# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2011 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Dr Tamotsu Inabe' _publ_contact_author_email inabe@sci.hokudai.ac.jp _publ_section_title ; Charge-Transport in Tin-Iodide Perovskite CH3NH3SnI3: Origin of High Conductivity ; loop_ _publ_author_name Y.Takashi R.Obara 'Zheng-Zhong Lin' Y.Takahashi T.Naito S.Ishibashi K.Terakura data__SnI_cubic _database_code_depnum_ccdc_archive 'CCDC 801226' #TrackingRef '- SnI_total_rev.cif' #============================================================================== # CHEMICAL DATA _chemical_formula_sum 'C H6 I3 N Sn ' _chemical_formula_moiety 'C H6 I3 N Sn ' _chemical_formula_weight 531.47 _chemical_melting_point ? #============================================================================== # CRYSTAL DATA _symmetry_cell_setting cubic _symmetry_space_group_name_H-M 'P m -3 m' _symmetry_space_group_name_Hall '-P 4 2 3' _symmetry_Int_Tables_number 221 loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 +X,+Y,+Z 2 +Y,+Z,+X 3 +Z,+X,+Y 4 +X,+Y,-Z 5 +Y,+Z,-X 6 +Z,+X,-Y 7 +Y,-Z,-X 8 +Z,-X,-Y 9 -Z,+X,-Y 10 -X,+Y,-Z 11 -Y,+Z,-X 12 +X,-Y,-Z 13 +Y,+X,+Z 14 +Z,+Y,+X 15 +X,+Z,+Y 16 +Y,+X,-Z 17 +Z,+Y,-X 18 +X,+Z,-Y 19 -Z,+Y,-X 20 -X,+Z,-Y 21 +X,-Z,-Y 22 +Y,-X,-Z 23 +Z,-Y,-X 24 -Y,+X,-Z 25 -X,-Y,-Z 26 -Y,-Z,-X 27 -Z,-X,-Y 28 -X,-Y,+Z 29 -Y,-Z,+X 30 -Z,-X,+Y 31 -Y,+Z,+X 32 -Z,+X,+Y 33 +Z,-X,+Y 34 +X,-Y,+Z 35 +Y,-Z,+X 36 -X,+Y,+Z 37 -Y,-X,-Z 38 -Z,-Y,-X 39 -X,-Z,-Y 40 -Y,-X,+Z 41 -Z,-Y,+X 42 -X,-Z,+Y 43 +Z,-Y,+X 44 +X,-Z,+Y 45 -X,+Z,+Y 46 -Y,+X,+Z 47 -Z,+Y,+X 48 +Y,-X,+Z #------------------------------------------------------------------------------ _cell_length_a 6.2434(14) _cell_length_b 6.2434(14) _cell_length_c 6.2434(14) _cell_angle_alpha 90.0000 _cell_angle_beta 90.0000 _cell_angle_gamma 90.0000 _cell_volume 243.37(9) _cell_formula_units_Z 1 _cell_measurement_reflns_used 3811 _cell_measurement_theta_min 4.6 _cell_measurement_theta_max 27.3 _cell_measurement_temperature 295 #------------------------------------------------------------------------------ _exptl_crystal_description block _exptl_crystal_colour black _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.10 _exptl_crystal_density_diffrn 3.626 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 228.00 _exptl_absorpt_coefficient_mu 12.057 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; Higashi, T. (1995). Program for Absorption Correction. Rigaku Corporation, Tokyo, Japan. ; _exptl_absorpt_correction_T_min 0.129 _exptl_absorpt_correction_T_max 0.299 #============================================================================== # EXPERIMENTAL DATA _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71075 _diffrn_measurement_device_type 'Rigaku RAXIS-RAPID' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 10.00 _diffrn_reflns_number 2155 _diffrn_reflns_av_R_equivalents 0.032 _diffrn_reflns_theta_max 27.32 _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 27.32 _diffrn_measured_fraction_theta_full 1.000 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -7 _diffrn_reflns_limit_l_max 8 _diffrn_ambient_temperature 295 #============================================================================== # REFINEMENT DATA _refine_special_details ; CH3NH3 was not included in the analysis due to disorder. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F^2^. R-factor (gt) are based on F. The threshold expression of F^2^ > 2.0 sigma(F^2^) is used only for calculating R-factor (gt). ; _reflns_number_total 82 _reflns_number_gt 81 _reflns_threshold_expression F^2^>2.0\s(F^2^) _refine_ls_structure_factor_coef Fsqd _refine_ls_R_factor_gt 0.0700 _refine_ls_wR_factor_ref 0.2520 _refine_ls_hydrogen_treatment 'not included' _refine_ls_number_reflns 82 _refine_ls_number_parameters 4 _refine_ls_goodness_of_fit_ref 1.236 _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'w = 1/[0.0100Fo^2^ + 1.0000?(Fo^2^)]/(4Fo^2^)' _refine_ls_shift/su_max 0.0000 _refine_diff_density_max 0.62 _refine_diff_density_min -2.93 _refine_ls_extinction_method none _refine_ls_extinction_coef ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.003 0.002 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; H H 0.000 0.000 ; International Tables for Crystallography (1992, Vol. C, Table 6.1.1.4) ; N N 0.006 0.003 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; Sn Sn -0.654 1.425 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; I I -0.474 1.812 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; #============================================================================== # ATOMIC COORDINATES AND THERMAL PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _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 _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group I(1) I 0.0000 0.0000 0.5000 0.0809(10) Uani 1.00 16 d S . . Sn(1) Sn 0.0000 0.0000 0.0000 0.0240(7) Uani 1.00 48 d S . . loop_ _atom_site_aniso_label _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 I(1) 0.112(2) 0.112(2) 0.0186(16) 0.0000 0.0000 0.0000 Sn(1) 0.0240(14) 0.0240(14) 0.0240(14) 0.0000 0.0000 0.0000 #============================================================================== _computing_data_collection PROCESS-AUTO _computing_cell_refinement PROCESS-AUTO _computing_data_reduction CrystalStructure _computing_structure_solution DirectMethod _computing_structure_refinement CRYSTALS _computing_publication_material 'CrystalStructure 3.8' _computing_molecular_graphics ? #============================================================================== # MOLECULAR GEOMETRY _geom_special_details ; ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_publ_flag _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 I(1) Sn(1) 3.1217 yes . . I(1) Sn(1) 3.1217 yes . 1_556 loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_publ_flag _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_2 _geom_angle_site_symmetry_3 Sn(1) I(1) Sn(1) 180.0000 yes . . 1_556 I(1) Sn(1) I(1) 180.0000 yes 1_554 . . I(1) Sn(1) I(1) 90.0000 yes 1_554 . 2_545 I(1) Sn(1) I(1) 90.0000 yes 1_554 . 2_555 I(1) Sn(1) I(1) 90.0000 yes 1_554 . 3_455 I(1) Sn(1) I(1) 90.0000 yes 1_554 . 3_555 I(1) Sn(1) I(1) 90.0000 yes . . 2_545 I(1) Sn(1) I(1) 90.0000 yes . . 2_555 I(1) Sn(1) I(1) 90.0000 yes . . 3_455 I(1) Sn(1) I(1) 90.0000 yes . . 3_555 I(1) Sn(1) I(1) 180.0000 yes 2_545 . 2_555 I(1) Sn(1) I(1) 90.0000 yes 2_545 . 3_455 I(1) Sn(1) I(1) 90.0000 yes 2_545 . 3_555 I(1) Sn(1) I(1) 90.0000 yes 2_555 . 3_455 I(1) Sn(1) I(1) 90.0000 yes 2_555 . 3_555 I(1) Sn(1) I(1) 180.0000 yes 3_455 . 