Bis(dinitrogen)cobalt(-I) Complexes with NHC Ligation: Synthesis, Characterization and Their Dinitrogen Functionalization Reactions Affording Side-On Bound Diazene Complexes.
Gao, Yafei; Li, Guangyu; Deng, Liang; Journal of the American Chemical Society  (2018) –; doi:10.1021/jacs.7b11660

data_4127124
_publ_section_title
;
 Bis(dinitrogen)cobalt(-I) Complexes with NHC Ligation: Synthesis,
 Characterization and Their Dinitrogen Functionalization Reactions
 Affording Side-On Bound Diazene Complexes.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b11660
_journal_year                    2018
_chemical_formula_moiety         'C42 H72 Co K N8 O6'
_chemical_formula_sum            'C42 H72 Co K N8 O6'
_chemical_formula_weight         883.10
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-06-15
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                102.495(2)
_cell_angle_beta                 90.430(2)
_cell_angle_gamma                98.117(2)
_cell_formula_units_Z            4
_cell_length_a                   12.7838(12)
_cell_length_b                   18.2289(18)
_cell_length_c                   20.971(2)
_cell_measurement_reflns_used    8039
_cell_measurement_temperature    130
_cell_measurement_theta_max      26.08
_cell_measurement_theta_min      2.20
_cell_volume                     4719.8(8)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.982
_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  0.0382
_diffrn_reflns_av_unetI/netI     0.0710
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            38124
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.515
_diffrn_reflns_theta_min         1.350
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.503
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6517
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0485 before and 0.0422 after correction.
The Ratio of minimum to maximum transmission is 0.8742.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.243
_exptl_crystal_description       block
_exptl_crystal_F_000             1896
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         2.456
_refine_diff_density_min         -1.005
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.007
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1192
_refine_ls_number_reflns         21317
_refine_ls_number_restraints     250
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.1061
_refine_ls_R_factor_gt           0.0617
_refine_ls_shift/su_max          0.070
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0841P)^2^+5.9305P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1552
_refine_ls_wR_factor_ref         0.1853
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13674
_reflns_number_total             21317
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b11660_si_001.cif
_cod_data_source_block           4
_cod_database_code               4127124
_shelx_estimated_absorpt_t_max   0.928
_shelx_estimated_absorpt_t_min   0.884
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 C78-C77 = C76-C75 = C73-C74 = C83-C84 = C81-C82 = C80-C79
 1.52 with sigma of 0.02
 O9-C76 = O8-C75 = O7-C73 = O7-C84 = O12-C83 = O12-C82 = O11-C81 = O11-C80 =
 O10-C79 = O10-C78 = O9-C77
 1.46 with sigma of 0.02
 C78-C79
 2.3 with sigma of 0.02
 C80-C79
 1.52 with sigma of 0.02
 O11-C79
 2.25 with sigma of 0.02
 O11-C79
 2.25 with sigma of 0.02
 C80-C79
 1.52 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O7 \\sim O8 \\sim O9 \\sim O10 \\sim O11 \\sim O12 \\sim C73 \\sim C74 \\sim
C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81 \\sim C82 \\sim
C83 \\sim C84: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O13 \\sim O14 \\sim O15 \\sim O16 \\sim O17 \\sim O18 \\sim C1AA \\sim C85
\\sim C86 \\sim C87 \\sim C88 \\sim C89 \\sim C90 \\sim C91 \\sim C92: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C80 \\sim O11 \\sim O17: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(C89) \\sim Ueq, Uanis(O11) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(O17) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O11) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O11) \\sim Ueq, Uanis(O17) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(C17) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Fixed Sof: O7(0.5) O8(0.5) O9(0.5) O10(0.5) O11(0.5) O12(0.5) O13(0.5)
 O14(0.5) O15(0.5) O16(0.5) O17(0.5) O18(0.5) C1AA(0.5) H1AA(0.5) H1AB(0.5)
 H73A(0.5) H73B(0.5) H73C(0.5) H73D(0.5) C74(0.5) H74A(0.5) H74B(0.5) H75A(0.5)
 H75B(0.5) H75C(0.5) H75D(0.5) C76(0.5) H76A(0.5) H76B(0.5) C77(0.5) H77A(0.5)
 H77B(0.5) C78(0.5) H78A(0.5) H78B(0.5) C79(0.5) H79A(0.5) H79B(0.5) H80A(0.5)
 H80B(0.5) H80C(0.5) H80D(0.5) C81(0.5) H81A(0.5) H81B(0.5) C82(0.5) H82A(0.5)
 H82B(0.5) C83(0.5) H83A(0.5) H83B(0.5) C84(0.5) H84A(0.5) H84B(0.5) C85(0.5)
 H85A(0.5) H85B(0.5) C86(0.5) H86A(0.5) H86B(0.5) C87(0.5) H87A(0.5) H87B(0.5)
 C88(0.5) H88A(0.5) H88B(0.5) C89(0.5) H89A(0.5) H89B(0.5) C90(0.5) H90A(0.5)
 H90B(0.5) C91(0.5) H91A(0.5) H91B(0.5) C92(0.5) H92A(0.5) H92B(0.5)
5.a Ternary CH refined with riding coordinates:
 C47(H47), C53(H53), C61(H61), C67(H67), C7(H7), C13(H13), C21(H21), C27(H27)
5.b Secondary CH2 refined with riding coordinates:
 C1AA(H1AA,H1AB), C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,
 H51B), C52(H52A,H52B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B),
 C57(H57A,H57B), C58(H58A,H58B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B),
  C65(H65A,H65B), C66(H66A,H66B), C68(H68A,H68B), C69(H69A,H69B), C70(H70A,
 H70B), C71(H71A,H71B), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B),
 C75(H75A,H75B), C76(H76A,H76B), C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B),
  C80(H80A,H80B), C80(H80C,H80D), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,
 H83B), C84(H84A,H84B), C85(H85A,H85B), C86(H86A,H86B), C87(H87A,H87B),
 C88(H88A,H88B), C89(H89A,H89B), C90(H90A,H90B), C91(H91A,H91B), C92(H92A,H92B),
  C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B),
 C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B),
  C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,
 H26B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B),
 C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B),
  C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,
 H41B), C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B)
5.c Aromatic/amide H refined with riding coordinates:
 C45(H45), C46(H46), C59(H59), C60(H60), C5(H5), C6(H6), C19(H19), C20(H20)
;
_shelx_res_checksum              24778
_shelx_hkl_checksum              67337
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'