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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o263.
Published online 2007 December 12. doi:  10.1107/S160053680706583X
PMCID: PMC2915319

N-(4-Amino­phen­yl)-1,8-naphthalimide hemihydrate

Abstract

The title compound, C18H12N2O2·0.5H2O, was prepared by the reaction of 1,4-phenyl­enediamine with 1,8-naphthalic anhydride in refluxing dimethyl­formamide. The structure is stabilized by N—H(...)O and O—H(...)O hydrogen bonds. There are π–π stacking inter­actions [centroid-centroid distances of 3.718 (2), 3.510 (2) and 3.546 (2) Å] and C—H(...)π inter­actions between the mol­ecules. The water molecule lies on a twofold rotation axis. Its two H atoms are disordered equally over two positions.

Related literature

For related literature, see: Ofir (2006 [triangle]); Cederfur et al. (2003 [triangle]); Lavin & Shimizu (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o263-scheme1.jpg

Experimental

Crystal data

  • C18H12N2O2·0.5H2O
  • M r = 297.31
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o263-efi1.jpg
  • a = 22.926 (5) Å
  • b = 17.930 (4) Å
  • c = 6.836 (1) Å
  • V = 2810 (1) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 295 (2) K
  • 0.40 × 0.40 × 0.20 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: none
  • 5656 measured reflections
  • 1359 independent reflections
  • 1308 reflections with I > 2σ(I)
  • R int = 0.027
  • 3 standard reflections every 200 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.069
  • wR(F 2) = 0.164
  • S = 1.33
  • 1359 reflections
  • 204 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe et al., 1989 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL/PC (Sheldrick, 1990 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680706583X/ez2108sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680706583X/ez2108Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Natural Science Foundation of Shandong Province (grant No. Y2005B04).

supplementary crystallographic information

Comment

Recently combinatorial and high throughput stategies have emerged as efficient methods to prepare large numbers of potential receptors (Cederfur et al., 2003). Since the naphthyl group has the potential to be a good receptor (Lavin & Shimizu, 2006), we have studied 1,8-naphthalimide derivatives, such as the pure compound (I) described here.

In the title compound (Fig. 1), the bond lengths and angles in the 1,8-naphthalenedicarboximide group and benzene ring are normal (Ofir, 2006), including the two C?O bond lengths (Table 1). The dihedral angle formed by the benzene ring (C13—C18) and naphthalic ring (N1/C1—C12) is 72.5 (2)°.

The crystal packing is realised by N2—H2A···O1w, N2—H2B···O1, O1W—H11W···O1 and C7- H7A···O2 hydrogen bonds (Table 2 and Fig 2). C—H···π interactions exist between C15—H15A and Cg(1)i, the centroid of the benzene ring C13—C18 [symmetry code: (i) –X,1/2-Y,1/2+Z]. There are π-stacking interactions between the naphthylamide groups, with distances between ring centroids of 3.718 (2), 3.510 (2) and 3.546 (2) Å, for Cg(2)···Cg(3)ii, Cg(3)···Cg(2)iii and Cg(2)···Cg(4)ii, respectively [Cg(2) = C2—C6/C11, Cg(3) = C1—C2/N1/C10—C12, Cg(4)=C6—C11; symmetry codes: (ii) 1/2-X,Y,-1/2 + z; (iii) 1/2-X,Y,1/2 + z].

Experimental

The title compound was obtained by reaction of 1,4-phenylenediamine (0.1 mol) with 1,8-naphthalic anhydride (0.1 mol) in refluxing DMF (50 ml) for 4 h. Single crystals of the title compound suitable for X-ray measurements were obtained by recrystallization from a DMF solution at room temperature.

Refinement

The two hydrogen atoms in the water molecule were found to be disordered, each with 50% site occupancies. H atoms were fixed geometrically and allowed to ride on their attached atoms, with N—H=0.86, O—H=0.85, C—H=0.93 Å, and with Uiso=1.2Ueq. In the absence of significant anomalous scattering effects Friedel pairs have been merged.

Figures

Fig. 1.
The molecular structure and atom-labeling scheme for (I), with displacement ellipsoids drawn at the 30% probability level. Only one of the disorder positions is shown for the water H atoms.
Fig. 2.
The packing of (I), viewed down the c axis, showing one layer of molecules connected by N—H···O and O—H···O hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonding have been ...

