organic compounds
2,9,16,23-Tetrakis(1-methylethyl)-5,6,11,12,13,14,19,20,25,26,27,28-dodecadehydrotetrabenzo[a,e,k,o]cycloeicosene1
aDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804, USA
*Correspondence e-mail: ffroncz@lsu.edu
The title compound, C48H40, is a tetraisopropyl-substituted polyannulenoenyne. The unsubstituted polyannulenoenyne, C36H16 (CSD: RICVEE; CAS: 186494-87-1), has quasi-D2 (222) symmetry, as determined by least-squares fit (excluding H atoms) to a model optimized in D2 symmetry by molecular mechanics (r.m.s. deviation = 0.239 Å). The least-squares fits of 36 common C atoms of the title compound (at 90 K) to the parent (at 295 K) and to the optimized model show r.m.s. deviations of 0.419 and 0.426 Å, respectively.
Related literature
For a description of the Cambridge Structural Database, see: Allen (2002). For the synthesis and a related structure, see: Boese et al. (1997). For molecular mechanics software, see: Cambridgesoft (2010).
Experimental
Crystal data
|
Data collection: COLLECT (Nonius, 2000); cell SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; 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: IDEAL (Gould et al., 1988) and WinGX (Farrugia, 1999).
Supporting information
https://doi.org/10.1107/S1600536811048604/kj2194sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811048604/kj2194Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536811048604/kj2194Isup3.cml
The preparation of the title compound has been described by Boese et al. (1997). Crystals were grown by slow evaporation from dichloromethane and deuterochloroform.
All H atoms were placed in calculated positions guided by difference maps. The C—H bond distances were constrained to the range from 0.95 to 1.0 Å, depending on C atom type, and Uiso= 1.2Ueq (1.5 for methyl groups), thereafter refined as riding. A torsional parameter was refined for each methyl group.
The title compound, C48H40, is a tetraisopropyl-substituted polyannulenoenyne and its structure was determined at 90 K. The 295 K structure of the unsubstituted parent annulene, C36H16, was previously determined by Boese et al. (1997; CSD: RICVEE, Allen, 2002; CAS: 186494–87-1), and is of quasi-D2 (222) symmetry, as determined by least-squares fit (Gould et al., 1988; δr.m.s. = 0.239 Å) of all 36 common carbon atoms of the parent to a model of C36H16 optimized in D2 symmetry by molecular mechanics (Cambridgesoft, 2010). Reasonable agreements result from the same least-squares fit of the title compound (at 90 K) to the parent (δr.m.s. =0.419 Å) and to the optimized model (δr.m.s. = 0.426 Å).
The six C≡C triple bond distances are all experimentally equal, falling in the narrow range 1.203 (2) - 1.206 (2) Å, while the C–C bonds linking the triple bonds have length C16—C17 1.370 (2) and C34—C35 1.377 (2) Å. The acetylenic bridges are slightly bowed outward, with C–C≡C angles in the range 177.59 (18) - 179.17 (18)° for the butadiyne bridges and in the range 174.43 (17) - 176.80 (17)° for the acetylene bridges. Distances between the following bond centroids provide a measure of overall molecular dimensions: C16—C17 to C34—C35 = 3.341 (2) Å, C7 ≡C8 to C25 ≡C26 = 7.650 (2) Å.
For a description of the Cambridge Structural Database, see: Allen (2002). For the synthesis and a related structure, see: Boese et al. (1997). For molecular mechanics software, see: Cambridgesoft (2010).
