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

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.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.111
• wR factor = 0.274
• Data-to-parameter ratio = 17.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT063_ALERT_4_B Crystal Probably too Large for Beam Size .......       0.90 mm

Alert level C
RFACG01_ALERT_3_C  The value of the R factor is > 0.10
            R factor given   0.111
RFACR01_ALERT_3_C  The value of the weighted R factor is > 0.25
            Weighted R factor given   0.274
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.139
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.14
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT082_ALERT_2_C High R1 Value ..................................       0.11
PLAT084_ALERT_2_C High R2 Value ..................................       0.27
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C1
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2B    ...          ?

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  12 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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.

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).

S2. 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.

S3. 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).

Computing details

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

	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

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) Å^3	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 monochromator	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 F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.111	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.274	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0574P)^2 + 2.6221P] where P = (Fo^2 + 2Fc^2)/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)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.86	2.02	2.870 (3)	168

Symmetry code: (i) x−1, y, z.