Cobalt catalyzed sp3C–H amination utilizing aryl azides
Villanueva, Omar; Weldy, Nina Mace; Blakey, Simon B.; MacBeth, Cora E.; Chem. Sci. 6 (2015) 6672–; doi:10.1039/C5SC01162K

data_1529316
_publ_section_title
;
 Cobalt catalyzed sp3C--H amination utilizing aryl azides
;
_journal_issue                   11
_journal_name_full               'Chem. Sci.'
_journal_page_first              6672
_journal_paper_doi               10.1039/C5SC01162K
_journal_volume                  6
_journal_year                    2015
_chemical_formula_moiety
'2.5(C20.83 H14.42 Co0.8 N2.4 O1.6), 2(C8 H20 N), 0.5(C4 H6 N2)'
_chemical_formula_sum            'C70 H79 Co2 N9 O4'
_chemical_formula_weight         1228.28
_space_group_crystal_system      trigonal
_space_group_IT_number           154
_space_group_name_Hall           'P 32 2"'
_space_group_name_H-M_alt        'P 32 2 1'
_symmetry_space_group_name_Hall  'P 32 2"'
_symmetry_space_group_name_H-M   'P 32 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-03-19
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-03-31 deposited with the CCDC.
2015-07-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   14.064(3)
_cell_length_b                   14.064(3)
_cell_length_c                   27.143(5)
_cell_measurement_reflns_used    9106
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      25.595
_cell_measurement_theta_min      2.247
_cell_volume                     4649.5(16)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2014.1-1 (Bruker, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      110(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0553
_diffrn_reflns_av_unetI/netI     0.0487
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            20628
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        23.256
_diffrn_reflns_theta_max         23.256
_diffrn_reflns_theta_min         1.672
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_current           30
_diffrn_source_voltage           45
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.592
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.5274
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0720 before and 0.0529 after correction.
The Ratio of minimum to maximum transmission is 0.7076.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.316
_exptl_crystal_description       prism
_exptl_crystal_F_000             1944
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.351
_exptl_crystal_size_min          0.285
_refine_diff_density_max         0.412
_refine_diff_density_min         -0.429
_refine_diff_density_rms         0.065
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.51(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     487
_refine_ls_number_reflns         4466
_refine_ls_number_restraints     444
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.1305
_refine_ls_R_factor_gt           0.0814
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1170P)^2^+6.2454P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2058
_refine_ls_wR_factor_ref         0.2493
_reflns_Friedel_coverage         0.756
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                2703
_reflns_number_total             4466
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5sc01162k2.cif
_cod_data_source_block           ov158
_cod_depositor_comments
'Adding full bibliography for 1529314--1529316.cif.'
_cod_original_cell_volume        4649(2)
_cod_database_code               1529316
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.49(8) 0.51(8)
2. 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
3. Restrained distances
 N4-C29 \\sim N4-C31 \\sim N4-C33 \\sim N4-C27
 with sigma of 0.005
 C22B-C17B \\sim C18B-C17B \\sim C19B-C18B \\sim C21B-C20B \\sim C22B-C21B
\\sim C19B-C20B
 with sigma of 0.002
 C9B-C10B \\sim C8B-C13B \\sim C13B-C12B \\sim C12B-C11B \\sim C11B-C10B
 with sigma of 0.005
 C18A-C17A \\sim C19A-C18A \\sim C21A-C20A \\sim C22A-C21A \\sim C22A-C17A
\\sim C20A-C19A
 with sigma of 0.005
 O2A-C16A \\sim O2B-C16B
 with sigma of 0.005
 C17A-C16A \\sim C17B-C16B
 with sigma of 0.005
 N1A-C14A \\sim N3A-C15A
 with sigma of 0.005
 C6A-C5A \\sim C5A-C4A
 with sigma of 0.005
4. Restrained planarity
 C17B, C18B, C19B, C20B, C21B, C22B
 with sigma of 0.002
 C16A, C17A, C18A, C19A, C20A, C21A, C22A
 with sigma of 0.005
 C14A, C15A, C23A, C24A, C25A, C26A
 with sigma of 0.005
5. Uiso/Uaniso restraints and constraints
