# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Silke Buehler-Paschen' _publ_contact_author_email PASCHEN@IFP.TUWIEN.AC.AT _publ_section_title ; Atomic ordering and thermoelectric properties of the n-type clathrate Ba8Ni3.5Ge42.1..0.4 ; loop_ _publ_author_name 'Silke Buehler-Paschen' 'W. Assmus' 'U Aydemir' 'Michael Baitinger' 'E. Bauer' ; H.Borrmann ; 'U. Burkhardt' 'J Custers' 'Yuri Grin' 'A. Haghighirad' 'R. Hofler' ; K.D.Luther ; 'L. T. K. Nguyen' 'F. Ritter' # Attachment 'Ba8Ni3.5Ge42.1rev.cif' data_Ba8Ni3.5Ge42.1rev.cif _database_code_depnum_ccdc_archive 'CCDC 749600' #============================================================================= #----------------------- CHEMICAL DATA --------------------------------------# #============================================================================= # _chemical_name_systematic _chemical_formula_sum 'Ba8 Ge42.1 Ni3.5 ' _chemical_formula_weight 4360.92 _chemical_formula_analytical 'Ba8.00(3) Ni3.45(3)Ge42.3(2) ' # according to WDXS _chemical_melting_point 1103 _chemical_compound_source 'Synthesized with Bridgman technique' loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Ba Ba -0.6940 1.5004 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ge Ge 0.3016 1.1903 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ni Ni 0.3147 0.7232 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' #============================================================================= #----------------------- CRYSTAL DATA --------------------------------------# #============================================================================= _symmetry_cell_setting cubic _symmetry_space_group_name_H-M 'P m -3 n' _symmetry_int_tables_number 223 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' # The lattice parameters were refined from XRPD data # by using LaB6 as an internal standard. # XRPD was performed using CuK\a1 radiation, # the single crystal was measured using Ag K\a radiation. _cell_length_a 10.6798(2) _cell_length_b 10.6798(2) _cell_length_c 10.6798(2) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1218.12(7) _cell_formula_units_Z 1 _cell_measurement_wavelength 1.540598 _cell_measurement_radiation CuK\a1 _cell_measurement_temperature 295(2) _cell_measurement_reflns_used 75 _cell_measurement_theta_min 1.5 _cell_measurement_theta_max 50 #------------------ CRYSTAL INFORMATION -------------------------------------# _exptl_crystal_description plate _exptl_crystal_colour metallic-grey _exptl_crystal_size_max 0.185 _exptl_crystal_size_mid 0.040 _exptl_crystal_size_min 0.015 _exptl_crystal_density_diffrn 5.9319 _exptl_crystal_density_meas 5.93 _exptl_crystal_density_method 'helium pycnometry' _exptl_crystal_F_000 1893.2 #------------------ ABSORPTION CORRECTION -----------------------------------# _exptl_absorpt_coefficient_mu 17.415 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.5346 _exptl_absorpt_correction_T_max 1.0000 _exptl_absorpt_process_details 'Algorithm by T. Higashi, Rigaku Corp. 2001, as implemented in CrystalClear' #------------------ DATA COLLECTION INFORMATION -----------------------------# _diffrn_ambient_temperature 295(2) _diffrn_radiation_probe x-ray _diffrn_radiation_type AgK\a _diffrn_radiation_wavelength 0.56087 _diffrn_source 'micro-focus rotating anode' _diffrn_radiation_monochromator 'multilayer optics' _diffrn_measurement_device_type 'RIGAKU Spider' _diffrn_measurement_method omega-scans _diffrn_detector_area_resol_mean 10.000 _diffrn_reflns_number 19334 _diffrn_reflns_av_R_equivalents 0.0313 _diffrn_reflns_av_sigmaI/netI 0.0210 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -25 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -26 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 3.01 _diffrn_reflns_theta_max 44.60 _reflns_number_total 1784 _reflns_number_gt 1409 _reflns_threshold_expression 'F~o~ > 4\s(F~o~)' #------------------ COMPUTER PROGRAMS USED ----------------------------------# _computing_data_collection 'CrystalClear (Rigaku Inc. 2005)' _computing_cell_refinement WinCSD _computing_data_reduction 'CrystalClear (Rigaku Inc. 2005)' _computing_structure_solution WinCSD _computing_structure_refinement WinCSD _computing_publication_material ; Akselrud, L.G., Zavalii, P.Y., Grin, Yu.N., Pecharsky, V.K., Baumgartner, B., W\"olfel, E. (1993) Materials Science Forum, v.133-136, 335-340 ; _refine_ls_structure_factor_coef F _refine_ls_matrix_type fullcycle _refine_ls_weighting_scheme unit _refine_ls_extinction_method ; Gaussian isotropic P.J. Becker, P. Coppens, Acta Crystallogr. A 30 (1974) 129-153 ; _refine_ls_extinction_coef 0.0036(1) _refine_ls_number_reflns 1784 _refine_ls_number_parameters 31 _refine_ls_R_factor_gt 0.0392 _refine_ls_wR_factor_gt 0.0392 _refine_ls_R_factor_all 0.0508 _refine_ls_wR_factor_all 0.0508 _refine_ls_goodness_of_fit_ref 1.01 _refine_diff_density_max 2.335 _refine_diff_density_min -1.772 _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 44.60 _diffrn_measured_fraction_theta_full 0.998 #============================================================================= # 9. ATOMIC COORDINATES AND THERMAL PARAMETERS loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_thermal_displace_type _atom_site_U_iso_or_equiv _atom_site_symmetry_multiplicity _atom_site_type_symbol _atom_site_occupancy Ba1 0 0 0 Uani 0.01132(6) 2 Ba 1. Ba2 0.2409(3) 0.5155(3) 0 Uani 0.0271(8) 24 Ba 0.25 Ni1 0.5 0.25 0 Uani 0.0104(2) 6 Ni 0.583 Ge1 0.5 0.25 0 Uani 0.0104(2) 6 Ge 0.346(6) Ge2 0.18363(3) 0.18363(3) 0.18363(3) Uani 0.00998(4) 16 Ge 1. Ge31 0 0.30757(1) 0.10980(1) Uani 