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_7160361
_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_absolute_configuration unk
_chemical_formula_moiety         'C13 H16 F2 N4'
_chemical_formula_sum            'C13 H16 F2 N4'
_chemical_formula_weight         266.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-05-22
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-05-22 deposited with the CCDC.	2025-02-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.315(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.1731(3)
_cell_length_b                   9.5526(5)
_cell_length_c                   11.6141(5)
_cell_measurement_reflns_used    5959
_cell_measurement_temperature    301.22(10)
_cell_measurement_theta_max      76.3010
_cell_measurement_theta_min      3.8140
_cell_volume                     680.72(6)
_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 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      air
_diffrn_ambient_temperature      301.22(10)
_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 0.966
_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    112.00 167.00   0.50    0.07    --  112.00  45.00  90.00  110
  2  \w     61.00 166.00   0.50    0.07    --  112.00  11.00  40.00  210
  3  \w     -6.00 113.00   0.50    0.05    --   45.34  11.00  40.00  238
  4  \w     39.00  65.00   0.50    0.07    --  112.00-125.00-180.00   52
  5  \w     45.00  79.00   0.50    0.07    --  112.00-125.00-150.00   68
  6  \w     83.00 112.00   0.50    0.07    --  112.00-125.00-150.00   58
  7  \w     75.00 106.00   0.50    0.07    --  112.00-125.00-180.00   62
  8  \w     81.00 106.00   0.50    0.07    --  112.00 -94.00-180.00   50
  9  \w     48.00  91.00   0.50    0.07    --  112.00 -94.00 120.00   86
 10  \w    -25.00   1.00   0.50    0.05    --   45.34 -11.00-132.00   52
 11  \w     42.00  87.00   0.50    0.07    --  112.00 -77.00-180.00   90
 12  \w     40.00  68.00   0.50    0.07    --  112.00 -61.00-180.00   56
 13  \w     42.00  67.00   0.50    0.07    --  112.00 -61.00-150.00   50
 14  \w     41.00  67.00   0.50    0.07    --  112.00 -61.00-120.00   52
 15  \w     40.00  66.00   0.50    0.07    --  112.00 -61.00 -90.00   52
 16  \w   -108.00 -75.00   0.50    0.07    -- -100.00  77.00 150.00   66
 17  \w    -66.00 -38.00   0.50    0.07    -- -100.00  77.00 150.00   56
 18  \w    -53.00 -27.00   0.50    0.07    -- -100.00  45.00   0.00   52
 19  \w    -67.00 -37.00   0.50    0.07    -- -100.00  61.00-120.00   60
 20  \w    -52.00 -26.00   0.50    0.07    -- -100.00  45.00-150.00   52
 21  \w    -87.00 -44.00   0.50    0.05    --  -45.34 -11.00-132.00   86
 22  \w   -122.00 -90.00   0.50    0.05    --  -45.34 -11.00-132.00   64
 23  \w   -144.00 -73.00   0.50    0.07    -- -100.00 -11.00-132.00  142
 24  \w   -121.00 -60.00   0.50    0.05    --  -45.34-179.00  30.00  122
 25  \w   -173.00-147.00   0.50    0.07    -- -100.00 -11.00-132.00   52
 26  \w    -58.00 -32.00   0.50    0.05    --  -45.28 -77.00  90.00   52
 27  \w    -61.00 -27.00   0.50    0.05    --  -45.28 -57.00 120.00   68
 28  \w     40.00  67.00   0.50    0.05    --   45.28  37.00  90.00   54
 29  \w     24.00  52.00   0.50    0.05    --   45.28  19.00 150.00   56
 30  \w     29.00  63.00   0.50    0.05    --   45.28  57.00  90.00   68
 31  \w     23.00  48.00   0.50    0.05    --   45.28  77.00-150.00   50
 32  \w     18.00  74.00   0.50    0.05    --   45.28  77.00 150.00  112
 33  \w   -170.00-145.00   0.50    0.07    -- -100.00 -59.00  74.20   50
 34  \w    -98.00 -73.00   0.50    0.07    -- -100.00 -77.00 120.00   50
 35  \w   -101.00 -75.00   0.50    0.07    -- -100.00 -71.00-140.35   52
 36  \w   -122.00 -79.00   0.50    0.07    -- -100.00 -61.00 150.00   86
 37  \w    -99.00 -73.00   0.50    0.07    -- -100.00 -77.00-120.00   52
 38  \w   -108.00 -83.00   0.50    0.07    -- -100.00 -51.00-174.74   50
 39  \w   -141.00-115.00   0.50    0.07    -- -100.00 -77.00-180.00   52
 40  \w   -165.00-139.00   0.50    0.07    -- -100.00 -77.00 120.00   52
 41  \w   -103.00 -77.00   0.50    0.07    -- -100.00 -66.00-176.20   52
 42  \w   -101.00 -73.00   0.50    0.07    -- -100.00 -77.00-150.00   56
 43  \w   -106.00 -80.00   0.50    0.07    -- -100.00 -61.00  90.00   52
 44  \w   -105.00 -73.00   0.50    0.07    -- -100.00 -77.00  60.00   64
 45  \w   -113.00 -88.00   0.50    0.07    -- -100.00 -41.00 134.25   50
 46  \w   -165.00-139.00   0.50    0.07    -- -100.00 -77.00-150.00   52
 47  \w   -160.00-134.00   0.50    0.07    -- -100.00 -61.00 150.00   52
 48  \w   -120.00 -82.00   0.50    0.07    -- -100.00 -61.00 120.00   76
 49  \w   -126.00 -82.00   0.50    0.07    -- -100.00-125.00-120.00   88
 50  \w   -167.00-142.00   0.50    0.07    -- -100.00 -65.00 141.23   50
 51  \w   -129.00 -78.00   0.50    0.07    -- -100.00 -65.00 141.23  102
 52  \w   -104.00 -79.00   0.50    0.07    -- -100.00 -61.00-150.00   50
 53  \w   -105.00 -80.00   0.50    0.07    -- -100.00 -47.00 102.57   50
 54  \w   -106.00 -81.00   0.50    0.07    -- -100.00 -51.00  69.03   50
 55  \w   -105.00 -80.00   0.50    0.07    -- -100.00 -50.00  82.24   50
 56  \w    -99.00 -74.00   0.50    0.07    -- -100.00 -77.00-180.00   50
 57  \w   -105.00 -80.00   0.50    0.07    -- -100.00 -59.00  74.20   50
 58  \w   -172.00-147.00   0.50    0.07    -- -100.00 -45.00-155.60   50
 59  \w   -106.00 -79.00   0.50    0.07    -- -100.00 -45.00-155.60   54
 60  \w   -171.00-146.00   0.50    0.07    -- -100.00 -71.00-140.35   50
 61  \w   -102.00 -77.00   0.50    0.07    -- -100.00 -73.00 163.05   50
 62  \w   -101.00 -76.00   0.50    0.07    -- -100.00 -74.00 141.52   50
 63  \w     86.00 112.00   0.50    0.07    --  112.00  77.00  60.00   52
 64  \w    150.00 175.00   0.50    0.07    --  112.00  77.00 150.00   50
 65  \w     87.00 113.00   0.50    0.07    --  112.00  77.00 150.00   52
 66  \w     39.00  64.00   0.50    0.07    --  112.00 -61.00  60.00   50
;
_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      0.0046061000
_diffrn_orient_matrix_UB_12      0.0166577000
_diffrn_orient_matrix_UB_13      0.1321233000
_diffrn_orient_matrix_UB_21      -0.2496418000
_diffrn_orient_matrix_UB_22      -0.0167027000
_diffrn_orient_matrix_UB_23      -0.0107429000
_diffrn_orient_matrix_UB_31      0.0267422000
_diffrn_orient_matrix_UB_32      -0.1595680000
_diffrn_orient_matrix_UB_33      0.0150962000
_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  0.0614
_diffrn_reflns_av_unetI/netI     0.0413
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            8813
_diffrn_reflns_point_group_measured_fraction_full 0.942
_diffrn_reflns_point_group_measured_fraction_max 0.893
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.917
_diffrn_reflns_theta_min         3.829
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.842
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33466
_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    1.299
_exptl_crystal_description       needle
_exptl_crystal_F_000             280
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.395
_refine_diff_density_min         -0.358
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details
;
 Flack x determined using 892 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.12(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     175
_refine_ls_number_reflns         2592
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0723
_refine_ls_R_factor_gt           0.0686
_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^)+(0.1512P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1831
_refine_ls_wR_factor_ref         0.1899
_reflns_Friedel_coverage         0.742
_reflns_Friedel_fraction_full    0.878
_reflns_Friedel_fraction_max     0.811
_reflns_number_gt                2287
_reflns_number_total             2592
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01821d2.cif
_cod_data_source_block           c7_0522_auto
_cod_depositor_comments
'Adding full bibliography for 7160360--7160361.cif.'
_cod_database_code               7160361
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2A)
2.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C5(H5), C8(H8), C10(H10), C11(H11), C13(H13)
2.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C7(H7A,H7B,H7C), C9(H9A,H9B,H9C)
;
_shelx_res_checksum              44762
_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 2.241
_oxdiff_exptl_absorpt_empirical_full_min 0.385