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_7062994
_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         'C17 H11 Cl I N3 O'
_chemical_formula_sum            'C17 H11 Cl I N3 O'
_chemical_formula_weight         435.64
_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
_audit_creation_date             2018-09-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-09-25 deposited with the CCDC.	2024-01-29 downloaded from the CCDC.
;
_cell_angle_alpha                82.0610(11)
_cell_angle_beta                 79.0302(12)
_cell_angle_gamma                89.6967(13)
_cell_formula_units_Z            2
_cell_length_a                   7.21715(13)
_cell_length_b                   7.40565(11)
_cell_length_c                   15.40204(16)
_cell_measurement_reflns_used    11325
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.4860
_cell_measurement_theta_min      2.9280
_cell_volume                     800.23(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_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    -82.00 -49.00   0.50    0.20    --  -41.22 115.00  22.00   66
  2  \w   -105.00 -57.00   0.50    0.20    --  -41.22-170.00 149.00   96
  3  \w    -34.00   3.00   0.50    0.20    --  -41.22 115.00  22.00   74
  4  \w    -96.00 -71.00   0.50    0.20    --  -41.22 170.00 165.00   50
  5  \w     31.00  79.00   0.50    0.20    --   41.22-115.00 -67.00   96
  6  \w     51.00  76.00   0.50    0.20    --   41.22 170.00 165.00   50
  7  \w     60.00  95.00   0.50    0.20    --   41.22-170.00 149.00   70
  8  \w     70.00 100.00   0.50    0.20    --  101.00-115.00 -67.00   60
  9  \w    115.00 153.00   0.50    0.20    --  101.00 115.00  22.00   76
 10  \w     92.00 121.00   0.50    0.20    --  101.00-170.00 149.00   58
 11  \w    -44.00  20.00   0.50    0.20    --  -41.22  65.00-150.00  128
 12  \w     -3.00  29.00   0.50    0.20    --  -41.22  11.00  30.00   64
 13  \w    -64.00  -6.00   0.50    0.20    --  -41.22  11.00  30.00  116
 14  \w    -92.00 -64.00   0.50    0.20    --  -41.22 138.00  30.00   56
 15  \w    -50.00 -11.00   0.50    0.20    --  -41.22 138.00  30.00   78
 16  \w     42.00 102.00   0.50    0.20    --   41.22  32.00 -90.00  120
 17  \w     70.00 107.00   0.50    0.20    --   41.22  32.00  30.00   74
 18  \w     39.00 105.00   0.50    0.20    --   41.22  32.00 150.00  132
 19  \w     27.00  55.00   0.50    0.20    --   41.22-138.00-180.00   56
 20  \w     28.00  55.00   0.50    0.20    --   41.22 -43.00 -90.00   54
 21  \w     72.00  97.00   0.50    0.20    --   41.22  54.00  60.00   50
 22  \w     -3.00  22.00   0.50    0.20    --   41.22 -43.00 -90.00   50
 23  \w     79.00 104.00   0.50    0.20    --   41.22  54.00-180.00   50
 24  \w     35.00  61.00   0.50    0.20    --   41.22  54.00-180.00   52
 25  \w     36.00  61.00   0.50    0.20    --   41.22  32.00   0.00   50
 26  \w     24.00  60.00   0.50    0.20    --   41.22  54.00  60.00   72
 27  \w     98.00 155.00   0.50    0.20    --  101.00  25.00  30.00  114
 28  \w     63.00 123.00   0.50    0.20    --  101.00-133.00 -90.00  120
 29  \w     34.00 129.00   0.50    0.20    --  101.00 -93.00  90.00  190
 30  \w    112.00 152.00   0.50    0.20    --  101.00  33.00 -30.00   80
 31  \w     98.00 149.00   0.50    0.20    --  101.00  93.00  60.00  102
 32  \w     88.00 155.00   0.50    0.20    --  101.00  42.00 120.00  134
 33  \w     41.00 116.00   0.50    0.20    --  101.00 -50.00  90.00  150
 34  \w     45.00  86.00   0.50    0.20    --  101.00 -68.00  90.00   82
 35  \w     60.00  88.00   0.50    0.20    --  101.00-111.00  30.00   56
 36  \w     94.00 140.00   0.50    0.20    --  101.00  25.00 -60.00   92
 37  \w     65.00 110.00   0.50    0.20    --  101.00 -25.00-120.00   90
 38  \w     39.00 122.00   0.50    0.20    --  101.00 -77.00 -90.00  166
 39  \w     40.00  65.00   0.50    0.20    --  101.00 -59.00  60.00   50
 40  \w     36.00 111.00   0.50    0.20    --  101.00-111.00  60.00  150
 41  \w     35.00  62.00   0.50    0.20    --  101.00 -25.00-120.00   54
 42  \w     80.00 156.00   0.50    0.20    --  101.00 111.00   0.00  152
 43  \w     73.00 110.00   0.50    0.20    --  101.00 -25.00  60.00   74
 44  \w     92.00 150.00   0.50    0.20    --  101.00  33.00-120.00  116
 45  \w     85.00 112.00   0.50    0.20    --  101.00-111.00   0.00   54
