Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112046392/ln3153sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112046392/ln3153Isup2.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112046392/ln3153Isup3.cml |
CCDC reference: 808555
m-Quinquephenyl was synthesized using the Suzuki–Miyaura aryl cross-coupling method by adapting the procedure described in the literature (Miyaura & Suzuki, 1995; Liu et al., 2006). The compound was synthesized by the reaction of a mixture of 1,3-dibromobenzene (3 mmol), 3-boronic acid (11 mmol), Pd(OAc)2 (0.1 mmol) and K2CO3 (15 mmol) in distilled water (15 ml), toluene (30 ml) and ethanol (10 ml). The mixture was stirred under a nitrogen atmosphere for approximately 10 h at 350 K. The product was purified by recrystallization from methanol and by sublimation under reduced pressure (<10 Pa). The purity of the compounds was checked by gas chromatography, using an HP 4890 apparatus equipped with an HP-5 column, cross-linked, 5% diphenyl and 95% dimethylpolysiloxane, showing a % (m/m) purity greater than 99.8%. The relative atomic masses used were those recommended by the IUPAC Commission in 2007 (Wieser & Berglund, 2009). Crystals suitable for X-ray diffraction were obtained by recrystallization by evaporation from a solution in methanol–acetone (3:1 v/v).
H atoms were treated as riding, with aromatic C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). The positions of the H atoms were calculated and checked on a difference map during the refinement.
The crystal was a three-component nonmerohedral twin and was refined using an HKLF 5 reflection file (Sheldrick, 2008) with BASF values of 0.246 (2) and 0.0491 (3). This was discovered after an initial attempt at refinement gave a high R factor and the TwinRotMat option in PLATON (Spek, 2009) revealed the existence of three twin domains. The TwinRotMat option was used to generate the HKLF 5 reflection file from the original data, which had been integrated initially as a nontwinned data set.
The 202, 202, 200, 200, 204 and 102 reflections were omitted as they were obscured by the beam stop.
Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and OSCAIL (McArdle et al., 2004); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C30H22 | F(000) = 1616 |
Mr = 382.48 | Dx = 1.233 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 28626 reflections |
a = 13.5740 (7) Å | θ = 2.9–26.5° |
b = 7.1809 (4) Å | µ = 0.07 mm−1 |
c = 42.833 (2) Å | T = 150 K |
β = 99.274 (4)° | Needle, colourless |
V = 4120.5 (4) Å3 | 0.30 × 0.08 × 0.02 mm |
Z = 8 |
Bruker APEXII CCD area-detector diffractometer | 8455 independent reflections |
Radiation source: fine-focus sealed tube | 6424 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 8.33 pixels mm-1 | θmax = 26.5°, θmin = 2.9° |
ω scans | h = −17→16 |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | k = −9→9 |
Tmin = 0.979, Tmax = 0.999 | l = −53→15 |
28626 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0988P)2] where P = (Fo2 + 2Fc2)/3 |
8453 reflections | (Δ/σ)max = 0.001 |
543 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C30H22 | V = 4120.5 (4) Å3 |
Mr = 382.48 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.5740 (7) Å | µ = 0.07 mm−1 |
b = 7.1809 (4) Å | T = 150 K |
c = 42.833 (2) Å | 0.30 × 0.08 × 0.02 mm |
β = 99.274 (4)° |
Bruker APEXII CCD area-detector diffractometer | 8455 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 6424 reflections with I > 2σ(I) |
Tmin = 0.979, Tmax = 0.999 | Rint = 0.042 |
28626 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.22 e Å−3 |
8453 reflections | Δρmin = −0.27 e Å−3 |
543 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. |
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 > σ(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 | ||
C11A | 0.42665 (17) | 0.7263 (3) | 0.15232 (5) | 0.0275 (5) | |
C12A | 0.51917 (18) | 0.7150 (4) | 0.17196 (5) | 0.0339 (6) | |
H12A | 0.5753 | 0.6695 | 0.1636 | 0.041* | |
C13A | 0.5304 (2) | 0.7688 (4) | 0.20333 (6) | 0.0409 (6) | |
H13A | 0.5937 | 0.7587 | 0.2164 | 0.049* | |
C14A | 0.4496 (2) | 0.8374 (4) | 0.21572 (6) | 0.0419 (7) | |
H14A | 0.4576 | 0.8785 | 0.2371 | 0.050* | |
C15A | 0.3572 (2) | 0.8456 (4) | 0.19677 (5) | 0.0396 (6) | |
H15A | 0.3011 | 0.8894 | 0.2053 | 0.048* | |
C16A | 0.34562 (18) | 0.7908 (3) | 0.16549 (5) | 0.0324 (5) | |
H16A | 0.2815 | 0.7970 | 0.1528 | 0.039* | |
C21A | 0.41579 (16) | 0.6744 (3) | 0.11825 (5) | 0.0253 (5) | |
C22A | 0.49255 (16) | 0.7142 (3) | 0.10122 (5) | 0.0261 (5) | |
H22A | 0.5506 | 0.7761 | 0.1116 | 0.031* | |
