Solvent promoted reversible cyclometalation in a tethered NHC iridium complex
James E. Wheatley; C. Andre Ohlin; Adrian B. Chaplin; Chem.Commun. 50 (2014) 685–; doi:10.1039/c3cc48015a

data_7110239
_publ_section_title
;
 Solvent promoted reversible cyclometalation in a tethered NHC iridium
 complex
;
_journal_name_full               Chem.Commun.
_journal_page_first              685
_journal_paper_doi               10.1039/c3cc48015a
_journal_volume                  50
_journal_year                    2014
_chemical_formula_moiety         'C21 H29 Ir N3, C32 H12 B F24'
_chemical_formula_sum            'C53 H41 B F24 Ir N3'
_chemical_formula_weight         1378.90
_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'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-09-27
_audit_creation_method
;
  Olex2 1.2
  (compiled 2013.04.25 svn.r2679, GUI svn.r4466)
;
_cell_angle_alpha                102.455(2)
_cell_angle_beta                 108.834(2)
_cell_angle_gamma                99.854(2)
_cell_formula_units_Z            2
_cell_length_a                   12.1985(3)
_cell_length_b                   14.5752(4)
_cell_length_c                   16.9130(4)
_cell_measurement_reflns_used    14293
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      30.4711
_cell_measurement_theta_min      2.8397
_cell_volume                     2683.11(13)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_molecular_graphics
;
Ortep-3 for Windows: L. J. Farrugia, J. Appl. Cryst (1997), 30, 565.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G. M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      150(2)
_diffrn_detector_area_resol_mean 10.2833
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega   50.00   84.00   1.0000    6.0400
omega____ theta____ kappa____ phi______ frames
    -       13.7933  178.0000  120.0000 34

  2 omega   36.00   62.00   1.0000    6.0400
omega____ theta____ kappa____ phi______ frames
    -       13.7933  178.0000 -120.0000 26

  3 omega  -96.00  -70.00   1.0000    6.0400
omega____ theta____ kappa____ phi______ frames
    -      -14.7308  178.0000 -180.0000 26

  4 omega  -71.00   10.00   1.0000    6.0400
omega____ theta____ kappa____ phi______ frames
    -      -14.7308  -38.0000 -120.0000 81

  5 omega  -25.00   27.00   1.0000    6.0400
omega____ theta____ kappa____ phi______ frames
    -      -14.7308  -99.0000  -30.0000 52

  6 omega  -81.00   12.00   1.0000    6.0400
omega____ theta____ kappa____ phi______ frames
    -      -14.7308  -38.0000   30.0000 93

  7 omega  -24.00   47.00   1.0000    6.0400
omega____ theta____ kappa____ phi______ frames
    -      -14.7308   57.0000 -150.0000 71

  8 omega  -26.00   11.00   1.0000    6.0400
omega____ theta____ kappa____ phi______ frames
    -      -14.7308  -57.0000   90.0000 37
;
_diffrn_measurement_device_type  'Oxford Diffraction: Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0324501000
_diffrn_orient_matrix_UB_12      0.0320027000
_diffrn_orient_matrix_UB_13      0.0427218000
_diffrn_orient_matrix_UB_21      0.0193073000
_diffrn_orient_matrix_UB_22      -0.0389481000
_diffrn_orient_matrix_UB_23      0.0141642000
_diffrn_orient_matrix_UB_31      0.0512196000
_diffrn_orient_matrix_UB_32      0.0111137000
_diffrn_orient_matrix_UB_33      -0.0108929000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0314
_diffrn_reflns_av_unetI/netI     0.0431
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            26951
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.372
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.965
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.612
_exptl_absorpt_correction_T_max  0.732
_exptl_absorpt_correction_T_min  0.595
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.707
_exptl_crystal_density_meas      ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1356
_exptl_crystal_recrystallization_method
'Crystals grown from CH2Cl2/pentane at 293 K'
_exptl_crystal_size_max          0.3257
_exptl_crystal_size_mid          0.2276
_exptl_crystal_size_min          0.1797
_refine_diff_density_max         5.601
_refine_diff_density_min         -1.075
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     826
_refine_ls_number_reflns         10965
_refine_ls_number_restraints     451
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0508
_refine_ls_R_factor_gt           0.0443
_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^)+(0.0521P)^2^+7.3274P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1059
_refine_ls_wR_factor_ref         0.1107
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9819
_reflns_number_total             10965
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c3cc48015a.txt
_cod_data_source_block           2
_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 1891 2012-01-12 08:04:46Z andrius 

