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_7245420
_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         '2(Br2 C46 F4 N2 Ni)'
_chemical_formula_sum            'C92 H81.01 Br4 F8 N4 Ni2'
_chemical_formula_weight         1831.67
_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_primary     dual
_audit_creation_date             2021-09-23
_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                78.343(4)
_cell_angle_beta                 78.089(5)
_cell_angle_gamma                78.104(6)
_cell_formula_units_Z            2
_cell_length_a                   15.1623(12)
_cell_length_b                   15.6426(9)
_cell_length_c                   18.6622(9)
_cell_measurement_reflns_used    8952
_cell_measurement_temperature    170.00(13)
_cell_measurement_theta_max      62.4550
_cell_measurement_theta_min      2.9240
_cell_volume                     4178.7(5)
_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(13)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     26.00 114.00   0.50    1.50    --   47.45  78.00 -29.00  176
  2  \w     80.00 160.00   0.50    6.50    --  103.25  78.00 -29.00  160
  3  \w     98.00 167.00   0.50    6.50    --  103.25  45.00 -60.00  138
  4  \w     87.00 169.00   0.50    6.50    --  103.25  61.00 -90.00  164
  5  \w     88.00 168.00   0.50    6.50    --  103.25  61.00-120.00  160
  6  \w     81.00 120.00   0.50    6.50    --  103.25 125.00  60.00   78
  7  \w     49.00  74.00   0.50    6.50    --  103.25 -61.00 -30.00   50
  8  \w     32.00  75.00   0.50    6.50    --  103.25 -61.00   0.00   86
  9  \w     20.00  95.00   0.50    1.50    --   47.45-125.00  90.00  150
 10  \w     56.00  90.00   0.50    6.50    --  103.25 -94.00 150.00   68
 11  \w     48.00  74.00   0.50    6.50    --  103.25-125.00 120.00   52
 12  \w     31.00  84.00   0.50    6.50    --  103.25 -94.00  90.00  106
 13  \w    -27.00  26.00   0.50    1.50    --   47.45 -19.00-150.00  106
 14  \w    -11.00  57.00   0.50    1.50    --   47.45 -78.00-154.00  136
 15  \w     34.00 113.00   0.50    6.50    --  103.25 -78.00-154.00  158
 16  \w     31.00 104.00   0.50    6.50    --  103.25 -94.00-180.00  146
 17  \w    -22.00  15.00   0.50    1.50    --  -47.45  19.00 -90.00   74
 18  \w    -60.00   2.00   0.50    1.50    --  -47.45  78.00 -29.00  124
 19  \w    -53.00 -28.00   0.50    6.50    --  -99.00 125.00 120.00   50
 20  \w    -73.00 -27.00   0.50    6.50    --  -99.00 125.00   0.00   92
 21  \w    -81.00 -33.00   0.50    6.50    --  -99.00  78.00 -29.00   96
 22  \w   -112.00 -68.00   0.50    6.50    --  -99.00 125.00  30.00   88
 23  \w   -110.00 -84.00   0.50    6.50    --  -99.00 125.00   0.00   52
 24  \w   -111.00 -31.00   0.50    6.50    --  -99.00 125.00 -60.00  160
 25  \w   -110.00 -79.00   0.50    6.50    --  -99.00 125.00-120.00   62
 26  \w   -125.00 -98.00   0.50    6.50    --  -99.00 144.00-109.28   54
 27  \w   -106.00 -30.00   0.50    6.50    --  -99.00 125.00 -30.00  152
 28  \w   -108.00 -74.00   0.50    6.50    --  -99.00 125.00 120.00   68
 29  \w    -86.00 -26.00   0.50    6.50    --  -99.00 144.00 158.87  120
 30  \w   -109.00 -28.00   0.50    6.50    --  -99.00 116.00 103.30  162
 31  \w   -125.00 -96.00   0.50    6.50    --  -99.00 144.00 158.87   58
 32  \w   -111.00 -85.00   0.50    6.50    --  -99.00 -53.00  99.64   52
 33  \w   -109.00 -80.00   0.50    1.50    --  -47.45-125.00  30.00   58
 34  \w   -119.00 -74.00   0.50    1.50    --  -47.45-125.00 -60.00   90
 35  \w   -105.00 -39.00   0.50    1.50    --  -47.45 -78.00-154.00  132
 36  \w   -139.00 -83.00   0.50    6.50    --  -99.00 -78.00-154.00  112
 37  \w   -161.00 -82.00   0.50    6.50    --  -99.00 -64.00  81.69  158
 38  \w   -165.00-123.00   0.50    6.50    --  -99.00 -53.00  99.64   84
;
_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      -0.1027948000
_diffrn_orient_matrix_UB_12      0.0027266000
_diffrn_orient_matrix_UB_13      0.0028350000
_diffrn_orient_matrix_UB_21      -0.0029876000
_diffrn_orient_matrix_UB_22      -0.0675545000
_diffrn_orient_matrix_UB_23      0.0726729000
_diffrn_orient_matrix_UB_31      -0.0231143000
_diffrn_orient_matrix_UB_32      0.0764709000
_diffrn_orient_matrix_UB_33      0.0450716000
_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  0.1001
_diffrn_reflns_av_unetI/netI     0.0840
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            55023
