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_4345656
_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         'C36 H33 Fe N7 O, C32 H12 B F24, 1(C6 H6)'
_chemical_formula_sum            'C74 H51 B F24 Fe N7 O'
_chemical_formula_weight         1576.87
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2016-09-07
_audit_creation_method
; 
Olex2 1.2 
(compiled 2016.08.31 svn.r3340 for OlexSys, GUI svn.r5221) 
;
_cell_angle_alpha                108.756(15)
_cell_angle_beta                 96.652(10)
_cell_angle_gamma                101.866(14)
_cell_formula_units_Z            2
_cell_length_a                   11.646(4)
_cell_length_b                   16.072(6)
_cell_length_c                   20.491(6)
_cell_measurement_reflns_used    9351
_cell_measurement_temperature    100.03
_cell_measurement_theta_max      27.15
_cell_measurement_theta_min      2.59
_cell_volume                     3485(2)
_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      100.03
_diffrn_detector                 'Bruker Photon 100 area detector'
_diffrn_detector_type            'photon counter area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture/Photon 100'
_diffrn_measurement_method       'profile data from \f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_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  0.0434
_diffrn_reflns_av_unetI/netI     0.0213
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            140152
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.219
_diffrn_reflns_theta_min         2.288
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.332
_exptl_absorpt_correction_T_max  0.9963
_exptl_absorpt_correction_T_min  0.8634
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
; 
SADABS-2014/4 (Bruker,2014) was used for absorption correction. 
wR2(int) was 0.1261 before and 0.0686 after correction. 
The Ratio of minimum to maximum transmission is 0.8666. 
The \l/2 correction factor is 0.00150. 
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.503
_exptl_crystal_description       rectangular
_exptl_crystal_F_000             1598
_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          0.740
_exptl_crystal_size_mid          0.229
_exptl_crystal_size_min          0.102
_refine_diff_density_max         1.684
_refine_diff_density_min         -0.755
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1379
_refine_ls_number_reflns         15485
_refine_ls_number_restraints     1406
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0523
_refine_ls_R_factor_gt           0.0469
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0507P)^2^+3.8806P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1145
_refine_ls_wR_factor_ref         0.1179
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14013
_reflns_number_total             15485
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b03071_si_001.cif
_cod_data_source_block           2_av4
_cod_depositor_comments
'Adding full bibliography for 4345651--4345656.cif.'
_cod_database_code               4345656
_olex2_refinement_description
; 
1. Fixed Uiso 
 At 1.2 times of: 
  All C(H,H) groups, H16 of C16, H10A of C10A, H10 of C10, H11 of C11, H12 of 
  C12, H35 of C35, H42 of C42, H36 of C36, H8 of C8, H9 of C9, H22 of C22, H23 
  of C23, H24 of C24, H27 of C27, H28 of C28, H30 of C30, H32 of C32, H33 of 
  C33, H34 of C34, H72 of C72, H73 of C73, H74 of C74, H46 of C46, H48 of C48, 
