N-(2,3,4-Trifluoro­phen­yl)phthalimide

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

doi:10.1107/S1600536810024177

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1859

doi:10.1107/S1600536810024177

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N-(2,3,4-Trifluorophenyl)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 30 June 2010)

In the title compound, C₁₄H₆F₃NO₂, the benzene ring and the phthalimide ring system make a dihedral angle of 60.12 (7)°. Weak intermolecular C—H⋯O and C—H⋯F hydrogen bonds are present in the crystal structure.

Related literature

The title compound is a key 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 related structures, see: Xu et al. (2006 ); Fu et al. (2010 ).

Experimental

Crystal data

C₁₄H₆F₃NO₂
M_r = 277.20
Monoclinic, P 2₁ /n
a = 6.8422 (14) Å
b = 21.082 (4) Å
c = 7.9727 (16) Å
β = 101.98 (3)°
V = 1125.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.12 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.972, T_max = 0.983
8049 measured reflections
1980 independent reflections
1603 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.094
S = 1.03
1980 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O2ⁱ	0.95	2.55	3.1855 (18)	124
C10—H10⋯F1ⁱⁱ	0.95	2.54	3.3647 (18)	145
C11—H11⋯O1ⁱⁱⁱ	0.95	2.55	3.428 (2)	154
Symmetry codes: (i) x, y, z-1; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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/S1600536810024177/ng2787sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810024177/ng2787Isup2.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, two rings are nearly planar, but the molecule as a whole is not planar. The dihedral angle between the benzene ring and the phthalimide plane is 60.12 (7) °, which is similar to 59.95 (4) ° found in a related compound N-(2-fluorophenyl)phthalimide (Xu et al. 2006). Weak intermolecular C—H···O and C—H···F hydrogen bonding are present in the crystal structure (Table 1).

Related literature top

The title compound is a key 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 related structures, see: Xu et al. (2006); Fu et al. (2010).

Experimental top

An acetic acid solution of phthalic anhydride (14.8 g, 100 mmol) and 2,3,4-trifluoroaniline (10.55 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-(2,3,4-Trifluorophenyl)phthalimide top

Crystal data top

C₁₄H₆F₃NO₂	F(000) = 560
M_r = 277.20	D_x = 1.637 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3644 reflections
a = 6.8422 (14) Å	θ = 1.9–27.8°
b = 21.082 (4) Å	µ = 0.14 mm⁻¹
c = 7.9727 (16) Å	T = 113 K
β = 101.98 (3)°	Prism, colorless
V = 1125.0 (4) Å³	0.20 × 0.18 × 0.12 mm
Z = 4

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1980 independent reflections
Radiation source: rotating anode	1603 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.034
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 1.9°
ω and ϕ scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −24→25
T_min = 0.972, T_max = 0.983	l = −7→9
8049 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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0663P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.002
1980 reflections	Δρ_max = 0.34 e Å⁻³
182 parameters	Δρ_min = −0.21 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: 0.097 (6)