Data collection: COLLECT (Nonius, 2000); cell
SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); 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: IDEAL (Gould et al., 1988) and WinGX (Farrugia, 1999).C48H40 | F(000) = 1312 |
Mr = 616.8 | Dx = 1.133 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7618 reflections |
a = 18.0007 (4) Å | θ = 2.6–29.1° |
b = 12.5083 (3) Å | µ = 0.06 mm−1 |
c = 16.0674 (4) Å | T = 90 K |
β = 91.004 (1)° | Prism, golden yellow |
V = 3617.15 (15) Å3 | 0.45 × 0.30 × 0.30 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 8186 independent reflections |
Radiation source: sealed tube | 5354 reflections with I > 2σ(I) |
Horizonally mounted graphite crystal monochromator | Rint = 0.035 |
Detector resolution: 9 pixels mm-1 | θmax = 28.9°, θmin = 2.8° |
CCD rotation images, thick slices scans | h = −23→23 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor 1997) | k = −16→14 |
Tmin = 0.972, Tmax = 0.981 | l = −19→20 |
13998 measured reflections |
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)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.127 | w = 1/[σ2(Fo2) + (0.0543P)2 + 1.183P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
8186 reflections | Δρmax = 0.25 e Å−3 |
442 parameters | Δρmin = −0.28 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.0017 (4) |
Primary atom site location: structure-invariant direct methods |
C48H40 | V = 3617.15 (15) Å3 |
Mr = 616.8 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 18.0007 (4) Å | µ = 0.06 mm−1 |
b = 12.5083 (3) Å | T = 90 K |
c = 16.0674 (4) Å | 0.45 × 0.30 × 0.30 mm |
β = 91.004 (1)° |
Nonius KappaCCD diffractometer | 8186 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor 1997) | 5354 reflections with I > 2σ(I) |
Tmin = 0.972, Tmax = 0.981 | Rint = 0.035 |
13998 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.25 e Å−3 |
8186 reflections | Δρmin = −0.28 e Å−3 |
442 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.34021 (9) | 0.67572 (12) | −0.03559 (9) | 0.0209 (3) | |
C2 | 0.37458 (9) | 0.65496 (13) | −0.11163 (9) | 0.0230 (4) | |
H2 | 0.3986 | 0.5882 | −0.1196 | 0.028* | |
C3 | 0.37425 (9) | 0.72994 (13) | −0.17553 (9) | 0.0239 (4) | |
C4 | 0.33685 (9) | 0.82602 (13) | −0.16283 (9) | 0.0250 (4) | |
H4 | 0.3348 | 0.8774 | −0.2064 | 0.03* | |
C5 | 0.30274 (9) | 0.84840 (13) | −0.08857 (9) | 0.0240 (4) | |
H5 | 0.2781 | 0.9149 | −0.0816 | 0.029* | |
C6 | 0.30408 (9) | 0.77426 (12) | −0.02347 (9) | 0.0211 (3) | |
C7 | 0.26840 (9) | 0.79587 (12) | 0.05395 (9) | 0.0221 (3) | |
C8 | 0.23760 (9) | 0.80786 (12) | 0.11918 (9) | 0.0221 (3) | |
C9 | 0.20160 (8) | 0.81294 (12) | 0.19792 (9) | 0.0215 (3) | |
C10 | 0.20544 (9) | 0.90410 (13) | 0.24814 (10) | 0.0264 (4) | |
H10 | 0.2289 | 0.9669 | 0.2282 | 0.032* | |
C11 | 0.17525 (9) | 0.90345 (13) | 0.32691 (10) | 0.0269 (4) | |
H11 | 0.1793 | 0.9658 | 0.3604 | 0.032* | |
C12 | 0.13916 (9) | 0.81390 (13) | 0.35838 (9) | 0.0223 (3) | |
C13 | 0.13314 (9) | 0.72469 (12) | 0.30736 (9) | 0.0208 (3) | |
H13 | 0.1073 | 0.6636 | 0.3267 | 0.025* | |
