# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2004 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Prof Mercouri Kanatzidis' _publ_contact_author_address ; Department of Chemistry Michigan State University East Lansing MI 48824 UNITED STATES OF AMERICA ; _publ_contact_author_email KANATZIDIS@CHEMISTRY.MSU.EDU _publ_section_title ; K6Cd4Sn3Se13: A polar open-framework compound based on the partially destroyed supertetrahedral [Cd4Sn4Se17]10- cluster ; loop_ _publ_author_name 'Mercouri Kanatzidis' 'Duck-Young Chung' 'Nan Ding' data_r3m _database_code_depnum_ccdc_archive 'CCDC 232407' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'Cd4 K6 Se13 Sn3' _chemical_formula_weight 2066.75 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source K K 0.2009 0.2494 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Se Se -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cd Cd -0.8075 1.2024 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Sn Sn -0.6537 1.4246 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Rhombohedral _symmetry_space_group_name_H-M R3m loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' '-y, -x, z' '-x+y, y, z' 'x, x-y, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' '-y+2/3, -x+1/3, z+1/3' '-x+y+2/3, y+1/3, z+1/3' 'x+2/3, x-y+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-y+1/3, -x+2/3, z+2/3' '-x+y+1/3, y+2/3, z+2/3' 'x+1/3, x-y+2/3, z+2/3' _cell_length_a 15.0338(11) _cell_length_b 15.0338(11) _cell_length_c 16.512(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 3231.9(6) _cell_formula_units_Z 3 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description cube-like _exptl_crystal_colour yellow _exptl_crystal_size_max 0.101 _exptl_crystal_size_mid 0.094 _exptl_crystal_size_min 0.084 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.186 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2694 _exptl_absorpt_coefficient_mu 15.203 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type CCD _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 11764 _diffrn_reflns_av_R_equivalents 0.0593 _diffrn_reflns_av_sigmaI/netI 0.0606 _diffrn_reflns_limit_h_min -20 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -19 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 1.99 _diffrn_reflns_theta_max 28.42 _reflns_number_total 1849 _reflns_number_gt 1313 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of 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. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0721P)^2^+5.7345P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.00(3) _refine_ls_number_reflns 1849 _refine_ls_number_parameters 53 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0804 _refine_ls_R_factor_gt 0.0453 _refine_ls_wR_factor_ref 0.1344 _refine_ls_wR_factor_gt 0.1188 _refine_ls_goodness_of_fit_ref 1.044 _refine_ls_restrained_S_all 1.044 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 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 Cd1 Cd 0.0000 0.0000 0.53600(13) 0.0332(5) Uani 1 6 d S . . Cd2 Cd -0.09695(6) -0.19391(12) 0.73663(8) 0.0410(4) Uani 1 2 d S . . Sn1 Sn 0.15083(5) -0.15083(5) 0.60144(9) 0.0373(3) Uani 1 2 d S . . Se1 Se 0.0000 0.0000 0.69189(19) 0.0324(7) Uani 1 6 d S . . Se2 Se 0.09496(8) -0.09496(8) 0.47726(12) 0.0497(6) Uani 1 2 d S . . Se3 Se -0.08919(7) -0.17838(14) 0.89548(11) 0.0451(5) Uani 1 2 d S . . Se4 Se 0.00279(17) -0.28336(14) 0.68304(15) 0.0743(6) Uani 1 1 d . . . K1 K -0.2982(8) -0.1491(4) 0.8689(9) 0.154(4) Uani 1 2 d S . . K2 K -0.1527(5) -0.3054(10) 0.4881(17) 0.265(12) Uani 1 2 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_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cd1 0.0342(8) 0.0342(8) 0.0312(11) 0.000 0.000 0.0171(4) Cd2 0.0368(5) 0.0471(8) 0.0424(8) 0.0089(6) 0.0044(3) 0.0236(4) Sn1 0.0364(5) 0.0364(5) 0.0437(7) -0.0053(3) 0.0053(3) 0.0217(6) Se1 0.0346(10) 0.0346(10) 0.0281(14) 0.000 0.000 0.0173(5) Se2 0.0620(10) 0.0620(10) 0.0416(11) -0.0060(4) 0.0060(4) 0.0435(12) Se3 0.0571(10) 0.0302(10) 0.0390(11) 0.0077(8) 0.0039(4) 0.0151(5) Se4 0.0707(12) 0.0518(11) 0.1120(15) 0.0251(11) 0.0483(11) 0.0394(10) K1 0.108(8) 0.138(7) 0.206(13) 0.008(4) 0.016(8) 0.054(4) K2 0.149(10) 0.129(10) 0.51(4) -0.100(15) -0.050(7) 0.064(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The 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 used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cd1 Se1 2.574(4) . ? Cd1 Se2 2.656(2) 3 ? Cd1 Se2 2.656(2) 2 ? Cd1 Se2 2.656(2) . ? Cd1 K2 4.054(12) . ? Cd1 K2 4.054(12) 2 ? Cd1 K2 4.054(12) 3 ? Cd2 Se4 2.618(2) 5 ? Cd2 Se4 2.619(2) . ? Cd2 Se1 2.6305(17) . ? Cd2 Se3 2.631(2) . ? Cd2 K1 4.052(10) . ? Cd2 K1 4.052(10) 2 ? Sn1 Se4 2.511(2) . ? Sn1 Se4 2.511(2) 4 ? Sn1 Se2 2.514(2) . ? Sn1 Se3 2.515(2) 15_544 ? Se1 Cd2 2.6305(17) 2 ? Se1 Cd2 2.6305(17) 3 ? Se2 K2 3.482(11) . ? Se2 K2 3.482(11) 2 ? Se3 Sn1 2.515(2) 8_445 ? Se3 K1 3.412(8) 2 ? Se3 K1 3.412(8) . ? Se4 K1 3.727(13) 2 ? Se4 K2 3.89(2) . ? K1 Se3 3.412(8) 3 ? K1 Se4 3.727(13) 3 ? K1 Se4 3.727(13) 5 ? K1 Cd2 4.052(10) 3 ? K1 K2 4.79(3) 14_445 ? K1 K2 4.816(11) 9_445 ? K1 K2 4.816(11) 7_455 ? K2 Se2 3.482(11) 3 ? K2 Se4 3.89(2) 5 ? K2 K1 4.79(3) 9_444 ? K2 K1 4.816(11) 14_444 ? K2 K1 4.816(11) 13_544 ? 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_3 _geom_angle_publ_flag Se1 Cd1 Se2 111.42(6) . 3 ? Se1 Cd1 Se2 111.42(6) . 2 ? Se2 Cd1 Se2 107.46(7) 3 2 ? Se1 Cd1 Se2 111.42(6) . . ? Se2 Cd1 Se2 107.45(7) 3 . ? Se2 Cd1 Se2 107.45(7) 2 . ? Se1 Cd1 K2 101.3(4) . . ? Se2 Cd1 K2 58.14(13) 3 . ? Se2 Cd1 K2 147.3(4) 2 . ? Se2 Cd1 K2 58.14(13) . . ? Se1 Cd1 K2 101.3(4) . 2 ? Se2 Cd1 K2 147.3(4) 3 2 ? Se2 Cd1 K2 58.14(13) 2 2 ? Se2 Cd1 K2 58.14(13) . 2 ? K2 Cd1 K2 116.3(3) . 2 ? Se1 Cd1 K2 101.3(4) . 3 ? Se2 Cd1 K2 58.14(13) 3 3 ? Se2 Cd1 K2 58.14(13) 2 3 ? Se2 Cd1 K2 147.3(4) . 3 ? K2 Cd1 K2 116.3(3) . 3 ? K2 Cd1 K2 116.3(3) 2 3 ? Se4 Cd2 Se4 112.09(12) 5 . ? Se4 Cd2 Se1 109.39(6) 5 . ? Se4 Cd2 Se1 109.39(6) . . ? Se4 Cd2 Se3 111.78(7) 5 . ? Se4 Cd2 Se3 111.78(7) . . ? Se1 Cd2 Se3 101.90(9) . . ? Se4 Cd2 K1 63.76(19) 5 . ? Se4 Cd2 K1 159.15(12) . . ? Se1 Cd2 K1 90.76(10) . . ? Se3 Cd2 K1 56.7(2) . . ? Se4 Cd2 K1 159.15(12) 5 2 ? Se4 Cd2 K1 63.76(19) . 