organic compounds Polymorphism in pentacene Comment

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1 organic compounds Acta Crystallographica Section C Crystal Structure Communications ISSN Polymorphism in pentacene Christine C. Mattheus, Anne B. Dros, Jacob Baas, Auke Meetsma, Jan L. de Boer and Thomas T. M. Palstra* Solid State Chemistry Laboratory, Materials Science Centre, University of Groningen, Nijenborgh 4, NL-9747 AG Groningen, The Netherlands Correspondence palstra@chem.rug.nl Received 5 April 2001 Accepted 27 April 2001 Pentacene, C 22 H 14, crystallizes in different morphologies characterized by their d(001)-spacings of 14.1, 14.5, 15.0 and 15.4 A Ê. We have studied the crystal structure of the 14.1 and 14.5 A Ê d-spacing morphologies grown by vapour transport and from solution. We nd a close correspondence between the 14.1 A Ê structure reported by Holmes, Kumaraswamy, Matzeger & Vollhardt [Chem. Eur. J. (1999), 5, 3399±3412] and the 14.5 A Ê structure reported by Campbell, Monteath Robertson & Trotter [Acta Cryst. (1961), 14, 705±711]. Single crystals commonly adopt the 14.1 A Ê d-spacing morphology with an inversion centre on both molecules in the unit cell. Thin lms grown on SiO 2 substrates above 350 K preferentially adopt the 14.5 A Ê d-spacing morphology, with a slightly smaller unit-cell volume. Comment 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 ultrapure single crystals. In these crystals, the electronic mobility is comparable with singlecrystal silicon (SchoÈ n et al., 2000a), which has been shown to be essential for phenomena such as electric- eld-induced superconductivity (SchoÈ n et al., 2000b), Quantum Hall oscillations (SchoÈ n, Berg et al., 2000) and ampli ed spontaneous emission resulting in an injection laser (SchoÈ n, Kloc et al., 2000). A number of molecular conductors were shown to exhibit these properties, such as C 60, thiophenes and the acenes. The acenes, from anthracene to hexacene, have been widely studied for electronic transport properties in the thin lm as well as the single-crystal form. constructed a triclinic crystal structure using 0kl and h0l Weissenberg lms. The molecules are detected along the c axis with a d(001)-spacing of 14.5 A Ê. Because this d-spacing is by far the largest in this structure, it becomes characteristic for the structure. A much smaller d-spacing of 14.1 A Ê was recently reported by Holmes et al. (1999), also for crystals grown from solution. For thin lms, different values for the d(001)-spacing have been reported, although the unit cell is not known. For thin lms evaporated on SiO 2 at temperatures above 350 K, a d-spacing of 14.5 A Ê has been reported (Minakata et al., 1992; Bouchoms et al., 1999). Lower substrate temperatures and different types of substrate result in thin lms with d-spacings of 15.0 and 15.4 A Ê. 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 and 14.5 A Ê modi cations. 