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The non-hydrogen skeleton of the title mol­ecule, C10H10N2O3, is planar and intramolecular N—H...O and O—H...O hydrogen bonds contribute to this planarity. The mol­ecule exists in the space isomeric Z stereoisomer.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802014757/ci6148sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802014757/ci6148Isup2.hkl
Contains datablock I

CCDC reference: 197472

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.058
  • wR factor = 0.183
  • Data-to-parameter ratio = 13.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

As a part of our project to study the crystal structures of a series of phenylhydrazones and their stereochemistry, the crystal structure of the title compound, (I), has been determined. Ealier we reported the structure of 2-(2-methoxyphenylhydrazono)-3-oxobutanoic acid, (II) (Rani et al., 2002). The bond lengths and angles in (I) show normal values and are comparable with those observed for (II). The molecule is planar, with atom O1 deviating by a maximum of 0.066 (2) Å. The planarity of the molecule is facilitated by the intramolecular hydrogen bonds. The NH group forms an intramolecular N—H···O hydrogen bond with the carbonyl O atom of the carboxyl group. The carbonyl O atom of the carbomethoxy group is also involved in an intramolecular O—H···O hydrogen bond with the carboxyl group (Fig. 1). In the crystal, the molecules exit as centrosymmetrically N1—H1N···O2(1 − x, 1 − y, 2 − z) hydrogen-bonded dimers (Table 2). Along the a-cell direction, the molecules related by inversion are stacked alternatively 3.412 and 3.501 Å apart, which are optimum distances for ππ stacking interactions. The short contacts observed in the structure are listed in Table 3.

Experimental top

The title compound was prepared by partial hydrolysis of ethyl 3-oxo-2-(2-phenylhydrazono)butyrate by the action of strong acids (Prasad et al., 1994) and was recrystallized from methanol at room temperature.

Refinement top

After checking their presence in a difference Fourier map, all the H atoms were placed at calculated positions and were allowed to ride on their respective parent atoms using SHELXL97 (Sheldrick, 1997) defaults.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.
3-Oxo-2-(phenylhydrazono)butanoic acid top
Crystal data top
C10H10N2O3F(000) = 432
Mr = 206.20Dx = 1.388 Mg m3
Monoclinic, P21/nCu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 6.9138 (10) Åθ = 16.7–49.7°
b = 21.309 (2) ŵ = 0.88 mm1
c = 7.0783 (10) ÅT = 293 K
β = 108.917 (10)°Needle, colourless
V = 986.5 (2) Å30.2 × 0.15 × 0.1 mm
Z = 4
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.019
Radiation source: fine-focus sealed tubeθmax = 70.1°, θmin = 4.2°
Graphite monochromatorh = 87
ω–2θ scansk = 025
2026 measured reflectionsl = 08
1878 independent reflections3 standard reflections every 1 hr min
1230 reflections with I > 2σ(I) intensity decay: 0.0%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.183H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.1093P)2 + 0.0037P]
where P = (Fo2 + 2Fc2)/3
1878 reflections(Δ/σ)max < 0.001
136 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C10H10N2O3V = 986.5 (2) Å3
Mr = 206.20Z = 4
Monoclinic, P21/nCu Kα radiation
a = 6.9138 (10) ŵ = 0.88 mm1
b = 21.309 (2) ÅT = 293 K
c = 7.0783 (10) Å0.2 × 0.15 × 0.1 mm
β = 108.917 (10)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.019
2026 measured reflections3 standard reflections every 1 hr min
1878 independent reflections intensity decay: 0.0%
1230 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.183H-atom parameters constrained
S = 1.08Δρmax = 0.20 e Å3
1878 reflectionsΔρmin = 0.26 e Å3
136 parameters
Special details top

Geometry. All su's are estimated using the full covariance matrix. The cell su's are taken into account individually in the estimation of su's in distances, angles and torsion angles; correlations between su's in cell parameters are only used when they are defined by crystal symmetry.

