N-(2-Hydroxy­phen­yl)-4-nitro­phthalimide

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

doi:10.1107/S1600536808025920

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1770

doi:10.1107/S1600536808025920

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N-(2-Hydroxyphenyl)-4-nitrophthalimide

Shahirah Mansor,^a Norzalida Zakaria,^a Azhar Ariffin ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 11 August 2008; accepted 11 August 2008; online 16 August 2008)

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.

Related literature

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

Experimental

Crystal data

C₁₄H₈N₂O₅
M_r = 284.22
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.1114 (2) Å
b = 11.7646 (3) Å
c = 14.5304 (4) Å
V = 1215.65 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 (2) K
0.32 × 0.06 × 0.06 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: none
13791 measured reflections
1618 independent reflections
1356 reflections with I > 2σ(I)
R_int = 0.087

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.142
S = 1.04
1618 reflections
199 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.84	1.99	2.747 (4)	149
O1′—H1′⋯O2ⁱⁱ	0.84	2.23	2.779 (4)	123
Symmetry codes: (i) x-1, y, z; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808025920/lh2681sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808025920/lh2681Isup2.hkl

checkCIF report

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.

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

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

C₁₄H₈N₂O₅	F(000) = 584
M_r = 284.22	D_x = 1.553 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2147 reflections
a = 7.1114 (2) Å	θ = 2.8–23.8°
b = 11.7646 (3) Å	µ = 0.12 mm⁻¹
c = 14.5304 (4) Å	T = 100 K
V = 1215.65 (6) Å³	Prism, yellow
Z = 4	0.32 × 0.06 × 0.06 mm

Data collection top

Bruker SMART APEX diffractometer	1356 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.087
Graphite monochromator	θ_max = 27.5°, θ_min = 2.2°
ω scans	h = −9→9
13791 measured reflections	k = −15→15
1618 independent reflections	l = −18→18

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0803P)² + 0.3691P] where P = (F_o² + 2F_c²)/3
1618 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.36 e Å⁻³
2 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₄H₈N₂O₅	V = 1215.65 (6) Å³
M_r = 284.22	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.1114 (2) Å	µ = 0.12 mm⁻¹
b = 11.7646 (3) Å	T = 100 K
c = 14.5304 (4) Å	0.32 × 0.06 × 0.06 mm

