The non-hydrogen skeleton of the title molecule, C
10H
10N
2O
3, 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
CCDC reference: 197472
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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.
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.
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.
3-Oxo-2-(phenylhydrazono)butanoic acid
top
Crystal data top
C10H10N2O3 | F(000) = 432 |
Mr = 206.20 | Dx = 1.388 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 6.9138 (10) Å | θ = 16.7–49.7° |
b = 21.309 (2) Å | µ = 0.88 mm−1 |
c = 7.0783 (10) Å | T = 293 K |
β = 108.917 (10)° | Needle, colourless |
V = 986.5 (2) Å3 | 0.2 × 0.15 × 0.1 mm |
Z = 4 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.019 |
Radiation source: fine-focus sealed tube | θmax = 70.1°, θmin = 4.2° |
Graphite monochromator | h = −8→7 |
ω–2θ scans | k = 0→25 |
2026 measured reflections | l = 0→8 |
1878 independent reflections | 3 standard reflections every 1 hr min |
1230 reflections with I > 2σ(I) | intensity decay: 0.0% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.183 | H-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 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
Crystal data top
C10H10N2O3 | V = 986.5 (2) Å3 |
Mr = 206.20 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 6.9138 (10) Å | µ = 0.88 mm−1 |
b = 21.309 (2) Å | T = 293 K |
c = 7.0783 (10) Å | 0.2 × 0.15 × 0.1 mm |
β = 108.917 (10)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.019 |
2026 measured reflections | 3 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)] = 0.058 | 0 restraints |
wR(F2) = 0.183 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.20 e Å−3 |
1878 reflections | Δρmin = −0.26 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
O1 | 0.4124 (3) | 0.33645 (8) | 0.9715 (2) | 0.0722 (6) | |
H1O | 0.3856 | 0.3080 | 0.8890 | 0.108* | |
O2 | 0.3966 (3) | 0.43968 (7) | 0.9743 (2) | 0.0645 (5) | |
O3 | 0.3018 (3) | 0.27992 (7) | 0.6413 (3) | 0.0731 (5) | |
N1 | 0.2913 (2) | 0.49671 (7) | 0.6210 (2) | 0.0459 (4) | |
H1N | 0.3347 | 0.5026 | 0.7480 | 0.055* | |
N2 | 0.2631 (2) | 0.43964 (8) | 0.5461 (3) | 0.0447 (4) | |
C1 | 0.2486 (3) | 0.54780 (9) | 0.4882 (3) | 0.0449 (5) | |
C2 | 0.2716 (3) | 0.60768 (10) | 0.5690 (3) | 0.0517 (6) | |
H2 | 0.3116 | 0.6134 | 0.7065 | 0.062* | |
C3 | 0.2340 (3) | 0.65905 (12) | 0.4410 (4) | 0.0629 (7) | |
H3 | 0.2521 | 0.6994 | 0.4940 | 0.076* | |
C4 | 0.1697 (4) | 0.65096 (12) | 0.2357 (4) | 0.0643 (7) | |
H4 | 0.1396 | 0.6854 | 0.1506 | 0.077* | |
C5 | 0.1513 (4) | 0.59106 (12) | 0.1603 (4) | 0.0663 (6) | |
H5 | 0.1116 | 0.5854 | 0.0227 | 0.080* | |
C6 | 0.1899 (4) | 0.53932 (12) | 0.2824 (3) | 0.0585 (6) | |
H6 | 0.1770 | 0.4992 | 0.2283 | 0.070* | |
C7 | 0.3021 (3) | 0.38939 (9) | 0.6590 (3) | 0.0475 (5) | |
C8 | 0.3763 (3) | 0.39060 (10) | 0.8793 (3) | 0.0509 (5) | |
C9 | 0.2690 (3) | 0.32992 (10) | 0.5497 (4) | 0.0523 (5) | |
C10 | 0.1899 (4) | 0.33061 (12) | 0.3295 (3) | 0.0677 (7) | |
H10A | 0.1758 | 0.2883 | 0.2803 | 0.102* | |
