# Supplementary Material (ESI) for Dalton Transactions
# This journal is (c) The Royal Society of Chemistry 2010

data_global

_journal_coden_Cambridge         222

loop_
_publ_author_name
'Hou Ran Low'
'Clemens Ritter'
'T J White'

_publ_contact_author_name        'Hou Ran Low'
_publ_contact_author_email       HRLOW@NTU.EDU.SG

_publ_section_title              
;
Crystal Structures of Ferric Carbonate-Hydroxyapatite-2H
and 2M Pseudomorphs
;

# Attachment 'Fe-ap.cif'

data_Ca9.77Fe0.1P5.8O25.12H1.92C0.28O0.84
_database_code_depnum_ccdc_archive 'CCDC 763319'
#TrackingRef 'Fe-ap.cif'

_chemical_formula_sum            'Ca9.77 H1.92 Fe0.13 O25.96 P5.8 C0.28'
_chemical_name_mineral           
;
Apatite
;
_chemical_formula_weight         999.282
_symmetry_cell_setting           hexagonal
_symmetry_int_tables_number      176
_symmetry_space_group_name_H-M   'P 63/m'
_symmetry_space_group_name_Hall  -P_6c
loop_
_symmetry_equiv_pos_site_id
_symmetry_equiv_pos_as_xyz
1 '-x, -y, -z'
2 '-x, -y, z+1/2'
3 '-x+y, -x, -z+1/2'
4 '-x+y, -x, z'
5 '-y, x-y, -z+1/2'
6 '-y, x-y, z'
7 'y, -x+y, -z'
8 'y, -x+y, z+1/2'
9 'x-y, x, -z'
10 'x-y, x, z+1/2'
11 'x, y, -z+1/2'
12 'x, y, z'
_cell_length_a                   9.37109(96)
_cell_length_b                   9.37109(96)
_cell_length_c                   6.8367(11)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     519.94(13)

_cell_formula_units_Z            1
_cell_measurement_reflns_used    482
_cell_measurement_temperature    300

_exptl_crystal_density_diffrn    3.182
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             32.0
_exptl_absorpt_coefficient_mu    'not measured'

_pd_spec_mounting                'vanadium can'
_pd_spec_mount_mode              reflection
_pd_spec_shape                   cylinder

_diffrn_ambient_temperature      300
_diffrn_source_type              'ILL beamline D1A'
_diffrn_radiation_type           neutron
_diffrn_radiation_wavelength     1.38
_diffrn_measurement_device_type  local
_diffrn_detector                 'He~3~ detector'
_diffrn_radiation_monochromator  'Ge 331'

_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_limit_l_max       9

_pd_meas_scan_method             fixed
_pd_meas_number_of_points        1579
_pd_meas_2theta_range_min        0
_pd_meas_2theta_range_max        157.9
_pd_proc_ls_prof_R_factor        2.12
_pd_proc_ls_prof_wR_factor       2.71
_pd_proc_ls_prof_wR_expected     11.21

_refine_ls_R_I_factor            1.475
_refine_ls_goodness_of_fit_all   0.24
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      sigma
_refine_ls_number_parameters     66
_refine_ls_number_restraints     0
_refine_ls_number_constraints    24

_pd_proc_2theta_range_min        10
_pd_proc_2theta_range_max        135
_pd_proc_wavelength              1.38
_pd_proc_info_excluded_regions   
'0 to 15 and 135 to 157.9 degrees unreliable due to background'

_computing_data_collection       local
_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 (Dowty, 2002)'

loop_
_atom_type_symbol
_atom_type_scat_length_neutron
_atom_type_scat_source
Ca 4.70 'International Tables for Crystallography Volume C'
Fe 9.45 'International Tables for Crystallography Volume C'
P 5.13 'International Tables for Crystallography Volume C'
O 5.803 'International Tables for Crystallography Volume C'
H -3.7390 'International Tables for Crystallography Volume C'
C 6.646 'International Tables for Crystallography Volume C'

