# 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_ZnBP-1
_database_code_depnum_ccdc_archive 'CCDC 2431041'
loop_
_audit_author_name
_audit_author_address
'Kazuyuki Maeda'
;Tokyo University of Agriculture and Technology
Japan
;
_audit_update_record             
;
2025-05-20 deposited with the CCDC.	2025-11-17 downloaded from the CCDC.
;

# 5. CHEMICAL DATA

_chemical_name_common            ZnBP-1
# Get _chemical_formula_moiety using checkCIF
_chemical_formula_moiety         'C2 H O3 P Zn0.61'
_chemical_formula_sum            'C2 H O3 P Zn0.61'
_chemical_formula_weight         143.62

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Zn Zn 0.1248 1.7610 'International Tables for Crystallography, Vol. C'
P P 0.1127 0.1202 'International Tables for Crystallography, Vol. C'
O O 0.0113 0.0079 'International Tables for Crystallography, Vol. C'
C C 0.0033 0.0021 'International Tables for Crystallography, Vol. C'
H H -0.0006 0.0000 'International Tables for Crystallography, Vol. C'

#===============================================================================
# 6. POWDER SPECIMEN AND CRYSTAL DATA

_space_group_crystal_system      hexagonal
_space_group_name_H-M_alt        'P 63/m'
_space_group_name_Hall           '-P 6c'
_space_group_IT_number           176

loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 x,y,z
2 -y,x-y,z
3 -x+y,-x,z
4 -x,-y,z+1/2
5 y,-x+y,z+1/2
6 x-y,x,z+1/2
7 -x,-y,-z
8 y,-x+y,-z
9 x-y,x,-z
10 x,y,-z+1/2
11 -y,x-y,-z+1/2
12 -x+y,-x,-z+1/2

_cell_length_a                   8.85701(6)
_cell_length_b                   8.85701(6)
_cell_length_c                   7.55059(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     512.962(6)
_cell_formula_units_Z            6
_cell_measurement_temperature    300

_exptl_crystal_density_diffrn    2.8053
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             425.90

_pd_spec_mounting                'glass capillary'
_pd_spec_mount_mode              transmission
_pd_spec_shape                   cylinder
_pd_char_colour                  colorless

#===============================================================================

# 7. EXPERIMENTAL DATA

_diffrn_ambient_temperature      300
_diffrn_source                   Synchrotron
_diffrn_source_type              'SPring-8, BL02B2'
_pd_instr_location               
;
SPring-8, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan
;
_diffrn_measurement_device_type  Debye-Scherrer
_diffrn_detector                 'MYTHEN detector'
_pd_meas_scan_method             fixed
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.79960
_pd_meas_number_of_points        12686
_pd_meas_2theta_range_min        2.1000
_pd_meas_2theta_range_max        78.2100
_pd_meas_2theta_range_inc        0.0060

#===============================================================================

# 8. REFINEMENT DATA

# Use the next field to give any special details about the fitting of the
# powder pattern.

_pd_proc_ls_special_details      
;
. Anisotropic line broadening factors Ue and Pe were refined.
. Since the hydrogen positions of the OH groups were not confirmed, 
the expected OH groups were treated as a virtual atom at the O1 site, 
which virtually contains O + 0.40H so as to satisfy the neutrality 
of the compositions.  
;

# The next three items are given as text.

_pd_calc_method                  'Rietveld Refinement'
_pd_proc_ls_profile_function     'split pseudo-Voigt function'
_pd_proc_ls_background_function  'Legendre polynomials'

_pd_proc_ls_prof_R_factor        0.02227
_pd_proc_ls_prof_wR_factor       0.02988
_pd_proc_ls_prof_wR_expected     0.01442
_refine_ls_R_I_factor            0.05609
_refine_ls_R_Fsqd_factor         0.03651
_refine_ls_R_factor_all          0.03651

_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      sigma
_refine_ls_weighting_details     1/yi
_refine_ls_extinction_method     none
_refine_ls_number_parameters     48
_refine_ls_number_restraints     0
_refine_ls_number_constraints    1

# The following item is the same as CHI, the square root of 'CHI squared'
_refine_ls_goodness_of_fit_all   2.0726
_refine_ls_shift/su_max          0.0
_refine_diff_density_max         0.0
_refine_diff_density_min         0.0

# The following four items apply to angular dispersive measurements.
# 2theta minimum, maximum and increment (in degrees) are for the
# intensities used in the refinement.

