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Acta Cryst. (2008). E64, o1770    [ doi:10.1107/S1600536808025920 ]

N-(2-Hydroxyphenyl)-4-nitrophthalimide

S. Mansor, N. Zakaria, A. Ariffin and S. W. Ng

Abstract top

Molecules of the title compound, C14H8N2O5, are linked by a hydroxy-amide O-H...O hydrogen bond into a linear chain. The hydroxy group is disordered over two positions of the benzene ring in an approximate 0.57:0.43 ratio.

Comment top

The title compound (Fig. 1) was synthesized for studies on intramolecular general base (IGB) and intramolecular general acid (IGA) catalysis in the hydrolysis of N-substitutedphthalimide (Sim et al., 2006; 2007).

Related literature top

For literature on the hydrolysis of N-substituted phthalimides, see: Sim et al. (2006; 2007).

Experimental top

4-Nitrophthalic anhydride (5.0 g, 26 mmol) and o-hydroxyaniline (3.4 g, 31 mmol) were heated in glacial acetic acid (15 mol) for 4 h at 393–401 K. The reaction was shown to be complete by thin layer chromatography. The mixture was poured into water. The yellow solid was collected in 90% yield; purification was effected by recrystallization from chloroform.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2Ueq(C). The hydroxy group is disordered over two positions on the phenylene ring; the disorder refined to a 0.571 (1):429 (1) ratio.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of O–H···O hydrogen-bonded structure of C14H8N2O3 at the 70% probability level. Dashed lines denote the intermolecular hydrogen bonds. Hydrogen atoms are drawn as spheres of arbitrary radius. Only the major component of disorder is shown.
N-(2-Hydroxyphenyl)-4-nitrophthalimide top
Crystal data top
C14H8N2O5F000 = 584
Mr = 284.22Dx = 1.553 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2147 reflections
a = 7.1114 (2) Åθ = 2.8–23.8º
b = 11.7646 (3) ŵ = 0.12 mm−1
c = 14.5304 (4) ÅT = 100 (2) K
V = 1215.65 (6) Å3Prism, yellow
Z = 40.32 × 0.06 × 0.06 mm
Data collection top
Bruker SMART APEX
diffractometer		1356 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.087
Monochromator: graphiteθmax = 27.5º
T = 100(2) Kθmin = 2.2º
ω scansh = −9→9
Absorption correction: Nonek = −15→15
13791 measured reflectionsl = −18→18
1618 independent reflections
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)] = 0.049H-atom parameters constrained
wR(F2) = 0.142  w = 1/[σ2(Fo2) + (0.0803P)2 + 0.3691P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
1618 reflectionsΔρmax = 0.36 e Å−3
199 parametersΔρmin = −0.28 e Å−3
2 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C14H8N2O5V = 1215.65 (6) Å3
Mr = 284.22Z = 4
Orthorhombic, P212121Mo Kα
a = 7.1114 (2) ŵ = 0.12 mm−1
b = 11.7646 (3) ÅT = 100 (2) K
c = 14.5304 (4) Å0.32 × 0.06 × 0.06 mm
Data collection top
Bruker SMART APEX
diffractometer		1618 independent reflections
Absorption correction: None1356 reflections with I > 2σ(I)
13791 measured reflectionsRint = 0.087
Refinement top
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.142Δρmax = 0.36 e Å−3
S = 1.05Δρmin = −0.28 e Å−3