Uanis(C20A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C17A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C25A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C2A) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C18A) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C2S) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(Co2B) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C8B) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C16A) = Uanis(C16B)
Uanis(C1A) = Uanis(C1B)
Uanis(C2A) = Uanis(C2B)
Uanis(N2A) = Uanis(N2B)
Uanis(O1A) = Uanis(O1B)
Uanis(C3A) = Uanis(C3B)
Uanis(C7A) = Uanis(C7B)
Uanis(C8A) = Uanis(C8B)
Uanis(Co2A) = Uanis(Co2B)
Uanis(C4A) = Uanis(C4B)
Uanis(C6A) = Uanis(C6B)
Uanis(C9A) = Uanis(C9B)
Uanis(C13A) = Uanis(C13B)
Uanis(N1A) = Uanis(N1B)
Uanis(Co1A) = Uanis(Co1B)
Uanis(C5A) = Uanis(C5B)
Uanis(C10A) = Uanis(C10B)
Uanis(C12A) = Uanis(C12B)
Uanis(C14A) = Uanis(C14B)
Uanis(N3A) = Uanis(N3B)
Uanis(C11A) = Uanis(C11B)
Uanis(C15A) = Uanis(C15B)
Uanis(C26A) = Uanis(C26B)
Uanis(C23A) = Uanis(C23B)
Uanis(C25A) = Uanis(C25B)
Uanis(C17A) = Uanis(C17B)
Uanis(O2A) = Uanis(O2B)
Uanis(C24A) = Uanis(C24B)
Uanis(C18A) = Uanis(C18B)
Uanis(C22A) = Uanis(C22B)
Uanis(C19A) = Uanis(C19B)
Uanis(C21A) = Uanis(C21B)
Uanis(C20A) = Uanis(C20B)
6. Rigid body (RIGU) restrains
 C33, C34, N4
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C14A, C15A, N3A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 N3A, C16A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C16A, C17A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 N3A, C16A, O2A, C17A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C17A, C18A, C22A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C18A, C19A, C20A, C21A, C22A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C14A, C15A, C23A, C24A, C25A, C26A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C8A, C9A, C10A, C11A, C12A, C13A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C1A, O1A, C2A, C3A, C4A, C5A, C6A, C7A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C2S, N3S, C1S
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
7. Same fragment restrains
{Co2B, N2B, C1B, O1B, C2B, C3B, C4B, C5B, C6B, C7B, C8B, C9B, C10B, C11B, C12B,
C13B, N1B, Co1B, C14B, C15B, C23B, C24B, C25B, C26B, N3B, C16B, O2B, C17B,
C18B, C19B, C20B, C21B, C22B} sigma for 1-2: 0.002, 1-3: 0.002
as
{Co2A, N2A, C1A, O1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A, C11A, C12A,
C13A, N1A, Co1A, C14A, C15A, C23A, C24A, C25A, C26A, N3A, C16A, O2A, C17A,
C18A, C19A, C20A, C21A, C22A}
8. Others
 Sof(N2B)=Sof(C1B)=Sof(O1B)=Sof(C2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(H4B)=
 Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(C9B)=
 Sof(C10B)=Sof(H10B)=Sof(C11B)=Sof(H11B)=Sof(C12B)=Sof(H12B)=Sof(C13B)=
 Sof(H13B)=Sof(N1B)=Sof(C14B)=Sof(C15B)=Sof(C23B)=Sof(H23B)=Sof(C24B)=Sof(H24B)=
 Sof(C25B)=Sof(H25B)=Sof(C26B)=Sof(H26B)=Sof(N3B)=Sof(C16B)=Sof(O2B)=Sof(C17B)=
 Sof(C18B)=Sof(H18B)=Sof(C19B)=Sof(H19B)=Sof(C20B)=Sof(H20B)=Sof(C21B)=
 Sof(H21B)=Sof(C22B)=Sof(H22B)=1-FVAR(1)
 Sof(Co2B)=Sof(Co1B)=0.5*(1-FVAR(2))
 Sof(Co2A)=Sof(Co1A)=0.5*FVAR(2)
 Sof(N2A)=Sof(C1A)=Sof(O1A)=Sof(C2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=
 Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(C9A)=
 Sof(C10A)=Sof(H10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=
 Sof(H13A)=Sof(N1A)=Sof(C14A)=Sof(C15A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=
 Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(N3A)=Sof(C16A)=Sof(O2A)=Sof(C17A)=
 Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=
 Sof(H21A)=Sof(C22A)=Sof(H22A)=FVAR(1)
 Fixed Sof: H1SA(0.5) H1SB(0.5) H1SC(0.5)
9.a Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C29(H29A,H29B), C31(H31A,H31B), C33(H33A,H33B)
9.b Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A), C7A(H7A), C10A(H10A), C11A(H11A),
 C12A(H12A), C13A(H13A), C23A(H23A), C24A(H24A), C25A(H25A), C26A(H26A),
 C18A(H18A), C19A(H19A), C20A(H20A), C21A(H21A), C22A(H22A), C3B(H3B), C4B(H4B),
  C5B(H5B), C6B(H6B), C7B(H7B), C10B(H10B), C11B(H11B), C12B(H12B), C13B(H13B),
 C23B(H23B), C24B(H24B), C25B(H25B), C26B(H26B), C18B(H18B), C19B(H19B),
 C20B(H20B), C21B(H21B), C22B(H22B)
9.c Idealised Me refined with everything fixed:
 C1S(H1SA,H1SB,H1SC)
9.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C34(H34A,H34B,
 H34C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_original_sample_id Ov-B5-158
_olex2_submission_special_instructions 'No special instructions were received'