_pd_proc_2theta_range_min        4.5060
_pd_proc_2theta_range_max        77.0040
_pd_proc_2theta_range_inc        0.0060
_pd_proc_wavelength              0.79960

# The following items are used to identify the programs used.

_computing_cell_refinement       'RIETAN-FP (Izumi and Momma, 2007)'
_computing_structure_solution    'EXPO-2014 (Altomare et al., 2013)'
_computing_structure_refinement  'RIETAN-FP (Izumi and Momma, 2007)'
_computing_molecular_graphics    'VESTA3 (Momma and Izumi, 2011)'

#===============================================================================

# 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS

loop_
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_Wyckoff_symbol
_atom_site_adp_type
_atom_site_U_iso_or_equiv
_atom_site_type_symbol
Zn1 0.3333 0.6667 0.54975(8) 0.909(2) 4 f Uiso 0.0148(2) Zn
P1 0.0328(2) 0.3753(1) 0.25 1 6 h Uiso 0.0130(4) P
O1 0.1272(2) 0.4741(2) 0.0835(2) 1 12 i Uiso 0.0282(7) O
O2 0.8457(3) 0.3459(4) 0.25 1 6 h Uiso 0.0166(8) O
C1 0.0158(7) 0.1639(6) 0.25 1 6 h Uiso 0.0048(7) C
C2 0.8498(6) 0.0142(7) 0.25 1 6 h Uiso 0.0048(7) C
H1 0.737(3) 0.029(4) 0.25 1 6 h Uiso 0.01267 H
#===============================================================================

#10. GEOMETRICAL PARAMETERS

_geom_special_details            ?

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
_geom_bond_publ_flag
Zn1 O1 2.035(2) . 10_555 ?
Zn1 O2 2.154(2) . 9_556 ?
P1 O1 1.522(2) . 1_555 ?
P1 O2 1.543(2) . 1_455 ?
P1 C1 1.802(4) . 1_555 ?
C1 C2 1.382(5) . 3_665 ?
C1 C2 1.403(5) . 1_455 ?
C2 H1 1.07(4) . 1_555 ?

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
_geom_angle_publ_flag
O1 Zn1 O1 97.69(6) 10_555 . 11_665 ?
O1 Zn1 O2 96.04(8) 10_555 . 8_566 ?
O1 Zn1 O2 88.55(9) 10_555 . 7_666 ?
O1 Zn1 O2 164.05(7) 10_555 . 9_556 ?
O2 Zn1 O2 76.16(7) 9_556 . 8_566 ?
O1 P1 O1 111.5(1) 1_555 . 10_555 ?
O1 P1 O2 109.4(1) 1_555 . 1_455 ?
O1 P1 C1 109.5(1) 1_555 . 1_555 ?
O2 P1 C1 107.4(2) 1_455 . 1_555 ?
P1 O1 Zn1 153.6(1) 1_555 . 10_555 ?
P1 O2 Zn1 135.20(5) 1_655 . 4_664 ?
Zn1 O2 Zn1 89.18(9) 7_666 . 4_664 ?
C2 C1 C2 120.9(5) 3_665 . 1_455 ?
C2 C1 P1 120.1(4) 3_665 . 1_555 ?
C2 C1 P1 119.0(4) 1_455 . 1_555 ?
C1 C2 C1 119.1(5) 2_655 . 1_655 ?
C1 C2 H1 119.0(17) 1_655 . 1_555 ?
C1 C2 H1 121.7(16) 2_655 . 1_555 ?

