# Supplementary Information (SI) for Journal of Materials Chemistry A.
# 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_cr1_a
_database_code_depnum_ccdc_archive 'CCDC 2421202'
loop_
_audit_author_name
_audit_author_address
'Dmitry Chernyshov'
;SNBL at the European Synchrotron Radiation Facility, Grenoble
France
;
_audit_update_record             
;
2025-02-03 deposited with the CCDC.	2025-05-12 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT029_cr1_a               
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.872 Why?
RESPONSE: Simple measurement with only 1 rotation axis.
;
# Added during the CSD deposition process: Monday 03 February 2025 02:27 PM
# end Validation Reply Form


_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        'Tetraproylammonium bromotrichloroferrate(III)'
_chemical_name_common            'TPA FBC'
_chemical_melting_point          414
_chemical_formula_moiety         ?
_chemical_formula_sum            'C5.33 H12.44 Br0.44 Cl1.33 Fe0.44 N0.44'
_chemical_formula_weight         190.42

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0036 0.0018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe 0.3509 0.8789 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.3337 2.5396 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1547 0.1665 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0069 0.0036 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

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

_cell_length_a                   13.9778(2)
_cell_length_b                   16.49680(10)
_cell_length_c                   17.5282(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4041.81(8)
_cell_formula_units_Z            18
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    5322
_cell_measurement_theta_min      2.2800
_cell_measurement_theta_max      26.1600

