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_7713455
_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_common            Ir1-B
_chemical_name_systematic        Ir(phpyr)2tmd
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-03
_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                 107.520(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.090(9)
_cell_length_b                   42.98(4)
_cell_length_c                   9.476(9)
_cell_measurement_reflns_used    5844
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      25.078
_cell_measurement_theta_min      2.169
_cell_volume                     3919(6)
_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      273.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.1401
_diffrn_reflns_av_unetI/netI     0.1344
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       45
_diffrn_reflns_limit_k_min       -51
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            18526
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         0.948
_diffrn_source_current           20.0
_diffrn_source_power             0.9
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    3.449
_exptl_absorpt_correction_T_max  0.617
_exptl_absorpt_correction_T_min  0.582
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Bruker, 2005)'
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.498
_exptl_crystal_description       block
_exptl_crystal_F_000             1776
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.14
_refine_diff_density_max         3.008
_refine_diff_density_min         -2.744
_refine_diff_density_rms         0.198
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.973
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     493
_refine_ls_number_reflns         6882
_refine_ls_number_restraints     312
_refine_ls_restrained_S_all      0.979
_refine_ls_R_factor_all          0.0968
_refine_ls_R_factor_gt           0.0645
_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^)+(0.0746P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1437
_refine_ls_wR_factor_ref         0.1555
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4777
_reflns_number_total             6882
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01809a2.cif
_cod_data_source_block           2
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7713455
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.644
_shelx_estimated_absorpt_t_min   0.608
_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. Rigid bond restraints
 C15, C16
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 1
 C15, C16, C17, C18, C19, N1
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 N2, C34, C35, C36, C37, C38
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C33, C20, C34, C32, C27, C21, C26, C28, C29, C30, C31, C25, C24, C23, C22
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 O2, O1, O2, C43, C44, C45
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C42, C39, C40, C41
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C10 \\sim C9: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C2 \\sim C3 \\sim C1 \\sim C6 \\sim C5 \\sim C4: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
C15 \\sim N1 \\sim C19 \\sim C16 \\sim C17 \\sim C18: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 2A
Uanis(C36) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38)
\\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq,
Uanis(C46) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C40)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C33) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C27)
\\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C31) \\sim Ueq: with sigma of 0.008 and
sigma for terminal atoms of 0.016
Uanis(C17) \\sim Ueq, Uanis(C16) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C8) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O2) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N2) \\sim Ueq, Uanis(N1) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
4.a Aromatic/amide H refined with riding coordinates:
 C25(H25), C31(H31), C3(H3), C4(H4), C29(H29), C23(H23), C38(H38), C10(H10),
 C19(H19), C30(H30), C28(H28), C17(H17), C36(H36), C13(H13), C37(H37), C18(H18),
  C22(H22), C24(H24), C9(H9), C44(H44), C11(H11), C8(H8), C16(H16), C35(H35),
 C5(H5)
4.b Idealised Me refined as rotating group:
 C49(H49A,H49B,H49C), C39(H39A,H39B,H39C), C48(H48A,H48B,H48C), C40(H40A,H40B,
 H40C), C41(H41A,H41B,H41C), C47(H47A,H47B,H47C)
;
_olex2_submission_special_instructions 'No special instructions were received'