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 0.6666667 0.3333333 -0.004(2) 0.975 0.9(3)
Ca1 Fe 4 0.6666667 0.3333333 -0.004(2) 0.025 0.9(3)
Ca2 Ca 6 0.992(2) 0.239(2) 0.25 0.978(17) 1.6(2)
P P 6 0.370(1) 0.404(1) 0.25 0.967(1) 1.4(8)
O1 O 6 0.471(1) 0.315(1) 0.25 0.967(1) 1.4(8)
O2 O 6 0.470(1) 0.590(1) 0.25 0.967(1) 1.4(8)
O3 O 12 0.254(1) 0.3414(8) 0.0740(9) 0.967(1) 1.4(8)
O4 O 4 0 0 0.190(3) 0.48(1) 2.1(4)
H1 H 4 0 0 0.084(6) 0.48(1) 2.1(4)
C1 C 6 0.3618 0.3522 0.25 0.017(5) 0.05
C2 C 6 0.355 0.438 0.25 0.017(5) 0.05
O5 O 12 0.306(8) 0.364(8) 0.090(1) 0.05(1) 0.05
C C 2 0 0 0 0.04(2) 0.05
O6 O 12 0.03(6) 1.01(9) 0.68(4) 0.01(5) 0.05
O7 O 12 0.97(4) 0.12(4) 0.52(8) 0.01(5) 0.05

data_Ca9.8Fe0.2P6O25.76H1.76C0.24O0.72
_database_code_depnum_ccdc_archive 'CCDC 763320'
#TrackingRef 'Fe-ap.cif'

_chemical_formula_sum            'Ca9.8 H1.71 Fe0.2 O26.55 P6 C0.24'
_chemical_name_mineral           
;
Apatite
;
_chemical_formula_weight         1019.41
_symmetry_cell_setting           monoclinic
_symmetry_int_tables_number      11
_symmetry_space_group_name_H-M   'P 21/m'
_symmetry_space_group_name_Hall  '-P 2c'
loop_
_symmetry_equiv_pos_as_xyz
1
'-x, -y, -z'
2
'-x, -y, z+1/2'
3
'x, y, -z+1/2'
4
'x, y, z'
_cell_length_a                   9.4323(60)
_cell_length_b                   9.3678(67)
_cell_length_c                   6.8269(26)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120.305(59)
_cell_volume                     520.80(62)

_cell_formula_units_Z            1
_cell_measurement_reflns_used    1302
_cell_measurement_temperature    300

_exptl_crystal_density_diffrn    3.2307
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             32.0
_exptl_absorpt_coefficient_mu    'not measured'

_pd_spec_mounting                'vanadium can'
_pd_spec_mount_mode              reflection
_pd_spec_shape                   cylinder

_diffrn_ambient_temperature      300
_diffrn_source_type              'ILL beamline D1A'
_diffrn_radiation_type           neutron
_diffrn_radiation_wavelength     1.38
_diffrn_measurement_device_type  local
_diffrn_detector                 'He~3~ detector'
_diffrn_radiation_monochromator  'Ge 331'

_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_h_max       12
_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        1579
_pd_meas_2theta_range_min        0
_pd_meas_2theta_range_max        157.9
_pd_proc_ls_prof_R_factor        2.57
_pd_proc_ls_prof_wR_factor       3.27
_pd_proc_ls_prof_wR_expected     10.95

_refine_ls_R_I_factor            12.228
_refine_ls_goodness_of_fit_all   0.3
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      sigma
_refine_ls_number_parameters     113
_refine_ls_number_restraints     0
_refine_ls_number_constraints    43

_pd_proc_2theta_range_min        10
_pd_proc_2theta_range_max        135
_pd_proc_wavelength              1.38
_pd_proc_info_excluded_regions   
'0 to 15 and 135 to 157.9 degrees unreliable due to background'

_computing_data_collection       local
_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 (Dowty, 2002)'

loop_
_atom_type_symbol
_atom_type_scat_length_neutron
_atom_type_scat_source
Ca 4.70 'International Tables for Crystallography Volume C'
Fe 9.45 'International Tables for Crystallography Volume C'
P 5.13 'International Tables for Crystallography Volume C'
O 5.803 'International Tables for Crystallography Volume C'
H -3.7390 'International Tables for Crystallography Volume C'
C 6.646 'International Tables for Crystallography Volume C'

