Acid-base-induced fac → mer isomerization of luminescent iridium(iii) complexes
Yu. Gitlina, Anastasia; Fadaei-Tirani, Farzaneh; Ruggi, Albert; Plaice, Carolina; Severin, Kay; Chemical Science  (2022) –; doi:10.1039/D2SC02808E

data_1567511
_publ_section_title
;
 Acid-base-induced fac \\rightarrow mer isomerization of luminescent
 iridium(iii) complexes
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC02808E
_journal_year                    2022
_chemical_formula_moiety         'C69 H48 Ir N3'
_chemical_formula_sum            'C69 H48 Ir N3'
_chemical_formula_weight         1111.30
_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     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-08-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-08-10 deposited with the CCDC.	2022-07-22 downloaded from the CCDC.
;
_cell_angle_alpha                68.335(3)
_cell_angle_beta                 85.431(3)
_cell_angle_gamma                64.368(3)
_cell_formula_units_Z            4
_cell_length_a                   18.0800(5)
_cell_length_b                   18.3585(7)
_cell_length_c                   19.0127(7)
_cell_measurement_reflns_used    25613
_cell_measurement_temperature    139.99(10)
_cell_measurement_theta_max      74.3130
_cell_measurement_theta_min      2.4980
_cell_volume                     5263.6(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (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      139.99(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 0.997
_diffrn_measured_fraction_theta_max 0.952
_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     63.00 109.00   0.50    2.50    --   59.51  32.00 -99.00   92
  2  \w     10.00  39.00   0.50    2.50    --   59.51 -32.00 101.00   58
  3  \w     74.00 120.00   0.50    2.50    --   70.39  32.00 -99.00   92
  4  \w     77.00 123.00   0.50   10.00    --   73.41  32.00 -99.00   92
  5  \w   -123.00 -77.00   0.50   10.00    --  -73.98 -32.00 101.00   92
  6  \w   -125.00 -79.00   0.50   10.00    --  -75.91 -32.00 101.00   92
  7  \w     84.00 130.00   0.50   10.00    --   80.28  32.00 -99.00   92
  8  \w    -24.00   2.00   0.50    2.50    --   -6.00 105.00-147.40   52
  9  \w     -3.00  26.00   0.50    2.50    --   10.00  98.00  60.00   58
 10  \w    -34.00  -5.00   0.50    2.50    --  -10.00 113.00  -4.95   58
 11  \w      4.00  33.00   0.50    2.50    --   14.00  94.00-116.87   58
 12  \w     10.00  41.00   0.50    2.50    --   18.00  91.00  21.63   62
 13  \w    -47.00 -11.00   0.50    2.50    --  -18.00 121.00  63.93   72
 14  \w     15.00  42.00   0.50    2.50    --   22.00  89.00 167.03   54
 15  \w     16.00  42.00   0.50    2.50    --   22.00  88.00  79.65   52
 16  \w     14.00  41.00   0.50    2.50    --   22.00  91.00-118.37   54
 17  \w     14.00  41.00   0.50    2.50    --   22.00  91.00 -32.90   54
 18  \w     32.00  68.00   0.50    2.50    --   30.00  75.00  66.90   72
 19  \w     32.00  68.00   0.50    2.50    --   30.00  75.00 133.04   72
 20  \w     33.00  69.00   0.50    2.50    --   30.00  74.00 -77.53   72
 21  \w     32.00  68.00   0.50    2.50    --   30.00  75.00 104.33   72
 22  \w     35.00  71.00   0.50    2.50    --   34.00  77.00 164.99   72
