Supporting Information. The Structure of the Strongest Brønsted Acid: The Carborane Acid H(CHB 11 Cl 11 )

Transcription

1 Supporting Information for The Structure of the Strongest Brønsted Acid: The Carborane Acid H(CHB 11 Cl 11 ) Evgenii S. Stoyanov, Stephan P. Hoffmann, Mark Juhasz, and Christopher A. Reed* 31 pages 1

2 Infrared Spectra The IR gas cell was designed from a modified rectangular Schlenk tube. Two holes 15 mm in diameter were cut opposite each other on the rectangular faces. Two circular silicon windows (20 mm in diameter and 1 mm thick) were glued to the cell using a very thin layer of Permatex Ultra Copper hi-temp silicon adhesive. The distance between windows was 16 mm. The cell was connected to the vacuum line and heated to 230º (using a rope heater) for 6-8 hours under high vacuum to remove volatile impurities and byproducts of the glue. Inside a glove-box under helium atmosphere, mg of H(CHB 11 Cl 11 ) acid was placed in the bottom of the cell. After removal from the drybox, the cell was evacuated ( torr) and flame-sealed to remove the Teflon stopcock. The cell was then wrapped with copper tape and a rope heater, attached to a Variac. The temperature was monitoring using the thermocouple. The quoted temperatures are those measured on the exterior of the cell. The actual gas temperature may be somewhat lower (~10 C). In spite of the heat pretreatment, IR spectra developed a weak rotational spectrum of gaseous impurities, presumably arising from the glue. These persisted even after condensation of the acid upon cooling (Figures 1, 3 and S1) Absorbance Absorbance ν, cm ν, c m - 1 Figure S1. Gas phase IR spectra (1-5 in Figure 1) normalized to the intensity of νhcl absorption (2332 cm -1 ). The increasing intensity of the band at 3016 cm -1 (see right side figure) compared to the more nearly coincident 3035 cm -1 peaks indicates that the 3016 cm -1 band does not belong to H(CHB 11 Cl 11 ). It is assigned to products of acid reactions with impurities (e,g, from cell window sealant). 2

3 Table S1. The fingerprint vibration frequencies of H(CHB 11 Cl 11 ) acid in gas and solid phases (experimental IR and calculated) and of solid H(CHB 11 Me 5 Br 6 ). Acid Phase Stretching HCl (νhcl or ν as ClHCl) H(CHB 11 Cl 11 ) Gas A, Exp DFT Calcd. Gas B, Exp DFT Calcd. Amorphous A Amorphous B Amorphous dimer Crystal polymer (X-ray form) Other polymer form 2357 A-B A-B ~1100 ~1100 Bending ClHCl * - * - * * * ~615 ~615 νch H(CHB 11 Me 5 Br 6 ) Crystal 1073 ~580 ( ) 3044 Essentially coincident bands from A and B states. * Not identified. 3

4 DFT Calculations All calculations were performed using the Gaussian 03 suite of programs. 1 A pruned (99,590) integration grid was used for the calculation of numerical integrals. Optimized geometries were calculated at the B3LYP/6-311+G(d,p) level for structural isomers of H(CHB 11 Cl 11 ). Calculations of vibrational frequencies at the same level verified that stationary points were minima having no imaginary frequencies, and provided zero point vibrational energy (ZPVE) values. Calculated Gibbs energies take into account a ZPVE scaling factor of References: 1. Gaussian 03 (Revision B.03), Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Montgomery, Jr., J. A., Vreven, T., Kudin, K. N., Burant, J. C., Millam, J. M., Iyengar, J., Tomasi, J., Barone, V., Mennucci, B., Cossi, M, Scalmani, G., Rega, N., Petersson, G. A., Nakatsuji, H., Hada, M., Ehare, M., Tokyo, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Klene, M., Li, X., Knox, J. E., Hratchian, H. P., Cross, J. B., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J. W., Ayala, P. Y., Morokuma, K., Voth, G. A., Salvador, P., Dannenberg, J. J., Zakrzewski, V. G., Dapprich, S., Daniels, A. D., Strain, M. C., Farkas, O., Malick, D. K., Rabuck, A. D., Raghavachari, K., Foresman, J. B., Ortiz, J. V., Cui, Q., Baboul, A. G., Clifford, S., Cioslowski, J., Stefanov, B. B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Martin, R. L., Fox, D. J., Keith, T., Al-Laham, M. A., Peng, C. Y., Nanayakkara, A., Challacombe, M., Gill, P. M. W., Johsnson, B., Chen, W., Wong, M. W., Gonzalez, C., Pople, J. A., Gaussian, Inc. Pittsburgh, PA, Scott, A.P., Radom, L. Journal of Physical Chemistry, 1996, 100, Table S2. Calculated Thermochemical Data for Isomers of HCHB 11 Cl 11 12,(7) isomer a 7,(8) isomer a 7,(2) isomer a 2,(3) isomer a E(B3LYP) (Hartree) ZPVE (scaled by , in Hartree) ZPVE Corrected Energy (scaled, in Hartree) Thermal Correction to Gibbs Free Energy (scaled) Gibbs Energy, (in Hartree, scaled) Rel. Gibbs Energy (kcal/mol) a Isomers are defined by the chlorine with the shortest bond to the proton; the second closest chlorine is given in ( ). 4

