Predicting the catalytic activity of azolium-based halogen bond donors: an experimentally-verified theoretical study.
Sysoeva, Alexandra A.; Novikov, Alexander S.; Il'in, Mikhail V.; Suslonov, Vitalii V.; Bolotin, Dmitrii S.; Organic & biomolecular chemistry 19 (2021) 7611–7620; doi:10.1039/d1ob01158h

data_7158206
_publ_section_title
;
 Predicting the catalytic activity of azolium-based halogen bond donors:
 an experimentally-verified theoretical study.
;
_journal_issue                   35
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              7611
_journal_page_last               7620
_journal_paper_doi               10.1039/d1ob01158h
_journal_volume                  19
_journal_year                    2021
_chemical_formula_moiety         'C12 H14 I N2, I'
_chemical_formula_sum            'C12 H14 I2 N2'
_chemical_formula_weight         440.05
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2021-05-24
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.01.05 svn.r3372 for Rigaku Oxford Diffraction, GUI svn.r5289)
;
_audit_update_record
;
2021-05-24 deposited with the CCDC.	2021-07-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.7742(2)
_cell_length_b                   7.18240(10)
_cell_length_c                   15.7199(2)
_cell_measurement_reflns_used    14998
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      70.3360
_cell_measurement_theta_min      3.3930
_cell_volume                     1442.29(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -64.00 -14.00   0.50    0.24    --  -38.95  77.00-107.00  100
  2  \w     89.00 127.00   0.50    0.96    --  100.00 -77.00 127.00   76
  3  \w    131.00 157.00   0.50    0.96    --  100.00  77.00-107.00   52
  4  \w     83.00 123.00   0.50    0.96    --  100.00  77.00-107.00   80
  5  \w    -88.00 -55.00   0.50    0.24    --  -38.95 -43.00 -90.00   66
  6  \w    -54.00 -29.00   0.50    0.24    --  -38.95  43.00-120.00   50
  7  \w    -62.00 -16.00   0.50    0.24    --  -38.95  65.00   0.00   92
  8  \w    -95.00 -16.00   0.50    0.24    --  -38.95 138.00 -30.00  158
  9  \w    -75.00 -31.00   0.50    0.24    --  -38.95 -43.00  30.00   88
 10  \w    -52.00   4.00   0.50    0.24    --  -38.95  32.00 -60.00  112
 11  \w      1.00  26.00   0.50    0.24    --  -38.95  65.00   0.00   50
 12  \w    -27.00  -2.00   0.50    0.24    --  -38.95  43.00-120.00   50
 13  \w    -47.00 -22.00   0.50    0.24    --  -38.95 -43.00 -90.00   50
 14  \w    -18.00  41.00   0.50    0.24    --   38.95 -43.00  60.00  118
 15  \w     36.00  61.00   0.50    0.24    --   38.95 -77.00 127.00   50
 16  \w     -4.00  21.00   0.50    0.24    --   38.95 -77.00 127.00   50
 17  \w     78.00 105.00   0.50    0.96    --  100.00 -93.00-150.00   54
 18  \w     28.00  57.00   0.50    0.96    --  100.00 -93.00-150.00   58
 19  \w     97.00 123.00   0.50    0.96    --  100.00  30.00   0.00   52
 20  \w     75.00 100.00   0.50    0.96    --  100.00  15.00 150.00   50
 21  \w     36.00  61.00   0.50    0.96    --  100.00 -69.00-120.00   50
 22  \w     86.00 122.00   0.50    0.96    --  100.00 -61.00 -60.00   72
 23  \w     86.00 157.00   0.50    0.96    --  100.00  45.00-180.00  142
 24  \w     89.00 114.00   0.50    0.96    --  100.00 -30.00 -30.00   50
 25  \w     56.00  84.00   0.50    0.96    --  100.00 -30.00 -30.00   56
 26  \w     87.00 117.00   0.50    0.96    --  100.00 178.00  60.00   60
 27  \w     33.00  98.00   0.50    0.96    --  100.00 -37.00  90.00  130
 28  \w     71.00 125.00   0.50    0.96    --  100.00 -69.00-120.00  108
 29  \w     30.00 107.00   0.50    0.96    --  100.00 -22.00 150.00  154
 30  \w    106.00 157.00   0.50    0.96    --  100.00  15.00 150.00  102
