# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry # This journal is © The Royal Society of Chemistry 2012 data_global _journal_coden_Cambridge 1145 _journal_volume ? _journal_page_first ? _journal_year ? _publ_requested_journal 'Journal of Materials Chemistry' _publ_section_title ; Synthesis and characterisation of vanadium doped alkaline earth lanthanum germanate oxyapatite electrolyte ; _publ_section_abstract ; The crystal chemistry and oxygen conductivity of vanadium-doped apatites of nominal composition [La8AE2][Ge6-xVx]O26+x/2 (AE = Ca, Sr, Ba; 0 U x U 1.5) were studied to establish their potential as intermediate temperature solid oxide fuel cell (SOFC) electrolytes. Single-phase products obtained for x iU 0.5 were found, using a combination of powder synchrotron X-ray and neutron diffraction, to be P63/m apatites. The ionic conductivities extracted by complex impedance spectroscopy showed that small vanadium amendments enhanced oxygen mobility at intermediate temperatures (500 - 700 oC) by more than one order of magnitude, as the incorporation of V5+ through displacement of Ge4+ is charge balanced with interstitial O2- that improves ionic conduction. The most promising composition was La7.88Ca2Ge5.35V0.65O26.15 that delivered |O = 3.44 A10-4 S?cm-1 at 500 oC. The superstoichiometric oxygen was delocalised, without fixed X-ray or neutron scattering centres. Crystal chemistry systematics demonstrate that the Ca-apatite was superior because the relatively small framework expanded through (La/AE)O6 metaprism twisting (|O) that widened the tunnel, ensuring P63/m symmetry was adopted, which favours the passage of O2- with lower activation energy. ; _publ_contact_author_name 'T. J. White' _publ_contact_author_address ;School of Materials Science and Engineering Nanyang Technological University 50 Nanyang Avenue Singapore 639798 ; _publ_contact_author_email tjwhite@ntu.edu.sg _publ_contact_author_phone (65)67904586 _publ_contact_author_fax (65)67909081 loop_ _publ_author_name _publ_author_address 'Li, H' ;School of Materials Science and Engineering Nanyang Technological University 50 Nanyang Avenue Singapore 639798 ; 'Baikie, T' ;School of Materials Science and Engineering Nanyang Technological University 50 Nanyang Avenue Singapore 639798 ; 'Pramana, S. S' ;School of Materials Science and Engineering Nanyang Technological University 50 Nanyang Avenue Singapore 639798 ; 'Shin, J. F' ;School of Chemistry University of Birmingham Edgbaston Birmingham B15 2TT UK ; 'Slater, P.R' ;School of Chemistry University of Birmingham Edgbaston Birmingham B15 2TT UK ; 'Brink, F' ;Centre for Advanced Microscopy R N Robertson Building (Bldg 46) The Australian National University Canberra ACT 0200 ; 'Hester, J' ;Australian Nuclear Science and Technology Organisation (ANSTO) New Illawarra Road Lucas Heights NSW Australia ; 'Wallwork, K' ;Australian Synchrotron Company Ltd 800 Blackburn Rd Clayton VIC 3168 ; 'White, T.J' ;School of Materials Science and Engineering Nanyang Technological University 50 Nanyang Avenue Singapore 639798 ; #loop_ #_atom_type_symbol #_atom_type_scat_length_neutron #_atom_type_scat_source #La 8.24 'Neutron News, Vol. 3, No. 3, 1992, pp. 29-37.' #Sr 7.02 'Neutron News, Vol. 3, No. 3, 1992, pp. 29-37.' #Ca 4.70 'Neutron News, Vol. 3, No. 3, 1992, pp. 29-37.' #Ba 5.07 'Neutron News, Vol. 3, No. 3, 1992, pp. 29-37.' #Ge 8.185 'Neutron News, Vol. 3, No. 3, 1992, pp. 29-37.' #V -0.3824 'Neutron News, Vol. 3, No. 3, 1992, pp. 29-37.' #O 5.803 'Neutron News, Vol. 3, No. 3, 1992, pp. 29-37.' #_computing_data_collection ? #_computing_cell_refinement 'TOPAS' #_computing_data_reduction 'TOPAS' #_computing_structure_solution 'TOPAS' #_computing_structure_refinement 'TOPAS' #_computing_molecular_graphics 'ATOMS' data_La7.93Sr2Ge6O25.90 _database_code_depnum_ccdc_archive 'CCDC 838422' #TrackingRef '- Combined