C14 | 0.16417 (8) | 0.72248 (12) | 0.22813 (9) | 0.0198 (3) | |
C15 | 0.15945 (9) | 0.62679 (12) | 0.17971 (9) | 0.0216 (3) | |
C16 | 0.15709 (9) | 0.54517 (12) | 0.13983 (9) | 0.0215 (3) | |
C17 | 0.15610 (9) | 0.45239 (12) | 0.09457 (9) | 0.0223 (3) | |
C18 | 0.15587 (9) | 0.36996 (13) | 0.05588 (9) | 0.0232 (3) | |
C19 | 0.15470 (9) | 0.27065 (12) | 0.01184 (9) | 0.0219 (3) | |
C20 | 0.12070 (9) | 0.26396 (13) | −0.06716 (9) | 0.0237 (4) | |
H20 | 0.0977 | 0.3257 | −0.0905 | 0.028* | |
C21 | 0.11988 (9) | 0.16932 (13) | −0.11210 (10) | 0.0256 (4) | |
C22 | 0.15239 (10) | 0.07952 (13) | −0.07467 (10) | 0.0300 (4) | |
H22 | 0.1519 | 0.0136 | −0.104 | 0.036* | |
C23 | 0.18519 (9) | 0.08346 (13) | 0.00358 (10) | 0.0281 (4) | |
H23 | 0.2058 | 0.0204 | 0.0275 | 0.034* | |
C24 | 0.18827 (9) | 0.17957 (12) | 0.04787 (9) | 0.0230 (3) | |
C25 | 0.22660 (9) | 0.18904 (12) | 0.12662 (10) | 0.0235 (4) | |
C26 | 0.25924 (9) | 0.20612 (12) | 0.19125 (10) | 0.0240 (4) | |
C27 | 0.29570 (9) | 0.23181 (12) | 0.26867 (9) | 0.0228 (3) | |
C28 | 0.29559 (9) | 0.16136 (14) | 0.33603 (10) | 0.0289 (4) | |
H28 | 0.2728 | 0.0932 | 0.3298 | 0.035* | |
C29 | 0.32799 (9) | 0.18895 (13) | 0.41168 (10) | 0.0286 (4) | |
H29 | 0.3269 | 0.1394 | 0.4564 | 0.034* | |
C30 | 0.36228 (9) | 0.28784 (13) | 0.42378 (9) | 0.0238 (4) | |
C31 | 0.36368 (9) | 0.35806 (13) | 0.35677 (9) | 0.0225 (3) | |
H31 | 0.387 | 0.4257 | 0.3636 | 0.027* | |
C32 | 0.33159 (9) | 0.33165 (12) | 0.27927 (9) | 0.0213 (3) | |
C33 | 0.33649 (9) | 0.40474 (12) | 0.21094 (9) | 0.0224 (3) | |
C34 | 0.34108 (9) | 0.46519 (12) | 0.15295 (9) | 0.0233 (4) | |
C35 | 0.34333 (9) | 0.53578 (12) | 0.08726 (9) | 0.0232 (4) | |
C36 | 0.34260 (9) | 0.59846 (12) | 0.03031 (9) | 0.0228 (3) | |
C37 | 0.41549 (10) | 0.71348 (14) | −0.25636 (10) | 0.0301 (4) | |
H37 | 0.3804 | 0.7324 | −0.303 | 0.036* | |
C38 | 0.48096 (10) | 0.79092 (15) | −0.26042 (11) | 0.0377 (5) | |
H38A | 0.4631 | 0.8642 | −0.2528 | 0.057* | |
H38B | 0.5045 | 0.7847 | −0.3148 | 0.057* | |
H38C | 0.5173 | 0.7735 | −0.2163 | 0.057* | |
C39 | 0.44060 (12) | 0.59924 (15) | −0.27061 (12) | 0.0442 (5) | |
H39A | 0.4774 | 0.5793 | −0.2277 | 0.066* | |
H39B | 0.4628 | 0.5934 | −0.3257 | 0.066* | |
H39C | 0.3977 | 0.5512 | −0.2676 | 0.066* | |
C40 | 0.10830 (9) | 0.81729 (13) | 0.44585 (9) | 0.0261 (4) | |
H40 | 0.1495 | 0.8419 | 0.4838 | 0.031* | |
C41 | 0.08181 (10) | 0.70983 (14) | 0.47865 (10) | 0.0315 (4) | |
H41A | 0.0394 | 0.685 | 0.4449 | 0.047* | |
H41B | 0.0668 | 0.7177 | 0.5367 | 0.047* | |
H41C | 0.1222 | 0.6576 | 0.4755 | 0.047* | |
C42 | 0.04634 (10) | 0.89944 (14) | 0.45132 (10) | 0.0308 (4) | |
H42A | 0.0642 | 0.9687 | 0.4315 | 0.046* | |
H42B | 0.0309 | 0.9062 | 0.5093 | 0.046* | |
H42C | 0.0039 | 0.8764 | 0.4167 | 0.046* | |
C43 | 0.08507 (10) | 0.16014 (14) | −0.19909 (10) | 0.0317 (4) | |
H43 | 0.1231 | 0.1266 | −0.2354 | 0.038* | |
C44 | 0.06418 (11) | 0.26707 (15) | −0.23850 (10) | 0.0359 (4) | |
H44A | 0.0244 | 0.3003 | −0.2067 | 0.054* | |
H44B | 0.0471 | 0.2555 | −0.296 | 0.054* | |
H44C | 0.1077 | 0.3142 | −0.2381 | 0.054* | |