2 ? Se1 Cd2 K1 90.76(10) . 2 ? Se3 Cd2 K1 56.7(2) . 2 ? K1 Cd2 K1 112.2(4) . 2 ? Se4 Sn1 Se4 114.28(13) . 4 ? Se4 Sn1 Se2 113.02(7) . . ? Se4 Sn1 Se2 113.02(7) 4 . ? Se4 Sn1 Se3 102.48(6) . 15_544 ? Se4 Sn1 Se3 102.48(6) 4 15_544 ? Se2 Sn1 Se3 110.41(8) . 15_544 ? Cd1 Se1 Cd2 106.31(7) . . ? Cd1 Se1 Cd2 106.31(7) . 2 ? Cd2 Se1 Cd2 112.44(6) . 2 ? Cd1 Se1 Cd2 106.31(7) . 3 ? Cd2 Se1 Cd2 112.44(6) . 3 ? Cd2 Se1 Cd2 112.44(6) 2 3 ? Sn1 Se2 Cd1 103.94(8) . . ? Sn1 Se2 K2 92.2(4) . . ? Cd1 Se2 K2 81.47(18) . . ? Sn1 Se2 K2 92.2(4) . 2 ? Cd1 Se2 K2 81.47(18) . 2 ? K2 Se2 K2 162.9(3) . 2 ? Sn1 Se3 Cd2 100.55(8) 8_445 . ? Sn1 Se3 K1 98.12(12) 8_445 2 ? Cd2 Se3 K1 83.1(3) . 2 ? Sn1 Se3 K1 98.11(12) 8_445 . ? Cd2 Se3 K1 83.1(3) . . ? K1 Se3 K1 160.4(4) 2 . ? Sn1 Se4 Cd2 106.37(8) . . ? Sn1 Se4 K1 87.89(15) . 2 ? Cd2 Se4 K1 77.18(17) . 2 ? Sn1 Se4 K2 83.1(3) . . ? Cd2 Se4 K2 81.34(19) . . ? K1 Se4 K2 153.3(2) 2 . ? Se3 K1 Se3 72.2(2) 3 . ? Se3 K1 Se4 74.86(17) 3 3 ? Se3 K1 Se4 113.9(3) . 3 ? Se3 K1 Se4 113.9(3) 3 5 ? Se3 K1 Se4 74.86(17) . 5 ? Se4 K1 Se4 68.9(3) 3 5 ? Se3 K1 Cd2 40.14(11) 3 3 ? Se3 K1 Cd2 82.6(2) . 3 ? Se4 K1 Cd2 39.06(12) 3 3 ? Se4 K1 Cd2 80.5(3) 5 3 ? Se3 K1 Cd2 82.6(2) 3 . ? Se3 K1 Cd2 40.14(11) . . ? Se4 K1 Cd2 80.5(3) 3 . ? Se4 K1 Cd2 39.06(12) 5 . ? Cd2 K1 Cd2 65.32(19) 3 . ? Se3 K1 K2 90.6(3) 3 14_445 ? Se3 K1 K2 90.6(3) . 14_445 ? Se4 K1 K2 144.93(14) 3 14_445 ? Se4 K1 K2 144.93(14) 5 14_445 ? Cd2 K1 K2 129.9(3) 3 14_445 ? Cd2 K1 K2 129.9(3) . 14_445 ? Se3 K1 K2 157.6(2) 3 9_445 ? Se3 K1 K2 85.83(14) . 9_445 ? Se4 K1 K2 111.5(4) 3 9_445 ? Se4 K1 K2 53.7(3) 5 9_445 ? Cd2 K1 K2 134.2(4) 3 9_445 ? Cd2 K1 K2 77.5(2) . 9_445 ? K2 K1 K2 94.2(3) 14_445 9_445 ? Se3 K1 K2 85.83(14) 3 7_455 ? Se3 K1 K2 157.6(2) . 7_455 ? Se4 K1 K2 53.7(3) 3 7_455 ? Se4 K1 K2 111.5(4) 5 7_455 ? Cd2 K1 K2 77.5(2) 3 7_455 ? Cd2 K1 K2 134.2(4) . 7_455 ? K2 K1 K2 94.2(3) 14_445 7_455 ? K2 K1 K2 115.5(3) 9_445 7_455 ? Se2 K2 Se2 75.9(3) 3 . ? Se2 K2 Se4 109.1(5) 3 . ? Se2 K2 Se4 69.0(3) . . ? Se2 K2 Se4 69.0(3) 3 5 ? Se2 K2 Se4 109.1(5) . 5 ? Se4 K2 Se4 67.8(5) . 5 ? Se2 K2 Cd1 40.39(14) 3 . ? Se2 K2 Cd1 40.39(14) . . ? Se4 K2 Cd1 76.5(3) . . ? Se4 K2 Cd1 76.5(3) 5 . ? Se2 K2 K1 94.8(6) 3 9_444 ? Se2 K2 K1 94.8(6) . 9_444 ? Se4 K2 K1 145.8(2) . 9_444 ? Se4 K2 K1 145.8(2) 5 9_444 ? Cd1 K2 K1 111.1(6) . 9_444 ? Se2 K2 K1 81.63(13) 3 14_444 ? Se2 K2 K1 156.3(3) . 14_444 ? Se4 K2 K1 112.4(6) . 14_444 ? Se4 K2 K1 54.5(2) 5 14_444 ? Cd1 K2 K1 116.0(2) . 14_444 ? K1 K2 K1 94.5(3) 9_444 14_444 ? Se2 K2 K1 156.3(3) 3 13_544 ? Se2 K2 K1 81.63(13) . 13_544 ? Se4 K2 K1 54.5(2) . 13_544 ? Se4 K2 K1 112.4(6) 5 13_544 ? Cd1 K2 K1 116.0(2) . 13_544 ? K1 K2 K1 94.5(3) 9_444 13_544 ? K1 K2 K1 119.2(4) 14_444 13_544 ? _diffrn_measured_fraction_theta_max 0.945 _diffrn_reflns_theta_full 28.42 _diffrn_measured_fraction_theta_full 0.945 _refine_diff_density_max 1.535 _refine_diff_density_min -1.287 _refine_diff_density_rms 0.255