Bis-cycloheptyl-fused bis(imino)pyridine-cobalt catalysts for PE wax formation: positive effects of fluoride substitution on catalytic performance and thermal stability.
Zhang, Qiuyue; Wu, Ningning; Xiang, Junfeng; Solan, Gregory A.; Suo, Hongyi; Ma, Yanping; Liang, Tongling; Sun, Wen-Hua; Dalton transactions (Cambridge, England : 2003) 49 (2020) 9425–9437; doi:10.1039/d0dt01876g

data_7704715
_publ_section_title
;
 Bis-cycloheptyl-fused bis(imino)pyridine-cobalt catalysts for PE wax
 formation: positive effects of fluoride substitution on catalytic
 performance and thermal stability.
;
_journal_issue                   27
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9425
_journal_page_last               9437
_journal_paper_doi               10.1039/d0dt01876g
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety         '2(C79 H57 Cl4 Co F8 N3)'
_chemical_formula_sum            'C158 H114 Cl8 Co2 F16 N6'
_chemical_formula_weight         2802.01
_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
_atom_sites_solution_primary     iterative
_audit_creation_date             2020-01-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-04-21 deposited with the CCDC.	2020-06-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.8590(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.65280(10)
_cell_length_b                   25.4947(2)
_cell_length_c                   35.8638(2)
_cell_measurement_reflns_used    41190
_cell_measurement_temperature    169.99(10)
_cell_measurement_theta_max      75.2960
_cell_measurement_theta_min      2.6700
_cell_volume                     15083.26(17)
_computing_cell_refinement       'CrysAlisPro 1.171.40.14e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.14e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.14e (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)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      169.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.960
_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    -40.00 -15.00   0.50    1.42    --  -47.20  27.00 -65.00   50
  2  \w    -92.00 -67.00   0.50    5.70    --  -99.00  27.00 -65.00   50
  3  \w    -67.00 -42.00   0.50    5.70    --  -99.00 125.00 -30.00   50
  4  \w   -107.00 -82.00   0.50    5.70    --  -99.00 125.00 -30.00   50
  5  \w   -109.00 -27.00   0.50    5.70    --  -99.00  45.00 150.00  164
  6  \w   -105.00 -36.00   0.50    1.42    --  -47.20 -27.00 132.00  138
  7  \w     37.00 113.00   0.50    1.42    --   47.20  27.00 -65.00  152
  8  \w     94.00 169.00   0.50    5.70    --  103.25  27.00 -65.00  150
  9  \w     93.00 169.00   0.50    5.70    --  103.25  30.00   0.00  152
 10  \w     83.00 109.00   0.50    5.70    --  103.25 -94.00 -90.00   52
 11  \w     28.00 116.00   0.50    5.70    --  103.25 -30.00   0.00  176
 12  \w     70.00 103.00   0.50    5.70    --  103.25 -94.00  90.00   66
 13  \w     53.00 114.00   0.50    5.70    --  103.25 -27.00 132.00  122
 14  \w     21.00  94.00   0.50    1.42    --   47.20-125.00   0.00  146
 15  \w     32.00 110.00   0.50    5.70    --  103.25 -45.00 -60.00  156
 16  \w     -7.00  55.00   0.50    1.42    --   47.20 -27.00 132.00  124
 17  \w   -114.00 -88.00   0.50    5.70    --  -99.00 -27.00 132.00   52
 18  \w   -166.00 -88.00   0.50    5.70    --  -99.00 -45.00   0.00  156
;
_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      0.0034902000
_diffrn_orient_matrix_UB_12      -0.0179574000
_diffrn_orient_matrix_UB_13      -0.0407519000
_diffrn_orient_matrix_UB_21      0.0910956000
_diffrn_orient_matrix_UB_22      -0.0119250000
_diffrn_orient_matrix_UB_23      0.0100860000
_diffrn_orient_matrix_UB_31      -0.0204606000
_diffrn_orient_matrix_UB_32      -0.0564353000
_diffrn_orient_matrix_UB_33      0.0108296000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0477
_diffrn_reflns_av_unetI/netI     0.0424
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            108973
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.583
_diffrn_reflns_theta_min         2.487
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.607
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58743
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.14e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.234
_exptl_crystal_description       block
_exptl_crystal_F_000             5752
_exptl_crystal_size_max          0.225
_exptl_crystal_size_mid          0.145
_exptl_crystal_size_min          0.078
_refine_diff_density_max         0.408
_refine_diff_density_min         -0.339
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1748
_refine_ls_number_reflns         30074
_refine_ls_number_restraints     169
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0747
_refine_ls_R_factor_gt           0.0569
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0650P)^2^+13.9753P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1476
_refine_ls_wR_factor_ref         0.1606
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23170
_reflns_number_total             30074
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt01876g2.cif
_cod_data_source_block           Co4
_cod_depositor_comments
'Adding full bibliography for 7704715--7704718.cif.'