C45 | 0.01798 (11) | 0.08507 (15) | −0.19878 (11) | 0.0392 (5) | |
H45A | 0.0326 | 0.0164 | −0.1741 | 0.059* | |
H45B | 0.0001 | 0.0736 | −0.256 | 0.059* | |
H45C | −0.0217 | 0.1171 | −0.166 | 0.059* | |
C46 | 0.40087 (9) | 0.31230 (14) | 0.50654 (9) | 0.0294 (4) | |
H46 | 0.3752 | 0.27 | 0.5504 | 0.035* | |
C47 | 0.39803 (11) | 0.42839 (15) | 0.53199 (11) | 0.0393 (5) | |
H47A | 0.4255 | 0.4716 | 0.492 | 0.059* | |
H47B | 0.4205 | 0.4367 | 0.5876 | 0.059* | |
H47C | 0.3462 | 0.4522 | 0.5329 | 0.059* | |
C48 | 0.48084 (12) | 0.2742 (2) | 0.50436 (13) | 0.0581 (7) | |
H48A | 0.4818 | 0.1969 | 0.4948 | 0.087* | |
H48B | 0.5057 | 0.2906 | 0.5576 | 0.087* | |
H48C | 0.5066 | 0.3106 | 0.4592 | 0.087* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0265 (8) | 0.0179 (8) | 0.0181 (7) | −0.0032 (7) | −0.0015 (6) | 0.0005 (6) |
C2 | 0.0273 (9) | 0.0204 (8) | 0.0212 (8) | −0.0019 (7) | −0.0010 (6) | −0.0032 (6) |
C3 | 0.0281 (9) | 0.0263 (9) | 0.0174 (8) | −0.0052 (7) | −0.0001 (6) | −0.0020 (6) |
C4 | 0.0298 (9) | 0.0244 (9) | 0.0208 (8) | −0.0027 (7) | −0.0001 (7) | 0.0048 (7) |
C5 | 0.0274 (9) | 0.0193 (8) | 0.0251 (8) | 0.0011 (7) | 0.0005 (7) | 0.0019 (6) |
C6 | 0.0240 (8) | 0.0198 (8) | 0.0196 (8) | −0.0029 (7) | 0.0001 (6) | −0.0008 (6) |
C7 | 0.0268 (8) | 0.0158 (8) | 0.0238 (8) | −0.0017 (7) | −0.0011 (7) | 0.0006 (6) |
C8 | 0.0272 (8) | 0.0154 (8) | 0.0237 (8) | −0.0013 (7) | −0.0002 (7) | −0.0001 (6) |
C9 | 0.0250 (8) | 0.0194 (8) | 0.0200 (8) | 0.0021 (7) | 0.0001 (6) | −0.0015 (6) |
C10 | 0.0321 (9) | 0.0175 (8) | 0.0296 (9) | −0.0049 (7) | 0.0045 (7) | −0.0040 (7) |
C11 | 0.0329 (9) | 0.0209 (9) | 0.0269 (9) | −0.0021 (7) | 0.0035 (7) | −0.0084 (7) |
C12 | 0.0232 (8) | 0.0218 (8) | 0.0220 (8) | 0.0043 (7) | 0.0008 (6) | −0.0030 (6) |
C13 | 0.0251 (8) | 0.0170 (8) | 0.0204 (8) | 0.0016 (7) | 0.0001 (6) | −0.0001 (6) |
C14 | 0.0230 (8) | 0.0162 (8) | 0.0200 (7) | 0.0024 (7) | −0.0019 (6) | −0.0026 (6) |
C15 | 0.0280 (9) | 0.0186 (8) | 0.0182 (8) | 0.0013 (7) | 0.0019 (6) | 0.0015 (6) |
C16 | 0.0271 (9) | 0.0190 (8) | 0.0186 (8) | 0.0000 (7) | −0.0001 (6) | 0.0024 (6) |
C17 | 0.0285 (9) | 0.0185 (8) | 0.0198 (8) | 0.0002 (7) | −0.0009 (6) | −0.0003 (6) |
C18 | 0.0266 (9) | 0.0218 (8) | 0.0212 (8) | 0.0004 (7) | 0.0004 (6) | 0.0002 (7) |
C19 | 0.0259 (8) | 0.0179 (8) | 0.0220 (8) | −0.0006 (7) | 0.0025 (6) | −0.0043 (6) |
C20 | 0.0274 (9) | 0.0210 (8) | 0.0228 (8) | 0.0024 (7) | −0.0004 (7) | −0.0017 (6) |
C21 | 0.0278 (9) | 0.0244 (9) | 0.0247 (8) | 0.0020 (7) | −0.0013 (7) | −0.0062 (7) |
C22 | 0.0384 (10) | 0.0209 (9) | 0.0306 (9) | 0.0025 (8) | −0.0061 (8) | −0.0100 (7) |
C23 | 0.0354 (10) | 0.0175 (8) | 0.0311 (9) | 0.0039 (7) | −0.0051 (7) | −0.0039 (7) |
C24 | 0.0263 (8) | 0.0213 (8) | 0.0214 (8) | −0.0015 (7) | −0.0004 (6) | −0.0019 (6) |
C25 | 0.0300 (9) | 0.0156 (8) | 0.0251 (8) | −0.0001 (7) | 0.0020 (7) | −0.0015 (6) |
C26 | 0.0314 (9) | 0.0163 (8) | 0.0243 (8) | −0.0020 (7) | 0.0015 (7) | 0.0011 (6) |
C27 | 0.0271 (9) | 0.0211 (8) | 0.0203 (8) | 0.0009 (7) | 0.0001 (6) | 0.0004 (6) |
C28 | 0.0365 (10) | 0.0219 (9) | 0.0283 (9) | −0.0067 (8) | −0.0015 (7) | 0.0037 (7) |