5 Table S3. Calculated Gas Phase Structure for HCHB 11 Cl 11 : 12,(7) isomer atom x y z B Cl Cl B B Cl Cl B B Cl H Cl B B C H B Cl B B B Cl Cl Cl Cl

6 Table S4. Calculated Gas Phase Structure for HCHB 11 Cl 11 : 7,(8) isomer atom x y z B Cl Cl B B Cl Cl B B Cl Cl B B C H B Cl B B B Cl Cl Cl Cl H

7 Table S5. Calculated Gas Phase Structure for HCHB 11 Cl 11 : 7,(2) isomer atom x y z B Cl Cl B B Cl Cl B B Cl Cl B B C H B Cl B B B Cl Cl Cl Cl H

8 Table S6. Calculated Gas Phase Structure for HCHB 11 Cl 11 : 2,(3) isomer atom x y z B Cl Cl B B Cl Cl B B Cl Cl B B C H B Cl H B B B Cl Cl Cl Cl

9 X-ray Structure of [H(CHB 11 Cl 11 )] n A colorless fragment of a thin needle (0.11 x 0.02 x 0.02 mm 3 ) was used for the single crystal x-ray diffraction study of H + - CHB 11 Cl 11 (sample cr80_0m). The crystal was coated with perfluoropolyethers (PFPE) oil and mounted on to a glass fiber. X-ray intensity data were collected at 100(2) K on a Bruker APEX2 (version , ref. 1) platform-ccd x-ray diffractometer system (Mo-radiation, λ = Å, 50KV/45mA power). The CCD detector was placed at a distance of cm from the crystal. A total of 1585 frames were collected for a sphere of reflections (with scan width of 0.3 o in ω and φ angles of 0 o, 90 o, and 180 o, for every 600 frames, 120 sec/frame exposure time; due to the lost of low temperature cooling during data collection, only the first 385 frames of the φ = 180 o run were used). The frames were integrated using the Bruker SAINT software package (version V7.06A, ref. 2) and using a narrow-frame integration algorithm. Based on a triclinic crystal system, the integrated frames yielded a total of 9611 reflections at a maximum 2θ angle of o (0.95 Å resolution), of which 4376 were independent reflections (R int = , R sig = , redundancy = 2.2, completeness = 99.9%) and 2497 (57.1%) reflections were greater than 2σ(I). The unit cell parameters were, a = (11) Å, b = (17) Å, c = (17) Å, α = (3) o, β = (3) o, γ = (3) o, V = (4) Å 3, Z = 4, calculated density D c = g/cm 3. Absorption corrections were applied (absorption coefficient µ = mm -1 ; max/min transmission = /0.8361) to the raw intensity data using the SADABS program (version 2004/1, ref. 3). The Bruker SHELXTL software package (Version 6.14, ref. 4) was used for phase determination and structure refinement. The distribution of intensities (E 2-1 = 0.963) and no systematic absent reflections indicated two possible space groups; P-1 and P1. The space group P-1 was later determined to be correct. Direct methods of phase determination followed by two Fourier cycles of refinement led to an electron density map from which most of the non-hydrogen atoms were identified in the asymmetry unit of the unit cell. With subsequent isotropic refinement, all of the non-hydrogen atoms were identified. There were two H + CHB 11 Cl 11 - present in the asymmetry unit of the unit cell. The H-atoms interacting with the Cl-atoms were identified from the difference map and were refined unrestrained (see Table 7 for hydrogen bond angles and distances). Atomic coordinates, isotropic and anisotropic displacement parameters of all the nonhydrogen atoms were refined by means of a full matrix least-squares procedure on F 2. The H-atoms were included in the refinement in calculated positions riding on the atoms to which they were attached. The refinement converged at R1 = , wr2 = , with intensity, I>2σ(I). The largest peak/hole in the final difference map was 0.497/ e/å 3. 9

10 REFERENCES 1. APEX 2, version , Bruker (2004), Bruker AXS Inc., Madison, Wisconsin, USA. 2. SAINT, version V7.06A, Bruker (2003), Bruker AXS Inc., Madison, Wisconsin, USA. 3. SADABS, version 2004/1, Bruker (2004), Bruker AXS Inc., Madison, Wisconsin, USA. 4. SHELXTL, version 6.14, Bruker (2003), Bruker AXS Inc., Madison, Wisconsin, USA. 10

11 Table S7. Crystal data and structure refinement for [H(CHB 11 Cl 11 )] n Identification code cr80_0m Empirical formula C H2 B11 Cl11 Formula weight Temperature 100(2) K Wavelength Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = (11) Å α= (3). b = (17) Å β= (3). c = (17) Å γ = (3). Volume (4) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1000 Crystal size 0.11 x 0.02 x 0.02 mm 3 Theta range for data collection 1.46 to Index ranges -9<=h<=9, -13<=k<=15, -15<=l<=15 Reflections collected 9611 Independent reflections 4376 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4376 / 460 / 423 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 11

