Are activation barriers of 50-70 kcal mol<sup>-1</sup> accessible for transformations in organic synthesis in solution?
Shaydullin, Ruslan R.; Galushko, Alexey S.; Ilyushenkova, Valentina V.; Vlasova, Yulia S.; Ananikov, Valentine P.; Chemical science 16 (2025) 5289–5298; doi:10.1039/d4sc08243e

data_1573968
_publ_section_title
;
 Are activation barriers of 50-70 kcal mol<sup>-1</sup> accessible for
 transformations in organic synthesis in solution?
;
_journal_issue                   12
_journal_name_full               'Chemical science'
_journal_page_first              5289
_journal_page_last               5298
_journal_paper_doi               10.1039/d4sc08243e
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C15 H12 N2'
_chemical_formula_sum            'C15 H12 N2'
_chemical_formula_weight         220.27
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-04-10
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-24 deposited with the CCDC.	2025-02-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.8320(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.55130(10)
_cell_length_b                   9.08050(10)
_cell_length_c                   22.6176(3)
_cell_measurement_reflns_used    9439
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.0750
_cell_measurement_theta_min      3.9280
_cell_volume                     1137.57(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.117a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.109a 64-bit (release 21-02-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.117a (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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_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 0.996
_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   -122.00 -30.00   0.50    0.60    --  -46.59 -16.00  53.00  184
  2  \w   -122.00 -30.00   0.50    0.60    --  -46.59 -16.00  53.00  184
  3  \w     30.00 122.00   0.50    0.60    --   46.59  16.00-137.00  184
  4  \w    -28.00  25.00   0.50    0.60    --   46.59 -16.00  53.00  106
  5  \w   -167.00 -75.00   0.50    2.40    --  -91.75 -16.00  53.00  184
  6  \w     96.00 178.00   0.50    2.40    --  113.25  16.00-137.00  164
  7  \w    -25.00  30.00   0.50    0.60    --  -46.59  16.00-137.00  110
  8  \w     34.00  93.00   0.50    0.60    --   46.59-125.00-120.00  118
  9  \w    -29.00  27.00   0.50    0.60    --   46.59 -19.00 -60.00  112
 10  \w    -85.00 -27.00   0.50    2.40    --  -91.75 125.00 -90.00  116
 11  \w    -51.00 -23.00   0.50    2.40    --  -91.75  45.00-150.00   56
 12  \w     44.00  69.00   0.50    2.40    --  113.25 -61.00-180.00   50
 13  \w     41.00 106.00   0.50    2.40    --  113.25 -95.00 -90.00  130
 14  \w     66.00  96.00   0.50    2.40    --  113.25 -77.00 -30.00   60
 15  \w     69.00 102.00   0.50    2.40    --  113.25 -95.00 -30.00   66
 16  \w    142.00 168.00   0.50    2.40    --  113.25  15.00 120.00   52
 17  \w     77.00 110.00   0.50    2.40    --  113.25-125.00  30.00   66
 18  \w     43.00  70.00   0.50    2.40    --  113.25 -61.00 -30.00   54
 19  \w     55.00 103.00   0.50    2.40    --  113.25 -87.00-141.53   96
 20  \w    110.00 141.00   0.50    2.40    --  113.25 -87.00-141.53   62
 21  \w     43.00  70.00   0.50    2.40    --  113.25 -61.00-150.00   54
 22  \w     95.00 128.00   0.50    2.40    --  113.25 125.00 -90.00   66
 23  \w     44.00  95.00   0.50    2.40    --  113.25 -95.00 -60.00  102
 24  \w    111.00 138.00   0.50    2.40    --  113.25  15.00 120.00   54
 25  \w    140.00 177.00   0.50    2.40    --  113.25 125.00 -90.00   74
 26  \w     56.00  98.00   0.50    2.40    --  113.25 -77.00-120.00   84
 27  \w     55.00  82.00   0.50    2.40    --  113.25 -77.00-180.00   54
 28  \w     43.00  69.00   0.50    2.40    --  113.25-125.00  30.00   52
 29  \w     96.00 177.00   0.50    2.40    --  113.25  15.00 -90.00  162
 30  \w    102.00 128.00   0.50    2.40    --  113.25  45.00-120.00   52
 31  \w     97.00 127.00   0.50    2.40    --  113.25 125.00-150.00   60
 32  \w    101.00 130.00   0.50    2.40    --  113.25  30.00 150.00   58
 33  \w     42.00 103.00   0.50    2.40    --  113.25 -77.00  90.00  122
 34  \w     48.00  74.00   0.50    2.40    --  113.25 -95.00  90.00   52
 35  \w     81.00 106.00   0.50    2.40    --  113.25 -95.00  90.00   50
 36  \w     76.00 101.00   0.50    2.40    --  113.25 -95.00   0.00   50
 37  \w    106.00 168.00   0.50    2.40    --  113.25  45.00-180.00  124
 38  \w    122.00 168.00   0.50    2.40    --  113.25  61.00 -60.00   92
 39  \w    111.00 137.00   0.50    2.40    --  113.25  61.00 -90.00   52
 40  \w     85.00 111.00   0.50    2.40    --  113.25 -81.00 -89.37   52
 41  \w    118.00 146.00   0.50    2.40    --  113.25  30.00 -60.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.2686652000
_diffrn_orient_matrix_UB_12      -0.0267226000
_diffrn_orient_matrix_UB_13      -0.0096255000
_diffrn_orient_matrix_UB_21      0.0637204000
_diffrn_orient_matrix_UB_22      0.0247163000
_diffrn_orient_matrix_UB_23      0.0666011000
_diffrn_orient_matrix_UB_31      -0.0337303000
_diffrn_orient_matrix_UB_32      -0.1656861000
_diffrn_orient_matrix_UB_33      0.0114799000
_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     0.0198
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            13169
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.783
_diffrn_reflns_theta_min         3.918
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.599
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.512
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.117a (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            yellow
_exptl_crystal_density_diffrn    1.286
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             464
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.391
_refine_diff_density_min         -0.253
_refine_diff_density_rms         0.042
_refine_ls_extinction_coef       0.0020(5)
_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   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     155
_refine_ls_number_reflns         2471
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0420
_refine_ls_R_factor_gt           0.0397
_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^)+(0.0578P)^2^+0.4766P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1100
_refine_ls_wR_factor_ref         0.1123
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2305
_reflns_number_total             2471
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08243e2.cif
_cod_data_source_block           rus-197
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_crystal_density_meas' value 'none' was changed to
'?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1573968.cif.
;
_cod_database_code               1573968
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C15 H12 N2'
_chemical_oxdiff_usercomment     RUS-197
_shelx_estimated_absorpt_t_max   0.976
_shelx_estimated_absorpt_t_min   0.836
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C11(H11), C12(H12),
 C13(H13), C14(H14), C15(H15)
;
_shelx_res_checksum              40328
_shelx_hkl_checksum              57543
_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 1.235
_oxdiff_exptl_absorpt_empirical_full_min 0.850