Crystal data

C18H12N2O2·0.5H2ODx = 1.406 Mg m3
Mr = 297.31Melting point: 286 K
Orthorhombic, Aba2Mo Kα radiation λ = 0.71073 Å
Hall symbol: A2 -2acCell parameters from 512 reflections
a = 22.926 (5) Åθ = 2–22º
b = 17.930 (4) ŵ = 0.10 mm1
c = 6.836 (1) ÅT = 295 (2) K
V = 2810 (1) Å3Block, yellow
Z = 80.40 × 0.40 × 0.20 mm
F000 = 1240

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.027
Radiation source: fine-focus sealed tubeθmax = 25.0º
Monochromator: graphiteθmin = 2.3º
T = 295(2) Kh = −27→23
ω scansk = −20→21
Absorption correction: nonel = −8→7
5656 measured reflections3 standard reflections
1359 independent reflections every 200 reflections
1308 reflections with I > 2σ(I) intensity decay: none

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.069H-atom parameters constrained
wR(F2) = 0.164  w = 1/[σ2(Fo2) + (0.062P)2 + 2.2916P] where P = (Fo2 + 2Fc2)/3
S = 1.33(Δ/σ)max < 0.001
1359 reflectionsΔρmax = 0.24 e Å3
204 parametersΔρmin = −0.21 e Å3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

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)

xyzUiso*/UeqOcc. (<1)
O10.42928 (16)0.07821 (19)0.8275 (7)0.0704 (12)
O20.27279 (15)0.22571 (18)0.9326 (8)0.0675 (12)
N10.35109 (17)0.15181 (19)0.8761 (6)0.0447 (10)
N20.4972 (2)0.3999 (3)0.9511 (11)0.095 (2)
H2A0.50020.43140.85660.115*
H2B0.51700.40641.05670.115*
C10.2903 (2)0.1646 (3)0.8953 (8)0.0502 (13)
C20.2527 (2)0.0997 (2)0.8651 (7)0.0481 (12)
C30.1932 (2)0.1090 (3)0.8646 (8)0.0609 (15)
H3A0.17720.15630.88000.073*
C40.1569 (3)0.0475 (4)0.8411 (10)0.080 (2)
H4A0.11670.05430.83940.096*
C50.1787 (3)−0.0214 (4)0.8208 (10)0.080 (2)
H5A0.1533−0.06160.80900.096*
C60.2396 (3)−0.0341 (3)0.8168 (9)0.0641 (16)
C70.2649 (4)−0.1041 (3)0.7944 (10)0.082 (2)
H7A0.2409−0.14570.78390.099*
C80.3234 (4)−0.1134 (3)0.7875 (11)0.083 (2)
H8A0.3391−0.16100.77320.100*
C90.3604 (3)−0.0517 (3)0.8017 (9)0.0669 (16)
H9A0.4005−0.05810.79270.080*
C100.3376 (3)0.0183 (3)0.8289 (8)0.0538 (13)
C110.2765 (2)0.0281 (3)0.8369 (8)0.0509 (12)
C120.3765 (2)0.0826 (2)0.8410 (8)0.0512 (13)
C130.3889 (2)0.2158 (3)0.8965 (9)0.0522 (14)
C140.4212 (2)0.2260 (3)1.0623 (10)0.0602 (15)
H14A0.41900.19141.16320.072*
C150.4569 (3)0.2869 (3)1.0813 (11)0.0629 (15)
H15A0.47870.29321.19490.075*
C160.4609 (2)0.3390 (3)0.9330 (10)0.0577 (14)
C170.4289 (2)0.3279 (3)0.7643 (9)0.0565 (14)
H17A0.43190.36190.66190.068*
C180.3928 (2)0.2670 (3)0.7466 (9)0.0544 (14)
H18A0.37100.26030.63320.065*
O1W0.50000.00000.0917 (13)0.089 (2)
H1W10.48300.04210.09660.107*0.50
H2W10.52390.0012−0.00330.107*0.50

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.055 (2)0.063 (2)0.094 (3)0.0129 (17)0.011 (3)0.010 (2)
O20.067 (2)0.0447 (18)0.091 (3)0.0124 (16)−0.001 (3)0.000 (2)
N10.053 (2)0.0357 (18)0.046 (2)−0.0006 (16)−0.004 (2)0.0032 (18)
N20.102 (4)0.079 (3)0.106 (5)−0.039 (3)−0.022 (4)0.011 (4)
C10.055 (3)0.045 (2)0.050 (3)0.009 (2)−0.003 (3)0.005 (2)
C20.055 (3)0.055 (2)0.034 (3)−0.004 (2)−0.004 (2)0.010 (2)
C30.063 (3)0.078 (4)0.042 (3)−0.004 (3)−0.004 (3)0.009 (3)
C40.065 (4)0.116 (5)0.060 (4)−0.028 (4)−0.001 (3)0.021 (4)
C50.097 (5)0.087 (4)0.056 (4)−0.044 (4)−0.012 (4)0.018 (4)
C60.090 (5)0.059 (3)0.043 (3)−0.027 (3)−0.005 (3)0.013 (3)
C70.136 (7)0.052 (3)0.058 (4)−0.030 (4)−0.018 (4)0.013 (3)
C80.142 (7)0.042 (3)0.065 (4)0.002 (4)−0.006 (5)−0.001 (3)
C90.102 (4)0.047 (3)0.052 (4)0.008 (3)0.001 (3)0.001 (3)
C100.079 (4)0.037 (2)0.045 (3)0.003 (2)0.006 (3)0.011 (2)
C110.072 (3)0.048 (3)0.032 (2)−0.007 (2)−0.002 (3)0.008 (2)
C120.060 (3)0.043 (3)0.050 (3)0.010 (2)0.001 (3)0.007 (2)
C130.053 (3)0.038 (2)0.066 (4)0.004 (2)0.001 (3)0.004 (3)
C140.063 (3)0.055 (3)0.063 (4)−0.002 (3)−0.015 (3)0.012 (3)
C150.061 (3)0.058 (3)0.071 (4)−0.006 (3)−0.016 (3)−0.003 (3)
C160.053 (3)0.045 (3)0.075 (4)−0.007 (2)0.000 (3)−0.007 (3)
C170.067 (3)0.039 (2)0.063 (4)−0.003 (2)−0.006 (3)0.012 (3)
C180.059 (3)0.044 (3)0.060 (4)0.000 (2)−0.007 (3)0.001 (3)
O1W0.098 (5)0.093 (4)0.078 (4)0.028 (4)0.0000.000

