Cu-catalyzed cycloaddition of aryl azides to 1-iodobuta-1,3-diynes: an experimental and quantum chemical study of unusual regiochemistry
Govdi, Anastasia I.; Danilkina, Natalia A.; Shtyrov, Andrey A.; Ryazantsev, Mikhail N.; Kim, Mia D.; Kryukova, Mariya A.; Balova, Irina A.; New Journal of Chemistry 48 (2024) 4831–4845; doi:10.1039/D3NJ03823H

data_7062997
_publ_section_title
;
 Cu-catalyzed cycloaddition of aryl azides to 1-iodobuta-1,3-diynes: an
 experimental and quantum chemical study of unusual regiochemistry
;
_journal_issue                   11
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              4831
_journal_page_last               4845
_journal_paper_doi               10.1039/D3NJ03823H
_journal_volume                  48
_journal_year                    2024
_chemical_formula_moiety         'C18 H14 I N3 O'
_chemical_formula_sum            'C18 H14 I N3 O'
_chemical_formula_weight         415.22
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-06
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-07 deposited with the CCDC.	2024-01-29 downloaded from the CCDC.
;
_cell_angle_alpha                98.052(2)
_cell_angle_beta                 101.391(2)
_cell_angle_gamma                90.231(2)
_cell_formula_units_Z            2
_cell_length_a                   7.2957(2)
_cell_length_b                   7.4157(2)
_cell_length_c                   15.3505(2)
_cell_measurement_reflns_used    16573
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.6830
_cell_measurement_theta_min      2.8340
_cell_volume                     805.69(3)
_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 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, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.982
_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    -20.00  25.00   0.50    0.05    --  -47.20  19.00 -90.00   90
  2  \w    -26.00  26.00   0.50    0.05    --  -47.20  19.00-180.00  104
  3  \w     70.00  95.00   0.50    0.05    --   47.20 132.00-108.00   50
  4  \w     77.00 115.00   0.50    0.05    --   47.20 125.00 -30.00   76
  5  \w     90.00 117.00   0.50    0.05    --   47.20 125.00  30.00   54
  6  \w     85.00 111.00   0.50    0.05    --   47.20 137.00  67.00   52
  7  \w    122.00 147.00   0.50    0.06    --  107.75 137.00  67.00   50
  8  \w    129.00 171.00   0.50    0.06    --  107.75 125.00   0.00   84
  9  \w    133.00 173.00   0.50    0.06    --  107.75  61.00   0.00   80
 10  \w     91.00 116.00   0.50    0.06    --  107.75 132.00-108.00   50
 11  \w     86.00 153.00   0.50    0.06    --  107.75  77.00 -30.00  134
 12  \w     94.00 123.00   0.50    0.06    --  107.75  61.00   0.00   58
 13  \w     74.00 115.00   0.50    0.06    --  107.75 125.00   0.00   82
 14  \w     90.00 121.00   0.50    0.06    --  107.75  77.00 150.00   62
 15  \w    140.00 166.00   0.50    0.06    --  107.75  77.00 150.00   52
 16  \w     35.00  91.00   0.50    0.06    --  107.75 -77.00 120.00  112
 17  \w     62.00 102.00   0.50    0.06    --  107.75 -94.00  90.00   80
 18  \w     81.00 120.00   0.50    0.06    --  107.75-137.00   5.00   78
 19  \w     79.00 105.00   0.50    0.06    --  107.75 -94.00 -30.00   52
