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_7704716
_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         'C81 H60 Cl Co F10 N3 O2'
_chemical_formula_sum            'C81 H60 Cl Co F10 N3 O2'
_chemical_formula_weight         1391.70
_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                 116.265(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.5816(3)
_cell_length_b                   27.4361(2)
_cell_length_c                   16.5226(3)
_cell_measurement_reflns_used    20584
_cell_measurement_temperature    169.99(11)
_cell_measurement_theta_max      75.0100
_cell_measurement_theta_min      3.0780
_cell_volume                     7553.7(2)
_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(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.964
_diffrn_measured_fraction_theta_max 0.922
_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    -41.00 -16.00   0.50    2.00    --  -47.20  20.00-155.00   50
  2  \w    -64.00 -31.00   0.50    6.00    --  -99.00  77.00-150.00   66
  3  \w   -105.00 -80.00   0.50    6.00    --  -99.00  20.00-155.00   50
  4  \w   -122.00 -35.00   0.50    2.00    --  -47.20 -20.00  37.00  174
  5  \w     35.00 104.00   0.50    2.00    --   47.20  20.00-155.00  138
  6  \w     93.00 167.00   0.50    6.00    --  103.25  20.00-155.00  148
  7  \w     91.00 155.00   0.50    6.00    --  103.25  45.00-120.00  128
  8  \w     92.00 164.00   0.50    6.00    --  103.25  15.00 -30.00  144
  9  \w     80.00 105.00   0.50    6.00    --  103.25 -94.00   0.00   50
 10  \w     79.00 108.00   0.50    6.00    --  103.25-125.00 -30.00   58
 11  \w     50.00 103.00   0.50    6.00    --  103.25 -94.00  90.00  106
 12  \w     33.00  71.00   0.50    6.00    --  103.25 -94.00   0.00   76
 13  \w     32.00  71.00   0.50    6.00    --  103.25-125.00 -30.00   78
 14  \w     17.00  91.00   0.50    2.00    --   47.20-125.00 -30.00  148
 15  \w     28.00 105.00   0.50    6.00    --  103.25 -20.00  37.00  154
 16  \w     -9.00  50.00   0.50    2.00    --   47.20 -20.00  37.00  118
 17  \w   -115.00 -26.00   0.50    6.00    --  -99.00  61.00  60.00  178
 18  \w   -127.00-102.00   0.50    6.00    --  -99.00 -20.00  37.00   50
;
_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      0.0124986000
_diffrn_orient_matrix_UB_12      -0.0154821000
_diffrn_orient_matrix_UB_13      0.0949630000
_diffrn_orient_matrix_UB_21      -0.0210424000
_diffrn_orient_matrix_UB_22      -0.0529610000
_diffrn_orient_matrix_UB_23      -0.0329242000
_diffrn_orient_matrix_UB_31      0.0891538000
_diffrn_orient_matrix_UB_32      -0.0103897000
_diffrn_orient_matrix_UB_33      0.0265978000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0501
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_Laue_measured_fraction_full 0.964
_diffrn_reflns_Laue_measured_fraction_max 0.922
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            48495
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.922
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.639
_diffrn_reflns_theta_min         2.652
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.704
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71121
_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    1.224
_exptl_crystal_description       block
_exptl_crystal_F_000             2868
_exptl_crystal_size_max          0.519
_exptl_crystal_size_mid          0.256
_exptl_crystal_size_min          0.089
_refine_diff_density_max         0.548
_refine_diff_density_min         -0.392
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1173
_refine_ls_number_reflns         14476
_refine_ls_number_restraints     867
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.1508
_refine_ls_R_factor_gt           0.1101
_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^)+(0.1102P)^2^+18.2135P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2728
_refine_ls_wR_factor_ref         0.3026
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9558
_reflns_number_total             14476
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt01876g2.cif
_cod_data_source_block           Co5-1
_cod_depositor_comments
'Adding full bibliography for 7704715--7704718.cif.'
