Tuning the Fe(II/III) Redox Potential in Nonheme Fe(II)-Hydroxo Complexes through Primary and Secondary Coordination Sphere Modifications.
Gordon, Zachary; Drummond, Michael J.; Matson, Ellen M.; Bogart, Justin A.; Schelter, Eric J.; Lord, Richard L.; Fout, Alison R.; Inorganic chemistry 56 (2017) 4852–4863; doi:10.1021/acs.inorgchem.6b03071

data_4345654
_publ_section_title
;
 Tuning the Fe(II/III) Redox Potential in Nonheme Fe(II)-Hydroxo Complexes
 through Primary and Secondary Coordination Sphere Modifications.
;
_journal_issue                   9
_journal_name_full               'Inorganic chemistry'
_journal_page_first              4852
_journal_page_last               4863
_journal_paper_doi               10.1021/acs.inorgchem.6b03071
_journal_volume                  56
_journal_year                    2017
_chemical_formula_moiety         '4(C36 H48 Br3 Fe N7 O), 4(C F3 O3 S)'
_chemical_formula_sum            'C148 H192 Br12 F12 Fe4 N28 O16 S4'
_chemical_formula_weight         4157.84
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-08-08
_audit_creation_method
; 
Olex2 1.2 
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155) 
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   19.9852(8)
_cell_length_b                   20.8204(9)
_cell_length_c                   10.3313(4)
_cell_measurement_reflns_used    9901
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      24.34
_cell_measurement_theta_min      2.20
_cell_volume                     4298.9(3)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2013.10-0 (Bruker, 2013)'
_computing_data_reduction
; 
SAINT V8.34A, XPREP v2013/3, SADABS V2012/1, TWINABS V2012/1 
(Bruker, 2012 & 2013) 
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELX-2013-4 (Sheldrick, 2013)'
_computing_structure_solution    'SHELX-2013-4 (Sheldrick, 2013)'
_diffrn_ambient_temperature      296.15
_diffrn_detector                 'Bruker APEXII CCD area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'Bruker Kappa/ApexII CCD'
_diffrn_measurement_method       'profile data from \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  dm38a
_diffrn_reflns_av_R_equivalents  0.0713
_diffrn_reflns_av_unetI/netI     0.0483
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            109275
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.358
_diffrn_reflns_theta_min         1.412
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Siemens fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.247
_exptl_absorpt_correction_T_max  0.8127
_exptl_absorpt_correction_T_min  0.6392
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
; 
SADABS-2014/4 (Bruker,2014) was used for absorption correction. 
wR2(int) was 0.0788 before and 0.0729 after correction. 
The Ratio of minimum to maximum transmission is 0.7865. 
The \l/2 correction factor is 0.00150. 
;
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.606
_exptl_crystal_description       rectangular
_exptl_crystal_F_000             2100
_exptl_crystal_id                dm38a
_exptl_crystal_preparation
; 
The data crystal was mounted using oil (Parantone-N, Exxon) to a 
0.3 mm cryo-loop (Hampton Research) with the (0,5,-1) scattering 
planes roughly normal to the spindle axis. 
;
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.084
_refine_diff_density_max         1.407
_refine_diff_density_min         -0.999
_refine_diff_density_rms         0.114
_refine_ls_abs_structure_details
; 
 Flack x determined using 3640 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.011(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     660
_refine_ls_number_reflns         10680
_refine_ls_number_restraints     185
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0541
_refine_ls_R_factor_gt           0.0394
_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^)+(0.0499P)^2^+2.2393P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0916
_refine_ls_wR_factor_ref         0.1021
_reflns_Friedel_coverage         0.894
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                9031
_reflns_number_total             10680
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b03071_si_001.cif
_cod_data_source_block           dm38a_0m
_cod_depositor_comments
'Adding full bibliography for 4345651--4345656.cif.'