C29 | 0.0359 (10) | 0.0275 (9) | 0.0225 (8) | −0.0015 (8) | 0.0010 (7) | 0.0076 (7) |
C30 | 0.0259 (8) | 0.0255 (9) | 0.0202 (8) | 0.0054 (7) | 0.0014 (6) | −0.0001 (7) |
C31 | 0.0251 (8) | 0.0192 (8) | 0.0232 (8) | 0.0006 (7) | 0.0002 (6) | −0.0013 (6) |
C32 | 0.0254 (8) | 0.0191 (8) | 0.0194 (8) | 0.0030 (7) | 0.0013 (6) | 0.0002 (6) |
C33 | 0.0269 (9) | 0.0186 (8) | 0.0215 (8) | −0.0006 (7) | −0.0021 (6) | −0.0030 (7) |
C34 | 0.0289 (9) | 0.0188 (8) | 0.0221 (8) | −0.0002 (7) | −0.0011 (7) | −0.0025 (7) |
C35 | 0.0292 (9) | 0.0192 (8) | 0.0211 (8) | −0.0002 (7) | 0.0002 (7) | −0.0016 (6) |
C36 | 0.0267 (9) | 0.0196 (8) | 0.0221 (8) | −0.0008 (7) | −0.0001 (7) | −0.0035 (7) |
C37 | 0.0373 (10) | 0.0342 (10) | 0.0188 (8) | −0.0040 (8) | 0.0036 (7) | −0.0022 (7) |
C38 | 0.0444 (11) | 0.0346 (11) | 0.0346 (10) | −0.0041 (9) | 0.0157 (8) | −0.0031 (8) |
C39 | 0.0608 (13) | 0.0367 (11) | 0.0358 (10) | −0.0074 (10) | 0.0218 (9) | −0.0126 (8) |
C40 | 0.0319 (9) | 0.0263 (9) | 0.0203 (8) | 0.0034 (8) | 0.0017 (7) | −0.0054 (7) |
C41 | 0.0420 (11) | 0.0312 (10) | 0.0216 (8) | 0.0035 (8) | 0.0060 (7) | 0.0005 (7) |
C42 | 0.0346 (10) | 0.0300 (10) | 0.0278 (9) | 0.0053 (8) | 0.0055 (7) | −0.0044 (7) |
C43 | 0.0375 (10) | 0.0329 (10) | 0.0245 (9) | 0.0040 (8) | −0.0054 (7) | −0.0093 (7) |
C44 | 0.0410 (11) | 0.0415 (11) | 0.0251 (9) | 0.0019 (9) | −0.0056 (8) | −0.0020 (8) |
C45 | 0.0453 (11) | 0.0364 (11) | 0.0356 (10) | −0.0001 (9) | −0.0124 (9) | −0.0080 (8) |
C46 | 0.0348 (10) | 0.0362 (10) | 0.0172 (8) | 0.0052 (8) | −0.0012 (7) | −0.0009 (7) |
C47 | 0.0482 (12) | 0.0394 (11) | 0.0299 (10) | −0.0024 (9) | −0.0119 (8) | −0.0046 (8) |
C48 | 0.0526 (14) | 0.0865 (18) | 0.0347 (11) | 0.0291 (13) | −0.0175 (10) | −0.0187 (11) |
C1—C2 | 1.403 (2) | C29—C30 | 1.394 (2) |
C1—C6 | 1.409 (2) | C29—H29 | 0.95 |
C1—C36 | 1.434 (2) | C30—C31 | 1.390 (2) |
C2—C3 | 1.391 (2) | C30—C46 | 1.520 (2) |
C2—H2 | 0.95 | C31—C32 | 1.403 (2) |
C3—C4 | 1.394 (2) | C31—H31 | 0.95 |
C3—C37 | 1.521 (2) | C32—C33 | 1.432 (2) |
C4—C5 | 1.380 (2) | C33—C34 | 1.204 (2) |
C4—H4 | 0.95 | C34—C35 | 1.377 (2) |
C5—C6 | 1.398 (2) | C35—C36 | 1.205 (2) |
C5—H5 | 0.95 | C37—C39 | 1.517 (3) |
C6—C7 | 1.436 (2) | C37—C38 | 1.528 (2) |
C7—C8 | 1.204 (2) | C37—H37 | 1 |
C8—C9 | 1.433 (2) | C38—H38A | 0.98 |
C9—C10 | 1.398 (2) | C38—H38B | 0.98 |
C9—C14 | 1.408 (2) | C38—H38C | 0.98 |
C10—C11 | 1.386 (2) | C39—H39A | 0.98 |
C10—H10 | 0.95 | C39—H39B | 0.98 |
C11—C12 | 1.394 (2) | C39—H39C | 0.98 |
C11—H11 | 0.95 | C40—C42 | 1.520 (2) |
C12—C13 | 1.388 (2) | C40—C41 | 1.523 (2) |
C12—C40 | 1.521 (2) | C40—H40 | 1 |
C13—C14 | 1.399 (2) | C41—H41A | 0.98 |
C13—H13 | 0.95 | C41—H41B | 0.98 |
C14—C15 | 1.429 (2) | C41—H41C | 0.98 |
C15—C16 | 1.206 (2) | C42—H42A | 0.98 |
C16—C17 | 1.370 (2) | C42—H42B | 0.98 |
C17—C18 | 1.204 (2) | C42—H42C | 0.98 |
C18—C19 | 1.430 (2) | C43—C44 | 1.524 (2) |
C19—C20 | 1.402 (2) | C43—C45 | 1.530 (3) |
C19—C24 | 1.409 (2) | C43—H43 | 1 |
C20—C21 | 1.386 (2) | C44—H44A | 0.98 |
C20—H20 | 0.95 | C44—H44B | 0.98 |
