Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106008262/gg3004sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106008262/gg3004Isup2.hkl |
CCDC reference: 295896
Pentacene-6,13-dione (5.00 g, 16.2 mmol) was dissolved in freshly distilled diethyl ether (50 ml) and the solution was added to a mixture of (triisopropylsilyl)ethyne (6.00 ml, 4.88 g, 26.7 mmol) and n-BuLi (5 ml, 1.6 M in tetrahydrofuran, 8 mmol) in tetrahydrofuran (10 ml). The mixture was stirred at room temperature under nitrogen for 24 h, and then the solvent was removed in vacuo and the residue purified by chromatography over silica gel (hexanes–CHCl3 1:1) to give 13-hydroxy-13-[(triisopropylsilyl)ethynyl]pentacen-6(13H)-one, (I), as a green solid (5.50 g, 69.2%; m.p. > 673 K), together with some 6,13-bis[(triisopropylsilyl)ethynyl]pentacene (1.26 g, 11.7%). Spectroscopic analysis: 1H NMR (250 MHz, CDCl3, 297 K, δ, p.p.m.): 8.811 (HP5,7, s, 2H), 8.722 (HP12,14, s, 2H), 8.03 (HP4,8, d, 2H, J = 8.2 Hz), 7.92 (HP1,11, d, 2H, J = 8.2 Hz), 7.62 (HP2,10, d, 2H, J = 8.2, 6.8 and 1.3 Hz), 7.60 (HP3,9, d, 2H, J = 8.2, 6.8 and 1.3 Hz), 1.78 (HTIPS, m, 3H), 1.15 (HTIPS, m, 18H); 13C NMR (CDCl3, 62.5 MHz, 297 K, δ, p.p.m.): 206.9, 138.8, 135.6, 132.8, 129.7, 129.6, 128.9, 128.6, 128.2, 127.3, 127.2, 108.2, 90.0, 68.6, 18.6, 11.2; EIMS: m/z 474.1 [M+H]+; UV–VIS (nm): 266, 276, 320, 356; Emission (nm): 434 (λex 356 nm).
Hydroxy atom H1 was located in a difference map and refined freely. All other H atoms were treated as riding, with C—H distances of 1.00 Å and with Uiso(H) = 1.5Ueq(C). [Please check added text]
Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CRYSTALS.
C33H34O2Si | Z = 2 |
Mr = 490.72 | F(000) = 524 |
Triclinic, P1 | Dx = 1.201 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.8875 (3) Å | Cell parameters from 5830 reflections |
b = 8.9910 (3) Å | θ = 1–27° |
c = 17.6023 (7) Å | µ = 0.11 mm−1 |
α = 90.406 (2)° | T = 173 K |
β = 92.2227 (19)° | Plate, colourless |
γ = 105.032 (2)° | 0.40 × 0.34 × 0.02 mm |
V = 1357.19 (9) Å3 |
Nonius Kappa area-detector CCD diffractometer | 3673 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.015 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997) | h = −11→11 |
Tmin = 0.96, Tmax = 1.00 | k = −11→11 |
11207 measured reflections | l = −22→22 |
6138 independent reflections |
Refinement on F | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.064 | w = 1/[σ(F) + 0.04P] where P = [max(Fo,0) + 2Fc]/3 |
S = 1.07 | (Δ/σ)max = 0.000204 |
3673 reflections | Δρmax = 0.30 e Å−3 |
329 parameters | Δρmin = −0.22 e Å−3 |
2 restraints |
C33H34O2Si | γ = 105.032 (2)° |
