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_7110240
_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         'C35 H39 Ir N3, C32 H12 B F24'
_chemical_formula_sum            'C67 H51 B F24 Ir N3'
_chemical_formula_weight         1557.11
_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             2013-09-23
_audit_creation_method
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Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
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_cell_formula_units_Z            2
_cell_length_a                   12.84071(12)
_cell_length_b                   13.68282(19)
_cell_length_c                   19.1287(4)
_cell_measurement_reflns_used    40092
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      31.1100
_cell_measurement_theta_min      3.2300
_cell_volume                     3161.40(9)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
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_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics
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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
;
SHELX, 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 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Oxford Diffraction: Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0011805000
_diffrn_orient_matrix_UB_12      -0.0530908000
_diffrn_orient_matrix_UB_13      0.0039454000
_diffrn_orient_matrix_UB_21      -0.0024302000
_diffrn_orient_matrix_UB_22      0.0106005000
_diffrn_orient_matrix_UB_23      -0.0382305000
_diffrn_orient_matrix_UB_31      0.0561440000
_diffrn_orient_matrix_UB_32      -0.0018856000
_diffrn_orient_matrix_UB_33      -0.0082566000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0366
_diffrn_reflns_av_unetI/netI     0.0264
_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       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            69259
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.372
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.990
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.227
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79254
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.636
_exptl_crystal_density_meas      ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1544
_exptl_crystal_recrystallization_method
'Crystals grown from CH2Cl2/pentane at 293 K'
_exptl_crystal_size_max          0.4000
_exptl_crystal_size_mid          0.2000
_exptl_crystal_size_min          0.0800
_refine_diff_density_max         4.122
_refine_diff_density_min         -2.789
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.131
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     929
_refine_ls_number_reflns         12888
_refine_ls_number_restraints     500
_refine_ls_restrained_S_all      1.144
_refine_ls_R_factor_all          0.0512
_refine_ls_R_factor_gt           0.0481
_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^)+(0.0326P)^2^+15.7476P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1091
_refine_ls_wR_factor_ref         0.1110
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12200
_reflns_number_total             12888
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c3cc48015a.txt
_cod_data_source_block           0039abc13
_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        3161.40(8)
_cod_database_code               7110240
_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
 C223-F13 \\sim C223-F14 \\sim C223-F15 \\sim C323-F113 \\sim C323-F114 \\sim
C323-F115
 with sigma of 0.01
 F13-F14 \\sim F14-F15 \\sim F15-F13 \\sim F113-F114 \\sim F114-F115 \\sim
F115-F113
 with sigma of 0.01
 C219-F13 \\sim C219-F14 \\sim C219-F15 \\sim C219-F113 \\sim C219-F114 \\sim
C219-F115
 with sigma of 0.01
 C219-C223 \\sim C219-C323
 with sigma of 0.01
 C231-F19 \\sim C231-F20 \\sim C231-F21 \\sim C331-F119 \\sim C331-F120 \\sim
C331-F121
 with sigma of 0.01
 F19-F20 \\sim F20-F21 \\sim F21-F19 \\sim F119-F120 \\sim F120-F121 \\sim
F121-F119
 with sigma of 0.01
 C227-F19 \\sim C227-F20 \\sim C227-F21 \\sim C227-F119 \\sim C227-F120 \\sim
C227-F121
 with sigma of 0.01
 C227-C231 \\sim C227-C331
 with sigma of 0.01
3. 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
F113 \\sim F114 \\sim F115 \\sim F119 \\sim F120 \\sim F121 \\sim C231 \\sim
C331 \\sim C223 \\sim C323: 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(F113) \\sim Ueq,
Uanis(F114) \\sim Ueq, Uanis(F115) \\sim Ueq, Uanis(F119) \\sim Ueq,
Uanis(F120) \\sim Ueq, Uanis(F121) \\sim Ueq, Uanis(C231) \\sim Ueq,
Uanis(C331) \\sim Ueq, Uanis(C223) \\sim Ueq, Uanis(C323) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C231) = Uanis(C331)
Uanis(C223) = Uanis(C323)
4. Others
 Sof(F113)=Sof(F114)=Sof(F115)=Sof(C323)=1-FVAR(1)
 Sof(F13)=Sof(F14)=Sof(F15)=Sof(C223)=FVAR(1)
 Sof(F119)=Sof(F120)=Sof(F121)=Sof(C331)=1-FVAR(2)
 Sof(F19)=Sof(F20)=Sof(F21)=Sof(C231)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C6(H6)
5.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C7(H7A,H7B), C8(H8A,H8B), C13(H13A,H13B), C16(H16A,
 H16B)
5.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C18(H18), C19(H19), C20(H20), C21(H21), C23(H23),
 C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C31(H31), C32(H32), C33(H33),
  C34(H34), C35(H35), 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.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C)
;