Synthesis of di/trifluoromethyl bis(1,2,4-triazoline)spiranes and 1,2,4-triazoles <i>via</i> 1,3-dipolar cycloaddition of nitrilimines and carbodiimides.
Zhou, Yuxiu; Li, Xiaoyong; Liu, Xiaokang; Huang, Danfeng; Wang, Ke-Hu; Wang, Junjiao; Hu, Yulai; Organic & biomolecular chemistry 23 (2025) 2662–2671; doi:10.1039/d4ob01821d

data_7160360
_publ_section_title
;
 Synthesis of di/trifluoromethyl bis(1,2,4-triazoline)spiranes and
 1,2,4-triazoles <i>via</i> 1,3-dipolar cycloaddition of nitrilimines and
 carbodiimides.
;
_journal_issue                   11
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2662
_journal_page_last               2671
_journal_paper_doi               10.1039/d4ob01821d
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C23 H26 F4 N6'
_chemical_formula_sum            'C23 H26 F4 N6'
_chemical_formula_weight         462.50
_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     direct
_audit_creation_date             2023-03-21
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2023-03-21 deposited with the CCDC.	2025-02-03 downloaded from the CCDC.
;
_cell_angle_alpha                84.4953(15)
_cell_angle_beta                 88.2625(15)
_cell_angle_gamma                89.6565(15)
_cell_formula_units_Z            4
_cell_length_a                   9.52305(17)
_cell_length_b                   13.1270(2)
_cell_length_c                   18.3358(3)
_cell_measurement_reflns_used    15631
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      76.1840
_cell_measurement_theta_min      2.3970
_cell_volume                     2280.51(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(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 0.942
_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     26.00  54.00   0.50    0.05    --   44.32  57.00 -60.00   56
  2  \w     69.00 118.00   0.50    0.05    --   44.32  57.00 -60.00   98
  3  \w    138.00 164.00   0.50    0.20    --  109.62  30.00-180.00   52
  4  \w    148.00 173.00   0.50    0.20    --  109.62  45.00-120.00   50
  5  \w    100.00 144.00   0.50    0.20    --  109.62  45.00-120.00   88
  6  \w    -26.00  22.00   0.50    0.05    --   44.32 -19.00-150.00   96
  7  \w    -31.00  11.00   0.50    0.05    --   44.32 -19.00 -90.00   84
  8  \w    -23.00   2.00   0.50    0.05    --   44.32 -19.00 -60.00   50
  9  \w    -18.00  19.00   0.50    0.05    --   44.32 -19.00   0.00   74
 10  \w    -30.00  36.00   0.50    0.05    --   44.32 -37.00 150.00  132
 11  \w     37.00  72.00   0.50    0.20    --  109.62 -94.00  60.00   70
 12  \w     59.00 109.00   0.50    0.20    --  109.62-125.00   0.00  100
 13  \w     38.00  82.00   0.50    0.05    --   44.32-108.00-174.00   88
 14  \w      9.00  35.00   0.50    0.05    --   44.32-108.00-174.00   52
 15  \w     82.00 107.00   0.50    0.20    --  109.62-108.00-174.00   50
 16  \w     72.00 103.00   0.50    0.20    --  109.62 -77.00-180.00   62
 17  \w     40.00  68.00   0.50    0.20    --  109.62 -61.00-120.00   56
 18  \w     37.00  67.00   0.50    0.20    --  109.62 -61.00 -90.00   60
 19  \w     69.00  95.00   0.50    0.20    --  109.62 -77.00 -30.00   52
 20  \w     40.00  89.00   0.50    0.20    --  109.62 -77.00   0.00   98
 21  \w     39.00  65.00   0.50    0.20    --  109.62 -77.00 -30.00   52
 22  \w     91.00 124.00   0.50    0.20    --  109.62 108.00 -77.00   66
 23  \w    128.00 167.00   0.50    0.20    --  109.62 108.00 -77.00   78
 24  \w    100.00 175.00   0.50    0.20    --  109.62 125.00-120.00  150
 25  \w     49.00 119.00   0.50    0.05    --   44.32 179.00  90.00  140
 26  \w    -74.00 -28.00   0.50    0.20    -- -100.00  61.00  30.00   92
 27  \w    -53.00 -28.00   0.50    0.20    -- -100.00  45.00  30.00   50
 28  \w    -74.00 -38.00   0.50    0.20    -- -100.00  61.00 -60.00   72
