SUPPLEMENTARY INFORMATION

Transcription

1 SUPPLEMENTARY INFORMATION General procedure Nuclear magnetic resonance (NMR) spectra were recorded on a Bruker AVANCE-300 spectrometer (117 MHz for 7 Li NMR) and a Bruker AVANCE-600 (151 MHz for 13 C NMR). A 7 Li NMR spectrum was referred to LiCl/D 2 O as the external reference. Laser desorption ionization time-of-flight mass spectra (LDI-TOF-MS) were measured on a Shimadzu AXIMA CFR plus. Elemental analysis was carried out on a J-SCIECNCE LAB Micro Corder JM10 for C and H contents. The content of Li was determined by ICP-OES (Jarrell-Ash IRIS-AP) after the sample treatment by a wet digestion method with HNO 3 /H 2 SO 4. All electrochemical measurements were performed in o-dichlorobenzene with 50 mm tetra-n-butylammonium hexafluorophosphate (TBAPF 6, Wako) as the supporting electrolyte. The sample concentration was ca. 0.5 mm in all cases. Cyclic voltammograms (CV) and differential pulse voltammograms (DPV) were recorded on a BAS-100B/W with a three-electrode configuration (working electrode, platinum disk of 1.6 mm diameter; counter electrode, Pt wire; reference electrode, Ag/10 mm AgNO 3 and 100 mm TBAPF 6 in CH 3 CN). All the redox potentials were referenced to that of the redox couple Fc/Fc +. The CV were measured at a scan rate of 100 mv/s. The DPV were recorded with pulse amplitude, 50 mv; pulse width, 50 ms; pulse period, 200 ms; and scan rate, 20 mv/s. All solvents were purchased and used without further purification. o-dichlorobenzene for electrochemical measurements was distilled from CaH 2. Tris(4-bromophenyl)ammoniumyl hexachloroantimonate 1 and tetraethylammonium hexachloroantimonate (Et 4 N)(SbCl 6 ) 2 were synthesized by the literature method. All filtrations were performed through polytetrafluoroethylene (PTFE) membrane filter (pore size 0.2 m). Synthesis and Oxidation of Li@C 60 to prepare [Li@C 60 ](SbCl 6 ) Li@C 60 was synthesized by irradiation of energetic Li ions to C 60. Li + ions, generated by contact ionization, were irradiated onto a target plate applied negative bias while the vapor of C 60 was deposited on the same plate. A certain amount of black deposit (A) is obtained by this process. LDI-TOF mass spectra of the deposit A are depicted in Fig. S1.Deposit A on the substrate was transferred into a vacuum desiccator or glove box immediately after the synthetic procedure, and used for the next oxidation process. Oxidation was carried out under an argon atmosphere. The deposit A (2.31 g) and tris(4-bromophenyl)ammoniumyl hexachloroantimonate (4.84 g, 5.93 mmol) were placed in a 200 nature chemistry 1

2 supplementary information ml flask, and dehydrated o-dichlorobenzene (115 ml) and acetonitrile (57 ml) were added into it. The flask was then brought out of the grove box, and the dark blue suspension was heated at 100 ºC for 23 h with stirring under Ar atmosphere. The purification of the product was carried out in air. After most of acetonitrile was removed from the resulting dark purplish-brown suspension under reduced pressure, the suspension was filtered, and to the filtrate was added hexane (300 ml). The mixture was left for 1 hour to produce a brown fine-grained precipitate, which was filtered and washed repeatedly with acetonitrile (three times, ml) and then toluene (twice, ml). The brown residue was dissolved in o-dichlorobenzene (20mL) and the mixture was filtered. The brown filtrate was cooled at 5 ºC for 2 days to give [Li@C 60 ](SbCl 6 ) (1) as a brown precipitate. After filtration, 1 (10.8 mg) was obtained as a brown solid. In order to get a purer sample suitable for elemental analysis, it was recrystallized as follows: 1 (41.5 mg, prepared by the above mentioned method) was dissolved in o-dichlorobenzene/acetonitrile (v/v = 1/1, 52 ml) and filtered. Acetonitrile was removed from the filtrate under reduced pressure, and the solution was kept at 5 ºC. After 2 days, precipitates were collected by filtration and washed with toluene and hexane to afford 9.1 mg of brown crystals of [Li@C 60 ](SbCl 6 ) C 6 H 4 Cl 2 (1 C 6 H 4 Cl 2 ). An elemental analysis indicates the existence of an o-dichlorobenzene molecule as a solvent for crystallization. Anal. Calcd. for C 66 H 4 Cl 8 LiSb: C, 65.56; H, 0.33; Li, Found: C, ; H, 0.536; Li, LDI-TOF mass spectra of 1 are depicted in Fig. S2. LDI-TOF MS: 727 (M + ). The 7 Li and 13 C{ 1 H} NMR spectra of 1 are shown in Figs. S3 and S4, respectively. 13 C{ 1 H} NMR (151 MHz, o-dichlorobenzene-d 4 /acetonitrile-d 3 = 1/1): Li NMR (117 MHz, o-dichlorobenzene-d 4 /acetonitrile-d 3 = 1/1, LiCl in D 2 O as external standard): Ultraviolet-visible-nearinfrared (UV-Vis-NIR) absorption spectra of 1 in o-dichlorobenzene at room temperature are shown in Fig. S5. Preparation of a single crystal of [Li@C 60 ](SbCl 6 ) (1) 1 C 6 H 4 Cl 2 (8.4 mg) was dissolved in o-dichlorobenzene/acetonitrile (v/v = 1/1, 11 ml) and filtered. The solution in a glass tube (3.5 mm i.d.) was placed in a screw vial together with a glass tube containing 1 ml of CS 2 (Fig. S6). The vial was closed with a screw cap and kept at 23 ºC. After 6 days, brown platelet crystals were grown. The single crystals were annealed at 200 C for solvent desorption. The single crystal of [Li@C 60 ](SbCl 6 ) has twinned monoclinic structure below room temperature. The phase transition from the monoclinic to the untwined orthorhombic structure was observed at ca. 320 K (space group Amm2, a = Å, b = 9.95 Å, c = Å, V = 3555 Å 3 at 370 K). Unpolarized Raman spectra for the crystals at room temperature are shown in Fig. S7. Structure determination of a single crystal of [Li@C 60 ](SbCl 6 ) (1) 2 nature chemistry