C21—C22 | 1.398 (2) | C44—H44C | 0.98 |
C21—C43 | 1.526 (2) | C45—H45A | 0.98 |
C22—C23 | 1.381 (2) | C45—H45B | 0.98 |
C22—H22 | 0.95 | C45—H45C | 0.98 |
C23—C24 | 1.398 (2) | C46—C47 | 1.510 (2) |
C23—H23 | 0.95 | C46—C48 | 1.517 (3) |
C24—C25 | 1.436 (2) | C46—H46 | 1 |
C25—C26 | 1.203 (2) | C47—H47A | 0.98 |
C26—C27 | 1.433 (2) | C47—H47B | 0.98 |
C27—C28 | 1.396 (2) | C47—H47C | 0.98 |
C27—C32 | 1.415 (2) | C48—H48A | 0.98 |
C28—C29 | 1.383 (2) | C48—H48B | 0.98 |
C28—H28 | 0.95 | C48—H48C | 0.98 |
C2—C1—C6 | 119.60 (13) | C31—C32—C33 | 120.00 (14) |
C2—C1—C36 | 120.68 (14) | C27—C32—C33 | 120.34 (13) |
C6—C1—C36 | 119.71 (13) | C34—C33—C32 | 179.17 (18) |
C3—C2—C1 | 121.45 (15) | C33—C34—C35 | 177.59 (18) |
C3—C2—H2 | 119.3 | C36—C35—C34 | 177.59 (18) |
C1—C2—H2 | 119.3 | C35—C36—C1 | 177.89 (17) |
C2—C3—C4 | 117.98 (14) | C39—C37—C3 | 114.04 (14) |
C2—C3—C37 | 122.91 (15) | C39—C37—C38 | 111.02 (15) |
C4—C3—C37 | 119.06 (14) | C3—C37—C38 | 109.82 (13) |
C5—C4—C3 | 121.64 (14) | C39—C37—H37 | 107.2 |
C5—C4—H4 | 119.2 | C3—C37—H37 | 107.2 |
C3—C4—H4 | 119.2 | C38—C37—H37 | 107.2 |
C4—C5—C6 | 120.69 (15) | C37—C38—H38A | 109.5 |
C4—C5—H5 | 119.7 | C37—C38—H38B | 109.5 |
C6—C5—H5 | 119.7 | H38A—C38—H38B | 109.5 |
C5—C6—C1 | 118.62 (14) | C37—C38—H38C | 109.5 |
C5—C6—C7 | 121.42 (14) | H38A—C38—H38C | 109.5 |
C1—C6—C7 | 119.95 (13) | H38B—C38—H38C | 109.5 |
C8—C7—C6 | 176.25 (16) | C37—C39—H39A | 109.5 |
C7—C8—C9 | 175.33 (17) | C37—C39—H39B | 109.5 |
C10—C9—C14 | 118.40 (14) | H39A—C39—H39B | 109.5 |
C10—C9—C8 | 121.83 (14) | C37—C39—H39C | 109.5 |
C14—C9—C8 | 119.70 (14) | H39A—C39—H39C | 109.5 |
C11—C10—C9 | 120.41 (15) | H39B—C39—H39C | 109.5 |
C11—C10—H10 | 119.8 | C42—C40—C12 | 110.63 (13) |
C9—C10—H10 | 119.8 | C42—C40—C41 | 110.00 (14) |
C10—C11—C12 | 121.90 (14) | C12—C40—C41 | 114.63 (13) |
C10—C11—H11 | 119 | C42—C40—H40 | 107.1 |
C12—C11—H11 | 119 | C12—C40—H40 | 107.1 |
C13—C12—C11 | 117.63 (14) | C41—C40—H40 | 107.1 |
C13—C12—C40 | 122.84 (14) | C40—C41—H41A | 109.5 |
C11—C12—C40 | 119.53 (14) | C40—C41—H41B | 109.5 |
C12—C13—C14 | 121.67 (14) | H41A—C41—H41B | 109.5 |
C12—C13—H13 | 119.2 | C40—C41—H41C | 109.5 |
C14—C13—H13 | 119.2 | H41A—C41—H41C | 109.5 |
C13—C14—C9 | 119.93 (14) | H41B—C41—H41C | 109.5 |
C13—C14—C15 | 119.39 (14) | C40—C42—H42A | 109.5 |
C9—C14—C15 | 120.64 (13) | C40—C42—H42B | 109.5 |
C16—C15—C14 | 178.34 (17) | H42A—C42—H42B | 109.5 |
C15—C16—C17 | 178.73 (18) | C40—C42—H42C | 109.5 |
C18—C17—C16 | 178.88 (18) | H42A—C42—H42C | 109.5 |
C17—C18—C19 | 178.44 (17) | H42B—C42—H42C | 109.5 |
C20—C19—C24 | 120.06 (14) | C44—C43—C21 | 114.14 (14) |
C20—C19—C18 | 120.17 (14) | C44—C43—C45 | 110.55 (15) |
C24—C19—C18 | 119.78 (13) | C21—C43—C45 | 110.78 (14) |
C21—C20—C19 | 121.53 (15) | C44—C43—H43 | 107 |
C21—C20—H20 | 119.2 | C21—C43—H43 | 107 |
C19—C20—H20 | 119.2 | C45—C43—H43 | 107 |
C20—C21—C22 | 117.49 (14) | C43—C44—H44A | 109.5 |
C20—C21—C43 | 122.80 (15) | C43—C44—H44B | 109.5 |
C22—C21—C43 | 119.72 (14) | H44A—C44—H44B | 109.5 |
C23—C22—C21 | 122.16 (15) | C43—C44—H44C | 109.5 |
