Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010100703X/sk1477sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010100703X/sk1477Iat293Ksup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010100703X/sk1477Iat90Ksup3.hkl |
CCDC references: 170186; 170187
The source material, 99.9% pure pentacene, was purchased from Aldrich and not further purified. Single crystals of pentacene were grown using physical vapour transport in a horizontal glass tube (Laudize et al., 1998). A temperature gradient was applied over the tube. The source material was sublimed at 550 K and crystallized at the other end of the tube at approximately 490 K. The growth was performed under a stream of N2 (99.999% purity, AGA gas) and H2 gas (99.995% purity, AGA gas), with a volume percentage of 5.1 (1)% hydrogen. (structure I, at 293 K) This yielded almost centimetre sized violet crystals, in different forms, platelets and needles. The c* axis was normal to the plane of the very thin platelets (typically 10 to 100 µm), the growth of the needles was along the [1,1,0] direction. At a different part of the tube also a small amount of hydrogenated pentacene crystals, red needles, was found. Lowering the flow rate yielded a larger fraction of hydrogenated pentacene. At lower hydrogen content or if no ultrapure inert transport gas is used, the pentacene oxidizes forming 6,13-pentacenequinone, and small brown needles crystallize (Dzyabchenko et al., 1979). The crystal structure of hydrogenated pentacene will be reported separately. Crystals were also grown from solution in trichlorobenzene by slowly evaporating the solvent over four weeks at 450 K, under a stream of ultra pure nitrogen gas. Crystals thus obtained (structure 2, at 90 K) exhibit the same crystal structure as the crystals grown by vapour transport. Pentacene thin films have been deposited using high vacuum sublimation (10-8 mbar). The source material was heated in a crucible and evaporated onto a thermally oxidized Si wafer heated to 370 K. A low evaporation rate of 0.1 nm/sec was used to ensure crystallinity and the sample was rapidly cooled afterwards. The layer thickness was 2 µm.
The needle axis appeared to be along the [1,1,0] vector (9.52 Å) in the chosen (standard) unit cell setting. The studied plate-shaped crystals were all twinned and the plane-normal is along the c*-axis (meaning a and b axis in the plate). The relation between the twin-orientations is 180° rotation around the [1,1,0] axis (rotation matrix: 0 1 0, 1 0 0, 0 0 1) Although an X-ray structure determination was thwarted by persistent crystal twinning and weak scattering power of the crystals, ultimately we found a single-crystal (needle shaped) fit to the X-ray diffraction experiment. The data collection was performed on an Enraf–Nonius CAD4F diffractometer at 293 K.
The crystals from the crystallization (TCB) were analysed at 90 K with a Bruker SMART APEX CCD diffractometer.
Data collection: CAD4-UNIX Software (Enraf-Nonius, 1994) for Iat293K; SMART (Bruker, 2000) for Iat90K. Cell refinement: SET4 (de Boer & Duisenberg, 1984) for Iat293K; SAINT (Bruker, 2000) for Iat90K. Data reduction: HELENA (Spek, 1997) for Iat293K; XPREP (Bruker, 2000) for Iat90K. Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for Iat293K; SIR97 (Altomare et al., 1997) for Iat90K. For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: PLUTO (Meetsma, 2000) and PLATON (Spek, 1994) for Iat293K; PLUTO (Meetsma, 2000), ORTEP (Farrugia, 2000; Johnson et al., 2000) and PLATON (Spek, 1994) for Iat90K. Software used to prepare material for publication: PLATON (Spek, 1990) for Iat293K; PLATON (Spek, 1990) and SHELXL97 for Iat90K.
C22H14 | Z = 2 |
Mr = 278.35 | F(000) = 292 |
Triclinic, P1 | Unit cell parameters (Duisenberg, 1992) and orientation matrix were determined from a least-squares treatment of SET4 (de Boer & Duisenberg, 1984) setting. Reduced cell calculations did not indicate any higher metric lattice symmetry and examination of the final atomic coordinates of the structure did not yield extra symmetry elements (Spek, 1988; Le Page 1987, 1988) |
Hall symbol: -P 1 | Dx = 1.349 Mg m−3 |
a = 6.266 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.775 (1) Å | Cell parameters from 23 reflections |
c = 14.530 (1) Å | θ = 17.9–21.7° |
α = 76.475 (4)° | µ = 0.08 mm−1 |
β = 87.682 (4)° | T = 293 K |
γ = 84.684 (4)° | Needle-block, violet |
V = 685.15 (15) Å3 | 0.10 × 0.08 × 0.08 mm |
