# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2024

####################################################################### 
# 
# 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_shelx
_audit_block_doi                 10.5517/ccdc.csd.cc2j7bch
_database_code_depnum_ccdc_archive 'CCDC 2330746'
loop_
_audit_author_name
_audit_author_address
'M Carmen Munoz'
;Universitat Politecnica de Valenciaat
Spain
;
_audit_update_record             
;
2024-02-03 deposited with the CCDC.	2024-04-17 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C34 H28 F2 Fe N12 O2'
_chemical_formula_weight         730.53

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 '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'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe 0.3463 0.8444 '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'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_H-M_alt        'P b c n'
_space_group_name_Hall           '-P 2n 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+1/2, z+1/2'
'-x, y, -z+1/2'
'x+1/2, -y+1/2, -z'
'-x, -y, -z'
'x-1/2, y-1/2, -z-1/2'
'x, -y, z-1/2'
'-x-1/2, y-1/2, z'

_cell_length_a                   12.7752(8)
_cell_length_b                   10.7048(7)
_cell_length_c                   24.3576(16)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3331.0(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    220(2)
_cell_measurement_reflns_used    2597
_cell_measurement_theta_min      2.482
_cell_measurement_theta_max      24.355

_exptl_crystal_description       plate
_exptl_crystal_colour            orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.457
_exptl_crystal_F_000             1504
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.090
_exptl_crystal_size_mid          0.080
_exptl_crystal_size_min          0.040
_exptl_absorpt_coefficient_mu    0.517
_shelx_estimated_absorpt_T_min   0.955
_shelx_estimated_absorpt_T_max   0.980
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.809
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_process_details   'Empirical absorption correction'
_exptl_absorpt_special_details   
;
SADABS-2016/2 - Bruker AXS area detector scaling and absorption correction
;
_diffrn_ambient_temperature      220(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'APEX3 v2018.7-2'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            22138
_diffrn_reflns_av_unetI/netI     0.0637
_diffrn_reflns_av_R_equivalents  0.1270
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_theta_min         2.310
_diffrn_reflns_theta_max         25.050
_diffrn_reflns_theta_full        25.050
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             2946
_reflns_number_gt                1978
_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       'SAINT V8.38A (Bruker AXS Inc., 2017)'
_computing_cell_refinement       'SAINT V8.38A (Bruker AXS Inc., 2017)'
_computing_data_reduction        'SAINT V8.38A (Bruker AXS Inc., 2017)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_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)+(0.0368P)²+16.2874P] 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     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2946
_refine_ls_number_parameters     233
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1149
_refine_ls_R_factor_gt           0.0703
_refine_ls_wR_factor_ref         0.1929
_refine_ls_wR_factor_gt          0.1626
_refine_ls_goodness_of_fit_ref   1.105
_refine_ls_restrained_S_all      1.105
_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
Fe Fe 0.500000 0.65616(10) 0.250000 0.0313(3) Uani 1 2 d S T P . .
N2 N 0.6471(3) 0.6659(4) 0.23589(17) 0.0321(10) Uani 1 1 d . . . . .
N1 N 0.5022(3) 0.7868(4) 0.19282(18) 0.0347(10) Uani 1 1 d . . . . .
N3 N 0.5515(4) 0.5275(4) 0.30166(18) 0.0371(11) Uani 1 1 d . . . . .
N4 N 0.6026(3) 0.8220(4) 0.17850(18) 0.0370(11) Uani 1 1 d . . . . .
O O 0.3236(3) 0.5406(5) 0.3841(2) 0.0617(13) Uani 1 1 d . . . . .
H1O H 0.378044 0.503063 0.375556 0.092 Uiso 1 1 calc R U . . .
N6 N 0.5136(4) 0.4476(4) 0.34068(19) 0.0383(11) Uani 1 1 d . . . . .
N5 N 0.6902(3) 0.4223(4) 0.3348(2) 0.0409(12) Uani 1 1 d . . . . .
F F 0.4312(4) 0.3329(5) 0.4341(2) 0.1073(18) Uani 1 1 d . . . . .
C4 C 0.6839(4) 0.7533(5) 0.2023(2) 0.0349(13) Uani 1 1 d . . . . .
C9 C 0.6570(4) 0.5101(5) 0.2998(2) 0.0359(13) Uani 1 1 d . . . . .
C8 C 0.7157(4) 0.5909(5) 0.2631(2) 0.0374(13) Uani 1 1 d . . . . .
C10 C 0.5997(4) 0.3872(5) 0.3591(2) 0.0379(13) Uani 1 1 d . . . . .
C1 C 0.4404(5) 0.8611(5) 0.1643(2) 0.0418(14) Uani 1 1 d . . . . .
H1 H 0.366862 0.858631 0.165337 0.050 Uiso 1 1 calc R U . . .
C2 C 0.4988(5) 0.9442(5) 0.1321(2) 0.0441(14) Uani 1 1 d . . . . .
H2 H 0.472363 1.005728 0.108320 0.053 Uiso 1 1 calc R U . . .
C3 C 0.6014(5) 0.9183(5) 0.1420(2) 0.0423(14) Uani 1 1 d . . . . .
H3 H 0.659822 0.958790 0.126712 0.051 Uiso 1 1 calc R U . . .
C11 C 0.5992(5) 0.2909(6) 0.4025(2) 0.0446(15) Uani 1 1 d . . . . .
C5 C 0.7890(4) 0.7726(6) 0.1931(2) 0.0437(15) Uani 1 1 d . . . . .
H5 H 0.812631 0.835755 0.169329 0.052 Uiso 1 1 calc R U . . .
C7 C 0.8211(4) 0.6028(6) 0.2553(3) 0.0445(15) Uani 1 1 d . . . . .
H7 H 0.868028 0.549159 0.273397 0.053 Uiso 1 1 calc R U . . .
C6 C 0.8582(5) 0.6953(6) 0.2203(3) 0.0491(16) Uani 1 1 d . . . . .
H6 H 0.930687 0.705307 0.215120 0.059 Uiso 1 1 calc R U . . .
C16 C 0.5175(6) 0.2681(6) 0.4377(3) 0.0543(17) Uani 1 1 d . . . . .
C12 C 0.6909(6) 0.2174(6) 0.4102(3) 0.068(2) Uani 1 1 d . . . . .
H12 H 0.748953 0.228295 0.387031 0.082 Uiso 1 1 calc R U . . .
C15 C 0.5216(7) 0.1832(7) 0.4803(3) 0.070(2) Uani 1 1 d . . . . .
H15 H 0.464170 0.172580 0.503998 0.084 Uiso 1 1 calc R U . . .
C14 C 0.6116(8) 0.1147(7) 0.4874(3) 0.073(2) Uani 1 1 d . . . . .
H14 H 0.616527 0.057401 0.516541 0.088 Uiso 1 1 calc R U . . .
C13 C 0.6944(7) 0.1300(8) 0.4519(3) 0.079(2) Uani 1 1 d . . . . .
H13 H 0.754370 0.080047 0.456119 0.094 Uiso 1 1 calc R U . . .
C17 C 0.3414(7) 0.6117(8) 0.4311(3) 0.086(3) Uani 1 1 d . . . . .
H17C H 0.406851 0.656754 0.427341 0.129 Uiso 1 1 calc R U . . .
H17A H 0.345144 0.557013 0.462840 0.129 Uiso 1 1 calc R U . . .
H17B H 0.284521 0.670719 0.435991 0.129 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
Fe N1 1.974(4) 3_655 ?
Fe N1 1.974(4) . ?
Fe N2 1.913(4) 3_655 ?
Fe N2 1.913(4) . ?
Fe N3 1.978(5) . ?
Fe N3 1.978(5) 3_655 ?
N2 C4 1.328(7) . ?
N2 C8 1.362(7) . ?
N1 C1 1.319(7) . ?
N1 N4 1.382(6) . ?
N3 C9 1.362(7) . ?
N3 N6 1.367(6) . ?
N4 C3 1.361(7) . ?
N4 C4 1.398(7) . ?
O C17 1.394(8) . ?
O H1O 0.8300 . ?
N6 C10 1.352(7) . ?
N5 C9 1.338(7) . ?
N5 C10 1.352(7) . ?
F C16 1.306(8) . ?
C4 C5 1.378(7) . ?
C9 C8 1.453(7) . ?
C8 C7 1.366(7) . ?
C10 C11 1.477(8) . ?
C1 C2 1.400(8) . ?
C1 H1 0.9400 . ?
C2 C3 1.362(8) . ?
C2 H2 0.9400 . ?
C3 H3 0.9400 . ?
C11 C16 1.373(9) . ?
C11 C12 1.424(9) . ?
C5 C6 1.380(8) . ?
C5 H5 0.9400 . ?
C7 C6 1.390(8) . ?
C7 H7 0.9400 . ?
C6 H6 0.9400 . ?
C16 C15 1.380(9) . ?
C12 C13 1.381(9) . ?
C12 H12 0.9400 . ?
C15 C14 1.374(11) . ?
C15 H15 0.9400 . ?
C14 C13 1.376(11) . ?
C14 H14 0.9400 . ?
C13 H13 0.9400 . ?
C17 H17C 0.9700 . ?
C17 H17A 0.9700 . ?
C17 H17B 0.9700 . ?

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
N1 Fe N1 89.8(3) 3_655 . ?
N2 Fe N1 79.67(18) 3_655 3_655 ?
N2 Fe N1 95.84(19) . 3_655 ?
N2 Fe N1 95.84(19) 3_655 . ?
N2 Fe N1 79.67(18) . . ?
N1 Fe N3 92.81(18) 3_655 . ?
N1 Fe N3 159.64(18) . . ?
N1 Fe N3 159.64(18) 3_655 3_655 ?
N1 Fe N3 92.81(18) . 3_655 ?
N2 Fe N2 173.7(3) 3_655 . ?
N2 Fe N3 104.49(18) 3_655 . ?
N2 Fe N3 79.98(18) . . ?
N2 Fe N3 79.98(18) 3_655 3_655 ?
N2 Fe N3 104.49(18) . 3_655 ?
N3 Fe N3 91.8(3) . 3_655 ?
C4 N2 C8 119.2(5) . . ?
C4 N2 Fe 119.8(3) . . ?
C8 N2 Fe 120.9(4) . . ?
C1 N1 N4 105.0(5) . . ?
C1 N1 Fe 142.3(4) . . ?
N4 N1 Fe 112.6(3) . . ?
C9 N3 N6 106.7(4) . . ?
C9 N3 Fe 113.8(4) . . ?
N6 N3 Fe 139.5(4) . . ?
C3 N4 N1 111.1(4) . . ?
C3 N4 C4 132.6(5) . . ?
N1 N4 C4 116.2(4) . . ?
C17 O H1O 109.5 . . ?
C10 N6 N3 104.0(4) . . ?
C9 N5 C10 101.7(5) . . ?
N2 C4 C5 123.4(5) . . ?
N2 C4 N4 111.3(4) . . ?
C5 C4 N4 125.3(5) . . ?
N5 C9 N3 112.9(5) . . ?
N5 C9 C8 130.2(5) . . ?
N3 C9 C8 116.8(5) . . ?
N2 C8 C7 120.8(5) . . ?
N2 C8 C9 108.5(5) . . ?
C7 C8 C9 130.6(5) . . ?
N5 C10 N6 114.7(5) . . ?
N5 C10 C11 120.8(5) . . ?
N6 C10 C11 124.6(5) . . ?
N1 C1 C2 111.0(5) . . ?
N1 C1 H1 124.5 . . ?
C2 C1 H1 124.5 . . ?
C3 C2 C1 106.5(5) . . ?
C3 C2 H2 126.7 . . ?
C1 C2 H2 126.7 . . ?
N4 C3 C2 106.3(5) . . ?
N4 C3 H3 126.8 . . ?
C2 C3 H3 126.8 . . ?
C16 C11 C12 116.3(6) . . ?
C16 C11 C10 125.1(6) . . ?
C12 C11 C10 118.5(6) . . ?
C4 C5 C6 117.2(5) . . ?
C4 C5 H5 121.4 . . ?
C6 C5 H5 121.4 . . ?
C8 C7 C6 119.2(5) . . ?
C8 C7 H7 120.4 . . ?
C6 C7 H7 120.4 . . ?
C5 C6 C7 120.2(5) . . ?
C5 C6 H6 119.9 . . ?
C7 C6 H6 119.9 . . ?
F C16 C11 120.3(6) . . ?
F C16 C15 115.6(7) . . ?
C11 C16 C15 124.0(7) . . ?
C13 C12 C11 119.9(8) . . ?
C13 C12 H12 120.1 . . ?
C11 C12 H12 120.1 . . ?
C14 C15 C16 118.5(7) . . ?
C14 C15 H15 120.7 . . ?
C16 C15 H15 120.7 . . ?
C15 C14 C13 120.0(7) . . ?
C15 C14 H14 120.0 . . ?
C13 C14 H14 120.0 . . ?
C14 C13 C12 121.2(8) . . ?
C14 C13 H13 119.4 . . ?
C12 C13 H13 119.4 . . ?
O C17 H17C 109.5 . . ?
O C17 H17A 109.5 . . ?
H17C C17 H17A 109.5 . . ?
O C17 H17B 109.5 . . ?
H17C C17 H17B 109.5 . . ?
H17A C17 H17B 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C1 N1 N4 C3 0.8(6) . . . . ?
Fe N1 N4 C3 -175.6(4) . . . . ?
C1 N1 N4 C4 -177.9(5) . . . . ?
Fe N1 N4 C4 5.7(6) . . . . ?
C9 N3 N6 C10 -0.5(6) . . . . ?
Fe N3 N6 C10 -179.8(5) . . . . ?
C8 N2 C4 C5 0.1(8) . . . . ?
Fe N2 C4 C5 175.0(5) . . . . ?
C8 N2 C4 N4 -179.4(5) . . . . ?
Fe N2 C4 N4 -4.4(6) . . . . ?
C3 N4 C4 N2 -179.5(5) . . . . ?
N1 N4 C4 N2 -1.1(7) . . . . ?
C3 N4 C4 C5 1.0(10) . . . . ?
N1 N4 C4 C5 179.5(5) . . . . ?
C10 N5 C9 N3 -0.8(7) . . . . ?
C10 N5 C9 C8 176.1(6) . . . . ?
N6 N3 C9 N5 0.8(7) . . . . ?
Fe N3 C9 N5 -179.6(4) . . . . ?
N6 N3 C9 C8 -176.6(5) . . . . ?
Fe N3 C9 C8 3.0(7) . . . . ?
C4 N2 C8 C7 -1.3(8) . . . . ?
Fe N2 C8 C7 -176.2(5) . . . . ?
C4 N2 C8 C9 176.0(5) . . . . ?
Fe N2 C8 C9 1.1(6) . . . . ?
N5 C9 C8 N2 -179.5(6) . . . . ?
N3 C9 C8 N2 -2.6(7) . . . . ?
N5 C9 C8 C7 -2.5(11) . . . . ?
N3 C9 C8 C7 174.4(6) . . . . ?
C9 N5 C10 N6 0.5(7) . . . . ?
C9 N5 C10 C11 -178.9(5) . . . . ?
N3 N6 C10 N5 0.0(6) . . . . ?
N3 N6 C10 C11 179.4(5) . . . . ?
N4 N1 C1 C2 -0.5(6) . . . . ?
Fe N1 C1 C2 174.1(5) . . . . ?
N1 C1 C2 C3 -0.1(7) . . . . ?
N1 N4 C3 C2 -0.9(6) . . . . ?
C4 N4 C3 C2 177.6(6) . . . . ?
C1 C2 C3 N4 0.6(7) . . . . ?
N5 C10 C11 C16 164.9(6) . . . . ?
N6 C10 C11 C16 -14.5(10) . . . . ?
N5 C10 C11 C12 -13.0(9) . . . . ?
N6 C10 C11 C12 167.5(6) . . . . ?
N2 C4 C5 C6 0.6(9) . . . . ?
N4 C4 C5 C6 180.0(6) . . . . ?
N2 C8 C7 C6 1.8(9) . . . . ?
C9 C8 C7 C6 -174.9(6) . . . . ?
C4 C5 C6 C7 -0.1(10) . . . . ?
C8 C7 C6 C5 -1.1(10) . . . . ?
C12 C11 C16 F 178.8(6) . . . . ?
C10 C11 C16 F 0.7(10) . . . . ?
C12 C11 C16 C15 2.6(10) . . . . ?
C10 C11 C16 C15 -175.4(6) . . . . ?
C16 C11 C12 C13 -0.8(10) . . . . ?
C10 C11 C12 C13 177.4(6) . . . . ?
F C16 C15 C14 -178.1(7) . . . . ?
C11 C16 C15 C14 -1.7(11) . . . . ?
C16 C15 C14 C13 -1.0(11) . . . . ?
C15 C14 C13 C12 2.8(12) . . . . ?
C11 C12 C13 C14 -1.9(12) . . . . ?

_refine_diff_density_max         0.913
_refine_diff_density_min         -0.556
_refine_diff_density_rms         0.083

####################################################################### 
# 
# 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_shelx_CCDC1
_audit_block_doi                 10.5517/ccdc.csd.cc2j7bdj
_database_code_depnum_ccdc_archive 'CCDC 2330747'
loop_
_audit_author_name
_audit_author_address
'M Carmen Munoz'
;Universitat Politecnica de Valenciaat
Spain
;
_audit_update_record             
;
2024-02-03 deposited with the CCDC.	2024-04-17 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_RINTA01_shelx               
;
PROBLEM: The value of Rint is greater than 0.18
RESPONSE: the crystal deteriorates upon spin transition from low- to high-spin state
;
# Added during the CSD deposition process: Saturday 03 February 2024 07:39 PM
# end Validation Reply Form


_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C34 H28 F2 Fe N12 O2'
_chemical_formula_weight         730.53

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 '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'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe 0.3463 0.8444 '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'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_H-M_alt        'P b c n'
_space_group_name_Hall           '-P 2n 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+1/2, z+1/2'
'-x, y, -z+1/2'
'x+1/2, -y+1/2, -z'
'-x, -y, -z'
'x-1/2, y-1/2, -z-1/2'
'x, -y, z-1/2'
'-x-1/2, y-1/2, z'

_cell_length_a                   13.05(2)
_cell_length_b                   10.401(18)
_cell_length_c                   25.06(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3402(10)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    1190
_cell_measurement_theta_min      2.6325
_cell_measurement_theta_max      21.615

_exptl_crystal_description       plate
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.426
_exptl_crystal_F_000             1504
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.090
_exptl_crystal_size_mid          0.080
_exptl_crystal_size_min          0.040
_exptl_absorpt_coefficient_mu    0.506
_shelx_estimated_absorpt_T_min   0.956
_shelx_estimated_absorpt_T_max   0.980
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.769
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_process_details   'Empirical absorption correction'
_exptl_absorpt_special_details   
;
SADABS-2016/2 - Bruker AXS area detector scaling and absorption correction
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'APEX3 v2018.7-2'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            23664
_diffrn_reflns_av_unetI/netI     0.0917
_diffrn_reflns_av_R_equivalents  0.2049
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_theta_min         2.504
_diffrn_reflns_theta_max         25.012
_diffrn_reflns_theta_full        25.012
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             3001
_reflns_number_gt                1473
_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       'SAINT V8.38A (Bruker AXS Inc., 2017)'
_computing_cell_refinement       'SAINT V8.38A (Bruker AXS Inc., 2017)'
_computing_data_reduction        'SAINT V8.38A (Bruker AXS Inc., 2017)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_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)+(0.0904P)²+2.9107P] 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-2018/3 (Sheldrick 2018)'
_refine_ls_extinction_coef       0.0033(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         3001
_refine_ls_number_parameters     243
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1520
_refine_ls_R_factor_gt           0.0624
_refine_ls_wR_factor_ref         0.2283
_refine_ls_wR_factor_gt          0.1477
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_restrained_S_all      1.085
_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
Fe Fe 0.500000 0.36607(13) 0.250000 0.0512(5) Uani 1 2 d S T P . .
N2 N 0.3394(3) 0.3440(5) 0.23633(18) 0.0493(13) Uani 1 1 d . . . . .
N4 N 0.3793(4) 0.1852(5) 0.1764(2) 0.0533(13) Uani 1 1 d . . . . .
N1 N 0.4808(4) 0.2127(5) 0.1884(2) 0.0541(14) Uani 1 1 d . . . . .
N3 N 0.4292(4) 0.4983(5) 0.30335(19) 0.0551(14) Uani 1 1 d . . . . .
O O 0.6419(4) 0.4818(6) 0.3854(2) 0.0912(17) Uani 1 1 d . . . . .
H1O H 0.593593 0.530414 0.379779 0.137 Uiso 1 1 calc R U . . .
N5 N 0.2856(4) 0.5933(5) 0.3329(2) 0.0593(14) Uani 1 1 d . . . . .
N6 N 0.4576(4) 0.5835(5) 0.3428(2) 0.0599(14) Uani 1 1 d . . . . .
C4 C 0.3032(4) 0.2580(6) 0.2025(2) 0.0497(15) Uani 1 1 d . . . . .
C9 C 0.3263(4) 0.5068(6) 0.2996(2) 0.0517(16) Uani 1 1 d . . . . .
C8 C 0.2729(4) 0.4207(6) 0.2632(2) 0.0518(16) Uani 1 1 d . . . . .
C10 C 0.3699(5) 0.6376(6) 0.3592(2) 0.0539(16) Uani 1 1 d . . . . .
C5 C 0.1996(5) 0.2401(7) 0.1927(3) 0.0624(18) Uani 1 1 d . . . . .
H5 H 0.176183 0.178853 0.168511 0.075 Uiso 1 1 calc R U . . .
C11 C 0.3626(6) 0.7338(7) 0.4019(3) 0.0624(18) Uani 1 1 d . . . . .
C3 C 0.3721(6) 0.0905(7) 0.1398(3) 0.0655(19) Uani 1 1 d . . . . .
H3 H 0.311935 0.055886 0.125944 0.079 Uiso 1 1 calc R U . . .
C7 C 0.1689(5) 0.4097(7) 0.2554(3) 0.0670(19) Uani 1 1 d . . . . .
H7 H 0.123730 0.463632 0.273331 0.080 Uiso 1 1 calc R U . . .
C1 C 0.5331(5) 0.1329(7) 0.1573(2) 0.0613(18) Uani 1 1 d . . . . .
H1 H 0.604302 0.129338 0.156111 0.074 Uiso 1 1 calc R U . . .
F1A F 0.5243(5) 0.6919(8) 0.4366(3) 0.127(3) Uani 0.75 1 d . . P A 1
C6 C 0.1330(5) 0.3182(8) 0.2208(3) 0.074(2) Uani 1 1 d . . . . .
H6 H 0.062686 0.308472 0.216148 0.088 Uiso 1 1 calc R U . . .
C2 C 0.4692(6) 0.0552(7) 0.1269(3) 0.070(2) Uani 1 1 d . . . . .
H2 H 0.488915 -0.007911 0.102641 0.084 Uiso 1 1 calc R U . . .
C16 C 0.4395(7) 0.7541(8) 0.4391(3) 0.079(2) Uani 1 1 d . . . . .
H12B H 0.499676 0.706685 0.436201 0.095 Uiso 0.25 1 calc R U P A 2
C15 C 0.4308(9) 0.8413(9) 0.4802(3) 0.096(3) Uani 1 1 d . . . . .
H15 H 0.484377 0.853076 0.504142 0.115 Uiso 1 1 calc R U . . .
C12 C 0.2771(9) 0.8083(10) 0.4095(4) 0.109(3) Uani 1 1 d . . . . .
H12A H 0.223372 0.799356 0.385421 0.131 Uiso 0.75 1 calc R U P B 1
C14 C 0.3428(11) 0.9100(9) 0.4852(3) 0.113(4) Uani 1 1 d . . . . .
H14 H 0.335814 0.968099 0.513166 0.136 Uiso 1 1 calc R U . . .
C17 C 0.6209(8) 0.4067(9) 0.4301(4) 0.116(3) Uani 1 1 d . . . . .
H17C H 0.572861 0.340579 0.420693 0.175 Uiso 1 1 calc R U . . .
H17A H 0.592260 0.459678 0.457679 0.175 Uiso 1 1 calc R U . . .
H17B H 0.683153 0.368011 0.442688 0.175 Uiso 1 1 calc R U . . .
C13 C 0.2657(10) 0.8952(10) 0.4502(4) 0.138(5) Uani 1 1 d . . . . .
H13 H 0.205799 0.942856 0.453589 0.166 Uiso 1 1 calc R U . . .
F1B F 0.2031(17) 0.798(2) 0.3840(10) 0.136(9) Uani 0.25 1 d . . P C 2


_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
Fe N1 2.235(6) 3_655 ?
Fe N1 2.235(6) . ?
Fe N2 2.136(6) . ?
Fe N2 2.136(6) 3_655 ?
Fe N3 2.129(6) 3_655 ?
Fe N3 2.129(6) . ?
N2 C4 1.320(7) . ?
N2 C8 1.357(8) . ?
N4 C3 1.351(8) . ?
N4 N1 1.388(7) . ?
N4 C4 1.409(7) . ?
N1 C1 1.327(8) . ?
N3 C9 1.350(7) . ?
N3 N6 1.379(7) . ?
O C17 1.392(9) . ?
O H1O 0.8200 . ?
N5 C9 1.337(7) . ?
N5 C10 1.362(8) . ?
N6 C10 1.341(8) . ?
C4 C5 1.388(8) . ?
C9 C8 1.456(8) . ?
C8 C7 1.375(8) . ?
C10 C11 1.469(9) . ?
C5 C6 1.383(9) . ?
C5 H5 0.9300 . ?
C11 C12 1.371(11) . ?
C11 C16 1.387(10) . ?
C3 C2 1.360(9) . ?
C3 H3 0.9300 . ?
C7 C6 1.371(9) . ?
C7 H7 0.9300 . ?
C1 C2 1.390(9) . ?
C1 H1 0.9300 . ?
F1A C16 1.284(10) . ?
C6 H6 0.9300 . ?
C2 H2 0.9300 . ?
C16 C15 1.376(11) . ?
C16 H12B 0.9300 . ?
C15 C14 1.359(13) . ?
C15 H15 0.9300 . ?
C12 F1B 1.16(2) . ?
C12 C13 1.371(11) . ?
C12 H12A 0.9300 . ?
C14 C13 1.342(14) . ?
C14 H14 0.9300 . ?
C17 H17C 0.9600 . ?
C17 H17A 0.9600 . ?
C17 H17B 0.9600 . ?
C13 H13 0.9300 . ?

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
N1 Fe N1 88.9(3) 3_655 . ?
N2 Fe N1 98.30(18) . 3_655 ?
N2 Fe N1 72.68(18) 3_655 3_655 ?
N2 Fe N1 72.69(18) . . ?
N2 Fe N1 98.30(18) 3_655 . ?
N3 Fe N1 94.4(2) 3_655 . ?
N3 Fe N1 147.82(19) . . ?
N3 Fe N1 147.82(18) 3_655 3_655 ?
N3 Fe N1 94.4(2) . 3_655 ?
N3 Fe N3 99.5(3) 3_655 . ?
N3 Fe N2 113.24(19) 3_655 . ?
N3 Fe N2 75.17(19) . . ?
N3 Fe N2 75.17(19) 3_655 3_655 ?
N3 Fe N2 113.24(19) . 3_655 ?
N2 Fe N2 167.7(3) . 3_655 ?
C4 N2 C8 119.2(5) . . ?
C4 N2 Fe 121.8(4) . . ?
C8 N2 Fe 119.0(4) . . ?
C3 N4 N1 111.3(5) . . ?
C3 N4 C4 131.2(6) . . ?
N1 N4 C4 117.5(5) . . ?
C1 N1 N4 103.7(5) . . ?
C1 N1 Fe 142.5(5) . . ?
N4 N1 Fe 113.8(4) . . ?
C9 N3 N6 106.0(5) . . ?
C9 N3 Fe 115.5(4) . . ?
N6 N3 Fe 138.5(4) . . ?
C17 O H1O 109.5 . . ?
C9 N5 C10 102.1(5) . . ?
C10 N6 N3 105.0(5) . . ?
N2 C4 C5 123.7(6) . . ?
N2 C4 N4 114.2(5) . . ?
C5 C4 N4 122.2(6) . . ?
N5 C9 N3 113.3(5) . . ?
N5 C9 C8 127.9(6) . . ?
N3 C9 C8 118.7(5) . . ?
N2 C8 C7 120.8(6) . . ?
N2 C8 C9 111.4(5) . . ?
C7 C8 C9 127.8(6) . . ?
N6 C10 N5 113.6(6) . . ?
N6 C10 C11 124.4(6) . . ?
N5 C10 C11 122.1(6) . . ?
C6 C5 C4 116.3(6) . . ?
C6 C5 H5 121.8 . . ?
C4 C5 H5 121.8 . . ?
C12 C11 C16 114.2(8) . . ?
C12 C11 C10 122.6(7) . . ?
C16 C11 C10 123.1(7) . . ?
N4 C3 C2 107.1(6) . . ?
N4 C3 H3 126.5 . . ?
C2 C3 H3 126.5 . . ?
C6 C7 C8 119.0(6) . . ?
C6 C7 H7 120.5 . . ?
C8 C7 H7 120.5 . . ?
N1 C1 C2 112.1(6) . . ?
N1 C1 H1 123.9 . . ?
C2 C1 H1 123.9 . . ?
C7 C6 C5 121.0(6) . . ?
C7 C6 H6 119.5 . . ?
C5 C6 H6 119.5 . . ?
C3 C2 C1 105.8(6) . . ?
C3 C2 H2 127.1 . . ?
C1 C2 H2 127.1 . . ?
F1A C16 C15 116.2(8) . . ?
F1A C16 C11 121.0(8) . . ?
C15 C16 C11 122.9(9) . . ?
C15 C16 H12B 118.6 . . ?
C11 C16 H12B 118.6 . . ?
C14 C15 C16 119.1(9) . . ?
C14 C15 H15 120.5 . . ?
C16 C15 H15 120.5 . . ?
F1B C12 C11 123.1(14) . . ?
F1B C12 C13 112.3(15) . . ?
C11 C12 C13 124.3(9) . . ?
C11 C12 H12A 117.8 . . ?
C13 C12 H12A 117.8 . . ?
C13 C14 C15 120.8(9) . . ?
C13 C14 H14 119.6 . . ?
C15 C14 H14 119.6 . . ?
