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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2010 Aug 28;66(Pt 9):o2432. doi: 10.1107/S1600536810032575

4,5,6,7-Tetra­chloro-N-(2-fluoro­phen­yl)phthalimide

Xian-Shu Fu a, Xiao-Ping Yu a, Wei-Min Wang a,*, Fang Lin a
PMCID: PMC3008021  PMID: 21588756

Abstract

In the title compound, C14H4Cl4FNO2, the benzene ring and the phthalimide plane are nearly planar, the maximum deviations being 0.005 (2) and 0.010 (2) Å, respectively, but the mol­ecule as a whole is not planar: the dihedral angle between the two planar ring systems is 68.06 (10)°. A short Cl⋯O contact of 2.914 (2) Å exists in the crystal structure.

Related literature

The title compound is an inter­mediate in the synthesis of organic electroluminescent materials; see: Han & Kay (2005 ▶). For details of the synthesis, see: Valkonen et al. (2007 ▶); Barchin et al. (2002 ▶). For related structures, see: Xu et al. (2006 ▶); Fu et al. (2010a ▶,b ▶,c ▶).graphic file with name e-66-o2432-scheme1.jpg

Experimental

Crystal data

  • C14H4Cl4FNO2

  • M r = 378.98

  • Monoclinic, Inline graphic

  • a = 12.032 (2) Å

  • b = 13.393 (3) Å

  • c = 8.7244 (17) Å

  • β = 95.33 (3)°

  • V = 1399.8 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.86 mm−1

  • T = 113 K

  • 0.22 × 0.20 × 0.16 mm

Data collection

  • Rigaku Saturn CCD area-detector diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.833, T max = 0.875

  • 9870 measured reflections

  • 2462 independent reflections

  • 2120 reflections with I > 2σ(I)

  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032

  • wR(F 2) = 0.085

  • S = 1.14

  • 2462 reflections

  • 199 parameters

  • H-atom parameters constrained

  • Δρmax = 0.55 e Å−3

  • Δρmin = −0.54 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810032575/bv2150sup1.cif

e-66-o2432-sup1.cif (17.6KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032575/bv2150Isup2.hkl

e-66-o2432-Isup2.hkl (121KB, hkl)

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

Acknowledgments

This work was supported by the Major Research Program of Zhejiang Province (grant No. 2008 C02007-2) and the Zhejiang Provincial Natural Science Foundation of China (grant 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 two rings are nearly planar, the maximum deviations being 0.005 (2) and 0.010 (2) Å, respectively, but the molecule as a whole is not planar. The dihedral angle between the benzene ring and the phthalimide plane is 68.06 (10) °, which is greater than 59.95 (4) ° found in a related compound N-(2-fluorophenyl)phthalimide (Xu et al., 2006). A short Cl···O contact of 2.914 (2) Å exists in the crystal structure.

Experimental

An acetic acid solution of 4,5,6,7-tetrachlorophthalic anhydride (28.6 g, 100 mmol) and 2-fluoroaniline (9.65 ml, 100 mmol) was refluxed overnight, and then filtered. The crude produce 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).

Figures

Fig. 1.

Fig. 1.

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

Crystal data

C14H4Cl4FNO2 F(000) = 752
Mr = 378.98 Dx = 1.798 Mg m−3
Monoclinic, P21/c Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc Cell parameters from 4679 reflections
a = 12.032 (2) Å θ = 2.3–27.9°
b = 13.393 (3) Å µ = 0.86 mm−1
c = 8.7244 (17) Å T = 113 K
β = 95.33 (3)° Prism, colorless
V = 1399.8 (5) Å3 0.22 × 0.20 × 0.16 mm
Z = 4
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Data collection

Rigaku Saturn CCD area-detector diffractometer 2462 independent reflections
Radiation source: rotating anode 2120 reflections with I > 2σ(I)
confocal Rint = 0.027
Detector resolution: 7.31 pixels mm-1 θmax = 25.0°, θmin = 2.3°
ω and φ scans h = −14→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) k = −15→15
Tmin = 0.833, Tmax = 0.875 l = −7→10
9870 measured reflections
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Refinement

