5-(2-Phenyl­ethyn­yl)isobenzofuran-1,3-dione

Yang, M.-J.; Men, J.; Ma, X.-Y.; Yi, S.-X.; Gao, G.-W.

doi:10.1107/S1600536808028407

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2193

doi:10.1107/S1600536808028407

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5-(2-Phenylethynyl)isobenzofuran-1,3-dione

Mei-Jia Yang,^a Jian Men,^a Xiao-Yan Ma,^b Shi-Xu Yi ^a and Guo-Wei Gao ^a ^*

^aCollege of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China, and ^bCollege of Materials and Chemical Engineering, Chengdu University of Technology, Chengdu 610059, People's Republic of China
^*Correspondence e-mail: gaosunday@yahoo.com.cn

(Received 30 August 2008; accepted 4 September 2008; online 25 October 2008)

The title compound, C₁₆H₈O₃, was synthesized by the Pd-coupling reaction of phenylacetylene with 4-bromophthalic anhydride. The phenyl and isobenzofurane rings are nearly coplanar, forming a dihedral angle of 6.70 (10)°. In the crystal structure, centrosymmetrically related molecules are linked into dimers by C—H⋯O hydrogen bonds.

Related literature

For a general background to the synthesis and applications of the title compound, see: Hergenrother & Smith (1994 , 1996 ); Takekoshi & Terry (1994 ); Urazoe et al. (2005 ); Urazoe & Mori (2006 ). For the properties of polyimides, see: Feger et al. (1989 ); Ghosh & Mittal (1996 ). For the crystal structure of related compounds, see: Wright & Schorzman (2000 ).

Experimental

Crystal data

C₁₆H₈O₃
M_r = 248.22
Triclinic, $[P \overline 1]$
a = 6.998 (3) Å
b = 7.518 (3) Å
c = 11.683 (4) Å
α = 89.06 (2)°
β = 79.31 (3)°
γ = 81.04 (2)°
V = 596.6 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 294 (2) K
0.50 × 0.40 × 0.22 mm

Data collection

Enraf–Nonius CAD4 diffractometer
Absorption correction: none
2227 measured reflections
2198 independent reflections
1105 reflections with I > 2σ(I)
R_int = 0.007
3 standard reflections every 100 reflections intensity decay: 1.8%

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.158
S = 1.09
2198 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.21 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
C16—H16⋯O2ⁱ	0.93	2.56	3.436 (5)	158
Symmetry code: (i) -x, -y+1, -z+1.

Data collection: DIFRAC (Gabe & White, 1993 ); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808028407/rz2241sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808028407/rz2241Isup2.hkl

checkCIF report

Comment top

Polyimides are well known for possessing excellent thermal and oxidative stability, as well as excellent mechanical properties (Ghosh & Mittal, 1996; Feger et al.,1989). The title compound is used as terminal endcapping agent which imparts thermal curability, thermal resistance and solvent resistance to polyimide (Hergenrother & Smith, 1994, 1996; Takekoshi & Terry, 1994). Further, various types of method for producing 4-phenylethynylphthalic anhydride have been described (Urazoe et al., 2005; Urazoe & Mori, 2006). We report here the crystal sturcture of the title compound.

In the molecule of the title compound (Fig. 1) the phenyl and isobenzofurane rings are nearly coplanar, making a dihedral angle of 6.70 (10)°. Bond distances of the ethyne chain show similar values to those in C₂₂H₁₃O₂N (Wright & Schorzman, 2000), with the C7—C9, C9—C10 and C10—C11 distances of 1.418 (4), 1.203 (4) and 1.429 (4) Å, respectively. The bond angles within the ethyne chain are slightly bent, with the C7—C9—C10 and C9—C10—C11 angles of 176.3 (4) and 173.6 (4)°, respectively. The isobenzofurane ring is flat, atoms C2 deviating only by 0.027 (5) Å from the mean plane. In the crystal structure, centrosymmetrically related molecules are linked into dimers by intermolecular C—H···O hydrogen interactions (Table 1).

Related literature top

For a general background to the synthesis and applications of the title compound, see: Hergenrother & Smith (1994, 1996); Takekoshi & Terry (1994); Urazoe et al. (2005); Urazoe & Mori (2006). For the properties of polyimides, see: Feger et al. (1989); Ghosh & Mittal (1996). For the crystal structure of related compounds, see: Wright & Schorzman (2000).