CIFS.cif' _chemical_name_mineral Apatite _chemical_formula_sum 'Ge6 La7.93 O26 Sr2' _cell_length_a 9.91022(13) _cell_length_b 9.91022(13) _cell_length_c 7.32094(14) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 622.68(2) _chemical_formula_weight 2128.574 _symmetry_cell_setting hexagonal _symmetry_space_group_name_H-M P63/m _symmetry_space_group_name_Hall '-P 6c' _symmetry_Int_Tables_number 176 _cell_formula_units_Z 1 _cell_measurement_reflns_used 411 _cell_measurement_temperature 298 _exptl_crystal_colour white _exptl_crystal_density_diffrn 5.6764 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 ? _pd_spec_mounting 'vanadium can' _pd_spec_mount_mode transmission _pd_spec_shape cylinder _diffrn_ambient_temperature 298 _diffrn_source_type 'Echidna (high resolution powder diffractometer) beamline' _diffrn_radiation_type Neutron _diffrn_radiation_wavelength 1.62200 _diffrn_measurement_device_type local _diffrn_detector '128 linear position sensitive detectors' _diffrn_radiation_monochromator 'Ge 335' _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 0 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 8 _pd_meas_scan_method fixed _pd_meas_number_of_points 3200 _pd_meas_2theta_range_min 4.00068 _pd_meas_2theta_range_max 163.94985 _pd_proc_ls_prof_R_factor 0.03477 _pd_proc_ls_prof_wR_factor 0.04358 _pd_proc_ls_prof_wR_expected 0.03060 _refine_ls_goodness_of_fit_all 1.424 _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_number_parameters 45 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_shift/su_max ? _pd_proc_2theta_range_min 10 _pd_proc_2theta_range_max 163.95 _pd_proc_wavelength 1.622 _pd_proc_info_excluded_regions "4 to 10 degrees unreliable due to background'" loop_ _symmetry_equiv_pos_as_xyz '-x, -y, -z' '-x, -y, z+1/2' '-x+y, -x, -z+1/2' '-x+y, -x, z' '-y, x-y, -z+1/2' '-y, x-y, z' 'y, -x+y, -z' 'y, -x+y, z+1/2' 'x-y, x, -z' 'x-y, x, z+1/2' 'x, y, -z+1/2' 'x, y, z' loop_ _atom_site_label _atom_site_type_symbol _atom_site_symmetry_multiplicity _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_B_iso_or_equiv La1 La 4 0.3333333 0.6666667 0.49803(47) 0.5611(42) 0.461(41) Sr1 Sr 4 0.3333333 0.6666667 0.49803(47) 0.4217(72) 0.461(41) La2 La 6 0.23088(22) -0.00936(28) 0.25 0.9478(48) 0.324(32) Sr2 Sr 6 0.23088(22) -0.00936(28) 0.25 0.0522(48) 0.324(32) Ge1 Ge 6 0.40031(25) 0.37236(21) 0.25 1 0.506(35) O1 O 6 0.31177(37) 0.48614(36) 0.25 1 ? O2 O 6 0.60378(33) 0.47648(36) 0.25 1 ? O3 O 12 0.33960(30) 0.24713(28) 0.06284(25) 1 ? O4 O 2 0 0 0.25 1 ? loop_ _atom_site_aniso_label _atom_site_type_aniso_symbol _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 O1 O 0.0196(17) 0.0084(16) 0.0086(15) 0.0112(15) 0 0 O2 O 0.0068(15) 0.0094(15) 0.0098(16) 0.0013(13) 0 0 O3 O 0.0318(18) 0.0158(13) 0.0101(10) 0.0126(11) -0.01122(95) -0.00367(90) O4 O 0.0191(17) 0.0191(17) 0.0239(29) 0.00954(87) 0 0 #==end data_La7.93Sr2Ge5.84V0.16O25.98 _database_code_depnum_ccdc_archive 'CCDC 838423' #TrackingRef '- Combined CIFS.cif' _chemical_name_mineral Apatite _chemical_formula_sum Ge5.84La7.93O26Sr2V0.16 _cell_length_a 9.90847(18) _cell_length_b 9.90847(18) _cell_length_c 7.32192(16) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 622.54(3) _chemical_formula_weight 2125.2(9) _symmetry_cell_setting hexagonal _symmetry_space_group_name_H-M P63/m _symmetry_space_group_name_Hall '-P 6c' _symmetry_Int_Tables_number 176 _cell_formula_units_Z 1 _cell_measurement_reflns_used 409 _cell_measurement_temperature 298 _exptl_crystal_colour yellow _exptl_crystal_density_diffrn 5.669(2) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 ? _pd_spec_mounting 'vanadium can' _pd_spec_mount_mode transmission _pd_spec_shape cylinder _diffrn_ambient_temperature 298 _diffrn_source_type 'Echidna (high resolution powder diffractometer) beamline' _diffrn_radiation_type Neutron _diffrn_radiation_wavelength 1.62200 _diffrn_measurement_device_type local _diffrn_detector '128 linear position sensitive detectors' _diffrn_radiation_monochromator 'Ge 335' _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 0 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 8 _pd_meas_scan_method fixed _pd_meas_number_of_points 3200 _pd_meas_2theta_range_min 4.00081 _pd_meas_2theta_range_max 163.94978 _pd_proc_ls_prof_R_factor 0.03381 _pd_proc_ls_prof_wR_factor 0.04219 _pd_proc_ls_prof_wR_expected 0.03041 _refine_ls_goodness_of_fit_all 1.388 _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_number_parameters 45 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_shift/su_max ? _pd_proc_2theta_range_min 10 _pd_proc_2theta_range_max 163.95 _pd_proc_wavelength 1.622 _pd_proc_info_excluded_regions "4 to 10 degrees unreliable due to background'" loop_ _symmetry_equiv_pos_as_xyz '-x, -y, -z' '-x, -y, z+1/2' '-x+y, -x, -z+1/2' '-x+y, -x, z' '-y, x-y, -z+1/2' '-y, x-y, z' 'y, -x+y, -z' 'y, -x+y, z+1/2' 'x-y, x, -z' 'x-y, x, z+1/2' 'x, y, -z+1/2' 'x, y, z' loop_ _atom_site_label _atom_site_type_symbol _atom_site_symmetry_multiplicity _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_B_iso_or_equiv La1 La 4 0.3333333 0.6666667 0.49836(47) 0.5337(46) 0.460(42) Sr1 Sr 4 0.3333333 0.6666667 0.49836(47) 0.4490(80) 0.460(42) La2 La 6 0.23105(22) -0.00949(27) 0.25 0.9660(53) 0.272(31) Sr2 Sr 6 0.23105(22) -0.00949(27) 0.25 0.0340(53) 0.272(31) Ge1 Ge 6 0.39993(26) 0.37230(21) 0.25 0.9741(66) 0.545(45) V1 V 6 0.39993(26) 0.37230(21) 0.25 0.0259(66) 0.545(45) O1 O 6 0.31032(36) 0.48475(36) 0.25 1 ? O2 O 6 0.60368(32) 0.47674(34) 0.25 1 ? O3 O 12 0.33901(30) 0.24651(27) 0.06358(25) 1 ? O4 O 2 0 0 0.25 1 ? loop_ _atom_site_aniso_label _atom_site_type_aniso_symbol _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 O1 O 0.0180(16) 0.0125(17) 0.0071(15) 0.0134(15) 0 0 O2 O 0.0037(14) 0.0069(14) 0.0134(16) -0.0008(12) 0 0 O3 O 0.0371(18) 0.0138(12) 0.00896(95) 0.0152(11) -0.00970(96) -0.00303(87) O4 O 0.0145(16) 0.0145(16) 0.0212(27) 0.00727(81) 0 0 #==end data_La7.99Sr2Ge5.58V0.42O26.20 _database_code_depnum_ccdc_archive 'CCDC 838424' #TrackingRef '- Combined CIFS.cif' _chemical_name_mineral Apatite _chemical_formula_sum Ge5.58La7.99O26Sr2V0.42 _cell_length_a 9.90941(13) _cell_length_b 9.90941(13) _cell_length_c 7.32414(15) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 622.85(2) _chemical_formula_weight 2127.6(9) _symmetry_cell_setting hexagonal _symmetry_space_group_name_H-M P63/m _symmetry_space_group_name_Hall '-P 6c' _symmetry_Int_Tables_number 176 _cell_formula_units_Z 1 _cell_measurement_reflns_used 413 _cell_measurement_temperature 298 _exptl_crystal_colour yellow _exptl_crystal_density_diffrn 5.669(2) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 ? _pd_spec_mounting 'vanadium can' _pd_spec_mount_mode transmission _pd_spec_shape cylinder _diffrn_ambient_temperature 298 _diffrn_source_type 'Echidna (high resolution powder diffractometer) beamline' _diffrn_radiation_type Neutron _diffrn_radiation_wavelength 1.62200 _diffrn_measurement_device_type local _diffrn_detector '128 linear position sensitive detectors' _diffrn_radiation_monochromator 'Ge 335' _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 0 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 8 _pd_meas_scan_method fixed _pd_meas_number_of_points 3200 _pd_meas_2theta_range_min 4.00068 _pd_meas_2theta_range_max 163.94985 _pd_proc_ls_prof_R_factor 0.03519 _pd_proc_ls_prof_wR_factor 0.04401 _pd_proc_ls_prof_wR_expected 0.03056 _refine_ls_goodness_of_fit_all 1.440 _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_number_parameters 45 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_shift/su_max ? _pd_proc_2theta_range_min 10 _pd_proc_2theta_range_max 163.95 _pd_proc_wavelength 1.622 _pd_proc_info_excluded_regions "4 to 10 degrees unreliable due to background'" loop_ _symmetry_equiv_pos_as_xyz '-x, -y, -z' '-x, -y, z+1/2' '-x+y, -x, -z+1/2' '-x+y, -x, z' '-y, x-y, -z+1/2' '-y, x-y, z' 'y, -x+y, -z' 'y, -x+y, z+1/2' 'x-y, x, -z' 'x-y, x, z+1/2' 'x, y, -z+1/2' 'x, y, z' loop_ _atom_site_label _atom_site_type_symbol _atom_site_symmetry_multiplicity _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_B_iso_or_equiv La1 La 4 0.3333333 0.6666667 0.49771(49) 0.5112(77) 0.456(43) Sr1 Sr 4 0.3333333 0.6666667 0.49771(49) 0.486(13) 0.456(43) La2 La 6 0.23039(24) -0.00964(29) 0.25 0.9906(89) 0.307(32) Sr2 Sr 6 0.23039(24) -0.00964(29) 0.25 0.0094(89) 0.307(32) Ge1 Ge 6 0.39933(28) 0.37229(23) 0.25 0.9308(69) 0.490(50) V1 V 6 0.39933(28) 0.37229(23) 0.25 0.0692(69) 0.490(50) O1 O 6 0.30984(38) 0.48461(38) 0.25 1 ? O2 O 6 0.60347(34) 0.47612(36) 0.25 1 ? O3 O 12 0.33932(33) 0.24688(28) 0.06397(27) 1 ? O4 O 2 0 0 0.25 1 ? loop_ _atom_site_aniso_label _atom_site_type_aniso_symbol _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 O1 O 0.0161(17) 0.0102(18) 0.0064(16) 0.0117(15) 0 0 O2 O 0.0044(15) 0.0047(15) 0.0129(17) -0.0015(13) 0 0 O3 O 0.0392(19) 0.0110(12) 0.0107(10) 0.0160(11) -0.0104(11) -0.00187(92) O4 O 0.0139(17) 0.0139(17) 0.0221(29) 0.00693(86) 0 0 #==end data_La7.8Ca2Ge6O25.7 _database_code_depnum_ccdc_archive 'CCDC 838425' #TrackingRef '- Combined CIFS.cif' _chemical_name_mineral Apatite _chemical_formula_sum Ca2Ge6La7.8O26 _cell_length_a 9.87089(15) _cell_length_b 9.87089(15) _cell_length_c 7.22428(17) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 609.59(2) _chemical_formula_weight 2013.950 _symmetry_cell_setting hexagonal _symmetry_space_group_name_H-M P63/m _symmetry_space_group_name_Hall '-P 6c' _symmetry_Int_Tables_number 176 _cell_formula_units_Z 1 _cell_measurement_reflns_used 407 _cell_measurement_temperature 298 _exptl_crystal_colour white _exptl_crystal_density_diffrn 5.4861(2) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 ? _pd_spec_mounting 'vanadium can' _pd_spec_mount_mode transmission _pd_spec_shape cylinder _diffrn_ambient_temperature 298 _diffrn_source_type 'Echidna (high resolution powder diffractometer) beamline' _diffrn_radiation_type Neutron _diffrn_radiation_wavelength 1.62200 _diffrn_measurement_device_type local _diffrn_detector '128 linear position sensitive detectors' _diffrn_radiation_monochromator 'Ge 335' _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 0 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 8 _pd_meas_scan_method fixed _pd_meas_number_of_points 3200 _pd_meas_2theta_range_min 4.00072 _pd_meas_2theta_range_max 163.94985 _pd_proc_ls_prof_R_factor 0.03585 _pd_proc_ls_prof_wR_factor 0.04535 _pd_proc_ls_prof_wR_expected 0.02973 _refine_ls_goodness_of_fit_all 1.526 _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_number_parameters 45 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_shift/su_max ? _pd_proc_2theta_range_min 10 _pd_proc_2theta_range_max 163.95 _pd_proc_wavelength 1.622 _pd_proc_info_excluded_regions "4 to 10 degrees unreliable due to background'" loop_ _symmetry_equiv_pos_as_xyz '-x, -y, -z' '-x, -y, z+1/2' '-x+y, -x, -z+1/2' '-x+y, -x, z' '-y, x-y, -z+1/2' '-y, x-y, z' 'y, -x+y, -z' 'y, -x+y, z+1/2' 'x-y, x, -z' 'x-y, x, z+1/2' 'x, y, -z+1/2' 'x, y, z' loop_ _atom_site_label _atom_site_type_symbol _atom_site_symmetry_multiplicity _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_B_iso_or_equiv La1 La 4 0.3333333 0.6666667 0.49938(55) 0.573(20) 0.803(67) Ca1 Ca 4 0.3333333 0.6666667 0.49938(55) 0.375(31) 0.803(67) La2 La 6 0.23112(26) -0.01151(32) 0.25 0.917(21) 0.500(39) Ca2 Ca 6 0.23112(26) -0.01151(32) 0.25 0.083(21) 0.500(39) Ge1 Ge 6 0.40211(27) 0.37352(26) 0.25 1 0.628(41) O1 O 6 0.31575(41) 0.49049(38) 0.25 1 ? O2 O 6 0.60643(40) 0.47511(41) 0.25 1 ? O3 O 12 0.34075(48) 0.25063(35) 0.06262(32) 1 ? O4 O 2 0 0 0.25 1 ? loop_ _atom_site_aniso_label _atom_site_type_aniso_symbol _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 O1 O 0.0369(23) 0.0167(19) 0.0024(16) 0.0251(19) 0 0 O2 O 0.0090(16) 0.0081(16) 0.0436(23) 0.0049(14) 0 0 O3 O 0.1025(33) 0.0205(16) 0.0176(14) 0.0414(19) -0.0297(15) -0.0089(12) O4 O 0.0123(21) 0.0123(21) 0.0666(58) 0.0062(11) 0 0 #==end data_La7.82Ca2Ge5.62V0.38O25.92 _database_code_depnum_ccdc_archive 'CCDC 838426' #TrackingRef '- Combined CIFS.cif' _chemical_name_mineral Apatite _chemical_formula_sum Ca2Ge5.62La7.82O26V0.38 _cell_length_a 9.86956(14) _cell_length_b 9.86956(14) _cell_length_c 7.22553(16) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 609.53(2) _chemical_formula_weight 2011.0(9) _symmetry_cell_setting hexagonal _symmetry_space_group_name_H-M P63/m _symmetry_space_group_name_Hall '-P 6c' _symmetry_Int_Tables_number 176 _cell_formula_units_Z 1 _cell_measurement_reflns_used 407 _cell_measurement_temperature 298 _exptl_crystal_colour yellow _exptl_crystal_density_diffrn 5.479(2) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 ? _pd_spec_mounting 'vanadium can' _pd_spec_mount_mode transmission _pd_spec_shape cylinder _diffrn_ambient_temperature 298 _diffrn_source_type 'Echidna (high resolution powder diffractometer) beamline' _diffrn_radiation_type Neutron _diffrn_radiation_wavelength 1.62200 _diffrn_measurement_device_type local _diffrn_detector '128 linear position sensitive detectors' _diffrn_radiation_monochromator 'Ge 335' _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 0 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 8 _pd_meas_scan_method fixed _pd_meas_number_of_points 3200 _pd_meas_2theta_range_min 4.00075 _pd_meas_2theta_range_max 163.94986 _pd_proc_ls_prof_R_factor 0.03554 _pd_proc_ls_prof_wR_factor 0.04447 _pd_proc_ls_prof_wR_expected 0.02988 _refine_ls_goodness_of_fit_all 1.489 _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_number_parameters 45 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_shift/su_max ? _pd_proc_2theta_range_min 10 _pd_proc_2theta_range_max 163.95 _pd_proc_wavelength 1.622 _pd_proc_info_excluded_regions "4 to 10 degrees unreliable due to background'" loop_ _symmetry_equiv_pos_as_xyz '-x, -y, -z' '-x, -y, z+1/2' '-x+y, -x, -z+1/2' '-x+y, -x, z' '-y, x-y, -z+1/2' '-y, x-y, z' 'y, -x+y, -z' 'y, -x+y, z+1/2' 'x-y, x, -z' 'x-y, x, z+1/2' 'x, y, -z+1/2' 'x, y, z' loop_ _atom_site_label _atom_site_type_symbol _atom_site_symmetry_multiplicity _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_B_iso_or_equiv La1 La 4 0.3333333 0.6666667 0.49805(54) 0.561(20) 1.119(68) Ca1 Ca 4 0.3333333 0.6666667 0.49805(54) 0.396(32) 1.119(68) La2 La 6 0.23113(24) -0.01084(30) 0.25 0.931(21) 0.599(40) Ca2 Ca 6 0.23113(24) -0.01084(30) 0.25 0.069(21) 0.599(40) Ge1 Ge 6 0.40297(27) 0.37411(26) 0.25 0.9369(70) 0.567(53) V1 V 6 0.40297(27) 0.37411(26) 0.25 0.0631(70) 0.567(53) O1 O 6 0.31692(40) 0.49089(38) 0.25 1 ? O2 O 6 0.60618(38) 0.47494(39) 0.25 1 ? O3 O 12 0.34115(45) 0.25076(35) 0.06283(31) 1 ? O4 O 2 0 0 0.25 1 ? loop_ _atom_site_aniso_label _atom_site_type_aniso_symbol _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 O1 O 0.0370(22) 0.0224(19) 0.0081(16) 0.0268(18) 0 0 O2 O 0.0069(15) 0.0060(15) 0.0458(22) 0.0019(13) 0 0 O3 O 0.1004(31) 0.0251(16) 0.0177(13) 0.0409(18) -0.0309(14) -0.0096(12) O4 O 0.0072(19) 0.0072(19) 0.0786(57) 0.00359(94) 0 0 #==end data_La7.88Ca2Ge5.35V0.65O26.15 _database_code_depnum_ccdc_archive 'CCDC 838427' #TrackingRef '- Combined CIFS.cif' _chemical_name_mineral Apatite _chemical_formula_sum Ca2Ge5.35La7.88O26V0.65 _cell_length_a 9.87087(16) _cell_length_b 9.87087(16) _cell_length_c 7.22604(19) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 609.74(3) _chemical_formula_weight 2011(1) _symmetry_cell_setting hexagonal _symmetry_space_group_name_H-M P63/m _symmetry_space_group_name_Hall '-P 6c' _symmetry_Int_Tables_number 176 _cell_formula_units_Z 1 _cell_measurement_reflns_used 406 _cell_measurement_temperature 298 _exptl_crystal_colour yellow _exptl_crystal_density_diffrn 5.477(3) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 ? _pd_spec_mounting 'vanadium can' _pd_spec_mount_mode transmission _pd_spec_shape cylinder _diffrn_ambient_temperature 298 _diffrn_source_type 'Echidna (high resolution powder diffractometer) beamline' _diffrn_radiation_type Neutron _diffrn_radiation_wavelength 1.62200 _diffrn_measurement_device_type local _diffrn_detector '128 linear position sensitive detectors' _diffrn_radiation_monochromator 'Ge 335' _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 0 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 8 _pd_meas_scan_method fixed _pd_meas_number_of_points 3200 _pd_meas_2theta_range_min 4.00071 _pd_meas_2theta_range_max 163.94989 _pd_proc_ls_prof_R_factor 0.04186 _pd_proc_ls_prof_wR_factor 0.05272 _pd_proc_ls_prof_wR_expected 0.03723 _refine_ls_goodness_of_fit_all 1.416 _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_number_parameters 45 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_shift/su_max ? _pd_proc_2theta_range_min 10 _pd_proc_2theta_range_max 163.95 _pd_proc_wavelength 1.622 _pd_proc_info_excluded_regions "4 to 10 degrees unreliable due to background'" loop_ _symmetry_equiv_pos_as_xyz '-x, -y, -z' '-x, -y, z+1/2' '-x+y, -x, -z+1/2' '-x+y, -x, z' '-y, x-y, -z+1/2' '-y, x-y, z' 'y, -x+y, -z' 'y, -x+y, z+1/2' 'x-y, x, -z' 'x-y, x, z+1/2' 'x, y, -z+1/2' 'x, y, z' loop_ _atom_site_label _atom_site_type_symbol _atom_site_symmetry_multiplicity _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_B_iso_or_equiv La1 La 4 0.3333333 0.6666667 0.49978(68) 0.563(23) 1.247(84) Ca1 Ca 4 0.3333333 0.6666667 0.49978(68) 0.405(36) 1.247(84) La2 La 6 0.23095(30) -0.01082(38) 0.25 0.937(24) 0.763(49) Ca2 Ca 6 0.23095(30) -0.01082(38) 0.25 0.063(24) 0.763(49) Ge1 Ge 6 0.40214(35) 0.37411(33) 0.25 0.8909(82) 0.562(67) V1 V 6 0.40214(35) 0.37411(33) 0.25 0.1091(82) 0.562(67) O1 O 6 0.31645(49) 0.49086(47) 0.25 1 ? O2 O 6 0.60612(49) 0.47430(49) 0.25 1 ? O3 O 12 0.34159(54) 0.25144(41) 0.06366(38) 1 ? O4 O 2 0 0 0.25 1 ? loop_ _atom_site_aniso_label _atom_site_type_aniso_symbol _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 O1 O 0.0403(27) 0.0237(24) 0.0056(19) 0.0286(23) 0 0 O2 O 0.0106(19) 0.0093(19) 0.0507(29) 0.0064(16) 0 0 O3 O 0.1065(38) 0.0230(19) 0.0174(15) 0.0401(22) -0.0288(17) -0.0046(14) O4 O 0.0075(24) 0.0075(24) 0.1013(82) 0.0038(12) 0 0 #==end data_La7.88Ba2Ge6O25.82 _database_code_depnum_ccdc_archive 'CCDC 838428' #TrackingRef '- Combined CIFS.cif' _chemical_name_mineral Apatite _chemical_formula_sum Ba2Ge6La7.88O26 _cell_length_a 9.97963(16) _cell_length_b 9.97963(16) _cell_length_c 7.41046(17) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 639.15(3) _chemical_formula_weight 2220.390 _symmetry_cell_setting hexagonal _symmetry_space_group_name_H-M P63/m _symmetry_space_group_name_Hall '-P 6c' _symmetry_Int_Tables_number 176 _cell_formula_units_Z 1 _cell_measurement_reflns_used 427 _cell_measurement_temperature 298 _exptl_crystal_colour white _exptl_crystal_density_diffrn 5.7686(2) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 ? _pd_spec_mounting 'vanadium can' _pd_spec_mount_mode transmission _pd_spec_shape cylinder _diffrn_ambient_temperature 298 _diffrn_source_type 'Echidna (high resolution powder diffractometer) beamline' _diffrn_radiation_type Neutron _diffrn_radiation_wavelength 1.62200 _diffrn_measurement_device_type local _diffrn_detector '128 linear position sensitive detectors' _diffrn_radiation_monochromator 'Ge 335' _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 0 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 8 _pd_meas_scan_method fixed _pd_meas_number_of_points 3200 _pd_meas_2theta_range_min 