Supporting Information

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1 Supporting Information Self-Assembly of 4-(Diethylboryl)pyridine: Crystal Structures of Cyclic Pentamer and Hexamer and Their Solvent-Dependent Selective Crystallization Shigeharu Wakabayashi, * Yuka Hori, Seiji Komeda, Yuki Shimizu,Yasuhiro Ohki, Contents S2 Misaki Horiuchi, Takahito Itoh, Yoshikazu Sugihara, and Kazuyuki Tatsumi General methods. s-waka@suzuka-u.ac.jp S3 Figure S1. 1 H NMR spectrum of 1. Figure S2. 13 C NMR spectrum of 1. S4 Figure S3. NOESY spectrum of 1. Figure S4. 11 B NMR spectrum of 1. S5 Figure S5. 1 H NMR spectrum of a THF complex of 1. S6 S7 S9 S10 Figure S6. Partial 1 H NMR spectrum of a chloroform complex of 1. Figure S7. 1 H NMR spectrum of hexamer of 1 separated under a microscope. Crystallographic analysis. Table S1. Crystal data and refinement parameters for 1 6 THF crystallized at 7 C. Table S2. Crystal data and refinement parameters for 1 6 THF crystallized at 20 C. S11 Table S3. Crystal data and refinement parameters for 1 6 CHCl 3. S12 Table S4. Crystal data and refinement parameters for 1 5 C 6 H 6. S13 Figure S8. Packing diagram in crystal structure of 1 6 THF crystallized at 7 C. Figure S9. Packing diagram in crystal structure of 1 6 THF crystallized at 20 C. S14 Figure S10. Packing diagram in crystal structure of 1 5 C 6 H 6. S15 Figure S11. ORTEP diagram of crystal structure of 1 6 THF crystallized at 7 C. Figure S12. ORTEP diagram of crystal structure of 1 6 THF crystallized at 20 C. S16 Figure S13. ORTEP diagram of crystal structure of 1 6 CHCl 3. Figure S14. ORTEP diagram of crystal structure of 1 5 C 6 H 6. S17 Figure S15. TGA of a chloroform complex of 1. Figure S16. TGA of a benzene complex of 1. S1

2 General methods. Melting points are uncorrected. All 1 H and 13 C NMR spectra in CDCl 3 were recorded at 400 and 600 MHz, and 100 MHz, respectively. The chemical shifts are described as values in ppm relative to a Si(CH 3 ) 4 standard for 1 H NMR. 11 B NMR spectrum in CDCl 3 was recorded at 192 MHz using BF 3 -etherate as internal standard. High-resolution mass spectrum (HRMS) was measured on an electron-impact ionization time-of-flight mass spectrometer. ESI mass spectra were recorded in THF in the presence of LiCl at a flow rate of 3 μl min -1 with the following parameters, capillary voltage (4500 V), collision cell RF (1100 Vpp), nebulizer gas (0.4 bar) and dry heater temperature (180 ºC). Thermogravimetric analysis was performed at the temperature rising rate of 5 C min -1. Analytical thin-layer chromatography was conducted on a plate coated with silicagel plate (0.25 mm thickness), and visualization was effected with short wavelength UV light (254 nm). The reactions were carried out in septum-capped, oven-dried, and argon-purged flask. All reagents were used directly as obtained commercially unless otherwise noted. S2

3 Figure S1. 1 H NMR spectrum of 1 (400 MHz, CDCl 3 ). Singlet signal at ppm is ascribed to C 6 H 6. Figure S2. 13 C NMR spectrum of 1 (100 MHz, CDCl 3 ). Signal at ppm is ascribed to C 6 H 6. S3

4 Figure S3. NOESY spectrum of 1 (600 MHz, CDCl 3 ). Figure S4. 11 B NMR spectrum of 1 (100 MHz, CDCl 3 ). S4

5 Figure S5. 1 H NMR spectrum of a THF complex of 1 (400 MHz, CDCl 3 ). Two multiplet signals at and ppm are ascribed to THF. Figure S6. Partial 1 H NMR spectrum of a chloroform complex of 1 (400 MHz, C 6 D 6 ). Singlet signal at ppm is ascribed to CHCl 3. S5

