Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803017483/ob6273sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803017483/ob6273Isup2.hkl |
CCDC reference: 222856
The crystals were provided by Philip Eaton and Todd Emrick of the University of Chicago. Details of the synthesis of the title molecule, (I), from 1,4-diiodocubane, p-biphenyllithium and naphthalene-1,4-oxide were reported by Eaton et al. (1999). Crystals were grown by slow evaporation from an n-octane solution.
Although the space group is acentric, with Mo Kα radiation and only carbon and hydrogen elements there is no basis for determining the absolute configuration. Friedel equivalents were merged, and the `handedness' displayed by the structure (if any) is purely arbitrary. The Flack (1983) parameter, before merging, refined to a value of 2(5). All H atoms were found in difference Fourier maps, but during the refinement they were placed at ideal (SHELXTL) tetrahedral or trigonal positions. They were riding on their bonded neighbors during the refinement, with periodic reidealization, and their displacement parameters were set to be isotropic, with a value equal to 1.2Ueq of the neighboring C atom.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C30H22 | F(000) = 404 |
Mr = 382.48 | Dx = 1.276 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2yb | Cell parameters from 22 reflections |
a = 5.9788 (4) Å | θ = 6.2–42.2° |
b = 7.579 (1) Å | µ = 0.55 mm−1 |
c = 22.044 (1) Å | T = 294 K |
β = 94.570 (8)° | Thin lath, colorless |
V = 995.71 (15) Å3 | 0.52 × 0.16 × 0.02 mm |
Z = 2 |
Siemens P4 diffractometer | 1271 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.038 |
Graphite monochromator | θmax = 68.8°, θmin = 4.0° |
ω scans | h = −7→7 |
Absorption correction: integration (Wuensch et al., 1965) | k = −9→1 |
Tmin = 0.847, Tmax = 0.988 | l = 0→26 |
2001 measured reflections | 3 standard reflections every 97 reflections |
2001 independent reflections | intensity decay: none |
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.062 | w = 1/[σ2(Fo2) + (0.0582P)2 + 0.2164P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.168 | (Δ/σ)max = 0.002 |
S = 1.08 | Δρmax = 0.17 e Å−3 |
2001 reflections | Δρmin = −0.19 e Å−3 |
273 parameters | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
7 restraints | Extinction coefficient: 0.0034 (7) |
