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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1809.
Published online 2010 June 26. doi:  10.1107/S1600536810024189
PMCID: PMC3006687

N-(3,4-Difluoro­phen­yl)phthalimide

Abstract

In the title compound, C14H7F2NO2, the phthalimide ring system is nearly planar [maximum atomic deviation = 0.028 (1) Å] and it is twisted with respect to the attached benzene ring, making a dihedral angle of 55.70 (6)°. Weak inter­molecular C—H(...)F hydrogen bonds are present in the crystal structure.

Related literature

The title compound is an inter­mediate in the synthesis of organic electro-luminescent materials, see: Han & Kay (2005 [triangle]). For the synthesis, see: Valkonen et al. (2007 [triangle]); Barchin et al. (2002 [triangle]). For a related structure, see: Xu et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1809-scheme1.jpg

Experimental

Crystal data

  • C14H7F2NO2
  • M r = 259.21
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1809-efi1.jpg
  • a = 15.101 (3) Å
  • b = 5.8093 (12) Å
  • c = 24.866 (5) Å
  • V = 2181.4 (8) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.13 mm−1
  • T = 113 K
  • 0.20 × 0.10 × 0.08 mm

Data collection

  • Rigaku Saturn CCD area-detector diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.975, T max = 0.990
  • 14468 measured reflections
  • 1920 independent reflections
  • 1780 reflections with I > 2σ(I)
  • R int = 0.040

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.115
  • S = 1.03
  • 1920 reflections
  • 173 parameters
  • H-atom parameters constrained
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.06 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810024189/ng2786sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810024189/ng2786Isup2.hkl

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

Acknowledgments

The work was supported by the Major Research Program of Zhejiang Province (No. 2008 C02007–2) and the Zhejiang Provincial Natural Science Foundation of China (No. Y307128).

supplementary crystallographic information

Comment

The title compound is a key intermediate in the synthesis of organic electro-luminescent materials. The emission of light by organic molecules exposed to an electric field has been wide investigated in both an academic and industrial context. (Han & Kay, 2005).

The molecular structure of the title compound is illustrated in Fig. 1. In the title compound, the phthalimide ring system is nearly planar [maximum atomic deviation 0.028 (1) Å for N1 atom] and the dihedral angle between the benzene ring and the phthalimide plane is 55.70 (6)°, which is similar to 59.95 (4) ° found in a related compound N-(2-fluorophenyl)phthalimide (Xu et al., 2006). Weak intermolecular C—H···F hydrogen bonding is present in the crystal structure (Table 1).

Experimental

An acetic acid solution of phthalic anhydride (14.8 g, 100 mmol) and 3,4-difluoroaniline (9.91 ml, 100 mmol) was refluxed overnight, and then filtered. The crude product was recrystallized from ethyl acetate.

Refinement

H atoms were positioned geometrically and refined as riding with C—H = 0.95 Å, and Uiso(H) = 1.2Ueq(C). The (002) and (102) reflections were omitted in the refinement.

Figures

Fig. 1.
View of the molecule of showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Crystal data

C14H7F2NO2F(000) = 1056
Mr = 259.21Dx = 1.579 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 5269 reflections
a = 15.101 (3) Åθ = 1.6–27.9°
b = 5.8093 (12) ŵ = 0.13 mm1
c = 24.866 (5) ÅT = 113 K
V = 2181.4 (8) Å3Prism, colorless
Z = 80.20 × 0.10 × 0.08 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer1920 independent reflections
Radiation source: rotating anode1780 reflections with I > 2σ(I)
confocalRint = 0.040
Detector resolution: 7.31 pixels mm-1θmax = 25.0°, θmin = 1.6°
ω and [var phi] scansh = −17→17
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −6→6
Tmin = 0.975, Tmax = 0.990l = −29→20
14468 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.115w = 1/[σ2(Fo2) + (0.0736P)2 + 0.7186P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
1920 reflectionsΔρmax = 0.34 e Å3
173 parametersΔρmin = −0.06 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.046 (4)

