# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.
# This journal is © The Royal Society of Chemistry 2015

 
data_shelx 
 
_audit_creation_method            SHELXL-97 
_chemical_name_systematic 
; 
 ? 
; 
_chemical_name_common             ? 
_chemical_melting_point           ? 
_chemical_formula_moiety          ? 
_chemical_formula_sum 
 'Ba8 Cu5.10 Ge40.20 Sn0.70' 
_chemical_formula_weight          4424.72 
 
loop_ 
 _atom_type_symbol 
 _atom_type_description 
 _atom_type_scat_dispersion_real 
 _atom_type_scat_dispersion_imag 
 _atom_type_scat_source 
 'Ba'  'Ba'  -0.3240   2.2820 
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 
 'Cu'  'Cu'   0.3200   1.2650 
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 
 'Ge'  'Ge'   0.1550   1.8000 
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 
 'Sn'  'Sn'  -0.6540   1.4250 
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 
 
_symmetry_cell_setting            ? 
_symmetry_space_group_name_H-M    ? 
 
loop_ 
 _symmetry_equiv_pos_as_xyz 
 'x, y, z' 
 'x, -y, -z' 
 '-x, -y, z' 
 '-x, y, -z' 
 '-y+1/2, x+1/2, z+1/2' 
 'y+1/2, x+1/2, -z+1/2' 
 'y+1/2, -x+1/2, z+1/2' 
 '-y+1/2, -x+1/2, -z+1/2' 
 'y, z, x' 
 '-y, -z, x' 
 'y, -z, -x' 
 '-y, z, -x' 
 '-z+1/2, y+1/2, x+1/2' 
 '-z+1/2, -y+1/2, -x+1/2' 
 'z+1/2, -y+1/2, x+1/2' 
 'z+1/2, y+1/2, -x+1/2' 
 'z, x, y' 
 '-z, x, -y' 
 '-z, -x, y' 
 'z, -x, -y' 
 '-x+1/2, -z+1/2, -y+1/2' 
 '-x+1/2, z+1/2, y+1/2' 
 'x+1/2, -z+1/2, y+1/2' 
 'x+1/2, z+1/2, -y+1/2' 
 '-x, -y, -z' 
 '-x, y, z' 
 'x, y, -z' 
 'x, -y, z' 
 'y-1/2, -x-1/2, -z-1/2' 
 '-y-1/2, -x-1/2, z-1/2' 
 '-y-1/2, x-1/2, -z-1/2' 
 'y-1/2, x-1/2, z-1/2' 
 '-y, -z, -x' 
 'y, z, -x' 
 '-y, z, x' 
 'y, -z, x' 
 'z-1/2, -y-1/2, -x-1/2' 
 'z-1/2, y-1/2, x-1/2' 
 '-z-1/2, y-1/2, -x-1/2' 
 '-z-1/2, -y-1/2, x-1/2' 
 '-z, -x, -y' 
 'z, -x, y' 
 'z, x, -y' 
 '-z, x, y' 
 'x-1/2, z-1/2, y-1/2' 
 'x-1/2, -z-1/2, -y-1/2' 
 '-x-1/2, z-1/2, -y-1/2' 
 '-x-1/2, -z-1/2, y-1/2' 
 
_cell_length_a                    10.6742(10) 
_cell_length_b                    10.6742(10) 
_cell_length_c                    10.6742(10) 
_cell_angle_alpha                 90.00 
_cell_angle_beta                  90.00 
_cell_angle_gamma                 90.00 
_cell_volume                      1216.2(2) 
_cell_formula_units_Z             1 
_cell_measurement_temperature     293(2) 
_cell_measurement_reflns_used     ? 
_cell_measurement_theta_min       ? 
_cell_measurement_theta_max       ? 
 