Enraf Nonius CAD-4F diffractometer | Rint = 0.034 |
Radiation source: fine focus sealed Philips Mo tube | θmax = 26.0°, θmin = 1.4° |
Perpendicular mounted graphite monochromator | h = −7→6 |
ω/2θ scans | k = −6→9 |
2856 measured reflections | l = −17→17 |
2684 independent reflections | 3 standard reflections every 180 min |
843 reflections with I > 2σ(I) | intensity decay: no decay, variation 0.2% |
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)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.179 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0608P)2] where P = (Fo2 + 2Fc2)/3 |
2684 reflections | (Δ/σ)max < 0.001 |
199 parameters | Δρmax = 0.14 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C22H14 | γ = 84.684 (4)° |
Mr = 278.35 | V = 685.15 (15) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.266 (1) Å | Mo Kα radiation |
b = 7.775 (1) Å | µ = 0.08 mm−1 |
c = 14.530 (1) Å | T = 293 K |
α = 76.475 (4)° | 0.10 × 0.08 × 0.08 mm |
β = 87.682 (4)° |
Enraf Nonius CAD-4F diffractometer | Rint = 0.034 |
2856 measured reflections | 3 standard reflections every 180 min |
2684 independent reflections | intensity decay: no decay, variation 0.2% |
843 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.179 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.14 e Å−3 |
2684 reflections | Δρmin = −0.21 e Å−3 |
199 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
C1 | 0.6994 (8) | 0.4035 (6) | 0.0149 (3) | 0.0319 (19) | |
C2 | 0.5410 (9) | 0.3719 (6) | 0.0864 (3) | 0.0294 (17) | |
C3 | 0.5776 (8) | 0.2470 (6) | 0.1736 (3) | 0.035 (2) | |
C4 | 0.4200 (9) | 0.2212 (7) | 0.2443 (3) | 0.0321 (19) | |
C5 | 0.4551 (8) | 0.0979 (6) | 0.3327 (3) | 0.0397 (17) | |
C6 | 0.2986 (9) | 0.0764 (7) | 0.4009 (4) | 0.050 (2) | |
C7 | 0.0967 (9) | 0.1741 (7) | 0.3851 (4) | 0.048 (2) | |
C8 | 0.0548 (8) | 0.2913 (6) | 0.3020 (3) | 0.0394 (19) | |
C9 | 0.2132 (8) | 0.3216 (6) | 0.2283 (3) | 0.0322 (19) | |
C10 | 0.1755 (8) | 0.4436 (6) | 0.1432 (3) | 0.0336 (19) | |
C11 | 0.6641 (9) | 0.5285 (7) | −0.0709 (3) | 0.0301 (17) | |
C12 | −0.1814 (8) | −0.0442 (6) | −0.0408 (3) | 0.0309 (17) | |
C13 | −0.1548 (8) | −0.0991 (6) | 0.0582 (3) | 0.0268 (17) | |
C14 | −0.3054 (8) | −0.1986 (6) | 0.1172 (3) | 0.0318 (19) | |
C15 | −0.2797 (8) | −0.2530 (7) | 0.2129 (3) | 0.035 (2) | |
C16 | −0.4310 (8) | −0.3542 (6) | 0.2754 (3) | 0.0387 (17) | |
C17 | −0.4010 (9) | −0.4079 (7) | 0.3704 (4) | 0.046 (2) | |
C18 | −0.2131 (9) | −0.3636 (7) | 0.4114 (4) | 0.047 (2) | |
C19 | −0.0681 (8) | −0.2681 (6) | 0.3564 (3) | 0.0407 (19) | |
C20 | −0.0957 (9) | −0.2083 (6) | 0.2554 (3) | 0.0336 (19) | |
C21 | 0.0555 (8) | −0.1106 (6) | 0.1985 (3) | 0.0317 (19) | |
C22 | −0.0332 (8) | 0.0537 (6) | −0.1004 (3) | 0.0308 (19) | |
H1 | 0.83247 | 0.33915 | 0.02479 | 0.0383* | |
H3 | 0.70958 | 0.18106 | 0.18368 | 0.0422* | |
H5 | 0.58649 | 0.03122 | 0.34389 | 0.0474* | |
H6 | 0.32476 | −0.00351 | 0.45863 | 0.0595* | |
H7 | −0.00866 | 0.15758 | 0.43255 | 0.0583* | |
H8 | −0.07976 | 0.35329 | 0.29283 | 0.0471* | |
H10 | 0.04263 | 0.50821 | 0.13324 | 0.0400* | |
H12 | −0.30151 | −0.07431 | −0.06712 | 0.0370* | |
H14 | −0.42529 | −0.22804 | 0.09045 | 0.0383* | |
H16 | −0.55280 | −0.38368 | 0.25004 | 0.0465* | |
H17 | −0.50152 | −0.47306 | 0.40892 | 0.0554* | |
H18 | −0.19243 | −0.40143 | 0.47625 | 0.0563* | |
H19 | 0.05188 | −0.24014 | 0.38370 | 0.0488* | |
H21 | 0.17444 | −0.08227 | 0.22636 | 0.0381* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.028 (4) | 0.021 (3) | 0.046 (3) | 0.000 (3) | −0.009 (3) | −0.006 (3) |
C2 | 0.027 (3) | 0.024 (3) | 0.038 (3) | −0.003 (3) | −0.003 (3) | −0.008 (2) |
C3 | 0.035 (4) | 0.037 (4) | 0.036 (3) | 0.004 (3) | −0.011 (3) | −0.014 (3) |
C4 | 0.041 (4) | 0.030 (3) | 0.029 (3) | 0.000 (3) | −0.009 (3) | −0.014 (3) |
C5 | 0.036 (3) | 0.044 (3) | 0.039 (3) | −0.001 (3) | −0.003 (3) | −0.010 (3) |
C6 | 0.048 (4) | 0.057 (4) | 0.041 (4) | −0.007 (3) | −0.006 (3) | −0.003 (3) |
C7 | 0.046 (4) | 0.065 (4) | 0.034 (3) | −0.007 (3) | 0.000 (3) | −0.010 (3) |
C8 | 0.034 (3) | 0.045 (4) | 0.042 (3) | −0.001 (3) | 0.003 (3) | −0.017 (3) |
C9 | 0.033 (4) | 0.024 (3) | 0.042 (3) | −0.002 (3) | −0.006 (3) | −0.012 (3) |
C10 | 0.024 (3) | 0.036 (4) | 0.042 (3) | 0.002 (3) | −0.001 (3) | −0.013 (3) |
C11 | 0.027 (3) | 0.032 (3) | 0.035 (3) | 0.000 (3) | −0.003 (3) | −0.016 (3) |
C12 | 0.024 (3) | 0.032 (3) | 0.039 (3) | 0.001 (3) | 0.000 (3) | −0.014 (3) |
