# Supplementary Material (ESI) for Journal of Materials Chemistry # This journal is © The Royal Society of Chemistry 2001 # CCDC Number: 1145/272 data_shelxl _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'Bi Br Cu3 O8 Se2' _chemical_formula_weight 765.43 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'Cu' 'Cu' 0.3240 0.8257 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Bi' 'Bi' -1.3494 7.2566 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Se' 'Se' 0.2367 1.4831 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0056 0.0036 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Br' 'Br' 0.1811 1.6452 '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+1/2, -z' 'x+1/2, -y, -z' '-x+1/2, -y+1/2, z' '-x, -y, -z' 'x, -y-1/2, z' '-x-1/2, y, z' 'x-1/2, y-1/2, -z' _cell_length_a 6.3900(3) _cell_length_b 9.6940(4) _cell_length_c 7.2870(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 451.39(3) _cell_formula_units_Z 2 _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 5.632 _exptl_crystal_density_method ? _exptl_crystal_F_000 674 _exptl_absorpt_coefficient_mu 20.942 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.56230 _diffrn_radiation_type ? _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device ? _diffrn_measurement_method ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8082 _diffrn_reflns_av_R_equivalents 0.1290 _diffrn_reflns_av_sigmaI/netI 0.0524 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.77 _diffrn_reflns_theta_max 25.01 _reflns_number_total 910 _reflns_number_observed 870 _reflns_observed_criterion >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-96 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-96 (Sheldrick, 1996)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0447P)^2^+1.3193P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0201(16) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 910 _refine_ls_number_parameters 47 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0358 _refine_ls_R_factor_obs 0.0313 _refine_ls_wR_factor_all 0.0820 _refine_ls_wR_factor_obs 0.0791 _refine_ls_goodness_of_fit_all 1.083 _refine_ls_goodness_of_fit_obs 1.070 _refine_ls_restrained_S_all 1.083 _refine_ls_restrained_S_obs 1.070 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Bi Bi 0.2500 0.2500 0.24012(4) 0.00846(14) Uani 1 d S . Se Se 0.2500 0.55649(6) 0.61157(9) 0.00976(17) Uani 1 d S . Cu1 Cu 0.0000 0.0000 0.0000 0.0127(2) Uani 1 d S . Cu2 Cu 0.2500 0.2500 0.79253(18) 0.0132(2) Uani 1 d S . Br Br 0.2500 0.7500 0.15790(16) 0.0224(2) Uani 1 d S . O1 O 0.2500 0.1138(5) 0.9916(6) 0.0089(8) Uani 1 d S . O2 O 0.0410(7) 0.5836(5) 0.7558(5) 0.0169(8) Uani 1 d . . O3 O 0.2500 0.1159(5) 0.5897(7) 0.0195(11) Uani 1 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 Bi 0.0069(2) 