Crystal data top

C₁₄H₆F₃NO₂	V = 1125.0 (4) Å³
M_r = 277.20	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.8422 (14) Å	µ = 0.14 mm⁻¹
b = 21.082 (4) Å	T = 113 K
c = 7.9727 (16) Å	0.20 × 0.18 × 0.12 mm
β = 101.98 (3)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1980 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1603 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.983	R_int = 0.034
8049 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.03	Δρ_max = 0.34 e Å⁻³
1980 reflections	Δρ_min = −0.21 e Å⁻³
182 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	0.36805 (13)	0.27803 (5)	1.30697 (12)	0.0324 (3)
F2	0.04277 (12)	0.20200 (5)	1.25161 (11)	0.0286 (3)
F3	0.00346 (11)	0.10870 (4)	1.01757 (10)	0.0245 (3)
O1	0.29321 (15)	0.14544 (5)	0.58108 (12)	0.0246 (3)
O2	0.28164 (15)	0.00092 (5)	1.01024 (12)	0.0228 (3)
N1	0.28999 (17)	0.08556 (6)	0.82561 (14)	0.0181 (3)
C1	0.28328 (19)	0.09456 (7)	0.64828 (17)	0.0176 (3)
C2	0.26306 (18)	0.02990 (7)	0.57338 (17)	0.0162 (3)
C3	0.2489 (2)	0.01067 (7)	0.40531 (18)	0.0193 (4)
H3	0.2475	0.0406	0.3160	0.023*
C4	0.23668 (19)	−0.05431 (8)	0.37222 (18)	0.0214 (4)
H4	0.2272	−0.0690	0.2582	0.026*
C5	0.2381 (2)	−0.09816 (8)	0.50331 (18)	0.0231 (4)
H5	0.2302	−0.1422	0.4771	0.028*
C6	0.2507 (2)	−0.07859 (7)	0.67177 (18)	0.0200 (3)
H6	0.2510	−0.1083	0.7613	0.024*
C7	0.26293 (18)	−0.01410 (7)	0.70366 (16)	0.0161 (3)
C8	0.27847 (19)	0.02073 (7)	0.86743 (17)	0.0168 (3)
C9	0.31396 (19)	0.13524 (7)	0.94859 (17)	0.0175 (3)
C10	0.4794 (2)	0.17526 (7)	0.97522 (18)	0.0216 (4)
H10	0.5796	0.1693	0.9102	0.026*
C11	0.4998 (2)	0.22367 (8)	1.09549 (19)	0.0240 (4)
H11	0.6125	0.2510	1.1129	0.029*
C12	0.3538 (2)	0.23125 (7)	1.18896 (18)	0.0225 (4)
C13	0.1879 (2)	0.19236 (8)	1.16429 (18)	0.0207 (4)
C14	0.16934 (19)	0.14500 (7)	1.04425 (17)	0.0181 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0371 (5)	0.0252 (6)	0.0336 (5)	−0.0042 (4)	0.0044 (4)	−0.0152 (4)
F2	0.0289 (5)	0.0319 (6)	0.0280 (5)	0.0003 (4)	0.0132 (4)	−0.0096 (4)
F3	0.0213 (5)	0.0273 (6)	0.0262 (5)	−0.0077 (4)	0.0080 (3)	−0.0059 (4)
O1	0.0342 (6)	0.0189 (7)	0.0220 (6)	0.0039 (5)	0.0086 (4)	0.0058 (4)
O2	0.0300 (6)	0.0236 (7)	0.0159 (5)	−0.0026 (4)	0.0072 (4)	0.0024 (4)
N1	0.0239 (6)	0.0158 (7)	0.0156 (6)	−0.0014 (5)	0.0062 (5)	−0.0003 (5)
C1	0.0159 (7)	0.0224 (9)	0.0150 (7)	0.0029 (6)	0.0044 (6)	0.0032 (6)
C2	0.0126 (6)	0.0191 (9)	0.0172 (7)	0.0018 (6)	0.0039 (5)	0.0014 (6)
C3	0.0164 (7)	0.0271 (10)	0.0145 (7)	0.0022 (6)	0.0030 (5)	0.0015 (6)
C4	0.0175 (7)	0.0288 (10)	0.0177 (7)	0.0014 (6)	0.0029 (6)	−0.0041 (6)
C5	0.0228 (8)	0.0215 (9)	0.0253 (8)	−0.0002 (6)	0.0053 (6)	−0.0065 (6)
C6	0.0210 (7)	0.0184 (9)	0.0209 (8)	0.0001 (6)	0.0047 (6)	0.0006 (6)
C7	0.0139 (7)	0.0190 (9)	0.0157 (7)	0.0007 (6)	0.0035 (5)	−0.0001 (5)
C8	0.0157 (7)	0.0179 (9)	0.0176 (7)	0.0003 (6)	0.0051 (5)	0.0010 (6)
C9	0.0216 (7)	0.0165 (9)	0.0141 (7)	0.0006 (6)	0.0027 (6)	0.0007 (6)
C10	0.0222 (7)	0.0198 (9)	0.0242 (8)	−0.0010 (6)	0.0076 (6)	0.0027 (6)
C11	0.0229 (8)	0.0199 (9)	0.0280 (8)	−0.0045 (6)	0.0025 (6)	0.0012 (6)
C12	0.0285 (8)	0.0165 (9)	0.0200 (7)	0.0011 (6)	−0.0003 (6)	−0.0041 (6)
C13	0.0215 (7)	0.0233 (9)	0.0181 (7)	0.0027 (6)	0.0058 (6)	0.0008 (6)
C14	0.0172 (7)	0.0180 (9)	0.0179 (7)	−0.0029 (6)	0.0011 (6)	0.0005 (6)

Geometric parameters (Å, º) top

F1—C12	1.3525 (17)	C4—H4	0.9500
F2—C13	1.3411 (17)	C5—C6	1.390 (2)
F3—C14	1.3486 (16)	C5—H5	0.9500
O1—C1	1.2072 (18)	C6—C7	1.382 (2)
O2—C8	1.2087 (16)	C6—H6	0.9500
N1—C8	1.4129 (19)	C7—C8	1.4824 (19)
N1—C1	1.4178 (17)	C9—C14	1.384 (2)
N1—C9	1.4207 (18)	C9—C10	1.392 (2)
C1—C2	1.483 (2)	C10—C11	1.387 (2)
C2—C3	1.3840 (19)	C10—H10	0.9500
C2—C7	1.3927 (19)	C11—C12	1.374 (2)
C3—C4	1.394 (2)	C11—H11	0.9500
C3—H3	0.9500	C12—C13	1.381 (2)
C4—C5	1.394 (2)	C13—C14	1.371 (2)