# start Validation Reply Form
_vrf_PLAT430_ZnBP-1              
;
PROBLEM: Short Inter D...A Contact  O1       ..O1       .       2.81 Ang.  
RESPONSE: This short contact is probably related to partially protonated O1 
and partial Zn1 site vacancy.  Even without the Zn1 site vacancy, 1/3 of the  
O1 atoms are protonated for charge compensation.  Where a Zn1 atom site is 
vacant, all the neighboring three O1 oxygen atoms should be protonated to 
compensate the missing positive charge.  The protonated O1 atoms should be 
hydrogen-bonded with close O1 acceptors, which should contribute to shorten
the average O1 - O1 distance.
;
####################################################################### 
# 
# 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_MnBP-1_45eq
_database_code_depnum_ccdc_archive 'CCDC 2452711'
loop_
_audit_author_name
_audit_author_address
'Kazuyuki Maeda'
;Tokyo University of Agriculture and Technology
Japan
;
_audit_update_record             
;
2025-05-20 deposited with the CCDC.	2025-11-17 downloaded from the CCDC.
;

# 5. CHEMICAL DATA

_chemical_name_systematic        MnBP-1_prepared_with_4.5eq_LiOH
_chemical_name_common            MnBP-1_4.5eq
# Get _chemical_formula_moiety using checkCIF
_chemical_formula_moiety         'C2 H Mn0.667 O3 P'
_chemical_formula_sum            'C2 H Mn0.667 O3 P'
_chemical_formula_weight         140.63

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Mn Mn 0.3172 0.9073 'International Tables for Crystallography, Vol. C'
P P 0.1127 0.1202 'International Tables for Crystallography, Vol. C'
O O 0.0113 0.0079 'International Tables for Crystallography, Vol. C'
C C 0.0033 0.0021 'International Tables for Crystallography, Vol. C'
H H -0.0006 0.0000 'International Tables for Crystallography, Vol. C'

#===============================================================================
# 6. POWDER SPECIMEN AND CRYSTAL DATA

_space_group_crystal_system      hexagonal
_space_group_name_H-M_alt        'P 63/m'
_space_group_name_Hall           '-P 6c'
_space_group_IT_number           176

loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 x,y,z
2 -y,x-y,z
3 -x+y,-x,z
4 -x,-y,z+1/2
5 y,-x+y,z+1/2
6 x-y,x,z+1/2
7 -x,-y,-z
8 y,-x+y,-z
9 x-y,x,-z
10 x,y,-z+1/2
11 -y,x-y,-z+1/2
12 -x+y,-x,-z+1/2

_cell_length_a                   8.9818(3)
_cell_length_b                   8.9818(3)
_cell_length_c                   7.6950(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     537.61(3)
# If checkCIF gives a different Z value, change both
# _chemical_formula_sum and _chemical_formula_weight.
_cell_formula_units_Z            6
_cell_measurement_temperature    300

_exptl_crystal_density_diffrn    2.6186
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             416.00

_pd_spec_mounting                'glass capillary'
_pd_spec_mount_mode              transmission
_pd_spec_shape                   cylinder
_pd_char_colour                  colorless

#===============================================================================

# 7. EXPERIMENTAL DATA

_diffrn_ambient_temperature      300
_diffrn_source                   Synchrotron
_diffrn_source_type              'Aichi Synchrotron Radiation Center, BL5S2'
_pd_instr_location               
;
Aichi Synchrotron Radiation Center, Seto, Aichi 489-0965, Japan
;
_diffrn_measurement_device_type  Debye-Scherrer
_diffrn_detector                 'PILATUS 100K, flat 2D detector'
_pd_meas_scan_method             fixed
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.80044
_pd_meas_number_of_points        9497
_pd_meas_2theta_range_min        0.0700
_pd_meas_2theta_range_max        95.0300
_pd_meas_2theta_range_inc        0.0100

#===============================================================================

# 8. REFINEMENT DATA

# Use the next field to give any special details about the fitting of the
# powder pattern.

_pd_proc_ls_special_details      
; 
. Anisotropic line broadening factors Ue and Pe were refined.
. Since the hydrogen positions of the OH groups were not confirmed, 
the expected OH groups were treated as a virtual atom at the O1 site, 
which virtually contains O + 0.333H so as to satisfy the neutrality 
of the compositions.  
;

# The next three items are given as text.

_pd_calc_method                  'Rietveld Refinement'
_pd_proc_ls_profile_function     'split pseudo-Voigt function'
_pd_proc_ls_background_function  'Legendre polynomials'
_pd_proc_ls_pref_orient_corr     
; $P_k = \sum_{j=1}^{m_k} \frac{1}{m_k}
\left( r^2 \cos^2 \alpha_j +r^{-1}\ sin^2 \alpha_j \right)^{-3/2}$
with a preferred-orientation vector, (hkl),
and <i>r</i> = 1.0(0)
;
_pd_proc_ls_prof_R_factor        0.03376
_pd_proc_ls_prof_wR_factor       0.04121
_pd_proc_ls_prof_wR_expected     0.01144
_refine_ls_R_I_factor            0.01962
_refine_ls_R_Fsqd_factor         0.01001
_refine_ls_R_factor_all          0.00988