Mr = 490.72 | V = 1357.19 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.8875 (3) Å | Mo Kα radiation |
b = 8.9910 (3) Å | µ = 0.11 mm−1 |
c = 17.6023 (7) Å | T = 173 K |
α = 90.406 (2)° | 0.40 × 0.34 × 0.02 mm |
β = 92.2227 (19)° |
Nonius Kappa area-detector CCD diffractometer | 6138 independent reflections |
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997) | 3673 reflections with I > 3σ(I) |
Tmin = 0.96, Tmax = 1.00 | Rint = 0.015 |
11207 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 2 restraints |
wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.30 e Å−3 |
3673 reflections | Δρmin = −0.22 e Å−3 |
329 parameters |
x | y | z | Uiso*/Ueq | ||
Si1 | 0.67081 (8) | 0.77144 (8) | 0.34415 (4) | 0.0337 | |
O1 | 1.05215 (18) | 0.75981 (18) | 0.13917 (10) | 0.0347 | |
O2 | 0.8191 (2) | 0.23865 (19) | 0.00023 (10) | 0.0411 | |
C1 | 0.7094 (3) | 0.6404 (3) | 0.42131 (15) | 0.0482 | |
C2 | 0.6365 (5) | 0.4710 (4) | 0.4004 (2) | 0.0794 | |
C3 | 0.8841 (4) | 0.6686 (5) | 0.4409 (2) | 0.0775 | |
C4 | 0.7663 (3) | 0.9783 (3) | 0.37053 (16) | 0.0464 | |
C5 | 0.7399 (4) | 1.0248 (4) | 0.45210 (19) | 0.0643 | |
C6 | 0.7254 (4) | 1.0935 (3) | 0.31480 (19) | 0.0573 | |
C7 | 0.4566 (3) | 0.7267 (3) | 0.31777 (14) | 0.0339 | |
C8 | 0.3618 (3) | 0.7656 (3) | 0.38301 (16) | 0.0445 | |
C9 | 0.4186 (3) | 0.8003 (3) | 0.24335 (15) | 0.0437 | |
C10 | 0.7644 (3) | 0.7220 (3) | 0.25978 (14) | 0.0346 | |
C11 | 0.8276 (3) | 0.6826 (3) | 0.20661 (14) | 0.0325 | |
C12 | 0.9130 (3) | 0.6359 (3) | 0.14352 (13) | 0.0309 | |
C13 | 0.8160 (3) | 0.6219 (3) | 0.06896 (14) | 0.0325 | |
C14 | 0.7609 (3) | 0.7449 (3) | 0.04626 (14) | 0.0359 | |
C15 | 0.6725 (3) | 0.7404 (3) | −0.02269 (14) | 0.0358 | |
C16 | 0.6140 (3) | 0.8663 (3) | −0.04628 (16) | 0.0449 | |
C17 | 0.5245 (3) | 0.8552 (3) | −0.11228 (16) | 0.0481 | |
C18 | 0.4908 (3) | 0.7209 (3) | −0.15789 (16) | 0.0495 | |
C19 | 0.5461 (3) | 0.5987 (3) | −0.13749 (15) | 0.0430 | |
C20 | 0.6382 (3) | 0.6051 (3) | −0.06913 (14) | 0.0364 | |
C21 | 0.6963 (3) | 0.4807 (3) | −0.04522 (14) | 0.0352 | |
C22 | 0.7836 (3) | 0.4872 (3) | 0.02178 (13) | 0.0318 | |
C23 | 0.8420 (3) | 0.3531 (3) | 0.04289 (14) | 0.0331 | |
C24 | 0.9284 (3) | 0.3572 (3) | 0.11640 (14) | 0.0317 | |
C25 | 0.9820 (3) | 0.2311 (3) | 0.13689 (15) | 0.0354 | |
C26 | 1.0618 (3) | 0.2265 (3) | 0.20697 (15) | 0.0360 | |
C27 | 1.1146 (3) | 0.0965 (3) | 0.22980 (17) | 0.0427 | |
C28 | 1.1856 (3) | 0.0943 (3) | 0.29933 (18) | 0.0486 | |
C29 | 1.2097 (3) | 0.2221 (3) | 0.34961 (17) | 0.0477 | |
C30 | 1.1623 (3) | 0.3492 (3) | 0.32941 (16) | 0.0432 | |
C31 | 1.0875 (3) | 0.3559 (3) | 0.25764 (15) | 0.0363 | |
C32 | 1.0347 (3) | 0.4851 (3) | 0.23450 (14) | 0.0347 | |
C33 | 0.9578 (3) | 0.4879 (3) | 0.16589 (14) | 0.0314 | |
H1 | 1.097 (3) | 0.752 (3) | 0.0919 (9) | 0.058 (7)* | |
H11 | 0.6590 | 0.6645 | 0.4680 | 0.0608* | |
H21 | 0.6592 | 0.4050 | 0.4426 | 0.0972* | |
H22 | 0.6817 | 0.4443 | 0.3526 | 0.0972* | |
H23 | 0.5211 | 0.4528 | 0.3924 | 0.0972* | |
H31 | 0.9000 | 0.5972 | 0.4819 | 0.0980* | |
H32 | 0.9279 | 0.7776 | 0.4588 | 0.0980* | |
H33 | 0.9385 | 0.6492 | 0.3946 | 0.0980* | |
H41 | 0.8811 | 0.9911 | 0.3677 | 0.0539* | |
H51 | 0.7943 | 1.1359 | 0.4615 | 0.0746* | |
H52 | 0.7822 | 0.9603 | 0.4890 | 0.0746* | |
H53 | 0.6256 | 1.0085 | 0.4589 | 0.0746* | |
H61 | 0.7801 | 1.2008 | 0.3321 | 0.0668* | |
H62 | 0.6101 | 1.0809 | 0.3130 | 0.0668* | |
H63 | 0.7591 | 1.0741 | 0.2629 | 0.0668* | |
H71 | 0.4205 | 0.6127 | 0.3092 | 0.0404* | |
H81 | 0.2489 | 0.7401 | 0.3666 | 0.0538* | |
H82 | 0.3992 | 0.8778 | 0.3962 | 0.0538* | |
H83 | 0.3758 | 0.7038 | 0.4285 | 0.0538* | |
H91 | 0.3031 | 0.7716 | 0.2330 | 0.0526* | |
H92 | 0.4577 | 0.9148 | 0.2482 | 0.0526* | |
H93 | 0.4701 | 0.7624 | 0.2005 | 0.0526* | |
H141 | 0.7841 | 0.8397 | 0.0793 | 0.0412* | |
H161 | 0.6381 | 0.9629 | −0.0145 | 0.0519* | |
H171 | 0.4830 | 0.9440 | −0.1282 | 0.0567* | |
H181 | 0.4255 | 0.7149 | −0.2059 | 0.0566* | |
H191 | 0.5214 | 0.5039 | −0.1706 | 0.0492* | |
H211 | 0.6733 | 0.3850 | −0.0777 | 0.0398* | |
H251 | 0.9628 | 0.1408 | 0.1010 | 0.0415* | |
H271 | 1.0987 | 0.0057 | 0.1945 | 0.0520* | |
H281 | 1.2213 | 0.0019 | 0.3150 | 0.0580* | |
H291 | 1.2625 | 0.2194 | 0.4006 | 0.0562* | |
H301 | 1.1805 | 0.4387 | 0.3657 | 0.0505* | |
H321 | 1.0546 | 0.5769 | 0.2694 | 0.0406* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1 | 0.0307 (4) | 0.0414 (4) | 0.0299 (4) | 0.0107 (3) | 0.0037 (3) | −0.0042 (3) |
O1 | 0.0320 (9) | 0.0325 (9) | 0.0343 (10) | −0.0012 (7) | 0.0047 (7) | −0.0081 (7) |
O2 | 0.0432 (10) | 0.0371 (10) | 0.0391 (11) | 0.0029 (8) | 0.0069 (8) | −0.0140 (8) |
C1 | 0.0516 (17) | 0.0682 (19) | 0.0318 (15) | 0.0278 (14) | 0.0047 (12) | 0.0054 (13) |
C2 | 0.111 (3) | 0.063 (2) | 0.071 (2) | 0.034 (2) | −0.001 (2) | 0.0235 (18) |
C3 | 0.065 (2) | 0.127 (3) | 0.054 (2) | 0.051 (2) | −0.0079 (17) | 0.007 (2) |
C4 | 0.0334 (14) | 0.0525 (17) | 0.0494 (17) | 0.0042 (12) | 0.0066 (12) | −0.0162 (13) |
C5 | 0.065 (2) | 0.065 (2) | 0.056 (2) | 0.0065 (16) | 0.0051 (16) | −0.0272 (16) |
C6 | 0.0535 (18) | 0.0390 (16) | 0.074 (2) | −0.0006 (13) | 0.0164 (16) | −0.0026 (15) |
C7 | 0.0309 (12) | 0.0355 (13) | 0.0351 (14) | 0.0078 (10) | 0.0041 (10) | −0.0012 (10) |