 20  \w     80.00 107.00   0.50    0.06    --  107.75-125.00 -60.00   54
 21  \w     72.00 104.00   0.50    0.06    --  107.75 -94.00   0.00   64
 22  \w     73.00 112.00   0.50    0.06    --  107.75-125.00 -30.00   78
 23  \w     58.00  83.00   0.50    0.05    --   47.20-137.00   5.00   50
 24  \w     35.00  71.00   0.50    0.06    --  107.75 -61.00  60.00   72
 25  \w     44.00  71.00   0.50    0.06    --  107.75 -61.00   0.00   54
 26  \w     35.00  60.00   0.50    0.06    --  107.75 -61.00 -30.00   50
 27  \w     35.00  60.00   0.50    0.06    --  107.75 -94.00   0.00   50
 28  \w     36.00  82.00   0.50    0.06    --  107.75-125.00   0.00   92
 29  \w     47.00  72.00   0.50    0.06    --  107.75-125.00 -60.00   50
 30  \w     39.00  64.00   0.50    0.06    --  107.75 -61.00  30.00   50
 31  \w     65.00 112.00   0.50    0.06    --  107.75-125.00  90.00   94
 32  \w     55.00 101.00   0.50    0.06    --  107.75-125.00-150.00   92
 33  \w     60.00  88.00   0.50    0.06    --  107.75-132.00-178.00   56
 34  \w     60.00  87.00   0.50    0.05    --   47.20-132.00-178.00   54
 35  \w    -68.00 -34.00   0.50    0.06    -- -106.00  61.00 -60.00   68
 36  \w    -69.00 -35.00   0.50    0.06    -- -106.00  61.00-120.00   68
 37  \w    -75.00 -50.00   0.50    0.06    -- -106.00 132.00-108.00   50
 38  \w    -92.00 -64.00   0.50    0.06    -- -106.00  77.00-120.00   56
 39  \w   -108.00 -83.00   0.50    0.06    -- -106.00 109.00-165.43   50
 40  \w    -97.00 -21.00   0.50    0.05    --  -47.20 132.00-108.00  152
 41  \w    -87.00 -57.00   0.50    0.05    --  -47.20 137.00  67.00   60
 42  \w     74.00 119.00   0.50    0.05    --   47.20 125.00-180.00   90
 43  \w    -94.00 -69.00   0.50    0.05    --  -47.20-132.00-178.00   50
 44  \w   -131.00-106.00   0.50    0.06    -- -106.00-132.00-178.00   50
 45  \w   -175.00 -92.00   0.50    0.06    -- -106.00 -61.00-180.00  166
 46  \w   -105.00 -76.00   0.50    0.06    -- -106.00-125.00 -30.00   58
 47  \w   -123.00 -97.00   0.50    0.06    -- -106.00-137.00   5.00   52
 48  \w   -115.00 -83.00   0.50    0.06    -- -106.00 -94.00  60.00   64
 49  \w   -120.00 -73.00   0.50    0.05    --  -47.20-137.00   5.00   94
 50  \w   -114.00 -79.00   0.50    0.05    --  -47.20-125.00  90.00   70
 51  \w   -166.00-141.00   0.50    0.06    -- -106.00 -94.00  60.00   50
 52  \w   -175.00 -83.00   0.50    0.06    -- -106.00 -94.00 120.00  184
 53  \w   -175.00 -92.00   0.50    0.06    -- -106.00 -15.00  90.00  166
 54  \w   -175.00-130.00   0.50    0.06    -- -106.00-125.00 -30.00   90
 55  \w   -175.00-138.00   0.50    0.06    -- -106.00 -30.00-120.00   74
 56  \w   -114.00 -65.00   0.50    0.06    -- -106.00 137.00  67.00   98
 57  \w    123.00 148.00   0.50    0.06    --  107.75 132.00-108.00   50
 58  \w    -54.00 -29.00   0.50    0.05    --   10.00 156.00 135.78   50
 59  \w    -10.00  15.00   0.50    0.05    --   22.00  96.00  30.09   50
 60  \w    -13.00  12.00   0.50    0.05    --   22.00 102.00 -58.10   50
 61  \w     15.00  40.00   0.50    0.05    --   42.00  87.00  94.01   50
 62  \w     15.00  41.00   0.50    0.05    --   42.00  89.00-146.06   52
 63  \w     13.00  38.00   0.50    0.05    --   42.00  91.00 145.89   50
