# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.
# This journal is © The Royal Society of Chemistry 2022

####################################################################### 
# 
# 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_MIL178_Fe
_database_code_depnum_ccdc_archive 'CCDC 2112974'
loop_
_audit_author_name
_audit_author_address
'Jerome Marrot'
;Institut Lavoisier de Versailles
France
;
_audit_update_record             
;
2021-11-16 deposited with the CCDC.	2022-03-03 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2017/1
_shelx_SHELXL_version_number     2017/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C19 H14 Fe O13.50'
_chemical_formula_weight         514.15

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0037 0.0018 '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'
O O 0.0123 0.0067 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe 0.3528 0.9025 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_H-M_alt        'P n m a'
_space_group_name_Hall           '-P 2ac 2n'

_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'
'x+1/2, -y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'x, -y-1/2, z'
'-x-1/2, y-1/2, z-1/2'

_cell_length_a                   6.9300(14)
_cell_length_b                   28.420(6)
_cell_length_c                   9.5600(19)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1882.8(7)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       parallelepiped
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.814
_exptl_crystal_F_000             1048
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.010
_exptl_crystal_size_mid          0.005
_exptl_crystal_size_min          0.005
_exptl_absorpt_coefficient_mu    0.955
_shelx_estimated_absorpt_T_min   0.991
_shelx_estimated_absorpt_T_max   0.995
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.73319
_diffrn_radiation_type           synchrotron
_diffrn_source                   synchrotron
_diffrn_measurement_device_type  'PROXIMA 2A - Synchrotron SOLEIL'
_diffrn_measurement_method       'φ scan'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            17325
_diffrn_reflns_av_unetI/netI     0.0487
_diffrn_reflns_av_R_equivalents  0.1150
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_theta_min         1.478
_diffrn_reflns_theta_max         24.708
_diffrn_reflns_theta_full        24.708
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             1491
_reflns_number_gt                1192
_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       'XDS package'
_computing_cell_refinement       'XDS package'
_computing_data_reduction        'XDS package'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2017)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_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)+(0.1889P)²+4.4875P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         1491
_refine_ls_number_parameters     171
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0963
_refine_ls_R_factor_gt           0.0814
_refine_ls_wR_factor_ref         0.2605
_refine_ls_wR_factor_gt          0.2146
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_restrained_S_all      1.020
_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 0.70889(19) 0.750000 0.74338(12) 0.0454(6) Uani 1 2 d S T P . .
O1 O 0.6216(6) 0.69930(15) 0.6065(5) 0.0516(11) Uani 1 1 d . . . . .
O2 O 0.2948(6) 0.69942(15) 0.6220(5) 0.0520(12) Uani 1 1 d . . . . .
O3 O 0.4678(7) 0.62591(17) 0.8019(5) 0.0529(12) Uani 1 1 d . . . . .
O4 O 0.3343(8) 0.55399(16) 0.7931(5) 0.0614(13) Uani 1 1 d . . . . .
H4 H 0.340879 0.556533 0.880535 0.092 Uiso 1 1 calc R U . . .
O5 O 0.3637(7) 0.55799(16) 0.0666(4) 0.0563(12) Uani 1 1 d . . . . .
O6 O 0.4589(7) 0.63374(17) 0.0748(5) 0.0557(12) Uani 1 1 d . . . . .
H6 H 0.456376 0.630992 -0.012694 0.084 Uiso 1 1 calc R U . . .
O7 O 0.9622(9) 0.750000 0.6555(7) 0.0535(16) Uani 1 2 d DS T P . .
H7O H 1.005(17) 0.750000 0.578(5) 0.080 Uiso 1 2 d DS U P . .
C1 C 0.4565(9) 0.6815(2) 0.5870(6) 0.0494(16) Uani 1 1 d . . . . .
C2 C 0.4018(11) 0.5922(2) 0.7348(6) 0.0490(16) Uani 1 1 d . . . . .
C3 C 0.4094(9) 0.5942(2) 0.1319(7) 0.0507(16) Uani 1 1 d . . . . .
C4 C 0.4413(8) 0.6353(2) 0.5076(6) 0.0456(15) Uani 1 1 d . . . . .
C5 C 0.3997(9) 0.5930(2) 0.5790(6) 0.0476(15) Uani 1 1 d . . . . .
C6 C 0.3598(9) 0.5521(2) 0.5032(6) 0.0498(15) Uani 1 1 d . . . . .
H6A H 0.328372 0.523802 0.550855 0.060 Uiso 1 1 calc R U . . .
C7 C 0.3662(9) 0.5529(2) 0.3589(6) 0.0503(16) Uani 1 1 d . . . . .
H7 H 0.341061 0.524970 0.307510 0.060 Uiso 1 1 calc R U . . .
C8 C 0.4088(9) 0.5940(2) 0.2889(6) 0.0481(15) Uani 1 1 d . . . . .
C9 C 0.4477(8) 0.6354(2) 0.3646(7) 0.0462(15) Uani 1 1 d . . . . .
H9 H 0.478623 0.663565 0.316057 0.055 Uiso 1 1 calc R U . . .
C10 C 0.953(3) 0.7653(7) 0.3719(19) 0.044(7) Uani 0.25 1 d D . P . .
C11 C 0.757(3) 0.750000 0.3135(19) 0.085(8) Uani 0.5 2 d DS T P . .
O8 O 0.645(4) 0.750000 0.188(2) 0.170(13) Uani 0.5 2 d DS 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
Fe1 O7 1.946(6) . ?
Fe1 O7 1.964(6) 6_557 ?
Fe1 O2 2.019(4) 4_566 ?
Fe1 O2 2.019(4) 6_657 ?
Fe1 O1 2.038(4) 7_575 ?
Fe1 O1 2.038(4) . ?
O1 C1 1.265(8) . ?
O2 C1 1.276(8) . ?
O3 C2 1.240(8) . ?
O4 C2 1.307(8) . ?
O4 H4 0.8400 . ?
O5 C3 1.244(8) . ?
O6 C3 1.296(8) . ?
O6 H6 0.8400 . ?
O7 H7O 0.80(2) . ?
C1 C4 1.520(9) . ?
C2 C5 1.490(8) . ?
C3 C8 1.501(8) . ?
C4 C9 1.368(9) . ?
C4 C5 1.413(9) . ?
C5 C6 1.396(9) . ?
C6 C7 1.380(9) . ?
C6 H6A 0.9500 . ?
C7 C8 1.377(9) . ?
C7 H7 0.9500 . ?
C8 C9 1.407(9) . ?
C9 H9 0.9500 . ?
C10 C11 1.528(18) . ?
C11 O8 1.43(2) . ?

