2-Acetyl­hydrazono-2-phenyl­aceto­hydrazide

Feng, B.-C.; Yang, Z.; Yi, X.

doi:10.1107/S160053680802624X

organic compounds

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Volume 64| Part 9| September 2008| Page o1828

doi:10.1107/S160053680802624X

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2-Acetylhydrazono-2-phenylacetohydrazide

Bai-Cheng Feng,^a ^* Zhi Yang ^b and Xu Yi ^b

^aCollege of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China, and ^bCollege of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China
^*Correspondence e-mail: fengbaicheng_2008@yahoo.cn

(Received 12 June 2008; accepted 14 August 2008; online 23 August 2008)

The title compound, C₁₀H₁₂N₄O₂, was prepared as an intermediate for the synthesis of metamitron. The benzene ring plane forms dihedral angles of 66.0 (1) and 3.5 (5)° with the hydrazine plane and the acetylimino plane, respectively. The crystal structure involves intermolecular N—H⋯O hydrogen bonds.

Related literature

For related literature on the biological activity, see: Javier et al. (2006 ). For a similar structure, see: Glaser et al. (1993 ). For the preparation, see: Pan et al. (2007 ).

Experimental

Crystal data

C₁₀H₁₂N₄O₂
M_r = 220.24
Monoclinic, P 2₁ /c
a = 12.737 (3) Å
b = 4.5867 (10) Å
c = 21.002 (7) Å
β = 117.62 (2)°
V = 1087.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 153 (2) K
0.42 × 0.31 × 0.22 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi 1995 ) T_min = 0.804, T_max = 0.979
7793 measured reflections
1878 independent reflections
1624 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.103
S = 1.08
1878 reflections
155 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O2ⁱ	0.88	2.09	2.9512 (16)	167
N3—H3B⋯O1ⁱⁱ	0.88	2.08	2.8450 (15)	145
N4—H4B⋯O2ⁱ	0.90 (2)	2.396 (19)	3.0903 (19)	134.5 (15)
N4—H4C⋯O1ⁱⁱⁱ	0.890 (18)	2.274 (18)	3.0514 (19)	145.8 (15)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) x, y-1, z; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); 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: 10.1107/S160053680802624X/bv2104sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680802624X/bv2104Isup2.hkl

checkCIF report

Comment top

Metamitron (Trade name: Goltix) is used against grass and broad-leaved weeds in sugar and fodder beets. Metamitron is applied pre-drilling and pre- and post-emergence (post-emergence as sequential treatment tank-mixed with oil or other herbicides). Metamitron is also used in mangold, red 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. Wettable powder (70%) has been used for the control of morel goosefoot chickweed Lamium barbatum etc. Metamitron can be used before and after planting. It can be applied to the control of the entire crop growing period with better efficacy when it cooperates 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 66.0 (1)° and 3.5 (5)° with the hydrazine plane consisting of O1, N3, N4, and C8, and the acetylimino plane consisting of O2, N1, N2, C9, and C10, respectively. The crystal structure is stabilized by intermolecular N–H–O hydrogen bonds.

Related literature top

For related literature on the biological activity, see: Javier et al. (2006). For a similar structure, see: Glaser et al. (1993). For the preparation, see: Pan et al. (2007).

Experimental top

Phenylglyoxylic acid ethyl ester 2-acetylhydrazone 23.4 g (0.1 mol), was dissolved in 100 ml ethanol in a flask equipped with stirrer and reflux condenser. Hydrazine hydrate 7.5 g (0.1 mmol) was slowly added from a dropping-funnel during 30 minutes while maintaining the temperature at 25–30°C for two hours. Portions of the solvent were distilled and the remaining solution cooled in ice water. White crystals separated out after a short time (18.9 g, yield 87.3%) (Pan et al., 2007). Single crystals suitable for X-ray measurement were obtained by recrystallization from petrol ether at room temperature.