 46  \w     94.00 124.00   0.50    0.20    --  101.00 -77.00 150.00   60
 47  \w     35.00  61.00   0.50    0.20    --  101.00 -17.00  90.00   52
 48  \w     68.00  99.00   0.50    0.20    --  101.00 -17.00  90.00   62
 49  \w     50.00  75.00   0.50    0.20    --  101.00 -77.00 150.00   50
 50  \w     39.00 114.00   0.50    0.20    --  101.00 -42.00 -30.00  150
 51  \w     39.00  69.00   0.50    0.20    --  101.00 -25.00  60.00   60
 52  \w     80.00 138.00   0.50    0.20    --  101.00  68.00  60.00  116
 53  \w     60.00 117.00   0.50    0.20    --  101.00 -50.00-120.00  114
 54  \w     93.00 133.00   0.50    0.20    --  101.00  93.00 -30.00   80
 55  \w     75.00 100.00   0.50    0.20    --  101.00 170.00 165.00   50
 56  \w     37.00  62.00   0.50    0.20    --   41.22  77.00-150.00   50
 57  \w    -37.00 -12.00   0.50    0.20    --    4.00 113.00 113.25   50
 58  \w    -30.00  -5.00   0.50    0.20    --   12.00 115.00 -96.36   50
 59  \w    -12.00  13.00   0.50    0.20    --   24.00 104.00 -17.58   50
 60  \w    -12.00  14.00   0.50    0.20    --   24.00 104.00  93.42   52
 61  \w     -3.00  22.00   0.50    0.20    --   28.00  97.00-132.96   50
 62  \w     -1.00  24.00   0.50    0.20    --   28.00  90.00 155.05   50
 63  \w     -4.00  21.00   0.50    0.20    --   28.00  97.00  21.88   50
 64  \w     15.00  40.00   0.50    0.20    --   40.00  80.00 -20.45   50
 65  \w     17.00  43.00   0.50    0.20    --   40.00  82.00 -79.22   52
 66  \w     14.00  43.00   0.50    0.20    --   40.00  82.00-152.18   58
 67  \w      1.00  27.00   0.50    0.20    --   41.22 -32.00 -30.00   52
 68  \w     21.00  47.00   0.50    0.20    --   41.22  77.00 150.00   52
 69  \w     18.00  43.00   0.50    0.20    --   44.00  82.00  37.38   50
 70  \w     18.00  43.00   0.50    0.20    --   44.00  82.00 178.36   50
 71  \w     19.00  44.00   0.50    0.20    --   44.00  81.00  75.08   50
 72  \w     19.00  44.00   0.50    0.20    --   44.00  80.00  11.94   50
 73  \w     24.00  52.00   0.50    0.20    --   48.00  77.00-105.33   56
 74  \w     27.00  53.00   0.50    0.20    --   52.00  76.00 108.30   52
 75  \w     28.00  54.00   0.50    0.20    --   52.00  77.00 -15.61   52
 76  \w     31.00  65.00   0.50    0.20    --   52.00  68.00 174.23   68
 77  \w     90.00 116.00   0.50    0.20    --   52.00  68.00 174.23   52
 78  \w     36.00  65.00   0.50    0.20    --   56.00  75.00 128.64   58
 79  \w     37.00  65.00   0.50    0.20    --   56.00  77.00 -78.43   56
 80  \w     72.00  98.00   0.50    0.20    --   56.00  77.00 -78.43   52
 81  \w     36.00  62.00   0.50    0.20    --   60.00  75.00 -56.19   52
 82  \w     48.00  79.00   0.50    0.20    --   60.00  65.00   2.37   62
 83  \w     37.00  83.00   0.50    0.20    --   60.00  75.00  32.68   92
 84  \w     84.00 110.00   0.50    0.20    --   60.00  75.00  32.68   52
 85  \w     36.00  62.00   0.50    0.20    --   60.00  75.00-161.96   52
 86  \w     92.00 122.00   0.50    0.20    --   60.00  75.00 -56.19   60
 87  \w     54.00  80.00   0.50    0.20    --   64.00  45.00 148.26   52
 88  \w     88.00 114.00   0.50    0.20    --   64.00  76.00-131.98   52
 89  \w     44.00  83.00   0.50    0.20    --   64.00  76.00-131.98   78
 90  \w     51.00  84.00   0.50    0.20    --   68.00  57.00-145.82   66
 91  \w     50.00  76.00   0.50    0.20    --   68.00  72.00  56.10   52
 92  \w     53.00  79.00   0.50    0.20    --   68.00  50.00 -36.61   52
 93  \w     52.00  87.00   0.50    0.20    --   72.00  70.00 -39.52   70
 94  \w     53.00  89.00   0.50    0.20    --   76.00  73.00  74.63   72
 95  \w     83.00 109.00   0.50    0.20    --  101.00  59.00 -90.00   52
 96  \w     78.00 113.00   0.50    0.20    --  101.00  77.00 -90.00   70
 97  \w     76.00 119.00   0.50    0.20    --  101.00  77.00   0.00   86
 98  \w     80.00 106.00   0.50    0.20    --  101.00  68.00 120.00   52
 99  \w     77.00 116.00   0.50    0.20    --  101.00  77.00 -30.00   78
100  \w     77.00 102.00   0.50    0.20    --  101.00  77.00-180.00   50
101  \w    128.00 154.00   0.50    0.20    --  101.00  77.00 150.00   52
102  \w    113.00 144.00   0.50    0.20    --  101.00  77.00 120.00   62
103  \w     77.00 103.00   0.50    0.20    --  101.00  77.00 150.00   52
