶); El-Emam et al. (2004 ▶); Furniss et al. (1978 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

• C₁₁H₁₄N₂O₃

• M _r = 222.24

• Monoclinic,

• a = 4.8910 (19) Å

• b = 30.358 (11) Å

• c = 8.3440 (14) Å

• β = 113.02 (3)°

• V = 1140.4 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 150 (1) K

• 0.90 × 0.17 × 0.12 mm

Data collection

• Bruker–Nonius KappaCCD area-detector diffractometer

• Absorption correction: gaussian (Coppens, 1970 ▶) T _min = 0.961, T _max = 0.993

• 7864 measured reflections

• 2522 independent reflections

• 1547 reflections with I > 2σ(I)

• R _int = 0.139

Refinement

• R[F ² > 2σ(F ²)] = 0.111

• wR(F ²) = 0.274

• S = 1.13

• 2522 reflections

• 145 parameters

• H-atom parameters constrained

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.41 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶) and DENZO (Otwinowski & Minor, 1997 ▶); cell refinement: DIRAX/LSQ (Duisenberg, 1992 ▶); data reduction: EvalCCD (Duisenberg, 1992 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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
N1—H1⋯O1i	0.86	2.02	2.870 (3)	168

Symmetry code: (i) .

supplementary crystallographic information

Comment

Aromatic hydrazides are important intermediates in heterocyclic chemistry and have been used for the synthesis of various biologically active five-membered heterocycles such as 2,5-disubstituted-1,3,4-oxadiazoles (Zheng et al., 2003; Al-Talib et al., 1990) and 5-substituted-2-mercapto-1,3,4-oxadiazoles (Yousif et al., 1986; Ahmad et al., 2001; Al-Soud et al., 2004; El-Emam et al., 2004). In view of the versatility of these compounds, we have synthesized the title compound, and report herein its crystal structure.

In the molecule of the title compound, (Fig. 1), the bond lengths (Allen et al., 1987) and angles are generally within normal ranges. The benzene ring (C4-C9) is oriented with respect to the planar hydrazide group (O1/N1/N2/C1) at a dihedral angle of 48.00 (3)°.

In the crystal structure, intermolecular N-H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

The title compound was synthesized by the reaction of methyl ester of (E)-3 -(3,5-dimethoxyphenyl)acrylic acid with hdyrazine hydrate according to the literature method (Furniss et al., 1978). For the preparation of the title compound, a mixture of (E)-methyl 3-(3,5-dimethoxyphenyl)acrylate (2.22 g, 10 mmol) and hydrazine hydrate (15 ml, 80%) in absolute ethanol (50 ml) was refluxed for 5 h at 413-423 K. The excess solvent was removed by distillation. The solid residue was filtered off, washed with water and recrystallized from ethanol (30%) to give the title compound (yield; 1.55 g, 70%, m.p. 401-402 K). Colorless single crystals were obtained by slow evaporation of an ethanol solution at room temperature.

Refinement

H atoms were positioned geometrically, with N-H = 0.86 Å (for NH and NH₂) and C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C,N).

Figures

Fig. 1.

The molecular structure of the title molecule with the atom-numbering scheme.

Fig. 2.

A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Fig. 3.

Reaction scheme.

Crystal data

C11H14N2O3	F(000) = 472
Mr = 222.24	Dx = 1.294 Mg m−3
Monoclinic, P21/c	Melting point: 401(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 4.8910 (19) Å	Cell parameters from 7914 reflections
b = 30.358 (11) Å	θ = 1–27.5°
c = 8.3440 (14) Å	µ = 0.10 mm−1
β = 113.02 (3)°	T = 150 K
V = 1140.4 (7) Å3	Needle, colorless
Z = 4	0.90 × 0.17 × 0.12 mm

