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_7712830
_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         'C61 H41 Ir N4 O4 S, 1.25(C H2 Cl2)'
_chemical_formula_sum            'C62.25 H43.5 Cl2.5 Ir N4 O4 S'
_chemical_formula_weight         1224.39
_chemical_melting_point          540
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.7713(15)
_cell_length_b                   21.0313(17)
_cell_length_c                   27.802(2)
_cell_measurement_reflns_used    9558
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      26.37
_cell_measurement_theta_min      2.34
_cell_volume                     10975.8(15)
_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      100.0
_diffrn_detector                 'Bruker PHOTON II'
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'CMOS sensor'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0639
_diffrn_reflns_av_unetI/netI     0.0155
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            356673
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.050
_diffrn_reflns_theta_max         25.050
_diffrn_reflns_theta_min         1.628
_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    2.644
_exptl_absorpt_correction_T_max  0.5633
_exptl_absorpt_correction_T_min  0.4598
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1125 before and 0.0631 after correction.
The Ratio of minimum to maximum transmission is 0.8163.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.482
_exptl_crystal_description       plate
_exptl_crystal_F_000             4900
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2, CH3OH'
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.819
_refine_diff_density_min         -1.703
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.187
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     695
_refine_ls_number_reflns         9707
_refine_ls_number_restraints     47
_refine_ls_restrained_S_all      1.192
_refine_ls_R_factor_all          0.0624
_refine_ls_R_factor_gt           0.0572
_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^)+(0.0384P)^2^+98.1588P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1348
_refine_ls_wR_factor_ref         0.1376
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8791
_reflns_number_total             9707
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00200d2.cif
_cod_data_source_block           mo_st330c_0m
_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_cell_volume        10975.6(15)
_cod_original_formula_sum        'C62.25 H43.50 Cl2.50 Ir N4 O4 S'
_cod_database_code               7712830
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.494
_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
 Cl2-C76
 1.7 with sigma of 0.02
 O5-C63
 1.18 with sigma of 0.02
 O7-C63
 1.4 with sigma of 0.02
 Cl3-C024
 1.7 with sigma of 0.01
 Cl-C024
 1.7 with sigma of 0.01
 C71-C00S
 1.3 with sigma of 0.02
 S2-C62
 1.75 with sigma of 0.02
 C01X-C00S
 1.35 with sigma of 0.02
 S2-C71
 1.7 with sigma of 0.02
 C75-Cl4
 1.7 with sigma of 0.02
 Cl5-C75
 1.7 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C61) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C77) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C75) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C024) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O5) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(Cl5) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C12) = Uanis(C17) = Uanis(C16) = Uanis(C15) = Uanis(C14) = Uanis(C13) =
Uanis(C68) = Uanis(C65) = Uanis(C66) = Uanis(C1D) = Uanis(C1C) = Uanis(C70)
Uanis(C54) = Uanis(C55) = Uanis(C56) = Uanis(C57) = Uanis(C58) = Uanis(C59)
Uanis(C50) = Uanis(C49) = Uanis(C48) = Uanis(C47)
Uanis(C74) = Uanis(C69) = Uanis(C73) = Uanis(C64) = Uanis(C72) = Uanis(C67)
Uanis(C71) = Uanis(C00S) = Uanis(C01X) = Uanis(C62)
Uanis(Cl5) = Uanis(Cl4)
4. Others
 Fixed Sof: S1(0.6) Cl3(0.5) C59(0.6) H59(0.6) C58(0.6) C57(0.6) H57(0.6)
 C56(0.6) H56(0.6) C55(0.6) H55(0.6) C54(0.6) C00S(0.4) H00S(0.4) C12(0.5)
 C17(0.5) H17(0.5) C16(0.5) H16(0.5) C15(0.5) H15(0.5) C14(0.5) H14(0.5)
 C13(0.5) H13(0.5) C50(0.6) O2(0.6) Cl(0.5) C49(0.6) H49(0.6) O1(0.6) C01X(0.4)
 H01X(0.4) C47(0.6) H47(0.6) C60(0.6) C48(0.6) H48(0.6) C024(0.5) H02A(0.5)
 H02B(0.5) C61(0.6) H61A(0.6) H61B(0.6) H61C(0.6) Cl2(0.6) Cl1(0.6) C76(0.6)
 H76A(0.6) H76B(0.6) O5(0.4) O7(0.4) C63(0.4) C69(0.4) H69(0.4) C73(0.4)
 C64(0.4) H64(0.4) C72(0.4) H72(0.4) C67(0.4) H67(0.4) C74(0.4) C77(0.4)
 H77A(0.4) H77B(0.4) H77C(0.4) S2(0.4) C71(0.4) C62(0.4) H62(0.4) C68(0.5)
 C65(0.5) H65(0.5) C66(0.5) H66(0.5) C1D(0.5) H1D(0.5) C1C(0.5) H1C(0.5)
 C70(0.5) H70(0.5) Cl4(0.15) Cl5(0.15) C75(0.15) H75A(0.15) H75B(0.15)
5.a Riding coordinates:
 C61(H61A,H61B,H61C)
5.b Secondary CH2 refined with riding coordinates:
 C024(H02A,H02B), C76(H76A,H76B), C75(H75A,H75B)
5.c Aromatic/amide H refined with riding coordinates:
 C59(H59), C57(H57), C56(H56), C55(H55), C25(H25), C7(H7), C2(H2), C9(H9),
 C00S(H00S), C36(H36), C45(H45), C17(H17), C16(H16), C15(H15), C14(H14),
 C13(H13), C27(H27), C32(H32), C19(H19), C4(H4), C29(H29), C40(H40), C6(H6),
 C52(H52), C28(H28), C37(H37), C5(H5), C44(H44), C39(H39), C42(H42), C43(H43),
 C20(H20), C30(H30), C38(H38), C49(H49), C21(H21), C22(H22), C01X(H01X),
 C47(H47), C48(H48), C69(H69), C64(H64), C72(H72), C67(H67), C62(H62), C65(H65),
  C66(H66), C1D(H1D), C1C(H1C), C70(H70)
5.d Fitted hexagon refined as free rotating group:
 C59(C58,C57,C56,C55,C54), C12(C17,C16,C15,C14,C13), C69(C73,C64,C72,C67,C74),
 C68(C65,C66,C1D,C1C,C70)
5.e Idealised Me refined as rotating group:
 C77(H77A,H77B,H77C)
;
_shelx_res_checksum              47032
_shelx_hkl_checksum              52498
_olex2_submission_special_instructions 'No special instructions were received'