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.600
_diffrn_reflns_theta_max         66.600
_diffrn_reflns_theta_min         2.454
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.337
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76743
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.456
_exptl_crystal_description       block
_exptl_crystal_F_000             1858
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_refine_diff_density_max         2.883
_refine_diff_density_min         -0.965
_refine_diff_density_rms         0.217
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.344
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1200
_refine_ls_number_reflns         14739
_refine_ls_number_restraints     1068
_refine_ls_restrained_S_all      1.314
_refine_ls_R_factor_all          0.1802
_refine_ls_R_factor_gt           0.1352
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3446
_refine_ls_wR_factor_ref         0.3816
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8882
_reflns_number_total             14739
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ra04321a2.cif
_cod_data_source_block           Ni5
_cod_database_code               7245420
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_usercomment     'C H N F Ni Br'
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Restrained distances
 C60-C65 = C64-C63 = C62-C61
 1.39 with sigma of 0.01
 C66-C71 = C67-C68 = C70-C69
 1.39 with sigma of 0.01
2. Uiso/Uaniso restraints and constraints
C57 \\sim C51 \\sim C56 \\sim C58 \\sim C55 \\sim C52 \\sim C53 \\sim C54 \\sim
C99 \\sim C109 \\sim C103 \\sim C93 \\sim C98 \\sim C102 \\sim C111 \\sim C110:
within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
F9 \\sim C01W \\sim C020 \\sim C87 \\sim C91 \\sim C92 \\sim C89 \\sim C90
\\sim C105 \\sim C104 \\sim C81 \\sim C82 \\sim C86 \\sim C80 \\sim C95 \\sim
C106 \\sim C107 \\sim C108 \\sim F5 \\sim C94 \\sim C97 \\sim F10 \\sim C96
\\sim C83 \\sim C84 \\sim C85 \\sim F6 \\sim C88 \\sim C100 \\sim C101: within
1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
F8 \\sim C62 \\sim C63 \\sim C60 \\sim C69 \\sim C65 \\sim C67 \\sim F7 \\sim
C64 \\sim C70 \\sim C68 \\sim C66 \\sim C71 \\sim C59 \\sim C61: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
Uanis(C57) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C58)
\\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C53) \\sim Ueq,
Uanis(C54) \\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C109) \\sim Ueq, Uanis(C103)
\\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C98) \\sim Ueq, Uanis(C102) \\sim Ueq,
Uanis(C111) \\sim Ueq, Uanis(C110) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F9) \\sim Ueq, Uanis(C01W) \\sim Ueq, Uanis(C020) \\sim Ueq, Uanis(C87)
\\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C89) \\sim Ueq,
Uanis(C90) \\sim Ueq, Uanis(C105) \\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C94)
\\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C96) \\sim Ueq, Uanis(C81) \\sim Ueq,
Uanis(C82) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C85)
\\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C95) \\sim Ueq,
Uanis(C106) \\sim Ueq, Uanis(C107) \\sim Ueq, Uanis(C108) \\sim Ueq, Uanis(F5)
\\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(C88) \\sim Ueq,
Uanis(C100) \\sim Ueq, Uanis(C101) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F8) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C60)
\\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C67) \\sim Ueq,
Uanis(F7) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C68)
\\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C61) \\sim Ueq,
Uanis(C59) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Sof(C99)=Sof(C109)=Sof(C103)=Sof(C93)=Sof(C98)=Sof(C102)=Sof(C111)=Sof(C110)=
 1-FVAR(1)
 Sof(C57)=Sof(C51)=Sof(C56)=Sof(C58)=Sof(C55)=Sof(C52)=Sof(C53)=Sof(C54)=FVAR(1)
 Sof(C81)=Sof(C82)=Sof(C83)=Sof(C84)=Sof(C85)=Sof(F6)=Sof(C86)=Sof(C80)=
 Sof(C95)=Sof(C100)=Sof(C106)=Sof(C101)=Sof(C107)=Sof(C108)=Sof(F5)=1-FVAR(2)
 Sof(F9)=Sof(C01W)=Sof(C020)=Sof(C87)=Sof(C91)=Sof(C92)=Sof(C88)=Sof(C89)=
 Sof(C90)=Sof(C105)=Sof(C104)=Sof(C94)=Sof(C97)=Sof(F10)=Sof(C96)=FVAR(2)
;
_shelx_res_checksum              67791
_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 1.752
_oxdiff_exptl_absorpt_empirical_full_min 0.655