Refinement on F2 Primary atom site location: structure-invariant direct methods
Least-squares matrix: full Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032 Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085 H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.0567P)2] where P = (Fo2 + 2Fc2)/3
2462 reflections (Δ/σ)max = 0.001
199 parameters Δρmax = 0.55 e Å−3
0 restraints Δρmin = −0.54 e Å−3
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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.
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
Cl1 0.86460 (4) 0.88811 (4) 0.87885 (5) 0.02115 (15)
Cl2 1.12105 (4) 0.89461 (4) 0.84021 (6) 0.02482 (16)
Cl3 1.20515 (4) 0.87608 (4) 0.51578 (6) 0.02211 (16)
Cl4 1.03483 (4) 0.86419 (3) 0.22341 (5) 0.01784 (15)
F1 0.59427 (10) 1.01280 (10) 0.21749 (17) 0.0449 (4)
O1 0.64955 (11) 0.87452 (10) 0.64858 (16) 0.0242 (4)
O2 0.77309 (11) 0.84862 (10) 0.17056 (15) 0.0222 (3)
N1 0.68479 (12) 0.85955 (12) 0.39299 (18) 0.0179 (4)
C1 0.71360 (15) 0.86955 (14) 0.5529 (2) 0.0175 (4)
C2 0.83872 (15) 0.87331 (13) 0.5693 (2) 0.0145 (4)
C3 0.91144 (15) 0.88264 (13) 0.6996 (2) 0.0159 (4)
C4 1.02658 (15) 0.88421 (13) 0.6811 (2) 0.0157 (4)
C5 1.06451 (15) 0.87662 (12) 0.5352 (2) 0.0158 (4)
C6 0.98857 (15) 0.86904 (13) 0.4041 (2) 0.0140 (4)
C7 0.87595 (15) 0.86712 (13) 0.4244 (2) 0.0143 (4)
C8 0.77660 (15) 0.85734 (14) 0.3073 (2) 0.0162 (4)
C9 0.57195 (15) 0.85497 (15) 0.3257 (2) 0.0196 (4)
C10 0.50639 (15) 0.77220 (16) 0.3485 (2) 0.0252 (5)
H10 0.5353 0.7180 0.4101 0.030*
C11 0.39733 (16) 0.76994 (17) 0.2793 (2) 0.0315 (5)
H11 0.3512 0.7139 0.2947 0.038*
C12 0.35573 (17) 0.84825 (18) 0.1888 (3) 0.0318 (5)
H12 0.2816 0.8452 0.1410 0.038*
C13 0.42123 (16) 0.93161 (18) 0.1668 (2) 0.0313 (5)
H13 0.3926 0.9862 0.1057 0.038*
C14 0.52798 (15) 0.93280 (16) 0.2357 (2) 0.0243 (5)
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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
Cl1 0.0284 (3) 0.0246 (3) 0.0108 (3) −0.00137 (19) 0.0036 (2) −0.00012 (18)
Cl2 0.0242 (3) 0.0309 (3) 0.0178 (3) 0.0013 (2) −0.0064 (2) −0.0022 (2)
Cl3 0.0141 (3) 0.0256 (3) 0.0263 (3) 0.00246 (18) 0.0001 (2) −0.00010 (19)
Cl4 0.0185 (3) 0.0213 (3) 0.0145 (2) −0.00069 (17) 0.00566 (19) −0.00100 (18)
F1 0.0410 (7) 0.0357 (8) 0.0559 (9) −0.0095 (6) −0.0078 (6) 0.0140 (7)
O1 0.0213 (7) 0.0350 (9) 0.0178 (7) −0.0025 (6) 0.0088 (6) −0.0029 (6)
O2 0.0208 (7) 0.0331 (8) 0.0127 (7) −0.0050 (6) 0.0025 (5) −0.0015 (6)
N1 0.0134 (8) 0.0252 (10) 0.0156 (8) −0.0030 (6) 0.0037 (7) −0.0021 (7)
C1 0.0196 (10) 0.0162 (11) 0.0166 (10) −0.0009 (7) 0.0017 (8) 0.0000 (7)
C2 0.0181 (9) 0.0104 (10) 0.0155 (10) −0.0004 (7) 0.0035 (8) 0.0016 (7)
C3 0.0235 (10) 0.0125 (10) 0.0119 (10) 0.0000 (7) 0.0032 (8) −0.0001 (7)
C4 0.0198 (10) 0.0105 (10) 0.0157 (10) −0.0005 (7) −0.0044 (8) 0.0001 (7)
C5 0.0156 (9) 0.0106 (10) 0.0211 (11) 0.0014 (7) 0.0007 (8) −0.0001 (7)
C6 0.0187 (9) 0.0107 (10) 0.0132 (9) 0.0001 (7) 0.0044 (8) 0.0012 (7)
C7 0.0174 (9) 0.0122 (10) 0.0129 (9) −0.0015 (7) 0.0002 (7) 0.0000 (7)
C8 0.0166 (9) 0.0144 (10) 0.0176 (10) −0.0026 (7) 0.0009 (8) −0.0002 (8)
C9 0.0142 (9) 0.0269 (12) 0.0180 (10) −0.0014 (8) 0.0030 (8) −0.0057 (8)
C10 0.0208 (10) 0.0286 (13) 0.0270 (11) −0.0041 (8) 0.0056 (8) −0.0016 (9)
C11 0.0187 (10) 0.0390 (14) 0.0375 (13) −0.0123 (9) 0.0064 (9) −0.0100 (10)
C12 0.0149 (10) 0.0509 (16) 0.0295 (13) −0.0006 (10) 0.0008 (9) −0.0137 (11)
C13 0.0244 (11) 0.0406 (14) 0.0282 (12) 0.0073 (10) −0.0012 (9) −0.0020 (10)
C14 0.0231 (10) 0.0253 (12) 0.0243 (11) −0.0040 (8) 0.0011 (8) −0.0012 (9)
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Geometric parameters (Å, °)

