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_7704076
_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         'C80 H49 Ir N9 O4, F6 P, C2 H5 O0.5'
_chemical_formula_sum            'C82 H54 F6 Ir N9 O4.5 P'
_chemical_formula_weight         1574.51
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-11-03
_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                 113.642(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   30.2713(6)
_cell_length_b                   15.7377(2)
_cell_length_c                   31.0641(6)
_cell_measurement_reflns_used    52741
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.8040
_cell_measurement_theta_min      3.1050
_cell_volume                     13556.9(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_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_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -23.00  35.00   0.50    7.32    --   41.35 -80.00 -64.00  116
  2  \w     81.00 107.00   0.50   29.29    --  101.00  80.00  58.00   52
  3  \w    119.00 151.00   0.50   29.29    --  101.00  80.00  58.00   64
  4  \w     44.00 111.00   0.50   29.29    --  101.00 -80.00 -64.00  134
  5  \w    -57.00 -29.00   0.50    7.32    --  -41.35  80.00  58.00   56
  6  \w   -106.00 -33.00   0.50    7.32    --  -41.35 -32.00 -30.00  146
  7  \w    -25.00  17.00   0.50    7.32    --  -41.35  80.00  58.00   84
  8  \w     68.00  97.00   0.50    7.32    --   41.35  43.00 -30.00   58
  9  \w     18.00  59.00   0.50    7.32    --   41.35 -54.00 -30.00   82
 10  \w     23.00  62.00   0.50    7.32    --   41.35 -65.00  60.00   78
 11  \w     77.00 102.00   0.50    7.32    --   41.35  21.00 -30.00   50
 12  \w     14.00  60.00   0.50    7.32    --   41.35-138.00  30.00   92
 13  \w     16.00  50.00   0.50    7.32    --   41.35 -32.00 120.00   68
 14  \w    -32.00  65.00   0.50    7.32    --   41.35 -11.00 150.00  194
 15  \w     40.00  65.00   0.50    7.32    --   41.35  43.00 150.00   50
 16  \w    -22.00  13.00   0.50    7.32    --   41.35 -54.00 -30.00   70
 17  \w     57.00  83.00   0.50    7.32    --   41.35  32.00 -90.00   52
 18  \w     39.00  64.00   0.50    7.32    --   41.35  21.00 -30.00   50
 19  \w    -17.00  12.00   0.50    7.32    --   41.35 -32.00 120.00   58
 20  \w     37.00  62.00   0.50    7.32    --   41.35  43.00 -30.00   50
 21  \w    -16.00   9.00   0.50    7.32    --   41.35 -65.00  60.00   50
 22  \w     39.00  73.00   0.50   29.29    --  101.00 -42.00-150.00   68
 23  \w     92.00 157.00   0.50   29.29    --  101.00  33.00  90.00  130
 24  \w    130.00 157.00   0.50   29.29    --  101.00  77.00 -30.00   54
 25  \w     64.00 104.00   0.50   29.29    --  101.00 -25.00  60.00   80
 26  \w     33.00  59.00   0.50   29.29    --  101.00 -25.00  60.00   52
 27  \w     77.00 102.00   0.50   29.29    --  101.00  77.00 -30.00   50
 28  \w     38.00 124.00   0.50   29.29    --  101.00-133.00 -60.00  172
 29  \w     88.00 156.00   0.50   29.29    --  101.00  42.00   0.00  136
 30  \w     86.00 126.00   0.50   29.29    --  101.00  93.00-180.00   80
 31  \w    102.00 127.00   0.50   29.29    --  101.00  33.00   0.00   50
 32  \w     73.00 122.00   0.50   29.29    --  101.00 -68.00 -30.00   98
 33  \w     41.00  66.00   0.50   29.29    --  101.00 -42.00  90.00   50
 34  \w     80.00 105.00   0.50   29.29    --  101.00 -42.00  90.00   50
 35  \w     95.00 157.00   0.50   29.29    --  101.00  77.00  90.00  124
 36  \w    117.00 155.00   0.50   29.29    --  101.00  50.00  30.00   76
 37  \w    110.00 154.00   0.50   29.29    --  101.00  17.00-180.00   88
 38  \w    119.00 145.00   0.50   29.29    --  101.00  25.00  30.00   52
 39  \w     38.00 117.00   0.50   29.29    --  101.00 -50.00 -60.00  158
 40  \w     71.00  96.00   0.50   29.29    --  101.00 -59.00 -90.00   50
 41  \w     39.00  92.00   0.50   29.29    --  101.00 -42.00-120.00  106
 42  \w     90.00 120.00   0.50   29.29    --  101.00  68.00  30.00   60
 43  \w     79.00 136.00   0.50   29.29    --  101.00   8.00-180.00  114
 44  \w     85.00 110.00   0.50   29.29    --  101.00  50.00  90.00   50
 45  \w     89.00 114.00   0.50   29.29    --  101.00 -42.00-150.00   50
 46  \w     86.00 111.00   0.50   29.29    --  101.00  50.00  30.00   50
 47  \w    -66.00 -41.00   0.50    7.32    --  -41.35  80.00  58.00   50
 48  \w   -104.00 -29.00   0.50    7.32    --  -41.35 -43.00 150.00  150
 49  \w    -55.00 -24.00   0.50    7.32    --  -41.35  54.00  30.00   62
 50  \w    -71.00 -40.00   0.50    7.32    --  -41.35 -65.00-120.00   62
 51  \w    -23.00   3.00   0.50    7.32    --  -41.35  54.00  30.00   52
 52  \w    -73.00 -47.00   0.50    7.32    --  -41.35 -32.00 -60.00   52
 53  \w     42.00  68.00   0.50    7.32    --   41.35  32.00-150.00   52
 54  \w     74.00 105.00   0.50    7.32    --   41.35  32.00 150.00   62
 55  \w     54.00 102.00   0.50    7.32    --   41.35  54.00-150.00   96
 56  \w     38.00  64.00   0.50    7.32    --   41.35  32.00 150.00   52
 57  \w     79.00 105.00   0.50    7.32    --   41.35  32.00-150.00   52
 58  \w     31.00  58.00   0.50   29.29    --  101.00  -8.00  30.00   54
 59  \w    127.00 156.00   0.50   29.29    --  101.00  33.00-180.00   58
 60  \w     38.00  82.00   0.50   29.29    --  101.00 -59.00-180.00   88
 61  \w     74.00 105.00   0.50   29.29    --  101.00 -50.00  60.00   62
 62  \w     95.00 120.00   0.50   29.29    --  101.00  33.00 120.00   50
 63  \w     95.00 121.00   0.50   29.29    --  101.00  33.00-180.00   52
 64  \w     77.00 115.00   0.50   29.29    --  101.00-111.00 -60.00   76
 65  \w     78.00 103.00   0.50   29.29    --  101.00-111.00  60.00   50
 66  \w    123.00 155.00   0.50   29.29    --  101.00 111.00 150.00   64
 67  \w     88.00 113.00   0.50   29.29    --  101.00 111.00-180.00   50
 68  \w     86.00 134.00   0.50   29.29    --  101.00  50.00-180.00   96
 69  \w     49.00  75.00   0.50   29.29    --  101.00 -93.00 -60.00   52
 70  \w     67.00  93.00   0.50   29.29    --  101.00 -50.00 -30.00   52
 71  \w    128.00 154.00   0.50   29.29    --  101.00  33.00 120.00   52
 72  \w     86.00 116.00   0.50   29.29    --  101.00  50.00-150.00   60
 73  \w     38.00  64.00   0.50   29.29    --  101.00-111.00  60.00   52
 74  \w     35.00  74.00   0.50   29.29    --  101.00-111.00 -60.00   78
 75  \w     62.00 106.00   0.50   29.29    --  101.00 -17.00-120.00   88
 76  \w     86.00 112.00   0.50   29.29    --  101.00 -59.00-180.00   52
 77  \w     38.00  70.00   0.50   29.29    --  101.00-133.00  60.00   64
 78  \w     83.00 109.00   0.50   29.29    --  101.00  59.00-180.00   52
 79  \w     31.00  57.00   0.50   29.29    --  101.00 -17.00-120.00   52
 80  \w     95.00 121.00   0.50   29.29    --  101.00  33.00 150.00   52
 81  \w     85.00 110.00   0.50   29.29    --  101.00 -33.00   0.00   50
 82  \w     94.00 121.00   0.50   29.29    --  101.00-133.00  60.00   54
 83  \w     40.00  69.00   0.50   29.29    --  101.00 -33.00   0.00   58
 84  \w     51.00  77.00   0.50   29.29    --  101.00 -33.00-120.00   52
 85  \w     85.00 110.00   0.50   29.29    --  101.00 -33.00-120.00   50
 86  \w     82.00 130.00   0.50   29.29    --  101.00  -8.00  30.00   96
 87  \w    118.00 152.00   0.50   29.29    --  101.00 111.00-180.00   68
 88  \w     94.00 155.00   0.50   29.29    --  101.00  68.00-150.00  122
 89  \w    121.00 147.00   0.50   29.29    --  101.00  33.00 -30.00   52
 90  \w     55.00  81.00   0.50   29.29    --  101.00 -87.00 -30.00   52
 91  \w     93.00 119.00   0.50   29.29    --  101.00 -87.00 -30.00   52