C23A | 0.48663 (16) | 0.6657 (3) | 0.06951 (5) | 0.0259 (5) | |
C24A | 0.39996 (17) | 0.5785 (3) | 0.05429 (5) | 0.0306 (5) | |
H24A | 0.3941 | 0.5452 | 0.0326 | 0.037* | |
C25A | 0.32251 (17) | 0.5406 (3) | 0.07084 (5) | 0.0325 (5) | |
H25A | 0.2636 | 0.4818 | 0.0604 | 0.039* | |
C26A | 0.33005 (17) | 0.5873 (3) | 0.10237 (5) | 0.0291 (5) | |
H26A | 0.2764 | 0.5600 | 0.1134 | 0.035* | |
C31A | 0.57269 (17) | 0.7040 (3) | 0.05304 (5) | 0.0271 (5) | |
C32A | 0.66903 (16) | 0.6970 (3) | 0.06998 (5) | 0.0243 (5) | |
H32A | 0.6777 | 0.6626 | 0.0917 | 0.029* | |
C33A | 0.75358 (17) | 0.7381 (3) | 0.05658 (5) | 0.0261 (5) | |
C34A | 0.73898 (19) | 0.7850 (3) | 0.02437 (5) | 0.0309 (5) | |
H34A | 0.7948 | 0.8152 | 0.0145 | 0.037* | |
C35A | 0.6439 (2) | 0.7877 (4) | 0.00687 (5) | 0.0363 (6) | |
H35A | 0.6352 | 0.8170 | −0.0150 | 0.044* | |
C36A | 0.56147 (18) | 0.7482 (4) | 0.02089 (5) | 0.0325 (6) | |
H36A | 0.4967 | 0.7512 | 0.0086 | 0.039* | |
C41A | 0.85465 (17) | 0.7337 (3) | 0.07602 (5) | 0.0248 (5) | |
C42A | 0.86803 (17) | 0.7796 (3) | 0.10822 (5) | 0.0254 (5) | |
H42A | 0.8116 | 0.8152 | 0.1174 | 0.030* | |
C43A | 0.96152 (17) | 0.7749 (3) | 0.12728 (5) | 0.0265 (5) | |
C44A | 1.04363 (17) | 0.7258 (3) | 0.11342 (5) | 0.0309 (5) | |
H44A | 1.1082 | 0.7238 | 0.1259 | 0.037* | |
C45A | 1.03228 (18) | 0.6799 (4) | 0.08169 (5) | 0.0336 (6) | |
H45A | 1.0890 | 0.6464 | 0.0725 | 0.040* | |
C46A | 0.93914 (18) | 0.6825 (3) | 0.06326 (5) | 0.0309 (5) | |
H46A | 0.9323 | 0.6489 | 0.0416 | 0.037* | |
C51A | 0.97332 (17) | 0.8216 (3) | 0.16150 (5) | 0.0285 (5) | |
C52A | 0.91403 (18) | 0.9567 (4) | 0.17280 (5) | 0.0329 (5) | |
H52A | 0.8646 | 1.0196 | 0.1584 | 0.039* | |
C53A | 0.9262 (2) | 1.0006 (4) | 0.20470 (5) | 0.0421 (7) | |
H53A | 0.8852 | 1.0930 | 0.2120 | 0.051* | |
C54A | 0.9979 (2) | 0.9097 (4) | 0.22598 (6) | 0.0436 (7) | |
H54A | 1.0062 | 0.9393 | 0.2479 | 0.052* | |
C55A | 1.0573 (2) | 0.7761 (4) | 0.21525 (5) | 0.0398 (6) | |
H55A | 1.1070 | 0.7143 | 0.2298 | 0.048* | |
C56A | 1.04489 (18) | 0.7315 (4) | 0.18329 (5) | 0.0337 (6) | |
H56A | 1.0858 | 0.6382 | 0.1762 | 0.040* | |
C11B | 1.23715 (18) | 0.2329 (3) | 0.15439 (5) | 0.0304 (5) | |
C12B | 1.16226 (19) | 0.2218 (3) | 0.17298 (5) | 0.0337 (6) | |
H12B | 1.0981 | 0.1773 | 0.1639 | 0.040* | |
C13B | 1.1797 (2) | 0.2747 (4) | 0.20446 (5) | 0.0418 (7) | |
H13B | 1.1277 | 0.2659 | 0.2168 | 0.050* | |
C14B | 1.2732 (2) | 0.3407 (4) | 0.21809 (6) | 0.0465 (7) | |
H14B | 1.2849 | 0.3792 | 0.2396 | 0.056* | |
C15B | 1.3488 (2) | 0.3497 (4) | 0.20014 (6) | 0.0464 (7) | |
H15B | 1.4130 | 0.3928 | 0.2094 | 0.056* | |
C16B | 1.33127 (19) | 0.2963 (4) | 0.16878 (6) | 0.0385 (6) | |
H16B | 1.3841 | 0.3027 | 0.1567 | 0.046* | |
C21B | 1.21749 (17) | 0.1790 (3) | 0.12044 (5) | 0.0278 (5) | |
C22B | 1.12411 (17) | 0.2146 (3) | 0.10239 (5) | 0.0272 (5) | |
H22B | 1.0748 | 0.2758 | 0.1121 | 0.033* | |
C23B | 1.10068 (17) | 0.1635 (3) | 0.07061 (5) | 0.0276 (5) | |
C24B | 1.17384 (19) | 0.0753 (3) | 0.05660 (5) | 0.0335 (6) | |
H24B | 1.1597 | 0.0389 | 0.0350 | 0.040* | |
C25B | 1.26747 (19) | 0.0403 (4) | 0.07411 (6) | 0.0351 (6) | |
H25B | 1.3169 | −0.0201 | 0.0643 | 0.042* | |
C26B | 1.28958 (18) | 0.0923 (3) | 0.10552 (5) | 0.0329 (5) | |
H26B | 1.3542 | 0.0689 | 0.1171 | 0.039* | |
C31B | 0.99907 (18) | 0.2009 (3) | 0.05315 (5) | 0.0286 (5) | |
C32B | 0.91739 (17) | 0.1939 (3) | 0.06889 (5) | 0.0259 (5) | |
H32B | 0.9279 | 0.1582 | 0.0905 | 0.031* | |
C33B | 0.82084 (18) | 0.2366 (3) | 0.05441 (5) | 0.0285 (5) | |
C34B | 0.8064 (2) | 0.2864 (3) | 0.02240 (5) | 0.0356 (6) | |
H34B | 0.7415 | 0.3178 | 0.0118 | 0.043* | |
C35B | 0.8863 (2) | 0.2897 (4) | 0.00617 (5) | 0.0404 (7) | |
H35B | 0.8754 | 0.3206 | −0.0157 | 0.048* | |
C36B | 0.9814 (2) | 0.2493 (4) | 0.02097 (5) | 0.0365 (6) | |
H36B | 1.0354 | 0.2542 | 0.0094 | 0.044* | |
C41B | 0.73715 (17) | 0.2329 (3) | 0.07294 (5) | 0.0283 (5) | |
C42B | 0.75414 (17) | 0.2748 (3) | 0.10511 (5) | 0.0273 (5) | |
H42B | 0.8198 | 0.3068 | 0.1149 | 0.033* | |
C43B | 0.67802 (17) | 0.2713 (3) | 0.12340 (5) | 0.0300 (5) | |
C44B | 0.58204 (19) | 0.2254 (4) | 0.10854 (6) | 0.0375 (6) | |
H44B | 0.5288 | 0.2225 | 0.1205 | 0.045* | |
C45B | 0.56377 (19) | 0.1843 (4) | 0.07672 (6) | 0.0396 (6) | |
H45B | 0.4979 | 0.1538 | 0.0669 | 0.048* | |
C46B | 0.63964 (18) | 0.1867 (4) | 0.05895 (5) | 0.0342 (6) | |
H46B | 0.6259 | 0.1569 | 0.0371 | 0.041* | |
C51B | 0.69879 (17) | 0.3198 (4) | 0.15763 (5) | 0.0311 (5) | |
C52B | 0.76721 (18) | 0.4578 (4) | 0.16903 (5) | 0.0331 (6) | |
