The title compound, C
16H
8O
3, 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.
Supporting information
CCDC reference: 709421
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean
(C-C) = 0.005 Å
- R factor = 0.065
- wR factor = 0.158
- Data-to-parameter ratio = 12.7
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for C10 -- C11 .. 8.26 su
Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for C7 -- C9 .. 5.59 su
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5
PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C7 - C9 ... 1.42 Ang.
PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C10 - C11 ... 1.43 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1
C16 H8 O3
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
4 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
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).
5-(2-Phenylethynyl)isobenzofuran-1,3-dione
top
Crystal data top
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 | |
Data collection top
Enraf–Nonius CAD4 diffractometer | Rint = 0.007 |
Radiation source: fine-focus sealed tube | θmax = 25.5°, θmin = 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(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) |
Crystal data top
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)° | |
Data collection top
Enraf–Nonius CAD4 diffractometer | Rint = 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 | Δρmax = 0.22 e Å−3 |
2198 reflections | Δρmin = −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 | 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* | |
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 |
Mr | 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 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.22, −0.21 |
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. |
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).