 23  \w     36.00  72.00   0.50    2.50    --   34.00  75.00-148.62   72
 24  \w     36.00  72.00   0.50    2.50    --   34.00  75.00  81.21   72
 25  \w     37.00  73.00   0.50    2.50    --   34.00  73.00  48.62   72
 26  \w     39.00  74.00   0.50    2.50    --   34.00  70.00 -98.18   70
 27  \w     36.00  72.00   0.50    2.50    --   34.00  76.00 -61.45   72
 28  \w     37.00  73.00   0.50    2.50    --   34.00  74.00   0.48   72
 29  \w     39.00  75.00   0.50    2.50    --   38.00  77.00-179.20   72
 30  \w     39.00  75.00   0.50    2.50    --   38.00  77.00 140.63   72
 31  \w     39.00  75.00   0.50    2.50    --   38.00  77.00   7.56   72
 32  \w     40.00  76.00   0.50    2.50    --   38.00  75.00 -38.36   72
 33  \w     40.00  76.00   0.50    2.50    --   38.00  75.00  94.32   72
 34  \w     47.00  82.00   0.50    2.50    --   42.00  70.00  54.76   70
 35  \w     47.00  82.00   0.50    2.50    --   42.00  71.00  38.38   70
 36  \w     45.00  81.00   0.50    2.50    --   42.00  74.00-116.72   72
 37  \w     44.00  80.00   0.50    2.50    --   42.00  75.00 -82.40   72
 38  \w     44.00  80.00   0.50    2.50    --   42.00  75.00-136.08   72
 39  \w     48.00  84.00   0.50    2.50    --   46.00  76.00 102.98   72
 40  \w     53.00  88.00   0.50    2.50    --   46.00  64.00-169.32   70
 41  \w     50.00  85.00   0.50    2.50    --   46.00  72.00 138.78   70
 42  \w     51.00  86.00   0.50    2.50    --   46.00  71.00-108.35   70
 43  \w    -88.00 -52.00   0.50    2.50    --  -50.00 -75.00 -52.38   72
 44  \w     55.00  90.00   0.50    2.50    --   50.00  71.00 -13.23   70
 45  \w     53.00  89.00   0.50    2.50    --   50.00  73.00 -54.19   72
 46  \w     55.00  90.00   0.50    2.50    --   50.00  70.00 -96.76   70
 47  \w    -88.00 -52.00   0.50    2.50    --  -50.00 -75.00  -4.51   72
 48  \w     53.00  89.00   0.50    2.50    --   50.00  74.00  74.73   72
 49  \w     55.00  90.00   0.50    2.50    --   50.00  70.00  63.28   70
 50  \w     55.00  91.00   0.50    2.50    --   50.00  69.00 152.74   72
 51  \w     51.00  87.00   0.50    2.50    --   50.00  77.00-141.11   72
 52  \w     54.00  89.00   0.50    2.50    --   50.00  72.00   0.69   70
 53  \w     55.00  90.00   0.50    2.50    --   50.00  71.00-165.46   70
 54  \w     61.00  96.00   0.50    2.50    --   54.00  64.00-118.52   70
 55  \w     58.00  93.00   0.50    2.50    --   54.00  72.00 108.67   70
 56  \w     58.00  93.00   0.50    2.50    --   54.00  72.00 101.12   70
 57  \w     59.00  84.00   0.50    2.50    --   54.00  70.00  57.14   50
 58  \w     59.00  84.00   0.50    2.50    --   54.00  71.00 -68.04   50
 59  \w     57.00  82.00   0.50    2.50    --   54.00  73.00  27.29   50
 60  \w     59.00  84.00   0.50    2.50    --   54.00  70.00  75.14   50
 61  \w     58.00  83.00   0.50    2.50    --   54.00  72.00 115.83   50
 62  \w     63.00  88.00   0.50    2.50    --   58.00  69.00-148.62   50
 63  \w     61.00  86.00   0.50    2.50    --   58.00  73.00 -42.68   50
 64  \w    -89.00 -63.00   0.50    2.50    --  -58.00 -70.00 168.13   52
 65  \w     62.00  87.00   0.50    2.50    --   58.00  72.00 -61.58   50
 66  \w     11.00  36.00   0.50    2.50    --   59.51 -30.00  30.00   50
 67  \w     20.00  45.00   0.50    2.50    --   59.51 -95.00 -60.00   50
