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_7714142
_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         'C53 H35 Cl2 Ir N4 O4 S'
_chemical_formula_sum            'C53 H35 Cl2 Ir N4 O4 S'
_chemical_formula_weight         1087.01
_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   mixed
_atom_sites_solution_primary     dual
_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                90
_cell_angle_beta                 90.525(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.2139(5)
_cell_length_b                   24.0162(16)
_cell_length_c                   13.8114(8)
_cell_measurement_reflns_used    9974
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      25.29
_cell_measurement_theta_min      2.25
_cell_volume                     4382.8(4)
_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    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            8297
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.703
_diffrn_reflns_theta_min         1.701
_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    3.270
_exptl_absorpt_correction_T_max  0.8620
_exptl_absorpt_correction_T_min  0.7513
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0973 before and 0.0473 after correction.
The Ratio of minimum to maximum transmission is 0.8716.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.647
_exptl_crystal_description       plate
_exptl_crystal_F_000             2160
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.01
_refine_diff_density_max         3.049
_refine_diff_density_min         -2.274
_refine_diff_density_rms         0.154
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.141
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     592
_refine_ls_number_reflns         8297
_refine_ls_number_restraints     257
_refine_ls_restrained_S_all      1.211
_refine_ls_R_factor_all          0.0797
_refine_ls_R_factor_gt           0.0649
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0490P)^2^+48.5307P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1562
_refine_ls_wR_factor_ref         0.1637
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6843
_reflns_number_total             8297
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02789a2.cif
_cod_data_source_block           st319new_1_tw
_cod_database_code               7714142
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.657
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9307(12)
 0.0693(12)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 S1-C52
 1.7 with sigma of 0.02
 C40-C41
 1.45 with sigma of 0.02
 C55-O5
 1.45 with sigma of 0.02
 C40-O2
 1.4 with sigma of 0.02
 O1-C40
 1.2 with sigma of 0.02
 C52-C51
 1.35 with sigma of 0.02
 C66-C29A
 1.35 with sigma of 0.02
 C52-C53
 1.35 with sigma of 0.02
 O5-C54
 1.45 with sigma of 0.02
 O2-C39
 1.5 with sigma of 0.02
 C50-C51
 1.35 with sigma of 0.02
 O5-C55
 1.4 with sigma of 0.02
 C55-O6
 1.2 with sigma of 0.02
 O6-O5
 2.5 with sigma of 0.04
 C49-C13A
 2.4 with sigma of 0.04
 S1-C52
 2.4 with sigma of 0.001
 C55-C54
 2.4 with sigma of 0.04
 O6-C54
 2.4 with sigma of 0.04
 N2-C8 \\sim N2-C56
 with sigma of 0.02
 N4-C71 \\sim N4-C27
 with sigma of 0.02
 C9A-C47 \\sim C46-C47
 with sigma of 0.02
4. Restrained planarity
 O5, C55, O6, C67
 with sigma of 0.1
 O6, C55, O5, C54
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C56 \\sim C59 \\sim C62 \\sim C61 \\sim C57 \\sim C58: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
C71 \\sim C60 \\sim C69 \\sim C0 \\sim C65 \\sim C70: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
C30 \\sim C31 \\sim C32 \\sim C27 \\sim C28 \\sim C29: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C45) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C43)
\\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(O2) \\sim Ueq,
Uanis(O1) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C40) \\sim Ueq: with sigma of
0.05 and sigma for terminal atoms of 0.1
Uanis(C50) \\sim Ueq, Uanis(S1) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C52)
\\sim Ueq, Uanis(C51) \\sim Ueq: with sigma of 0.02 and sigma for terminal
atoms of 0.04
Uiso(C63) = Uiso(C64) = Uiso(C67) = Uiso(C13A) = Uiso(C68) = Uiso(C72) =
Uiso(O6) = Uiso(C55) = Uiso(O5) = Uiso(C54)
Uanis(C45) = Uanis(C41) = Uanis(C42) = Uanis(C43) = Uanis(C44) = Uanis(C46) =
Uanis(O2) = Uanis(O1) = Uanis(C39) = Uanis(C40)
Uanis(C50) = Uanis(C52) = Uanis(C51) = Uanis(C53) = Uanis(S1)
Uanis(C9A) = Uanis(C23A) = Uanis(C29A) = Uanis(C66) = Uanis(S22A)
6. Others
 Fixed Sof: C56(0.45) C59(0.45) H59(0.45) C62(0.45) H62(0.45) C61(0.45)
 H61(0.45) C57(0.45) H57(0.45) C58(0.45) H58(0.45) C71(0.5) C60(0.5) H60(0.5)
 C69(0.5) H69(0.5) C0(0.5) H0(0.5) C65(0.5) H65(0.5) C70(0.5) H70(0.5) C30(0.5)
 H30(0.5) C31(0.5) H31(0.5) C32(0.5) H32(0.5) C27(0.5) C28(0.5) H28(0.5)
 C29(0.5) H29(0.5) C8(0.55) C9(0.55) H9(0.55) C10(0.55) H10(0.55) C11(0.55)
 H11(0.55) C12(0.55) H12(0.55) C13(0.55) H13(0.55) C45(0.6) H45(0.6) C41(0.6)
 C42(0.6) H42(0.6) C43(0.6) H43(0.6) C44(0.6) H44(0.6) C46(0.6) O2(0.6) O1(0.6)
 C39(0.6) H39A(0.6) H39B(0.6) H39C(0.6) C40(0.6) C23A(0.4) H23A(0.4) S22A(0.4)
 C9A(0.4) C29A(0.4) H29A(0.4) C66(0.4) H66(0.4) C63(0.4) H63(0.4) C64(0.4)
 H64(0.4) C67(0.4) C13A(0.4) H13A(0.4) C68(0.4) C72(0.4) H72(0.4) C50(0.6)
 S1(0.6) C52(0.6) H52(0.6) C51(0.6) H51(0.6) O6(0.4) C55(0.4) O5(0.4) C53(0.6)
 H53(0.6) C54(0.4) H54A(0.4) H54B(0.4) H54C(0.4)
 Fixed X: C9A(0.105221) C51(-0.025512)
 Fixed Y: C9A(0.34911) C51(0.164221)
 Fixed Z: C9A(0.7586) C51(0.57307)
7.a Riding coordinates:
 C54(H54A,H54B,H54C)
7.b Aromatic/amide H refined with riding coordinates:
 C18(H18), C21(H21), C59(H59), C62(H62), C61(H61), C57(H57), C58(H58),
 C37(H37), C16(H16), C36(H36), C24(H24), C60(H60), C69(H69), C0(H0), C65(H65),
 C70(H70), C5(H5), C15(H15), C22(H22), C17(H17), C3(H3), C34(H34), C2(H2),
 C48(H48), C35(H35), C30(H30), C31(H31), C32(H32), C28(H28), C29(H29), C9(H9),
 C10(H10), C11(H11), C12(H12), C13(H13), C45(H45), C42(H42), C43(H43), C44(H44),
  C23A(H23A), C29A(H29A), C66(H66), C63(H63), C64(H64), C13A(H13A), C72(H72),
 C52(H52), C51(H51), C53(H53)
7.c Fitted hexagon refined as free rotating group:
 C56(C59,C62,C61,C57,C58), C71(C60,C69,C0,C65,C70), C30(C31,C32,C27,C28,C29),
 C8(C9,C10,C11,C12,C13), C45(C41,C42,C43,C44,C46), C63(C64,C67,C13A,C68,C72)
7.d Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C)
;
_shelx_res_checksum              56008
_olex2_submission_special_instructions 'No special instructions were received'