0.0084(2) 24 Ge 0.317(3) Ge32 0 0.32013(1) 0.12612(1) Uani 0.0120(2) 24 Ge 0.583 Ge33 0 0.3282(13) 0.1415(10) Uani 0.0139(14) 24 Ge 0.096(2) 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 Ba1 0.01132(1) 0.01132(1) 0.01132(1) 0 0 0 Ba2 0.0097(10) 0.0255(13) 0.046(2) 0.0040(6) 0 0 Ni1 0.0088(2) 0.0137(4) 0.0088(2) 0 0 0 Ge1 0.0088(2) 0.0137(4) 0.0088(2) 0 0 0 Ge2 0.00998(7) 0.00998(7) 0.00998(7) -0.00138(6) -0.00138(6) -0.00138(6) Ge31 0.0102(4) 0.0059(3) 0.0092(4) 0 0 -0.0009(3) Ge32 0.0100(2) 0.0120(3) 0.0139(5) 0 0 0.0008(3) Ge33 0.014(2) 0.019(3) 0.009(2) 0 0 -0.005(2) # The interatomic distances and angles are calculated by Mercury software, # Mercury CSD 2.0 - new features for the visualization and investigation of # crystal structures,C. F. Macrae, I. J. Bruno, J. A. Chisholm, P. R. Edgington, # P. McCabe, E. Pidcock, L. Rodriguez-Monge, R. Taylor, J. van de Streek and # P. A. Wood, J. Appl. Cryst., 41, 466-470, 2008. 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 # Void@6c Ge33 2.170(7) 9 ? Ba1 Ge2 3.3968(3) 25 ? Ba1 Ge31 3.4878(1) 33 ? Ba2 Ge32 3.393(3) 25_565 ? Ba2 Ge31 3.401(3) 25_565 ? Ba2 Ge33 3.419(8) 25_565 ? Ba2 Ge32 3.570(3) 47_666 ? Ba2 Ge32 3.576(3) 27 ? Ni1 Ge32 2.3325(1) 21 ? Ge1 Ge31 2.5427(1) 21 ? Ge2 Ge2 2.4554(5) 8 ? Ge2 Ge31 2.4940(3) 17 ? Ge2 Ge32 2.5196(3) 17 ? Ge2 Ge33 2.54(1) 17 ? Ge2 Ba2 3.814(3) 18_556 ? Ge31 Ge31 2.3453(2) 27 ? Ge31 Ge2 2.4940(3) 26 ? Ge31 Ge32 2.5231(2) 27 ? Ge31 Ge1 2.5427(1) 17 ? Ge31 Ge33 2.69(1) 27 ? Ge31 Ba2 3.401(3) 2_565 ? Ge31 Ba2 3.591(3) 22_554 ? Ge32 Ge32 2.6939(2) 27 ? Ge32 Ge33 2.86(1) 27 ? Ge33 Ba2 3.583(9) 22_554 ? Ge33 Ba2 3.592(1) 26 ? 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 # Ge33 Void@6c Ge33 106.6(5) 9 21 ? # Ge33 Void@6c Ge33 115.5(5) 21 23_554 ? Ge32 Ni1 Ge32 108.77(1) 21 9 ? Ge32 Ni1 Ge32 110.89(1) 21 23_554 ? Ge31 Ge1 Ge31 110.29(1) 21 9 ? Ge31 Ge1 Ge31 107.85(1) 21 23_554 ? Ge2 Ge2 Ge31 109.28(1) 8 17 ? Ge31 Ge2 Ge31 109.67(1) 17 . ? Ge2 Ge2 Ge32 104.84(1) 8 17 ? Ge31 Ge2 Ge32 113.85(1) . 17 ? Ge31 Ge2 Ge32 109.77(1) 9 17 ? Ge32 Ge2 Ge32 113.68(1) 17 . ? Ge2 Ge2 Ge33 101.4(3) 8 17 ? Ge31 Ge2 Ge33 117.6(3) . 17 ? Ge31 Ge2 Ge33 109.2(3) 9 17 ? Ge32 Ge2 Ge33 117.2(3) . 17 ? Ge32 Ge2 Ge33 112.8(3) 9 17 ? Ge33 Ge2 Ge33 116.2(4) 17 9 ? Ge31 Ge31 Ge2 108.43(1) 27 26 ? Ge2 Ge31 Ge2 103.69(1) 26 . ? Ge2 Ge31 Ge32 110.12(1) 26 27 ? Ge31 Ge31 Ge1 126.08(1) 27 17 ? Ge2 Ge31 Ge1 104.05(1) 26 17 ? Ge32 Ge31 Ge1 123.03(1) 27 17 ? Ge2 Ge31 Ge33 111.0(3) 26 27 ? Ge1 Ge31 Ge33 121.4(3) 17 27 ? Ni1 Ge32 Ge2 109.77(1) 17 26 ? Ge2 Ge32 Ge2 102.22(1) 26 . ? Ni1 Ge32 Ge31 127.60(1) 17 27 ? Ge2 Ge32 Ge31 102.28(1) . 27 ? Ni1 Ge32 Ge32 124.56(1) 17 27 ? Ge2 Ge32 Ge32 104.11(1) . 27 ? Ge2 Ge33 Ge2 101.3(4) 26 . ? Ge2 Ge33 Ge31 97.3(4) . 27 ? Ge2 Ge33 Ge32 99.2(3) . 27 ?