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_1564108
_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         'C59 H59 Cl2 Fe N3'
_chemical_formula_sum            'C59 H59 Cl2 Fe N3'
_chemical_formula_weight         936.84
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-01-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-04-21 deposited with the CCDC.	2021-07-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.6180(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   48.0435(5)
_cell_length_b                   12.54440(10)
_cell_length_c                   16.9753(2)
_cell_measurement_reflns_used    12251
_cell_measurement_temperature    169.99(11)
_cell_measurement_theta_max      74.1740
_cell_measurement_theta_min      3.6360
_cell_volume                     10230.03(18)
_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 0.994
_diffrn_measured_fraction_theta_max 0.947
_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    -24.00  57.00   0.50    3.02    --   47.20 -32.00  39.00  162
  2  \w     34.00 116.00   0.50   12.08    --  103.25 -32.00  39.00  164
  3  \w     36.00  73.00   0.50    3.02    --   47.20-125.00 -60.00   74
  4  \w     42.00 105.00   0.50   12.08    --  103.25 -94.00 -90.00  126
  5  \w     34.00 122.00   0.50    3.02    --   47.20  32.00-161.00  176
  6  \w     93.00 151.00   0.50   12.08    --  103.25  32.00-161.00  116
  7  \w     92.00 168.00   0.50   12.08    --  103.25  30.00-120.00  152
  8  \w    -92.00 -67.00   0.50   12.08    --  -99.00  32.00-161.00   50
  9  \w   -111.00 -73.00   0.50   12.08    --  -99.00  45.00   0.00   76
 10  \w    -88.00 -26.00   0.50   12.08    --  -99.00  61.00  30.00  124
 11  \w   -109.00 -25.00   0.50   12.08    --  -99.00  15.00  30.00  168
 12  \w   -116.00 -43.00   0.50    3.02    --  -47.20 -32.00  39.00  146
 13  \w   -112.00 -25.00   0.50   12.08    --  -99.00  30.00  30.00  174
 14  \w   -127.00 -94.00   0.50   12.08    --  -99.00 -32.00  39.00   66
;
_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      -0.0196894000
_diffrn_orient_matrix_UB_12      0.0244893000
_diffrn_orient_matrix_UB_13      -0.0698960000
_diffrn_orient_matrix_UB_21      -0.0246819000
_diffrn_orient_matrix_UB_22      -0.0445511000
_diffrn_orient_matrix_UB_23      0.0468574000
_diffrn_orient_matrix_UB_31      -0.0055356000
_diffrn_orient_matrix_UB_32      0.1118185000
_diffrn_orient_matrix_UB_33      0.0340513000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0293
_diffrn_reflns_av_unetI/netI     0.0298
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.947
_diffrn_reflns_limit_h_max       59
_diffrn_reflns_limit_h_min       -59
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            31816
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.411
_diffrn_reflns_theta_min         3.642
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.624
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73907
_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            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.217
_exptl_crystal_description       plate
_exptl_crystal_F_000             3952
_exptl_crystal_size_max          0.194
_exptl_crystal_size_mid          0.131
_exptl_crystal_size_min          0.071
_refine_diff_density_max         0.762
_refine_diff_density_min         -0.330
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     899
_refine_ls_number_reflns         10039
_refine_ls_number_restraints     881
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.0722
_refine_ls_R_factor_gt           0.0597
_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^)+(0.1233P)^2^+9.3711P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1736
_refine_ls_wR_factor_ref         0.1919
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8206
_reflns_number_total             10039
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1py00660f2.cif
_cod_data_source_block           Fe2
_cod_depositor_comments
'Adding full bibliography for 1564108--1564109.cif.'
_cod_original_cell_volume        10230.02(18)
_cod_database_code               1564108
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_usercomment     'C H N Fe Cl'
_reflns_odcompleteness_completeness 99.51
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C34-C33 = C32-C31 = C33-C32 = C31-C30 = C30-C29 = C34-C29 = C24-C23 = C23-C22
 = C22-C21 = C25-C24 = C26-C25
 1.39 with sigma of 0.01
 C28-C27
 1.54 with sigma of 0.01
 C34-C20 = C21-C20 = C29-C28 = C27-C26
 1.51 with sigma of 0.01
 C34A-C29A = C34A-C33A = C32A-C33A = C31A-C32A = C31A-C30A = C30A-C29A
 1.39 with sigma of 0.01
 C34A-C20 = C21A-C20
 1.51 with sigma of 0.01
 C56-C55 = C54-C55 = C57-C56 = C57-C58 = C59-C58
 1.39 with sigma of 0.01
 C51-C52 = C54-C53
 1.51 with sigma of 0.01
 C52-C53
 1.54 with sigma of 0.01
 C47-C48 = C48-C49
 1.39 with sigma of 0.01
 C50-C51 = C49-C50 = C48-C49 = C47-C48 = C46-C47 = C46-C51 = C54-C59
 1.39 with sigma of 0.01
 C58A-C59A = C57A-C58A = C57A-C56A = C55A-C56A = C54A-C55A = C54A-C59A
 1.39 with sigma of 0.01
 C54A-C53A = C52A-C51A