Data collection

Bruker–Nonius KappaCCD area-detector diffractometer	2522 independent reflections
Radiation source: fine-focus sealed tube	1547 reflections with I > 2σ(I)
graphite	Rint = 0.139
Detector resolution: 9.091 pixels mm-1	θmax = 27.5°, θmin = 3.0°
φ and ω scans	h = −5→6
Absorption correction: gaussian (Coppens, 1970)	k = −39→35
Tmin = 0.961, Tmax = 0.993	l = −10→9
7864 measured reflections

Refinement

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)] = 0.111	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.274	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.0574P)2 + 2.6221P] where P = (Fo2 + 2Fc2)/3
2522 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
O1	0.5287 (7)	0.28398 (13)	0.5987 (6)	0.0682 (12)
O2	−0.4491 (7)	0.08832 (12)	0.3236 (4)	0.0538 (9)
O3	0.3626 (7)	0.04751 (12)	0.8379 (5)	0.0544 (10)
N1	0.0720 (8)	0.30545 (13)	0.5611 (6)	0.0468 (10)
H1	−0.0993	0.2975	0.5571	0.056*
N2	0.1165 (9)	0.34981 (14)	0.5371 (6)	0.0548 (11)
H2A	0.2856	0.3587	0.5404	0.066*
H2B	−0.0256	0.3683	0.5186	0.066*
C1	0.2785 (10)	0.27498 (16)	0.5905 (7)	0.0469 (12)
C2	0.1853 (14)	0.22916 (18)	0.6146 (10)	0.074 (2)
H2	0.0374	0.2236	0.6559	0.089*
C3	0.3475 (11)	0.19327 (16)	0.5674 (7)	0.0516 (13)
H3	0.5095	0.1979	0.5373	0.062*
C4	0.2192 (10)	0.14822 (15)	0.5752 (6)	0.0437 (11)
C5	−0.0544 (10)	0.13674 (16)	0.4480 (6)	0.0451 (11)
H5	−0.1530	0.1561	0.3573	0.054*
C6	−0.1797 (9)	0.09645 (15)	0.4560 (6)	0.0408 (10)
C7	−0.0380 (9)	0.06710 (16)	0.5864 (6)	0.0417 (10)
H7	−0.1233	0.0400	0.5912	0.050*
C8	0.2389 (10)	0.07918 (15)	0.7127 (6)	0.0404 (10)
C9	0.3672 (9)	0.11891 (15)	0.7090 (6)	0.0391 (10)
H9	0.5512	0.1261	0.7945	0.047*
C10	−0.5868 (11)	0.0472 (2)	0.3233 (7)	0.0605 (15)
H10A	−0.4515	0.0237	0.3308	0.073*
H10B	−0.7611	0.0443	0.2179	0.073*
H10C	−0.6420	0.0461	0.4217	0.073*
C11	0.6609 (10)	0.05504 (18)	0.9613 (7)	0.0547 (13)
H11A	0.7879	0.0602	0.8999	0.066*
H11B	0.7292	0.0296	1.0344	0.066*
H11C	0.6652	0.0802	1.0318	0.066*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0387 (18)	0.061 (2)	0.117 (4)	−0.0048 (17)	0.043 (2)	0.001 (2)
O2	0.0457 (18)	0.065 (2)	0.0394 (19)	−0.0032 (17)	0.0038 (15)	−0.0008 (16)
O3	0.0441 (18)	0.056 (2)	0.049 (2)	−0.0058 (16)	0.0027 (15)	0.0103 (16)
N1	0.0296 (18)	0.050 (2)	0.062 (3)	−0.0042 (17)	0.0198 (18)	−0.005 (2)
N2	0.043 (2)	0.049 (2)	0.072 (3)	0.0035 (19)	0.022 (2)	0.009 (2)
C1	0.040 (2)	0.050 (3)	0.056 (3)	−0.005 (2)	0.024 (2)	−0.003 (2)
C2	0.076 (4)	0.048 (3)	0.134 (6)	−0.010 (3)	0.080 (4)	−0.008 (3)
C3	0.048 (3)	0.046 (3)	0.069 (4)	0.000 (2)	0.032 (3)	0.006 (2)
C4	0.043 (2)	0.047 (3)	0.049 (3)	−0.003 (2)	0.026 (2)	−0.004 (2)
C5	0.048 (3)	0.051 (3)	0.035 (2)	0.008 (2)	0.015 (2)	0.008 (2)
C6	0.038 (2)	0.049 (3)	0.037 (2)	0.002 (2)	0.0157 (19)	−0.006 (2)
C7	0.040 (2)	0.043 (2)	0.043 (3)	−0.005 (2)	0.017 (2)	−0.004 (2)
C8	0.042 (2)	0.045 (3)	0.035 (2)	0.003 (2)	0.0155 (19)	0.0017 (19)
C9	0.033 (2)	0.045 (3)	0.038 (2)	−0.0019 (19)	0.0119 (18)	−0.0043 (19)
C10	0.043 (3)	0.078 (4)	0.049 (3)	−0.008 (3)	0.006 (2)	−0.009 (3)
C11	0.046 (3)	0.064 (3)	0.045 (3)	−0.003 (2)	0.007 (2)	0.006 (2)