H10B | 0.2834 | 0.3530 | 0.2792 | 0.102* | |
H10C | 0.0590 | 0.3510 | 0.2858 | 0.102* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0995 (15) | 0.0591 (9) | 0.0572 (10) | 0.0049 (9) | 0.0242 (10) | 0.0134 (8) |
O2 | 0.0740 (11) | 0.0648 (10) | 0.0478 (9) | −0.0083 (8) | 0.0104 (8) | −0.0081 (7) |
O3 | 0.0892 (13) | 0.0498 (9) | 0.0764 (12) | −0.0006 (8) | 0.0214 (10) | 0.0027 (8) |
N1 | 0.0399 (10) | 0.0461 (9) | 0.0475 (9) | −0.0039 (7) | 0.0084 (8) | −0.0019 (7) |
N2 | 0.0341 (8) | 0.0477 (9) | 0.0525 (10) | 0.0013 (7) | 0.0145 (8) | 0.0027 (7) |
C1 | 0.0374 (10) | 0.0437 (10) | 0.0570 (11) | 0.0044 (8) | 0.0202 (9) | 0.0056 (8) |
C2 | 0.0436 (12) | 0.0545 (12) | 0.0542 (12) | 0.0044 (9) | 0.0123 (10) | −0.0057 (10) |
C3 | 0.0469 (13) | 0.0512 (12) | 0.0899 (18) | −0.0015 (10) | 0.0211 (13) | 0.0062 (12) |
C4 | 0.0466 (13) | 0.0625 (14) | 0.0754 (17) | 0.0008 (10) | 0.0082 (12) | 0.0217 (12) |
C5 | 0.0618 (14) | 0.0703 (14) | 0.0598 (14) | −0.0044 (13) | 0.0100 (12) | 0.0102 (12) |
C6 | 0.0584 (13) | 0.0604 (13) | 0.0526 (13) | 0.0021 (11) | 0.0124 (11) | 0.0037 (10) |
C7 | 0.0404 (11) | 0.0518 (11) | 0.0520 (12) | 0.0059 (8) | 0.0172 (10) | −0.0008 (9) |
C8 | 0.0442 (12) | 0.0529 (11) | 0.0541 (12) | −0.0059 (9) | 0.0137 (10) | 0.0041 (9) |
C9 | 0.0418 (11) | 0.0492 (11) | 0.0635 (13) | −0.0018 (9) | 0.0138 (10) | −0.0006 (10) |
C10 | 0.0732 (16) | 0.0647 (14) | 0.0604 (15) | −0.0062 (13) | 0.0149 (13) | −0.0115 (12) |
Geometric parameters (Å, º) top
O1—C8 | 1.309 (2) | C3—H3 | 0.93 |
O1—H1O | 0.82 | C4—C5 | 1.374 (3) |
O2—C8 | 1.227 (2) | C4—H4 | 0.93 |
O3—C9 | 1.229 (3) | C5—C6 | 1.373 (3) |
N1—N2 | 1.316 (2) | C5—H5 | 0.93 |
N1—C1 | 1.406 (2) | C6—H6 | 0.93 |
N1—H1N | 0.86 | C7—C9 | 1.464 (3) |
N2—C7 | 1.311 (3) | C7—C8 | 1.475 (3) |
C1—C2 | 1.386 (3) | C9—C10 | 1.475 (3) |
C1—C6 | 1.391 (3) | C10—H10A | 0.96 |
C2—C3 | 1.390 (3) | C10—H10B | 0.96 |
C2—H2 | 0.93 | C10—H10C | 0.96 |
C3—C4 | 1.386 (4) | | |
| | | |
O1···C2i | 3.487 (3) | C3···C9iv | 3.423 (3) |
O1···C10ii | 3.366 (3) | C4···C7iv | 3.587 (4) |
O2···O2i | 2.907 (2) | C5···C8iii | 3.588 (4) |
O2···C2i | 3.453 (3) | C5···C8iv | 3.390 (4) |
C3···C9iii | 3.507 (3) | | |
| | | |
C8—O1—H1O | 109.5 | C4—C5—H5 | 119.1 |
N2—N1—C1 | 118.36 (16) | C5—C6—C1 | 119.1 (2) |
N2—N1—H1N | 120.8 | C5—C6—H6 | 120.5 |
C1—N1—H1N | 120.8 | C1—C6—H6 | 120.5 |
C7—N2—N1 | 122.36 (17) | N2—C7—C9 | 114.78 (19) |
C2—C1—C6 | 120.5 (2) | N2—C7—C8 | 124.22 (18) |
C2—C1—N1 | 117.77 (18) | C9—C7—C8 | 121.00 (19) |
C6—C1—N1 | 121.75 (19) | O2—C8—O1 | 120.6 (2) |
C1—C2—C3 | 118.9 (2) | O2—C8—C7 | 122.23 (18) |
C1—C2—H2 | 120.5 | O1—C8—C7 | 117.16 (19) |
C3—C2—H2 | 120.5 | O3—C9—C7 | 120.1 (2) |
C4—C3—C2 | 120.9 (2) | O3—C9—C10 | 120.5 (2) |
C4—C3—H3 | 119.5 | C7—C9—C10 | 119.38 (19) |
C2—C3—H3 | 119.5 | C9—C10—H10A | 109.5 |
C5—C4—C3 | 118.8 (2) | C9—C10—H10B | 109.5 |
C5—C4—H4 | 120.6 | H10A—C10—H10B | 109.5 |
C3—C4—H4 | 120.6 | C9—C10—H10C | 109.5 |
C6—C5—C4 | 121.8 (2) | H10A—C10—H10C | 109.5 |
C6—C5—H5 | 119.1 | H10B—C10—H10C | 109.5 |
| | | |