_refine_special_details          
'Rietveld refinement using powder X-ray diffraction data'

_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      sigma
_refine_ls_weighting_details     1/yi
_refine_ls_extinction_method     none
_refine_ls_number_parameters     52
_refine_ls_number_restraints     7
_refine_ls_number_constraints    1

# The following item is the same as CHI, the square root of 'CHI squared'
_refine_ls_goodness_of_fit_all   3.6036
_refine_ls_shift/su_max          0.0
_refine_diff_density_max         0.0
_refine_diff_density_min         0.0

# The following four items apply to angular dispersive measurements.
# 2theta minimum, maximum and increment (in degrees) are for the
# intensities used in the refinement.

_pd_proc_2theta_range_min        4.2100
_pd_proc_2theta_range_max        78.0000
_pd_proc_2theta_range_inc        0.0100
_pd_proc_wavelength              0.80044

# The following items are used to identify the programs used.

_computing_cell_refinement       'RIETAN-FP (Izumi and Momma, 2007)'
_computing_structure_solution    'EXPO-2014 (Altomare et al., 2013)'
_computing_structure_refinement  'RIETAN-FP (Izumi and Momma, 2007)'
_computing_molecular_graphics    'VESTA3 (Momma and Izumi, 2011)'

#===============================================================================

# 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS

loop_
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_Wyckoff_symbol
_atom_site_adp_type
_atom_site_U_iso_or_equiv
_atom_site_type_symbol
Mn1 0.33333 0.66667 0.5445(1) 1 4 f Uiso 0.0099(2) Mn
P1 0.0271(1) 0.3690(1) 0.25 1 6 h Uiso 0.0097(3) P
O1 0.1209(3) 0.4685(3) 0.4135(3) 1 12 i Uiso 0.0379(8) O
O2 -0.1544(4) 0.3371(5) 0.25 1 6 h Uiso 0.0068(7) O
C1 0.0138(4) 0.1602(2) 0.25 1 6 h Uiso 0.0050(7) C
C2 0.1619(3) 0.1480(3) 0.25 1 6 h Uiso 0.0050(7) C
H1 0.271(4) 0.247(4) 0.25 1 6 h Uiso 0.01267 H

#===============================================================================

#10. GEOMETRICAL PARAMETERS

_geom_special_details            ?

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
_geom_bond_publ_flag
Mn1 O1 2.104(2) . 1_555 ?
Mn1 O2 2.243(3) . 5_555 ?
P1 O1 1.529(2) . 1_555 ?
P1 O2 1.507(4) . 1_555 ?
P1 C1 1.818(3) . 1_555 ?
C1 C2 1.389(5) . 1_555 ?
C1 C2 1.388(4) . 2_555 ?
C2 H1 0.94(3) . 1_555 ?

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
_geom_angle_publ_flag
O1 Mn1 O1 98.97(8) 1_555 . 2_665 ?
O1 Mn1 O2 93.99(13) 1_555 . 8_556 ?
O1 Mn1 O2 89.15(9) 1_555 . 7_566 ?
O1 Mn1 O2 163.39(11) 1_555 . 9_666 ?
O2 Mn1 O2 75.78(11) 8_556 . 7_566 ?
O2 P1 O1 109.80(15) 1_555 . 1_555 ?
O2 P1 C1 107.27(19) 1_555 . 1_555 ?
O1 P1 O1 110.71(15) 1_555 . 10_555 ?
O1 P1 C1 109.59(14) 1_555 . 1_555 ?
P1 O1 Mn1 152.87(13) 1_555 . 1_555 ?
P1 O2 Mn1 134.55(6) 1_555 . 4_564 ?
Mn1 O2 Mn1 89.67(15) 7_566 . 4_564 ?
C2 C1 C2 121.0(3) 2_555 . 1_555 ?
C2 C1 P1 118.3(3) 2_555 . 1_555 ?
C2 C1 P1 120.68(17) 1_555 . 1_555 ?
C1 C2 C1 119.0(3) 1_555 . 3_555 ?
H1 C2 C1 120(3) 1_555 . 3_555 ?
H1 C2 C1 121(3) 1_555 . 1_555 ?