Experimental top

4-Bromophthalic anhydride (5.00 g, 22.0 mmol), phenylacetylene (2.69 g, 26.4 mmol), PdCl₂(PPh₃)₂ (0.11 g, 0.157 mmol), and PPh₃ (0.22 g, 0.840 mmol) were dissolved in 40 ml of dry NEt₃ under argon, and the mixture was heated to 333 K. Then CuI (0.10 g, 0.524 mmol) was added and the solution was stirred at 353 K for 12 h. The precipitated triethylammonium bromide was separated after cooling and the solvent was evaporated. The residue was recrystallized from toluene/n-hexane (1:1 v/v) twice to give 4-phenylethynylphthalic anhydride as pale yellow crystals (yield 83.6%; m.p. 424–425 K). Colourless crystals suitable for X-ray analysis were obtained by slow evaporation of an acetic anhydride solution at room temperature.

Computing details top

Data collection: DIFRAC (Gabe & White, 1993); cell refinement: DIFRAC (Gabe & White, 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.

5-(2-Phenylethynyl)isobenzofuran-1,3-dione top

Crystal data top

C₁₆H₈O₃	Z = 2
M_r = 248.22	F(000) = 256
Triclinic, P1	D_x = 1.382 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.998 (3) Å	Cell parameters from 25 reflections
b = 7.518 (3) Å	θ = 4.5–11.8°
c = 11.683 (4) Å	µ = 0.10 mm⁻¹
α = 89.06 (2)°	T = 294 K
β = 79.31 (3)°	Block, colourless
γ = 81.04 (2)°	0.50 × 0.40 × 0.22 mm
V = 596.6 (4) Å³

Data collection top

Enraf–Nonius CAD4 diffractometer	R_int = 0.007
Radiation source: fine-focus sealed tube	θ_max = 25.5°, θ_min = 2.7°
Graphite monochromator	h = −8→8
ω/2θ scans	k = −3→9
2227 measured reflections	l = −14→14
2198 independent reflections	3 standard reflections every 100 reflections
1105 reflections with I > 2σ(I)	intensity decay: 1.8%

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)] = 0.064	H-atom parameters constrained
wR(F²) = 0.158	w = 1/[σ²(F_o²) + (0.0535P)²] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2198 reflections	Δρ_max = 0.22 e Å⁻³
173 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4'
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (4)

Crystal data top

C₁₆H₈O₃	γ = 81.04 (2)°
M_r = 248.22	V = 596.6 (4) Å³
Triclinic, P1	Z = 2
a = 6.998 (3) Å	Mo Kα radiation
b = 7.518 (3) Å	µ = 0.10 mm⁻¹
c = 11.683 (4) Å	T = 294 K
α = 89.06 (2)°	0.50 × 0.40 × 0.22 mm
β = 79.31 (3)°

