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_7116655
_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
'C38 H43 Ir N6 O4, C H2 Cl2, 2(F), C32 H12 B F24'
_chemical_formula_sum            'C71 H58 B Cl2 F26 Ir N6 O4'
_chemical_formula_weight         1827.14
_chemical_melting_point          ?
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-10-15
_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                 104.772(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.5682(4)
_cell_length_b                   18.7483(3)
_cell_length_c                   20.3900(5)
_cell_measurement_reflns_used    24181
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      31.3730
_cell_measurement_theta_min      3.5100
_cell_volume                     7233.2(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_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  -19.00  102.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2639   19.0000    0.0000 121

  2 omega  -10.00   98.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2639   77.0000  120.0000 108

  3 omega  -48.00   51.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -23.3576   38.0000  150.0000 99

  4 omega -112.00  -57.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -23.3576 -178.0000  -90.0000 55

  5 omega   -2.00   85.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -       22.2639   38.0000 -120.0000 87

  6 omega  -49.00   50.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -23.3576   45.0000 -114.0000 99
;
_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      -0.0231832000
_diffrn_orient_matrix_UB_12      -0.0105146000
_diffrn_orient_matrix_UB_13      0.0198784000
_diffrn_orient_matrix_UB_21      0.0094958000
_diffrn_orient_matrix_UB_22      -0.0361798000
_diffrn_orient_matrix_UB_23      -0.0028412000
_diffrn_orient_matrix_UB_31      0.0278803000
_diffrn_orient_matrix_UB_32      0.0035828000
_diffrn_orient_matrix_UB_33      0.0298428000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0566
_diffrn_reflns_av_unetI/netI     0.0382
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            84388
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.682
_diffrn_reflns_theta_max         25.681
_diffrn_reflns_theta_min         3.314
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.041
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75673
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.678
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             3632
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.04
_refine_diff_density_max         6.088
_refine_diff_density_min         -1.556
_refine_diff_density_rms         0.136
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1154
_refine_ls_number_reflns         13701
_refine_ls_number_restraints     663
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0708
_refine_ls_R_factor_gt           0.0543
_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^)+(0.0637P)^2^+48.1943P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1327
_refine_ls_wR_factor_ref         0.1423
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11020
_reflns_number_total             13701
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc00529a2.cif
_cod_data_source_block           0094abc14
_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 
;
_cod_database_code               7116655
_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
 C215-F7 \\sim C215-F80 \\sim C215-F90 \\sim C215-F7A \\sim C215-F800 \\sim
C215-F900
 with sigma of 0.01
 F7-F80 \\sim F80-F90 \\sim F90-F7 \\sim F7A-F800 \\sim F800-F900 \\sim F900-F7A
 with sigma of 0.01
 C211-F7 \\sim C211-F80 \\sim C211-F90 \\sim C211-F7A \\sim C211-F800 \\sim
C211-F900
 with sigma of 0.01