104  \w     78.00 108.00   0.50    0.20    --  101.00  77.00 120.00   60
105  \w     80.00 138.00   0.50    0.20    --  101.00  68.00-180.00  116
106  \w    128.00 157.00   0.50    0.20    --  101.00  77.00-120.00   58
107  \w    110.00 136.00   0.50    0.20    --  101.00  68.00-120.00   52
108  \w     84.00 110.00   0.50    0.20    --  101.00  59.00-150.00   52
109  \w    125.00 151.00   0.50    0.20    --  101.00  59.00-150.00   52
110  \w     80.00 106.00   0.50    0.20    --  101.00  68.00 -30.00   52
111  \w     80.00 152.00   0.50    0.20    --  101.00  68.00 150.00  144
112  \w     81.00 107.00   0.50    0.20    --  101.00  68.00-120.00   52
113  \w     78.00 104.00   0.50    0.20    --  101.00  77.00  90.00   52
114  \w    120.00 146.00   0.50    0.20    --  101.00  77.00  90.00   52
115  \w     76.00 112.00   0.50    0.20    --  101.00  77.00 -60.00   72
116  \w    121.00 146.00   0.50    0.20    --  101.00  77.00  60.00   50
117  \w     77.00 103.00   0.50    0.20    --  101.00  77.00  60.00   52
118  \w    125.00 151.00   0.50    0.20    --  101.00  59.00 -90.00   52
119  \w     78.00 109.00   0.50    0.20    --  101.00  77.00-120.00   62
120  \w    117.00 149.00   0.50    0.20    --  101.00  77.00  30.00   64
121  \w     76.00 102.00   0.50    0.20    --  101.00  77.00  30.00   52
122  \w    132.00 157.00   0.50    0.20    --  101.00  59.00  90.00   50
123  \w     84.00 110.00   0.50    0.20    --  101.00  59.00  90.00   52
124  \w     79.00 105.00   0.50    0.20    --  101.00 -33.00 120.00   52
125  \w     69.00  95.00   0.50    0.20    --  101.00 -33.00-180.00   52
126  \w     83.00 109.00   0.50    0.20    --  101.00  59.00   0.00   52
127  \w     76.00 102.00   0.50    0.20    --  101.00  77.00-150.00   52
128  \w    126.00 153.00   0.50    0.20    --  101.00  77.00 -90.00   54
129  \w    129.00 156.00   0.50    0.20    --  101.00  77.00-180.00   54
;
_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      0.0370870000
_diffrn_orient_matrix_UB_12      0.1129185000
_diffrn_orient_matrix_UB_13      -0.0936408000
_diffrn_orient_matrix_UB_21      -0.1022013000
_diffrn_orient_matrix_UB_22      0.1622858000
_diffrn_orient_matrix_UB_23      0.0391368000
_diffrn_orient_matrix_UB_31      0.1883559000
_diffrn_orient_matrix_UB_32      0.0710588000
_diffrn_orient_matrix_UB_33      0.0169343000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0742
_diffrn_reflns_av_unetI/netI     0.0412
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            13674
_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         69.902
_diffrn_reflns_theta_min         2.951
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    17.320
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39726
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35a (Rigaku Oxford Diffraction, 2017)
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    1.808
_exptl_crystal_description       prism
_exptl_crystal_F_000             424
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.22
_refine_diff_density_max         1.681
_refine_diff_density_min         -1.615
_refine_diff_density_rms         0.167
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         3015
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0358
_refine_ls_R_factor_gt           0.0355
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0666P)^2^+0.6126P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0907
_refine_ls_wR_factor_ref         0.0911
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2980
_reflns_number_total             3015
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nj03823h3.cif
_cod_data_source_block           pav-304
_cod_depositor_comments
'Adding full bibliography for 7062994--7063002.cif.'
_cod_database_code               7062994
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C17 N3 O Cl I'
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.55
_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.a Aromatic/amide H refined with riding coordinates:
 C10(H10), C18(H18), C14(H14), C23(H23), C13(H13), C17(H17), C22(H22), C9(H9)
2.b Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C)
;
_shelx_res_checksum              74180
_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 1.982
_oxdiff_exptl_absorpt_empirical_full_min 0.633