O C17 H17C 109.5 . . ?
O C17 H17A 109.5 . . ?
H17C C17 H17A 109.5 . . ?
O C17 H17B 109.5 . . ?
H17C C17 H17B 109.5 . . ?
H17A C17 H17B 109.5 . . ?
C14 C13 C12 118.7(10) . . ?
C14 C13 H13 120.7 . . ?
C12 C13 H13 120.7 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C3 N4 N1 C1 0.7(7) . . . . ?
C4 N4 N1 C1 -178.4(5) . . . . ?
C3 N4 N1 Fe -178.9(4) . . . . ?
C4 N4 N1 Fe 2.0(6) . . . . ?
C9 N3 N6 C10 -0.7(6) . . . . ?
Fe N3 N6 C10 178.9(5) . . . . ?
C8 N2 C4 C5 -0.4(9) . . . . ?
Fe N2 C4 C5 179.6(5) . . . . ?
C8 N2 C4 N4 179.1(5) . . . . ?
Fe N2 C4 N4 -0.8(7) . . . . ?
C3 N4 C4 N2 -179.8(6) . . . . ?
N1 N4 C4 N2 -0.9(8) . . . . ?
C3 N4 C4 C5 -0.2(10) . . . . ?
N1 N4 C4 C5 178.7(5) . . . . ?
C10 N5 C9 N3 -1.3(7) . . . . ?
C10 N5 C9 C8 175.7(6) . . . . ?
N6 N3 C9 N5 1.4(7) . . . . ?
Fe N3 C9 N5 -178.4(4) . . . . ?
N6 N3 C9 C8 -176.0(5) . . . . ?
Fe N3 C9 C8 4.3(7) . . . . ?
C4 N2 C8 C7 -0.1(9) . . . . ?
Fe N2 C8 C7 179.9(5) . . . . ?
C4 N2 C8 C9 178.4(5) . . . . ?
Fe N2 C8 C9 -1.6(7) . . . . ?
N5 C9 C8 N2 -178.7(6) . . . . ?
N3 C9 C8 N2 -1.8(8) . . . . ?
N5 C9 C8 C7 -0.3(11) . . . . ?
N3 C9 C8 C7 176.6(7) . . . . ?
N3 N6 C10 N5 -0.1(7) . . . . ?
N3 N6 C10 C11 178.9(6) . . . . ?
C9 N5 C10 N6 0.8(7) . . . . ?
C9 N5 C10 C11 -178.2(6) . . . . ?
N2 C4 C5 C6 -0.2(10) . . . . ?
N4 C4 C5 C6 -179.8(6) . . . . ?
N6 C10 C11 C12 164.6(8) . . . . ?
N5 C10 C11 C12 -16.5(11) . . . . ?
N6 C10 C11 C16 -17.8(11) . . . . ?
N5 C10 C11 C16 161.1(7) . . . . ?
N1 N4 C3 C2 -0.5(7) . . . . ?
C4 N4 C3 C2 178.5(6) . . . . ?
N2 C8 C7 C6 1.2(10) . . . . ?
C9 C8 C7 C6 -177.0(7) . . . . ?
N4 N1 C1 C2 -0.8(7) . . . . ?
Fe N1 C1 C2 178.7(5) . . . . ?
C8 C7 C6 C5 -1.9(11) . . . . ?
C4 C5 C6 C7 1.4(11) . . . . ?
N4 C3 C2 C1 0.0(8) . . . . ?
N1 C1 C2 C3 0.5(8) . . . . ?
C12 C11 C16 F1A -179.3(9) . . . . ?
C10 C11 C16 F1A 2.9(12) . . . . ?
C12 C11 C16 C15 0.1(12) . . . . ?
C10 C11 C16 C15 -177.7(7) . . . . ?
F1A C16 C15 C14 -179.8(9) . . . . ?
C11 C16 C15 C14 0.8(13) . . . . ?
C16 C11 C12 F1B -175(2) . . . . ?
C10 C11 C12 F1B 3(3) . . . . ?
C16 C11 C12 C13 -0.7(15) . . . . ?
C10 C11 C12 C13 177.1(9) . . . . ?
C16 C15 C14 C13 -1.1(16) . . . . ?
C15 C14 C13 C12 0.5(18) . . . . ?
F1B C12 C13 C14 175(2) . . . . ?
C11 C12 C13 C14 0.4(18) . . . . ?

_refine_diff_density_max         0.588
_refine_diff_density_min         -0.388
_refine_diff_density_rms         0.073

