Exploring the o-aryl halogen effects of α-diimine Pd(ii) catalysts on ethylene (co)polymerization
Wang, Yan; Dai, Shengyu; Catalysis Science & Technology 15 (2025) 2822–2828; doi:10.1039/D5CY00187K

data_1574072
_publ_section_title
;
 Exploring the o-aryl halogen effects of \a-diimine Pd(ii) catalysts on
 ethylene (co)polymerization
;
_journal_issue                   9
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              2822
_journal_page_last               2828
_journal_paper_doi               10.1039/D5CY00187K
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C44.229 H41 Cl1.771 F2 N2 Pd'
_chemical_formula_sum            'C44.22 H41 Cl1.78 F2 N2 Pd'
_chemical_formula_weight         807.93
_chemical_name_systematic        WY
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-11-22
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-12-02 deposited with the CCDC.	2025-03-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.0240(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.5561(3)
_cell_length_b                   9.39102(13)
_cell_length_c                   19.5924(3)
_cell_measurement_reflns_used    11126
_cell_measurement_temperature    296.18(10)
_cell_measurement_theta_max      77.7820
_cell_measurement_theta_min      4.2430
_cell_volume                     3812.06(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      296.18(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.951
_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    -22.00  24.00   0.50    0.05    --  -49.49  19.00  90.00   92
  2  \w    -20.00  19.00   0.50    0.05    --  -49.49  19.00  60.00   78
  3  \w    -15.00  24.00   0.50    0.05    --  -49.49  19.00  30.00   78
  4  \w    -19.00  15.00   0.50    0.05    --  -49.49  19.00   0.00   68
  5  \w    -22.00  23.00   0.50    0.05    --  -49.49  19.00-180.00   90
  6  \w    -62.00 -37.00   0.50    0.05    -- -104.50  57.00 -90.00   50
  7  \w    -62.00 -37.00   0.50    0.05    -- -104.50  57.00 -60.00   50
  8  \w   -112.00 -53.00   0.50    0.05    --  -49.49 158.00-127.00  118
  9  \w    -73.00 -48.00   0.50    0.05    -- -104.50 119.00  78.00   50
 10  \w    -62.00 -37.00   0.50    0.05    -- -104.50  57.00  90.00   50
 11  \w   -149.00-124.00   0.50    0.05    -- -104.50-119.00  -6.00   50
 12  \w    -86.00 -61.00   0.50    0.05    --  -49.49-158.00-160.00   50
 13  \w   -174.00-100.00   0.50    0.05    -- -104.50 -19.00-180.00  148
 14  \w     35.00  74.00   0.50    0.05    --  106.94 -77.00 150.00   78
 15  \w     41.00  69.00   0.50    0.05    --  106.94 -57.00 150.00   56
 16  \w     41.00  67.00   0.50    0.05    --  106.94 -57.00 120.00   52
 17  \w     37.00  69.00   0.50    0.05    --  106.94 -57.00   0.00   64
 18  \w     37.00  81.00   0.50    0.05    --  106.94 -99.00 -60.00   88
 19  \w     51.00  76.00   0.50    0.05    --   49.49-158.00-160.00   50
 20  \w     36.00 134.00   0.50    0.05    --  106.94-158.00-160.00  196
 21  \w     53.00 104.00   0.50    0.05    --  106.94 -99.00-150.00  102
 22  \w     76.00 109.00   0.50    0.05    --  106.94-119.00  -6.00   66
 23  \w     44.00 111.00   0.50    0.05    --  106.94-125.00  60.00  134
 24  \w    102.00 127.00   0.50    0.05    --  106.94  19.00   0.00   50
 25  \w    133.00 178.00   0.50    0.05    --  106.94  19.00   0.00   90
 26  \w     96.00 137.00   0.50    0.05    --  106.94 119.00  78.00   82
 27  \w     62.00 121.00   0.50    0.05    --   49.49 158.00-127.00  118
;
_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      0.0427684000
_diffrn_orient_matrix_UB_12      -0.1320429000
_diffrn_orient_matrix_UB_13      0.0245143000
_diffrn_orient_matrix_UB_21      -0.0526869000
_diffrn_orient_matrix_UB_22      -0.0950520000
_diffrn_orient_matrix_UB_23      -0.0476666000
_diffrn_orient_matrix_UB_31      0.0304153000
_diffrn_orient_matrix_UB_32      0.0210003000
_diffrn_orient_matrix_UB_33      -0.0617990000
_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  0.0399
_diffrn_reflns_av_unetI/netI     0.0294
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            13933
_diffrn_reflns_point_group_measured_fraction_full 0.688
_diffrn_reflns_point_group_measured_fraction_max 0.646
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.505
_diffrn_reflns_theta_min         4.268
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.420
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.02493
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.408
_exptl_crystal_description       block
_exptl_crystal_F_000             1658
_exptl_crystal_preparation       'low TEMperature'
_exptl_crystal_recrystallization_method 'low temperature'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.346
_refine_diff_density_min         -1.295
_refine_diff_density_rms         0.127
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.16(3)
_refine_ls_extinction_coef       0.00028(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.107
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     395
_refine_ls_number_reflns         5242
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.107
_refine_ls_R_factor_all          0.0758
_refine_ls_R_factor_gt           0.0734
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1693P)^2^+9.4040P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2296
_refine_ls_wR_factor_ref         0.2330
_reflns_Friedel_coverage         0.359
_reflns_Friedel_fraction_full    0.379
_reflns_Friedel_fraction_max     0.341
_reflns_number_gt                4886
_reflns_number_total             5242
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00187k2.cif
_cod_data_source_block           w2_auto
_cod_depositor_comments          'Adding full bibliography for 1574072.cif.'
_cod_database_code               1574072
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C N H Cl Pd F'
_shelx_estimated_absorpt_t_max   0.613
_shelx_estimated_absorpt_t_min   0.562
_olex2_refinement_description
;
1. Shared sites
{C3, Cl2}
2. Uiso/Uaniso restraints and constraints
Uanis(C3) = Uanis(Cl2)
3. Others
 Sof(Cl2)=1-FVAR(1)
 Sof(C3)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C5(H5), C9(H9)
4.b Aromatic/amide H refined with riding coordinates:
 C30(H30), C56(H56), C35(H35), C21(H21), C58(H58), C38(H38), C60(H60),
 C42(H42), C29(H29), C20(H20), C25(H25), C37(H37), C43(H43), C63(H63), C53(H53),
  C28(H28), C15(H15), C26(H26), C7(H7), C32(H32), C62(H62), C39(H39), C23(H23),
 C34(H34)
4.c Fitted hexagon refined as free rotating group:
 C30(C56,C35,C12,C21,C58), C16(C38,C60,C42,C29,C20), C25(C37,C43,C63,C53,C8),
 C28(C17,C15,C6,C4,C19), C24(C14,C33,C26,C18,C7), C11(C32,C62,C39,C23,C34)
4.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C27(H27A,H27B,H27C), C36(H36A,H36B,H36C), C40(H40A,H40B,
 H40C), C3(H3A,H3B,H3C)
;
_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 17.039
_oxdiff_exptl_absorpt_empirical_full_min 0.540