 68  \w     10.00  35.00   0.50    2.50    --   59.51 -30.00   0.00   50
 69  \w     22.00  51.00   0.50    2.50    --   59.51 -95.00-120.00   58
 70  \w     11.00  37.00   0.50    2.50    --   59.51 -30.00  60.00   52
 71  \w     11.00  36.00   0.50    2.50    --   59.51 -30.00 150.00   50
 72  \w     24.00  59.00   0.50    2.50    --   59.51 -95.00-180.00   70
 73  \w     10.00  35.00   0.50    2.50    --   59.51 -30.00-180.00   50
 74  \w     10.00  36.00   0.50    2.50    --   59.51 -30.00 -60.00   52
 75  \w     10.00  35.00   0.50    2.50    --   59.51 -30.00 -30.00   50
 76  \w     65.00  92.00   0.50    2.50    --   62.00  73.00  -1.11   54
 77  \w     67.00  92.00   0.50    2.50    --   62.00  70.00 -98.07   50
 78  \w     67.00  92.00   0.50    2.50    --   62.00  71.00 -79.14   50
 79  \w     67.00  92.00   0.50    2.50    --   62.00  71.00  81.14   50
 80  \w     67.00  96.00   0.50    2.50    --   62.00  70.00-170.64   58
 81  \w     67.00  92.00   0.50    2.50    --   62.00  71.00 131.67   50
 82  \w     67.00  92.00   0.50    2.50    --   62.00  70.00 -85.37   50
 83  \w     67.00  92.00   0.50    2.50    --   62.00  71.00  42.31   50
 84  \w    -97.00 -71.00   0.50    2.50    --  -66.00 -68.00-144.76   52
 85  \w     69.00  99.00   0.50    2.50    --   66.00  75.00-127.47   60
 86  \w     70.00  95.00   0.50    2.50    --   66.00  72.00  20.50   50
 87  \w     69.00  95.00   0.50    2.50    --   66.00  74.00 -21.68   52
 88  \w     69.00 102.00   0.50    2.50    --   66.00  75.00 -48.04   66
 89  \w    -98.00 -69.00   0.50    2.50    --  -66.00 -73.00 156.20   58
 90  \w    -99.00 -73.00   0.50    2.50    --  -66.00 -59.00  71.55   52
 91  \w     70.00  97.00   0.50    2.50    --   66.00  72.00  49.61   54
 92  \w   -100.00 -73.00   0.50    2.50    --  -70.00 -73.00  64.68   54
 93  \w   -104.00 -75.00   0.50    2.50    --  -70.00 -70.00 108.55   58
 94  \w   -103.00 -75.00   0.50    2.50    --  -70.00 -73.00  11.07   56
 95  \w   -102.00 -72.00   0.50    2.50    --  -70.00 -75.00 147.38   60
 96  \w    -99.00 -73.00   0.50    2.50    --  -70.00 -73.00 -83.48   52
 97  \w   -108.00 -74.00   0.50    2.50    --  -70.00 -71.00 137.35   68
 98  \w     34.00  83.00   0.50   10.00    --   73.41 -95.00 120.00   98
 99  \w     35.00  64.00   0.50   10.00    --   73.41 -95.00  60.00   58
100  \w     28.00  74.00   0.50   10.00    --   73.41-125.00-120.00   92
101  \w     34.00  67.00   0.50   10.00    --   73.41 -95.00  90.00   66
102  \w     34.00  80.00   0.50   10.00    --   73.41 -95.00-180.00   92
103  \w     28.00 104.00   0.50   10.00    --   73.41-125.00 -60.00  152
104  \w   -118.00 -86.00   0.50   10.00    --  -73.98-125.00  30.00   64
105  \w   -120.00 -93.00   0.50   10.00    --  -73.98-125.00-180.00   54
106  \w   -117.00 -91.00   0.50   10.00    --  -73.98-125.00-120.00   52
107  \w   -103.00 -34.00   0.50   10.00    --  -73.98 125.00 -30.00  138
108  \w   -108.00 -78.00   0.50   10.00    --  -74.00 -73.00-151.01   60
109  \w   -111.00 -81.00   0.50   10.00    --  -74.00 -62.00  76.59   60
110  \w   -110.00 -77.00   0.50   10.00    --  -74.00 -73.00  60.15   66
111  \w   -110.00 -77.00   0.50   10.00    --  -74.00 -74.00  -0.42   66