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, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

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, view down b axis. Hydrogen bonds are shown as dashed lines.

2-Acetylhydrazono-2-phenylacetohydrazide top

Crystal data top

C₁₀H₁₂N₄O₂	F(000) = 464
M_r = 220.24	D_x = 1.346 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2652 reflections
a = 12.737 (3) Å	θ = 2.6–25.6°
b = 4.5867 (10) Å	µ = 0.10 mm⁻¹
c = 21.002 (7) Å	T = 153 K
β = 117.62 (2)°	Block, colorless
V = 1087.1 (5) Å³	0.42 × 0.31 × 0.22 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	1878 independent reflections
Radiation source: Rotating Anode	1624 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω Oscillation scans	θ_max = 25.0°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi 1995)	h = −15→15
T_min = 0.805, T_max = 0.979	k = −5→5
7793 measured reflections	l = −24→24

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 atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.0567P)² + 0.2207P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
1878 reflections	Δρ_max = 0.20 e Å⁻³
155 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.024 (4)

Crystal data top

C₁₀H₁₂N₄O₂	V = 1087.1 (5) Å³
M_r = 220.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.737 (3) Å	µ = 0.10 mm⁻¹
b = 4.5867 (10) Å	T = 153 K
c = 21.002 (7) Å	0.42 × 0.31 × 0.22 mm
β = 117.62 (2)°

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	1878 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi 1995)	1624 reflections with I > 2σ(I)
T_min = 0.805, T_max = 0.979	R_int = 0.024
7793 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.20 e Å⁻³
1878 reflections	Δρ_min = −0.16 e Å⁻³
155 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	0.40065 (9)	1.19619 (19)	0.29348 (5)	0.0427 (3)
O2	0.44401 (10)	0.7702 (2)	0.54459 (5)	0.0531 (3)
N1	0.27633 (9)	0.7290 (2)	0.35864 (6)	0.0362 (3)
N2	0.36620 (10)	0.8004 (3)	0.42552 (6)	0.0390 (3)
H2B	0.4245	0.9138	0.4292	0.047*
N3	0.49466 (9)	0.7681 (2)	0.33409 (6)	0.0359 (3)
H3B	0.4858	0.5829	0.3415	0.043*