3 supplementary information The synchrotron radiation x-ray diffraction experiment was carried out at SPring-8 BL02B1. The experimental and analytical conditions are given in Table S1. The initial positions of 60 and SbCl 6 molecules in the unit cell were determined by a direct method using SIR Although the molecular arrangement suggested Cmcm space group, the space group was uniquely determined as Amm2 from weak forbidden reflections of Cmcm. The positions of molecules were refined by a rigid body refinement using SP 4. The orientations of the C 60 cages and the positions of Li cation inside the cage were determined based on the charge density distributions which were calculated by the maximum entropy method (MEM) 5. The C 60 cage was disordered with four kinds of orientation and the Li cation was also disordered with two-sites. The structure model was refined by full-matrix least-squares methods with anisotropic displacement parameters using SHELXL The rigid-body translation, libration and screw-rotation (TLS) approach was used for the thermal displacement parameters of C 60 molecules in the refinement. The reliability factor of final structure model (Fig. S8) was 4.69 % (for 1349 F > 4, d > 0.8 Å). The perspective view of the determined crystal structure along a axis is drawn in Fig. S9 using PyMol 7. A crystal information file (CIF) of the crystal structure of [Li@C 60 ](SbCl 6 ) can be obtained free of charge from The Cambridge Crystallographic Data Centre via The deposition number is CCDC Supporting References 1. D. W. Reynolds et al., J. Am. Chem. Soc. 109, 4960 (1987). 2. R. Decressain et al., J. Phys. Chem. Solids, 59, 1487 (1998). 3. M. C. Burla et al., J. Appl. Cryst. 38, 381 (2005). 4. E. Nishibori et al., Acta Cryst. A 63, 43 (2007). 5. M. Sakata, M. Sato, Acta Cryst. A 46, 263 (1990). 6. G. M. Sheldrick, Acta Cryst. A 64, 112 (2008). 7. W. L. DeLano, The PyMol Molecular Graphics System on the World Wide Web. (2002). nature chemistry 3

4 supplementary information %Int mv[sum= 2633 mv] Profiles Smooth Gauss 7 -Baseline 21 (a) %Int mv[sum= mv] Profiles Smooth Gauss 7 -Baseline Mass/Charge Mass/Charge %Int. 198 mv[sum= mv] Profiles Smooth Gauss 7 -Baseline (b) %Int. 198 mv[sum= mv] Profiles Smooth Gauss 7 -Baseline Mass/Charge Mass/Charge Figure S1 LDI-TOF mass spectra of black deposit (A). (a) linear positive mode and (b) reflectron negative mode. 4 nature chemistry

5 supplementary information %Int. 198 mv[sum= mv] Profiles Smooth Gauss 7 -Baseline (a) %Int. 198 mv[sum= mv] Profiles Smooth Gauss 7 -Baseline Mass/Charge %Int Mass/Charge 124 mv[sum= mv] Profiles Smooth Gauss 7 -Baseline (b) %Int mv[sum= mv] Profiles Smooth Gauss 7 -Baseline Mass/Charge Mass/Charge Figure S2 LDI-TOF mass spectra of of [Li@C 60 ](SbCl 6 ) (1). (a) linear positive mode and (b) reflectron negative mode. nature chemistry 5

6 supplementary information ppm Figure S3 A 7 Li NMR spectrum of [Li@C 60 ](SbCl 6 ) (1) (117 MHz, o-dichlorobenzene-d 4 /acetonitrile-d 3 = 1/1). 6 nature chemistry

7 supplementary information * * * *: solvent [Li@C60] ppm ppm Figure S4 A 13 C{ 1 H} NMR spectrum of [Li@C 60 ](SbCl 6 ) (1) (151 MHz, o-dichlorobenzene-d 4 /acetonitrile-d 3 = 1/1). nature chemistry 7

8 supplementary information Figure S5 UV-Vis-NIR absorption spectra of 60 ](SbCl 6 ) (1) (in red) and pristine C 60 (in blue) in o-dichlorobenzene solution at room temperature. The onset of the dipole-allowed transitions (t 1u g g +h g ) are shown. The inset is the dipole-forbidden transitions (t 1u h u ) in a magnified absorbance scale. The crystalline powder of [Li@C 60 ](SbCl 6 ) is dispersed in o-dichlorobenzene by ultrasonication, which is followed by a centrifuge at 145,000 rpm for 30 min to achieve an extensive dispersion in the solution. The resultant supernatant is then collected and used for obtaining the absorption spectra. 8 nature chemistry

9 supplementary information 2 mm i.d. 3.5 mm i.d. glass tube 1 ml of CS L of a solution of [Li@C 60 ](SbCl 6 ) (1) Figure S6 A recrystallization vessel for [Li@C 60 ](SbCl 6 ) (1) to prepare single crystals. nature chemistry 9

10 supplementary information Figure S7 Unpolarized Raman spectra for solid 60 ](SbCl 6 ) (1) (in red) and pristine C 60 (in blue) at room temperature. Peaks due to the tangential A g (2) mode, which is a well known measure of the charge state of C 60, is presented. No softening of the tangential mode is observed in reference to that of C 60, indicating that the interaction between the encapsulated Li + ion and C 60 is weak with virtually no spin reside on the C 60 cage The spectra are taken at 488 nm of a weak laser power to avoid any degradation of the sample during the measurement. 10 nature chemistry

11 supplementary information Figure S8 Determined molecular structure of 60 ](SbCl 6 ) (1) at 370 K. The structure of one molecular orientation for Li@C 60 extracted from disordered structure is shown. nature chemistry 11

12 supplementary information Figure S9 Crystal structure of 60 ](SbCl 6 ) (1). The perspective view along the a axis. Li cations are shown in purple sphere. C 60 and SbCl 6 are shown in green and orange sticks, respectively. The structure of one molecular orientation for Li@C 60 extracted from disordered structure is shown. Three slabs (one layer of thick color and two outer layers of light color) are shown in the figure. 12 nature chemistry