12 Figure S2. Atom numbering scheme for [H(CHB 11 Cl 11 )] n. Thermal ellipsoids at the 50% level. 12

13 Figure S3. Packing of polymeric chains in [H(CHB 11 Cl 11 )] n. 13

14 Table S8. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for H + CHB 11 Cl U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) C(1) 5469(9) 3934(6) 1314(6) 11(1) B(2) 4213(11) 4648(7) 1935(6) 10(2) B(3) 6231(11) 4908(7) 1506(7) 14(2) B(4) 7301(10) 3786(7) 1531(7) 12(2) B(5) 5884(11) 2837(7) 1993(6) 13(2) B(6) 3999(11) 3377(7) 2227(6) 13(2) B(7) 3864(11) 3964(8) 3155(7) 15(2) B(8) 5264(11) 4870(7) 2691(7) 13(2) B(9) 7167(11) 4352(7) 2465(7) 13(2) B(10) 6905(11) 3088(7) 2758(7) 14(2) B(11) 4925(11) 2838(7) 3181(7) 13(2) B(12) 5704(11) 3760(7) 3471(7) 14(2) Cl(1) 2858(2) 5443(2) 1387(2) 16(1) Cl(2) 6866(2) 5941(2) 563(2) 17(1) Cl(3) 8987(2) 3703(2) 661(2) 17(1) Cl(4) 6158(2) 1813(2) 1539(2) 16(1) Cl(5) 2417(2) 2928(2) 1987(2) 19(1) Cl(6) 2099(2) 4078(2) 3973(2) 18(1) Cl(7) 5009(2) 6003(2) 3039(2) 16(1) Cl(8) 8821(2) 4839(2) 2599(2) 18(1) Cl(9) 8416(2) 2243(2) 3197(2) 15(1) Cl(10) 4301(2) 1728(2) 4063(2) 19(1) Cl(11) 5860(2) 3678(2) 4664(1) 19(1) C(1') 11050(9) -801(6) 1240(6) 11(1) B(2') 12315(11) -414(7) 1743(6) 13(2) B(3') 10390(10) 83(7) 1807(6) 11(2) B(4') 9155(10) -862(7) 1862(6) 13(2) B(5') 10332(11) -1925(7) 1828(6) 12(2) B(6') 12293(11) -1644(7) 1748(6) 12(2) B(7') 12328(11) -1337(7) 2828(7) 13(2) B(8') 11149(11) -254(7) 2850(7) 14(2) 14

15 B(9') 9235(11) -544(7) 2903(7) 12(2) B(10') 9159(11) -1786(7) 2949(7) 10(2) B(11') 11095(11) -2238(7) 2867(7) 11(2) B(12') 10399(11) -1409(7) 3547(7) 12(2) Cl(12) 13865(2) 319(2) 1023(2) 16(1) Cl(13) 10093(2) 1274(2) 1142(2) 18(1) Cl(14) 7595(2) -594(2) 1285(2) 16(1) Cl(15) 9936(2) -2728(2) 1240(2) 19(1) Cl(16) 13875(2) -2148(2) 1054(2) 18(1) Cl(17) 13989(2) -1606(2) 3315(2) 19(1) Cl(18) 11550(2) 592(2) 3400(2) 19(1) Cl(19) 7540(2) 51(2) 3532(2) 17(1) Cl(20) 7558(2) -2523(2) 3584(2) 17(1) Cl(21) 11393(2) -3524(2) 3457(2) 16(1) Cl(22) 10040(2) -1775(2) 4820(2) 17(1) 15

16 Table S9. Bond lengths [Å] and angles [ ] for H + CHB 11 Cl C(1)-B(5) 1.683(12) C(1)-B(6) 1.709(11) C(1)-B(4) 1.724(11) C(1)-B(2) 1.728(11) C(1)-B(3) 1.745(11) B(2)-B(8) 1.746(13) B(2)-Cl(1) 1.769(10) B(2)-B(7) 1.775(13) B(2)-B(6) 1.781(13) B(2)-B(3) 1.792(13) B(3)-B(8) 1.755(13) B(3)-Cl(2) 1.763(10) B(3)-B(9) 1.789(13) B(3)-B(4) 1.794(14) B(4)-Cl(3) 1.745(10) B(4)-B(9) 1.784(14) B(4)-B(10) 1.790(13) B(4)-B(5) 1.824(13) B(5)-B(10) 1.758(13) B(5)-Cl(4) 1.769(10) B(5)-B(11) 1.770(13) B(5)-B(6) 1.777(13) B(6)-Cl(5) 1.762(9) B(6)-B(11) 1.774(13) B(6)-B(7) 1.797(14) B(7)-Cl(6) 1.763(10) B(7)-B(8) 1.769(13) B(7)-B(12) 1.792(13) B(7)-B(11) 1.795(14) B(8)-B(12) 1.768(13) B(8)-B(9) 1.778(13) B(8)-Cl(7) 1.831(10) B(9)-Cl(8) 1.773(10) B(9)-B(10) 1.777(14) 16

