Tailoring the π-system of benzimidazole ligands towards stable light-harvesting cyclometalated iridium(III) complexes
Tatarin, Sergei V.; Smirnov, Daniil E.; Taydakov, Ilya V.; Metlin, Mikhail T.; Emets, Victor; Bezzubov, Stanislav; Dalton Transactions  (2023) –; doi:10.1039/D3DT00200D

data_7712821
_publ_section_title
;
 Tailoring the \p-system of benzimidazole ligands towards stable
 light-harvesting cyclometalated iridium(III) complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00200D
_journal_year                    2023
_chemical_formula_moiety         'C69 H45 Ir N4 O4 S, 0.733(C2 H3 N)'
_chemical_formula_sum            'C70.47 H47.2 Ir N4.73 O4 S'
_chemical_formula_weight         1248.45
_chemical_melting_point          559
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-01-18
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2022-01-19 deposited with the CCDC.	2023-04-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.6220(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.4518(6)
_cell_length_b                   20.9908(9)
_cell_length_c                   18.0568(6)
_cell_measurement_reflns_used    9948
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      26.37
_cell_measurement_theta_min      2.35
_cell_volume                     5804.9(4)
_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      150.0
_diffrn_detector                 'Bruker PHOTON II'
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'CMOS sensor'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       '3-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       \w-scan
_diffrn_radiation_monochromator  'focusing mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0290
_diffrn_reflns_av_unetI/netI     0.0245
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            61714
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.401
_diffrn_reflns_theta_min         1.631
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'Incoatec I\mS microsource'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.391
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5493
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1088 before and 0.0450 after correction.
The Ratio of minimum to maximum transmission is 0.7369.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.429
_exptl_crystal_description       block
_exptl_crystal_F_000             2513
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2, CH3CN'
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.562
_refine_diff_density_min         -1.243
_refine_diff_density_rms         0.121
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     770
_refine_ls_number_reflns         11836
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0553
_refine_ls_R_factor_gt           0.0459
_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^)+(0.0682P)^2^+17.2880P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1281
_refine_ls_wR_factor_ref         0.1352
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10061
_reflns_number_total             11836
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00200d2.cif
_cod_data_source_block           st322_al
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 
;
_cod_original_formula_sum        'C70.47 H47.20 Ir N4.73 O4 S'
_cod_database_code               7712821
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.796
_shelx_estimated_absorpt_t_min   0.480
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N5-C77
 1.15 with sigma of 0.02
 C61-C62 \\sim C61-C82
 with sigma of 0.02
 N2-C1C \\sim N2-C16
 with sigma of 0.01
