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Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): o1828.
Published online 2008 August 23. doi:  10.1107/S160053680802624X
PMCID: PMC2960741

2-Acetyl­hydrazono-2-phenyl­aceto­hydrazide

Abstract

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 [triangle]). For a similar structure, see: Glaser et al. (1993 [triangle]). For the preparation, see: Pan et al. (2007 [triangle]).

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Object name is e-64-o1828-scheme1.jpg

Experimental

Crystal data

  • C10H12N4O2
  • M r = 220.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1828-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.103
  • S = 1.08
  • 1878 reflections
  • 155 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2004 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680802624X/bv2104sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H atoms were found on difference maps. The hydrazine H atoms were refined freely, giving an N—H bond distance of 0.89 or 0.90 Å. The remaining H atoms were positioned geometrically [N—H = 0.88 Å C—H = 0.95 Å (CH), C—H = 0.98 Å (CH3), andUiso (H) = 1.5 times (Methyl) or Uiso(H) = 1.2 times (other H atoms)].

Figures

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.

Crystal data

C10H12N4O2F000 = 464
Mr = 220.24Dx = 1.346 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2652 reflections
a = 12.737 (3) Åθ = 2.6–25.6º
b = 4.5867 (10) ŵ = 0.10 mm1
c = 21.002 (7) ÅT = 153 (2) K
β = 117.62 (2)ºBlock, colorless
V = 1087.1 (5) Å30.42 × 0.31 × 0.22 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer1878 independent reflections
Radiation source: Rotating Anode1624 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.024
T = 153(2) Kθmax = 25.0º
ω Oscillation scansθmin = 3.2º
Absorption correction: multi-scan(ABSCOR; Higashi 1995)h = −15→15
Tmin = 0.805, Tmax = 0.979k = −5→5
7793 measured reflectionsl = −24→24

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.035  w = 1/[σ2(Fo2) + (0.0567P)2 + 0.2207P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.103(Δ/σ)max = 0.001
S = 1.08Δρmax = 0.20 e Å3
1878 reflectionsΔρmin = −0.16 e Å3
155 parametersExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.024 (4)
Secondary atom site location: difference Fourier map

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 (Å2)

xyzUiso*/Ueq
O10.40065 (9)1.19619 (19)0.29348 (5)0.0427 (3)
O20.44401 (10)0.7702 (2)0.54459 (5)0.0531 (3)
N10.27633 (9)0.7290 (2)0.35864 (6)0.0362 (3)
N20.36620 (10)0.8004 (3)0.42552 (6)0.0390 (3)
H2B0.42450.91380.42920.047*
N30.49466 (9)0.7681 (2)0.33409 (6)0.0359 (3)
H3B0.48580.58290.34150.043*
N40.60867 (10)0.8674 (3)0.34944 (7)0.0423 (3)
C10.19350 (13)0.8340 (4)0.17011 (7)0.0469 (4)
H1A0.25730.95300.17420.056*
C20.10157 (15)0.7697 (4)0.10282 (8)0.0573 (4)
H2A0.10270.84550.06100.069*
C30.00929 (13)0.5978 (4)0.09616 (8)0.0585 (5)
H3A−0.05360.55420.04990.070*
C40.00809 (14)0.4882 (4)0.15689 (9)0.0634 (5)
H4A−0.05600.36910.15240.076*
C50.09888 (13)0.5496 (4)0.22391 (8)0.0517 (4)
H5A0.09750.47110.26540.062*
C60.19282 (11)0.7257 (3)0.23147 (7)0.0348 (3)
C70.28992 (11)0.7937 (3)0.30347 (6)0.0321 (3)
C80.40034 (10)0.9387 (3)0.30915 (6)0.0301 (3)
C90.36513 (12)0.6973 (3)0.48520 (7)0.0378 (3)
C100.26833 (13)0.4954 (4)0.47702 (8)0.0514 (4)
H10A0.28360.42160.52430.077*
H10B0.26500.33170.44620.077*
H10C0.19260.59980.45520.077*
H4C0.6083 (14)0.900 (4)0.3076 (10)0.055 (5)*
H4B0.6174 (15)1.039 (4)0.3717 (9)0.061 (5)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0494 (6)0.0282 (5)0.0425 (5)−0.0037 (4)0.0144 (4)0.0028 (4)
O20.0597 (7)0.0632 (7)0.0316 (5)−0.0165 (5)0.0171 (5)−0.0079 (5)
N10.0332 (6)0.0421 (7)0.0320 (6)−0.0033 (4)0.0138 (5)−0.0042 (5)
N20.0379 (6)0.0480 (7)0.0313 (6)−0.0107 (5)0.0162 (5)−0.0060 (5)
N30.0363 (6)0.0275 (5)0.0472 (6)−0.0034 (4)0.0220 (5)0.0000 (5)
N40.0367 (6)0.0480 (8)0.0463 (7)−0.0055 (5)0.0227 (5)−0.0012 (6)
C10.0449 (8)0.0560 (9)0.0371 (7)−0.0082 (7)0.0166 (6)−0.0022 (7)
C20.0578 (10)0.0741 (12)0.0323 (7)−0.0047 (8)0.0144 (7)−0.0015 (7)
C30.0421 (9)0.0794 (12)0.0399 (8)−0.0050 (8)0.0070 (6)−0.0153 (8)
C40.0437 (9)0.0879 (13)0.0532 (9)−0.0243 (8)0.0180 (7)−0.0173 (9)
C50.0452 (8)0.0679 (11)0.0417 (7)−0.0158 (7)0.0200 (6)−0.0075 (7)
C60.0316 (7)0.0370 (7)0.0339 (7)0.0014 (5)0.0136 (5)−0.0044 (5)
C70.0343 (7)0.0295 (7)0.0323 (6)0.0009 (5)0.0155 (5)−0.0023 (5)
C80.0364 (7)0.0274 (7)0.0249 (6)−0.0032 (5)0.0128 (5)−0.0041 (5)
C90.0406 (7)0.0401 (8)0.0331 (7)0.0008 (6)0.0176 (6)−0.0023 (6)
C100.0490 (9)0.0602 (10)0.0434 (8)−0.0078 (7)0.0200 (7)0.0072 (7)