17 B(9)-B(12) 1.791(13) B(10)-B(12) 1.744(14) B(10)-B(11) 1.757(13) B(10)-Cl(9) 1.842(10) B(11)-B(12) 1.763(14) B(11)-Cl(10) 1.796(10) B(12)-Cl(11) 1.794(10) C(1')-B(6') 1.707(11) C(1')-B(3') 1.708(12) C(1')-B(4') 1.711(11) C(1')-B(5') 1.713(11) C(1')-B(2') 1.713(11) B(2')-Cl(12) 1.757(10) B(2')-B(6') 1.777(14) B(2')-B(3') 1.784(13) B(2')-B(7') 1.785(13) B(2')-B(8') 1.787(13) B(3')-B(9') 1.751(13) B(3')-Cl(13) 1.757(10) B(3')-B(8') 1.777(13) B(3')-B(4') 1.809(13) B(4')-B(9') 1.763(13) B(4')-Cl(14) 1.768(9) B(4')-B(5') 1.778(13) B(4')-B(10') 1.786(13) B(5')-Cl(15) 1.751(10) B(5')-B(11') 1.773(13) B(5')-B(10') 1.796(13) B(5')-B(6') 1.801(13) B(6')-Cl(16) 1.761(10) B(6')-B(11') 1.776(13) B(6')-B(7') 1.800(13) B(7')-B(11') 1.765(13) B(7')-Cl(17) 1.770(9) B(7')-B(12') 1.782(13) B(7')-B(8') 1.801(14) 17

18 B(8')-Cl(18) 1.762(10) B(8')-B(9') 1.774(13) B(8')-B(12') 1.789(13) B(9')-B(12') 1.765(13) B(9')-B(10') 1.784(14) B(9')-Cl(19) 1.845(10) B(10')-Cl(20) 1.767(9) B(10')-B(11') 1.771(13) B(10')-B(12') 1.791(13) B(11')-B(12') 1.758(14) B(11')-Cl(21) 1.840(10) B(12')-Cl(22) 1.779(10) B(5)-C(1)-B(6) 63.2(5) B(5)-C(1)-B(4) 64.7(5) B(6)-C(1)-B(4) 117.0(6) B(5)-C(1)-B(2) 114.6(6) B(6)-C(1)-B(2) 62.4(5) B(4)-C(1)-B(2) 114.4(6) B(5)-C(1)-B(3) 115.6(6) B(6)-C(1)-B(3) 114.7(6) B(4)-C(1)-B(3) 62.3(5) B(2)-C(1)-B(3) 62.1(5) C(1)-B(2)-B(8) 103.7(6) C(1)-B(2)-Cl(1) 120.2(5) B(8)-B(2)-Cl(1) 126.9(6) C(1)-B(2)-B(7) 105.0(7) B(8)-B(2)-B(7) 60.3(5) Cl(1)-B(2)-B(7) 125.6(6) C(1)-B(2)-B(6) 58.3(4) B(8)-B(2)-B(6) 107.9(7) Cl(1)-B(2)-B(6) 119.7(6) B(7)-B(2)-B(6) 60.7(5) C(1)-B(2)-B(3) 59.4(4) B(8)-B(2)-B(3) 59.5(5) Cl(1)-B(2)-B(3) 118.8(6) 18

19 B(7)-B(2)-B(3) 109.2(7) B(6)-B(2)-B(3) 109.0(6) C(1)-B(3)-B(8) 102.6(6) C(1)-B(3)-Cl(2) 121.8(6) B(8)-B(3)-Cl(2) 127.2(6) C(1)-B(3)-B(9) 103.3(6) B(8)-B(3)-B(9) 60.2(5) Cl(2)-B(3)-B(9) 125.4(6) C(1)-B(3)-B(2) 58.5(4) B(8)-B(3)-B(2) 59.0(5) Cl(2)-B(3)-B(2) 121.0(6) B(9)-B(3)-B(2) 107.7(7) C(1)-B(3)-B(4) 58.3(4) B(8)-B(3)-B(4) 107.5(7) Cl(2)-B(3)-B(4) 119.2(6) B(9)-B(3)-B(4) 59.7(5) B(2)-B(3)-B(4) 108.0(6) C(1)-B(4)-Cl(3) 123.7(6) C(1)-B(4)-B(9) 104.4(6) Cl(3)-B(4)-B(9) 124.5(6) C(1)-B(4)-B(10) 101.0(6) Cl(3)-B(4)-B(10) 125.9(6) B(9)-B(4)-B(10) 59.6(5) C(1)-B(4)-B(3) 59.4(4) Cl(3)-B(4)-B(3) 121.5(6) B(9)-B(4)-B(3) 60.0(5) B(10)-B(4)-B(3) 106.3(7) C(1)-B(4)-B(5) 56.6(4) Cl(3)-B(4)-B(5) 121.7(7) B(9)-B(4)-B(5) 106.7(7) B(10)-B(4)-B(5) 58.2(5) B(3)-B(4)-B(5) 106.6(6) C(1)-B(5)-B(10) 104.0(7) C(1)-B(5)-Cl(4) 121.0(6) B(10)-B(5)-Cl(4) 126.6(6) C(1)-B(5)-B(11) 104.9(7) 19

