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The title compound, C8H8N2O2, is a key inter­mediate in the synthesis of oxindole. The crystal packing is stabilized by O—H...O, N—H...O and N—H...N hydrogen-bond inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805042030/rz6147sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805042030/rz6147Isup2.hkl
Contains datablock I

CCDC reference: 296724

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.048
  • wR factor = 0.139
  • Data-to-parameter ratio = 12.0

checkCIF/PLATON results

No syntax errors found



Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.764 0.970 Tmin(prime) and Tmax expected: 0.948 0.967 RR(prime) = 0.803 Please check that your absorption correction is appropriate. RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.115 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.12 PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.80 PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The title compound, (I), is a key intermediate in the synthesis of oxindole (Marvel & Hiers, 1941). The molecular structure of (I) is illustrated in Fig. 1. The molecule is roughly planar, the largest deviation from the mean plane being 0.224 (2) Å for atom C3. Bond lengths and angles are within normal ranges (Allen et al., 1987). The values of the N1—C7 [1.338 (2) Å] and O1—C7 [1.226(2 Å] bond lengths suggest partial sp2 character of the N atom. In the crystal structure (Fig. 2), the molecules are linked by intermolecular O—H···O, N—H···O and N—H···N hydrogen-bonding interactions (Table 1).

Experimental top

A mixture of chloral hydrate (90 g, 0.54 mol) in water (1200 ml), sodium sulfate (1300 g), aniline (46.5 g, 0.5 mol) in water (300 ml), hydrochloric acid (43 ml, 0.52 mol) and hydroxylamine hydrochloride (110 g, 1.58 mol) was heated to boiling. After two minutes of vigorous boiling, the reaction was complete. The mixture was cooled to room temperature and the solid collected by vacuum filtration to give the title compound (yield 82%). Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Refinement top