C8 | 0.0355 (14) | 0.0529 (16) | 0.0471 (17) | 0.0140 (12) | 0.0099 (12) | 0.0001 (13) |
C9 | 0.0377 (14) | 0.0531 (16) | 0.0405 (16) | 0.0125 (12) | −0.0015 (12) | 0.0004 (12) |
C10 | 0.0294 (12) | 0.0394 (14) | 0.0356 (15) | 0.0098 (10) | 0.0035 (11) | −0.0035 (11) |
C11 | 0.0298 (12) | 0.0320 (12) | 0.0340 (14) | 0.0054 (10) | −0.0003 (10) | −0.0030 (10) |
C12 | 0.0264 (11) | 0.0306 (12) | 0.0324 (13) | 0.0015 (9) | 0.0039 (10) | −0.0073 (10) |
C13 | 0.0273 (12) | 0.0320 (13) | 0.0340 (14) | 0.0000 (9) | 0.0054 (10) | −0.0055 (10) |
C14 | 0.0362 (13) | 0.0350 (13) | 0.0328 (14) | 0.0026 (10) | 0.0037 (11) | −0.0070 (10) |
C15 | 0.0305 (12) | 0.0392 (14) | 0.0336 (14) | 0.0008 (10) | 0.0073 (10) | 0.0007 (11) |
C16 | 0.0472 (16) | 0.0421 (15) | 0.0423 (16) | 0.0056 (12) | 0.0028 (13) | 0.0014 (12) |
C17 | 0.0484 (16) | 0.0511 (17) | 0.0427 (17) | 0.0088 (13) | 0.0022 (13) | 0.0103 (13) |
C18 | 0.0416 (16) | 0.0652 (19) | 0.0361 (16) | 0.0039 (13) | −0.0005 (12) | 0.0070 (14) |
C19 | 0.0372 (14) | 0.0512 (16) | 0.0353 (15) | 0.0019 (12) | 0.0044 (12) | −0.0022 (12) |
C20 | 0.0287 (12) | 0.0406 (14) | 0.0334 (14) | −0.0032 (10) | 0.0067 (10) | −0.0022 (11) |
C21 | 0.0296 (12) | 0.0397 (13) | 0.0309 (14) | −0.0015 (10) | 0.0073 (10) | −0.0087 (10) |
C22 | 0.0250 (12) | 0.0347 (13) | 0.0307 (13) | −0.0017 (9) | 0.0073 (10) | −0.0074 (10) |
C23 | 0.0277 (12) | 0.0327 (13) | 0.0343 (14) | −0.0015 (9) | 0.0115 (10) | −0.0082 (10) |
C24 | 0.0245 (11) | 0.0314 (12) | 0.0353 (14) | −0.0008 (9) | 0.0102 (10) | −0.0063 (10) |
C25 | 0.0311 (12) | 0.0296 (13) | 0.0423 (15) | 0.0012 (10) | 0.0097 (11) | −0.0100 (11) |
C26 | 0.0276 (12) | 0.0308 (13) | 0.0465 (16) | 0.0011 (10) | 0.0099 (11) | −0.0051 (11) |
C27 | 0.0380 (14) | 0.0309 (13) | 0.0588 (19) | 0.0073 (11) | 0.0108 (13) | −0.0042 (12) |
C28 | 0.0459 (16) | 0.0393 (15) | 0.062 (2) | 0.0135 (12) | 0.0036 (14) | 0.0067 (13) |
C29 | 0.0471 (16) | 0.0432 (16) | 0.0513 (18) | 0.0096 (12) | −0.0024 (13) | 0.0034 (13) |
C30 | 0.0439 (15) | 0.0377 (14) | 0.0456 (17) | 0.0067 (11) | 0.0004 (12) | −0.0049 (12) |
C31 | 0.0307 (13) | 0.0323 (13) | 0.0435 (15) | 0.0036 (10) | 0.0054 (11) | −0.0034 (11) |
C32 | 0.0340 (13) | 0.0290 (12) | 0.0388 (15) | 0.0045 (10) | 0.0013 (11) | −0.0086 (10) |
C33 | 0.0258 (12) | 0.0307 (12) | 0.0353 (14) | 0.0024 (9) | 0.0072 (10) | −0.0071 (10) |
Si1—C1 | 1.883 (3) | C12—C33 | 1.535 (3) |
Si1—C4 | 1.880 (3) | C13—C14 | 1.376 (3) |
Si1—C7 | 1.880 (2) | C13—C22 | 1.424 (3) |
Si1—C10 | 1.837 (2) | C14—C15 | 1.415 (3) |
O1—C12 | 1.439 (3) | C14—H141 | 1.000 |
O1—H1 | 0.944 (10) | C15—C16 | 1.421 (4) |
O2—C23 | 1.238 (3) | C15—C20 | 1.420 (3) |
C1—C2 | 1.529 (5) | C16—C17 | 1.370 (4) |
