Sterically hindered phenanthroimidazole ligands drive the structural flexibility and facile ligand exchange in cyclometalated iridium(III) complexes.
Tatarin, Sergei V.; Kalle, Paulina; Taydakov, Ilya V.; Varaksina, Evgenia A.; Korshunov, Vladislav M.; Bezzubov, Stanislav I.; Dalton transactions (Cambridge, England : 2003) 50 (2021) 6889–6900; doi:10.1039/d1dt00820j

data_7707211
_publ_section_title
;
 Sterically hindered phenanthroimidazole ligands drive the structural
 flexibility and facile ligand exchange in cyclometalated iridium(III)
 complexes.
;
_journal_issue                   20
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              6889
_journal_page_last               6900
_journal_paper_doi               10.1039/d1dt00820j
_journal_volume                  50
_journal_year                    2021
_chemical_formula_moiety         'C69 H45 Ir N4 O4 S, 0.65(C2 H3 N)'
_chemical_formula_sum            'C70.3 H46.95 Ir N4.65 O4 S'
_chemical_formula_weight         1245.03
_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             2020-12-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2020-12-23 deposited with the CCDC.	2021-04-27 downloaded from the CCDC.
;
_cell_angle_alpha                84.9820(10)
_cell_angle_beta                 68.2350(10)
_cell_angle_gamma                77.2280(10)
_cell_formula_units_Z            4
_cell_length_a                   15.7615(4)
_cell_length_b                   19.7594(6)
_cell_length_c                   21.2004(6)
_cell_measurement_reflns_used    9792
_cell_measurement_temperature    150
_cell_measurement_theta_max      30.48
_cell_measurement_theta_min      2.29
_cell_volume                     5980.1(3)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_collection       'APEX3 v.2017.3_0 (Bruker AXS, 2017)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker SMART CCD area detector'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX II'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0303
_diffrn_reflns_av_unetI/netI     0.0501
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            50466
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.049
_diffrn_reflns_theta_max         25.049
_diffrn_reflns_theta_min         2.114
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_type              'X-ray tube'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.320
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.5592
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0829 before and 0.0448 after correction.
The Ratio of minimum to maximum transmission is 0.7495.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.383
_exptl_crystal_description       plate
_exptl_crystal_F_000             2505
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2, CH3CN'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.262
_refine_diff_density_min         -1.514
_refine_diff_density_rms         0.142
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1426
_refine_ls_number_reflns         21080
_refine_ls_number_restraints     123
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0727
_refine_ls_R_factor_gt           0.0528
_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^)+(0.1050P)^2^+6.8733P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1554
_refine_ls_wR_factor_ref         0.1676
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15910
_reflns_number_total             21080
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt00820j2.cif
_cod_data_source_block           st35_2
_cod_depositor_comments
'Adding full bibliography for 7707205--7707218.cif.'
_cod_original_formula_sum        'C70.30 H46.95 Ir N4.65 O4 S'
_cod_database_code               7707211
_shelx_shelxl_version_number     2018/3
_computing.bruker_data_scaling   'SADABS V2012/1 (Bruker AXS Inc.)'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C92-C91
 1.5 with sigma of 0.02
 C68-O0B
 1.2 with sigma of 0.01
 O35-C92
 1.2 with sigma of 0.02
 O2-C68
 1.4 with sigma of 0.01
 O5-C104
 1.45 with sigma of 0.02
 C92-O14
 1.35 with sigma of 0.02
 C103-O5
 1.35 with sigma of 0.02
 C89-C71 = C88-C72
 1.4 with sigma of 0.02
 C102-O14
 1.45 with sigma of 0.02
 S2-C80 = S2-C19A
 1.7 with sigma of 0.02
 O6-C103
 1.2 with sigma of 0.02
 O1-C3B
 1.2 with sigma of 0.02
 C3B-O1
 1.2 with sigma of 0.01
 C3B-O3A
 1.35 with sigma of 0.02
 O2-C69
 1.45 with sigma of 0.02
 C110-C109
 1.53 with sigma of 0.02
 N108-C109
 1.1 with sigma of 0.02
 N111-C108
 1.1 with sigma of 0.02
 C112-C108
 1.5 with sigma of 0.02
 C103-C104
 2.349 with sigma of 0.04
 C68-C67 \\sim C3B-C67
 with sigma of 0.02
 S0-C88 \\sim S0-C89
 with sigma of 0.02
 C02N-C01W \\sim C76-C02N \\sim C76-C73 \\sim C79-C73 \\sim C79-C03B \\sim
C03B-C01W
 with sigma of 0.02
 C84-C1I \\sim C84-C1F \\sim C1F-C1D \\sim C1E-C1D \\sim C1G-C1E \\sim C1I-C1G
 with sigma of 0.02
 C85-C83 \\sim C87-C85 \\sim C87-C86 \\sim C86-C84 \\sim C84-C82 \\sim C83-C82
 with sigma of 0.02
 C97-C035 \\sim C80-C035
 with sigma of 0.02
3. Restrained planarity
 C69, O2, O1, C3B, C67
 with sigma of 0.1
 C101, C70, O5, O6, C104, C103, C19B
 with sigma of 0.1
 C68, O0B, O2, C69, C67
 with sigma of 0.1
 C90, C91, C1L, C92, O14, O35
 with sigma of 0.1
 C1I, C84, C1F, C1D, C1E, C1G
 with sigma of 0.1
 C82, C86, C87, C85, C83, C84
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C1G \\sim C1I \\sim C1F \\sim C1D \\sim C1E: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C93 \\sim C94 \\sim N31: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(O0B) = Uanis(C81) = Uanis(C3B) = Uanis(O2) = Uanis(O1) = Uanis(C68) =
Uanis(O3A) = Uanis(C69)
Uanis(C67) = Uanis(C68) = Uanis(C3B)
Uanis(C19B) = Uanis(C99) = Uanis(C98) = Uanis(C70) = Uanis(O5) = Uanis(O6) =
Uanis(C104) = Uanis(C103) = Uanis(C97) = Uanis(C101)
Uiso(O35) = Uiso(C1J) = Uiso(C1K) = Uiso(C1L) = Uiso(C91) = Uiso(C92) =
Uiso(O14) = Uiso(C102) = Uiso(C1H) = Uiso(C90)
Uanis(C75) = Uanis(C0) = Uanis(C100) = Uanis(C77) = Uanis(C1C) = Uanis(C74) =
Uanis(C1B) = Uanis(C107)
Uanis(C79) = Uanis(C73) = Uanis(C76)
Uanis(C80) = Uanis(C1M) = Uanis(C1N) = Uanis(C19A)
Uanis(C89) = Uanis(C71) = Uanis(C72) = Uanis(C88)
Uanis(C84) = Uanis(C1F) = Uanis(C86)
Uanis(C35) = Uanis(C36) = Uanis(C37) = Uanis(C38) = Uanis(C39) = Uanis(C40)
Uanis(C66) = Uanis(C67) = Uanis(C65) = Uanis(C64) = Uanis(C63) = Uanis(C62)
5. Others
 Fixed Sof: C19B(0.5) H19B(0.5) C99(0.5) H99(0.5) C98(0.5) H98(0.5) C97(0.5)
