# Supplementary Information (SI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2025

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_Al4P12O36
_database_code_depnum_ccdc_archive 'CCDC 2485462'
loop_
_audit_author_name
_audit_author_address
'Joern Schmedt auf der Guenne'
;University of Siegen
Germany
;
_audit_update_record             
;
2025-09-04 deposited with the CCDC.	2025-10-01 downloaded from the CCDC.
;

_diffrn_measurement_device_type  'Huber Guinier powder camera G621'
_diffrn_source                   'sealed X-ray tube'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_polarisn_ratio 0
_diffrn_radiation_wavelength     1.540596
_diffrn_radiation_type           'Cu K\a~1~'
_diffrn_radiation_monochromator  Ge-111
_diffrn_ambient_temperature      298
_diffrn_ambient_pressure         1
_cell_measurement_temperature    298

_solution_special_details        
; 

_computing_molecular_graphics     	  		'Diamond 4'
_computing_publication_material   	  		'TOPAS ACADEMIC 7.24'
_audit_creation_method		      	  		'TOPAS ACADEMIC 7.24'
_pd_calc_method                   	  		'Rietveld Refinement'
_computing_structure_refinement   	  		'TOPAS ACADEMIC 7.24'
;


_refine_ls_shift/su_mean         1.820
_refine_ls_shift/su_max          0.001
_refine_ls_matrix_type           full
_refine_ls_number_parameters     40
_refine_ls_number_restraints     0
_refine_ls_goodness_of_fit_all   1.820
_refine_ls_R_factor_all          4.278
_pd_proc_ls_prof_wR_factor       5.805
_pd_proc_ls_prof_wR_expected     3.189
_pd_proc_ls_prof_R_factor        1.779

_pd_char_particle_morphology     powder
_pd_char_colour                  white
_chemical_name_common            'Aluminium tris(catena-phosphate(V))'
_chemical_formula_structural     'Al4 (P4 O12)3'
_chemical_formula_sum            'Al8 O72 P24'
_chemical_formula_moiety         'Al8 O72 P24'
_chemical_name_structure_type    Al4(P4O12)3
_chemical_formula_weight         2111.1792
_exptl_crystal_density_diffrn    2.706(1)
_exptl_absorpt_coefficient_mu    10.240(5)

_cell_measurement_theta_min      0
_cell_measurement_theta_max      90
_diffrn_reflns_theta_max         90
_pd_meas_number_of_points        3672
_pd_proc_number_of_points        3672
_diffrn_reflns_number            106
_reflns_number_total             106
_reflns_limit_h_min              0
_reflns_limit_h_max              15
_reflns_limit_k_min              -15
_reflns_limit_k_max              15
_reflns_limit_l_min              -15
_reflns_limit_l_max              15


_cell_length_a                   13.735(2)
_cell_length_b                   13.735(2)
_cell_length_c                   13.735(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2591.1(13)
_cell_formula_units_Z            2
_symmetry_cell_setting           cubic
_symmetry_space_group_name_H-M   'I -4 3 d'
_symmetry_space_group_name_Hall  'I -4bd 2c 3'
_space_group_IT_number           220