13 supplementary information Table S1 Data collection and refinement statistics for X-ray structure determination of 60 ](SbCl 6 ) (1) [Li@C 60 ](SbCl 6 ) Data collection Temperature 370 K Space group Amm2 Cell dimensions a, b, c (Å) (1), 9.951(1), (3) 90, 90, 90 Resolution (Å) 0.75 R merge > 0 Completeness (%) 0.95 Redundancy 4.22 Refinement Resolution (Å) 0.80 No. reflections 1985 R1 No. atoms 130 nature chemistry 13

14 supplementary information Crystallographic data for 60 ](SbCl 6 ) (1) The crystallographic data for [Li@C 60 ](SbCl 6 ) in CIF format (CCDC ) is as follows. data_sw11-15_370k _audit_creation_method SHELXL-97 _chemical_name_common? _chemical_melting_point? _chemical_formula_moiety '(C60 Li1),(Cl6 Sb1)' _publ_requested_journal 'Nature Chemistry' _chemical_formula_sum 'C60 Cl6 Li1 Sb1' _publ_contact_author_name _publ_contact_author_ hiroshi.sawa@cc.nagoya-u.ac.jp loop publ_author_name 'Aoyagi, Shinobu' 'Nishibori, Eiji' 'Sawa, Hiroshi' 'Sugimoto, Kunihisa' 'Takata, Masaki' 'Yasumitsu, Miyata' 'Kitaura, Ryo' 'Shinohara, Hisanori' 'Okada, Hiroshi' 'Sakai, Takeshi' 'Ono, Yoshihiro' 'Kawachi, Kazuhiko' 'Hiroshi Sawa' _chemical_formula_weight loop atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 'International Tables Vol C Tables and ' 'Cl' 'Cl1-' 'International Tables Vol C Tables and ' 'Sb' 'Sb5+' 'International Tables Vol C Tables and ' 'Li' 'Li1+' 'International Tables Vol C Tables and ' 'Yokoo, Kuniyoshi' _symmetry_cell_setting orthorhombic 'Ono, Shoichi' 'Omote, Kenji' _symmetry_space_group_name_h-m 'A m m 2' _symmetry_int_tables_number 38 'Kasama, Yasuhiko' 'Ishikawa, Shinsuke' 'Komuro, Takashi' 'Tobita, Hiromi' loop symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' _chemical_name_systematic ;? ; 'x, -y, z' '-x, y, z' 'x, y+1/2, z+1/2' '-x, -y+1/2, z+1/2' 14 nature chemistry

15 supplementary information 'x, -y+1/2, z+1/2' _diffrn_radiation_wavelength '-x, y+1/2, z+1/2' _diffrn_radiation_type synchrotron _diffrn_radiation_source 'bending magnet' _cell_length_a (10) _diffrn_radiation_monochromator silicon _cell_length_b (10) _diffrn_measurement_device_type _cell_length_c (3) cylindrical_ip_camera_at_spring-8_bl02b1 _cell_angle_alpha _diffrn_measurement_method? _cell_angle_beta _diffrn_detector_area_resol_mean? _cell_angle_gamma _diffrn_standards_number? _cell_volume (6) _diffrn_standards_interval_count? _cell_formula_units_z 4 _diffrn_standards_interval_time? _cell_measurement_temperature 370 _diffrn_standards_decay_%? _cell_measurement_reflns_used? _diffrn_reflns_number 8797 _cell_measurement_theta_min? _diffrn_reflns_av_r_equivalents _cell_measurement_theta_max? _diffrn_reflns_av_sigmai/neti _diffrn_reflns_limit_h_min -15 _exptl_crystal_description platelet _diffrn_reflns_limit_h_max 15 _exptl_crystal_colour brown _diffrn_reflns_limit_k_min -12 _exptl_crystal_size_max 0.06 _diffrn_reflns_limit_k_max 12 _exptl_crystal_size_mid 0.04 _diffrn_reflns_limit_l_min -36 _exptl_crystal_size_min 0.01 _diffrn_reflns_limit_l_max 36 _exptl_crystal_density_meas? _diffrn_reflns_theta_min 0.69 _exptl_crystal_density_diffrn _diffrn_reflns_theta_max _exptl_crystal_density_method 'not measured' _reflns_number_total 1985 _exptl_crystal_f_ _reflns_number_gt 1349 _exptl_absorpt_coefficient_mu _reflns_threshold_expression >2sigma(I) _exptl_absorpt_correction_type none _exptl_absorpt_correction_t_min? _computing_data_collection? _exptl_absorpt_correction_t_max? _computing_cell_refinement? _exptl_absorpt_process_details? _computing_data_reduction? _computing_structure_solution 'SIR 2004' _exptl_special_details _computing_structure_refinement 'SHELXL-97 ; (Sheldrick, 1997)'? _computing_molecular_graphics? ; _computing_publication_material? _diffrn_ambient_temperature 370 _refine_special_details nature chemistry 15

16 supplementary information ; 'Flack H D (1983), Acta Cryst. A39, ' Although the molecular arrangement suggested Cmcm space group, the space group was uniquely determined as Amm2 from weak forbidden reflections of Cmcm. The C60 cage was disordered with four kinds of orientation and the _refine_ls_abs_structure_flack 0.05(4) _refine_ls_number_reflns 1985 _refine_ls_number_parameters 301 _refine_ls_number_restraints 2779 _refine_ls_r_factor_all _refine_ls_r_factor_gt Li cation was also disordered with two-sites. _refine_ls_wr_factor_ref _refine_ls_wr_factor_gt Refinement of F^2^ against ALL reflections. weighted R-factor wr and The _refine_ls_goodness_of_fit_ref _refine_ls_restrained_s_all goodness of fit S are based on F^2^, conventional R-factors R are based _refine_ls_shift/su_max _refine_ls_shift/su_mean on F. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is the choice of not relevant to loop atom_site_label _atom_site_type_symbol 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. _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_u_iso_or_equiv _atom_site_adp_type ; _atom_site_occupancy _atom_site_symmetry_multiplicity _refine_ls_structure_factor_coef Fsqd _atom_site_calc_flag _refine_ls_matrix_type full _atom_site_refinement_flags _refine_ls_weighting_scheme calc _atom_site_disorder_assembly _refine_ls_weighting_details _atom_site_disorder_group 'calc w=1/[ s^2^(fo^2^)+(0.0857p)^2^ p] Li1 Li Uani where P=(Fo^2^+2Fc^2^)/3' d SPU.. _atom_sites_solution_primary direct Li2 Li Uani _atom_sites_solution_secondary difmap d SPU.. _atom_sites_solution_hydrogens none Sb11 Sb (3) (5) _refine_ls_hydrogen_treatment none Uani 1 4 d SDU.. _refine_ls_extinction_method none Cl11 Cl (4) (4) 0.090(2) _refine_ls_extinction_coef? _refine_ls_abs_structure_details Uani 1 2 d SDU.. Cl12 Cl (5) (3) (19) 16 nature chemistry