C8—N1—C1	111.90 (11)	C2—C7—C8	108.41 (13)
C8—N1—C9	123.66 (11)	O2—C8—N1	124.44 (13)
C1—N1—C9	124.39 (12)	O2—C8—C7	129.98 (14)
O1—C1—N1	124.63 (13)	N1—C8—C7	105.58 (11)
O1—C1—C2	130.33 (13)	C14—C9—C10	118.52 (13)
N1—C1—C2	105.04 (12)	C14—C9—N1	119.76 (12)
C3—C2—C7	121.07 (14)	C10—C9—N1	121.72 (12)
C3—C2—C1	129.87 (13)	C11—C10—C9	120.87 (13)
C7—C2—C1	109.05 (12)	C11—C10—H10	119.6
C2—C3—C4	117.42 (13)	C9—C10—H10	119.6
C2—C3—H3	121.3	C12—C11—C10	118.70 (14)
C4—C3—H3	121.3	C12—C11—H11	120.7
C5—C4—C3	121.26 (14)	C10—C11—H11	120.7
C5—C4—H4	119.4	F1—C12—C11	120.43 (13)
C3—C4—H4	119.4	F1—C12—C13	118.06 (13)
C6—C5—C4	121.12 (15)	C11—C12—C13	121.50 (14)
C6—C5—H5	119.5	F2—C13—C14	120.11 (13)
C4—C5—H5	119.5	F2—C13—C12	120.76 (13)
C7—C6—C5	117.30 (14)	C14—C13—C12	119.08 (13)
C7—C6—H6	121.3	F3—C14—C13	118.45 (12)
C5—C6—H6	121.3	F3—C14—C9	120.21 (12)
C6—C7—C2	121.82 (13)	C13—C14—C9	121.32 (13)
C6—C7—C8	129.77 (13)

C8—N1—C1—O1	−179.01 (13)	C2—C7—C8—O2	179.32 (13)
C9—N1—C1—O1	−1.5 (2)	C6—C7—C8—N1	178.93 (13)
C8—N1—C1—C2	0.83 (14)	C2—C7—C8—N1	−0.75 (14)
C9—N1—C1—C2	178.32 (11)	C8—N1—C9—C14	−61.69 (18)
O1—C1—C2—C3	−0.5 (2)	C1—N1—C9—C14	121.12 (15)
N1—C1—C2—C3	179.72 (13)	C8—N1—C9—C10	118.90 (15)
O1—C1—C2—C7	178.52 (14)	C1—N1—C9—C10	−58.29 (18)
N1—C1—C2—C7	−1.30 (14)	C14—C9—C10—C11	0.3 (2)
C7—C2—C3—C4	−0.67 (19)	N1—C9—C10—C11	179.76 (13)
C1—C2—C3—C4	178.21 (12)	C9—C10—C11—C12	0.3 (2)
C2—C3—C4—C5	0.2 (2)	C10—C11—C12—F1	−179.77 (13)
C3—C4—C5—C6	0.3 (2)	C10—C11—C12—C13	−0.7 (2)
C4—C5—C6—C7	−0.34 (19)	F1—C12—C13—F2	1.9 (2)
C5—C6—C7—C2	−0.13 (19)	C11—C12—C13—F2	−177.27 (13)
C5—C6—C7—C8	−179.77 (13)	F1—C12—C13—C14	179.41 (13)
C3—C2—C7—C6	0.7 (2)	C11—C12—C13—C14	0.3 (2)
C1—C2—C7—C6	−178.43 (12)	F2—C13—C14—F3	−0.3 (2)
C3—C2—C7—C8	−179.64 (11)	C12—C13—C14—F3	−177.88 (12)
C1—C2—C7—C8	1.28 (14)	F2—C13—C14—C9	178.01 (12)
C1—N1—C8—O2	179.85 (12)	C12—C13—C14—C9	0.4 (2)
C9—N1—C8—O2	2.3 (2)	C10—C9—C14—F3	177.54 (12)
C1—N1—C8—C7	−0.09 (14)	N1—C9—C14—F3	−1.9 (2)
C9—N1—C8—C7	−177.60 (11)	C10—C9—C14—C13	−0.7 (2)
C6—C7—C8—O2	−1.0 (2)	N1—C9—C14—C13	179.83 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2ⁱ	0.95	2.55	3.1855 (18)	124
C10—H10···F1ⁱⁱ	0.95	2.54	3.3647 (18)	145
C11—H11···O1ⁱⁱⁱ	0.95	2.55	3.428 (2)	154

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

Experimental details

Crystal data
Chemical formula	C₁₄H₆F₃NO₂
M_r	277.20
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	6.8422 (14), 21.082 (4), 7.9727 (16)
β (°)	101.98 (3)
V (Å³)	1125.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.20 × 0.18 × 0.12

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.972, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	8049, 1980, 1603
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.094, 1.03
No. of reflections	1980
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.21

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···O2ⁱ	0.95	2.55	3.1855 (18)	124
C10—H10···F1ⁱⁱ	0.95	2.54	3.3647 (18)	145
C11—H11···O1ⁱⁱⁱ	0.95	2.55	3.428 (2)	154

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