Direct Manipulation of Metal Imido Geometry: Key Principles to Enhance C-H Amination Efficacy.
Baek, Yunjung; Hennessy, Elisabeth T.; Betley, Theodore A.; Journal of the American Chemical Society 141 (2019) 16944–16953; doi:10.1021/jacs.9b09015

data_4127965
_publ_section_title
;
 Direct Manipulation of Metal Imido Geometry: Key Principles to Enhance
 C-H Amination Efficacy.
;
_journal_issue                   42
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16944
_journal_page_last               16953
_journal_paper_doi               10.1021/jacs.9b09015
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C61 H50 Co N3'
_chemical_formula_sum            'C61 H50 Co N3'
_chemical_formula_weight         883.97
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-06-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.02.23 svn.r3390 for OlexSys, GUI svn.r5320)
;
_cell_angle_alpha                90
_cell_angle_beta                 117.576(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   43.246(4)
_cell_length_b                   9.1582(9)
_cell_length_c                   30.563(3)
_cell_measurement_reflns_used    9995
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.06
_cell_measurement_theta_min      2.29
_cell_volume                     10729.5(18)
_computing_cell_refinement       'SAINT 8.37A (Bruker-AXS, 2016)'
_computing_data_collection       'APEX3 v2016.1.0 (Bruker-AXS, 2016)'
_computing_data_reduction        'SAINT 8.37A (Bruker-AXS, 2016)'
_computing_molecular_graphics    "'Bruker SHELXTL (Sheldrick, 2015)"
_computing_publication_material  'Bruker SHELXTL (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.2481
_diffrn_reflns_av_unetI/netI     0.1428
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       51
_diffrn_reflns_limit_h_min       -50
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            54632
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.078
_diffrn_reflns_theta_max         25.078
_diffrn_reflns_theta_min         2.207
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.358
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6008
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1531 before and 0.0795 after correction.
The Ratio of minimum to maximum transmission is 0.8062.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.094
_exptl_crystal_description       needle
_exptl_crystal_F_000             3712
_exptl_crystal_size_max          0.54
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.070
_refine_diff_density_min         -1.433
_refine_diff_density_rms         0.176
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.144
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     277
_refine_ls_number_reflns         9499
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.144
_refine_ls_R_factor_all          0.2244
_refine_ls_R_factor_gt           0.1937
_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^)+(0.0001P)^2^+654.2696P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4041
_refine_ls_wR_factor_ref         0.4212
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7285
_reflns_number_total             9499
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b09015_si_002.cif
_cod_data_source_block           (TrL)Copy
_cod_original_cell_volume        10729.6(17)
_cod_database_code               4127965
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.7452
_shelx_estimated_absorpt_t_min   0.6008
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(N002) = Uanis(N004)
Uanis(C18) = Uanis(C17)
Uanis(C47) = Uanis(C46)
Uanis(C58) = Uanis(C59)
Uanis(C42) = Uanis(C43)
Uanis(C7) = Uanis(C10)
Uanis(C28) = Uanis(C15)
Uanis(C28) = Uanis(C29)
Uanis(C8) = Uanis(C9)
Uanis(C4) = Uanis(C3)
Uanis(C10) = Uanis(C34)
Uanis(C36) = Uanis(C35)
Uanis(C51) = Uanis(C52)
Uanis(C12) = Uanis(C11)
Uanis(C21) = Uanis(C16)
Uanis(C60) = Uanis(C59)
Uanis(C49) = Uanis(C50)
Uanis(C50) = Uanis(C47)
Uanis(C50) = Uanis(C45)
Uanis(C45) = Uanis(C48)
Uanis(C32) = Uanis(C31)
Uanis(C6) = Uanis(C7)
Uanis(C53) = Uanis(C54)
Uanis(C56) = Uanis(C40)
Uanis(C55) = Uanis(C43)
Uanis(C55) = Uanis(C54)
Uanis(C38) = Uanis(C45)
Uanis(C21) = Uanis(C20)
Uanis(C41) = Uanis(C40)
Uanis(C39) = Uanis(C42)
Uanis(C56) = Uanis(C52)
Uanis(C24B) = Uanis(C25B)
Uanis(C23B) = Uanis(C22B)
Uanis(C27B) = Uanis(C26B)
Uanis(C24B) = Uanis(C27B)
Uanis(C30) = Uanis(C31)
Uanis(C27) = Uanis(C22)
Uanis(C61) = Uanis(C57)
Uanis(C26) = Uanis(C23)
Uanis(C27) = Uanis(C51)
Uanis(C25) = Uanis(C54)
Uanis(C24) = Uanis(C53)
Uanis(C5) = Uanis(C6)
Uanis(C24B) = Uanis(C52)
Uanis(C24) = Uanis(C23)
Uanis(C28) = Uanis(C39)
Uanis(C32) = Uanis(C41)
Uanis(C30) = Uanis(C33)
Uanis(C22B) = Uanis(C25B)
Uanis(C14) = Uanis(C11)
Uanis(C16) = Uanis(C15)
Uanis(C37) = Uanis(C14)
Uanis(C12) = Uanis(C35)
3. Others
 Fixed Sof: C22(0.5) C27(0.5) H27(0.5) C26(0.5) H26(0.5) C25(0.5) H25(0.5)
 C24(0.5) H24(0.5) C23(0.5) H23(0.5) C23B(0.5) H23B(0.5) C24B(0.5) H24B(0.5)
 C25B(0.5) H25B(0.5) C26B(0.5) H26B(0.5) C27B(0.5) H27B(0.5) C22B(0.5)
4.a Aromatic/amide H refined with riding coordinates:
 C49(H49), C56(H56), C54(H54), C61(H61), C50(H50), C47(H47), C46(H46),
 C40(H40), C36(H36), C48(H48), C43(H43), C44(H44), C52(H52), C35(H35), C60(H60),
  C53(H53), C42(H42), C41(H41), C55(H55), C3(H3), C59(H59), C4(H4), C12(H12),
 C30(H30), C31(H31), C32(H32), C33(H33), C29(H29), C58(H58), C21(H21), C17(H17),
  C18(H18), C19(H19), C20(H20), C13(H13), C27(H27), C26(H26), C25(H25),
 C24(H24), C23(H23), C57(H57), C23B(H23B), C24B(H24B), C25B(H25B), C26B(H26B),
 C27B(H27B)
4.b Fitted hexagon refined as free rotating group:
 C30(C31,C32,C33,C28,C29), C21(C16,C17,C18,C19,C20), C22(C27,C26,C25,C24,C23),
 C23B(C24B,C25B,C26B,C27B,C22B)
4.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C1(H1A,H1B,H1C)
;
_olex2_submission_special_instructions 'No special instructions were received'