 64  \w     95.00 121.00   0.50    0.05    --   47.20  19.00-180.00   52
 65  \w     25.00  50.00   0.50    0.05    --   47.20  77.00 -60.00   50
 66  \w     39.00  74.00   0.50    0.05    --   47.20  19.00-180.00   70
 67  \w     -4.00  22.00   0.50    0.05    --   47.20 -19.00 -90.00   52
 68  \w     27.00  53.00   0.50    0.05    --   50.00  78.00 -14.92   52
 69  \w     34.00  60.00   0.50    0.05    --   54.00  74.00  22.40   52
 70  \w     31.00  57.00   0.50    0.05    --   54.00  80.00 146.44   52
 71  \w     32.00  57.00   0.50    0.05    --   54.00  78.00-168.81   50
 72  \w     32.00  59.00   0.50    0.05    --   54.00  80.00  49.42   54
 73  \w     35.00  61.00   0.50    0.05    --   58.00  77.00 104.57   52
 74  \w     34.00  60.00   0.50    0.05    --   58.00  80.00 -71.74   52
 75  \w     36.00  62.00   0.50    0.05    --   58.00  75.00-142.00   52
 76  \w     41.00  66.00   0.50    0.05    --   62.00  72.00-127.33   50
 77  \w     41.00  67.00   0.50    0.05    --   62.00  73.00 -85.45   52
 78  \w    -71.00 -45.00   0.50    0.05    --  -66.00 -72.00 -19.28   52
 79  \w     42.00  67.00   0.50    0.05    --   66.00  80.00 135.76   50
 80  \w    -76.00 -50.00   0.50    0.05    --  -70.00 -69.00  23.71   52
 81  \w    -77.00 -52.00   0.50    0.05    --  -70.00 -66.00 170.28   50
 82  \w     54.00  80.00   0.50    0.05    --   70.00  78.00-125.99   52
 83  \w    -80.00 -54.00   0.50    0.05    --  -74.00 -69.00 -88.19   52
 84  \w    -83.00 -57.00   0.50    0.05    --  -74.00 -64.00 119.15   52
 85  \w    -83.00 -57.00   0.50    0.05    --  -74.00 -65.00  79.13   52
 86  \w    -95.00 -69.00   0.50    0.05    --  -74.00 -58.00 -44.32   52
 87  \w    -80.00 -55.00   0.50    0.05    --  -74.00 -68.00  -9.40   50
 88  \w    -77.00 -52.00   0.50    0.05    --  -74.00 -75.00 155.31   50
 89  \w     52.00  78.00   0.50    0.05    --   74.00  76.00  96.65   52
 90  \w    108.00 134.00   0.50    0.05    --   74.00  76.00-128.09   52
 91  \w     52.00  78.00   0.50    0.05    --   74.00  76.00-128.09   52
 92  \w   -150.00-121.00   0.50    0.06    --  -78.00 -73.00 -47.53   58
 93  \w    -86.00 -60.00   0.50    0.06    --  -78.00 -66.00  28.70   52
 94  \w    -82.00 -57.00   0.50    0.06    --  -78.00 -73.00 -47.53   50
 95  \w    -90.00 -65.00   0.50    0.06    --  -82.00 -63.00 177.84   50
 96  \w    -87.00 -61.00   0.50    0.06    --  -82.00 -72.00 -87.99   52
 97  \w    -96.00 -70.00   0.50    0.06    --  -82.00 -54.00-152.86   52
 98  \w    -95.00 -69.00   0.50    0.06    --  -86.00 -62.00 -59.30   52
 99  \w    -93.00 -67.00   0.50    0.06    --  -86.00 -67.00-107.40   52
100  \w    -91.00 -66.00   0.50    0.06    --  -86.00 -70.00-137.04   50
101  \w    -90.00 -65.00   0.50    0.06    --  -86.00 -72.00  13.59   50
102  \w    -93.00 -67.00   0.50    0.06    --  -86.00 -69.00 156.41   52
103  \w   -102.00 -69.00   0.50    0.06    --  -86.00 -62.00 -72.67   66
104  \w    -97.00 -71.00   0.50    0.06    --  -86.00 -55.00  40.13   52
105  \w    -95.00 -69.00   0.50    0.06    --  -90.00 -74.00 -18.00   52
106  \w    -94.00 -68.00   0.50    0.06    --  -90.00 -74.00 126.49   52
107  \w    -99.00 -73.00   0.50    0.06    --  -90.00 -65.00  67.30   52
