Sterically hindered phenanthroimidazole ligands drive the structural flexibility and facile ligand exchange in cyclometalated iridium(III) complexes.
Tatarin, Sergei V.; Kalle, Paulina; Taydakov, Ilya V.; Varaksina, Evgenia A.; Korshunov, Vladislav M.; Bezzubov, Stanislav I.; Dalton transactions (Cambridge, England : 2003) 50 (2021) 6889–6900; doi:10.1039/d1dt00820j

data_7707208
_publ_section_title
;
 Sterically hindered phenanthroimidazole ligands drive the structural
 flexibility and facile ligand exchange in cyclometalated iridium(III)
 complexes.
;
_journal_issue                   20
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              6889
_journal_page_last               6900
_journal_paper_doi               10.1039/d1dt00820j
_journal_volume                  50
_journal_year                    2021
_chemical_formula_moiety         'C69 H43 F2 Ir N4 O4 S, 1.5(C H2 Cl2)'
_chemical_formula_sum            'C70.5 H46 Cl3 F2 Ir N4 O4 S'
_chemical_formula_weight         1381.72
_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
_audit_creation_date             2020-12-22
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2020-12-23 deposited with the CCDC.	2021-04-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.663(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.5656(15)
_cell_length_b                   17.6138(11)
_cell_length_c                   29.183(2)
_cell_measurement_reflns_used    9889
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.40
_cell_measurement_theta_min      2.31
_cell_volume                     11975.1(13)
_computing_cell_refinement       'APEX3 v.2017.3_0 (Bruker AXS, 2017)'
_computing_data_collection       'APEX3 v.2017.3_0 (Bruker AXS, 2017)'
_computing_data_reduction        'SAINT v8.38A (Bruker AXS, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker SMART CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX II'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0574
_diffrn_reflns_av_unetI/netI     0.0434
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            57032
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.049
_diffrn_reflns_theta_max         25.049
_diffrn_reflns_theta_min         1.748
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_type              'fine-focus sealed X-ray tube'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.460
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5588
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1005 before and 0.0669 after correction.
The Ratio of minimum to maximum transmission is 0.7497.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.533
_exptl_crystal_description       block
_exptl_crystal_F_000             5528
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method 'recrystallization from CH2Cl2/CH3OH'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.717
_refine_diff_density_min         -1.562
_refine_diff_density_rms         0.204
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     627
_refine_ls_number_reflns         10610
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0930
_refine_ls_R_factor_gt           0.0733
_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^)+(0.1197P)^2^+209.5360P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2026
_refine_ls_wR_factor_ref         0.2188
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8299
_reflns_number_total             10610
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt00820j2.cif
_cod_data_source_block           st39_2
_cod_depositor_comments
'Adding full bibliography for 7707205--7707218.cif.'
_cod_original_cell_volume        11974.9(13)
_cod_original_formula_sum        'C70.50 H46 Cl3 F2 Ir N4 O4 S'
_cod_database_code               7707208
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.791
_shelx_estimated_absorpt_t_min   0.639
_computing.bruker_data_scaling   'SADABS V2012/1 (Bruker AXS Inc.)'
