Supplementary Material (ESI) for J. Mater. Chem. This journal is (C) The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 1145 _publ_contact_author_name 'Dr Torbjörn Gustafsson' _publ_contact_author_address ; Torbjorn Gustafsson Materials Chemistry Angstrom Laboratory Uppsala University Box 538 SE-751 21 Uppsala SWEDEN ; _publ_contact_author_phone '+46-18-471 37 66' _publ_contact_author_fax '+46-18-51 35 48' _publ_contact_author_email 'tgn@mkem.uu.se' loop_ _publ_author_name _publ_author_address 'Helen Bjork' ; Materials Chemistry Angstrom Laboratory Uppsala University Box 538 SE-751 21 Uppsala SWEDEN ; 'T. Gustafsson' ; Materials Chemistry Angstrom Laboratory Uppsala University Box 538 SE-751 21 Uppsala Sweden ; 'J. O. Thomas' ; Materials Chemistry Angstrom Laboratory Uppsala University Box 538 SE-751 21 Uppsala Sweden ; 'Sven Lidin' ; Inorganic Chemistry Arrhenius Laboratory Stockholm University SE-106 91 Stockholm Sweden ; 'Vaclav Petricek' ; Institute of Physics Academy of Sciences of the Czech Republic 162 53 Praha 6 Czech Republic ; _publ_requested_journal Journal_of_Materials_Chemistry _publ_section_title ; Long-range-ordering during delithiation of the LiMn2O4 cathode material ; data_spinell _database_code_CSD 184354 _cell_length_a 8.244(4) _cell_length_b 8.244(4) _cell_length_c 8.244(4) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 560.5(5) _cell_measurement_pressure ? _cell_measurement_radiation 'Mo K\a' _cell_measurement_reflns_used 25 _cell_measurement_temperature 295 _cell_measurement_theta_max 20 _cell_measurement_theta_min 19 _cell_measurement_wavelength 0.71073 _cell_formula_units_Z 8 _symmetry_cell_setting cubic _symmetry_space_group_name_H-M Fd-3m loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 x,y,z 2 y,z,x 3 z,x,y 4 1/4+x,1/4+y,-z 5 1/4+y,1/4+z,-x 6 1/4+z,1/4+x,-y 7 1/2+y,1/4-z,3/4-x 8 1/2+z,1/4-x,3/4-y 9 1/4-z,1/2+x,3/4-y 10 1/4-x,1/2+y,3/4-z 11 1/4-y,1/2+z,3/4-x 12 1/2+x,1/4-y,3/4-z 13 y,x,z 14 z,y,x 15 x,z,y 16 1/4+y,1/4+x,-z 17 1/4+z,1/4+y,-x 18 1/4+x,1/4+z,-y 19 1/4-z,1/2+y,3/4-x 20 1/4-x,1/2+z,3/4-y 21 1/2+x,1/4-z,3/4-y 22 1/2+y,1/4-x,3/4-z 23 1/2+z,1/4-y,3/4-x 24 1/4-y,1/2+x,3/4-z 25 -x,-y,-z 26 -y,-z,-x 27 -z,-x,-y 28 1/4-x,1/4-y,z 29 1/4-y,1/4-z,x 30 1/4-z,1/4-x,y 31 1/2-y,1/4+z,3/4+x 32 1/2-z,1/4+x,3/4+y 33 1/4+z,1/2-x,3/4+y 34 1/4+x,1/2-y,3/4+z 35 1/4+y,1/2-z,3/4+x 36 1/2-x,1/4+y,3/4+z 37 -y,-x,-z 38 -z,-y,-x 39 -x,-z,-y 40 1/4-y,1/4-x,z 41 1/4-z,1/4-y,x 42 1/4-x,1/4-z,y 43 1/4+z,1/2-y,3/4+x 44 1/4+x,1/2-z,3/4+y 45 1/2-x,1/4+z,3/4+y 