# Supplementary Information (SI) for Chemical Communications.
# 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_Ca6Mn2N6O
_database_code_depnum_ccdc_archive 'CCDC 2477089'
loop_
_audit_author_name
_audit_author_address
'Simon Kloss'
;LMU Munich
Germany
;
_audit_update_record             
;
2025-07-30 deposited with the CCDC.	2025-09-09 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT306_Ca6Mn2N6O           
;
PROBLEM: Isolated Oxygen Atom (H-atoms Missing ?) .......         O2 Check
RESPONSE: Oxide Anion
;
# Added during the CSD deposition process: Wednesday 30 July 2025 09:56 AM
# end Validation Reply Form


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

# 2. CHEMICAL DATA

_chemical_name_systematic        
;
;
_chemical_name_common            'Calcium nitridomanganate oxide'
_chemical_melting_point          ?
_chemical_formula_moiety         '2(Mn N3), O, 6(Ca)'
# Ex: 'C12 H16 N2 O6, H2 O' and '(Cd 2+)3, (C6 N6 Cr 3-)2, 2(H2 O)'
_chemical_formula_structural     ?
_chemical_formula_sum            'Ca6 Mn2 N6 O'
_chemical_formula_iupac          ?
_chemical_formula_weight         450.39
_chemical_compound_source        'see text'

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ca Ca 0.2262 0.3064 ' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mn Mn 0.3368 0.7283 ' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 ' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 ' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

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

# 3. POWDER SPECIMEN AND CRYSTAL DATA

_symmetry_cell_setting           trigonal
_symmetry_space_group_name_Hall  '-R 3'
_symmetry_space_group_name_H-M   'R -3'
_symmetry_Int_Tables_number      148

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
5 y,-x+y,-z
6 x-y,x,-z
7 1/3+x,2/3+y,2/3+z
8 1/3-y,2/3+x-y,2/3+z
9 1/3-x+y,2/3-x,2/3+z
10 1/3-x,2/3-y,2/3-z
11 1/3+y,2/3-x+y,2/3-z
12 1/3+x-y,2/3+x,2/3-z
13 2/3+x,1/3+y,1/3+z
14 2/3-y,1/3+x-y,1/3+z
15 2/3-x+y,1/3-x,1/3+z
16 2/3-x,1/3-y,1/3-z
17 2/3+y,1/3-x+y,1/3-z
18 2/3+x-y,1/3+x,1/3-z

_cell_length_a                   8.92557(7)
_cell_length_b                   8.92557(7)
_cell_length_c                   9.23716(14)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     637.296(14)
_cell_formula_units_Z            3
_cell_measurement_temperature    100
_exptl_crystal_density_diffrn    3.521

_cell_special_details            
; ?
;

# The next three fields give the specimen dimensions in mm.  The equatorial 
# plane contains the incident and diffracted beam.

_pd_spec_size_axial              ? # perpendicular to 
# equatorial plane

_pd_spec_size_equat              ? # parallel to 
# scattering vector 
# in transmission

_pd_spec_size_thick              ? # parallel to 
# scattering vector 
# in reflection

# The next five fields are character fields that describe the specimen.

_pd_spec_mounting                
# This field should be
# used to give details of the 
# container.
; ?
;
_pd_spec_mount_mode              ? # options are 'reflection' 
# or 'transmission'

_pd_spec_shape                   cylinder # options are 'cylinder' 
# 'flat_sheet' or 'irregular'

_pd_char_particle_morphology     ?
_pd_char_colour                  ? # use ICDD colour descriptions


# The following three fields describe the preparation of the specimen.   
# The cooling rate is in K/min.  The pressure at which the sample was  
# prepared is in kPa.  The temperature of preparation is in K.

_pd_prep_cool_rate               ?
_pd_prep_pressure                ?
_pd_prep_temperature             ?