loop_
_space_group_symop_operation_xyz
'x, y, z '
'-x, y+1/2, -z+1/2 '
'-x+1/4, -z-1/4, y-1/4 '
'-x+1/4, z+1/4, -y-1/4 '
'-x+1/2, -y, z+1/2 '
'-x+1/2, y, -z '
'-x-1/4, -z+1/4, y+1/4 '
'-x-1/4, z-1/4, -y+1/4 '
'-y, -z+1/2, x '
'-y, z+1/2, -x+1/2 '
'-y+1/4, -x-1/4, z-1/4 '
'-y+1/4, x+1/4, -z-1/4 '
'-y+1/2, -z, x+1/2 '
'-y+1/2, z, -x '
'-y-1/4, -x+1/4, z+1/4 '
'-y-1/4, x-1/4, -z+1/4 '
'-z, -x+1/2, y '
'-z, x+1/2, -y+1/2 '
'-z+1/4, -y-1/4, x-1/4 '
'-z+1/4, y+1/4, -x-1/4 '
'-z+1/2, -x, y+1/2 '
'-z+1/2, x, -y '
'-z-1/4, -y+1/4, x+1/4 '
'-z-1/4, y-1/4, -x+1/4 '
'z, -x, -y+1/2 '
'z, x, y '
'z+1/4, -y-1/4, -x+1/4 '
'z+1/4, y+1/4, x+1/4 '
'z+1/2, -x+1/2, -y '
'z+1/2, x+1/2, y+1/2 '
'z-1/4, -y+1/4, -x-1/4 '
'z-1/4, y-1/4, x-1/4 '
'y, -z, -x+1/2 '
'y, z, x '
'y+1/4, -x-1/4, -z+1/4 '
'y+1/4, x+1/4, z+1/4 '
'y+1/2, -z+1/2, -x '
'y+1/2, z+1/2, x+1/2 '
'y-1/4, -x+1/4, -z-1/4 '
'y-1/4, x-1/4, z-1/4 '
'x, -y, -z+1/2 '
'-x, -y+1/2, z '
'x+1/4, -z-1/4, -y+1/4 '
'x+1/4, z+1/4, y+1/4 '
'x+1/2, -y+1/2, -z '
'x+1/2, y+1/2, z+1/2 '
'x-1/4, -z+1/4, -y-1/4 '
'x-1/4, z-1/4, y-1/4 '

loop_
_atom_type_symbol
_atom_type_oxidation_number
P 5
Al 3
O -2


loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_Wyckoff_symbol
_atom_site_symmetry_multiplicity
_atom_site_occupancy
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_B_iso_or_equiv

Al1 Al 16c 16 1.0 0.1063(2) 0.1063(2) 0.1063(2) 0.77(10)
P1 P 48e 48 1.0 0.1197(1) 0.3316(2) 0.0469(2) 0.64(5)
O1 O 48e 48 1.0 0.1498(3) 0.2315(3) 0.0768(3) 0.61(6)
O2 O 48e 48 1.0 0.0179(3) 0.3611(3) 0.0597(3) 0.61(6)
O3 O 48e 48 1.0 0.1871(4) 0.4085(3) 0.1002(3) 0.61(6)






loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_1
_geom_bond_site_symmetry_2

Al1 O1 1.865(6) . .
Al1 O2 3.759(6) . .
Al1 O3 4.297(6) . .
P1 O1 1.493(6) . .
P1 O3 1.589(9) . .
O1 O2 2.551(6) . .
O1 O3 2.505(8) . .
O2 O3 2.477(7) . .


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_2
_geom_angle_site_symmetry_3

Al1 O1 O2 115.9(2) . . .
Al1 O1 O3 158.8(3) . . .
Al1 O2 O3 84.46(15) . . .
P1 O2 O1 30.79(17) . . .
P1 O2 O3 37.33(18) . . .
P1 O3 O2 34.15(17) . . .
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_C-AlH6P3O12
_database_code_depnum_ccdc_archive 'CCDC 2485463'
loop_
_audit_author_name
_audit_author_address
'Joern Schmedt auf der Guenne'
;University of Siegen
Germany
;
_audit_update_record             
;
2025-09-04 deposited with the CCDC.	2025-10-01 downloaded from the CCDC.
;
_diffrn_measurement_device_type  'STOE Stadi P'
_diffrn_source                   'sealed X-ray tube'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_polarisn_ratio 0
_diffrn_radiation_wavelength     1.54056
_diffrn_radiation_type           'Cu K\a~1~'
_diffrn_radiation_monochromator  Ge-111
_diffrn_ambient_temperature      298(2)
_geom_special_details            Debye-Scherrer
_diffrn_ambient_pressure         1
_cell_measurement_temperature    298

##########################################
# 2. OVERALL SOLUTION/REFINEMENT DETAILS #
##########################################


_computing_molecular_graphics    'Diamond 4.0'
_computing_publication_material  'TOPAS ACADEMIC 7.24'
_audit_creation_method           'TOPAS ACADEMIC 7.24 + PLATON'
_pd_calc_method                  'Rietveld Refinement'
_computing_structure_refinement  'TOPAS ACADEMIC 7.24'