C1—N1—N2—C7 | 178.89 (16) | N1—N2—C7—C9 | −177.78 (14) |
N2—N1—C1—C2 | 177.63 (15) | N1—N2—C7—C8 | 1.5 (3) |
N2—N1—C1—C6 | −3.9 (3) | N2—C7—C8—O2 | 4.1 (3) |
C6—C1—C2—C3 | 0.4 (3) | C9—C7—C8—O2 | −176.7 (2) |
N1—C1—C2—C3 | 178.86 (16) | N2—C7—C8—O1 | −178.66 (19) |
C1—C2—C3—C4 | 1.5 (3) | C9—C7—C8—O1 | 0.5 (3) |
C2—C3—C4—C5 | −2.5 (3) | N2—C7—C9—O3 | 179.73 (18) |
C3—C4—C5—C6 | 1.6 (4) | C8—C7—C9—O3 | 0.5 (3) |
C4—C5—C6—C1 | 0.2 (4) | N2—C7—C9—C10 | −2.2 (3) |
C2—C1—C6—C5 | −1.2 (3) | C8—C7—C9—C10 | 178.5 (2) |
N1—C1—C6—C5 | −179.66 (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···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2 | 0.86 | 2.03 | 2.661 (2) | 130 |
N1—H1N···O2i | 0.86 | 2.54 | 3.270 (2) | 143 |
O1—H1O···O3 | 0.82 | 1.76 | 2.518 (2) | 152 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Experimental details
Crystal data |
Chemical formula | C10H10N2O3 |
Mr | 206.20 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 6.9138 (10), 21.309 (2), 7.0783 (10) |
β (°) | 108.917 (10) |
V (Å3) | 986.5 (2) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.88 |
Crystal size (mm) | 0.2 × 0.15 × 0.1 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2026, 1878, 1230 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.610 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.183, 1.08 |
No. of reflections | 1878 |
No. of parameters | 136 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.26 |
Selected geometric parameters (Å, º) topO1—C8 | 1.309 (2) | N2—C7 | 1.311 (3) |
O2—C8 | 1.227 (2) | C7—C9 | 1.464 (3) |
O3—C9 | 1.229 (3) | C7—C8 | 1.475 (3) |
N1—N2 | 1.316 (2) | C9—C10 | 1.475 (3) |
N1—C1 | 1.406 (2) | | |
| | | |
O1···C2i | 3.487 (3) | C3···C9iv | 3.423 (3) |
O1···C10ii | 3.366 (3) | C4···C7iv | 3.587 (4) |
O2···O2i | 2.907 (2) | C5···C8iii | 3.588 (4) |
O2···C2i | 3.453 (3) | C5···C8iv | 3.390 (4) |
C3···C9iii | 3.507 (3) | | |
| | | |
N2—N1—C1 | 118.36 (16) | O2—C8—O1 | 120.6 (2) |
C7—N2—N1 | 122.36 (17) | O2—C8—C7 | 122.23 (18) |
C2—C1—N1 | 117.77 (18) | O1—C8—C7 | 117.16 (19) |
C6—C1—N1 | 121.75 (19) | O3—C9—C7 | 120.1 (2) |
N2—C7—C9 | 114.78 (19) | O3—C9—C10 | 120.5 (2) |
N2—C7—C8 | 124.22 (18) | C7—C9—C10 | 119.38 (19) |
C9—C7—C8 | 121.00 (19) | | |
| | | |
C1—N1—N2—C7 | 178.89 (16) | C9—C7—C8—O2 | −176.7 (2) |
N2—N1—C1—C2 | 177.63 (15) | N2—C7—C8—O1 | −178.66 (19) |
N2—N1—C1—C6 | −3.9 (3) | C9—C7—C8—O1 | 0.5 (3) |
N1—C1—C2—C3 | 178.86 (16) | N2—C7—C9—O3 | 179.73 (18) |
N1—C1—C6—C5 | −179.66 (19) | C8—C7—C9—O3 | 0.5 (3) |
N1—N2—C7—C9 | −177.78 (14) | N2—C7—C9—C10 | −2.2 (3) |
N1—N2—C7—C8 | 1.5 (3) | C8—C7—C9—C10 | 178.5 (2) |
N2—C7—C8—O2 | 4.1 (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···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2 | 0.86 | 2.03 | 2.661 (2) | 130.0 |
N1—H1N···O2i | 0.86 | 2.54 | 3.270 (2) | 143.1 |
O1—H1O···O3 | 0.82 | 1.76 | 2.518 (2) | 152.2 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
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 π–π stacking interactions. The short contacts observed in the structure are listed in Table 3.