H52B | 0.8021 | 0.5211 | 0.1547 | 0.040* | |
C53B | 0.7855 (2) | 0.5049 (4) | 0.20080 (5) | 0.0415 (6) | |
H53B | 0.8321 | 0.6003 | 0.2080 | 0.050* | |
C54B | 0.7358 (2) | 0.4127 (4) | 0.22196 (6) | 0.0470 (7) | |
H54B | 0.7477 | 0.4449 | 0.2438 | 0.056* | |
C55B | 0.6686 (2) | 0.2728 (4) | 0.21110 (6) | 0.0477 (7) | |
H55B | 0.6347 | 0.2085 | 0.2256 | 0.057* | |
C56B | 0.6506 (2) | 0.2261 (4) | 0.17936 (6) | 0.0405 (6) | |
H56B | 0.6048 | 0.1291 | 0.1723 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C11A | 0.0309 (12) | 0.0237 (13) | 0.0284 (11) | −0.0015 (10) | 0.0065 (9) | 0.0036 (9) |
C12A | 0.0314 (13) | 0.0375 (15) | 0.0325 (12) | −0.0010 (11) | 0.0042 (10) | 0.0000 (11) |
C13A | 0.0428 (15) | 0.0443 (17) | 0.0331 (13) | −0.0040 (13) | −0.0011 (11) | −0.0004 (11) |
C14A | 0.0567 (17) | 0.0425 (17) | 0.0272 (12) | −0.0016 (14) | 0.0094 (12) | −0.0011 (11) |
C15A | 0.0484 (15) | 0.0392 (16) | 0.0348 (13) | 0.0080 (13) | 0.0177 (11) | 0.0064 (11) |
C16A | 0.0335 (13) | 0.0297 (14) | 0.0342 (12) | 0.0018 (11) | 0.0064 (10) | 0.0067 (10) |
C21A | 0.0249 (11) | 0.0191 (12) | 0.0305 (11) | 0.0018 (9) | 0.0004 (9) | 0.0034 (9) |
C22A | 0.0239 (11) | 0.0240 (13) | 0.0290 (11) | 0.0006 (10) | −0.0002 (9) | −0.0001 (9) |
C23A | 0.0277 (12) | 0.0209 (12) | 0.0270 (11) | 0.0035 (10) | −0.0014 (9) | 0.0013 (9) |
C24A | 0.0336 (13) | 0.0265 (13) | 0.0286 (11) | 0.0009 (10) | −0.0041 (9) | −0.0014 (10) |
C25A | 0.0268 (12) | 0.0269 (13) | 0.0405 (13) | −0.0013 (10) | −0.0048 (10) | 0.0000 (10) |
C26A | 0.0262 (11) | 0.0248 (13) | 0.0353 (12) | 0.0006 (10) | 0.0021 (9) | 0.0050 (10) |
C31A | 0.0345 (12) | 0.0223 (12) | 0.0233 (10) | 0.0005 (10) | 0.0014 (9) | −0.0034 (9) |
C32A | 0.0340 (12) | 0.0220 (12) | 0.0168 (9) | 0.0017 (10) | 0.0037 (8) | 0.0003 (8) |
C33A | 0.0373 (13) | 0.0199 (12) | 0.0221 (10) | 0.0022 (10) | 0.0080 (9) | 0.0005 (8) |
C34A | 0.0445 (14) | 0.0295 (14) | 0.0206 (10) | 0.0008 (11) | 0.0107 (10) | −0.0007 (9) |
C35A | 0.0534 (15) | 0.0365 (16) | 0.0185 (11) | 0.0011 (13) | 0.0043 (10) | 0.0009 (10) |
C36A | 0.0382 (13) | 0.0340 (14) | 0.0222 (11) | 0.0008 (11) | −0.0046 (9) | 0.0005 (9) |
C41A | 0.0329 (12) | 0.0191 (12) | 0.0240 (10) | 0.0005 (10) | 0.0094 (9) | 0.0032 (8) |
C42A | 0.0302 (11) | 0.0224 (12) | 0.0249 (10) | 0.0006 (10) | 0.0088 (9) | 0.0031 (9) |
C43A | 0.0310 (12) | 0.0218 (12) | 0.0269 (11) | −0.0013 (10) | 0.0052 (9) | 0.0032 (9) |
C44A | 0.0254 (11) | 0.0325 (14) | 0.0346 (12) | −0.0008 (11) | 0.0041 (9) | 0.0019 (10) |
C45A | 0.0322 (13) | 0.0345 (14) | 0.0376 (13) | 0.0029 (11) | 0.0161 (10) | 0.0011 (11) |
C46A | 0.0405 (14) | 0.0277 (13) | 0.0278 (11) | −0.0008 (11) | 0.0154 (10) | −0.0001 (10) |
C51A | 0.0268 (11) | 0.0282 (13) | 0.0300 (11) | −0.0040 (10) | 0.0035 (9) | 0.0015 (10) |
C52A | 0.0326 (13) | 0.0360 (15) | 0.0291 (12) | 0.0054 (11) | 0.0020 (9) | −0.0015 (10) |
C53A | 0.0434 (15) | 0.0498 (18) | 0.0330 (13) | 0.0016 (13) | 0.0055 (11) | −0.0103 (12) |
C54A | 0.0519 (16) | 0.0514 (18) | 0.0258 (12) | −0.0068 (14) | 0.0010 (11) | −0.0051 (11) |
C55A | 0.0390 (14) | 0.0443 (17) | 0.0323 (12) | −0.0024 (13) | −0.0056 (11) | 0.0062 (11) |
C56A | 0.0333 (13) | 0.0313 (14) | 0.0354 (12) | −0.0008 (11) | 0.0022 (10) | 0.0021 (10) |
C11B | 0.0323 (12) | 0.0234 (13) | 0.0348 (12) | −0.0012 (10) | 0.0030 (10) | 0.0081 (10) |
C12B | 0.0356 (13) | 0.0303 (14) | 0.0343 (12) | 0.0030 (11) | 0.0033 (10) | 0.0018 (10) |
C13B | 0.0531 (16) | 0.0390 (17) | 0.0328 (13) | 0.0066 (13) | 0.0049 (12) | 0.0049 (11) |
C14B | 0.069 (2) | 0.0340 (16) | 0.0307 (13) | 0.0040 (14) | −0.0096 (13) | 0.0015 (11) |
C15B | 0.0513 (17) | 0.0342 (16) | 0.0470 (15) | −0.0056 (14) | −0.0120 (12) | 0.0093 (12) |
C16B | 0.0375 (14) | 0.0322 (15) | 0.0433 (14) | −0.0026 (12) | −0.0014 (11) | 0.0108 (11) |
C21B | 0.0308 (12) | 0.0206 (12) | 0.0336 (12) | −0.0035 (10) | 0.0097 (9) | 0.0065 (9) |
C22B | 0.0323 (12) | 0.0224 (13) | 0.0288 (11) | −0.0011 (10) | 0.0106 (9) | 0.0020 (9) |
C23B | 0.0353 (13) | 0.0213 (12) | 0.0283 (11) | −0.0022 (10) | 0.0112 (9) | 0.0011 (9) |
C24B | 0.0460 (14) | 0.0239 (13) | 0.0343 (12) | −0.0038 (11) | 0.0176 (11) | 0.0008 (10) |
C25B | 0.0393 (14) | 0.0256 (14) | 0.0454 (14) | 0.0043 (11) | 0.0215 (11) | 0.0066 (11) |
C26B | 0.0302 (12) | 0.0256 (14) | 0.0449 (14) | 0.0016 (11) | 0.0121 (10) | 0.0072 (10) |
C31B | 0.0416 (13) | 0.0201 (12) | 0.0249 (11) | −0.0017 (10) | 0.0083 (9) | −0.0007 (9) |
C32B | 0.0359 (12) | 0.0207 (12) | 0.0197 (10) | −0.0023 (10) | 0.0003 (9) | 0.0018 (8) |
C33B | 0.0368 (13) | 0.0199 (12) | 0.0269 (11) | −0.0018 (10) | −0.0004 (9) | −0.0022 (9) |