Geometric parameters (Å, °)

O1—C121.217 (6)C7—H7A0.9300
O2—C11.194 (6)C8—C91.397 (9)
N1—C121.391 (6)C8—H8A0.9300
N1—C11.419 (6)C9—C101.372 (7)
N1—C131.445 (6)C9—H9A0.9300
N2—C161.379 (6)C10—C111.413 (7)
N2—H2A0.8600C10—C121.461 (7)
N2—H2B0.8600C13—C141.366 (8)
C1—C21.462 (7)C13—C181.379 (7)
C2—C31.375 (8)C14—C151.371 (7)
C2—C111.408 (7)C14—H14A0.9300
C3—C41.391 (8)C15—C161.381 (8)
C3—H3A0.9300C15—H15A0.9300
C4—C51.340 (9)C16—C171.381 (8)
C4—H4A0.9300C17—C181.375 (7)
C5—C61.416 (9)C17—H17A0.9300
C5—H5A0.9300C18—H18A0.9300
C6—C71.391 (8)O1W—H1W10.8501
C6—C111.406 (6)O1W—H2W10.8501
C7—C81.353 (10)
C12—N1—C1124.8 (4)C10—C9—H9A119.9
C12—N1—C13118.3 (4)C8—C9—H9A119.9
C1—N1—C13116.9 (4)C9—C10—C11119.8 (5)
C16—N2—H2A120.0C9—C10—C12119.8 (5)
C16—N2—H2B120.0C11—C10—C12120.3 (4)
H2A—N2—H2B120.0C6—C11—C2120.3 (5)
O2—C1—N1119.8 (4)C6—C11—C10119.5 (5)
O2—C1—C2124.2 (5)C2—C11—C10120.2 (5)
N1—C1—C2115.9 (4)O1—C12—N1119.2 (4)
C3—C2—C11119.6 (5)O1—C12—C10123.5 (4)
C3—C2—C1119.2 (5)N1—C12—C10117.3 (4)
C11—C2—C1121.1 (5)C14—C13—C18119.5 (5)
C2—C3—C4119.9 (6)C14—C13—N1120.8 (5)
C2—C3—H3A120.1C18—C13—N1119.7 (5)
C4—C3—H3A120.1C13—C14—C15120.6 (6)
C5—C4—C3121.3 (6)C13—C14—H14A119.7
C5—C4—H4A119.4C15—C14—H14A119.7
C3—C4—H4A119.4C14—C15—C16120.5 (6)
C4—C5—C6121.2 (6)C14—C15—H15A119.7
C4—C5—H5A119.4C16—C15—H15A119.7
C6—C5—H5A119.4N2—C16—C17120.6 (6)
C7—C6—C11118.5 (6)N2—C16—C15120.6 (6)
C7—C6—C5123.9 (6)C17—C16—C15118.8 (5)
C11—C6—C5117.6 (5)C18—C17—C16120.4 (5)
C8—C7—C6121.9 (6)C18—C17—H17A119.8
C8—C7—H7A119.1C16—C17—H17A119.8
C6—C7—H7A119.1C17—C18—C13120.2 (5)
C7—C8—C9120.1 (6)C17—C18—H18A119.9
C7—C8—H8A120.0C13—C18—H18A119.9
C9—C8—H8A120.0H1W1—O1W—H2W1107.7
C10—C9—C8120.2 (7)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···O1Wi0.862.193.046 (6)172
N2—H2B···O1ii0.862.243.099 (5)178
O1W—H1W1···O1iii0.852.302.800 (5)118
O1W—H2W1···O1iv0.852.122.800 (5)136
C15—H15A···Cg1v0.932.96.140

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: EZ2108).

References

  • Cederfur, J., Pei, Y. X., Meng, Z. H. & Kempe, M. (2003). J. Comb. Chem.5, 67–72. [PubMed]
  • Enraf–Nonius (1989). CAD-4 Software Version 5.0. Enraf–Nonius, Delft, The Netherlands.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst.22, 384–387.
  • Lavin, J. M. & Shimizu, K. D. (2006). Org. Lett.8, 2389–2392. [PubMed]
  • Ofir, Y. (2006). J. Mater. Chem.16, 2142–2143.
  • Sheldrick, G. M. (1990). SHELXTL/PC Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.

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