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_7063000
_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         'C19 H14 I N3 O2'
_chemical_formula_sum            'C19 H14 I N3 O2'
_chemical_formula_weight         443.23
_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
_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                90
_cell_angle_beta                 108.3930(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.2828(2)
_cell_length_b                   7.42180(10)
_cell_length_c                   16.4916(2)
_cell_measurement_reflns_used    16542
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.8700
_cell_measurement_theta_min      5.5330
_cell_volume                     1658.87(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 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 2014/4 (Sheldrick, 2014)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.989
_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    -15.00  46.00   0.50    0.05    --   47.20 -42.00   3.00  122
  2  \w    113.00 139.00   0.50    0.10    --  107.75  45.00-120.00   52
  3  \w    150.00 176.00   0.50    0.10    --  107.75  45.00-120.00   52
  4  \w    132.00 176.00   0.50    0.10    --  107.75  77.00-150.00   88
  5  \w     99.00 124.00   0.50    0.10    --  107.75  77.00-150.00   50
  6  \w     78.00 119.00   0.50    0.05    --   47.20 125.00  30.00   82
  7  \w    149.00 176.00   0.50    0.10    --  107.75  42.00 156.00   54
  8  \w    123.00 178.00   0.50    0.10    --  107.75  45.00  60.00  110
  9  \w    101.00 127.00   0.50    0.10    --  107.75  42.00 156.00   52
 10  \w     36.00 116.00   0.50    0.05    --   47.20  42.00 156.00  160
 11  \w     39.00  70.00   0.50    0.10    --  107.75 -61.00 150.00   62
 12  \w     73.00  99.00   0.50    0.10    --  107.75 -77.00 120.00   52
 13  \w     45.00  80.00   0.50    0.10    --  107.75 -77.00 150.00   70
 14  \w     37.00  63.00   0.50    0.10    --  107.75 -77.00 120.00   52
 15  \w     36.00 104.00   0.50    0.10    --  107.75 -77.00  90.00  136
 16  \w     37.00  68.00   0.50    0.10    --  107.75 -61.00  30.00   62
 17  \w     43.00  69.00   0.50    0.10    --  107.75 -61.00   0.00   52
 18  \w     50.00 106.00   0.50    0.10    --  107.75 -77.00 -30.00  112
 19  \w     79.00 110.00   0.50    0.10    --  107.75-125.00 -60.00   62
 20  \w     70.00  96.00   0.50    0.10    --  107.75 -94.00-150.00   52
 21  \w     60.00 104.00   0.50    0.10    --  107.75 -77.00 -90.00   88
 22  \w     36.00  68.00   0.50    0.10    --  107.75 -94.00-150.00   64
 23  \w     36.00  70.00   0.50    0.10    --  107.75 -61.00 -90.00   68
 24  \w     41.00  68.00   0.50    0.10    --  107.75-125.00 -60.00   54
 25  \w    -25.00  25.00   0.50    0.05    --   47.20 -19.00-150.00  100
 26  \w   -119.00 -37.00   0.50    0.05    --  -47.20 -42.00   3.00  164
 27  \w    -31.00   3.00   0.50    0.05    --  -47.20  42.00 156.00   68
 28  \w   -103.00 -73.00   0.50    0.10    -- -106.00 125.00 -30.00   60
 29  \w    -58.00 -33.00   0.50    0.10    -- -106.00 125.00 -30.00   50
 30  \w    -67.00 -39.00   0.50    0.10    -- -106.00  61.00 -90.00   56
 31  \w    -62.00 -34.00   0.50    0.10    -- -106.00  61.00   0.00   56
 32  \w    -61.00 -36.00   0.50    0.10    -- -106.00  61.00 150.00   50
 33  \w   -177.00-101.00   0.50    0.10    -- -106.00 -42.00   3.00  152
 34  \w     22.00  47.00   0.50    0.05    --   47.20 -42.00   3.00   50
 35  \w     -6.00  21.00   0.50    0.05    --   47.20 -19.00   0.00   54
 36  \w     32.00 102.00   0.50    0.05    --   47.20  57.00-120.00  140
 37  \w     37.00  95.00   0.50    0.05    --   47.20  57.00 -60.00  116
 38  \w   -104.00 -79.00   0.50    0.10    -- -106.00 -86.00 -70.08   50
 39  \w   -111.00 -85.00   0.50    0.10    -- -106.00 -77.00 -60.00   52
 40  \w   -175.00-149.00   0.50    0.10    -- -106.00 -61.00-150.00   52
 41  \w   -117.00 -91.00   0.50    0.10    -- -106.00 -55.00 -63.74   52
 42  \w   -139.00 -94.00   0.50    0.10    -- -106.00 -30.00 -60.00   90
 43  \w   -161.00-135.00   0.50    0.10    -- -106.00 -77.00 -60.00   52
 44  \w   -108.00 -83.00   0.50    0.10    -- -106.00 -77.00 -30.00   50
 45  \w   -176.00-134.00   0.50    0.10    -- -106.00 -79.00 -43.67   84
 46  \w   -126.00 -94.00   0.50    0.10    -- -106.00 -30.00-120.00   64
 47  \w   -120.00 -95.00   0.50    0.10    -- -106.00 -77.00  90.00   50
 48  \w   -106.00 -80.00   0.50    0.10    -- -106.00 -83.00 -74.93   52
 49  \w   -107.00 -82.00   0.50    0.10    -- -106.00 -79.00 -97.52   50
 50  \w   -150.00 -97.00   0.50    0.10    -- -106.00 -49.00-132.30  106
 51  \w   -129.00 -87.00   0.50    0.10    -- -106.00 -68.00 -60.83   84
 52  \w   -107.00 -82.00   0.50    0.10    -- -106.00 -79.00 -43.67   50
 53  \w   -175.00-141.00   0.50    0.10    -- -106.00 -77.00-120.00   68
 54  \w   -110.00 -84.00   0.50    0.10    -- -106.00 -77.00-120.00   52
 55  \w   -176.00-150.00   0.50    0.10    -- -106.00 -52.00-142.31   52
 56  \w   -161.00-133.00   0.50    0.10    -- -106.00 -77.00 -30.00   56
 57  \w   -175.00-140.00   0.50    0.10    -- -106.00 -30.00  90.00   70
 58  \w   -135.00 -94.00   0.50    0.10    -- -106.00 -52.00-142.31   82
 59  \w   -136.00 -95.00   0.50    0.10    -- -106.00 -30.00  90.00   82
 60  \w   -176.00-150.00   0.50    0.10    -- -106.00 -77.00  90.00   52
 61  \w   -153.00 -95.00   0.50    0.10    -- -106.00 -49.00 -65.82  116
 62  \w   -115.00 -90.00   0.50    0.10    -- -106.00 -61.00 -90.00   50
 63  \w   -138.00 -92.50   0.50    0.10    -- -106.00 -61.00-150.00   91
;
_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      -0.1131877000
_diffrn_orient_matrix_UB_12      0.0193095000
_diffrn_orient_matrix_UB_13      -0.0306791000
_diffrn_orient_matrix_UB_21      0.0053071000
_diffrn_orient_matrix_UB_22      0.1084936000
_diffrn_orient_matrix_UB_23      -0.0780606000
_diffrn_orient_matrix_UB_31      -0.0091552000
_diffrn_orient_matrix_UB_32      -0.1760223000
_diffrn_orient_matrix_UB_33      -0.0514297000
_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  0.0429
_diffrn_reflns_av_unetI/netI     0.0240
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            25287
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.210
_diffrn_reflns_theta_min         3.261
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    15.322
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60604
_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    1.775
_exptl_crystal_description       plate
_exptl_crystal_F_000             872
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.723
_refine_diff_density_min         -1.009
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     222
_refine_ls_number_reflns         3475
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0247
_refine_ls_R_factor_gt           0.0242
_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^)+(0.0407P)^2^+1.0858P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0643
_refine_ls_wR_factor_ref         0.0648
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3384
_reflns_number_total             3475
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nj03823h3.cif
_cod_data_source_block           16779_982_b
_cod_depositor_comments
'Adding full bibliography for 7062994--7063002.cif.'
_cod_database_code               7063000
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C19 H14 I1 N3 O2'
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(O1) = Uanis(C11)
2.a Aromatic/amide H refined with riding coordinates:
 C14(H14), C13(H13), C17(H17), C9(H9), C7(H7), C10(H10), C6(H6), C16(H16)
2.b Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              53259
_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 1.531
_oxdiff_exptl_absorpt_empirical_full_min 0.729