Ligand-Unsymmetrical Phenoxyiminato Dinickel Catalyst for High Molecular Weight Long-Chain Branched Polyethylenes
Shu, Dongxu; Mouat, Aidan R.; Stephenson, Casey J.; Invergo, Anna M.; Delferro, Massimiliano; Marks, Tobin J.; ACS Macro Letters 4 (2015) 1297–; doi:10.1021/acsmacrolett.5b00781

data_4516801
_publ_section_title
;
 Ligand-Unsymmetrical Phenoxyiminato Dinickel Catalyst for High Molecular
 Weight Long-Chain Branched Polyethylenes
;
_journal_issue                   11
_journal_name_full               'ACS Macro Letters'
_journal_page_first              1297
_journal_paper_doi               10.1021/acsmacrolett.5b00781
_journal_volume                  4
_journal_year                    2015
_chemical_formula_moiety         'C58 H56 F12 N2 Ni2 O4 P2 S, 1/3(C6 H14)'
_chemical_formula_sum            'C60 H60.6667 F12 N2 Ni2 O4 P2 S'
_chemical_formula_weight         1312.85
_chemical_name_systematic        FI2-CF3SO2-Ni2
_chemical_properties_physical    air-sensitive
_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_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-03-11
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                93.299(2)
_cell_angle_beta                 100.959(3)
_cell_angle_gamma                99.890(2)
_cell_formula_units_Z            6
_cell_length_a                   14.3837(7)
_cell_length_b                   20.8951(9)
_cell_length_c                   34.7537(16)
_cell_measurement_reflns_used    9719
_cell_measurement_temperature    100
_cell_measurement_theta_max      66.47
_cell_measurement_theta_min      3.19
_cell_volume                     10058.3(8)
_computing_cell_refinement       'SAINT V7.23A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2.1-4 (Bruker, 2007)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      99.99
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.930
_diffrn_measured_fraction_theta_max 0.930
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0449
_diffrn_reflns_av_unetI/netI     0.0582
_diffrn_reflns_Laue_measured_fraction_full 0.930
_diffrn_reflns_Laue_measured_fraction_max 0.930
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            74297
_diffrn_reflns_point_group_measured_fraction_full 0.930
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        66.805
_diffrn_reflns_theta_max         66.805
_diffrn_reflns_theta_min         2.412
_diffrn_source                   microsource
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.101
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.6155
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0730 before and 0.0504 after correction.
The Ratio of minimum to maximum transmission is 0.8176.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.300
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             4058
_exptl_crystal_recrystallization_method
;
X-ray quality crystals were difficult to obtain. 
Severe twinning and polycry
;
_exptl_crystal_size_max          0.235
_exptl_crystal_size_mid          0.149
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.823
_refine_diff_density_min         -1.263
_refine_diff_density_rms         0.115
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.337
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2146
_refine_ls_number_reflns         33217
_refine_ls_number_restraints     2192
_refine_ls_restrained_S_all      1.399
_refine_ls_R_factor_all          0.1336
_refine_ls_R_factor_gt           0.1077
_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          0.3238
_refine_ls_wR_factor_ref         0.3486
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23107
_reflns_number_total             33217
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            mz5b00781_si_003.cif
_cod_data_source_block           150219_dxs_ni2_0m
_cod_depositor_comments
;

2020-06-09
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C180 H181 F36 N6 Ni6 O12 P6 S3'
_cod_original_formula_weight         3938.56
_cod_original_formula_moiety
'2(C58 H56 F12 N2 Ni2 O4 P2 S), C58 H55 F12 N2 Ni2 O4 P2 S, C6 H14'
_cod_original_formula_units_Z            2
_cod_database_code               4516801
_shelx_estimated_absorpt_t_max   0.772
_shelx_estimated_absorpt_t_min   0.638
_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
2. Restrained distances
 C8-C11
 1.455 with sigma of 0.02
 Ni1-N1