Data collection top

Enraf–Nonius CAD4 diffractometer	R_int = 0.007
2227 measured reflections	3 standard reflections every 100 reflections
2198 independent reflections	intensity decay: 1.8%
1105 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 1.09	Δρ_max = 0.22 e Å⁻³
2198 reflections	Δρ_min = −0.21 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 > 2σ(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
O1	0.5201 (3)	0.1623 (3)	0.3262 (2)	0.0689 (8)
O2	0.3130 (4)	0.3047 (4)	0.4814 (2)	0.0912 (10)
O3	0.6535 (3)	0.0590 (3)	0.1454 (2)	0.0814 (9)
C1	0.3406 (5)	0.2634 (5)	0.3814 (4)	0.0655 (11)
C2	0.5145 (5)	0.1372 (5)	0.2089 (4)	0.0621 (10)
C3	0.2138 (5)	0.2980 (4)	0.2931 (3)	0.0484 (9)
C4	0.3202 (4)	0.2205 (4)	0.1897 (3)	0.0489 (9)
C5	0.2391 (5)	0.2304 (4)	0.0913 (3)	0.0604 (10)
H5	0.3096	0.1777	0.0216	0.072*
C6	0.0505 (5)	0.3205 (4)	0.0986 (3)	0.0570 (10)
H6	−0.0073	0.3273	0.0329	0.068*
C7	−0.0562 (4)	0.4021 (4)	0.2025 (3)	0.0505 (9)
C8	0.0267 (5)	0.3885 (4)	0.3023 (3)	0.0521 (9)
H8	−0.0430	0.4392	0.3728	0.062*
C9	−0.2470 (5)	0.5020 (4)	0.2070 (3)	0.0607 (10)
C10	−0.4084 (5)	0.5899 (4)	0.2170 (3)	0.0603 (10)
C11	−0.6025 (4)	0.6902 (4)	0.2426 (3)	0.0534 (9)
C12	−0.7133 (5)	0.7369 (4)	0.1575 (3)	0.0594 (10)
H12	−0.6615	0.7056	0.0801	0.071*
C13	−0.9015 (5)	0.8304 (5)	0.1881 (4)	0.0667 (11)
H13	−0.9752	0.8638	0.1305	0.080*
C14	−0.9807 (5)	0.8744 (5)	0.3007 (4)	0.0697 (11)
H14	−1.1088	0.9354	0.3204	0.084*
C15	−0.8719 (5)	0.8288 (5)	0.3852 (3)	0.0726 (11)
H15	−0.9272	0.8589	0.4624	0.087*
C16	−0.6828 (5)	0.7396 (4)	0.3586 (3)	0.0647 (11)
H16	−0.6088	0.7123	0.4167	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0505 (16)	0.0776 (17)	0.076 (2)	0.0049 (13)	−0.0171 (14)	0.0015 (15)
O2	0.081 (2)	0.137 (3)	0.0513 (18)	0.0076 (17)	−0.0214 (16)	−0.0083 (17)
O3	0.0510 (16)	0.0859 (19)	0.095 (2)	0.0177 (14)	−0.0024 (15)	−0.0271 (16)
C1	0.054 (2)	0.075 (3)	0.065 (3)	0.000 (2)	−0.011 (2)	0.001 (2)
C2	0.056 (3)	0.058 (2)	0.070 (3)	−0.0026 (19)	−0.010 (2)	−0.004 (2)
C3	0.046 (2)	0.049 (2)	0.049 (2)	−0.0002 (16)	−0.0090 (18)	−0.0020 (17)
C4	0.0405 (19)	0.047 (2)	0.056 (2)	0.0001 (15)	−0.0068 (18)	−0.0085 (17)
C5	0.057 (2)	0.061 (2)	0.058 (2)	0.0036 (18)	−0.007 (2)	−0.0159 (19)
C6	0.053 (2)	0.064 (2)	0.051 (2)	0.0041 (18)	−0.0135 (18)	−0.0154 (18)
C7	0.041 (2)	0.050 (2)	0.057 (2)	0.0056 (16)	−0.0105 (18)	−0.0051 (17)
C8	0.044 (2)	0.058 (2)	0.048 (2)	0.0031 (17)	−0.0006 (18)	−0.0095 (17)
C9	0.054 (2)	0.059 (2)	0.068 (3)	−0.004 (2)	−0.013 (2)	−0.0032 (19)
C10	0.061 (2)	0.058 (2)	0.064 (3)	−0.006 (2)	−0.019 (2)	−0.0029 (19)
C11	0.036 (2)	0.0445 (19)	0.076 (3)	0.0035 (16)	−0.009 (2)	−0.0023 (18)
C12	0.058 (2)	0.058 (2)	0.061 (2)	−0.0038 (18)	−0.012 (2)	−0.0039 (18)
C13	0.057 (2)	0.063 (2)	0.085 (3)	−0.005 (2)	−0.028 (2)	−0.003 (2)
C14	0.055 (2)	0.063 (2)	0.083 (3)	0.0072 (19)	−0.006 (2)	−0.014 (2)
C15	0.074 (3)	0.070 (3)	0.066 (3)	0.011 (2)	−0.009 (2)	−0.016 (2)
C16	0.061 (2)	0.067 (3)	0.065 (3)	0.004 (2)	−0.020 (2)	−0.008 (2)

Geometric parameters (Å, º) top

O1—C2	1.395 (4)	C8—H8	0.9300
O1—C1	1.411 (4)	C9—C10	1.203 (4)
O2—C1	1.186 (4)	C10—C11	1.429 (4)
O3—C2	1.187 (4)	C11—C12	1.379 (5)
C1—C3	1.476 (5)	C11—C16	1.399 (4)
C2—C4	1.461 (4)	C12—C13	1.379 (4)
C3—C8	1.365 (4)	C12—H12	0.9300
C3—C4	1.381 (4)	C13—C14	1.354 (4)
C4—C5	1.369 (4)	C13—H13	0.9300
C5—C6	1.375 (4)	C14—C15	1.363 (5)
C5—H5	0.9300	C14—H14	0.9300
C6—C7	1.397 (4)	C15—C16	1.370 (4)
C6—H6	0.9300	C15—H15	0.9300
C7—C8	1.391 (4)	C16—H16	0.9300
C7—C9	1.418 (4)

