Aromatic alkyne insertion into six-membered cyclometalated pyridine complexes of iridium: different insertion modes and structurally novel products
Chu, Xiaodan; Zhang, Shaowei; Wang, Zhuo; Li, Tongyu; Zhu, Bolin; RSC Advances 8 (2018) 7164–; doi:10.1039/C7RA13547E

data_7230167
_publ_section_title
;
 Aromatic alkyne insertion into six-membered cyclometalated pyridine
 complexes of iridium: different insertion modes and structurally novel
 products
;
_journal_issue                   13
_journal_name_full               'RSC Advances'
_journal_page_first              7164
_journal_paper_doi               10.1039/C7RA13547E
_journal_volume                  8
_journal_year                    2018
_chemical_formula_moiety         'C30 H27 F Ir N O'
_chemical_formula_sum            'C30 H27 F Ir N O'
_chemical_formula_weight         628.72
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-01-18
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-01-26 deposited with the CCDC.
2018-02-07 downloaded from the CCDC.
;
_cell_angle_alpha                82.995(2)
_cell_angle_beta                 79.253(3)
_cell_angle_gamma                89.665(2)
_cell_formula_units_Z            8
_cell_length_a                   13.1460(4)
_cell_length_b                   14.8634(4)
_cell_length_c                   27.0887(9)
_cell_measurement_reflns_used    14250
_cell_measurement_temperature    157.39(15)
_cell_measurement_theta_max      74.0320
_cell_measurement_theta_min      4.0850
_cell_volume                     5160.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (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      157.39(15)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2740
_diffrn_detector_type            AtlasS2
_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   -115.00 -16.00   1.00    2.41    --  -40.99 -38.00 150.00   99
  2  \w    -66.00  33.00   1.00    2.41    --  -40.99  38.00 -30.00   99
  3  \w    -69.00  32.00   1.00    2.41    --  -40.99  57.00  90.00  101
  4  \w     23.00  97.00   1.00    2.41    --   40.99-125.00 -30.00   74
  5  \w      8.00 117.00   1.00    2.41    --   40.99  77.00-180.00  109
  6  \w      1.00  82.00   1.00    2.41    --   40.99 -99.00  60.00   81
  7  \w    101.00 178.00   1.00    9.64    --  107.08 103.00-138.00   77
  8  \w     25.00 109.00   1.00    9.64    --  107.08 -95.00-150.00   84
  9  \w     31.00 135.00   1.00    9.64    --  107.08 -30.00 150.00  104
 10  \w     34.00 121.00   1.00    9.64    --  107.08-125.00 150.00   87
 11  \w     35.00 136.00   1.00    9.64    --  107.08 -61.00-120.00  101
 12  \w     81.00 178.00   1.00    9.64    --  107.08  45.00 -30.00   97
 13  \w     25.00 109.00   1.00    9.64    --  107.08 -95.00 -60.00   84
 14  \w     94.00 178.00   1.00    9.64    --  107.08 125.00-120.00   84
 15  \w     54.00 178.00   1.00    9.64    --  107.08  15.00  90.00  124
 16  \w     34.00 133.00   1.00    9.64    --  107.08 -45.00 -60.00   99
 17  \w     94.00 178.00   1.00    9.64    --  107.08 125.00 -90.00   84
 18  \w     25.00 109.00   1.00    9.64    --  107.08 -95.00 -30.00   84
 19  \w     31.00 140.00   1.00    9.64    --  107.08 -77.00 -60.00  109
 20  \w      8.00 117.00   1.00    2.41    --   40.99  77.00 -30.00  109
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0439205000
_diffrn_orient_matrix_UB_12      0.0143878000
_diffrn_orient_matrix_UB_13      0.0552491000
_diffrn_orient_matrix_UB_21      -0.1106442000
_diffrn_orient_matrix_UB_22      -0.0148980000
_diffrn_orient_matrix_UB_23      -0.0090012000
_diffrn_orient_matrix_UB_31      0.0078193000
_diffrn_orient_matrix_UB_32      -0.1023692000
