Synthesis of dinuclear pyridyl-amido hafnium and zirconium complexes toward olefin polymerization with unexpected stereospecificity and ultra-high molecular weight capability
Xing, Yanhong; Liu, Shaofeng; Li, Zhibo; Polymer Chemistry 15 (2024) 4141–4150; doi:10.1039/D4PY00794H

data_1572615
_publ_section_title
;
 Synthesis of dinuclear pyridyl-amido hafnium and zirconium complexes
 toward olefin polymerization with unexpected stereospecificity and
 ultra-high molecular weight capability
;
_journal_issue                   40
_journal_name_full               'Polymer Chemistry'
_journal_page_first              4141
_journal_page_last               4150
_journal_paper_doi               10.1039/D4PY00794H
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C52 H46 Hf2 N4, 2(C7 H8)'
_chemical_formula_sum            'C66 H62 Hf2 N4'
_chemical_formula_weight         1268.17
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-03-02
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-04-23 deposited with the CCDC.	2024-09-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.2440(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.6490(4)
_cell_length_b                   12.8229(3)
_cell_length_c                   24.5818(6)
_cell_measurement_reflns_used    9798
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      27.49
_cell_measurement_theta_min      2.24
_cell_volume                     5456.4(2)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2019)'
_computing_data_collection       'APEX4 V2022.10-1 (Bruker, 2022)'
_computing_data_reduction        'SAINT V8.40B (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      193.00
_diffrn_detector                 CPAD
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE TXS PHOTON 100'
_diffrn_measurement_method       '\w and \f shutterless scans'
_diffrn_measurement_specimen_support 'nylon loop'
_diffrn_radiation_monochromator  'Helios Multi-layer Optic'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0418
_diffrn_reflns_av_unetI/netI     0.0367
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            50389
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.496
_diffrn_reflns_theta_min         1.799
_diffrn_source                   TXS
_diffrn_source_current           40.0
_diffrn_source_power             2.0
_diffrn_source_type              'Rotaing Anode'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.847
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5086
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0914 before and 0.0533 after correction.
The Ratio of minimum to maximum transmission is 0.6821.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.544
_exptl_crystal_description       block
_exptl_crystal_F_000             2520
_refine_diff_density_max         0.897
_refine_diff_density_min         -0.549
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     698
_refine_ls_number_reflns         12503
_refine_ls_number_restraints     210
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0410
_refine_ls_R_factor_gt           0.0283
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0160P)^2^+6.4495P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0556
_refine_ls_wR_factor_ref         0.0605
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10362
_reflns_number_total             12503
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4py00794h2.cif
_cod_data_source_block           230228lu_lgpz216096_0m
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1572615.cif.
;
_cod_database_code               1572615
_shelx_shelxl_version_number     2019/3
_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
C60 \\sim C62 \\sim C63 \\sim C61 \\sim C64 \\sim C66 \\sim C65 \\sim C60A
\\sim C62A \\sim C63A \\sim C61A \\sim C64A \\sim C66A \\sim C65A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
3. Others
 Sof(C62A)=Sof(H62A)=Sof(C63A)=Sof(H63A)=Sof(C64A)=Sof(H64A)=Sof(C65A)=
 Sof(H65A)=Sof(C66A)=Sof(H66A)=Sof(C61A)=Sof(C60A)=Sof(H60D)=Sof(H60E)=
 Sof(H60F)=1-FVAR(1)
 Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=Sof(C65)=Sof(H65)=
 Sof(C66)=Sof(H66)=Sof(C61)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C16(H16), C51(H51)
4.b Aromatic/amide H refined with riding coordinates:
 C32(H32), C21(H21), C23(H23), C12(H12), C49(H49), C8(H8), C13(H13), C22(H22),
 C14(H14), C29(H29), C25(H25), C27(H27), C43(H43), C28(H28), C7(H7), C48(H48),
 C47(H47), C38(H38), C40(H40), C6(H6), C42(H42), C5(H5), C2(H2), C37(H37),
 C3(H3), C41(H41), C59(H59), C56(H56), C57(H57), C58(H58), C55(H55), C62(H62),
 C63(H63), C64(H64), C65(H65), C66(H66), C62A(H62A), C63A(H63A), C64A(H64A),
 C65A(H65A), C66A(H66A)
4.c Fitted hexagon refined as free rotating group:
 C62(C63,C64,C65,C66,C61), C62A(C63A,C64A,C65A,C66A,C61A)
4.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C35(H35A,H35B,H35C), C19(H19A,H19B,H19C), C34(H34A,H34B,
 H34C), C52(H52A,H52B,H52C), C17(H17A,H17B,H17C), C53(H53A,H53B,H53C), C60(H60A,
 H60B,H60C), C60A(H60D,H60E,H60F)
;
_shelx_res_checksum              56040
_shelx_hkl_checksum              19785
_olex2_submission_special_instructions 'No special instructions were received'
_site                            XU