C1—C3 | 1.532 (4) | C16—H161 | 1.000 |
C1—H11 | 1.000 | C17—C18 | 1.405 (4) |
C2—H21 | 1.000 | C17—H171 | 1.000 |
C2—H22 | 1.000 | C18—C19 | 1.359 (4) |
C2—H23 | 1.000 | C18—H181 | 1.000 |
C3—H31 | 1.000 | C19—C20 | 1.421 (4) |
C3—H32 | 1.000 | C19—H191 | 1.000 |
C3—H33 | 1.000 | C20—C21 | 1.409 (4) |
C4—C5 | 1.536 (4) | C21—C22 | 1.379 (3) |
C4—C6 | 1.533 (4) | C21—H211 | 1.000 |
C4—H41 | 1.000 | C22—C23 | 1.476 (3) |
C5—H51 | 1.000 | C23—C24 | 1.474 (3) |
C5—H52 | 1.000 | C24—C25 | 1.384 (3) |
C5—H53 | 1.000 | C24—C33 | 1.420 (3) |
C6—H61 | 1.000 | C25—C26 | 1.405 (4) |
C6—H62 | 1.000 | C25—H251 | 1.000 |
C6—H63 | 1.000 | C26—C27 | 1.422 (3) |
C7—C8 | 1.540 (3) | C26—C31 | 1.426 (3) |
C7—C9 | 1.536 (3) | C27—C28 | 1.358 (4) |
C7—H71 | 1.000 | C27—H271 | 1.000 |
C8—H81 | 1.000 | C28—C29 | 1.412 (4) |
C8—H82 | 1.000 | C28—H281 | 1.000 |
C8—H83 | 1.000 | C29—C30 | 1.361 (4) |
C9—H91 | 1.000 | C29—H291 | 1.000 |
C9—H92 | 1.000 | C30—C31 | 1.413 (4) |
C9—H93 | 1.000 | C30—H301 | 1.000 |
C10—C11 | 1.206 (3) | C31—C32 | 1.418 (3) |
C11—C12 | 1.486 (3) | C32—C33 | 1.368 (3) |
C12—C13 | 1.528 (3) | C32—H321 | 1.000 |
C1—Si1—C4 | 110.52 (14) | C11—C12—C33 | 108.54 (19) |
C1—Si1—C7 | 110.67 (12) | O1—C12—C33 | 109.28 (18) |
C4—Si1—C7 | 115.38 (12) | C13—C12—C33 | 114.05 (18) |
C1—Si1—C10 | 105.87 (12) | C12—C13—C14 | 118.7 (2) |
C4—Si1—C10 | 107.88 (11) | C12—C13—C22 | 122.1 (2) |
C7—Si1—C10 | 105.95 (11) | C14—C13—C22 | 119.2 (2) |
C12—O1—H1 | 108.5 (18) | C13—C14—C15 | 121.6 (2) |
Si1—C1—C2 | 111.6 (2) | C13—C14—H141 | 119.2 |
Si1—C1—C3 | 111.7 (2) | C15—C14—H141 | 119.2 |
C2—C1—C3 | 110.7 (3) | C14—C15—C16 | 122.0 (2) |
Si1—C1—H11 | 107.6 | C14—C15—C20 | 119.2 (2) |
C2—C1—H11 | 107.5 | C16—C15—C20 | 118.8 (2) |
C3—C1—H11 | 107.5 | C15—C16—C17 | 120.1 (3) |
C1—C2—H21 | 109.4 | C15—C16—H161 | 119.8 |
C1—C2—H22 | 109.4 | C17—C16—H161 | 120.1 |
H21—C2—H22 | 109.5 | C16—C17—C18 | 120.8 (3) |
C1—C2—H23 | 109.6 | C16—C17—H171 | 119.5 |
H21—C2—H23 | 109.5 | C18—C17—H171 | 119.7 |
H22—C2—H23 | 109.5 | C17—C18—C19 | 120.8 (3) |
C1—C3—H31 | 109.4 | C17—C18—H181 | 119.7 |
C1—C3—H32 | 109.6 | C19—C18—H181 | 119.6 |
H31—C3—H32 | 109.5 | C18—C19—C20 | 120.2 (3) |
C1—C3—H33 | 109.4 | C18—C19—H191 | 119.9 |
H31—C3—H33 | 109.5 | C20—C19—H191 | 119.9 |
H32—C3—H33 | 109.5 | C19—C20—C15 | 119.4 (2) |
Si1—C4—C5 | 114.6 (2) | C19—C20—C21 | 122.2 (2) |
Si1—C4—C6 | 113.70 (19) | C15—C20—C21 | 118.4 (2) |
C5—C4—C6 | 109.5 (2) | C20—C21—C22 | 121.7 (2) |
Si1—C4—H41 | 106.1 | C20—C21—H211 | 119.1 |
C5—C4—H41 | 106.1 | C22—C21—H211 | 119.2 |
C6—C4—H41 | 106.2 | C13—C22—C21 | 119.9 (2) |
C4—C5—H51 | 109.5 | C13—C22—C23 | 121.4 (2) |
C4—C5—H52 | 109.6 | C21—C22—C23 | 118.8 (2) |
H51—C5—H52 | 109.5 | C22—C23—O2 | 121.2 (2) |
C4—C5—H53 | 109.3 | C22—C23—C24 | 118.7 (2) |
H51—C5—H53 | 109.5 | O2—C23—C24 | 120.2 (2) |
H52—C5—H53 | 109.5 | C23—C24—C25 | 118.9 (2) |
C4—C6—H61 | 109.5 | C23—C24—C33 | 121.2 (2) |
C4—C6—H62 | 109.4 | C25—C24—C33 | 119.8 (2) |
H61—C6—H62 | 109.5 | C24—C25—C26 | 121.7 (2) |
C4—C6—H63 | 109.5 | C24—C25—H251 | 119.1 |
H61—C6—H63 | 109.5 | C26—C25—H251 | 119.2 |
H62—C6—H63 | 109.5 | C25—C26—C27 | 122.5 (2) |
Si1—C7—C8 | 112.09 (17) | C25—C26—C31 | 118.5 (2) |
Si1—C7—C9 | 113.94 (17) | C27—C26—C31 | 119.0 (2) |
C8—C7—C9 | 110.9 (2) | C26—C27—C28 | 120.6 (2) |
Si1—C7—H71 | 106.4 | C26—C27—H271 | 119.7 |
C8—C7—H71 | 106.5 | C28—C27—H271 | 119.7 |
C9—C7—H71 | 106.4 | C27—C28—C29 | 120.3 (2) |
C7—C8—H81 | 109.5 | C27—C28—H281 | 119.9 |
C7—C8—H82 | 109.5 | C29—C28—H281 | 119.8 |
H81—C8—H82 | 109.5 | C28—C29—C30 | 120.8 (3) |
C7—C8—H83 | 109.4 | C28—C29—H291 | 119.6 |
H81—C8—H83 | 109.5 | C30—C29—H291 | 119.6 |
H82—C8—H83 | 109.5 | C29—C30—C31 | 120.7 (2) |
C7—C9—H91 | 109.5 | C29—C30—H301 | 119.7 |
C7—C9—H92 | 109.4 | C31—C30—H301 | 119.7 |
H91—C9—H92 | 109.5 | C26—C31—C30 | 118.7 (2) |
C7—C9—H93 | 109.5 | C26—C31—C32 | 118.7 (2) |
H91—C9—H93 | 109.5 | C30—C31—C32 | 122.6 (2) |
H92—C9—H93 | 109.5 | C31—C32—C33 | 122.0 (2) |
Si1—C10—C11 | 176.3 (2) | C31—C32—H321 | 118.9 |
C10—C11—C12 | 177.1 (2) | C33—C32—H321 | 119.1 |
C11—C12—O1 | 104.51 (17) | C12—C33—C24 | 122.2 (2) |
C11—C12—C13 | 110.18 (18) | C12—C33—C32 | 118.50 (19) |
O1—C12—C13 | 109.83 (19) | C24—C33—C32 | 119.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.94 (2) | 1.81 (2) | 2.746 (2) | 173 (?) |
Symmetry code: (i) −x+2, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C33H34O2Si |
Mr | 490.72 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 8.8875 (3), 8.9910 (3), 17.6023 (7) |
α, β, γ (°) | 90.406 (2), 92.2227 (19), 105.032 (2) |
V (Å3) | 1357.19 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.40 × 0.34 × 0.02 |
Data collection | |
Diffractometer | Nonius Kappa area-detector CCD diffractometer |
Absorption correction | Multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.96, 1.00 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 11207, 6138, 3673 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.064, 1.07 |
No. of reflections | 3673 |
No. of parameters | 329 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.22 |
Computer programs: COLLECT (Nonius, 2001), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), ORTEP-3 for Windows (Farrugia, 1997), CRYSTALS.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.944 (19) | 1.807 (19) | 2.746 (2) | 173(?) |
