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_7707213
_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         'C73 H53 Ir N4 O8 S, 0.45(C H4 O)'
_chemical_formula_sum            'C73.45 H54.8 Ir N4 O8.45 S'
_chemical_formula_weight         1352.87
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2020-12-23
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.0818(17)
_cell_length_b                   11.7771(8)
_cell_length_c                   22.3446(16)
_cell_measurement_reflns_used    9657
_cell_measurement_temperature    150
_cell_measurement_theta_max      30.221
_cell_measurement_theta_min      2.543
_cell_volume                     6074.1(7)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_collection       'APEX3 v.2017.3_0 (Bruker AXS, 2017)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_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 0.999
_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  0.0385
_diffrn_reflns_av_unetI/netI     0.0373
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            70959
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.000
_diffrn_reflns_theta_min         1.941
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    2.296
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8622
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0833 before and 0.0491 after correction. The Ratio of minimum to maximum transmission is 0.8622. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'light brown'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.479
_exptl_crystal_description       block
_exptl_crystal_F_000             2736
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2, CH3OH'
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.18
_refine_diff_density_max         1.589
_refine_diff_density_min         -1.156
_refine_diff_density_rms         0.107
_refine_ls_abs_structure_details
;
 Flack x determined using 5985 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.011(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     699
_refine_ls_number_reflns         16116
_refine_ls_number_restraints     10
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0493
_refine_ls_R_factor_gt           0.0400
_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^)+(0.0543P)^2^+8.9077P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0964
_refine_ls_wR_factor_ref         0.1010
_reflns_Friedel_coverage         0.950
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                13959
_reflns_number_total             16116
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt00820j2.cif
_cod_data_source_block           st36_b
_cod_depositor_comments
'Adding full bibliography for 7707205--7707218.cif.'
_cod_original_formula_sum        'C73.45 H54.80 Ir N4 O8.45 S'
_cod_database_code               7707213
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.683
_shelx_estimated_absorpt_t_min   0.527
_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, All O(H) groups
2. Restrained distances
 C86-C87
 2.4 with sigma of 0.01
 O1AA-C2AA
 1.43 with sigma of 0.02
 S1-C62
 1.7 with sigma of 0.001
 C60-C59
 1.4 with sigma of 0.001
 S2-C66
 1.7 with sigma of 0.001
 S2-C91
 1.72 with sigma of 0.02
 C87-C4AA
 1.5 with sigma of 0.02
 O1-C72
 1.23 with sigma of 0.02
 S2-C91 \\sim S2-C66
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C62) = Uanis(C3AA) = Uanis(C61) = Uanis(C60) = Uanis(C89) = Uanis(C59) =
Uanis(C0AA) = Uanis(C4AA) = Uanis(S1)
Uanis(C8) = Uanis(C1AA) = Uanis(C9) = Uanis(C9AA) = Uanis(C10) = Uanis(C8AA) =
Uanis(C7AA) = Uanis(C11) = Uanis(C6AA) = Uanis(C12) = Uanis(C13) = Uanis(C5AA)
Uanis(S2) = Uanis(C70)
Uanis(C91) = Uanis(C69)
Uanis(C70) = Uanis(S2) = Uanis(C71) = Uanis(C91) = Uanis(C69) = Uanis(C68) =
Uanis(C67) = Uanis(C66)
Uanis(C35) = Uanis(C36) = Uanis(C37) = Uanis(C38) = Uanis(C39) = Uanis(C40)
Uiso(O9) = Uiso(C86)
Uiso(C87) = Uiso(O10)
4. Others
 Fixed Sof: C3AA(0.33333) H3AA(0.33333) H60A(0.33333) H60(0.66667)
 C89(0.33333) H89(0.33333) C4AA(0.33333) C0AA(0.33333) H0AA(0.33333)
 C61(0.66667) H61(0.66667) C70(0.66667) H70(0.66667) C71(0.66667) C69(0.66667)
 H69(0.66667) H68(0.66667) H68A(0.33333) C1AA(0.66667) C5AA(0.66667)
 H5AA(0.66667) C6AA(0.66667) H6AA(0.66667) C7AA(0.66667) H7AA(0.66667)
 C8AA(0.66667) H8AA(0.66667) C9AA(0.66667) H9AA(0.66667) C0BA(0.33333)
 C5BA(0.33333) H5BA(0.33333) C4BA(0.33333) H4BA(0.33333) C3BA(0.33333)
 H3BA(0.33333) C2BA(0.33333) H2BA(0.33333) C1BA(0.33333) H1BA(0.33333)
 C59(0.66667) H59(0.66667) O2(0.66667) O1(0.66667) C73(0.66667) H73A(0.66667)
 H73B(0.66667) H73C(0.66667) C72(0.66667) O9(0.33333) O10(0.33333) S2(0.33333)
 C87(0.33333) C86(0.33333) H86A(0.33333) H86B(0.33333) H86C(0.33333)
 C8(0.33333) C13(0.33333) H13(0.33333) C12(0.33333) H12(0.33333) C11(0.33333)
 H11(0.33333) C10(0.33333) H10(0.33333) C9(0.33333) H9(0.33333) C35(0.66667)
 C36(0.66667) H36(0.66667) C37(0.66667) H37(0.66667) C38(0.66667) H38(0.66667)
 C39(0.66667) H39(0.66667) C40(0.66667) H40(0.66667) C91(0.33333) H91(0.33333)
 S1(0.66667) O1AA(0.45) H1AA(0.45) C2AA(0.45) H2AA(0.45) H2AB(0.45) H2AC(0.45)
5.a Riding coordinates:
 O1AA(H1AA)
5.b Aromatic/amide H refined with riding coordinates:
 C18(H18), C23(H23), C19(H19), C3AA(H3AA), C60(H60A), C60(H60), C89(H89),
 C0AA(H0AA), C61(H61), C29(H29), C70(H70), C69(H69), C68(H68), C68(H68A),
 C67(H67), C16(H16), C64(H64), C24(H24), C46(H46), C50(H50), C25(H25), C17(H17),
  C5(H5), C5AA(H5AA), C6AA(H6AA), C7AA(H7AA), C8AA(H8AA), C9AA(H9AA), C22(H22),
 C43(H43), C49(H49), C32(H32), C2(H2), C52(H52), C51(H51), C44(H44), C45(H45),
 C5BA(H5BA), C4BA(H4BA), C3BA(H3BA), C2BA(H2BA), C1BA(H1BA), C59(H59), C13(H13),
  C12(H12), C11(H11), C10(H10), C9(H9), C36(H36), C37(H37), C38(H38), C39(H39),
 C40(H40), C91(H91)
5.c Fitted hexagon refined as free rotating group:
 C62(C3AA,C60,C89,C4AA,C0AA), C66(C70,C71,C69,C68,C67), C1AA(C5AA,C6AA,C7AA,
 C8AA,C9AA), C0BA(C5BA,C4BA,C3BA,C2BA,C1BA), C8(C13,C12,C11,C10,C9)
5.d Idealised Me refined as rotating group:
 C57(H57A,H57B,H57C), C56(H56A,H56B,H56C), C58(H58A,H58B,H58C), C55(H55A,H55B,
 H55C), C73(H73A,H73B,H73C), C86(H86A,H86B,H86C), C2AA(H2AA,H2AB,H2AC)
;
_shelx_res_checksum              14254
_shelx_hkl_checksum              47290
_olex2_submission_special_instructions 'No special instructions were received'