112  \w     86.00 112.00   0.50   10.00    --   75.33  73.00-127.85   52
113  \w     85.00 111.00   0.50   10.00    --   75.33  71.00-104.64   52
114  \w     77.00 110.00   0.50   10.00    --   75.33  77.00 -78.44   66
115  \w   -122.00 -82.00   0.50   10.00    --  -75.91-125.00 -90.00   80
116  \w   -122.00 -97.00   0.50   10.00    --  -75.91-125.00 -30.00   50
117  \w   -121.00 -84.00   0.50   10.00    --  -75.91-125.00   0.00   74
118  \w   -119.00 -86.00   0.50   10.00    --  -75.91-125.00 150.00   66
119  \w   -119.00 -64.00   0.50   10.00    --  -75.91 -15.00   0.00  110
120  \w    -77.00 -44.00   0.50   10.00    --  -75.91 125.00 -90.00   66
121  \w   -115.00 -82.00   0.50   10.00    --  -78.00 -71.00 164.06   66
122  \w   -108.00 -80.00   0.50   10.00    --  -78.77 -76.00 130.22   56
123  \w   -112.00 -81.00   0.50   10.00    --  -78.77 -77.00-160.32   62
124  \w     82.00 113.00   0.50   10.00    --   80.28 125.00 -30.00   62
125  \w     79.00 126.00   0.50   10.00    --   80.28 125.00 -60.00   94
126  \w     42.00 111.00   0.50   10.00    --   80.28-125.00 120.00  138
127  \w     41.00 108.00   0.50   10.00    --   80.28-125.00 -30.00  134
128  \w     90.00 119.00   0.50   10.00    --   80.28 125.00  90.00   58
129  \w     37.00 111.00   0.50   10.00    --   80.28-125.00 -90.00  148
130  \w     97.00 124.00   0.50   10.00    --   80.28 125.00-150.00   54
131  \w     86.00 117.00   0.50   10.00    --   80.28 125.00-120.00   62
132  \w     79.00 109.00   0.50   10.00    --   80.28-125.00-180.00   60
133  \w     41.00  72.00   0.50   10.00    --   80.28-125.00-180.00   62
134  \w     37.00 111.00   0.50   10.00    --   80.28-125.00  30.00  148
135  \w     89.00 121.00   0.50   10.00    --   80.28 125.00  30.00   64
136  \w     94.00 120.00   0.50   10.00    --   80.28 125.00 120.00   52
;
_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      -0.0415332000
_diffrn_orient_matrix_UB_12      0.0676816000
_diffrn_orient_matrix_UB_13      0.0373976000
_diffrn_orient_matrix_UB_21      -0.0799950000
_diffrn_orient_matrix_UB_22      -0.0106491000
_diffrn_orient_matrix_UB_23      0.0001892000
_diffrn_orient_matrix_UB_31      0.0298331000
_diffrn_orient_matrix_UB_32      -0.0732391000
_diffrn_orient_matrix_UB_33      0.0792021000
_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     0.0423
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            26115
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.272
_diffrn_reflns_theta_min         2.512
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.255
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.425
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (Rigaku Oxford Diffraction, 2021)
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            'clear intense orange'
_exptl_crystal_density_diffrn    1.402
_exptl_crystal_description       plate
_exptl_crystal_F_000             2240
_exptl_crystal_size_max          0.176
_exptl_crystal_size_mid          0.061
_exptl_crystal_size_min          0.011
_refine_diff_density_max         5.309
_refine_diff_density_min         -2.857
_refine_diff_density_rms         0.209
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.402
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1028