 31  \w     54.00  80.00   0.50    0.96    --  100.00 178.00  60.00   52
 32  \w     72.00  99.00   0.50    0.96    --  100.00 -77.00   0.00   54
 33  \w     38.00  66.00   0.50    0.96    --  100.00 -86.00 120.00   56
 34  \w     46.00 122.00   0.50    0.96    --  100.00 -61.00 120.00  152
 35  \w     34.00  62.00   0.50    0.96    --  100.00 -77.00   0.00   56
 36  \w    109.00 140.00   0.50    0.96    --  100.00  69.00-120.00   62
 37  \w     54.00  79.00   0.50    0.96    --  100.00 -22.00 140.48   50
 38  \w     65.00 100.00   0.50    0.96    --  100.00  10.00  38.89   70
 39  \w     85.00 143.00   0.50    0.96    --  100.00  93.00-150.00  116
 40  \w    -69.00 -36.00   0.50    0.24    --  -38.95 102.00 140.00   66
 41  \w    -42.00 -12.00   0.50    0.24    --    0.00 120.00 -93.84   60
 42  \w    -30.00  -4.00   0.50    0.24    --   16.00 117.00  30.13   52
 43  \w    -12.00  13.00   0.50    0.24    --   24.00 101.00 -90.69   50
 44  \w    -13.00  12.00   0.50    0.24    --   24.00 102.00 128.18   50
 45  \w     -5.00  20.00   0.50    0.24    --   28.00  92.00  10.01   50
 46  \w      1.00  26.00   0.50    0.24    --   32.00  89.00 -59.34   50
 47  \w      1.00  26.00   0.50    0.24    --   32.00  88.00-137.69   50
 48  \w      1.00  26.00   0.50    0.24    --   32.00  88.00 179.86   50
 49  \w      7.00  32.00   0.50    0.24    --   36.00  83.00-106.42   50
 50  \w      7.00  32.00   0.50    0.24    --   36.00  83.00 109.26   50
 51  \w    -12.00  13.00   0.50    0.24    --  -38.95 102.00 140.00   50
 52  \w     12.00  37.00   0.50    0.24    --   40.00  80.00 -84.64   50
 53  \w     12.00  37.00   0.50    0.24    --   40.00  80.00  47.48   50
 54  \w     12.00  37.00   0.50    0.24    --   40.00  80.00  88.69   50
 55  \w     16.00  41.00   0.50    0.24    --   44.00  81.00 134.20   50
 56  \w     16.00  41.00   0.50    0.24    --   44.00  82.00  11.24   50
 57  \w     16.00  41.00   0.50    0.24    --   44.00  81.00 -33.86   50
 58  \w     16.00  41.00   0.50    0.24    --   44.00  80.00 -79.07   50
 59  \w     16.00  41.00   0.50    0.24    --   44.00  81.00-161.15   50
 60  \w     16.00  41.00   0.50    0.24    --   44.00  82.00 159.59   50
 61  \w     30.00  58.00   0.50    0.24    --   48.00  72.00 158.55   56
 62  \w     23.00  52.00   0.50    0.24    --   48.00  73.00 101.77   58
 63  \w     27.00  60.00   0.50    0.24    --   52.00  73.00 -82.47   66
 64  \w     26.00  52.00   0.50    0.24    --   52.00  74.00  38.85   52
 65  \w     46.00  71.00   0.50    0.24    --   60.00  65.00  37.55   50
 66  \w     37.00  70.00   0.50    0.24    --   60.00  67.00-150.45   66
 67  \w     37.00  89.00   0.50    0.24    --   60.00  73.00 175.83  104
 68  \w     45.00 101.00   0.50    0.24    --   60.00  72.00 121.44  112
 69  \w     71.00  97.00   0.50    0.24    --   60.00  67.00-150.45   52
 70  \w     39.00 103.00   0.50    0.24    --   64.00  72.00-133.72  128
 71  \w     39.00  64.00   0.50    0.24    --   64.00  73.00 -49.05   50
 72  \w    100.00 127.00   0.50    0.24    --   64.00  73.00 -49.05   54
 73  \w     86.00 134.00   0.50    0.24    --   68.00  67.00  57.28   96
 74  \w     44.00  79.00   0.50    0.24    --   68.00  67.00  57.28   70
 75  \w     45.00  76.00   0.50    0.24    --   68.00  74.00  -6.89   62
 76  \w     48.00  79.00   0.50    0.96    --   72.00  67.00 -92.04   62
 77  \w     47.00  73.00   0.50    0.96    --   72.00  70.00 101.63   52
 78  \w     47.00  72.00   0.50    0.96    --   72.00  71.00 -15.66   50
 79  \w    107.00 137.00   0.50    0.96    --   76.00  73.00 131.42   60
 80  \w     53.00  80.00   0.50    0.96    --   76.00  65.00 -83.86   54
 81  \w     51.00  79.00   0.50    0.96    --   76.00  70.00 -50.82   56
