High molecular weight PE elastomers through 4,4-difluorobenzhydryl substitution in symmetrical α-diimino-nickel ethylene polymerization catalysts
Zheng, Yuting; Jiang, Shu; Liu, Ming; Yu, Zhixin; Ma, Yanping; Solan, Gregory A.; Zhang, Wenjuan; Liang, Tongling; Sun, Wen-Hua; RSC Advances 12 (2022) 24037–24049; doi:10.1039/D2RA04321A

data_7245418
_publ_section_title
;
 High molecular weight PE elastomers through 4,4-difluorobenzhydryl
 substitution in symmetrical \a-diimino-nickel ethylene polymerization
 catalysts
;
_journal_issue                   37
_journal_name_full               'RSC Advances'
_journal_page_first              24037
_journal_page_last               24049
_journal_paper_doi               10.1039/D2RA04321A
_journal_volume                  12
_journal_year                    2022
_chemical_formula_moiety         'C70 H52 F8 N2'
_chemical_formula_sum            'C70 H52 F8 N2'
_chemical_formula_weight         1073.13
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-10-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-03-24 deposited with the CCDC.	2022-08-17 downloaded from the CCDC.
;
_cell_angle_alpha                89.0030(10)
_cell_angle_beta                 84.9140(10)
_cell_angle_gamma                83.4140(10)
_cell_formula_units_Z            6
_cell_length_a                   11.08370(10)
_cell_length_b                   19.80860(10)
_cell_length_c                   37.8410(3)
_cell_measurement_reflns_used    44419
_cell_measurement_temperature    170.00(10)
_cell_measurement_theta_max      75.0220
_cell_measurement_theta_min      2.2010
_cell_volume                     8220.55(11)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      170.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.955
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -24.00  25.00   0.50    0.05    --  -47.57  21.00 169.00   98
  2  \w   -107.00 -68.00   0.50    0.05    --  -47.57 -21.00   2.00   78
  3  \w    -65.00 -37.00   0.50    0.05    --  -47.57 -21.00   2.00   56
  4  \w     55.00  81.00   0.50    0.05    --   47.57  21.00 169.00   52
  5  \w   -166.00 -89.00   0.50    0.18    --  -99.00 -21.00   2.00  154
  6  \w     91.00 156.00   0.50    0.18    --  103.25  21.00 169.00  130
  7  \w    -23.00  28.00   0.50    0.05    --  -47.57  19.00 -60.00  102
  8  \w    -23.00  28.00   0.50    0.05    --  -47.57  19.00-150.00  102
  9  \w    -40.00  25.00   0.50    0.05    --  -47.57  38.00-120.00  130
 10  \w   -119.00 -94.00   0.50    0.05    --  -47.57-125.00 -90.00   50
 11  \w     36.00  91.00   0.50    0.05    --   47.57-125.00  90.00  110
 12  \w     59.00  84.00   0.50    0.05    --   47.57-125.00-180.00   50
 13  \w      6.00  31.00   0.50    0.05    --   47.57 -21.00   2.00   50
 14  \w     17.00  61.00   0.50    0.05    --   47.57 -57.00  60.00   88
 15  \w    -23.00  10.00   0.50    0.05    --   47.57 -57.00  60.00   66
 16  \w   -124.00 -96.00   0.50    0.18    --  -99.00 142.00-108.34   56
 17  \w    -56.00 -30.00   0.50    0.18    --  -99.00  77.00-150.00   52
 18  \w   -121.00 -82.00   0.50    0.18    --  -99.00 138.00 137.14   78
 19  \w   -112.00 -86.00   0.50    0.18    --  -99.00 125.00  60.00   52
 20  \w   -165.00 -93.00   0.50    0.18    --  -99.00 -15.00 -60.00  144
 21  \w    -54.00 -28.00   0.50    0.18    --  -99.00 138.00 137.14   52
 22  \w   -112.00 -34.00   0.50    0.18    --  -99.00 125.00  90.00  156
 23  \w    -60.00 -27.00   0.50    0.18    --  -99.00  61.00  90.00   66
 24  \w   -106.00 -81.00   0.50    0.18    --  -99.00 -69.00-114.59   50
 25  \w   -101.00 -61.00   0.50    0.18    --  -99.00  77.00-150.00   80
 26  \w   -127.00-100.00   0.50    0.18    --  -99.00 146.00 -12.30   54
 27  \w    -98.00 -72.00   0.50    0.18    --  -99.00 146.00 -12.30   52
 28  \w    -56.00 -27.00   0.50    0.18    --  -99.00 146.00 -12.30   58
 29  \w   -168.00 -77.00   0.50    0.18    --  -99.00 -77.00  97.90  182
 30  \w   -159.00-129.00   0.50    0.18    --  -99.00 -69.00-114.59   60
 31  \w   -168.00 -93.00   0.50    0.18    --  -99.00 -66.00 116.12  150
 32  \w   -107.00 -30.00   0.50    0.18    --  -99.00 105.00-111.51  154
 33  \w    -68.00 -33.00   0.50    0.18    --  -99.00  61.00-150.00   70
 34  \w    -82.00 -40.00   0.50    0.18    --  -99.00 125.00  60.00   84
 35  \w    -63.00 -37.00   0.50    0.18    --  -99.00  61.00  30.00   52
 36  \w   -116.00 -87.00   0.50    0.18    --  -99.00 -30.00 120.00   58
 37  \w    -98.00 -47.00   0.50    0.18    --  -99.00 125.00-180.00  102
 38  \w     75.00 106.00   0.50    0.18    --  103.25 -94.00 -90.00   62
 39  \w     40.00  71.00   0.50    0.18    --  103.25 -94.00 -90.00   62
 40  \w     41.00  67.00   0.50    0.18    --  103.25 -77.00 -60.00   52