C13 | 0.028 (3) | 0.020 (3) | 0.032 (3) | 0.002 (2) | 0.001 (2) | −0.007 (2) |
C14 | 0.034 (4) | 0.031 (3) | 0.032 (3) | −0.001 (3) | −0.013 (3) | −0.009 (3) |
C15 | 0.027 (4) | 0.039 (4) | 0.041 (3) | −0.002 (3) | −0.003 (3) | −0.016 (3) |
C16 | 0.033 (3) | 0.033 (3) | 0.050 (3) | −0.008 (3) | 0.004 (3) | −0.008 (3) |
C17 | 0.051 (4) | 0.044 (4) | 0.041 (3) | −0.009 (3) | 0.012 (3) | −0.004 (3) |
C18 | 0.046 (4) | 0.054 (4) | 0.042 (3) | −0.006 (3) | −0.002 (3) | −0.012 (3) |
C19 | 0.043 (4) | 0.036 (3) | 0.043 (3) | −0.003 (3) | −0.003 (3) | −0.009 (3) |
C20 | 0.048 (4) | 0.025 (3) | 0.027 (3) | 0.000 (3) | 0.003 (3) | −0.006 (2) |
C21 | 0.025 (3) | 0.039 (4) | 0.035 (3) | −0.004 (3) | −0.011 (3) | −0.014 (3) |
C22 | 0.022 (3) | 0.034 (4) | 0.040 (3) | −0.001 (3) | −0.009 (3) | −0.015 (3) |
C1—C2 | 1.403 (7) | C12—C13 | 1.414 (6) |
C1—C11 | 1.401 (6) | C12—C22 | 1.396 (7) |
C2—C3 | 1.417 (6) | C13—C14 | 1.408 (7) |
C2—C11i | 1.435 (8) | C13—C22ii | 1.458 (7) |
C3—C4 | 1.389 (7) | C14—C15 | 1.367 (6) |
C4—C5 | 1.423 (6) | C15—C16 | 1.441 (7) |
C4—C9 | 1.447 (7) | C15—C20 | 1.437 (7) |
C5—C6 | 1.359 (7) | C16—C17 | 1.361 (7) |
C6—C7 | 1.412 (8) | C17—C18 | 1.445 (8) |
C7—C8 | 1.351 (7) | C18—C19 | 1.343 (7) |
C8—C9 | 1.424 (7) | C19—C20 | 1.444 (6) |
C9—C10 | 1.385 (6) | C20—C21 | 1.391 (7) |
C10—C11i | 1.417 (7) | C21—C22ii | 1.399 (6) |
C1—H1 | 0.9300 | C12—H12 | 0.9302 |
C3—H3 | 0.9297 | C14—H14 | 0.9300 |
C5—H5 | 0.9302 | C16—H16 | 0.9303 |
C6—H6 | 0.9300 | C17—H17 | 0.9299 |
C7—H7 | 0.9301 | C18—H18 | 0.9297 |
C8—H8 | 0.9299 | C19—H19 | 0.9298 |
C10—H10 | 0.9299 | C21—H21 | 0.9297 |
C1···H10iii | 3.0860 | H5···C20iii | 3.0516 |
C1···H14ii | 2.9627 | H5···H3 | 2.4746 |
C2···H12ii | 2.9435 | H6···H6x | 2.5569 |
C3···H8iii | 3.0973 | H8···C3vi | 3.0973 |
C3···H12ii | 2.9678 | H8···H10 | 2.4773 |
C4···H21 | 2.9992 | H8···C16xi | 2.9881 |
C5···H21 | 3.0218 | H8···C17xi | 2.9787 |
C6···H19 | 3.0876 | H10···H1i | 2.4588 |
C7···H18iv | 3.0825 | H10···C1vi | 3.0860 |
C9···H16v | 2.9153 | H10···C14xi | 2.9796 |
C10···H1vi | 3.0848 | H10···C15xi | 2.9979 |
C10···H16v | 2.9537 | H10···H8 | 2.4773 |
C11···H14ii | 2.9614 | H12···H14 | 2.4536 |
C12···H1vii | 2.9926 | H12···C2ii | 2.9435 |
C12···H14viii | 3.0883 | H12···C3ii | 2.9678 |
C13···H1vii | 3.0288 | H12···C14viii | 3.0908 |
C14···H10ix | 2.9796 | H12···H21ii | 2.4865 |
C14···H12viii | 3.0908 | H14···H12 | 2.4536 |
C15···H10ix | 2.9979 | H14···H16 | 2.4893 |
C16···H8ix | 2.9881 | H14···C1ii | 2.9627 |
C16···H21vi | 3.0918 | H14···C11ii | 2.9614 |
C17···H8ix | 2.9787 | H14···C12viii | 3.0883 |
C19···H5vi | 3.0057 | H16···C9xii | 2.9153 |
C20···H5vi | 3.0516 | H16···C10xii | 2.9537 |
C21···H16iii | 3.0874 | H16···C21vi | 3.0874 |
C21···H3vi | 2.9640 | H16···H14 | 2.4893 |
C22···H3vii | 3.0094 | H17···H17xiii | 2.5817 |
H1···C10iii | 3.0848 | H17···H18xiii | 2.5962 |
H1···H10i | 2.4588 | H18···C7iv | 3.0825 |
H1···C13vii | 3.0288 | H18···H17xiii | 2.5962 |
H1···H3 | 2.4775 | H19···C6 | 3.0876 |
H1···C12vii | 2.9926 | H19···H21 | 2.4582 |
H3···H1 | 2.4775 | H21···C4 | 2.9992 |
H3···C21iii | 2.9640 | H21···C5 | 3.0218 |
H3···H5 | 2.4746 | H21···C16iii | 3.0918 |
H3···C22vii | 3.0094 | H21···H19 | 2.4582 |
H5···C19iii | 3.0057 | H21···H12ii | 2.4865 |
C2—C1—C11 | 122.3 (5) | C13—C12—C22 | 122.1 (4) |
C1—C2—C3 | 122.3 (5) | C12—C13—C14 | 121.4 (4) |
C1—C2—C11i | 118.7 (4) | C12—C13—C22ii | 119.6 (4) |
C3—C2—C11i | 119.0 (4) | C14—C13—C22ii | 119.1 (4) |
C2—C3—C4 | 121.2 (5) | C13—C14—C15 | 121.6 (5) |
C3—C4—C5 | 121.9 (5) | C14—C15—C16 | 123.1 (5) |
C3—C4—C9 | 119.5 (4) | C14—C15—C20 | 119.9 (4) |
C5—C4—C9 | 118.5 (4) | C16—C15—C20 | 117.0 (4) |
C4—C5—C6 | 120.7 (5) | C15—C16—C17 | 122.0 (5) |
C5—C6—C7 | 120.7 (5) | C16—C17—C18 | 120.0 (5) |
C6—C7—C8 | 120.8 (5) | C17—C18—C19 | 120.4 (5) |
C7—C8—C9 | 121.1 (5) | C18—C19—C20 | 121.0 (5) |
C4—C9—C8 | 118.1 (4) | C15—C20—C19 | 119.6 (4) |
C4—C9—C10 | 119.7 (4) | C15—C20—C21 | 119.5 (4) |
C8—C9—C10 | 122.2 (5) | C19—C20—C21 | 120.9 (5) |
C9—C10—C11i | 121.1 (5) | C20—C21—C22ii | 121.7 (4) |
C1—C11—C2i | 119.0 (4) | C12—C22—C13ii | 118.3 (4) |
C1—C11—C10i | 121.6 (5) | C12—C22—C21ii | 123.5 (4) |
C2i—C11—C10i | 119.4 (4) | C13ii—C22—C21ii | 118.2 (4) |
C2—C1—H1 | 118.82 | C13—C12—H12 | 118.95 |
C11—C1—H1 | 118.87 | C22—C12—H12 | 118.91 |
C2—C3—H3 | 119.38 | C13—C14—H14 | 119.24 |
C4—C3—H3 | 119.37 | C15—C14—H14 | 119.16 |
C4—C5—H5 | 119.67 | C15—C16—H16 | 119.01 |
C6—C5—H5 | 119.65 | C17—C16—H16 | 119.03 |
