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_7713458
_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 H41 F2 Ir N2 O2, 0.5[CH3CN]'
_chemical_formula_sum            'C50 H42.5 F2 Ir N2.5 O2'
_chemical_formula_weight         940.56
_chemical_name_systematic        Ir(phpyr-F)2tmd
_space_group_crystal_system      trigonal
_space_group_IT_number           161
_space_group_name_Hall           'R 3 -2"c'
_space_group_name_H-M_alt        'R 3 c :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-06-23
_audit_creation_method
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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                120
_cell_formula_units_Z            18
_cell_length_a                   32.426(2)
_cell_length_b                   32.426(2)
_cell_length_c                   20.568(3)
_cell_measurement_reflns_used    9956
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      26.876
_cell_measurement_theta_min      2.175
_cell_volume                     18729(3)
_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 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  0.0560
_diffrn_reflns_av_unetI/netI     0.0317
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            44159
_diffrn_reflns_point_group_measured_fraction_full 0.965
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        24.991
_diffrn_reflns_theta_max         24.991
_diffrn_reflns_theta_min         1.256
_diffrn_source_current           20.0
_diffrn_source_power             0.9
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    3.260
_exptl_absorpt_correction_T_max  0.655
_exptl_absorpt_correction_T_min  0.562
_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    1.501
_exptl_crystal_description       block
_exptl_crystal_F_000             8478
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.753
_refine_diff_density_min         -1.235
_refine_diff_density_rms         0.084
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.020(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     526
_refine_ls_number_reflns         7088
_refine_ls_number_restraints     180
_refine_ls_restrained_S_all      1.121
_refine_ls_R_factor_all          0.0540
_refine_ls_R_factor_gt           0.0445
_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^)+(0.0847P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1173
_refine_ls_wR_factor_ref         0.1237
_reflns_Friedel_coverage         0.925
_reflns_Friedel_fraction_full    0.930
_reflns_Friedel_fraction_max     0.930
_reflns_number_gt                6004
_reflns_number_total             7088
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01809a2.cif
_cod_data_source_block           167
_cod_original_sg_symbol_H-M      'R 3 c'
_cod_original_formula_sum        'C50 H42.50 F2 Ir N2.50 O2'
_cod_database_code               7713458
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.677
_shelx_estimated_absorpt_t_min   0.562
_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
 C43-C42A \\sim C43-C42
 with sigma of 0.02
 C42A-C40A \\sim C42-C40
 with sigma of 0.02
 C39-C43 \\sim C39A-C43
 with sigma of 0.04
 C40-C43 \\sim C40A-C43
 with sigma of 0.04
 C42-C39 \\sim C42A-C39A
 with sigma of 0.02
 C39-C40 \\sim C39A-C40A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C39A \\sim C42A \\sim C40A \\sim C41A \\sim C43: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01 within 2A
C40 \\sim C42 \\sim C41 \\sim C39 \\sim C43: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01 within 2A
C7 \\sim C12 \\sim C11 \\sim C9 \\sim C10 \\sim C8: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 2A
Uanis(C12) \\sim Ueq, Uanis(C7) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C17) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C48) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C40A, C39A, C42A, C41A, C43
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C40A)=Sof(H40D)=Sof(H40E)=Sof(H40F)=Sof(C41A)=Sof(H41D)=Sof(H41E)=
 Sof(H41F)=Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C42A)=1-FVAR(1)
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42)=FVAR(1)
 Fixed Z: Ir1(0.530429)
6.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C11(H11), C10(H10), C9(H9), C8(H8), C13(H13),
 C16(H16), C17(H17), C19(H19), C22(H22), C23(H23), C24(H24), C25(H25), C31(H31),
  C30(H30), C29(H29), C28(H28), C35(H35), C36(H36), C38(H38), C44(H44)
6.b Fitted hexagon refined as free rotating group:
 C7(C12,C11,C10,C9,C8), C31(C30,C29,C28,C27,C32)
6.c Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C47(H47A,H47B,
 H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C40A(H40D,H40E,H40F),
 C41A(H41D,H41E,H41F), C39A(H39D,H39E,H39F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 198 electrons were 
found in a volume of 1620\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
0.5[CH3CN] per Asymmetric Unit 
which account for 198 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_submission_special_instructions 'No special instructions were received'