 92  \w     85.00 110.00   0.50   29.29    --  101.00  59.00 150.00   50
 93  \w    122.00 147.00   0.50   29.29    --  101.00 111.00 120.00   50
 94  \w    122.00 153.00   0.50   29.29    --  101.00  77.00-180.00   62
 95  \w     77.00 103.00   0.50   29.29    --  101.00-111.00 -30.00   52
 96  \w     78.00 104.00   0.50   29.29    --  101.00  77.00-180.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0214219000
_diffrn_orient_matrix_UB_12      0.0840785000
_diffrn_orient_matrix_UB_13      0.0250773000
_diffrn_orient_matrix_UB_21      -0.0331601000
_diffrn_orient_matrix_UB_22      -0.0045411000
_diffrn_orient_matrix_UB_23      0.0267990000
_diffrn_orient_matrix_UB_31      0.0391265000
_diffrn_orient_matrix_UB_32      -0.0498860000
_diffrn_orient_matrix_UB_33      0.0397737000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0
_diffrn_reflns_av_unetI/netI     0.0192
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_number            12833
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.998
_diffrn_reflns_theta_min         3.187
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.697
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89640
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'translucent orange'
_exptl_crystal_density_diffrn    1.543
_exptl_crystal_description       prism
_exptl_crystal_F_000             6328
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_platon_squeeze_details
;
The unit cell contains disordered acetonitrile
molecules which have been treated
as a diffuse contribution to the overall scattering
without specific atom positions by SQUEEZE/PLATON:
total Potential Solvent Accessible Void Vol is 779 Ang^3
and electron Count Voids / Cell =    94
that is approximately equal to 0.5 acetonitrile molecules
per formula unit.
;
_refine_diff_density_max         1.044
_refine_diff_density_min         -0.976
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     939
_refine_ls_number_reflns         12833
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0287
_refine_ls_R_factor_gt           0.0266
_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^)+(0.0363P)^2^+31.8283P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0679
_refine_ls_wR_factor_ref         0.0691
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12011
_reflns_number_total             12833
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt00568a2.cif
_cod_data_source_block           Compound_6_7093-9151-kkm3_sq
_cod_depositor_comments
'Adding full bibliography for 7704075--7704080.cif.'
_cod_original_formula_sum        'C82 H54 F6 Ir N9 O4.50 P'
_cod_database_code               7704076
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.39
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C82-C81 = C81-C82A
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C82A) = Uanis(C82)
4. Others
 Sof(H81C)=Sof(H81D)=Sof(C82A)=Sof(H82D)=Sof(H82E)=Sof(H82F)=1-FVAR(1)
 Sof(H81A)=Sof(H81B)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C81(H81C,H81D), C81(H81A,H81B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13),
 C16(H16), C17(H17), C18(H18), C19(H19), C22(H22), C23(H23), C24(H24), C25(H25),
  C29(H29), C31(H31), C32(H32), C36(H36), C37(H37), C38(H38), C39(H39),
 C40(H40), C43(H43), C44(H44), C45(H45), C46(H46), C49(H49), C50(H50), C51(H51),
  C52(H52), C55(H55), C56(H56), C57(H57), C58(H58), C62(H62), C63(H63),
 C64(H64), C65(H65), C66(H66), C69(H69), C70(H70), C71(H71), C72(H72), C75(H75),
  C76(H76), C77(H77), C78(H78)
5.c Idealised Me refined as rotating group:
 C82(H82A,H82B,H82C), C82A(H82D,H82E,H82F)
;
_shelx_res_checksum              46306
_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 3.473
_oxdiff_exptl_absorpt_empirical_full_min 0.792