# The next four fields are normally only needed for transmission experiments.
_exptl_absorpt_coefficient_mu    ?
_exptl_absorpt_correction_type   ? # include if applicable
_exptl_absorpt_process_details   ? # include if applicable
_exptl_absorpt_correction_T_min  ? # include if applicable
_exptl_absorpt_correction_T_max  ? # include if applicable

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

# 7. EXPERIMENTAL DATA

_exptl_special_details           
; ?
;

# The following item is used to identify the equipment used to record 
# the powder pattern when the diffractogram was measured at a laboratory 
# other than the authors' home institution, e.g. when neutron or synchrotron
# radiation is used.

_pd_instr_location               
; WISH beamline at the ISIS Neutron and Muon Source
;
_pd_calibration_special_details  
# description of the method used
# to calibrate the instrument
; Calibrated on a Na2Ca3Al2F14 standard
;

_diffrn_ambient_temperature      100
_diffrn_source                   Reactor
_diffrn_source_target            ?
_diffrn_source_type              ?
_diffrn_radiation_type           Neutron
_diffrn_measurement_device_type  'D20 Beamline'
_diffrn_detector                 'position sensitive detector'
_diffrn_detector_type            ? # make or model of detector

_pd_meas_scan_method             cont # options are 'step', 'cont',
# 'tof', 'fixed' or
# 'disp' (= dispersive)
_pd_meas_special_details         
;  ?
;

# The following six items are used for angular dispersive measurements only.

_diffrn_radiation_wavelength     ?
_diffrn_radiation_monochromator  ?

#  The following four items give details of the measured (not processed)
#  powder pattern.  Angles are in degrees.

_pd_meas_number_of_points        ?
_pd_meas_2theta_range_min        ?
_pd_meas_2theta_range_max        ?
_pd_meas_2theta_range_inc        ?

# The following three items are used for time-of-flight measurements only.

_pd_instr_dist_src/spec          ?
_pd_instr_dist_spec/detc         ?
_pd_meas_2theta_fixed            ?
#===============================================================================

# 8. REFINEMENT DATA

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

_pd_proc_ls_special_details      
; Data refinement performed with TOPAS Academic V6
;

# The next three items are given as text.

_pd_proc_ls_profile_function     'Pseudo-Voigt II'
_pd_proc_ls_background_function  shifted-Chebychev
_pd_proc_ls_pref_orient_corr     
; ?
;

_pd_proc_ls_prof_R_factor        0.020
_pd_proc_ls_prof_wR_factor       0.027
_pd_proc_ls_prof_wR_expected     0.010
_refine_ls_R_I_factor            0.020
_refine_ls_R_Fsqd_factor         ?
_refine_ls_R_factor_all          ?


_refine_special_details          
; ?
;

_refine_ls_matrix_type           ?
_refine_ls_weighting_scheme      
? # options are 'sigma' (based on measured su's)
# or 'calc' (calculated weights)
_refine_ls_weighting_details     ?
_refine_ls_hydrogen_treatment    ?
_refine_ls_extinction_method     ?
_refine_ls_extinction_coef       ?
_refine_ls_number_parameters     13
_refine_ls_number_restraints     ?
_refine_ls_number_constraints    ?

# The following item is the same as CHI, the square root of 'CHI squared'
_refine_ls_goodness_of_fit_all   0.029

_refine_ls_restrained_S_all      ?
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         ?

# 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        ?
_pd_proc_2theta_range_max        ?
_pd_proc_2theta_range_inc        ?
_pd_proc_wavelength              ?

# Each refinement must be accompanied by a listing of the powder data
# in CIF format. Each listing should be sent as a separate file consisting 
# of one data block containing a single powder profile. The value of 
# _pd_block_diffractogram_id is used to associate each refinement with 
# its corresponding powder profile, since it must match the value
# of _pd_block_id in the file containing the powder data. A template 
# for supplying powder data in CIF format is available by ftp at
# ftp://ftp.iucr.org/pub/rietdataform.cif and an example is given 
# at ftp://ftp.iucr.org/pub/rietdataxmpl.cif.