0.00889(18) 0.00956(19) 0.000 0.000 0.000 Se 0.0087(3) 0.0109(3) 0.0096(3) 0.00169(19) 0.000 0.000 Cu1 0.0098(4) 0.0147(4) 0.0137(4) -0.0045(3) 0.0017(3) -0.0054(3) Cu2 0.0199(6) 0.0097(5) 0.0099(5) 0.000 0.000 0.000 Br 0.0234(5) 0.0238(5) 0.0201(5) 0.000 0.000 0.000 O1 0.007(2) 0.0090(18) 0.011(2) -0.0009(14) 0.000 0.000 O2 0.0130(19) 0.0203(17) 0.0176(19) 0.0069(12) 0.0039(12) 0.0059(14) O3 0.036(3) 0.012(2) 0.010(2) -0.0012(18) 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 Bi O1 2.241(5) 1_554 ? Bi O1 2.241(5) 6_564 ? Bi O2 2.462(4) 3_566 ? Bi O2 2.462(4) 2_546 ? Bi O2 2.462(4) 8_656 ? Bi O2 2.462(4) 5_566 ? Bi Cu2 3.2617(13) 1_554 ? Se O3 1.679(5) 6_565 ? Se O2 1.719(4) . ? Se O2 1.719(4) 7_655 ? Cu1 O1 1.942(3) 5_556 ? Cu1 O1 1.942(3) 1_554 ? Cu1 O2 1.973(3) 6_564 ? Cu1 O2 1.973(3) 2_546 ? Cu2 O1 1.962(5) 6_565 ? Cu2 O1 1.962(5) . ? Cu2 O3 1.968(5) 6_565 ? Cu2 O3 1.968(5) . ? Cu2 Bi 3.2616(13) 1_556 ? O1 Cu1 1.942(3) 1_556 ? O1 Cu1 1.942(3) 3_556 ? O1 Bi 2.241(5) 1_556 ? O2 Cu1 1.973(3) 2_556 ? O2 Bi 2.462(4) 5_566 ? O3 Se 1.679(5) 6_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 O1 Bi O1 72.2(2) 1_554 6_564 ? O1 Bi O2 113.32(11) 1_554 3_566 ? O1 Bi O2 67.90(10) 6_564 3_566 ? O1 Bi O2 67.90(10) 1_554 2_546 ? O1 Bi O2 113.32(12) 6_564 2_546 ? O2 Bi O2 178.61(16) 3_566 2_546 ? O1 Bi O2 67.90(10) 1_554 8_656 ? O1 Bi O2 113.32(11) 6_564 8_656 ? O2 Bi O2 81.9(2) 3_566 8_656 ? O2 Bi O2 98.1(2) 2_546 8_656 ? O1 Bi O2 113.32(12) 1_554 5_566 ? O1 Bi O2 67.90(10) 6_564 5_566 ? O2 Bi O2 98.1(2) 3_566 5_566 ? O2 Bi O2 81.9(2) 2_546 5_566 ? O2 Bi O2 178.61(16) 8_656 5_566 ? O1 Bi Cu2 36.09(12) 1_554 1_554 ? O1 Bi Cu2 36.09(12) 6_564 1_554 ? O2 Bi Cu2 90.69(8) 3_566 1_554 ? O2 Bi Cu2 90.69(8) 2_546 1_554 ? O2 Bi Cu2 90.69(8) 8_656 1_554 ? O2 Bi Cu2 90.69(8) 5_566 1_554 ? O3 Se O2 102.12(19) 6_565 . ? O3 Se O2 102.12(19) 6_565 7_655 ? O2 Se O2 101.9(3) . 7_655 ? O1 Cu1 O1 180.0 5_556 1_554 ? O1 Cu1 O2 84.51(18) 5_556 6_564 ? O1 Cu1 O2 95.49(18) 1_554 6_564 ? O1 Cu1 O2 95.49(18) 5_556 2_546 ? O1 Cu1 O2 84.51(18) 1_554 2_546 ? O2 Cu1 O2 180.0 6_564 2_546 ? O1 Cu2 O1 84.6(3) 6_565 . ? O1 Cu2 O3 96.4(2) 6_565 6_565 ? O1 Cu2 O3 179.0(2) . 6_565 ? O1 Cu2 O3 179.0(2) 6_565 . ? O1 Cu2 O3 96.4(2) . . ? O3 Cu2 O3 82.7(3) 6_565 . ? O1 Cu2 Bi 42.30(14) 6_565 1_556 ? O1 Cu2 Bi 42.30(14) . 1_556 ? O3 Cu2 Bi 138.67(15) 6_565 1_556 ? O3 Cu2 Bi 138.67(15) . 1_556 ? Cu1 O1 Cu1 110.7(2) 1_556 3_556 ? Cu1 O1 Cu2 113.92(15) 1_556 . ? Cu1 O1 Cu2 113.92(15) 3_556 . ? Cu1 O1 Bi 108.02(15) 1_556 1_556 ? Cu1 O1 Bi 108.02(15) 3_556 1_556 ? Cu2 O1 Bi 101.6(2) . 1_556 ? Se O2 Cu1 126.3(2) . 2_556 ? Se O2 Bi 133.95(19) . 5_566 ? Cu1 O2 Bi 99.08(16) 2_556 5_566 ? Se O3 Cu2 125.9(3) 6_565 . ? _refine_diff_density_max 2.940 _refine_diff_density_min -3.657 _refine_diff_density_rms 0.617