Cl1—C3 1.7122 (19) C4—C5 1.396 (3)
Cl2—C4 1.7159 (19) C5—C6 1.400 (3)
Cl3—C5 1.7162 (18) C6—C7 1.383 (3)
Cl4—C6 1.7213 (19) C7—C8 1.505 (3)
F1—C14 1.354 (2) C9—C14 1.380 (3)
O1—C1 1.189 (2) C9—C10 1.385 (3)
O2—C8 1.195 (2) C10—C11 1.393 (3)
N1—C8 1.391 (2) C10—H10 0.9500
N1—C1 1.412 (2) C11—C12 1.379 (3)
N1—C9 1.430 (2) C11—H11 0.9500
C1—C2 1.500 (3) C12—C13 1.390 (3)
C2—C3 1.374 (3) C12—H12 0.9500
C2—C7 1.382 (3) C13—C14 1.367 (3)
C3—C4 1.410 (3) C13—H13 0.9500
C8—N1—C1 113.51 (15) C6—C7—C8 129.85 (18)
C8—N1—C9 123.34 (16) O2—C8—N1 125.63 (17)
C1—N1—C9 123.13 (16) O2—C8—C7 129.69 (17)
O1—C1—N1 125.66 (17) N1—C8—C7 104.68 (16)
O1—C1—C2 129.89 (18) C14—C9—C10 119.51 (18)
N1—C1—C2 104.45 (16) C14—C9—N1 120.02 (17)
C3—C2—C7 121.77 (18) C10—C9—N1 120.46 (18)
C3—C2—C1 129.66 (18) C9—C10—C11 118.8 (2)
C7—C2—C1 108.56 (16) C9—C10—H10 120.6
C2—C3—C4 117.62 (18) C11—C10—H10 120.6
C2—C3—Cl1 121.41 (15) C12—C11—C10 120.6 (2)
C4—C3—Cl1 120.94 (15) C12—C11—H11 119.7
C5—C4—C3 120.75 (17) C10—C11—H11 119.7
C5—C4—Cl2 119.71 (14) C11—C12—C13 120.64 (19)
C3—C4—Cl2 119.54 (15) C11—C12—H12 119.7
C4—C5—C6 120.45 (17) C13—C12—H12 119.7
C4—C5—Cl3 119.95 (15) C14—C13—C12 118.1 (2)
C6—C5—Cl3 119.60 (15) C14—C13—H13 121.0
C7—C6—C5 118.03 (18) C12—C13—H13 121.0
C7—C6—Cl4 121.36 (15) F1—C14—C13 119.8 (2)
C5—C6—Cl4 120.61 (14) F1—C14—C9 117.75 (16)
C2—C7—C6 121.36 (17) C13—C14—C9 122.4 (2)
C2—C7—C8 108.79 (16)
C8—N1—C1—O1 178.91 (18) C5—C6—C7—C2 0.5 (3)
C9—N1—C1—O1 0.6 (3) Cl4—C6—C7—C2 −178.51 (13)
C8—N1—C1—C2 −0.4 (2) C5—C6—C7—C8 −178.53 (17)
C9—N1—C1—C2 −178.80 (16) Cl4—C6—C7—C8 2.4 (3)
O1—C1—C2—C3 0.6 (3) C1—N1—C8—O2 179.37 (17)
N1—C1—C2—C3 179.94 (17) C9—N1—C8—O2 −2.3 (3)
O1—C1—C2—C7 −178.47 (19) C1—N1—C8—C7 −0.1 (2)
N1—C1—C2—C7 0.85 (19) C9—N1—C8—C7 178.26 (16)
C7—C2—C3—C4 −0.9 (3) C2—C7—C8—O2 −178.79 (19)
C1—C2—C3—C4 −179.94 (17) C6—C7—C8—O2 0.4 (3)
C7—C2—C3—Cl1 −178.88 (14) C2—C7—C8—N1 0.6 (2)
C1—C2—C3—Cl1 2.1 (3) C6—C7—C8—N1 179.79 (18)