 C216-F10 \\sim C216-F11 \\sim C216-F12 \\sim C216-F10A \\sim C216-F11A \\sim
C216-F12A
 with sigma of 0.01
 F10-F11 \\sim F11-F12 \\sim F12-F10 \\sim F10A-F11A \\sim F11A-F12A \\sim
F12A-F10A
 with sigma of 0.01
 C213-F10 \\sim C213-F11 \\sim C213-F12 \\sim C213-F10A \\sim C213-F11A \\sim
C213-F12A
 with sigma of 0.01
 C231-F19 \\sim C231-F20 \\sim C231-F21 \\sim C231-F19A \\sim C231-F20A \\sim
C231-F21A
 with sigma of 0.01
 F19-F20 \\sim F20-F21 \\sim F21-F19 \\sim F19A-F20A \\sim F20A-F21A \\sim
F21A-F19A
 with sigma of 0.01
 C227-F19 \\sim C227-F20 \\sim C227-F21 \\sim C227-F19A \\sim C227-F20A \\sim
C227-F21A
 with sigma of 0.01
 C207-F1 \\sim C207-F2 \\sim C207-F3 \\sim C207-F1A \\sim C207-F2A \\sim
C207-F3A
 with sigma of 0.01
 F1-F2 \\sim F2-F3 \\sim F3-F1 \\sim F1A-F2A \\sim F2A-F3A \\sim F3A-F1A
 with sigma of 0.01
 C203-F1 \\sim C203-F2 \\sim C203-F3 \\sim C203-F1A \\sim C203-F2A \\sim
C203-F3A
 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
 C7-F9C \\sim C6-F8A \\sim C5-F9 \\sim C4-F8 \\sim C3-F9B
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
F8A \\sim F9B \\sim F9 \\sim F1 \\sim F1A \\sim F2 \\sim F2A \\sim F3 \\sim F3A
\\sim F4 \\sim F5 \\sim F6 \\sim F7 \\sim F7A \\sim F10 \\sim F10A \\sim F11
\\sim F11A \\sim F12 \\sim F12A \\sim F13 \\sim F13A \\sim F14 \\sim F14A \\sim
F15 \\sim F15A \\sim F16 \\sim F17 \\sim F18 \\sim F19 \\sim F19A \\sim F20
\\sim F20A \\sim F21 \\sim F21A \\sim F22 \\sim F23 \\sim F24 \\sim F80 \\sim
F90 \\sim F800 \\sim F900 \\sim F9C \\sim F8: within 1.7A with sigma of 0.01
and sigma for terminal atoms of 0.02
Uanis(F8A) \\sim Ueq, Uanis(F9B) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F1)
\\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F2A) \\sim Ueq,
Uanis(F3) \\sim Ueq, Uanis(F3A) \\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F5) \\sim
Ueq, Uanis(F6) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F7A) \\sim Ueq, Uanis(F10)
\\sim Ueq, Uanis(F10A) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F11A) \\sim Ueq,
Uanis(F12) \\sim Ueq, Uanis(F12A) \\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(F19A) \\sim Ueq, Uanis(F20) \\sim Ueq,
Uanis(F20A) \\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(F21A) \\sim Ueq, Uanis(F22)
\\sim Ueq, Uanis(F23) \\sim Ueq, Uanis(F24) \\sim Ueq, Uanis(F80) \\sim Ueq,
Uanis(F90) \\sim Ueq, Uanis(F800) \\sim Ueq, Uanis(F900) \\sim Ueq, Uanis(F9C)
\\sim Ueq, Uanis(F8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms
of 0.02
Uanis(F9C) = Uanis(F8A) = Uanis(F9) = Uanis(F8) = Uanis(F9B)
4. Others
 2*[Sof(H7)+Sof(F9C)]+2*[Sof(H5)+Sof(F9)]+2*[Sof(H3)+Sof(F9B)]=2 with esd of
 0.00001
 1*[Sof(H7)+Sof(F9C)]+1*[Sof(H5)+Sof(F9)]+1*[Sof(H3)+Sof(F9B)]-1*[Sof(H6)+
 Sof(F8A)]-1*[Sof(H4)+Sof(F8)]=0 with esd of 0.00001
 Sof(H7)=1-FVAR(1)
 Sof(F9C)=FVAR(1)
 Sof(H5)=1-FVAR(2)
 Sof(F9)=FVAR(2)
 Sof(H3)=1-FVAR(3)
 Sof(F9B)=FVAR(3)
 Sof(H6)=1-FVAR(4)
 Sof(F8A)=FVAR(4)
 Sof(H4)=1-FVAR(5)
 Sof(F8)=FVAR(5)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=1-FVAR(6)
 Sof(F19)=Sof(F20)=Sof(F21)=FVAR(6)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(7)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(7)
 Sof(F7A)=Sof(F800)=Sof(F900)=1-FVAR(8)
 Sof(F7)=Sof(F80)=Sof(F90)=FVAR(8)
 Fixed Sof: F1(0.5) F1A(0.5) F2(0.5) F2A(0.5) F3(0.5) F3A(0.5) F13(0.5)
 F13A(0.5) F14(0.5) F14A(0.5) F15(0.5) F15A(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C20(H20A,H20B), C32(H32A,H32B), C35(H35A,H35B), C900(H90A,H90B)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C42(H42), C43(H43), C44(H44),
 C45(H45), C48(H48), C49(H49), C50(H50), C51(H51), 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:
 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)
;
_olex2_submission_special_instructions 'No special instructions were received'