Sulfur-ligated iron(iv)-imido and iron(iv)-oxo complexes, which one is more reactive?
Satpathy, Jagnyesh Kumar; Yadav, Rolly; Sahoo, Limashree; Uhlig, Jens; Nordlander, Ebbe; Sastri, Chivukula V.; de Visser, Sam P.; Chemical Science  (2025) –; doi:10.1039/D5SC07586F

data_1576320
_publ_section_title
;
 Sulfur-ligated iron(iv)-imido and iron(iv)-oxo complexes, which one is
 more reactive?
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC07586F
_journal_year                    2025
_chemical_formula_moiety         'C22 H25 Fe N5 S, 2(C F3 O3 S)'
_chemical_formula_sum            'C24 H25 F6 Fe N5 O6 S3'
_chemical_formula_weight         745.52
_chemical_name_systematic        Fe-STPen-OTf
_chemical_properties_physical    Moisture-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-06-17
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-11-24 deposited with the CCDC.	2025-11-17 downloaded from the CCDC.
;
_cell_angle_alpha                109.78(3)
_cell_angle_beta                 95.38(4)
_cell_angle_gamma                110.84(3)
_cell_formula_units_Z            2
_cell_length_a                   11.840(13)
_cell_length_b                   12.227(13)
_cell_length_c                   12.436(13)
_cell_measurement_reflns_used    6662
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      22.86
_cell_measurement_theta_min      2.27
_cell_volume                     1536(3)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_diffrn_ambient_temperature      298.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0663
_diffrn_reflns_av_unetI/netI     0.0665
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            38490
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.667
_diffrn_reflns_theta_min         1.794
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.779
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6601
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1307 before and 0.0614 after correction.
The Ratio of minimum to maximum transmission is 0.8856.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.612
_exptl_crystal_description       block
_exptl_crystal_F_000             760
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile and diethyl ether'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.581
_refine_diff_density_min         -0.382
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     407
_refine_ls_number_reflns         6333
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0913
_refine_ls_R_factor_gt           0.0518
_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/[\s^2^(Fo^2^)+(0.0718P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1260
_refine_ls_wR_factor_ref         0.1379
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4158
_reflns_number_total             6333
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07586f2.cif
_cod_data_source_block           fe_stpen_otf_0m_a
_cod_database_code               1576320
_shelx_shelxl_version_number     2019/1
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C6(H6A,H6B), C8(H8A,H8B), C9(H9A,H9B), C15(H15A,H15B)
2.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C14(H14), C19(H19), C17(H17), C13(H13), C1(H1), C11(H11), C18(H18),
 C4(H4), C3(H3), C12(H12), C2(H2)
2.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 30 electrons were 
found in a volume of 99\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1.5[H2O] per Asymmetric Unit 
which account for 30 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              88559
_shelx_fab_checksum              75449
_olex2_submission_special_instructions 'No special instructions were received'