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ISSN: 2056-9890

4-Amino­phthalimide

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[Paul, A. & Samanta, A. (2007). J. Phys. Chem. B, 111, 4724-4731.]).

[Scheme 1]

Experimental

Crystal data
  • C8H6N2O2

  • Mr = 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[Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.]) Tmin = 0.97, Tmax = 0.99

  • 7856 measured reflections

  • 978 independent reflections

  • 636 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.17 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (1997). SAINT andSMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SAINT andSMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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).

Refinement top

All H atoms were placed geometrically at idealized positions and refined in the riding-model approximation with the follwing constraints: C–H = 0.93 Å, N–H = 0.86 Å and with Uiso(H) = 1.2Ueq(C),Uiso(H) = 1.2Ueq(N). In the abscense of any significant anomalous effect, the data set was merged.

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
[Figure 1] 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.
[Figure 2] Fig. 2. Molecular chain along the c axis.
[Figure 3] Fig. 3. Packing diagram showing N—H···O intermolecular hydrogen bonds. [(1) N1—H1···O1a, (2) N1b– H1b···O1, (3) N2c—H2Ac···O2, (4) N2 –H2A···O2d, (5) N2—H2B···O1e; 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
C8H6N2O2F(000) = 336
Mr = 162.15Dx = 1.518 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 704 reflections
a = 14.5786 (19) Åθ = 2.8–18.3°
b = 13.0728 (17) ŵ = 0.11 mm1
c = 3.7216 (5) ÅT = 298 K
V = 709.27 (16) Å3Needle, yellow
Z = 40.25 × 0.08 × 0.06 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
978 independent reflections
Radiation source: fine-focus sealed tube636 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.086
phi and ω scansθmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 1919
Tmin = 0.97, Tmax = 0.99k = 1717
7856 measured reflectionsl = 44
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0542P)2 + 0.1098P]
where P = (Fo2 + 2Fc2)/3
978 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.22 e Å3
1 restraintΔρmin = 0.17 e Å3
Crystal data top
C8H6N2O2V = 709.27 (16) Å3
Mr = 162.15Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 14.5786 (19) ŵ = 0.11 mm1
b = 13.0728 (17) ÅT = 298 K
c = 3.7216 (5) Å0.25 × 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)
Tmin = 0.97, Tmax = 0.99Rint = 0.086
7856 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0631 restraint
wR(F2) = 0.126H-atom parameters constrained
S = 1.09Δρmax = 0.22 e Å3
978 reflectionsΔρmin = 0.17 e Å3
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
xyzUiso*/Ueq
O10.60766 (19)0.53133 (19)1.0695 (10)0.0556 (10)
O20.41159 (18)0.7846 (2)1.4175 (11)0.0559 (9)
N10.4932 (2)0.6407 (2)1.2599 (11)0.0445 (9)
H10.45420.59541.32840.053*
N20.6919 (2)1.0180 (2)0.8617 (13)0.0599 (12)
H2A0.65511.06690.91640.072*
H2B0.74431.03150.76630.072*
C10.5777 (3)0.6181 (3)1.1116 (14)0.0411 (10)