20 B(10)-B(5)-B(11) 59.7(5) Cl(4)-B(5)-B(11) 124.9(6) C(1)-B(5)-B(6) 59.1(5) B(10)-B(5)-B(6) 107.6(7) Cl(4)-B(5)-B(6) 119.2(6) B(11)-B(5)-B(6) 60.0(5) C(1)-B(5)-B(4) 58.7(4) B(10)-B(5)-B(4) 59.9(5) Cl(4)-B(5)-B(4) 120.4(6) B(11)-B(5)-B(4) 108.5(7) B(6)-B(5)-B(4) 108.7(6) C(1)-B(6)-Cl(5) 120.9(6) C(1)-B(6)-B(11) 103.6(6) Cl(5)-B(6)-B(11) 126.7(6) C(1)-B(6)-B(5) 57.7(4) Cl(5)-B(6)-B(5) 121.1(7) B(11)-B(6)-B(5) 59.8(5) C(1)-B(6)-B(2) 59.3(4) Cl(5)-B(6)-B(2) 119.5(6) B(11)-B(6)-B(2) 107.3(7) B(5)-B(6)-B(2) 107.6(6) C(1)-B(6)-B(7) 104.9(6) Cl(5)-B(6)-B(7) 124.8(6) B(11)-B(6)-B(7) 60.4(5) B(5)-B(6)-B(7) 108.3(7) B(2)-B(6)-B(7) 59.5(5) Cl(6)-B(7)-B(8) 123.2(7) Cl(6)-B(7)-B(2) 121.6(6) B(8)-B(7)-B(2) 59.1(5) Cl(6)-B(7)-B(12) 123.6(6) B(8)-B(7)-B(12) 59.5(5) B(2)-B(7)-B(12) 106.7(6) Cl(6)-B(7)-B(11) 123.2(6) B(8)-B(7)-B(11) 106.0(7) B(2)-B(7)-B(11) 106.6(7) B(12)-B(7)-B(11) 58.9(5) 20

21 Cl(6)-B(7)-B(6) 121.9(6) B(8)-B(7)-B(6) 106.2(6) B(2)-B(7)-B(6) 59.8(5) B(12)-B(7)-B(6) 106.2(7) B(11)-B(7)-B(6) 59.2(5) B(2)-B(8)-B(3) 61.6(5) B(2)-B(8)-B(12) 109.0(7) B(3)-B(8)-B(12) 109.6(7) B(2)-B(8)-B(7) 60.6(5) B(3)-B(8)-B(7) 111.2(7) B(12)-B(8)-B(7) 60.9(5) B(2)-B(8)-B(9) 110.3(7) B(3)-B(8)-B(9) 60.8(5) B(12)-B(8)-B(9) 60.7(5) B(7)-B(8)-B(9) 110.9(7) B(2)-B(8)-Cl(7) 121.6(6) B(3)-B(8)-Cl(7) 117.8(6) B(12)-B(8)-Cl(7) 122.1(6) B(7)-B(8)-Cl(7) 122.6(7) B(9)-B(8)-Cl(7) 118.0(6) Cl(8)-B(9)-B(10) 122.5(6) Cl(8)-B(9)-B(8) 124.0(7) B(10)-B(9)-B(8) 105.1(7) Cl(8)-B(9)-B(4) 120.9(6) B(10)-B(9)-B(4) 60.4(5) B(8)-B(9)-B(4) 106.9(7) Cl(8)-B(9)-B(3) 122.4(6) B(10)-B(9)-B(3) 107.0(6) B(8)-B(9)-B(3) 58.9(5) B(4)-B(9)-B(3) 60.3(5) Cl(8)-B(9)-B(12) 122.3(6) B(10)-B(9)-B(12) 58.5(5) B(8)-B(9)-B(12) 59.4(5) B(4)-B(9)-B(12) 107.8(7) B(3)-B(9)-B(12) 107.1(7) B(12)-B(10)-B(11) 60.5(6) 21

22 B(12)-B(10)-B(5) 109.2(7) B(11)-B(10)-B(5) 60.5(5) B(12)-B(10)-B(9) 61.1(5) B(11)-B(10)-B(9) 110.1(7) B(5)-B(10)-B(9) 109.9(7) B(12)-B(10)-B(4) 109.6(7) B(11)-B(10)-B(4) 110.6(7) B(5)-B(10)-B(4) 61.8(5) B(9)-B(10)-B(4) 60.0(5) B(12)-B(10)-Cl(9) 121.5(6) B(11)-B(10)-Cl(9) 122.1(6) B(5)-B(10)-Cl(9) 121.1(7) B(9)-B(10)-Cl(9) 119.3(6) B(4)-B(10)-Cl(9) 119.0(6) B(10)-B(11)-B(12) 59.4(5) B(10)-B(11)-B(5) 59.8(5) B(12)-B(11)-B(5) 107.8(7) B(10)-B(11)-B(6) 107.7(7) B(12)-B(11)-B(6) 108.4(7) B(5)-B(11)-B(6) 60.2(5) B(10)-B(11)-B(7) 107.9(7) B(12)-B(11)-B(7) 60.5(5) B(5)-B(11)-B(7) 108.7(7) B(6)-B(11)-B(7) 60.4(6) B(10)-B(11)-Cl(10) 120.6(6) B(12)-B(11)-Cl(10) 121.7(6) B(5)-B(11)-Cl(10) 120.5(7) B(6)-B(11)-Cl(10) 122.5(6) B(7)-B(11)-Cl(10) 122.9(6) B(10)-B(12)-B(11) 60.1(5) B(10)-B(12)-B(8) 107.0(7) B(11)-B(12)-B(8) 107.4(7) B(10)-B(12)-B(9) 60.3(6) B(11)-B(12)-B(9) 109.2(7) B(8)-B(12)-B(9) 60.0(5) B(10)-B(12)-B(7) 108.7(7) 22