Primary atom site location: structure-invariant direct methods | Absolute structure: see text |
Secondary atom site location: structure-invariant direct methods |
C30H22 | V = 995.71 (15) Å3 |
Mr = 382.48 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 5.9788 (4) Å | µ = 0.55 mm−1 |
b = 7.579 (1) Å | T = 294 K |
c = 22.044 (1) Å | 0.52 × 0.16 × 0.02 mm |
β = 94.570 (8)° |
Siemens P4 diffractometer | 1271 reflections with I > 2σ(I) |
Absorption correction: integration (Wuensch et al., 1965) | Rint = 0.038 |
Tmin = 0.847, Tmax = 0.988 | 3 standard reflections every 97 reflections |
2001 measured reflections | intensity decay: none |
2001 independent reflections |
R[F2 > 2σ(F2)] = 0.062 | 7 restraints |
wR(F2) = 0.168 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.17 e Å−3 |
2001 reflections | Δρmin = −0.19 e Å−3 |
273 parameters | Absolute structure: see text |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 1.1372 (9) | 0.8394 (10) | 0.3325 (2) | 0.0527 (15) | |
C2 | 1.1800 (12) | 0.6999 (11) | 0.2828 (3) | 0.073 (2) | |
H2A | 1.2573 | 0.5872 | 0.2906 | 0.088* | |
C3 | 1.2549 (10) | 0.8428 (11) | 0.2393 (2) | 0.0686 (19) | |
H3A | 1.3888 | 0.8365 | 0.2165 | 0.082* | |
C4 | 1.0094 (10) | 0.8620 (10) | 0.2106 (2) | 0.0548 (15) | |
C5 | 0.9345 (12) | 0.7187 (10) | 0.2554 (3) | 0.070 (2) | |
H5A | 0.8334 | 0.6202 | 0.2442 | 0.084* | |
C6 | 0.8926 (9) | 0.8608 (13) | 0.3032 (3) | 0.068 (2) | |
H6A | 0.7588 | 0.8669 | 0.3260 | 0.081* | |
C7 | 0.9657 (11) | 1.0056 (10) | 0.2597 (3) | 0.0657 (19) | |
H7A | 0.8884 | 1.1182 | 0.2517 | 0.079* | |
C8 | 1.2112 (12) | 0.9841 (10) | 0.2875 (3) | 0.0658 (19) | |
H8A | 1.3126 | 1.0823 | 0.2990 | 0.079* | |
C1A | 0.7824 (9) | 0.8760 (9) | 0.0197 (2) | 0.0490 (13) | |
C2A | 0.9826 (10) | 0.7938 (9) | 0.0406 (2) | 0.0619 (18) | |
H2AA | 1.0680 | 0.7374 | 0.0129 | 0.074* | |
C3A | 1.0565 (11) | 0.7943 (9) | 0.1014 (2) | 0.0627 (18) | |
H3AA | 1.1919 | 0.7395 | 0.1136 | 0.075* | |
C4A | 0.9363 (10) | 0.8737 (10) | 0.1450 (2) | 0.0553 (16) | |
C5A | 0.7383 (10) | 0.9570 (10) | 0.1244 (3) | 0.0634 (18) | |
H5AA | 0.6544 | 1.0148 | 0.1521 | 0.076* | |
C6A | 0.6633 (10) | 0.9557 (10) | 0.0635 (3) | 0.0608 (18) | |
H6AA | 0.5276 | 1.0103 | 0.0516 | 0.073* | |
C1B | 0.6999 (9) | 0.8777 (8) | −0.0457 (2) | 0.0478 (13) | |
C2B | 0.8221 (12) | 0.8024 (10) | −0.0894 (3) | 0.074 (2) | |
