Sterically Controlled Self-Assembly of a Robust Multinuclear Palladium Catalyst for Ethylene Polymerization.
Liu, Qian; Jordan, Richard F.; Journal of the American Chemical Society 141 (2019) 6827–6831; doi:10.1021/jacs.9b02465

data_4128121
_publ_section_title
;
 Sterically Controlled Self-Assembly of a Robust Multinuclear Palladium
 Catalyst for Ethylene Polymerization.
;
_journal_issue                   17
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6827
_journal_page_last               6831
_journal_paper_doi               10.1021/jacs.9b02465
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety
'C148 H188 Cl2 Li6 N4 O40 P4 Pd4 S8, 6(C2 H2 Cl4)'
_chemical_formula_sum            'C160 H200 Cl26 Li6 N4 O40 P4 Pd4 S8'
_chemical_formula_weight         4588.53
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_symmetry_space_group_name_Hall  'P 2 2ab'
_symmetry_space_group_name_H-M   'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-04-19
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   23.055(3)
_cell_length_b                   23.056(2)
_cell_length_c                   23.990(3)
_cell_measurement_reflns_used    9626
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      22.03
_cell_measurement_theta_min      2.45
_cell_volume                     12752(3)
_computing_cell_refinement       'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_computing_data_collection       'APEX3 v.2015.9-0 (Bruker AXS Inc., 2015)'
_computing_data_reduction        'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_computing_molecular_graphics
;
OLEX2: a complete structure solution, refinement and analysis program 
Dolomanov et al., 2009

Mercury: visualization and analysis of crystal structures
Macrae, et al., 2006

O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann.
J. Appl. Cryst. (2009). 42, 339-341;

C. F. Macrae, P. R. Edgington, P. McCabe, E. Pidcock, G. P. Shields, R. Taylor,
M. Towler and J. van de Streek, J. Appl. Cryst. (2006). 39, 453-457.
;
_computing_publication_material
;
 APEX3 v.2015.5-2 (Bruker AXS Inc., 2015)
 OLEX2 (Dolomanov et al., 2009)
;
_computing_structure_refinement  'XL-2014/7 (Sheldrick, 2015b)'
_computing_structure_solution    'XT 2014/5 (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.4167
_diffrn_measured_fraction_theta_full 0.950
_diffrn_measured_fraction_theta_max 0.950
_diffrn_measurement_device_type  'Bruker D8 Venture PHOTON 100 CMOS'
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_monochromator  mirrors
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0565
_diffrn_reflns_av_unetI/netI     0.0565
_diffrn_reflns_Laue_measured_fraction_full 0.950
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            164653
_diffrn_reflns_point_group_measured_fraction_full 0.921
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        25.080
_diffrn_reflns_theta_max         25.080
_diffrn_reflns_theta_min         2.108
_diffrn_source                   'INCOATEC ImuS micro-focus source'
_exptl_absorpt_coefficient_mu    0.695
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6429
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0852 before and 0.0606 after correction.
The Ratio of minimum to maximum transmission is 0.8627.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.195
_exptl_crystal_description       block
_exptl_crystal_F_000             4680
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.586
_refine_diff_density_min         -0.433
_refine_diff_density_rms         0.090
_refine_ls_abs_structure_details
;
 Flack x determined using 6552 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.068(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1147
_refine_ls_number_reflns         20879
_refine_ls_number_restraints     183
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0788
_refine_ls_R_factor_gt           0.0563
_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^)+(0.0609P)^2^+37.2394P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1297
_refine_ls_wR_factor_ref         0.1371
_reflns_Friedel_coverage         0.797
_reflns_Friedel_fraction_full    0.888
_reflns_Friedel_fraction_max     0.888
_reflns_number_gt                16842
_reflns_number_total             20879
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b02465_si_002.cif
_cod_data_source_block           ortho_p2122_sq
_cod_original_cell_volume        12752(2)
_cod_database_code               4128121
_shelx_estimated_absorpt_t_max   0.921
_shelx_estimated_absorpt_t_min   0.868
_olex2_refinement_description
;
1. 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
2. Restrained distances
 C52-C51
 1.55 with sigma of 0.01
 C51-C50
 1.46 with sigma of 0.01
 Cl9-C78 \\sim Cl8-C78 \\sim Cl7-C77 \\sim Cl6-C77 \\sim Cl4-C76 \\sim Cl5-C76
\\sim Cl3-C75 \\sim Cl2-C75
 \\sim Cl13-C80 \\sim Cl12-C80 \\sim Cl11-C79 \\sim Cl10-C79
 with sigma of 0.02
 C80-C79 \\sim C78-C77 \\sim C76-C75
 with sigma of 0.02
 C8-C7 \\sim C49-C44
 with sigma of 0.02
 C9-C8 \\sim C50-C49
 with sigma of 0.02
 C9-C10 \\sim C51-C50
 with sigma of 0.02
 C11-C10 \\sim C52-C51
 with sigma of 0.02
 C7-C12 \\sim C45-C44
 with sigma of 0.02
 C13-C12 \\sim C46-C45
 with sigma of 0.02
 C14-C13 \\sim C47-C46
 with sigma of 0.02
 C15-C14 \\sim C48-C47
 with sigma of 0.02
 C51A-C50 \\sim C51-C50
 with sigma of 0.005
 C52-C51 \\sim C52A-C51A
 with sigma of 0.005
3. Rigid body (RIGU) restrains
 Cl10, Cl11, Cl12, Cl13, C79, C80
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C53, C54, C55, C56, C57, C58
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C44, C45, C46, C47, C48, C49, C50, C51, C52
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: H50A(0.5) H50B(0.5) H50C(0.5) H50D(0.5) C51(0.6) H51A(0.6)
 H51B(0.6) C52(0.6) H52A(0.6) H52B(0.6) H52C(0.6) C51A(0.4) H51C(0.4) H51D(0.4)
 C52A(0.4) H52D(0.4) H52E(0.4) H52F(0.4)
 Fixed Uiso: C51(0.128)
5.a Ternary CH refined with riding coordinates:
 C7(H7), C44(H44), C77(H77), C78(H78), C75(H75), C76(H76), C79(H79), C80(H80)
5.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C12(H12A,H12B), C13(H13A,H13B),
 C14(H14A,H14B), C45(H45A,H45B), C46(H46A,H46B), C47(H47A,H47B), C49(H49A,H49B),
  C50(H50A,H50B), C50(H50C,H50D), C51(H51A,H51B), C51A(H51C,H51D)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C17(H17), C18(H18), C19(H19), C20(H20),
 C21(H21), C24(H24), C27(H27), C32(H32), C35(H35), C39(H39), C40(H40), C42(H42),
  C43(H43), C54(H54), C55(H55), C56(H56), C57(H57), C58(H58), C61(H61),
 C64(H64), C69(H69), C72(H72)
5.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C11(H11A,H11B,H11C), C15(H15A,H15B,H15C), C28(H28A,H28B,
 H28C), C29(H29A,H29B,H29C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,
 H38B,H38C), C48(H48A,H48B,H48C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C),
 C73(H73A,H73B,H73C), C74(H74A,H74B,H74C), C52(H52A,H52B,H52C), C52A(H52D,H52E,
 H52F)
;
_shelx_res_checksum              11474
_shelx_hkl_checksum              17329
_shelx_fab_checksum              71719
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'