# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2023

####################################################################### 
# 
# 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_test
_database_code_depnum_ccdc_archive 'CCDC 2221175'
loop_
_audit_author_name
_audit_author_address
'Elena Bykova'
;Bayerisches Geoinstitut, University of Bayreuth
Germany
;
_audit_update_record             
;
2022-11-21 deposited with the CCDC.	2023-02-22 downloaded from the CCDC.
;
_audit_creation_date             2022-11-21
_audit_creation_method           
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            'iron(II, III) oxide'
_chemical_name_systematic        dioxo(oxoferriooxy)iron
_chemical_formula_moiety         'Fe4 O5'
_chemical_formula_sum            'Fe4 O5'
_chemical_formula_weight         303.40
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Fe Fe 0.3463 0.8444 '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'

_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.
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           63
_space_group_name_H-M_alt        'C m c m'
_space_group_name_Hall           '-C 2c 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z+1/2'
'x, -y, -z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, -y+1/2, z+1/2'
'x+1/2, -y+1/2, -z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, y, -z-1/2'
'-x, y, z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, y+1/2, -z-1/2'
'-x+1/2, y+1/2, z'
'x+1/2, -y+1/2, z-1/2'

_cell_length_a                   2.89060(10)
_cell_length_b                   9.8024(3)
_cell_length_c                   12.5804(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     356.46(2)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    3143
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      36.9210
_cell_measurement_theta_min      3.2320
_shelx_estimated_absorpt_T_max   0.742
_shelx_estimated_absorpt_T_min   0.505
_exptl_absorpt_coefficient_mu    15.847
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62880
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    5.653
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             576
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_exptl_special_details           
;
 ? 
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0397
_diffrn_reflns_av_unetI/netI     0.0172
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            5477
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         37.365
_diffrn_reflns_theta_min         4.158
_diffrn_ambient_temperature      296.15
_diffrn_detector_area_resol_mean 8.3370
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Xcalibur, Sapphire2, large Be window'
_diffrn_measurement_method       'ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                469
_reflns_number_total             540
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction        
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_refine_diff_density_max         1.421
_refine_diff_density_min         -1.596
_refine_diff_density_rms         0.206
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.166
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     31
_refine_ls_number_reflns         540
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0321
_refine_ls_R_factor_gt           0.0257
_refine_ls_restrained_S_all      1.166
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0294P)²+0.6581P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0610
_refine_ls_wR_factor_ref         0.0631
_refine_special_details          ?
_olex2_refinement_description    
;
;
_atom_sites_solution_hydrogens   .
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
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
Fe2 Fe 0.0000 0.0000 0.0000 0.00859(12) Uani 1 4 d S T P . .
Fe1 Fe 0.0000 0.50518(5) 0.2500 0.01199(13) Uani 1 4 d S T P . .
Fe3 Fe 0.0000 0.26036(3) 0.11744(3) 0.00894(11) Uani 1 2 d S T P . .
O1 O 0.0000 0.1601(3) 0.2500 0.0082(4) Uani 1 4 d S T P . .
O3 O 0.0000 0.09297(17) 0.64237(15) 0.0090(3) Uani 1 2 d S T P . .
O2 O 0.0000 0.35898(18) 0.54413(15) 0.0101(3) Uani 1 2 d S T P . .


_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
Fe2 Fe2 2.89060(10) 1_455 ?
Fe2 Fe2 2.89060(10) 1_655 ?
Fe2 Fe3 2.9489(4) 9 ?
Fe2 Fe3 2.9489(4) . ?
Fe2 O3 2.0096(18) 2_554 ?
Fe2 O3 2.0096(18) 10_556 ?
Fe2 O2 2.0756(13) 6_554 ?
Fe2 O2 2.0756(13) 14_446 ?
Fe2 O2 2.0756(13) 6_454 ?
Fe2 O2 2.0756(13) 14_546 ?
Fe1 Fe1 2.89060(10) 1_655 ?
Fe1 Fe1 2.89060(10) 1_455 ?
Fe1 Fe3 2.9224(5) . ?
Fe1 Fe3 2.9224(5) 10_556 ?
Fe1 O1 2.0961(19) 5_455 ?
Fe1 O1 2.0961(19) 5 ?
Fe1 O3 2.2018(14) 13_456 ?
Fe1 O3 2.2018(14) 13_556 ?
Fe1 O3 2.2018(14) 6_554 ?