_pd_block_diffractogram_id       ?


# Give appropriate details in the next two text fields.

_pd_proc_info_excluded_regions   ?
_pd_proc_info_data_reduction     ?

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

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  ?
_computing_molecular_graphics    ?
_computing_publication_material  ?


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

# 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_thermal_displace_type
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_U_iso_or_equiv
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Mn1 Mn Uiso 0.00000 0.00000 0.3788(3) 1.000 0.0032(6) . . . .
Ca1 Ca Uiso 0.0541(3) 0.25661(19) 0.15059(18) 1.000 0.0074(4) . . . .
N1 N Uiso 0.21089(9) 0.16708(10) 0.32415(10) 1.000 0.0067(2) . . . .
O2 O Uiso 0.00000 0.00000 0.00000 1.000 0.0086(6) . . . .

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


_geom_special_details            
;
 Bond distances, angles etc. have been calculated using the
 rounded fractional coordinates. All su's are estimated
 from the variances of the (full) variance-covariance matrix.
 The cell esds are taken into account in the estimation of
 distances, angles and torsion angles
;

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 N1 1.7930(12) . . yes
Mn1 N1 1.7930(13) . 2_555 yes
Mn1 N1 1.7930(11) . 3_555 yes

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
N1 Mn1 N1 112.40(9) . . 2_555 yes
N1 Mn1 N1 112.40(9) . . 3_555 yes
N1 Mn1 N1 112.40(9) 2_555 . 3_555 yes

# Loop Mechanism for Extra Tables(s)

#loop_
#_publ_manuscript_incl_extra_item
#'_geom_extra_tableA_col_1'
#'_geom_extra_tableA_col_2'
#'_geom_extra_tableA_col_3'
#'_geom_extra_table_head_A'
#'_geom_table_footnote_A'
#'_geom_extra_tableB_col_1'
#'_geom_extra_tableB_col_2'
#'_geom_extra_tableB_col_3'
#'_geom_extra_table_head_B'
#'_geom_table_footnote_B'


#
#loop_
#_geom_extra_tableA_col_1
#_geom_extra_tableA_col_2
#_geom_extra_tableA_col_3
# ? ? ?


#
#loop_
#_geom_extra_tableB_col_1
#_geom_extra_tableB_col_2
#_geom_extra_tableB_col_3
# ? ? ?


#
#_geom_table_footnote_A
#;
# ?
#;


#
#_geom_table_footnote_B
#;
# ?
#;


#
#_geom_table_footnote_A
#;
# ?
#;


#
#_geom_table_footnote_B
#;
# ?
#;

_iucr_refine_instructions_details 
;
;
_iucr_refine_reflections_details 
;
;
####################################################################### 
# 
# 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_Ca6Mn2N6O_CCDC1
_database_code_depnum_ccdc_archive 'CCDC 2477090'
loop_
_audit_author_name
_audit_author_address
'Simon Kloss'
;LMU Munich
Germany
;
_audit_update_record             
;
2025-09-03 deposited with the CCDC.	2025-09-09 downloaded from the CCDC.
;

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

# 2. CHEMICAL DATA

_chemical_name_systematic        
;
;
_chemical_name_common            'Calcium nitridomanganate oxide'
_chemical_melting_point          ?
_chemical_formula_moiety         '2(Mn N3), O, 6(Ca)'
# Ex: 'C12 H16 N2 O6, H2 O' and '(Cd 2+)3, (C6 N6 Cr 3-)2, 2(H2 O)'
_chemical_formula_structural     ?
_chemical_formula_sum            'Ca6 Mn2 N6 O'
_chemical_formula_iupac          ?
_chemical_formula_weight         450.39
_chemical_compound_source        'see text'

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ca Ca 0.1611 0.1926 ' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mn Mn 0.2704 0.4681 ' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0030 0.0019 ' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0056 0.0036 ' International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