H2BA | 0.9591 | 0.7494 | −0.0777 | 0.089* | |
C3B | 0.7447 (12) | 0.8043 (12) | −0.1505 (3) | 0.086 (3) | |
H3BA | 0.8292 | 0.7507 | −0.1790 | 0.103* | |
C4B | 0.5461 (12) | 0.8839 (12) | −0.1693 (3) | 0.077 (2) | |
H4BA | 0.4964 | 0.8884 | −0.2103 | 0.092* | |
C5B | 0.4242 (12) | 0.9556 (11) | −0.1269 (3) | 0.079 (2) | |
H5BA | 0.2870 | 1.0078 | −0.1388 | 0.095* | |
C6B | 0.4978 (10) | 0.9533 (10) | −0.0663 (3) | 0.0665 (19) | |
H6BA | 0.4090 | 1.0042 | −0.0383 | 0.080* | |
C1C | 1.0753 (9) | 0.8718 (9) | 0.4430 (2) | 0.0485 (14) | |
H1CA | 0.9358 | 0.9219 | 0.4321 | 0.058* | |
C2C | 1.2093 (9) | 0.8218 (8) | 0.3984 (2) | 0.0485 (15) | |
C3C | 1.4193 (9) | 0.7448 (9) | 0.4153 (3) | 0.0584 (17) | |
H3CA | 1.5101 | 0.7089 | 0.3853 | 0.070* | |
C4C | 1.4920 (10) | 0.7219 (8) | 0.4749 (3) | 0.0546 (15) | |
H4CA | 1.6328 | 0.6731 | 0.4849 | 0.065* | |
C5C | 1.4256 (10) | 0.7481 (8) | 0.5842 (2) | 0.0585 (17) | |
H5CA | 1.5643 | 0.6975 | 0.5955 | 0.070* | |
C6C | 1.2907 (11) | 0.7991 (11) | 0.6277 (3) | 0.069 (2) | |
H6CA | 1.3382 | 0.7839 | 0.6686 | 0.083* | |
C7C | 1.0822 (10) | 0.8738 (10) | 0.6116 (2) | 0.0637 (17) | |
H7CA | 0.9904 | 0.9062 | 0.6419 | 0.076* | |
C8C | 1.0104 (10) | 0.9003 (9) | 0.5520 (2) | 0.0548 (16) | |
H8CA | 0.8717 | 0.9528 | 0.5420 | 0.066* | |
C9C | 1.1454 (8) | 0.8485 (8) | 0.5053 (2) | 0.0417 (12) | |
C10C | 1.3566 (9) | 0.7712 (8) | 0.5214 (2) | 0.0481 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.060 (3) | 0.056 (4) | 0.043 (3) | −0.007 (4) | 0.010 (3) | −0.001 (3) |
C2 | 0.103 (6) | 0.067 (4) | 0.050 (4) | 0.011 (4) | 0.011 (4) | −0.001 (3) |
C3 | 0.072 (4) | 0.090 (5) | 0.047 (3) | −0.006 (4) | 0.020 (3) | −0.001 (4) |
C4 | 0.069 (4) | 0.057 (4) | 0.039 (3) | −0.003 (4) | 0.012 (3) | 0.003 (3) |
C5 | 0.095 (5) | 0.068 (5) | 0.047 (4) | −0.025 (4) | −0.001 (3) | 0.002 (3) |
C6 | 0.056 (3) | 0.102 (6) | 0.048 (3) | −0.008 (5) | 0.018 (3) | 0.006 (4) |
C7 | 0.087 (5) | 0.065 (4) | 0.046 (3) | 0.018 (4) | 0.007 (3) | −0.002 (3) |
C8 | 0.088 (5) | 0.069 (4) | 0.040 (3) | −0.024 (4) | 0.003 (3) | 0.000 (3) |
C1A | 0.058 (3) | 0.046 (3) | 0.044 (3) | 0.000 (3) | 0.013 (2) | 0.004 (3) |
C2A | 0.071 (4) | 0.067 (4) | 0.047 (3) | 0.024 (4) | 0.007 (3) | −0.005 (3) |
C3A | 0.077 (4) | 0.065 (4) | 0.047 (3) | 0.021 (4) | 0.008 (3) | 0.000 (3) |