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 14.1 A Ê, in good agreement with Holmes et al. (1999). Despite the different d-spacings, the molecular ordering of the structures exhibit remarkable resemblances (Figs. 1 and 2). In order to compare the 14.1 A Ê morphology with the structure reported by Campbell et al. (1961), we transformed the 14.1 A Ê unit cell to yield a c axis that has approximately the length of the molecule of 16 A Ê. The three possible unit-cell transformations (100, 010, 111), (100, 010, 101) and (100, 010, 111) result in c- axis values of 16.01, and A Ê, respectively. Only for the last transformation does the long axis of the molecule runs approximately along the new c axis, which was also the guideline used by Campbell. This comparison shows that the 14.1 A Ê 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 The crystal structure of pentacene, (I), was reported by Campbell et al. (1961) for crystals grown from solution. They Figure 1 Stacking of the pentacene molecules in the unit cell, viewed along the [110] axis. The heart-lines of the pentacene molecules lie at angles of (2) and (2), respectively, with respect to the c* axis. The d(001)-spacing is clearly visible. Acta Cryst. (2001). C57, 939±941 # 2001 International Union of Crystallography Printed in Great Britain ± all rights reserved 939

2 organic compounds determination of the handedness in triclinic systems was a very delicate problem at that time. Even with this identi cation, there remain discrepancies between the two solutions of almost 10 in the unit-cell angles, which is beyond standard deviations. These discrepancies concern the angles and, the two angles that are important in determining the d(001)- spacing and the discrepancies may have been the reason for a redetermination by Campbell et al. (1962), where the lattice parameters were revised, but not the angles. We recall that the d-spacing of 14.5 A Ê reported by Campbell et al. (1961) is in fact observed in thin lms. We deposited pentacene thin lms on thermally oxidized Si wafers. The pentacene layer of 2 m 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 [001] axis. Besides the 14.5 A Ê phase, (00l) lines of the 14.1 and 15.4 A Ê phases were clearly observable. The 15.4 A Ê phase was transformed into the 14.5 A Ê phase by exposure to ethanol (Gundlach et al., 1999). The diffraction pattern could be indexed with a = (1), b = (2), c = (4) A Ê, = (2), = (2), = (2) and V = A Ê 3, yielding d(001) = A Ê. This is in good agreement with reports on the 14.5 A Ê d-spacing, but the unit-cell parameters are distinctly different from the values reported by Campbell et al. (1961, 1962). We will report this unit-cell determination separately. We conclude that pentacene exhibits at least four morphologies, which can be identi ed by their d(00l)-spacings. Single crystals commonly adopt the smallest d(001)-spacing of 14.1 A Ê. Thin lms grown above 350 K adopt preferentially the 14.5 A Ê d(001)-spacing with a slightly smaller unit-cell volume. Experimental The source material, 99.9% pure pentacene, was purchased from Aldrich and not puri ed further. Single crystals of pentacene were grown using physical vapour transport in a horizontal glass tube (Laudise 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 N 2 (99.999% purity, AGA gas) and H 2 gases (99.995% purity, AGA gas), with a volume percentage of 5.1 (1)% H 2 [for (I) at 293 K]. This yielded almost centimetre-sized