C5—C6—H6 | 119.63 | C16—C17—H17 | 119.97 |
C7—C6—H6 | 119.64 | C18—C17—H17 | 120.01 |
C6—C7—H7 | 119.57 | C17—C18—H18 | 119.80 |
C8—C7—H7 | 119.61 | C19—C18—H18 | 119.80 |
C7—C8—H8 | 119.41 | C18—C19—H19 | 119.55 |
C9—C8—H8 | 119.49 | C20—C19—H19 | 119.49 |
C9—C10—H10 | 119.47 | C20—C21—H21 | 119.18 |
C11i—C10—H10 | 119.40 | C22ii—C21—H21 | 119.12 |
C11—C1—C2—C3 | −179.2 (5) | C22—C12—C13—C14 | −179.7 (5) |
C11—C1—C2—C11i | −0.1 (7) | C22—C12—C13—C22ii | −0.3 (7) |
C2—C1—C11—C2i | 0.1 (8) | C13—C12—C22—C13ii | 0.3 (7) |
C2—C1—C11—C10i | −178.7 (5) | C13—C12—C22—C21ii | −179.7 (5) |
C1—C2—C3—C4 | 178.4 (5) | C12—C13—C14—C15 | 179.6 (5) |
C11i—C2—C3—C4 | −0.8 (7) | C22ii—C13—C14—C15 | 0.2 (8) |
C1—C2—C11i—C10 | −178.8 (5) | C12—C13—C22ii—C21 | −179.7 (4) |
C1—C2—C11i—C1i | 0.1 (7) | C12—C13—C22ii—C12ii | 0.3 (7) |
C3—C2—C11i—C10 | 0.4 (8) | C14—C13—C22ii—C21 | −0.3 (7) |
C3—C2—C11i—C1i | 179.3 (5) | C14—C13—C22ii—C12ii | 179.7 (4) |
C2—C3—C4—C5 | −179.2 (5) | C13—C14—C15—C16 | 179.7 (5) |
C2—C3—C4—C9 | 1.0 (8) | C13—C14—C15—C20 | 0.1 (7) |
C3—C4—C5—C6 | 179.5 (5) | C14—C15—C16—C17 | 179.5 (5) |
C9—C4—C5—C6 | −0.7 (8) | C20—C15—C16—C17 | −0.9 (8) |
C3—C4—C9—C8 | 179.7 (5) | C14—C15—C20—C19 | −179.2 (5) |
C3—C4—C9—C10 | −0.7 (7) | C14—C15—C20—C21 | −0.3 (8) |
C5—C4—C9—C8 | −0.2 (7) | C16—C15—C20—C19 | 1.2 (7) |
C5—C4—C9—C10 | 179.4 (5) | C16—C15—C20—C21 | −179.9 (5) |
C4—C5—C6—C7 | 0.9 (8) | C15—C16—C17—C18 | 0.0 (8) |
C5—C6—C7—C8 | −0.2 (8) | C16—C17—C18—C19 | 0.6 (8) |
C6—C7—C8—C9 | −0.8 (8) | C17—C18—C19—C20 | −0.3 (8) |
C7—C8—C9—C4 | 0.9 (7) | C18—C19—C20—C15 | −0.6 (7) |
C7—C8—C9—C10 | −178.7 (5) | C18—C19—C20—C21 | −179.5 (5) |
C4—C9—C10—C11i | 0.4 (8) | C15—C20—C21—C22ii | 0.2 (8) |
C8—C9—C10—C11i | 180.0 (6) | C19—C20—C21—C22ii | 179.1 (5) |
C9—C10—C11i—C2 | −0.2 (7) | C20—C21—C22ii—C13 | 0.1 (7) |
C9—C10—C11i—C1i | −179.0 (5) | C20—C21—C22ii—C12ii | −179.9 (5) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y, −z; (iii) x+1, y, z; (iv) −x, −y, −z+1; (v) x+1, y+1, z; (vi) x−1, y, z; (vii) −x+1, −y, −z; (viii) −x−1, −y, −z; (ix) x, y−1, z; (x) −x+1, −y, −z+1; (xi) x, y+1, z; (xii) x−1, y−1, z; (xiii) −x−1, −y−1, −z+1. |
C22H14 | Z = 2 |
Mr = 278.35 | F(000) = 292 |
Triclinic, P1 | The final unit cell was obtained from the xyz centroids of 1108 reflections after integration using the SAINT software package(Bruker, 2000). |
Hall symbol: -P 1 | Dx = 1.396 Mg m−3 |
a = 6.239 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.636 (1) Å | Cell parameters from 1062 reflections |
c = 14.330 (2) Å | θ = 2.8–26.1° |
α = 76.978 (3)° | µ = 0.08 mm−1 |
β = 88.136 (3)° | T = 90 K |
γ = 84.415 (3)° | Platelet, violet-blue |
V = 661.94 (17) Å3 | 0.25 × 0.24 × 0.01 mm |
Bruker Smart Apex diffractometer | 2584 independent reflections |
Radiation source: fine focus sealed Siemens Mo tube | 1252 reflections with I > 2σ(I) |
Parallel mounted graphite monochromator | Rint = 0.030 |
Detector resolution: 4096x4096 / 62x62 (binned 512) pixels mm-1 | θmax = 26.1°, θmin = 2.8° |
phi and ω scans | h = −7→7 |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | k = −9→9 |
Tmin = 0.981, Tmax = 0.999 | l = −15→17 |
5619 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.145 | All H-atom parameters refined |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0643P)2] where P = (Fo2 + 2Fc2)/3 |
2584 reflections | (Δ/σ)max < 0.001 |
255 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C22H14 | γ = 84.415 (3)° |
Mr = 278.35 | V = 661.94 (17) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.239 (1) Å | Mo Kα radiation |
b = 7.636 (1) Å | µ = 0.08 mm−1 |
c = 14.330 (2) Å | T = 90 K |
α = 76.978 (3)° | 0.25 × 0.24 × 0.01 mm |
β = 88.136 (3)° |
Bruker Smart Apex diffractometer | 2584 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1252 reflections with I > 2σ(I) |
Tmin = 0.981, Tmax = 0.999 | Rint = 0.030 |
5619 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.145 | All H-atom parameters refined |
S = 0.97 | Δρmax = 0.26 e Å−3 |
2584 reflections | Δρmin = −0.20 e Å−3 |
255 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
C1 | 0.7017 (3) | 0.4007 (3) | 0.01588 (15) | 0.0188 (7) | |
C2 | 0.5428 (3) | 0.3707 (3) | 0.08731 (15) | 0.0186 (7) | |
C3 | 0.5783 (3) | 0.2454 (3) | 0.17494 (15) | 0.0190 (7) | |
C4 | 0.4209 (3) | 0.2176 (3) | 0.24525 (15) | 0.0189 (7) | |
C5 | 0.4567 (4) | 0.0927 (3) | 0.33498 (15) | 0.0210 (7) | |
C6 | 0.3002 (4) | 0.0702 (3) | 0.40265 (16) | 0.0237 (8) | |