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

# 3. POWDER SPECIMEN AND CRYSTAL DATA

_symmetry_cell_setting           trigonal
_symmetry_space_group_name_Hall  '-R 3'
_symmetry_space_group_name_H-M   'R -3'
_symmetry_Int_Tables_number      148

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
5 y,-x+y,-z
6 x-y,x,-z
7 1/3+x,2/3+y,2/3+z
8 1/3-y,2/3+x-y,2/3+z
9 1/3-x+y,2/3-x,2/3+z
10 1/3-x,2/3-y,2/3-z
11 1/3+y,2/3-x+y,2/3-z
12 1/3+x-y,2/3+x,2/3-z
13 2/3+x,1/3+y,1/3+z
14 2/3-y,1/3+x-y,1/3+z
15 2/3-x+y,1/3-x,1/3+z
16 2/3-x,1/3-y,1/3-z
17 2/3+y,1/3-x+y,1/3-z
18 2/3+x-y,1/3+x,1/3-z

_cell_length_a                   8.95635(12)
_cell_length_b                   8.95635(12)
_cell_length_c                   9.25969(16)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     643.264(20)
_cell_formula_units_Z            3
_cell_measurement_temperature    300
_exptl_crystal_density_diffrn    3.487

_cell_special_details            
; ?
;

# The next three fields give the specimen dimensions in mm.  The equatorial 
# plane contains the incident and diffracted beam.

_pd_spec_size_axial              ? # perpendicular to 
# equatorial plane

_pd_spec_size_equat              ? # parallel to 
# scattering vector 
# in transmission

_pd_spec_size_thick              ? # parallel to 
# scattering vector 
# in reflection

# The next five fields are character fields that describe the specimen.

_pd_spec_mounting                
# This field should be
# used to give details of the 
# container.
; ?
;
_pd_spec_mount_mode              ? # options are 'reflection' 
# or 'transmission'

_pd_spec_shape                   cylinder # options are 'cylinder' 
# 'flat_sheet' or 'irregular'

_pd_char_particle_morphology     ?
_pd_char_colour                  ? # use ICDD colour descriptions


# The following three fields describe the preparation of the specimen.   
# The cooling rate is in K/min.  The pressure at which the sample was  
# prepared is in kPa.  The temperature of preparation is in K.

_pd_prep_cool_rate               ?
_pd_prep_pressure                ?
_pd_prep_temperature             ?

# The next four fields are normally only needed for transmission experiments.
_exptl_absorpt_coefficient_mu    ?
_exptl_absorpt_correction_type   ? # include if applicable
_exptl_absorpt_process_details   ? # include if applicable
_exptl_absorpt_correction_T_min  ? # include if applicable
_exptl_absorpt_correction_T_max  ? # include if applicable

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

# 7. EXPERIMENTAL DATA

_exptl_special_details           
;
;
_diffrn_ambient_temperature      300
_diffrn_radiation_wavelength     0.5595378
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           AgK\a
_diffrn_radiation_source         ?
_diffrn_radiation_monochromator  ?

_diffrn_measurement_device_type  'Stoe StadiP'
_diffrn_measurement_method       transmission
_diffrn_detector_area_resol_mean ?
#===============================================================================

# 8. REFINEMENT DATA

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

_pd_proc_ls_special_details      
; Data refinement performed with TOPAS Academic V6
;

# The next three items are given as text.

_pd_proc_ls_profile_function     'Pseudo-Voigt II'
_pd_proc_ls_background_function  shifted-Chebychev
_pd_proc_ls_pref_orient_corr     
; ?
;

_pd_proc_ls_prof_R_factor        0.047
_pd_proc_ls_prof_wR_factor       0.064
_pd_proc_ls_prof_wR_expected     0.043
_refine_ls_R_I_factor            0.023
_refine_ls_R_Fsqd_factor         ?
_refine_ls_R_factor_all          ?