3_555 #============================================================================== data__SnI_tetragonal _database_code_depnum_ccdc_archive 'CCDC 801227' #TrackingRef '- SnI_total_rev.cif' #============================================================================== # CHEMICAL DATA _chemical_formula_sum 'C H6 I3 N Sn ' _chemical_formula_moiety 'C H6 I3 N Sn ' _chemical_formula_weight 531.47 _chemical_melting_point ? #============================================================================== # CRYSTAL DATA _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M 'I 4/m c m' _symmetry_space_group_name_Hall '-I 4 2c' _symmetry_Int_Tables_number 140 loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 +X,+Y,+Z 2 -Y,+X,+Z 3 -X,-Y,+Z 4 +Y,-X,+Z 5 -X,+Y,1/2+Z 6 +Y,+X,1/2+Z 7 +X,-Y,1/2+Z 8 -Y,-X,1/2+Z 9 -X,-Y,-Z 10 +Y,-X,-Z 11 +X,+Y,-Z 12 -Y,+X,-Z 13 +X,-Y,1/2-Z 14 -Y,-X,1/2-Z 15 -X,+Y,1/2-Z 16 +Y,+X,1/2-Z 17 1/2+X,1/2+Y,1/2+Z 18 1/2-Y,1/2+X,1/2+Z 19 1/2-X,1/2-Y,1/2+Z 20 1/2+Y,1/2-X,1/2+Z 21 1/2-X,1/2+Y,+Z 22 1/2+Y,1/2+X,+Z 23 1/2+X,1/2-Y,+Z 24 1/2-Y,1/2-X,+Z 25 1/2-X,1/2-Y,1/2-Z 26 1/2+Y,1/2-X,1/2-Z 27 1/2+X,1/2+Y,1/2-Z 28 1/2-Y,1/2+X,1/2-Z 29 1/2+X,1/2-Y,-Z 30 1/2-Y,1/2-X,-Z 31 1/2-X,1/2+Y,-Z 32 1/2+Y,1/2+X,-Z #------------------------------------------------------------------------------ _cell_length_a 8.7271(8) _cell_length_b 8.7271(8) _cell_length_c 12.5022(15) _cell_angle_alpha 90.0000 _cell_angle_beta 90.0000 _cell_angle_gamma 90.0000 _cell_volume 952.20(17) _cell_formula_units_Z 4 _cell_measurement_reflns_used 7424 _cell_measurement_theta_min 3.3 _cell_measurement_theta_max 27.4 _cell_measurement_temperature 140.1 #------------------------------------------------------------------------------ _exptl_crystal_description prism _exptl_crystal_colour black _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.10 _exptl_crystal_density_diffrn 3.707 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 912.00 _exptl_absorpt_coefficient_mu 12.327 _exptl_absorpt_correction_type psi-scan _exptl_absorpt_process_details '(North, Phillips & Mathews, 1968)' _exptl_absorpt_correction_T_min 0.162 _exptl_absorpt_correction_T_max 0.292 #============================================================================== # EXPERIMENTAL DATA _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71075 _diffrn_measurement_device_type 'Rigaku RAXIS-RAPID' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 10.00 _diffrn_reflns_number 4078 _diffrn_reflns_av_R_equivalents 0.064 _diffrn_reflns_theta_max 27.43 _diffrn_measured_fraction_theta_max 0.980 _diffrn_reflns_theta_full 27.43 _diffrn_measured_fraction_theta_full 0.980 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_ambient_temperature 140 #============================================================================== # REFINEMENT DATA _refine_special_details ; CH3NH3 was not included in the analysis due to disorder. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F^2^. R-factor (gt) are based on F. The threshold expression of F^2^ > 2.0 sigma(F^2^) is used only for calculating R-factor (gt). ; _reflns_number_total 292 _reflns_number_gt 283 _reflns_threshold_expression F^2^>2.0\s(F^2^) _refine_ls_structure_factor_coef Fsqd _refine_ls_R_factor_gt 0.0573 _refine_ls_wR_factor_ref 0.2681 _refine_ls_hydrogen_treatment 'not included' _refine_ls_number_reflns 292 _refine_ls_number_parameters 9 _refine_ls_goodness_of_fit_ref 0.914 _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'w = 1/[0.0200Fo^2^ + 1.5000?