 1.916 with sigma of 0.02
 Ni1-O1
 1.919 with sigma of 0.02
 Ni1-P1
 2.154 with sigma of 0.02
 Ni1-C51
 1.951 with sigma of 0.02
 Ni2-O2
 1.919 with sigma of 0.02
 Ni2-C52
 1.951 with sigma of 0.02
 Ni2-N2
 1.952 with sigma of 0.02
 Ni2-N2
 1.32 with sigma of 0.02
 Ni2-N2
 1.952 with sigma of 0.02
 C1AA-C34
 1.32 with sigma of 0.02
 C25-C22
 1.554 with sigma of 0.02
 Ni2-P2
 2.146 with sigma of 0.02
 C32-C28
 1.641 with sigma of 0.02
 F7A-C32A = F8A-C32A = F9A-C32A
 1.32 with sigma of 0.02
 F12A-C33A = F10A-C33A = F11A-C33A
 1.32 with sigma of 0.02
 F1A-C24A = F3A-C24A = F2A-C24A
 1.32 with sigma of 0.02
 F6A-C25A = F5A-C25A = F4A-C25A
 1.32 with sigma of 0.02
 F10-C33 = F12-C33 = F11-C33
 1.32 with sigma of 0.02
 F8-C32 = F9-C32 = F7-C32
 1.32 with sigma of 0.02
 F3-C24 = F2-C24 = F1-C24
 1.32 with sigma of 0.02
 F4-C25 = F5-C25 = F6-C25
 1.32 with sigma of 0.02
 F4B-C25B = F6B-C25B = F5B-C25B
 1.32 with sigma of 0.02
 F2B-C24B = F1B-C24B = F3B-C24B
 1.32 with sigma of 0.02
 F11B-C33B = F10B-C33B = F12B-C33B
 1.32 with sigma of 0.02
 F9B-C32B = F7B-C32B = F8B-C32B
 1.32 with sigma of 0.02
 C41-C42 \\sim C41-C46 \\sim C45-C46 \\sim C44-C45 \\sim C44-C43 \\sim C42-C43
 with sigma of 0.02
 C39-C40 \\sim C38-C39 \\sim C38-C37 \\sim C37-C36 \\sim C36-C35 \\sim C40-C35
 with sigma of 0.02
 P1-C58 \\sim P1-C56 \\sim P1-C57
 with sigma of 0.02
 C21-C22 \\sim C21-C20 \\sim C20-C19 \\sim C18-C19 \\sim C18-C23 \\sim C23-C22
 with sigma of 0.02
 C30-C29 \\sim C29-C28 \\sim C28-C27 \\sim C26-C27 \\sim C31-C26 \\sim C31-C30
 with sigma of 0.02
 F11-C33 \\sim F10-C33 \\sim F12-C33
 with sigma of 0.02
 F9-C32 \\sim F7-C32 \\sim F8-C32
 with sigma of 0.02
 F5-C25 \\sim F4-C25 \\sim F6-C25
 with sigma of 0.02
 F3-C24 \\sim F2-C24 \\sim F1-C24
 with sigma of 0.02
 P2-C55 \\sim P2-C53 \\sim P2-C54
 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.02
5.a Secondary CH2 refined with riding coordinates:
 C2D(H2DA,H2DB), C3D(H3DA,H3DB), C4D(H4DA,H4DB), C5D(H5DA,H5DB)
5.b Me refined with riding coordinates:
 C48A(H48A,H48B,H48C), C49A(H49A,H49B,H49C), C50A(H50A,H50B,H50C), C51A(H51A,
 H51B,H51C), C52A(H52A,H52B,H52C), C53A(H53A,H53B,H53C), C54A(H54A,H54B,H54C),
 C55A(H55A,H55B,H55C), C56A(H56A,H56B,H56C), C57A(H57A,H57B,H57C), C58A(H58A,
 H58B,H58C), C48(H48G,H48H,H48I), C49(H49G,H49H,H49I), C50(H50G,H50H,H50I),
 C51(H51G,H51H,H51I), C52(H52G,H52H,H52I), C53(H53G,H53H,H53I), C54(H54G,H54H,
 H54I), C55(H55G,H55H,H55I), C56(H56G,H56H,H56I), C57(H57G,H57H,H57I), C58(H58G,
 H58H,H58I), C48B(H48D,H48E,H48F), C49B(H49D,H49E,H49F), C50B(H50D,H50E,H50F),
 C51B(H51D,H51E,H51F), C52B(H52D,H52E,H52F), C53B(H53D,H53E,H53F), C54B(H54D,
 H54E,H54F), C55B(H55D,H55E,H55F), C56B(H56D,H56E,H56F), C57B(H57D,H57E,H57F),
 C58B(H58D,H58E,H58F), C1D(H1DA,H1DB,H1DC), C6D(H6DA,H6DB,H6DC)
5.c Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C4A(H4A), C9A(H9A), C10A(H10A), C11A(H11A), C16A(H16A), C15A(H15A),
 C14A(H14A), C23A(H23A), C21A(H21A), C19A(H19A), C27A(H27A), C29A(H29A),
 C31A(H31A), C34A(H34A), C36A(H36A), C37A(H37A), C38A(H38A), C39A(H39A),
 C42A(H42A), C43A(H43A), C45A(H45A), C46A(H46A), C2AA(H2AA), C3AA(H3AA),
 C6AA(H6AA), C7AA(H7AA), C11(H11), C14(H14), C16(H16), C0AA(H0AA), C21(H21),
 C19(H19), C23(H23), C31(H31), C29(H29), C27(H27), C39(H39), C38(H38), C37(H37),
  C36(H36), C42(H42), C46(H46), C45(H45), C43(H43), C3B(H3B), C4B(H4B),
 C9B(H9B), C10B(H10B), C11B(H11B), C14B(H14B), C15B(H15B), C16B(H16B),
 C19B(H19B), C21B(H21B), C23B(H23B), C27B(H27B), C29B(H29B), C31B(H31B),
 C34B(H34B), C36B(H36B), C37B(H37B), C38B(H38B), C39B(H39B), C42B(H42B),
 C43B(H43B), C45B(H45B), C46B(H46B)
5.d Fitted hexagon refined as free rotating group:
 C16A(C15A,C14A,C13A,C12A,C17A), C18A(C23A,C22A,C21A,C20A,C19A), C7(C4AA,C5,
 C6AA,C7AA,C8), C14(C13,C12,C17,C16,C0AA), C22(C21,C20,C19,C18,C23), C26(C31,
 C30,C29,C28,C27), C35(C40,C39,C38,C37,C36), C42(C41,C46,C45,C44,C43)
;
_shelx_res_checksum              8818
_shelx_hkl_checksum              32859
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_completion    2015-02-20
_olex2_date_sample_data_collection 2015-02-19
_olex2_date_sample_submission    2015-02-19
_olex2_exptl_crystal_mounting_method
'The crystal was mounted under air-free conditions in Paratone-N.'
_olex2_submission_original_sample_id DXS_Ni2
_olex2_submission_special_instructions 'No special instructions were received'