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Acta Cryst. (2009). E65, o1552    [ doi:10.1107/S1600536809020777 ]

N-(4-Chlorophenyl)-1,8-naphthalimide

S. Jie and S. Shao

Abstract top

In the title compound, C18H10ClNO2, the naphthalimide ring system is almost planar, the rings forming dihedral angles of 2.05 (3), 2.26 (3) and 0.80 (3)°. The attached benzene ring of the 4-chlorophenyl substituent is inclined to the mean plane of the naphthalimide ring system by 75.77 (11)°. In the crystal structure, symmetry-related molecules are linked by C-H...O interactions. There are also weak [pi]-[pi] contacts between the naphthalimide rings [centroid-centroid distance = 3.732 (3) Å].

Comment top

As part of our ongoing studies on N-substituted 1,8-naphthalimides (De Souza et al., 2002), we report herein on the crystal structure of the title compound.

In the title compound, illustrated in Fig. 1, the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (N/C4/C5/C7/C11/C13), B (C1—C6) and C (C5—C11) are oriented with respect to one another by dihedral angles of A/B = 2.05 (3), A/C = 2.26 (3) and B/C = 0.80 (3) °, hence almost coplanar. Rings A, B (C5—C10), C (C9—C14) and D (C12/C14—C18) are oriented at dihedral angles of A/D = 76.89 (3), B/D = 75.93 (3) and C/D = 75.19 (3) °.

In the crystal structure, intermolecular C—H···O hydrogen bonds (Table 1) link the molecules into multimers (Fig. 2) (Bernstein et al., 1996), in which they may be effective in the stabilization of the structure. The π–π contacts between the naphthalimide rings, Cg1—Cg1i [symmetry codes: (i) –X,-Y,-Z, where Cg1 is centroid of ring C] with centroid-centroid distances of 3.732 (3) Å, may further stabilize the structure.

Related literature top

For related literature on N-substituted 1,8-naphthalimides, see: De Souza et al. (2002). For a description of the Cambridge Structural Database, see: Allen (2002). For hydrogen bonding, see: Bernstein et al. (1996).

Experimental top

For the preparation of the title compound: 1,8-naphthalic anhydride (1.98 g, 0.01 mol) and 2-aminoethanol (1.275 g,0.01 mol) were mixed with acetic acid (50 ml). The reaction mixture was refluxed for 8 h, and then poured into cold water. The resulting solids were filtered off and boiled with an aqueous solution of sodium bicarbonate (10%, 50 ml) for 20 min, and the insoluble solid residues were dried in vacuo. Column chromatography on aluminium oxide with benzene as eluent gave a light-brown solution. Crystals suitable for X-ray analysis were obtained by slow evaporation of an acetone solution (yield 94%; m.p. 489 K).

