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_7116656
_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         'C39 H52 F Ir N6 O6, C6 H5 F, C32 H12 B F24'
_chemical_formula_sum            'C77 H70 B F26 Ir N6 O6'
_chemical_formula_weight         1872.40
_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             2014-10-14
_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                 116.331(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.7249(5)
_cell_length_b                   22.1162(3)
_cell_length_c                   18.7709(4)
_cell_measurement_reflns_used    16080
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      31.2900
_cell_measurement_theta_min      3.4290
_cell_volume                     7711.1(3)
_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
;
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  -10.00  110.00   1.0000   75.0000
omega____ theta____ kappa____ phi______ frames
    -       25.9384   77.0000   60.0000 120

  2 omega  -10.00  110.00   1.0000   75.0000
omega____ theta____ kappa____ phi______ frames
    -       25.9384   77.0000  -90.0000 120

  3 omega    9.00   82.00   1.0000   75.0000
omega____ theta____ kappa____ phi______ frames
    -       25.9384   77.0000  -30.0000 73

  4 omega  -25.00   33.00   1.0000   75.0000
omega____ theta____ kappa____ phi______ frames
    -      -26.8759   77.0000  120.0000 58
;
_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      -0.0240937000
_diffrn_orient_matrix_UB_12      -0.0186042000
_diffrn_orient_matrix_UB_13      -0.0312749000
_diffrn_orient_matrix_UB_21      -0.0295961000
_diffrn_orient_matrix_UB_22      0.0161727000
_diffrn_orient_matrix_UB_23      -0.0000880000
_diffrn_orient_matrix_UB_31      0.0014755000
_diffrn_orient_matrix_UB_32      0.0205083000
_diffrn_orient_matrix_UB_33      -0.0282787000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0605
_diffrn_reflns_av_unetI/netI     0.0592
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            53806
_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         25.682
_diffrn_reflns_theta_min         3.290
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.851
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91182
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.613
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             3752
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_refine_diff_density_max         4.107
_refine_diff_density_min         -2.129
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1368
_refine_ls_number_reflns         14602
_refine_ls_number_restraints     1905
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0724
_refine_ls_R_factor_gt           0.0500
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0508P)^2^+25.8087P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1136
_refine_ls_wR_factor_ref         0.1247
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11199
_reflns_number_total             14602
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc00529a2.cif
_cod_data_source_block           0085abc14a
_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               7116656
_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
 C216-F10 \\sim C216-F11 \\sim C216-F12 \\sim C316-F10A \\sim C316-F11A \\sim
C316-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 C313-F10A \\sim C313-F11A \\sim