C2—O1—C1	109.3 (3)	C3—C8—H8	121.2
O2—C1—O1	121.4 (4)	C7—C8—H8	121.2
O2—C1—C3	131.4 (4)	C10—C9—C7	176.3 (4)
O1—C1—C3	107.2 (3)	C9—C10—C11	173.6 (4)
O3—C2—O1	120.3 (3)	C12—C11—C16	119.3 (3)
O3—C2—C4	132.2 (4)	C12—C11—C10	122.3 (3)
O1—C2—C4	107.5 (3)	C16—C11—C10	118.3 (3)
C8—C3—C4	122.4 (3)	C11—C12—C13	119.6 (3)
C8—C3—C1	130.3 (3)	C11—C12—H12	120.2
C4—C3—C1	107.3 (3)	C13—C12—H12	120.2
C5—C4—C3	120.6 (3)	C14—C13—C12	121.0 (4)
C5—C4—C2	130.8 (3)	C14—C13—H13	119.5
C3—C4—C2	108.7 (3)	C12—C13—H13	119.5
C4—C5—C6	118.1 (3)	C13—C14—C15	119.7 (4)
C4—C5—H5	121.0	C13—C14—H14	120.2
C6—C5—H5	121.0	C15—C14—H14	120.2
C5—C6—C7	121.6 (3)	C14—C15—C16	121.3 (4)
C5—C6—H6	119.2	C14—C15—H15	119.3
C7—C6—H6	119.2	C16—C15—H15	119.3
C8—C7—C6	119.8 (3)	C15—C16—C11	119.0 (3)
C8—C7—C9	119.4 (3)	C15—C16—H16	120.5
C6—C7—C9	120.8 (3)	C11—C16—H16	120.5
C3—C8—C7	117.6 (3)

C2—O1—C1—O2	−178.4 (4)	C2—C4—C5—C6	−179.3 (3)
C2—O1—C1—C3	1.8 (4)	C4—C5—C6—C7	0.7 (5)
C1—O1—C2—O3	178.1 (3)	C5—C6—C7—C8	−1.8 (5)
C1—O1—C2—C4	−2.1 (4)	C5—C6—C7—C9	176.9 (3)
O2—C1—C3—C8	0.0 (7)	C4—C3—C8—C7	−0.4 (5)
O1—C1—C3—C8	179.7 (3)	C1—C3—C8—C7	179.1 (3)
O2—C1—C3—C4	179.5 (4)	C6—C7—C8—C3	1.6 (5)
O1—C1—C3—C4	−0.8 (4)	C9—C7—C8—C3	−177.2 (3)
C8—C3—C4—C5	−0.7 (5)	C16—C11—C12—C13	−0.4 (5)
C1—C3—C4—C5	179.7 (3)	C10—C11—C12—C13	178.6 (3)
C8—C3—C4—C2	179.1 (3)	C11—C12—C13—C14	−1.2 (5)
C1—C3—C4—C2	−0.4 (4)	C12—C13—C14—C15	1.3 (6)
O3—C2—C4—C5	1.1 (7)	C13—C14—C15—C16	0.3 (6)
O1—C2—C4—C5	−178.6 (3)	C14—C15—C16—C11	−1.8 (6)
O3—C2—C4—C3	−178.7 (4)	C12—C11—C16—C15	1.9 (5)
O1—C2—C4—C3	1.5 (4)	C10—C11—C16—C15	−177.2 (3)
C3—C4—C5—C6	0.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···O2ⁱ	0.93	2.56	3.436 (5)	158

Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₆H₈O₃
M_r	248.22
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	6.998 (3), 7.518 (3), 11.683 (4)
α, β, γ (°)	89.06 (2), 79.31 (3), 81.04 (2)
V (Å³)	596.6 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.50 × 0.40 × 0.22

Data collection
Diffractometer	Enraf–Nonius CAD4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2227, 2198, 1105
R_int	0.007
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.158, 1.09
No. of reflections	2198
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.21

Computer programs: DIFRAC (Gabe & White, 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···O2ⁱ	0.93	2.56	3.436 (5)	157.7

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

The authors thank Mr Zhi-Hua Mao of Sichuan University for the X-ray data collection.

References

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Feger, C., Khohasteh, M. M. & McGrath, J. E. (1989). Polyimides: Chemistry, Materials, and Characterization. Amsterdam: Elsevier. Google Scholar
Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387. CrossRef CAS Web of Science IUCr Journals Google Scholar
Gabe, E. J. & White, P. S. (1993). DIFRAC. American Crystallographic Association Pittsburgh Meetting,. Abstract PA 104. Google Scholar
Ghosh, M. K. & Mittal, K. L. (1996). Polymides: Fundamentals and Applications. New York: Dekker. Google Scholar
Hergenrother, P. M. & Smith, J. G. Jr (1994). Polymer, 35, 4857–4864. CrossRef CAS Web of Science Google Scholar
Hergenrother, P. M. & Smith, J. G. Jr (1996). US Patent 5 567 800. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Takekoshi, T. & Terry, J. M. (1994). Polymer, 35, 4874–4880. CrossRef CAS Web of Science Google Scholar
Urazoe, D. & Mori, H. (2006). Jpn Patent JP 2 006 151 904. Google Scholar
Urazoe, D., Mori, H. & Yamakawa, K. (2005). US Patent 2 005 215 820. Google Scholar
Wright, M. E. & Schorzman, D. A. (2000). Macromolecules, 33, 8611–8617. Web of Science CrossRef CAS Google Scholar