17 supplementary information Uani 1 2 d SDU.. C110 C (17) 0.845(2) (9) 0.138(8) Cl13 Cl (5) (3) (18) Uani Uani 1 2 d SDU.. C112 C (3) (11) 0.144(5) Sb21 Sb (3) (6) Uani d SPDU.. Uani 1 4 d SDU.. C113 C 0.056(3) 0.262(3) (12) Cl21 Cl (5) (4) (16) Uani Uani 1 2 d SDU.. C114 C 0.108(2) 0.376(3) (9) Uani Cl22 Cl (5) (3) (16) Uani 1 2 d SDU.. C125 C (16) 0.393(3) (6) Uani Cl23 Cl (7) (4) 0.123(3) Uani 1 2 d SDU.. C126 C (17) 0.292(2) (7) Uani C101 C 0.060(2) 0.744(3) (8) Uani C128 C 0.112(2) 0.211(2) (9) Uani C102 C (17) 0.631(3) (8) Uani C115 C (15) 0.490(3) (5) 0.156(7) C109 C (14) 0.612(3) (6) Uani Uani C116 C (14) 0.620(3) (7) 0.140(4) C127 C (17) 0.712(2) (7) Uani Uani C117 C (3) (8) 0.141(6) C111 C (19) 0.793(3) (8) Uani Uani d SPDU.. C118 C (3) (10) 0.136(5) C103 C (15) 0.521(3) (5) 0.145(5) Uani d SPDU.. Uani C119 C (15) 0.818(2) (8) 0.139(3) C104 C (3) (9) 0.139(5) Uani Uani d SPDU.. C120 C (14) 0.736(2) (7) Uani C105 C (13) 0.389(3) (7) 0.140(4) Uani C121 C (12) 0.637(2) (8) Uani C106 C (12) 0.370(2) (8) Uani C124 C (12) 0.522(3) (5) Uani C108 C (10) 0.483(3) (5) Uani C123 C (11) 0.553(2) (6) Uani C107 C (10) 0.449(2) (6) Uani C122 C (14) 0.685(2) (7) Uani C132 C (13) 0.320(2) (7) Uani C129 C (17) 0.160(2) (9) 0.133(7) C131 C (15) 0.269(2) (7) Uani Uani C130 C (15) 0.187(2) (8) 0.136(4) nature chemistry 17

18 supplementary information Uani C144 C (15) 0.567(2) (5) Uani C133 C (11) 0.823(1) (6) Uani d DU.. C143 C (19) 0.480(2) (6) Uani C139 C (1) (6) Uani d SDU.. C147 C (12) 0.670(2) (6) Uani C135 C 0.491(2) 0.741(2) (6) Uani C148 C (11) 0.541(2) (7) Uani C136 C (17) 0.699(2) (6) Uani C152 C (10) 0.461(2) (6) Uani C159 C (16) 0.748(2) (6) Uani C153 C (12) 0.540(2) (6) Uani C134 C (10) 0.823(1) (6) Uani d DU.. C158 C (13) 0.671(2) (6) Uani C140 C (1) (6) Uani d SDU.. C150 C (17) 0.273(2) (8) 0.127(4) C160 C 0.497(2) 0.743(2) (6) Uani Uani d SDU.. C151 C (14) 0.327(2) (7) 0.139(5) C145 C (15) 0.699(2) (6) Uani Uani C157 C (18) 0.273(2) (8) 0.135(5) C146 C (14) 0.747(2) (6) Uani Uani C201 C 0.447(2) 0.746(3) (9) Uani C137 C (16) 0.568(2) (5) Uani C202 C (18) 0.632(3) (8) Uani C138 C 0.440(2) 0.476(2) (7) Uani C209 C (15) 0.610(3) (6) Uani C156 C 0.416(2) 0.342(3) (9) Uani C227 C (18) 0.711(2) (7) Uani C155 C (18) 0.352(2) (7) Uani C211 C 0.384(2) 0.791(3) (9) Uani C154 C (15) 0.485(2) (6) Uani C203 C (16) 0.521(3) (6) 0.142(5) C141 C 0.422(2) 0.348(3) (8) Uani Uani C204 C (3) (9) 0.141(5) C142 C (17) 0.352(2) (7) Uani Uani d SPDU.. C205 C (14) 0.388(3) (7) 0.140(4) C149 C (15) 0.485(2) (6) Uani Uani C206 C (12) 0.370(2) (8) Uani 18 nature chemistry