C7 | 0.0949 (4) | 0.1710 (3) | 0.38653 (16) | 0.0231 (8) | |
C8 | 0.0530 (4) | 0.2905 (3) | 0.30304 (16) | 0.0216 (7) | |
C9 | 0.2135 (3) | 0.3199 (3) | 0.22889 (15) | 0.0191 (7) | |
C10 | 0.1749 (3) | 0.4431 (3) | 0.14305 (15) | 0.0191 (7) | |
C11 | 0.6655 (3) | 0.5265 (3) | −0.07058 (15) | 0.0181 (7) | |
C12 | −0.1824 (3) | −0.0435 (3) | −0.04184 (15) | 0.0192 (7) | |
C13 | −0.1556 (3) | −0.0996 (2) | 0.05714 (15) | 0.0188 (7) | |
C14 | −0.3063 (3) | −0.1992 (3) | 0.11710 (15) | 0.0189 (7) | |
C15 | −0.2786 (3) | −0.2548 (3) | 0.21511 (15) | 0.0187 (7) | |
C16 | −0.4308 (3) | −0.3567 (3) | 0.27577 (16) | 0.0211 (7) | |
C17 | −0.3996 (4) | −0.4104 (3) | 0.37095 (16) | 0.0226 (7) | |
C18 | −0.2155 (3) | −0.3658 (3) | 0.41382 (17) | 0.0232 (8) | |
C19 | −0.0658 (4) | −0.2702 (3) | 0.35905 (15) | 0.0214 (7) | |
C20 | −0.0916 (3) | −0.2108 (3) | 0.25783 (15) | 0.0191 (7) | |
C21 | 0.0580 (3) | −0.1125 (3) | 0.20012 (15) | 0.0194 (7) | |
C22 | −0.0325 (3) | 0.0546 (3) | −0.10050 (15) | 0.0185 (7) | |
H1 | 0.846 (3) | 0.331 (3) | 0.0268 (13) | 0.026 (6)* | |
H3 | 0.724 (3) | 0.177 (2) | 0.1846 (12) | 0.014 (5)* | |
H5 | 0.599 (3) | 0.023 (3) | 0.3467 (14) | 0.039 (7)* | |
H6 | 0.320 (3) | −0.013 (3) | 0.4647 (14) | 0.022 (6)* | |
H7 | −0.014 (3) | 0.148 (2) | 0.4392 (14) | 0.022 (6)* | |
H8 | −0.090 (3) | 0.359 (3) | 0.2900 (13) | 0.027 (6)* | |
H10 | 0.034 (3) | 0.516 (2) | 0.1316 (13) | 0.019 (5)* | |
H12 | −0.315 (3) | −0.072 (2) | −0.0695 (13) | 0.020 (5)* | |
H14 | −0.436 (3) | −0.227 (2) | 0.0862 (13) | 0.019 (5)* | |
H16 | −0.560 (3) | −0.385 (2) | 0.2465 (13) | 0.021 (6)* | |
H17 | −0.506 (3) | −0.484 (3) | 0.4127 (15) | 0.034 (6)* | |
H18 | −0.198 (3) | −0.407 (3) | 0.4850 (16) | 0.036 (7)* | |
H19 | 0.062 (3) | −0.237 (2) | 0.3898 (13) | 0.026 (6)* | |
H21 | 0.193 (3) | −0.081 (3) | 0.2296 (13) | 0.027 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0192 (13) | 0.0123 (11) | 0.0268 (14) | −0.0008 (9) | −0.0034 (10) | −0.0080 (9) |
C2 | 0.0187 (12) | 0.0124 (10) | 0.0264 (13) | −0.0042 (9) | −0.0022 (10) | −0.0063 (9) |
C3 | 0.0206 (13) | 0.0120 (11) | 0.0262 (14) | −0.0009 (10) | −0.0001 (10) | −0.0083 (10) |
C4 | 0.0216 (12) | 0.0129 (11) | 0.0238 (13) | −0.0025 (9) | −0.0018 (10) | −0.0069 (9) |
C5 | 0.0240 (13) | 0.0169 (11) | 0.0231 (13) | −0.0028 (10) | −0.0029 (10) | −0.0057 (10) |
C6 | 0.0299 (14) | 0.0170 (12) | 0.0250 (14) | −0.0042 (10) | −0.0019 (11) | −0.0053 (10) |
C7 | 0.0243 (13) | 0.0212 (12) | 0.0260 (14) | −0.0066 (10) | 0.0041 (11) | −0.0085 (10) |
C8 | 0.0222 (13) | 0.0176 (11) | 0.0271 (14) | −0.0048 (10) | 0.0008 (11) | −0.0084 (10) |
C9 | 0.0225 (13) | 0.0120 (10) | 0.0253 (13) | −0.0035 (9) | −0.0008 (10) | −0.0083 (10) |
C10 | 0.0189 (13) | 0.0131 (11) | 0.0271 (14) | −0.0024 (9) | −0.0006 (10) | −0.0080 (10) |
C11 | 0.0189 (12) | 0.0118 (10) | 0.0258 (13) | −0.0028 (9) | −0.0026 (10) | −0.0080 (9) |
C12 | 0.0189 (13) | 0.0129 (10) | 0.0269 (14) | −0.0009 (9) | −0.0010 (10) | −0.0072 (10) |
C13 | 0.0201 (12) | 0.0097 (10) | 0.0273 (14) | 0.0005 (9) | 0.0026 (10) | −0.0066 (9) |
C14 | 0.0200 (13) | 0.0113 (10) | 0.0273 (14) | 0.0005 (9) | −0.0019 (10) | −0.0086 (9) |
C15 | 0.0193 (12) | 0.0121 (10) | 0.0252 (13) | 0.0001 (9) | 0.0018 (10) | −0.0061 (9) |
C16 | 0.0217 (13) | 0.0150 (11) | 0.0268 (14) | 0.0001 (9) | −0.0002 (11) | −0.0061 (10) |
C17 | 0.0227 (13) | 0.0190 (11) | 0.0260 (14) | −0.0027 (10) | 0.0038 (10) | −0.0050 (10) |
C18 | 0.0273 (14) | 0.0175 (11) | 0.0250 (14) | 0.0000 (10) | −0.0010 (11) | −0.0057 (10) |
C19 | 0.0259 (13) | 0.0133 (10) | 0.0263 (13) | −0.0012 (9) | −0.0010 (11) | −0.0071 (9) |
C20 | 0.0193 (12) | 0.0132 (11) | 0.0260 (13) | 0.0010 (9) | 0.0002 (10) | −0.0081 (9) |
C21 | 0.0199 (13) | 0.0140 (11) | 0.0260 (14) | −0.0013 (9) | −0.0003 (10) | −0.0083 (10) |
C22 | 0.0195 (12) | 0.0113 (10) | 0.0264 (13) | 0.0013 (9) | 0.0003 (10) | −0.0089 (9) |
C1—C2 | 1.398 (3) | C12—C13 | 1.397 (3) |
C1—C11 | 1.396 (3) | C12—C22 | 1.394 (3) |
C2—C3 | 1.406 (3) | C13—C14 | 1.412 (3) |
C2—C11i | 1.449 (3) | C13—C22ii | 1.450 (3) |
C3—C4 | 1.380 (3) | C14—C15 | 1.384 (3) |
C4—C5 | 1.427 (3) | C15—C16 | 1.431 (3) |
C4—C9 | 1.442 (3) | C15—C20 | 1.437 (3) |
C5—C6 | 1.349 (3) | C16—C17 | 1.348 (3) |
C6—C7 | 1.426 (3) | C17—C18 | 1.424 (3) |
C7—C8 | 1.347 (3) | C18—C19 | 1.359 (3) |
C8—C9 | 1.432 (3) | C19—C20 | 1.428 (3) |
C9—C10 | 1.382 (3) | C20—C21 | 1.387 (3) |
C10—C11i | 1.412 (3) | C21—C22ii | 1.405 (3) |
C1—H1 | 1.00 (2) | C12—H12 | 0.992 (18) |