C4A | 0.067 (4) | 0.058 (4) | 0.043 (3) | 0.002 (4) | 0.014 (3) | 0.001 (3) |
C5A | 0.061 (4) | 0.084 (5) | 0.048 (3) | 0.004 (4) | 0.021 (3) | −0.007 (4) |
C6A | 0.054 (3) | 0.076 (5) | 0.054 (3) | 0.017 (4) | 0.011 (3) | −0.003 (3) |
C1B | 0.051 (3) | 0.042 (3) | 0.051 (3) | −0.003 (3) | 0.006 (2) | 0.003 (3) |
C2B | 0.083 (5) | 0.086 (6) | 0.053 (3) | 0.020 (4) | 0.001 (3) | −0.009 (4) |
C3B | 0.099 (5) | 0.111 (7) | 0.046 (3) | 0.020 (5) | 0.002 (3) | −0.018 (4) |
C4B | 0.086 (5) | 0.079 (6) | 0.063 (4) | −0.006 (5) | −0.017 (4) | 0.001 (4) |
C5B | 0.073 (4) | 0.092 (6) | 0.072 (4) | 0.016 (5) | −0.006 (4) | 0.014 (4) |
C6B | 0.065 (4) | 0.082 (5) | 0.052 (3) | 0.018 (4) | 0.007 (3) | 0.007 (4) |
C1C | 0.048 (3) | 0.052 (4) | 0.046 (3) | 0.003 (3) | 0.006 (2) | 0.001 (3) |
C2C | 0.050 (3) | 0.054 (4) | 0.042 (3) | −0.006 (3) | 0.008 (2) | 0.005 (3) |
C3C | 0.053 (3) | 0.065 (5) | 0.060 (4) | 0.010 (3) | 0.017 (3) | 0.007 (3) |
C4C | 0.050 (3) | 0.051 (4) | 0.063 (4) | 0.002 (3) | 0.006 (3) | 0.003 (3) |
C5C | 0.062 (4) | 0.057 (4) | 0.055 (3) | −0.005 (4) | −0.008 (3) | 0.010 (3) |
C6C | 0.078 (4) | 0.084 (6) | 0.044 (3) | −0.001 (4) | 0.001 (3) | 0.015 (4) |
C7C | 0.071 (4) | 0.077 (5) | 0.044 (3) | −0.001 (4) | 0.010 (3) | 0.000 (4) |
C8C | 0.055 (3) | 0.064 (4) | 0.046 (3) | 0.005 (3) | 0.006 (2) | −0.004 (3) |
C9C | 0.044 (3) | 0.041 (3) | 0.041 (3) | −0.002 (3) | 0.001 (2) | 0.001 (3) |
C10C | 0.046 (3) | 0.046 (3) | 0.052 (3) | −0.003 (3) | 0.000 (2) | 0.003 (3) |
C1—C2C | 1.487 (7) | C6A—H6AA | 0.9300 |
C1—C2 | 1.559 (9) | C1B—C2B | 1.378 (8) |
C1—C6 | 1.560 (8) | C1B—C6B | 1.381 (7) |
C1—C8 | 1.566 (9) | C2B—C3B | 1.390 (7) |
C2—C3 | 1.535 (9) | C2B—H2BA | 0.9300 |
C2—C5 | 1.549 (10) | C3B—C4B | 1.366 (9) |
C2—H2A | 0.9800 | C3B—H3BA | 0.9300 |
C3—C8 | 1.546 (9) | C4B—C5B | 1.345 (9) |
C3—C4 | 1.559 (8) | C4B—H4BA | 0.9300 |
C3—H3A | 0.9800 | C5B—C6B | 1.373 (8) |
C4—C4A | 1.480 (7) | C5B—H5BA | 0.9300 |
C4—C5 | 1.558 (9) | C6B—H6BA | 0.9300 |
C4—C7 | 1.573 (9) | C1C—C2C | 1.370 (7) |
C5—C6 | 1.540 (10) | C1C—C9C | 1.415 (6) |
C5—H5A | 0.9800 | C1C—H1CA | 0.9300 |
C6—C7 | 1.542 (10) | C2C—C3C | 1.408 (8) |
C6—H6A | 0.9800 | C3C—C4C | 1.360 (7) |
C7—C8 | 1.553 (9) | C3C—H3CA | 0.9300 |
C7—H7A | 0.9800 | C4C—C10C | 1.407 (7) |
C8—H8A | 0.9800 | C4C—H4CA | 0.9300 |
C1A—C6A | 1.385 (7) | C5C—C6C | 1.359 (8) |
