Experimental and Computational Evidence for "Double Pancake Bonds": The Role of Dispersion-Corrected DFT Methods in Strongly Dimerized 5-Aryl-1λ<sup>2</sup>,3λ<sup>2</sup>-dithia-2,4,6-triazines.
Boeré, René T; ACS omega 3 (2018) 18170–18180; doi:10.1021/acsomega.8b03211

data_4516168
_publ_section_title
;
 Experimental and Computational Evidence for &quot;Double Pancake
 Bonds&quot;: The Role of Dispersion-Corrected DFT Methods in Strongly
 Dimerized 5-Aryl-1\l<sup>2</sup>,3\l<sup>2</sup>-dithia-2,4,6-triazines.
;
_journal_issue                   12
_journal_name_full               'ACS omega'
_journal_page_first              18170
_journal_page_last               18180
_journal_paper_doi               10.1021/acsomega.8b03211
_journal_volume                  3
_journal_year                    2018
_chemical_formula_moiety         'C8 H4 F3 N5 S3'
_chemical_formula_sum            'C8 H4 F3 N5 S3'
_chemical_formula_weight         323.34
_chemical_melting_point          386
_chemical_name_common
;
 mCF3-bicyclic
;
_chemical_name_systematic
;
 7-[3-(Trifluoromethyl)phenyl]-1l4,3l4,5l4-trithia-2,4,6,8,9-pentaazabicyclo
 [3.3.1]nona-1(9),2,3,5,7-pentaene
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-09-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.6781(9)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.90772(16)
_cell_length_b                   4.66989(3)
_cell_length_c                   22.2724(2)
_cell_measurement_reflns_used    19022
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      77.1460
_cell_measurement_theta_min      4.0260
_cell_volume                     2282.39(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200/300K'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.989
_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    -71.00  -1.00   0.50    0.50    --   -4.52 -38.00 -60.00  140
  2  \w    -16.00  59.00   0.50    0.50    --   -4.52  57.00-150.00  150
  3  \w    -29.00  25.00   0.50    0.50    --    4.52  95.00  82.00  108
  4  \w    -30.00  22.00   0.50    0.50    --    4.52  97.00 -16.00  104
  5  \w     37.00 109.00   0.50    1.09    --  105.46 -94.00 -90.00  144
  6  \w    101.00 170.00   0.50    1.09    --  105.46  45.00-150.00  138
  7  \w     82.00 170.00   0.50    1.09    --  105.46  77.00 -30.00  176
  8  \w     37.00 109.00   0.50    1.09    --  105.46 -94.00-150.00  144
  9  \w    102.00 174.00   0.50    1.09    --  105.46  30.00 -90.00  144
 10  \w    102.00 174.00   0.50    1.09    --  105.46  30.00 -60.00  144
 11  \w     37.00 109.00   0.50    1.09    --  105.46 -30.00 -90.00  144
 12  \w     41.00 110.00   0.50    1.09    --  105.46 -45.00 -90.00  138
 13  \w     43.00 119.00   0.50    1.09    --  105.46 -61.00-150.00  152
 14  \w     43.00 119.00   0.50    1.09    --  105.46 -61.00 -90.00  152
 15  \w     82.00 170.00   0.50    1.09    --  105.46  77.00 -60.00  176
 16  \w     -7.00  68.00   0.50    0.50    --    4.52  57.00 150.00  150
 17  \w      1.00  71.00   0.50    0.50    --    4.52  38.00 -90.00  140
 18  \w    -64.00  10.00   0.50    0.50    --    4.52 -19.00 120.00  148
 19  \w    102.00 174.00   0.50    1.09    --  105.46  30.00  30.00  144
 20  \w    102.00 174.00   0.50    1.09    --  105.46  30.00-120.00  144
 21  \w     97.00 174.00   0.50    1.09    --  105.46  15.00 150.00  154
 22  \w     43.00 119.00   0.50    1.09    --  105.46 -61.00  30.00  152
 23  \w     40.00 122.00   0.50    1.09    --  105.46-125.00 120.00  164
 24  \w     82.00 170.00   0.50    1.09    --  105.46  77.00  90.00  176
 25  \w     82.00 170.00   0.50    1.09    --  105.46  77.00  30.00  176
 26  \w     82.00 170.00   0.50    1.09    --  105.46  77.00-180.00  176
 27  \w     97.00 174.00   0.50    1.09    --  105.46  15.00  90.00  154
