Iridium-catalyzed tandem olefination/aza-Michael reaction: rapid access to N-N functionalized hydrazides.
Zhang, Chao; Dong, Lin; Organic & biomolecular chemistry 23 (2025) 673–678; doi:10.1039/d4ob01631a

data_7160204
_publ_section_title
;
 Iridium-catalyzed tandem olefination/aza-Michael reaction: rapid access
 to N-N functionalized hydrazides.
;
_journal_issue                   3
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              673
_journal_page_last               678
_journal_paper_doi               10.1039/d4ob01631a
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C H Cl3, C33 H22 N2 O7'
_chemical_formula_sum            'C34 H23 Cl3 N2 O7'
_chemical_formula_weight         677.89
_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             2024-07-20
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.17 svn.r577a77a9 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-08-28 deposited with the CCDC.	2024-11-04 downloaded from the CCDC.
;
_cell_angle_alpha                81.5570(10)
_cell_angle_beta                 67.5690(10)
_cell_angle_gamma                73.6290(10)
_cell_formula_units_Z            2
_cell_length_a                   11.40750(10)
_cell_length_b                   12.09380(10)
_cell_length_c                   13.11160(10)
_cell_measurement_reflns_used    35884
_cell_measurement_temperature    300.57(10)
_cell_measurement_theta_max      75.6720
_cell_measurement_theta_min      3.7940
_cell_volume                     1602.65(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      300.57(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.947
_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     40.00  66.00   0.50    0.05    --   66.00  76.00   1.65   52
  2  \w     35.00  75.00   0.50    0.05    --   62.00  77.00 114.11   80
  3  \w     81.00 128.00   0.50    0.05    --   62.00  77.00 114.11   94
  4  \w    107.00 133.00   0.50    0.05    --   66.00  76.00   1.65   52
  5  \w     71.00 115.00   0.50    0.05    --   44.45  37.00  60.00   88
  6  \w     25.00  57.00   0.50    0.05    --   44.45  37.00  60.00   64
  7  \w     38.00  72.00   0.50    0.05    --   66.00  80.00-122.40   68
  8  \w      2.00  27.00   0.50    0.05    --   38.00  97.00 -72.96   50
  9  \w      8.00  33.00   0.50    0.05    --   42.00  93.00 124.91   50
 10  \w     18.00  43.00   0.50    0.05    --   50.00  89.00  88.71   50
 11  \w     18.00  43.00   0.50    0.05    --   50.00  89.00  27.73   50
 12  \w     18.00  43.00   0.50    0.05    --   50.00  88.00   1.70   50
 13  \w      3.00  28.00   0.50    0.05    --   34.00  86.00   9.52   50
 14  \w     18.00  43.00   0.50    0.05    --   50.00  89.00-116.67   50
 15  \w     15.00  40.00   0.50    0.05    --   46.00  86.00-179.28   50
 16  \w     20.00  45.00   0.50    0.05    --   50.00  88.00-167.41   50
 17  \w    100.00 126.00   0.50    0.11    --  107.48  90.00-170.00   52
 18  \w     29.00  55.00   0.50    0.05    --   58.00  81.00 -62.92   52
 19  \w     29.00  91.00   0.50    0.05    --   58.00  81.00 172.23  124
 20  \w     98.00 128.00   0.50    0.05    --   58.00  81.00 172.23   60
 21  \w    -23.00  43.00   0.50    0.05    --   44.45 -37.00 120.00  132
 22  \w     51.00 117.00   0.50    0.11    --  107.48-125.00 -90.00  132
 23  \w     39.00 114.00   0.50    0.11    --  107.48-125.00-120.00  150
 24  \w     35.00  70.00   0.50    0.11    --  107.48 -61.00-150.00   70
 25  \w     35.00  60.00   0.50    0.11    --  107.48 -61.00 -90.00   50
 26  \w     34.00  87.00   0.50    0.11    --  107.48 -90.00  74.00  106
 27  \w     39.00  97.00   0.50    0.11    --  107.48 -94.00  30.00  116
 28  \w     45.00 107.00   0.50    0.11    --  107.48 -94.00 -30.00  124
 29  \w     36.00 100.00   0.50    0.11    --  107.48 -94.00 -60.00  128
 30  \w    -22.00  75.00   0.50    0.05    --   44.45 -90.00  74.00  194
 31  \w   -103.00 -77.00   0.50    0.05    --  -44.45 -57.00   0.00   52
 32  \w    -53.00 -27.00   0.50    0.05    --  -44.45 -57.00   0.00   52
