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_7712819
_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         'C57 H37 Ir N4 O4 S3, 1.4(C H2 Cl2)'
_chemical_formula_sum            'C58.4 H39.8 Cl2.8 Ir N4 O4 S3'
_chemical_formula_weight         1249.18
_chemical_melting_point          243.5(5)
_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   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                87.025(2)
_cell_angle_beta                 74.0030(10)
_cell_angle_gamma                77.2810(10)
_cell_formula_units_Z            2
_cell_length_a                   10.4137(4)
_cell_length_b                   15.4601(7)
_cell_length_c                   17.0359(7)
_cell_measurement_reflns_used    9915
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      26.33
_cell_measurement_theta_min      2.70
_cell_volume                     2571.71(19)
_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 2018/2 (Sheldrick, 2018)'
_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 0.985
_diffrn_measured_fraction_theta_max 0.979
_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  0.0309
_diffrn_reflns_av_unetI/netI     0.0431
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            26981
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.380
_diffrn_reflns_theta_min         2.083
_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    2.916
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5825
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1076 before and 0.0407 after correction.
The Ratio of minimum to maximum transmission is 0.7815.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.613
_exptl_crystal_description       plate
_exptl_crystal_F_000             1246
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2, CH3CN'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.072
_refine_diff_density_min         -1.035
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     700
_refine_ls_number_reflns         10302
_refine_ls_number_restraints     49
_refine_ls_restrained_S_all      2.236
_refine_ls_R_factor_all          0.0427
_refine_ls_R_factor_gt           0.0350
_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^)+(0.0253P)^2^+7.0058P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0752
_refine_ls_wR_factor_ref         0.0777
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9228
_reflns_number_total             10302
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00200d2.cif
_cod_data_source_block           st312neo
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value '243-244' was changed to
'243.5(5)' -- the average value was taken and precision was
estimated.

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        'C58.40 H39.80 Cl2.80 Ir N4 O4 S3'
_cod_database_code               7712819
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.868
_shelx_estimated_absorpt_t_min   0.475
_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
 S3-C46
 1.75 with sigma of 0.01
 O5-C68
 1.5 with sigma of 0.01
 S3-C43
 1.75 with sigma of 0.01
 S5A-C1A
 1.75 with sigma of 0.01
 C1A-C16A
 1.3 with sigma of 0.01
 C5B-C1B = C5B-C11B
 1.75 with sigma of 0.02
 C5B-C1B
 1.3 with sigma of 0.01
 S16B-C1B
 1.75 with sigma of 0.01
 C58-C60
 1.35 with sigma of 0.01
 S12-C59 = S12-C58
 1.3 with sigma of 0.02