  H50 of C50, H62 of C62, H64 of C64, H66 of C66, H54 of C54, H56 of C56, H58 
  of C58, H54A of C54A, H56A of C56A, H58A of C58A, H69A of C69A, H70A of C70A, 
  H71A of C71A, H72A of C72A, H73A of C73A, H74A of C74A, H69 of C69, H70 of 
  C70, H71 of C71, H4 of C4, H3 of C3, H18 of C18, H21 of C21, H6A of C6, H38 
  of C38, H40 of C40, H8A of C8A, H9A of C9A, H11A of C11A, H12A of C12A, H15 
  of C15, H20 of C20 
 At 1.5 times of: 
  All N(H) groups, H7 of C74 
2. Restrained distances 
 N7-H7 
 0.88 with sigma of 0.02 
 N5-C7 \\sim N5-C7A 
 with sigma of 0.02 
3. Uiso/Uaniso restraints and constraints 
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F1A \\sim F2A \\sim F3A 
\\sim F4A \\sim F5A \\sim F6A: within 2A with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
F10 \\sim F11 \\sim F12 \\sim F10A \\sim F11A \\sim F12A: within 2A with sigma 
of 0.01 and sigma for terminal atoms of 0.02 
F19 \\sim F20 \\sim F21 \\sim F19A \\sim F20A \\sim F21A: within 2A with sigma 
of 0.01 and sigma for terminal atoms of 0.02 
F13 \\sim F14 \\sim F15 \\sim F16 \\sim F17 \\sim F18 \\sim F13A \\sim F13C 
\\sim F14A \\sim F14C \\sim F15A \\sim F15C \\sim F16A \\sim F17A \\sim F18A: 
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 
F16 \\sim F16B \\sim F17 \\sim F17B \\sim F18 \\sim F18B: within 2A with sigma 
of 0.01 and sigma for terminal atoms of 0.02 
F16A \\sim F16C \\sim F17A \\sim F17C \\sim F18A \\sim F18C: within 2A with 
sigma of 0.01 and sigma for terminal atoms of 0.02 
C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim 
C53A \\sim C54A \\sim C55A \\sim C56A \\sim C57A \\sim C58A \\sim C59A \\sim 
C60A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 
C69A \\sim C70A \\sim C71A \\sim C72A \\sim C73A \\sim C74A \\sim C69 \\sim C70 
\\sim C71 \\sim C72 \\sim C73 \\sim C74: within 2A with sigma of 0.01 and sigma 
for terminal atoms of 0.02 
C7 \\sim C7A \\sim C8 \\sim C8A \\sim C9 \\sim C9A \\sim C10 \\sim C10A \\sim 
C11 \\sim C11A \\sim C12 \\sim C12A: within 2A with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
Uanis(F1) \\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F2A) 
\\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F3A) \\sim Ueq, Uanis(F4) \\sim Ueq, 
Uanis(F4A) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F5A) \\sim Ueq, Uanis(F6) 
\\sim Ueq, Uanis(F6A) \\sim Ueq: with sigma of 0.01 and sigma for terminal 
atoms of 0.02 
Uanis(F10) \\sim Ueq, Uanis(F10A) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F11A) 
\\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F12A) \\sim Ueq: with sigma of 0.01 and 
sigma for terminal atoms of 0.02 
Uanis(F13) \\sim Ueq, Uanis(F13A) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F14A) 
\\sim Ueq, Uanis(F15) \\sim Ueq, Uanis(F15A) \\sim Ueq, Uanis(F16) \\sim Ueq, 
Uanis(F16A) \\sim Ueq, Uanis(F17) \\sim Ueq, Uanis(F17A) \\sim Ueq, Uanis(F18) 
\\sim Ueq, Uanis(F18A) \\sim Ueq: with sigma of 0.01 and sigma for terminal 
atoms of 0.02 
Uanis(F16B) \\sim Ueq, Uanis(F16C) \\sim Ueq, Uanis(F17B) \\sim Ueq, 
Uanis(F17C) \\sim Ueq, Uanis(F18B) \\sim Ueq, Uanis(F18C) \\sim Ueq: with sigma 
of 0.01 and sigma for terminal atoms of 0.02 
Uanis(F19) \\sim Ueq, Uanis(F19A) \\sim Ueq, Uanis(F20) \\sim Ueq, Uanis(F20A) 
\\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(F21A) \\sim Ueq: with sigma of 0.01 and 
sigma for terminal atoms of 0.02 
Uanis(C53) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C56) 
