Ruthenium-catalyzed synthesis of tricyclic 1,5-fused 1,2,3-triazole piperazines.
Said Stålsmeden, Anna; Ferrara, Flavia; Ekebergh, Andreas; Gumbo, Maureen; Runemark, August; Johansson, Johan R.; Norrby, Per-Ola; Kann, Nina; Organic & biomolecular chemistry 23 (2025) 8001–8011; doi:10.1039/d5ob01137j

data_7160695
_publ_section_title
;
 Ruthenium-catalyzed synthesis of tricyclic 1,5-fused 1,2,3-triazole
 piperazines.
;
_journal_issue                   35
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              8001
_journal_page_last               8011
_journal_paper_doi               10.1039/d5ob01137j
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C20 H22 N4 O'
_chemical_formula_sum            'C20 H22 N4 O'
_chemical_formula_weight         334.41
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-13
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-13 deposited with the CCDC.	2025-08-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.456(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.4836(2)
_cell_length_b                   6.00559(14)
_cell_length_c                   12.6737(3)
_cell_measurement_reflns_used    5375
_cell_measurement_temperature    107.02(10)
_cell_measurement_theta_max      75.1450
_cell_measurement_theta_min      3.5300
_cell_volume                     859.54(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.144a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.144a 64-bit (release 23-01-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.43.144a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      107.02(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 0.960
_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     35.00  92.00   0.50    1.02    --  109.13 -95.00-180.00  114
  2  \w    109.00 178.00   0.50    1.02    --  109.13 104.00-132.00  138
  3  \w     35.00  79.00   0.50    1.02    --  109.13 -77.00 120.00   88
  4  \w     35.00  92.00   0.50    1.02    --  109.13-104.00 126.00  114
  5  \w      6.00  79.00   0.50    0.26    --   43.31-104.00 126.00  146
  6  \w     35.00  79.00   0.50    1.02    --  109.13 -77.00-180.00   88
  7  \w    -42.00  31.00   0.50    0.26    --  -43.31  57.00 -30.00  146
  8  \w    -15.00  34.00   0.50    0.26    --  -43.31  38.00  30.00   98
  9  \w    -15.00  34.00   0.50    0.26    --  -43.31  38.00 -60.00   98
 10  \w    -15.00  34.00   0.50    0.26    --  -43.31  38.00 -90.00   98
 11  \w    -15.00  34.00   0.50    0.26    --  -43.31  38.00-180.00   98
 12  \w   -120.00 -29.00   0.50    0.26    --  -43.31 -38.00-120.00  182
 13  \w   -120.00 -58.00   0.50    0.26    --  -43.31 -38.00 -60.00  124
 14  \w   -120.00 -29.00   0.50    0.26    --  -43.31 -38.00   0.00  182
 15  \w   -120.00 -29.00   0.50    0.26    --  -43.31 -38.00 150.00  182
 16  \w   -174.00-103.00   0.50    1.02    -- -104.50-104.00 126.00  142
 17  \w   -163.00 -90.00   0.50    1.02    -- -104.50 -30.00 150.00  146
 18  \w   -132.00 -89.00   0.50    1.02    -- -104.50 -15.00 -30.00   86
 19  \w   -132.00 -89.00   0.50    1.02    -- -104.50 -15.00  60.00   86
 20  \w   -132.00 -89.00   0.50    1.02    -- -104.50 -15.00  90.00   86
 21  \w   -174.00-103.00   0.50    1.02    -- -104.50 -77.00 -90.00  142
 22  \w   -174.00-103.00   0.50    1.02    -- -104.50 -77.00 -90.00  142
 23  \w   -132.00 -89.00   0.50    1.02    -- -104.50 -15.00-180.00   86
 24  \w    -72.00 -30.00   0.50    1.02    -- -104.50  77.00-150.00   84
 25  \w    -92.00 -30.00   0.50    1.02    -- -104.50 104.00-132.00  124
 26  \w    -79.00   0.00   0.50    0.26    --  -43.31 104.00-132.00  158
 27  \w    -72.00 -30.00   0.50    1.02    -- -104.50  77.00 -30.00   84
 28  \w    -72.00 -30.00   0.50    1.02    -- -104.50  77.00   0.00   84
 29  \w   -101.00 -33.00   0.50    1.02    -- -104.50 125.00 150.00  136
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0334379000
_diffrn_orient_matrix_UB_12      0.2466131000
_diffrn_orient_matrix_UB_13      -0.0103035000
_diffrn_orient_matrix_UB_21      -0.0440799000
_diffrn_orient_matrix_UB_22      -0.0116148000
_diffrn_orient_matrix_UB_23      -0.1222418000
_diffrn_orient_matrix_UB_31      -0.1246296000
_diffrn_orient_matrix_UB_32      0.0694426000
_diffrn_orient_matrix_UB_33      0.0158665000
_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  0.0364
_diffrn_reflns_av_unetI/netI     0.0351
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            8807
_diffrn_reflns_point_group_measured_fraction_full 0.891
_diffrn_reflns_point_group_measured_fraction_max 0.836
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.263
_diffrn_reflns_theta_min         3.546
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.653
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.924
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.144a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic whiteish white'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.292
_exptl_crystal_description       prism
_exptl_crystal_F_000             356
_exptl_crystal_size_max          0.143
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.035
_refine_diff_density_max         0.216
_refine_diff_density_min         -0.207
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 975 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.5(2)
_refine_ls_extinction_coef       0.0029(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.109
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     231
_refine_ls_number_reflns         2986
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.109
_refine_ls_R_factor_all          0.0407
_refine_ls_R_factor_gt           0.0347
_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^)+(0.0421P)^2^+0.3402P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0835
_refine_ls_wR_factor_ref         0.1009
_reflns_Friedel_coverage         0.585
_reflns_Friedel_fraction_full    0.758
_reflns_Friedel_fraction_max     0.686
_reflns_number_gt                2763
_reflns_number_total             2986
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01137j2.cif
_cod_data_source_block           flavia2_auto
_cod_depositor_comments
'Adding full bibliography for 7160694--7160695.cif.'
_cod_database_code               7160695
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H N O'
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.912
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C18(H18), C14(H14)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C15(H15A,H15B), C17(H17A,H17B), C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C21(H21), C5(H5), C25(H25), C3(H3), C24(H24), C23(H23),
 C22(H22), C4(H4)
2.d Idealised tetrahedral OH refined as rotating group:
 O19(H19)
;
_shelx_res_checksum              54194
_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 1.388
_oxdiff_exptl_absorpt_empirical_full_min 0.790