 82  \w     55.00  91.00   0.50    0.96    --   76.00  56.00-102.26   72
 83  \w     58.00  90.00   0.50    0.96    --   76.00  57.00  31.97   64
 84  \w     53.00 113.00   0.50    0.96    --   76.00  69.00 114.32  120
 85  \w     55.00 104.00   0.50    0.96    --   76.00  73.00 131.42   98
 86  \w     59.00 143.00   0.50    0.96    --   80.00  57.00-170.36  168
 87  \w     63.00  92.00   0.50    0.96    --   84.00  56.00-120.86   58
 88  \w     62.00  98.00   0.50    0.96    --   84.00  70.00  -7.76   72
 89  \w     96.00 123.00   0.50    0.96    --   88.00  70.00 -67.93   54
 90  \w     63.00  88.00   0.50    0.96    --   88.00  70.00 -67.93   50
 91  \w     83.00 132.00   0.50    0.96    --  100.00  77.00 -30.00   98
 92  \w     76.00 129.00   0.50    0.96    --  100.00  69.00 120.00  106
 93  \w     61.00 108.00   0.50    0.96    --  100.00-111.00  60.00   94
 94  \w     48.00  97.00   0.50    0.96    --  100.00 178.00   0.00   98
 95  \w    127.00 153.00   0.50    0.96    --  100.00  69.00 -30.00   52
 96  \w     91.00 117.00   0.50    0.96    --  100.00 -77.00  60.00   52
 97  \w    118.00 144.00   0.50    0.96    --  100.00 178.00   0.00   52
 98  \w     76.00 107.00   0.50    0.96    --  100.00  69.00  30.00   62
 99  \w     77.00 102.00   0.50    0.96    --  100.00  69.00 -30.00   50
100  \w     45.00  71.00   0.50    0.96    --  100.00 -77.00  60.00   52
101  \w     85.00 151.00   0.50    0.96    --  100.00  77.00  90.00  132
102  \w     87.00 147.00   0.50    0.96    --  100.00  77.00 -90.00  120
103  \w     69.00 102.00   0.50    0.96    --  100.00 -93.00 120.00   66
104  \w     65.00  91.00   0.50    0.96    --  100.00 -15.00   0.00   52
105  \w     66.00  94.00   0.50    0.96    --  100.00-133.00  30.00   56
106  \w     27.00  52.00   0.50    0.96    --  100.00 -93.00 120.00   50
107  \w     37.00  63.00   0.50    0.96    --  100.00-133.00  30.00   52
108  \w    131.00 157.00   0.50    0.96    --  100.00  37.00 -30.00   52
109  \w     94.00 119.00   0.50    0.96    --  100.00  37.00 -30.00   50
110  \w    126.00 154.00   0.50    0.96    --  100.00  69.00 150.00   56
111  \w     78.00 104.00   0.50    0.96    --  100.00  61.00  60.00   52
112  \w     83.00 115.00   0.50    0.96    --  100.00  77.00 -60.00   64
113  \w    132.00 157.00   0.50    0.96    --  100.00  69.00 -60.00   50
114  \w     78.00 104.00   0.50    0.96    --  100.00  69.00 150.00   52
115  \w     87.00 113.00   0.50    0.96    --  100.00 -37.00 -30.00   52
116  \w     36.00  66.00   0.50    0.96    --  100.00 -37.00 -30.00   60
117  \w     79.00 105.00   0.50    0.96    --  100.00  61.00  90.00   52
118  \w     57.00 108.00   0.50    0.96    --  100.00 -30.00-120.00  102
119  \w     81.00 109.00   0.50    0.96    --  100.00 -45.00-180.00   56
120  \w     37.00  68.00   0.50    0.96    --  100.00 -45.00-180.00   62
121  \w     76.00 132.00   0.50    0.96    --  100.00  69.00-150.00  112
122  \w     76.00 139.00   0.50    0.96    --  100.00  69.00   0.00  126
123  \w     80.00 108.00   0.50    0.96    --  100.00-111.00 -30.00   56
124  \w     31.00  64.00   0.50    0.96    --  100.00-111.00 -30.00   66
125  \w     81.00 155.00   0.50    0.96    --  100.00  53.00  60.00  148
126  \w     80.00 106.00   0.50    0.96    --  100.00  53.00-180.00   52
127  \w     93.00 118.00   0.50    0.96    --  100.00-133.00 -30.00   50
128  \w     58.00 104.00   0.50    0.96    --  100.00-111.00  30.00   92
129  \w     38.00  85.00   0.50    0.96    --  100.00-133.00 -30.00   94
130  \w     77.00 102.00   0.50    0.96    --  100.00  69.00 -60.00   50
131  \w     77.00 104.00   0.50    0.96    --  100.00  69.00-120.00   54
132  \w     83.00 108.00   0.50    0.96    --  100.00-111.00-150.00   50
