Acta Cryst. (2008). E64, o2193 [ doi:10.1107/S1600536808028407 ]
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.
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.
H atoms were positioned geometrically (C—H = 0.93 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq (C).
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).
![[Figure 1]](./rz2241fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. |
| C16H8O3 | Z = 2 |
| Mr = 248.22 | F(000) = 256 |
| Triclinic, P1 | Dx = 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 |
| Enraf–Nonius CAD4 diffractometer | Rint = 0.007 |
| Radiation source: fine-focus sealed tube | θmax = 25.5°, θmin = 2.7° |
| graphite | 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 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(Fo2) + (0.0535P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.09 | (Δ/σ)max < 0.001 |
| 2198 reflections | Δρmax = 0.22 e Å−3 |
| 173 parameters | Δρmin = −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) |
| C16H8O3 | γ = 81.04 (2)° |
| Mr = 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)° |
| Enraf–Nonius CAD4 diffractometer | Rint = 0.007 |
| 2227 measured reflections | θmax = 25.5° |
| 2198 independent reflections | 3 standard reflections every 100 reflections |
| 1105 reflections with I > 2σ(I) | intensity decay: 1.8% |
| R[F2 > 2σ(F2)] = 0.064 | H-atom parameters constrained |
| wR(F2) = 0.158 | Δρmax = 0.22 e Å−3 |
| S = 1.09 | Δρmin = −0.21 e Å−3 |
| 2198 reflections | Absolute structure: ? |
| 173 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| 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* |
| 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) |
| 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) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C16—H16···O2i | 0.93 | 2.56 | 3.436 (5) | 158 |
| Symmetry codes: (i) −x, −y+1, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C16—H16···O2i | 0.93 | 2.56 | 3.436 (5) | 158 |
| Symmetry codes: (i) −x, −y+1, −z+1. |
The authors thank Mr Zhi-Hua Mao of Sichuan University for the X-ray data collection.
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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).