6 Figure S7. 1 H NMR spectrum of hexamer of 1 separated under a microscope (400 MHz, CDCl 3 ). S6

7 Crystallographic Analysis. X-ray crystallographic analyses of three crystals, one of the hexamer-thf complexes (1 6 THF), which was crystallized at 280 K, hexamer-chloroform complex (1 6 CHCl 3 ) and pentamer-benzene (1 5 C 6 H 6 ) complex were done at 173 K. For another 1 6 THF crystallized at 293K, X-ray diffraction data were collected on a imaging plate area detector using graphite-monochromated Mo-Kα radiation (λ= Å) at 293K. The structures were solved by direct methods 1 and expanded using Fourier techniques. For 1 6 CHCl 3, some non-hydrogen atoms were refined anisotropically, while the rest were refined isotropically. Hydrogen atoms were refined using the riding model. For 1 5 C 6 H 6, the non-hydrogen atoms were refined anisotropically. Hydrogen atoms were refined using the riding model. Neutral atom scattering factors were taken from International Tables for Crystallography (IT), Vol. C, Table Anomalous dispersion effects were included in Fcalc 3 ; the values for Δf' and Δf" were those of Creagh and McAuley 4. The values for the mass attenuation coefficients are those of Creagh and Hubbell 5. All calculations were performed using the CrystalStructure 6 crystallographic software package except for refinement, which was performed using SHELXL For both 1 6 THF structure, solved for the single crystals obtained at different temperatures, were refined on F 2 by full-matrix least squares techniques (SHELXL 2013) 7. Anisotropic refinement was applied to all nonhydrogen atoms except those for THF molecules, which were partially disordered and restrained using SHELXL2013. The initial THF models were generated using Chem3D Pro version 4.0 (CambridgeSoft). All hydrogen atoms but those for THF molecules were placed and refined using the riding model. The structural drawing and geometrical calculations were performed with MERCURY 8 and PLATON 9 software. For the structural refinement of 1 5 C 6 H 6, it was difficult to assign which electron density is N1 nitrogen atom or C4 carbon atom of each pyridine ring. Therefore, refinements were performed for both models that are current assignment in the manuscript and otherwise, and R factors resulted to be exactly the same. Indeed, the crystal may consist of these two cyclic pentamer assembled in opposite arrangements of N1 and C4. We have then ended up with taking current assignment which resulted to generate less number of errors (Alert Level B) by Hirshfeld Rigid-Bond Test in S7

8 "checkcif". For the crystallographic data of 1 6 THF (crystallized at 7 C), the "checkcif" program gave an Alert Level A denoting "Short Inter D...A Contact". This alert appears due to the contact between O1 oxygen atoms originating from two THF molecules disordered over the two-fold axis, which is inevitable as far as an appropriate disorder treatment is included. References 1. SIR92: Altomare, A., Cascarano, G., Giacovazzo, C. and Guagliardi, A. (1993). J. Appl. Cryst. 26, International Tables for Crystallography, Vol.C (1992). Ed. A.J.C. Wilson, Kluwer Academic Publishers, Dordrecht, Netherlands, Table , pp Ibers, J. A. & Hamilton, W. C.; Acta Crystallogr. 1964, 17, Creagh, D. C. & McAuley, W. J.; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table , pages (1992). 5. Creagh, D. C. & Hubbell, J. H.; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table , pages (1992). 6. CrystalStructure 4.1: Crystal Structure Analysis Package, Rigaku Corporation ( ). Tokyo , Japan. 7. SHELXL2013: Sheldrick, G. M. (2008). Acta Cryst. A64, Macrae, C. F.; Bruno, I. J.; Chisholm, J. A.; Edgington, P. R.; McCabe, P.; Pidcock, E.; Rodriguez-Monge, L.; Taylor, R.; van de Streek, J.; Wood, P. A. J. Appl. Crsytallogr., 2008, 41, Spek, A. L. Acta Crystallogr., Sect. D: Biol.Crystallogr. 2009, 65, 148. S8