violet crystals in the form of platelets and needles. The c* axis was normal to the plane of the very thin platelets (typically 10 to 100 mm) and the growth of the needles was along the [110] direction. Also, at a different part of the tube, a small amount of hydrogenated pentacene crystals (red needles) was found. Lowering the ow 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 a period of four weeks at 450 K, under a stream of ultrapure N 2 gas. Crystals thus obtained [(I) at 90 K] exhibit the same crystal structure as the crystals grown by vapour transport. Pentacene thin lms have been deposited using high-vacuum sublimation (10 8 mbar; 1 mbar = 100 Pa). 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 s 1 was used to ensure crystallinity and the sample was cooled rapidly afterwards. The layer thickness was 2 mm. Figure 2 Perspective ORTEP-3 (Farrugia, 1997) drawing of the pentacene molecules at (a) 293 K and (b) 90 K, showing the non-h atom-numbering scheme. All C atoms are represented by displacement ellipsoids at the 50% probability level and the H atoms are drawn with arbitrary radii. Both molecules have a crystallographically imposed centre of inversion: C1ÐC11 i at ( 1 2, 1 2, 0) and C12ÐC22ii at (0, 0,0) [symmetry codes: (i) 1 x, 1 y, z; (ii) x, y, z]. Compound (I) at 293 K Crystal data C 22 H 14 M r = Triclinic, P1 a = (1) A Ê b = (1) A Ê c = (1) A Ê = (4) = (4) = (4) V = (15) A Ê 3 Data collection Enraf±Nonius CAD-4F diffractometer!/2 scans 2856 measured re ections 2684 independent re ections 843 re ections with I > 2(I) R int = Z =2 D x = Mg m 3 Mo K radiation Cell parameters from 23 re ections = 17.9±21.7 = 0.08 mm 1 T = 293 K Needle±block, violet mm max = 26.0 h = 7! 6 k = 6! 9 l = 17! 17 3 standard re ections frequency: 180 min 940 Christine C. Mattheus et al. C 22 H 14 at 293 and 90 K Acta Cryst. (2001). C57, 939±941

3 organic compounds Re nement Re nement on F 2 R(F ) = wr(f 2 ) = S = re ections 199 parameters Compound (I) at 90 K Crystal data C 22 H 14 M r = Triclinic, P1 a = (1) A Ê b = (1) A Ê c = (2) A Ê = (3) = (3) = (3) V = (17) A Ê 3 Data collection Bruker SMART APEX diffractometer ' and! scans Absorption correction: multi-scan (SADABS; Bruker, 2000) T min = 0.981, T max = measured re ections Re nement Re nement on F 2 R(F ) = wr(f 2 ) = S = re ections 255 parameters H-atom parameters constrained w = 1/[ 2 (F o 2 ) + (0.0608P) 2 ] where P =(F o 2 +2F c 2 )/3 (/) max < max = 0.14 e A Ê 3 min = 0.21 e A Ê 3 Z =2 D x = Mg m 3 Mo K radiation Cell parameters from 1062 re ections = 2.8±26.1 = 0.08 mm 1 T =90K Platelet, violet±blue mm 2584 independent re ections 1252 re ections with I > 2(I) R int = max = 26.1 h = 7! 7 k = 9! 9 l = 15! 17 All H-atom parameters re ned w = 1/[ 2 (F o 2 ) + (0.0643P) 2 ] where P =(F o 2 +2F c 2 )/3 (/) max < max = 0.26 e A Ê 3 min = 0.20 e A Ê 3 The needle axis appeared to be along the [110] vector (9.52 A Ê ) 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 the a and b axes in the plate). The relation between the twin orientations is a 180 rotation around the [110] axis (rotation matrix: 010, 100, 001). Although an X-ray structure determination was thwarted by persistent crystal twinning and the weak scattering power of the crystals, we ultimately found a single crystal (needle-shaped) t to the X-ray diffraction experiment. For compound (I) at 293 K, data collection: CAD-4-UNIX Software (Enraf±Nonius, 1994); cell re nement: SET4 (de Boer & Duisenberg, 1984); data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTO (Meetsma, 2000) and PLATON (Spek, 1994); software used to prepare material for publication: PLATON (Spek, 1990). For compound (I) at 90 K, data collection: SMART (Bruker, 2000); cell re nement: SAINT (Bruker, 2000); data reduction: XPREP (Bruker, 2000); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to re ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTO (Meetsma, 2000), ORTEP- 3 (Farrugia, 1997; Johnson et al., 2000) and PLATON (Spek, 1994); software used to prepare material for publication: PLATON (Spek, 1990) and SHELXL97. Supplementary data for this paper are available from the IUCr electronic archives (Reference: SK1477). Services for accessing these data are described at the back of the journal. References Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115±119. Boer, J. L. de & Duisenberg, A. J. M. (1984). Acta Cryst. A40, C-410. Bouchoms, I. P. M., Schoonveld, W. A., Vrijmoeth, J. & Klapwijk, T. M. (1999). Synth. Met. 104, 175±178. Bruker (2000). SMART, SAINT, SADABS, XPREP and SHELXTL/NT. Bruker AXS Inc., Madison, Wisconsin, USA. Campbell, R. B., Monteath Robertson, J. & Trotter, J. (1961). Acta Cryst. 14, 705±711. Campbell, R. B., Monteath Robertson, J. & Trotter, J. (1962). Acta Cryst. 15, 289±290. Dzyabchenko, A. V., Zavodnik, V. E. & Belsky, V. K. (1979). Acta Cryst. B35, 2250±2253. Enraf±Nonius (1994). CAD-4-UNIX Software. Version 5.1. Utrecht modi ed version of October Enraf±Nonius, Delft, The Netherlands. Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Gundlach, D. J., Jackson, T. N., Schlom, D. G. & Nelson, S. F. (1999). Appl. Phys. Lett. 74, 3302±3305. Holmes, D., Kumaraswamy, S., Matzeger, A. & Vollhardt, K. P. C. (1999). Chem. Eur. J. 5, 3399±3412. Laudise, R. A., Kloc, C., Simpkins, P. G. & Siegrist, T. (1998). J. Cryst. Growth, 187, 449±454. Meetsma, A. (2000). PLUTO, extended version. University of Groningen, The Netherlands. (Unpublished.) Minakata, T., Imai, H. & Ozaki, M. (1992). J. Appl. Phys. 72, 5220±5225. SchoÈ n, J. H., Berg, S., Kloc, C. & Batlogg, B. (2000). Science, 287, 1022±1023. SchoÈ n, J. H., Kloc, C. & Batlogg, B. (2000a). Nature, 406, 702±704. SchoÈ n, J. H., Kloc, C. & Batlogg, B. (2000b). Nature, 408, 549±552. SchoÈ n, J. H., Kloc, C., Dodabalapur, A. & Batlogg, B. (2000). Science, 289, 599± 601. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany. Spek, A. L. (1990). Acta Cryst. A46, C-34. Spek, A. L. (1994). Am. Crystallogr. Assoc. Abstr. 22, 66. Spek, A. L. (1997). HELENA. University of Utrecht, The Netherlands. Acta Cryst. (2001). C57, 939±941 Christine C. Mattheus et al. C 22 H 14 at 293 and 90 K 941