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 0.661(6) 0.33(1) 0.002(3) 0.948(48) 0.4(3)
Ca1 Fe 4 0.661(6) 0.33(1) 0.002(3) 0.052(48) 0.4(3)
Ca2 Ca 2 0.259(6) 0.035(8) 0.25 1 0.9(8)
Ca3 Ca 2 0.773(7) 0.788(7) 0.25 1 1.0(7)
Ca4 Ca 2 0.979(8) 0.236(8) 0.25 1 1.0(8)
P1 P 2 0.030(4) -0.360(4) 0.25 0.991(22) 0.8(1)
P2 P 2 -0.425(4) 0.965(5) 0.25 0.991(22) 0.8(1)
P3 P 2 0.368(5) 0.387(5) 0.25 0.991(22) 0.8(1)
O1 O 2 0.494(5) 0.331(3) 0.25 0.991(22) 0.8(1)
O2 O 2 0.842(4) -0.444(5) 0.25 0.0.991(22) 0.8(1)
O3 O 2 -0.333(5) 0.153(4) 0.25 0.991(22) 0.8(1)
O4 O 2 0.466(4) 0.578(4) 0.25 0.991(22) 0.8(1)
O5 O 2 0.132(4) 0.554(4) 0.25 0.991(22) 0.8(1)
O6 O 2 0.387(4) 0.880(4) 0.25 0.0.991(22) 0.8(1)
O7 O 4 0.255(3) 0.355(3) 0.074(3) 0.991(22) 0.8(1)
O8 O 4 0.076(3) 0.755(3) 0.076(5) 0.991(22) 0.8(1)
O9 O 4 0.635(4) -0.085(3) 0.071(3) 0.991(22) 0.8(1)
O10 O 4 0.01(2) -0.01(2) 0.173(8) 0.44(2) 0.6(5)
H H 4 -0.00(2) -0.00(2) 0.08(1) 0.44(2) 0.6(5)
C3 C 2 0 0 0 0.12(3) 0.05
O14 O 4 0.97(2) 0.11(2) 0.55(3) 0.03(1) 0.05
O15 O 4 -0.13(3) 0.86(2) 0.52(2) 0.03(1) 0.05
O16 O 4 0.14(2) -0.97(2) 0.55(4) 0.03(1) 0.05
O17 O 4 0.00(3) 0.05(2) 0.67(2) 0.03(1) 0.05
O18 O 4 -0.01(4) -0.98(3) 0.68(2) 0.03(1) 0.05
O19 O 4 0.06(2) -0.05(2) 0.62(2) 0.03(1) 0.05

#End of data_Ca9.8Fe0.2P6O25.71H1.71C0.24O0.72

data_Ca9.49Fe0.51P6O26H1.48
_database_code_depnum_ccdc_archive 'CCDC 763321'
#TrackingRef 'Fe-ap.cif'

_chemical_formula_sum            'Ca9.8 H1.48 Fe0.51 O26 P6'
_chemical_name_mineral           
;
Apatite
;
_chemical_formula_weight         1023.964
_symmetry_cell_setting           monoclinic
_symmetry_int_tables_number      11
_symmetry_space_group_name_H-M   'P 21/m'
_symmetry_space_group_name_Hall  '-P 2c'
loop_
_symmetry_equiv_pos_as_xyz
1
'-x, -y, -z'
2
'-x, -y, z+1/2'
3
'x, y, -z+1/2'
4
'x, y, z'
_cell_length_a                   9.4241(45)
_cell_length_b                   9.3619(53)
_cell_length_c                   6.8206(18)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120.221(53)
_cell_volume                     519.98(49)

_cell_formula_units_Z            1
_cell_measurement_reflns_used    1301
_cell_measurement_temperature    300

_exptl_crystal_density_diffrn    3.207
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             15.4
_exptl_absorpt_coefficient_mu    'not measured'