46 1/2-y,1/4+x,3/4+z 47 1/2-z,1/4+y,3/4+x 48 1/4+y,1/2-x,3/4+z 49 x,1/2+y,1/2+z 50 y,1/2+z,1/2+x 51 z,1/2+x,1/2+y 52 1/4+x,3/4+y,1/2-z 53 1/4+y,3/4+z,1/2-x 54 1/4+z,3/4+x,1/2-y 55 1/2+y,3/4-z,1/4-x 56 1/2+z,3/4-x,1/4-y 57 1/4-z,x,1/4-y 58 1/4-x,y,1/4-z 59 1/4-y,z,1/4-x 60 1/2+x,3/4-y,1/4-z 61 y,1/2+x,1/2+z 62 z,1/2+y,1/2+x 63 x,1/2+z,1/2+y 64 1/4+y,3/4+x,1/2-z 65 1/4+z,3/4+y,1/2-x 66 1/4+x,3/4+z,1/2-y 67 1/4-z,y,1/4-x 68 1/4-x,z,1/4-y 69 1/2+x,3/4-z,1/4-y 70 1/2+y,3/4-x,1/4-z 71 1/2+z,3/4-y,1/4-x 72 1/4-y,x,1/4-z 73 -x,1/2-y,1/2-z 74 -y,1/2-z,1/2-x 75 -z,1/2-x,1/2-y 76 1/4-x,3/4-y,1/2+z 77 1/4-y,3/4-z,1/2+x 78 1/4-z,3/4-x,1/2+y 79 1/2-y,3/4+z,1/4+x 80 1/2-z,3/4+x,1/4+y 81 1/4+z,-x,1/4+y 82 1/4+x,-y,1/4+z 83 1/4+y,-z,1/4+x 84 1/2-x,3/4+y,1/4+z 85 -y,1/2-x,1/2-z 86 -z,1/2-y,1/2-x 87 -x,1/2-z,1/2-y 88 1/4-y,3/4-x,1/2+z 89 1/4-z,3/4-y,1/2+x 90 1/4-x,3/4-z,1/2+y 91 1/4+z,-y,1/4+x 92 1/4+x,-z,1/4+y 93 1/2-x,3/4+z,1/4+y 94 1/2-y,3/4+x,1/4+z 95 1/2-z,3/4+y,1/4+x 96 1/4+y,-x,1/4+z 97 1/2+x,y,1/2+z 98 1/2+y,z,1/2+x 99 1/2+z,x,1/2+y 100 3/4+x,1/4+y,1/2-z 101 3/4+y,1/4+z,1/2-x 102 3/4+z,1/4+x,1/2-y 103 y,1/4-z,1/4-x 104 z,1/4-x,1/4-y 105 3/4-z,1/2+x,1/4-y 106 3/4-x,1/2+y,1/4-z 107 3/4-y,1/2+z,1/4-x 108 x,1/4-y,1/4-z 109 1/2+y,x,1/2+z 110 1/2+z,y,1/2+x 111 1/2+x,z,1/2+y 112 3/4+y,1/4+x,1/2-z 113 3/4+z,1/4+y,1/2-x 114 3/4+x,1/4+z,1/2-y 115 3/4-z,1/2+y,1/4-x 116 3/4-x,1/2+z,1/4-y 117 x,1/4-z,1/4-y 118 y,1/4-x,1/4-z 119 z,1/4-y,1/4-x 120 3/4-y,1/2+x,1/4-z 121 1/2-x,-y,1/2-z 122 1/2-y,-z,1/2-x 123 1/2-z,-x,1/2-y 124 3/4-x,1/4-y,1/2+z 125 3/4-y,1/4-z,1/2+x 126 3/4-z,1/4-x,1/2+y 127 -y,1/4+z,1/4+x 128 -z,1/4+x,1/4+y 129 3/4+z,1/2-x,1/4+y 130 3/4+x,1/2-y,1/4+z 131 3/4+y,1/2-z,1/4+x 132 -x,1/4+y,1/4+z 133 1/2-y,-x,1/2-z 134 1/2-z,-y,1/2-x 135 1/2-x,-z,1/2-y 136 3/4-y,1/4-x,1/2+z 137 3/4-z,1/4-y,1/2+x 138 3/4-x,1/4-z,1/2+y 139 3/4+z,1/2-y,1/4+x 140 3/4+x,1/2-z,1/4+y 141 -x,1/4+z,1/4+y 142 -y,1/4+x,1/4+z 143 -z,1/4+y,1/4+x 144 3/4+y,1/2-x,1/4+z 145 1/2+x,1/2+y,z 146 1/2+y,1/2+z,x 147 1/2+z,1/2+x,y 148 3/4+x,3/4+y,-z 149 3/4+y,3/4+z,-x 150 3/4+z,3/4+x,-y 151 y,3/4-z,3/4-x 152 z,3/4-x,3/4-y 153 3/4-z,x,3/4-y 154 3/4-x,y,3/4-z 155 3/4-y,z,3/4-x 156 x,3/4-y,3/4-z 157 1/2+y,1/2+x,z 158 1/2+z,1/2+y,x 159 1/2+x,1/2+z,y 160 3/4+y,3/4+x,-z 161 3/4+z,3/4+y,-x 162 3/4+x,3/4+z,-y 163 3/4-z,y,3/4-x 164 3/4-x,z,3/4-y 165 x,3/4-z,3/4-y 166 y,3/4-x,3/4-z 167 z,3/4-y,3/4-x 168 3/4-y,x,3/4-z 169 1/2-x,1/2-y,-z 170 1/2-y,1/2-z,-x 171 1/2-z,1/2-x,-y 172 3/4-x,3/4-y,z 173 3/4-y,3/4-z,x 174 3/4-z,3/4-x,y 175 -y,3/4+z,3/4+x 176 -z,3/4+x,3/4+y 177 3/4+z,-x,3/4+y 178 3/4+x,-y,3/4+z 179 3/4+y,-z,3/4+x 180 -x,3/4+y,3/4+z 181 1/2-y,1/2-x,-z 182 1/2-z,1/2-y,-x 183 1/2-x,1/2-z,-y 184 3/4-y,3/4-x,z 185 3/4-z,3/4-y,x 186 3/4-x,3/4-z,y 187 3/4+z,-y,3/4+x 188 3/4+x,-z,3/4+y 189 -x,3/4+z,3/4+y 190 -y,3/4+x,3/4+z 191 -z,3/4+y,3/4+x 192 3/4+y,-x,3/4+z loop_ _atom_type_symbol _atom_type_oxidation_number _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c Li 0 0.000 0.000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 1.1282 3.9546 0.7508 1.0524 0.6175 85.390503 0.4653 168.261002 0.0377 Mn 0 0.337 0.728 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 11.2819 5.3409 7.3573 0.3432 3.0193 17.867399 2.2441 83.754303 1.0896 O 0 0.011 0.006 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.867 32.908901 0.2508 _chemical_formula_sum 'Li Mn2 O4' _chemical_formula_weight 180.1 _exptl_crystal_colour black _exptl_crystal_description octahedral _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.2 _exptl_crystal_size_min 0.2 _exptl_crystal_size_rad ? _exptl_crystal_density_diffrn 4.262 _exptl_crystal_density_meas ? _exptl_crystal_density_meas_temp ? _exptl_crystal_density_method ? _exptl_crystal_F_000 680 _exptl_absorpt_correction_type none _exptl_absorpt_coefficient_mu 8.688 _exptl_absorpt_correction_T_min 0.182 _exptl_absorpt_correction_T_max 0.377 _diffrn_measurement_device 'Image plate diffractometer' _diffrn_measurement_device_type 'STOE IPDS' _diffrn_measurement_method 'omega scans' _diffrn_radiation_probe 'X-ray' _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_monochromator graphite _diffrn_standards_number 'none' _diffrn_standards_decay_% 'none' _diffrn_standards_interval_count 'none' _diffrn_standards_interval_time 'none' _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 18 _reflns_limit_h_min 1 _reflns_limit_h_max 14 _reflns_limit_k_min 0 _reflns_limit_k_max 10 _reflns_limit_l_min 0 _reflns_limit_l_max 8 _diffrn_reflns_number 1766 _diffrn_reflns_theta_min 0 _diffrn_reflns_theta_max 40 _diffrn_reflns_av_R_equivalents 0.0568 _diffrn_reflns_av_sigmaI/netI ? _diffrn_ambient_temperature 'ambient' _reflns_observed_criterion '3\s' _reflns_number_total 108 _reflns_number_observed 85 _refine_ls_structure_factor_coef F _refine_ls_weighting_scheme sigma _refine_ls_weighting_details 'w==1/(\s^2^(F)+0.000064F^2^)' _refine_ls_R_factor_gt 0.0207 _refine_ls_wR_factor_gt 0.0256 _refine_ls_R_factor_all 0.0307 _refine_ls_wR_factor_ref 0.0262 _refine_ls_number_reflns 108 _refine_ls_number_parameters 7 _refine_ls_goodness_of_fit_ref 2.03 _refine_ls_goodness_of_fit_obs 2.26 _refine_ls_shift/su_max 0.060 _refine_ls_shift/su_mean 0.0000 _refine_diff_density_max 0.67 _refine_diff_density_min -0.77 _refine_ls_extinction_method 'none' _refine_ls_extinction_coef ? _computing_data_collection 'STOE IPDS' _computing_cell_refinement 'STOE IPDS' _computing_data_reduction 'X-red and X-shape (STOE & Cie GmbH, 1996)' _computing_structure_solution '-' _computing_structure_refinement 'DUPALS' _computing_molecular_graphics '-' _computing_publication_material 'JANA2000' loop_ _atom_site_label _atom_site_type_symbol _atom_site_adp_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_symmetry_multiplicity _atom_site_occupancy Li8a Li Uiso 0.125 0.125 0.125 0.0093(18) 8 1.0000 Mn1 Mn Uani 0.5 0.5 0.5 0.01115(9) 16 1.0 O O Uani 0.26339(19) 0.26339(19) 0.26339(19) 0.0180(3) 32 1.0 loop_ _atom_site_aniso_label _atom_site_aniso_type_symbol _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 Mn1 Mn .01115(16) .01115(16) .01115(16) -0.00116(12) -0.00116(12) -0.00116(12) O O 0.0180(4) 0.0180(4) 0.0180(4) -0.0028(4) -0.0028(4) -0.0028(4) loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 Li8a O 1.9738(10) . . Li8a O 1.9738(10) . 28_555 Li8a O 1.9738(10) . 105_533 Mn1 Mn1 2.915 . 4_556 Mn1 Mn1 2.915 . 105_634 Mn1 O 1.9584(10) . 4_556 Mn1 O 1.9584(10) . 129_543 O Li8a 1.9738(10) . . O O 2.9232(15) . 100_545 O O 2.9232(15) . 31_554 O O 2.9232(15) . 127_543 O O 2.9232(15) . 33_554 loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_2 _geom_angle_site_symmetry_3 O Li8a O 109.47(4) . . 28_555 O Li8a O 109.47(4) . . 105_533 O Li8a O 109.47(4) 28_555 . . O Li8a O 109.47(4) 28_555 . 105_533 O Li8a O 109.47(4) 105_533 . . O Li8a O 109.47(4) 105_533 . 28_555 Mn1 Mn1 Mn1 60 4_556 . 105_634 Mn1 Mn1 O 85.49(3) 4_556 . 4_556 Mn1 Mn1 O 41.90(3) 4_556 . 129_543 Mn1 Mn1 Mn1 60 105_634 . 4_556 Mn1 Mn1 O 41.90(3) 105_634 . 4_556 Mn1 Mn1 O 85.49(3) 105_634 . 129_543 O Mn1 O 83.45(4) 4_556 . 129_543 O Mn1 O 83.45(4) 129_543 . 4_556 Li8a O O 87.53(4) . . 100_545 Li8a O O 87.53(4) . . 31_554 Li8a O O 87.53(4) . . 127_543 Li8a O O 87.53(4) . . 33_554 O O O 119.82(5) 100_545 . 31_554 O O O 66.91(4) 100_545 . 127_543 O O O 52.96(3) 100_545 . 33_554 O O O 119.82(5) 31_554 . 100_545 O O O 171.45(5) 31_554 . 127_543 O O O 66.91(4) 31_554 . 33_554 O O O 66.91(4) 127_543 . 100_545 O O O 171.45(5) 127_543 . 31_554 O O O 119.82(5) 127_543 . 33_554 O O O 52.96(3) 33_554 . 100_545 O O O 66.91(4) 33_554 . 31_554 O O O 119.82(5) 33_554 . 127_543