_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
 S2A-C62 = S2A-C0AA
 1.71 with sigma of 0.01
 C41A-C63
 1.376 with sigma of 0.01
 C41A-C0AA
 1.35 with sigma of 0.01
 O7-C3AA
 1.45 with sigma of 0.02
 N4-C2BA \\sim N4-C35
 with sigma of 0.01
 C64-C0AA \\sim C64-C63 \\sim C63-C62
 with sigma of 0.01
3. Restrained planarity
 C62, S2A, C0AA, C64, C63
 with sigma of 0.01
 C66, C65, C64, C63, C62, C67
 with sigma of 0.01
 S2A, C0AA, C41A, C63, C62
 with sigma of 0.01
 C66, C68, O1, O2
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(O1) = Uanis(C68) = Uanis(O2) = Uanis(C69)
Uanis(C35) = Uanis(C40) = Uanis(C39) = Uanis(C38) = Uanis(C37) = Uanis(C36) =
Uanis(C2BA) = Uanis(C4BA) = Uanis(C1BA) = Uanis(C3BA) = Uanis(C0BA) =
Uanis(C8AA)
Uanis(C6AA) = Uanis(C9AA) = Uanis(C4AA) = Uanis(C5AA) = Uanis(C1AA)
Uanis(O11) = Uanis(C2AA) = Uanis(O7)
Uanis(C58) = Uanis(C1AA) = Uanis(S1) = Uanis(C5AA) = Uanis(C55) = Uanis(C4AA) =
Uanis(C56) = Uanis(C9AA) = Uanis(C6AA) = Uanis(C57)
Uanis(C42) = Uanis(C47) = Uanis(C46) = Uanis(C45) = Uanis(C44) = Uanis(C43)
Uanis(C62) = Uanis(C63) = Uanis(C64) = Uanis(C66)
Uanis(C66) = Uanis(C62) = Uanis(C63) = Uanis(C64) = Uanis(C65)
Uanis(C20) = Uanis(C15) = Uanis(C16) = Uanis(C17) = Uanis(C18) = Uanis(C19)
Uiso(S2A) = Uiso(C41A) = Uiso(C0AA)
Uanis(C67) = Uanis(C62) = Uanis(C63) = Uanis(C65) = Uanis(C66) = Uanis(C64)
Uanis(C7AA) = Uanis(Cl1)
Uanis(C69) = Uanis(O2) = Uanis(C68) = Uanis(O1) = Uanis(C66) = Uanis(C65) =
Uanis(C64) = Uanis(C63) = Uanis(C62) = Uanis(C67)
5. Others
 Fixed Sof: S1(0.82) H63(0.82) H63A(0.18) C64(0.82) H64(0.82) C66(0.82)
 C67(0.82) H67(0.82) C1AA(0.18) H1AA(0.18) C5AA(0.18) H5AA(0.18) C4AA(0.18)
 H4AA(0.18) C9AA(0.18) C6AA(0.18) H6AA(0.18) C57(0.82) H57(0.82) C35(0.5)
 C40(0.5) H40(0.5) C39(0.5) H39(0.5) C38(0.5) H38(0.5) C37(0.5) H37(0.5)
 C36(0.5) H36(0.5) C55(0.82) H55(0.82) C56(0.82) H56(0.82) C2BA(0.5) C0BA(0.5)
 H0BA(0.5) C3BA(0.5) H3BA(0.5) C1BA(0.5) H1BA(0.5) C8AA(0.5) H8AA(0.5)
 C4BA(0.5) H4BA(0.5) O7(0.18) O11(0.18) C2AA(0.18) C3AA(0.18) H3AA(0.18)
 H3AB(0.18) H3AC(0.18) H7AA(0.5) H7AB(0.5) C65(0.82) H65(0.82) O1(0.82)
 C68(0.82) O2(0.82) C69(0.82) H69A(0.82) H69B(0.82) H69C(0.82) S2A(0.18)
 C0AA(0.18) H0AA(0.18) C41A(0.18) H41A(0.18)
6.a Secondary CH2 refined with riding coordinates:
 C7AA(H7AA,H7AB), C70(H70A,H70B)
6.b Aromatic/amide H refined with riding coordinates:
 C60(H60), C63(H63), C63(H63A), C64(H64), C67(H67), C32(H32), C29(H29), C2(H2),
  C5(H5), C1AA(H1AA), C5AA(H5AA), C4AA(H4AA), C6AA(H6AA), C4(H4), C25(H25),
 C9(H9), C31(H31), C23(H23), C12(H12), C44(H44), C46(H46), C45(H45), C13(H13),
 C43(H43), C24(H24), C57(H57), C22(H22), C40(H40), C39(H39), C38(H38), C37(H37),
  C36(H36), C52(H52), C49(H49), C55(H55), C50(H50), C11(H11), C16(H16),
 C51(H51), C17(H17), C19(H19), C10(H10), C18(H18), C56(H56), C0BA(H0BA),
 C3BA(H3BA), C1BA(H1BA), C8AA(H8AA), C4BA(H4BA), C65(H65), C0AA(H0AA),
 C41A(H41A)
6.c Fitted hexagon refined as free rotating group:
 C58(C1AA,C5AA,C4AA,C9AA,C6AA), C35(C40,C39,C38,C37,C36), C2BA(C0BA,C3BA,C1BA,
 C8AA,C4BA)
6.d Idealised Me refined as rotating group:
 C3AA(H3AA,H3AB,H3AC), C69(H69A,H69B,H69C)
;
_shelx_res_checksum              61088
_shelx_hkl_checksum              32661
_olex2_submission_special_instructions 'No special instructions were received'