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_7713456
_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         'C51 H47 Ir N2 O2, 0.5[CH3OH]'
_chemical_formula_sum            'C51.5 H49 Ir N2 O2.5'
_chemical_formula_weight         928.12
_chemical_name_systematic        Ir(phpyr-CH3)2tmd
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -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                103.4490(10)
_cell_angle_beta                 106.0490(10)
_cell_angle_gamma                102.6860(10)
_cell_formula_units_Z            4
_cell_length_a                   13.0713(6)
_cell_length_b                   17.6161(7)
_cell_length_c                   21.1346(9)
_cell_measurement_reflns_used    7987
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      23.584
_cell_measurement_theta_min      2.208
_cell_volume                     4333.7(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 0.990
_diffrn_measured_fraction_theta_max 0.970
_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  0.0411
_diffrn_reflns_av_unetI/netI     0.0657
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            33515
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_min         1.359
_diffrn_source_current           20.0
_diffrn_source_power             0.9
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    3.124
_exptl_absorpt_correction_T_max  0.688
_exptl_absorpt_correction_T_min  0.632
_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    1.423
_exptl_crystal_description       block
_exptl_crystal_F_000             1876
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.646
_refine_diff_density_min         -0.505
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.926
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1056
_refine_ls_number_reflns         16513
_refine_ls_number_restraints     211
_refine_ls_restrained_S_all      0.933
_refine_ls_R_factor_all          0.0595
_refine_ls_R_factor_gt           0.0353
_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^)+(0.0283P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0662
_refine_ls_wR_factor_ref         0.0714
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11874
_reflns_number_total             16513
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01809a2.cif
_cod_data_source_block           2_CCDC1
_cod_original_formula_sum        'C51.50 H49 Ir N2 O2.50'
_cod_database_code               7713456
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.706
_shelx_estimated_absorpt_t_min   0.652
_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
 C50A-C48 = C50-C48 = C51A-C48 = C51-C48 = C49A-C48 = C49-C48
 1.53 with sigma of 0.01
 C49-C50
 2.515 with sigma of 0.01
 C50-C51
 2.515 with sigma of 0.01
 C51-C49
 2.515 with sigma of 0.01
 C50A-C49A
 2.515 with sigma of 0.01
 C51A-C50A
 2.515 with sigma of 0.01
 C49A-C51A
 2.515 with sigma of 0.01
3. Rigid bond restraints
 C61, C62
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C48 \\sim C50 \\sim C49 \\sim C51 \\sim C51A \\sim C49A \\sim C50A: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C99 \\sim C102 \\sim C100 \\sim C101: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 2A
Uanis(C50A) \\sim Ueq, Uanis(C49A) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C51)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C44) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C42)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C51A, C50A, C49A, C48
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C50, C51, C49, C48
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C51A)=Sof(H51D)=Sof(H51E)=Sof(H51F)=Sof(C49A)=Sof(H49D)=Sof(H49E)=
 Sof(H49F)=Sof(C50A)=Sof(H50D)=Sof(H50E)=Sof(H50F)=1-FVAR(1)
 Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=FVAR(1)
7.a Aromatic/amide H refined with riding coordinates:
 C23(H23), C74(H74), C19(H19), C90(H90), C80(H80), C3(H3), C70(H70), C46(H46),
 C17(H17), C81(H81), C24(H24), C25(H25), C39(H39), C68(H68), C77(H77), C16(H16),
  C97(H97), C54(H54), C87(H87), C32(H32), C75(H75), C36(H36), C12(H12),
 C88(H88), C83(H83), C60(H60), C76(H76), C57(H57), C31(H31), C55(H55), C67(H67),
  C26(H26), C63(H63), C30(H30), C4(H4), C82(H82), C62(H62), C10(H10), C29(H29),
 C11(H11), C61(H61), C5(H5), C37(H37), C9(H9), C56(H56), C6(H6)
7.b Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C93(H93A,H93B,H93C), C92(H92A,H92B,H92C), C91(H91A,H91B,
 H91C), C41(H41A,H41B,H41C), C100(H10A,H10B,H10C), C94(H94A,H94B,H94C),
 C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C71(H71A,H71B,H71C), C40(H40A,H40B,
 H40C), C101(H10D,H10E,H10F), C102(H10G,H10H,H10I), C50(H50A,H50B,H50C),
 C49(H49A,H49B,H49C), C51(H51A,H51B,H51C), C51A(H51D,H51E,H51F), C49A(H49D,H49E,
 H49F), C50A(H50D,H50E,H50F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 36 electrons were 
found in a volume of 548\%A^3^ in 4 voids per unit cell. 
This is consistent with the presence of 
1[CH3OH] per Asymmetric Unit 
which account for 36 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'