Luminescent organic dyes containing a phenanthro[9,10-D]imidazole core and [Ir(N^C)(N^N)]<sup>+</sup> complexes based on the cyclometalating and diimine ligands of this type.
Solomatina, Anastasia I.; Kuznetsov, Kirill M.; Gurzhiy, Vladislav V.; Pavlovskiy, Vladimir V.; Porsev, Vitaly V.; Evarestov, Robert A.; Tunik, Sergey P.; Dalton transactions (Cambridge, England : 2003) 49 (2020) 6751–6763; doi:10.1039/d0dt00568a

data_7704080
_publ_section_title
;
 Luminescent organic dyes containing a phenanthro[9,10-D]imidazole core
 and [Ir(N^C)(N^N)]<sup>+</sup> complexes based on the cyclometalating and
 diimine ligands of this type.
;
_journal_issue                   20
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              6751
_journal_page_last               6763
_journal_paper_doi               10.1039/d0dt00568a
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety
'C52 H33 Ir N5 S2, 2.13(C4 H10 O), 0.75(C H2 Cl2), F6 P'
_chemical_formula_sum            'C61.25 H55.75 Cl1.5 F6 Ir N5 O2.12 P S2'
_chemical_formula_weight         1350.32
_space_group_crystal_system      orthorhombic
_space_group_IT_number           43
_space_group_name_Hall           'F 2 -2d'
_space_group_name_H-M_alt        'F d d 2'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2019-11-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-11-10 deposited with the CCDC.	2020-04-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   35.6730(5)
_cell_length_b                   33.4826(5)
_cell_length_c                   19.7402(2)
_cell_measurement_reflns_used    60215
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.0480
_cell_measurement_theta_min      4.4970
_cell_volume                     23578.2(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3829
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -101.00 -60.00   1.00    3.00    --  -40.38 -38.00  60.00   41
  2  \w   -108.00 -14.00   1.00    3.00    --  -40.38 -38.00 150.00   94
  3  \w   -129.00 -36.00   1.00    3.00    --  -40.38-178.00-120.00   93
  4  \w     29.00 107.00   1.00    9.00    --  113.00 -95.00  30.00   78
  5  \w     60.00 133.00   1.00    9.00    --  113.00 -77.00 150.00   73
  6  \w     62.00 141.00   1.00    9.00    --  113.00 -45.00 150.00   79
  7  \w     97.00 126.00   1.00    9.00    --  113.00  61.00  90.00   29
  8  \w    130.00 176.00   1.00    9.00    --  113.00  61.00  90.00   46
  9  \w    106.00 143.00   1.00    9.00    --  113.00  61.00 120.00   37
 10  \w     91.00 137.00   1.00    9.00    --  113.00 178.00  30.00   46
 11  \w     97.00 123.00   1.00    3.00    --   40.38 178.00 -60.00   26
 12  \w    101.00 162.00   1.00    9.00    --  113.00  45.00-150.00   61
 13  \w     42.00 140.00   1.00    9.00    --  113.00 -45.00   0.00   98
 14  \w     37.00  81.00   1.00    9.00    --  113.00-112.00-180.00   44
 15  \w    -62.00  28.00   1.00    3.00    --  -40.38  38.00 -30.00   90
 16  \w    -39.00   3.00   1.00    3.00    --  -40.38  38.00 120.00   42
 17  \w    -14.00  65.00   1.00    3.00    --   40.38 -38.00 150.00   79
 18  \w     43.00  76.00   1.00    3.00    --   40.38  38.00  60.00   33
 19  \w     25.00  51.00   1.00    3.00    --   40.38  57.00-120.00   26
 20  \w    108.00 177.00   1.00    9.00    --  113.00 112.00 120.00   69
 21  \w     38.00  64.00   1.00    9.00    --  113.00 -95.00 -90.00   26
 22  \w     38.00 103.00   1.00    9.00    --  113.00-112.00   0.00   65
 23  \w    132.00 158.00   1.00    9.00    --  113.00  30.00  90.00   26
 24  \w     89.00 126.00   1.00    9.00    --  113.00  30.00  90.00   37
 25  \w    107.00 168.00   1.00    9.00    --  113.00 -15.00  90.00   61
 26  \w     84.00 109.00   1.00    9.00    --  113.00 -95.00 -90.00   25
 27  \w     88.00 114.00   1.00    9.00    --  113.00-112.00-120.00   26
 28  \w    110.00 136.00   1.00    9.00    --  113.00 178.00 -90.00   26
 29  \w     98.00 137.00   1.00    9.00    --  113.00  45.00  30.00   39
 30  \w     85.00 112.00   1.00    9.00    --  113.00-112.00 150.00   27
 31  \w     89.00 116.00   1.00    9.00    --  113.00  61.00-120.00   27