Fe1 O3 2.2018(14) 6_454 ?
Fe3 Fe3 2.89060(10) 1_655 ?
Fe3 Fe3 2.89060(10) 1_455 ?
Fe3 O1 1.9360(13) . ?
Fe3 O3 2.0626(12) 6_454 ?
Fe3 O3 2.0626(13) 6_554 ?
Fe3 O2 2.2507(19) 10_556 ?
Fe3 O2 2.0755(13) 6_454 ?
Fe3 O2 2.0755(13) 6_554 ?
O1 Fe1 2.0962(19) 5_445 ?
O1 Fe1 2.0962(18) 5_545 ?
O1 Fe3 1.9359(13) 10_556 ?
O3 Fe2 2.0096(18) 2 ?
O3 Fe1 2.2018(14) 13_556 ?
O3 Fe1 2.2018(14) 13_456 ?
O3 Fe3 2.0626(12) 6 ?
O3 Fe3 2.0626(12) 6_455 ?
O2 Fe2 2.0756(13) 6 ?
O2 Fe2 2.0756(13) 6_455 ?
O2 Fe3 2.0755(13) 6 ?
O2 Fe3 2.2507(19) 10_556 ?
O2 Fe3 2.0755(13) 6_455 ?

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
Fe2 Fe2 Fe2 180.0 1_455 1_655 ?
Fe2 Fe2 Fe3 90.0 1_655 9 ?
Fe2 Fe2 Fe3 90.0 1_455 9 ?
Fe2 Fe2 Fe3 90.0 1_455 . ?
Fe2 Fe2 Fe3 90.0 1_655 . ?
Fe3 Fe2 Fe3 180.0 . 9 ?
O3 Fe2 Fe2 90.0 10_556 1_455 ?
O3 Fe2 Fe2 90.0 2_554 1_655 ?
O3 Fe2 Fe2 90.0 10_556 1_655 ?
O3 Fe2 Fe2 90.0 2_554 1_455 ?
O3 Fe2 Fe3 93.10(5) 2_554 9 ?
O3 Fe2 Fe3 93.10(5) 10_556 . ?
O3 Fe2 Fe3 86.90(5) 10_556 9 ?
O3 Fe2 Fe3 86.90(5) 2_554 . ?
O3 Fe2 O3 180.00(10) 10_556 2_554 ?
O3 Fe2 O2 93.65(6) 10_556 14_546 ?
O3 Fe2 O2 86.35(6) 2_554 14_546 ?
O3 Fe2 O2 86.35(6) 10_556 6_554 ?
O3 Fe2 O2 86.35(6) 10_556 6_454 ?
O3 Fe2 O2 93.65(6) 2_554 6_454 ?
O3 Fe2 O2 93.65(6) 10_556 14_446 ?
O3 Fe2 O2 93.65(6) 2_554 6_554 ?
O3 Fe2 O2 86.35(6) 2_554 14_446 ?
O2 Fe2 Fe2 134.13(3) 14_446 1_655 ?
O2 Fe2 Fe2 45.87(3) 6_454 1_455 ?
O2 Fe2 Fe2 134.13(3) 14_546 1_455 ?
O2 Fe2 Fe2 45.87(3) 14_446 1_455 ?
O2 Fe2 Fe2 45.87(3) 14_546 1_655 ?
O2 Fe2 Fe2 134.13(3) 6_554 1_455 ?
O2 Fe2 Fe2 134.13(3) 6_454 1_655 ?
O2 Fe2 Fe2 45.87(3) 6_554 1_655 ?
O2 Fe2 Fe3 44.73(4) 6_554 . ?
O2 Fe2 Fe3 44.73(4) 6_454 . ?
O2 Fe2 Fe3 135.27(4) 6_454 9 ?
O2 Fe2 Fe3 135.27(4) 14_446 . ?
O2 Fe2 Fe3 44.73(4) 14_546 9 ?
O2 Fe2 Fe3 135.27(4) 14_546 . ?
O2 Fe2 Fe3 44.73(4) 14_446 9 ?
O2 Fe2 Fe3 135.27(4) 6_554 9 ?
O2 Fe2 O2 91.73(7) 14_446 6_454 ?
O2 Fe2 O2 88.27(7) 6_554 6_454 ?
O2 Fe2 O2 91.73(7) 6_554 14_546 ?
O2 Fe2 O2 180.00(12) 14_546 6_454 ?