_exptl_crystal_description       'irregular block'
_exptl_crystal_colour            brown
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.408
_exptl_crystal_F_000             1752
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_exptl_absorpt_coefficient_mu    3.230
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_T_min  0.61914
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.79a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_oxdiff_exptl_absorpt_empirical_full_min 0.740
_oxdiff_exptl_absorpt_empirical_full_max 1.335
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.72254
_diffrn_measurement_method       'ω scans'
_diffrn_radiation_monochromator  synchrotron
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  
'dectris-CrysAlisPro-abstract goniometer imported dectris images'
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_reflns_number            13935
_diffrn_reflns_av_unetI/netI     0.0095
_diffrn_reflns_av_R_equivalents  0.0168
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         2.273
_diffrn_reflns_theta_max         24.835
_diffrn_reflns_theta_full        24.835
_diffrn_measured_fraction_theta_max 0.872
_diffrn_measured_fraction_theta_full 0.872
_diffrn_reflns_Laue_measured_fraction_max 0.872
_diffrn_reflns_Laue_measured_fraction_full 0.872
_diffrn_reflns_point_group_measured_fraction_max 0.872
_diffrn_reflns_point_group_measured_fraction_full 0.872
_reflns_number_total             2898
_reflns_number_gt                2720
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0796P)²+3.1664P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_extinction_coef       0.0039(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         2898
_refine_ls_number_parameters     172
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0527
_refine_ls_R_factor_gt           0.0505
_refine_ls_wR_factor_ref         0.1541
_refine_ls_wR_factor_gt          0.1519
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_restrained_S_all      1.072
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Fe1 Fe 0.28424(5) 0.59856(4) 0.65897(4) 0.0855(3) Uani 1 1 d . . . . .
Br1 Br 0.22250(7) 0.66980(6) 0.75460(6) 0.1066(5) Uani 0.226(3) 1 d . . P A 1
Cl1 Cl 0.22250(7) 0.66980(6) 0.75460(6) 0.1066(5) Uani 0.774(3) 1 d . . P A 1
Br2 Br 0.43896(8) 0.57118(6) 0.68235(8) 0.1375(6) Uani 0.368(4) 1 d . . P A 2
Cl2 Cl 0.43896(8) 0.57118(6) 0.68235(8) 0.1375(6) Uani 0.632(4) 1 d . . P A 2
Br3 Br 0.20054(11) 0.48543(8) 0.64145(9) 0.1521(8) Uani 0.288(4) 1 d . . P A 3
Cl3 Cl 0.20054(11) 0.48543(8) 0.64145(9) 0.1521(8) Uani 0.712(4) 1 d . . P A 3
Br4 Br 0.27415(13) 0.67212(12) 0.55462(10) 0.1634(10) Uani 0.118(4) 1 d . . P A
4
Cl4 Cl 0.27415(13) 0.67212(12) 0.55462(10) 0.1634(10) Uani 0.882(4) 1 d . . P A
4
N6 N 0.4734(2) 0.69335(17) 0.36161(17) 0.0637(7) Uani 1 1 d . . . . .
C7 C 0.4301(3) 0.7684(2) 0.3993(3) 0.0796(11) Uani 1 1 d . . . . .
H7A H 0.3715 0.7818 0.3724 0.096 Uiso 1 1 calc R U . . .
H7AB H 0.4126 0.7542 0.4511 0.096 Uiso 1 1 calc R U . . .
C8 C 0.5687(3) 0.6716(3) 0.3982(2) 0.0801(11) Uani 1 1 d . . . . .
H8A H 0.5913 0.6216 0.3753 0.096 Uiso 1 1 calc R U . . .
H8AB H 0.6145 0.7136 0.3856 0.096 Uiso 1 1 calc R U . . .
C9 C 0.4056(3) 0.6219(3) 0.3738(3) 0.0828(11) Uani 1 1 d . . . . .
H9A H 0.4369 0.5735 0.3549 0.099 Uiso 1 1 calc R U . . .
H9AB H 0.3969 0.6149 0.4283 0.099 Uiso 1 1 calc R U . . .
C3 C 0.5213(4) 0.6461(3) 0.2289(3) 0.1048(15) Uani 1 1 d . . . . .
H3A H 0.4801 0.5991 0.2338 0.126 Uiso 1 1 calc R U . . .
H3AB H 0.5853 0.6307 0.2445 0.126 Uiso 1 1 calc R U . . .
C4 C 0.5226(5) 0.6749(4) 0.1450(3) 0.1194(19) Uani 1 1 d . . . . .
H4A H 0.5456 0.6319 0.1130 0.179 Uiso 1 1 calc R U . . .
H4B H 0.5640 0.7210 0.1403 0.179 Uiso 1 1 calc R U . . .
H4C H 0.4590 0.6896 0.1297 0.179 Uiso 1 1 calc R U . . .
C0 C 0.4905(4) 0.8423(3) 0.4021(3) 0.0990(14) Uani 1 1 d . . . . .
H0A H 0.5116 0.8557 0.3509 0.119 Uiso 1 1 calc R U . . .
H0AB H 0.5468 0.8315 0.4328 0.119 Uiso 1 1 calc R U . . .
C13 C 0.6603(5) 0.6345(5) 0.5135(4) 0.144(2) Uani 1 1 d . . . . .
H13A H 0.6688 0.5778 0.5033 0.216 Uiso 1 1 calc R U . . .
H13B H 0.6621 0.6436 0.5676 0.216 Uiso 1 1 calc R U . . .
H13C H 0.7106 0.6648 0.4894 0.216 Uiso 1 1 calc R U . . .
C12 C 0.2548(4) 0.5496(3) 0.3570(4) 0.1165(18) Uani 1 1 d . . . . .
H12A H 0.1952 0.5492 0.3297 0.175 Uiso 1 1 calc R U . . .
H12B H 0.2424 0.5476 0.4108 0.175 Uiso 1 1 calc R U . . .
H12C H 0.2921 0.5034 0.3423 0.175 Uiso 1 1 calc R U . . .
C11 C 0.3093(4) 0.6266(3) 0.3381(3) 0.1026(15) Uani 1 1 d . . . . .
H11A H 0.3155 0.6322 0.2832 0.123 Uiso 1 1 calc R U . . .
H11B H 0.2750 0.6734 0.3575 0.123 Uiso 1 1 calc R U . . .
C10 C 0.5680(4) 0.6610(4) 0.4834(3) 0.1128(17) Uani 1 1 d . . . . .
H10A H 0.5506 0.7121 0.5071 0.135 Uiso 1 1 calc R U . . .
H10B H 0.5196 0.6214 0.4969 0.135 Uiso 1 1 calc R U . . .
C2 C 0.4859(3) 0.7119(3) 0.2781(2) 0.0819(11) Uani 1 1 d . . . . .
H2A H 0.4246 0.7297 0.2582 0.098 Uiso 1 1 calc R U . . .
H2AB H 0.5297 0.7572 0.2737 0.098 Uiso 1 1 calc R U . . .
C1 C 0.4378(4) 0.9125(3) 0.4348(4) 0.1133(18) Uani 1 1 d . . . . .
H1A H 0.4792 0.9589 0.4363 0.170 Uiso 1 1 calc R U . . .
H1B H 0.4171 0.8995 0.4856 0.170 Uiso 1 1 calc R U . . .
H1C H 0.3831 0.9243 0.4036 0.170 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Fe1 Br4 2.1996(16) . ?
Fe1 Br1 2.2215(11) . ?
Fe1 Br3 2.2240(13) . ?
Fe1 Br2 2.2471(12) . ?
N6 C2 1.505(5) . ?
N6 C8 1.521(5) . ?
N6 C9 1.528(5) . ?
N6 C7 1.528(5) . ?
C7 C0 1.484(6) . ?
C8 C10 1.504(7) . ?
C9 C11 1.486(7) . ?
C3 C2 1.473(7) . ?
C3 C4 1.545(7) . ?
C0 C1 1.487(6) . ?
C13 C10 1.461(8) . ?
C12 C11 1.517(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_3
_geom_angle_publ_flag
C2 N6 C8 110.9(3) . . ?
C2 N6 C9 111.4(3) . . ?
C8 N6 C9 107.6(3) . . ?
C2 N6 C7 107.5(3) . . ?
C8 N6 C7 110.9(3) . . ?
C9 N6 C7 108.6(3) . . ?
C0 C7 N6 117.0(4) . . ?
C10 C8 N6 116.1(4) . . ?
C11 C9 N6 117.6(4) . . ?
C2 C3 C4 109.6(5) . . ?
C7 C0 C1 111.7(4) . . ?
C9 C11 C12 108.6(4) . . ?
C13 C10 C8 112.8(5) . . ?
C3 C2 N6 117.3(4) . . ?

_refine_diff_density_max         0.447
_refine_diff_density_min         -0.316
_refine_diff_density_rms         0.054



_exptl_crystal_recrystallization_method 'Slow evaporation'