C313-F12A
 with sigma of 0.01
 C213-C216 \\sim C313-C316
 with sigma of 0.01
 C207-F1 \\sim C207-F2 \\sim C207-F3 \\sim C307-F1A \\sim C307-F2A \\sim
C307-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 C303-F1A \\sim C303-F2A \\sim
C303-F3A
 with sigma of 0.01
 C203-C207 \\sim C303-C307
 with sigma of 0.01
 C208-F4 \\sim C208-F5 \\sim C208-F6 \\sim C308-F4A \\sim C308-F5A \\sim
C308-F6A
 with sigma of 0.01
 F4-F5 \\sim F5-F6 \\sim F6-F4 \\sim F4A-F5A \\sim F5A-F6A \\sim F6A-F4A
 with sigma of 0.01
 C205-F4 \\sim C205-F5 \\sim C205-F6 \\sim C305-F4A \\sim C305-F5A \\sim
C305-F6A
 with sigma of 0.01
 C205-C208 \\sim C305-C308
 with sigma of 0.01
 F7-F8B \\sim F8B-F9 \\sim F9-F7 \\sim F7A-F8A \\sim F8A-F9A \\sim F9A-F7A
 with sigma of 0.01
 C211-F7 \\sim C211-F8B \\sim C211-F9 \\sim C311-F7A \\sim C311-F8A \\sim
C311-F9A
 with sigma of 0.01
 C224-F16 \\sim C224-F17 \\sim C224-F18 \\sim C224-F16A \\sim C224-F17A \\sim
C224-F18A
 with sigma of 0.01
 F16-F17 \\sim F17-F18 \\sim F18-F16 \\sim F16A-F17A \\sim F17A-F18A \\sim
F18A-F16A
 with sigma of 0.01
 C221-F16 \\sim C221-F17 \\sim C221-F18 \\sim C221-F16A \\sim C221-F17A \\sim
C221-F18A
 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
 C232-F22 \\sim C232-F23 \\sim C232-F24 \\sim C232-F22A \\sim C232-F23A \\sim
C232-F24A
 with sigma of 0.01
 F22-F23 \\sim F23-F24 \\sim F24-F22 \\sim F22A-F23A \\sim F23A-F24A \\sim
F24A-F22A
 with sigma of 0.01
 C229-F22 \\sim C229-F23 \\sim C229-F24 \\sim C229-F22A \\sim C229-F23A \\sim
C229-F24A
 with sigma of 0.01
 C211-C215 \\sim C311-C315
 with sigma of 0.01
 C215-F7 \\sim C215-F8B \\sim C215-F9 \\sim C315-F7A \\sim C315-F8A \\sim
C315-F9A
 with sigma of 0.01
 F91-C900 \\sim F93-C901 \\sim F92-C902
 with sigma of 0.01
 C905-F91 \\sim F91-C901 \\sim C900-F93 \\sim F93-C902 \\sim C901-F92 \\sim
F92-C903
 with sigma of 0.01
3. Restrained planarity
 C209, C210, C211, C212, C213, C214, C215, C216
 with sigma of 0.01
 C201, C202, C203, C204, C205, C206, C207, C208
 with sigma of 0.01
 C201, C302, C303, C304, C305, C306, C307, C308
 with sigma of 0.01
 C209, C310, C311, C312, C313, C314, C315, C316
 with sigma of 0.01
 C900, C901, C902, C903, C904, C905, F91, F92, F93
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
F8 \\sim F91 \\sim F92 \\sim F93 \\sim F1 \\sim F1A \\sim F2 \\sim F2A \\sim F3
\\sim F3A \\sim F4 \\sim F4A \\sim F5 \\sim F5A \\sim F6 \\sim F6A \\sim F7
\\sim F7A \\sim F8A \\sim F8B \\sim F9 \\sim F9A \\sim F10 \\sim F10A \\sim F11
\\sim F11A \\sim F12 \\sim F12A \\sim F13 \\sim F14 \\sim F15 \\sim F16 \\sim
F16A \\sim F17 \\sim F17A \\sim F18 \\sim F18A \\sim F19 \\sim F19A \\sim F20
\\sim F20A \\sim F21 \\sim F21A \\sim F22 \\sim F22A \\sim F23 \\sim F23A \\sim
F24 \\sim F24A \\sim C302 \\sim C303 \\sim C304 \\sim C305 \\sim C306 \\sim
C307 \\sim C308 \\sim C209 \\sim C210 \\sim C211 \\sim C212 \\sim C213 \\sim
C214 \\sim C215 \\sim C216 \\sim C310 \\sim C311 \\sim C312 \\sim C313 \\sim
C314 \\sim C315 \\sim C316 \\sim C201 \\sim C202 \\sim C203 \\sim C204 \\sim
C205 \\sim C206 \\sim C207 \\sim C208 \\sim C231 \\sim C232 \\sim C224 \\sim
F93 \\sim C901 \\sim F91 \\sim C900 \\sim C905 \\sim C904 \\sim C903 \\sim C902
\\sim F92: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F8) \\sim Ueq, Uanis(F91) \\sim Ueq, Uanis(F92) \\sim Ueq, Uanis(F93)
