Modulation of 2-imino-6,7-dihydroquinlin-8(5H)-imine-iron ethylene polymerization catalysts through (cyclo)alkyl, benzhydryl and halide substitution
Zhang, Randi; Ma, Yanping; Solan, Gregory A.; Wang, Yizhou; Gao, Jiahao; Liang, Tongling; Sun, Wen-Hua; RSC Advances 15 (2025) 35055–35067; doi:10.1039/D5RA06630A

data_7250907
_publ_section_title
;
 Modulation of 2-imino-6,7-dihydroquinlin-8(5H)-imine-iron ethylene
 polymerization catalysts through (cyclo)alkyl, benzhydryl and halide
 substitution
;
_journal_issue                   42
_journal_name_full               'RSC Advances'
_journal_page_first              35055
_journal_page_last               35067
_journal_paper_doi               10.1039/D5RA06630A
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C87 H81 Cl2 Fe N3'
_chemical_formula_sum            'C87 H81 Cl2 Fe N3'
_chemical_formula_weight         1295.29
_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             2020-08-15
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2025-09-01 deposited with the CCDC.	2025-09-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.352(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.2417(18)
_cell_length_b                   17.0632(12)
_cell_length_c                   17.8586(12)
_cell_measurement_reflns_used    5462
_cell_measurement_temperature    170.00(16)
_cell_measurement_theta_max      72.2820
_cell_measurement_theta_min      3.0030
_cell_volume                     8437.6(10)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_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      170.00(16)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.955
_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    -17.00  48.00   0.50    2.50    --   46.95 -54.00 -30.00  130
  2  \w     38.00  65.00   0.50    8.00    --  103.25 -54.00 -30.00   54
  3  \w     46.00 105.00   0.50    8.00    --  103.25 -94.00  30.00  118
  4  \w     51.00  96.00   0.50    8.00    --  103.25 -77.00  60.00   90
  5  \w     52.00 106.00   0.50    8.00    --  103.25 -94.00  60.00  108
  6  \w     35.00  60.00   0.50    8.00    --  103.25 -61.00  60.00   50
  7  \w    106.00 159.00   0.50    8.00    --  103.25  30.00   0.00  106
  8  \w     90.00 168.00   0.50    8.00    --  103.25  54.00 113.00  156
  9  \w    136.00 166.00   0.50    8.00    --  103.25  45.00 150.00   60
 10  \w     98.00 137.00   0.50    8.00    --  103.25  61.00  30.00   78
 11  \w     92.00 122.00   0.50    8.00    --  103.25  45.00 150.00   60
 12  \w     53.00  82.00   0.50    2.50    --   46.95  54.00 113.00   58
 13  \w     94.00 166.00   0.50    8.00    --  103.25  45.00-120.00  144
 14  \w     91.00 168.00   0.50    8.00    --  103.25  45.00-180.00  154
 15  \w     41.00  73.00   0.50    8.00    --  103.25 -61.00-150.00   64
 16  \w     32.00 106.00   0.50    8.00    --  103.25-125.00 -60.00  148
 17  \w    -58.00  26.00   0.50    2.50    --  -46.95  54.00 113.00  168
 18  \w    -57.00 -32.00   0.50    8.00    --  -99.00  54.00 113.00   50
 19  \w    -67.00 -33.00   0.50    8.00    --  -99.00  61.00 -30.00   68
 20  \w    -59.00 -27.00   0.50    8.00    --  -99.00  61.00-120.00   64
 21  \w    -83.00 -27.00   0.50    8.00    --  -99.00  77.00 -90.00  112
 22  \w   -118.00 -36.00   0.50    2.50    --  -46.95 -54.00 -30.00  164
 23  \w   -118.00 -74.00   0.50    2.50    --  -46.95-125.00 120.00   88
 24  \w   -117.00 -84.00   0.50    2.50    --  -46.95-125.00  90.00   66
 25  \w   -151.00-126.00   0.50    8.00    --  -99.00 -54.00 -30.00   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      0.0348304000
_diffrn_orient_matrix_UB_12      -0.0432771000
_diffrn_orient_matrix_UB_13      -0.0422532000
_diffrn_orient_matrix_UB_21      -0.0433645000
_diffrn_orient_matrix_UB_22      -0.0382478000
_diffrn_orient_matrix_UB_23      -0.0531020000
_diffrn_orient_matrix_UB_31      -0.0022185000
_diffrn_orient_matrix_UB_32      0.0693734000
_diffrn_orient_matrix_UB_33      -0.0558982000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.2270
_diffrn_reflns_av_unetI/netI     0.1703
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            66083
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.490
_diffrn_reflns_theta_min         3.042
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.317
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.09300
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
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    1.020
_exptl_crystal_description       needle
