4-Amino­phthalimide

Sarkar, M.

doi:10.1107/S160053680802388X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1654

doi:10.1107/S160053680802388X

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4-Aminophthalimide

Moloy Sarkar ^a ^*

^aDepartment of Chemistry, National Institute of Science Education and Research (NISER), Bhubaneswar 751005, Orissa, India
^*Correspondence e-mail: msarkar@iopb.res.in

(Received 11 June 2008; accepted 28 July 2008; online 31 July 2008)

The molecules in the title compound (systematic name: 5-aminoisoindole-1,3-dione), C₈H₆N₂O₂, are packed through N—H⋯O intermolecular hydrogen-bonding interactions. Two types of hydrogen bonds are observed: one, involving the imide group, forms molecular chains along the c axis and another two, involving the amino group, connect the molecular chains.

Related literature

For related literature, see Paul & Samanta (2007 ).

Experimental

Crystal data

C₈H₆N₂O₂
M_r = 162.15
Orthorhombic, P n a 2₁
a = 14.5786 (19) Å
b = 13.0728 (17) Å
c = 3.7216 (5) Å
V = 709.27 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 K
0.25 × 0.08 × 0.06 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.97, T_max = 0.99
7856 measured reflections
978 independent reflections
636 reflections with I > 2σ(I)
R_int = 0.086

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.126
S = 1.09
978 reflections
109 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.09	2.924 (4)	164
N2—H2B⋯O1ⁱⁱ	0.86	2.28	3.122 (5)	167
N2—H2A⋯O2ⁱⁱⁱ	0.86	2.17	2.996 (4)	161
Symmetry codes: (i) $[-x+1, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, -y+2, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680802388X/bg2195sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680802388X/bg2195Isup2.hkl

checkCIF report

Comment top

Fluorescent electron donor-acceptor (EDA) systems, 4-aminophthalimide and its derivatives in particular, are found to be attractive candidates for the study of various photophysical processes both in conventional and non-conventional media. Very recently, 4-aminophthalimide has been used in order to investigate specific hydrogen bonding interactions in the solvation and rotational dynamics in room temperature ionic liquids (Paul and Samanta, 2007). Since the ground state structure also influences considerably the photophysical properties of the EDA molecules, we have determined the crystal structure of the title compound C₈H₆N₂O₂, (I), shown in Fig. 1. We observe that the imide group forms N—H···O hydrogen bonds (Table 1) in a helical pattern to form molecular chains along c axis (Figure 2). The molecules in the chains are further stabilized by π-π stacking (centroid-to-centroid distance = 3.722 Å). These chains are connected through another type of N—H···O hydrogen bonds (Table 1) involving the amino hydrogen and the unused oxygen of the phthalimide group (Figure 3).

Related literature top

For related literature, see Paul & Samanta (2007).

Experimental top

The title compound was purchased from Aldrich. Tiny single crystals suitable for X-ray diffraction were obtained by slow evaporation from a solution of the compound in ethanol:water (9:1).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level for non-H atoms.
	Fig. 2. Molecular chain along the c axis.
	Fig. 3. Packing diagram showing N—H···O intermolecular hydrogen bonds. [(1) N1—H1···O1^a, (2) N1^b– H1^b···O1, (3) N2^c—H2A^c···O2, (4) N2 –H2A···O2^d, (5) N2—H2B···O1^e; symmetry codes: (a) 1 - x, 1 - y, 1/2 + z; (b) 1 - x, 1 - y, -1/2 + z; (c) 1 - x, 2 - y, 1/2 + z; (d) 1 - x, 2 - y, -1/2 + z; (e) 3/2 - x, 1/2 + y, -1/2 + z; (1) and (2), (3) and (4) are symmetry related hydrogen bonds].