23 B(11)-B(12)-B(7) 60.7(5) B(8)-B(12)-B(7) 59.6(5) B(9)-B(12)-B(7) 109.2(7) B(10)-B(12)-Cl(11) 122.6(6) B(11)-B(12)-Cl(11) 122.7(6) B(8)-B(12)-Cl(11) 121.5(7) B(9)-B(12)-Cl(11) 119.8(6) B(7)-B(12)-Cl(11) 121.1(6) B(6')-C(1')-B(3') 115.4(6) B(6')-C(1')-B(4') 115.7(6) B(3')-C(1')-B(4') 63.9(5) B(6')-C(1')-B(5') 63.6(5) B(3')-C(1')-B(5') 115.9(6) B(4')-C(1')-B(5') 62.6(5) B(6')-C(1')-B(2') 62.6(5) B(3')-C(1')-B(2') 62.9(5) B(4')-C(1')-B(2') 116.0(6) B(5')-C(1')-B(2') 115.6(6) C(1')-B(2')-Cl(12) 121.0(6) C(1')-B(2')-B(6') 58.5(4) Cl(12)-B(2')-B(6') 121.0(6) C(1')-B(2')-B(3') 58.4(4) Cl(12)-B(2')-B(3') 118.5(7) B(6')-B(2')-B(3') 108.2(6) C(1')-B(2')-B(7') 104.5(6) Cl(12)-B(2')-B(7') 126.6(6) B(6')-B(2')-B(7') 60.7(5) B(3')-B(2')-B(7') 108.1(7) C(1')-B(2')-B(8') 104.2(6) Cl(12)-B(2')-B(8') 124.4(6) B(6')-B(2')-B(8') 109.2(7) B(3')-B(2')-B(8') 59.7(5) B(7')-B(2')-B(8') 60.6(5) C(1')-B(3')-B(9') 103.2(7) C(1')-B(3')-Cl(13) 120.5(6) B(9')-B(3')-Cl(13) 127.2(6) 23

24 C(1')-B(3')-B(8') 104.9(7) B(9')-B(3')-B(8') 60.4(5) Cl(13)-B(3')-B(8') 125.3(6) C(1')-B(3')-B(2') 58.7(5) B(9')-B(3')-B(2') 107.5(7) Cl(13)-B(3')-B(2') 119.5(6) B(8')-B(3')-B(2') 60.2(5) C(1')-B(3')-B(4') 58.2(4) B(9')-B(3')-B(4') 59.4(5) Cl(13)-B(3')-B(4') 120.3(6) B(8')-B(3')-B(4') 108.5(7) B(2')-B(3')-B(4') 107.8(6) C(1')-B(4')-B(9') 102.5(6) C(1')-B(4')-Cl(14) 122.5(6) B(9')-B(4')-Cl(14) 125.7(6) C(1')-B(4')-B(5') 58.8(5) B(9')-B(4')-B(5') 107.8(7) Cl(14)-B(4')-B(5') 120.4(6) C(1')-B(4')-B(10') 104.6(6) B(9')-B(4')-B(10') 60.4(5) Cl(14)-B(4')-B(10') 124.6(6) B(5')-B(4')-B(10') 60.5(5) C(1')-B(4')-B(3') 58.0(4) B(9')-B(4')-B(3') 58.7(5) Cl(14)-B(4')-B(3') 120.6(6) B(5')-B(4')-B(3') 107.8(6) B(10')-B(4')-B(3') 107.9(6) C(1')-B(5')-Cl(15) 123.4(6) C(1')-B(5')-B(11') 102.4(6) Cl(15)-B(5')-B(11') 126.1(6) C(1')-B(5')-B(4') 58.7(4) Cl(15)-B(5')-B(4') 120.3(6) B(11')-B(5')-B(4') 106.6(7) C(1')-B(5')-B(10') 104.1(7) Cl(15)-B(5')-B(10') 123.8(6) B(11')-B(5')-B(10') 59.5(5) 24