Data collection top

Bruker SMART APEX diffractometer	1356 reflections with I > 2σ(I)
13791 measured reflections	R_int = 0.087
1618 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	2 restraints
wR(F²) = 0.142	H-atom parameters constrained
S = 1.05	Δρ_max = 0.36 e Å⁻³
1618 reflections	Δρ_min = −0.28 e Å⁻³
199 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.3544 (4)	0.2939 (3)	0.8037 (3)	0.0308 (10)	0.571 (3)
H1	0.2490	0.3065	0.7797	0.046*	0.571 (3)
O1'	0.8498 (5)	0.4876 (3)	0.9237 (4)	0.0287 (13)	0.429 (3)
H1'	0.9140	0.4284	0.9162	0.043*	0.429 (3)
O2	0.4761 (4)	0.1944 (2)	0.97117 (17)	0.0362 (6)
O3	0.9695 (3)	0.3018 (2)	0.78879 (18)	0.0347 (6)
O4	1.3585 (4)	−0.0916 (2)	0.8641 (2)	0.0455 (8)
O5	1.1873 (5)	−0.2264 (2)	0.9238 (2)	0.0533 (9)
N1	0.7000 (4)	0.2751 (2)	0.87514 (18)	0.0217 (6)
N2	1.2106 (5)	−0.1285 (3)	0.8959 (2)	0.0383 (8)
C1	0.4328 (5)	0.3850 (3)	0.8206 (2)	0.0307 (8)
H1A	0.3676	0.3163	0.8080	0.037*	0.429 (3)
C2	0.3486 (7)	0.4888 (4)	0.8022 (3)	0.0493 (12)
H2	0.2230	0.4915	0.7800	0.059*
C3	0.4465 (8)	0.5871 (4)	0.8161 (3)	0.0537 (13)
H3	0.3904	0.6578	0.8006	0.064*
C4	0.6260 (9)	0.5852 (3)	0.8525 (3)	0.0543 (14)
H4	0.6931	0.6542	0.8616	0.065*
C5	0.7071 (6)	0.4825 (3)	0.8755 (3)	0.0390 (9)
H5A	0.8276	0.4806	0.9037	0.047*	0.571 (3)
C6	0.6120 (5)	0.3820 (3)	0.8574 (2)	0.0271 (7)
C7	0.6224 (5)	0.1884 (3)	0.9290 (2)	0.0237 (7)
C8	0.7584 (5)	0.0922 (3)	0.9252 (2)	0.0236 (7)
C9	0.7433 (5)	−0.0146 (3)	0.9637 (2)	0.0287 (7)
H9	0.6348	−0.0371	0.9972	0.034*
C10	0.8946 (5)	−0.0877 (3)	0.9510 (2)	0.0305 (8)
H10	0.8915	−0.1625	0.9756	0.037*
C11	1.0478 (5)	−0.0508 (3)	0.9029 (2)	0.0270 (7)
C12	1.0651 (5)	0.0568 (3)	0.8618 (2)	0.0276 (7)
H12	1.1733	0.0793	0.8281	0.033*
C13	0.9122 (4)	0.1269 (3)	0.8746 (2)	0.0244 (7)
C14	0.8758 (4)	0.2439 (3)	0.8398 (2)	0.0226 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.021 (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)
O2	0.0371 (14)	0.0391 (13)	0.0322 (14)	0.0103 (12)	0.0161 (11)	0.0066 (11)
O3	0.0246 (12)	0.0454 (15)	0.0341 (13)	0.0017 (12)	0.0003 (11)	0.0114 (12)
O4	0.0307 (14)	0.0623 (19)	0.0435 (15)	0.0172 (13)	0.0023 (13)	−0.0015 (14)
O5	0.070 (2)	0.0364 (14)	0.0534 (18)	0.0275 (15)	0.0170 (17)	0.0133 (14)
N1	0.0209 (12)	0.0235 (13)	0.0206 (13)	0.0047 (10)	−0.0020 (11)	0.0006 (11)
N2	0.0418 (17)	0.0448 (18)	0.0285 (16)	0.0170 (15)	0.0059 (14)	−0.0016 (15)
C1	0.0310 (17)	0.0420 (19)	0.0191 (15)	0.0149 (16)	0.0059 (13)	0.0048 (15)
C2	0.053 (3)	0.058 (3)	0.036 (2)	0.035 (2)	0.017 (2)	0.025 (2)
C3	0.081 (3)	0.048 (3)	0.032 (2)	0.042 (3)	0.021 (2)	0.0186 (19)
C4	0.109 (4)	0.0286 (19)	0.0250 (19)	0.013 (2)	0.011 (3)	0.0013 (16)
C5	0.066 (3)	0.0290 (17)	0.0217 (18)	0.0023 (18)	−0.0074 (19)	0.0015 (15)
C6	0.0371 (17)	0.0255 (15)	0.0186 (15)	0.0124 (14)	0.0028 (14)	0.0026 (13)
C7	0.0313 (16)	0.0246 (14)	0.0152 (14)	0.0044 (13)	−0.0018 (13)	−0.0005 (12)
C8	0.0268 (15)	0.0257 (15)	0.0184 (15)	0.0057 (12)	0.0005 (13)	−0.0024 (13)
C9	0.0309 (16)	0.0302 (16)	0.0250 (17)	0.0010 (14)	0.0018 (14)	−0.0009 (14)
C10	0.0351 (17)	0.0284 (17)	0.0280 (17)	0.0038 (14)	−0.0024 (15)	−0.0038 (14)
C11	0.0324 (16)	0.0288 (16)	0.0198 (15)	0.0129 (14)	−0.0041 (13)	−0.0051 (14)
C12	0.0255 (15)	0.0382 (18)	0.0191 (15)	0.0056 (14)	−0.0033 (13)	−0.0003 (14)
C13	0.0229 (14)	0.0288 (16)	0.0214 (14)	0.0054 (12)	−0.0057 (13)	−0.0038 (14)
C14	0.0206 (14)	0.0279 (15)	0.0194 (15)	0.0014 (12)	−0.0040 (12)	0.0012 (13)

Geometric parameters (Å, º) top

O1—C1	1.233 (5)	C3—C4	1.382 (8)
O1—H1	0.8400	C3—H3	0.9500
O1'—C5	1.234 (5)	C4—C5	1.380 (6)
O1'—H1'	0.8400	C4—H4	0.9500
O2—C7	1.210 (4)	C5—C6	1.388 (5)
O3—C14	1.207 (4)	C5—H5A	0.9500
O4—N2	1.228 (4)	C7—C8	1.490 (4)
O5—N2	1.232 (4)	C8—C9	1.380 (5)
N1—C14	1.401 (4)	C8—C13	1.379 (4)
N1—C7	1.399 (4)	C9—C10	1.389 (5)
N1—C6	1.428 (4)	C9—H9	0.9500
N2—C11	1.478 (4)	C10—C11	1.366 (5)
C1—C6	1.382 (5)	C10—H10	0.9500
C1—C2	1.386 (5)	C11—C12	1.405 (5)
C1—H1A	0.9500	C12—C13	1.377 (4)
C2—C3	1.365 (8)	C12—H12	0.9500
C2—H2	0.9500	C13—C14	1.490 (5)

