N-(3,4-Difluoro­phen­yl)phthalimide

Fu, X.-S.; Yu, X.-P.; Wang, W.-M.; Lin, F.

doi:10.1107/S1600536810024189

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1809

doi:10.1107/S1600536810024189

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N-(3,4-Difluorophenyl)phthalimide

Xian-Shu Fu,^a Xiao-Ping Yu,^a Wei-Min Wang ^a ^* and Fang Lin ^a

^aCollege of Life Sciences, China Jiliang University, Hangzhou 310018, People's Republic of China
^*Correspondence e-mail: clshangzhou@yahoo.com.cn

(Received 7 June 2010; accepted 22 June 2010; online 26 June 2010)

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 ). For the synthesis, see: Valkonen et al. (2007 ); Barchin et al. (2002 ). For a related structure, see: Xu et al. (2006 ).

Experimental

Crystal data

C₁₄H₇F₂NO₂
M_r = 259.21
Orthorhombic, P b c a
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 ) 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[F² > 2σ(F²)] = 0.040
wR(F²) = 0.115
S = 1.03
1920 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.06 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯F2ⁱ	0.95	2.47	3.317 (2)	149
C5—H5⋯F2ⁱⁱ	0.95	2.54	3.321 (2)	139
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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.

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Sheldrick, 2008).

Figures top

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

N-(3,4-Difluorophenyl)phthalimide top

Crystal data top

C₁₄H₇F₂NO₂	F(000) = 1056
M_r = 259.21	D_x = 1.579 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5269 reflections
a = 15.101 (3) Å	θ = 1.6–27.9°
b = 5.8093 (12) Å	µ = 0.13 mm⁻¹
c = 24.866 (5) Å	T = 113 K
V = 2181.4 (8) Å³	Prism, colorless
Z = 8	0.20 × 0.10 × 0.08 mm

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1920 independent reflections
Radiation source: rotating anode	1780 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.040
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 1.6°
ω and ϕ scans	h = −17→17
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −6→6
T_min = 0.975, T_max = 0.990	l = −29→20
14468 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.0736P)² + 0.7186P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
1920 reflections	Δρ_max = 0.34 e Å⁻³
173 parameters	Δρ_min = −0.06 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.046 (4)

Crystal data top

C₁₄H₇F₂NO₂	V = 2181.4 (8) Å³
M_r = 259.21	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 15.101 (3) Å	µ = 0.13 mm⁻¹
b = 5.8093 (12) Å	T = 113 K
c = 24.866 (5) Å	0.20 × 0.10 × 0.08 mm

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1920 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1780 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.990	R_int = 0.040
14468 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.03	Δρ_max = 0.34 e Å⁻³
1920 reflections	Δρ_min = −0.06 e Å⁻³
173 parameters