C34B | 0.0478 (15) | 0.0308 (15) | 0.0246 (11) | −0.0001 (12) | −0.0050 (10) | −0.0012 (10) |
C35B | 0.0599 (17) | 0.0397 (17) | 0.0201 (11) | −0.0001 (13) | 0.0023 (11) | −0.0003 (10) |
C36B | 0.0523 (16) | 0.0337 (15) | 0.0251 (11) | −0.0008 (12) | 0.0113 (11) | −0.0014 (10) |
C41B | 0.0321 (12) | 0.0186 (12) | 0.0312 (11) | 0.0019 (10) | −0.0042 (9) | 0.0035 (9) |
C42B | 0.0267 (11) | 0.0226 (13) | 0.0313 (11) | 0.0012 (10) | 0.0006 (9) | 0.0024 (9) |
C43B | 0.0293 (12) | 0.0219 (13) | 0.0380 (12) | 0.0010 (10) | 0.0031 (10) | 0.0033 (10) |
C44B | 0.0276 (12) | 0.0273 (14) | 0.0579 (16) | 0.0022 (11) | 0.0074 (11) | 0.0018 (11) |
C45B | 0.0261 (13) | 0.0309 (15) | 0.0566 (16) | −0.0004 (11) | −0.0094 (11) | −0.0031 (12) |
C46B | 0.0330 (13) | 0.0285 (14) | 0.0370 (13) | 0.0028 (11) | −0.0069 (10) | −0.0018 (10) |
C51B | 0.0282 (12) | 0.0288 (14) | 0.0381 (12) | 0.0048 (11) | 0.0109 (10) | 0.0047 (10) |
C52B | 0.0326 (13) | 0.0359 (15) | 0.0318 (12) | 0.0023 (11) | 0.0087 (10) | 0.0035 (10) |
C53B | 0.0414 (15) | 0.0477 (17) | 0.0358 (13) | 0.0022 (13) | 0.0074 (11) | −0.0030 (11) |
C54B | 0.0562 (17) | 0.0526 (19) | 0.0347 (13) | 0.0138 (15) | 0.0149 (12) | 0.0055 (13) |
C55B | 0.0569 (18) | 0.0451 (18) | 0.0478 (15) | 0.0113 (15) | 0.0284 (14) | 0.0117 (13) |
C56B | 0.0411 (15) | 0.0351 (16) | 0.0501 (15) | 0.0030 (12) | 0.0216 (12) | 0.0061 (12) |
C11A—C16A | 1.394 (3) | C11B—C12B | 1.391 (3) |
C11A—C12A | 1.397 (3) | C11B—C16B | 1.402 (3) |
C11A—C21A | 1.490 (3) | C11B—C21B | 1.487 (3) |
C12A—C13A | 1.383 (3) | C12B—C13B | 1.384 (3) |
C12A—H12A | 0.9500 | C12B—H12B | 0.9500 |
C13A—C14A | 1.384 (4) | C13B—C14B | 1.393 (4) |
C13A—H13A | 0.9500 | C13B—H13B | 0.9500 |
C14A—C15A | 1.381 (4) | C14B—C15B | 1.379 (4) |
C14A—H14A | 0.9500 | C14B—H14B | 0.9500 |
C15A—C16A | 1.381 (3) | C15B—C16B | 1.380 (4) |
C15A—H15A | 0.9500 | C15B—H15B | 0.9500 |
C16A—H16A | 0.9500 | C16B—H16B | 0.9500 |
C21A—C22A | 1.394 (3) | C21B—C22B | 1.398 (3) |
C21A—C26A | 1.398 (3) | C21B—C26B | 1.398 (3) |
C22A—C23A | 1.392 (3) | C22B—C23B | 1.396 (3) |
C22A—H22A | 0.9500 | C22B—H22B | 0.9500 |
C23A—C24A | 1.398 (3) | C23B—C24B | 1.393 (3) |
C23A—C31A | 1.484 (3) | C23B—C31B | 1.484 (3) |
C24A—C25A | 1.386 (3) | C24B—C25B | 1.390 (3) |
C24A—H24A | 0.9500 | C24B—H24B | 0.9500 |
C25A—C26A | 1.379 (3) | C25B—C26B | 1.382 (3) |
C25A—H25A | 0.9500 | C25B—H25B | 0.9500 |
C26A—H26A | 0.9500 | C26B—H26B | 0.9500 |
C31A—C32A | 1.391 (3) | C31B—C32B | 1.388 (3) |
C31A—C36A | 1.397 (3) | C31B—C36B | 1.404 (3) |
C32A—C33A | 1.395 (3) | C32B—C33B | 1.391 (3) |
C32A—H32A | 0.9500 | C32B—H32B | 0.9500 |
C33A—C34A | 1.403 (3) | C33B—C34B | 1.400 (3) |
C33A—C41A | 1.486 (3) | C33B—C41B | 1.487 (3) |
C34A—C35A | 1.384 (3) | C34B—C35B | 1.380 (4) |
C34A—H34A | 0.9500 | C34B—H34B | 0.9500 |
C35A—C36A | 1.382 (3) | C35B—C36B | 1.374 (4) |
C35A—H35A | 0.9500 | C35B—H35B | 0.9500 |
C36A—H36A | 0.9500 | C36B—H36B | 0.9500 |
C41A—C46A | 1.397 (3) | C41B—C42B | 1.393 (3) |
C41A—C42A | 1.401 (3) | C41B—C46B | 1.402 (3) |
C42A—C43A | 1.395 (3) | C42B—C43B | 1.394 (3) |
C42A—H42A | 0.9500 | C42B—H42B | 0.9500 |
C43A—C44A | 1.390 (3) | C43B—C44B | 1.394 (3) |
C43A—C51A | 1.487 (3) | C43B—C51B | 1.489 (3) |
C44A—C45A | 1.383 (3) | C44B—C45B | 1.377 (3) |
C44A—H44A | 0.9500 | C44B—H44B | 0.9500 |
C45A—C46A | 1.379 (3) | C45B—C46B | 1.376 (4) |
C45A—H45A | 0.9500 | C45B—H45B | 0.9500 |
C46A—H46A | 0.9500 | C46B—H46B | 0.9500 |
C51A—C56A | 1.393 (3) | C51B—C52B | 1.392 (3) |
C51A—C52A | 1.396 (3) | C51B—C56B | 1.394 (3) |
C52A—C53A | 1.386 (3) | C52B—C53B | 1.385 (3) |
C52A—H52A | 0.9500 | C52B—H52B | 0.9500 |
C53A—C54A | 1.385 (4) | C53B—C54B | 1.383 (4) |
C53A—H53A | 0.9500 | C53B—H53B | 0.9500 |
C54A—C55A | 1.379 (4) | C54B—C55B | 1.386 (4) |
C54A—H54A | 0.9500 | C54B—H54B | 0.9500 |
C55A—C56A | 1.389 (3) | C55B—C56B | 1.383 (4) |
C55A—H55A | 0.9500 | C55B—H55B | 0.9500 |
C56A—H56A | 0.9500 | C56B—H56B | 0.9500 |
C16A—C11A—C12A | 117.9 (2) | C12B—C11B—C16B | 117.7 (2) |
C16A—C11A—C21A | 121.3 (2) | C12B—C11B—C21B | 120.8 (2) |
C12A—C11A—C21A | 120.8 (2) | C16B—C11B—C21B | 121.4 (2) |
C13A—C12A—C11A | 121.1 (2) | C13B—C12B—C11B | 121.1 (2) |
C13A—C12A—H12A | 119.5 | C13B—C12B—H12B | 119.5 |
C11A—C12A—H12A | 119.5 | C11B—C12B—H12B | 119.5 |
C12A—C13A—C14A | 120.1 (2) | C12B—C13B—C14B | 120.2 (3) |
C12A—C13A—H13A | 119.9 | C12B—C13B—H13B | 119.9 |
C14A—C13A—H13A | 119.9 | C14B—C13B—H13B | 119.9 |
C15A—C14A—C13A | 119.4 (2) | C15B—C14B—C13B | 119.5 (2) |
C15A—C14A—H14A | 120.3 | C15B—C14B—H14B | 120.3 |
C13A—C14A—H14A | 120.3 | C13B—C14B—H14B | 120.3 |
