Rhodium(I) and Iridium(I) Complexes of the Conformationally Rigid IBioxMe4 Ligand: Computational and Experimental Studies of Unusually Tilted NHC Coordination Geometries
Luy, Jan-Niclas; Hauser, Simone A.; Chaplin, Adrian B.; Tonner, Ralf; Organometallics 34 (2015) 5099–; doi:10.1021/acs.organomet.5b00692

data_4087904
_publ_section_title
;
 Rhodium(I) and Iridium(I) Complexes of the Conformationally Rigid
 IBioxMe4 Ligand: Computational and Experimental Studies of Unusually
 Tilted NHC Coordination Geometries
;
_journal_issue                   20
_journal_name_full               Organometallics
_journal_page_first              5099
_journal_paper_doi               10.1021/acs.organomet.5b00692
_journal_volume                  34
_journal_year                    2015
_chemical_formula_moiety
'C34 H48 Ir N6 O7, 0.5(C H2 Cl2), C32 H12 B F24'
_chemical_formula_sum            'C66.5 H61 B Cl F24 Ir N6 O7'
_chemical_formula_weight         1750.67
_chemical_melting_point          ?
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -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)
;
_cell_angle_alpha                105.7531(13)
_cell_angle_beta                 101.3983(12)
_cell_angle_gamma                93.5564(11)
_cell_formula_units_Z            2
_cell_length_a                   13.18759(16)
_cell_length_b                   13.44313(19)
_cell_length_c                   21.8724(3)
_cell_measurement_reflns_used    37333
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      30.2680
_cell_measurement_theta_min      2.7990
_cell_volume                     3630.74(9)
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -53.00   50.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       23.1653  -38.0000  150.0000 103

  2 omega   -6.00   97.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       23.1653   57.0000  -60.0000 103

  3 omega   35.00  113.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       23.1653  178.0000 -180.0000 78

  4 omega -103.00    9.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -24.2590  -77.0000   60.0000 112

  5 omega  -78.00  -13.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -24.2590  119.0000  -83.0000 65

  6 omega -114.00  -57.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -24.2590 -178.0000   90.0000 57

  7 omega  -51.00   52.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -24.2590   38.0000    0.0000 103

  8 omega -114.00  -57.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -24.2590 -178.0000 -120.0000 57

  9 omega -114.00  -57.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -24.2590 -178.0000 -180.0000 57

 10 omega  -98.00    5.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -24.2590  -57.0000   60.0000 103

 11 omega   -3.00   99.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       23.1653   38.0000 -120.0000 102

 12 omega   35.00  113.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       23.1653  178.0000    0.0000 78

 13 omega -103.00    9.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -24.2590  -77.0000  -60.0000 112
;
_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      -0.0137850000
_diffrn_orient_matrix_UB_12      -0.0520983000
_diffrn_orient_matrix_UB_13      -0.0201898000
_diffrn_orient_matrix_UB_21      -0.0138578000
_diffrn_orient_matrix_UB_22      0.0182771000
_diffrn_orient_matrix_UB_23      -0.0276867000
_diffrn_orient_matrix_UB_31      0.0517140000
_diffrn_orient_matrix_UB_32      -0.0017487000
_diffrn_orient_matrix_UB_33      -0.0045504000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0494
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            86670
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.373
_diffrn_reflns_theta_max         26.373
_diffrn_reflns_theta_min         2.940
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.992
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84006
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.601
_exptl_crystal_density_meas      ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1746
_exptl_crystal_recrystallization_method
'Crystals grown from CH2Cl2-heptane at 293 K'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.060
_refine_diff_density_min         -1.101
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1066
_refine_ls_number_reflns         14834
_refine_ls_number_restraints     772
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0385
_refine_ls_R_factor_gt           0.0332
_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^)+(0.0439P)^2^+4.5265P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0810
_refine_ls_wR_factor_ref         0.0835
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13487
_reflns_number_total             14834
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om5b00692_si_003.cif
_cod_data_source_block           0120abc14
_cod_depositor_comments
;
The following automatic conversions were performed:

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

data item '_exptl_crystal_density_meas' value 'not measured' was
changed to '?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 
;
_cod_original_formula_sum        'C66.50 H61 B Cl F24 Ir N6 O7'
_cod_database_code               4087904
_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
 Cl1-C800 \\sim Cl2-C800
 with sigma of 0.01
 C215-F7 \\sim C215-F8 \\sim C215-F9 \\sim C215-F7A \\sim C215-F8A \\sim
C215-F9A
 with sigma of 0.01
 F7-F8 \\sim F8-F9 \\sim F9-F7 \\sim F7A-F8A \\sim F8A-F9A \\sim F9A-F7A
 with sigma of 0.01
 C211-F7 \\sim C211-F8 \\sim C211-F9 \\sim C211-F7A \\sim C211-F8A \\sim
C211-F9A
 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
 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
 O3B-C2B \\sim O3A-C2A \\sim O3-C2
 with sigma of 0.007
 Ir1-C2B \\sim Ir1-C2A \\sim Ir1-C2
 with sigma of 0.007
 Ir1-O3A \\sim Ir1-O3 \\sim Ir1-O3B
 with sigma of 0.01
 C2-C2A \\sim C2-C2B
 with sigma of 0.01
 O3-O3A \\sim O3-O3B
 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
3. Restrained planarity
 Ir1, C2A, O3A, C2, O3, C2B, O3B
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Cl1 \\sim C800 \\sim Cl2: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F7 \\sim F7A \\sim F8
\\sim F8A \\sim F9 \\sim F9A \\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 C215 \\sim C216 \\sim C2A
\\sim C2B \\sim O3 \\sim O3A \\sim O3B \\sim C45 \\sim C46: within 1.7A with
sigma of 0.007 and sigma for terminal atoms of 0.02
Uanis(Cl1) \\sim Ueq, Uanis(C800) \\sim Ueq, Uanis(Cl2) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(F1) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F4) \\sim
Ueq, Uanis(F5) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F7A)
\\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(F8A) \\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(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(C215) \\sim Ueq, Uanis(C216) \\sim Ueq, Uanis(C2) \\sim Ueq,
Uanis(C2A) \\sim Ueq, Uanis(C2B) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(O3A)
\\sim Ueq, Uanis(O3B) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C46) \\sim Ueq:
with sigma of 0.007 and sigma for terminal atoms of 0.02
Uanis(Cl1) = Uanis(Cl2)
Uanis(C2A) = Uanis(C2) = Uanis(C2B)
Uanis(O3A) = Uanis(O3) = Uanis(O3B)
Uanis(F15) = Uanis(F15A)
Uanis(F13) = Uanis(F13A)
Uanis(F14A) = Uanis(F14)
Uanis(F19A) = Uanis(F19)
Uanis(F20) = Uanis(F20A)
Uanis(F21) = Uanis(F21A)
5. Others
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(1)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(1)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(2)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(2)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(3)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(3)
 Fixed Sof: O3(0.5) O3A(0.25) O3B(0.25) C2(0.5) C2A(0.25) C2B(0.25) Cl1(0.5)
 Cl2(0.5) C800(0.5) H80A(0.5) H80B(0.5) F19(0.5) F19A(0.5) F20(0.5) F20A(0.5)
 F21(0.5) F21A(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C13(H13A,H13B), C25(H25A,H25B), C28(H28A,H28B), C40(H40A,
 H40B), C43(H43A,H43B), C800(H80A,H80B)
6.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)
6.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C),
 C48(H48A,H48B,H48C)
;
_olex2_submission_special_instructions 'No special instructions were received'