# start Validation Reply Form
_vrf_PLAT430_MnBP-1_45eq         
;
PROBLEM: Short Inter D...A Contact  O2       ..O2       .       2.76 Ang.  
RESPONSE: Three O2 atoms are located at the corners of the triangle face  
shared by two MnO6 octahedra.  Because of small O2-Mn1-O2 angle (75.78deg), 
it is assumed that the distance between O2 atoms included in the same face 
tends to be short.
;
# end Validation Reply Form
#===END
_exptl_crystal_recrystallization_method 'hydrothermal synthesis'
####################################################################### 
# 
# 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_CdBP-1
_database_code_depnum_ccdc_archive 'CCDC 2431042'
loop_
_audit_author_name
_audit_author_address
'Kazuyuki Maeda'
;Tokyo University of Agriculture and Technology
Japan
;
_audit_update_record             
;
2025-05-20 deposited with the CCDC.	2025-11-17 downloaded from the CCDC.
;

# 5. CHEMICAL DATA

_chemical_name_common            CdBP-1
# Get _chemical_formula_moiety using checkCIF
_chemical_formula_moiety         'C2 Cd0.65 O3 P'
_chemical_formula_sum            'C2 Cd0.65 O3 P'
_chemical_formula_weight         177.90

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Cd Cd -0.8946 1.5122 'International Tables for Crystallography, Vol. C'
P P 0.1043 0.1224 'International Tables for Crystallography, Vol. C'
O O 0.0087 0.0080 'International Tables for Crystallography, Vol. C'
C C 0.0013 0.0021 'International Tables for Crystallography, Vol. C'
H H -0.0006 0.0000 'International Tables for Crystallography, Vol. C'

#===============================================================================
# 6. POWDER SPECIMEN AND CRYSTAL DATA

_space_group_crystal_system      hexagonal
_space_group_name_H-M_alt        'P 63/m'
_space_group_name_Hall           '-P 6c'
_space_group_IT_number           176

loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 x,y,z
2 -y,x-y,z
3 -x+y,-x,z
4 -x,-y,z+1/2
5 y,-x+y,z+1/2
6 x-y,x,z+1/2
7 -x,-y,-z
8 y,-x+y,-z
9 x-y,x,-z
10 x,y,-z+1/2
11 -y,x-y,-z+1/2
12 -x+y,-x,-z+1/2

_cell_length_a                   9.1222(1)
_cell_length_b                   9.1222(1)
_cell_length_c                   7.84046(9)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     565.03(1)
_cell_formula_units_Z            6
_cell_measurement_temperature    300

_exptl_crystal_density_diffrn    3.1370
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             503.73

_pd_spec_mounting                'glass capillary'
_pd_spec_mount_mode              transmission
_pd_spec_shape                   cylinder
_pd_char_colour                  colorless

#===============================================================================

# 7. EXPERIMENTAL DATA

_diffrn_ambient_temperature      300
_diffrn_source                   Synchrotron
_diffrn_source_type              'SPring-8, BL02B2'
_pd_instr_location               
;
SPring-8, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan
;
_diffrn_measurement_device_type  Debye-Scherrer
_diffrn_detector                 'MYTHEN detector'
_pd_meas_scan_method             fixed
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.79960
_pd_meas_number_of_points        12686
_pd_meas_2theta_range_min        2.1000
_pd_meas_2theta_range_max        78.2100
_pd_meas_2theta_range_inc        0.0060

#===============================================================================

# 8. REFINEMENT DATA

# Use the next field to give any special details about the fitting of the
# powder pattern.

_pd_proc_ls_special_details      
;
. Anisotropic line broadening factors Ue and Pe were refined.
. Two diffraction lines 100 and 110 were independently refined 
by using partial profile relaxation.
. Since the hydrogen positions of the CH and OH groups were not confirmed, 
the expected CH and OH groups were treated as virtual atoms at the C2 and  
O1 sites, respectively.  The former virtually contains "C + H" at the same  
site, and the latter does "O + 0.35H" so as to satisfy the neutrality of    
the compositions.
;