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
F10.18581 (6)0.83152 (17)0.21976 (4)0.0398 (3)
F20.12250 (7)0.45784 (18)0.17125 (4)0.0409 (3)
O10.04193 (7)0.85824 (18)0.40561 (4)0.0289 (3)
O20.19778 (7)0.17995 (18)0.40802 (4)0.0282 (3)
N10.11557 (7)0.5119 (2)0.39257 (5)0.0217 (3)
C10.08090 (9)0.6931 (2)0.42336 (6)0.0221 (4)
C20.10111 (9)0.6332 (3)0.48041 (6)0.0223 (4)
C30.08065 (10)0.7479 (3)0.52755 (6)0.0277 (4)
H30.04990.89050.52710.033*
C40.10706 (10)0.6458 (3)0.57568 (6)0.0315 (4)
H40.09420.72060.60870.038*
C50.15184 (10)0.4367 (3)0.57625 (6)0.0314 (4)
H50.16880.37080.60970.038*
C60.17221 (10)0.3224 (3)0.52856 (6)0.0276 (4)
H60.20280.17940.52870.033*
C70.14620 (9)0.4251 (3)0.48107 (6)0.0225 (4)
C80.15903 (9)0.3464 (2)0.42484 (6)0.0218 (4)
C90.11494 (9)0.5016 (3)0.33528 (6)0.0232 (4)
C100.15100 (9)0.6824 (3)0.30585 (6)0.0251 (4)
H100.17440.81470.32320.030*
C110.15153 (9)0.6626 (3)0.25060 (6)0.0276 (4)
C120.11839 (10)0.4696 (3)0.22544 (6)0.0284 (4)
C130.08237 (10)0.2919 (3)0.25441 (6)0.0297 (4)
H130.05910.16010.23670.036*
C140.08046 (9)0.3082 (3)0.31032 (6)0.0262 (4)
H140.05570.18740.33120.031*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
F10.0481 (6)0.0388 (7)0.0325 (6)−0.0077 (5)0.0028 (4)0.0079 (4)
F20.0557 (7)0.0463 (7)0.0206 (5)0.0059 (5)−0.0013 (4)−0.0034 (4)
O10.0296 (6)0.0255 (6)0.0315 (6)0.0052 (4)−0.0016 (4)0.0006 (4)
O20.0294 (6)0.0246 (6)0.0305 (6)0.0059 (4)−0.0002 (4)−0.0033 (4)
N10.0215 (6)0.0225 (7)0.0211 (7)0.0022 (5)−0.0005 (4)−0.0009 (5)
C10.0179 (7)0.0223 (8)0.0262 (8)−0.0003 (6)0.0012 (5)−0.0009 (6)
C20.0189 (7)0.0235 (8)0.0247 (8)−0.0018 (6)0.0008 (6)−0.0007 (6)
C30.0241 (7)0.0277 (9)0.0313 (8)−0.0013 (6)0.0036 (6)−0.0033 (7)
C40.0322 (8)0.0381 (10)0.0242 (8)−0.0065 (7)0.0071 (6)−0.0039 (7)
C50.0334 (8)0.0366 (10)0.0242 (8)−0.0064 (7)0.0018 (6)0.0054 (7)
C60.0273 (8)0.0272 (8)0.0282 (8)−0.0022 (7)0.0012 (6)0.0048 (6)
C70.0198 (7)0.0217 (8)0.0260 (8)−0.0027 (6)0.0018 (6)−0.0007 (6)
C80.0188 (7)0.0208 (8)0.0257 (8)−0.0012 (5)−0.0009 (6)0.0003 (6)
C90.0194 (7)0.0265 (8)0.0236 (8)0.0034 (6)−0.0015 (5)−0.0016 (6)
C100.0235 (7)0.0249 (8)0.0270 (8)−0.0010 (6)−0.0021 (6)−0.0007 (6)
C110.0254 (7)0.0289 (9)0.0287 (8)0.0021 (6)0.0025 (6)0.0061 (7)
C120.0293 (8)0.0344 (9)0.0217 (8)0.0080 (7)−0.0011 (6)−0.0024 (6)
C130.0301 (8)0.0289 (9)0.0300 (8)0.0032 (7)−0.0042 (6)−0.0070 (7)
C140.0248 (7)0.0248 (8)0.0289 (8)0.0006 (6)−0.0001 (6)−0.0007 (6)

Geometric parameters (Å, °)