Geometric parameters (Å, °)

O1—C81.2263 (15)C2—C31.368 (2)
O2—C91.2308 (17)C2—H2A0.9500
N1—C71.2833 (17)C3—C41.378 (2)
N1—N21.3783 (16)C3—H3A0.9500
N2—C91.3455 (18)C4—C51.374 (2)
N2—H2B0.8800C4—H4A0.9500
N3—C81.3218 (16)C5—C61.391 (2)
N3—N41.4093 (15)C5—H5A0.9500
N3—H3B0.8800C6—C71.4762 (18)
N4—H4C0.890 (18)C7—C81.5097 (17)
N4—H4B0.90 (2)C9—C101.487 (2)
C1—C61.385 (2)C10—H10A0.9800
C1—C21.386 (2)C10—H10B0.9800
C1—H1A0.9500C10—H10C0.9800
C7—N1—N2117.99 (11)C4—C5—C6120.46 (15)
C9—N2—N1120.24 (11)C4—C5—H5A119.8
C9—N2—H2B119.9C6—C5—H5A119.8
N1—N2—H2B119.9C1—C6—C5118.57 (12)
C8—N3—N4123.36 (11)C1—C6—C7120.92 (12)
C8—N3—H3B118.3C5—C6—C7120.51 (12)
N4—N3—H3B118.3N1—C7—C6118.45 (12)
N3—N4—H4C107.2 (11)N1—C7—C8122.77 (11)
N3—N4—H4B105.6 (11)C6—C7—C8118.78 (11)
H4C—N4—H4B108.0 (16)O1—C8—N3124.14 (12)
C6—C1—C2120.39 (14)O1—C8—C7121.45 (11)
C6—C1—H1A119.8N3—C8—C7114.37 (10)
C2—C1—H1A119.8O2—C9—N2119.50 (13)
C3—C2—C1120.44 (15)O2—C9—C10122.00 (12)
C3—C2—H2A119.8N2—C9—C10118.49 (12)
C1—C2—H2A119.8C9—C10—H10A109.5
C2—C3—C4119.58 (14)C9—C10—H10B109.5
C2—C3—H3A120.2H10A—C10—H10B109.5
C4—C3—H3A120.2C9—C10—H10C109.5
C5—C4—C3120.55 (15)H10A—C10—H10C109.5
C5—C4—H4A119.7H10B—C10—H10C109.5
C3—C4—H4A119.7
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—C40.0 (3)C5—C6—C7—C8169.07 (13)
C2—C3—C4—C5−0.2 (3)N4—N3—C8—O13.72 (19)
C3—C4—C5—C60.6 (3)N4—N3—C8—C7−174.25 (11)
C2—C1—C6—C50.7 (2)N1—C7—C8—O1−106.29 (15)
C2—C1—C6—C7−179.71 (14)C6—C7—C8—O173.11 (15)
C4—C5—C6—C1−0.9 (2)N1—C7—C8—N371.75 (15)
C4—C5—C6—C7179.52 (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—C81.09 (19)N1—N2—C9—C102.8 (2)
C1—C6—C7—N1168.88 (13)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2B···O2i0.882.092.9512 (16)167
N3—H3B···O1ii0.882.082.8450 (15)145
N4—H4B···O2i0.90 (2)2.396 (19)3.0903 (19)134.5 (15)
N4—H4C···O1iii0.890 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BV2104).

References

  • Glaser, R., Chen, G. S. & Barnes, C. L. (1993). J. Org. Chem.58, 7446–7455.
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Javier, M., Sergio, A. & Salvador, G. (2006). Anal. Chim. Acta, 565, 255–260.
  • Pan, Z. W. & Gao, H. X. (2007). Pesticides, 46, 166–167.
  • Rigaku (2004). RAPID-AUTO Rigaku Corporation, Takyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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