A Cyclopenta Hi Acephenanthrylene Fused with Two 5.5.5 Propellane Units:Extension Of

Supporting Information

A Cyclopenta[hi]acephenanthrylene Fused with Two [5.5.5]Propellane Units:Extension of Triptindane Chemistry

Thorsten Hackfort,[a] Beate Neumann,[a] Hans-Georg Stammler[a] and Dietmar Kuck[a,b]*

[a]Department of Chemistry and [b]Center of Molecular Materials (CM2),

Bielefeld University, Universitätsstraße 25, 33615 Bielefeld, Germany

E-mail:

Figure S1. Mass spectrum of hydrocarbon 5

Figure S2.1H NMR spectrum of hydrocarbon 5

Figure S3. UV spectrum of hydrocarbon 5

Figure S4.Conformation of hydrocarbon 5, calculated by molecular modeling

Figure S5. Truncated 1H NMR spectrum of hydrocarbon 7(mixture of diastereomers)

Figure S6A.Two stable conformations of the (9S,9’S)-diastereomer of hydrocarbon 7, calculated by molecular modeling

Figure S6B.Most stable conformation of the (9R,9’S)-diastereomer of hydrocarbon 7, calculated by molecular modeling

Figure S7A.1H NMR spectrum of the 55:45 mixture of hydrocarbons 5 and8 obtained by photoisomerization

Figure S7B.1H,1H-COSY NMR spectrum of the 55:45 mixture of hydrocarbons 5 and 8 obtained by photoisomerization

Figure S7C.1H,1H-NOESY NMR spectrum of the 55:45 mixture of hydrocarbons 5 and 8 (500 MHz, CDCl3) obtained by photoisomerization

Figure S8. Mass spectrum of compound6

Figure S9A.1H NMR spectrum of compound6

Figure S9B/C.1H,1H-COSY NMR spectrum of hydrocarbon6

Figure S10.13C NMR spectrum of hydrocarbon 6

Tables S1S4. X-ray single crystal structure analysis data of hydrocarbon6

Compound 5:

trans-9-(9H,10H-4b,9a-([1,2]Benzenomethano)indeno[1,2-a]inden-9’-ylideno)-9H,10H-4b,9a-([1,2]benzenomethano)indeno[1,2-a]indene (trans-9,9’-Bitriptindanylidene)

Figure S1. Mass spectrum of hydrocarbon 5 (EI, 70 eV)

Figure S2.1H NMR spectrum of hydrocarbon 5 (500 MHz, CDCl3)

Figure S3. UV spectrum of hydrocarbon 5 (CH2Cl2), c = 5105 M)

Figure S4.Conformation of hydrocarbon 5, calculated by molecular modeling (AM1, HyperChem). Top view (top) and tilted side view (bottom) onto the central double bond.

Compound 7:

9-(9H,10H-4b,9a-([1,2]Benzenomethano)indeno[1,2-a]inden-9’-yl)-9H,10H-4b,9a-([1,2]benzenomethano)indeno[1,2-a]indene (9,9’-Bitriptindanyl, mixture of diastereomers)

Figure S5. Truncated 1H NMR spectrum of hydrocarbon 7 (500 MHz, CDCl3) (mixture of diastereomers). The major isomer gives rise to two AB patterns at  3.54 and 3.12 (4 H) and  3.31 and 3.12 (4 H) due to two sets of equivalent methylene groups, the singlet at  3.72 for 9-H and 9’-H as well as the doublet at  6.40 (2 H) and the triplet at  6.82 (2 H) which indicates the magnetic shielding of the rims of two equivalent benzene rings. Some resonances of the minor diastereomer are indicated by the lettering in italics.

Figure S6A.Two stable conformations of the (9S,9’S)-diastereomer of hydrocarbon 7, calculated by molecular modeling (AM1, HyperChem). Left column: most stable form with gauche orientationof 9-H and 9’-H; right column: by3.3 kcal mol1 less stable form with nearly antiperiplanar orientation of 9-H and 9’-H; (a) and (b) views along the C9-C9’ bond, (c) and (d) side views, (e) and (f) back views showing the cis-stilbene moieties.