1618 reflectionsAbsolute structure: ?
199 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O10.3544 (4)0.2939 (3)0.8037 (3)0.0308 (10)0.571 (3)
H10.24900.30650.77970.046*0.571 (3)
O1'0.8498 (5)0.4876 (3)0.9237 (4)0.0287 (13)0.429 (3)
H1'0.91400.42840.91620.043*0.429 (3)
O20.4761 (4)0.1944 (2)0.97117 (17)0.0362 (6)
O30.9695 (3)0.3018 (2)0.78879 (18)0.0347 (6)
O41.3585 (4)−0.0916 (2)0.8641 (2)0.0455 (8)
O51.1873 (5)−0.2264 (2)0.9238 (2)0.0533 (9)
N10.7000 (4)0.2751 (2)0.87514 (18)0.0217 (6)
N21.2106 (5)−0.1285 (3)0.8959 (2)0.0383 (8)
C10.4328 (5)0.3850 (3)0.8206 (2)0.0307 (8)
H1A0.36760.31630.80800.037*0.429 (3)
C20.3486 (7)0.4888 (4)0.8022 (3)0.0493 (12)
H20.22300.49150.78000.059*
C30.4465 (8)0.5871 (4)0.8161 (3)0.0537 (13)
H30.39040.65780.80060.064*
C40.6260 (9)0.5852 (3)0.8525 (3)0.0543 (14)
H40.69310.65420.86160.065*
C50.7071 (6)0.4825 (3)0.8755 (3)0.0390 (9)
H5A0.82760.48060.90370.047*0.571 (3)
C60.6120 (5)0.3820 (3)0.8574 (2)0.0271 (7)
C70.6224 (5)0.1884 (3)0.9290 (2)0.0237 (7)
C80.7584 (5)0.0922 (3)0.9252 (2)0.0236 (7)
C90.7433 (5)−0.0146 (3)0.9637 (2)0.0287 (7)
H90.6348−0.03710.99720.034*
C100.8946 (5)−0.0877 (3)0.9510 (2)0.0305 (8)
H100.8915−0.16250.97560.037*
C111.0478 (5)−0.0508 (3)0.9029 (2)0.0270 (7)
C121.0651 (5)0.0568 (3)0.8618 (2)0.0276 (7)
H121.17330.07930.82810.033*
C130.9122 (4)0.1269 (3)0.8746 (2)0.0244 (7)
C140.8758 (4)0.2439 (3)0.8398 (2)0.0226 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.021 (2)0.032 (2)0.039 (2)0.0014 (18)−0.0039 (18)0.000 (2)
O1'0.025 (3)0.023 (2)0.039 (3)−0.003 (2)−0.014 (2)0.000 (2)
O20.0371 (14)0.0391 (13)0.0322 (14)0.0103 (12)0.0161 (11)0.0066 (11)
O30.0246 (12)0.0454 (15)0.0341 (13)0.0017 (12)0.0003 (11)0.0114 (12)
O40.0307 (14)0.0623 (19)0.0435 (15)0.0172 (13)0.0023 (13)−0.0015 (14)
O50.070 (2)0.0364 (14)0.0534 (18)0.0275 (15)0.0170 (17)0.0133 (14)
N10.0209 (12)0.0235 (13)0.0206 (13)0.0047 (10)−0.0020 (11)0.0006 (11)
N20.0418 (17)0.0448 (18)0.0285 (16)0.0170 (15)0.0059 (14)−0.0016 (15)
C10.0310 (17)0.0420 (19)0.0191 (15)0.0149 (16)0.0059 (13)0.0048 (15)
C20.053 (3)0.058 (3)0.036 (2)0.035 (2)0.017 (2)0.025 (2)
C30.081 (3)0.048 (3)0.032 (2)0.042 (3)0.021 (2)0.0186 (19)
C40.109 (4)0.0286 (19)0.0250 (19)0.013 (2)0.011 (3)0.0013 (16)
C50.066 (3)0.0290 (17)0.0217 (18)0.0023 (18)−0.0074 (19)0.0015 (15)
C60.0371 (17)0.0255 (15)0.0186 (15)0.0124 (14)0.0028 (14)0.0026 (13)
C70.0313 (16)0.0246 (14)0.0152 (14)0.0044 (13)−0.0018 (13)−0.0005 (12)
C80.0268 (15)0.0257 (15)0.0184 (15)0.0057 (12)0.0005 (13)−0.0024 (13)
C90.0309 (16)0.0302 (16)0.0250 (17)0.0010 (14)0.0018 (14)−0.0009 (14)
C100.0351 (17)0.0284 (17)0.0280 (17)0.0038 (14)−0.0024 (15)−0.0038 (14)
C110.0324 (16)0.0288 (16)0.0198 (15)0.0129 (14)−0.0041 (13)−0.0051 (14)
C120.0255 (15)0.0382 (18)0.0191 (15)0.0056 (14)−0.0033 (13)−0.0003 (14)
C130.0229 (14)0.0288 (16)0.0214 (14)0.0054 (12)−0.0057 (13)−0.0038 (14)
C140.0206 (14)0.0279 (15)0.0194 (15)0.0014 (12)−0.0040 (12)0.0012 (13)
Geometric parameters (Å, °) top
O1—C11.233 (5)C3—C41.382 (8)
O1—H10.8400C3—H30.9500
O1'—C51.234 (5)C4—C51.380 (6)
O1'—H1'0.8400C4—H40.9500