C1—O1—H1	109.5	C1—C6—C5	120.1 (3)
C5—O1'—H1'	109.5	C1—C6—N1	119.8 (3)
C14—N1—C7	111.5 (3)	C5—C6—N1	120.1 (3)
C14—N1—C6	123.7 (3)	O2—C7—N1	125.5 (3)
C7—N1—C6	124.8 (3)	O2—C7—C8	128.4 (3)
O4—N2—O5	124.7 (3)	N1—C7—C8	106.1 (3)
O4—N2—C11	118.6 (3)	C9—C8—C13	123.1 (3)
O5—N2—C11	116.7 (3)	C9—C8—C7	128.8 (3)
O1—C1—C6	118.1 (3)	C13—C8—C7	108.1 (3)
O1—C1—C2	122.1 (4)	C8—C9—C10	116.8 (3)
C6—C1—C2	119.7 (4)	C8—C9—H9	121.6
C6—C1—H1A	120.1	C10—C9—H9	121.6
C2—C1—H1A	120.1	C11—C10—C9	119.2 (3)
C3—C2—C1	119.8 (4)	C11—C10—H10	120.4
C3—C2—H2	120.1	C9—C10—H10	120.4
C1—C2—H2	120.1	C10—C11—C12	125.0 (3)
C2—C3—C4	121.0 (4)	C10—C11—N2	117.6 (3)
C2—C3—H3	119.5	C12—C11—N2	117.3 (3)
C4—C3—H3	119.5	C13—C12—C11	114.4 (3)
C5—C4—C3	119.5 (5)	C13—C12—H12	122.8
C5—C4—H4	120.2	C11—C12—H12	122.8
C3—C4—H4	120.2	C12—C13—C8	121.4 (3)
O1'—C5—C4	116.1 (4)	C12—C13—C14	130.2 (3)
O1'—C5—C6	123.4 (3)	C8—C13—C14	108.4 (3)
C4—C5—C6	119.7 (4)	O3—C14—N1	124.8 (3)
C4—C5—H5A	120.1	O3—C14—C13	129.3 (3)
C6—C5—H5A	120.1	N1—C14—C13	105.8 (3)

O1—C1—C2—C3	−175.3 (4)	C13—C8—C9—C10	1.3 (5)
C6—C1—C2—C3	3.3 (5)	C7—C8—C9—C10	−178.6 (3)
C1—C2—C3—C4	−3.1 (6)	C8—C9—C10—C11	0.5 (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—N2	176.2 (3)
C3—C4—C5—C6	3.5 (6)	O4—N2—C11—C10	−170.1 (3)
O1—C1—C6—C5	178.5 (4)	O5—N2—C11—C10	9.1 (5)
C2—C1—C6—C5	−0.1 (5)	O4—N2—C11—C12	7.9 (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—C13	0.9 (5)
O1'—C5—C6—C1	165.7 (4)	N2—C11—C12—C13	−177.0 (3)
C4—C5—C6—C1	−3.2 (5)	C11—C12—C13—C8	1.0 (5)
O1'—C5—C6—N1	−15.3 (6)	C11—C12—C13—C14	−177.8 (3)
C4—C5—C6—N1	175.7 (3)	C9—C8—C13—C12	−2.1 (5)
C14—N1—C6—C1	124.8 (3)	C7—C8—C13—C12	177.8 (3)
C7—N1—C6—C1	−54.7 (4)	C9—C8—C13—C14	176.9 (3)
C14—N1—C6—C5	−54.1 (4)	C7—C8—C13—C14	−3.2 (3)
C7—N1—C6—C5	126.3 (4)	C7—N1—C14—O3	177.4 (3)
C14—N1—C7—O2	176.5 (3)	C6—N1—C14—O3	−2.1 (5)
C6—N1—C7—O2	−3.9 (5)	C7—N1—C14—C13	0.0 (3)
C14—N1—C7—C8	−1.8 (3)	C6—N1—C14—C13	−179.6 (3)
C6—N1—C7—C8	177.8 (3)	C12—C13—C14—O3	3.7 (6)
O2—C7—C8—C9	4.8 (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—N1	2.1 (3)
N1—C7—C8—C13	3.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.84	1.99	2.747 (4)	149
O1′—H1′···O2ⁱⁱ	0.84	2.23	2.779 (4)	123

Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+1/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₄H₈N₂O₅
M_r	284.22
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	7.1114 (2), 11.7646 (3), 14.5304 (4)
V (Å³)	1215.65 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.32 × 0.06 × 0.06

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	13791, 1618, 1356
R_int	0.087
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.142, 1.05
No. of reflections	1618
No. of parameters	199
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.28

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.84	1.99	2.747 (4)	149
O1'—H1'···O2ⁱⁱ	0.84	2.23	2.779 (4)	123

Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+1/2, −z+2.

Acknowledgements

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

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sim, Y. L., Ariffin, A. & Khan, M. N. (2006). Int. J. Chem. Kinet. 38, 746–758. Web of Science CrossRef CAS Google Scholar
Sim, Y. L., Ariffin, A. & Khan, M. N. (2007). J. Org. Chem. 72, 2392–2401. Web of Science CrossRef PubMed CAS Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar