Rational design of efficient photosensitizers based on cyclometalated iridium(III) complexes with 2-arylbenzimidazole and aromatic 1,3-diketone ligands
Tatarin, Sergei V.; Meshcheriakova, Elizaveta A.; Kozyukhin, Sergey; Emets, Victor; Bezzubov, Stanislav; Dalton Transactions  (2023) –; doi:10.1039/D3DT02789A

data_7714143
_publ_section_title
;
 Rational design of efficient photosensitizers based on cyclometalated
 iridium(III) complexes with 2-arylbenzimidazole and aromatic 1,3-diketone
 ligands
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02789A
_journal_year                    2023
_chemical_formula_moiety
'C55 H35 F6 Ir N4 O4 S, 0.5(C H2 Cl2), 0.5(C H4 O)'
_chemical_formula_sum            'C56 H38 Cl F6 Ir N4 O4.5 S'
_chemical_formula_weight         1212.61
_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
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-08-27
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-08-27 deposited with the CCDC.	2023-10-06 downloaded from the CCDC.
;
_cell_angle_alpha                91.2080(10)
_cell_angle_beta                 96.2940(10)
_cell_angle_gamma                100.4940(10)
_cell_formula_units_Z            2
_cell_length_a                   11.6380(3)
_cell_length_b                   12.0786(4)
_cell_length_c                   18.5157(5)
_cell_measurement_reflns_used    9811
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      26.36
_cell_measurement_theta_min      2.22
_cell_volume                     2541.56(13)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_collection       'APEX3 v.2017.3_0 (Bruker AXS, 2017)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       \w-scan
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0272
_diffrn_reflns_av_unetI/netI     0.0217
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            53682
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.387
_diffrn_reflns_theta_min         1.995
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_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    2.794
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6588
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0574 before and 0.0407 after correction.
The Ratio of minimum to maximum transmission is 0.8838.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.585
_exptl_crystal_description       plate
_exptl_crystal_F_000             1204
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.02
_refine_diff_density_max         2.159
_refine_diff_density_min         -1.420
_refine_diff_density_rms         0.137
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.154
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         10384
_refine_ls_number_restraints     61
_refine_ls_restrained_S_all      1.171
_refine_ls_R_factor_all          0.0477
_refine_ls_R_factor_gt           0.0450
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0511P)^2^+12.4310P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1164
_refine_ls_wR_factor_ref         0.1179
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9851
_reflns_number_total             10384
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02789a2.cif
_cod_data_source_block           st316
_cod_original_formula_sum        'C56 H38 Cl F6 Ir N4 O4.50 S'
_cod_database_code               7714143
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.946
_shelx_estimated_absorpt_t_min   0.730
_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
 C66-O5
 1.4 with sigma of 0.02
 Cl5A-C9B \\sim Cl2B-C9B
 with sigma of 0.02
 N4-C29 \\sim N4-C61
 with sigma of 0.02
 C48-C49 \\sim C65-C49
 with sigma of 0.02
 F0-C24 \\sim F3-C24 \\sim F4-C24 \\sim F1-C24 \\sim F2-C24 \\sim F5-C24
 with sigma of 0.02
 F1-C24 \\sim F4-C24 \\sim F3-C24 \\sim F0-C24 \\sim F5-C24 \\sim F2-C24
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl5A) \\sim Ueq, Uanis(C9B) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C41) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(O1) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(F0) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(Cl5A) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C55) = Uanis(C54)
Uanis(O2) = Uanis(C41) = Uanis(O1)
Uanis(C29) = Uanis(C34) = Uanis(C33) = Uanis(C32) = Uanis(C31) = Uanis(C30) =
Uanis(C57) = Uanis(C62) = Uanis(C61) = Uanis(C64) = Uanis(C60) = Uanis(C58)
Uanis(F00D) = Uanis(F27) = Uanis(F00N) = Uanis(F14) = Uanis(F007) = Uanis(F25)
Uanis(C47) = Uanis(C48) = Uanis(C46) = Uanis(C45) = Uanis(C44) = Uanis(C43) =
Uanis(C56) = Uanis(C67) = Uanis(C3B) = Uanis(C59) = Uanis(C65) = Uanis(C63)
Uanis(O1) = Uanis(C42) = Uanis(O2) = Uanis(C41)
Uanis(F2) = Uanis(F1) = Uanis(F0) = Uanis(F3) = Uanis(F4) = Uanis(F5)
4. Others
 Fixed Sof: F2(0.4) F007(0.5) F1(0.4) F0(0.6) F00D(0.5) F00N(0.5) C47(0.3)
 H47(0.3) C48(0.3) C46(0.3) H46(0.3) C45(0.3) H45(0.3) C44(0.3) H44(0.3)
 C43(0.3) C56(0.7) C67(0.7) H67(0.7) C3B(0.7) H3B(0.7) C59(0.7) H59(0.7)
 C65(0.7) C63(0.7) H63(0.7) C29(0.5) C34(0.5) H34(0.5) C33(0.5) H33(0.5)
 C32(0.5) H32(0.5) C31(0.5) H31(0.5) C30(0.5) H30(0.5) C57(0.5) H57(0.5)
 C62(0.5) H62(0.5) C61(0.5) C64(0.5) H64(0.5) C60(0.5) H60(0.5) C58(0.5)
 H58(0.5) F14(0.5) F25(0.5) F27(0.5) Cl2B(0.5) C9B(0.5) H9BA(0.5) H9BB(0.5)
 Cl5A(0.5) O5(0.5) H5A(0.5) C66(0.5) H66A(0.5) H66B(0.5) H66C(0.5) F3(0.4)
 F4(0.6) F5(0.6)
 Fixed X: O5(-0.12621)
 Fixed Y: O5(-0.27383)
 Fixed Z: O5(0.25608)
5.a Secondary CH2 refined with riding coordinates:
 C9B(H9BA,H9BB)
5.b Aromatic/amide H refined with riding coordinates:
 C47(H47), C46(H46), C45(H45), C44(H44), C67(H67), C3B(H3B), C59(H59),
 C63(H63), C36(H36), C26(H26), C25(H25), C34(H34), C33(H33), C32(H32), C31(H31),
  C30(H30), C39(H39), C14(H14), C2(H2), C53(H53), C22(H22), C50(H50), C16(H16),
 C19(H19), C5(H5), C13(H13), C37(H37), C18(H18), C17(H17), C54(H54), C10(H10),
 C6(H6), C38(H38), C12(H12), C11(H11), C55(H55), C57(H57), C62(H62), C64(H64),
 C60(H60), C58(H58)
5.c Fitted hexagon refined as free rotating group:
 C47(C48,C46,C45,C44,C43), C56(C67,C3B,C59,C65,C63), C29(C34,C33,C32,C31,C30),
 C57(C62,C61,C64,C60,C58)
5.d Idealised Me refined as rotating group:
 C41(H41A,H41B,H41C), C66(H66A,H66B,H66C)
5.e Idealised tetrahedral OH refined as rotating group:
 O5(H5A)
;
_shelx_res_checksum              77883
_olex2_submission_special_instructions 'No special instructions were received'