Refinement top

H-atoms were positioned geometrically and constrained to ride on their parent atoms: C—H = 0.93 Å with Uiso(H) = 1.2Ueq(parent C-atom).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (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.
[Figure 2] Fig. 2. A view of the C-H···O hydrogen bonded (dashed lines) molecules in the title compound.
N-(4-Chlorophenyl)-1,8-naphthalimide top
Crystal data top
C18H10ClNO2F(000) = 632
Mr = 307.72Dx = 1.459 Mg m−3
Monoclinic, P21/nMelting point: 505 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 8.6800 (17) ÅCell parameters from 25 reflections
b = 17.553 (4) Åθ = 9–13°
c = 9.4600 (19) ŵ = 0.28 mm−1
β = 103.53 (3)°T = 293 K
V = 1401.3 (5) Å3Block, green
Z = 40.30 × 0.20 × 0.20 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		1843 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.048
graphiteθmax = 25.3°, θmin = 2.3°
ω/2θ scansh = 0→10
Absorption correction: ψ scan
(North et al., 1968)		k = 0→21
Tmin = 0.921, Tmax = 0.946l = −11→11
2719 measured reflections3 standard reflections every 200 reflections
2549 independent reflections intensity decay: 1%
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)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.157H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.07P)2 + 1.5P]
where P = (Fo2 + 2Fc2)/3
2549 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.30 e Å−3
0 restraintsΔρmin = −0.23 e Å−3
Crystal data top
C18H10ClNO2V = 1401.3 (5) Å3
Mr = 307.72Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.6800 (17) ŵ = 0.28 mm−1
b = 17.553 (4) ÅT = 293 K
c = 9.4600 (19) Å0.30 × 0.20 × 0.20 mm
β = 103.53 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		1843 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.048
Tmin = 0.921, Tmax = 0.946θmax = 25.3°
2719 measured reflections3 standard reflections every 200 reflections
2549 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.157Δρmax = 0.30 e Å−3
S = 1.00Δρmin = −0.23 e Å−3
2549 reflectionsAbsolute structure: ?
199 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Cl0.48706 (11)0.18516 (6)0.29044 (9)0.0612 (3)
N0.6288 (3)0.39484 (14)−0.1550 (2)0.0381 (6)
O10.7353 (3)0.48058 (14)0.0210 (2)0.0637 (7)
C10.8795 (5)0.5908 (2)−0.4218 (4)0.0606 (10)
H1A0.91820.6195−0.48860.073*
O20.5248 (3)0.30743 (13)−0.3284 (2)0.0555 (6)
C20.9122 (5)0.6132 (2)−0.2792 (4)0.0705 (11)
H2A0.97100.6572−0.25070.085*
C30.8580 (4)0.57040 (19)−0.1762 (4)0.0570 (9)
H3A0.88240.5856−0.07940.068*
C40.7693 (4)0.50637 (17)−0.2166 (3)0.0413 (7)
C50.7317 (4)0.48249 (17)−0.3649 (3)0.0385 (7)
C60.7888 (4)0.52546 (18)−0.4695 (3)0.0459 (8)
C70.6412 (3)0.41605 (17)−0.4090 (3)0.0373 (7)
C80.6044 (4)0.3947 (2)−0.5531 (3)0.0498 (8)
H8A0.54350.3514−0.58180.060*
C90.6577 (4)0.4375 (2)−0.6567 (3)0.0585 (10)
H9A0.63110.4227−0.75380.070*