_cod_database_code               7704716
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         CHNOClCo
_chemical_oxdiff_usercomment     'C H N Co Cl F O'
_reflns_odcompleteness_completeness 96.43
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C2-C1 = C8-C9 = C10-C9 = C11-C10 = C12-C11 = C13-C12
 1.54 with sigma of 0.01
 C69-C68 = C73-C68 = C73-C72 = C72-C71 = C71-C70 = C70-C69
 1.39 with sigma of 0.01
 C4A-C3A = C3A-C2A = C5A-C4A = C6A-C5A = C7A-C6A = C9A-C10A = C11A-C10A = C12A-
 C11A = C13A-C12A = C13-C13A
 1.54 with sigma of 0.01
 C53A-C48A = C49A-C48A = C50A-C49A = C51A-C50A = C52A-C51A = C53A-C52A
 1.39 with sigma of 0.01
 F1A-C49A
 1.34 with sigma of 0.01
 C73A-C68A = C69A-C68A = C73A-C72A = C72A-C71A = C71A-C70A = C70A-C69A
 1.39 with sigma of 0.01
 F5A-C71A
 1.34 with sigma of 0.01
 C11A-C9A
 2.5 with sigma of 0.02
 C10A-C12A
 2.5 with sigma of 0.02
3. Rigid bond restraints
 O2, C80
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
F1 \\sim N1 \\sim C50 \\sim C15 \\sim C1 \\sim C16 \\sim C12 \\sim C6 \\sim C53
\\sim C8 \\sim C68 \\sim F5 \\sim C9 \\sim C52 \\sim C2 \\sim C69 \\sim C5
\\sim C4 \\sim C70 \\sim C73 \\sim C74 \\sim C67 \\sim C3 \\sim C51 \\sim C72
\\sim C71 \\sim C11 \\sim C10 \\sim C75 \\sim C76 \\sim C7 \\sim C49: within
1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A \\sim C7A \\sim C8A \\sim C9A \\sim
C1A \\sim C10A \\sim C11A \\sim C12A \\sim C13A \\sim N1A \\sim C48A \\sim C53A
\\sim C52A \\sim C49A \\sim C51A \\sim C50A \\sim F1A \\sim C67A \\sim C74A
\\sim C75A \\sim C76A \\sim C68A \\sim C69A \\sim C70A \\sim C71A \\sim F5A
\\sim C72A \\sim C73A: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04
Uanis(C13) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C11A) \\sim Ueq,
Uanis(C12A) \\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C14)
\\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C8) \\sim Ueq,
Uanis(C5) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C6A)
\\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C1A) \\sim Ueq,
Uanis(F6) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C4) \\sim
Ueq, Uanis(C3) \\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(C3A) \\sim Ueq,
Uanis(C4A) \\sim Ueq, Uanis(N1A) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C79)
\\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(F5) \\sim Ueq,
Uanis(C77) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C73)
\\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C72) \\sim Ueq,
Uanis(C71) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C67A)
\\sim Ueq, Uanis(C74A) \\sim Ueq, Uanis(C68A) \\sim Ueq, Uanis(C69A) \\sim Ueq,
Uanis(C70A) \\sim Ueq, Uanis(C71A) \\sim Ueq, Uanis(F5A) \\sim Ueq, Uanis(C72A)
\\sim Ueq, Uanis(C73A) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(C50) \\sim Ueq,