_pd_spec_mounting                'vanadium can'
_pd_spec_mount_mode              reflection
_pd_spec_shape                   cylinder

_diffrn_ambient_temperature      300
_diffrn_source_type              'ILL beamline D1A'
_diffrn_radiation_type           neutron
_diffrn_radiation_wavelength     1.38
_diffrn_measurement_device_type  local
_diffrn_detector                 'He~3~ detector'
_diffrn_radiation_monochromator  'Ge 331'

_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_h_max       12
_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        1579
_pd_meas_2theta_range_min        0
_pd_meas_2theta_range_max        157.9
_pd_proc_ls_prof_R_factor        2.17
_pd_proc_ls_prof_wR_factor       2.76
_pd_proc_ls_prof_wR_expected     9.05

_refine_ls_R_I_factor            1.134
_refine_ls_goodness_of_fit_all   0.3
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      sigma
_refine_ls_number_parameters     100
_refine_ls_number_restraints     0
_refine_ls_number_constraints    39

_pd_proc_2theta_range_min        10
_pd_proc_2theta_range_max        135
_pd_proc_wavelength              1.38
_pd_proc_info_excluded_regions   
'0 to 15 and 135 to 157.9 degrees unreliable due to background'

_computing_data_collection       local
_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 (Dowty, 2002)'

loop_
_atom_type_symbol
_atom_type_scat_length_neutron
_atom_type_scat_source
Ca 4.70 'International Tables for Crystallography Volume C'
Fe 9.45 'International Tables for Crystallography Volume C'
P 5.13 'International Tables for Crystallography Volume C'
O 5.803 'International Tables for Crystallography Volume C'
H -3.7390 'International Tables for Crystallography Volume C'

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 0.662(4) 0.332(5) -0.002(2) 0.942(40) 1.0(2)
Ca1 Fe 4 0.662(4) 0.332(5) -0.002(2) 0.058(40) 1.0(2)
Ca2 Ca 2 0.256(6) 0.029(6) 0.25 1 0.9(6)
Ca2 Fe 2 0.256(6) 0.029(6) 0.25 0 0.9(6)
Ca3 Ca 2 0.739(5) 0.746(6) 0.25 1 1.1(5)
Ca3 Fe 2 0.739(5) 0.746(6) 0.25 0 1.1(5)
Ca4 Ca 2 0.980(4) 0.216(4) 0.25 0.860(54) 0.24(5)
Ca4 Fe 2 0.980(4) 0.216(4) 0.25 0.140(54) 0.24(5)
P1 P 2 0.030(3) -0.360(4) 0.25 1.00(2) 0.92(9)
P2 P 2 -0.432(4) 0.965(4) 0.25 1.00(2) 0.92(9)
P3 P 2 0.361(3) 0.385(3) 0.25 1.00(2) 0.92(9)
O1 O 2 0.479(3) 0.316(3) 0.25 1.00(2) 0.92(9)
O2 O 2 0.850(4) -0.493(3) 0.25 1.00(2) 0.92(9)
O3 O 2 -0.329(3) 0.153(3) 0.25 1.00(2) 0.92(9)
O4 O 2 0.462(3) 0.576(3) 0.25 1.00(2) 0.92(9)
O5 O 2 0.135(3) 0.561(3) 0.25 1.00(2) 0.92(9)
O6 O 2 0.382(3) 0.874(3) 0.25 1.00(2) 0.92(9)
O7 O 4 0.243(3) 0.340(3) 0.076(3) 1.00(2) 0.92(9)
O8 O 4 0.053(3) 0.752(2) 0.075(3) 1.00(2) 0.92(9)
O9 O 4 0.629(2) -0.086(2) 0.070(2) 1.00(2) 0.92(9)
O10 O 4 0.002(5) -0.005(6) 0.160(5) 0.370(79) 0.05
H H 4 -0.008(7) -0.047(6) 0.115(8) 0.370(79) 0.05
O11 O 4 -0.000(2) -0.01(2) 0.32(2) 0.130(79) 0.05

#End of data_Ca9.49Fe0.51P6O26H1.48