C1A—C2A | 1.395 (8) | C5C—C10C | 1.423 (7) |
C1A—C1B | 1.485 (7) | C5C—H5CA | 0.9300 |
C2A—C3A | 1.378 (7) | C6C—C7C | 1.389 (8) |
C2A—H2AA | 0.9300 | C6C—H6CA | 0.9300 |
C3A—C4A | 1.382 (7) | C7C—C8C | 1.365 (7) |
C3A—H3AA | 0.9300 | C7C—H7CA | 0.9300 |
C4A—C5A | 1.386 (8) | C8C—C9C | 1.414 (7) |
C5A—C6A | 1.380 (7) | C8C—H8CA | 0.9300 |
C5A—H5AA | 0.9300 | C9C—C10C | 1.411 (7) |
C2C—C1—C2 | 125.1 (6) | C3A—C4A—C5A | 116.7 (5) |
C2C—C1—C6 | 127.1 (5) | C3A—C4A—C4 | 121.6 (6) |
C2—C1—C6 | 88.8 (5) | C5A—C4A—C4 | 121.7 (5) |
C2C—C1—C8 | 127.3 (6) | C6A—C5A—C4A | 121.2 (6) |
C2—C1—C8 | 87.6 (4) | C6A—C5A—H5AA | 119.4 |
C6—C1—C8 | 88.1 (5) | C4A—C5A—H5AA | 119.4 |
C3—C2—C5 | 90.4 (5) | C5A—C6A—C1A | 122.5 (6) |
C3—C2—C1 | 91.9 (6) | C5A—C6A—H6AA | 118.8 |
C5—C2—C1 | 90.5 (5) | C1A—C6A—H6AA | 118.8 |
C3—C2—H2A | 124.6 | C2B—C1B—C6B | 116.2 (5) |
C5—C2—H2A | 124.6 | C2B—C1B—C1A | 121.4 (5) |
C1—C2—H2A | 124.6 | C6B—C1B—C1A | 122.4 (5) |
C2—C3—C8 | 89.2 (4) | C1B—C2B—C3B | 121.3 (7) |
C2—C3—C4 | 90.4 (5) | C1B—C2B—H2BA | 119.4 |
C8—C3—C4 | 90.5 (5) | C3B—C2B—H2BA | 119.4 |
C2—C3—H3A | 125.2 | C4B—C3B—C2B | 120.8 (7) |
C8—C3—H3A | 125.2 | C4B—C3B—H3BA | 119.6 |
C4—C3—H3A | 125.2 | C2B—C3B—H3BA | 119.6 |
C4A—C4—C5 | 125.7 (6) | C5B—C4B—C3B | 118.3 (7) |
C4A—C4—C3 | 126.8 (5) | C5B—C4B—H4BA | 120.8 |
C5—C4—C3 | 89.2 (5) | C3B—C4B—H4BA | 120.8 |
C4A—C4—C7 | 125.4 (6) | C4B—C5B—C6B | 121.4 (7) |
C5—C4—C7 | 88.5 (4) | C4B—C5B—H5BA | 119.3 |
C3—C4—C7 | 89.2 (5) | C6B—C5B—H5BA | 119.3 |
C6—C5—C2 | 89.9 (5) | C5B—C6B—C1B | 122.0 (6) |
C6—C5—C4 | 91.0 (6) | C5B—C6B—H6BA | 119.0 |
C2—C5—C4 | 90.0 (5) | C1B—C6B—H6BA | 119.0 |
C6—C5—H5A | 125.1 | C2C—C1C—C9C | 121.1 (5) |
C2—C5—H5A | 125.1 | C2C—C1C—H1CA | 119.4 |
C4—C5—H5A | 125.1 | C9C—C1C—H1CA | 119.4 |
C5—C6—C7 | 90.2 (4) | C1C—C2C—C3C | 119.0 (5) |
C5—C6—C1 | 90.7 (5) | C1C—C2C—C1 | 122.3 (5) |
C7—C6—C1 | 91.7 (5) | C3C—C2C—C1 | 118.7 (5) |
C5—C6—H6A | 124.6 | C4C—C3C—C2C | 121.3 (6) |
C7—C6—H6A | 124.6 | C4C—C3C—H3CA | 119.4 |
C1—C6—H6A | 124.6 | C2C—C3C—H3CA | 119.4 |
C6—C7—C8 | 89.2 (5) | C3C—C4C—C10C | 120.8 (6) |
C6—C7—C4 | 90.3 (5) | C3C—C4C—H4CA | 119.6 |
C8—C7—C4 | 89.8 (5) | C10C—C4C—H4CA | 119.6 |
C6—C7—H7A | 125.4 | C6C—C5C—C10C | 120.7 (6) |
C8—C7—H7A | 125.4 | C6C—C5C—H5CA | 119.7 |
C4—C7—H7A | 125.4 | C10C—C5C—H5CA | 119.7 |
C3—C8—C7 | 90.5 (5) | C5C—C6C—C7C | 120.4 (6) |