Figure S6B.Most stable conformation of the (9R,9’S)-diastereomer of hydrocarbon 7, calculated by molecular modeling (AM1, HyperChem). According to the calculations, this diastereomer is 2.9 kcal mol1 less stable than the (9S,9’S)-diastereomer. (a) frontside view onto the four methlene groups and (b) backside view.

 ppm

Figure S7A.1H NMR spectrum of the 55:45 mixture of hydrocarbons 5 and8 (500 MHz, CDCl3) obtained by photoisomerization.Some additional signals originating from the cis-isomer 8 are marked by dots in the arene range (left); likewise, the two additional AB resonances of 8 are marked in the aliphatic range (right).

Figure S7B.1H,1H-COSY NMR spectrum of the 55:45 mixture of hydrocarbons 5 and 8 (500 MHz, CDCl3) obtained by photoisomerization.

Figure S7C.1H,1H-NOESY NMR spectrum of the 55:45 mixture of hydrocarbons 5 and 8 (500 MHz, CDCl3) obtained by photoisomerization. Note the correlation of the between the protons of conformationally nonequivalent methylene groups (grey box).

Compound6:

15H,16H-4b,15d:10b,15a-bis([1,2]benzenomethano)benzo[4,5]pentaleno[1,2,3-hi]indeno[1,2-e]acephenanthrylene

Figure S8. Mass spectrum of hydrocarbon 6 (EI, 70 eV)

Figure S9A.1H NMR spectrum of hydrocarbon 6 (500 MHz, CDCl3)

Figure S9B.1H,1H-COSY NMR spectrum of hydrocarbon 6 (126 MHz, CDCl3)

Figure S9C.1H,1H-COSY NMR spectrum of hydrocarbon 6 (126 MHz, CDCl3); magnification of the aromatic range.

Figure S10.13C NMR spectrum of hydrocarbon 6 (126 MHz, CDCl3)

X-ray single crystal structure analysis compound 6

Table S1.Crystal data and structure refinement for hydrocarbon 6

Empirical formulaC46H30

Formula weight582.70

Crystal color and habitlight yellow, needles

Crystal size1.00 x 0.40 x 0.20 mm

Temperature293(2) K

Wavelength0.71073 Å (graphite monochromator)

Space groupP21/n

Unit cell dimensionsa = 16.10 (2) Å = 90 °

b = 12.507 (9) Å = 117.25 (6)°

c = 16.844 (12) Å = 90 °

Volume3016 (5) Å3

Z4

Density (calculated)1.283 Mg/m3

Absorption coefficient0.073 mm1

F(000)1224

 range for data collection2.12 to 25.04 °

Index ranges0 h 19, 0 k 14, 20 l 17

Reflections collected5458

Independent reflections5263 (R int = 0.0624)

Absorption correctionNone

Data / restraints / parameters5263 / 0 / 415

Goodness-of-fit on F21.008

Final R indices [I > 2 (I)] R1 = 0. 0592 for 2890 reflections, wR2 = 0.1316

R indices (all data)R1 = 0.1242, wR2 = 0.1635

Largest and mean /0.000 and 0.000

Largest diff. peak and hole0.2 and 0.2 eÅ-3

Table S2.Measurement and program parameters for hydrocarbon 6

Diffractometer usedSiemens P2(1) diffractometer

Scan typeOmega-scan

Scan range1.2° in  around K1,2 - maximum

Scan speed3.929.3° / min in 

Standard-reflections3 of 100 measured reflections

Programs usedSiemens SHELXTL plus / SHELXL-93

Structure solutiondirect

Structure refinementFull-matrix least-squares on F2

Structure factor sourceInternational Tables Vol.C

Definition of R values:R1 =  F0  Fc  / F0 

wR2 = [  [w(F0 2 Fc2) 2 ] /  [ w(F0 2)2 ]]½

Definition of the weighting scheme:

calc w = 1/[2 (Fo2) + (0.0701 P)2 + 0.8175 P] where P = (Fo2 + 2Fc2 ) / 3

Table S3.Selected bond lengths [Å] for hydrocarbon 6

Table S4.Selected bond angles [°] for hydrocarbon 6