# The next three items are given as text.

_pd_calc_method                  'Rietveld Refinement'
_pd_proc_ls_profile_function     'split pseudo-Voigt function'
_pd_proc_ls_background_function  'Legendre polynomials'

_pd_proc_ls_prof_R_factor        0.04127
_pd_proc_ls_prof_wR_factor       0.05345
_pd_proc_ls_prof_wR_expected     0.01728
_refine_ls_R_I_factor            0.04214
_refine_ls_R_Fsqd_factor         0.02819
_refine_ls_R_factor_all          0.02828

_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      sigma
_refine_ls_weighting_details     1/yi
_refine_ls_extinction_method     none
_refine_ls_number_parameters     55
_refine_ls_number_restraints     14
_refine_ls_number_constraints    0

# The following item is the same as CHI, the square root of 'CHI squared'
_refine_ls_goodness_of_fit_all   3.0940
_refine_ls_shift/su_max          0.0
_refine_diff_density_max         0.0
_refine_diff_density_min         0.0

# The following four items apply to angular dispersive measurements.
# 2theta minimum, maximum and increment (in degrees) are for the
# intensities used in the refinement.

_pd_proc_2theta_range_min        5.0040
_pd_proc_2theta_range_max        78.0000
_pd_proc_2theta_range_inc        0.0060
_pd_proc_wavelength              0.79960

# The following items are used to identify the programs used.

_computing_cell_refinement       'RIETAN-FP (Izumi and Momma, 2007)'
_computing_structure_solution    'EXPO-2014 (Altomare et al., 2013)'
_computing_structure_refinement  'RIETAN-FP (Izumi and Momma, 2007)'
_computing_molecular_graphics    'VESTA3 (Momma and Izumi, 2011)'

#===============================================================================

# 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS

loop_
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_Wyckoff_symbol
_atom_site_adp_type
_atom_site_U_iso_or_equiv
_atom_site_type_symbol
Cd1 0.33333 0.66667 0.03845(6) 0.977(2) 4 f Uiso 0.0157(2) Cd
P1 0.3628(2) 0.0230(2) 0.25 1 6 h Uiso 0.0101(4) P
O1 0.4600(3) 0.1105(3) 0.0911(3) 1 12 i Uiso 0.038 O
O2 0.1572(4) 0.4890(4) 0.25 1 6 h Uiso 0.0060(9) O
C1 0.1586(1) 0.00923(9) 0.25 1 6 h Uiso 0.004(1) C
C2 0.1510(1) 0.1602(1) 0.25 1 6 h Uiso 0.038 C

#===============================================================================

#10. GEOMETRICAL PARAMETERS

_geom_special_details            ?

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
_geom_bond_publ_flag
Cd1 O1 2.211(3) . 9_555 ?
Cd1 O2 2.314(2) . 1_555 ?
P1 O1 1.506(3) . 1_555 ?
P1 O2 1.522(3) . 3_555 ?
P1 C1 1.803(2) . 1_555 ?
C1 C2 1.413(1) . 1_555 ?
C1 C2 1.415(1) . 3_555 ?

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
_geom_angle_publ_flag
O1 Cd1 O1 100.56(8) 9_555 . 8_565 ?
O1 Cd1 O2 92.9(1) 9_555 . 1_555 ?
O1 Cd1 O2 161.38(8) 9_555 . 3_565 ?
O1 Cd1 O2 89.4(1) 9_555 . 2_665 ?
O2 Cd1 O2 74.30(8) 1_555 . 3_565 ?
O1 P1 O1 111.6(2) 1_555 . 10_555 ?
O1 P1 O2 108.3(1) 1_555 . 3_555 ?
O1 P1 C1 110.6(1) 1_555 . 1_555 ?
O2 P1 C1 107.3(2) 3_555 . 1_555 ?
P1 O1 Cd1 150.8(2) 1_555 . 7_665 ?
P1 O2 Cd1 133.44(7) 2_555 . 1_555 ?
Cd1 O2 Cd1 91.6(1) 1_555 . 10_555 ?
C2 C1 C2 121.00(2) 1_555 . 3_555 ?
C2 C1 P1 119.00(2) 1_555 . 1_555 ?
C2 C1 P1 120.00(2) 3_555 . 1_555 ?
C1 C2 C1 119.00(2) 1_555 . 2_555 ?
####################################################################### 
# 
# 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_MnBP-1
_database_code_depnum_ccdc_archive 'CCDC 2431043'
loop_
_audit_author_name
_audit_author_address
'Kazuyuki Maeda'
;Tokyo University of Agriculture and Technology
Japan
;
_audit_update_record             
;
2025-05-20 deposited with the CCDC.	2025-11-17 downloaded from the CCDC.
;