 33  \w    -69.00 -25.00   0.50    0.05    --  -44.45 -57.00 -90.00   88
 34  \w    -48.00 -20.00   0.50    0.05    --  -44.45 -19.00-120.00   56
 35  \w    -51.00 -25.00   0.50    0.05    --  -44.45 -57.00-180.00   52
 36  \w   -117.00 -59.00   0.50    0.05    --  -44.45 -57.00-180.00  116
 37  \w   -121.00 -92.00   0.50    0.05    --  -44.45 -19.00-120.00   58
 38  \w   -154.00 -77.00   0.50    0.11    -- -102.00 -90.00  74.00  154
 39  \w    -70.00 -44.00   0.50    0.11    --  -74.00 -83.00  80.02   52
 40  \w    -58.00 -32.00   0.50    0.05    --  -62.00 -83.00  44.89   52
 41  \w    -70.00 -44.00   0.50    0.11    --  -74.00 -83.00  15.19   52
 42  \w    -54.00 -29.00   0.50    0.05    --  -58.00 -82.00 -36.94   50
 43  \w    -70.00 -33.00   0.50    0.05    --  -62.00 -82.00 -66.90   74
 44  \w   -119.00 -85.00   0.50    0.05    --  -58.00 -83.00-158.46   68
 45  \w    -83.00 -49.00   0.50    0.11    --  -78.00 -82.00-172.86   68
 46  \w    -53.00 -28.00   0.50    0.05    --  -58.00 -83.00-158.46   50
 47  \w    -76.00 -41.00   0.50    0.05    --  -70.00 -81.00 176.80   70
 48  \w   -135.00-109.00   0.50    0.05    --  -70.00 -81.00 176.80   52
 49  \w   -171.00-119.00   0.50    0.11    --  -98.00 -57.00 166.55  104
 50  \w    -79.00 -54.00   0.50    0.11    --  -82.00 -79.00  61.21   50
 51  \w   -105.00 -70.00   0.50    0.11    --  -98.00 -78.00   0.28   70
 52  \w   -112.00 -70.00   0.50    0.11    --  -98.00 -78.00 -38.19   84
 53  \w    -68.00 -42.00   0.50    0.05    --  -70.00 -80.00 -62.29   52
 54  \w   -169.00 -70.00   0.50    0.11    --  -98.00 -78.00 -70.94  198
 55  \w   -171.00-131.00   0.50    0.11    --  -98.00 -78.00 -38.19   80
 56  \w   -171.00-140.00   0.50    0.11    --  -98.00 -77.00-153.03   62
 57  \w   -134.00 -71.00   0.50    0.11    --  -98.00 -77.00-153.03  126
 58  \w   -103.00 -78.00   0.50    0.11    -- -102.00 -77.00-120.00   50
 59  \w   -175.00 -74.00   0.50    0.11    -- -102.00 -78.00 -23.93  202
 60  \w   -171.00-110.00   0.50    0.11    --  -98.00 -78.00   0.28  122
 61  \w    -89.00 -59.00   0.50    0.11    --  -86.00 -77.00  99.17   60
 62  \w   -155.00 -67.00   0.50    0.11    --  -94.00 -77.00 120.53  176
 63  \w   -100.00 -75.00   0.50    0.11    -- -102.00 -77.00 -16.38   50
 64  \w   -140.00-115.00   0.50    0.11    -- -102.00 -77.00 -16.38   50
 65  \w   -175.00-106.00   0.50    0.11    -- -102.00 -77.00-120.00  138
 66  \w   -171.00-114.00   0.50    0.11    -- -102.00 -77.00-138.05  114
 67  \w   -111.00 -77.00   0.50    0.11    -- -102.00 -77.00-138.05   68
 68  \w    -83.00 -57.00   0.50    0.11    --  -82.00 -76.00-138.78   52
 69  \w    -76.00 -51.00   0.50    0.11    --  -78.00 -76.00-116.90   50
 70  \w    -69.00 -44.00   0.50    0.05    --  -70.00 -75.00-103.21   50
 71  \w   -160.00 -77.00   0.50    0.11    -- -102.00 -76.00-173.13  166
 72  \w   -130.00-104.00   0.50    0.05    --  -70.00 -75.00-103.21   52
 73  \w   -167.00 -73.00   0.50    0.11    --  -98.00 -76.00  39.23  188
 74  \w    -77.00 -52.00   0.50    0.11    --  -78.00 -75.00 -37.43   50
 75  \w    -86.00 -60.00   0.50    0.11    --  -86.00 -75.00 -54.30   52
 76  \w   -163.00 -68.00   0.50    0.11    --  -94.00 -75.00 -95.67  190
 77  \w   -150.00 -68.00   0.50    0.11    --  -94.00 -75.00 -64.20  164
 78  \w    -85.00 -59.00   0.50    0.11    --  -86.00 -76.00  79.68   52
 79  \w    -82.00 -48.00   0.50    0.11    --  -74.00 -74.00 100.86   68
 80  \w   -137.00 -64.00   0.50    0.11    --  -90.00 -74.00 134.33  146
 81  \w   -144.00-118.00   0.50    0.11    --  -74.00 -75.00 138.90   52
 82  \w    -87.00 -61.00   0.50    0.11    --  -86.00 -74.00 177.64   52
 83  \w    -75.00 -49.00   0.50    0.11    --  -74.00 -75.00 138.90   52
 84  \w    -78.00 -46.00   0.50    0.05    --  -70.00 -70.00  70.54   64
 85  \w    -86.00 -60.00   0.50    0.11    --  -86.00 -74.00  33.60   52
 86  \w    -88.00 -61.00   0.50    0.11    --  -86.00 -73.00  -7.64   54
 87  \w   -155.00-119.00   0.50    0.11    --  -94.00 -69.00  55.30   72