 28  \w    -39.00  22.00   0.50    0.50    --   -4.52  97.00 -16.00  122
 29  \w    -19.00  69.00   0.50    0.50    --    4.52  77.00-120.00  176
 30  \w    -64.00  10.00   0.50    0.50    --    4.52 -19.00  60.00  148
 31  \w     82.00 170.00   0.50    1.09    --  105.46  77.00 120.00  176
 32  \w     97.00 174.00   0.50    1.09    --  105.46  15.00 -30.00  154
 33  \w     82.00 170.00   0.50    1.09    --  105.46  77.00  60.00  176
 34  \w     82.00 170.00   0.50    1.09    --  105.46  77.00 -90.00  176
 35  \w     92.00 168.00   0.50    1.09    --  105.46  61.00   0.00  152
 36  \w     82.00 170.00   0.50    1.09    --  105.46  77.00-120.00  176
 37  \w     82.00 170.00   0.50    1.09    --  105.46  77.00-150.00  176
 38  \w     37.00 109.00   0.50    1.09    --  105.46 -94.00-180.00  144
 39  \w     82.00 170.00   0.50    1.09    --  105.46  77.00 150.00  176
 40  \w    -19.00  69.00   0.50    0.50    --    4.52  77.00 120.00  176
 41  \w    -64.00  10.00   0.50    0.50    --    4.52 -19.00-180.00  148
 42  \w    -64.00  10.00   0.50    0.50    --    4.52 -19.00 -60.00  148
 43  \w     82.00 170.00   0.50    1.09    --  105.46  77.00   0.00  176
 44  \w     97.00 174.00   0.50    1.09    --  105.46  15.00-150.00  154
 45  \w     40.00  92.00   0.50    1.09    --  105.46-125.00  90.00  104
 46  \w    101.00 170.00   0.50    1.09    --  105.46  45.00  30.00  138
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0583550000
_diffrn_orient_matrix_UB_12      0.1015329000
_diffrn_orient_matrix_UB_13      0.0147907000
_diffrn_orient_matrix_UB_21      -0.0297820000
_diffrn_orient_matrix_UB_22      -0.2934491000
_diffrn_orient_matrix_UB_23      -0.0205413000
_diffrn_orient_matrix_UB_31      0.0252710000
_diffrn_orient_matrix_UB_32      -0.1114735000
_diffrn_orient_matrix_UB_33      0.0676113000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0276
_diffrn_reflns_av_unetI/netI     0.0108
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            23650
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.607
_diffrn_reflns_theta_min         4.029
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.306
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46145
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.882
_exptl_crystal_description       block
_exptl_crystal_F_000             1296
_exptl_crystal_preparation
'From 3-CF3C6H4CN(SiMe,)2NS and S3N3Cl3 in hot CH3CN.'
_exptl_crystal_recrystallization_method 'Cooling a hot CH3CN solution.'
_exptl_crystal_size_max          0.385
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.063
_refine_diff_density_max         0.411
_refine_diff_density_min         -0.315
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     172
_refine_ls_number_reflns         2390
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0286
_refine_ls_R_factor_gt           0.0280
_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^)+(0.0399P)^2^+3.9061P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0741
_refine_ls_wR_factor_ref         0.0744
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2373
_reflns_number_total             2390
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ao8b03211_si_002.cif
_cod_data_source_block           4
_cod_database_code               4516168
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C8H4F3N5S3
_chemical_oxdiff_usercomment
'Nice yellow to orange needles. Large, had to cut this block. In mp capillary.'
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C6(H6), C7(H7)
;
_olex2_exptl_crystal_mounting_method 'MiTeGen-100um loop in Paratone TM oil.'
_olex2_submission_original_sample_id RB16083rf1
_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 1.759
_oxdiff_exptl_absorpt_empirical_full_min 0.740