4 supporting information [doi: /s x] Polymorphism in pentacene Christine C. Mattheus, Anne B. Dros, Jacob Baas, Auke Meetsma, Jan L. de Boer and Thomas T. M. Palstra Computing details 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. (Iat293K) pentacene Crystal data C 22 H 14 M r = Triclinic, P1 Hall symbol: -P 1 a = (1) Å b = (1) Å c = (1) Å α = (4) β = (4) γ = (4) V = (15) Å 3 Z = 2 F(000) = 292 Data collection Enraf Nonius CAD-4F diffractometer Radiation source: fine focus sealed Philips Mo tube Perpendicular mounted graphite monochromator ω/2θ scans Unit cell parameters (Duisenberg, 1992) and orientation matrix were determined from a leastsquares 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) D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 23 reflections θ = µ = 0.08 mm 1 T = 293 K Needle-block, violet mm 2856 measured reflections 2684 independent reflections 843 reflections with I > 2σ(I) R int = θ max = 26.0, θ min = 1.4 h = 7 6 k = 6 9 sup-1

5 l = standard reflections every 180 min Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 199 parameters 0 restraints Primary atom site location: structure-invariant direct methods intensity decay: no decay, variation 0.2% Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.0608P) 2 ] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.14 e Å 3 Δρ min = 0.21 e Å 3 Special details 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 F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > σ(f 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq C (8) (6) (3) (19) C (9) (6) (3) (17) C (8) (6) (3) (2) C (9) (7) (3) (19) C (8) (6) (3) (17) C (9) (7) (4) (2) C (9) (7) (4) (2) C (8) (6) (3) (19) C (8) (6) (3) (19) C (8) (6) (3) (19) C (9) (7) (3) (17) C (8) (6) (3) (17) C (8) (6) (3) (17) C (8) (6) (3) (19) C (8) (7) (3) (2) C (8) (6) (3) (17) C (9) (7) (4) (2) C (9) (7) (4) (2) C (8) (6) (3) (19) C (9) (6) (3) (19) C (8) (6) (3) (19) C (8) (6) (3) (19) H * sup-2

6 H * H * H * H * H * H * H * H * H * H * H * H * H * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 C (4) (3) (3) (3) (3) (3) C (3) (3) (3) (3) (3) (2) C (4) (4) (3) (3) (3) (3) C (4) (3) (3) (3) (3) (3) C (3) (3) (3) (3) (3) (3) C (4) (4) (4) (3) (3) (3) C (4) (4) (3) (3) (3) (3) C (3) (4) (3) (3) (3) (3) C (4) (3) (3) (3) (3) (3) C (3) (4) (3) (3) (3) (3) C (3) (3) (3) (3) (3) (3) C (3) (3) (3) (3) (3) (3) C (3) (3) (3) (2) (2) (2) C (4) (3) (3) (3) (3) (3) C (4) (4) (3) (3) (3) (3) C (3) (3) (3) (3) (3) (3) C (4) (4) (3) (3) (3) (3) C (4) (4) (3) (3) (3) (3) C (4) (3) (3) (3) (3) (3) C (4) (3) (3) (3) (3) (2) C (3) (4) (3) (3) (3) (3) C (3) (4) (3) (3) (3) (3) Geometric parameters (Å, º) C1 C (7) C12 C (6) C1 C (6) C12 C (7) C2 C (6) C13 C (7) C2 C11 i (8) C13 C22 ii (7) C3 C (7) C14 C (6) C4 C (6) C15 C (7) sup-3

7 C4 C (7) C15 C (7) C5 C (7) C16 C (7) C6 C (8) C17 C (8) C7 C (7) C18 C (7) C8 C (7) C19 C (6) C9 C (6) C20 C (7) C10 C11 i (7) C21 C22 ii (6) C1 H C12 H C3 H C14 H C5 H C16 H C6 H C17 H C7 H C18 H C8 H C19 H C10 H C21 H C1 H10 iii H5 C20 iii C1 H14 ii H5 H C2 H12 ii H6 H6 x C3 H8 iii H8 C3 vi C3 H12 ii H8 H C4 H H8 C16 xi C5 H H8 C17 xi C6 H H10 H1 i C7 H18 iv H10 C1 vi C9 H16 v H10 C14 xi C10 H1 vi H10 C15 xi C10 H16 v H10 H C11 H14 ii H12 H C12 H1 vii H12 C2 ii C12 H14 viii H12 C3 ii C13 H1 vii H12 C14 viii C14 H10 ix H12 H21 ii C14 H12 viii H14 H C15 H10 ix H14 H C16 H8 ix H14 C1 ii C16 H21 vi H14 C11 ii C17 H8 ix H14 C12 viii C19 H5 vi H16 C9 xii C20 H5 vi H16 C10 xii C21 H16 iii H16 C21 vi C21 H3 vi H16 H C22 H3 vii H17 H17 xiii H1 C10 iii H17 H18 xiii H1 H10 i H18 C7 iv H1 C13 vii H18 H17 xiii H1 H H19 C H1 C12 vii H19 H H3 H H21 C sup-4