_refine_special_details          
; ?
;

_refine_ls_matrix_type           ?
_refine_ls_weighting_scheme      
? # options are 'sigma' (based on measured su's)
# or 'calc' (calculated weights)
_refine_ls_weighting_details     ?
_refine_ls_hydrogen_treatment    ?
_refine_ls_extinction_method     ?
_refine_ls_extinction_coef       ?
_refine_ls_number_parameters     12
_refine_ls_number_restraints     ?
_refine_ls_number_constraints    ?

# The following item is the same as CHI, the square root of 'CHI squared'
_refine_ls_goodness_of_fit_all   0.015

_refine_ls_restrained_S_all      ?
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         ?

# 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        ?
_pd_proc_2theta_range_max        ?
_pd_proc_2theta_range_inc        ?
_pd_proc_wavelength              ?

# Each refinement must be accompanied by a listing of the powder data
# in CIF format. Each listing should be sent as a separate file consisting 
# of one data block containing a single powder profile. The value of 
# _pd_block_diffractogram_id is used to associate each refinement with 
# its corresponding powder profile, since it must match the value
# of _pd_block_id in the file containing the powder data. A template 
# for supplying powder data in CIF format is available by ftp at
# ftp://ftp.iucr.org/pub/rietdataform.cif and an example is given 
# at ftp://ftp.iucr.org/pub/rietdataxmpl.cif.

_pd_block_diffractogram_id       ?


# Give appropriate details in the next two text fields.

_pd_proc_info_excluded_regions   ?
_pd_proc_info_data_reduction     ?

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

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  ?
_computing_molecular_graphics    ?
_computing_publication_material  ?


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

# 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_thermal_displace_type
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_U_iso_or_equiv
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Mn1 Mn Uiso 0.00000 0.00000 0.37701(14) 1.000 0.0066(4) . . . .
Ca1 Ca Uiso 0.05300(14) 0.25859(12) 0.15150(12) 1.000 0.0093(3) . . . .
N1 N Uiso 0.2108(4) 0.1679(5) 0.3247(4) 1.000 0.0063(9) . . . .
O1 O Uiso 0.00000 0.00000 0.00000 1.000 0.042(4) . . . .

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

# 10. MOLECULAR GEOMETRY

_geom_special_details            
;
 Bond distances, angles etc. have been calculated using the
 rounded fractional coordinates. All su's are estimated
 from the variances of the (full) variance-covariance matrix.
 The cell esds are taken into account in the estimation of
 distances, angles and torsion angles
;

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 N1 1.795(4) . . yes
Mn1 N1 1.795(5) . 2_555 yes
Mn1 N1 1.795(4) . 3_555 yes

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
N1 Mn1 N1 113.0(2) . . 2_555 yes
N1 Mn1 N1 113.0(2) . . 3_555 yes
N1 Mn1 N1 113.0(2) 2_555 . 3_555 yes

# Loop Mechanism for Extra Tables(s)

#loop_
#_publ_manuscript_incl_extra_item
#'_geom_extra_tableA_col_1'
#'_geom_extra_tableA_col_2'
#'_geom_extra_tableA_col_3'
#'_geom_extra_table_head_A'
#'_geom_table_footnote_A'
#'_geom_extra_tableB_col_1'
#'_geom_extra_tableB_col_2'
#'_geom_extra_tableB_col_3'
#'_geom_extra_table_head_B'
#'_geom_table_footnote_B'


#
#loop_
#_geom_extra_tableA_col_1
#_geom_extra_tableA_col_2
#_geom_extra_tableA_col_3
# ? ? ?


#
#loop_
#_geom_extra_tableB_col_1
#_geom_extra_tableB_col_2
#_geom_extra_tableB_col_3
# ? ? ?


#
#_geom_table_footnote_A
#;
# ?
#;


#
#_geom_table_footnote_B
#;
# ?
#;


#
#_geom_table_footnote_A
#;
# ?
#;


#
#_geom_table_footnote_B
#;
# ?
#;

_iucr_refine_instructions_details 
;
;
_iucr_refine_reflections_details 
;
;