19 supplementary information C224 C (12) 0.521(3) (6) Uani C208 C (11) 0.481(3) (6) Uani C223 C (11) 0.553(2) (6) Uani C207 C (11) 0.449(2) (7) Uani C222 C (15) 0.684(2) (7) Uani C232 C (14) 0.319(2) (7) Uani C229 C (18) 0.159(2) (10) 0.133(8) C231 C (15) 0.271(3) (7) Uani Uani C230 C (16) 0.190(2) (8) 0.135(4) C210 C (18) 0.844(2) (10) 0.139(10) Uani Uani C233 C (11) 0.823(1) (6) Uani C212 C (3) (11) 0.146(6) d DU.. Uani d SPDU.. C239 C (2) (6) Uani C213 C 0.440(3) 0.263(3) (12) d SDU.. Uani C235 C 0.003(2) 0.742(2) (7) Uani C214 C 0.387(3) 0.375(3) (9) Uani d SDU.. C236 C (17) 0.701(2) (6) Uani C225 C (17) 0.392(3) (7) Uani C259 C (16) 0.748(2) (7) Uani C226 C (18) 0.291(2) (7) Uani C234 C (11) 0.824(1) (6) Uani C228 C 0.384(2) 0.209(3) (9) Uani d DU.. C240 C (2) (6) Uani C215 C (16) 0.488(3) (6) 0.156(7) d SDU.. Uani C260 C 0.011(2) 0.741(2) (7) Uani C216 C (14) 0.618(3) (8) 0.142(5) Uani C245 C (16) 0.697(2) (6) Uani C217 C (3) (9) 0.141(6) Uani d SPDU.. C246 C (15) 0.747(2) (7) Uani C218 C (3) (10) 0.136(5) Uani d SPDU.. C237 C (16) 0.570(2) (5) Uani C219 C (16) 0.819(2) (8) 0.139(3) Uani C238 C 0.054(2) 0.478(2) (7) Uani C220 C (15) 0.738(2) (7) Uani C256 C 0.079(2) 0.343(3) (9) Uani C221 C (13) 0.636(3) (8) Uani C255 C (19) 0.352(2) (8) Uani nature chemistry 19

20 supplementary information _atom_site_aniso_u_12 C254 C (15) 0.486(2) (6) Uani Li C241 C 0.086(2) 0.348(3) (8) Uani Li Sb (10) (9) (14) C242 C (18) 0.351(2) (7) Uani Cl (3) 0.050(2) 0.151(6) (5) Cl (3) 0.116(5) 0.067(3) (3) C249 C (15) 0.484(2) (6) Uani Cl (3) 0.058(3) 0.114(4) (3) Sb (10) (11) (14) C244 C (16) 0.565(2) (6) Uani Cl (3) 0.079(3) 0.097(4) 0.018(5) C243 C 0.058(2) 0.478(2) (7) Uani Cl (3) 0.108(4) 0.050(2) (3) Cl (6) 0.167(8) 0.101(5) (6) C247 C (13) 0.670(2) (6) Uani C C C248 C (12) 0.540(2) (7) Uani C C252 C (11) 0.461(2) (6) Uani C C C (17) 0.191(3) 0.049(11) 0.004(5) (11) C253 C (12) 0.541(2) (7) Uani 0.004(4) C (4) 0.156(10) 0.073(13) 0.073(10) C258 C (13) 0.671(2) (6) Uani C (7) 0.172(2) 0.066(10) 0.045(5) (6) C250 C (18) 0.272(2) (9) 0.129(5) 0.012(5) Uani C C251 C (15) 0.326(2) (7) 0.141(5) Uani C257 C (19) 0.273(2) (9) 0.136(5) Uani C C C C C (3) 0.044(14) 0.186(4) (5) (4) loop_ (18) _atom_site_aniso_label C (4) 0.092(15) 0.152(10) 0.067(12) _atom_site_aniso_u_ _atom_site_aniso_u_22 C _atom_site_aniso_u_33 C _atom_site_aniso_u_23 C _atom_site_aniso_u_13 C nature chemistry

21 supplementary information C C C (2) 0.192(4) 0.049(10) 0.001(6) (14) (4) C (7) 0.174(2) 0.066(10) 0.044(5) 0.037(6) (5) C (4) 0.162(11) 0.080(15) 0.067(12) C (3) 0.077(12) 0.144(11) 0.076(9) C (6) 0.071(7) 0.173(2) 0.044(4) 0.017(4) C C C C C C C C (17) 0.131(9) 0.164(5) (5) (6) (11) (4) C (15) 0.146(3) 0.178(3) (18) 0.011(2) C (7) C C (19) 0.118(8) 0.181(5) 0.021(4) 0.022(6) C (9) C C C C C (2) 0.044(13) 0.186(4) (5) 0.002(4) 0.029(15) C (7) 0.058(8) 0.180(2) 0.046(4) (4) 0.050(6) C C C C C (17) 0.192(4) 0.054(12) (6) (10) (5) C C (4) 0.164(11) 0.071(14) (11) C C C (8) 0.176(2) 0.060(9) (5) (6) C (5) C C C C C C C C C C C C (3) 0.030(17) 0.187(4) 0.009(6) 0.002(4) C (2) C C (4) 0.095(16) 0.153(11) (13) C C C C C C C nature chemistry 21

22 supplementary information C C C C C (2) 0.191(3) 0.048(10) 0.001(6) (14) (4) C (7) 0.171(2) 0.070(11) (6) 0.033(7) 0.010(5) C (4) 0.157(11) 0.081(15) (12) C (3) 0.075(12) 0.146(12) (9) C (6) 0.071(8) 0.173(2) (4) 0.017(4) C C C C C C C C (19) 0.124(10) 0.166(5) 0.018(5) (6) 0.070(12) 0.045(5) C (17) 0.147(4) 0.176(3) (19) 0.017(2) C (7) C C (2) 0.119(9) 0.163(5) (5) 0.044(7) C (11) C C C (3) 0.044(14) 0.186(4) 0.008(5) 0.002(4) (16) C (7) 0.056(8) 0.177(2) (5) (4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) (6) are estimated using the full covariance matrix. The C C C C C cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only C used when they are defined by crystal symmetry. An C C C approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. C ; C C C C C C loop geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 22 nature chemistry

