High-Spin Iron Imido Complexes Competent for C-H Bond Amination.
Wilding, Matthew J. T.; Iovan, Diana A.; Betley, Theodore A.; Journal of the American Chemical Society 139 (2017) 12043–12049; doi:10.1021/jacs.7b06682

data_4131545
_publ_section_title
;
 High-Spin Iron Imido Complexes Competent for C-H Bond Amination.
;
_journal_issue                   34
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12043
_journal_page_last               12049
_journal_paper_doi               10.1021/jacs.7b06682
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C75.93 H63.8 Fe N3, C7 H8'
_chemical_formula_sum            'C82.81 H70.64 Fe N3'
_chemical_formula_weight         1163.67
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-11-13
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                84.768(16)
_cell_angle_beta                 68.757(15)
_cell_angle_gamma                67.129(15)
_cell_formula_units_Z            2
_cell_length_a                   13.500(18)
_cell_length_b                   16.28(2)
_cell_length_c                   16.45(2)
_cell_measurement_temperature    100(2)
_cell_volume                     3100(7)
_computing_cell_refinement       'SAINT 7.46A (Bruker-AXS, 2009)'
_computing_data_collection       'APEX2 v2009.3.0 (Bruker-AXS, 2009)'
_computing_data_reduction        'SAINT 7.46A (Bruker-AXS, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XLMP (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.01
_diffrn_measured_fraction_theta_full 0.826
_diffrn_measured_fraction_theta_max 0.826
_diffrn_measurement_device_type
;
Bruker C8 goniometer with CCD area detector
;
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1408
_diffrn_reflns_av_unetI/netI     0.3537
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            17561
_diffrn_reflns_theta_full        25.41
_diffrn_reflns_theta_max         25.41
_diffrn_reflns_theta_min         1.33
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.293
_exptl_absorpt_correction_T_max  0.9634
_exptl_absorpt_correction_T_min  0.7736
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick,2008'
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.247
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       cube
_exptl_crystal_F_000             1229
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.870
_refine_diff_density_min         -0.408
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.924
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     772
_refine_ls_number_reflns         9448
_refine_ls_number_restraints     29
_refine_ls_restrained_S_all      0.924
_refine_ls_R_factor_all          0.3553
_refine_ls_R_factor_gt           0.1263
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.2000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2980
_refine_ls_wR_factor_ref         0.4359
_reflns_number_gt                2328
_reflns_number_total             9448
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja7b06682_si_002.cif
_cod_data_source_block           ArLFeNAd
_cod_database_code               4131545
_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
2. Restrained distances
 C67-C69 \\sim C67-C69A
 with sigma of 0.02
 C67-C70 \\sim C67-C70A
 with sigma of 0.02
 C67-C68 \\sim C67-C68A
 with sigma of 0.02
 C72-C73 \\sim C72A-C73A
 with sigma of 0.02
 C73-C74 \\sim C73A-C74A
 with sigma of 0.02
 C74-C75 \\sim C74A-C75A
 with sigma of 0.02
 C75-C76 \\sim C75A-C76A
 with sigma of 0.02
 C76-C71 \\sim C76A-C71A
 with sigma of 0.02
3. Rigid bond restraints
 C58, C59
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C75, C74
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C72, C71
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C58 \\sim C59: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C75 \\sim C74: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C72 \\sim C71: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
Uanis(C69) = Uanis(C69A)
Uanis(C68) = Uanis(C68A)
Uanis(C70) = Uanis(C70A)
Uanis(C72) = Uanis(C72A)
Uanis(C73) = Uanis(C73A)
Uanis(C74) = Uanis(C74A)
Uanis(C75) = Uanis(C75A)
Uanis(C76) = Uanis(C76A)
Uanis(C71) = Uanis(C71A)
Uanis(C70) = Uanis(C76)
Uanis(C31) = Uanis(C32)
Uanis(C68) = Uanis(C70)
Uanis(C71) = Uanis(C68)
5. Others
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=
 FVAR(1)
 Sof(C68A)=Sof(H68C)=Sof(H68D)=Sof(C73A)=Sof(H73A)=Sof(C72A)=Sof(H72C)=
 Sof(H72D)=Sof(C71A)=Sof(H71A)=Sof(C76A)=Sof(H76C)=Sof(H76D)=Sof(C75A)=
 Sof(H75A)=Sof(C69A)=Sof(H69C)=Sof(H69D)=Sof(C70A)=Sof(H70C)=Sof(H70D)=
 Sof(C74A)=Sof(H74C)=Sof(H74D)=1-FVAR(2)
 Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(C70)=Sof(H70A)=
 Sof(H70B)=Sof(C71)=Sof(H71)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(C73)=Sof(H73)=
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(C75)=Sof(H75)=Sof(C76)=Sof(H76A)=Sof(H76B)=
 FVAR(2)
6.a Free rotating group:
 C68A(C73A,C72A,C71A,C76A,C75A,C69A,C70A,C74A)
6.b Ternary CH refined with riding coordinates:
 C71(H71), C73(H73), C75(H75), C73A(H73A), C71A(H71A), C75A(H75A)
6.c Secondary CH2 refined with riding coordinates:
 C68(H68A,H68B), C69(H69A,H69B), C70(H70A,H70B), C72(H72A,H72B), C74(H74A,
 H74B), C76(H76A,H76B), C68A(H68C,H68D), C72A(H72C,H72D), C76A(H76C,H76D),
 C69A(H69C,H69D), C70A(H70C,H70D), C74A(H74C,H74D)
6.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C12(H12), C14(H14), C15(H15),
 C16(H16), C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24),
  C26(H26), C27(H27), C33(H33), C36(H36), C40(H40), C41(H41), C45(H45),
 C47(H47), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57),
  C58(H58), C59(H59), C60(H60), C62(H62), C63(H63), C64(H64), C65(H65),
 C66(H66), C79(H79), C80(H80), C81(H81), C82(H82), C83(H83)
6.e Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C35(H35A,H35B,H35C), C38(H38A,H38B,H38C), C77(H77A,H77B,
 H77C)
;
_olex2_submission_special_instructions 'No special instructions were received'