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

	x	y	z	U_iso*/U_eq
F1	0.18581 (6)	0.83152 (17)	0.21976 (4)	0.0398 (3)
F2	0.12250 (7)	0.45784 (18)	0.17125 (4)	0.0409 (3)
O1	0.04193 (7)	0.85824 (18)	0.40561 (4)	0.0289 (3)
O2	0.19778 (7)	0.17995 (18)	0.40802 (4)	0.0282 (3)
N1	0.11557 (7)	0.5119 (2)	0.39257 (5)	0.0217 (3)
C1	0.08090 (9)	0.6931 (2)	0.42336 (6)	0.0221 (4)
C2	0.10111 (9)	0.6332 (3)	0.48041 (6)	0.0223 (4)
C3	0.08065 (10)	0.7479 (3)	0.52755 (6)	0.0277 (4)
H3	0.0499	0.8905	0.5271	0.033*
C4	0.10706 (10)	0.6458 (3)	0.57568 (6)	0.0315 (4)
H4	0.0942	0.7206	0.6087	0.038*
C5	0.15184 (10)	0.4367 (3)	0.57625 (6)	0.0314 (4)
H5	0.1688	0.3708	0.6097	0.038*
C6	0.17221 (10)	0.3224 (3)	0.52856 (6)	0.0276 (4)
H6	0.2028	0.1794	0.5287	0.033*
C7	0.14620 (9)	0.4251 (3)	0.48107 (6)	0.0225 (4)
C8	0.15903 (9)	0.3464 (2)	0.42484 (6)	0.0218 (4)
C9	0.11494 (9)	0.5016 (3)	0.33528 (6)	0.0232 (4)
C10	0.15100 (9)	0.6824 (3)	0.30585 (6)	0.0251 (4)
H10	0.1744	0.8147	0.3232	0.030*
C11	0.15153 (9)	0.6626 (3)	0.25060 (6)	0.0276 (4)
C12	0.11839 (10)	0.4696 (3)	0.22544 (6)	0.0284 (4)
C13	0.08237 (10)	0.2919 (3)	0.25441 (6)	0.0297 (4)
H13	0.0591	0.1601	0.2367	0.036*
C14	0.08046 (9)	0.3082 (3)	0.31032 (6)	0.0262 (4)
H14	0.0557	0.1874	0.3312	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0481 (6)	0.0388 (7)	0.0325 (6)	−0.0077 (5)	0.0028 (4)	0.0079 (4)
F2	0.0557 (7)	0.0463 (7)	0.0206 (5)	0.0059 (5)	−0.0013 (4)	−0.0034 (4)
O1	0.0296 (6)	0.0255 (6)	0.0315 (6)	0.0052 (4)	−0.0016 (4)	0.0006 (4)
O2	0.0294 (6)	0.0246 (6)	0.0305 (6)	0.0059 (4)	−0.0002 (4)	−0.0033 (4)
N1	0.0215 (6)	0.0225 (7)	0.0211 (7)	0.0022 (5)	−0.0005 (4)	−0.0009 (5)
C1	0.0179 (7)	0.0223 (8)	0.0262 (8)	−0.0003 (6)	0.0012 (5)	−0.0009 (6)
C2	0.0189 (7)	0.0235 (8)	0.0247 (8)	−0.0018 (6)	0.0008 (6)	−0.0007 (6)
C3	0.0241 (7)	0.0277 (9)	0.0313 (8)	−0.0013 (6)	0.0036 (6)	−0.0033 (7)
C4	0.0322 (8)	0.0381 (10)	0.0242 (8)	−0.0065 (7)	0.0071 (6)	−0.0039 (7)
C5	0.0334 (8)	0.0366 (10)	0.0242 (8)	−0.0064 (7)	0.0018 (6)	0.0054 (7)
C6	0.0273 (8)	0.0272 (8)	0.0282 (8)	−0.0022 (7)	0.0012 (6)	0.0048 (6)
C7	0.0198 (7)	0.0217 (8)	0.0260 (8)	−0.0027 (6)	0.0018 (6)	−0.0007 (6)
C8	0.0188 (7)	0.0208 (8)	0.0257 (8)	−0.0012 (5)	−0.0009 (6)	0.0003 (6)
C9	0.0194 (7)	0.0265 (8)	0.0236 (8)	0.0034 (6)	−0.0015 (5)	−0.0016 (6)
C10	0.0235 (7)	0.0249 (8)	0.0270 (8)	−0.0010 (6)	−0.0021 (6)	−0.0007 (6)
C11	0.0254 (7)	0.0289 (9)	0.0287 (8)	0.0021 (6)	0.0025 (6)	0.0061 (7)
C12	0.0293 (8)	0.0344 (9)	0.0217 (8)	0.0080 (7)	−0.0011 (6)	−0.0024 (6)
C13	0.0301 (8)	0.0289 (9)	0.0300 (8)	0.0032 (7)	−0.0042 (6)	−0.0070 (7)
C14	0.0248 (7)	0.0248 (8)	0.0289 (8)	0.0006 (6)	−0.0001 (6)	−0.0007 (6)

Geometric parameters (Å, º) top

F1—C11	1.3486 (18)	C5—C6	1.394 (2)
F2—C12	1.3507 (17)	C5—H5	0.9500
O1—C1	1.2088 (17)	C6—C7	1.380 (2)
O2—C8	1.2051 (18)	C6—H6	0.9500
N1—C1	1.4032 (18)	C7—C8	1.484 (2)
N1—C8	1.4139 (18)	C9—C14	1.385 (2)
N1—C9	1.4257 (19)	C9—C10	1.391 (2)
C1—C2	1.4923 (19)	C10—C11	1.379 (2)
C2—C3	1.383 (2)	C10—H10	0.9500
C2—C7	1.388 (2)	C11—C12	1.378 (2)
C3—C4	1.394 (2)	C12—C13	1.371 (2)
C3—H3	0.9500	C13—C14	1.394 (2)
C4—C5	1.390 (3)	C13—H13	0.9500
C4—H4	0.9500	C14—H14	0.9500

