Controlling polar monomer incorporation ratio via steric attenuation: Pd-catalyzed synthesis of polar hyperbranched polyethylenes
Zhang, Hongli; Dai, Shengyu; New Journal of Chemistry 49 (2025) 18430–18435; doi:10.1039/D5NJ03147H

data_7064023
_publ_section_title
;
 Controlling polar monomer incorporation ratio via steric attenuation:
 Pd-catalyzed synthesis of polar hyperbranched polyethylenes
;
_journal_issue                   42
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              18430
_journal_page_last               18435
_journal_paper_doi               10.1039/D5NJ03147H
_journal_volume                  49
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C23 H29 Cl N2 Pd'
_chemical_formula_sum            'C23 H29 Cl N2 Pd'
_chemical_formula_weight         475.33
_chemical_name_systematic        zhL
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-09-16
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-09-17 deposited with the CCDC.	2025-09-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.2485(3)
_cell_length_b                   13.0365(2)
_cell_length_c                   8.37460(10)
_cell_measurement_reflns_used    6829
_cell_measurement_temperature    295.63(10)
_cell_measurement_theta_max      77.2430
_cell_measurement_theta_min      4.0130
_cell_volume                     2210.64(5)
_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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      295.63(10)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.954
_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   -173.00 -86.00   0.50    0.12    -- -104.50-102.00 -62.00  174
  2  \w    -62.00 -37.00   0.50    0.12    -- -104.50  57.00-150.00   50
  3  \w    -61.00 -36.00   0.50    0.12    -- -104.50  57.00   0.00   50
  4  \w    -88.00 -38.00   0.50    0.12    -- -104.50  99.00 138.00  100
  5  \w    -34.00  20.00   0.50    0.05    --  -49.62  34.00 -61.00  108
  6  \w     63.00  88.00   0.50    0.12    --  106.94 -99.00  31.00   50
  7  \w     43.00 106.00   0.50    0.12    --  106.94 -77.00 -60.00  126
  8  \w     37.00  62.00   0.50    0.12    --  106.94 -57.00-150.00   50
  9  \w    -21.00  30.00   0.50    0.05    --   49.62 -19.00   0.00  102
 10  \w    -20.00  30.00   0.50    0.05    --   49.62 -19.00  90.00  100
 11  \w     35.00  60.00   0.50    0.12    --  106.94 -57.00 150.00   50
 12  \w    111.00 167.00   0.50    0.12    --  106.94  34.00 -61.00  112
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0331
_diffrn_reflns_av_unetI/netI     0.0359
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -4
_diffrn_reflns_number            8345
_diffrn_reflns_point_group_measured_fraction_full 0.917
_diffrn_reflns_point_group_measured_fraction_max 0.854
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.861
_diffrn_reflns_theta_min         4.033
_exptl_absorpt_coefficient_mu    7.938
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50356
_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    1.428
_exptl_crystal_description       block
_exptl_crystal_F_000             976
_exptl_crystal_preparation       'low temperature'
_exptl_crystal_recrystallization_method 'low temperature'
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.961
_refine_diff_density_min         -0.691
_refine_diff_density_rms         0.090
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.367(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.137
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     265
_refine_ls_number_reflns         4036
_refine_ls_number_restraints     122
_refine_ls_restrained_S_all      1.130
_refine_ls_R_factor_all          0.0396
_refine_ls_R_factor_gt           0.0377
_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^)+(0.0521P)^2^+2.0583P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1035
_refine_ls_wR_factor_ref         0.1058
_reflns_Friedel_coverage         0.572
_reflns_Friedel_fraction_full    0.808
_reflns_Friedel_fraction_max     0.722
_reflns_number_gt                3868
_reflns_number_total             4036
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj03147h2.cif
_cod_data_source_block           d1_auto
_cod_depositor_comments          'Adding full bibliography for 7064023.cif.'
_cod_database_code               7064023
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.504
_shelx_estimated_absorpt_t_min   0.475
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.633(18)
 0.367(18)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 Pd1-C1 \\sim Pd1-C1A
 with sigma of 0.01
 Pd1-Cl1 \\sim Pd1-Cl1A
 with sigma of 0.01
 Cl1-C1 \\sim Cl1A-C1A
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Pd1 \\sim Cl1 \\sim C1 \\sim Cl1A \\sim C1A: within 3A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 3A
C4 \\sim C6 \\sim C5 \\sim C7 \\sim C5A \\sim C7A: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
Uanis(C1) \\sim Ueq, Uanis(C1A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5. Same fragment restrains
{C4, C6, C5A, C7A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C4, C6, C5, C7}
6. Others
 Sof(Cl1A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=1-FVAR(1)
 Sof(Cl1)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=FVAR(1)
 Sof(H4BC)=Sof(H4BD)=Sof(H6BC)=Sof(H6BD)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C7A)=
 Sof(H7AA)=Sof(H7AB)=1-FVAR(2)
 Sof(H4AA)=Sof(H4AB)=Sof(H6AA)=Sof(H6AB)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C7)=
 Sof(H7A)=Sof(H7B)=FVAR(2)
7.a Secondary CH2 refined with riding coordinates:
 C4(H4AA,H4AB), C4(H4BC,H4BD), C6(H6AA,H6AB), C6(H6BC,H6BD), C5(H5A,H5B),
 C7(H7A,H7B), C5A(H5AA,H5AB), C7A(H7AA,H7AB)
7.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C11(H11), C10(H10), C20(H20), C21(H21), C22(H22)
7.c Fitted hexagon refined as free rotating group:
 C13(C12,C11,C10,C9,C8), C16(C17,C20,C21,C22,C18)
7.d Idealised Me refined as rotating group:
 C00K(H00A,H00B,H00C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C19(H19A,H19B,
 H19C), C1(H1A,H1B,H1C), C1A(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              1135
_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
;