C16A—C15A—C14A | 120.6 (2) | C14B—C15B—C16B | 120.2 (3) |
C16A—C15A—H15A | 119.7 | C14B—C15B—H15B | 119.9 |
C14A—C15A—H15A | 119.7 | C16B—C15B—H15B | 119.9 |
C15A—C16A—C11A | 120.9 (2) | C15B—C16B—C11B | 121.3 (2) |
C15A—C16A—H16A | 119.5 | C15B—C16B—H16B | 119.3 |
C11A—C16A—H16A | 119.5 | C11B—C16B—H16B | 119.3 |
C22A—C21A—C26A | 118.09 (19) | C22B—C21B—C26B | 117.9 (2) |
C22A—C21A—C11A | 119.79 (19) | C22B—C21B—C11B | 119.8 (2) |
C26A—C21A—C11A | 122.12 (19) | C26B—C21B—C11B | 122.3 (2) |
C23A—C22A—C21A | 121.9 (2) | C23B—C22B—C21B | 122.3 (2) |
C23A—C22A—H22A | 119.0 | C23B—C22B—H22B | 118.8 |
C21A—C22A—H22A | 119.0 | C21B—C22B—H22B | 118.8 |
C22A—C23A—C24A | 118.6 (2) | C24B—C23B—C22B | 118.3 (2) |
C22A—C23A—C31A | 119.44 (19) | C24B—C23B—C31B | 122.3 (2) |
C24A—C23A—C31A | 121.94 (19) | C22B—C23B—C31B | 119.40 (19) |
C25A—C24A—C23A | 120.0 (2) | C25B—C24B—C23B | 120.2 (2) |
C25A—C24A—H24A | 120.0 | C25B—C24B—H24B | 119.9 |
C23A—C24A—H24A | 120.0 | C23B—C24B—H24B | 119.9 |
C26A—C25A—C24A | 120.7 (2) | C26B—C25B—C24B | 120.8 (2) |
C26A—C25A—H25A | 119.7 | C26B—C25B—H25B | 119.6 |
C24A—C25A—H25A | 119.7 | C24B—C25B—H25B | 119.6 |
C25A—C26A—C21A | 120.7 (2) | C25B—C26B—C21B | 120.5 (2) |
C25A—C26A—H26A | 119.7 | C25B—C26B—H26B | 119.8 |
C21A—C26A—H26A | 119.7 | C21B—C26B—H26B | 119.8 |
C32A—C31A—C36A | 117.8 (2) | C32B—C31B—C36B | 117.5 (2) |
C32A—C31A—C23A | 119.41 (17) | C32B—C31B—C23B | 119.94 (18) |
C36A—C31A—C23A | 122.8 (2) | C36B—C31B—C23B | 122.5 (2) |
C31A—C32A—C33A | 122.98 (18) | C31B—C32B—C33B | 122.97 (19) |
C31A—C32A—H32A | 118.5 | C31B—C32B—H32B | 118.5 |
C33A—C32A—H32A | 118.5 | C33B—C32B—H32B | 118.5 |
C32A—C33A—C34A | 117.4 (2) | C32B—C33B—C34B | 117.8 (2) |
C32A—C33A—C41A | 120.76 (17) | C32B—C33B—C41B | 120.25 (18) |
C34A—C33A—C41A | 121.83 (19) | C34B—C33B—C41B | 121.9 (2) |
C35A—C34A—C33A | 120.5 (2) | C35B—C34B—C33B | 120.0 (2) |
C35A—C34A—H34A | 119.8 | C35B—C34B—H34B | 120.0 |
C33A—C34A—H34A | 119.8 | C33B—C34B—H34B | 120.0 |
C36A—C35A—C34A | 120.77 (19) | C36B—C35B—C34B | 121.3 (2) |
C36A—C35A—H35A | 119.6 | C36B—C35B—H35B | 119.3 |
C34A—C35A—H35A | 119.6 | C34B—C35B—H35B | 119.3 |
C35A—C36A—C31A | 120.5 (2) | C35B—C36B—C31B | 120.3 (2) |
C35A—C36A—H36A | 119.8 | C35B—C36B—H36B | 119.9 |
C31A—C36A—H36A | 119.8 | C31B—C36B—H36B | 119.9 |
C46A—C41A—C42A | 117.6 (2) | C42B—C41B—C46B | 117.9 (2) |
C46A—C41A—C33A | 121.90 (18) | C42B—C41B—C33B | 120.3 (2) |
C42A—C41A—C33A | 120.53 (18) | C46B—C41B—C33B | 121.73 (19) |
C43A—C42A—C41A | 122.1 (2) | C41B—C42B—C43B | 122.2 (2) |
C43A—C42A—H42A | 118.9 | C41B—C42B—H42B | 118.9 |
C41A—C42A—H42A | 118.9 | C43B—C42B—H42B | 118.9 |
C44A—C43A—C42A | 118.21 (19) | C42B—C43B—C44B | 118.0 (2) |
C44A—C43A—C51A | 120.8 (2) | C42B—C43B—C51B | 120.6 (2) |
C42A—C43A—C51A | 121.01 (19) | C44B—C43B—C51B | 121.3 (2) |
C45A—C44A—C43A | 120.7 (2) | C45B—C44B—C43B | 120.6 (2) |
C45A—C44A—H44A | 119.7 | C45B—C44B—H44B | 119.7 |
C43A—C44A—H44A | 119.7 | C43B—C44B—H44B | 119.7 |
C46A—C45A—C44A | 120.4 (2) | C46B—C45B—C44B | 120.9 (2) |
C46A—C45A—H45A | 119.8 | C46B—C45B—H45B | 119.6 |
C44A—C45A—H45A | 119.8 | C44B—C45B—H45B | 119.6 |
C45A—C46A—C41A | 121.0 (2) | C45B—C46B—C41B | 120.4 (2) |
C45A—C46A—H46A | 119.5 | C45B—C46B—H46B | 119.8 |
C41A—C46A—H46A | 119.5 | C41B—C46B—H46B | 119.8 |
C56A—C51A—C52A | 118.0 (2) | C52B—C51B—C56B | 117.9 (2) |
C56A—C51A—C43A | 120.5 (2) | C52B—C51B—C43B | 121.5 (2) |
C52A—C51A—C43A | 121.5 (2) | C56B—C51B—C43B | 120.7 (2) |
C53A—C52A—C51A | 121.1 (2) | C53B—C52B—C51B | 121.5 (2) |
C53A—C52A—H52A | 119.5 | C53B—C52B—H52B | 119.2 |
C51A—C52A—H52A | 119.5 | C51B—C52B—H52B | 119.2 |
C54A—C53A—C52A | 120.0 (2) | C54B—C53B—C52B | 119.8 (3) |
C54A—C53A—H53A | 120.0 | C54B—C53B—H53B | 120.1 |
C52A—C53A—H53A | 120.0 | C52B—C53B—H53B | 120.1 |
C55A—C54A—C53A | 119.7 (2) | C53B—C54B—C55B | 119.4 (2) |
C55A—C54A—H54A | 120.1 | C53B—C54B—H54B | 120.3 |
C53A—C54A—H54A | 120.1 | C55B—C54B—H54B | 120.3 |
C54A—C55A—C56A | 120.3 (2) | C56B—C55B—C54B | 120.6 (2) |
C54A—C55A—H55A | 119.9 | C56B—C55B—H55B | 119.7 |
C56A—C55A—H55A | 119.9 | C54B—C55B—H55B | 119.7 |
C55A—C56A—C51A | 120.9 (2) | C55B—C56B—C51B | 120.7 (3) |
C55A—C56A—H56A | 119.5 | C55B—C56B—H56B | 119.6 |
C51A—C56A—H56A | 119.5 | C51B—C56B—H56B | 119.6 |
C16A—C11A—C12A—C13A | −1.0 (4) | C16B—C11B—C12B—C13B | 1.1 (4) |
C21A—C11A—C12A—C13A | 177.8 (2) | C21B—C11B—C12B—C13B | −178.9 (2) |
C11A—C12A—C13A—C14A | −0.8 (4) | C11B—C12B—C13B—C14B | 0.2 (4) |
C12A—C13A—C14A—C15A | 2.2 (4) | C12B—C13B—C14B—C15B | −1.2 (4) |
C13A—C14A—C15A—C16A | −1.7 (4) | C13B—C14B—C15B—C16B | 1.0 (4) |
