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_7707206
_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 Cl2 Ir N4 O4 S, 1.3(C H2 Cl2)'
_chemical_formula_sum            'C70.3 H45.6 Cl4.6 Ir N4 O4 S'
_chemical_formula_weight         1397.64
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -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                93.940(2)
_cell_angle_beta                 107.762(2)
_cell_angle_gamma                106.996(2)
_cell_formula_units_Z            2
_cell_length_a                   14.6748(9)
_cell_length_b                   15.3911(8)
_cell_length_c                   15.5092(10)
_cell_measurement_reflns_used    9890
_cell_measurement_temperature    150
_cell_measurement_theta_max      26.41
_cell_measurement_theta_min      2.38
_cell_volume                     3141.9(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'APEX3 v.2017.3_0 (Bruker AXS, 2017)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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      150
_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 0.989
_diffrn_measured_fraction_theta_max 0.989
_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  0.0650
_diffrn_reflns_av_unetI/netI     0.0621
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            45730
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        25.028
_diffrn_reflns_theta_max         25.028
_diffrn_reflns_theta_min         2.365
_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    2.406
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6435
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0777 before and 0.0587 after correction.
The Ratio of minimum to maximum transmission is 0.8633.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.477
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1397
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2, CH3OH'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.12
_refine_diff_density_max         2.166
_refine_diff_density_min         -1.855
_refine_diff_density_rms         0.157
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     750
_refine_ls_number_reflns         10988
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0934
_refine_ls_R_factor_gt           0.0699
_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^)+(0.1221P)^2^+7.8628P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1847
_refine_ls_wR_factor_ref         0.2006
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8372
_reflns_number_total             10988
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt00820j2.cif
_cod_data_source_block           st37_150
_cod_depositor_comments
'Adding full bibliography for 7707205--7707218.cif.'
_cod_original_formula_sum        'C70.30 H45.60 Cl4.60 Ir N4 O4 S'
_cod_database_code               7707206
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.761
_shelx_estimated_absorpt_t_min   0.645
_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
 C58-C57
 1.38 with sigma of 0.02
 C69-O2
 1.45 with sigma of 0.01
 O02D-C8AA
 1.45 with sigma of 0.02
 Cl3A-C1AA = Cl1A-C1AA
 1.77 with sigma of 0.02
 C69-C68
 2.363 with sigma of 0.04
 C58-C57 \\sim C7AA-C2AA \\sim C5AA-C3AA
 with sigma of 0.02
 C62-C67 \\sim C66-C67 \\sim C66-C65 \\sim C65-C64 \\sim C64-C63 \\sim C63-C62
 with sigma of 0.02
 C2AA-C58 \\sim C7AA-C2AA \\sim C7AA-C3AA \\sim C5AA-C3AA \\sim C5AA-C57 \\sim
C57-C58
 with sigma of 0.02
 S02F-C65 \\sim S02F-C62
 with sigma of 0.01
3. Restrained planarity
 C58, C57, C3AA, C5AA, C7AA, C2AA
 with sigma of 0.1
 S005, C58, C55, C57, C56
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C67) = Uanis(C66) = Uanis(C68) = Uanis(O1) = Uanis(O2) = Uanis(C69)
Uanis(C2AA) = Uanis(C57) = Uanis(C5AA) = Uanis(C3AA) = Uanis(C7AA)
Uanis(S005) = Uanis(C55) = Uanis(C56)
Uanis(C8AA) = Uanis(O02D) = Uanis(C4AA) = Uanis(O02G)
Uanis(Cl1A) = Uanis(C1AA) = Uanis(Cl3A)
Uanis(Cl2A) = Uanis(C6AA) = Uanis(Cl0A) = Uanis(C0AA)
5. Others
 Fixed Sof: S005(0.6) C67(0.6) H67(0.6) C66(0.6) H65A(0.4) H65(0.6) C55(0.6)
 H55(0.6) H57(0.6) H57A(0.4) C56(0.6) H56(0.6) O2(0.6) O02D(0.4) O1(0.6)
 S02F(0.4) O02G(0.4) C7AA(0.4) H7AA(0.4) C68(0.6) C2AA(0.4) H2AA(0.4) C3AA(0.4)
 H3AA(0.4) C4AA(0.4) C5AA(0.4) C6AA(0.6) H6AA(0.6) H6AB(0.6) C0AA(0.4)
 H0AA(0.4) H0AB(0.4) C69(0.6) H69A(0.6) H69B(0.6) H69C(0.6) C8AA(0.4) H8AA(0.4)
 H8AB(0.4) H8AC(0.4) Cl1A(0.3) Cl3A(0.3) C1AA(0.3) H1AA(0.3) H1AB(0.3)
6.a Secondary CH2 refined with riding coordinates:
 C6AA(H6AA,H6AB), C0AA(H0AA,H0AB), C1AA(H1AA,H1AB)
6.b Aromatic/amide H refined with riding coordinates:
 C67(H67), C65(H65A), C65(H65), C64(H64), C63(H63), C60(H60), C2(H2), C19(H19),
  C29(H29), C40(H40), C52(H52), C25(H25), C22(H22), C49(H49), C16(H16), C5(H5),
 C17(H17), C24(H24), C51(H51), C9(H9), C18(H18), C23(H23), C50(H50), C13(H13),
 C43(H43), C46(H46), C32(H32), C31(H31), C44(H44), C36(H36), C4(H4), C45(H45),
 C10(H10), C11(H11), C37(H37), C39(H39), C55(H55), C12(H12), C57(H57),
 C57(H57A), C38(H38), C56(H56), C7AA(H7AA), C2AA(H2AA), C3AA(H3AA)
6.c Fitted hexagon refined as free rotating group:
 C62(C67,C66,C65,C64,C63)
6.d Idealised Me refined as rotating group:
 C69(H69A,H69B,H69C), C8AA(H8AA,H8AB,H8AC)
;
_shelx_res_checksum              46167
_shelx_hkl_checksum              95478
_olex2_submission_special_instructions 'No special instructions were received'