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
O7 Fe1 O7 176.09(18) . 6_557 ?
O7 Fe1 O2 90.53(19) . 4_566 ?
O7 Fe1 O2 86.72(18) 6_557 4_566 ?
O7 Fe1 O2 90.53(19) . 6_657 ?
O7 Fe1 O2 86.72(18) 6_557 6_657 ?
O2 Fe1 O2 90.8(3) 4_566 6_657 ?
O7 Fe1 O1 89.46(18) . 7_575 ?
O7 Fe1 O1 93.31(18) 6_557 7_575 ?
O2 Fe1 O1 89.62(19) 4_566 7_575 ?
O2 Fe1 O1 179.59(18) 6_657 7_575 ?
O7 Fe1 O1 89.46(18) . . ?
O7 Fe1 O1 93.31(18) 6_557 . ?
O2 Fe1 O1 179.59(18) 4_566 . ?
O2 Fe1 O1 89.62(19) 6_657 . ?
O1 Fe1 O1 90.0(3) 7_575 . ?
C1 O1 Fe1 130.2(4) . . ?
C1 O2 Fe1 135.3(4) . 6_557 ?
C2 O4 H4 109.5 . . ?
C3 O6 H6 109.5 . . ?
Fe1 O7 Fe1 124.9(3) . 6_657 ?
Fe1 O7 H7O 138(9) . . ?
Fe1 O7 H7O 97(9) 6_657 . ?
O1 C1 O2 126.6(6) . . ?
O1 C1 C4 118.8(5) . . ?
O2 C1 C4 114.5(5) . . ?
O3 C2 O4 123.6(6) . . ?
O3 C2 C5 120.6(6) . . ?
O4 C2 C5 115.8(6) . . ?
O5 C3 O6 124.9(6) . . ?
O5 C3 C8 119.9(6) . . ?
O6 C3 C8 115.2(6) . . ?
C9 C4 C5 119.4(6) . . ?
C9 C4 C1 119.7(6) . . ?
C5 C4 C1 120.6(5) . . ?
C6 C5 C4 119.9(6) . . ?
C6 C5 C2 120.6(6) . . ?
C4 C5 C2 119.6(6) . . ?
C7 C6 C5 119.9(6) . . ?
C7 C6 H6A 120.1 . . ?
C5 C6 H6A 120.1 . . ?
C8 C7 C6 120.4(6) . . ?
C8 C7 H7 119.8 . . ?
C6 C7 H7 119.8 . . ?
C7 C8 C9 120.0(6) . . ?
C7 C8 C3 119.3(6) . . ?
C9 C8 C3 120.7(6) . . ?
C4 C9 C8 120.4(6) . . ?
C4 C9 H9 119.8 . . ?
C8 C9 H9 119.8 . . ?
O8 C11 C10 142.1(19) . . ?

_refine_diff_density_max         0.726
_refine_diff_density_min         -1.206
_refine_diff_density_rms         0.156



