Diazomethyl-λ3-iodane meets aryne: dipolar cycloaddition and C-to-N iodane shift leading to indazolyl-λ3-iodanes
Otsuki, Shinya; Kanemoto, Kazuya; Martos, Daniel Carter; Kwon, Eunsang; Wencel-Delord, Joanna; Yoshikai, Naohiko; Chemical Science 16 (2025) 8053–8059; doi:10.1039/D5SC00266D

data_1574288
_publ_section_title
;
 Diazomethyl-\l3-iodane meets aryne: dipolar cycloaddition and C-to-N
 iodane shift leading to indazolyl-\l3-iodanes
;
_journal_issue                   18
_journal_name_full               'Chemical Science'
_journal_page_first              8053
_journal_page_last               8059
_journal_paper_doi               10.1039/D5SC00266D
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C20 H15 F6 I N2 O4'
_chemical_formula_sum            'C20 H15 F6 I N2 O4'
_chemical_formula_weight         588.24
_chemical_melting_point          461
_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             2024-02-14
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-11-20 deposited with the CCDC.	2025-03-31 downloaded from the CCDC.
;
_cell_angle_alpha                73.4200(10)
_cell_angle_beta                 86.6070(10)
_cell_angle_gamma                82.9770(10)
_cell_formula_units_Z            2
_cell_length_a                   8.32510(10)
_cell_length_b                   8.88170(10)
_cell_length_c                   14.9449(2)
_cell_measurement_reflns_used    44328
_cell_measurement_temperature    99.8(3)
_cell_measurement_theta_max      31.5050
_cell_measurement_theta_min      2.3980
_cell_volume                     1050.81(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.98a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.98a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.98a (Rigaku OD, 2023)'
_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      99.8(3)
_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 0.892
_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     -2.00  89.00   0.50    0.21    --   12.22  38.00-180.00  182
  2  \w     -2.00  60.00   0.50    0.21    --   12.22  57.00-180.00  124
  3  \w     -9.00  24.00   0.50    0.21    --   12.22  74.00 -73.65   66
  4  \w     -2.00  60.00   0.50    0.21    --   12.22  57.00  60.00  124
  5  \w     -2.00  89.00   0.50    0.21    --   12.22  38.00   0.00  182
  6  \w     -2.00  81.00   0.50    0.21    --   12.22  38.00-150.00  166
  7  \w     22.00  71.00   0.50    0.21    --  -10.03  19.00-120.00   98
  8  \w     22.00  71.00   0.50    0.21    --  -10.03  19.00 -90.00   98
  9  \w     22.00  71.00   0.50    0.21    --  -10.03  19.00  30.00   98
 10  \w    -33.00  21.00   0.50    0.21    --  -10.03  77.00  90.00  108
 11  \w     22.00  71.00   0.50    0.21    --  -10.03  19.00 150.00   98
 12  \w     22.00  71.00   0.50    0.21    --  -10.03  19.00 120.00   98
 13  \w    -90.00 -16.00   0.50    0.21    --  -10.03 -19.00  90.00  148
 14  \w    -41.00   8.00   0.50    0.21    --  -10.03  93.00   9.00   98
 15  \w    -54.00   5.00   0.50    0.21    --  -10.03 -57.00-150.00  118
 16  \w    -54.00   5.00   0.50    0.21    --  -10.03 -57.00 -30.00  118
 17  \w    -54.00   5.00   0.50    0.21    --  -10.03 -57.00   0.00  118
 18  \w    -90.00 -16.00   0.50    0.21    --  -10.03 -19.00 150.00  148
 19  \w    -54.00   5.00   0.50    0.21    --  -10.03 -57.00 -90.00  118
 20  \w    -54.00   5.00   0.50    0.21    --  -10.03 -57.00-180.00  118
 21  \w    -68.00 -16.00   0.50    0.21    --   12.22 -19.00-120.00  104
 22  \w    -15.00  35.00   0.50    0.21    --   12.22 -77.00-180.00  100
 23  \w    -15.00  35.00   0.50    0.21    --   12.22 -77.00   0.00  100
 24  \w    -54.00  27.00   0.50    0.21    --   12.22 -57.00  30.00  162
 25  \w    -19.00   7.00   0.50    0.21    --   12.22  95.00 145.82   52
 26  \w    -68.00 -16.00   0.50    0.21    --   12.22 -19.00  60.00  104
 27  \w    -15.00  35.00   0.50    0.21    --   12.22 -77.00  90.00  100
 28  \w     -4.00  41.00   0.50    0.21    --   12.22 -90.00  78.85   90
 29  \w      0.00  44.00   0.50    0.21    --   12.22 -95.00 138.17   88
 30  \w      0.00  44.00   0.50    0.21    --   12.22 -95.00  49.55   88
 31  \w     -1.00  43.00   0.50    0.21    --   12.22 -94.00  12.65   88
 32  \w     -2.00  43.00   0.50    0.21    --   12.22 -93.00 -24.16   90
 33  \w     -1.00  43.00   0.50    0.21    --   12.22 -94.00 -41.13   88
 34  \w     26.00  66.00   0.50    0.21    --   12.22-135.00 -93.55   80
 35  \w      0.00  44.00   0.50    0.21    --   12.22 -95.00 -92.65   88
 36  \w     -2.00  43.00   0.50    0.21    --   12.22 -93.00-163.40   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0504205000
_diffrn_orient_matrix_UB_12      -0.0169860000
_diffrn_orient_matrix_UB_13      -0.0316935000
_diffrn_orient_matrix_UB_21      -0.0127020000
_diffrn_orient_matrix_UB_22      -0.0729330000
_diffrn_orient_matrix_UB_23      0.0330917000
_diffrn_orient_matrix_UB_31      -0.0683411000
_diffrn_orient_matrix_UB_32      0.0376900000
_diffrn_orient_matrix_UB_33      0.0188220000
_diffrn_radiation_monochromator  'multilayered conforcal mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0418
_diffrn_reflns_av_unetI/netI     0.0230
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.892
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            61227
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.892
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.415
_diffrn_reflns_theta_min         2.407
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.608
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94300
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.98a (Rigaku Oxford Diffraction, 2023)
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    1.859
_exptl_crystal_description       plate
_exptl_crystal_F_000             576
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane/dichloromethane'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.569
_refine_diff_density_min         -0.351
_refine_diff_density_rms         0.073
_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     300
_refine_ls_number_reflns         6176
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0204
_refine_ls_R_factor_gt           0.0183
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0181P)^2^+0.4706P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0410
_refine_ls_wR_factor_ref         0.0417
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5804
_reflns_number_total             6176
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00266d2.cif
_cod_data_source_block           kanamoto240229_auto
_cod_depositor_comments          'Adding full bibliography for 1574288.cif.'
_cod_database_code               1574288
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C20H15F6I1N2O4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C00O(H00A,H00B)
2.b Aromatic/amide H refined with riding coordinates:
 C00G(H00G), C00I(H00I), C00J(H00J), C00K(H00K), C00Q(H00Q), C00R(H00R),
 C00T(H00T)
2.c Idealised Me refined as rotating group:
 C00U(H00C,H00D,H00E), C00W(H00F,H00H,H00L)
;
_olex2_exptl_crystal_mounting_method loop
_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 1.979
_oxdiff_exptl_absorpt_empirical_full_min 0.643