Intramolecular C-H and C-F Bond Oxygenation Mediated by a Putative Terminal Oxo Species in Tetranuclear Iron Complexes.
de Ruiter, Graham; Thompson, Niklas B.; Takase, Michael K.; Agapie, Theodor; Journal of the American Chemical Society 138 (2016) 1486–1489; doi:10.1021/jacs.5b12214

data_4129962
_publ_section_title
;
 Intramolecular C-H and C-F Bond Oxygenation Mediated by a Putative
 Terminal Oxo Species in Tetranuclear Iron Complexes.
;
_journal_issue                   5
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1486
_journal_page_last               1489
_journal_paper_doi               10.1021/jacs.5b12214
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety
'C84 H54 F5 Fe4 N12 O5, 2(C F3 O3 S), C4 H10 O, H2 O, 1.6(C2 H3 N)'
_chemical_formula_sum            'C93.2 H70.8 F11 Fe4 N13.6 O13 S2'
_chemical_formula_weight         2085.75
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-10-14
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
SHELXL-2014,
and manual edit
;
_cell_angle_alpha                90
_cell_angle_beta                 100.818(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.9873(4)
_cell_length_b                   26.9656(7)
_cell_length_c                   22.7659(6)
_cell_measurement_reflns_used    9831
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      78.82
_cell_measurement_theta_min      2.57
_cell_volume                     9037.1(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker-AXS, 2007)'
_computing_data_collection       'APEX2 v2014.11-0 (Bruker-AXS, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker-AXS, 2007)'
_computing_molecular_graphics    'DIAMOND 3 (Crystal Impact, 1999)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'XT-2014/4 (Sheldrick, 2012)'
_diffrn_ambient_temperature      100.02
_diffrn_detector                 'CMOS Area Detector'
_diffrn_detector_area_resol_mean 10.24
_diffrn_detector_type            'Bruker PHOTON 100 CMOS'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1846
_diffrn_reflns_av_unetI/netI     0.0999
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            120779
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         74.540
_diffrn_reflns_theta_min         2.567
_diffrn_source                   'I\mS HB micro-focus sealed tube'
_diffrn_source_current           1
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatech I\mS HB'
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.292
_exptl_absorpt_correction_T_max  0.7543
_exptl_absorpt_correction_T_min  0.6134
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS-2014/5 (Sheldrick, 2014)'
_exptl_crystal_colour            'clear blackish brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   blackish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.533
_exptl_crystal_description       plate
_exptl_crystal_F_000             4257
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.429
_refine_diff_density_min         -0.818
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1292
_refine_ls_number_reflns         18469
_refine_ls_number_restraints     89
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.1350
_refine_ls_R_factor_gt           0.0857
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
'w=1/[\s^2^(Fo^2^)+(0.1214P)^2^+19.9553P] where P=(Fo^2^+2Fc^2^)/3'
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2060
_refine_ls_wR_factor_ref         0.2402
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11631
_reflns_number_total             18469
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b12214_si_001.cif
_cod_data_source_block           p15457_f
_cod_original_formula_sum        'C93.20 H70.80 F11 Fe4 N13.60 O13 S2'
_cod_database_code               4129962
_shelxl_version_number           2014-2
_exptl_absorpt_special_details
;
SADABS-2014/5 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.1228 before and 0.0972 after correction.
The Ratio of minimum to maximum transmission is 0.8132.
The \l/2 correction factor is Not present.
;
_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 O(H,H) groups
2. Restrained distances
 C211-C210
 1.517 with sigma of 0.01
 C209-C208
 1.517 with sigma of 0.01
 C211-O201
 2.3756 with sigma of 0.01
 O201-C208
 2.3756 with sigma of 0.01
 C210-O201
 1.411 with sigma of 0.01
 O201-C209
 1.411 with sigma of 0.01
 C210-C209
 2.3401 with sigma of 0.01
 C211-C208
 4.7431 with sigma of 0.01
 N2-C203
 1.157 with sigma of 0.01
 C202-C203
 1.458 with sigma of 0.01
 C202-N2
 2.615 with sigma of 0.01
3. Rigid bond restraints
 C201, N1, C200
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C201 \\sim N1 \\sim C200: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
5. Rigid body (RIGU) restrains
 O200, C204, H20F, H20G, H20H, C207, H20I, H20J, H20K, C206, H20L, H20M, C205,
 H20N, H20O
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O201, C211, H21A, H21B, H21C, C210, H21D, H21E, C208, H20A, H20B, H20C, C209,
 H20D, H20E
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N2, C203, C202, H20S, H20T, H20U
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C201, N1, C200
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Same fragment restrains
{N2, C203, C202} sigma for 1-2: 0.02, 1-3: 0.04
as
{N1, C201, C200}
7. Others
 Sof(O201)=Sof(C211)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C210)=Sof(H21D)=
 Sof(H21E)=Sof(C208)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C209)=Sof(H20D)=
 Sof(H20E)=1-FVAR(1)
 Sof(O200)=Sof(C204)=Sof(H20F)=Sof(H20G)=Sof(H20H)=Sof(C207)=Sof(H20I)=
 Sof(H20J)=Sof(H20K)=Sof(C206)=Sof(H20L)=Sof(H20M)=Sof(C205)=Sof(H20N)=
 Sof(H20O)=Sof(N2)=Sof(C203)=Sof(C202)=Sof(H20S)=Sof(H20T)=Sof(H20U)=FVAR(1)
8.a Free rotating group:
 O100(H10A,H10B)
8.b Secondary CH2 refined with riding coordinates:
 C210(H21D,H21E), C209(H20D,H20E), C206(H20L,H20M), C205(H20N,H20O)
8.c Me refined with riding coordinates:
 C211(H21A,H21B,H21C), C208(H20A,H20B,H20C), C204(H20F,H20G,H20H), C207(H20I,
 H20J,H20K), C200(H20P,H20Q,H20R), C202(H20S,H20T,H20U)
8.d Aromatic/amide H refined with riding coordinates:
 C35(H35), C72(H72), C2(H2), C71(H71), C56(H56), C54(H54), C51(H51), C4(H4),
 C46(H46), C69(H69), C82(H82), C33(H33), C34(H34), C52(H52), C81(H81), C26(H26),
  C59(H59), C49(H49), C63(H63), C24(H24), C57(H57), C41(H41), C67(H67),
 C43(H43), C16(H16), C64(H64), C58(H58), C62(H62), C25(H25), C76(H76), C61(H61),
  C78(H78), C77(H77), C97(H97), C96(H96), C98(H98), C36(H36), C6(H6), C66(H66),
 C53(H53), C23(H23), C44(H44), C47(H47), C42(H42), C13(H13), C48(H48), C86(H86),
  C15(H15), C91(H91), C87(H87), C92(H92), C14(H14), C68(H68), C88(H88)
;
_shelx_res_checksum              99367
_shelx_hkl_checksum              73799
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'