25 B(4')-B(5')-B(10') 59.9(5) C(1')-B(5')-B(6') 58.0(4) Cl(15)-B(5')-B(6') 121.2(6) B(11')-B(5')-B(6') 59.6(5) B(4')-B(5')-B(6') 107.9(6) B(10')-B(5')-B(6') 108.1(6) C(1')-B(6')-Cl(16) 122.0(6) C(1')-B(6')-B(11') 102.6(6) Cl(16)-B(6')-B(11') 127.3(6) C(1')-B(6')-B(2') 58.9(5) Cl(16)-B(6')-B(2') 119.6(6) B(11')-B(6')-B(2') 106.4(7) C(1')-B(6')-B(7') 104.2(7) Cl(16)-B(6')-B(7') 124.8(6) B(11')-B(6')-B(7') 59.2(5) B(2')-B(6')-B(7') 59.9(5) C(1')-B(6')-B(5') 58.4(4) Cl(16)-B(6')-B(5') 121.0(6) B(11')-B(6')-B(5') 59.4(5) B(2')-B(6')-B(5') 108.2(6) B(7')-B(6')-B(5') 107.8(7) B(11')-B(7')-Cl(17) 122.6(7) B(11')-B(7')-B(12') 59.4(5) Cl(17)-B(7')-B(12') 123.2(6) B(11')-B(7')-B(2') 106.5(6) Cl(17)-B(7')-B(2') 121.8(6) B(12')-B(7')-B(2') 107.2(7) B(11')-B(7')-B(6') 59.7(5) Cl(17)-B(7')-B(6') 120.7(6) B(12')-B(7')-B(6') 107.5(6) B(2')-B(7')-B(6') 59.4(5) B(11')-B(7')-B(8') 107.0(7) Cl(17)-B(7')-B(8') 122.8(6) B(12')-B(7')-B(8') 59.9(5) B(2')-B(7')-B(8') 59.8(5) B(6')-B(7')-B(8') 107.6(6) 25

26 Cl(18)-B(8')-B(9') 122.8(7) Cl(18)-B(8')-B(3') 122.9(7) B(9')-B(8')-B(3') 59.1(5) Cl(18)-B(8')-B(2') 123.1(6) B(9')-B(8')-B(2') 106.4(6) B(3')-B(8')-B(2') 60.1(5) Cl(18)-B(8')-B(12') 121.3(6) B(9')-B(8')-B(12') 59.4(5) B(3')-B(8')-B(12') 107.1(6) B(2')-B(8')-B(12') 106.9(7) Cl(18)-B(8')-B(7') 121.5(6) B(9')-B(8')-B(7') 106.6(7) B(3')-B(8')-B(7') 107.8(7) B(2')-B(8')-B(7') 59.7(5) B(12')-B(8')-B(7') 59.5(5) B(3')-B(9')-B(4') 61.9(5) B(3')-B(9')-B(12') 109.3(7) B(4')-B(9')-B(12') 109.2(7) B(3')-B(9')-B(8') 60.5(5) B(4')-B(9')-B(8') 110.7(7) B(12')-B(9')-B(8') 60.7(5) B(3')-B(9')-B(10') 110.5(7) B(4')-B(9')-B(10') 60.4(5) B(12')-B(9')-B(10') 60.6(5) B(8')-B(9')-B(10') 110.4(7) B(3')-B(9')-Cl(19) 121.1(6) B(4')-B(9')-Cl(19) 120.0(6) B(12')-B(9')-Cl(19) 121.1(6) B(8')-B(9')-Cl(19) 121.0(6) B(10')-B(9')-Cl(19) 119.5(6) Cl(20)-B(10')-B(11') 122.1(7) Cl(20)-B(10')-B(9') 124.5(6) B(11')-B(10')-B(9') 105.2(6) Cl(20)-B(10')-B(4') 123.0(6) B(11')-B(10')-B(4') 106.4(6) B(9')-B(10')-B(4') 59.2(5) 26

27 Cl(20)-B(10')-B(12') 122.2(6) B(11')-B(10')-B(12') 59.1(5) B(9')-B(10')-B(12') 59.2(5) B(4')-B(10')-B(12') 107.1(6) Cl(20)-B(10')-B(5') 121.5(6) B(11')-B(10')-B(5') 59.6(5) B(9')-B(10')-B(5') 106.1(6) B(4')-B(10')-B(5') 59.5(5) B(12')-B(10')-B(5') 107.3(6) B(12')-B(11')-B(7') 60.8(5) B(12')-B(11')-B(10') 61.0(5) B(7')-B(11')-B(10') 110.8(7) B(12')-B(11')-B(5') 109.8(7) B(7')-B(11')-B(5') 110.6(7) B(10')-B(11')-B(5') 60.9(5) B(12')-B(11')-B(6') 109.7(7) B(7')-B(11')-B(6') 61.1(5) B(10')-B(11')-B(6') 110.4(7) B(5')-B(11')-B(6') 61.0(5) B(12')-B(11')-Cl(21) 120.9(6) B(7')-B(11')-Cl(21) 122.7(6) B(10')-B(11')-Cl(21) 117.4(6) B(5')-B(11')-Cl(21) 118.7(6) B(6')-B(11')-Cl(21) 122.1(6) B(11')-B(12')-B(9') 106.5(7) B(11')-B(12')-Cl(22) 121.2(7) B(9')-B(12')-Cl(22) 123.6(6) B(11')-B(12')-B(7') 59.8(5) B(9')-B(12')-B(7') 107.8(7) Cl(22)-B(12')-B(7') 120.9(6) B(11')-B(12')-B(8') 107.8(7) B(9')-B(12')-B(8') 59.9(5) Cl(22)-B(12')-B(8') 122.4(6) B(7')-B(12')-B(8') 60.6(5) B(11')-B(12')-B(10') 59.9(5) B(9')-B(12')-B(10') 60.2(5) 27