C3—C8—C1 | 91.2 (5) | C5C—C6C—H6CA | 119.8 |
C7—C8—C1 | 91.0 (5) | C7C—C6C—H6CA | 119.8 |
C3—C8—H8A | 124.6 | C8C—C7C—C6C | 120.9 (6) |
C7—C8—H8A | 124.6 | C8C—C7C—H7CA | 119.6 |
C1—C8—H8A | 124.6 | C6C—C7C—H7CA | 119.6 |
C6A—C1A—C2A | 116.1 (5) | C7C—C8C—C9C | 120.4 (6) |
C6A—C1A—C1B | 121.6 (5) | C7C—C8C—H8CA | 119.8 |
C2A—C1A—C1B | 122.3 (5) | C9C—C8C—H8CA | 119.8 |
C3A—C2A—C1A | 121.4 (6) | C10C—C9C—C8C | 118.9 (5) |
C3A—C2A—H2AA | 119.3 | C10C—C9C—C1C | 119.1 (5) |
C1A—C2A—H2AA | 119.3 | C8C—C9C—C1C | 122.0 (5) |
C2A—C3A—C4A | 122.2 (6) | C4C—C10C—C9C | 118.8 (5) |
C2A—C3A—H3AA | 118.9 | C4C—C10C—C5C | 122.5 (6) |
C4A—C3A—H3AA | 118.9 | C9C—C10C—C5C | 118.7 (5) |
C2C—C1—C2—C3 | −134.8 (6) | C2C—C1—C8—C7 | −136.3 (6) |
C6—C1—C2—C3 | 88.8 (5) | C2—C1—C8—C7 | 89.8 (5) |
C8—C1—C2—C3 | 0.7 (5) | C6—C1—C8—C7 | 0.9 (5) |
C2C—C1—C2—C5 | 134.8 (6) | C6A—C1A—C2A—C3A | −0.6 (9) |
C6—C1—C2—C5 | −1.6 (5) | C1B—C1A—C2A—C3A | 179.8 (7) |
C8—C1—C2—C5 | −89.8 (5) | C1A—C2A—C3A—C4A | 0.9 (11) |
C5—C2—C3—C8 | 89.8 (5) | C2A—C3A—C4A—C5A | −1.4 (11) |
C1—C2—C3—C8 | −0.7 (5) | C2A—C3A—C4A—C4 | 175.5 (6) |
C5—C2—C3—C4 | −0.7 (6) | C5—C4—C4A—C3A | −91.9 (9) |
C1—C2—C3—C4 | −91.2 (5) | C3—C4—C4A—C3A | 29.1 (12) |
C2—C3—C4—C4A | −135.2 (7) | C7—C4—C4A—C3A | 149.9 (7) |
C8—C3—C4—C4A | 135.5 (7) | C5—C4—C4A—C5A | 84.8 (9) |
C2—C3—C4—C5 | 0.7 (6) | C3—C4—C4A—C5A | −154.2 (7) |
C8—C3—C4—C5 | −88.5 (5) | C7—C4—C4A—C5A | −33.4 (10) |
C2—C3—C4—C7 | 89.2 (5) | C3A—C4A—C5A—C6A | 1.8 (11) |
C8—C3—C4—C7 | 0.0 (6) | C4—C4A—C5A—C6A | −175.1 (7) |
C3—C2—C5—C6 | −90.3 (6) | C4A—C5A—C6A—C1A | −1.7 (11) |
C1—C2—C5—C6 | 1.6 (5) | C2A—C1A—C6A—C5A | 1.0 (10) |
C3—C2—C5—C4 | 0.7 (6) | C1B—C1A—C6A—C5A | −179.4 (7) |
C1—C2—C5—C4 | 92.6 (6) | C6A—C1A—C1B—C2B | 178.2 (7) |
C4A—C4—C5—C6 | −134.1 (6) | C2A—C1A—C1B—C2B | −2.2 (10) |
C3—C4—C5—C6 | 89.2 (5) | C6A—C1A—C1B—C6B | −2.0 (10) |
C7—C4—C5—C6 | 0.0 (5) | C2A—C1A—C1B—C6B | 177.6 (7) |
C4A—C4—C5—C2 | 136.0 (6) | C6B—C1B—C2B—C3B | 0.3 (11) |
C3—C4—C5—C2 | −0.7 (6) | C1A—C1B—C2B—C3B | −179.9 (7) |
C7—C4—C5—C2 | −90.0 (5) | C1B—C2B—C3B—C4B | 1.2 (12) |
C2—C5—C6—C7 | 90.0 (5) | C2B—C3B—C4B—C5B | −2.0 (12) |
C4—C5—C6—C7 | 0.0 (5) | C3B—C4B—C5B—C6B | 1.5 (12) |
C2—C5—C6—C1 | −1.6 (5) | C4B—C5B—C6B—C1B | 0.0 (12) |
C4—C5—C6—C1 | −91.6 (5) | C2B—C1B—C6B—C5B | −0.8 (10) |
C2C—C1—C6—C5 | −133.3 (7) | C1A—C1B—C6B—C5B | 179.4 (7) |