C100.7487 (4)0.5009 (2)−0.6164 (4)0.0541 (9)
H10A0.78490.5284−0.68630.065*
C110.7125 (4)0.46182 (17)−0.1071 (3)0.0421 (7)
C120.5915 (4)0.34481 (17)−0.0448 (3)0.0376 (7)
C130.5918 (4)0.36798 (18)−0.2992 (3)0.0393 (7)
C140.7103 (4)0.30126 (18)0.0375 (3)0.0442 (8)
H14A0.81210.30400.02220.053*
C150.6788 (4)0.25313 (19)0.1435 (3)0.0464 (8)
H15A0.75920.22430.20140.056*
C160.5257 (4)0.24902 (17)0.1611 (3)0.0406 (7)
C170.4056 (4)0.29174 (19)0.0787 (3)0.0477 (8)
H17A0.30290.28750.09150.057*
C180.4389 (4)0.34117 (19)−0.0239 (3)0.0445 (7)
H18A0.35950.3718−0.07850.053*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0701 (6)0.0711 (6)0.0452 (5)−0.0106 (5)0.0189 (4)0.0156 (4)
N0.0516 (15)0.0418 (14)0.0203 (11)−0.0043 (12)0.0073 (10)0.0008 (10)
O10.103 (2)0.0626 (16)0.0255 (11)−0.0126 (14)0.0140 (12)−0.0104 (11)
C10.074 (2)0.057 (2)0.055 (2)−0.0123 (19)0.0224 (19)0.0097 (17)
O20.0732 (16)0.0572 (15)0.0352 (12)−0.0234 (13)0.0107 (11)−0.0085 (11)
C20.089 (3)0.055 (2)0.067 (3)−0.022 (2)0.017 (2)−0.001 (2)
C30.075 (2)0.047 (2)0.0460 (19)−0.0097 (18)0.0081 (17)−0.0038 (16)
C40.0537 (19)0.0380 (17)0.0310 (15)−0.0019 (14)0.0074 (13)0.0002 (12)
C50.0443 (16)0.0425 (17)0.0282 (14)0.0057 (13)0.0073 (12)0.0060 (12)
C60.0541 (19)0.0453 (18)0.0392 (17)0.0081 (15)0.0128 (14)0.0128 (14)
C70.0448 (16)0.0425 (17)0.0244 (14)0.0038 (13)0.0079 (12)0.0004 (12)
C80.066 (2)0.057 (2)0.0255 (15)−0.0026 (17)0.0088 (14)−0.0026 (14)
C90.077 (3)0.078 (3)0.0226 (15)0.002 (2)0.0153 (15)−0.0007 (16)
C100.066 (2)0.061 (2)0.0386 (17)0.0044 (18)0.0202 (16)0.0125 (16)
C110.0581 (19)0.0406 (17)0.0260 (14)−0.0014 (14)0.0065 (13)−0.0029 (12)
C120.0516 (18)0.0420 (16)0.0199 (13)−0.0037 (14)0.0099 (12)−0.0026 (11)
C130.0484 (17)0.0465 (18)0.0219 (13)−0.0011 (15)0.0057 (12)−0.0026 (12)
C140.0404 (16)0.059 (2)0.0346 (16)0.0050 (15)0.0117 (13)0.0071 (14)
C150.0506 (19)0.056 (2)0.0323 (15)0.0046 (15)0.0080 (14)0.0054 (14)
C160.0516 (18)0.0461 (17)0.0243 (14)−0.0066 (14)0.0094 (13)−0.0001 (12)
C170.0428 (17)0.064 (2)0.0399 (17)−0.0018 (16)0.0164 (14)−0.0010 (15)
C180.0435 (17)0.0544 (19)0.0346 (16)0.0051 (14)0.0070 (13)0.0025 (14)
Geometric parameters (Å, °) top
Cl—C161.749 (3)C7—C81.377 (4)
N—C111.401 (4)C7—C131.477 (4)
N—C131.408 (3)C8—C91.396 (5)
N—C121.457 (3)C8—H8A0.9300
O1—C111.226 (3)C9—C101.367 (5)
C1—C21.370 (5)C9—H9A0.9300
C1—C61.404 (5)C10—H10A0.9300
C1—H1A0.9300C12—C141.370 (4)
O2—C131.212 (3)C12—C181.386 (4)
C2—C31.396 (5)C14—C151.386 (4)
C2—H2A0.9300C14—H14A0.9300
C3—C41.365 (4)C15—C161.379 (4)
C3—H3A0.9300C15—H15A0.9300
C4—C51.427 (4)C16—C171.370 (4)
C4—C111.472 (4)C17—C181.382 (4)
C5—C71.414 (4)C17—H17A0.9300
C5—C61.423 (4)C18—H18A0.9300
C6—C101.418 (5)
C11—N—C13125.3 (2)C8—C9—H9A119.8
C11—N—C12117.4 (2)C9—C10—C6120.9 (3)
C13—N—C12117.0 (2)C9—C10—H10A119.5
C2—C1—C6121.5 (3)C6—C10—H10A119.5