28 Cl(22)-B(12')-B(10') 120.1(6) B(7')-B(12')-B(10') 109.1(7) B(8')-B(12')-B(10') 109.4(7) Symmetry transformations used to generate equivalent atoms: 28

29 Table S10. Anisotropic displacement parameters (Å 2 x 10 3 )for H + CHB 11 Cl The anisotropic displacement factor exponent takes the form: -2π 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 C(1) 12(3) 14(3) 8(3) -6(2) -2(2) 3(2) B(2) 16(4) 9(4) 6(4) -6(3) 1(3) 2(3) B(3) 19(4) 13(4) 8(4) -1(3) -4(3) -3(3) B(4) 9(4) 17(4) 10(4) -2(3) -3(3) 1(3) B(5) 15(4) 11(4) 13(4) -8(3) 2(3) -2(3) B(6) 12(4) 13(4) 9(4) 0(3) 1(3) -3(3) B(7) 16(4) 20(4) 6(4) -2(3) 3(3) -3(3) B(8) 17(4) 9(4) 13(4) -1(3) -3(3) 0(3) B(9) 14(4) 15(4) 9(4) -1(3) -4(3) 2(3) B(10) 16(4) 14(4) 11(4) -2(3) -5(3) 2(3) B(11) 14(4) 15(4) 9(4) -4(3) -1(3) 0(3) B(12) 22(4) 12(4) 7(4) -1(3) -4(3) 0(3) Cl(1) 15(1) 16(1) 17(1) -5(1) -3(1) 4(1) Cl(2) 18(1) 16(1) 14(1) -2(1) -1(1) -2(1) Cl(3) 17(1) 20(2) 13(1) -8(1) 0(1) 2(1) Cl(4) 23(1) 16(1) 15(1) -10(1) -7(1) 5(1) Cl(5) 19(1) 20(2) 21(1) -6(1) -6(1) -5(1) Cl(6) 18(1) 18(2) 14(1) -2(1) 2(1) 0(1) Cl(7) 18(1) 13(1) 20(1) -10(1) -4(1) 1(1) Cl(8) 17(1) 16(1) 23(1) -6(1) -7(1) -3(1) Cl(9) 17(1) 14(1) 16(1) -3(1) -7(1) 2(1) Cl(10) 22(1) 14(1) 16(1) 0(1) -2(1) -4(1) Cl(11) 25(1) 22(1) 9(1) -4(1) -6(1) 2(1) C(1') 12(3) 14(3) 8(3) -6(2) -2(2) 3(2) B(2') 11(4) 15(4) 12(4) -4(3) -3(3) 1(3) B(3') 8(4) 14(4) 10(4) -5(3) 1(3) -1(3) B(4') 14(4) 8(4) 16(4) -3(3) -5(3) -2(3) B(5') 13(4) 13(4) 12(4) -6(4) -5(3) 4(3) B(6') 15(4) 17(4) 7(4) -2(3) -6(3) -1(3) B(7') 11(4) 15(4) 14(4) -4(3) -7(3) 0(3) B(8') 18(4) 14(4) 11(4) -2(3) -6(3) -5(3) 29

30 B(9') 12(4) 14(4) 9(4) -2(3) -2(3) 2(3) B(10') 11(4) 12(4) 8(4) -5(3) -2(3) 2(3) B(11') 9(4) 12(4) 11(4) -4(3) -1(3) -1(3) B(12') 16(4) 11(4) 12(4) -6(3) -6(3) -1(3) Cl(12) 16(1) 17(2) 15(1) -5(1) 0(1) -5(1) Cl(13) 19(1) 14(1) 17(1) -2(1) -3(1) 3(1) Cl(14) 17(1) 21(2) 13(1) -4(1) -7(1) 2(1) Cl(15) 29(1) 15(2) 15(1) -8(1) -7(1) -1(1) Cl(16) 19(1) 16(2) 17(1) -6(1) 1(1) 3(1) Cl(17) 17(1) 22(2) 20(1) -5(1) -8(1) -1(1) Cl(18) 26(1) 16(1) 19(1) -10(1) -8(1) -1(1) Cl(19) 18(1) 14(1) 17(1) -4(1) 1(1) 2(1) Cl(20) 14(1) 21(2) 15(1) -4(1) -2(1) -3(1) Cl(21) 19(1) 12(1) 15(1) -2(1) -2(1) 4(1) Cl(22) 21(1) 20(1) 8(1) -2(1) -5(1) 0(1) 30

31 Table S11. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for H + CHB 11 Cl x y z U(eq) H(1) 5400(13) 4012(8) 667(9) 13 H(1') 11241(13) -616(8) 555(9) 13 H(2) 12840(110) -3700(70) 3410(70) 70(30) H(3) 7950(120) 1060(80) 3360(80) 110(40) Table S12. Hydrogen bonds for H + CHB 11 Cl - 11 [Å and ]. D-H...A d(d-h) d(h...a) d(d...a) <(DHA) Cl(21)-H(2)...Cl(7)#1 1.28(9) 1.92(10) 3.171(3) 166(7) Cl(19)-H(3)...Cl(9) 1.47(11) 1.74(11) 3.209(3) 179(8) Symmetry transformations used to generate equivalent atoms: #1 x+1,y-1,z 31