C3—H3 | 1.001 (18) | C14—H14 | 0.998 (18) |
C5—H5 | 0.99 (2) | C16—H16 | 0.984 (18) |
C6—H6 | 0.97 (2) | C17—H17 | 1.00 (2) |
C7—H7 | 0.996 (19) | C18—H18 | 1.00 (2) |
C8—H8 | 0.99 (2) | C19—H19 | 1.003 (19) |
C10—H10 | 0.991 (18) | C21—H21 | 1.03 (2) |
C1···C10iii | 3.598 (3) | H3···C21iii | 2.862 (17) |
C4···C16iv | 3.587 (3) | H3···C22x | 2.904 (17) |
C10···C1v | 3.598 (3) | H3···H5 | 2.49 (3) |
C12···C14vi | 3.598 (3) | H5···C20iii | 2.95 (2) |
C14···C12vi | 3.598 (3) | H5···C19iii | 2.89 (2) |
C16···C4vii | 3.587 (3) | H5···C18iii | 3.03 (2) |
C1···H14ii | 2.847 (18) | H5···H3 | 2.49 (3) |
C1···H10iii | 3.010 (18) | H6···C6viii | 3.023 (19) |
C2···H14ii | 3.051 (18) | H6···H6viii | 2.54 (3) |
C2···H12ii | 2.864 (17) | H6···H7ix | 2.49 (3) |
C2···H14iv | 3.084 (16) | H7···H7ix | 2.52 (2) |
C3···H8iii | 2.99 (2) | H7···H6ix | 2.49 (3) |
C3···H12ii | 2.867 (18) | H8···C3v | 2.99 (2) |
C4···H21 | 2.86 (2) | H8···C17xiii | 2.88 (2) |
C4···H12ii | 3.087 (18) | H8···C15xiii | 3.04 (2) |
C4···H16iv | 3.053 (16) | H8···C16xiii | 2.86 (2) |
C5···H21 | 2.87 (2) | H8···H10 | 2.46 (3) |
C6···H21 | 3.08 (2) | H8···C18xiii | 3.07 (2) |
C6···H6viii | 3.023 (19) | H10···C15xiii | 2.903 (17) |
C6···H19 | 2.939 (17) | H10···C14xiii | 2.865 (17) |
C7···H18ix | 2.97 (2) | H10···H1i | 2.44 (3) |
C8···H3v | 3.013 (18) | H10···C20xiii | 3.087 (17) |
C9···H21 | 3.07 (2) | H10···H8 | 2.46 (3) |
C9···H16iv | 2.835 (17) | H10···C1v | 3.010 (18) |
C10···H16iv | 2.849 (18) | H10···C13xiii | 3.025 (16) |
C10···H1v | 2.988 (19) | H12···C11vii | 3.084 (16) |
C11···H12iv | 3.084 (16) | H12···H14 | 2.41 (3) |
C11···H16ii | 3.071 (18) | H12···C2ii | 2.864 (17) |
C11···H14ii | 2.867 (17) | H12···C3ii | 2.867 (18) |
C12···H1x | 2.86 (2) | H12···C4ii | 3.087 (18) |
C12···H14vi | 2.981 (18) | H12···C14vi | 2.975 (18) |
C13···H10xi | 3.025 (16) | H12···H21ii | 2.46 (3) |
C13···H1x | 2.91 (2) | H14···C2vii | 3.084 (16) |
C14···H10xi | 2.865 (17) | H14···H12 | 2.41 (3) |
C14···H12vi | 2.975 (18) | H14···H16 | 2.48 (3) |
C15···H8xi | 3.04 (2) | H14···C1ii | 2.847 (18) |
C15···H10xi | 2.903 (17) | H14···C2ii | 3.051 (18) |
C16···H8xi | 2.86 (2) | H14···C11ii | 2.867 (17) |
C16···H21v | 2.98 (2) | H14···C12vi | 2.981 (18) |
C17···H17xii | 3.08 (2) | H16···C4vii | 3.053 (16) |
C17···H8xi | 2.88 (2) | H16···C9vii | 2.835 (17) |
C18···H5v | 3.03 (2) | H16···C10vii | 2.849 (18) |
C18···H8xi | 3.07 (2) | H16···C21v | 2.994 (18) |
C18···H17xii | 3.06 (2) | H16···H14 | 2.48 (3) |
C19···H5v | 2.89 (2) | H16···C11ii | 3.071 (18) |
C20···H5v | 2.95 (2) | H17···C17xii | 3.08 (2) |
C20···H10xi | 3.087 (17) | H17···C18xii | 3.06 (2) |
C20···H3v | 3.035 (16) | H17···H17xii | 2.46 (3) |
C21···H3v | 2.862 (17) | H17···H18xii | 2.41 (3) |
C21···H16iii | 2.994 (18) | H18···C7ix | 2.97 (2) |
C22···H1x | 3.03 (2) | H18···H17xii | 2.41 (3) |
C22···H3x | 2.904 (17) | H19···C6 | 2.939 (17) |
H1···H3 | 2.44 (3) | H19···H21 | 2.49 (3) |
H1···C12x | 2.86 (2) | H21···C4 | 2.86 (2) |
H1···C10iii | 2.988 (19) | H21···C5 | 2.87 (2) |
H1···H10i | 2.44 (3) | H21···C6 | 3.08 (2) |
H1···C13x | 2.91 (2) | H21···C9 | 3.07 (2) |
H1···C22x | 3.03 (2) | H21···C16iii | 2.98 (2) |
H3···C8iii | 3.013 (18) | H21···H19 | 2.49 (3) |
H3···H1 | 2.44 (3) | H21···H12ii | 2.46 (3) |
H3···C20iii | 3.035 (16) | ||
C2—C1—C11 | 121.99 (19) | C13—C12—C22 | 121.74 (18) |
C1—C2—C3 | 122.41 (19) | C12—C13—C14 | 122.16 (18) |
C1—C2—C11i | 118.74 (19) | C12—C13—C22ii | 119.40 (18) |
C3—C2—C11i | 118.85 (18) | C14—C13—C22ii | 118.45 (19) |
C2—C3—C4 | 121.98 (19) | C13—C14—C15 | 121.89 (18) |
C3—C4—C5 | 122.3 (2) | C14—C15—C16 | 121.86 (18) |
C3—C4—C9 | 119.31 (19) | C14—C15—C20 | 119.55 (18) |
C5—C4—C9 | 118.35 (19) | C16—C15—C20 | 118.59 (19) |
C4—C5—C6 | 120.9 (2) | C15—C16—C17 | 120.8 (2) |
C5—C6—C7 | 120.9 (2) | C16—C17—C18 | 120.9 (2) |
C6—C7—C8 | 120.6 (2) | C17—C18—C19 | 120.5 (2) |
C7—C8—C9 | 120.8 (2) | C18—C19—C20 | 120.7 (2) |
C4—C9—C8 | 118.50 (19) | C15—C20—C19 | 118.61 (19) |
C4—C9—C10 | 119.63 (18) | C15—C20—C21 | 119.41 (19) |
C8—C9—C10 | 121.86 (19) | C19—C20—C21 | 121.98 (19) |
C9—C10—C11i | 121.71 (19) | C20—C21—C22ii | 121.87 (18) |
C1—C11—C2i | 119.27 (18) | C12—C22—C13ii | 118.86 (19) |
C1—C11—C10i | 122.22 (19) | C12—C22—C21ii | 122.31 (18) |
C2i—C11—C10i | 118.51 (19) | C13ii—C22—C21ii | 118.83 (18) |
C2—C1—H1 | 119.4 (11) | C13—C12—H12 | 117.9 (11) |
C11—C1—H1 | 118.6 (11) | C22—C12—H12 | 120.3 (11) |
C2—C3—H3 | 117.0 (10) | C13—C14—H14 | 117.3 (11) |