23 supplementary information _geom_bond_publ_flag C101 C (5) 4? Li1 Li (12) 2_565? C101 C (17).? Li1 C (16).? C101 C (16).? Li1 C (16) 3_565? C102 C (17).? Li1 C (16) 2_565? C102 C (17).? Li1 C (16) 2_565? C109 C (17).? Li1 C (16) 3_565? C109 C (15).? Li1 C (17).? C127 C (17).? Li1 C (15) 2_565? C127 C (16).? Li1 C (15) 3_565? C111 C (18).? Li1 C (17) 4? C103 C (4) 4? Li1 C (17).? C103 C (17).? Li1 C (2) 2_565? C104 C (18).? Li2 Li (12) 2_665? C104 C (15).? Li2 C (16).? C104 C (15) 4? Li2 C (15) 2_665? C105 C (17).? Li2 C (16) 3_565? C106 C (15).? Li2 C (17).? C106 C (16).? Li2 C (17) 4_655? C108 C (15).? Li2 C (15) 2_665? C107 C (17).? Li2 C (15) 3_565? C107 C (15).? Li2 C (17) 4_655? C132 C (17).? Li2 C (17).? C132 C (15).? Li2 C (16) 2_665? C131 C (18).? Li2 C (16) 3_565? C110 C (4) 4? Sb11 Cl (5).? C110 C (16).? Sb11 Cl (5) 2_565? C112 C (15).? Sb11 Cl (6) 2_565? C112 C (15) 4? Sb11 Cl (6).? C113 C (7) 4? Sb11 Cl (4) 2_565? C113 C (17).? Sb11 Cl (4).? C113 C (4).? Sb21 Cl (5).? C114 C (19).? Sb21 Cl (5) 2_665? C114 C (4).? Sb21 Cl (7) 2_665? C125 C (18).? Sb21 Cl (7).? C125 C (15).? Sb21 Cl (5) 2_665? C126 C (16).? Sb21 Cl (5).? C128 C (18).? nature chemistry 23

24 supplementary information C115 C (17).? C138 C (5) 2_665? C115 C (4) 2_565? C138 C (17).? C116 C (18).? C156 C (17).? C116 C (15).? C155 C (16).? C117 C (18).? C155 C (18).? C117 C (15) 4? C154 C (17).? C118 C (15) 4? C141 C (17).? C118 C (15).? C141 C (17).? C119 C (17).? C142 C (18).? C120 C (15).? C142 C (16).? C120 C (15).? C149 C (17).? C121 C (15).? C149 C (15).? C124 C (15).? C144 C (16).? C123 C (15).? C143 C (5) 2_665? C129 C (4) 4? C147 C (15).? C129 C (16).? C147 C (15).? C133 C (15).? C148 C (15).? C133 C (13).? C152 C (15).? C133 C (15).? C152 C (18).? C139 C (13) 4_655? C153 C (15).? C139 C (16).? C150 C (16).? C135 C (4) 2_665? C150 C (3) 3_565? C135 C (18).? C151 C (16).? C136 C (16).? C157 C (3) 3_565? C136 C (18).? C201 C (5) 4_655? C159 C (18).? C201 C (18).? C134 C (12).? C201 C (17).? C134 C (15).? C202 C (17).? C140 C (16).? C202 C (18).? C140 C (12) 4_655? C209 C (17).? C160 C (18).? C209 C (16).? C160 C (4) 2_665? C227 C (18).? C145 C (18).? C227 C (17).? C145 C (16).? C211 C (19).? C146 C (17).? C203 C (4) 4_655? C137 C (15).? C203 C (17).? C137 C (16).? C204 C (19).? 24 nature chemistry

25 supplementary information C204 C (16) 4_655? C223 C (16).? C204 C (16).? C229 C (5) 4_655? C205 C (18).? C229 C (17).? C206 C (16).? C233 C (16).? C206 C (16).? C233 C (13).? C208 C (15).? C233 C (16).? C207 C (18).? C239 C (13) 4? C207 C (16).? C239 C (17).? C232 C (18).? C235 C (4) 2_565? C232 C (16).? C235 C (18).? C231 C (18).? C236 C (17).? C210 C (4) 4_655? C236 C (19).? C210 C (17).? C259 C (18).? C212 C (15).? C234 C (13).? C212 C (15) 4_655? C234 C (16).? C213 C (7) 4_655? C240 C (16).? C213 C (18).? C240 C (13) 4? C213 C (5).? C260 C (18).? C214 C (2).? C260 C (4) 2_565? C214 C (4).? C245 C (19).? C225 C (18).? C245 C (16).? C225 C (16).? C246 C (18).? C226 C (17).? C237 C (16).? C228 C (19).? C237 C (17).? C215 C (4) 4_655? C238 C (5) 2_565? C215 C (18).? C238 C (18).? C216 C (19).? C256 C (18).? C216 C (15).? C255 C (17).? C217 C (19).? C255 C (19).? C217 C (15) 4_655? C254 C (17).? C218 C (16) 4_655? C241 C (18).? C218 C (16).? C241 C (18).? C219 C (18).? C242 C (19).? C220 C (16).? C242 C (17).? C220 C (16).? C249 C (17).? C221 C (16).? C249 C (15).? C224 C (16).? C244 C (17).? nature chemistry 25

26 supplementary information C243 C (5) 2_565? Cl11 Sb11 Cl (5) 2_565.? C247 C (16).? Cl22 Sb21 Cl (3). 2_665? C247 C (16).? Cl22 Sb21 Cl (3). 2_665? C248 C (15).? Cl22 Sb21 Cl (3) 2_665 2_665? C252 C (16).? Cl22 Sb21 Cl (3)..? C252 C (19).? Cl22 Sb21 Cl (3) 2_665.? C253 C (16).? Cl23 Sb21 Cl (5) 2_665.? C250 C (17).? Cl22 Sb21 Cl (16). 2_665? C250 C (3) 3_565? Cl22 Sb21 Cl (16) 2_665 2_665? C251 C (17).? Cl23 Sb21 Cl (16) 2_665 2_665? C257 C (3) 3_565? Cl23 Sb21 Cl (16). 2_665? Cl22 Sb21 Cl (16)..? Cl22 Sb21 Cl (16) 2_665.? Cl23 Sb21 Cl (16) 2_665.? Cl23 Sb21 Cl (16)..? loop_ Cl21 Sb21 Cl (5) 2_665.? _geom_angle_atom_site_label_1 C101 C101 C (11) 4.? _geom_angle_atom_site_label_2 C101 C101 C (11) 4.? _geom_angle_atom_site_label_3 C102 C101 C (2)..? _geom_angle C103 C102 C (15)..? _geom_angle_site_symmetry_1 C103 C102 C (14)..? _geom_angle_site_symmetry_3 C101 C102 C (2)..? _geom_angle_publ_flag C108 C109 C (14)..? Cl12 Sb11 Cl (3). 2_565? C108 C109 C (13)..? Cl12 Sb11 Cl (3). 2_565? C127 C109 C (14)..? Cl12 Sb11 Cl (2) 2_565 2_565? C122 C127 C (14)..? Cl12 Sb11 Cl (2)..? C122 C127 C (14)..? Cl12 Sb11 Cl (3) 2_565.? C109 C127 C (14)..? Cl13 Sb11 Cl (4) 2_565.? C110 C111 C (15)..? Cl12 Sb11 Cl (19). 2_565? C110 C111 C (16)..? Cl12 Sb11 Cl (19) 2_565 2_565? C127 C111 C (2)..? Cl13 Sb11 Cl (18) 2_565 2_565? C102 C103 C (8). 4? Cl13 Sb11 Cl (18). 2_565? C102 C103 C (15)..? Cl12 Sb11 Cl (19)..? C103 C103 C (8) 4.? Cl12 Sb11 Cl (19) 2_565.? C112 C104 C (12)..? Cl13 Sb11 Cl (18) 2_565.? C112 C104 C (12). 4? Cl13 Sb11 Cl (18)..? C105 C104 C (19). 4? 26 nature chemistry