C2—C1—C6—C5 | 1.6 (5) | C9C—C1C—C2C—C3C | 0.5 (10) |
C8—C1—C6—C5 | 89.3 (5) | C9C—C1C—C2C—C1 | 178.0 (6) |
C2C—C1—C6—C7 | 136.4 (7) | C2—C1—C2C—C1C | −139.1 (7) |
C2—C1—C6—C7 | −88.6 (5) | C6—C1—C2C—C1C | −19.0 (11) |
C8—C1—C6—C7 | −0.9 (5) | C8—C1—C2C—C1C | 102.6 (8) |
C5—C6—C7—C8 | −89.8 (5) | C2—C1—C2C—C3C | 38.4 (9) |
C1—C6—C7—C8 | 0.9 (5) | C6—C1—C2C—C3C | 158.4 (7) |
C5—C6—C7—C4 | 0.0 (5) | C8—C1—C2C—C3C | −79.9 (8) |
C1—C6—C7—C4 | 90.7 (5) | C1C—C2C—C3C—C4C | −1.0 (10) |
C4A—C4—C7—C6 | 134.3 (6) | C1—C2C—C3C—C4C | −178.6 (6) |
C5—C4—C7—C6 | 0.0 (5) | C2C—C3C—C4C—C10C | 1.4 (10) |
C3—C4—C7—C6 | −89.2 (5) | C10C—C5C—C6C—C7C | 0.4 (11) |
C4A—C4—C7—C8 | −136.5 (6) | C5C—C6C—C7C—C8C | −1.2 (12) |
C5—C4—C7—C8 | 89.3 (5) | C6C—C7C—C8C—C9C | 1.4 (11) |
C3—C4—C7—C8 | 0.0 (6) | C7C—C8C—C9C—C10C | −0.8 (9) |
C2—C3—C8—C7 | −90.4 (5) | C7C—C8C—C9C—C1C | 179.2 (7) |
C4—C3—C8—C7 | 0.0 (6) | C2C—C1C—C9C—C10C | −0.5 (9) |
C2—C3—C8—C1 | 0.7 (5) | C2C—C1C—C9C—C8C | 179.6 (6) |
C4—C3—C8—C1 | 91.1 (5) | C3C—C4C—C10C—C9C | −1.3 (9) |
C6—C7—C8—C3 | 90.3 (6) | C3C—C4C—C10C—C5C | 179.4 (6) |
C4—C7—C8—C3 | 0.0 (6) | C8C—C9C—C10C—C4C | −179.2 (6) |
C6—C7—C8—C1 | −0.9 (5) | C1C—C9C—C10C—C4C | 0.8 (8) |
C4—C7—C8—C1 | −91.3 (5) | C8C—C9C—C10C—C5C | 0.1 (8) |
C2C—C1—C8—C3 | 133.2 (6) | C1C—C9C—C10C—C5C | −179.9 (6) |
C2—C1—C8—C3 | −0.6 (5) | C6C—C5C—C10C—C4C | 179.3 (6) |
C6—C1—C8—C3 | −89.5 (5) | C6C—C5C—C10C—C9C | 0.1 (9) |
Experimental details
Crystal data | |
Chemical formula | C30H22 |
Mr | 382.48 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 294 |
a, b, c (Å) | 5.9788 (4), 7.579 (1), 22.044 (1) |
β (°) | 94.570 (8) |
V (Å3) | 995.71 (15) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.55 |
Crystal size (mm) | 0.52 × 0.16 × 0.02 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Integration (Wuensch et al., 1965) |
Tmin, Tmax | 0.847, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2001, 2001, 1271 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.605 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.168, 1.08 |
No. of reflections | 2001 |
No. of parameters | 273 |
No. of restraints | 7 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.19 |
Absolute structure | See text |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Sheldrick, 1997), SHELXS97 (Sheldrick, 1990), SHELXTL.