_diffrn_orient_matrix_UB_33      0.0163966000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0947
_diffrn_reflns_av_unetI/netI     0.1020
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            54928
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.077
_diffrn_reflns_theta_max         67.077
_diffrn_reflns_theta_min         3.517
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.245
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41406
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.618
_exptl_crystal_description       block
_exptl_crystal_F_000             2464
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_platon_squeeze_details
;
TITL A160711a  P -1         R = 0.09
CELL   13.1460   14.8634   27.0887     83.00     79.25     89.67
SPGR P-1
Q101 0.091 0.795 0.360 !       8.21 eA-3
Q102 0.060 0.768 0.433 !       8.15 eA-3
Q103 0.521 0.296 0.359 !       7.93 eA-3
Q104 0.490 0.270 0.432 !       7.55 eA-3
Q105 0.237 0.160 0.141 !       6.27 eA-3
Q106 0.998 0.659 0.143 !       5.76 eA-3
Q107 0.784 0.665 0.111 !       5.60 eA-3
Q108 0.752 0.639 0.182 !       5.54 eA-3
Q109 0.990 0.136 0.183 !       5.26 eA-3
Q110 0.020 0.176 0.103 !       5.23 eA-3
Q111 0.498 0.341 0.395 !       3.58 eA-3
C112 0.560 0.167 0.069 !       3.55 eA-3
C113 0.262 0.593 0.043 !       3.22 eA-3
C114 0.235 0.747 0.088 !       3.20 eA-3
Q115 0.298 0.774 0.398 !       3.06 eA-3
C116 0.577 0.126 0.058 !       3.01 eA-3
C117 0.583 0.101 0.014 !       3.00 eA-3
Q118 0.296 0.276 0.401 !       2.88 eA-3
Q119 0.515 0.158 0.140 !       2.87 eA-3
Q120 0.066 0.843 0.395 !       2.85 eA-3
C121 0.501 0.011 0.024 !       2.64 eA-3
Q122 0.519 0.237 0.386 !       2.54 eA-3
Q123 0.548 0.685 0.137 !       2.51 eA-3
C124 0.392 0.609 0.009 !       2.48 eA-3
Q125 0.247 0.677 0.131 !       2.44 eA-3
C126 0.448 0.515 0.024 !       2.27 eA-3
Q127 1.000 0.222 0.137 !       2.24 eA-3
Q128 0.083 0.734 0.386 !       2.20 eA-3
C129 0.619 0.296 0.071 !       2.17 eA-3
Q130 0.762 0.252 0.394 !       2.17 eA-3
C131 0.381 0.795 0.055 !       2.15 eA-3
Q132 0.578 0.622 0.147 !       2.12 eA-3
Q133 0.816 0.627 0.151 !       2.08 eA-3
Q134 0.076 0.138 0.140 !       2.05 eA-3
Q135 0.752 0.723 0.141 !       2.04 eA-3
C136 0.608 0.375 0.034 !       2.04 eA-3
Q137 0.532 0.301 0.313 !       2.01 eA-3
Q138 0.147 0.782 0.390 !       1.91 eA-3
Q139 0.017 0.094 0.144 !       1.87 eA-3
Q140 0.390 0.110 0.048 !       1.85 eA-3
Q141 0.581 0.888 0.342 !       1.84 eA-3
C142 0.640 0.314 0.029 !       1.83 eA-3
C143 0.292 0.710 0.062 !       1.82 eA-3
C144 0.408 0.107 0.009 !       1.81 eA-3
Q145 0.487 0.340 0.441 !       1.76 eA-3
Q146 0.057 0.094 0.169 !       1.74 eA-3
Q147 0.280 0.392 0.345 !       1.74 eA-3
Q148 0.519 0.374 0.317 !       1.74 eA-3
C149 0.238 0.629 0.071 !       1.73 eA-3
Q150 0.982 0.155 0.215 !       1.73 eA-3
Q151 0.360 0.046 0.208 !       1.73 eA-3
Q152 0.060 0.845 0.433 !       1.73 eA-3
Q153 0.094 0.778 0.323 !       1.72 eA-3
Q154 0.481 0.269 0.471 !       1.71 eA-3
Q155 0.112 0.656 0.393 !       1.68 eA-3
Q156 0.909 0.280 0.114 !       1.67 eA-3
Q157 0.566 0.628 0.101 !       1.66 eA-3
Q158 0.014 0.734 0.197 !       1.66 eA-3
C159 0.256 0.671 0.096 !       1.66 eA-3
Q160 0.720 0.276 0.399 !       1.64 eA-3
C161 0.332 0.921 0.022 !       1.64 eA-3
C162 0.608 0.436 0.040 !       1.62 eA-3
C163 0.532 0.951 0.017 !       1.62 eA-3
Q164 0.329 0.391 0.336 !       1.61 eA-3
Q165 0.111 0.968 0.439 !       1.61 eA-3
Q166 0.937 0.153 0.148 !       1.61 eA-3
C167 0.574 0.192 0.030 !       1.61 eA-3
Q168 0.113 0.826 0.308 !       1.61 eA-3
Q169 0.799 0.686 0.047 !       1.61 eA-3
Q170 0.329 0.343 0.058 !       1.60 eA-3
Q171 0.091 0.719 0.358 !       1.60 eA-3