 C14B-C11B
 1.3 with sigma of 0.01
 C68-H68C = C68-H68A = C68-H68B
 0.98 with sigma of 0.01
 C68-H68A = C68-H68B = C68-H68C
 0.98 with sigma of 0.001
 C68-H68A
 0.98 with sigma of 0.001
 C68-H68C
 0.98 with sigma of 0.001
 C68-H68B
 0.98 with sigma of 0.001
 C44-C45
 1.3 with sigma of 0.01
 C45-C46
 1.3 with sigma of 0.01
 C43-C44
 1.35 with sigma of 0.01
 S12-C59
 1.75 with sigma of 0.01
 C59-C0
 1.3 with sigma of 0.01
 S12-C58
 1.75 with sigma of 0.01
 C16A-C14A
 1.35 with sigma of 0.01
 S5A-C11A
 1.75 with sigma of 0.01
 C5B-C11B
 1.35 with sigma of 0.01
 S16B-C14B
 1.75 with sigma of 0.01
 O6-C67
 1.15 with sigma of 0.02
 S3-C45
 2.6 with sigma of 0.01
 S3-C44
 2.6 with sigma of 0.01
 C0-C58
 2.4 with sigma of 0.01
 C49-C1B \\sim C49-C50
 with sigma of 0.02
 C59-C47 \\sim C47-C66
 with sigma of 0.02
 Cl12-C9B \\sim Cl9-C9B
 with sigma of 0.02
3. Restrained planarity
 C46, C45, C44, C43, S3
 with sigma of 0.1
 S12, C0, C59, C60, C58
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(S3) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O5) = Uanis(O6) = Uanis(C67) = Uanis(C68)
Uanis(C66) = Uanis(C61) = Uanis(C65) = Uanis(C63) = Uanis(C64) = Uanis(C62)
Uanis(C59) = Uanis(C60) = Uanis(C58) = Uanis(S12)
Uanis(C50) = Uanis(C55) = Uanis(C54) = Uanis(C53) = Uanis(C52) = Uanis(C51)
Uanis(Cl12) = Uanis(C9B) = Uanis(Cl9)
Uiso(H68A) = Uiso(H68C) = Uiso(H68B)
Uanis(S12) = Uanis(C0) = Uanis(C59) = Uanis(C60) = Uanis(C58)
Uanis(C46) = Uanis(C45) = Uanis(C44) = Uanis(C43)
Uiso(C11B) = Uiso(C14B) = Uiso(C1B) = Uiso(C5B)
Uiso(C14A) = Uiso(C16A)
5. Others
 Fixed Sof: S12(0.25) C51(0.5) H51(0.5) C52(0.5) C53(0.5) H53(0.5) C54(0.5)
 H54(0.5) C55(0.5) H55(0.5) C50(0.5) C0(0.25) H0(0.25) C59(0.25) O1(0.5)
 O2(0.5) C60(0.25) H60(0.25) C56(0.5) C58(0.25) H58(0.25) S16B(0.25) C66(0.5)
 C61(0.5) H61(0.5) C65(0.5) C63(0.5) H63(0.5) C64(0.5) H64(0.5) C62(0.5)
 H62(0.5) C11B(0.25) H11B(0.25) C14B(0.25) H14B(0.25) O5(0.5) O6(0.5) C67(0.5)
 C68(0.5) H68A(0.5) H68B(0.5) H68C(0.5) C1B(0.25) C5B(0.25) H5B(0.25) Cl9(0.4)
 C57(0.5) H57A(0.5) H57B(0.5) H57C(0.5) Cl12(0.4) C9B(0.4) H9BA(0.4) H9BB(0.4)
 C46(0.25) C45(0.25) H45(0.25) C44(0.25) H44(0.25) C43(0.25) H43(0.25) S3(0.25)
 C1A(0.25) C16A(0.25) H16A(0.25) C14A(0.25) H14A(0.25) C11A(0.25) H11A(0.25)
 S5A(0.25)
 Fixed X: C1A(0.51825)
 Fixed Y: C1A(0.57154)
 Fixed Z: C1A(0.76287)
6.a Riding coordinates:
 C68(H68A,H68B,H68C)
6.b Secondary CH2 refined with riding coordinates:
 C01T(H01A,H01B), C9B(H9BA,H9BB)
6.c Aromatic/amide H refined with riding coordinates:
 C51(H51), C53(H53), C54(H54), C55(H55), C0(H0), C3(H3), C24(H24), C48(H48),
 C41(H41), C11(H11), C6(H6), C27(H27), C4(H4), C5(H5), C20(H20), C36(H36),
 C25(H25), C38(H38), C34(H34), C35(H35), C40(H40), C12(H12), C26(H26), C15(H15),
  C13(H13), C17(H17), C14(H14), C32(H32), C39(H39), C33(H33), C18(H18),
 C19(H19), C60(H60), C58(H58), C61(H61), C63(H63), C64(H64), C62(H62),
 C11B(H11B), C14B(H14B), C5B(H5B), C45(H45), C44(H44), C43(H43), C16A(H16A),
 C14A(H14A), C11A(H11A)
6.d Fitted hexagon refined as free rotating group:
 C51(C52,C53,C54,C55,C50), C66(C61,C65,C63,C64,C62)
6.e Idealised Me refined as rotating group:
 C57(H57A,H57B,H57C)
;
_shelx_res_checksum              86922
_shelx_hkl_checksum              69297
_olex2_submission_special_instructions 'No special instructions were received'