Remote dibenzocycloheptyl substitution on a bis(arylimino)pyridyl-iron ethylene polymerization catalyst; enhanced thermal stability and unexpected effects on polymer properties
Guo, Liwei; Zhang, Wenjuan; Cao, Furong; Jiang, Youshu; Zhang, Randi; Ma, Yanping; Solan, Gregory A.; Sun, Yang; Sun, Wen-Hua; Polymer Chemistry 12 (2021) 4214–4225; doi:10.1039/D1PY00660F

data_1564109
_publ_section_title
;
 Remote dibenzocycloheptyl substitution on a bis(arylimino)pyridyl-iron
 ethylene polymerization catalyst; enhanced thermal stability and
 unexpected effects on polymer properties
;
_journal_issue                   29
_journal_name_full               'Polymer Chemistry'
_journal_page_first              4214
_journal_page_last               4225
_journal_paper_doi               10.1039/D1PY00660F
_journal_volume                  12
_journal_year                    2021
_chemical_formula_moiety         'C57 H55 Cl2 Fe N3'
_chemical_formula_sum            'C57 H55 Cl2 Fe N3'
_chemical_formula_weight         908.79
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2018-04-17
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2021-04-21 deposited with the CCDC.	2021-07-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.716(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.6551(4)
_cell_length_b                   17.1174(3)
_cell_length_c                   16.8958(3)
_cell_measurement_reflns_used    27475
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      30.2550
_cell_measurement_theta_min      1.7090
_cell_volume                     6109.3(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.9d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.9d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.9d (Rigaku OD, 2015)'
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      173.1500
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.920
_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   -110.00  70.00   0.50   11.00    --  -20.00  45.00 270.00  360
  2  \w   -110.00  57.00   0.50   11.00    --  -20.00  45.00  90.00  334
  3  \w    -80.00  58.00   0.50   11.00    --  -20.00  45.00 180.00  276
  4  \w   -110.00  27.00   0.50   11.00    --  -20.00  45.00   0.00  274
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0786
_diffrn_reflns_av_unetI/netI     0.0771
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.920
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            100995
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.920
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.539
_diffrn_reflns_theta_min         1.531
_exptl_absorpt_coefficient_mu    0.366
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81516
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.9d (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    0.988
_exptl_crystal_description       Plate
_exptl_crystal_F_000             1912
_exptl_crystal_size_max          0.231
_exptl_crystal_size_mid          0.103
_exptl_crystal_size_min          0.036
_refine_diff_density_max         0.559
_refine_diff_density_min         -0.341
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     595
_refine_ls_number_reflns         18760
_refine_ls_number_restraints     27
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.1300
_refine_ls_R_factor_gt           0.0783
_refine_ls_shift/su_max          0.159
_refine_ls_shift/su_mean         0.004
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0842P)^2^+4.0967P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1812
_refine_ls_wR_factor_ref         0.2040
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11529
_reflns_number_total             18760
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1py00660f2.cif
_cod_data_source_block           Fe4_sq
_cod_depositor_comments
'Adding full bibliography for 1564108--1564109.cif.'
_cod_database_code               1564109
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   1.00000
_shelx_estimated_absorpt_t_min   0.50315
_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
 C18-C17A
 1.54 with sigma of 0.01
 C41-C40 = C42-C41A
 1.54 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C41 \\sim C40: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04
Uanis(C17A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C41) \\sim Ueq, Uanis(C41A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Sof(H16C)=Sof(H16D)=Sof(H16E)=Sof(H18D)=Sof(H18E)=Sof(C17A)=Sof(H17D)=
 Sof(H17E)=Sof(H17F)=1-FVAR(1)
 Sof(H16A)=Sof(H16B)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C17)=Sof(H17A)=
 Sof(H17B)=Sof(H17C)=FVAR(1)
 Sof(H40C)=Sof(H40D)=Sof(H40E)=Sof(H42D)=Sof(H42E)=Sof(C41A)=Sof(H41D)=
 Sof(H41E)=Sof(H41F)=1-FVAR(2)
 Sof(H40A)=Sof(H40B)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C41)=Sof(H41A)=
 Sof(H41B)=Sof(H41C)=FVAR(2)
5.a Riding coordinates:
 C16(H16A,H16B), C16(H16C,H16D,H16E), C18(H18A,H18B,H18C), C18(H18D,H18E)
5.b Ternary CH refined with riding coordinates:
 C19(H19), C43(H43)
5.c Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C26(H26A,H26B), C40(H40A,H40B), C42(H42D,H42E), C51(H51A,
 H51B), C50(H50A,H50B)
5.d Me refined with riding coordinates:
 C41(H41A,H41B,H41C)
5.e Aromatic/amide H refined with riding coordinates:
 C32(H32), C31(H31), C30(H30), C29(H29), C24(H24), C23(H23), C22(H22),
 C21(H21), C12(H12), C14(H14), C2(H2), C3(H3), C4(H4), C38(H38), C36(H36),
 C56(H56), C55(H55), C54(H54), C53(H53), C48(H48), C47(H47), C46(H46), C45(H45)
5.f Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C40(H40C,H40D,H40E), C42(H42A,H42B,H42C),
 C17(H17A,H17B,H17C), C17A(H17D,H17E,H17F), C41A(H41D,H41E,H41F)
;
_shelx_res_checksum              16483
_shelx_fab_checksum              50465
_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
- Detector area scaling
;