27 supplementary information C106 C105 C (14)..? C129 C128 C (17)..? C106 C105 C (14)..? C126 C128 C (2)..? C104 C105 C (15)..? C114 C115 C (11). 4? C105 C106 C (12)..? C114 C115 C (15)..? C105 C106 C (12)..? C115 C115 C (9) 4.? C108 C106 C (18)..? C121 C116 C (15)..? C109 C108 C (13)..? C121 C116 C (14)..? C109 C108 C (12)..? C117 C116 C (16)..? C107 C108 C (16)..? C118 C117 C (13). 4? C123 C107 C (12)..? C118 C117 C (13)..? C123 C107 C (12)..? C116 C117 C (2) 4.? C132 C107 C (14)..? C117 C118 C (12). 4? C126 C132 C (14)..? C117 C118 C (12)..? C126 C132 C (13)..? C119 C118 C (2) 4.? C131 C132 C (15)..? C120 C119 C (15)..? C130 C131 C (14)..? C120 C119 C (15)..? C130 C131 C (12)..? C118 C119 C (17)..? C132 C131 C (18)..? C119 C120 C (13)..? C111 C110 C (9). 4? C119 C120 C (14)..? C111 C110 C (16)..? C121 C120 C (18)..? C110 C110 C (9) 4.? C116 C121 C (12)..? C104 C112 C (13)..? C116 C121 C (13)..? C104 C112 C (13). 4? C120 C121 C (18)..? C130 C112 C (2). 4? C125 C124 C (14)..? C113 C113 C (19) 4.? C125 C124 C (13)..? C113 C113 C (13) 4.? C123 C124 C (15)..? C114 C113 C (3)..? C107 C123 C (12)..? C115 C114 C (16)..? C107 C123 C (12)..? C115 C114 C (3)..? C124 C123 C (14)..? C125 C114 C (3)..? C127 C122 C (13)..? C124 C125 C (15)..? C127 C122 C (13)..? C124 C125 C (13)..? C123 C122 C (15)..? C126 C125 C (15)..? C128 C129 C (9). 4? C132 C126 C (14)..? C128 C129 C (17)..? C132 C126 C (14)..? C129 C129 C (10) 4.? C128 C126 C (14)..? C131 C130 C (15)..? C129 C128 C (16)..? C131 C130 C (15)..? nature chemistry 27

28 supplementary information C112 C130 C (18)..? C154 C155 C (2)..? C134 C133 C (12)..? C154 C155 C (16)..? C134 C133 C (12)..? C156 C155 C (16)..? C139 C133 C (12)..? C153 C154 C (14)..? C133 C139 C (15) 4_655.? C153 C154 C (12)..? C135 C139 C (11) 4_655.? C155 C154 C (14)..? C135 C139 C (15)..? C142 C141 C (2)..? C156 C135 C (19) 2_665.? C142 C141 C (19). 2_665? C156 C135 C (18) 2_665.? C143 C141 C (2). 2_665? C139 C135 C (17)..? C150 C142 C (15)..? C158 C159 C (11)..? C150 C142 C (15)..? C158 C159 C (13)..? C141 C142 C (18)..? C136 C159 C (12)..? C148 C149 C (13)..? C133 C134 C (12)..? C148 C149 C (12)..? C133 C134 C (12)..? C142 C149 C (13)..? C140 C134 C (12)..? C145 C144 C (13)..? C134 C140 C (15)..? C145 C144 C (12)..? C134 C140 C (11). 4_655? C143 C144 C (14)..? C134 C140 C (15). 4_655? C144 C143 C (19)..? C145 C160 C (16)..? C144 C143 C (2). 2_665? C145 C160 C (18). 2_665? C141 C143 C (2). 2_665? C140 C160 C (18). 2_665? C146 C147 C (11)..? C144 C145 C (12)..? C146 C147 C (11)..? C144 C145 C (11)..? C148 C147 C (13)..? C160 C145 C (14)..? C149 C148 C (12)..? C147 C146 C (11)..? C149 C148 C (11)..? C147 C146 C (13)..? C152 C148 C (13)..? C145 C146 C (11)..? C148 C152 C (13)..? C154 C137 C (14)..? C148 C152 C (12)..? C154 C137 C (12)..? C153 C152 C (13)..? C138 C137 C (13)..? C154 C153 C (12)..? C138 C138 C (2) 2_665.? C154 C153 C (12)..? C138 C138 C (18) 2_665.? C158 C153 C (13)..? C156 C138 C (2)..? C159 C158 C (12)..? C135 C156 C (2) 2_665.? C159 C158 C (11)..? C135 C156 C (2) 2_665.? C153 C158 C (13)..? C138 C156 C (2)..? C142 C150 C (16)..? 28 nature chemistry