O2 Fe2 O2 88.27(7) 14_446 14_546 ?
O2 Fe2 O2 180.00(12) 14_446 6_554 ?
Fe1 Fe1 Fe1 180.0 1_655 1_455 ?
Fe1 Fe1 Fe3 90.0 1_455 . ?
Fe1 Fe1 Fe3 90.0 1_655 10_556 ?
Fe1 Fe1 Fe3 90.0 1_655 . ?
Fe1 Fe1 Fe3 90.0 1_455 10_556 ?
Fe3 Fe1 Fe3 69.594(18) 10_556 . ?
O1 Fe1 Fe1 133.59(5) 5_455 1_655 ?
O1 Fe1 Fe1 46.41(5) 5_455 1_455 ?
O1 Fe1 Fe1 133.59(5) 5 1_455 ?
O1 Fe1 Fe1 46.41(5) 5 1_655 ?
O1 Fe1 Fe3 126.50(3) 5 . ?
O1 Fe1 Fe3 126.50(3) 5_455 . ?
O1 Fe1 Fe3 126.50(3) 5_455 10_556 ?
O1 Fe1 Fe3 126.50(3) 5 10_556 ?
O1 Fe1 O1 87.18(10) 5 5_455 ?
O1 Fe1 O3 82.18(5) 5 13_556 ?
O1 Fe1 O3 140.27(5) 5 6_454 ?
O1 Fe1 O3 82.18(5) 5_455 6_454 ?
O1 Fe1 O3 140.27(5) 5 13_456 ?
O1 Fe1 O3 82.18(5) 5 6_554 ?
O1 Fe1 O3 82.18(5) 5_455 13_456 ?
O1 Fe1 O3 140.27(5) 5_455 13_556 ?
O1 Fe1 O3 140.27(5) 5_455 6_554 ?
O3 Fe1 Fe1 131.03(3) 6_454 1_655 ?
O3 Fe1 Fe1 131.03(3) 6_554 1_455 ?
O3 Fe1 Fe1 48.97(3) 6_454 1_455 ?
O3 Fe1 Fe1 131.03(3) 13_556 1_455 ?
O3 Fe1 Fe1 48.97(3) 6_554 1_655 ?
O3 Fe1 Fe1 48.97(3) 13_556 1_655 ?
O3 Fe1 Fe1 48.97(3) 13_456 1_455 ?
O3 Fe1 Fe1 131.03(3) 13_456 1_655 ?
O3 Fe1 Fe3 44.78(3) 6_454 . ?
O3 Fe1 Fe3 89.55(5) 6_454 10_556 ?
O3 Fe1 Fe3 89.55(5) 13_556 . ?
O3 Fe1 Fe3 89.55(5) 6_554 10_556 ?
O3 Fe1 Fe3 89.55(5) 13_456 . ?
O3 Fe1 Fe3 44.78(3) 13_456 10_556 ?
O3 Fe1 Fe3 44.78(3) 6_554 . ?
O3 Fe1 Fe3 44.78(3) 13_556 10_556 ?
O3 Fe1 O3 128.18(9) 13_456 6_554 ?
O3 Fe1 O3 82.06(6) 13_556 13_456 ?
O3 Fe1 O3 128.18(9) 6_454 13_556 ?
O3 Fe1 O3 75.90(8) 6_454 13_456 ?
O3 Fe1 O3 75.90(8) 13_556 6_554 ?
O3 Fe1 O3 82.06(6) 6_454 6_554 ?
Fe1 Fe3 Fe2 175.268(15) . . ?
Fe3 Fe3 Fe2 90.0 1_455 . ?
Fe3 Fe3 Fe2 90.0 1_655 . ?
Fe3 Fe3 Fe1 90.0 1_655 . ?
Fe3 Fe3 Fe1 90.0 1_455 . ?
Fe3 Fe3 Fe3 180.0 1_655 1_455 ?
O1 Fe3 Fe2 89.54(6) . . ?
O1 Fe3 Fe1 85.72(6) . . ?
O1 Fe3 Fe3 90.0 . 1_455 ?
O1 Fe3 Fe3 90.0 . 1_655 ?
O1 Fe3 O3 102.88(7) . 6_454 ?
O1 Fe3 O3 102.88(7) . 6_554 ?
O1 Fe3 O2 95.54(7) . 6_454 ?