 29  \w    -54.00 -29.00   0.50    0.20    -- -100.00  45.00 -90.00   50
 30  \w    -54.00 -25.00   0.50    0.20    -- -100.00  45.00-120.00   58
 31  \w    -70.00 -26.00   0.50    0.20    -- -100.00  61.00-180.00   88
 32  \w   -107.00 -71.00   0.50    0.20    -- -100.00 108.00 -77.00   72
 33  \w   -112.00 -54.00   0.50    0.20    -- -100.00 125.00 -90.00  116
 34  \w   -121.00 -95.00   0.50    0.20    -- -100.00 140.00  15.41   52
 35  \w   -106.00 -40.00   0.50    0.20    -- -100.00 125.00 150.00  132
 36  \w   -107.00 -60.00   0.50    0.20    -- -100.00 125.00  90.00   94
 37  \w   -109.00 -27.00   0.50    0.20    -- -100.00 115.00  59.71  164
 38  \w    -59.00 -33.00   0.50    0.20    -- -100.00 140.00  15.41   52
 39  \w    -73.00 -48.00   0.50    0.05    --  -44.32 108.00 -77.00   50
 40  \w   -143.00 -70.00   0.50    0.20    -- -100.00 -15.00 -90.00  146
 41  \w   -177.00 -80.00   0.50    0.20    -- -100.00 -30.00  30.00  194
 42  \w   -164.00-139.00   0.50    0.20    -- -100.00 -61.00 -90.00   50
 43  \w   -134.00 -80.00   0.50    0.20    -- -100.00 -61.00 -90.00  108
 44  \w   -120.00 -90.00   0.50    0.20    -- -100.00-108.00-174.00   60
 45  \w   -167.00-144.50   0.50    0.20    -- -100.00-125.00  90.00   45
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0528719000
_diffrn_orient_matrix_UB_12      -0.0952898000
_diffrn_orient_matrix_UB_13      0.0484034000
_diffrn_orient_matrix_UB_21      0.0728161000
_diffrn_orient_matrix_UB_22      0.0377067000
_diffrn_orient_matrix_UB_23      0.0662781000
_diffrn_orient_matrix_UB_31      -0.1345246000
_diffrn_orient_matrix_UB_32      0.0583016000
_diffrn_orient_matrix_UB_33      0.0198876000
_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  0.0307
_diffrn_reflns_av_unetI/netI     0.0310
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            26437
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.349
_diffrn_reflns_theta_min         2.422
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.897
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62976
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (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    1.347
_exptl_crystal_description       block
_exptl_crystal_F_000             968
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.557
_refine_diff_density_min         -0.222
_refine_diff_density_rms         0.039
_refine_ls_extinction_coef       0.00210(19)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     604
_refine_ls_number_reflns         9012
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0466
_refine_ls_R_factor_gt           0.0406
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0512P)^2^+0.7138P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1054
_refine_ls_wR_factor_ref         0.1091
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7855
_reflns_number_total             9012
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01821d2.cif
_cod_data_source_block           d3-0321_auto
_cod_depositor_comments
'Adding full bibliography for 7160360--7160361.cif.'
_cod_database_code               7160360
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.957
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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 Ternary CH refined with riding coordinates:
 C3(H3), C5(H5), C12(H12), C21(H21), C26(H26), C28(H28), C29(H29), C32(H32)
2.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20), C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C42(H42),
  C43(H43), C44(H44), C45(H45), C46(H46)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C34(H34A,
 H34B,H34C)
;
_shelx_res_checksum              98063
_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 3.103
_oxdiff_exptl_absorpt_empirical_full_min 0.557