Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2007
Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2007 Supporting Information for Silicon Analogues of the Retinoid Agonists TTNPB and 3-Methyl-TTNPB, Disila-TTNPB and Disila-3-methyl-TTNPB: Chemistry and Biology Matthias W. Büttner, Christian Burschka, Jürgen O. Daiss, Diana Ivanova, Natacha Rochel, Sabrina Kammerer, Carole Peluso-Iltis, Audrey Bindler, Claudine Gaudon, Pierre Germain, Dino Moras, Hinrich Gronemeyer, and Reinhold Tacke* Index Crystal structure analyses References S2 S7 S1
Crystal Structure Analyses Experimental: Suitable single crystals of 1b, 2b, and 2b H 2 N(CH 2 ) 3 OH resulted directly from the preparation. The crystals of 1b, 2b, and 2b H 2 N(CH 2 ) 3 OH were mounted in inert oil (perfluoroalkyl ether, ABCR) on a glass fiber and then transferred to the cold nitrogen gas stream of the diffractometer (Stoe IPDS; graphite-monochromated Mo Kα radiation (λ = 0.71073 Å)). The structures were solved by direct methods. [1] All non-hydrogen atoms were refined anisotropically. [2] A riding model was employed in the refinement of the CH hydrogen atoms. The OH hydrogen atoms were localized in difference Fourier syntheses and refined freely (with the exception of the OH hydrogen atoms in 2b and 2b H 2 N(CH 2 ) 3 OH where a riding model was employed). The molecular structures of 1b, 2b, and 2b H 2 N(CH 2 ) 3 OH are depicted in Figures S1 S3. Figure S1. Structures of Molecule I (top) and Molecule II (bottom) in the crystal of 1b (probability level of displacement ellipsoids 50%). S2
Figure S2. Molecular structure of 2b in the crystal (probability level of displacement ellipsoids 50%). Figure S3. Structure of the carboxylate anion in the crystal of 2b H 2 N(CH 2 ) 3 OH (probability level of displacement ellipsoids 50%). S3
Table S1. Crystal data and structure refinement for 1b. Identification code 1b Empirical formula C 22 H 28 O 2 Si 2 Formula weight 380.62 Temperature 173(2) K Wavelength 0.71073 Å Crystal system, space group triclinic, P1 Unit cell dimensions a = 10.319(2) Å α = 77.75(3) b = 10.564(2) Å β = 87.31(3) c = 20.760(4) Å γ = 88.69(3) Volume 2208.9(7) Å 3 Z, Calculated density 4, 1.145 Mg/m 3 Absorption coefficient 0.173 mm 1 F(000) 816 Crystal size 0.5 x 0.3 x 0.1 mm θ range for data collection 1.97 to 25.68 Limiting indices -12=h=12, -12=k=12, -24=l=25 Reflections collected / unique 6911 / 6911 [R(int) = 0.0000] Completeness to θ = 25.68 82.3% Absorption correction None Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 6911 / 179 / 522 Goodness-of-fit on F 2 1.025 Final R indices [I>2σ(I)] R1 = 0.0409, wr2 = 0.1111 R indices (all data) R1 = 0.0573, wr2 = 0.1192 Largest diff. peak and hole 0.239 and -0.180 e.a 3 S4
Table S7. Crystal data and structure refinement for 2b. Identification code 2b Empirical formula C 23 H 30 O 2 Si 2 Formula weight 394.65 Temperature 173(2) K Wavelength 0.71073 Å Crystal system, space group monoclinic, P2 1 /c Unit cell dimensions a = 6.1386(4) Å α = 90 b = 27.265(2) Å β = 96.261(8) c = 13.3945(10) Å γ = 90 Volume 2228.5(3) Å 3 Z, Calculated density 4, 1.176 Mg/m 3 Absorption coefficient 0.174 mm 1 F(000) 848 Crystal size 0.5 x 0.2 x 0.1 mm θ range for data collection 2.14 to 27.41 Limiting indices -7=h=7, -35=k=35, -17=l=17 Reflections collected / unique 27342 / 4711 [R(int) = 0.0435] Completeness to θ = 27.41 93.1% Absorption correction None Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4711 / 0 / 251 Goodness-of-fit on F 2 1.018 Final R indices [I>2σ(I)] R1 = 0.0424, wr2 = 0.1069 R indices (all data) R1 = 0.0654, wr2 = 0.1197 Largest diff. peak and hole 0.257 and -0.357 e.a 3 S5
Table S13. Crystal data and structure refinement for 2b H 2 N(CH 2 ) 3 OH. Identification code 2b H 2 N(CH 2 ) 3 OH Empirical formula C 26 H 39 NO 3 Si 2 Formula weight 469.76 Temperature 193(2) K Wavelength 0.71073 Å Crystal system, space group triclinic, P1 Unit cell dimensions a = 5.9760(12) Å α = 99.92(3) b = 9.2353(18) Å β = 94.68(3) c = 24.994(5) Å γ = 95.61(3) Volume 1345.5(5) Å 3 Z, Calculated density 2, 1.160 Mg/m 3 Absorption coefficient 0.158 mm 1 F(000) 508 Crystal size 0.5 x 0.1 x 0.1 mm θ range for data collection 2.25 to 24.71 Limiting indices -7=h=7, -9=k=10, -29=l=29 Reflections collected / unique 8344 / 4314 [R(int) = 0.0470] Completeness to θ = 24.71 94.4 % Absorption correction None Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4314 / 31 / 297 Goodness-of-fit on F 2 0.886 Final R indices [I>2σ(I)] R1 = 0.0561, wr2 = 0.1424 R indices (all data) R1 = 0.0997, wr2 = 0.1589 Largest diff. peak and hole 0.593 and -0.351 e A 3 S6
References [1] a) G. M. Sheldrick, SHELXS-97, University of Göttingen, Germany, 1997; b) G. M. Sheldrick, Acta Crystallogr., Sect. A 1990, 46, 467 473. [2] G. M. Sheldrick, SHELXL-97, University of Göttingen, Germany, 1997. [3] The hydrogen-bonding system was analyzed by using the program system PLATON: A. L. Spek, PLATON, University of Utrecht, The Netherlands, 1998. In this context, see also: G. A. Jeffrey, W. Saenger, Hydrogen Bonding in Biological Structures; Springer, Berlin, 1991, pp 15 24. S7