_exptl_crystal_description        ? 
_exptl_crystal_colour             ? 
_exptl_crystal_size_max           ? 
_exptl_crystal_size_mid           ? 
_exptl_crystal_size_min           ? 
_exptl_crystal_density_meas       ? 
_exptl_crystal_density_diffrn     6.041 
_exptl_crystal_density_method     'not measured' 
_exptl_crystal_F_000              1916 
_exptl_absorpt_coefficient_mu     33.265 
_exptl_absorpt_correction_type    ? 
_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      0.35385 
_diffrn_radiation_type            ? 
_diffrn_radiation_source          'fine-focus sealed tube' 
_diffrn_radiation_monochromator   graphite 
_diffrn_measurement_device_type   ? 
_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             6874 
_diffrn_reflns_av_R_equivalents   0.0340 
_diffrn_reflns_av_sigmaI/netI     0.0508 
_diffrn_reflns_limit_h_min        -9 
_diffrn_reflns_limit_h_max        19 
_diffrn_reflns_limit_k_min        -20 
_diffrn_reflns_limit_k_max        20 
_diffrn_reflns_limit_l_min        -20 
_diffrn_reflns_limit_l_max        20 
_diffrn_reflns_theta_min          1.34 
_diffrn_reflns_theta_max          20.68 
_reflns_number_total              844 
_reflns_number_gt                 542 
_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 F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² 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/[σ²(Fo²)+(0.0070P)²+0.0000P] where P=(Fo²+2Fc²)/3' 
_atom_sites_solution_primary      direct 
_atom_sites_solution_secondary    difmap 
_atom_sites_solution_hydrogens    geom 
_refine_ls_hydrogen_treatment     mixed 
_refine_ls_extinction_method      SHELXL 
_refine_ls_extinction_coef        0.00000(15) 
_refine_ls_extinction_expression 
 'Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^' 
_refine_ls_number_reflns          844 
_refine_ls_number_parameters      20 
_refine_ls_number_restraints      0 
_refine_ls_R_factor_all           0.0388 
_refine_ls_R_factor_gt            0.0220 
_refine_ls_wR_factor_ref          0.0306 
_refine_ls_wR_factor_gt           0.0302 
_refine_ls_goodness_of_fit_ref    1.017 
_refine_ls_restrained_S_all       1.017 
_refine_ls_shift/su_max           4.684 
_refine_ls_shift/su_mean          0.297 
 
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 
Ba1 Ba 0.0000 0.0000 0.0000 0.00540(11) Uani 1 24 d S . . 
Ba2 Ba 0.0000 0.498(2) 0.2434(10) 0.0200(4) Uani 0.50 4 d SP . . 
Ge3 Ge 0.11986(3) 0.31465(3) 0.0000 0.00341(6) Uani 0.97 2 d SP . . 
Sn3 Sn 0.11986(3) 0.31465(3) 0.0000 0.00341(6) Uani 0.03 2 d SP . . 
Ge2 Ge 0.183231(18) 0.183231(18) 0.183231(18) 0.00203(6) Uani 1 3 d S . . 
Cu1 Cu 0.2500 0.5000 0.0000 0.00319(14) Uani 0.85 8 d SP . . 
Ge1 Ge 0.2500 0.5000 0.0000 0.00319(14) Uani 0.15 8 d SP . . 
 
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 
Ba1 0.00540(11) 0.00540(11) 0.00540(11) 0.000 0.000 0.000 
Ba2 0.0077(6) 0.0428(16) 0.0095(17) 0.0132(18) 0.000 0.000 
Ge3 0.00412(14) 0.00383(13) 0.00229(13) 0.000 0.000 0.00142(13) 
Sn3 0.00412(14) 0.00383(13) 0.00229(13) 0.000 0.000 0.00142(13) 
Ge2 0.00203(6) 0.00203(6) 0.00203(6) -0.00041(7) -0.00041(7) -0.00041(7) 
Cu1 0.0051(3) 0.00225(19) 0.00225(19) 0.000 0.000 0.000 
Ge1 0.0051(3) 0.00225(19) 0.00225(19) 0.000 0.000 0.000 
 
_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 
Ge3 Cu1 2.4174(4) . ? 
Ge3 Ge2 2.5002(3) . ? 
Ge3 Ge2 2.5002(3) 27 ? 
Ge3 Ge3 2.5587(7) 26 ? 
Ge3 Sn3 2.5587(7) 26 ? 
Ge2 Ge2 2.4689(7) 8 ? 
Ge2 Sn3 2.5002(3) 17 ? 
Ge2 Sn3 2.5002(3) 9 ? 
Ge2 Ge3 2.5002(3) 9 ? 
Ge2 Ge3 2.5002(3) 17 ? 
Cu1 Sn3 2.4175(4) 21 ? 
Cu1 Ge3 2.4175(4) 21 ? 
Cu1 Sn3 2.4175(4) 22_554 ? 
Cu1 Ge3 2.4175(4) 22_554 ? 
Cu1 Sn3 2.4175(4) 2_565 ? 
Cu1 Ge3 2.4175(4) 2_565 ? 
 