9 Table S1. Crystal Data and Refinement Parameters for 1 6 THF a Chemical formula C 58 H 92 B 6 N 6 O Formula Mass Crystal system Triclinic a/ Å 9.356(2) b/ Å (3) c/ Å (3) α/ (3) β/ (4) γ/ (5) Unit cell volume/ Å (5) Temperature/K 173(2) Space group P -1 No. of formula units per unit cell, Z 1 No. of reflections measured No. of independent reflections 6508 R int Final R 1 values (I > 2σ(I)) Final wr(f 2 ) values (I > 2σ(I)) Final R 1 values (all data) Final wr(f 2 ) values (all data) a Crystallization was performed in THF by vapor diffusion of EtOH at 7 C. S9

10 Table S2. Crystal Data and Refinement Parameters for 1 6 THF a. Chemical formula C 174 H 276 B 18 N 18 O 3 Formula mass Crystal system trigonal a/å (6) b/å (6) c/å (6) α/ 90 β/ 90 γ/ 120 Unit cell volume/å (3) Temperature/K 293(2) Space group P-3 (#25) No. of formula units per unit cell, Z 1 No. of reflections measured No. of independent reflections 4076 R int Final R 1 values (I > 2σ(I)) Final wr(f 2 ) values (I > 2σ(I)) Final R 1 values (all data) Final wr(f 2 ) values (all data) a Crystallization was performed in THF by vapor diffusion of EtOH at 20 C. S10

11 Table S3. Crystal Data and Refinement Parameters for 1 6 CHCl 3. Chemical formula C 111 H 171 B 12 Cl 9 N 12 Formula mass Crystal system trigonal a/å (5) b/å (5) c/å (11) α/ 90 β/ 90 γ/ 120 Unit cell volume/å (5) Temperature/K 173(2) Space Group R-3 (#148) No. of formula units per unit cell, Z 3 No. of reflections measured No. of independent reflections 4637 R int Final R 1 values (I > 2σ(I)) Final wr(f 2 ) values (I > 2σ(I)) Final R 1 values (all data) Final wr(f 2 ) values (all data) S11

12 Table S4. Crystal Data and Refinement Parameters for 1 5 C 6 H 6. Chemical formula C 57 H 82 B 5 N 5 Formula mass Crystal system triclinic a/å (2) b/å (2) c/å (4) α/ (3) β/ (3) γ/ (4) Unit cell volume/å (8) Temperature/K 173(2) Space Group P-1 (#2) No. of formula units per unit cell, Z 2 No. of reflections measured No. of independent reflections R int Final R 1 values (I > 2σ(I)) Final wr(f 2 ) values (I > 2σ(I)) Final R 1 values (all data) Final wr(f 2 ) values (all data) S12

13 Figure S8. Packing diagram in crystal structure of 1 6 THF crystallized at 7 C. H atoms are omitted for clarity. Color codes: B (pink), C (gray), N (blue-gray), O (red). Figure S9. Packing diagram in crystal structure of 1 6 THF crystallized at 20 C. H atoms are omitted for clarity. Color codes: B (pink), C (gray), N (blue-gray), O (red). S13

14 Figure S10. Packing diagram in crystal structure of 1 5 C 6 H 6. H atoms are omitted for clarity. Color codes: B (pink), C (gray), N (blue-gray). S14

15 Figure S11. ORTEP diagram of crystal structure of 1 6 THF crystallized at 7 C with 50% probability (measured at 173 K). Color codes: B (pink), C (black), H (black), N (blue), O (red). Figure S12. ORTEP diagram of crystal structure of 1 6 THF crystallized at 20 C with 30% probability (measured at 293 K). Color codes: B (pink), C (black), H (black), N (blue), O (red). S15

16 Figure S13. ORTEP diagram of crystal structure of 1 6 CHCl 3 with 50% probability (measured at 173 K). Color codes: B (pink), C (black), H (black), N (blue), Cl (yellow-green). Figure S14. ORTEP diagram of crystal structure of 1 5 C 6 H 6 with 50% probability (measured at 173 K). Color codes: B (pink), C (black), H (black), N (blue). S16

17 Figure S15. TGA of a chloroform complex of 1. Figure S16. TGA of a benzene complex of 1. S17