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_4128248
_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         'C41 H46.96 Cl0.04 Fe N7 O0.96, C F3 O3 S'
_chemical_formula_sum            'C42 H46.96 Cl0.04 F3 Fe N7 O3.96 S'
_chemical_formula_weight         859.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2018-10-10
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.7000(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.6444(5)
_cell_length_b                   15.5720(7)
_cell_length_c                   20.5734(9)
_cell_measurement_reflns_used    9416
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.71
_cell_measurement_theta_min      2.41
_cell_volume                     4014.3(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX3 V2016.9-0 (Bruker, 2016)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELX-2014-7 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.01
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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  0.0406
_diffrn_reflns_av_unetI/netI     0.0198
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            72049
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.731
_diffrn_reflns_theta_min         2.217
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.496
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.6366
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.1025 before and 0.0686 after correction.
The Ratio of minimum to maximum transmission is 0.8542.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.422
_exptl_crystal_description       prism
_exptl_crystal_F_000             1797
_exptl_crystal_id                dd84e
_exptl_crystal_preparation
;
The data crystal was mounted using oil (Parantone-N) to a 
0.3 mm cryo-loop (Hampton Research) with the (-4, -1, 4) scattering 
planes roughly normal to the spindle axis. 
;
_exptl_crystal_size_max          0.371
_exptl_crystal_size_mid          0.184
_exptl_crystal_size_min          0.148
_refine_diff_density_max         0.493
_refine_diff_density_min         -0.576
_refine_diff_density_rms         0.062
_refine_ls_extinction_coef       0.0089(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     612
_refine_ls_number_reflns         7662
_refine_ls_number_restraints     402
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0443
_refine_ls_R_factor_gt           0.0395
_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^)+(0.0555P)^2^+3.4487P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1004
_refine_ls_wR_factor_ref         0.1032
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6842
_reflns_number_total             7662
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b01516_si_002.cif
_cod_data_source_block           dd84e
_cod_database_code               4128248
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.930
_shelx_estimated_absorpt_t_min   0.837
_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, All O(H) groups
2. Restrained distances
 N6-H6
 0.88 with sigma of 0.01
 S1-C11 \\sim S1A-C11A
 with sigma of 0.01
 S1A-O4A \\sim S1A-O3A \\sim S1A-O2A \\sim S1-O3 \\sim S1-O2 \\sim S1-O4
 with sigma of 0.01
 F1-C11 \\sim F3-C11 \\sim F2-C11 \\sim F1A-C11A \\sim F2A-C11A \\sim F3A-C11A
 with sigma of 0.01
 C11A-F1A \\sim C11A-F3A \\sim C11A-F2A
 with sigma of 0.01
 S1-O2 \\sim S1-O3 \\sim S1-O4
 with sigma of 0.01
 S1A-O2A \\sim S1A-O3A \\sim S1A-O4A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C11 \\sim S1 \\sim O2 \\sim O3 \\sim O4 \\sim F1 \\sim F2 \\sim F3 \\sim C11A
\\sim F3A \\sim F2A \\sim F1A \\sim S1A \\sim O3A \\sim O2A \\sim O4A: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O1 \\sim Cl1: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 O4A, S1, O2, O3, O4, C11, F1, F2, F3, O3A, S1A, F3A, C11A, O2A, F2A, F1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1, Cl1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F3A)=Sof(C11A)=Sof(F2A)=Sof(F1A)=Sof(O3A)=Sof(S1A)=Sof(O2A)=Sof(O4A)=1-
 FVAR(1)
 Sof(S1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(O2)=Sof(O3)=Sof(O4)=Sof(C11)=FVAR(1)
 Sof(Cl1)=1-FVAR(2)
 Sof(O1)=Sof(H1)=FVAR(2)
 Fixed X: H1(0.526)
 Fixed Y: H1(0.4587)
 Fixed Z: H1(0.191701)
6.a Ternary CH refined with riding coordinates:
 C60(H60), 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), 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), C31(H31), C32(H32),
 C34(H34), C41(H41), C42(H42), C43(H43), C44(H44), C51(H51), C52(H52), C53(H53),
  C54(H54)
6.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C9(H9A,H9B,H9C)
;
_shelx_res_checksum              75890
_shelx_hkl_checksum              65270
_olex2_submission_special_instructions 'No special instructions were received'