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 
Cu1 Ge3 Ge2 107.681(12) . . ? 
Cu1 Ge3 Ge2 107.680(12) . 27 ? 
Ge2 Ge3 Ge2 102.941(15) . 27 ? 
Cu1 Ge3 Ge3 125.076(8) . 26 ? 
Ge2 Ge3 Ge3 105.698(9) . 26 ? 
Ge2 Ge3 Ge3 105.699(9) 27 26 ? 
Cu1 Ge3 Sn3 125.076(8) . 26 ? 
Ge2 Ge3 Sn3 105.698(9) . 26 ? 
Ge2 Ge3 Sn3 105.699(9) 27 26 ? 
Ge3 Ge3 Sn3 0.000(15) 26 26 ? 
Ge2 Ge2 Sn3 106.495(10) 8 17 ? 
Ge2 Ge2 Sn3 106.495(10) 8 9 ? 
Sn3 Ge2 Sn3 112.277(9) 17 9 ? 
Ge2 Ge2 Ge3 106.495(10) 8 9 ? 
Sn3 Ge2 Ge3 112.277(9) 17 9 ? 
Sn3 Ge2 Ge3 0.000(14) 9 9 ? 
Ge2 Ge2 Ge3 106.495(10) 8 17 ? 
Sn3 Ge2 Ge3 0.000(14) 17 17 ? 
Sn3 Ge2 Ge3 112.277(9) 9 17 ? 
Ge3 Ge2 Ge3 112.277(9) 9 17 ? 
Ge2 Ge2 Ge3 106.494(10) 8 . ? 
Sn3 Ge2 Ge3 112.277(9) 17 . ? 
Sn3 Ge2 Ge3 112.277(9) 9 . ? 
Ge3 Ge2 Ge3 112.277(9) 9 . ? 
Ge3 Ge2 Ge3 112.277(9) 17 . ? 
Ge3 Cu1 Sn3 109.282(8) . 21 ? 
Ge3 Cu1 Ge3 109.282(8) . 21 ? 
Sn3 Cu1 Ge3 0.000(9) 21 21 ? 
Ge3 Cu1 Sn3 109.282(8) . 22_554 ? 
Sn3 Cu1 Sn3 109.849(16) 21 22_554 ? 
Ge3 Cu1 Sn3 109.849(16) 21 22_554 ? 
Ge3 Cu1 Ge3 109.282(8) . 22_554 ? 
Sn3 Cu1 Ge3 109.849(16) 21 22_554 ? 
Ge3 Cu1 Ge3 109.849(16) 21 22_554 ? 
Sn3 Cu1 Ge3 0.000(9) 22_554 22_554 ? 
Ge3 Cu1 Sn3 109.849(16) . 2_565 ? 
Sn3 Cu1 Sn3 109.282(8) 21 2_565 ? 
Ge3 Cu1 Sn3 109.282(8) 21 2_565 ? 
Sn3 Cu1 Sn3 109.283(8) 22_554 2_565 ? 
Ge3 Cu1 Sn3 109.283(8) 22_554 2_565 ? 
Ge3 Cu1 Ge3 109.849(16) . 2_565 ? 
Sn3 Cu1 Ge3 109.282(8) 21 2_565 ? 
Ge3 Cu1 Ge3 109.282(8) 21 2_565 ? 
Sn3 Cu1 Ge3 109.283(8) 22_554 2_565 ? 
Ge3 Cu1 Ge3 109.283(8) 22_554 2_565 ? 
Sn3 Cu1 Ge3 0.000(13) 2_565 2_565 ? 
 
_diffrn_measured_fraction_theta_max    0.891 
_diffrn_reflns_theta_full              20.68 
_diffrn_measured_fraction_theta_full   0.891 
_refine_diff_density_max    1.980 
_refine_diff_density_min   -4.326 
_refine_diff_density_rms    0.272 
