Radical Rebound Hydroxylation Versus H-Atom Transfer in Non-Heme Iron(III)-Hydroxo Complexes: Reactivity and Structural Differentiation.
Drummond, Michael J.; Ford, Courtney L.; Gray, Danielle L.; Popescu, Codrina V.; Fout, Alison R.; Journal of the American Chemical Society 141 (2019) 6639–6650; doi:10.1021/jacs.9b01516

data_4128247
_publ_section_title
;
 Radical Rebound Hydroxylation Versus H-Atom Transfer in Non-Heme
 Iron(III)-Hydroxo Complexes: Reactivity and Structural Differentiation.
;
_journal_issue                   16
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6639
_journal_page_last               6650
_journal_paper_doi               10.1021/jacs.9b01516
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C42 H47 F3 Fe N7 O3 S, C F3 O3 S, C2 H3 N'
_chemical_formula_sum            'C45 H50 F6 Fe N8 O6 S2'
_chemical_formula_weight         1032.90
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-12-22
_audit_creation_method
; 
Olex2 1.2 
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381) 
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.2527(4)
_cell_length_b                   21.2810(4)
_cell_length_c                   24.4192(5)
_cell_measurement_reflns_used    47242
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.34
_cell_measurement_theta_min      2.22
_cell_volume                     9485.3(3)
_computing_cell_refinement       'SAINT V8.37A (Bruker, 2005)'
_computing_data_collection       'APEX3 V2016.9-0 (Bruker, 2016)'
_computing_data_reduction
; 
SAINT V8.37A, XPREP v2014/2, SADABS V2014/7 (Bruker, 2014) 
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELX-2014-7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELX-2014-7 (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.98
_diffrn_detector                 'Bruker APEXII CCD area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_wavelength_id  dd88g
_diffrn_reflns_av_R_equivalents  0.0583
_diffrn_reflns_av_unetI/netI     0.0260
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            123374
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.369
_diffrn_reflns_theta_min         2.223
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_target            Cu
_diffrn_source_type              'Siemens fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.482
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8483
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; 
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 
wR2(int) was 0.0942 before and 0.0647 after correction. 
The Ratio of minimum to maximum transmission is 0.8483. 
The \l/2 correction factor is Not present. 
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.389
_exptl_crystal_description       Plank
_exptl_crystal_F_000             4112
_exptl_crystal_id                dd88g
_exptl_crystal_preparation
; 
The data crystal was mounted using oil (Parantone-N) to a 
0.3 mm cryo-loop (Hampton Research) with the (1, 2, -2) scattering 
planes roughly normal to the spindle axis. 
;
_exptl_crystal_size_max          0.292
_exptl_crystal_size_mid          0.238
_exptl_crystal_size_min          0.164
_refine_diff_density_max         1.452
_refine_diff_density_min         -1.672
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     690
_refine_ls_number_reflns         11848
_refine_ls_number_restraints     461
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0716
_refine_ls_R_factor_gt           0.0568
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0638P)^2^+21.7519P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1381
_refine_ls_wR_factor_ref         0.1497
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9708
