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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1552.
Published online 2009 June 13. doi:  10.1107/S1600536809020777
PMCID: PMC2969255

N-(4-Chloro­phenyl)-1,8-naphthalimide

Abstract

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 π–π contacts between the naphthalimide rings [centroid–centroid distance = 3.732 (3) Å].

Related literature

For related literature on N-substituted 1,8-naphthalimides, see: De Souza et al. (2002 [triangle]). For a description of the Cambridge Structural Database, see: Allen (2002 [triangle]). For hydrogen bonding, see: Bernstein et al. (1995 [triangle]).

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Object name is e-65-o1552-scheme1.jpg

Experimental

Crystal data

  • C18H10ClNO2
  • M r = 307.72
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1552-efi1.jpg
  • a = 8.6800 (17) Å
  • b = 17.553 (4) Å
  • c = 9.4600 (19) Å
  • β = 103.53 (3)°
  • V = 1401.3 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.28 mm−1
  • T = 293 K
  • 0.30 × 0.20 × 0.20 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.921, T max = 0.946
  • 2719 measured reflections
  • 2549 independent reflections
  • 1843 reflections with I > 2σ(I)
  • R int = 0.048
  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.053
  • wR(F 2) = 0.157
  • S = 1.00
  • 2549 reflections
  • 199 parameters
  • H-atom parameters constrained
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809020777/su2116sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809020777/su2116Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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

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).

Figures

Fig. 1.
The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
A view of the C-H···O hydrogen bonded (dashed lines) molecules in the title compound.

Crystal data

C18H10ClNO2F(000) = 632
Mr = 307.72Dx = 1.459 Mg m3
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 mm1
β = 103.53 (3)°T = 293 K
V = 1401.3 (5) Å3Block, green
Z = 40.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer1843 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

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 = 1.00w = 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 Å3
0 restraintsΔρmin = −0.23 e Å3

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*/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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SU2116).

References

  • Allen, F. H. (2002). Acta Cryst. B58, 380–388. [PubMed]
  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • De Souza, M. M., Correa, R., Cechinel Filho, V., Grabchev, I. & Bojinov, V. (2002). Pharmazie, 57, 430-431. [PubMed]
  • 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. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography