# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_coden_Cambridge 222 _journal_volume ? _journal_page_first ? _journal_year ? loop_ _publ_author_name 'Tom Baikie' 'Kevin Blake' 'Margaret M. Elcombe' 'S. Madhavi' 'George M. H. Ng' 'Stevin Pramana' 'T. J. White' _publ_contact_author_name 'Tom Baikie' _publ_contact_author_email TBAIKIE@NTU.EDU.SG _publ_section_title ; The Crystal Chemistry of the Alkaline Earth Apatites A10(PO4)6CuxOy(H)z (A = Ca, Sr and Ba) ; # Attachment 'Combined CIFS - B906639J.cif' data_Ca10(PO4)6Cu0.2O0.56(OH)1.28 _database_code_depnum_ccdc_archive 'CCDC 726699' _chemical_name_mineral Ca10(PO4)6Cu0.2O0.56(OH)1.28 _cell_length_a 9.4145(1) _cell_length_b 9.4145(1) _cell_length_c 6.8811(1) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 528.18(1) _chemical_formula_weight 1014.06 _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 255 _cell_measurement_temperature 298 _exptl_crystal_density_diffrn 3.188 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 37.1 _pd_spec_mounting 'vanadium can with He exchange gas' _pd_spec_mount_mode reflection _pd_spec_shape cylinder _diffrn_ambient_temperature 298 _diffrn_source_type 'HIFAR beamline HRPD' _diffrn_radiation_type neutron _diffrn_radiation_wavelength 1.883 _diffrn_measurement_device_type local _diffrn_detector 'He~3~ detector' _diffrn_radiation_monochromator 'Ge 115' _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 7 _pd_meas_scan_method fixed _pd_meas_number_of_points 3001 _pd_meas_2theta_range_min 0.027 _pd_meas_2theta_range_max 150.027 _pd_proc_ls_prof_R_factor 0.0522 _pd_proc_ls_prof_wR_factor 0.0685 _pd_proc_ls_prof_wR_expected 0.1269 _refine_ls_goodness_of_fit_all 0.54 _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_number_parameters 36 _refine_ls_number_restraints 1 _refine_ls_number_constraints 0 _pd_proc_2theta_range_min 10 _pd_proc_2theta_range_max 150 _pd_proc_wavelength 1.883 _pd_proc_info_excluded_regions '0.027 to 10 degrees unreliable due to background' _computing_data_collection 'Shimadzu XRD 6000' _computing_cell_refinement 'TOPAS (Bruker, 2005)' _computing_data_reduction 'TOPAS (Bruker, 2005)' _computing_structure_solution 'TOPAS (Bruker, 2005)' _computing_structure_refinement 'TOPAS (Bruker, 2005)' _computing_molecular_graphics ;ATOMS (Shape, 2004), GFOURIER (Gonzales-Platas, J. & Rodriguez-Carvajal, J. (2006) ; loop_ _atom_type_symbol _atom_type_scat_length_neutron _atom_type_scat_source Ca 4.700 'International Tables for Crystallography Volume C' P 5.130 'International Tables for Crystallography Volume C' O 5.805 'International Tables for Crystallography Volume C' Cu 7.718 'International Tables for Crystallography Volume C' H -3.739 'International Tables for Crystallography Volume C' 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 Ca1 Ca 4 0.3333333 0.6666667 -0.0024(7) 1 0.68(9) Ca2 Ca 6 0.2521(5) 0.0071(5) 0.25 1 0.58(8) P1 P 6 0.3684(4) 0.3986(5) 0.25 1 0.41(7) O1 O 6 0.4846(4) 0.3281(4) 0.25 1 0.52(7) O2 O 6 0.4668(5) 0.5888(4) 0.25 1 1.15(8) O3 O 12 0.2584(3) 0.3441(3) 0.0708(3) 1 1.25(5) O4 O 4 0 0 0.2016(4) 0.46(1) 0.6(2) Cu1 Cu 2 0 0 0 0.10(1) 0.6(2) H H 4 0 0 -0.0539(3) 0.32(1) 1 #===END data_Ca10(PO4)6Cu0.6O1.20(OH)0.80 _database_code_depnum_ccdc_archive 'CCDC 726700' _chemical_name_mineral Ca10(PO4)6Cu0.6O1.20(OH)0.80 _cell_length_a 9.4262(1) _cell_length_b 9.4262(1) _cell_length_c 6.9003(1) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 530.97(1) _chemical_formula_weight 1041.56 __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 255 _cell_measurement_temperature 298 _exptl_crystal_density_diffrn 3.253 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 37.1 _pd_spec_mounting 'vanadium can with He exchange gas' _pd_spec_mount_mode reflection _pd_spec_shape cylinder _diffrn_ambient_temperature 298 _diffrn_source_type 'HIFAR beamline HRPD' _diffrn_radiation_type neutron _diffrn_radiation_wavelength 1.883 _diffrn_measurement_device_type local _diffrn_detector 'He~3~ detector' _diffrn_radiation_monochromator 'Ge 115' _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 7 _pd_meas_scan_method fixed _pd_meas_number_of_points 3001 _pd_meas_2theta_range_min 0.027 _pd_meas_2theta_range_max 150.027 _pd_proc_ls_prof_R_factor 0.0535 _pd_proc_ls_prof_wR_factor 0.0689 _pd_proc_ls_prof_wR_expected 0.1315 _refine_ls_goodness_of_fit_all 0.52 _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_number_parameters 37 _refine_ls_number_restraints 1 _refine_ls_number_constraints 0 _pd_proc_2theta_range_min 10 _pd_proc_2theta_range_max 150 _pd_proc_wavelength 1.883 _pd_proc_info_excluded_regions '0.027 to 10 degrees unreliable due to background' _computing_data_collection 'Shimadzu XRD 6000' _computing_cell_refinement 'TOPAS (Bruker, 2005)' _computing_data_reduction 'TOPAS (Bruker, 2005)' _computing_structure_solution 'TOPAS (Bruker, 2005)' _computing_structure_refinement 'TOPAS (Bruker, 2005)' _computing_molecular_graphics ;ATOMS (Shape, 2004), GFOURIER (Gonzales-Platas, J. & Rodriguez-Carvajal, J. (2006) ; loop_ _atom_type_symbol _atom_type_scat_length_neutron _atom_type_scat_source Ca 4.700 'International Tables for Crystallography Volume C' P 5.130 'International Tables for Crystallography Volume C' O 5.805 'International Tables for Crystallography Volume C' Cu 7.718 'International Tables for Crystallography Volume C' H -3.739 'International Tables for Crystallography Volume C' 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 Ca1 Ca 4 0.3333333 0.6666667 -0.0029(7) 1 1.02(9) Ca2 Ca 6 0.2549(5) 0.0080(5) 0.25 1 0.64(8) P1 P 6 0.3696(4) 0.3999(5) 0.25 1 0.56(7) O1 O 6 0.4846(4) 0.3292(4) 0.25 1 0.43(7) O2 O 6 0.4667(5) 0.5890(4) 0.25 1 1.16(8) O3 O 12 0.2589(3) 0.3455(3) 0.0712(3) 1 1.26(5) O4 O 4 0 0 0.2058(12) 0.50(1) 0.7(2) Cu1 Cu 2 0 0 0 0.30(1) 0.7(2) H H 4 0 0 -0.043(6) 0.20(1) 1 #===END data_Ca10(PO4)6Cu0.72O1.44(OH)0.56 _database_code_depnum_ccdc_archive 'CCDC 726701' _chemical_name_mineral Ca10(PO4)6Cu0.72O1.44(OH)0.56 _cell_length_a 9.4392(2) _cell_length_b 9.4392(2) _cell_length_c 6.9166(1) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 533.702(19) _chemical_formula_weight 1048.94 __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 255 _cell_measurement_temperature 298 _exptl_crystal_density_diffrn 3.264 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 37.1 _pd_spec_mounting 'vanadium can with He exchange gas' _pd_spec_mount_mode reflection _pd_spec_shape cylinder _diffrn_ambient_temperature 298 _diffrn_source_type 'HIFAR beamline HRPD' _diffrn_radiation_type neutron _diffrn_radiation_wavelength 1.883 _diffrn_measurement_device_type local _diffrn_detector 'He~3~ detector' _diffrn_radiation_monochromator 'Ge 115' _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 7 _pd_meas_scan_method fixed _pd_meas_number_of_points 3001 _pd_meas_2theta_range_min 0.027 _pd_meas_2theta_range_max 150.027 _pd_proc_ls_prof_R_factor 0.0578 _pd_proc_ls_prof_wR_factor 0.0739 _pd_proc_ls_prof_wR_expected 0.1392 _refine_ls_goodness_of_fit_all 0.53 _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_number_parameters 37 _refine_ls_number_restraints 1 _refine_ls_number_constraints 0 _pd_proc_2theta_range_min 10 _pd_proc_2theta_range_max 150 _pd_proc_wavelength 1.883 _pd_proc_info_excluded_regions '0.027 to 10 degrees unreliable due to background' _computing_data_collection 'Shimadzu XRD 6000' _computing_cell_refinement 'TOPAS (Bruker, 2005)' _computing_data_reduction 'TOPAS (Bruker, 2005)' _computing_structure_solution 'TOPAS (Bruker, 2005)' _computing_structure_refinement 'TOPAS (Bruker, 2005)' _computing_molecular_graphics ;ATOMS (Shape, 2004), GFOURIER (Gonzales-Platas, J. & Rodriguez-Carvajal, J. (2006) ; loop_ _atom_type_symbol _atom_type_scat_length_neutron _atom_type_scat_source Ca 4.700 'International Tables for Crystallography Volume C' P 5.130 'International Tables for Crystallography Volume C' O 5.805 'International Tables for Crystallography Volume C' Cu 7.718 'International Tables for Crystallography Volume C' H -3.739 'International Tables for Crystallography Volume C' 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 Ca1 Ca 4 0.3333333 0.6666667 -0.0015(8) 1 0.9(1) Ca2 Ca 6 0.2554(6) 0.0080(6) 0.25 1 0.6(1) P1 P 6 0.3697(5) 0.3994(5) 0.25 1 0.5(1) O1 O 6 0.4850(5) 0.3293(4) 0.25 1 0.4(1) O2 O 6 0.4661(5) 0.5891(5) 0.25 1 1.4(1) O3 O 12 0.2589(4) 0.3463(4) 0.0704(3) 1 1.2(1) O4 O 4 0 0 0.2111(16) 0.50(1) 1.3(2) Cu1 Cu 2 0 0 0 0.36(1) 1.3(2) H H 4 0 0 0.0472(7) 0.14(1) 1 #===END data_Sr10(PO4)6Cu0.88O1.76(OH)0.24 _database_code_depnum_ccdc_archive 'CCDC 726702' _chemical_name_mineral Sr10(PO4)6Cu0.88O1.76(OH)0.24 _cell_length_a 9.7952(1) _cell_length_b 9.7952(1) _cell_length_c 7.2931(1) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 606.0(2) _chemical_formula_weight 1534.18 _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 255 _cell_measurement_temperature 298 _exptl_crystal_density_diffrn 4.204 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 41.1 _pd_spec_mounting 'vanadium can with He exchange gas' _pd_spec_mount_mode reflection _pd_spec_shape cylinder _diffrn_ambient_temperature 298 _diffrn_source_type 'HIFAR beamline HRPD' _diffrn_radiation_type neutron _diffrn_radiation_wavelength 1.883 _diffrn_measurement_device_type local _diffrn_detector 'He~3~ detector' _diffrn_radiation_monochromator 'Ge 115' _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 7 _pd_meas_scan_method fixed _pd_meas_number_of_points 3001 _pd_meas_2theta_range_min 0.027 _pd_meas_2theta_range_max 150.027 _pd_proc_ls_prof_R_factor 0.0454 _pd_proc_ls_prof_wR_factor 0.0595 _pd_proc_ls_prof_wR_expected 0.1058 _refine_ls_goodness_of_fit_all 0.56 _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_number_parameters 37 _refine_ls_number_restraints 1 _refine_ls_number_constraints 0 _pd_proc_2theta_range_min 10 _pd_proc_2theta_range_max 150 _pd_proc_wavelength 1.883 _pd_proc_info_excluded_regions '0.027 to 10 degrees unreliable due to background' _computing_data_collection 'Shimadzu XRD 6000' _computing_cell_refinement 'TOPAS (Bruker, 2005)' _computing_data_reduction 'TOPAS (Bruker, 2005)' _computing_structure_solution 'TOPAS (Bruker, 2005)' _computing_structure_refinement 'TOPAS (Bruker, 2005)' _computing_molecular_graphics ;ATOMS (Shape, 2004), GFOURIER (Gonzales-Platas, J. & Rodriguez-Carvajal, J. (2006) ; loop_ _atom_type_symbol _atom_type_scat_length_neutron _atom_type_scat_source Sr 7.072 'International Tables for Crystallography Volume C' P 5.130 'International Tables for Crystallography Volume C' O 5.805 'International Tables for Crystallography Volume C' Cu 7.718 'International Tables for Crystallography Volume C' H -3.739 'International Tables for Crystallography Volume C' 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 Sr1 Sr 4 0.3333333 0.6666667 -0.0024(6) 1 0.51(8) Sr2 Sr 6 0.2609(4) 0.0150(4) 0.25 1 0.67(7) P1 P 6 0.3675(5) 0.4008(5) 0.25 1 0.32(9) O1 O 6 0.4826(5) 0.3347(4) 0.25 1 0.82(8) O2 O 6 0.4616(5) 0.5828(5) 0.25 1 1.09(8) O3 O 12 0.2624(4) 0.3482(4) 0.0790(4) 1 1.03(7) O4 O 4 0 0 0.2150(4) 0.5 1.8(2) Cu1 Cu 2 0 0 0 0.44(1) 1.8(2) H H 4 0 0 0.041(2) 0.058 1 #===END data_Ba10(PO4)6Cu0.90O1.80(OH)0.20 _database_code_depnum_ccdc_archive 'CCDC 726703' _chemical_name_mineral Ba10(PO4)6Cu0.90O1.80(OH)0.20 _cell_length_a 10.2168(2) _cell_length_b 10.2168(2) _cell_length_c 7.7347(2) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 699.20(3) _chemical_formula_weight 2032.92 _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 255 _cell_measurement_temperature 298 _exptl_crystal_density_diffrn 4.828 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 37.4 _pd_spec_mounting 'vanadium can with He exchange gas' _pd_spec_mount_mode reflection _pd_spec_shape cylinder _diffrn_ambient_temperature 298 _diffrn_source_type 'HIFAR beamline HRPD' _diffrn_radiation_type neutron _diffrn_radiation_wavelength 1.883 _diffrn_measurement_device_type local _diffrn_detector 'He~3~ detector' _diffrn_radiation_monochromator 'Ge 115' _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 7 _pd_meas_scan_method fixed _pd_meas_number_of_points 3001 _pd_meas_2theta_range_min 0.027 _pd_meas_2theta_range_max 150.027 _pd_proc_ls_prof_R_factor 0.0620 _pd_proc_ls_prof_wR_factor 0.0803 _pd_proc_ls_prof_wR_expected 0.1445 _refine_ls_goodness_of_fit_all 0.56 _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_number_parameters 36 _refine_ls_number_restraints 1 _refine_ls_number_constraints 0 _pd_proc_2theta_range_min 10 _pd_proc_2theta_range_max 150 _pd_proc_wavelength 1.883 _pd_proc_info_excluded_regions '0.027 to 10 degrees unreliable due to background' _computing_data_collection 'Shimadzu XRD 6000' _computing_cell_refinement 'TOPAS (Bruker, 2005)' _computing_data_reduction 'TOPAS (Bruker, 2005)' _computing_structure_solution 'TOPAS (Bruker, 2005)' _computing_structure_refinement 'TOPAS (Bruker, 2005)' _computing_molecular_graphics ;ATOMS (Shape, 2004), GFOURIER (Gonzales-Platas, J. & Rodriguez-Carvajal, J. (2006) ; loop_ _atom_type_symbol _atom_type_scat_length_neutron _atom_type_scat_source Ba 5.070 'International Tables for Crystallography Volume C' P 5.130 'International Tables for Crystallography Volume C' O 5.805 'International Tables for Crystallography Volume C' Cu 7.718 'International Tables for Crystallography Volume C' H -3.739 'International Tables for Crystallography Volume C' 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 Ba1 Ba 4 0.3333333 0.6666667 0.0017(8) 1 0.7(1) Ba2 Ba 6 0.2629(6) 0.0176(6) 0.25 1 0.9(1) P1 P 6 0.3689(5) 0.4026(6) 0.25 1 0.8(1) O1 O 6 0.4796(5) 0.3412(5) 0.25 1 1.2(1) O2 O 6 0.4578(5) 0.5774(5) 0.25 1 1.0(1) O3 O 12 0.2670(4) 0.3478(4) 0.0886(4) 1 1.4(1) O4 O 4 0 0 0.196(2) 0.50(1) 3.4(4) Cu1 Cu 2 0 0 0 0.4544 3.4(4) H H 4 0 0 0.0002(4) 0.05(1) 1 #===END