Switchable living nickel(ii) α-diimine catalyst for ethylene polymerisation
Padilla-Vélez, Omar; O’Connor, Kyle S.; LaPointe, Anne M.; MacMillan, Samantha N.; Coates, Geoffrey W.; Chemical Communications  (2019) –; doi:10.1039/C9CC03154E

data_7123651
_publ_section_title
;
 Switchable living nickel(ii) \a-diimine catalyst for ethylene
 polymerisation
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC03154E
_journal_year                    2019
_chemical_formula_moiety
'C88 H48 Br2 F8 N4 Ni2, 2(C32 H12 B F24), C H2 Cl2'
_chemical_formula_sum            'C153 H74 B2 Br2 Cl2 F56 N4 Ni2'
_chemical_formula_weight         3401.92
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_symmetry_space_group_name_Hall  '-P 2n 2ab'
_symmetry_space_group_name_H-M   'P b c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-04-24 deposited with the CCDC.    2019-05-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   35.5335(4)
_cell_length_b                   18.9692(2)
_cell_length_c                   20.8833(2)
_cell_measurement_reflns_used    38236
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.1410
_cell_measurement_theta_min      3.2590
_cell_volume                     14076.2(3)
_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)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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     -9.00  28.00   0.50    1.48    --  -47.20  19.00 -30.00   74
  2  \w    -42.00 -14.00   0.50    5.94    --  -86.25  45.00 -60.00   56
  3  \w    -42.00 -14.00   0.50    5.94    --  -86.25  45.00-120.00   56
  4  \w     -9.00  28.00   0.50    1.48    --  -47.20  19.00-180.00   74
  5  \w    -70.00  26.00   0.50    1.48    --  -47.20  77.00  90.00  192
  6  \w   -120.00 -73.00   0.50    1.48    --  -47.20-125.00 120.00   94
  7  \w     33.00  81.00   0.50    5.94    --  105.86 -61.00   0.00   96
  8  \w     33.00  81.00   0.50    5.94    --  105.86 -61.00  60.00   96
  9  \w     33.00  81.00   0.50    5.94    --  105.86 -61.00 120.00   96
 10  \w     33.00  81.00   0.50    5.94    --  105.86 -61.00  30.00   96
 11  \w     33.00  81.00   0.50    5.94    --  105.86 -61.00 -60.00   96
 12  \w     33.00  81.00   0.50    5.94    --  105.86 -61.00 -30.00   96
 13  \w     33.00  81.00   0.50    5.94    --  105.86 -61.00-120.00   96
 14  \w     33.00  81.00   0.50    5.94    --  105.86 -61.00-180.00   96
 15  \w     33.00  81.00   0.50    5.94    --  105.86 -61.00-150.00   96
 16  \w     33.00  81.00   0.50    5.94    --  105.86 -61.00 150.00   96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0133594000
_diffrn_orient_matrix_UB_12      -0.0725866000
_diffrn_orient_matrix_UB_13      -0.0239570000
_diffrn_orient_matrix_UB_21      -0.0371745000
_diffrn_orient_matrix_UB_22      -0.0091099000
_diffrn_orient_matrix_UB_23      -0.0369768000
_diffrn_orient_matrix_UB_31      0.0178883000
_diffrn_orient_matrix_UB_32      0.0352409000
_diffrn_orient_matrix_UB_33      -0.0591633000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0496
_diffrn_reflns_av_unetI/netI     0.0369
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            65136
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        66.600
_diffrn_reflns_theta_max         66.600
_diffrn_reflns_theta_min         2.487
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.503
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68671
_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            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.605
_exptl_crystal_description       block
_exptl_crystal_F_000             6776
_exptl_crystal_size_max          0.189
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.075
_refine_diff_density_max         1.111
_refine_diff_density_min         -0.968
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1123
_refine_ls_number_reflns         12392
_refine_ls_number_restraints     482
_refine_ls_restrained_S_all      1.122
_refine_ls_R_factor_all          0.0698
_refine_ls_R_factor_gt           0.0673
_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^)+(0.0965P)^2^+32.2158P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1829
_refine_ls_wR_factor_ref         0.1855
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11703
_reflns_number_total             12392
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc03154e2.cif
_cod_data_source_block           padilla_lnibr_cat
_cod_database_code               7123651
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C77 H38 B Br Cl2 N2 Ni F28'
_shelx_estimated_absorpt_t_max   0.835
_shelx_estimated_absorpt_t_min   0.649
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 F15B-C60 \\sim F15-C60 \\sim F14B-C60 \\sim F14-C60 \\sim F16B-C60 \\sim
F16-C60
 with sigma of 0.02
 F17B-C67 \\sim F17-C67 \\sim F19B-C67 \\sim F18-C67 \\sim F18B-C67 \\sim
F19-C67
 with sigma of 0.02
 C72-C71 \\sim C72B-C71 \\sim C73-C72 \\sim C73B-C72B \\sim C74-C73 \\sim
C74B-C73B \\sim C74B-C69 ~
 C74-C69
 with sigma of 0.02
 C76-C73 \\sim C76B-C73B
 with sigma of 0.02
 F26-C76 \\sim F28-C76 \\sim F27-C76 \\sim F28B-C76B \\sim F27B-C76B \\sim
F26B-C76B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C60 \\sim F14 \\sim F15 \\sim F16 \\sim F15B \\sim F16B \\sim F14B: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C67 \\sim F17 \\sim F18 \\sim F19 \\sim F17B \\sim F18B \\sim F19B: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C72 \\sim C72B \\sim C73 \\sim C73B \\sim C74 \\sim C74B: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C76 \\sim C76B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
F27B \\sim F26 \\sim F27 \\sim F28B \\sim F26B \\sim F28: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
Uanis(F14) = Uanis(F14B)
4. Rigid body (RIGU) restrains
 C60, F14, F15, F16, F15B, F16B, F14B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C67, F17, F18, F19, F17B, F18B, F19B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C72, C73, C74, C76, C72B, C73B, C74B, C76B, F26, F27, F28, F26B, F27B, F28B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C72B)=Sof(H72B)=Sof(C73B)=Sof(C74B)=Sof(H74B)=Sof(C76B)=Sof(F26B)=
 Sof(F27B)=Sof(F28B)=1-FVAR(1)
 Sof(C72)=Sof(H72)=Sof(C73)=Sof(C74)=Sof(H74)=Sof(C76)=Sof(F26)=Sof(F27)=
 Sof(F28)=FVAR(1)
 Sof(F17B)=Sof(F18B)=Sof(F19B)=1-FVAR(2)
 Sof(F17)=Sof(F18)=Sof(F19)=FVAR(2)
 Sof(F14B)=Sof(F15B)=Sof(F16B)=1-FVAR(3)
 Sof(F14)=Sof(F15)=Sof(F16)=FVAR(3)
 Fixed Sof: Cl1S(0.5) Cl2S(0.5) C1S(0.5) H1SA(0.5) H1SB(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C5(H5), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13),
 C14(H14), C19(H19), C20(H20), C21(H21), C23(H23), C24(H24), C25(H25), C30(H30),
  C31(H31), C32(H32), C34(H34), C35(H35), C36(H36), C40(H40), C42(H42),
 C44(H44), C46(H46), C48(H48), C50(H50), C54(H54), C56(H56), C58(H58), C62(H62),
  C64(H64), C66(H66), C70(H70), C72(H72), C74(H74), C72B(H72B), C74B(H74B)
;
_shelx_res_checksum              55684
_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 3.296
_oxdiff_exptl_absorpt_empirical_full_min 0.538