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_7230163
_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         'C50 H39 Br4 Cl Ir N O, 2(C H2 Cl2)'
_chemical_formula_sum            'C52 H43 Br4 Cl5 Ir N O'
_chemical_formula_weight         1386.96
_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'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-03-22
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2017-12-06 deposited with the CCDC.
2018-02-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.9383(18)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.3666(4)
_cell_length_b                   18.5319(4)
_cell_length_c                   23.8394(4)
_cell_measurement_reflns_used    8711
_cell_measurement_temperature    134.5(7)
_cell_measurement_theta_max      73.9630
_cell_measurement_theta_min      4.5320
_cell_volume                     10099.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (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      134.5(7)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2740
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     53.00 105.00   1.00    7.95    --  107.08 -95.00 150.00   52
  2  \w     84.00 132.00   1.00    7.95    --  107.08 -45.00  30.00   48
  3  \w     53.00 124.00   1.00    7.95    --  107.08 -30.00 -60.00   71
  4  \w     79.00 163.00   1.00    7.95    --  107.08  30.00-150.00   84
  5  \w    103.00 176.00   1.00    7.95    --  107.08  61.00-120.00   73
  6  \w     76.00 108.00   1.00    7.95    --  107.08 -95.00-150.00   32
  7  \w     34.00 102.00   1.00    7.95    --  107.08-125.00   0.00   68
  8  \w     40.00  65.00   1.00    7.95    --  107.08 -45.00  30.00   25
  9  \w      1.00  57.00   1.00    1.99    --   41.49 -99.00  30.00   56
 10  \w    -34.00  30.00   1.00    1.99    --  -41.49  77.00 -90.00   64
 11  \w    -69.00 -20.00   1.00    1.99    --  -41.49 -57.00  60.00   49
 12  \w   -114.00 -34.00   1.00    1.99    --  -41.49 -38.00 150.00   80
;
_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      0.0546982000
_diffrn_orient_matrix_UB_12      0.0073275000
_diffrn_orient_matrix_UB_13      0.0484125000
_diffrn_orient_matrix_UB_21      -0.0349223000
_diffrn_orient_matrix_UB_22      0.0469934000
_diffrn_orient_matrix_UB_23      0.0343916000
_diffrn_orient_matrix_UB_31      -0.0182581000
_diffrn_orient_matrix_UB_32      -0.0681638000
_diffrn_orient_matrix_UB_33      0.0288742000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0349
_diffrn_reflns_av_unetI/netI     0.0450
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            19852
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         3.790
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.563
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35774
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (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    1.824
_exptl_crystal_description       block
_exptl_crystal_F_000             5376
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.2
_refine_diff_density_max         2.133
_refine_diff_density_min         -1.064
_refine_diff_density_rms         0.127
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     582
_refine_ls_number_reflns         9000
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.166
_refine_ls_R_factor_all          0.0499
_refine_ls_R_factor_gt           0.0410
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0498P)^2^+52.6835P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0983
_refine_ls_wR_factor_ref         0.1035
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7689
_reflns_number_total             9000
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ra13547e2.cif
_cod_data_source_block           a170322a
_cod_database_code               7230163
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Uiso/Uaniso restraints and constraints
Uanis(Cl5) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.002
Uanis(C39) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(Br4) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.002
3.a Secondary CH2 refined with riding coordinates:
 C51(H51A,H51B), C52(H52A,H52B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C15(H15),
 C16(H16), C18(H18), C19(H19), C22(H22), C23(H23), C25(H25), C26(H26), C28(H28),
  C29(H29), C31(H31), C32(H32), C34(H34), C36(H36), C37(H37), C39(H39), C40(H40)
3.c Idealised Me refined as rotating group:
 C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,
 H49C), C50(H50A,H50B,H50C)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2017-03-22
_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 2.437
_oxdiff_exptl_absorpt_empirical_full_min 0.785