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_7230161
_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         'C22 H23 Cl N O Rh, C H2 Cl2'
_chemical_formula_sum            'C23 H25 Cl3 N O Rh'
_chemical_formula_weight         540.70
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_symmetry_space_group_name_Hall  'P 2c -2ac'
_symmetry_space_group_name_H-M   'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-10-17
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2017-12-06 deposited with the CCDC.
2018-02-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.166(5)
_cell_length_b                   10.162(2)
_cell_length_c                   8.6509(17)
_cell_measurement_reflns_used    8622
_cell_measurement_temperature    104.66(14)
_cell_measurement_theta_max      73.7740
_cell_measurement_theta_min      4.6490
_cell_volume                     2300.3(8)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      104.66(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2740
_diffrn_detector_type            AtlasS2
_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     50.00 103.00   1.00    1.00    --  107.08 -95.00  90.00   53
  2  \w     29.00  56.00   1.00    1.00    --   41.49-125.00   0.00   27
  3  \w     81.00 159.00   1.00    1.00    --  107.08  45.00   0.00   78
  4  \w    117.00 173.00   1.00    1.00    --  107.08 115.00 -49.00   56
  5  \w     81.00 175.00   1.00    1.00    --  107.08  61.00  90.00   94
  6  \w    -95.00 -12.00   1.00    1.00    --  -41.49 125.00-120.00   83
  7  \w   -112.00 -49.00   1.00    1.00    --  -41.49 -57.00 120.00   63
  8  \w    -45.00 -20.00   1.00    1.00    --  -41.49 -38.00  90.00   25
  9  \w   -116.00 -90.00   1.00    1.00    --  -41.49 -38.00  90.00   26
 10  \w   -112.00 -86.00   1.00    1.00    --  -41.49 -38.00 150.00   26
 11  \w   -116.00 -25.00   1.00    1.00    --  -41.49 -38.00-180.00   91
 12  \w    -73.00 -48.00   1.00    1.00    --  -41.49 -38.00 150.00   25
 13  \w      1.00  79.00   1.00    1.00    --   41.49 -99.00  60.00   78
 14  \w     46.00 126.00   1.00    1.00    --  107.08 -30.00 150.00   80
 15  \w    121.00 170.00   1.00    1.00    --  107.08  61.00 -60.00   49
 16  \w     94.00 121.00   1.00    1.00    --  107.08-125.00-180.00   27
 17  \w     89.00 115.00   1.00    1.00    --  107.08-125.00  60.00   26
 18  \w     43.00  69.00   1.00    1.00    --  107.08-125.00  60.00   26
 19  \w     34.00  80.00   1.00    1.00    --  107.08-125.00-180.00   46
 20  \w     72.00 139.00   1.00    1.00    --  107.08 -77.00-180.00   67
 21  \w    139.00 176.00   1.00    1.00    --  107.08  30.00-150.00   37
 22  \w     43.00  69.00   1.00    1.00    --  107.08 -77.00-180.00   26
 23  \w     39.00 133.00   1.00    1.00    --  107.08 -61.00 -60.00   94
 24  \w     79.00 104.00   1.00    1.00    --  107.08 -95.00 -90.00   25
;
_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      -0.0500946000
_diffrn_orient_matrix_UB_12      0.0104565000
_diffrn_orient_matrix_UB_13      0.0927418000
_diffrn_orient_matrix_UB_21      0.0084439000
_diffrn_orient_matrix_UB_22      0.1492558000
_diffrn_orient_matrix_UB_23      0.0183356000
_diffrn_orient_matrix_UB_31      -0.0297458000
_diffrn_orient_matrix_UB_32      0.0246398000
_diffrn_orient_matrix_UB_33      -0.1508854000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0567
_diffrn_reflns_av_unetI/netI     0.0423
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            15348
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.007
_diffrn_reflns_theta_max         25.007
_diffrn_reflns_theta_min         2.004
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.105
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.11591
_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    1.561
_exptl_crystal_description       block
_exptl_crystal_F_000             1096
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.17
_refine_diff_density_max         1.189
_refine_diff_density_min         -0.511
_refine_diff_density_rms         0.077
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -1.39(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     268
_refine_ls_number_reflns         3372
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0323
_refine_ls_R_factor_gt           0.0310
_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^)+(0.0411P)^2^+0.8277P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0757
_refine_ls_wR_factor_ref         0.0765
_reflns_Friedel_coverage         0.861
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                3265
_reflns_number_total             3372
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ra13547e2.cif
_cod_data_source_block           a161017a
_cod_database_code               7230161
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 2.39(6) -1.39(6)
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.a Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C4(H4), C11(H11), C9(H9), C12(H12), C10(H10)
3.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C19(H19A,H19B,H19C), C18(H18A,H18B,H18C), C21(H21A,H21B,
 H21C), C20(H20A,H20B,H20C)
;
_shelx_shelxl_version_number     2014/7
_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 3.477
_oxdiff_exptl_absorpt_empirical_full_min 0.516