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_7062999
_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         'C54 H44.956 Cu I P3'
_chemical_formula_sum            'C54 H44.96 Cu I P3'
_chemical_formula_weight         977.20
_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
_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                71.8942(7)
_cell_angle_beta                 84.0976(8)
_cell_angle_gamma                87.9689(8)
_cell_formula_units_Z            2
_cell_length_a                   13.11763(14)
_cell_length_b                   14.31799(12)
_cell_length_c                   14.44658(10)
_cell_measurement_reflns_used    29510
_cell_measurement_temperature    100.00(13)
_cell_measurement_theta_max      76.9740
_cell_measurement_theta_min      3.2030
_cell_volume                     2565.29(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(13)
_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 0.978
_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     18.00  66.00   0.50    0.70    --   47.20 -73.00 101.00   96
  2  \w     13.00  89.00   0.50    0.70    --   47.20-125.00 120.00  152
  3  \w     40.00  66.00   0.50    2.40    --  107.75 -73.00 101.00   52
  4  \w     46.00 107.00   0.50    2.40    --  107.75-112.00  44.33  122
  5  \w     93.00 118.00   0.50    2.40    --  107.75-133.00 104.38   50
  6  \w     87.00 112.00   0.50    2.40    --  107.75-125.00  60.00   50
  7  \w     79.00 109.00   0.50    2.40    --  107.75-116.00  -0.41   60
  8  \w     69.00  95.00   0.50    2.40    --  107.75 -94.00 -90.00   52
  9  \w     61.00 104.00   0.50    2.40    --  107.75 -77.00 -60.00   86
 10  \w     48.00 112.00   0.50    2.40    --  107.75-125.00 -60.00  128
 11  \w     56.00  90.00   0.50    2.40    --  107.75 -94.00  30.00   68
 12  \w     37.00 101.00   0.50    2.40    --  107.75 -77.00  30.00  128
 13  \w     35.00  72.00   0.50    2.40    --  107.75-133.00 104.38   74
 14  \w     37.00 112.00   0.50    2.40    --  107.75-125.00 150.00  150
 15  \w     37.00  62.00   0.50    2.40    --  107.75-116.00  -0.41   50
 16  \w     36.00  70.00   0.50    2.40    --  107.75 -94.00   0.00   68
 17  \w     41.00  70.00   0.50    2.40    --  107.75 -61.00 -30.00   58
 18  \w     36.00  61.00   0.50    2.40    --  107.75-125.00  60.00   50
 19  \w     36.00  68.00   0.50    2.40    --  107.75 -94.00  90.00   64
 20  \w     26.00  83.00   0.50    0.70    --   47.20-125.00 -30.00  114
 21  \w     53.00 110.00   0.50    2.40    --  107.75-125.00-150.00  114
 22  \w     62.00 109.00   0.50    2.40    --  107.75-125.00-180.00   94
 23  \w     67.00 119.00   0.50    0.70    --   47.20  37.00-180.00  104
 24  \w     87.00 165.00   0.50    2.40    --  107.75  73.00-129.00  156
 25  \w    142.00 171.00   0.50    2.40    --  107.75  45.00-180.00   58
 26  \w     96.00 154.00   0.50    2.40    --  107.75  30.00 -60.00  116
 27  \w    112.00 145.00   0.50    2.40    --  107.75  61.00   0.00   66
 28  \w     78.00 105.00   0.50    0.70    --   47.20 125.00  90.00   54
 29  \w    109.00 177.00   0.50    2.40    --  107.75  61.00 120.00  136
 30  \w    133.00 176.00   0.50    2.40    --  107.75  45.00 150.00   86
 31  \w     98.00 129.00   0.50    2.40    --  107.75  45.00 150.00   62
 32  \w     28.00 120.00   0.50    0.70    --   47.20  73.00-129.00  184
 33  \w    -67.00  -4.00   0.50    0.70    --  -47.20  73.00-129.00  126
 34  \w    -70.00 -33.00   0.50    2.40    -- -106.00  61.00-150.00   74
 35  \w    -70.00 -36.00   0.50    2.40    -- -106.00 109.00 -75.80   68
 36  \w    -87.00 -62.00   0.50    2.40    -- -106.00  73.00-129.00   50
 37  \w    -92.00 -66.00   0.50    2.40    -- -106.00  77.00 -90.00   52
 38  \w   -108.00 -82.00   0.50    2.40    -- -106.00 109.00 -75.80   52
 39  \w   -112.00 -69.00   0.50    2.40    -- -106.00 125.00-120.00   86
 40  \w   -126.00 -33.00   0.50    2.40    -- -106.00 144.00-123.47  186
 41  \w   -118.00 -35.00   0.50    2.40    -- -106.00 134.00-179.44  166
 42  \w   -133.00-107.00   0.50    2.40    -- -106.00 -45.00-180.00   52
 43  \w   -176.00 -94.00   0.50    2.40    -- -106.00 -15.00-180.00  164
 44  \w   -175.00-149.00   0.50    2.40    -- -106.00 -45.00-180.00   52
 45  \w   -116.00 -73.00   0.50    2.40    -- -106.00-125.00 -30.00   86
 46  \w   -120.00 -30.00   0.50    0.70    --  -47.20 -73.00 101.00  180
 47  \w    -71.00 -46.00   0.50    2.40    -- -106.00  61.00  90.00   50
 48  \w   -108.00 -67.00   0.50    2.40    -- -106.00 110.00 105.91   82
