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_4128249
_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_absolute_configuration ad
_chemical_formula_moiety         'C41 H48 Fe N7 O, 2(C F3 O3 S)'
_chemical_formula_sum            'C43 H48 F6 Fe N7 O7 S2'
_chemical_formula_weight         1008.85
_space_group_crystal_system      orthorhombic
_space_group_IT_number           31
_space_group_name_Hall           'P 2ac -2'
_space_group_name_H-M_alt        'P m n 21'
_symmetry_space_group_name_Hall  'P 2ac -2'
_symmetry_space_group_name_H-M   'P m n 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-02-09
_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            2
_cell_length_a                   13.5964(7)
_cell_length_b                   9.6432(5)
_cell_length_c                   17.6757(9)
_cell_measurement_reflns_used    44207
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.43
_cell_measurement_theta_min      2.30
_cell_volume                     2317.5(2)
_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      100.0
_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 0.993
_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  dd50i
_diffrn_reflns_av_R_equivalents  0.0553
_diffrn_reflns_av_unetI/netI     0.0290
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            45876
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.463
_diffrn_reflns_theta_min         2.406
_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    0.496
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7596
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; 
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 
wR2(int) was 0.1538 before and 0.0857 after correction. 
The Ratio of minimum to maximum transmission is 0.7596. 
The \l/2 correction factor is Not present. 
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.446
_exptl_crystal_description       Block
_exptl_crystal_F_000             1046
_exptl_crystal_id                dd50i
_exptl_crystal_preparation
; 
The data crystal was mounted using oil (Parantone-N) to a 
0.3 mm cryo-loop (Hampton Research) with the (-1, -4, -2) scattering 
planes roughly normal to the spindle axis. 
;
_exptl_crystal_size_max          0.281
_exptl_crystal_size_mid          0.126
_exptl_crystal_size_min          0.082
_refine_diff_density_max         0.632
_refine_diff_density_min         -1.077
_refine_diff_density_rms         0.126
_refine_ls_abs_structure_details
; 
 Refined as an inversion twin. 
;
_refine_ls_abs_structure_Flack   0.06(5)
_refine_ls_extinction_coef       0.0226(17)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.117
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     360
_refine_ls_number_reflns         4462
_refine_ls_number_restraints     406
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0687
_refine_ls_R_factor_gt           0.0682
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0121P)^2^+18.9009P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1650
_refine_ls_wR_factor_ref         0.1652
_reflns_Friedel_coverage         0.933
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                4424
_reflns_number_total             4462
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01516_si_003.cif
_cod_data_source_block           17
_cod_database_code               4128249
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.960
_shelx_estimated_absorpt_t_min   0.873
_olex2_refinement_description
; 
1. Twinned data refinement 
 Scales: 0.94(5) 
 0.06(5) 
2. Fixed Uiso 
 At 1.2 times of: 
  All C(H) groups, All C(H,H) groups, All N(H) groups 
 At 1.5 times of: 
  All C(H,H,H) groups, All O(H) groups 
3. Restrained distances 
 F7-C11 \\sim F8-C11 \\sim F9-C11 \\sim F1_$1-C10_$1 \\sim F2_$1-C10_$1 
 with sigma of 0.01 
 S2-O6 \\sim S2-O5 \\sim S2-O4 \\sim S1_$1-O2_$1 \\sim S1_$1-O3_$1 
 with sigma of 0.01 
 F7-F8 \\sim F8-F9 \\sim F9-F7 
 with sigma of 0.02 
 O4-O5 \\sim O5-O6 \\sim O6-O4 
 with sigma of 0.02 
 S2-C11 \\sim S1_$1-C10_$1 
 with sigma of 0.01 
4. Uiso/Uaniso restraints and constraints 
O4 \\sim S2 \\sim O5 \\sim O6 \\sim C11 \\sim F7 \\sim F8 \\sim F9: within 2A 
with sigma of 0.01 and sigma for terminal atoms of 0.02 
Uanis(C4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02 
5. Rigid body (RIGU) restrains 
 O4, S2, O5, O6, C11, F7, F8, F9 
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004 
 C2, Fe1, O1, N1, N2, N3, H1, C1, C5, C20, C23, C30, C34, C6, C4, C8, C21, C22, 
  C24, C31, C33, H34, H2, C3, C7, H4A, C9, H21, H22, N4, H24, H31, C32, H33, H3, 
  H7A, H7B, H7C, H9A, H9B, H9C, H4, C40, H32, H40, C41, C45, H41A, H41B, C42, 
 C44, H45A, H45B, H42A, H42B, C43, H44A, H44B, H43A, H43B 
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01 
6. Others 
 Fixed Sof: H7A(0.5) H7B(0.5) H7C(0.5) H9A(0.5) H9B(0.5) H9C(0.5) S2(0.5) 
 O4(0.5) O5(0.5) O6(0.5) C11(0.5) F7(0.5) F8(0.5) F9(0.5) 
7.a Ternary CH refined with riding coordinates: 
 C40(H40) 
7.b Secondary CH2 refined with riding coordinates: 
 C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B) 
7.c Me refined with riding coordinates: 
 C7(H7A,H7B,H7C), C9(H9A,H9B,H9C) 
7.d Aromatic/amide H refined with riding coordinates: 
 N4(H4), C2(H2), C3(H3), C4(H4A), C21(H21), C22(H22), C24(H24), C31(H31), 
 C32(H32), C33(H33), C34(H34) 
7.e Tetrahedral OH refined with riding coordinates: 
 O1(H1) 
;
_smtbx_masks_special_details
; 
The acetonitrile solvate was poorly determined so it was masked. A 
total of 33 electrons were squeezed from the unit cell, consistent 
with one acetonitrile solvate per unit cell. 
;
_olex2_submission_special_instructions 'No special instructions were received'