Low-coordinate iridium NHC complexes derived from selective and reversible C-H bond activation of fluoroarenes
Simone A. Hauser; Ivan Prokes; Adrian B. Chaplin; Chem.Commun. 51 (2015) 4425–; doi:10.1039/C5cc00529A

data_7116658
_publ_section_title
;
 Low-coordinate iridium NHC complexes derived from selective and
 reversible C-H bond activation of fluoroarenes
;
_journal_name_full               Chem.Commun.
_journal_page_first              4425
_journal_paper_doi               10.1039/C5cc00529A
_journal_volume                  51
_journal_year                    2015
_chemical_formula_moiety         'C35 H51 Ir N7 O6, C32 H12 B F24'
_chemical_formula_sum            'C67 H63 B F24 Ir N7 O6'
_chemical_formula_weight         1721.25
_chemical_melting_point          ?
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-10-08
_audit_creation_method
;
Olex2 1.2
(compiled 2014.08.28 svn.r2986 for OlexSys, GUI svn.r4874)
;
_audit_update_record
;
2014-12-04 deposited with the CCDC.
2015-02-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.1355(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.7820(2)
_cell_length_b                   20.0926(2)
_cell_length_c                   25.2535(3)
_cell_measurement_reflns_used    17947
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      32.0770
_cell_measurement_theta_min      3.4360
_cell_volume                     6991.73(15)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2833
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -52.00   58.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       25.7882  -57.0000  -30.0000 110

  2 omega   -5.00  105.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       25.7882   38.0000  150.0000 110

  3 omega   32.00  117.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       25.7882 -178.0000    0.0000 85

  4 omega   -5.00   58.00   1.0000   12.5000
omega____ theta____ kappa____ phi______ frames
    -       25.7882   38.0000  -30.0000 63
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Oxford Diffraction: Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0359811000
_diffrn_orient_matrix_UB_12      -0.0016926000
_diffrn_orient_matrix_UB_13      0.0204188000
_diffrn_orient_matrix_UB_21      0.0244221000
_diffrn_orient_matrix_UB_22      -0.0252620000
_diffrn_orient_matrix_UB_23      -0.0141553000
_diffrn_orient_matrix_UB_31      0.0275216000
_diffrn_orient_matrix_UB_32      0.0246105000
_diffrn_orient_matrix_UB_33      -0.0131125000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0618
_diffrn_reflns_av_unetI/netI     0.0648
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            57568
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        27.878
_diffrn_reflns_theta_max         27.878
_diffrn_reflns_theta_min         3.382
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.030
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81921
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.635
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3440
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.435
_refine_diff_density_min         -1.327
_refine_diff_density_rms         0.104
_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     1024
_refine_ls_number_reflns         16651
_refine_ls_number_restraints     360
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0643
_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^)+(0.0425P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0865
_refine_ls_wR_factor_ref         0.0967
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12576
_reflns_number_total             16651
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc00529a2.cif
_cod_data_source_block           0109abc14
_cod_depositor_comments
;
The following automatic conversions were performed:

'_chemical_melting_point' value 'not measured' was changed to '?' -
the value is undefined or not given.

Automatic conversion script
Id: cif_fix_values 2827 2014-09-09 07:05:25Z andrius 
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_cod_original_cell_volume        6991.72(16)
_cod_database_code               7116658
_shelxl_version_number           2013-4
_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. Restrained distances
 C208-F4A \\sim C208-F5A \\sim C208-F6A \\sim C208-F4 \\sim C208-F5 \\sim
C208-F6
 with sigma of 0.01
 F4A-F5A \\sim F5A-F6A \\sim F6A-F4A \\sim F4-F5 \\sim F5-F6 \\sim F6-F4
 with sigma of 0.01
 C205-F4A \\sim C205-F5A \\sim C205-F6A \\sim C205-F4 \\sim C205-F5 \\sim
C205-F6
 with sigma of 0.01
 C223-F13 \\sim C223-F14 \\sim C223-F15 \\sim C223-F13A \\sim C223-F14A \\sim
C223-F15A
 with sigma of 0.01
 F13-F14 \\sim F14-F15 \\sim F15-F13 \\sim F13A-F14A \\sim F14A-F15A \\sim
F15A-F13A
 with sigma of 0.01
 C219-F13 \\sim C219-F14 \\sim C219-F15 \\sim C219-F13A \\sim C219-F14A \\sim
C219-F15A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F4A \\sim F5 \\sim F5A \\sim F6 \\sim F6A
\\sim F7 \\sim F8 \\sim F9 \\sim F10 \\sim F11 \\sim F12 \\sim F13 \\sim F13A
\\sim F14 \\sim F14A \\sim F15 \\sim F15A \\sim F16 \\sim F17 \\sim F18 \\sim
F19 \\sim F20 \\sim F21 \\sim F22 \\sim F23 \\sim F24 \\sim C223: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.009
Uanis(F1) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F4) \\sim
Ueq, Uanis(F4A) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F5A) \\sim Ueq, Uanis(F6)
\\sim Ueq, Uanis(F6A) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F8) \\sim Ueq,
Uanis(F9) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F12)
\\sim Ueq, Uanis(F13) \\sim Ueq, Uanis(F13A) \\sim Ueq, Uanis(F14) \\sim Ueq,
Uanis(F14A) \\sim Ueq, Uanis(F15) \\sim Ueq, Uanis(F15A) \\sim Ueq, Uanis(F16)
\\sim Ueq, Uanis(F17) \\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(F19) \\sim Ueq,
Uanis(F20) \\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(F22) \\sim Ueq, Uanis(F23)
\\sim Ueq, Uanis(F24) \\sim Ueq, Uanis(C223) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.009
4. Others
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(1)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(1)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(2)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C20(H20A,H20B), C32(H32A,H32B), C35(H35A,H35B), C47(H47A,
 H47B), C50(H50A,H50B)
5.b Aromatic/amide H refined with riding coordinates:
 C202(H202), C204(H204), C206(H206), C210(H210), C212(H212), C214(H214),
 C218(H218), C220(H220), C222(H222), C226(H226), C228(H228), C230(H230)
5.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C25(H25A,H25B,H25C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,
 H39B,H39C), C40(H40A,H40B,H40C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C),
 C54(H54A,H54B,H54C), C55(H55A,H55B,H55C)
;
_olex2_submission_special_instructions 'No special instructions were received'