108  \w    -94.00 -68.00   0.50    0.06    --  -90.00 -76.00-174.64   52
109  \w    -96.00 -71.00   0.50    0.06    --  -94.00 -76.00 113.55   50
110  \w    -97.00 -72.00   0.50    0.06    --  -94.00 -74.00  16.77   50
111  \w   -108.00 -75.00   0.50    0.06    --  -98.00 -77.00  -6.46   66
112  \w   -105.00 -75.00   0.50    0.06    --  -98.00 -78.00 153.07   60
113  \w   -106.00 -80.00   0.50    0.06    --  -98.00 -64.00 -92.30   52
114  \w   -163.00-137.00   0.50    0.06    --  -98.00 -77.00  -6.46   52
115  \w   -100.00 -74.00   0.50    0.06    --  -98.00 -79.00 114.51   52
116  \w   -105.00 -79.00   0.50    0.06    --  -98.00 -67.00-137.79   52
117  \w   -114.00 -87.00   0.50    0.06    -- -102.00 -55.00  40.40   54
118  \w   -161.00-120.00   0.50    0.06    -- -106.00 -75.00  35.32   82
119  \w   -125.00 -82.00   0.50    0.06    -- -106.00 -82.00 -88.16   86
120  \w   -110.00 -84.00   0.50    0.06    -- -106.00 -75.00 113.13   52
121  \w   -159.00-133.00   0.50    0.06    -- -106.00 -68.00 118.16   52
122  \w   -176.00-151.00   0.50    0.06    -- -106.00 -82.00 -88.16   50
123  \w   -170.00-144.00   0.50    0.06    -- -106.00 -75.00 113.13   52
124  \w   -114.00 -85.00   0.50    0.06    -- -106.00 -80.00  26.44   58
125  \w   -113.00 -86.00   0.50    0.06    -- -106.00 -71.00-153.72   54
126  \w   -163.00-122.00   0.50    0.06    -- -106.00 -80.00  26.44   82
127  \w   -162.00-126.00   0.50    0.06    -- -106.00 -71.00-153.72   72
128  \w   -147.00 -89.00   0.50    0.06    -- -106.00 -69.00 -91.20  116
129  \w   -117.00 -89.00   0.50    0.06    -- -106.00 -64.00 -69.23   56
130  \w    -60.00 -34.00   0.50    0.06    -- -106.00  61.00-180.00   52
131  \w   -172.00-124.00   0.50    0.06    -- -106.00 -64.00 -69.23   96
132  \w   -142.00 -84.00   0.50    0.06    -- -106.00 -77.00  60.00  116
133  \w   -108.00 -83.00   0.50    0.06    -- -106.00 -77.00 -30.00   50
134  \w   -130.00 -89.00   0.50    0.06    -- -106.00 -61.00-150.00   82
135  \w   -113.00 -88.00   0.50    0.06    -- -106.00 -64.00-176.28   50
136  \w   -165.00-139.00   0.50    0.06    -- -106.00 -77.00 -30.00   52
137  \w   -124.00 -88.00   0.50    0.06    -- -106.00 -64.00  88.01   72
138  \w   -136.00 -89.00   0.50    0.06    -- -106.00 -63.00  32.50   94
139  \w   -121.00 -83.00   0.50    0.06    -- -106.00 -83.00  90.67   76
140  \w   -107.00 -82.00   0.50    0.06    -- -106.00 -80.00-169.23   50
141  \w    -78.00 -33.00   0.50    0.06    -- -106.00  77.00   0.00   90
142  \w   -113.00 -88.00   0.50    0.06    -- -106.00 -65.00-118.09   50
143  \w   -158.00-132.00   0.50    0.06    -- -106.00 -65.00-118.09   52
144  \w   -115.00 -89.00   0.50    0.06    -- -106.00 -64.00 159.83   52
145  \w   -147.00-121.00   0.50    0.06    -- -106.00 -64.00 159.83   52
146  \w   -126.00 -84.00   0.50    0.06    -- -106.00 -79.00-122.63   84
147  \w   -162.00-136.00   0.50    0.06    -- -106.00 -79.00-122.63   52
148  \w   -127.00 -83.00   0.50    0.06    -- -106.00 -76.00 143.22   88
149  \w   -142.00 -83.00   0.50    0.06    -- -106.00 -80.00  -1.40  118
150  \w   -126.00 -87.00   0.50    0.06    -- -106.00 -68.00 118.16   78
151  \w   -109.00 -84.00   0.50    0.06    -- -106.00 -75.00  35.32   50