C20.7055 (3)0.7394 (3)0.8804 (12)0.0400 (10)
H20.74590.68750.81530.048*
C30.7288 (3)0.8405 (3)0.8309 (11)0.0423 (11)
H30.78570.85690.73380.051*
C40.6676 (3)0.9196 (3)0.9256 (12)0.0386 (10)
C50.5831 (3)0.8952 (3)1.0800 (12)0.0359 (10)
H50.54240.94641.14890.043*
C60.4787 (3)0.7455 (3)1.2853 (12)0.0402 (10)
C70.5613 (2)0.7937 (3)1.1281 (12)0.0346 (9)
C80.6212 (3)0.7165 (3)1.0282 (11)0.0350 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.054 (2)0.0267 (15)0.086 (3)0.0020 (13)0.0039 (19)0.0037 (18)
O20.0478 (17)0.0435 (17)0.076 (2)0.0027 (14)0.0124 (18)0.0012 (19)
N10.0401 (19)0.0284 (17)0.065 (2)0.0068 (15)0.0033 (19)0.005 (2)
N20.056 (2)0.038 (2)0.086 (3)0.0050 (17)0.012 (3)0.001 (2)
C10.042 (2)0.033 (2)0.049 (3)0.0026 (19)0.005 (2)0.000 (2)
C20.039 (2)0.037 (2)0.044 (3)0.0043 (17)0.002 (2)0.002 (2)
C30.045 (2)0.039 (2)0.043 (3)0.0019 (18)0.002 (2)0.001 (2)
C40.040 (2)0.034 (2)0.041 (2)0.0048 (17)0.003 (2)0.002 (2)
C50.041 (2)0.025 (2)0.041 (2)0.0078 (16)0.004 (2)0.003 (2)
C60.039 (2)0.036 (2)0.047 (3)0.0022 (18)0.002 (2)0.001 (2)
C70.035 (2)0.033 (2)0.036 (2)0.0011 (16)0.0067 (19)0.0014 (19)
C80.040 (2)0.030 (2)0.035 (3)0.0012 (18)0.0032 (18)0.0008 (19)
Geometric parameters (Å, º) top
O1—C11.226 (4)C2—C81.380 (5)
O2—C61.209 (4)C2—H20.9300
N1—C11.381 (5)C3—C41.411 (5)
N1—C61.389 (5)C3—H30.9300
N1—H10.8600C4—C51.396 (5)
N2—C41.356 (5)C5—C71.377 (5)
N2—H2A0.8600C5—H50.9300
N2—H2B0.8600C6—C71.479 (5)
C1—C81.467 (5)C7—C81.385 (5)
C2—C31.378 (6)
C1—N1—C6112.0 (3)N2—C4—C5121.3 (4)
C1—N1—H1124.0N2—C4—C3119.0 (4)
C6—N1—H1124.0C5—C4—C3119.6 (3)
C4—N2—H2A120.0C7—C5—C4118.5 (3)
C4—N2—H2B120.0C7—C5—H5120.8
H2A—N2—H2B120.0C4—C5—H5120.8
O1—C1—N1124.6 (4)O2—C6—N1124.6 (4)
O1—C1—C8129.0 (4)O2—C6—C7129.8 (4)
N1—C1—C8106.4 (3)N1—C6—C7105.6 (3)
C3—C2—C8118.8 (4)C5—C7—C8121.5 (4)
C3—C2—H2120.6C5—C7—C6130.5 (4)
C8—C2—H2120.6C8—C7—C6108.0 (3)
C2—C3—C4120.9 (4)C2—C8—C7120.7 (3)
C2—C3—H3119.5C2—C8—C1131.3 (4)
C4—C3—H3119.5C7—C8—C1108.0 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.092.924 (4)164
N2—H2B···O1ii0.862.283.122 (5)167
N2—H2A···O2iii0.862.172.996 (4)161
Symmetry codes: (i) x+1, y+1, z+1/2; (ii) x+3/2, y+1/2, z1/2; (iii) x+1, y+2, z1/2.

Experimental details

Crystal data
Chemical formulaC8H6N2O2
Mr162.15
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)298
a, b, c (Å)14.5786 (19), 13.0728 (17), 3.7216 (5)
V3)709.27 (16)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.25 × 0.08 × 0.06
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.97, 0.99
No. of measured, independent and
observed [I > 2σ(I)] reflections
7856, 978, 636
Rint0.086
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.063, 0.126, 1.09
No. of reflections978
No. of parameters109
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.092.924 (4)163.7
N2—H2B···O1ii0.862.283.122 (5)166.6
N2—H2A···O2iii0.862.172.996 (4)161.0
Symmetry codes: (i) x+1, y+1, z+1/2; (ii) x+3/2, y+1/2, z1/2; (iii) x+1, y+2, z1/2.
 

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

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

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