_refine_ls_shift/su_mean         5.875
_refine_ls_shift/su_max          0.001
_refine_ls_matrix_type           full
_refine_ls_number_parameters     46
_refine_ls_number_constraints    2
_refine_ls_number_restraints     0
_refine_ls_goodness_of_fit_all   5.772
_pd_proc_ls_prof_wR_expected     0.885
_pd_proc_ls_prof_wR_factor       5.199
_pd_proc_ls_prof_R_factor        3.273
_refine_ls_R_I_factor            3.033



#####################
# 3. SAMPLE DETAILS #
#####################

_pd_char_particle_morphology     powder
_pd_char_colour                  white
_chemical_name_common            Aluminiumtrisdihydrogenphosphate
_chemical_formula_sum            'Al H6 O12 P3'
_chemical_formula_moiety         'Al H6 O12 P3'
_chemical_formula_weight         317.9430
_exptl_crystal_density_diffrn    2.13809(4)
_exptl_absorpt_coefficient_mu    7.089(1)
##_cell_special_details             none
_cell_measurement_theta_min      5.000
_cell_measurement_theta_max      65.5
_diffrn_reflns_theta_max         65.5
_diffrn_reflns_number            63
_reflns_number_total             63
_reflns_limit_h_min              0
_reflns_limit_h_max              15
_reflns_limit_k_min              -15
_reflns_limit_k_max              12
_reflns_limit_l_min              -10
_reflns_limit_l_max              10

###################
# 4. CRYSTAL DATA #
###################

_chemical_name_mineral           ??
_cell_length_a                   13.6862(1)
_cell_length_b                   13.6862(1)
_cell_length_c                   9.1333(1)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     1481.57(3)
_symmetry_cell_setting           hexagonal
_symmetry_space_group_name_H-M   'R 3 c'
_symmetry_space_group_name_Hall  'R 3 -2"c'
_cell_formula_units_Z            6

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z '
'-x+y, y, z+1/2 '
'-y, -x, z+1/2 '
'-y, x-y, z '
'-x+y, -x, z '
'x, x-y, z+1/2 '
'x-1/3, y+1/3, z+1/3 '
'-x+y-1/3, y+1/3, z-1/6 '
'-y-1/3, -x+1/3, z-1/6 '
'-y-1/3, x-y+1/3, z+1/3 '
'-x+y-1/3, -x+1/3, z+1/3 '
'x-1/3, x-y+1/3, z-1/6 '
'x+1/3, y-1/3, z-1/3 '
'-x+y+1/3, y-1/3, z+1/6 '
'-y+1/3, -x-1/3, z+1/6 '
'-y+1/3, x-y-1/3, z-1/3 '
'-x+y+1/3, -x-1/3, z-1/3 '
'x+1/3, x-y-1/3, z+1/6 '


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

P1 P 18 0.0033(3) 0.1623(2) 0.2656(9) 1 1.24(5)
AL1 Al 6 0 0 0 1 0.61(8)
O1 O 18 0.0340(5) 0.1271(5) 0.3998(9) 1 0.83(5)
O2 O 18 0.5811(3) 0.5354(3) 0.6204(9) 1 0.83(5)
O3 O 18 0.4512(3) 0.5045(3) 0.3784(8) 1 0.83(5)
O4 O 18 0.1251(5) 0.0307(5) 0.1256(9) 1 0.83(5)
H1 H 18 0.4967(2) 0.5153(2) 0.4631(6) 1 1.24(7)
H2 H 18 0.5506(2) 0.5401(2) 0.7123(6) 1 1.24(7)

#######################
# 5. BONDS AND ANGLES #
#######################

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
Al1 O1 3.971(8)
Al1 O2 9.528(6)
Al1 O3 7.424(5)
Al1 O4 1.925(8)
P1 O1 1.460(12)
P1 O2 7.664(7)
P1 O3 5.645(6)
P1 O4 3.270(10)

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
O1 Al1 O2 41.08(11)
O1 P1 O2 59.3(3)
_chemical_properties_physical    Hygroscopic