F1—C111.3486 (18)C5—C61.394 (2)
F2—C121.3507 (17)C5—H50.9500
O1—C11.2088 (17)C6—C71.380 (2)
O2—C81.2051 (18)C6—H60.9500
N1—C11.4032 (18)C7—C81.484 (2)
N1—C81.4139 (18)C9—C141.385 (2)
N1—C91.4257 (19)C9—C101.391 (2)
C1—C21.4923 (19)C10—C111.379 (2)
C2—C31.383 (2)C10—H100.9500
C2—C71.388 (2)C11—C121.378 (2)
C3—C41.394 (2)C12—C131.371 (2)
C3—H30.9500C13—C141.394 (2)
C4—C51.390 (3)C13—H130.9500
C4—H40.9500C14—H140.9500
C1—N1—C8111.94 (12)C2—C7—C8108.76 (12)
C1—N1—C9125.04 (12)O2—C8—N1125.03 (13)
C8—N1—C9122.80 (12)O2—C8—C7129.63 (13)
O1—C1—N1125.29 (13)N1—C8—C7105.34 (12)
O1—C1—C2129.18 (13)C14—C9—C10121.58 (15)
N1—C1—C2105.51 (12)C14—C9—N1118.96 (14)
C3—C2—C7121.30 (14)C10—C9—N1119.44 (13)
C3—C2—C1130.35 (14)C11—C10—C9117.63 (14)
C7—C2—C1108.34 (12)C11—C10—H10121.2
C2—C3—C4117.29 (15)C9—C10—H10121.2
C2—C3—H3121.4F1—C11—C10120.55 (14)
C4—C3—H3121.4F1—C11—C12118.25 (14)
C5—C4—C3121.32 (14)C10—C11—C12121.19 (14)
C5—C4—H4119.3F2—C12—C13120.28 (14)
C3—C4—H4119.3F2—C12—C11118.50 (14)
C4—C5—C6121.00 (15)C13—C12—C11121.21 (14)
C4—C5—H5119.5C12—C13—C14118.75 (14)
C6—C5—H5119.5C12—C13—H13120.6
C7—C6—C5117.33 (15)C14—C13—H13120.6
C7—C6—H6121.3C9—C14—C13119.63 (14)
C5—C6—H6121.3C9—C14—H14120.2
C6—C7—C2121.76 (14)C13—C14—H14120.2
C6—C7—C8129.48 (14)
C8—N1—C1—O1178.83 (13)C9—N1—C8—C7178.07 (12)
C9—N1—C1—O14.1 (2)C6—C7—C8—O2−3.1 (3)
C8—N1—C1—C2−2.26 (14)C2—C7—C8—O2176.76 (14)
C9—N1—C1—C2−177.01 (12)C6—C7—C8—N1177.27 (14)
O1—C1—C2—C30.4 (3)C2—C7—C8—N1−2.88 (15)
N1—C1—C2—C3−178.49 (14)C1—N1—C9—C14−127.38 (15)
O1—C1—C2—C7179.19 (14)C8—N1—C9—C1458.42 (17)
N1—C1—C2—C70.34 (15)C1—N1—C9—C1054.38 (18)
C7—C2—C3—C4−0.1 (2)C8—N1—C9—C10−119.82 (15)
C1—C2—C3—C4178.61 (14)C14—C9—C10—C11−0.1 (2)
C2—C3—C4—C5−0.2 (2)N1—C9—C10—C11178.06 (12)
C3—C4—C5—C60.3 (2)C9—C10—C11—F1−179.79 (12)
C4—C5—C6—C70.0 (2)C9—C10—C11—C12−0.7 (2)
C5—C6—C7—C2−0.4 (2)F1—C11—C12—F20.6 (2)
C5—C6—C7—C8179.47 (14)C10—C11—C12—F2−178.55 (13)
C3—C2—C7—C60.4 (2)F1—C11—C12—C13−179.79 (13)
C1—C2—C7—C6−178.56 (13)C10—C11—C12—C131.1 (2)
C3—C2—C7—C8−179.47 (13)F2—C12—C13—C14179.01 (13)
C1—C2—C7—C81.58 (16)C11—C12—C13—C14−0.6 (2)
C1—N1—C8—O2−176.48 (13)C10—C9—C14—C130.6 (2)
C9—N1—C8—O2−1.6 (2)N1—C9—C14—C13−177.63 (12)
C1—N1—C8—C73.18 (14)C12—C13—C14—C9−0.2 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C4—H4···F2i0.952.473.317 (2)149
C5—H5···F2ii0.952.543.321 (2)139

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2786).

References

  • Barchin, B. M., Cuadro, A. M. & Alvarez-Builla, J. (2002). Synlett, 2, 343–345.
  • Han, K. J. & Kay, K. Y. (2005). J. Korean Chem. Soc.49, 233–238.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Valkonen, A., Lahtinen, T. & Rissanen, K. (2007). Acta Cryst. E63, o472–o473.
  • Xu, D., Shi, Y.-Q., Chen, B., Cheng, Y.-H. & Gao, X. (2006). Acta Cryst. E62, o408–o409.

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