C14A—C15A—C16A—C11A | −0.1 (4) | C14B—C15B—C16B—C11B | 0.3 (4) |
C12A—C11A—C16A—C15A | 1.5 (4) | C12B—C11B—C16B—C15B | −1.3 (4) |
C21A—C11A—C16A—C15A | −177.4 (2) | C21B—C11B—C16B—C15B | 178.7 (2) |
C16A—C11A—C21A—C22A | 142.8 (2) | C12B—C11B—C21B—C22B | 35.2 (3) |
C12A—C11A—C21A—C22A | −36.0 (3) | C16B—C11B—C21B—C22B | −144.8 (2) |
C16A—C11A—C21A—C26A | −36.7 (3) | C12B—C11B—C21B—C26B | −144.7 (2) |
C12A—C11A—C21A—C26A | 144.5 (2) | C16B—C11B—C21B—C26B | 35.3 (3) |
C26A—C21A—C22A—C23A | −1.5 (3) | C26B—C21B—C22B—C23B | 1.3 (3) |
C11A—C21A—C22A—C23A | 178.9 (2) | C11B—C21B—C22B—C23B | −178.6 (2) |
C21A—C22A—C23A—C24A | 1.5 (3) | C21B—C22B—C23B—C24B | −0.5 (3) |
C21A—C22A—C23A—C31A | −177.2 (2) | C21B—C22B—C23B—C31B | 178.3 (2) |
C22A—C23A—C24A—C25A | −0.5 (3) | C22B—C23B—C24B—C25B | −0.1 (3) |
C31A—C23A—C24A—C25A | 178.1 (2) | C31B—C23B—C24B—C25B | −178.8 (2) |
C23A—C24A—C25A—C26A | −0.3 (4) | C23B—C24B—C25B—C26B | −0.1 (4) |
C24A—C25A—C26A—C21A | 0.2 (4) | C24B—C25B—C26B—C21B | 0.9 (4) |
C22A—C21A—C26A—C25A | 0.7 (3) | C22B—C21B—C26B—C25B | −1.4 (3) |
C11A—C21A—C26A—C25A | −179.8 (2) | C11B—C21B—C26B—C25B | 178.4 (2) |
C22A—C23A—C31A—C32A | 32.0 (3) | C24B—C23B—C31B—C32B | 145.9 (2) |
C24A—C23A—C31A—C32A | −146.6 (2) | C22B—C23B—C31B—C32B | −32.8 (3) |
C22A—C23A—C31A—C36A | −147.7 (2) | C24B—C23B—C31B—C36B | −36.0 (4) |
C24A—C23A—C31A—C36A | 33.7 (4) | C22B—C23B—C31B—C36B | 145.3 (2) |
C36A—C31A—C32A—C33A | 2.2 (3) | C36B—C31B—C32B—C33B | −1.6 (3) |
C23A—C31A—C32A—C33A | −177.5 (2) | C23B—C31B—C32B—C33B | 176.6 (2) |
C31A—C32A—C33A—C34A | −1.2 (3) | C31B—C32B—C33B—C34B | 0.9 (3) |
C31A—C32A—C33A—C41A | 178.2 (2) | C31B—C32B—C33B—C41B | −177.8 (2) |
C32A—C33A—C34A—C35A | −0.7 (3) | C32B—C33B—C34B—C35B | 0.7 (4) |
C41A—C33A—C34A—C35A | 179.9 (2) | C41B—C33B—C34B—C35B | 179.4 (2) |
C33A—C34A—C35A—C36A | 1.4 (4) | C33B—C34B—C35B—C36B | −1.6 (4) |
C34A—C35A—C36A—C31A | −0.3 (4) | C34B—C35B—C36B—C31B | 0.9 (4) |
C32A—C31A—C36A—C35A | −1.5 (4) | C32B—C31B—C36B—C35B | 0.7 (3) |
C23A—C31A—C36A—C35A | 178.2 (2) | C23B—C31B—C36B—C35B | −177.4 (2) |
C32A—C33A—C41A—C46A | 147.7 (2) | C32B—C33B—C41B—C42B | 30.6 (3) |
C34A—C33A—C41A—C46A | −32.9 (3) | C34B—C33B—C41B—C42B | −148.1 (2) |
C32A—C33A—C41A—C42A | −31.6 (3) | C32B—C33B—C41B—C46B | −149.1 (2) |
C34A—C33A—C41A—C42A | 147.7 (2) | C34B—C33B—C41B—C46B | 32.3 (3) |
C46A—C41A—C42A—C43A | −0.2 (3) | C46B—C41B—C42B—C43B | 0.2 (3) |
C33A—C41A—C42A—C43A | 179.2 (2) | C33B—C41B—C42B—C43B | −179.4 (2) |
C41A—C42A—C43A—C44A | 1.1 (3) | C41B—C42B—C43B—C44B | −0.5 (4) |
C41A—C42A—C43A—C51A | −179.1 (2) | C41B—C42B—C43B—C51B | −179.1 (2) |
C42A—C43A—C44A—C45A | −1.1 (3) | C42B—C43B—C44B—C45B | 0.3 (4) |
C51A—C43A—C44A—C45A | 179.1 (2) | C51B—C43B—C44B—C45B | 178.8 (2) |
C43A—C44A—C45A—C46A | 0.1 (4) | C43B—C44B—C45B—C46B | 0.3 (4) |
C44A—C45A—C46A—C41A | 0.9 (4) | C44B—C45B—C46B—C41B | −0.6 (4) |
C42A—C41A—C46A—C45A | −0.8 (4) | C42B—C41B—C46B—C45B | 0.3 (4) |
C33A—C41A—C46A—C45A | 179.8 (2) | C33B—C41B—C46B—C45B | 179.9 (2) |
C44A—C43A—C51A—C56A | −34.2 (3) | C42B—C43B—C51B—C52B | 35.9 (3) |
C42A—C43A—C51A—C56A | 146.1 (2) | C44B—C43B—C51B—C52B | −142.6 (3) |
C44A—C43A—C51A—C52A | 145.5 (2) | C42B—C43B—C51B—C56B | −143.4 (2) |
C42A—C43A—C51A—C52A | −34.3 (3) | C44B—C43B—C51B—C56B | 38.1 (3) |
C56A—C51A—C52A—C53A | 0.3 (4) | C56B—C51B—C52B—C53B | −1.6 (4) |
C43A—C51A—C52A—C53A | −179.4 (2) | C43B—C51B—C52B—C53B | 179.1 (2) |
C51A—C52A—C53A—C54A | −0.1 (4) | C51B—C52B—C53B—C54B | 0.6 (4) |
C52A—C53A—C54A—C55A | 0.2 (4) | C52B—C53B—C54B—C55B | 0.5 (4) |
C53A—C54A—C55A—C56A | −0.5 (4) | C53B—C54B—C55B—C56B | −0.4 (4) |
C54A—C55A—C56A—C51A | 0.7 (4) | C54B—C55B—C56B—C51B | −0.6 (4) |
C52A—C51A—C56A—C55A | −0.5 (4) | C52B—C51B—C56B—C55B | 1.6 (4) |
C43A—C51A—C56A—C55A | 179.1 (2) | C43B—C51B—C56B—C55B | −179.0 (2) |
Experimental details
Crystal data | |
Chemical formula | C30H22 |
Mr | 382.48 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 13.5740 (7), 7.1809 (4), 42.833 (2) |
β (°) | 99.274 (4) |
V (Å3) | 4120.5 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.30 × 0.08 × 0.02 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.979, 0.999 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28626, 8455, 6424 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.155, 1.02 |
No. of reflections | 8453 |
No. of parameters | 543 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.27 |
Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and OSCAIL (McArdle et al., 2004), PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008).