\\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(F4A) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F5A) \\sim Ueq,
Uanis(F6) \\sim Ueq, Uanis(F6A) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F7A)
\\sim Ueq, Uanis(F8A) \\sim Ueq, Uanis(F8B) \\sim Ueq, Uanis(F9) \\sim Ueq,
Uanis(F9A) \\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(F14) \\sim Ueq, Uanis(F15) \\sim Ueq, Uanis(F16)
\\sim Ueq, Uanis(F16A) \\sim Ueq, Uanis(F17) \\sim Ueq, Uanis(F17A) \\sim Ueq,
Uanis(F18) \\sim Ueq, Uanis(F18A) \\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(F22A) \\sim Ueq, Uanis(F23)
\\sim Ueq, Uanis(F23A) \\sim Ueq, Uanis(F24) \\sim Ueq, Uanis(F24A) \\sim Ueq,
Uanis(C302) \\sim Ueq, Uanis(C303) \\sim Ueq, Uanis(C304) \\sim Ueq,
Uanis(C305) \\sim Ueq, Uanis(C306) \\sim Ueq, Uanis(C307) \\sim Ueq,
Uanis(C308) \\sim Ueq, Uanis(C209) \\sim Ueq, Uanis(C210) \\sim Ueq,
Uanis(C211) \\sim Ueq, Uanis(C212) \\sim Ueq, Uanis(C213) \\sim Ueq,
Uanis(C214) \\sim Ueq, Uanis(C215) \\sim Ueq, Uanis(C216) \\sim Ueq,
Uanis(C310) \\sim Ueq, Uanis(C311) \\sim Ueq, Uanis(C312) \\sim Ueq,
Uanis(C313) \\sim Ueq, Uanis(C314) \\sim Ueq, Uanis(C315) \\sim Ueq,
Uanis(C316) \\sim Ueq, Uanis(C201) \\sim Ueq, Uanis(C202) \\sim Ueq,
Uanis(C203) \\sim Ueq, Uanis(C204) \\sim Ueq, Uanis(C205) \\sim Ueq,
Uanis(C206) \\sim Ueq, Uanis(C207) \\sim Ueq, Uanis(C208) \\sim Ueq,
Uanis(C231) \\sim Ueq, Uanis(C232) \\sim Ueq, Uanis(C224) \\sim Ueq, Uanis(F93)
\\sim Ueq, Uanis(C901) \\sim Ueq, Uanis(F91) \\sim Ueq, Uanis(C900) \\sim Ueq,
Uanis(C905) \\sim Ueq, Uanis(C904) \\sim Ueq, Uanis(C903) \\sim Ueq,
Uanis(C902) \\sim Ueq, Uanis(F92) \\sim Ueq: with sigma of 0.007 and sigma for
terminal atoms of 0.014
5. Others
 Sof(F7)=Sof(F8B)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(C210)=Sof(H210)=
 Sof(C211)=Sof(C212)=Sof(H212)=Sof(C213)=Sof(C214)=Sof(H214)=Sof(C215)=
 Sof(C216)=1-FVAR(1)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(C314)=Sof(H314)=
 Sof(C313)=Sof(C312)=Sof(H312)=Sof(C311)=Sof(C310)=Sof(H310)=Sof(C315)=
 Sof(C316)=FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(C302)=Sof(H302)=
 Sof(C303)=Sof(C304)=Sof(H304)=Sof(C305)=Sof(C306)=Sof(H306)=Sof(C307)=
 Sof(C308)=1-FVAR(2)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(C206)=Sof(H206)=Sof(C205)=
 Sof(C204)=Sof(H204)=Sof(C203)=Sof(C202)=Sof(H202)=Sof(C207)=Sof(C208)=FVAR(2)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=1-FVAR(3)
 Sof(F19)=Sof(F20)=Sof(F21)=FVAR(3)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(4)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(4)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(5)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(5)
 Fixed Sof: F91(0.5) F92(0.25) F93(0.25) H901(0.75) H900(0.5) H902(0.75)
6.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)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C901(H901), C900(H900), C905(H905),
 C904(H904), C903(H903), C902(H902), C206(H206), C204(H204), C202(H202),
 C314(H314), C312(H312), C310(H310), C210(H210), C212(H212), C214(H214),
 C218(H218), C220(H220), C222(H222), C226(H226), C228(H228), C230(H230),
 C302(H302), C304(H304), C306(H306)
6.c Fitted hexagon refined as free rotating group:
 C901(C900,C905,C904,C903,C902), C201(C206,C205,C204,C203,C202), C209(C314,
 C313,C312,C311,C310)
6.d 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), 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'