 O2-C67 \\sim O01U-C83
 with sigma of 0.04
 C66-C62 \\sim C0-C82
 with sigma of 0.02
 C66-C67 \\sim C0-C83
 with sigma of 0.02
 C65-C68 \\sim C81-C85
 with sigma of 0.04
 C62-C63 \\sim C82-C72
 with sigma of 0.02
 C62-C64 \\sim C82-C84
 with sigma of 0.04
 O2-C68 \\sim O01U-C85
 with sigma of 0.02
 O2-C69 \\sim O01U-C70
 with sigma of 0.02
 C67-C64 \\sim C83-C84
 with sigma of 0.04
 C68-C69 \\sim C85-C70
 with sigma of 0.04
 C65-C67 \\sim C81-C83
 with sigma of 0.02
 C66-C68 \\sim C0-C85
 with sigma of 0.04
 C65-C64 \\sim C81-C84
 with sigma of 0.02
 C62-C67 \\sim C82-C83
 with sigma of 0.04
 C63-C64 \\sim C72-C84
 with sigma of 0.02
 C67-C68 \\sim C83-C85
 with sigma of 0.02
 O2-O1 \\sim O01U-O0
 with sigma of 0.04
 C65-C63 \\sim C81-C72
 with sigma of 0.04
 O1-C68 \\sim O0-C85
 with sigma of 0.02
 C67-O1 \\sim C83-O0
 with sigma of 0.04
 C61-C66 \\sim C61-C0
 with sigma of 0.04
 C61-C63 \\sim C61-C72
 with sigma of 0.04
 C66-C65 \\sim C0-C81
 with sigma of 0.04
 C66-C63 \\sim C0-C72
 with sigma of 0.04
 N4-C43 \\sim N4-C74
 with sigma of 0.02
3. Restrained planarity
 C70, O01U, C85, O0, C83
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C79 \\sim C78 \\sim C1D \\sim C1C \\sim C80 \\sim C1H: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(O1) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uiso(C0) = Uiso(C82) = Uiso(C72) = Uiso(C84) = Uiso(C81) = Uiso(C83) =
Uiso(O01U) = Uiso(O0) = Uiso(C85) = Uiso(C70)
Uiso(C73) = Uiso(C1B) = Uiso(C1A) = Uiso(C76) = Uiso(C75) = Uiso(C74)
5. Others
 Fixed Sof: C43(0.66667) C48(0.66667) H48(0.66667) C47(0.66667) H47(0.66667)
 C46(0.66667) H46(0.66667) C45(0.66667) H45(0.66667) C44(0.66667) H44(0.66667)
 C16(0.6) C17(0.6) H17(0.6) C18(0.6) H18(0.6) C19(0.6) H19(0.6) C20(0.6)
 H20(0.6) C21(0.6) H21(0.6) C66(0.8) H66(0.8) C62(0.8) C63(0.8) H63(0.8)
 C64(0.8) H64(0.8) C65(0.8) H65(0.8) C67(0.8) C73(0.33333) H73(0.33333)
 C1B(0.33333) H1B(0.33333) C1A(0.33333) H1A(0.33333) C76(0.33333) H76(0.33333)
 C75(0.33333) H75(0.33333) C74(0.33333) C78(0.4) H78(0.4) C79(0.4) H79(0.4)
 C1H(0.4) H1H(0.4) C80(0.4) H80(0.4) C1C(0.4) C1D(0.4) H1D(0.4) O2(0.8)
 C025(0.4) O1(0.8) C68(0.8) C69(0.8) H69A(0.8) H69B(0.8) H69C(0.8) N02A(0.4)
 C02B(0.4) H02A(0.4) H02B(0.4) H02C(0.4) C0(0.2) H0(0.2) C82(0.2) C72(0.2)
 H72(0.2) C84(0.2) H84(0.2) C81(0.2) H81(0.2) C83(0.2) O01U(0.2) O0(0.2)
 C85(0.2) C70(0.2) H70A(0.2) H70B(0.2) H70C(0.2) N5(0.33333) C71(0.33333)
 H71A(0.33333) H71B(0.33333) H71C(0.33333) C77(0.33333)
6.a Me refined with riding coordinates:
 C69(H69A,H69B,H69C), C70(H70A,H70B,H70C)
6.b Aromatic/amide H refined with riding coordinates:
 C48(H48), C47(H47), C46(H46), C45(H45), C44(H44), C39(H39), C34(H34),
 C37(H37), C30(H30), C29(H29), C53(H53), C31(H31), C12(H12), C17(H17), C18(H18),
  C19(H19), C20(H20), C21(H21), C50(H50), C2(H2), C66(H66), C63(H63), C64(H64),
 C65(H65), C3(H3), C51(H51), C4(H4), C23(H23), C36(H36), C52(H52), C35(H35),
 C73(H73), C1B(H1B), C1A(H1A), C76(H76), C75(H75), C26(H26), C7(H7), C9(H9),
 C24(H24), C25(H25), C10(H10), C78(H78), C79(H79), C1H(H1H), C80(H80), C1D(H1D),
  C57(H57), C8(H8), C60(H60), C56(H56), C55(H55), C0(H0), C72(H72), C84(H84),
 C81(H81)
6.c Fitted hexagon refined as free rotating group:
 C43(C48,C47,C46,C45,C44), C16(C17,C18,C19,C20,C21), C66(C62,C63,C64,C65,C67),
 C73(C1B,C1A,C76,C75,C74), C78(C79,C1H,C80,C1C,C1D), C0(C82,C72,C84,C81,C83)
6.d Idealised Me refined as rotating group:
 C02B(H02A,H02B,H02C), C71(H71A,H71B,H71C)
;
_shelx_res_checksum              49225
_shelx_hkl_checksum              98965
_olex2_submission_special_instructions 'No special instructions were received'