C172 0.424 0.823 0.009 !       1.59 eA-3
Q173 0.440 0.672 0.468 !       1.59 eA-3
Q174 0.876 0.496 0.374 !       1.59 eA-3
Q175 0.404 0.623 0.105 !       1.59 eA-3
Q176 0.855 0.171 0.474 !       1.58 eA-3
Q177 0.687 0.921 0.298 !       1.58 eA-3
Q178 1.006 0.406 0.500 !       1.56 eA-3
Q179 0.904 0.606 0.132 !       1.56 eA-3
Q180 0.669 0.659 0.337 !       1.56 eA-3
Q181 0.641 0.058 0.360 !       1.55 eA-3
Q182 0.859 0.456 0.089 !       1.54 eA-3
Q183 0.355 0.859 0.096 !       1.53 eA-3
C184 0.518 0.434-0.001 !       1.52 eA-3
Q185 0.558 0.154 0.384 !       1.51 eA-3
Q186 0.137 0.565 0.160 !       1.51 eA-3
Q187 0.876 0.767 0.046 !       1.51 eA-3
Q188 0.703 0.301 0.382 !       1.50 eA-3
Q189 0.627 0.609 0.039 !       1.50 eA-3
Q190 0.720 0.294 0.427 !       1.50 eA-3
Q191 0.638 0.686 0.142 !       1.49 eA-3
Q192 0.956 0.233 0.070 !       1.49 eA-3
C193 0.655 0.171 0.075 !       1.48 eA-3
C194 0.422 0.045 0.044 !       1.47 eA-3
Q195 0.281 0.389 0.311 !       1.47 eA-3
Q196 0.294 0.408 0.294 !       1.46 eA-3
C197 0.580 0.281 0.107 !       1.46 eA-3
C198 0.531 0.252 0.070 !       1.46 eA-3
C199 0.467 0.980 0.046 !       1.45 eA-3
;
_refine_diff_density_max         7.070
_refine_diff_density_min         -2.630
_refine_diff_density_rms         0.278
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1245
_refine_ls_number_reflns         18391
_refine_ls_number_restraints     104
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.1063
_refine_ls_R_factor_gt           0.0836
_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^)+(0.0808P)^2^+142.1131P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1982
_refine_ls_wR_factor_ref         0.2121
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13852
_reflns_number_total             18391
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ra13547e2.cif
_cod_data_source_block           a160711a_sq
_cod_database_code               7230167
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.234
_shelx_estimated_absorpt_t_min   0.184
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Rigid bond restraints
 C101, C102
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C102, C103
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C17) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C22)
\\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C55) \\sim Ueq,
Uanis(C54) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(C115)
\\sim Ueq, Uanis(C113) \\sim Ueq, Uanis(C112) \\sim Ueq: with sigma of 0.005
and sigma for terminal atoms of 0.002
Uanis(C25) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.002
Uanis(C12) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C104) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.005
4.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C12(H12),
 C14(H14), C17(H17), C19(H19), C20(H20), C63(H63), C64(H64), C65(H65), C66(H66),
  C69(H69), C70(H70), C71(H71), C72(H72), C75(H75), C77(H77), C78(H78),
 C80(H80), C33(H33), C34(H34), C35(H35), C36(H36), C40(H40), C41(H41), C42(H42),
  C43(H43), C44(H44), C47(H47), C49(H49), C50(H50), C93(H93), C94(H94),
 C95(H95), C96(H96), C100(H100), C101(H101), C102(H102), C103(H103), C105(H105),
  C108(H108), C110(H110), C111(H111)
4.b Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C89(H89A,
 H89B,H89C), C90(H90A,H90B,H90C), C91(H91A,H91B,H91C), C56(H56A,H56B,H56C),
 C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,
 H60C), C117(H11A,H11B,H11C), C118(H11D,H11E,H11F), C119(H11G,H11H,H11I),
 C120(H12A,H12B,H12C), C121(H12D,H12E,H12F)
;
_platon_squeeze_void_probe_radius 1.20
_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 2.124
_oxdiff_exptl_absorpt_empirical_full_min 0.578