Geometric parameters (Å, °)

O1—C1	1.230 (5)	C4—C5	1.389 (7)
O2—C6	1.371 (5)	C5—H5	0.9301
O2—C10	1.416 (6)	C6—C5	1.381 (7)
O3—C8	1.374 (5)	C6—C7	1.367 (7)
O3—C11	1.438 (6)	C7—H7	0.9298
N1—N2	1.391 (6)	C8—C7	1.402 (6)
N1—C1	1.320 (6)	C8—C9	1.365 (6)
N1—H1	0.8600	C9—C4	1.389 (7)
N2—H2A	0.8601	C9—H9	0.9300
N2—H2B	0.8600	C10—H10A	0.9598
C1—C2	1.502 (7)	C10—H10B	0.9600
C2—H2	0.9300	C10—H10C	0.9600
C3—C2	1.489 (7)	C11—H11A	0.9601
C3—C4	1.517 (7)	C11—H11B	0.9600
C3—H3	0.9300	C11—H11C	0.9600
N2—N1—H1	118.2	C7—C6—C5	121.3 (4)
C1—N1—N2	123.6 (4)	O2—C6—C5	115.2 (4)
C1—N1—H1	118.2	C6—C7—C8	117.9 (4)
N1—N2—H2A	120.1	C6—C7—H7	120.9
N1—N2—H2B	119.9	C8—C7—H7	121.1
H2A—N2—H2B	120.0	C9—C8—O3	124.4 (4)
C6—O2—C10	117.8 (4)	C9—C8—C7	122.1 (4)
C8—O3—C11	117.1 (4)	O3—C8—C7	113.4 (4)
O1—C1—N1	121.8 (5)	C8—C9—C4	119.0 (4)
O1—C1—C2	123.1 (5)	C8—C9—H9	120.4
N1—C1—C2	115.1 (4)	C4—C9—H9	120.6
C1—C2—H2	122.6	O2—C10—H10A	109.9
C3—C2—C1	114.9 (4)	O2—C10—H10B	109.6
C3—C2—H2	122.5	O2—C10—H10C	108.9
C2—C3—C4	112.1 (4)	H10A—C10—H10B	109.5
C2—C3—H3	124.0	H10A—C10—H10C	109.5
C4—C3—H3	123.9	H10B—C10—H10C	109.5
C5—C4—C3	119.0 (4)	O3—C11—H11A	109.3
C5—C4—C9	119.8 (4)	O3—C11—H11B	109.3
C9—C4—C3	121.2 (4)	O3—C11—H11C	109.8
C4—C5—H5	120.1	H11A—C11—H11B	109.5
C6—C5—C4	119.9 (4)	H11A—C11—H11C	109.5
C6—C5—H5	120.0	H11B—C11—H11C	109.5
C7—C6—O2	123.6 (4)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.86	2.02	2.870 (3)	168.

Symmetry codes: (i) x−1, y, z.