 88  \w   -154.00-128.00   0.50    0.11    --  -86.00 -73.00  -7.64   52
 89  \w    -95.00 -70.00   0.50    0.11    --  -94.00 -69.00  55.30   50
 90  \w   -149.00-110.00   0.50    0.11    --  -90.00 -66.00 143.45   78
 91  \w   -124.00 -71.00   0.50    0.11    --  -94.00 -66.00  62.21  106
 92  \w   -102.00 -67.00   0.50    0.11    --  -90.00 -66.00 143.45   70
 93  \w   -175.00 -87.00   0.50    0.11    -- -102.00 -64.00  96.38  176
 94  \w   -137.00 -72.00   0.50    0.11    --  -94.00 -67.00  11.94  130
 95  \w    -91.00 -65.00   0.50    0.11    --  -90.00 -71.00-148.97   52
 96  \w   -109.00 -67.00   0.50    0.11    --  -90.00 -69.00-121.64   84
 97  \w    -69.00 -29.00   0.50    0.11    -- -102.00  61.00 -90.00   80
 98  \w    -91.00 -33.00   0.50    0.11    -- -102.00 125.00-120.00  116
 99  \w   -104.00 -56.00   0.50    0.11    -- -102.00 125.00   0.00   96
100  \w   -117.00 -69.00   0.50    0.11    -- -102.00 125.00  90.00   96
101  \w    -63.00 -37.00   0.50    0.11    -- -102.00 125.00  90.00   52
102  \w   -116.00 -30.00   0.50    0.11    -- -102.00 125.00 120.00  172
103  \w    -82.00 -51.00   0.50    0.11    -- -102.00  90.00-170.00   62
104  \w    -66.00  29.00   0.50    0.05    --  -44.45  90.00-170.00  190
;
_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      0.0699030000
_diffrn_orient_matrix_UB_12      -0.1018921000
_diffrn_orient_matrix_UB_13      -0.0771150000
_diffrn_orient_matrix_UB_21      -0.0821552000
_diffrn_orient_matrix_UB_22      -0.0760505000
_diffrn_orient_matrix_UB_23      0.0861627000
_diffrn_orient_matrix_UB_31      -0.1053409000
_diffrn_orient_matrix_UB_32      0.0386798000
_diffrn_orient_matrix_UB_33      -0.0530932000
_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  0.0266
_diffrn_reflns_av_unetI/netI     0.0130
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.947
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            46997
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.823
_diffrn_reflns_theta_min         3.813
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.028
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58120
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.405
_exptl_crystal_description       block
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.549
_refine_diff_density_min         -0.735
_refine_diff_density_rms         0.040
_refine_ls_extinction_coef       0.0045(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     416
_refine_ls_number_reflns         6332
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0544
_refine_ls_R_factor_gt           0.0515
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0655P)^2^+0.6206P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1424
_refine_ls_wR_factor_ref         0.1450
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5762
_reflns_number_total             6332
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01631a2.cif
_cod_data_source_block           3-co2ph_auto
_cod_depositor_comments          'Adding full bibliography for 7160204.cif.'
_cod_database_code               7160204
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         CHONCl
_shelx_estimated_absorpt_t_max   0.612
_shelx_estimated_absorpt_t_min   0.518
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Rigid bond restraints
 C13, C3, C19, C16, C14, C5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C13) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.2
4.a Ternary CH refined with riding coordinates:
 C4(H4), C33(H33)
4.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B)
4.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C28(H28), C30(H30), C32(H32), C9(H9), C19(H19), C5(H5), C21(H21),
 C11(H11), C23(H23), C3(H3), C25(H25), C13(H13), C27(H27), C7(H7), C29(H29),
 C15(H15), C31(H31), C2(H2)
;
_shelx_res_checksum              444
_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 2.065
_oxdiff_exptl_absorpt_empirical_full_min 0.739