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_7110241
_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 N3 Rh, C32 H12 B F24'
_chemical_formula_sum            'C53 H41 B F24 N3 Rh'
_chemical_formula_weight         1289.61
_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
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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                   12.1608(2)
_cell_length_b                   14.5984(2)
_cell_length_c                   16.9119(3)
_cell_measurement_reflns_used    27209
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      34.0042
_cell_measurement_theta_min      2.8452
_cell_volume                     2685.08(9)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
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_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
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_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
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_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 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Oxford Diffraction: Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0440906000
_diffrn_orient_matrix_UB_12      -0.0187594000
_diffrn_orient_matrix_UB_13      0.0255771000
_diffrn_orient_matrix_UB_21      -0.0251180000
_diffrn_orient_matrix_UB_22      0.0061977000
_diffrn_orient_matrix_UB_23      0.0327161000
_diffrn_orient_matrix_UB_31      -0.0384931000
_diffrn_orient_matrix_UB_32      -0.0475634000
_diffrn_orient_matrix_UB_33      -0.0202616000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0267
_diffrn_reflns_av_unetI/netI     0.0164
_diffrn_reflns_Laue_measured_fraction_full 0.998
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_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            64082
_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         2.958
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.441
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97469
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
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    1.595
_exptl_crystal_density_meas      ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1292
_exptl_crystal_recrystallization_method
'Crystals grown from CH2Cl2/pentane at 293 K'
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.5
_refine_diff_density_max         6.933
_refine_diff_density_min         -1.812
_refine_diff_density_rms         0.126
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     842
_refine_ls_number_reflns         10966
_refine_ls_number_restraints     508
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0834
_refine_ls_R_factor_gt           0.0790
_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^)+(0.1128P)^2^+12.3984P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2059
_refine_ls_wR_factor_ref         0.2100
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10084
_reflns_number_total             10966
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c3cc48015a.txt
_cod_data_source_block           8
_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        2685.07(9)
_cod_database_code               7110241
_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
 C208-F4 \\sim C208-F5 \\sim C208-F6 \\sim C208-F104 \\sim C208-F105 \\sim
C208-F106
 with sigma of 0.01
 F4-F5 \\sim F5-F6 \\sim F6-F4 \\sim F104-F105 \\sim F105-F106 \\sim F106-F104
 with sigma of 0.01
 C205-F4 \\sim C205-F5 \\sim C205-F6 \\sim C205-F104 \\sim C205-F105 \\sim
C205-F106
 with sigma of 0.01
 C215-F7 \\sim C215-F8 \\sim C215-F9 \\sim C215-F107 \\sim C215-F108 \\sim
C215-F109
 with sigma of 0.01
 F7-F8 \\sim F8-F9 \\sim F9-F7 \\sim F107-F108 \\sim F108-F109 \\sim F109-F107
 with sigma of 0.01
 C211-F7 \\sim C211-F8 \\sim C211-F9 \\sim C211-F107 \\sim C211-F108 \\sim
C211-F109
 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
C9: within 1.7A with sigma of 0.0001 and sigma for terminal atoms of 0.0002
F2 \\sim F14 \\sim F8 \\sim F1 \\sim F3 \\sim F19 \\sim F11 \\sim F7 \\sim F4
\\sim F12 \\sim F15 \\sim F21 \\sim F5 \\sim F20 \\sim F13 \\sim F18 \\sim F24
\\sim F9 \\sim F6 \\sim F22 \\sim F10 \\sim F17 \\sim F16 \\sim F23 \\sim F117
\\sim F116 \\sim F118 \\sim F122 \\sim F124 \\sim F123 \\sim F107 \\sim F109
\\sim F108 \\sim F106 \\sim F105 \\sim F104: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(F2) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(F1) \\sim
Ueq, Uanis(F3) \\sim Ueq, Uanis(F19) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F7)
\\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F15) \\sim Ueq,
Uanis(F21) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F20) \\sim Ueq, Uanis(F13)
\\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(F24) \\sim Ueq, Uanis(F9) \\sim Ueq,
Uanis(F6) \\sim Ueq, Uanis(F22) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F17)
\\sim Ueq, Uanis(F16) \\sim Ueq, Uanis(F23) \\sim Ueq, Uanis(F117) \\sim Ueq,
Uanis(F116) \\sim Ueq, Uanis(F118) \\sim Ueq, Uanis(F122) \\sim Ueq,
Uanis(F124) \\sim Ueq, Uanis(F123) \\sim Ueq, Uanis(F107) \\sim Ueq,
Uanis(F109) \\sim Ueq, Uanis(F108) \\sim Ueq, Uanis(F106) \\sim Ueq,
Uanis(F105) \\sim Ueq, Uanis(F104) \\sim Ueq: with sigma of 0.007 and sigma for
terminal atoms of 0.02
Uanis(C9) = Uanis(N1) = Uanis(N2)
5. Others
 Sof(F117)=Sof(F116)=Sof(F118)=1-FVAR(1)
 Sof(F18)=Sof(F17)=Sof(F16)=FVAR(1)
 Sof(F122)=Sof(F124)=Sof(F123)=1-FVAR(2)
 Sof(F24)=Sof(F22)=Sof(F23)=FVAR(2)
 Sof(F107)=Sof(F109)=Sof(F108)=1-FVAR(3)
 Sof(F8)=Sof(F7)=Sof(F9)=FVAR(3)
 Sof(F106)=Sof(F105)=Sof(F104)=1-FVAR(4)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C5(H5), C1(H1), C2(H2), C6(H6)
6.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C3(H3A,H3B), C4(H4A,H4B), C8(H8A,H8B), C7(H7A,H7B)
6.c Aromatic/amide H refined with riding coordinates:
 C230(H230), C214(H214), C218(H218), C222(H222), C206(H206), C210(H210),
 C202(H202), C226(H226), C228(H228), C204(H204), C220(H220), C212(H212),
 C11(H11), C10(H10), C21(H21), C18(H18), C19(H19), C20(H20)
6.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C)
;