29 supplementary information C142 C150 C (16). 3_565? C207 C208 C (17)..? C151 C150 C (17). 3_565? C223 C207 C (12)..? C157 C151 C (15)..? C223 C207 C (13)..? C157 C151 C (15)..? C208 C207 C (15)..? C152 C151 C (14)..? C226 C232 C (15)..? C151 C157 C (17). 3_565? C226 C232 C (14)..? C151 C157 C (16)..? C231 C232 C (16)..? C133 C157 C (17) 3_565.? C230 C231 C (15)..? C201 C201 C (12) 4_655.? C230 C231 C (13)..? C201 C201 C (12) 4_655.? C232 C231 C (19)..? C202 C201 C (2)..? C211 C210 C (9). 4_655? C203 C202 C (17)..? C211 C210 C (17)..? C203 C202 C (15)..? C210 C210 C (10) 4_655.? C201 C202 C (2)..? C204 C212 C (13)..? C208 C209 C (15)..? C204 C212 C (13). 4_655? C208 C209 C (13)..? C230 C212 C (2). 4_655? C227 C209 C (16)..? C213 C213 C (2) 4_655.? C222 C227 C (15)..? C213 C213 C (13) 4_655.? C222 C227 C (15)..? C214 C213 C (3)..? C209 C227 C (15)..? C215 C214 C (3)..? C210 C211 C (16)..? C215 C214 C (16)..? C210 C211 C (17)..? C213 C214 C (3)..? C227 C211 C (2)..? C224 C225 C (15)..? C202 C203 C (9). 4_655? C224 C225 C (14)..? C202 C203 C (16)..? C226 C225 C (15)..? C203 C203 C (9) 4_655.? C232 C226 C (15)..? C212 C204 C (13). 4_655? C232 C226 C (15)..? C212 C204 C (13)..? C225 C226 C (15)..? C205 C204 C (2) 4_655.? C229 C228 C (16)..? C206 C205 C (15)..? C229 C228 C (18)..? C206 C205 C (15)..? C226 C228 C (2)..? C204 C205 C (15)..? C214 C215 C (11). 4_655? C205 C206 C (13)..? C214 C215 C (16)..? C205 C206 C (13)..? C215 C215 C (10) 4_655.? C208 C206 C (19)..? C221 C216 C (16)..? C209 C208 C (14)..? C221 C216 C (15)..? C209 C208 C (12)..? C217 C216 C (17)..? nature chemistry 29

30 supplementary information C218 C217 C (13). 4_655? C256 C235 C (19) 2_565.? C218 C217 C (13)..? C239 C235 C (17)..? C216 C217 C (2) 4_655.? C258 C259 C (12)..? C217 C218 C (13). 4_655? C258 C259 C (13)..? C217 C218 C (13)..? C236 C259 C (13)..? C219 C218 C (2) 4_655.? C233 C234 C (13)..? C220 C219 C (16)..? C233 C234 C (12)..? C220 C219 C (16)..? C240 C234 C (13)..? C218 C219 C (18)..? C234 C240 C (16)..? C219 C220 C (13)..? C234 C240 C (11). 4? C219 C220 C (15)..? C234 C240 C (16). 4? C221 C220 C (19)..? C245 C260 C (18)..? C216 C221 C (13)..? C245 C260 C (18). 2_565? C216 C221 C (14)..? C240 C260 C (19). 2_565? C220 C221 C (19)..? C244 C245 C (12)..? C225 C224 C (13)..? C244 C245 C (12)..? C225 C224 C (15)..? C260 C245 C (14)..? C221 C224 C (17)..? C247 C246 C (11)..? C207 C223 C (12)..? C247 C246 C (13)..? C207 C223 C (13)..? C245 C246 C (12)..? C222 C223 C (15)..? C254 C237 C (15)..? C227 C222 C (14)..? C254 C237 C (13)..? C227 C222 C (14)..? C238 C237 C (14)..? C223 C222 C (16)..? C238 C238 C (2) 2_565.? C228 C229 C (9). 4_655? C238 C238 C (2) 2_565.? C228 C229 C (17)..? C256 C238 C (2)..? C229 C229 C (10) 4_655.? C235 C256 C (2) 2_565.? C231 C230 C (16)..? C235 C256 C (2) 2_565.? C231 C230 C (16)..? C238 C256 C (3)..? C212 C230 C (19)..? C254 C255 C (2)..? C234 C233 C (13)..? C254 C255 C (16)..? C234 C233 C (12)..? C256 C255 C (17)..? C239 C233 C (13)..? C253 C254 C (14)..? C233 C239 C (16) 4 4? C253 C254 C (12)..? C233 C239 C (12) 4.? C255 C254 C (15)..? C233 C239 C (16) 4.? C242 C241 C (2)..? C256 C235 C (2) 2.? C242 C241 C (19). 2_565? 30 nature chemistry

31 C243 C241 C (19). 2_565? C250 C242 C (16)..? C250 C242 C (16)..? C241 C242 C (19)..? C248 C249 C (14)..? C248 C249 C (12)..? C242 C249 C (13)..? C245 C244 C (13)..? C245 C244 C (13)..? C243 C244 C (14)..? C244 C243 C (2)..? C244 C243 C (2). 2_565? C241 C243 C (2). 2_565? C246 C247 C (11)..? supplementary information C254 C253 C (13)..? C258 C253 C (13)..? C259 C258 C (12)..? C259 C258 C (12)..? C253 C258 C (13)..? C242 C250 C (17)..? C242 C250 C (17). 3_565? C251 C250 C (18). 3_565? C257 C251 C (16)..? C257 C251 C (16)..? C252 C251 C (15)..? C251 C257 C (18). 3_565? C251 C257 C (17)..? C233 C257 C (18) 3_565.? C246 C247 C (12)..? C248 C247 C (14)..? C249 C248 C (13)..? C249 C248 C (12)..? C252 C248 C (14)..? C248 C252 C (14)..? C248 C252 C (13)..? C253 C252 C (14)..? _diffrn_measured_fraction_theta_max _diffrn_reflns_theta_full _diffrn_measured_fraction_theta_full _refine_diff_density_max _refine_diff_density_min _refine_diff_density_rms C254 C253 C (13)..? nature chemistry 31