\\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C59) \\sim Ueq, 
Uanis(C60) \\sim Ueq, Uanis(C53A) \\sim Ueq, Uanis(C54A) \\sim Ueq, Uanis(C55A) 
\\sim Ueq, Uanis(C56A) \\sim Ueq, Uanis(C57A) \\sim Ueq, Uanis(C58A) \\sim Ueq, 
Uanis(C59A) \\sim Ueq, Uanis(C60A) \\sim Ueq: with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
Uanis(F13) = Uanis(F13B) = Uanis(F14) = Uanis(F14B) = Uanis(F15) = Uanis(F13B) 
= Uanis(F14) = Uanis(F14B) = Uanis(F15) = Uanis(F15B) 
Uanis(F13A) = Uanis(F13C) = Uanis(F14A) = Uanis(F14C) = Uanis(F15A) = 
Uanis(F13C) = Uanis(F14A) = Uanis(F14C) = Uanis(F15A) = Uanis(F15C) 
4. Same fragment restrains 
{C7, C8, C9, C10, C11, C12} sigma for 1-2: 0.02, 1-3: 0.04 
as 
{C7A, C8A, C9A, C10A, C11A, C12A} 
{F1, F2, F3, F4, F5, F6, F10, F11, F12, F13, F13B, F14, F14B, F15, F15B, F16, 
F16B, F17, F17B, F18, F18B, F19, F20, F21, C53, C54, C55, C56, C57, C58, C59, 
C60} sigma for 1-2: 0.01, 1-3: 0.02 
as 
{F1A, F2A, F3A, F4A, F5A, F6A, F10A, F11A, F12A, F13A, F13C, F14A, F14C, F15A, 
F15C, F16A, F16C, F17A, F17C, F18A, F18C, F19A, F20A, F21A, C53A, C54A, C55A, 
C56A, C57A, C58A, C59A, C60A} 
{C69, C70, C71, C72, C73, C74} sigma for 1-2: 0.01, 1-3: 0.02 
as 
{C69A, C70A, C71A, C72A, C73A, C74A} 
5. Others 
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(1) 
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1) 
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(2) 
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(2) 
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(3) 
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(3) 
 Sof(F19A)=Sof(F20A)=Sof(F21A)=1-FVAR(4) 
 Sof(F19)=Sof(F20)=Sof(F21)=FVAR(4) 
 Sof(C69A)=Sof(H69A)=Sof(C70A)=Sof(H70A)=Sof(C71A)=Sof(H71A)=Sof(C72A)= 
 Sof(H72A)=Sof(C73A)=Sof(H73A)=Sof(C74A)=Sof(H74A)=1-FVAR(5) 
 Sof(C69)=Sof(H69)=Sof(C70)=Sof(H70)=Sof(C71)=Sof(H71)=Sof(C72)=Sof(H72)= 
 Sof(C73)=Sof(H73)=Sof(C74)=Sof(H74)=FVAR(5) 
 Sof(C53A)=Sof(C54A)=Sof(H54A)=Sof(C55A)=Sof(C56A)=Sof(H56A)=Sof(C57A)= 
 Sof(C58A)=Sof(H58A)=Sof(C59A)=Sof(C60A)=1-FVAR(6) 
 Sof(F13A)=Sof(F13C)=Sof(F14A)=Sof(F14C)=Sof(F15A)=Sof(F15C)=Sof(F16A)= 
 Sof(F16C)=Sof(F17A)=Sof(F17C)=Sof(F18A)=Sof(F18C)=0.5*(1-FVAR(7)) 
 Sof(F13)=Sof(F13B)=Sof(F14)=Sof(F14B)=Sof(F15)=Sof(F15B)=Sof(F16)=Sof(F16B)= 
 Sof(F17)=Sof(F17B)=Sof(F18)=Sof(F18B)=0.5*FVAR(7) 
 Sof(C53)=Sof(C54)=Sof(H54)=Sof(C55)=Sof(C56)=Sof(H56)=Sof(C57)=Sof(C58)= 
 Sof(H58)=Sof(C59)=Sof(C60)=FVAR(6) 
 Sof(C7A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=Sof(C11A)= 
 Sof(H11A)=Sof(C12A)=Sof(H12A)=1-FVAR(7) 
 Sof(C7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)= 
 Sof(C12)=Sof(H12)=FVAR(7) 
6.a Secondary CH2 refined with riding coordinates: 
 C1(H1A,H1B), C13(H13A,H13B), C25(H25A,H25B) 
6.b Aromatic/amide H refined with riding coordinates: 
 C3(H3), C4(H4), C6(H6A), C15(H15), C16(H16), C18(H18), C20(H20), C21(H21), 
 C22(H22), C23(H23), C24(H24), C27(H27), C28(H28), C30(H30), C32(H32), C33(H33), 
  C34(H34), C35(H35), C36(H36), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), 
 C8A(H8A), C9A(H9A), C10A(H10A), C11A(H11A), C12A(H12A), C38(H38), C40(H40), 
 C42(H42), C46(H46), C48(H48), C50(H50), C62(H62), C64(H64), C66(H66), C54(H54), 
  C56(H56), C58(H58), C54A(H54A), C56A(H56A), C58A(H58A), C69A(H69A), 
 C70A(H70A), C71A(H71A), C72A(H72A), C73A(H73A), C74A(H74A), C69(H69), C70(H70), 
  C71(H71), C72(H72), C73(H73), C74(H74) 
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'