Extending N-heterocyclic carbene ligands into the third dimension: a new type of hybrid phosphazane/NHC system
Roth, Torsten; Vasilenko, Vladislav; Benson, Callum G. M.; Wadepohl, Hubert; Wright, Dominic S.; Gade, Lutz H.; Chem. Sci. 6 (2015) 2506–; doi:10.1039/C4SC03966A

data_1518729
_publ_section_title
;
 Extending N-heterocyclic carbene ligands into the third dimension: a new
 type of hybrid phosphazane/NHC system
;
_journal_issue                   4
_journal_name_full               'Chem. Sci.'
_journal_page_first              2506
_journal_paper_doi               10.1039/C4SC03966A
_journal_volume                  6
_journal_year                    2015
_chemical_formula_moiety         'C47 H44 Cl Ir N4 O2 P2'
_chemical_formula_sum            'C54 H52 Cl Ir N4 O2 P2'
_chemical_formula_weight         1078.58
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3'
_symmetry_cell_setting           trigonal
_symmetry_Int_Tables_number      148
_symmetry_space_group_name_Hall  '-R 3'
_symmetry_space_group_name_H-M   'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_tro114
_audit_creation_date
;
'Tue Nov 11 16:37:55 2014'
;
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.28 svn.r3107 for OlexSys, GUI svn.r4959)
;
_audit_update_record
;
2014-12-19 deposited with the CCDC.
2015-02-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   30.1754(4)
_cell_length_b                   30.1754(4)
_cell_length_c                   27.5094(4)
_cell_measurement_reflns_used    47049
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      27.6260
_cell_measurement_theta_min      3.4790
_cell_volume                     21692.9(5)
_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
'encif (Wadepohl, 2009-14); encifer 1.5 (CCDC, 2014)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.974
_diffrn_measurement_details
;
  1 omega  -11.00   89.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942   77.0000 -180.0000 200

  2 omega   -6.00   88.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942   77.0000    0.0000 188

  3 omega    1.00   84.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942   57.0000  -60.0000 166

  4 omega    0.00   87.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942   57.0000  120.0000 174

  5 omega   15.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942  -77.0000  -90.0000 68

  6 omega  -42.00   48.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942  -77.0000   60.0000 180

  7 omega  -49.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942  -77.0000  150.0000 196

  8 omega   15.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942  -77.0000    0.0000 68

  9 omega  -43.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942  -77.0000 -120.0000 184

 10 omega   19.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942  -77.0000   90.0000 60

 11 omega  -40.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942  -77.0000  -30.0000 178

 12 omega   23.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942  -77.0000 -180.0000 52

 13 omega  -50.00   40.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942  -57.0000  150.0000 180

 14 omega   -3.00   87.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942   57.0000  -60.0000 180

 15 omega   -3.00   87.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942   57.0000   90.0000 180

 16 omega  -50.00   40.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942  -57.0000   30.0000 180

 17 omega  -50.00   40.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942  -57.0000 -150.0000 180

 18 omega   -3.00   87.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942   57.0000    0.0000 180

 19 omega  -51.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942  -77.0000  -30.0000 200

 20 omega  -51.00   49.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942  -77.0000   90.0000 200

 21 omega  -51.00  -20.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942  -77.0000 -120.0000 62

 22 omega  -54.00   44.00   0.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.6942  -38.0000  -90.0000 196

;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_UB_11      0.0097904000
_diffrn_orient_matrix_UB_12      -0.0117255000
_diffrn_orient_matrix_UB_13      -0.0156914000
_diffrn_orient_matrix_UB_21      -0.0250563000
_diffrn_orient_matrix_UB_22      -0.0166814000
_diffrn_orient_matrix_UB_23      -0.0087967000
_diffrn_orient_matrix_UB_31      0.0036224000
_diffrn_orient_matrix_UB_32      0.0179117000
_diffrn_orient_matrix_UB_33      -0.0184632000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0832
_diffrn_reflns_av_unetI/netI     0.0395
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            256938
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.034
_diffrn_reflns_theta_min         3.226
_diffrn_source                   'microfocus X-Ray tube'
_exptl_absorpt_coefficient_mu    2.937
_exptl_absorpt_correction_T_max  0.862
_exptl_absorpt_correction_T_min  0.758
_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            'light bronze'
_exptl_crystal_density_diffrn    1.486
_exptl_crystal_description       plate
_exptl_crystal_F_000             9792
_exptl_crystal_size_max          0.114
_exptl_crystal_size_mid          0.107
_exptl_crystal_size_min          0.061
_refine_diff_density_max         1.654
_refine_diff_density_min         -1.357
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     520
_refine_ls_number_reflns         12550
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0509
_refine_ls_R_factor_gt           0.0361
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0378P)^2^+84.2741P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0796
_refine_ls_wR_factor_ref         0.0839
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10220
_reflns_number_total             12550
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4sc03966a2.cif
_cod_data_source_block           ga_tro114_sq
_cod_depositor_comments
'Adding full bibliography for 1518727--1518731.cif.'
_cod_original_cell_volume        21693.0(6)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               1518729
_audit_block_refno               2250
_audit_block_usercomment         'tr1499, block, light bronze'
_shelx_estimated_absorpt_t_max   0.842
_shelx_estimated_absorpt_t_min   0.730
_shelxl_version_number           2014/7
_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. Restrained distances
 C47-O2
 1.13 with sigma of 0.001
 Ir-C47
 1.856 with sigma of 0.001
3.a Ternary CH refined with riding coordinates:
 C20(H20), C33(H33)
3.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C13(H13), C15(H15), C22(H22), C23(H23), C24(H24), C25(H25),
 C26(H26), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C35(H35), C36(H36),
  C37(H37), C38(H38), C39(H39), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45)
3.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C17(H17A,H17B,H17C),
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              38533
_olex2_submission_special_instructions 'No special instructions were received'
_cell_oxdiff_length_a            30.1658(4)
_cell_oxdiff_length_b            30.1701(4)
_cell_oxdiff_length_c            27.5160(4)
_cell_oxdiff_angle_alpha         90.0068(12)
_cell_oxdiff_angle_beta          89.9900(11)
_cell_oxdiff_angle_gamma         119.9747(15)
_cell_oxdiff_volume              21693.0(5)
_cell_oxdiff_measurement_reflns_used 47049
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_theta     26.32
_reflns_odcompleteness_iscentric 1
_platon_squeeze_void_probe_radius 1.20