152  \w   -175.00-149.00   0.50    0.06    -- -106.00 -76.00 143.22   52
153  \w     91.00 142.00   0.50    0.06    --  107.75  61.00 -60.00  102
154  \w     98.00 127.00   0.50    0.06    --  107.75  45.00 -30.00   58
155  \w     89.00 115.00   0.50    0.06    --  107.75  77.00 120.00   52
156  \w     35.00  60.00   0.50    0.06    --  107.75 -61.00-180.00   50
157  \w     36.00  63.00   0.50    0.06    --  107.75 -94.00 120.00   54
158  \w     62.00  88.00   0.50    0.06    --  107.75 -77.00  30.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0827101000
_diffrn_orient_matrix_UB_12      0.0874229000
_diffrn_orient_matrix_UB_13      -0.0839036000
_diffrn_orient_matrix_UB_21      0.0472613000
_diffrn_orient_matrix_UB_22      -0.1700667000
_diffrn_orient_matrix_UB_23      -0.0604821000
_diffrn_orient_matrix_UB_31      -0.1933210000
_diffrn_orient_matrix_UB_32      -0.0866197000
_diffrn_orient_matrix_UB_33      -0.0019581000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0866
_diffrn_reflns_av_unetI/netI     0.0555
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            26330
_diffrn_reflns_point_group_measured_fraction_full 0.952
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.043
_diffrn_reflns_theta_min         2.967
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    15.676
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27079
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.712
_exptl_crystal_description       plate
_exptl_crystal_F_000             408
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.962
_refine_diff_density_min         -1.695
_refine_diff_density_rms         0.136
_refine_ls_abs_structure_details
;
 Flack x determined using 2650 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.24(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     413
_refine_ls_number_reflns         6284
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0437
_refine_ls_R_factor_gt           0.0418
_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^)+(0.0782P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1095
_refine_ls_wR_factor_ref         0.1111
_reflns_Friedel_coverage         0.875
_reflns_Friedel_fraction_full    0.906
_reflns_Friedel_fraction_max     0.860
_reflns_number_gt                6011
_reflns_number_total             6284
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nj03823h3.cif
_cod_data_source_block           16409_gai-875
_cod_depositor_comments
'Adding full bibliography for 7062994--7063002.cif.'
_cod_database_code               7062997
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C18 H14 I N3 O '
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(C008) = Uanis(C00B)
2.a Aromatic/amide H refined with riding coordinates:
 C006(H006), C00E(H00E), C00G(H00G), C00H(H00H), C00J(H00J), C00K(H00K),
 C00N(H00N), C00O(H00O), C00T(H00T), C00U(H00U), C00W(H00W), C00X(H00X),
 C00Y(H00Y), C00Z(H00Z), C010(H010), C1(H1)
2.b Idealised Me refined as rotating group:
 C00P(H00D,H00F,H00I), C00S(H00A,H00B,H00C), C011(H01D,H01E,H01F), C012(H01A,
 H01B,H01C)
;
_shelx_res_checksum              34537
_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 6.266
_oxdiff_exptl_absorpt_empirical_full_min 0.347