5-aminoisoindole-1,3-dione top

Crystal data top

C₈H₆N₂O₂	F(000) = 336
M_r = 162.15	D_x = 1.518 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 704 reflections
a = 14.5786 (19) Å	θ = 2.8–18.3°
b = 13.0728 (17) Å	µ = 0.11 mm⁻¹
c = 3.7216 (5) Å	T = 298 K
V = 709.27 (16) Å³	Needle, yellow
Z = 4	0.25 × 0.08 × 0.06 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	978 independent reflections
Radiation source: fine-focus sealed tube	636 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.086
phi and ω scans	θ_max = 28.3°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −19→19
T_min = 0.97, T_max = 0.99	k = −17→17
7856 measured reflections	l = −4→4

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0542P)² + 0.1098P] where P = (F_o² + 2F_c²)/3
978 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.22 e Å⁻³
1 restraint	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₈H₆N₂O₂	V = 709.27 (16) Å³
M_r = 162.15	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 14.5786 (19) Å	µ = 0.11 mm⁻¹
b = 13.0728 (17) Å	T = 298 K
c = 3.7216 (5) Å	0.25 × 0.08 × 0.06 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	978 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	636 reflections with I > 2σ(I)
T_min = 0.97, T_max = 0.99	R_int = 0.086
7856 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	1 restraint
wR(F²) = 0.126	H-atom parameters constrained
S = 1.09	Δρ_max = 0.22 e Å⁻³
978 reflections	Δρ_min = −0.17 e Å⁻³
109 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

	x	y	z	U_iso*/U_eq
O1	0.60766 (19)	0.53133 (19)	1.0695 (10)	0.0556 (10)
O2	0.41159 (18)	0.7846 (2)	1.4175 (11)	0.0559 (9)
N1	0.4932 (2)	0.6407 (2)	1.2599 (11)	0.0445 (9)
H1	0.4542	0.5954	1.3284	0.053*
N2	0.6919 (2)	1.0180 (2)	0.8617 (13)	0.0599 (12)
H2A	0.6551	1.0669	0.9164	0.072*
H2B	0.7443	1.0315	0.7663	0.072*
C1	0.5777 (3)	0.6181 (3)	1.1116 (14)	0.0411 (10)
C2	0.7055 (3)	0.7394 (3)	0.8804 (12)	0.0400 (10)
H2	0.7459	0.6875	0.8153	0.048*
C3	0.7288 (3)	0.8405 (3)	0.8309 (11)	0.0423 (11)
H3	0.7857	0.8569	0.7338	0.051*
C4	0.6676 (3)	0.9196 (3)	0.9256 (12)	0.0386 (10)
C5	0.5831 (3)	0.8952 (3)	1.0800 (12)	0.0359 (10)
H5	0.5424	0.9464	1.1489	0.043*
C6	0.4787 (3)	0.7455 (3)	1.2853 (12)	0.0402 (10)
C7	0.5613 (2)	0.7937 (3)	1.1281 (12)	0.0346 (9)
C8	0.6212 (3)	0.7165 (3)	1.0282 (11)	0.0350 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.054 (2)	0.0267 (15)	0.086 (3)	0.0020 (13)	−0.0039 (19)	−0.0037 (18)
O2	0.0478 (17)	0.0435 (17)	0.076 (2)	0.0027 (14)	0.0124 (18)	0.0012 (19)
N1	0.0401 (19)	0.0284 (17)	0.065 (2)	−0.0068 (15)	0.0033 (19)	0.005 (2)
N2	0.056 (2)	0.038 (2)	0.086 (3)	−0.0050 (17)	0.012 (3)	0.001 (2)
C1	0.042 (2)	0.033 (2)	0.049 (3)	−0.0026 (19)	−0.005 (2)	0.000 (2)
C2	0.039 (2)	0.037 (2)	0.044 (3)	0.0043 (17)	0.002 (2)	−0.002 (2)
C3	0.045 (2)	0.039 (2)	0.043 (3)	−0.0019 (18)	0.002 (2)	0.001 (2)
C4	0.040 (2)	0.034 (2)	0.041 (2)	−0.0048 (17)	−0.003 (2)	0.002 (2)
C5	0.041 (2)	0.025 (2)	0.041 (2)	0.0078 (16)	−0.004 (2)	−0.003 (2)
C6	0.039 (2)	0.036 (2)	0.047 (3)	0.0022 (18)	−0.002 (2)	−0.001 (2)
C7	0.035 (2)	0.033 (2)	0.036 (2)	−0.0011 (16)	−0.0067 (19)	0.0014 (19)
C8	0.040 (2)	0.030 (2)	0.035 (3)	0.0012 (18)	−0.0032 (18)	0.0008 (19)