N4	0.60867 (10)	0.8674 (3)	0.34944 (7)	0.0423 (3)
C1	0.19350 (13)	0.8340 (4)	0.17011 (7)	0.0469 (4)
H1A	0.2573	0.9530	0.1742	0.056*
C2	0.10157 (15)	0.7697 (4)	0.10282 (8)	0.0573 (4)
H2A	0.1027	0.8455	0.0610	0.069*
C3	0.00929 (13)	0.5978 (4)	0.09616 (8)	0.0585 (5)
H3A	−0.0536	0.5542	0.0499	0.070*
C4	0.00809 (14)	0.4882 (4)	0.15689 (9)	0.0634 (5)
H4A	−0.0560	0.3691	0.1524	0.076*
C5	0.09888 (13)	0.5496 (4)	0.22391 (8)	0.0517 (4)
H5A	0.0975	0.4711	0.2654	0.062*
C6	0.19282 (11)	0.7257 (3)	0.23147 (7)	0.0348 (3)
C7	0.28992 (11)	0.7937 (3)	0.30347 (6)	0.0321 (3)
C8	0.40034 (10)	0.9387 (3)	0.30915 (6)	0.0301 (3)
C9	0.36513 (12)	0.6973 (3)	0.48520 (7)	0.0378 (3)
C10	0.26833 (13)	0.4954 (4)	0.47702 (8)	0.0514 (4)
H10A	0.2836	0.4216	0.5243	0.077*
H10B	0.2650	0.3317	0.4462	0.077*
H10C	0.1926	0.5998	0.4552	0.077*
H4C	0.6083 (14)	0.900 (4)	0.3076 (10)	0.055 (5)*
H4B	0.6174 (15)	1.039 (4)	0.3717 (9)	0.061 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0494 (6)	0.0282 (5)	0.0425 (5)	−0.0037 (4)	0.0144 (4)	0.0028 (4)
O2	0.0597 (7)	0.0632 (7)	0.0316 (5)	−0.0165 (5)	0.0171 (5)	−0.0079 (5)
N1	0.0332 (6)	0.0421 (7)	0.0320 (6)	−0.0033 (4)	0.0138 (5)	−0.0042 (5)
N2	0.0379 (6)	0.0480 (7)	0.0313 (6)	−0.0107 (5)	0.0162 (5)	−0.0060 (5)
N3	0.0363 (6)	0.0275 (5)	0.0472 (6)	−0.0034 (4)	0.0220 (5)	0.0000 (5)
N4	0.0367 (6)	0.0480 (8)	0.0463 (7)	−0.0055 (5)	0.0227 (5)	−0.0012 (6)
C1	0.0449 (8)	0.0560 (9)	0.0371 (7)	−0.0082 (7)	0.0166 (6)	−0.0022 (7)
C2	0.0578 (10)	0.0741 (12)	0.0323 (7)	−0.0047 (8)	0.0144 (7)	−0.0015 (7)
C3	0.0421 (9)	0.0794 (12)	0.0399 (8)	−0.0050 (8)	0.0070 (6)	−0.0153 (8)
C4	0.0437 (9)	0.0879 (13)	0.0532 (9)	−0.0243 (8)	0.0180 (7)	−0.0173 (9)
C5	0.0452 (8)	0.0679 (11)	0.0417 (7)	−0.0158 (7)	0.0200 (6)	−0.0075 (7)
C6	0.0316 (7)	0.0370 (7)	0.0339 (7)	0.0014 (5)	0.0136 (5)	−0.0044 (5)
C7	0.0343 (7)	0.0295 (7)	0.0323 (6)	0.0009 (5)	0.0155 (5)	−0.0023 (5)
C8	0.0364 (7)	0.0274 (7)	0.0249 (6)	−0.0032 (5)	0.0128 (5)	−0.0041 (5)
C9	0.0406 (7)	0.0401 (8)	0.0331 (7)	0.0008 (6)	0.0176 (6)	−0.0023 (6)
C10	0.0490 (9)	0.0602 (10)	0.0434 (8)	−0.0078 (7)	0.0200 (7)	0.0072 (7)

Geometric parameters (Å, º) top

O1—C8	1.2263 (15)	C2—C3	1.368 (2)
O2—C9	1.2308 (17)	C2—H2A	0.9500
N1—C7	1.2833 (17)	C3—C4	1.378 (2)
N1—N2	1.3783 (16)	C3—H3A	0.9500
N2—C9	1.3455 (18)	C4—C5	1.374 (2)
N2—H2B	0.8800	C4—H4A	0.9500
N3—C8	1.3218 (16)	C5—C6	1.391 (2)
N3—N4	1.4093 (15)	C5—H5A	0.9500
N3—H3B	0.8800	C6—C7	1.4762 (18)
N4—H4C	0.890 (18)	C7—C8	1.5097 (17)
N4—H4B	0.90 (2)	C9—C10	1.487 (2)
C1—C6	1.385 (2)	C10—H10A	0.9800
C1—C2	1.386 (2)	C10—H10B	0.9800
C1—H1A	0.9500	C10—H10C	0.9800

C7—N1—N2	117.99 (11)	C4—C5—C6	120.46 (15)
C9—N2—N1	120.24 (11)	C4—C5—H5A	119.8
C9—N2—H2B	119.9	C6—C5—H5A	119.8
N1—N2—H2B	119.9	C1—C6—C5	118.57 (12)
C8—N3—N4	123.36 (11)	C1—C6—C7	120.92 (12)
C8—N3—H3B	118.3	C5—C6—C7	120.51 (12)
N4—N3—H3B	118.3	N1—C7—C6	118.45 (12)
N3—N4—H4C	107.2 (11)	N1—C7—C8	122.77 (11)
N3—N4—H4B	105.6 (11)	C6—C7—C8	118.78 (11)
H4C—N4—H4B	108.0 (16)	O1—C8—N3	124.14 (12)
C6—C1—C2	120.39 (14)	O1—C8—C7	121.45 (11)
C6—C1—H1A	119.8	N3—C8—C7	114.37 (10)
C2—C1—H1A	119.8	O2—C9—N2	119.50 (13)
C3—C2—C1	120.44 (15)	O2—C9—C10	122.00 (12)
C3—C2—H2A	119.8	N2—C9—C10	118.49 (12)
C1—C2—H2A	119.8	C9—C10—H10A	109.5
C2—C3—C4	119.58 (14)	C9—C10—H10B	109.5
C2—C3—H3A	120.2	H10A—C10—H10B	109.5
C4—C3—H3A	120.2	C9—C10—H10C	109.5
C5—C4—C3	120.55 (15)	H10A—C10—H10C	109.5
C5—C4—H4A	119.7	H10B—C10—H10C	109.5
C3—C4—H4A	119.7

C7—N1—N2—C9	−169.43 (11)	C5—C6—C7—N1	−11.5 (2)
C6—C1—C2—C3	−0.2 (3)	C1—C6—C7—C8	−10.55 (19)
C1—C2—C3—C4	0.0 (3)	C5—C6—C7—C8	169.07 (13)
C2—C3—C4—C5	−0.2 (3)	N4—N3—C8—O1	3.72 (19)
C3—C4—C5—C6	0.6 (3)	N4—N3—C8—C7	−174.25 (11)
C2—C1—C6—C5	0.7 (2)	N1—C7—C8—O1	−106.29 (15)
C2—C1—C6—C7	−179.71 (14)	C6—C7—C8—O1	73.11 (15)
C4—C5—C6—C1	−0.9 (2)	N1—C7—C8—N3	71.75 (15)
C4—C5—C6—C7	179.52 (15)	C6—C7—C8—N3	−108.85 (13)
N2—N1—C7—C6	−178.31 (11)	N1—N2—C9—O2	−177.76 (12)
N2—N1—C7—C8	1.09 (19)	N1—N2—C9—C10	2.8 (2)
C1—C6—C7—N1	168.88 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O2ⁱ	0.88	2.09	2.9512 (16)	167
N3—H3B···O1ⁱⁱ	0.88	2.08	2.8450 (15)	145
N4—H4B···O2ⁱ	0.90 (2)	2.396 (19)	3.0903 (19)	134.5 (15)
N4—H4C···O1ⁱⁱⁱ	0.890 (18)	2.274 (18)	3.0514 (19)	145.8 (15)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, y−1, z; (iii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₄O₂
M_r	220.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	153
a, b, c (Å)	12.737 (3), 4.5867 (10), 21.002 (7)
β (°)	117.62 (2)
V (Å³)	1087.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.42 × 0.31 × 0.22

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi 1995)
T_min, T_max	0.805, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	7793, 1878, 1624
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.103, 1.08
No. of reflections	1878
No. of parameters	155
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.16

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O2ⁱ	0.88	2.09	2.9512 (16)	167.2
N3—H3B···O1ⁱⁱ	0.88	2.08	2.8450 (15)	144.9
N4—H4B···O2ⁱ	0.90 (2)	2.396 (19)	3.0903 (19)	134.5 (15)
N4—H4C···O1ⁱⁱⁱ	0.890 (18)	2.274 (18)	3.0514 (19)	145.8 (15)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, y−1, z; (iii) −x+1, y−1/2, −z+1/2.

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. Rigaku Corporation, Takyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S160053680802624X

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