Ultrahigh Activity and Broad Temperature Resistance of Amine-Imine Cobalt Precatalysts for Butadiene Polymerization
Fu, Yuan; Tang, Jian; Hua, Jing; Dalton Transactions  (2023) –; doi:10.1039/D3DT02460A

data_7713792
_publ_section_title
;
 Ultrahigh Activity and Broad Temperature Resistance of Amine-Imine Cobalt
 Precatalysts for Butadiene Polymerization
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02460A
_journal_year                    2023
_chemical_formula_moiety         '0.5(C50 H72 Cl4 Co2 N4)'
_chemical_formula_sum            'C25 H36 Cl2 Co N2'
_chemical_formula_weight         494.39
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-08-17
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-08-18 deposited with the CCDC.	2023-08-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.7263(8)
_cell_length_b                   17.7923(12)
_cell_length_c                   9.6321(6)
_cell_measurement_reflns_used    9907
_cell_measurement_temperature    300.00
_cell_measurement_theta_max      29.822
_cell_measurement_theta_min      2.767
_cell_volume                     2523.8(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker D8 Venture diffractrometer'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      300.00
_diffrn_detector                 'CCD area detector'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0852
_diffrn_reflns_av_unetI/netI     0.0342
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            72137
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.995
_diffrn_reflns_theta_min         3.411
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.906
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.4818
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1337 before and 0.0973 after correction.
The Ratio of minimum to maximum transmission is 0.6458.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.301
_exptl_crystal_description       block
_exptl_crystal_F_000             1044
_exptl_crystal_recrystallization_method
'The crystals were growth by means of evaporation of a mixture of n-hexane and toluene at RT.'
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.745
_refine_diff_density_min         -0.577
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     269
_refine_ls_number_reflns         3769
_refine_ls_number_restraints     325
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.1283
_refine_ls_R_factor_gt           0.1037
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0496P)^2^+16.3854P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2471
_refine_ls_wR_factor_ref         0.2585
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2818
_reflns_number_total             3769
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02460a2.cif
_cod_data_source_block           2262745
_cod_database_code               7713792
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.805
_shelx_estimated_absorpt_t_min   0.779
_exptl_crystal_mounting_method
'Crystals were removed from the crystallisation vial and immediately coated with polybutenes oil (CAS: 9003-29-6) on a glass slide. A suitable single crystal coated with polybutenes oil was sealed in capillary tube filled with argon. The capillary tube with single crystal was mounted on copper pin with solid paraffin.'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C8-C7
 1.54 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C15 \\sim C16 \\sim C21 \\sim C20 \\sim C19 \\sim C18 \\sim C17 \\sim C13 \\sim
C14 \\sim C22 \\sim C24 \\sim C23 \\sim C25 \\sim C12 \\sim C1 \\sim C6 \\sim
C5 \\sim C4 \\sim C3 \\sim C2 \\sim C11 \\sim C9 \\sim C7 \\sim C10 \\sim C8
\\sim N2 \\sim N1: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
4. Rigid body (RIGU) restrains
 Co1, C15, C16, C21, C20, C19, C18, C17, C13, C14, C22, C24, C23, C25, C12, C1,
  C6, C5, C4, C3, C2, C11, C9, C7, C10, C8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Others
 Fixed Sof: C15(0.5) H15A(0.5) H15B(0.5) H15C(0.5) C16(0.5) C21(0.5) C20(0.5)
 H20(0.5) C19(0.5) H19(0.5) C18(0.5) H18(0.5) C17(0.5) N2(0.5) H2(0.5) C13(0.5)
 C14(0.5) H14A(0.5) H14B(0.5) H14C(0.5) C22(0.5) H22A(0.5) H22B(0.5) C24(0.5)
 H24A(0.5) H24B(0.5) C23(0.5) H23A(0.5) H23B(0.5) H23C(0.5) C25(0.5) H25A(0.5)
 H25B(0.5) H25C(0.5) C12(0.5) H12A(0.5) H12B(0.5) H12C(0.5) C1(0.5) C6(0.5)
 C5(0.5) H5(0.5) C4(0.5) H4(0.5) C3(0.5) H3(0.5) C2(0.5) N1(0.5) C11(0.5)
 C9(0.5) H9A(0.5) H9B(0.5) C7(0.5) H7A(0.5) H7B(0.5) C10(0.5) H10A(0.5)
 H10B(0.5) H10C(0.5) C8(0.5) H8A(0.5) H8B(0.5) H8C(0.5)
6.a Ternary CH refined with riding coordinates:
 N2(H2)
6.b Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C24(H24A,H24B), C9(H9A,H9B), C7(H7A,H7B)
6.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C19(H19), C18(H18), C5(H5), C4(H4), C3(H3)
6.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C14(H14A,H14B,H14C), C23(H23A,H23B,H23C), C25(H25A,H25B,
 H25C), C12(H12A,H12B,H12C), C10(H10A,H10B,H10C), C8(H8A,H8B,H8C)
;
_shelx_res_checksum              89757
_olex2_submission_special_instructions 'No special instructions were received'