The acid-mediated isomerization of iridium(III) complexes with cyclometalated NHC ligands: kinetic <i>vs.</i> thermodynamic control.
Gitlina, Anastasia Yu; Fadaei-Tirani, Farzaneh; Severin, Kay; Dalton transactions (Cambridge, England : 2003) 52 (2023) 2833–2837; doi:10.1039/d2dt04039e

data_7712443
_publ_section_title
;
 The acid-mediated isomerization of iridium(III) complexes with
 cyclometalated NHC ligands: kinetic <i>vs.</i> thermodynamic control.
;
_journal_issue                   9
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2833
_journal_page_last               2837
_journal_paper_doi               10.1039/d2dt04039e
_journal_volume                  52
_journal_year                    2023
_chemical_formula_moiety
'C44 H34 F3 Ir N6 O2, C2 F3 O2, C6 H16 N, 2.5[C5H12]'
_chemical_formula_sum            'C52 H50 F6 Ir N7 O4'
_chemical_formula_weight         1143.19
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-02-01
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-01 deposited with the CCDC.	2023-02-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.416(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.2601(8)
_cell_length_b                   37.467(3)
_cell_length_c                   16.6652(12)
_cell_measurement_reflns_used    3930
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      60.1380
_cell_measurement_theta_min      2.3060
_cell_volume                     5646.7(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT 2018/2 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.970
_diffrn_measured_fraction_theta_max 0.975
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     10.00  36.00   0.50   20.00    --   59.56 -30.00 -30.00   52
  2  \w     11.00  36.00   0.50   20.00    --   59.56 -30.00  30.00   50
  3  \w     10.00  35.00   0.50   20.00    --   59.56 -30.00  60.00   50
  4  \w     69.00 108.00   0.50   20.00    --   59.56  30.00 -90.00   78
  5  \w     10.00  35.00   0.50   20.00    --   59.56 -30.00 -90.00   50
  6  \w     10.00  37.00   0.50   20.00    --   59.56 -30.00  90.00   54
  7  \w     44.00  78.00   0.50   20.00    --   73.45 -95.00 150.00   68
  8  \w     52.00  77.00   0.50   20.00    --   73.45 -95.00-180.00   50
  9  \w     77.00 112.00   0.50   20.00    --   73.45  30.00  60.00   70
 10  \w   -118.00 -75.00   0.50   20.00    --  -73.91 -30.00 -30.00   86
 11  \w   -118.00 -78.00   0.50   20.00    --  -73.91-125.00   0.00   80
 12  \w   -101.00 -75.00   0.50   20.00    --  -73.91-125.00 -30.00   52
 13  \w   -113.00 -88.00   0.50   20.00    --  -73.91-125.00-150.00   50
 14  \w   -104.00 -31.00   0.50   20.00    --  -73.91 125.00-150.00  146
 15  \w   -118.00 -80.00   0.50   20.00    --  -75.95 -30.00 150.00   76
 16  \w     50.00  90.00   0.50   20.00    --   80.01 -95.00 120.00   80
 17  \w     81.00 112.00   0.50   20.00    --   80.01 125.00  60.00   62
 18  \w     87.00 120.00   0.50   20.00    --   80.01 125.00-180.00   66
 19  \w     98.00 124.00   0.50   20.00    --   80.01 125.00 150.00   52
 20  \w     49.00  91.00   0.50   20.00    --   80.01 -95.00-150.00   84
 21  \w     42.00  86.00   0.50   20.00    --   80.01 -95.00 -30.00   88
 22  \w     83.00 122.00   0.50   20.00    --   80.01  30.00   0.00   78
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0256187000
_diffrn_orient_matrix_UB_12      0.0335383000
_diffrn_orient_matrix_UB_13      -0.0547385000
_diffrn_orient_matrix_UB_21      -0.1555936000
_diffrn_orient_matrix_UB_22      0.0040981000
_diffrn_orient_matrix_UB_23      0.0177808000
_diffrn_orient_matrix_UB_31      0.0640460000
_diffrn_orient_matrix_UB_32      0.0234749000
_diffrn_orient_matrix_UB_33      0.0751604000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0880
_diffrn_reflns_Laue_measured_fraction_full 0.970
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            6384
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        44.586
_diffrn_reflns_theta_max         44.586
_diffrn_reflns_theta_min         2.960
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.137
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.513
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.75a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on Gaussian integration over
a multifaceted crystal model.
Empirical absorption correction using spherical harmonics
as implemented in SCALE3 ABSPACK scaling algorithm
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.345
_exptl_crystal_description       plate
_exptl_crystal_F_000             2296
_exptl_crystal_size_max          0.192
_exptl_crystal_size_mid          0.048
_exptl_crystal_size_min          0.037
_refine_diff_density_max         2.025
_refine_diff_density_min         -1.495
_refine_diff_density_rms         0.198
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.114
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     638
_refine_ls_number_reflns         6384
_refine_ls_number_restraints     1034
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.1429
_refine_ls_R_factor_gt           0.1021
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2574
_refine_ls_wR_factor_ref         0.2932
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4301
_reflns_number_total             6384
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9022\% 
around [0.00 1.00 0.00] (reciprocal) or [0.07 1.00 0.01] (direct)
;
_cod_data_source_file            d2dt04039e2.cif
_cod_data_source_block           ag402_twin1_hklf5_sq
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Gaussian' was
changed to 'gaussian' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_database_code               7712443
_shelx_shelxl_version_number     2018/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C52 H50 F6 Ir N7 O4'
_shelx_estimated_absorpt_t_max   0.833
_shelx_estimated_absorpt_t_min   0.439
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.564(5)
 0.436(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 O4-C51
 1.4 with sigma of 0.02
 C52-F6 = C52-F4
 1.34 with sigma of 0.02
 C51-C52
 1.57 with sigma of 0.02
 C52-F5
 1.36 with sigma of 0.02
 C51-F6
 2.41 with sigma of 0.04
 C51-F5
 2.38 with sigma of 0.04
 O4-C52 = C51-F4
 2.43 with sigma of 0.04
 O4-C51 \\sim C51-O3
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Ternary CH refined with riding coordinates:
 N7(H7)
6.b Secondary CH2 refined with riding coordinates:
 C45(H45A,H45B), C47(H47A,H47B), C49(H49A,H49B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C12(H12),
 C16(H16), C17(H17), C18(H18), C19(H19), C23(H23), C24(H24), C25(H25), C26(H26),
  C31(H31), C32(H32), C33(H33), C34(H34), C37(H37), C38(H38), C39(H39),
 C40(H40), C41(H41)
6.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C28(H28A,H28B,H28C), C42(H42A,H42B,H42C), C46(H46A,H46B,
 H46C), C48(H48A,H48B,H48C), C50(H50A,H50B,H50C)
;
_shelx_res_checksum              74990
_shelx_fab_checksum              14275
_platon_squeeze_special_details
;
A solvent mask was calculated and 414 electrons were 
found in a volume of 1171\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
1[C5H12], 1[C5H12] per Asymmetric Unit 
which account for 336 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.071
_oxdiff_exptl_absorpt_empirical_full_min 0.428
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2