# 5. CHEMICAL DATA

_chemical_name_common            MnBP-1
# Get _chemical_formula_moiety using checkCIF
_chemical_formula_moiety         'C2 H Mn0.54 O3 P'
_chemical_formula_sum            'C2 H Mn0.54 O3 P'
_chemical_formula_weight         133.85

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Mn Mn 0.3172 0.9073 'International Tables for Crystallography, Vol. C'
P P 0.1127 0.1202 'International Tables for Crystallography, Vol. C'
O O 0.0113 0.0079 'International Tables for Crystallography, Vol. C'
C C 0.0033 0.0021 'International Tables for Crystallography, Vol. C'
H H -0.0006 0.0000 'International Tables for Crystallography, Vol. C'

#===============================================================================
# 6. POWDER SPECIMEN AND CRYSTAL DATA

_space_group_crystal_system      hexagonal
_space_group_name_H-M_alt        'P 63/m'
_space_group_name_Hall           '-P 6c'
_space_group_IT_number           176

loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 x,y,z
2 -y,x-y,z
3 -x+y,-x,z
4 -x,-y,z+1/2
5 y,-x+y,z+1/2
6 x-y,x,z+1/2
7 -x,-y,-z
8 y,-x+y,-z
9 x-y,x,-z
10 x,y,-z+1/2
11 -y,x-y,-z+1/2
12 -x+y,-x,-z+1/2

_cell_length_a                   8.98133(8)
_cell_length_b                   8.98133(8)
_cell_length_c                   7.72133(7)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     539.391(8)
_cell_formula_units_Z            6
_cell_measurement_temperature    300

_exptl_crystal_density_diffrn    2.4897
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             399.05


_pd_spec_mounting                'glass capillary'
_pd_spec_mount_mode              transmission
_pd_spec_shape                   cylinder
_pd_char_colour                  colorless

#===============================================================================

# 7. EXPERIMENTAL DATA

_diffrn_ambient_temperature      300
_diffrn_source                   Synchrotron
_diffrn_source_type              'SPring-8, BL02B2'
_pd_instr_location               
;
SPring-8, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan
;
_diffrn_measurement_device_type  Debye-Scherrer
_diffrn_detector                 'MYTHEN detector'
_pd_meas_scan_method             fixed
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.79980
_pd_meas_number_of_points        12686
_pd_meas_2theta_range_min        2.1000
_pd_meas_2theta_range_max        78.2100
_pd_meas_2theta_range_inc        0.0060

#===============================================================================

# 8. REFINEMENT DATA

# Use the next field to give any special details about the fitting of the
# powder pattern.

_pd_proc_ls_special_details      
;
. Anisotropic line broadening factors Ue and Pe were refined.
. Two diffraction lines 100 and 110 were independently refined 
by using partial profile relaxation.
. Since the hydrogen positions of the OH groups were not confirmed, 
the expected OH groups were treated as a virtual atom at the O1 site, 
which virtually contains O + 0.46H so as to satisfy the neutrality 
of the compositions.  
;

# The next three items are given as text.

_pd_calc_method                  'Rietveld Refinement'
_pd_proc_ls_profile_function     'split pseudo-Voigt function'
_pd_proc_ls_background_function  'Legendre polynomials'

_pd_proc_ls_prof_R_factor        0.04651
_pd_proc_ls_prof_wR_factor       0.05994
_pd_proc_ls_prof_wR_expected     0.02063
_refine_ls_R_I_factor            0.05796
_refine_ls_R_Fsqd_factor         0.03213
_refine_ls_R_factor_all          0.03210

_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      sigma
_refine_ls_weighting_details     1/yi
_refine_ls_extinction_method     none
_refine_ls_number_parameters     58
_refine_ls_number_restraints     0
_refine_ls_number_constraints    1

# The following item is the same as CHI, the square root of 'CHI squared'
_refine_ls_goodness_of_fit_all   2.9057
_refine_ls_shift/su_max          0.0
_refine_diff_density_max         0.0
_refine_diff_density_min         0.0

# The following four items apply to angular dispersive measurements.
# 2theta minimum, maximum and increment (in degrees) are for the
# intensities used in the refinement.