133  \w     37.00  63.00   0.50    0.96    --  100.00-111.00-150.00   52
134  \w    121.00 148.00   0.50    0.96    --  100.00  65.00  12.50   54
135  \w    120.00 157.00   0.50    0.96    --  100.00  69.00-180.00   74
136  \w     77.00 103.00   0.50    0.96    --  100.00  65.00  12.50   52
137  \w     76.00 108.00   0.50    0.96    --  100.00  69.00-180.00   64
138  \w     80.00 129.00   0.50    0.96    --  100.00  53.00-150.00   98
139  \w    113.00 138.00   0.50    0.96    --  100.00  61.00 150.00   50
140  \w     26.00  52.00   0.50    0.96    --  100.00 -15.00   0.00   52
141  \w     78.00 104.00   0.50    0.96    --  100.00  61.00 150.00   52
142  \w    104.00 129.00   0.50    0.96    --  100.00 -15.00   0.00   50
143  \w    113.00 154.00   0.50    0.96    --  100.00  61.00  30.00   82
144  \w    124.00 149.00   0.50    0.96    --  100.00  53.00  90.00   50
145  \w     80.00 106.00   0.50    0.96    --  100.00  53.00  90.00   52
146  \w     78.00 104.00   0.50    0.96    --  100.00  61.00  30.00   52
147  \w     45.00 108.00   0.50    0.96    --  100.00-111.00 120.00  126
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0997903000
_diffrn_orient_matrix_UB_12      0.0018289000
_diffrn_orient_matrix_UB_13      0.1203842000
_diffrn_orient_matrix_UB_21      -0.0178432000
_diffrn_orient_matrix_UB_22      0.0937654000
_diffrn_orient_matrix_UB_23      -0.0535830000
_diffrn_orient_matrix_UB_31      -0.0653326000
_diffrn_orient_matrix_UB_32      -0.0284133000
_diffrn_orient_matrix_UB_33      -0.1692589000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0749
_diffrn_reflns_av_unetI/netI     0.0223
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            25810
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.979
_diffrn_reflns_theta_min         4.460
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    34.066
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48240
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.71a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.027
_exptl_crystal_description       prism
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.530
_refine_diff_density_min         -0.707
_refine_diff_density_rms         0.119
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     93
_refine_ls_number_reflns         1483
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0222
_refine_ls_R_factor_gt           0.0216
_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^)+(0.0280P)^2^+2.3930P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0530
_refine_ls_wR_factor_ref         0.0535
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1434
_reflns_number_total             1483
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob01158h2.cif
_cod_data_source_block           '[5]I'
_cod_depositor_comments
'Adding full bibliography for 7158206--7158208.cif.'
_cod_database_code               7158206
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'N2 I C16 H10 '
_diffrn_oxdiff_ac3_digest_frames
;
01185852d6d990fd45a62bf378ba48738f0003498a1
;
_diffrn_oxdiff_ac3_digest_hkl
;
015dac30ce55cb710e2898bb2a92c7c626053f
;
_reflns_odcompleteness_completeness 98.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     70.93
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: H10A(0.5) H10B(0.5) H9A(0.5) H9B(0.5) H9C(0.5) H4A(0.5) H4B(0.5)
 H4C(0.5)
3.a Riding coordinates:
 C10(H10A,H10B,H10C)
3.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C6(H6), C7(H7)
3.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C4(H4A,H4B,H4C)
;
_shelx_res_checksum              96106
_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 1.800
_oxdiff_exptl_absorpt_empirical_full_min 0.671