Unprecedented hetero-coordinated Ir(C^N)2tmd complexes containing both five- and six-membered Ir-(C^N) rings based on phenanthrylpyridine ligands: Syntheses, crystal structures and photophysical properties
Liu, Sen; Wang, Mengyun; Hou, Tianjiao; Shen, Xuan; Dalton Transactions  (2023) –; doi:10.1039/D3DT01809A

data_7713459
_publ_section_title
;
 Unprecedented hetero-coordinated Ir(C^N)2tmd complexes containing both
 five- and six-membered Ir-(C^N) rings based on phenanthrylpyridine
 ligands: Syntheses, crystal structures and photophysical properties
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT01809A
_journal_year                    2023
_chemical_formula_moiety         '4(C51 H41 F6 Ir N2 O2), H2 O'
_chemical_formula_sum            'C204 H166 F24 Ir4 N8 O9'
_chemical_formula_weight         4098.24
_chemical_name_systematic        Ir(phpyr-CF3)2tmd
_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
_audit_creation_date             2023-06-27
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-06-27 deposited with the CCDC.	2023-07-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.6136(13)
_cell_length_b                   21.0053(16)
_cell_length_c                   24.6615(19)
_cell_measurement_reflns_used    9984
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      26.453
_cell_measurement_theta_min      2.438
_cell_volume                     8606.2(12)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0668
_diffrn_reflns_av_unetI/netI     0.0314
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            59638
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.651
_exptl_absorpt_coefficient_mu    3.173
_exptl_absorpt_correction_T_max  0.728
_exptl_absorpt_correction_T_min  0.640
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Bruker, 2005)'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.581
_exptl_crystal_description       block
_exptl_crystal_F_000             4084
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.930
_refine_diff_density_min         -0.553
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     673
_refine_ls_number_reflns         7567
_refine_ls_number_restraints     357
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0526
_refine_ls_R_factor_gt           0.0304
_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^)+(0.0442P)^2^+4.4428P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0788
_refine_ls_wR_factor_ref         0.0891
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5431
_reflns_number_total             7567
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01809a2.cif
_cod_data_source_block           61
_cod_database_code               7713459
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.742
_shelx_estimated_absorpt_t_min   0.648
_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, All O(H,H) groups
2. Restrained distances
 C20-F1 \\sim C20-F2 \\sim C20-F3
 with sigma of 0.02
 C20-F2A \\sim C20-F3A \\sim C20-F1A
 with sigma of 0.02
 C40-F4 \\sim C40-F5 \\sim C40-F6
 with sigma of 0.02
 C40-F5A \\sim C40-F4A \\sim C40-F6A
 with sigma of 0.02
 C49-C48 \\sim C49A-C48A
 with sigma of 0.02
 C50-C51 \\sim C50A-C51A
 with sigma of 0.02
 C51A-C49A \\sim C51-C49
 with sigma of 0.02
 C49-C50 \\sim C49A-C50A
 with sigma of 0.02
 C51-C48 \\sim C51A-C48A
 with sigma of 0.02
 C50A-C48A \\sim C50-C48
 with sigma of 0.02
 C49-C47 \\sim C49A-C47
 with sigma of 0.02
 C50-C47 \\sim C50A-C47
 with sigma of 0.02
 C51-C47 \\sim C51A-C47
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F4 \\sim F5 \\sim F6 \\sim C40 \\sim F5A \\sim F4A \\sim F6A: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
F1 \\sim F2 \\sim F3 \\sim C20 \\sim F2A \\sim F3A \\sim F1A: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C44 \\sim C41 \\sim C42 \\sim C43: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C51A \\sim C48A \\sim C49A \\sim C50A: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 2A
C48 \\sim C49 \\sim C50 \\sim C51: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
Uanis(O3) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 F4A, F5A, F6A, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F2A, F3A, F1A, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1, F2, F3, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F5, F4, F6, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C49, C50, C51, C48, C47
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C49A, C50A, C51A, C48A, C47
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F2A)=Sof(F3A)=Sof(F1A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(F5A)=Sof(F4A)=Sof(F6A)=1-FVAR(2)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(2)
 Sof(C50A)=Sof(H50D)=Sof(H50E)=Sof(H50F)=Sof(C51A)=Sof(H51D)=Sof(H51E)=
 Sof(H51F)=Sof(C49A)=Sof(H49D)=Sof(H49E)=Sof(H49F)=Sof(C48A)=1-FVAR(3)
 Sof(C48)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=Sof(C51)=Sof(H51A)=Sof(H51B)=
 Sof(H51C)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=FVAR(3)
 Fixed Sof: O3(0.25) H3A(0.25) H3B(0.25)
6.a Free rotating group:
 O3(H3A,H3B)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C16(H16), C17(H17), C19(H19), C23(H23), C24(H24), C25(H25), C26(H26), C29(H29),
  C30(H30), C31(H31), C32(H32), C36(H36), C37(H37), C39(H39), C46(H46)
6.c Idealised Me refined as rotating group:
 C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C49(H49A,H49B,
 H49C), C51(H51A,H51B,H51C), C50(H50A,H50B,H50C), C50A(H50D,H50E,H50F),
 C51A(H51D,H51E,H51F), C49A(H49D,H49E,H49F)
;
_olex2_submission_special_instructions 'No special instructions were received'