_pd_proc_2theta_range_min        4.5060
_pd_proc_2theta_range_max        78.0000
_pd_proc_2theta_range_inc        0.0060
_pd_proc_wavelength              0.79980

# The following items are used to identify the programs used.

_computing_cell_refinement       'RIETAN-FP (Izumi and Momma, 2007)'
_computing_structure_solution    'EXPO-2014 (Altomare et al., 2013)'
_computing_structure_refinement  'RIETAN-FP (Izumi and Momma, 2007)'
_computing_molecular_graphics    'VESTA3 (Momma and Izumi, 2011)'

#===============================================================================

# 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS

loop_
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_Wyckoff_symbol
_atom_site_adp_type
_atom_site_U_iso_or_equiv
_atom_site_type_symbol
Mn1 0.33333 0.66667 0.5470(1) 0.815(2) 4 f Uiso 0.0124(2) Mn
P1 0.0306(1) 0.3699(1) 0.25 1 6 h Uiso 0.0120(3) P
O1 0.1251(2) 0.4678(2) 0.4117(2) 1 12 i Uiso 0.0362(6) O
O2 -0.1535(3) 0.3397(4) 0.25 1 6 h Uiso 0.0177(6) O
C1 0.0152(6) 0.1648(5) 0.25 1 6 h Uiso 0.0090(6) C
C2 0.1605(4) 0.1471(5) 0.25 1 6 h Uiso 0.0090(6) C
H1 0.272(4) 0.256(3) 0.25 1 6 h Uiso 0.01267 H

#===============================================================================

#10. GEOMETRICAL PARAMETERS

_geom_special_details            ?

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
_geom_bond_publ_flag
Mn1 O1 2.107(2) . 1_555 ?
Mn1 O2 2.231(1) . 5_555 ?
P1 O1 1.518(2) . 1_555 ?
P1 O2 1.536(2) . 1_555 ?
P1 C1 1.777(3) . 1_555 ?
C2 C1 1.391(5) . 1_555 ?
C2 C1 1.411(5) . 3_555 ?
C2 H1 0.99(3) . 1_555 ?

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
_geom_angle_publ_flag
O1 Mn1 O1 97.53(6) 1_555 . 3_565 ?
O1 Mn1 O2 94.49(8) 1_555 . 5_555 ?
O1 Mn1 O2 90.13(9) 1_555 . 4_565 ?
O1 Mn1 O2 164.75(7) 1_555 . 6_665 ?
O2 Mn1 O2 76.08(6) 5_555 . 4_565 ?
O1 P1 O1 110.6(1) 1_555 . 10_555 ?
O1 P1 O2 110.0(1) 1_555 . 1_555 ?
O1 P1 C1 109.4(1) 1_555 . 1_555 ?
O2 P1 C1 107.3(2) 1_555 . 1_555 ?
P1 O1 Mn1 154.3(1) 1_555 . 1_555 ?
P1 O2 Mn1 134.93(5) 1_555 . 7_566 ?
Mn1 O2 Mn1 89.28(8) 7_566 . 4_564 ?
C2 C1 C2 117.8(4) 1_555 . 2_555 ?
C2 C1 P1 121.8(4) 1_555 . 1_555 ?
C2 C1 P1 120.4(3) 2_555 . 1_555 ?
C1 C2 C1 122.2(4) 1_555 . 3_555 ?
C1 C2 H1 115(3) 1_555 . 1_555 ?
C1 C2 H1 122(3) 3_555 . 1_555 ?

# start Validation Reply Form
_vrf_PLAT430_MnBP-1              
;
PROBLEM: Short Inter D...A Contact  O2       ..O2       .       2.75 Ang.  
RESPONSE: Three O2 atoms are located at the corners of the triangle face  
shared by two MnO6 octahedra.  Because of small O2-Mn1-O2 angle (76.08deg), 
it is assumed that the distance between O2 atoms included in the same face 
tends to be short.
;
