Chelating N-heterocyclic carbene-carboranes offer flexible ligand coordination to Ir(III), Rh(III) and Ru(II): effect of ligand cyclometallation in catalytic transfer hydrogenation.
Holmes, Jordan; Pask, Christopher M.; Willans, Charlotte E.; Dalton transactions (Cambridge, England : 2003) 45 (2016) 15818–15827; doi:10.1039/c6dt02079h

data_7039999
_publ_section_title
;
 Chelating N-heterocyclic carbene-carboranes offer flexible ligand
 coordination to Ir(III), Rh(III) and Ru(II): effect of ligand
 cyclometallation in catalytic transfer hydrogenation.
;
_journal_issue                   40
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              15818
_journal_page_last               15827
_journal_paper_doi               10.1039/c6dt02079h
_journal_volume                  45
_journal_year                    2016
_chemical_formula_moiety         'C18 H35 B10 Cl2 Ir N2, 0.5(C6 H14)'
_chemical_formula_sum            'C21 H42 B10 Cl2 Ir N2'
_chemical_formula_weight         693.76
_space_group_crystal_system      hexagonal
_space_group_IT_number           169
_space_group_name_Hall           'P 61'
_space_group_name_H-M_alt        'P 61'
_symmetry_space_group_name_Hall  'P 61'
_symmetry_space_group_name_H-M   'P 61'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-05
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2016-07-06 deposited with the CCDC.
2016-07-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   35.0294(11)
_cell_length_b                   35.0294(11)
_cell_length_c                   13.0675(4)
_cell_measurement_reflns_used    10199
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      53.7470
_cell_measurement_theta_min      3.8620
_cell_volume                     13886.4(7)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3095
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.976
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_details
;
  1 omega    7.00   41.00   1.0000  190.8250
omega____ theta____ kappa____ phi______ frames
    -       66.5980  -37.0000  120.0000 34

  2 omega   52.00   79.00   1.0000  190.8250
omega____ theta____ kappa____ phi______ frames
    -       66.5980  -65.0000  159.9207 27

  3 omega   71.00   96.00   1.0000  190.8250
omega____ theta____ kappa____ phi______ frames
    -       66.5980  -65.0000  139.4827 25

  4 omega   61.00   87.00   1.0000  190.8250
omega____ theta____ kappa____ phi______ frames
    -       66.5980  -65.0000  108.9109 26

  5 omega   38.00   94.00   1.0000  190.8250
omega____ theta____ kappa____ phi______ frames
    -       66.5980  -65.0000   77.4523 56

  6 omega   46.00  140.00   1.0000  190.8250
omega____ theta____ kappa____ phi______ frames
    -       66.5980   37.0000 -120.0000 94

  7 omega  -20.00   52.00   1.0000   47.7050
omega____ theta____ kappa____ phi______ frames
    -        0.0000   37.0000 -180.0000 72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0506105000
_diffrn_orient_matrix_UB_12      0.0234191000
_diffrn_orient_matrix_UB_13      0.0083613000
_diffrn_orient_matrix_UB_21      -0.0021188000
_diffrn_orient_matrix_UB_22      -0.0449930000
_diffrn_orient_matrix_UB_23      -0.0017415000
_diffrn_orient_matrix_UB_31      0.0036723000
_diffrn_orient_matrix_UB_32      0.0023484000
_diffrn_orient_matrix_UB_33      -0.1175809000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0622
_diffrn_reflns_av_unetI/netI     0.0756
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            25900
_diffrn_reflns_point_group_measured_fraction_full 0.876
_diffrn_reflns_point_group_measured_fraction_max 0.876
_diffrn_reflns_theta_full        54.165
_diffrn_reflns_theta_max         54.165
_diffrn_reflns_theta_min         2.913
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.053
_exptl_absorpt_correction_T_max  0.873
_exptl_absorpt_correction_T_min  0.579
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.493
_exptl_crystal_description       needle
_exptl_crystal_F_000             6174
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.102
_refine_diff_density_min         -0.950
_refine_diff_density_rms         0.147
_refine_ls_abs_structure_details
;
 Flack x determined using 2787 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.021(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     910
_refine_ls_number_reflns         9884
_refine_ls_number_restraints     1288
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0753
_refine_ls_R_factor_gt           0.0666
_refine_ls_shift/su_max          0.044
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0552P)^2^+153.9057P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1493
_refine_ls_wR_factor_ref         0.1544
_reflns_Friedel_coverage         0.703
_reflns_Friedel_fraction_full    0.765
_reflns_Friedel_fraction_max     0.765
_reflns_number_gt                8723
_reflns_number_total             9884
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6dt02079h2.cif
_cod_data_source_block           2b_sq
_cod_depositor_comments
'Adding full bibliography for 7039998--7040005.cif.'
_cod_original_cell_volume        13886.3(9)
_cod_database_code               7039999
_chemical_oxdiff_formula         'C324 H630 B180 Cl36 Ir18 N36'
_reflns_odcompleteness_completeness 96.03
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     54.51
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C3B(H3BA,H3BB), C4B(H4BA,H4BB), C3C(H3CA,H3CB),
 C4C(H4CA,H4CB)
3.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C5B(H5B), C6B(H6B), C5C(H5C), C6C(H6C)
3.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C8B(H8BA,H8BB,H8BC),
 C14B(H14D,H14E,H14F), C15B(H15D,H15E,H15F), C16B(H16D,H16E,H16F), C17B(H17D,
 H17E,H17F), C18B(H18D,H18E,H18F), C8C(H8CA,H8CB,H8CC), C14C(H14G,H14H,H14I),
 C15C(H15G,H15H,H15I), C16C(H16G,H16H,H16I), C17C(H17G,H17H,H17I), C18C(H18G,
 H18H,H18I)
3.d Boron cage BH refined with riding coordinates:
 C1(H1), B3(H3), B4(H4), B5(H5A), B6(H6A), B7(H7), B8(H8), B9(H9), B10(H10),
 B11(H11), B12(H12), C1B(H1B), B3B(H3BC), B4B(H4BC), B5B(H5BA), B6B(H6BA),
 B7B(H7B), B8B(H8BD), B9B(H9B), B10B(H10B), B11B(H11B), B12B(H12B), C1C(H1C),
 B3C(H3C), B4C(H4C), B5C(H5CA), B6C(H6CA), B7C(H7C), B8C(H8CD), B9C(H9C),
 B10C(H10C), B11C(H11C), B12C(H12C)
;
_shelx_res_checksum              62799
_shelx_fab_checksum              94882
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'