8 H3 C21 iii H21 C H3 H H21 C16 iii H3 C22 vii H21 H H5 C19 iii H21 H12 ii C2 C1 C (5) C13 C12 C (4) C1 C2 C (5) C12 C13 C (4) C1 C2 C11 i (4) C12 C13 C22 ii (4) C3 C2 C11 i (4) C14 C13 C22 ii (4) C2 C3 C (5) C13 C14 C (5) C3 C4 C (5) C14 C15 C (5) C3 C4 C (4) C14 C15 C (4) C5 C4 C (4) C16 C15 C (4) C4 C5 C (5) C15 C16 C (5) C5 C6 C (5) C16 C17 C (5) C6 C7 C (5) C17 C18 C (5) C7 C8 C (5) C18 C19 C (5) C4 C9 C (4) C15 C20 C (4) C4 C9 C (4) C15 C20 C (4) C8 C9 C (5) C19 C20 C (5) C9 C10 C11 i (5) C20 C21 C22 ii (4) C1 C11 C2 i (4) C12 C22 C13 ii (4) C1 C11 C10 i (5) C12 C22 C21 ii (4) C2 i C11 C10 i (4) C13 ii C22 C21 ii (4) C2 C1 H C13 C12 H C11 C1 H C22 C12 H C2 C3 H C13 C14 H C4 C3 H C15 C14 H C4 C5 H C15 C16 H C6 C5 H C17 C16 H C5 C6 H C16 C17 H C7 C6 H C18 C17 H C6 C7 H C17 C18 H C8 C7 H C19 C18 H C7 C8 H C18 C19 H C9 C8 H C20 C19 H C9 C10 H C20 C21 H C11 i C10 H C22 ii C21 H C11 C1 C2 C (5) C22 C12 C13 C (5) C11 C1 C2 C11 i 0.1 (7) C22 C12 C13 C22 ii 0.3 (7) C2 C1 C11 C2 i 0.1 (8) C13 C12 C22 C13 ii 0.3 (7) C2 C1 C11 C10 i (5) C13 C12 C22 C21 ii (5) C1 C2 C3 C (5) C12 C13 C14 C (5) C11 i C2 C3 C4 0.8 (7) C22 ii C13 C14 C (8) C1 C2 C11 i C (5) C12 C13 C22 ii C (4) C1 C2 C11 i C1 i 0.1 (7) C12 C13 C22 ii C12 ii 0.3 (7) C3 C2 C11 i C (8) C14 C13 C22 ii C (7) sup-5

9 C3 C2 C11 i C1 i (5) C14 C13 C22 ii C12 ii (4) C2 C3 C4 C (5) C13 C14 C15 C (5) C2 C3 C4 C9 1.0 (8) C13 C14 C15 C (7) C3 C4 C5 C (5) C14 C15 C16 C (5) C9 C4 C5 C6 0.7 (8) C20 C15 C16 C (8) C3 C4 C9 C (5) C14 C15 C20 C (5) C3 C4 C9 C (7) C14 C15 C20 C (8) C5 C4 C9 C8 0.2 (7) C16 C15 C20 C (7) C5 C4 C9 C (5) C16 C15 C20 C (5) C4 C5 C6 C7 0.9 (8) C15 C16 C17 C (8) C5 C6 C7 C8 0.2 (8) C16 C17 C18 C (8) C6 C7 C8 C9 0.8 (8) C17 C18 C19 C (8) C7 C8 C9 C4 0.9 (7) C18 C19 C20 C (7) C7 C8 C9 C (5) C18 C19 C20 C (5) C4 C9 C10 C11 i 0.4 (8) C15 C20 C21 C22 ii 0.2 (8) C8 C9 C10 C11 i (6) C19 C20 C21 C22 ii (5) C9 C10 C11 i C2 0.2 (7) C20 C21 C22 ii C (7) C9 C10 C11 i C1 i (5) C20 C21 C22 ii C12 ii (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. (Iat90K) Crystal data C 22 H 14 M r = Triclinic, P1 Hall symbol: -P 1 a = (1) Å b = (1) Å c = (2) Å α = (3) β = (3) γ = (3) V = (17) Å 3 Z = 2 F(000) = 292 Data collection Bruker Smart Apex diffractometer Radiation source: fine focus sealed Siemens Mo tube Parallel mounted graphite monochromator Detector resolution: 4096x4096 / 62x62 (binned 512) pixels mm -1 phi and ω scans Absorption correction: multi-scan (SADABS; Bruker, 2000) The final unit cell was obtained from the xyz centroids of 1108 reflections after integration using the SAINT software package(bruker, 2000). D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 1062 reflections θ = µ = 0.08 mm 1 T = 90 K Platelet, violet-blue mm T min = 0.981, T max = measured reflections 2584 independent reflections 1252 reflections with I > 2σ(I) R int = θ max = 26.1, θ min = 2.8 h = 7 7 k = 9 9 l = sup-6