C1—C2 | 1.559 (9) | C3—C4 | 1.559 (8) |
C1—C6 | 1.560 (8) | C4—C5 | 1.558 (9) |
C1—C8 | 1.566 (9) | C4—C7 | 1.573 (9) |
C2—C3 | 1.535 (9) | C5—C6 | 1.540 (10) |
C2—C5 | 1.549 (10) | C6—C7 | 1.542 (10) |
C3—C8 | 1.546 (9) | C7—C8 | 1.553 (9) |
C2A—C1A—C1B—C2B | −2.2 (10) | C6A—C1A—C1B—C6B | −2.0 (10) |
The title molecule, (I), was synthesized by Eaton et al. (1999) along with 1-(p-biphenyl)-4'-(2-naphthyl)-p-[2]cubyl, and a series of other polycubyl molecules to study the properties of cubanes that are linked together at the 1 and 4 positions. Because poly-1,4-cubanes are semi-rigid rod-like structures, the distances between two terminal substituents are fixed, even in solution, making them useful for studying the distance dependence of intramolecular electron-transfer reactions. Paulson et al. (1993) studied the electron-transfer reaction of the title compound by irradiating the molecules (in solution) with high-energy electrons and photometrically observing electron transfer in the anionic form of (I). They found that using cubane as a spacer enhanced the electron transfer rate between the biphenyl and naphthyl groups. Compared to the electron transfer between the same substituents on cyclohexane spacers, the rate of transfer was measured to be 10±3 times larger for the cubane compound. Stronger bond-to-bond couplings and a larger number of pathways are offered as explanations for the enhanced coupling through cubane spacers. Increasing the distance by doubling or tripling the number of cubyl or cyclohexyl spacers leads to an exponential decline in transfer rate with distance; the fall-off with distance was similar for both types of spacer.
The biphenyl groups of (I) are nearly planar, with all C atoms fitting a least-squares plane to within a full range of ±0.031 Å (Fig. 1 and Table 1). The average torsion angle of the biphenyl linkage is 2.1°, versus an average of 23.4° for 772 similar biphenyl linkages (all those with four H atoms adjacent to the central linkage bond) found in the Cambridge Structural Database (Version 5.24; Allen, 2002). The naphthyl groups are even more closely planar; their C atoms fit a least-squares plane to within ±0.007 Å.
The title molecule, (I), has a complex supramolecular assembly. Looking down the a axis (Fig. 2), one can see stacks of intercalated biphenyl groups at the ends of the cell, and a close-packed stack of naphthyl substituents in the center of the cell. There is a twofold screw axis along b which goes through the central naphthyl stack. Fig. 3 illustrates an end-on view of a naphthyl stack, showing that is actually a herring-bone stack, not a stack wherein all planes are parallel. Despite the presence of the close-packed naphthyl stacks and slightly looser biphenyl stacks there are no intermolecular contacts that are significantly less than the sum of van der Waals radii.