C23—C22—H22 | 118.9 | H44A—C44—H44C | 109.5 |
C21—C22—H22 | 118.9 | H44B—C44—H44C | 109.5 |
C22—C23—C24 | 120.46 (15) | C43—C45—H45A | 109.5 |
C22—C23—H23 | 119.8 | C43—C45—H45B | 109.5 |
C24—C23—H23 | 119.8 | H45A—C45—H45B | 109.5 |
C23—C24—C19 | 118.25 (14) | C43—C45—H45C | 109.5 |
C23—C24—C25 | 122.27 (15) | H45A—C45—H45C | 109.5 |
C19—C24—C25 | 119.44 (14) | H45B—C45—H45C | 109.5 |
C26—C25—C24 | 174.43 (17) | C47—C46—C48 | 110.17 (17) |
C25—C26—C27 | 176.80 (17) | C47—C46—C30 | 114.42 (14) |
C28—C27—C32 | 118.09 (14) | C48—C46—C30 | 109.62 (14) |
C28—C27—C26 | 121.65 (15) | C47—C46—H46 | 107.5 |
C32—C27—C26 | 120.24 (14) | C48—C46—H46 | 107.5 |
C29—C28—C27 | 121.18 (15) | C30—C46—H46 | 107.5 |
C29—C28—H28 | 119.4 | C46—C47—H47A | 109.5 |
C27—C28—H28 | 119.4 | C46—C47—H47B | 109.5 |
C28—C29—C30 | 121.52 (15) | H47A—C47—H47B | 109.5 |
C28—C29—H29 | 119.2 | C46—C47—H47C | 109.5 |
C30—C29—H29 | 119.2 | H47A—C47—H47C | 109.5 |
C31—C30—C29 | 117.81 (14) | H47B—C47—H47C | 109.5 |
C31—C30—C46 | 122.41 (15) | C46—C48—H48A | 109.5 |
C29—C30—C46 | 119.65 (14) | C46—C48—H48B | 109.5 |
C30—C31—C32 | 121.73 (15) | H48A—C48—H48B | 109.5 |
C30—C31—H31 | 119.1 | C46—C48—H48C | 109.5 |
C32—C31—H31 | 119.1 | H48A—C48—H48C | 109.5 |
C31—C32—C27 | 119.64 (14) | H48B—C48—H48C | 109.5 |
C6—C1—C2—C3 | 0.4 (2) | C22—C23—C24—C25 | −175.30 (16) |
C36—C1—C2—C3 | −178.54 (15) | C20—C19—C24—C23 | −1.3 (2) |
C1—C2—C3—C4 | −1.7 (2) | C18—C19—C24—C23 | 179.13 (15) |
C1—C2—C3—C37 | 175.55 (15) | C20—C19—C24—C25 | 176.40 (15) |
C2—C3—C4—C5 | 1.8 (2) | C18—C19—C24—C25 | −3.2 (2) |
C37—C3—C4—C5 | −175.55 (15) | C32—C27—C28—C29 | 1.5 (2) |
C3—C4—C5—C6 | −0.6 (2) | C26—C27—C28—C29 | −176.98 (16) |
C4—C5—C6—C1 | −0.7 (2) | C27—C28—C29—C30 | −0.2 (3) |
C4—C5—C6—C7 | −179.51 (15) | C28—C29—C30—C31 | −0.7 (2) |
C2—C1—C6—C5 | 0.8 (2) | C28—C29—C30—C46 | −176.65 (15) |
C36—C1—C6—C5 | 179.77 (14) | C29—C30—C31—C32 | 0.3 (2) |
C2—C1—C6—C7 | 179.63 (14) | C46—C30—C31—C32 | 176.14 (14) |
C36—C1—C6—C7 | −1.4 (2) | C30—C31—C32—C27 | 1.0 (2) |
C14—C9—C10—C11 | 2.2 (2) | C30—C31—C32—C33 | −177.81 (15) |
C8—C9—C10—C11 | −174.65 (15) | C28—C27—C32—C31 | −1.9 (2) |
C9—C10—C11—C12 | −1.1 (3) | C26—C27—C32—C31 | 176.64 (15) |
C10—C11—C12—C13 | −1.1 (2) | C28—C27—C32—C33 | 176.94 (15) |
C10—C11—C12—C40 | 178.95 (15) | C26—C27—C32—C33 | −4.5 (2) |
C11—C12—C13—C14 | 2.1 (2) | C2—C3—C37—C39 | 14.4 (2) |
C40—C12—C13—C14 | −177.86 (14) | C4—C3—C37—C39 | −168.35 (16) |
C12—C13—C14—C9 | −1.0 (2) | C2—C3—C37—C38 | −110.89 (18) |
C12—C13—C14—C15 | 177.02 (14) | C4—C3—C37—C38 | 66.3 (2) |
C10—C9—C14—C13 | −1.2 (2) | C13—C12—C40—C42 | −115.35 (17) |
C8—C9—C14—C13 | 175.78 (14) | C11—C12—C40—C42 | 64.6 (2) |
C10—C9—C14—C15 | −179.21 (14) | C13—C12—C40—C41 | 9.7 (2) |
C8—C9—C14—C15 | −2.3 (2) | C11—C12—C40—C41 | −170.28 (15) |
C24—C19—C20—C21 | −0.8 (2) | C20—C21—C43—C44 | 10.6 (2) |
C18—C19—C20—C21 | 178.76 (15) | C22—C21—C43—C44 | −169.67 (16) |
C19—C20—C21—C22 | 1.8 (2) | C20—C21—C43—C45 | −114.94 (18) |
C19—C20—C21—C43 | −178.43 (15) | C22—C21—C43—C45 | 64.8 (2) |
C20—C21—C22—C23 | −0.8 (3) | C31—C30—C46—C47 | 36.4 (2) |