_cod_original_cell_volume        15083.25(17)
_cod_database_code               7704715
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_usercomment     'C H F N  Cl'
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
2. Restrained distances
 C055-C82 = C82-C83 = C83-C84 = C055-C053 = C053-C85 = C85-C84 = C9-C0AA = C10-
 C9 = C11-C10 = C1AA-C0AA = C1AA-C12 = C11-C12
 1.54 with sigma of 0.01
3. Rigid bond restraints
 C77, C78
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C9 \\sim C12 \\sim C10 \\sim C11 \\sim C1AA \\sim C0AA: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04
C85 \\sim C82 \\sim C053 \\sim C055 \\sim C84 \\sim C83: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04
Uanis(C9) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C0AA) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C85) \\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C053) \\sim Ueq, Uanis(C055)
\\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C83) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
5. Others
 Sof(H85C)=Sof(H85D)=Sof(H82C)=Sof(H82D)=Sof(H9BC)=Sof(H9BD)=Sof(H12C)=
 Sof(H12D)=Sof(C1AA)=Sof(H1AA)=Sof(H1AB)=Sof(C0AA)=Sof(H0AA)=Sof(H0AB)=Sof(C84)=
 Sof(H84A)=Sof(H84B)=Sof(C83)=Sof(H83A)=Sof(H83B)=1-FVAR(1)
 Sof(H85A)=Sof(H85B)=Sof(H82A)=Sof(H82B)=Sof(H9AA)=Sof(H9AB)=Sof(H12A)=
 Sof(H12B)=Sof(C053)=Sof(H05A)=Sof(H05B)=Sof(C055)=Sof(H05C)=Sof(H05D)=Sof(C10)=
 Sof(H10A)=Sof(H10B)=Sof(C11)=Sof(H11A)=Sof(H11B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C114(H114), C36(H36), C101(H101), C54(H54), C23(H23), C146(H146), C133(H133),
 C67(H67)
6.b Secondary CH2 refined with riding coordinates:
 C92(H92A,H92B), C5(H5A,H5B), C91(H91A,H91B), C89(H89A,H89B), C2(H2A,H2B),
 C90(H90A,H90B), C3(H3A,H3B), C4(H4A,H4B), C85(H85A,H85B), C85(H85C,H85D),
 C82(H82A,H82B), C82(H82C,H82D), C9(H9BC,H9BD), C9(H9AA,H9AB), C12(H12A,H12B),
 C12(H12C,H12D), C053(H05A,H05B), C055(H05C,H05D), C10(H10A,H10B), C11(H11A,
 H11B), C1AA(H1AA,H1AB), C0AA(H0AA,H0AB), C84(H84A,H84B), C83(H83A,H83B)
6.c Aromatic/amide H refined with riding coordinates:
 C99(H99), C42(H42), C21(H21), C97(H97), C107(H107), C19(H19), C87(H87),
 C41(H41), C38(H38), C52(H52), C116(H116), C48(H48), C50(H50), C113(H113),
 C120(H120), C103(H103), C106(H106), C129(H129), C131(H131), C117(H117),
 C39(H39), C152(H152), C7(H7), C104(H104), C62(H62), C44(H44), C29(H29),
 C119(H119), C112(H112), C139(H139), C151(H151), C47(H47), C109(H109), C25(H25),
  C79(H79), C138(H138), C126(H126), C135(H135), C136(H136), C32(H32), C31(H31),
 C66(H66), C78(H78), C60(H60), C75(H75), C154(H154), C56(H56), C26(H26),
 C63(H63), C141(H141), C35(H35), C45(H45), C122(H122), C148(H148), C28(H28),
 C65(H65), C158(H158), C76(H76), C125(H125), C57(H57), C110(H110), C59(H59),
 C155(H155), C157(H157), C145(H145), C149(H149), C142(H142), C34(H34),
 C123(H123), C144(H144), C73(H73), C69(H69), C72(H72), C70(H70)
;
_shelx_res_checksum              69548
_shelx_fab_checksum              49071
_platon_squeeze_void_probe_radius 1.20
_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 1.642
_oxdiff_exptl_absorpt_empirical_full_min 0.632