The following automatic conversions were performed:

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

Automatic conversion script
Id: cif_fix_values 3008 2015-01-20 13:52:24Z robertas 
;
_cod_original_cell_volume        2683.10(13)
_cod_database_code               7110239
_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
 N1-C9 = N2-C9
 1.35 with sigma of 0.001
 C207-F1 \\sim C207-F2 \\sim C207-F3 \\sim C207-F101 \\sim C207-F102 \\sim
C207-F103
 with sigma of 0.01
 F1-F2 \\sim F2-F3 \\sim F3-F1 \\sim F101-F102 \\sim F102-F103 \\sim F103-F101
 with sigma of 0.01
 C203-F1 \\sim C203-F2 \\sim C203-F3 \\sim C203-F101 \\sim C203-F102 \\sim
C203-F103
 with sigma of 0.01
 C224-F16 \\sim C224-F17 \\sim C224-F18 \\sim C224-F116 \\sim C224-F117 \\sim
C224-F118
 with sigma of 0.01
 F16-F17 \\sim F17-F18 \\sim F18-F16 \\sim F116-F117 \\sim F117-F118 \\sim
F118-F116
 with sigma of 0.01
 C221-F16 \\sim C221-F17 \\sim C221-F18 \\sim C221-F116 \\sim C221-F117 \\sim
C221-F118
 with sigma of 0.01
 C232-F22 \\sim C232-F23 \\sim C232-F24 \\sim C232-F122 \\sim C232-F123 \\sim
C232-F124
 with sigma of 0.01
 F22-F23 \\sim F23-F24 \\sim F24-F22 \\sim F122-F123 \\sim F123-F124 \\sim
F124-F122
 with sigma of 0.01
 C229-F22 \\sim C229-F23 \\sim C229-F24 \\sim C229-F122 \\sim C229-F123 \\sim
C229-F124
 with sigma of 0.01
3. Restrained planarity
 N1, N2, C9, C10, C11
 with sigma of 0.001
4. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F7 \\sim F8 \\sim F9
\\sim F10 \\sim F11 \\sim F12 \\sim F13 \\sim F14 \\sim F15 \\sim F16 \\sim F17
\\sim F18 \\sim F19 \\sim F20 \\sim F21 \\sim F22 \\sim F23 \\sim F24 \\sim
F101 \\sim F102 \\sim F103 \\sim F116 \\sim F117 \\sim F118 \\sim F122 \\sim
F123 \\sim F124: within 1.7A 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(F8)
\\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F11) \\sim Ueq,
Uanis(F12) \\sim Ueq, Uanis(F13) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F15)
\\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(F101) \\sim Ueq,
Uanis(F102) \\sim Ueq, Uanis(F103) \\sim Ueq, Uanis(F116) \\sim Ueq,
Uanis(F117) \\sim Ueq, Uanis(F118) \\sim Ueq, Uanis(F122) \\sim Ueq,
Uanis(F123) \\sim Ueq, Uanis(F124) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C9) \\sim Ueq: with sigma of 0.0001 and sigma for terminal atoms of 0.0002
5. Others
 Sof(F116)=Sof(F117)=Sof(F118)=1-FVAR(1)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(1)
 Sof(F122)=Sof(F123)=Sof(F124)=1-FVAR(2)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(2)
 Sof(F101)=Sof(F102)=Sof(F103)=1-FVAR(3)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C6(H6)
6.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C7(H7A,H7B), C8(H8A,H8B), C16(H16A,H16B)
6.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C18(H18), C19(H19), C20(H20), C21(H21), 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.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C)
;