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_7713454
_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         'C49 H43 Ir N2 O2'
_chemical_formula_sum            'C49 H43 Ir N2 O2'
_chemical_formula_weight         884.05
_chemical_name_systematic        Ir(phpyr)2tmd
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-06-22
_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                 94.7690(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.417(2)
_cell_length_b                   11.2309(14)
_cell_length_c                   20.539(4)
_cell_measurement_reflns_used    9554
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      26.909
_cell_measurement_theta_min      2.347
_cell_volume                     4003.7(10)
_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 0.924
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0393
_diffrn_reflns_av_unetI/netI     0.0282
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.924
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            15305
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.924
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.271
_diffrn_reflns_theta_min         1.990
_diffrn_source_current           20.0
_diffrn_source_power             0.9
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    3.376
_exptl_absorpt_correction_T_max  0.713
_exptl_absorpt_correction_T_min  0.674
_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    1.467
_exptl_crystal_description       block
_exptl_crystal_F_000             1776
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.893
_refine_diff_density_min         -0.775
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     288
_refine_ls_number_reflns         4161
_refine_ls_number_restraints     88
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0285
_refine_ls_R_factor_gt           0.0234
_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^)+(0.0309P)^2^+1.0556P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0544
_refine_ls_wR_factor_ref         0.0566
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3736
_reflns_number_total             4161
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01809a2.cif
_cod_data_source_block           9
_cod_original_sg_symbol_H-M      'I 2/a'
_cod_database_code               7713454
_shelx_shelxl_version_number     2018/3
_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
2. Restrained distances
 C23-C22 \\sim C23A-C22A
 with sigma of 0.02
 C21A-C20A \\sim C21-C20
 with sigma of 0.04
 C23A-C21A \\sim C23-C21
 with sigma of 0.02
 C22A-C21A \\sim C22-C21
 with sigma of 0.04
 C23-C20 \\sim C23A-C20A
 with sigma of 0.02
 C24-C23 \\sim C24-C23A
 with sigma of 0.02
 C20-C22 \\sim C20A-C22A
 with sigma of 0.04
 C20-C24 \\sim C20A-C24
 with sigma of 0.04
 C21-C24 \\sim C21A-C24
 with sigma of 0.04
 C22-C24 \\sim C22A-C24
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C20A) \\sim Ueq, Uanis(C21A) \\sim Ueq, Uanis(C22) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C24, C23A, C20A, C21A, C22A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C24, C23, C22, C21, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21A)=Sof(H21D)=Sof(H21E)=
 Sof(H21F)=Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C23A)=1-FVAR(1)
 Sof(C23)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C20)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C9(H9), C6(H6), C25(H25), C19(H19), C4(H4), C5(H5), C16(H16),
 C12(H12), C18(H18), C10(H10), C17(H17), C11(H11)
6.b Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C20A(H20D,H20E,
 H20F), C21A(H21D,H21E,H21F), C22A(H22D,H22E,H22F)
;
_olex2_submission_special_instructions 'No special instructions were received'