 32  \w    141.00 167.00   1.00    9.00    --  113.00  61.00-120.00   26
 33  \w     79.00 105.00   1.00    9.00    --  113.00  77.00-120.00   26
 34  \w    107.00 154.00   1.00    9.00    --  113.00 112.00 -30.00   47
 35  \w     88.00 114.00   1.00    9.00    --  113.00-112.00-150.00   26
 36  \w     30.00  87.00   1.00    9.00    --  113.00 -15.00  90.00   57
 37  \w    136.00 161.00   1.00    9.00    --  113.00 112.00 -60.00   25
 38  \w     60.00 129.00   1.00    3.00    --   40.38 178.00-120.00   69
 39  \w     88.00 114.00   1.00    3.00    --   40.38  38.00  90.00   26
 40  \w     41.00  67.00   1.00    3.00    --   40.38  38.00  90.00   26
 41  \w     72.00 112.00   1.00    9.00    --  113.00-112.00 -30.00   40
 42  \w     87.00 113.00   1.00    9.00    --  113.00-112.00  60.00   26
 43  \w    122.00 148.00   1.00    9.00    --  113.00 112.00  90.00   26
 44  \w    130.00 178.00   1.00    9.00    --  113.00  77.00 -30.00   48
 45  \w     60.00  86.00   1.00    9.00    --  113.00 178.00-180.00   26
 46  \w    104.00 130.00   1.00    9.00    --  113.00 112.00 150.00   26
 47  \w     89.00 115.00   1.00    9.00    --  113.00-112.00-120.00   26
 48  \w     63.00 126.00   1.00    9.00    --  113.00 -77.00  30.00   63
 49  \w     98.00 123.00   1.00    9.00    --  113.00-127.00  35.15   25
 50  \w      9.00  35.00   1.00    3.00    --   40.38 -94.00 178.00   26
 51  \w     -3.00  22.00   1.00    3.00    --   36.00  92.00 -27.79   25
 52  \w      0.00  25.00   1.00    3.00    --   40.00  93.00 176.45   25
 53  \w    -93.00 -19.00   1.00    3.00    --  -40.38 -38.00-120.00   74
 54  \w   -114.00 -11.00   1.00    3.00    --  -40.38 -57.00 -30.00  103
 55  \w     12.00  37.00   1.00    3.00    --   48.00  84.00  88.76   25
 56  \w     18.00  43.00   1.00    3.00    --   52.00  80.00 -76.41   25
 57  \w     17.00  42.00   1.00    3.00    --   52.00  81.00 -12.04   25
 58  \w     18.00  43.00   1.00    3.00    --   52.00  80.00-121.18   25
 59  \w     18.00  43.00   1.00    3.00    --   52.00  80.00 172.25   25
 60  \w     22.00  47.00   1.00    3.00    --   56.00  78.00  12.56   25
 61  \w     30.00  56.00   1.00    3.00    --   64.00  77.00  39.10   26
 62  \w     31.00  57.00   1.00    3.00    --   64.00  76.00-119.68   26
 63  \w     91.00 127.00   1.00    3.00    --   64.00  77.00 -61.94   36
 64  \w    117.00 142.00   1.00    3.00    --   64.00  76.00-119.68   25
 65  \w     31.00  56.00   1.00    3.00    --   64.00  77.00 -61.94   25
 66  \w     34.00  60.00   1.00    3.00    --   68.00  77.00  78.84   26
 67  \w     35.00  62.00   1.00    3.00    --   68.00  76.00 -38.23   27
 68  \w     39.00  65.00   1.00    3.00    --   72.00  76.00  96.08   26
 69  \w    101.00 138.00   1.00    3.00    --   72.00  77.00 178.62   37
 70  \w     39.00  65.00   1.00    3.00    --   72.00  75.00 123.85   26
 71  \w     38.00  64.00   1.00    3.00    --   72.00  77.00 178.62   26
 72  \w     39.00  65.00   1.00    3.00    --   72.00  76.00 155.01   26
 73  \w     39.00  66.00   1.00    3.00    --   72.00  76.00  -3.83   27
 74  \w     40.00  65.00   1.00    3.00    --   72.00  72.00 -91.20   25
 75  \w     47.00  73.00   1.00    9.00    --   80.00  72.00 -30.29   26
 76  \w     46.00  72.00   1.00    9.00    --   80.00  77.00   4.64   26
 77  \w     47.00  74.00   1.00    9.00    --   80.00  74.00 -94.10   27
 78  \w     47.00  73.00   1.00    9.00    --   80.00  73.00  38.12   26
 79  \w     49.00  74.00   1.00    9.00    --   80.00  69.00-136.93   25
 80  \w     52.00  78.00   1.00    9.00    --   84.00  71.00-165.95   26
 81  \w     51.00  76.00   1.00    9.00    --   84.00  77.00  99.55   25
 82  \w     52.00  78.00   1.00    9.00    --   84.00  71.00 138.41   26
 83  \w     51.00  78.00   1.00    9.00    --   84.00  77.00 -88.29   27
 84  \w     57.00  82.00   1.00    9.00    --   88.00  68.00  59.66   25
 85  \w     60.00  86.00   1.00    9.00    --   92.00  70.00-125.11   26
 86  \w     58.00  84.00   1.00    9.00    --   92.00  77.00 -72.66   26
 87  \w     59.00  85.00   1.00    9.00    --   92.00  72.00 149.73   26
 88  \w     66.00 119.00   1.00    9.00    --   96.00  59.00-144.90   53
 89  \w     65.00  91.00   1.00    9.00    --   96.00  63.00  84.28   26
 90  \w     62.00  88.00   1.00    9.00    --   96.00  77.00  15.31   26
 91  \w     65.00  90.00   1.00    9.00    --   96.00  63.00 -28.33   25
 92  \w     65.00  93.00   1.00    9.00    --   96.00  67.00 109.11   28
 93  \w     64.00  90.00   1.00    9.00    --   96.00  71.00  -7.20   26
 94  \w     69.00  96.00   1.00    9.00    --  100.00  65.00 -99.88   27
 95  \w     67.00 158.00   1.00    9.00    --  100.00  76.00-153.83   91
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0240417000
_diffrn_orient_matrix_UB_12      -0.0380180500
_diffrn_orient_matrix_UB_13      -0.0081742500
_diffrn_orient_matrix_UB_21      -0.0320862000
_diffrn_orient_matrix_UB_22      0.0199878000
_diffrn_orient_matrix_UB_23      0.0395886000
_diffrn_orient_matrix_UB_31      -0.0159791000
_diffrn_orient_matrix_UB_32      0.0164898500
_diffrn_orient_matrix_UB_33      -0.0668224500
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0779
_diffrn_reflns_av_unetI/netI     0.0288
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       43
_diffrn_reflns_limit_h_min       -43
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            117136
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.995
_diffrn_reflns_theta_min         2.879
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.489
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.17929
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'translucent orange'
_exptl_crystal_density_diffrn    1.522
_exptl_crystal_description       prism
_exptl_crystal_F_000             10860
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         2.012
_refine_diff_density_min         -1.569
_refine_diff_density_rms         0.131
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -0.035(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     731
_refine_ls_number_reflns         11113
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0617
_refine_ls_R_factor_gt           0.0610
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1330P)^2^+143.1760P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1578
_refine_ls_wR_factor_ref         0.1590
_reflns_Friedel_coverage         0.926
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                10878
_reflns_number_total             11113
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt00568a2.cif
_cod_data_source_block           Compound_2_2103-7093-7020_sai_ir3
_cod_depositor_comments
'Adding full bibliography for 7704075--7704080.cif.'
_cod_original_cell_volume        23578.1(6)
_cod_original_formula_sum        'C61.25 H55.75 Cl1.50 F6 Ir N5 O2.12 P S2'
_cod_database_code               7704080
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.42
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.035(12)
 -0.035(12)
2. 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
3. Restrained distances
 O3-C62
 1.5 with sigma of 0.02
 C62-C62_$1
 2.3 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C57) = Uanis(C60)
Uanis(C63) = Uanis(C62) = Uanis(O3)
5. Others
 Fixed Sof: Cl1(0.75) Cl2(0.75) C61(0.75) H61A(0.75) H61B(0.75) O3(0.125)
 C62(0.25) H62A(0.25) H62B(0.25) C63(0.25) H63A(0.25) H63B(0.25) H63C(0.25)
6.a Everything fixed:
 H62A, H62B, H63A, H63B, H63C
6.b Secondary CH2 refined with riding coordinates:
 C58(H58A,H58B), C59(H59A,H59B), C54(H54A,H54B), C55(H55A,H55B), C61(H61A,H61B)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14),
 C15(H15), C16(H16), C17(H17), C21(H21), C22(H22), C23(H23), C24(H24), C27(H27),
  C28(H28), C29(H29), C30(H30), C34(H34), C35(H35), C36(H36), C37(H37),
 C38(H38), C41(H41), C42(H42), C43(H43), C44(H44), C47(H47), C48(H48), C49(H49),
  C50(H50)
6.d Idealised Me refined as rotating group:
 C57(H57A,H57B,H57C), C60(H60A,H60B,H60C), C53(H53A,H53B,H53C), C56(H56A,H56B,
 H56C)
;
_shelx_res_checksum              20159
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 13.064
_oxdiff_exptl_absorpt_empirical_full_min 0.228