C4—C3—H3 | 121.0 (10) | C15—C14—H14 | 120.8 (11) |
C4—C5—H5 | 118.6 (12) | C15—C16—H16 | 118.5 (11) |
C6—C5—H5 | 120.5 (12) | C17—C16—H16 | 120.8 (11) |
C5—C6—H6 | 122.8 (12) | C16—C17—H17 | 120.1 (12) |
C7—C6—H6 | 116.3 (12) | C18—C17—H17 | 119.0 (12) |
C6—C7—H7 | 117.0 (11) | C17—C18—H18 | 118.8 (11) |
C8—C7—H7 | 122.4 (11) | C19—C18—H18 | 120.7 (11) |
C7—C8—H8 | 121.6 (11) | C18—C19—H19 | 120.1 (10) |
C9—C8—H8 | 117.6 (11) | C20—C19—H19 | 119.2 (10) |
C9—C10—H10 | 120.3 (11) | C20—C21—H21 | 120.2 (10) |
C11i—C10—H10 | 118.0 (11) | C22ii—C21—H21 | 117.9 (11) |
C11—C1—C2—C3 | −179.5 (2) | C22—C12—C13—C14 | −179.9 (2) |
C11—C1—C2—C11i | 0.1 (3) | C22—C12—C13—C22ii | 0.2 (3) |
C2—C1—C11—C2i | −0.1 (3) | C13—C12—C22—C13ii | −0.2 (3) |
C2—C1—C11—C10i | −179.8 (2) | C13—C12—C22—C21ii | −179.7 (2) |
C1—C2—C3—C4 | 179.6 (2) | C12—C13—C14—C15 | 179.8 (2) |
C11i—C2—C3—C4 | 0.0 (3) | C22ii—C13—C14—C15 | −0.2 (3) |
C1—C2—C11i—C10 | −179.8 (2) | C12—C13—C22ii—C21 | −179.7 (2) |
C1—C2—C11i—C1i | −0.1 (3) | C12—C13—C22ii—C12ii | −0.2 (3) |
C3—C2—C11i—C10 | −0.2 (3) | C14—C13—C22ii—C21 | 0.3 (3) |
C3—C2—C11i—C1i | 179.5 (2) | C14—C13—C22ii—C12ii | 179.9 (2) |
C2—C3—C4—C5 | −179.0 (2) | C13—C14—C15—C16 | −179.6 (2) |
C2—C3—C4—C9 | −0.1 (3) | C13—C14—C15—C20 | −0.1 (3) |
C3—C4—C5—C6 | 179.2 (2) | C14—C15—C16—C17 | 179.5 (2) |
C9—C4—C5—C6 | 0.3 (3) | C20—C15—C16—C17 | 0.0 (3) |
C3—C4—C9—C8 | −179.4 (2) | C14—C15—C20—C19 | −179.7 (2) |
C3—C4—C9—C10 | 0.4 (3) | C14—C15—C20—C21 | 0.3 (3) |
C5—C4—C9—C8 | −0.4 (3) | C16—C15—C20—C19 | −0.2 (3) |
C5—C4—C9—C10 | 179.4 (2) | C16—C15—C20—C21 | 179.8 (2) |
C4—C5—C6—C7 | −0.2 (4) | C15—C16—C17—C18 | 0.6 (4) |
C5—C6—C7—C8 | 0.2 (4) | C16—C17—C18—C19 | −1.0 (4) |
C6—C7—C8—C9 | −0.4 (4) | C17—C18—C19—C20 | 0.8 (4) |
C7—C8—C9—C4 | 0.5 (3) | C18—C19—C20—C15 | −0.2 (3) |
C7—C8—C9—C10 | −179.3 (2) | C18—C19—C20—C21 | 179.8 (2) |
C4—C9—C10—C11i | −0.7 (3) | C15—C20—C21—C22ii | −0.2 (3) |
C8—C9—C10—C11i | 179.1 (2) | C19—C20—C21—C22ii | 179.8 (2) |
C9—C10—C11i—C2 | 0.6 (3) | C20—C21—C22ii—C13 | −0.1 (3) |
C9—C10—C11i—C1i | −179.1 (2) | C20—C21—C22ii—C12ii | −179.7 (2) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y, −z; (iii) x+1, y, z; (iv) x+1, y+1, z; (v) x−1, y, z; (vi) −x−1, −y, −z; (vii) x−1, y−1, z; (viii) −x+1, −y, −z+1; (ix) −x, −y, −z+1; (x) −x+1, −y, −z; (xi) x, y−1, z; (xii) −x−1, −y−1, −z+1; (xiii) x, y+1, z. |
Experimental details
(Iat293K) | (Iat90K) | |
Crystal data | ||
Chemical formula | C22H14 | C22H14 |
Mr | 278.35 | 278.35 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 293 | 90 |
a, b, c (Å) | 6.266 (1), 7.775 (1), 14.530 (1) | 6.239 (1), 7.636 (1), 14.330 (2) |
α, β, γ (°) | 76.475 (4), 87.682 (4), 84.684 (4) | 76.978 (3), 88.136 (3), 84.415 (3) |
V (Å3) | 685.15 (15) | 661.94 (17) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 |
Crystal size (mm) | 0.10 × 0.08 × 0.08 | 0.25 × 0.24 × 0.01 |
Data collection | ||
Diffractometer | Enraf Nonius CAD-4F diffractometer | Bruker Smart Apex diffractometer |
Absorption correction | – | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | – | 0.981, 0.999 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2856, 2684, 843 | 5619, 2584, 1252 |
Rint | 0.034 | 0.030 |
(sin θ/λ)max (Å−1) | 0.616 | 0.618 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.179, 0.94 | 0.045, 0.145, 0.97 |
No. of reflections | 2684 | 2584 |
No. of parameters | 199 | 255 |
H-atom treatment | H-atom parameters constrained | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.14, −0.21 | 0.26, −0.20 |
Computer programs: CAD4-UNIX Software (Enraf-Nonius, 1994), SMART (Bruker, 2000), SET4 (de Boer & Duisenberg, 1984), SAINT (Bruker, 2000), HELENA (Spek, 1997), XPREP (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SIR97 (Altomare et al., 1997), SHELXL97 (Sheldrick, 1997), PLUTO (Meetsma, 2000) and PLATON (Spek, 1994), PLUTO (Meetsma, 2000), ORTEP (Farrugia, 2000; Johnson et al., 2000) and PLATON (Spek, 1994), PLATON (Spek, 1990) and SHELXL97.
Recently, molecular organic conductors were shown to exhibit a number of physical phenomena that were previously reserved for inorganic materials. This new development was triggered by the growth of ultra pure single crystals. In these crystals the electronic mobility is comparable to single-crystal silicon (Schön, Kloc & Batlogg et al., 2000a), which has been shown essential for phenomena such as electric field induced superconductivity Schön, Kloc & Batlogg et al., 2000b), Quantum Hall oscillations (Schön, Berg et al., 2000) and amplified spontaneous emission resulting in an injection laser (Schön, Kloc et al., 2000a). A number of molecular conductors were shown to exhibit these properties, such as C60, thiophenes, and the acenes. The acenes, from anthracene to hexacene, are widely studied for electronic transport properties in thin film form as well as single crystals. \sch