Rings | LTA | LTB | RTA | RTB |
1–2 | 36.28 (11) | 35.30 (12) | 36.25 (9) | 36.11 (9) |
2–3 | 32.11 (11) | 33.91 (11) | 32.22 (8) | 34.39 (8) |
3–4 | 31.54 (11) | 30.89 (12) | 30.67 (8) | 30.51 (9) |
4–5 | 34.16 (12) | 37.07 (13) | 35.68 (10) | 35.68 (10) |
The angles are measured going from the ring containing atom C11 (ring 1) through to that containing C51 (ring 5) in all molecules. |
Molecule | Molecule | R.m.s. fit (wghtd) (Å) | Isometricity index (wghtd) | R.m.s. fit (unit weights) (Å) | Isometricity index (unit) | R.m.s. fit of bond lengths (Å) | R.m.s. fit of angles (°) | Fit Rotation Angle (°) |
LTA* | LTB | 0.044 | 95.6 | 0.038 | 96.2 | 0.0045 | 0.297 | 179.68 |
RTA* | RTB | 0.053 | 94.7 | 0.049 | 95.1 | 0.0042 | 0.270 | 179.79 |
LTA* | RTA | 0.036 | 96.4 | 0.032 | 96.8 | 0.0065 | 0.353 | 89.91 |
LTA | RTB | 0.063 | 93.7 | 0.060 | 94.0 | 0.0066 | 0.332 | 179.69 |
LTB | RTA | 0.037 | 96.3 | 0.036 | 96.4 | 0.0072 | 0.316 | -179.72 |
LTB* | RTB | 0.061 | 93.9 | 0.054 | 94.6 | 0.0076 | 0.292 | -90.58 |
Note: * denotes an inverted molecule. |
Molecule | x | y | z | Δx | Δy | Δz |
LTA | 0.6876 | 0.7492 | 0.1196 | |||
LTB | 0.9459 | 0.2502 | 0.1187 | 0.2583 | 0.4990 | 0.0009 |
RTA | 0.3231 | 0.1872 | 0.2602 | |||
RTB | 0.8220 | 0.4447 | 0.2655 | 0.4989 | 0.2575 | 0.0053 |
Polymorph | C | H | Ring (pivot atom) | Symmetry operator for ring | C—H | H···Cg | C···Cg | Angle at H |
LT | C53B | H53B | Cg(C51A) | x, y, z | 0.95 | 2.96 | 3.801 (3) | 149 |
LT | C25B | H25B | Cg(C21A) | x + 1, y - 1, z | 0.95 | 2.91 | 3.521 (3) | 123 |
LT | C15A | H15A | Cg(C11B) | x - 1, y + 1, z | 0.95 | 3.00 | 3.451 (3) | 111 |
LT | C46A | H46A | Cg(C31B) | x, y, z | 0.95 | 2.95 | 3.354 (2) | 107 |
LT | C46B | H46B | Cg(C31A) | x, y - 1, z | 0.95 | 3.00 | 3.319 (3) | 101 |
RT | C53B | H53B | Cg(C51A) | x, y - 1, z | 0.97 | 3.03 | 3.867 | 145 |
RT | C25B | H25B | Cg(C21A) | x + 1, y + 1, z | 1.03 | 2.97 | 3.606 | 122 |
RT | C15A | H15A | Cg(C11B) | x - 1, y - 1, z | 0.95 | 3.12 | 3.503 | 107 |
RT | C46A | H46A | Cg(C31B) | x, y, z | 1.00 | 2.97 | 3.404 | 107 |
RT | C46B | H46B | Cg(C31A) | x + 1, y, z | 0.99 | 3.06 | 3.346 | 98 |
Cg is the centre of gravity of the ring containing the indicated atom. |
Polyphenyls are used in technological industries, either directly (e.g. as dyes, thermal printing materials or coolants) or as starting materials for functionalized derivatives that are incorporated, for instance, in nonspreading lubricants, emulsifiers, optical brighteners, crop protection products and plastics. In spite of this, experimental data for thermochemical parameters of these compounds that would permit inferences to be made concerning not only their relative stability, but also structure/molecular energetics relationships or thermophysical properties, are scarce.
In the course of a thermochemical study of polyphenylenes, particularly with regard to the effect of isomerization on the fusion temperatures, heat capacities, enthalpies of formation and enthalpies of vaporization, m-quinquephenyl, (I), has been synthesized, following a similar procedure used for a previously optimized Suzuki–Miyaura cross-coupling reaction (Suzuki, 2011; Miyaura, 2002) for polyphenyl compounds (Lima et al., 2011). A search of the literature revealed that (I) had already been characterized structurally by X-ray diffraction at room temperature (283–303 K; [Reference?]). Nevertheless, it is well known that isomers belonging to the parent series of p-polyphenyl oligomers [n(phenyl) = 3–4] undergo solid-phase transitions (Baker et al., 1990, and references therein). Those transitions are characterized by an order/disorder phase change, from twisted (at lower temperatures) to planar (when heated) (Delugeard et al., 1976; Baudour et al., 1978), so the question of whether a phase transition would occur in the m-quinquephenyl isomer was raised, driving interest in the structural characterization of the compound at low temperatures. Furthermore, the identification and characterization of the polymorphic forms is essential to an accurate interpretation of, for instance, experimental calorimetric results.
The low-temperature (LT) measurement, performed at 150 K, revealed that (I) crystallizes in the space group P21/c with a unit-cell volume of 4120.5 (4) Å3, and with two molecules (LTA and LTB) in the asymmetric unit (Fig. 1). These data show that the structure at low temperature is a polymorph of the earlier structure of (I) found by Rabideau et al. (1993) in a room-temperature (RT) determination (R = 0.052). At RT, (I) crystallizes in the space group P1 with a unit-cell volume of 2102.3 (6) Å3, and with two molecules in the asymmetric unit (RTA and RTB; Fig. 2). The RT unit-cell dimensions are: a = 7.7620 (6), b = 13.618 (2) and c = 21.623 (5) Å, and α = 80.58 (2), β = 85.26 (1) and γ = 89.71 (1)°. As can be seen from the crystal data table for the LT structure, there is a rough relationship between the unit-cell dimensions for each compound: a'(RT) ≈ b(LT), b' ≈ a, c' ≈ c/2, α' ≈ (180 - β)°, and β' and γ' are quite close to 90°, so swapping the a and b axes and doubling c effectively changes the RT cell to the LT cell.
