Fast and Regioselective Polymerization of para-Alkoxystyrene by Palladium Catalysts for Precision Production of High-Molecular-Weight Polystyrene Derivatives
Liao, Guangfu; Xiao, Zefan; Chen, Xiaolin; Du, Cheng; Zhong, Liu; Cheung, Chi Shing; Gao, Haiyang; Macromolecules  (2019) –; doi:10.1021/acs.macromol.9b02274

data_1556733
_publ_section_title
;
 Fast and Regioselective Polymerization of para-Alkoxystyrene by Palladium
 Catalysts for Precision Production of High-Molecular-Weight Polystyrene
 Derivatives
;
_journal_name_full               Macromolecules
_journal_paper_doi               10.1021/acs.macromol.9b02274
_journal_year                    2019
_chemical_formula_moiety         'C50 H55.41 N2 O Pd, C32 H12 B F24'
_chemical_formula_sum            'C82 H69 B F24 N2 O Pd'
_chemical_formula_weight         1671.60
_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
_audit_creation_date             2019-01-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.602(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.8991(11)
_cell_length_b                   17.9848(10)
_cell_length_c                   24.2721(17)
_cell_measurement_reflns_used    5704
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      23.6640
_cell_measurement_theta_min      3.7790
_cell_volume                     7725.6(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2913
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.823
_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     34.00  99.00   1.00   20.00    --   13.26-178.00   0.00   65
  2  \w    -59.00  36.00   1.00   20.00    --   13.26 -38.00 150.00   95
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0294359000
_diffrn_orient_matrix_UB_12      -0.0134833000
_diffrn_orient_matrix_UB_13      -0.0138272000
_diffrn_orient_matrix_UB_21      -0.0189427000
_diffrn_orient_matrix_UB_22      0.0143438000
_diffrn_orient_matrix_UB_23      -0.0256710000
_diffrn_orient_matrix_UB_31      0.0193997000
_diffrn_orient_matrix_UB_32      0.0341738000
_diffrn_orient_matrix_UB_33      0.0051228000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0738
_diffrn_reflns_av_unetI/netI     0.1631
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.823
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            33836
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.823
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.399
_diffrn_reflns_theta_min         3.364
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.345
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69496
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.437
_exptl_crystal_description       block
_exptl_crystal_F_000             3400
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.982
_refine_diff_density_min         -0.910
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1059
_refine_ls_number_reflns         19237
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.2184
_refine_ls_R_factor_gt           0.1050
_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^)+(0.1452P)^2^+1.0856P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2658
_refine_ls_wR_factor_ref         0.3468
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7720
_reflns_number_total             19237
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ma9b02274_si_003.cif
_cod_data_source_block           19011107
_cod_database_code               1556733
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H N Pd B F'
_chemical_oxdiff_usercomment     c0
_shelx_estimated_absorpt_t_max   0.966
_shelx_estimated_absorpt_t_min   0.934
_reflns_odcompleteness_completeness 98.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.04
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Rigid bond restraints
 C022, C02D
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C4, C02M
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1AA, C02T
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1, C2, C3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C02T, C0AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C0AA \\sim C1AA: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C1 \\sim C2 \\sim C3: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02
Uanis(C0AA) \\sim Ueq, Uanis(C1B) \\sim Ueq, Uanis(C2AA) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
Uanis(C0AA) \\sim Ueq, Uanis(C1AA) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of
0.1 and sigma for terminal atoms of 0.2
Uanis(C02T) \\sim Ueq, Uanis(C0AA) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
4. Others
 Sof(F1)=1-FVAR(1)
 Sof(F2)=FVAR(1)
 Sof(F0)=1-FVAR(2)
 Sof(F3)=FVAR(2)
 Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=1-FVAR(3)
 Sof(C1A)=Sof(H1AB)=Sof(H1AC)=Sof(H1AD)=FVAR(3)
 Fixed Sof: Pd01(0.85) H1A(0.85) H1B(0.15) C0AA(0.6) H0AA(0.6) H2AD(0.6)
 H2AE(0.6) H2AF(0.6) H2AA(0.4) H2AB(0.4) H2AC(0.4) Pd1(0.15) C1AA(0.4) H1AA(0.4)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C00U(H00U), C01C(H01C), C7(H7), C1(H1A), C1(H1B), C4(H4),
 C0AA(H0AA), C1AA(H1AA)
5.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
5.c Aromatic/amide H refined with riding coordinates:
 C00C(H00C), C00D(H00D), C00H(H00H), C00J(H00J), C00T(H00T), C00V(H00V),
 C00X(H00X), C00Y(H00Y), C011(H011), C014(H014), C015(H015), C01D(H01D),
 C01E(H01E), C01I(H01I), C01M(H01M), C01O(H01O), C01R(H01R), C01T(H01T),
 C01W(H01W), C01Z(H01Z), C020(H020), C022(H022), C029(H029), C02C(H02C),
 C02D(H02D), C02I(H02I), C02P(H02P), C02U(H02U), C02V(H02V), C02Y(H02Y)
5.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C9(H9A,H9B,H9C), C8(H8A,H8B,H8C),
 C02W(H02A,H02B,H02E), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C2AA(H2AD,H2AE,H2AF),
 C2AA(H2AA,H2AB,H2AC), C033(H03A,H03B,H03C), C1B(H1BA,H1BB,H1BC)
;
_shelx_res_checksum              12891
_shelx_hkl_checksum              5553
_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 1.264
_oxdiff_exptl_absorpt_empirical_full_min 0.650