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_7713791
_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         'C29 H44 Cl2 Co N2, C H2 Cl2'
_chemical_formula_sum            'C30 H46 Cl4 Co N2'
_chemical_formula_weight         635.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_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                 93.145(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.271(4)
_cell_length_b                   19.167(9)
_cell_length_c                   21.451(10)
_cell_measurement_reflns_used    3895
_cell_measurement_temperature    300.00
_cell_measurement_theta_max      22.459
_cell_measurement_theta_min      2.328
_cell_volume                     3396(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 0.977
_diffrn_measured_fraction_theta_max 0.977
_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  0.0683
_diffrn_reflns_av_unetI/netI     0.0605
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            18116
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        22.907
_diffrn_reflns_theta_max         22.907
_diffrn_reflns_theta_min         1.426
_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    0.840
_exptl_absorpt_correction_T_max  0.7448
_exptl_absorpt_correction_T_min  0.2730
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1481 before and 0.0832 after correction.
The Ratio of minimum to maximum transmission is 0.3665.
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    1.243
_exptl_crystal_description       block
_exptl_crystal_F_000             1340
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.490
_refine_diff_density_min         -0.360
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     453
_refine_ls_number_reflns         4548
_refine_ls_number_restraints     393
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0863
_refine_ls_R_factor_gt           0.0602
_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^)+(0.0714P)^2^+5.0800P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1475
_refine_ls_wR_factor_ref         0.1644
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3331
_reflns_number_total             4548
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02460a2.cif
_cod_data_source_block           2262744
_cod_database_code               7713791
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.843
_shelx_estimated_absorpt_t_min   0.811
_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 = C8A-C7 = C9-C7 = C9A-C7 = C28-C27 = C28A-C27 = C29-C27 = C29A-C27
 1.54 with sigma of 0.01
 C9-C8 = C8A-C9A = C28-C29 = C28A-C29A
 2.515 with sigma of 0.02
 Cl4-C30 \\sim Cl4-C30A
 with sigma of 0.02
 C16A-C17A \\sim C17-C16
 with sigma of 0.02
 C17-C15 \\sim C16A-C15A
 with sigma of 0.02
 C14-C17 \\sim C14A-C16A
 with sigma of 0.02
 Cl3-C30 \\sim Cl3A-C30A
 with sigma of 0.02
 C17A-C15A \\sim C16-C15
 with sigma of 0.02
 Cl4-Cl3 \\sim Cl4-Cl3A
 with sigma of 0.02
 C14A-C13A \\sim C14-C13
 with sigma of 0.02
 C15A-C14A \\sim C15-C14
 with sigma of 0.02
 N1-C14 \\sim N2-C14A
 with sigma of 0.02
 N2-C15 \\sim N1-C15A
 with sigma of 0.02
 C18-C14A \\sim C15A-C1
 with sigma of 0.02
3. Restrained planarity
 N2, C14A, C15A, C13A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C14A \\sim C15A \\sim C17A
\\sim C16A \\sim C13A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Cl4 \\sim Cl3 \\sim C30 \\sim C30A \\sim Cl3A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C27 \\sim C28 \\sim C29 \\sim C28A \\sim C29A \\sim C7 \\sim C8 \\sim C9 \\sim
C8A \\sim C9A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(C30A) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(Cl3A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C13, C14, C15, C16, C17, C14A, C15A, C17A, C16A, C13A, N1, N2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 Cl3, C30, Cl4, C30A, Cl3A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
6. Others
 Sof(Cl3A)=Sof(C30A)=Sof(H30C)=Sof(H30D)=1-FVAR(1)
 Sof(Cl3)=Sof(C30)=Sof(H30A)=Sof(H30B)=FVAR(1)
 Sof(H1)=Sof(C14A)=Sof(C15A)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C16A)=
 Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=1-FVAR(2)
 Sof(H2)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(C15)=Sof(C16)=
 Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=FVAR(2)
 Sof(H27A)=Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29A)=Sof(H29D)=
 Sof(H29E)=Sof(H29F)=1-FVAR(3)
 Sof(H27)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=
 Sof(H29C)=FVAR(3)
 Sof(H7B)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=
 Sof(H9AC)=1-FVAR(4)
 Sof(H7A)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=
 Sof(H9C)=FVAR(4)
7.a Riding coordinates:
 C17A(H17D,H17E,H17F), C16A(H16D,H16E,H16F)
7.b Ternary CH refined with riding coordinates:
 N1(H1), N2(H2), C7(H7B), C7(H7A), C10(H10), C24(H24), C27(H27), C27(H27A)
7.c Secondary CH2 refined with riding coordinates:
 C30(H30A,H30B), C30A(H30C,H30D)
7.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C20(H20), C21(H21), C22(H22)
7.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C),
 C13A(H13D,H13E,H13F), C28A(H28D,H28E,H28F), C29A(H29D,H29E,H29F), C8A(H8AA,
 H8AB,H8AC), C9A(H9AA,H9AB,H9AC)
;
_shelx_res_checksum              55936
_olex2_submission_special_instructions 'No special instructions were received'