Uanis(C53) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C49)
\\sim Ueq, Uanis(C53A) \\sim Ueq, Uanis(C52A) \\sim Ueq, Uanis(C49A) \\sim Ueq,
Uanis(C51A) \\sim Ueq, Uanis(C50A) \\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(C75A)
\\sim Ueq, Uanis(C48A) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C76A) \\sim Ueq,
Uanis(C9A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(H54A)=Sof(H79A)=Sof(C2A)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C4A)=Sof(H4AA)=
 Sof(H4AB)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(C7A)=
 Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(C1A)=Sof(C10A)=Sof(H10C)=Sof(H10D)=Sof(C11A)=
 Sof(H11C)=Sof(H11D)=Sof(C12A)=Sof(H12C)=Sof(H12D)=Sof(C13A)=Sof(H13C)=
 Sof(H13D)=Sof(N1A)=Sof(C48A)=Sof(C53A)=Sof(C52A)=Sof(H52A)=Sof(C49A)=Sof(C51A)=
 Sof(C50A)=Sof(H50A)=Sof(F1A)=Sof(C67A)=Sof(H67A)=Sof(C74A)=Sof(C75A)=Sof(H75A)=
 Sof(C76A)=Sof(H76A)=Sof(C68A)=Sof(C69A)=Sof(H69A)=Sof(C70A)=Sof(H70A)=
 Sof(C71A)=Sof(F5A)=Sof(C72A)=Sof(H72A)=Sof(C73A)=Sof(H73A)=1-FVAR(1)
 Sof(F1)=Sof(N1)=Sof(C50)=Sof(H50)=Sof(C15)=Sof(C1)=Sof(C16)=Sof(C12)=
 Sof(H12a)=Sof(H12b)=Sof(C6)=Sof(H54)=Sof(H79)=Sof(C53)=Sof(C8)=Sof(C68)=
 Sof(F5)=Sof(C9)=Sof(H9a)=Sof(H9b)=Sof(C52)=Sof(H52)=Sof(C2)=Sof(H2a)=Sof(H2b)=
 Sof(C69)=Sof(H69)=Sof(C5)=Sof(H5a)=Sof(H5b)=Sof(C4)=Sof(H4a)=Sof(H4b)=Sof(C70)=
 Sof(H70)=Sof(C73)=Sof(H73)=Sof(C74)=Sof(C67)=Sof(H67)=Sof(C3)=Sof(H3a)=
 Sof(H3b)=Sof(C51)=Sof(C72)=Sof(H72)=Sof(C71)=Sof(C11)=Sof(H11a)=Sof(H11b)=
 Sof(C10)=Sof(H10a)=Sof(H10b)=Sof(C75)=Sof(H75)=Sof(C76)=Sof(H76)=Sof(C7)=
 Sof(H7)=Sof(C49)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C36(H36), C23(H23), C54(H54), C54(H54A), C67(H67), C67A(H67A)
6.b Secondary CH2 refined with riding coordinates:
 C12(H12a,H12b), C9(H9a,H9b), C2(H2a,H2b), C5(H5a,H5b), C4(H4a,H4b), C3(H3a,
 H3b), C11(H11a,H11b), C10(H10a,H10b), C3A(H3AA,H3AB), C4A(H4AA,H4AB), C5A(H5AA,
 H5AB), C6A(H6AA,H6AB), C10A(H10C,H10D), C11A(H11C,H11D), C12A(H12C,H12D),
 C13A(H13C,H13D)
6.c Aromatic/amide H refined with riding coordinates:
 C19(H19), C21(H21), C38(H38), C42(H42), C39(H39), C44(H44), C41(H41),
 C29(H29), C35(H35), C28(H28), C48(H48), C45(H45), C50(H50), C47(H47), C25(H25),
  C34(H34), C31(H31), C60(H60), C78(H78), C26(H26), C79(H79), C79(H79A),
 C59(H59), C62(H62), C57(H57), C66(H66), C56(H56), C32(H32), C65(H65), C52(H52),
  C69(H69), C63(H63), C70(H70), C73(H73), C72(H72), C75(H75), C76(H76), C7(H7),
 C8A(H8A), C52A(H52A), C50A(H50A), C75A(H75A), C76A(H76A), C69A(H69A),
 C70A(H70A), C72A(H72A), C73A(H73A)
6.d Idealised Me refined as rotating group:
 C81(H81a,H81b,H81c)
;
_shelx_res_checksum              51658
_shelx_fab_checksum              62233
_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 2.645
_oxdiff_exptl_absorpt_empirical_full_min 0.539