4.00067 _pd_meas_2theta_range_max 163.94984 _pd_proc_ls_prof_R_factor 0.03602 _pd_proc_ls_prof_wR_factor 0.04522 _pd_proc_ls_prof_wR_expected 0.03059 _refine_ls_goodness_of_fit_all 1.478 _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_number_parameters 45 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_shift/su_max ? _pd_proc_2theta_range_min 10 _pd_proc_2theta_range_max 163.95 _pd_proc_wavelength 1.622 _pd_proc_info_excluded_regions "4 to 10 degrees unreliable due to background'" loop_ _symmetry_equiv_pos_as_xyz '-x, -y, -z' '-x, -y, z+1/2' '-x+y, -x, -z+1/2' '-x+y, -x, z' '-y, x-y, -z+1/2' '-y, x-y, z' 'y, -x+y, -z' 'y, -x+y, z+1/2' 'x-y, x, -z' 'x-y, x, z+1/2' 'x, y, -z+1/2' 'x, y, z' loop_ _atom_site_label _atom_site_type_symbol _atom_site_symmetry_multiplicity _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_B_iso_or_equiv La1 La 4 0.3333333 0.6666667 0.50138(52) 0.601(19) 0.545(55) Ba1 Ba 4 0.3333333 0.6666667 0.50138(52) 0.369(29) 0.545(55) La2 La 6 0.23126(29) -0.00863(33) 0.25 0.912(19) 0.768(41) Ba2 Ba 6 0.23126(29) -0.00863(33) 0.25 0.088(19) 0.768(41) Ge1 Ge 6 0.39777(27) 0.37036(23) 0.25 1 0.626(45) O1 O 6 0.30937(49) 0.48421(49) 0.25 1 ? O2 O 6 0.60047(41) 0.47870(48) 0.25 1 ? O3 O 12 0.33896(38) 0.24663(34) 0.06412(30) 1 ? O4 O 2 0 0 0.25 1 ? loop_ _atom_site_aniso_label _atom_site_type_aniso_symbol _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 O1 O 0.0399(27) 0.0221(25) 0.0245(24) 0.0255(23) 0 0 O2 O 0.0158(19) 0.0141(18) 0.0347(24) -0.0009(16) 0 0 O3 O 0.0499(23) 0.0243(14) 0.0143(13) 0.0231(15) -0.0188(14) -0.0088(11) O4 O 0.0188(22) 0.0188(22) 0.0773(64) 0.0094(11) 0 0 #==end data_La7.88Ba2Ge5.66V0.34O25.99 _database_code_depnum_ccdc_archive 'CCDC 838429' #TrackingRef '- Combined CIFS.cif' _chemical_name_mineral Apatite _chemical_formula_sum Ba2Ge5.66La7.88O26v0.34 _cell_length_a 9.97623(15) _cell_length_b 9.97623(15) _cell_length_c 7.41273(16) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 638.91(2) _chemical_formula_weight 2214.2(9) _symmetry_cell_setting hexagonal _symmetry_space_group_name_H-M P63/m _symmetry_space_group_name_Hall '-P 6c' _symmetry_Int_Tables_number 176 _cell_formula_units_Z 1 _cell_measurement_reflns_used 425 _cell_measurement_temperature 298 _exptl_crystal_colour yellow _exptl_crystal_density_diffrn 5.755(2) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 ? _pd_spec_mounting 'vanadium can' _pd_spec_mount_mode transmission _pd_spec_shape cylinder _diffrn_ambient_temperature 298 _diffrn_source_type 'Echidna (high resolution powder diffractometer) beamline' _diffrn_radiation_type Neutron _diffrn_radiation_wavelength 1.62200 _diffrn_measurement_device_type local _diffrn_detector '128 linear position sensitive detectors' _diffrn_radiation_monochromator 'Ge 335' _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 0 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 8 _pd_meas_scan_method fixed _pd_meas_number_of_points 3200 _pd_meas_2theta_range_min 4.00067 _pd_meas_2theta_range_max 163.94988 _pd_proc_ls_prof_R_factor 0.03543 _pd_proc_ls_prof_wR_factor 0.04426 _pd_proc_ls_prof_wR_expected 0.03064 _refine_ls_goodness_of_fit_all 1.444 _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_number_parameters 45 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_shift/su_max ? _pd_proc_2theta_range_min 10 _pd_proc_2theta_range_max 163.95 _pd_proc_wavelength 1.622 _pd_proc_info_excluded_regions "4 to 10 degrees unreliable due to background'" loop_ _symmetry_equiv_pos_as_xyz '-x, -y, -z' '-x, -y, z+1/2' '-x+y, -x, -z+1/2' '-x+y, -x, z' '-y, x-y, -z+1/2' '-y, x-y, z' 'y, -x+y, -z' 'y, -x+y, z+1/2' 'x-y, x, -z' 'x-y, x, z+1/2' 'x, y, -z+1/2' 'x, y, z' loop_ _atom_site_label _atom_site_type_symbol _atom_site_symmetry_multiplicity _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_B_iso_or_equiv La1 La 4 0.3333333 0.6666667 0.50052(52) 0.582(19) 0.586(54) Ba1 Ba 4 0.3333333 0.6666667 0.50052(52) 0.390(29) 0.586(54) La2 La 6 0.23018(28) -0.00961(32) 0.25 0.926(19) 0.777(40) Ba2 Ba 6 0.23018(28) -0.00961(32) 0.25 0.074(19) 0.777(40) Ge1 Ge 6 0.39677(27) 0.37031(23) 0.25 0.9438(70) 0.497(54) V1 V 6 0.39677(27) 0.37031(23) 0.25 0.0562(70) 0.497(54) O1 O 6 0.30758(47) 0.48332(47) 0.25 1 ? O2 O 6 0.59827(40) 0.47805(47) 0.25 1 ? O3 O 12 0.33858(37) 0.24625(33) 0.06485(30) 1 ? O4 O 2 0 0 0.25 1 ? loop_ _atom_site_aniso_label _atom_site_type_aniso_symbol _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 O1 O 0.0400(26) 0.0191(23) 0.0261(24) 0.0247(21) 0 0 O2 O 0.0171(18) 0.0153(19) 0.0317(23) 0.0013(16) 0 0 O3 O 0.0517(23) 0.0213(14) 0.0168(13) 0.0227(15) -0.0170(14) -0.0067(10) O4 O 0.0186(22) 0.0186(22) 0.0732(60) 0.0093(11) 0 0 #==end data_La7.67Ba2Ge5.29V0.71O25.86 _database_code_depnum_ccdc_archive 'CCDC 838430' #TrackingRef '- Combined CIFS.cif' _chemical_name_mineral Apatite _chemical_formula_sum Ba2Ge5.29La7.67O26v0.71 _cell_length_a 9.97861(17) _cell_length_b 9.97861(17) _cell_length_c 7.41128(18) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 639.09(3) _chemical_formula_weight 2175.7(9) _symmetry_cell_setting hexagonal _symmetry_space_group_name_H-M P63/m _symmetry_space_group_name_Hall '-P 6c' _symmetry_Int_Tables_number 176 _cell_formula_units_Z 1 _cell_measurement_reflns_used 424 _cell_measurement_temperature 298 _exptl_crystal_colour yellow _exptl_crystal_density_diffrn 5.653(2) _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 ? _pd_spec_mounting 'vanadium can' _pd_spec_mount_mode transmission _pd_spec_shape cylinder _diffrn_ambient_temperature 298 _diffrn_source_type 'Echidna (high resolution powder diffractometer) beamline' _diffrn_radiation_type Neutron _diffrn_radiation_wavelength 1.62200 _diffrn_measurement_device_type local _diffrn_detector '128 linear position sensitive detectors' _diffrn_radiation_monochromator 'Ge 335' _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 0 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 8 _pd_meas_scan_method fixed _pd_meas_number_of_points 3200 _pd_meas_2theta_range_min 4.00071 _pd_meas_2theta_range_max 163.94981 _pd_proc_ls_prof_R_factor 0.03612 _pd_proc_ls_prof_wR_factor 0.04522 _pd_proc_ls_prof_wR_expected 0.02979 _refine_ls_goodness_of_fit_all 1.518 _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_number_parameters 45 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_shift/su_max ? _pd_proc_2theta_range_min 10 _pd_proc_2theta_range_max 163.95 _pd_proc_wavelength 1.622 _pd_proc_info_excluded_regions "4 to 10 degrees unreliable due to background'" loop_ _symmetry_equiv_pos_as_xyz '-x, -y, -z' '-x, -y, z+1/2' '-x+y, -x, -z+1/2' '-x+y, -x, z' '-y, x-y, -z+1/2' '-y, x-y, z' 'y, -x+y, -z' 'y, -x+y, z+1/2' 'x-y, x, -z' 'x-y, x, z+1/2' 'x, y, -z+1/2' 'x, y, z' loop_ _atom_site_label _atom_site_type_symbol _atom_site_symmetry_multiplicity _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_B_iso_or_equiv La1 La 4 0.3333333 0.6666667 0.50068(57) 0.609(20) 0.621(59) Ba1 Ba 4 0.3333333 0.6666667 0.50068(57) 0.307(30) 0.621(59) La2 La 6 0.23076(31) -0.00871(36) 0.25 0.872(20) 0.818(44) Ba2 Ba 6 0.23076(31) -0.00871(36) 0.25 0.128(20) 0.818(44) Ge1 Ge 6 0.39729(31) 0.37062(26) 0.25 0.8820(72) 0.493(62) V1 V 6 0.39729(31) 0.37062(26) 0.25 0.1180(72) 0.493(62) O1 O 6 0.30753(52) 0.48287(51) 0.25 1 ? O2 O 6 0.59979(45) 0.47773(52) 0.25 1 ? O3 O 12 0.33857(41) 0.24663(37) 0.06550(33) 1 ? O4 O 2 0 0 0.25 1 ? loop_ _atom_site_aniso_label _atom_site_type_aniso_symbol _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 O1 O 0.0438(29) 0.0202(26) 0.0286(27) 0.0245(23) 0 0 O2 O 0.0220(22) 0.0158(21) 0.0389(27) -0.0001(18) 0 0 O3 O 0.0579(26) 0.0265(16) 0.0171(14) 0.0253(17) -0.0194(15) -0.0072(12) O4 O 0.0213(26) 0.0213(26) 0.0986(81) 0.0107(13) 0 0 #==end