C1—N1—C8	111.94 (12)	C2—C7—C8	108.76 (12)
C1—N1—C9	125.04 (12)	O2—C8—N1	125.03 (13)
C8—N1—C9	122.80 (12)	O2—C8—C7	129.63 (13)
O1—C1—N1	125.29 (13)	N1—C8—C7	105.34 (12)
O1—C1—C2	129.18 (13)	C14—C9—C10	121.58 (15)
N1—C1—C2	105.51 (12)	C14—C9—N1	118.96 (14)
C3—C2—C7	121.30 (14)	C10—C9—N1	119.44 (13)
C3—C2—C1	130.35 (14)	C11—C10—C9	117.63 (14)
C7—C2—C1	108.34 (12)	C11—C10—H10	121.2
C2—C3—C4	117.29 (15)	C9—C10—H10	121.2
C2—C3—H3	121.4	F1—C11—C10	120.55 (14)
C4—C3—H3	121.4	F1—C11—C12	118.25 (14)
C5—C4—C3	121.32 (14)	C10—C11—C12	121.19 (14)
C5—C4—H4	119.3	F2—C12—C13	120.28 (14)
C3—C4—H4	119.3	F2—C12—C11	118.50 (14)
C4—C5—C6	121.00 (15)	C13—C12—C11	121.21 (14)
C4—C5—H5	119.5	C12—C13—C14	118.75 (14)
C6—C5—H5	119.5	C12—C13—H13	120.6
C7—C6—C5	117.33 (15)	C14—C13—H13	120.6
C7—C6—H6	121.3	C9—C14—C13	119.63 (14)
C5—C6—H6	121.3	C9—C14—H14	120.2
C6—C7—C2	121.76 (14)	C13—C14—H14	120.2
C6—C7—C8	129.48 (14)

C8—N1—C1—O1	178.83 (13)	C9—N1—C8—C7	178.07 (12)
C9—N1—C1—O1	4.1 (2)	C6—C7—C8—O2	−3.1 (3)
C8—N1—C1—C2	−2.26 (14)	C2—C7—C8—O2	176.76 (14)
C9—N1—C1—C2	−177.01 (12)	C6—C7—C8—N1	177.27 (14)
O1—C1—C2—C3	0.4 (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—C7	179.19 (14)	C8—N1—C9—C14	58.42 (17)
N1—C1—C2—C7	0.34 (15)	C1—N1—C9—C10	54.38 (18)
C7—C2—C3—C4	−0.1 (2)	C8—N1—C9—C10	−119.82 (15)
C1—C2—C3—C4	178.61 (14)	C14—C9—C10—C11	−0.1 (2)
C2—C3—C4—C5	−0.2 (2)	N1—C9—C10—C11	178.06 (12)
C3—C4—C5—C6	0.3 (2)	C9—C10—C11—F1	−179.79 (12)
C4—C5—C6—C7	0.0 (2)	C9—C10—C11—C12	−0.7 (2)
C5—C6—C7—C2	−0.4 (2)	F1—C11—C12—F2	0.6 (2)
C5—C6—C7—C8	179.47 (14)	C10—C11—C12—F2	−178.55 (13)
C3—C2—C7—C6	0.4 (2)	F1—C11—C12—C13	−179.79 (13)
C1—C2—C7—C6	−178.56 (13)	C10—C11—C12—C13	1.1 (2)
C3—C2—C7—C8	−179.47 (13)	F2—C12—C13—C14	179.01 (13)
C1—C2—C7—C8	1.58 (16)	C11—C12—C13—C14	−0.6 (2)
C1—N1—C8—O2	−176.48 (13)	C10—C9—C14—C13	0.6 (2)
C9—N1—C8—O2	−1.6 (2)	N1—C9—C14—C13	−177.63 (12)
C1—N1—C8—C7	3.18 (14)	C12—C13—C14—C9	−0.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···F2ⁱ	0.95	2.47	3.317 (2)	149
C5—H5···F2ⁱⁱ	0.95	2.54	3.321 (2)	139

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

Experimental details

Crystal data
Chemical formula	C₁₄H₇F₂NO₂
M_r	259.21
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	113
a, b, c (Å)	15.101 (3), 5.8093 (12), 24.866 (5)
V (Å³)	2181.4 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.20 × 0.10 × 0.08

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.975, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	14468, 1920, 1780
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.115, 1.03
No. of reflections	1920
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.06

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···F2ⁱ	0.95	2.47	3.317 (2)	149
C5—H5···F2ⁱⁱ	0.95	2.54	3.321 (2)	139

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

Acknowledgements

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).

References

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