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
xyzUiso*/Ueq
O10.4124 (3)0.33645 (8)0.9715 (2)0.0722 (6)
H1O0.38560.30800.88900.108*
O20.3966 (3)0.43968 (7)0.9743 (2)0.0645 (5)
O30.3018 (3)0.27992 (7)0.6413 (3)0.0731 (5)
N10.2913 (2)0.49671 (7)0.6210 (2)0.0459 (4)
H1N0.33470.50260.74800.055*
N20.2631 (2)0.43964 (8)0.5461 (3)0.0447 (4)
C10.2486 (3)0.54780 (9)0.4882 (3)0.0449 (5)
C20.2716 (3)0.60768 (10)0.5690 (3)0.0517 (6)
H20.31160.61340.70650.062*
C30.2340 (3)0.65905 (12)0.4410 (4)0.0629 (7)
H30.25210.69940.49400.076*
C40.1697 (4)0.65096 (12)0.2357 (4)0.0643 (7)
H40.13960.68540.15060.077*
C50.1513 (4)0.59106 (12)0.1603 (4)0.0663 (6)
H50.11160.58540.02270.080*
C60.1899 (4)0.53932 (12)0.2824 (3)0.0585 (6)
H60.17700.49920.22830.070*
C70.3021 (3)0.38939 (9)0.6590 (3)0.0475 (5)
C80.3763 (3)0.39060 (10)0.8793 (3)0.0509 (5)
C90.2690 (3)0.32992 (10)0.5497 (4)0.0523 (5)
C100.1899 (4)0.33061 (12)0.3295 (3)0.0677 (7)
H10A0.17580.28830.28030.102*
H10B0.28340.35300.27920.102*
H10C0.05900.35100.28580.102*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0995 (15)0.0591 (9)0.0572 (10)0.0049 (9)0.0242 (10)0.0134 (8)
O20.0740 (11)0.0648 (10)0.0478 (9)0.0083 (8)0.0104 (8)0.0081 (7)
O30.0892 (13)0.0498 (9)0.0764 (12)0.0006 (8)0.0214 (10)0.0027 (8)
N10.0399 (10)0.0461 (9)0.0475 (9)0.0039 (7)0.0084 (8)0.0019 (7)
N20.0341 (8)0.0477 (9)0.0525 (10)0.0013 (7)0.0145 (8)0.0027 (7)
C10.0374 (10)0.0437 (10)0.0570 (11)0.0044 (8)0.0202 (9)0.0056 (8)
C20.0436 (12)0.0545 (12)0.0542 (12)0.0044 (9)0.0123 (10)0.0057 (10)
C30.0469 (13)0.0512 (12)0.0899 (18)0.0015 (10)0.0211 (13)0.0062 (12)
C40.0466 (13)0.0625 (14)0.0754 (17)0.0008 (10)0.0082 (12)0.0217 (12)
C50.0618 (14)0.0703 (14)0.0598 (14)0.0044 (13)0.0100 (12)0.0102 (12)
C60.0584 (13)0.0604 (13)0.0526 (13)0.0021 (11)0.0124 (11)0.0037 (10)
C70.0404 (11)0.0518 (11)0.0520 (12)0.0059 (8)0.0172 (10)0.0008 (9)
C80.0442 (12)0.0529 (11)0.0541 (12)0.0059 (9)0.0137 (10)0.0041 (9)
C90.0418 (11)0.0492 (11)0.0635 (13)0.0018 (9)0.0138 (10)0.0006 (10)
C100.0732 (16)0.0647 (14)0.0604 (15)0.0062 (13)0.0149 (13)0.0115 (12)
Geometric parameters (Å, º) top
O1—C81.309 (2)C3—H30.93
O1—H1O0.82C4—C51.374 (3)
O2—C81.227 (2)C4—H40.93
O3—C91.229 (3)C5—C61.373 (3)
N1—N21.316 (2)C5—H50.93
N1—C11.406 (2)C6—H60.93
N1—H1N0.86C7—C91.464 (3)
N2—C71.311 (3)C7—C81.475 (3)
C1—C21.386 (3)C9—C101.475 (3)
C1—C61.391 (3)C10—H10A0.96
C2—C31.390 (3)C10—H10B0.96
C2—H20.93C10—H10C0.96
C3—C41.386 (4)
O1···C2i3.487 (3)C3···C9iv3.423 (3)
O1···C10ii3.366 (3)C4···C7iv3.587 (4)
O2···O2i2.907 (2)C5···C8iii3.588 (4)
O2···C2i3.453 (3)C5···C8iv3.390 (4)
C3···C9iii3.507 (3)
C8—O1—H1O109.5C4—C5—H5119.1
N2—N1—C1118.36 (16)C5—C6—C1119.1 (2)
N2—N1—H1N120.8C5—C6—H6120.5
C1—N1—H1N120.8C1—C6—H6120.5
C7—N2—N1122.36 (17)N2—C7—C9114.78 (19)
C2—C1—C6120.5 (2)N2—C7—C8124.22 (18)
C2—C1—N1117.77 (18)C9—C7—C8121.00 (19)
C6—C1—N1121.75 (19)O2—C8—O1120.6 (2)
C1—C2—C3118.9 (2)O2—C8—C7122.23 (18)
C1—C2—H2120.5O1—C8—C7117.16 (19)
C3—C2—H2120.5O3—C9—C7120.1 (2)
C4—C3—C2120.9 (2)O3—C9—C10120.5 (2)
C4—C3—H3119.5C7—C9—C10119.38 (19)
C2—C3—H3119.5C9—C10—H10A109.5
C5—C4—C3118.8 (2)C9—C10—H10B109.5
C5—C4—H4120.6H10A—C10—H10B109.5
C3—C4—H4120.6C9—C10—H10C109.5
C6—C5—C4121.8 (2)H10A—C10—H10C109.5
C6—C5—H5119.1H10B—C10—H10C109.5
C1—N1—N2—C7178.89 (16)N1—N2—C7—C9177.78 (14)
N2—N1—C1—C2177.63 (15)N1—N2—C7—C81.5 (3)
N2—N1—C1—C63.9 (3)N2—C7—C8—O24.1 (3)
C6—C1—C2—C30.4 (3)C9—C7—C8—O2176.7 (2)
N1—C1—C2—C3178.86 (16)N2—C7—C8—O1178.66 (19)
C1—C2—C3—C41.5 (3)C9—C7—C8—O10.5 (3)
C2—C3—C4—C52.5 (3)N2—C7—C9—O3179.73 (18)
C3—C4—C5—C61.6 (4)C8—C7—C9—O30.5 (3)
C4—C5—C6—C10.2 (4)N2—C7—C9—C102.2 (3)
C2—C1—C6—C51.2 (3)C8—C7—C9—C10178.5 (2)
N1—C1—C6—C5179.66 (19)
Symmetry codes: (i) x+1, y+1, z+2; (ii) x, y, z+1; (iii) x, y+1, z+1; (iv) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O20.862.032.661 (2)130
N1—H1N···O2i0.862.543.270 (2)143
O1—H1O···O30.821.762.518 (2)152
Symmetry code: (i) x+1, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC10H10N2O3
Mr206.20
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)6.9138 (10), 21.309 (2), 7.0783 (10)
β (°) 108.917 (10)
V3)986.5 (2)
Z4
Radiation typeCu Kα
µ (mm1)0.88
Crystal size (mm)0.2 × 0.15 × 0.1
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2026, 1878, 1230
Rint0.019
(sin θ/λ)max1)0.610
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.183, 1.08
No. of reflections1878
No. of parameters136
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.26

Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
O1—C81.309 (2)N2—C71.311 (3)
O2—C81.227 (2)C7—C91.464 (3)
O3—C91.229 (3)C7—C81.475 (3)
N1—N21.316 (2)C9—C101.475 (3)
N1—C11.406 (2)
O1···C2i3.487 (3)C3···C9iv3.423 (3)
O1···C10ii3.366 (3)C4···C7iv3.587 (4)
O2···O2i2.907 (2)C5···C8iii3.588 (4)
O2···C2i3.453 (3)C5···C8iv3.390 (4)
C3···C9iii3.507 (3)
N2—N1—C1118.36 (16)O2—C8—O1120.6 (2)
C7—N2—N1122.36 (17)O2—C8—C7122.23 (18)
C2—C1—N1117.77 (18)O1—C8—C7117.16 (19)
C6—C1—N1121.75 (19)O3—C9—C7120.1 (2)
N2—C7—C9114.78 (19)O3—C9—C10120.5 (2)
N2—C7—C8124.22 (18)C7—C9—C10119.38 (19)
C9—C7—C8121.00 (19)
C1—N1—N2—C7178.89 (16)C9—C7—C8—O2176.7 (2)
N2—N1—C1—C2177.63 (15)N2—C7—C8—O1178.66 (19)
N2—N1—C1—C63.9 (3)C9—C7—C8—O10.5 (3)
N1—C1—C2—C3178.86 (16)N2—C7—C9—O3179.73 (18)
N1—C1—C6—C5179.66 (19)C8—C7—C9—O30.5 (3)
N1—N2—C7—C9177.78 (14)N2—C7—C9—C102.2 (3)
N1—N2—C7—C81.5 (3)C8—C7—C9—C10178.5 (2)
N2—C7—C8—O24.1 (3)
Symmetry codes: (i) x+1, y+1, z+2; (ii) x, y, z+1; (iii) x, y+1, z+1; (iv) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O20.862.032.661 (2)130.0
N1—H1N···O2i0.862.543.270 (2)143.1
O1—H1O···O30.821.762.518 (2)152.2
Symmetry code: (i) x+1, y+1, z+2.
 

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