C43—C21—C22—C23 | 179.47 (16) | C29—C30—C46—C47 | −147.78 (16) |
C21—C22—C23—C24 | −1.3 (3) | C31—C30—C46—C48 | −87.9 (2) |
C22—C23—C24—C19 | 2.3 (2) | C29—C30—C46—C48 | 87.9 (2) |
Experimental details
Crystal data | |
Chemical formula | C48H40 |
Mr | 616.8 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 90 |
a, b, c (Å) | 18.0007 (4), 12.5083 (3), 16.0674 (4) |
β (°) | 91.004 (1) |
V (Å3) | 3617.15 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.06 |
Crystal size (mm) | 0.45 × 0.30 × 0.30 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor 1997) |
Tmin, Tmax | 0.972, 0.981 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13998, 8186, 5354 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.680 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.127, 1.02 |
No. of reflections | 8186 |
No. of parameters | 442 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.28 |
Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), IDEAL (Gould et al., 1988) and WinGX (Farrugia, 1999).
Footnotes
1CAS 186494-88-2.
Acknowledgements
The purchase of the diffractometer was made possible by Grant No. LEQSF(1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents. We are grateful to Professor Adam Matzger for providing the sample.
References
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Boese, R., Matzger, A. J. & Vollhardt, K. P. C. (1997). J. Am. Chem. Soc. 119, 2052–2053. CSD CrossRef CAS Web of Science Google Scholar
Cambridgesoft (2010). Chem3DPro. Cambridgesoft Corporation, Cambridge, MA, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Gould, R. O., Moulden, N., Taylor, N. & Taylor, P. (1988). IDEAL. Department of Chemistry, University of Edinburgh, Scotland. Google Scholar
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The title compound, C48H40, is a tetraisopropyl-substituted polyannulenoenyne and its structure was determined at 90 K. The 295 K structure of the unsubstituted parent annulene, C36H16, was previously determined by Boese et al. (1997; CSD: RICVEE, Allen, 2002; CAS: 186494–87-1), and is of quasi-D2 (222) symmetry, as determined by least-squares fit (Gould et al., 1988; δr.m.s. = 0.239 Å) of all 36 common carbon atoms of the parent to a model of C36H16 optimized in D2 symmetry by molecular mechanics (Cambridgesoft, 2010). Reasonable agreements result from the same least-squares fit of the title compound (at 90 K) to the parent (δr.m.s. =0.419 Å) and to the optimized model (δr.m.s. = 0.426 Å).
The six C≡C triple bond distances are all experimentally equal, falling in the narrow range 1.203 (2) - 1.206 (2) Å, while the C–C bonds linking the triple bonds have length C16—C17 1.370 (2) and C34—C35 1.377 (2) Å. The acetylenic bridges are slightly bowed outward, with C–C≡C angles in the range 177.59 (18) - 179.17 (18)° for the butadiyne bridges and in the range 174.43 (17) - 176.80 (17)° for the acetylene bridges. Distances between the following bond centroids provide a measure of overall molecular dimensions: C16—C17 to C34—C35 = 3.341 (2) Å, C7 ≡C8 to C25 ≡C26 = 7.650 (2) Å.