Geometric parameters (Å, º) top

O1—C1	1.226 (4)	C2—C8	1.380 (5)
O2—C6	1.209 (4)	C2—H2	0.9300
N1—C1	1.381 (5)	C3—C4	1.411 (5)
N1—C6	1.389 (5)	C3—H3	0.9300
N1—H1	0.8600	C4—C5	1.396 (5)
N2—C4	1.356 (5)	C5—C7	1.377 (5)
N2—H2A	0.8600	C5—H5	0.9300
N2—H2B	0.8600	C6—C7	1.479 (5)
C1—C8	1.467 (5)	C7—C8	1.385 (5)
C2—C3	1.378 (6)

C1—N1—C6	112.0 (3)	N2—C4—C5	121.3 (4)
C1—N1—H1	124.0	N2—C4—C3	119.0 (4)
C6—N1—H1	124.0	C5—C4—C3	119.6 (3)
C4—N2—H2A	120.0	C7—C5—C4	118.5 (3)
C4—N2—H2B	120.0	C7—C5—H5	120.8
H2A—N2—H2B	120.0	C4—C5—H5	120.8
O1—C1—N1	124.6 (4)	O2—C6—N1	124.6 (4)
O1—C1—C8	129.0 (4)	O2—C6—C7	129.8 (4)
N1—C1—C8	106.4 (3)	N1—C6—C7	105.6 (3)
C3—C2—C8	118.8 (4)	C5—C7—C8	121.5 (4)
C3—C2—H2	120.6	C5—C7—C6	130.5 (4)
C8—C2—H2	120.6	C8—C7—C6	108.0 (3)
C2—C3—C4	120.9 (4)	C2—C8—C7	120.7 (3)
C2—C3—H3	119.5	C2—C8—C1	131.3 (4)
C4—C3—H3	119.5	C7—C8—C1	108.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.09	2.924 (4)	164
N2—H2B···O1ⁱⁱ	0.86	2.28	3.122 (5)	167
N2—H2A···O2ⁱⁱⁱ	0.86	2.17	2.996 (4)	161

Symmetry codes: (i) −x+1, −y+1, z+1/2; (ii) −x+3/2, y+1/2, z−1/2; (iii) −x+1, −y+2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₈H₆N₂O₂
M_r	162.15
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	298
a, b, c (Å)	14.5786 (19), 13.0728 (17), 3.7216 (5)
V (Å³)	709.27 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.25 × 0.08 × 0.06

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.97, 0.99
No. of measured, independent and observed [I > 2σ(I)] reflections	7856, 978, 636
R_int	0.086
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.126, 1.09
No. of reflections	978
No. of parameters	109
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.17

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.09	2.924 (4)	163.7
N2—H2B···O1ⁱⁱ	0.86	2.28	3.122 (5)	166.6
N2—H2A···O2ⁱⁱⁱ	0.86	2.17	2.996 (4)	161.0

Symmetry codes: (i) −x+1, −y+1, z+1/2; (ii) −x+3/2, y+1/2, z−1/2; (iii) −x+1, −y+2, z−1/2.

Acknowledgements

MS thanks the National Institute of Science Education and Research (NISER), Bhubaneswar for financial support. The structure determination was performed at the National Single Crystal Diffractometer Facility (funded by the DST), School of Chemistry, University of Hyderabad.

References

Bruker (1997). SAINT andSMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Paul, A. & Samanta, A. (2007). J. Phys. Chem. B, 111, 4724–4731. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar