Ethyl 2-acetyl­hydrazono-2-phenyl­acetate

Xu, L.-Z.; Yi, X.; An, G.-W.; Zhang, G.-S.; Li, C.-F.

doi:10.1107/S1600536807060941

organic compounds

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Volume 64| Part 1| January 2008| Page o33

https://doi.org/10.1107/S1600536807060941

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Ethyl 2-acetylhydrazono-2-phenylacetate

Liang-Zhong Xu,^a ^* Xu Yi,^a Guang-Wei An,^a Gong-Sheng Zhang ^a and Chun-Fang Li ^a

^aCollege of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China
^*Correspondence e-mail: qknhs@yahoo.com.cn

(Received 9 November 2007; accepted 20 November 2007; online 6 December 2007)

The title compound, C₁₂H₁₄N₂O₃, was synthesized as an intermediate for the synthesis of metamitron. The benzene ring forms dihedral angles of 86.3 (2) and 10.0 (3)° with the ethyl group and the acetylimino plane, respectively. The crystal structure involves intermolecular C—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For related literature, see: Glaser et al. (1993 ); Javier et al. (2006 ); Pan & Gao (2007 ).

Experimental

Crystal data

C₁₂H₁₄N₂O₃
M_r = 234.25
Orthorhombic, P b c a
a = 9.3039 (19) Å
b = 15.752 (3) Å
c = 17.129 (3) Å
V = 2510.3 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 153 (2) K
0.32 × 0.22 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi 1995 ) T_min = 0.972, T_max = 0.991
18227 measured reflections
2206 independent reflections
1870 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.110
S = 1.09
2206 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3ⁱ	0.86	2.03	2.8737 (16)	165
C9—H9B⋯O3ⁱ	0.97	2.55	3.2023 (19)	124
Symmetry code: (i) -x+2, -y, -z+1.

Data collection: RAPID-AUTO (Rigaku 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXTL (Sheldrick, 2001 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807060941/hg2352sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807060941/hg2352Isup2.hkl

checkCIF report

Comment top

Metamitron(Trade name: Goltix) is a widely used herbicide for the control of grass and broad-leaved weeds in sugar and red beets, fodder beet, and certain strawberry varieties. The dose rates for metamitron are 0.35–4.2 kg active ingredient/ha for all crops. The currently used weed control strategy in sugarbeet involves a mixture of herbicides(phenmedipham, ethofumesate, metamitron, chloridazon etc) to control dicotyledonus weeds. 70% wettable powderand has been used for the control of morel goosefoot chickweed Lamium barbatum etc. Metamitron can be used before and after the plantingis. It can be applied to the control of the entire crop growing period with better efficacy when it cooperate with others herbicides and pesticides(Javier et al., 2006). The title compound (I) was synthesized as an intermediate for the synthesis of metamitron. We report here the crystal structure of (I).

In (I) (Fig. 1), all bond lengths and angles are normal and in a good agreement with those reported previously (Glaser et al., 1993). The benzene ring plane forms dihedral angles of 86.3 (2)° and 10.0 (3)° with the ethyl plane (O1/O2/C7/C8/C9) and the acetylimino plane (O3/N1/N2/C4/C5/C6/C7/C11/C12), respectively. The crystal structure is stabilized by intermolecular C–H–O and N–H–O hydrogen bonds.

Related literature top

For related literature, see: Glaser et al. (1993); Javier et al. (2006); Pan & Gao (2007).

Experimental top

Ethyl benzoylformate 12.1 g (6.8 mmol), was dissolved in 20 ml e thanol in a flask equipped with stirrer and reflux condenser. Acethydrazide 5.1 g(6.8 mmol) was slowly added from a dropping-funnel during 30 minutes while maintaining the temperature at 75–80°C for eight hours. Evaporation of portion of the solvent and cooling down the remaining solution in ice water yielded white crystals out after three hours (11.9 g, yield 78.9%) (Pan et al., 2007). Single crystals suitable for X-ray measurement were obtained by recrystallization from petroleum ether at room temperature.

Structure description top

For related literature, see: Glaser et al. (1993); Javier et al. (2006); Pan & Gao (2007).

Computing details top

Data collection: RAPID-AUTO (Rigaku 2004); cell refinement: RAPID-AUTO (Rigaku 2004); data reduction: RAPID-AUTO (Rigaku 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).

Figures top

	Fig. 1. View of the title compound (I), with displacement ellipsoids drawn at the 35% probability level.
	Fig. 2. A packing diagram of the molecule of the title compound, viewed down the a axis. Hydrogen bonds are shown as dashed lines.

Ethyl 2-acetylhydrazono-2-phenylacetate top

Crystal data top

C₁₂H₁₄N₂O₃	F(000) = 992
M_r = 234.25	D_x = 1.240 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2998 reflections
a = 9.3039 (19) Å	θ = 2.3–21.9°
b = 15.752 (3) Å	µ = 0.09 mm⁻¹
c = 17.129 (3) Å	T = 153 K
V = 2510.3 (8) Å³	Block, colorless
Z = 8	0.32 × 0.22 × 0.10 mm

Data collection top

Rigaku R-AXIS Rapid IP area-detector diffractometer	2206 independent reflections
Radiation source: Rotating Anode	1870 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω Oscillation scans	θ_max = 25.0°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi 1995)	h = −11→11
T_min = 0.972, T_max = 0.991	k = −18→18
18227 measured reflections	l = −20→20

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)] = 0.037	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0576P)² + 0.4358P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.002
2206 reflections	Δρ_max = 0.23 e Å⁻³
156 parameters	Δρ_min = −0.12 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.030 (2)

Crystal data top

C₁₂H₁₄N₂O₃	V = 2510.3 (8) Å³
M_r = 234.25	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.3039 (19) Å	µ = 0.09 mm⁻¹
b = 15.752 (3) Å	T = 153 K
c = 17.129 (3) Å	0.32 × 0.22 × 0.10 mm

Data collection top

Rigaku R-AXIS Rapid IP area-detector diffractometer	2206 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi 1995)	1870 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.991	R_int = 0.023
18227 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.09	Δρ_max = 0.23 e Å⁻³
2206 reflections	Δρ_min = −0.12 e Å⁻³
156 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	0.98377 (12)	0.11865 (7)	0.70415 (6)	0.0676 (4)
O2	0.84719 (10)	0.19284 (6)	0.62123 (6)	0.0504 (3)
O3	1.14302 (12)	−0.00717 (6)	0.44126 (6)	0.0628 (3)
N1	1.16667 (12)	0.17432 (7)	0.55542 (6)	0.0456 (3)
N2	1.11668 (13)	0.09905 (7)	0.52543 (6)	0.0485 (3)
H2A	1.0369	0.0782	0.5420	0.058*
C1	1.26329 (16)	0.33271 (9)	0.60630 (8)	0.0514 (4)
H1B	1.3104	0.3071	0.5646	0.062*
C2	1.30914 (19)	0.41054 (10)	0.63304 (9)	0.0616 (4)
H2B	1.3875	0.4369	0.6096	0.074*
C3	1.2401 (2)	0.44963 (10)	0.69408 (10)	0.0682 (5)
H3A	1.2713	0.5024	0.7117	0.082*
C4	1.1246 (2)	0.41045 (10)	0.72922 (10)	0.0675 (5)
H4A	1.0776	0.4368	0.7706	0.081*
C5	1.07824 (17)	0.33195 (9)	0.70302 (8)	0.0538 (4)
H5A	1.0005	0.3057	0.7271	0.065*
C6	1.14696 (14)	0.29215 (8)	0.64113 (7)	0.0416 (3)
C7	1.09697 (14)	0.20901 (8)	0.61165 (7)	0.0405 (3)
C8	0.97033 (15)	0.16787 (8)	0.65146 (7)	0.0422 (3)
C9	0.71683 (16)	0.15866 (11)	0.65747 (9)	0.0574 (4)
H9A	0.7085	0.1788	0.7108	0.069*
H9B	0.7202	0.0971	0.6582	0.069*
C10	0.5936 (2)	0.18798 (17)	0.61093 (13)	0.1044 (9)
H10A	0.5062	0.1667	0.6334	0.157*
H10B	0.6029	0.1675	0.5584	0.157*
H10C	0.5914	0.2489	0.6107	0.157*
C11	1.19254 (16)	0.05777 (9)	0.46999 (8)	0.0494 (4)
C12	1.33423 (19)	0.09243 (12)	0.44570 (12)	0.0758 (5)
H12A	1.3687	0.0617	0.4011	0.114*
H12B	1.4015	0.0867	0.4878	0.114*
H12C	1.3240	0.1513	0.4325	0.114*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0664 (7)	0.0730 (7)	0.0634 (6)	−0.0111 (6)	−0.0089 (5)	0.0261 (6)
O2	0.0413 (6)	0.0526 (6)	0.0575 (6)	0.0010 (4)	0.0043 (4)	0.0092 (4)
O3	0.0619 (7)	0.0551 (6)	0.0715 (7)	−0.0139 (5)	0.0159 (5)	−0.0241 (5)
N1	0.0468 (6)	0.0391 (6)	0.0508 (6)	−0.0053 (5)	0.0006 (5)	−0.0052 (5)
N2	0.0485 (7)	0.0406 (6)	0.0564 (7)	−0.0102 (5)	0.0089 (5)	−0.0100 (5)
C1	0.0531 (8)	0.0463 (8)	0.0548 (8)	−0.0067 (6)	0.0027 (7)	−0.0031 (6)
C2	0.0647 (10)	0.0519 (9)	0.0682 (10)	−0.0166 (8)	0.0005 (8)	−0.0013 (7)
C3	0.0787 (12)	0.0473 (9)	0.0785 (11)	−0.0158 (8)	−0.0044 (9)	−0.0145 (8)
C4	0.0750 (11)	0.0591 (9)	0.0683 (10)	−0.0048 (8)	0.0055 (8)	−0.0229 (8)
C5	0.0539 (9)	0.0521 (8)	0.0553 (8)	−0.0055 (7)	0.0032 (7)	−0.0076 (7)
C6	0.0435 (7)	0.0372 (7)	0.0442 (7)	0.0002 (5)	−0.0062 (5)	−0.0004 (5)
C7	0.0406 (7)	0.0372 (7)	0.0436 (7)	−0.0002 (5)	−0.0036 (5)	0.0007 (5)
C8	0.0473 (8)	0.0376 (7)	0.0416 (7)	−0.0023 (5)	−0.0030 (6)	−0.0020 (6)
C9	0.0470 (9)	0.0641 (9)	0.0610 (9)	−0.0050 (7)	0.0153 (7)	−0.0018 (7)
C10	0.0464 (11)	0.174 (3)	0.0925 (14)	−0.0096 (13)	−0.0001 (10)	0.0327 (15)
C11	0.0495 (8)	0.0437 (7)	0.0551 (8)	−0.0041 (6)	0.0056 (6)	−0.0057 (6)
C12	0.0617 (10)	0.0691 (11)	0.0964 (13)	−0.0160 (8)	0.0270 (9)	−0.0234 (10)

Geometric parameters (Å, º) top

O1—C8	1.1964 (16)	C4—H4A	0.9300
O2—C8	1.3173 (16)	C5—C6	1.3878 (19)
O2—C9	1.4650 (17)	C5—H5A	0.9300
O3—C11	1.2251 (16)	C6—C7	1.4787 (18)
N1—C7	1.2832 (17)	C7—C8	1.5078 (19)
N1—N2	1.3733 (15)	C9—C10	1.471 (2)
N2—C11	1.3501 (18)	C9—H9A	0.9700
N2—H2A	0.8600	C9—H9B	0.9700
C1—C2	1.377 (2)	C10—H10A	0.9600
C1—C6	1.391 (2)	C10—H10B	0.9600
C1—H1B	0.9300	C10—H10C	0.9600
C2—C3	1.373 (2)	C11—C12	1.486 (2)
C2—H2B	0.9300	C12—H12A	0.9600
C3—C4	1.378 (2)	C12—H12B	0.9600
C3—H3A	0.9300	C12—H12C	0.9600
C4—C5	1.384 (2)

C8—O2—C9	116.34 (11)	C6—C7—C8	118.16 (11)
C7—N1—N2	118.50 (11)	O1—C8—O2	125.51 (13)
C11—N2—N1	120.12 (11)	O1—C8—C7	122.55 (12)
C11—N2—H2A	119.9	O2—C8—C7	111.94 (11)
N1—N2—H2A	119.9	O2—C9—C10	107.46 (13)
C2—C1—C6	120.50 (14)	O2—C9—H9A	110.2
C2—C1—H1B	119.8	C10—C9—H9A	110.2
C6—C1—H1B	119.8	O2—C9—H9B	110.2
C3—C2—C1	120.52 (15)	C10—C9—H9B	110.2
C3—C2—H2B	119.7	H9A—C9—H9B	108.5
C1—C2—H2B	119.7	C9—C10—H10A	109.5
C2—C3—C4	119.78 (15)	C9—C10—H10B	109.5
C2—C3—H3A	120.1	H10A—C10—H10B	109.5
C4—C3—H3A	120.1	C9—C10—H10C	109.5
C3—C4—C5	120.10 (15)	H10A—C10—H10C	109.5
C3—C4—H4A	120.0	H10B—C10—H10C	109.5
C5—C4—H4A	120.0	O3—C11—N2	119.22 (13)
C4—C5—C6	120.51 (15)	O3—C11—C12	121.86 (13)
C4—C5—H5A	119.7	N2—C11—C12	118.92 (13)
C6—C5—H5A	119.7	C11—C12—H12A	109.5
C5—C6—C1	118.59 (12)	C11—C12—H12B	109.5
C5—C6—C7	121.07 (12)	H12A—C12—H12B	109.5
C1—C6—C7	120.33 (12)	C11—C12—H12C	109.5
N1—C7—C6	118.33 (12)	H12A—C12—H12C	109.5
N1—C7—C8	123.46 (11)	H12B—C12—H12C	109.5

C7—N1—N2—C11	−175.43 (12)	C1—C6—C7—N1	2.49 (19)
C6—C1—C2—C3	−0.5 (2)	C5—C6—C7—C8	−0.87 (19)
C1—C2—C3—C4	0.4 (3)	C1—C6—C7—C8	−179.93 (12)
C2—C3—C4—C5	0.0 (3)	C9—O2—C8—O1	1.9 (2)
C3—C4—C5—C6	−0.3 (3)	C9—O2—C8—C7	−178.08 (11)
C4—C5—C6—C1	0.2 (2)	N1—C7—C8—O1	85.17 (18)
C4—C5—C6—C7	−178.90 (14)	C6—C7—C8—O1	−92.28 (16)
C2—C1—C6—C5	0.2 (2)	N1—C7—C8—O2	−94.86 (15)
C2—C1—C6—C7	179.29 (13)	C6—C7—C8—O2	87.69 (14)
N2—N1—C7—C6	−177.00 (11)	C8—O2—C9—C10	−174.94 (15)
N2—N1—C7—C8	5.56 (19)	N1—N2—C11—O3	−176.56 (13)
C5—C6—C7—N1	−178.46 (12)	N1—N2—C11—C12	3.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3ⁱ	0.86	2.03	2.8737 (16)	165
C9—H9B···O3ⁱ	0.97	2.55	3.2023 (19)	124

Symmetry code: (i) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₂O₃
M_r	234.25
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	153
a, b, c (Å)	9.3039 (19), 15.752 (3), 17.129 (3)
V (Å³)	2510.3 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.32 × 0.22 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS Rapid IP area-detector
Absorption correction	Multi-scan (ABSCOR; Higashi 1995)
T_min, T_max	0.972, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	18227, 2206, 1870
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.110, 1.09
No. of reflections	2206
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.12

Computer programs: RAPID-AUTO (Rigaku 2004), SHELXTL (Sheldrick, 2001).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3ⁱ	0.86	2.03	2.8737 (16)	165.3
C9—H9B···O3ⁱ	0.97	2.55	3.2023 (19)	124.2

Symmetry code: (i) −x+2, −y, −z+1.

References

Glaser, R., Chen, G. S. & Barnes, C. L. (1993). J. Org. Chem. 58, 7446–7455. CSD CrossRef CAS Web of Science Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Javier, M., Sergio, A. & Salvador, G. (2006). Anal. Chim. Acta, 565, 255–260. Google Scholar
Pan, Z. W. & Gao, H. X. (2007). Pesticides, 46, 166–167. CAS Google Scholar
Rigaku (2004). RAPID-AUTO. Version 3.0. Rigaku Corporation, Takyo, Japan. Google Scholar
Sheldrick, G. M. (2001). SHELXTL. Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar

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