C2—C1—H1A119.2O1—C11—N119.8 (3)
C6—C1—H1A119.2O1—C11—C4123.3 (3)
C1—C2—C3120.4 (4)N—C11—C4116.9 (2)
C1—C2—H2A119.8C14—C12—C18120.7 (3)
C3—C2—H2A119.8C14—C12—N118.6 (3)
C4—C3—C2120.5 (3)C18—C12—N120.7 (3)
C4—C3—H3A119.7O2—C13—N120.2 (3)
C2—C3—H3A119.7O2—C13—C7122.9 (3)
C3—C4—C5120.1 (3)N—C13—C7116.9 (3)
C3—C4—C11120.0 (3)C12—C14—C15120.1 (3)
C5—C4—C11119.9 (3)C12—C14—H14A120.0
C7—C5—C6119.5 (3)C15—C14—H14A120.0
C7—C5—C4121.1 (3)C16—C15—C14118.5 (3)
C6—C5—C4119.4 (3)C16—C15—H15A120.7
C1—C6—C10123.6 (3)C14—C15—H15A120.7
C1—C6—C5118.0 (3)C17—C16—C15121.9 (3)
C10—C6—C5118.4 (3)C17—C16—Cl120.3 (2)
C8—C7—C5120.0 (3)C15—C16—Cl117.8 (2)
C8—C7—C13120.2 (3)C16—C17—C18119.1 (3)
C5—C7—C13119.8 (2)C16—C17—H17A120.4
C7—C8—C9120.7 (3)C18—C17—H17A120.4
C7—C8—H8A119.7C17—C18—C12119.6 (3)
C9—C8—H8A119.7C17—C18—H18A120.2
C10—C9—C8120.5 (3)C12—C18—H18A120.2
C10—C9—H9A119.8
C6—C1—C2—C31.1 (6)C12—N—C11—C4171.5 (3)
C1—C2—C3—C4−1.1 (6)C3—C4—C11—O12.9 (5)
C2—C3—C4—C50.2 (5)C5—C4—C11—O1−177.2 (3)
C2—C3—C4—C11−179.9 (4)C3—C4—C11—N−177.0 (3)
C3—C4—C5—C7179.5 (3)C5—C4—C11—N2.9 (4)
C11—C4—C5—C7−0.4 (4)C11—N—C12—C14−75.1 (4)
C3—C4—C5—C60.7 (5)C13—N—C12—C1498.6 (3)
C11—C4—C5—C6−179.3 (3)C11—N—C12—C18105.1 (3)
C2—C1—C6—C10178.5 (4)C13—N—C12—C18−81.2 (4)
C2—C1—C6—C5−0.3 (5)C11—N—C13—O2176.7 (3)
C7—C5—C6—C1−179.5 (3)C12—N—C13—O23.6 (4)
C4—C5—C6—C1−0.6 (5)C11—N—C13—C7−2.1 (4)
C7—C5—C6—C101.7 (4)C12—N—C13—C7−175.3 (3)
C4—C5—C6—C10−179.5 (3)C8—C7—C13—O23.4 (5)
C6—C5—C7—C8−2.1 (4)C5—C7—C13—O2−174.2 (3)
C4—C5—C7—C8179.1 (3)C8—C7—C13—N−177.8 (3)
C6—C5—C7—C13175.4 (3)C5—C7—C13—N4.6 (4)
C4—C5—C7—C13−3.4 (4)C18—C12—C14—C15−0.3 (5)
C5—C7—C8—C91.0 (5)N—C12—C14—C15179.9 (3)
C13—C7—C8—C9−176.5 (3)C12—C14—C15—C161.5 (5)
C7—C8—C9—C100.6 (5)C14—C15—C16—C17−0.9 (5)
C8—C9—C10—C6−1.1 (5)C14—C15—C16—Cl177.5 (2)
C1—C6—C10—C9−178.9 (3)C15—C16—C17—C18−0.9 (5)
C5—C6—C10—C9−0.1 (5)Cl—C16—C17—C18−179.3 (2)
C13—N—C11—O1178.5 (3)C16—C17—C18—C122.1 (5)
C12—N—C11—O1−8.4 (4)C14—C12—C18—C17−1.5 (5)
C13—N—C11—C4−1.6 (4)N—C12—C18—C17178.2 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15A···O2i0.932.453.138 (4)131
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15A···O2i0.932.453.138 (4)131
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2.
Acknowledgements top

The authors thank the Center of Testing and Analysis, Nanjing University for support.

references
References top

Allen, F. H. (2002). Acta Cryst. B58, 380–388.

Bernstein, J. ??????? (1996). ?????????? [Please provide reference]

De Souza, M. M., Correa, R., Cechinel Filho, V., Grabchev, I. & Bojinov, V. (2002). Pharmazie, 57, 430-431.

Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.

Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

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

Spek, A. L. (2009). Acta Cryst. D65, 148–155.