C2—C3—C4—C5 0.1 (3) C8—N1—C9—C14 −67.0 (3)
Cl1—C3—C4—C5 178.00 (13) C1—N1—C9—C14 111.2 (2)
C2—C3—C4—Cl2 −179.43 (13) C8—N1—C9—C10 112.3 (2)
Cl1—C3—C4—Cl2 −1.5 (2) C1—N1—C9—C10 −69.5 (2)
C3—C4—C5—C6 1.1 (3) C14—C9—C10—C11 0.1 (3)
Cl2—C4—C5—C6 −179.40 (13) N1—C9—C10—C11 −179.17 (18)
C3—C4—C5—Cl3 −178.64 (13) C9—C10—C11—C12 0.6 (3)
Cl2—C4—C5—Cl3 0.9 (2) C10—C11—C12—C13 −1.0 (3)
C4—C5—C6—C7 −1.4 (3) C11—C12—C13—C14 0.9 (3)
Cl3—C5—C6—C7 178.36 (13) C12—C13—C14—F1 −179.79 (18)
C4—C5—C6—Cl4 177.65 (13) C12—C13—C14—C9 −0.2 (3)
Cl3—C5—C6—Cl4 −2.6 (2) C10—C9—C14—F1 179.34 (18)
C3—C2—C7—C6 0.7 (3) N1—C9—C14—F1 −1.4 (3)
C1—C2—C7—C6 179.84 (16) C10—C9—C14—C13 −0.2 (3)
C3—C2—C7—C8 179.90 (16) N1—C9—C14—C13 179.00 (19)
C1—C2—C7—C8 −0.92 (19)
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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BV2150).

References

  1. Barchin, B. M., Cuadro, A. M. & Alvarez-Builla, J. (2002). Synlett, 2, 343–345.
  2. Fu, X.-S., Yu, X.-P., Wang, W.-M. & Lin, F. (2010a). Acta Cryst. E66, o1809.
  3. Fu, X.-S., Yu, X.-P., Wang, W.-M. & Lin, F. (2010b). Acta Cryst. E66, o1744.
  4. Fu, X.-S., Yu, X.-P., Wang, W.-M. & Lin, F. (2010c). Acta Cryst. E66, o1859.
  5. Han, K. J. & Kay, K. Y. (2005). J. Korean Chem. Soc.49, 233–238.
  6. Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  7. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
  8. Valkonen, A., Lahtinen, T. & Rissanen, K. (2007). Acta Cryst. E63, o472–o473.
  9. Xu, D., Shi, Y.-Q., Chen, B., Cheng, Y.-H. & Gao, X. (2006). Acta Cryst. E62, o408–o409.

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810032575/bv2150sup1.cif

e-66-o2432-sup1.cif (17.6KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032575/bv2150Isup2.hkl

e-66-o2432-Isup2.hkl (121KB, hkl)

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

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

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