_refine_ls_number_reflns         26115
_refine_ls_number_restraints     2270
_refine_ls_restrained_S_all      1.352
_refine_ls_R_factor_all          0.1771
_refine_ls_R_factor_gt           0.1321
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3576
_refine_ls_wR_factor_ref         0.3936
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15824
_reflns_number_total             26115
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9194\% 
around [-0.00 1.00 0.00] (reciprocal) or [-0.37 0.88 -0.29] (direct)
;
_cod_data_source_file            d2sc02808e3.cif
_cod_data_source_block           ag267_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_original_cell_volume        5263.6(3)
_cod_database_code               1567511
_shelx_shelxl_version_number     2018/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C69 H48 Ir N3'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.414(2)
 0.586(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3. Restrained distances
 C38-C41
 1.5 with sigma of 0.01
 C133-C130
 1.5 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.001 and sigma
for terminal atoms of 0.002 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 Aromatic/amide H refined with riding coordinates:
 C4(H), C3(HA), C2(HB), C1(HC), C50(HD), C49(HE), C48(HF), C47(HG), C10(HH),
 C11(HI), C8(HJ), C17(HK), C16(HL), C14(HM), C13(HN), C23(HO), C22(HP), C21(HQ),
  C20(HR), C19(HS), C26(HT), C27(HU), C24(HV), C25(HW), C31(HX), C34(HY),
 C33(HZ), C37(H1), C36(H2), C40(H3), C39(H4), C44(H5), C43(H6), C42(H7),
 C46(H8), C45(H9), C56(H10), C57(H11), C54(H12), C63(H13), C62(H14), C60(H15),
 C59(H16), C69(H17), C68(H18), C67(H19), C66(H20), C65(H21), C73(H73), C72(H72),
  C71(H71), C70(H70), C93(H93), C94(H94), C95(H95), C96(H96), C119(H119),
 C118(H118), C117(H117), C116(H116), C77(H77), C79(H79), C80(H80), C86(H86),
 C85(H85), C83(H83), C82(H82), C92(H92), C91(H91), C90(H90), C89(H89), C88(H88),
  C103(H103), C102(H102), C100(H100), C105(H105), C106(H106), C108(H108),
 C109(H109), C111(H111), C112(H112), C113(H113), C114(H114), C115(H115),
 C125(H125), C126(H126), C123(H123), C131(H131), C132(H132), C128(H128),
 C129(H129), C134(H134), C135(H135), C136(H136), C137(H137), C138(H138)
6.b Fitted hexagon refined as free rotating group:
 N1(C5,C4,C3,C2,C1), N3(C51,C50,C49,C48,C47), C9(C10,C11,C6,C7,C8), C12(C17,
 C16,C15,C14,C13), C18(C23,C22,C21,C20,C19), C26(C27,C28,N2,C24,C25), C32(C31,
 C30,C29,C34,C33), C38(C37,C36,C35,C40,C39), C44(C43,C42,C41,C46,C45), C55(C56,
 C57,C52,C53,C54), C58(C63,C62,C61,C60,C59), C64(C69,C68,C67,C66,C65), N4(C74,
 C73,C72,C71,C70), N5(C93,C94,C95,C96,C97), N6(C120,C119,C118,C117,C116),
 C75(C76,C77,C78,C79,C80), C81(C86,C85,C84,C83,C82), C87(C92,C91,C90,C89,C88),
 C98(C103,C102,C101,C100,C99), C104(C105,C106,C107,C108,C109), C110(C111,C112,
 C113,C114,C115), C124(C125,C126,C121,C122,C123), C130(C131,C132,C127,C128,
 C129), C133(C134,C135,C136,C137,C138)
;
_shelx_res_checksum              5959
_shelx_hkl_checksum              42915
_shelx_fab_checksum              23813
_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 2.284
_oxdiff_exptl_absorpt_empirical_full_min 0.531
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2