The crystal structure of pentacene, (I), was reported by Campbell et al. (1961) on crystals grown from solution. They constructed a triclinic crystal structure using 0kl and h0l Weissenberg films. The molecules are detected along the c axis with a d(001)-spacing of 14.52 Å. Because this d-spacing is by far the largest in this structure, it becomes characteristic for the structure. A much smaller d-spacing of 14.12 Å was recently reported by Holmes et al. (1999), also on crystals grown from solution. For thin films different values for the d(001)-spacing have been reported, although the unit cell is not known. For thin films evaporated on SiO2 at temperatures above 350 K a d-spacing of 14.5 Å is reported (Minakata et al., 1992; Bouchoms et al., 1999). Lower substrate temperatures and different types of substrate result in thin films with d-spacings of 15.0 Å and 15.4 Å. We have studied the structure of single crystals, grown both from vapour transport and solution, in detail and report on the relationship between the 14.1 Å and the 14.5 Å modifications.
We have grown single crystals of pentacene both by vapour transport and from a solution in trichlorobenzene. We found that both growth methods yield crystals with a d-spacing of 14.12 Å, in good agreement with Holmes et al. (1999). Despite the different d-spacings, the molecular ordering of the structures exhibit remarkable resemblances (Fig. 1). In order to compare the 14.1 Å morphology with the structure reported by Campbell et al. (1961) we transformed the 14.12 Å unit cell to yield a c axis that has approximately the length of the molecule of 16 Å. The three possible unit cell transformations (1 0 0, 0 1 0, 1 1 1), (1 0 0, 0 1 0, 1 0 1), and (1 0 0, 0 1 0, 1 1 1) result in c axis values of 16.01, 16.05 and 16.11 Å, respectively. Only for the last transformation the length axis of the molecule runs approximately along the new c axis, which was also the guideline for Campbell. This comparison shows that the 14.12 Å structure is very similar to the structure reported by Campbell et al. (1961) if we assume that their structure should be read in a left-handed coordinate system. We recall that the determination of the handedness in triclinic systems was a very delicate problem at that time. Even with this identification, there remain discrepancies between the two solutions of almost 10° in the unit cell angles, which is beyond standard deviations. It concerns the angles α and β, the two angles that are important in determining the d(001)-spacing. These discrepancies may have been the cause for a redetermination by Campbell et al. (1962), revising the lattice parameters but not the angles.
We recall that the d-spacing of 14.5 Å reported by Campbell et al. (1961) is in fact observed in thin films. We deposited pentacene thin films on thermally oxidized Si wafers. The pentacene layer of 2 µm thickness was then mechanically removed from the substrate and made into a powder. The diffraction pattern was measured in Bragg-Brentano and Guinier geometry and showed preferential orientation along the [0,0,1] axis. Besides the 14.5 Å phase, (00 l) lines of the 14.12 Å and the 15.4 Å phase were clearly observable. The 15.4 Å phase was transformed into the 14.5 Å phase by exposure to ethanol (Gundlach, 1999). The diffraction pattern could be indexed with a = 6.485 (1) Å, b = 7.407 (2) Å, c = 14.745 (4) Å, α = 77.25 (2)°, β = 85.72 (2)°, γ = 80.92 (2)° and V = 681.6 Å3, yielding d(001) = 14.37 Å. This is in good agreement with reports on the 14.5 Å d-spacing, but the unit-cell parameters are distinctly different from the values reported by Campbell et al. (1961, 1961). We will report this unit-cell determination separately. We conclude that pentacene exhibits at least four morphologies, which can be identified by their d(00 l)-spacings. Single crystals commonly adopt the smallest d(001)-spacing of 14.12 Å. Thin films grown above 350 K adopt preferentially the 14.5 Å d(001)-spacing with a slightly smaller unit-cell volume.