Symmetry code: (i) −x+2, −y+1, −z. |
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The design of photo- and redox-active systems with potential application as photocatalysts for solar energy conversion is a research imperative for the 21s t century (Eisenberg & Nocera, 2005). With the aim of designing photocatalytic systems involving redox- and photoactive transition metal complexes, we have focused on a modular approach using {M(tpy)2} metallotectons (tpy is 2,2':6',2''-terpyridine). We have shown that pendant or bridging aromatic units may be used to control energy- and electron-transfer processes (Constable et al., 2005; Figgemeier et al., 2003; Hjelm et al., 2005, and references therein). In the course of our synthetic programme to tune the highest occupied molecular orbital–lowest unoccupied molecular orbital properties and band gap of bridging aromatic moieties, our attention has turned to pentacene units, which have attractive energetic properties (Meng et al., 2005; Sakamoto et al., 2004; Swartz et al., 2005). In this paper, we report the structure of the title compound, (I), a product obtained in the synthesis of 6,13-bis(ethynyl)pentacene.
We required 6,13-bis(ethynyl)pentacene, (V), to introduce it as a spacer between two {M(tpy)2} units, and used minor variations on the literature procedure to prepare 6,13-bis[(triisopropylsilyl)ethynyl]pentacene, (II) (Anthony et al., 2001, 2002; Payne, Delcamp et al., 2004; Swartz et al., 2005). Pentacene-6,13-dione, (III), was prepared as a yellow solid from the reaction of cyclopentane-1,4-dione with 1,2-benzenedicarboxaldehyde in ethanolic KOH in 95% yield (Ried & Anthöfer, 1953). Reaction of (III) with (triisopropylsilyl)ethynyllithium (TIPSCCLi) in tetrahydrofuran gave a green solid comprising the desired diol, 6,13-bis[(triisopropylsilyl)ethynyl]-6,13-dihydropentacene-6,13-diol, (IV), and a highly fluorescent (λem 434 nm) product, characterized as 13-hydroxy-13-[(trisisopropylsilyl)ethynyl]pentacen-6(13H)-one, (I). We have subsequently optimized the yield of orange (I) by reaction of (III) with one equivalent of TIPSCCLi.
We have determined the solid-state crystal structure of compound (I). Fig. 1 shows the structure of a molecule of (I), together with the numbering scheme adopted. The bond distances and angles in (I) are unexceptional; the Si1—C1/C4/C7 distances lie in the range 1.880 (3)–1.883 (3) Å, with Si1—C10 being shorter at 1.837 (2) Å. Five of the C—Si—C bond angles fall in the range 105.9 (1)–110.7 (1)°, while C4—Si1—C7 is larger [115.4 (1)°].