10 Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 255 parameters 0 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: structureinvariant direct methods Hydrogen site location: inferred from neighbouring sites All H-atom parameters refined w = 1/[σ 2 (F o2 ) + (0.0643P) 2 ] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.26 e Å 3 Δρ min = 0.20 e Å 3 Special details 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 F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > σ(f 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq C (3) (3) (15) (7) C (3) (3) (15) (7) C (3) (3) (15) (7) C (3) (3) (15) (7) C (4) (3) (15) (7) C (4) (3) (16) (8) C (4) (3) (16) (8) C (4) (3) (16) (7) C (3) (3) (15) (7) C (3) (3) (15) (7) C (3) (3) (15) (7) C (3) (3) (15) (7) C (3) (2) (15) (7) C (3) (3) (15) (7) C (3) (3) (15) (7) C (3) (3) (16) (7) C (4) (3) (16) (7) C (3) (3) (17) (8) C (4) (3) (15) (7) C (3) (3) (15) (7) C (3) (3) (15) (7) C (3) (3) (15) (7) H (3) (3) (13) (6)* H (3) (2) (12) (5)* H (3) (3) (14) (7)* H (3) (3) (14) (6)* sup-7

11 H (3) (2) (14) (6)* H (3) (3) (13) (6)* H (3) (2) (13) (5)* H (3) (2) (13) (5)* H (3) (2) (13) (5)* H (3) (2) (13) (6)* H (3) (3) (15) (6)* H (3) (3) (16) (7)* H (3) (2) (13) (6)* H (3) (3) (13) (6)* Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 C (13) (11) (14) (9) (10) (9) C (12) (10) (13) (9) (10) (9) C (13) (11) (14) (10) (10) (10) C (12) (11) (13) (9) (10) (9) C (13) (11) (13) (10) (10) (10) C (14) (12) (14) (10) (11) (10) C (13) (12) (14) (10) (11) (10) C (13) (11) (14) (10) (11) (10) C (13) (10) (13) (9) (10) (10) C (13) (11) (14) (9) (10) (10) C (12) (10) (13) (9) (10) (9) C (13) (10) (14) (9) (10) (10) C (12) (10) (14) (9) (10) (9) C (13) (10) (14) (9) (10) (9) C (12) (10) (13) (9) (10) (9) C (13) (11) (14) (9) (11) (10) C (13) (11) (14) (10) (10) (10) C (14) (11) (14) (10) (11) (10) C (13) (10) (13) (9) (11) (9) C (12) (11) (13) (9) (10) (9) C (13) (11) (14) (9) (10) (10) C (12) (10) (13) (9) (10) (9) Geometric parameters (Å, º) C1 C (3) C12 C (3) C1 C (3) C12 C (3) C2 C (3) C13 C (3) C2 C11 i (3) C13 C22 ii (3) C3 C (3) C14 C (3) C4 C (3) C15 C (3) C4 C (3) C15 C (3) C5 C (3) C16 C (3) C6 C (3) C17 C (3) sup-8

12 C7 C (3) C18 C (3) C8 C (3) C19 C (3) C9 C (3) C20 C (3) C10 C11 i (3) C21 C22 ii (3) C1 H (2) C12 H (18) C3 H (18) C14 H (18) C5 H (2) C16 H (18) C6 H (2) C17 H (2) C7 H (19) C18 H (2) C8 H (2) C19 H (19) C10 H (18) C21 H (2) C1 C10 iii (3) H3 C21 iii (17) C4 C16 iv (3) H3 C22 x (17) C10 C1 v (3) H3 H (3) C12 C14 vi (3) H5 C20 iii 2.95 (2) C14 C12 vi (3) H5 C19 iii 2.89 (2) C16 C4 vii (3) H5 C18 iii 3.03 (2) C1 H14 ii (18) H5 H (3) C1 H10 iii (18) H6 C6 viii (19) C2 H14 ii (18) H6 H6 viii 2.54 (3) C2 H12 ii (17) H6 H7 ix 2.49 (3) C2 H14 iv (16) H7 H7 ix 2.52 (2) C3 H8 iii 2.99 (2) H7 H6 ix 2.49 (3) C3 H12 ii (18) H8 C3 v 2.99 (2) C4 H (2) H8 C17 xiii 2.88 (2) C4 H12 ii (18) H8 C15 xiii 3.04 (2) C4 H16 iv (16) H8 C16 xiii 2.86 (2) C5 H (2) H8 H (3) C6 H (2) H8 C18 xiii 3.07 (2) C6 H6 viii (19) H10 C15 xiii (17) C6 H (17) H10 C14 xiii (17) C7 H18 ix 2.97 (2) H10 H1 i 2.44 (3) C8 H3 v (18) H10 C20 xiii (17) C9 H (2) H10 H (3) C9 H16 iv (17) H10 C1 v (18) C10 H16 iv (18) H10 C13 xiii (16) C10 H1 v (19) H12 C11 vii (16) C11 H12 iv (16) H12 H (3) C11 H16 ii (18) H12 C2 ii (17) C11 H14 ii (17) H12 C3 ii (18) C12 H1 x 2.86 (2) H12 C4 ii (18) C12 H14 vi (18) H12 C14 vi (18) C13 H10 xi (16) H12 H21 ii 2.46 (3) C13 H1 x 2.91 (2) H14 C2 vii (16) C14 H10 xi (17) H14 H (3) C14 H12 vi (18) H14 H (3) C15 H8 xi 3.04 (2) H14 C1 ii (18) sup-9