 1.51 with sigma of 0.01
 C52A-C53A
 1.54 with sigma of 0.01
 C45-C59 = C45-C46
 1.51 with sigma of 0.01
 C36-C41 = C41-C36A
 1.51 with sigma of 0.01
 C40-C43 = C43-C40A
 1.51 with sigma of 0.01
 C47-C49
 2.2 with sigma of 0.02
 C55A-C53A
 2.5 with sigma of 0.02
 C56A-C58A
 2.2 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim
C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.04
C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim
C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04
C46 \\sim C45 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim
C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C45A
\\sim C47A \\sim C48A \\sim C49A \\sim C50A \\sim C51A \\sim C52A \\sim C53A
\\sim C54A \\sim C55A \\sim C56A \\sim C57A \\sim C58A \\sim C59A: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C34) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C33)
\\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C21) \\sim Ueq,
Uanis(C24) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C32)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C31) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C23A) \\sim Ueq, Uanis(C29A) \\sim Ueq, Uanis(C32A) \\sim Ueq,
Uanis(C26A) \\sim Ueq, Uanis(C22A) \\sim Ueq, Uanis(C21A) \\sim Ueq,
Uanis(C24A) \\sim Ueq, Uanis(C28A) \\sim Ueq, Uanis(C25A) \\sim Ueq,
Uanis(C27A) \\sim Ueq, Uanis(C30A) \\sim Ueq, Uanis(C33A) \\sim Ueq,
Uanis(C31A) \\sim Ueq, Uanis(C34A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C46) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C50)
\\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C52) \\sim Ueq,
Uanis(C48) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C55)
\\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C58) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C59) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C48) \\sim Ueq,
Uanis(C47) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C56)
\\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C45) \\sim Ueq,
Uanis(C46) \\sim Ueq, Uanis(C45A) \\sim Ueq, Uanis(C47A) \\sim Ueq, Uanis(C48A)
\\sim Ueq, Uanis(C49A) \\sim Ueq, Uanis(C51A) \\sim Ueq, Uanis(C50A) \\sim Ueq,
Uanis(C59A) \\sim Ueq, Uanis(C52A) \\sim Ueq, Uanis(C53A) \\sim Ueq,
Uanis(C55A) \\sim Ueq, Uanis(C56A) \\sim Ueq, Uanis(C58A) \\sim Ueq,
Uanis(C57A) \\sim Ueq, Uanis(C54A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C36) \\sim Ueq, Uanis(C36A) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C40A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(H20A)=Sof(C21A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=
 Sof(H24A)=Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(C27A)=Sof(H27C)=Sof(H27D)=
 Sof(C28A)=Sof(H28C)=Sof(H28D)=Sof(C29A)=Sof(C30A)=Sof(H30A)=Sof(C31A)=
 Sof(H31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33A)=Sof(C34A)=1-FVAR(1)
 Sof(H20)=Sof(C21)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=
 Sof(C25)=Sof(H25)=Sof(C26)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(C28)=Sof(H28A)=
 Sof(H28B)=Sof(C29)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32)=
 Sof(C33)=Sof(H33)=Sof(C34)=FVAR(1)
 Sof(H41C)=Sof(H41D)=Sof(H43C)=Sof(H43D)=Sof(C35A)=Sof(C36A)=Sof(C37A)=
 Sof(H37A)=Sof(C38A)=Sof(C39A)=Sof(H39A)=Sof(C40A)=Sof(C45A)=Sof(H45A)=
 Sof(C47A)=Sof(H47A)=Sof(C48A)=Sof(H48A)=Sof(C49A)=Sof(H49A)=Sof(C50A)=
 Sof(H50A)=Sof(C51A)=Sof(C52A)=Sof(H52C)=Sof(H52D)=Sof(C53A)=Sof(H53C)=
 Sof(H53D)=Sof(C54A)=Sof(C55A)=Sof(H55A)=Sof(C56A)=Sof(H56A)=Sof(C57A)=
 Sof(H57A)=Sof(C58A)=Sof(H58A)=Sof(C59A)=1-FVAR(2)
 Sof(H41A)=Sof(H41B)=Sof(H43A)=Sof(H43B)=Sof(C35)=Sof(C36)=Sof(C37)=Sof(H37)=
 Sof(C38)=Sof(C39)=Sof(H39)=Sof(C40)=Sof(C45)=Sof(H45)=Sof(C47)=Sof(H47)=
 Sof(C48)=Sof(H48)=Sof(C49)=Sof(H49)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(C52)=
 Sof(H52A)=Sof(H52B)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(C55)=Sof(H55)=
 Sof(C56)=Sof(H56)=Sof(C57)=Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=FVAR(2)
 Fixed X: C35A(0.59535)
5.a Ternary CH refined with riding coordinates:
 C20(H20), C20(H20A), C45(H45), C45A(H45A)
5.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C18(H18A,H18B), C41(H41A,H41B), C41(H41C,H41D), C43(H43A,
 H43B), C43(H43C,H43D), C27(H27A,H27B), C28(H28A,H28B), C52(H52A,H52B),
 C53(H53A,H53B), C27A(H27C,H27D), C28A(H28C,H28D), C52A(H52C,H52D), C53A(H53C,
 H53D)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C12(H12), C14(H14), C22(H22), C23(H23), C24(H24),
 C25(H25), C30(H30), C31(H31), C32(H32), C33(H33), C37(H37), C39(H39), C47(H47),
  C48(H48), C49(H49), C50(H50), C55(H55), C56(H56), C57(H57), C58(H58),
 C22A(H22A), C23A(H23A), C24A(H24A), C25A(H25A), C30A(H30A), C31A(H31A),
 C32A(H32A), C33A(H33A), C37A(H37A), C39A(H39A), C47A(H47A), C48A(H48A),
 C49A(H49A), C50A(H50A), C55A(H55A), C56A(H56A), C57A(H57A), C58A(H58A)
5.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C),
 C42(H42A,H42B,H42C), C44(H44A,H44B,H44C)
;
_shelx_res_checksum              91834
_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 1.332
_oxdiff_exptl_absorpt_empirical_full_min 0.715