O1 Fe3 O2 174.91(8) . 10_556 ?
O1 Fe3 O2 95.54(7) . 6_554 ?
O3 Fe3 Fe2 132.80(4) 6_454 . ?
O3 Fe3 Fe2 132.80(4) 6_554 . ?
O3 Fe3 Fe1 48.76(4) 6_554 . ?
O3 Fe3 Fe1 48.76(4) 6_454 . ?
O3 Fe3 Fe3 134.48(3) 6_554 1_455 ?
O3 Fe3 Fe3 45.52(3) 6_454 1_455 ?
O3 Fe3 Fe3 134.48(3) 6_454 1_655 ?
O3 Fe3 Fe3 45.52(3) 6_554 1_655 ?
O3 Fe3 O3 88.97(7) 6_554 6_454 ?
O3 Fe3 O2 161.51(8) 6_554 6_454 ?
O3 Fe3 O2 80.68(6) 6_454 10_556 ?
O3 Fe3 O2 88.42(5) 6_454 6_454 ?
O3 Fe3 O2 161.51(8) 6_454 6_554 ?
O3 Fe3 O2 88.42(5) 6_554 6_554 ?
O3 Fe3 O2 80.68(6) 6_554 10_556 ?
O2 Fe3 Fe2 44.73(4) 6_454 . ?
O2 Fe3 Fe2 85.37(5) 10_556 . ?
O2 Fe3 Fe2 44.73(4) 6_554 . ?
O2 Fe3 Fe1 135.76(4) 6_454 . ?
O2 Fe3 Fe1 99.36(5) 10_556 . ?
O2 Fe3 Fe1 135.76(4) 6_554 . ?
O2 Fe3 Fe3 134.14(4) 6_454 1_655 ?
O2 Fe3 Fe3 134.14(4) 6_554 1_455 ?
O2 Fe3 Fe3 45.86(4) 6_454 1_455 ?
O2 Fe3 Fe3 90.0 10_556 1_455 ?
O2 Fe3 Fe3 45.86(4) 6_554 1_655 ?
O2 Fe3 Fe3 90.0 10_556 1_655 ?
O2 Fe3 O2 80.84(6) 6_554 10_556 ?
O2 Fe3 O2 88.27(7) 6_454 6_554 ?
O2 Fe3 O2 80.84(6) 6_454 10_556 ?
Fe1 O1 Fe1 87.18(10) 5_445 5_545 ?
Fe3 O1 Fe1 111.58(3) . 5_445 ?
Fe3 O1 Fe1 111.58(3) . 5_545 ?
Fe3 O1 Fe1 111.58(3) 10_556 5_445 ?
Fe3 O1 Fe1 111.58(3) 10_556 5_545 ?
Fe3 O1 Fe3 118.96(13) 10_556 . ?
Fe2 O3 Fe1 110.48(6) 2 13_456 ?
Fe2 O3 Fe1 110.48(6) 2 13_556 ?
Fe2 O3 Fe3 100.40(7) 2 6_455 ?
Fe2 O3 Fe3 100.40(7) 2 6 ?
Fe1 O3 Fe1 82.06(6) 13_556 13_456 ?
Fe3 O3 Fe1 86.45(3) 6 13_556 ?
Fe3 O3 Fe1 86.45(3) 6_455 13_456 ?
Fe3 O3 Fe1 149.10(10) 6 13_456 ?
Fe3 O3 Fe1 149.10(10) 6_455 13_556 ?
Fe3 O3 Fe3 88.97(7) 6 6_455 ?
Fe2 O2 Fe2 88.27(7) 6 6_455 ?
Fe2 O2 Fe3 92.55(6) 6 10_556 ?
Fe2 O2 Fe3 92.55(6) 6_455 10_556 ?
Fe3 O2 Fe2 168.27(11) 6_455 6 ?
Fe3 O2 Fe2 90.535(13) 6_455 6_455 ?
Fe3 O2 Fe2 168.27(11) 6 6_455 ?
Fe3 O2 Fe2 90.535(13) 6 6 ?
Fe3 O2 Fe3 99.16(6) 6 10_556 ?
Fe3 O2 Fe3 99.16(6) 6_455 10_556 ?
Fe3 O2 Fe3 88.27(7) 6_455 6 ?

_olex2_submission_special_instructions 'No special instructions were received'
_exptl_crystal_recrystallization_method 
'high-pressure high-temperature synthesis'
