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_7713457
_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[CH3OH]'
_chemical_formula_sum            'C49.5 H43 F2 Ir N2 O2.5'
_chemical_formula_weight         936.06
_chemical_name_systematic        Ir(phpyr-F)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   mixed
_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                104.477(2)
_cell_angle_beta                 109.897(2)
_cell_angle_gamma                102.021(2)
_cell_formula_units_Z            4
_cell_length_a                   14.7888(19)
_cell_length_b                   18.451(2)
_cell_length_c                   18.850(2)
_cell_measurement_reflns_used    6490
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      22.787
_cell_measurement_theta_min      2.325
_cell_volume                     4433.2(9)
_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 0.991
_diffrn_measured_fraction_theta_max 0.991
_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  0.0564
_diffrn_reflns_av_unetI/netI     0.0865
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            32338
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.204
_diffrn_source_current           20.0
_diffrn_source_power             0.9
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    3.060
_exptl_absorpt_correction_T_max  0.714
_exptl_absorpt_correction_T_min  0.658
_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    1.402
_exptl_crystal_description       block
_exptl_crystal_F_000             1876
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.960
_refine_diff_density_min         -0.875
_refine_diff_density_rms         0.110
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.924
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     971
_refine_ls_number_reflns         15470
_refine_ls_number_restraints     512
_refine_ls_restrained_S_all      0.968
_refine_ls_R_factor_all          0.0918
_refine_ls_R_factor_gt           0.0481
_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^)+(0.0581P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1169
_refine_ls_wR_factor_ref         0.1291
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8677
_reflns_number_total             15470
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01809a2.cif
_cod_data_source_block           2_CCDC2
_cod_original_formula_sum        'C49.50 H43 F2 Ir N2 O2.50'
_cod_database_code               7713457
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.729
_shelx_estimated_absorpt_t_min   0.674
_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
 C91-C88 = C98-C95 = C49-C46 = C42-C39
 1.53 with sigma of 0.01
 C98-C95 = C95-C96
 1.53 with sigma of 0.02
 C96-C95 = C95-C97
 1.53 with sigma of 0.02
 C97-C95 = C95-C98
 1.53 with sigma of 0.02
 C28-C27 = C32-C31 = C31-C30 = C30-C29 = C29-C28 = C26-C25 = C22-C21 = C25-C24
 = C24-C23
 1.38 with sigma of 0.005
 C35-C34 = C36-C35 = C37-C36 = C38-C37
 1.38 with sigma of 0.005
 C11-C10 = C12-C11 = C13-C12 = C9-C8 = C7-C6 = C3-C2 = C18-C17 = C19-C18 = C17-
 C16 = C16-C15 = C4-C3 = C5-C4 = C6-C5 = C9-C10
 1.38 with sigma of 0.005
 C60-C59 = C59-C58 = C58-C57 = C61-C60 = C62-C61 = C52-C51 = C53-C52 = C54-C53
 = C56-C55 = C55-C54 = C67-C66 = C68-C67 = C66-C65 = C65-C64
 1.38 with sigma of 0.005
 C72-C71 = C73-C72 = C74-C73 = C75-C74 = C71-C70 = C80-C79 = C79-C78 = C78-C77
 = C77-C76 = C81-C80 = C84-C83 = C85-C84 = C87-C86 = C86-C85
 1.38 with sigma of 0.005
 C46-C45 = C43-C42 = C92-C91 = C95-C94
 1.51 with sigma of 0.005
 C77-C79
 2.425 with sigma of 0.04
 C96-C97
 2.65 with sigma of 0.04
 C97-C98
 2.65 with sigma of 0.04
 C98-C96
 2.65 with sigma of 0.04
 C49-C46 \\sim C48-C46 \\sim C47-C46 \\sim C42-C40 \\sim C42-C41 \\sim C42-C39
\\sim C97-C95 \\sim C96-C95
 \\sim C98-C95 \\sim C91-C90 \\sim C91-C89 \\sim C91-C88
 with sigma of 0.02
3. Rigid bond restraints
 C91, C92, O3
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C43, C42, C41, C39, C40
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C46, C47
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C57, C58, C59, C60, C61, C62
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 O4, C94, C95, C96, C98, C97
 with sigma for 1-2 distances of 0.008 and sigma for 1-3 distances of 0.016
 C89, C91
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C55, C56
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C70, C71
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C76, C77
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C81, C80
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C95 \\sim C96 \\sim C97 \\sim C98: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C95 \\sim C98 \\sim C97 \\sim C96: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C91 \\sim C90 \\sim C88 \\sim C89: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C42 \\sim C39 \\sim C40 \\sim C41: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
Uanis(C95) \\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C79)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C17) \\sim Ueq,
Uanis(C18) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C41) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C44)
\\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C98) \\sim Ueq,
Uanis(C91) \\sim Ueq, Uanis(C88) \\sim Ueq: with sigma of 0.008 and sigma for
terminal atoms of 0.016
Uanis(C96) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C93)
\\sim Ueq, Uanis(C94) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(C49) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C89)
\\sim Ueq, Uanis(C90) \\sim Ueq: with sigma of 0.003 and sigma for terminal
atoms of 0.01
Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C20) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C24) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C34) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C36) \\sim Ueq, Uanis(C35) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C59) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C61) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C74) \\sim Ueq, Uanis(C73) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C77) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C79)
\\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C81) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
5.a Riding coordinates:
 C40(H40A,H40B,H40C), C90(H90A,H90B,H90C)
5.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), C22(H22), C23(H23), C24(H24), C25(H25), C28(H28),
  C29(H29), C30(H30), C31(H31), C35(H35), C36(H36), C38(H38), C44(H44),
 C52(H52), C53(H53), C54(H54), C55(H55), C58(H58), C59(H59), C60(H60), C61(H61),
  C65(H65), C66(H66), C68(H68), C71(H71), C72(H72), C73(H73), C74(H74),
 C77(H77), C78(H78), C79(H79), C80(H80), C84(H84), C85(H85), C87(H87), C93(H93)
5.c Fitted hexagon refined as free rotating group:
 C14(C1,C2,C7,C8,C13), C21(C26,C27,C32,C33,C20), C63(C62,C57,C56,C51,C50),
 C69(C82,C81,C76,C75,C70)
5.d Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C47(H47A,H47B,H47C), C48(H48A,H48B,
 H48C), C49(H49A,H49B,H49C), C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C96(H96A,
 H96B,H96C), C97(H97A,H97B,H97C), C98(H98A,H98B,H98C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 34 electrons were 
found in a volume of 742\%A^3^ in 3 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'