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_4129959
_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 H53 F7 Fe4 N12 O4, 1(C H2 Cl2), 2(C F3 O3 S)'
_chemical_formula_sum            'C87 H53 Cl2 F13 Fe4 N12 O10 S2'
_chemical_formula_weight         2031.83
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-10-17
_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                 96.581(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.4130(9)
_cell_length_b                   16.4854(8)
_cell_length_c                   24.6252(12)
_cell_measurement_reflns_used    6354
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      69.21
_cell_measurement_theta_min      3.23
_cell_volume                     9038.7(7)
_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      99.99
_diffrn_detector                 'CMOS Area Detector'
_diffrn_detector_area_resol_mean 10.24
_diffrn_detector_type            'Bruker PHOTON 100 CMOS'
_diffrn_measured_fraction_theta_full 0.931
_diffrn_measured_fraction_theta_max 0.909
_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  0.1007
_diffrn_reflns_av_unetI/netI     0.1852
_diffrn_reflns_Laue_measured_fraction_full 0.931
_diffrn_reflns_Laue_measured_fraction_max 0.909
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            32812
_diffrn_reflns_point_group_measured_fraction_full 0.931
_diffrn_reflns_point_group_measured_fraction_max 0.909
_diffrn_reflns_theta_full        66.500
_diffrn_reflns_theta_max         70.551
_diffrn_reflns_theta_min         1.984
_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    6.809
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.4732
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS-2014/5 (Sheldrick, 2014)'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.493
_exptl_crystal_description       Needle
_exptl_crystal_F_000             4104
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.207
_refine_diff_density_min         -0.567
_refine_diff_density_rms         0.146
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.151
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1357
_refine_ls_number_reflns         15755
_refine_ls_number_restraints     1573
_refine_ls_restrained_S_all      1.119
_refine_ls_R_factor_all          0.2783
_refine_ls_R_factor_gt           0.1492
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3675
_refine_ls_wR_factor_ref         0.4403
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6134
_reflns_number_total             15755
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b12214_si_001.cif
_cod_data_source_block           p15231_f
_cod_database_code               4129959
_shelxl_version_number           2014-2
_exptl_absorpt_special_details
; 
'SADABS-2014/5 (Bruker,2014) was used for absorption correction. wR2(int) 
was 0.1302 before and 0.0668 after correction. The Ratio of minimum to maximum 
transmission is 0.6282. 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
2. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(Cl1) \\sim Ueq, Uanis(C2)
\\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(Cl4) \\sim Ueq, Uanis(C3) \\sim Ueq,
Uanis(Cl5) \\sim Ueq, Uanis(Cl6) \\sim Ueq, Uanis(Cl7) \\sim Ueq, Uanis(C4)
\\sim Ueq, Uanis(Cl8) \\sim Ueq, Uanis(Cl9) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(Cl10) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{Cl2, Cl1, C1} sigma for 1-2: 0.01, 1-3: 0.02
as
{Cl3, Cl4, C2}
{Cl2, Cl1, C1} sigma for 1-2: 0.01, 1-3: 0.02
as
{Cl5, Cl6, C3}
{Cl2, Cl1, C1} sigma for 1-2: 0.01, 1-3: 0.02
as
{Cl7, Cl8, C4}
{Cl2, Cl1, C1} sigma for 1-2: 0.01, 1-3: 0.02
as
{Cl9, Cl10, C5}
{S005, F00G, F00U, F00V, O1, O01H, O01V, C02S} sigma for 1-2: 0.02, 1-3: 0.04
as
{S2, F8, F11, F12, O2A, O13, O16, C10}
{S005, F00G, F00U, F00V, O1, O01H, O01V, C02S} sigma for 1-2: 0.02, 1-3: 0.04
as
{S3, F7, F13, F14, O6, O12, O15, C16}
5. Others
 1*[Sof(Cl2)+Sof(Cl1)+Sof(C1)+Sof(H1A)+Sof(H1B)]+1*[Sof(Cl5)+Sof(Cl6)+Sof(C3)+
 Sof(H3A)+Sof(H3B)]+1*[Sof(Cl9)+Sof(Cl10)+Sof(C5)+Sof(H5A)+Sof(H5B)]+1*
 [Sof(Cl3)+Sof(Cl4)+Sof(C2)+Sof(H2A)+Sof(H2B)]+1*[Sof(Cl7)+Sof(Cl8)+Sof(C4)+
 Sof(H4A)+Sof(H4B)]=1 with esd of 0.000001
 Sof(S2)=Sof(F8)=Sof(F11)=Sof(F12)=Sof(O2A)=Sof(O13)=Sof(O16)=Sof(C10)=1-FVAR(1)
 Sof(S3)=Sof(F7)=Sof(F13)=Sof(F14)=Sof(O6)=Sof(O12)=Sof(O15)=Sof(C16)=FVAR(1)
 Sof(Cl2)=Sof(Cl1)=Sof(C1)=Sof(H1A)=Sof(H1B)=FVAR(2)
 Sof(Cl5)=Sof(Cl6)=Sof(C3)=Sof(H3A)=Sof(H3B)=FVAR(3)
 Sof(Cl9)=Sof(Cl10)=Sof(C5)=Sof(H5A)=Sof(H5B)=FVAR(4)
 Sof(Cl3)=Sof(Cl4)=Sof(C2)=Sof(H2A)=Sof(H2B)=FVAR(5)
 Sof(Cl7)=Sof(Cl8)=Sof(C4)=Sof(H4A)=Sof(H4B)=FVAR(6)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B)
6.b Aromatic/amide H refined with riding coordinates:
 C00Z(H00Z), C01B(H01B), C01C(H01C), C01D(H01D), C01F(H01F), C01J(H01J),
 C01M(H01M), C01N(H01N), C01P(H01P), C01Q(H01Q), C01R(H01R), C01S(H01S),
 C01W(H01W), C01X(H01X), C01Y(H01Y), C02C(H02C), C02D(H02D), C02F(H02F),
 C02G(H02G), C02J(H02J), C02M(H02M), C02N(H02N), C02T(H02T), C02U(H02U),
 C02V(H02V), C02W(H02W), C02X(H02X), C02Y(H02Y), C03A(H03A), C03B(H03B),
 C03D(H03D), C03G(H03G), C03I(H03I), C03J(H03J), C03K(H03K), C015(H015),
 C016(H016), C020(H020), C021(H021), C023(H023), C024(H024), C026(H026),
 C027(H027), C028(H028), C029(H029), C030(H030), C031(H031), C033(H033),
 C034(H034), C035(H035), C036(H036), C037(H037), C038(H038)
;
_shelx_res_checksum              41466
_shelx_hkl_checksum              85634
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'