All H atoms were found in a difference Fourier map and refined isotropically.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), drawn with 30% probability ellipsoids.
[Figure 2] Fig. 2. Partial view of the crystal packing in (I), showing the hydrogen-bonding interactions as dashed lines. [Symmetry codes: (A) 3/2 − x, y − 1/2, z; (B) 1/2 + x, 5/2 − y, 1 − z.]
(E)-2-(hydroxyimino)-N-phenylacetamide top
Crystal data top
C8H8N2O2Dx = 1.394 Mg m3
Mr = 164.16Melting point: 448K K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2586 reflections
a = 9.6551 (11) Åθ = 4.6–49.5°
b = 9.1665 (10) ŵ = 0.10 mm1
c = 17.673 (2) ÅT = 293 K
V = 1564.1 (3) Å3Block, colourless
Z = 80.51 × 0.47 × 0.33 mm
F(000) = 688
Data collection top
Bruker SMART CCD area-detector
diffractometer
1710 independent reflections
Radiation source: fine-focus sealed tube1316 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.115
ϕ and ω scansθmax = 27.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 912
Tmin = 0.764, Tmax = 0.970k = 1111
8540 measured reflectionsl = 2220
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048All H-atom parameters refined
wR(F2) = 0.139 w = 1/[σ2(Fo2) + (0.087P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max < 0.001
1710 reflectionsΔρmax = 0.24 e Å3
142 parametersΔρmin = 0.21 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.014 (4)
Crystal data top
C8H8N2O2V = 1564.1 (3) Å3
Mr = 164.16Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 9.6551 (11) ŵ = 0.10 mm1
b = 9.1665 (10) ÅT = 293 K
c = 17.673 (2) Å0.51 × 0.47 × 0.33 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
1710 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1316 reflections with I > 2σ(I)
Tmin = 0.764, Tmax = 0.970Rint = 0.115
8540 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.139All H-atom parameters refined
S = 0.99Δρmax = 0.24 e Å3
1710 reflectionsΔρmin = 0.21 e Å3
142 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
xyzUiso*/Ueq
O10.66161 (12)1.18186 (11)0.42893 (7)0.0573 (4)
O20.95936 (13)1.11072 (14)0.58949 (7)0.0622 (4)
N10.62442 (14)0.93660 (13)0.43406 (7)0.0483 (4)
N20.86575 (13)1.14534 (13)0.53268 (7)0.0476 (4)
C10.52623 (14)0.91247 (15)0.37619 (8)0.0444 (4)
C20.48807 (19)1.01550 (19)0.32307 (9)0.0587 (5)
C30.3919 (2)0.9790 (2)0.26803 (10)0.0671 (5)
C40.3332 (2)0.8436 (2)0.26599 (11)0.0689 (5)
C50.3729 (2)0.7405 (2)0.31822 (10)0.0693 (5)
C60.46916 (17)0.77368 (19)0.37263 (9)0.0562 (4)
C70.68479 (14)1.06102 (14)0.45590 (8)0.0437 (4)
C80.78712 (16)1.03994 (16)0.51731 (8)0.0477 (4)
H10.6532 (18)0.854 (2)0.4560 (11)0.063 (5)*
H20.5335 (16)1.105 (2)0.3234 (10)0.059 (5)*
H30.3719 (18)1.049 (2)0.2317 (11)0.072 (5)*
H40.266 (2)0.816 (2)0.2313 (12)0.083 (6)*
H50.327 (2)0.647 (2)0.3169 (13)0.088 (7)*
H60.505 (2)0.700 (2)0.4115 (12)0.072 (5)*
H80.7932 (17)0.9489 (18)0.5438 (10)0.056 (4)*
H2A1.016 (2)1.190 (3)0.5903 (13)0.087 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0656 (7)0.0376 (6)0.0687 (8)0.0014 (5)0.0066 (5)0.0095 (5)
O20.0683 (8)0.0565 (7)0.0617 (8)0.0098 (6)0.0144 (6)0.0052 (5)
N10.0613 (8)0.0350 (7)0.0485 (7)0.0011 (5)0.0050 (6)0.0040 (5)
N20.0559 (8)0.0427 (7)0.0441 (7)0.0005 (5)0.0022 (5)0.0002 (5)
C10.0502 (8)0.0434 (8)0.0397 (8)0.0029 (6)0.0047 (6)0.0027 (6)
C20.0804 (12)0.0465 (9)0.0490 (9)0.0068 (8)0.0045 (8)0.0020 (7)
C30.0882 (13)0.0664 (11)0.0466 (10)0.0204 (10)0.0083 (9)0.0006 (8)
C40.0700 (11)0.0840 (14)0.0525 (10)0.0047 (10)0.0115 (9)0.0101 (9)
C50.0800 (12)0.0710 (12)0.0569 (10)0.0177 (10)0.0103 (9)0.0011 (9)
C60.0654 (11)0.0546 (9)0.0487 (9)0.0082 (7)0.0045 (7)0.0042 (7)
C70.0490 (8)0.0362 (7)0.0459 (8)0.0010 (6)0.0073 (6)0.0016 (6)
C80.0573 (9)0.0363 (8)0.0496 (9)0.0010 (6)0.0021 (7)0.0035 (6)
Geometric parameters (Å, º) top
O1—C71.2265 (17)C2—H20.930 (18)
O2—N21.3876 (17)C3—C41.364 (3)
O2—H2A0.91 (2)C3—H30.93 (2)
N1—C71.3377 (18)C4—C51.375 (3)
N1—C11.4120 (19)C4—H40.93 (2)
N1—H10.89 (2)C5—C61.372 (2)
N2—C81.2584 (19)C5—H50.96 (2)
C1—C21.382 (2)C6—H61.02 (2)
C1—C61.388 (2)C7—C81.480 (2)
C2—C31.386 (2)C8—H80.958 (17)
N2—O2—H2A102.7 (15)C3—C4—H4123.6 (13)
C7—N1—C1129.43 (13)C5—C4—H4116.9 (13)
C7—N1—H1117.4 (12)C6—C5—C4120.46 (19)
C1—N1—H1113.0 (12)C6—C5—H5121.6 (14)
C8—N2—O2111.93 (12)C4—C5—H5117.9 (14)
C2—C1—C6119.34 (15)C5—C6—C1120.27 (16)
C2—C1—N1124.34 (14)C5—C6—H6123.6 (12)
C6—C1—N1116.30 (13)C1—C6—H6116.1 (12)
C1—C2—C3119.36 (17)O1—C7—N1125.34 (14)
C1—C2—H2118.3 (11)O1—C7—C8121.64 (13)
C3—C2—H2122.2 (11)N1—C7—C8113.02 (12)
C4—C3—C2121.10 (18)N2—C8—C7117.43 (13)
C4—C3—H3121.8 (12)N2—C8—H8121.8 (10)
C2—C3—H3117.1 (12)C7—C8—H8120.8 (10)
C3—C4—C5119.44 (18)
C7—N1—C1—C29.6 (3)C2—C1—C6—C51.9 (2)
C7—N1—C1—C6172.32 (15)N1—C1—C6—C5179.98 (15)
C6—C1—C2—C31.0 (2)C1—N1—C7—O11.7 (3)
N1—C1—C2—C3179.05 (15)C1—N1—C7—C8177.72 (14)
C1—C2—C3—C40.7 (3)O2—N2—C8—C7178.22 (12)
C2—C3—C4—C51.7 (3)O1—C7—C8—N211.3 (2)
C3—C4—C5—C60.9 (3)N1—C7—C8—N2168.19 (13)
C4—C5—C6—C10.9 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O1i0.91 (2)1.86 (3)2.7448 (17)163 (2)
N1—H1···O1ii0.89 (2)2.434 (18)3.1191 (17)133.9 (15)
N1—H1···N2ii0.89 (2)2.35 (2)3.1898 (17)156.0 (15)
Symmetry codes: (i) x+1/2, y+5/2, z+1; (ii) x+3/2, y1/2, z.

Experimental details

Crystal data
Chemical formulaC8H8N2O2
Mr164.16
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)293
a, b, c (Å)9.6551 (11), 9.1665 (10), 17.673 (2)
V3)1564.1 (3)
Z8
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.51 × 0.47 × 0.33
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.764, 0.970
No. of measured, independent and
observed [I > 2σ(I)] reflections
8540, 1710, 1316
Rint0.115
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.139, 0.99
No. of reflections1710
No. of parameters142
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.24, 0.21

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O1i0.91 (2)1.86 (3)2.7448 (17)163 (2)
N1—H1···O1ii0.89 (2)2.434 (18)3.1191 (17)133.9 (15)
N1—H1···N2ii0.89 (2)2.35 (2)3.1898 (17)156.0 (15)
Symmetry codes: (i) x+1/2, y+5/2, z+1; (ii) x+3/2, y1/2, z.
 

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