Relatively few pentacene derivatives have been structurally characterized to date (Anthony et al., 2001; Borgen, 1966; Campbell et al., 1962; Chan et al., 2005; Dzyabchenko et al., 1979; Holmes et al., 1999; Klarner et al., 2001; Mattheus et al., 2001, 2002; Meng et al., 2005; Miller et al., 2003; Ohkita et al., 2000; Payne, Odom et al., 2004; Sakamoto et al., 2004; Siegrist et al., 2001; Swartz et al., 2005; Uno et al., 2005). As expected on the basis of hydrogen bonding (see later) and the non-aromatic ring structure, the carbonyl C—O bond in (I) is slightly longer [C23—O2 = 1.238 (3) Å] than that in the quinone pentacene-6,13-dione (1.215 Å; Dzyabchenko et al., 1979). Within the pentacene system, the aromatic rings exhibit typical delocalized C—C bond distances in the range 1.358 (4)–1.424 (3) Å, similar to those of the aromatic rings in other pentacenes and 6,13-dihydropentacenes. In the central ring, the C—C bonds to the carbonyl group are a little longer [1.476 (3) and 1.474 (3) Å] and similar in length to those in pentacene-6,13-dione (1.483 Å; Dzyabchenko et al., 1979). The formally single C—C bonds to C12 in the central ring show distances of 1.528 (3) and 1.535 (3) Å, which are similar to, if slightly longer than, those in 6,13-dihydropentacene (1.475 and 1.524 Å; Mattheus et al., 2002). In contrast with 6,13-dihydropentacene, where the least-squares planes through the `naphthalene' units intersect at the sp3 C atoms at an angle of 28° (Mattheus et al., 2002), the pentacene ring system in (I) is nearly planar, with the deviation of the sp3 atom C12 from the least-squares plane of the aromatic rings being only 0.16 Å.
The molecules of (I) form a hydrogen-bonded dimer in the solid state (Fig. 2), in which the hydroxy group of one molecule is strongly hydrogen-bonded to the carbonyl O atom of a second [O1···O2i = 2.746 (2) Å and O1—H1···O2i = 173 (2)°; symmetry code:(i) −x, −y, −z]. The consequence of this tight hydrogen bonding is efficient offset face-to-face π-stacking of the two pentacene rings; the distance between least-squares planes, each of 22 C atoms, is 3.60 Å. The dimers are linked along the b axis by hydrogen-bonded interactions [C16—H161···O2ii, with C16···O2ii = 3.447 (3) Å, and C27—H271···O1iii, with C27···O1iii = 3.318 (3) Å; symmetry codes: (ii) ?; (iii) ? Please complete]. When viewed along the b axis (Fig. 3), the solid-state structure reveals packing of the dimers into columns. The dimers are π-stacked with offset face-to-face π-stacking of pentacene rings (the distance between least-squares planes, each of 22 C atoms, is 3.52 Å). The (triisopropyl)silyl (TIPS) substituents are directed outwards from these columns and form an intermeshed assembly between them.
Of the 26 4-hydroxycyclohexa-2,5-dienones present in the Cambridge Structural Database (Version 5.2.7; Allen, 2002; Bruno et al., 2002), the majority exhibit extended or linear hydrogen-bond connectivity, and in only two cases is a dimeric structure related to (I) observed. In the case of 4-ethynyl-4-hydroxy-2,3,5,6-tetramethylcyclohexa-2,5-dienone (Bilton et al., 2000), the monomer unit is related to (I) and the dimer has similar metrical parameters, although the hydrogen bond is significantly weaker [O—H···O = 1.94 (3) and 1.96 (3) Å; O···O = 2.826 (2) and 2.786 (2) Å; O—H···O = 172 (2) and 178 (3)°]. Once again, the hydrogen-bonding facilitates offset face-to-face π-stacking, and the distance between the least-squares planes of the aromatic rings in the dimer is 3.54 Å. The second example is found in 4,5,7-trichloro-3a-hydroxy-1-(4-methylphenyl)-2-(4-methylphenylimino)-2,3,3a,6-tetrahydro-1H-indol-6-one (Doepp et al., 1995), in which strong hydrogen bonds (O···O = 2.722 Å) also support the coplanar arrangement of aromatic rings (the distance between the least-squares planes of the aromatic rings is 3.38 Å), although these are slipped such that there is no direct ring overlap.