_exptl_crystal_F_000             2736
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.721
_refine_diff_density_min         -0.930
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.931
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     958
_refine_ls_number_reflns         16933
_refine_ls_number_restraints     547
_refine_ls_restrained_S_all      0.921
_refine_ls_R_factor_all          0.1932
_refine_ls_R_factor_gt           0.1060
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1625P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2488
_refine_ls_wR_factor_ref         0.3119
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7150
_reflns_number_total             16933
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra06630a2.cif
_cod_data_source_block           Fe5
_cod_database_code               7250907
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N Fe Cl'
_reflns_odcompleteness_completeness 99.38
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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
 C75-C53 = C1AA-C53 = C75-C82 = C2AA-C1AA
 1.54 with sigma of 0.01
 C87-C82 = C86-C87 = C85-C86 = C0AA-C5AA = C85-C84 = C83-C84 = C83-C82 = C2AA-
 C4AA = C3AA-C4AA = C0AA-C3AA = C2AA-C88 = C5AA-C88
 1.39 with sigma of 0.01
 C63A-C62 = C69-C62
 1.54 with sigma of 0.01
 C70-C69 = C64A-C63A = C74-C69 = C68A-C63A = C68A-C67A = C70-C71 = C71-C72 =
 C65A-C64A = C73-C74 = C66A-C65A = C72-C73 = C67A-C66A
 1.39 with sigma of 0.01
 C81-C76
 1.39 with sigma of 0.01
 C77-C76 = C78-C77 = C80-C81 = C81-C76
 1.39 with sigma of 0.01
3. Rigid bond restraints
 C79, C80
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C78, C79
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
C82 \\sim C84 \\sim C83 \\sim C87 \\sim C85 \\sim C86 \\sim C1AA \\sim C4AA
\\sim C3AA \\sim C88 \\sim C2AA \\sim C0AA \\sim C5AA \\sim C75: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.04
C69 \\sim C72 \\sim C73 \\sim C74 \\sim C70 \\sim C71 \\sim C63A \\sim C64A
\\sim C65A \\sim C66A \\sim C68A \\sim C67A: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.04
Uanis(C82) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C87)
\\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C1AA) \\sim Ueq,
Uanis(C4AA) \\sim Ueq, Uanis(C3AA) \\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C2AA)
\\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(C5AA) \\sim Ueq, Uanis(C75) \\sim Ueq:
with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C69) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C74)
\\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C63A) \\sim Ueq,
Uanis(C64A) \\sim Ueq, Uanis(C65A) \\sim Ueq, Uanis(C66A) \\sim Ueq,
Uanis(C68A) \\sim Ueq, Uanis(C67A) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.1
5. Others
 Sof(C1AA)=Sof(H76)=Sof(C4AA)=Sof(H84)=Sof(C3AA)=Sof(H85)=Sof(C88)=Sof(H88)=
 Sof(C2AA)=Sof(C0AA)=Sof(H86)=Sof(C5AA)=Sof(H87)=1-FVAR(1)
 Sof(C82)=Sof(C75)=Sof(H75)=Sof(C84)=Sof(H84A)=Sof(C83)=Sof(H83)=Sof(C87)=
 Sof(H87A)=Sof(C85)=Sof(H85A)=Sof(C86)=Sof(H86A)=FVAR(1)
 Sof(H62A)=Sof(C63A)=Sof(C64A)=Sof(H64A)=Sof(C65A)=Sof(H65A)=Sof(C66A)=
 Sof(H66A)=Sof(C68A)=Sof(H68A)=Sof(C67A)=Sof(H67A)=1-FVAR(2)
 Sof(H62)=Sof(C69)=Sof(C72)=Sof(H72)=Sof(C73)=Sof(H73)=Sof(C74)=Sof(H74)=
 Sof(C70)=Sof(H70)=Sof(C71)=Sof(H71)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C37(H37), C24(H24), C18(H18), C62(H62), C62(H62A), C56(H56), C75(H75),
 C1AA(H76)
6.b Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C20(H20A,H20B), C7(H7A,H7B), C9(H9A,H9B), C23(H23A,H23B),
 C8(H8A,H8B), C22(H22A,H22B), C21(H21A,H21B), C60(H60A,H60B), C61(H61A,H61B),
 C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B)
6.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C45(H45), C14(H14), C32(H32), C30(H30), C39(H39), C52(H52),
 C26(H26), C4(H4), C43(H43), C5(H5), C46(H46), C63(H63), C49(H49), C54(H54),
 C33(H33), C27(H27), C29(H29), C42(H42), C65(H65), C47(H47), C28(H28), C77(H77),
  C36(H36), C34(H34), C48(H48), C72(H72), C35(H35), C81(H81), C40(H40),
 C73(H73), C41(H41), C68(H68), C78(H78), C66(H66), C74(H74), C70(H70), C79(H79),
  C71(H71), C67(H67), C80(H80), C84(H84A), C83(H83), C87(H87A), C85(H85A),
 C86(H86A), C4AA(H84), C3AA(H85), C88(H88), C0AA(H86), C5AA(H87), C64A(H64A),
 C65A(H65A), C66A(H66A), C68A(H68A), C67A(H67A)
6.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              99278
_shelx_fab_checksum              30777
_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 4.134
_oxdiff_exptl_absorpt_empirical_full_min 0.287