_reflns_number_total             11848
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01516_si_005.cif
_cod_data_source_block           dd88g
_cod_database_code               4128247
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.925
_shelx_estimated_absorpt_t_min   0.872
_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, All N(H) groups 
2. Restrained distances 
 N7-H7 
 0.88 with sigma of 0.01 
 C24-N6 \\sim C24-N6A 
 with sigma of 0.01 
 C11-F4 \\sim C11-F4A 
 with sigma of 0.01 
 C11-F5 \\sim C11-F5A 
 with sigma of 0.01 
 C11-F6 \\sim C11-F6A 
 with sigma of 0.01 
 S2-O4 \\sim S2-O4A 
 with sigma of 0.01 
 S2-O5 \\sim S2-O5A 
 with sigma of 0.01 
 S2-O6 \\sim S2-O6A 
 with sigma of 0.01 
3. Uiso/Uaniso restraints and constraints 
N6 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim N6A \\sim 
C60A \\sim C61A \\sim C62A \\sim C63A \\sim C64A \\sim C65A: within 2A with 
sigma of 0.01 and sigma for terminal atoms of 0.02 
F4 \\sim F5 \\sim F6 \\sim O4 \\sim O5 \\sim O6 \\sim F4A \\sim F5A \\sim F6A 
\\sim O4A \\sim O5A \\sim O6A: within 2A with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
Uanis(N6) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C62) 
\\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C65) \\sim Ueq, 
Uanis(N6A) \\sim Ueq, Uanis(C60A) \\sim Ueq, Uanis(C61A) \\sim Ueq, Uanis(C62A) 
\\sim Ueq, Uanis(C63A) \\sim Ueq, Uanis(C64A) \\sim Ueq, Uanis(C65A) \\sim Ueq: 
with sigma of 0.01 and sigma for terminal atoms of 0.02 
Uanis(F4) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(O4) \\sim 
Ueq, Uanis(O5) \\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(F4A) \\sim Ueq, Uanis(F5A) 
\\sim Ueq, Uanis(F6A) \\sim Ueq, Uanis(O4A) \\sim Ueq, Uanis(O5A) \\sim Ueq, 
Uanis(O6A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02 
Uanis(F6A) = Uanis(F5) 
Uanis(F6) = Uanis(F4A) 
Uanis(F5A) = Uanis(F4) 
Uanis(F6) = Uanis(F6A) = Uanis(F4) = Uanis(F4A) = Uanis(F5) = Uanis(F5A) 
Uanis(O6) = Uanis(O6A) 
Uanis(O4A) = Uanis(O5) 
Uanis(O4) = Uanis(O5A) 
4. Same fragment restrains 
{N6, C60, C61, C62, C63, C64, C65} sigma for 1-2: 0.01, 1-3: 0.04 
as 
{N6A, C60A, C61A, C62A, C63A, C64A, C65A} 
{F4, F5, F6, O4, O5, O6} sigma for 1-2: 0.01, 1-3: 0.04 
as 
{F4A, F5A, F6A, O4A, O5A, O6A} 
5. Others 
 Sof(H24A)=Sof(N6A)=Sof(H6A)=Sof(C60A)=Sof(H60A)=Sof(C61A)=Sof(H61C)=Sof(H61D)= 
 Sof(C62A)=Sof(H62C)=Sof(H62D)=Sof(C63A)=Sof(H63C)=Sof(H63D)=Sof(C64A)= 
 Sof(H64C)=Sof(H64D)=Sof(C65A)=Sof(H65C)=Sof(H65D)=1-FVAR(1) 
 Sof(H24)=Sof(N6)=Sof(H6)=Sof(C60)=Sof(H60)=Sof(C61)=Sof(H61A)=Sof(H61B)= 
 Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)= 
 Sof(H64B)=Sof(C65)=Sof(H65A)=Sof(H65B)=FVAR(1) 
 Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(O4A)=Sof(O5A)=Sof(O6A)=1-FVAR(2) 
 Sof(F4)=Sof(F5)=Sof(F6)=Sof(O4)=Sof(O5)=Sof(O6)=FVAR(2) 
6.a Ternary CH refined with riding coordinates: 
 C60(H60), C60A(H60A), C70(H70) 
6.b Secondary CH2 refined with riding coordinates: 
 C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B), C65(H65A, 
 H65B), C61A(H61C,H61D), C62A(H62C,H62D), C63A(H63C,H63D), C64A(H64C,H64D), 
 C65A(H65C,H65D), C71(H71A,H71B), C72(H72A,H72B), C73(H73A,H73B), C74(H74A, 
 H74B), C75(H75A,H75B) 
6.c Aromatic/amide H refined with riding coordinates: 
 C2(H2), C3(H3), C4(H4), C21(H21), C22(H22), C24(H24), C24(H24A), C31(H31), 
 C32(H32), C34(H34), C41(H41), C42(H42), C43(H43), C44(H44), C51(H51), C52(H52), 
  C53(H53), C54(H54), N6(H6), N6A(H6A) 
6.d Idealised Me refined as rotating group: 
 C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C12(H12A,H12B,H12C) 
;
_olex2_submission_special_instructions 'No special instructions were received'