 49  \w   -105.00 -79.00   0.50    2.40    -- -106.00 104.00 157.98   52
 50  \w   -127.00 -75.00   0.50    2.40    -- -106.00 146.00 137.15  104
 51  \w   -153.00 -92.00   0.50    2.40    -- -106.00 -73.00 101.00  122
 52  \w   -126.00 -84.00   0.50    2.40    -- -106.00-125.00  90.00   84
 53  \w   -141.00 -91.00   0.50    2.40    -- -106.00 -61.00 150.00  100
 54  \w   -163.00-129.00   0.50    2.40    -- -106.00-125.00  90.00   68
 55  \w   -160.00-134.00   0.50    2.40    -- -106.00-125.00 -30.00   52
 56  \w    -10.00  23.00   0.50    0.70    --   47.20 -73.00 101.00   66
 57  \w    -44.00 -17.00   0.50    0.70    --    6.00 129.00-139.68   54
 58  \w    -53.00 -28.00   0.50    0.70    --   10.00 151.00  -1.31   50
 59  \w    -23.00   3.00   0.50    0.70    --   14.00 105.00 177.01   52
 60  \w    -11.00  21.00   0.50    0.70    --   22.00 100.00   0.09   64
 61  \w     -7.00  18.00   0.50    0.70    --   26.00  98.00 109.10   50
 62  \w      9.00  34.00   0.50    0.70    --   38.00  90.00 -37.47   50
 63  \w     14.00  39.00   0.50    0.70    --   42.00  89.00 111.61   50
 64  \w     17.00  42.00   0.50    0.70    --   46.00  90.00 156.18   50
 65  \w     17.00  42.00   0.50    0.70    --   46.00  90.00 110.24   50
 66  \w     17.00  42.00   0.50    0.70    --   46.00  90.00-122.53   50
 67  \w     28.00  54.00   0.50    0.70    --   50.00  79.00  24.29   52
 68  \w     96.00 122.00   0.50    0.70    --   50.00  79.00  24.29   52
 69  \w     26.00  52.00   0.50    0.70    --   50.00  79.00 165.68   52
 70  \w     26.00  52.00   0.50    0.70    --   50.00  79.00 -22.42   52
 71  \w     95.00 107.50   0.50    0.70    --   50.00  79.00 165.68   25
;
_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      -0.0634341000
_diffrn_orient_matrix_UB_12      0.0366318000
_diffrn_orient_matrix_UB_13      -0.0885042000
_diffrn_orient_matrix_UB_21      -0.0212450000
_diffrn_orient_matrix_UB_22      0.0973658000
_diffrn_orient_matrix_UB_23      0.0230221000
_diffrn_orient_matrix_UB_31      0.0972884000
_diffrn_orient_matrix_UB_32      0.0446403000
_diffrn_orient_matrix_UB_33      -0.0659028000
_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  0.0506
_diffrn_reflns_av_unetI/netI     0.0369
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            49850
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.740
_diffrn_reflns_theta_min         4.453
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.447
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69391
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
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    1.265
_exptl_crystal_description       prizm
_exptl_crystal_F_000             992
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.489
_refine_diff_density_min         -1.114
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     562
_refine_ls_number_reflns         10717
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0348
_refine_ls_R_factor_gt           0.0329
_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^)+(0.0311P)^2^+2.8962P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0824
_refine_ls_wR_factor_ref         0.0835
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10158
_reflns_number_total             10717
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nj03823h3.cif
_cod_data_source_block           15015_kmd005
_cod_depositor_comments
'Adding full bibliography for 7062994--7063002.cif.'
_cod_database_code               7062999
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C54 H45 Cu1 I1 P3'
_olex2_refinement_description
;
1. Others
 Sof(C41)=Sof(H41)=1-FVAR(1)
 Sof(C41A)=Sof(H41A)=FVAR(1)
 Sof(H39A)=Sof(C40)=Sof(H40)=Sof(C42)=1-FVAR(2)
 Sof(H39)=Sof(C40A)=Sof(H40A)=Sof(C42A)=Sof(H42A)=FVAR(2)
2.a Aromatic/amide H refined with riding coordinates:
 C36(H36), C32(H32), C54(H54), C50(H50), C44(H44), C6(H6), C5(H5), C24(H24),
 C26(H26), C14(H14), C51(H51), C27(H27), C35(H35), C53(H53), C38(H38), C30(H30),
  C12(H12), C47(H47), C20(H20), C48(H48), C4(H4), C23(H23), C29(H29), C52(H52),
 C1(H1), C39(H39A), C39(H39), C46(H46), C17(H17), C18(H18), C28(H28), C45(H45),
 C8(H8), C3(H3), C11(H11), C33(H33), C34(H34), C22(H22), C15(H15), C21(H21),
 C16(H16), C10(H10), C9(H9), C40(H40), C42(H42), C41(H41), C41A(H41A),
 C40A(H40A), C42A(H42A)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              39471
_shelx_fab_checksum              72275
_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 2.098
_oxdiff_exptl_absorpt_empirical_full_min 0.626