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

Ahmed, S.; Qadeer, G.; Rama, N.H.; Ruzicka, A.

doi:10.1107/S1600536808028985

organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o1943

doi:10.1107/S1600536808028985

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

Shahzad Ahmed,^a Ghulam Qadeer,^a Nasim Hasan Rama ^a ^* and Ales Ruzicka ^b

^aDepartment of Chemistry, Quaid-i-Azam Univeristy, Islamabad 45320, Pakistan, and ^bDepartment of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Nam. Cs. Legii' 565, 53210 Pardubice, Czech Republic
^*Correspondence e-mail: nasimhrama@yahoo.com

(Received 8 September 2008; accepted 10 September 2008; online 13 September 2008)

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, P 2₁ /c
a = 4.8910 (19) Å
b = 30.358 (11) Å
c = 8.3440 (14) Å
β = 113.02 (3)°
V = 1140.4 (7) Å³
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[F² > 2σ(F²)] = 0.111
wR(F²) = 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

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) x-1, y, z.

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.

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S1600536808028985/hk2530sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808028985/hk2530Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

Data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); data reduction: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); 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 (Sheldrick, 2008).

Figures top

	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.

(E)-3-(3,5-dimethoxyphenyl)acrylohydrazide top

Crystal data top

C₁₁H₁₄N₂O₃	F(000) = 472
M_r = 222.24	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0574P)² + 2.6221P] where P = (F_o² + 2F_c²)/3
2522 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₁₁H₁₄N₂O₃	V = 1140.4 (7) Å³
M_r = 222.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.8910 (19) Å	µ = 0.10 mm⁻¹
b = 30.358 (11) Å	T = 150 K
c = 8.3440 (14) Å	0.90 × 0.17 × 0.12 mm
β = 113.02 (3)°

Data collection top

Bruker–Nonius KappaCCD area-detector diffractometer	2522 independent reflections
Absorption correction: gaussian (Coppens, 1970)	1547 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.993	R_int = 0.139
7864 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.111	0 restraints
wR(F²) = 0.274	H-atom parameters constrained
S = 1.13	Δρ_max = 0.33 e Å⁻³
2522 reflections	Δρ_min = −0.41 e Å⁻³
145 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N₂O₃
M_r	222.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	4.8910 (19), 30.358 (11), 8.3440 (14)
β (°)	113.02 (3)
V (Å³)	1140.4 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.90 × 0.17 × 0.12

Data collection
Diffractometer	Bruker–Nonius KappaCCD area-detector diffractometer
Absorption correction	Gaussian (Coppens, 1970)
T_min, T_max	0.961, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	7864, 2522, 1547
R_int	0.139
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.111, 0.274, 1.13
No. of reflections	2522
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.41

Computer programs: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.02	2.870 (3)	168.00

Symmetry code: (i) x−1, y, z.

Acknowledgements

The authors gratefully acknowledge funds from the Higher Education Commission, Islamabad, Pakistan.

References

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