O2—C71.210 (4)C5—C61.388 (5)
O3—C141.207 (4)C5—H5A0.9500
O4—N21.228 (4)C7—C81.490 (4)
O5—N21.232 (4)C8—C91.380 (5)
N1—C141.401 (4)C8—C131.379 (4)
N1—C71.399 (4)C9—C101.389 (5)
N1—C61.428 (4)C9—H90.9500
N2—C111.478 (4)C10—C111.366 (5)
C1—C61.382 (5)C10—H100.9500
C1—C21.386 (5)C11—C121.405 (5)
C1—H1A0.9500C12—C131.377 (4)
C2—C31.365 (8)C12—H120.9500
C2—H20.9500C13—C141.490 (5)
C1—O1—H1109.5C1—C6—C5120.1 (3)
C5—O1'—H1'109.5C1—C6—N1119.8 (3)
C14—N1—C7111.5 (3)C5—C6—N1120.1 (3)
C14—N1—C6123.7 (3)O2—C7—N1125.5 (3)
C7—N1—C6124.8 (3)O2—C7—C8128.4 (3)
O4—N2—O5124.7 (3)N1—C7—C8106.1 (3)
O4—N2—C11118.6 (3)C9—C8—C13123.1 (3)
O5—N2—C11116.7 (3)C9—C8—C7128.8 (3)
O1—C1—C6118.1 (3)C13—C8—C7108.1 (3)
O1—C1—C2122.1 (4)C8—C9—C10116.8 (3)
C6—C1—C2119.7 (4)C8—C9—H9121.6
C6—C1—H1A120.1C10—C9—H9121.6
C2—C1—H1A120.1C11—C10—C9119.2 (3)
C3—C2—C1119.8 (4)C11—C10—H10120.4
C3—C2—H2120.1C9—C10—H10120.4
C1—C2—H2120.1C10—C11—C12125.0 (3)
C2—C3—C4121.0 (4)C10—C11—N2117.6 (3)
C2—C3—H3119.5C12—C11—N2117.3 (3)
C4—C3—H3119.5C13—C12—C11114.4 (3)
C5—C4—C3119.5 (5)C13—C12—H12122.8
C5—C4—H4120.2C11—C12—H12122.8
C3—C4—H4120.2C12—C13—C8121.4 (3)
O1'—C5—C4116.1 (4)C12—C13—C14130.2 (3)
O1'—C5—C6123.4 (3)C8—C13—C14108.4 (3)
C4—C5—C6119.7 (4)O3—C14—N1124.8 (3)
C4—C5—H5A120.1O3—C14—C13129.3 (3)
C6—C5—H5A120.1N1—C14—C13105.8 (3)
O1—C1—C2—C3−175.3 (4)C13—C8—C9—C101.3 (5)
C6—C1—C2—C33.3 (5)C7—C8—C9—C10−178.6 (3)
C1—C2—C3—C4−3.1 (6)C8—C9—C10—C110.5 (5)
C2—C3—C4—C5−0.3 (6)C9—C10—C11—C12−1.6 (5)
C3—C4—C5—O1'−166.2 (4)C9—C10—C11—N2176.2 (3)
C3—C4—C5—C63.5 (6)O4—N2—C11—C10−170.1 (3)
O1—C1—C6—C5178.5 (4)O5—N2—C11—C109.1 (5)
C2—C1—C6—C5−0.1 (5)O4—N2—C11—C127.9 (5)
O1—C1—C6—N1−0.4 (5)O5—N2—C11—C12−172.9 (3)
C2—C1—C6—N1−179.1 (3)C10—C11—C12—C130.9 (5)
O1'—C5—C6—C1165.7 (4)N2—C11—C12—C13−177.0 (3)
C4—C5—C6—C1−3.2 (5)C11—C12—C13—C81.0 (5)
O1'—C5—C6—N1−15.3 (6)C11—C12—C13—C14−177.8 (3)
C4—C5—C6—N1175.7 (3)C9—C8—C13—C12−2.1 (5)
C14—N1—C6—C1124.8 (3)C7—C8—C13—C12177.8 (3)
C7—N1—C6—C1−54.7 (4)C9—C8—C13—C14176.9 (3)
C14—N1—C6—C5−54.1 (4)C7—C8—C13—C14−3.2 (3)
C7—N1—C6—C5126.3 (4)C7—N1—C14—O3177.4 (3)
C14—N1—C7—O2176.5 (3)C6—N1—C14—O3−2.1 (5)
C6—N1—C7—O2−3.9 (5)C7—N1—C14—C130.0 (3)
C14—N1—C7—C8−1.8 (3)C6—N1—C14—C13−179.6 (3)
C6—N1—C7—C8177.8 (3)C12—C13—C14—O33.7 (6)
O2—C7—C8—C94.8 (6)C8—C13—C14—O3−175.3 (3)
N1—C7—C8—C9−177.0 (3)C12—C13—C14—N1−179.0 (3)
O2—C7—C8—C13−175.1 (3)C8—C13—C14—N12.1 (3)
N1—C7—C8—C133.1 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O3i0.841.992.747 (4)149
O1'—H1'···O2ii0.842.232.779 (4)123
Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+1/2, −z+2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O3i0.841.992.747 (4)149
O1'—H1'···O2ii0.842.232.779 (4)123
Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+1/2, −z+2.
Acknowledgements top

We thank MOSTI (grant No. 14–02-03–4014) and the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Sim, Y. L., Ariffin, A. & Khan, M. N. (2006). Int. J. Chem. Kinet. 38, 746–758.

Sim, Y. L., Ariffin, A. & Khan, M. N. (2007). J. Org. Chem. 72, 2392–2401.

Westrip, S. P. (2008). publCIF. In preparation.