 C101(0.5) H101(0.5) C70(0.5) S0(0.5) N0(0.65) H03B(0.66667) H03A(0.33333)
 C100(0.5) H100(0.5) C75(0.5) C78(0.5) C1A(0.5) H1A(0.5) C1B(0.5) H1B(0.5)
 C1C(0.5) H1C(0.5) C03F(0.66667) H03F(0.66667) C89(0.5) C71(0.5) H71(0.5)
 C105(0.5) C106(0.5) H106(0.5) C107(0.5) H107(0.5) C74(0.5) H74(0.5) C77(0.5)
 H77(0.5) C0(0.5) C03O(0.66667) H03O(0.66667) C03Q(0.66667) H03Q(0.66667)
 C82(0.65) C86(0.65) H86(0.65) C87(0.65) H87(0.65) C85(0.65) H85(0.65)
 C83(0.65) C72(0.5) H72(0.5) O0B(0.5) C88(0.5) H88(0.5) C81(0.5) H81A(0.5)
 H81B(0.5) H81C(0.5) C3B(0.5) O2(0.5) O1(0.5) C68(0.5) O3A(0.5) C69(0.5)
 H69A(0.5) H69B(0.5) H69C(0.5) H82(0.65) C73(0.33333) H73(0.33333) C76(0.33333)
 H76(0.33333) C79(0.33333) H79(0.33333) N5(0.35) C1I(0.35) H1I(0.35) C1G(0.35)
 C1E(0.35) H1E(0.35) C1D(0.35) H1D(0.35) C1F(0.35) H1F(0.35) H84(0.65)
 H84A(0.35) O35(0.5) C1H(0.5) C1J(0.5) H1J(0.5) C1K(0.5) H1K(0.5) C1L(0.5)
 H1L(0.5) C91(0.5) C90(0.5) H90(0.5) N30(0.5) N31(0.3) C94(0.3) C95(0.5)
 H95A(0.5) H95B(0.5) H95C(0.5) C96(0.5) C92(0.5) C93(0.3) H93A(0.3) H93B(0.3)
 H93C(0.3) S2(0.5) C80(0.5) C1M(0.5) H1M(0.5) C1N(0.5) H1N(0.5) C19A(0.5)
 H19A(0.5) O14(0.5) C102(0.5) H10A(0.5) H10B(0.5) H10C(0.5) O5(0.5) O6(0.5)
 C104(0.5) H10D(0.5) H10E(0.5) H10F(0.5) C103(0.5) C110(0.25) H11A(0.25)
 H11B(0.25) H11C(0.25) N108(0.25) C109(0.25) C108(0.25) C112(0.25) H11D(0.25)
 H11E(0.25) H11F(0.25) N111(0.25)
 Fixed X: C3B(0.47734) C68(0.45176)
 Fixed Y: C3B(0.00544) C68(0.0108)
 Fixed Z: C3B(0.87519) C68(0.88587)
6.a Riding coordinates:
 C69(H82)
6.b Aromatic/amide H refined with riding coordinates:
 C19B(H19B), C99(H99), C98(H98), C101(H101), C52(H52), C25(H25), C16(H16),
 C29(H29), C22(H22), C019(H019), C24(H24), C9(H9), C01F(H01F), C2(H2), C30(H30),
  C57(H57), C3(H3), C01R(H01R), C18(H18), C01T(H01T), C43(H43), C17(H17),
 C50(H50), C020(H020), C021(H021), C022(H022), C46(H46), C32(H32), C025(H025),
 C66(H66), C19(H19), C51(H51), C49(H49), C02D(H02D), C63(H63), C02G(H02G),
 C02H(H02H), C02I(H02I), C23(H23), C60(H60), C5(H5), C40(H40), C44(H44),
 C11(H11), C02Q(H02Q), C10(H10), C31(H31), C56(H56), C45(H45), C64(H64),
 C02X(H02X), C13(H13), C02Z(H02Z), C030(H030), C032(H032), C033(H033),
 C034(H034), C4(H4), C037(H037), C038(H038), C36(H36), C03B(H03B), C03B(H03A),
 C100(H100), C1A(H1A), C1B(H1B), C1C(H1C), C12(H12), C03E(H03E), C03F(H03F),
 C39(H39), C71(H71), C106(H106), C107(H107), C74(H74), C77(H77), C38(H38),
 C65(H65), C55(H55), C03O(H03O), C37(H37), C03Q(H03Q), C86(H86), C87(H87),
 C85(H85), C72(H72), C88(H88), C73(H73), C76(H76), C79(H79), C1I(H1I), C1E(H1E),
  C1D(H1D), C1F(H1F), C84(H84), C84(H84A), C1J(H1J), C1K(H1K), C1L(H1L),
 C90(H90), C1M(H1M), C1N(H1N), C19A(H19A)
6.c Fitted hexagon refined as free rotating group:
 C19B(C99,C98,C97,C101,C70), C100(C75,C78,C1A,C1B,C1C), C105(C106,C107,C74,C77,
 C0), C1I(C1G,C1E,C1D,C1F,C84), C1H(C1J,C1K,C1L,C91,C90)
6.d Idealised Me refined as rotating group:
 C81(H81A,H81B,H81C), C69(H69A,H69B,H69C), C95(H95A,H95B,H95C), C93(H93A,H93B,
 H93C), C102(H10A,H10B,H10C), C104(H10D,H10E,H10F), C110(H11A,H11B,H11C),
 C112(H11D,H11E,H11F)
;
_shelx_res_checksum              48614
_shelx_hkl_checksum              39019
_olex2_submission_special_instructions 'No special instructions were received'