13 C15 H10 xi (17) H14 C2 ii (18) C16 H8 xi 2.86 (2) H14 C11 ii (17) C16 H21 v 2.98 (2) H14 C12 vi (18) C17 H17 xii 3.08 (2) H16 C4 vii (16) C17 H8 xi 2.88 (2) H16 C9 vii (17) C18 H5 v 3.03 (2) H16 C10 vii (18) C18 H8 xi 3.07 (2) H16 C21 v (18) C18 H17 xii 3.06 (2) H16 H (3) C19 H5 v 2.89 (2) H16 C11 ii (18) C20 H5 v 2.95 (2) H17 C17 xii 3.08 (2) C20 H10 xi (17) H17 C18 xii 3.06 (2) C20 H3 v (16) H17 H17 xii 2.46 (3) C21 H3 v (17) H17 H18 xii 2.41 (3) C21 H16 iii (18) H18 C7 ix 2.97 (2) C22 H1 x 3.03 (2) H18 H17 xii 2.41 (3) C22 H3 x (17) H19 C (17) H1 H (3) H19 H (3) H1 C12 x 2.86 (2) H21 C (2) H1 C10 iii (19) H21 C (2) H1 H10 i 2.44 (3) H21 C (2) H1 C13 x 2.91 (2) H21 C (2) H1 C22 x 3.03 (2) H21 C16 iii 2.98 (2) H3 C8 iii (18) H21 H (3) H3 H (3) H21 H12 ii 2.46 (3) H3 C20 iii (16) C2 C1 C (19) C13 C12 C (18) C1 C2 C (19) C12 C13 C (18) C1 C2 C11 i (19) C12 C13 C22 ii (18) C3 C2 C11 i (18) C14 C13 C22 ii (19) C2 C3 C (19) C13 C14 C (18) C3 C4 C (2) C14 C15 C (18) C3 C4 C (19) C14 C15 C (18) C5 C4 C (19) C16 C15 C (19) C4 C5 C (2) C15 C16 C (2) C5 C6 C (2) C16 C17 C (2) C6 C7 C (2) C17 C18 C (2) C7 C8 C (2) C18 C19 C (2) C4 C9 C (19) C15 C20 C (19) C4 C9 C (18) C15 C20 C (19) C8 C9 C (19) C19 C20 C (19) C9 C10 C11 i (19) C20 C21 C22 ii (18) C1 C11 C2 i (18) C12 C22 C13 ii (19) C1 C11 C10 i (19) C12 C22 C21 ii (18) C2 i C11 C10 i (19) C13 ii C22 C21 ii (18) C2 C1 H (11) C13 C12 H (11) C11 C1 H (11) C22 C12 H (11) C2 C3 H (10) C13 C14 H (11) sup-10

14 C4 C3 H (10) C15 C14 H (11) C4 C5 H (12) C15 C16 H (11) C6 C5 H (12) C17 C16 H (11) C5 C6 H (12) C16 C17 H (12) C7 C6 H (12) C18 C17 H (12) C6 C7 H (11) C17 C18 H (11) C8 C7 H (11) C19 C18 H (11) C7 C8 H (11) C18 C19 H (10) C9 C8 H (11) C20 C19 H (10) C9 C10 H (11) C20 C21 H (10) C11 i C10 H (11) C22 ii C21 H (11) C11 C1 C2 C (2) C22 C12 C13 C (2) C11 C1 C2 C11 i 0.1 (3) C22 C12 C13 C22 ii 0.2 (3) C2 C1 C11 C2 i 0.1 (3) C13 C12 C22 C13 ii 0.2 (3) C2 C1 C11 C10 i (2) C13 C12 C22 C21 ii (2) C1 C2 C3 C (2) C12 C13 C14 C (2) C11 i C2 C3 C4 0.0 (3) C22 ii C13 C14 C (3) C1 C2 C11 i C (2) C12 C13 C22 ii C (2) C1 C2 C11 i C1 i 0.1 (3) C12 C13 C22 ii C12 ii 0.2 (3) C3 C2 C11 i C (3) C14 C13 C22 ii C (3) C3 C2 C11 i C1 i (2) C14 C13 C22 ii C12 ii (2) C2 C3 C4 C (2) C13 C14 C15 C (2) C2 C3 C4 C9 0.1 (3) C13 C14 C15 C (3) C3 C4 C5 C (2) C14 C15 C16 C (2) C9 C4 C5 C6 0.3 (3) C20 C15 C16 C (3) C3 C4 C9 C (2) C14 C15 C20 C (2) C3 C4 C9 C (3) C14 C15 C20 C (3) C5 C4 C9 C8 0.4 (3) C16 C15 C20 C (3) C5 C4 C9 C (2) C16 C15 C20 C (2) C4 C5 C6 C7 0.2 (4) C15 C16 C17 C (4) C5 C6 C7 C8 0.2 (4) C16 C17 C18 C (4) C6 C7 C8 C9 0.4 (4) C17 C18 C19 C (4) C7 C8 C9 C4 0.5 (3) C18 C19 C20 C (3) C7 C8 C9 C (2) C18 C19 C20 C (2) C4 C9 C10 C11 i 0.7 (3) C15 C20 C21 C22 ii 0.2 (3) C8 C9 C10 C11 i (2) C19 C20 C21 C22 ii (2) C9 C10 C11 i C2 0.6 (3) C20 C21 C22 ii C (3) C9 C10 C11 i C1 i (2) C20 C21 C22 ii C12 ii (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. sup-11