 41  \w     75.00 102.00   0.50    0.18    --  103.25 -94.00 120.00   54
 42  \w     39.00  65.00   0.50    0.18    --  103.25 -94.00 120.00   52
 43  \w     39.00 105.00   0.50    0.18    --  103.25 -94.00  30.00  132
 44  \w     32.00  74.00   0.50    0.18    --  103.25 -61.00 -60.00   84
 45  \w     36.00  81.00   0.50    0.18    --  103.25-125.00 -30.00   90
 46  \w     34.00  93.00   0.50    0.18    --  103.25 -94.00 -30.00  118
 47  \w     60.00 106.00   0.50    0.18    --  103.25 -94.00-150.00   92
 48  \w     91.00 168.00   0.50    0.18    --  103.25  30.00  90.00  154
 49  \w     84.00 109.00   0.50    0.18    --  103.25 -77.00 -60.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1142974000
_diffrn_orient_matrix_UB_12      -0.0520233000
_diffrn_orient_matrix_UB_13      0.0007293000
_diffrn_orient_matrix_UB_21      -0.0811944000
_diffrn_orient_matrix_UB_22      -0.0561474000
_diffrn_orient_matrix_UB_23      0.0112503000
_diffrn_orient_matrix_UB_31      -0.0083817000
_diffrn_orient_matrix_UB_32      -0.0164481000
_diffrn_orient_matrix_UB_33      -0.0392879000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0293
_diffrn_reflns_av_unetI/netI     0.0299
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            120556
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.364
_diffrn_reflns_theta_min         2.245
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.778
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91821
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.301
_exptl_crystal_description       block
_exptl_crystal_F_000             3348
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.372
_refine_diff_density_min         -0.552
_refine_diff_density_rms         0.141
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.281
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2173
_refine_ls_number_reflns         32478
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.281
_refine_ls_R_factor_all          0.1223
_refine_ls_R_factor_gt           0.1097
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2897
_refine_ls_wR_factor_ref         0.3090
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24612
_reflns_number_total             32478
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ra04321a2.cif
_cod_data_source_block           L1
_cod_depositor_comments
;

2025-01-11
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C210 H156 F24 N6'
_cod_original_formula_weight         3219.40
_cod_original_formula_moiety         '2(C70 H52 F8 N2), C70 H53 F8 N2'
_cod_original_formula_units_Z            2
_cod_database_code               7245418
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N F Ni Br'
_reflns_odcompleteness_completeness 99.58
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C91(H91), C114(H114), C44(H44), C112(H112), C57(H57), C209(H209), C167(H167),
 C224(H224), C126(H126), C24(H24), C11(H11), C182(H182)
2.b Aromatic/amide H refined with riding coordinates:
 N200(H200), C92(H92), C97(H97), C42(H42), C125(H125), C88(H88), C208(H208),
 C89(H89), C9(H9), C162(H162), C104(H104), C115(H115), C65(H65), C40(H40),
 C108(H108), C17(H17), C123(H123), C46(H46), C96(H96), C111(H111), C206(H206),
 C217(H217), C215(H215), C179(H179), C221(H221), C50(H50), C52(H52), C118(H118),
  C173(H173), C128(H128), C77(H77), C23(H23), C59(H59), C214(H214), C164(H164),
 C69(H69), C107(H107), C30(H30), C105(H105), C63(H63), C230(H230), C60(H60),
 C56(H56), C66(H66), C7(H7), C184(H184), C47(H47), C94(H94), C194(H194),
 C129(H129), C99(H99), C53(H53), C16(H16), C132(H132), C110(H110), C72(H72),
 C101(H101), C229(H229), C49(H49), C62(H62), C76(H76), C36(H36), C190(H190),
 C29(H29), C211(H211), C172(H172), C121(H121), C236(H236), C131(H131), C78(H78),
  C175(H175), C220(H220), C178(H178), C13(H13), C138(H138), C19(H19),
 C185(H185), C226(H226), C35(H35), C227(H227), C22(H22), C188(H188), C117(H117),
  C134(H134), C68(H68), C232(H232), C75(H75), C193(H193), C32(H32), C26(H26),
 C169(H169), C191(H191), C73(H73), C218(H218), C27(H27), C55(H55), C235(H235),
 C20(H20), C33(H33), C102(H102), C187(H187), C14(H14), C176(H176), C137(H137),
 C212(H212), C135(H135), C233(H233), C119(H119), C170(H170)
2.c Idealised Me refined as rotating group:
 C201(H20A,H20B,H20C), C1(H1A,H1B,H1C), C84(H84A,H84B,H84C), C83(H83A,H83B,
 H83C), C2(H2A,H2B,H2C), C239(H23A,H23B,H23C), C202(H20D,H20E,H20F), C79(H79A,
 H79B,H79C), C70(H70A,H70B,H70C), C80(H80A,H80B,H80C), C240(H24A,H24B,H24C),
 C37(H37A,H37B,H37C)
;
_shelx_res_checksum              28697
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.212
_oxdiff_exptl_absorpt_empirical_full_min 0.839