The m-polyphenyls might be expected to adopt a zigzag conformation in order to minimize steric repulsion between the phenyl groups, but in both LT and RT crystal structures of (I) the U-shaped conformation is preferred. Theoretical calculations made earlier using MM2/87 (Rabideau et al., 1993) showed that there is no apparent energetic restraint preventing the zigzag conformation in favour of the U-shaped conformation. The calculations were indicative that both conformers and their intermediate geometries are energetically similar, with torsion barriers of about 5 kJ mol-1. All molecules have a very similar geometry. The dihedral angles between successive rings along the chain (Table 1) show that they lie within the same angular range and show similar trends. The results of a least-squares fit of the 30 C atoms using PLATON MOLFIT with quaternion transformation (Mackay, 1984; Spek, 2009) for the molecules in pairs are given in Table 2. Columns 3 and 5 provide values for the root mean-square (r.m.s.) distance between equivalent (overlapping/superimposed) atoms in the fitted molecules. These give rise to values for the molecular isometricity index, defined as Ii(n*) = |[Σ(ΔRi)2/n]1/2 - 1| × 100 for n = 30 (Kálmán et al., 1993), given in columns 4 and 6 of Table 2. The r.m.s. bond-length and bond-angle differences between equivalent bonds and angles within each pair of molecules are also given in Table 2. As a consequence of the arbitrary choice of asymmetric unit, molecules A and B are mirror images of one another, as shown by the need to invert one of them to optimize the fit with the other. The MOLFIT parameters and the dihedral angles are indicative that the molecules have very similar conformations, as can be best viewed in the plots of the fitted molecules given in Fig. 3.
The values in Table 3 are consistent with the molecules in each bimolecular asymmetric unit being related to one another by a noncrystallographic glide plane, which ensures the invariance of the z coordinates for each pair of molecules. For the RT structure it is an a-glide parallel to (010), while for the LT structure it is a b-glide parallel to (100). Thus, in both structures, the molecules in the asymmetric unit sit above one another, with a separation of 0.5 along the b or a axis and an offset of 0.25 along the a or b axis for the LT and RT structures, respectively. As shown in Figs. 4 and 5, the unit cell of the RT structure contains two layers of molecules centred on z = 1/4 and 3/4 and related to one another by the operation of crystallographic centres of symmetry, which is the only relationship between neighbouring layers as they are stacked in the direction of c. The situation in the LT structure is more complex. As shown in Figs. 6 and 7, the unit cell of the LT structure encompasses four layers of molecules centred on z = 1/8, 3/8, 5/8 and 7/8. The layers at z = 1/8 and 3/8 are related to one another by the operation of crystallographic twofold screw axes and the same is true for the layers at z = 5/8 and 7/8. The layers at z = 1/8 and 5/8 are related by the operation of crystallographic c-glide planes and the same is true for the layers at z = 3/8 and 7/8. Pairs of layers are now, of course, centred on z = 1/4 and 3/4 and are related to one another, as they are stacked in the direction of c, by the operation of crystallographic centres of inversion, together with the operation of the crystallographic c-glide planes already mentioned.
There are no π–π interactions in the structures. Table 4 lists values of distances and angles for the most relevant close contacts between molecules. These values are indicative that the contacts are too weak and may not be considered as significant C—H···π interactions. Comparison of the values between polymorphs, for corresponding contacts, suggests that they are stronger in the LT polymorph. The packing motifs, molecular conformations and mutual orientations of the molecules are very similar in the two structures. Nevertheless, the LT polymorph appears to have a more efficient packing than the RT one, as suggested by the volume allocated per molecule in the LT structure (approximately 10 Å3 less). This fact is obviously reflected in macroscopic terms by the slight differences in the values for the densities, of 1.233 (calculated) and 1.209 Mg m-3 (measured) (Rabideau et al., 1993) in the LT and RT structures, respectively. Roughly speaking, for organic compounds, the linear thermal expansion coefficient is less than 0.0001 K-1, which would give a density of about 1.19 Mg m-3 to the LT polymorph at room temperature, considering a temperature difference of 140 K between the measurements. The differences found in the densities may be attributed mainly to the thermal expansion of the compound, drawing attention to the role that entropy may play in the formation of the polymorphs.
This kind of polymorphism contrasts with that shown by the homologous p-quinquephenyl. The phase transitions in p-polyphenyls are well established for the case of p-terphenyl and p-quaterphenyl. Those transitions are accompanied by a change in the crystal structure (space group P1 before the transition and space group P21/n after the phase transition) associated with an energy change (heat of transition), and therefore a change in the absolute heat capacity of the compound, at the temperature of transition. The structure of the parent p-quinquephenyl has not been determined at low temperatures but Saito et al. (2000) have suggested, based on the measurement of heat capacity excess with temperature, that the parent p-quinquephenyl would have a twist phase transition at about 264 K, similar to what is observed in the p-polyphenyls (n = 3, 4). In the case of p-quaterphenyl, on the basis of the available structural data [p-quaterphenyl, 283–303 K, R = 0.045; Delugeard et al., 1976) and p-quaterphenyl (110 K, R = 0.104; Baudour et al., 1978)], it appears that the individual molecules have significantly different conformations in the high-temperature phase (virtually planar and centrosymmetric) and low-temperature phase (nonplanar and noncentrosymmetric). Furthermore, they each have entirely different supramolecular structures. In the case of the HT form, there are four potential but very weak C—H···π interactions (H···Cg distances in the range 2.83–2.97 Å, with angles at H of 130–137°) stabilizing the supramolecular structure. In the case of the LT form, there are ten potential C—H···π interactions (H···Cg distances of 2.69–2.97 Å and angles at H of 126–144°, of which eight have angles at H greater than 139°) which stabilize the packing. This is the converse of the situation for the high- and low-temperature forms of m-quinquephenyl presented here, where the impact of C—H···π interactions on the supramolecular structures is minimal compared with the p-isomer. Also, apart from the change in torsion angles for the outer phenyl rings in molecule LTB, the molecular geometry is virtually unaffected. These differences may help to understand the effect of isomerization on some of the physical properties of the polyphenyls, such as melting points, enthalpies of formation or vaporization.
Due to the simplicity of the elemental composition of polyphenyls, the only possible stabilization mechanism of their supramolecular structures is through the contribution of weak C—H···π and/or π–π interactions, thus making them good models for the study of the impact of these interactions on molecular geometry, packing or molecular motion constraints, parameters that will be reflected in their physical properties. As far as the p-polyphenyls are concerned, the phase change from low to high temperature leads to a reduction in the interactions and the molecular motion becomes less constrained. This may explain the high heat capacity of these compounds, which makes them good candidates for use as coolants. The molecular motion, symmetry and higher number of C—H···π interactions which the p-oligomers establish in relation to the m-oligomers may explain the higher melting points of the former. Despite that, a comparative analysis of the m-quinquephenyl polymorphs might highlight the role of weak close contacts on cell volume and densities.