(Fo^2^) + 0.5000]/(4Fo^2^)' _refine_ls_shift/su_max 0.0000 _refine_diff_density_max 2.60 _refine_diff_density_min -2.97 _refine_ls_extinction_method none _refine_ls_extinction_coef ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.003 0.002 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; H H 0.000 0.000 ; International Tables for Crystallography (1992, Vol. C, Table 6.1.1.4) ; N N 0.006 0.003 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; Sn Sn -0.654 1.425 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; I I -0.474 1.812 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; #============================================================================== # ATOMIC COORDINATES AND THERMAL PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _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 _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group I(1) I 0.2910(2) 0.2090(2) 0.0000 0.0357(6) Uani 1.00 4 d S . . I(2) I 0.0000 0.0000 0.2500 0.0240(6) Uani 1.00 8 d S . . Sn(1) Sn 0.0000 0.0000 0.0000 0.0146(6) Uani 1.00 8 d S . . loop_ _atom_site_aniso_label _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 I(1) 0.0338(11) 0.0338(11) 0.0394(13) -0.0219(8) 0.0000 0.0000 I(2) 0.0307(12) 0.0307(12) 0.0104(15) 0.0000 0.0000 0.0000 Sn(1) 0.0140(11) 0.0140(11) 0.0158(16) 0.0000 0.0000 0.0000 #============================================================================== _computing_data_collection PROCESS-AUTO _computing_cell_refinement PROCESS-AUTO _computing_data_reduction CrystalStructure _computing_structure_solution SHELXS97 _computing_structure_refinement CRYSTALS _computing_publication_material 'CrystalStructure 3.8' _computing_molecular_graphics ? #============================================================================== # MOLECULAR GEOMETRY _geom_special_details ; ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_publ_flag _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 I(1) Sn(1) 3.1268(18) yes . . I(1) Sn(1) 3.1268(18) yes . 21_555 I(2) Sn(1) 3.1256 yes . . I(2) Sn(1) 3.1256 yes . 5_555 loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_publ_flag _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_2 _geom_angle_site_symmetry_3 Sn(1) I(1) Sn(1) 161.35(6) yes . . 21_555 Sn(1) I(2) Sn(1) 180.0000 yes . . 5_555 I(1) Sn(1) I(1) 90.00(4) yes . . 2_555 I(1) Sn(1) I(1) 180.00(4) yes . . 3_555 I(1) Sn(1) I(1) 90.00(4) yes . . 4_555 I(1) Sn(1) I(2) 90.0000 yes . . . I(1) Sn(1) I(2) 90.0000 yes . . 5_554 I(1) Sn(1) I(1) 90.00(4) yes 2_555 . 3_555 I(1) Sn(1) I(1) 180.00(4) yes 2_555 . 4_555 I(1) Sn(1) I(2) 90.0000 yes 2_555 . . I(1) Sn(1) I(2) 90.0000 yes 2_555 . 5_554 I(1) Sn(1) I(1) 90.00(4) yes 3_555 . 4_555 I(1) Sn(1) I(2) 90.0000 yes 3_555 . . I(1) Sn(1) I(2) 90.0000 yes 3_555 . 5_554 I(1) Sn(1) I(2) 90.0000 yes 4_555 . . I(1) Sn(1) I(2) 90.0000 yes 4_555 . 5_554 I(2) Sn(1) I(2) 180.0000 yes . . 5_554 loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_publ_flag _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 Sn(1) I(1) Sn(1) I(2) 90.0 ? . . 21_555 21_555 Sn(1) I(1) Sn(1) I(2) -90.0 ? 21_555 . . . Sn(1) I(1) Sn(1) I(2) 90.0 ? 21_555 . . 5_554 #============================================================================== # End of CIF #==============================================================================