_cod_database_code               4345654
_shelx_estimated_absorpt_t_max   0.772
_shelx_estimated_absorpt_t_min   0.563
_olex2_refinement_description
; 
1. Fixed Uiso 
 At 1.2 times of: 
  All C(H,H) groups, H7 of C7, H6A of C6, H28 of C28, H4 of C4, H18 of C18, 
  H19 of C19, H30A of C30A, H31 of C31, H31A of C31A, H16 of C16, H30 of C30 
 At 1.5 times of: 
  All N(H) groups, H7AA of C36A, H7A of C36 
2. Restrained distances 
 N5-H5 
 0.88 with sigma of 0.02 
 N7-H7A 
 0.88 with sigma of 0.02 
 N7A-H7AA 
 0.88 with sigma of 0.02 
 C29-C30 \\sim C29-C30A 
 with sigma of 0.01 
3. Uiso/Uaniso restraints and constraints 
N7 \\sim N7A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 
C30 \\sim C30A: within 2A with sigma of 0.04 and sigma for terminal atoms of 
0.08 
C31 \\sim C31A: within 2A with sigma of 0.04 and sigma for terminal atoms of 
0.08 
C32 \\sim C32A: within 2A with sigma of 0.04 and sigma for terminal atoms of 
0.08 
C33 \\sim C33A: within 2A with sigma of 0.04 and sigma for terminal atoms of 
0.08 
C34 \\sim C34A: within 2A with sigma of 0.04 and sigma for terminal atoms of 
0.08 
C35 \\sim C35A: within 2A with sigma of 0.04 and sigma for terminal atoms of 
0.08 
C36 \\sim C36A: within 2A with sigma of 0.04 and sigma for terminal atoms of 
0.08 
Uanis(N7) \\sim Ueq, Uanis(N7A) \\sim Ueq: with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
Uanis(C30) \\sim Ueq, Uanis(C30A) \\sim Ueq: with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
Uanis(S1) \\sim Ueq, Uanis(S1A) \\sim Ueq: with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
Uanis(F1) \\sim Ueq, Uanis(F1A) \\sim Ueq: with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
Uanis(F2) \\sim Ueq, Uanis(F2A) \\sim Ueq: with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
Uanis(F3) \\sim Ueq, Uanis(F3A) \\sim Ueq: with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
Uanis(O2) \\sim Ueq, Uanis(O2A) \\sim Ueq: with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
Uanis(O3) \\sim Ueq, Uanis(O3A) \\sim Ueq: with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
Uanis(O4) \\sim Ueq, Uanis(O4A) \\sim Ueq: with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
Uanis(C37) \\sim Ueq, Uanis(C37A) \\sim Ueq: with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
4. Same fragment restrains 
{N7, C30, C31, C32, C33, C34, C35, C36} sigma for 1-2: 0.01, 1-3: 0.02 
as 
{N7A, C30A, C31A, C32A, C33A, C34A, C35A, C36A} 
{S1, F1, F2, F3, O2, O3, O4, C37} sigma for 1-2: 0.01, 1-3: 0.04 
as 
{S1A, F1A, F2A, F3A, O2A, O3A, O4A, C37A} 
5. Others 
 Sof(S1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(O2A)=Sof(O3A)=Sof(O4A)=Sof(C37A)=1- 
 FVAR(1) 
 Sof(S1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(O2)=Sof(O3)=Sof(O4)=Sof(C37)=FVAR(1) 
 Sof(N7A)=Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32C)= 
 Sof(H32D)=Sof(C33A)=Sof(H33C)=Sof(H33D)=Sof(C34A)=Sof(H34C)=Sof(H34D)= 
 Sof(C35A)=Sof(H35C)=Sof(H35D)=Sof(C36A)=Sof(H36C)=Sof(H36D)=Sof(H7AA)=1-FVAR(2) 
 Sof(N7)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32A)=Sof(H32B)= 
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(C35)=Sof(H35A)= 
 Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H7A)=FVAR(2) 
6.a Ternary CH refined with riding coordinates: 
 C7(H7), C19(H19), C31(H31), C31A(H31A) 
6.b Secondary CH2 refined with riding coordinates: 
 C1(H1A,H1B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), 
 C12(H12A,H12B), C13(H13A,H13B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), 
  C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C32(H32A,H32B), C33(H33A, 
 H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C32A(H32C,H32D), 
 C33A(H33C,H33D), C34A(H34C,H34D), C35A(H35C,H35D), C36A(H36C,H36D) 
6.c Aromatic/amide H refined with riding coordinates: 
 N6(H6), C4(H4), C6(H6A), C16(H16), C18(H18), C28(H28), C30(H30), C30A(H30A) 
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'