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_4516167
_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         '0.5(C16 H8 F6 N6 S4)'
_chemical_formula_sum            'C8 H4 F3 N3 S2'
_chemical_formula_weight         263.26
_chemical_melting_point          390
_chemical_name_common
;
 m-CF3-dithiatriazine dimer
;
_chemical_name_systematic
4,9-bis[3-(trifluoromethyl)phenyl]-1l4,2l4,6l4,7l4-Tetrathia-3,5,8,10,11,12-hexaazatricyclo[5.3.1.12,6]dodeca-1(11),2,4,6(12),7,9-hexaene
_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
_atom_sites_solution_secondary   difmap
_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                104.2308(10)
_cell_angle_beta                 94.4500(10)
_cell_angle_gamma                103.1503(12)
_cell_formula_units_Z            4
_cell_length_a                   7.62509(11)
_cell_length_b                   8.44847(12)
_cell_length_c                   15.92585(16)
_cell_measurement_reflns_used    27891
_cell_measurement_temperature    99.98(13)
_cell_measurement_theta_max      77.2740
_cell_measurement_theta_min      5.5340
_cell_volume                     958.65(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41r (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41r (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41r (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      99.98(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200/300K'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.985
_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  30.00  140
  2  \w    -68.00   7.00   0.50    0.50    --   -4.52 -57.00 -90.00  150
  3  \w    -71.00  -1.00   0.50    0.50    --   -4.52 -38.00 150.00  140
  4  \w     -7.00  68.00   0.50    0.50    --    4.52  57.00 -60.00  150
  5  \w    -19.00  69.00   0.50    0.50    --    4.52  77.00 150.00  176
  6  \w    -19.00  69.00   0.50    0.50    --    4.52  77.00   0.00  176
  7  \w     43.00 119.00   0.50    0.69    --  105.46 -61.00-120.00  152
  8  \w     37.00 109.00   0.50    0.69    --  105.46 -30.00 -60.00  144
  9  \w     37.00 109.00   0.50    0.69    --  105.46 -94.00  90.00  144
 10  \w     94.00 171.00   0.50    0.69    --  105.46 125.00   0.00  154
 11  \w    101.00 170.00   0.50    0.69    --  105.46  45.00 -30.00  138
 12  \w    101.00 170.00   0.50    0.69    --  105.46  45.00  90.00  138
 13  \w     37.00 109.00   0.50    0.69    --  105.46 -94.00 -90.00  144
 14  \w     41.00 110.00   0.50    0.69    --  105.46 -45.00  30.00  138
 15  \w     92.00 168.00   0.50    0.69    --  105.46  61.00  60.00  152
 16  \w     92.00 168.00   0.50    0.69    --  105.46  61.00   0.00  152
 17  \w     40.00 122.00   0.50    0.69    --  105.46-125.00-150.00  164
 18  \w     40.00 122.00   0.50    0.69    --  105.46-125.00  30.00  164
 19  \w     41.00 110.00   0.50    0.69    --  105.46 -45.00 150.00  138
 20  \w     43.00 119.00   0.50    0.69    --  105.46 -61.00  30.00  152
 21  \w     37.00 109.00   0.50    0.69    --  105.46 -30.00-150.00  144
 22  \w     37.00 109.00   0.50    0.69    --  105.46 -30.00  90.00  144
 23  \w    101.00 170.00   0.50    0.69    --  105.46  45.00 -60.00  138
 24  \w     92.00 168.00   0.50    0.69    --  105.46  61.00  30.00  152
 25  \w     40.00 122.00   0.50    0.69    --  105.46-125.00 120.00  164
 26  \w     41.00 110.00   0.50    0.69    --  105.46 -45.00 -60.00  138
 27  \w    -39.00  24.00   0.50    0.50    --   -4.52  96.00-123.00  126
 28  \w    -59.00  16.00   0.50    0.50    --    4.52 -57.00-150.00  150
 29  \w    -19.00  69.00   0.50    0.50    --    4.52  77.00-150.00  176
 30  \w    -59.00  16.00   0.50    0.50    --    4.52 -57.00  90.00  150
 31  \w    -19.00  69.00   0.50    0.50    --    4.52  77.00-120.00  176
 32  \w    -19.00  69.00   0.50    0.50    --    4.52  77.00  60.00  176
 33  \w     97.00 174.00   0.50    0.69    --  105.46  15.00-120.00  154
 34  \w     92.00 168.00   0.50    0.69    --  105.46  61.00 -60.00  152
 35  \w     82.00 170.00   0.50    0.69    --  105.46  77.00-120.00  176
 36  \w     82.00 170.00   0.50    0.69    --  105.46  77.00-180.00  176
 37  \w     82.00 170.00   0.50    0.69    --  105.46  77.00   0.00  176
 38  \w     82.00 170.00   0.50    0.69    --  105.46  77.00 -30.00  176
 39  \w     82.00 170.00   0.50    0.69    --  105.46  77.00-150.00  176
 40  \w     82.00 170.00   0.50    0.69    --  105.46  77.00  90.00  176
 41  \w     92.00 168.00   0.50    0.69    --  105.46  61.00 120.00  152
 42  \w     82.00 170.00   0.50    0.69    --  105.46  77.00  30.00  176
 43  \w     82.00 170.00   0.50    0.69    --  105.46  77.00 150.00  176
 44  \w    101.00 170.00   0.50    0.69    --  105.46  45.00 -90.00  138
 45  \w     82.00 170.00   0.50    0.69    --  105.46  77.00 -90.00  176
 46  \w     82.00 170.00   0.50    0.69    --  105.46  77.00  60.00  176
 47  \w     82.00 170.00   0.50    0.69    --  105.46  77.00 120.00  176
 48  \w     92.00 168.00   0.50    0.69    --  105.46  61.00-180.00  152
 49  \w     82.00 170.00   0.50    0.69    --  105.46  77.00 -60.00  176
 50  \w     97.00 174.00   0.50    0.69    --  105.46  15.00-180.00  154
 51  \w    -74.00   1.00   0.50    0.50    --   -4.52 -19.00-120.00  150
 52  \w    -74.00  65.00   0.50    0.50    --   -4.52   0.00  60.00  278
 53  \w    -10.00  65.00   0.50    0.50    --   -4.52  19.00  60.00  150
 54  \w    -19.00  69.00   0.50    0.50    --    4.52  77.00 -90.00  176
 55  \w    -30.00  24.00   0.50    0.50    --    4.52  96.00-123.00  108
 56  \w      1.00  71.00   0.50    0.50    --    4.52  38.00  60.00  140
 57  \w     97.00 174.00   0.50    0.69    --  105.46  15.00  30.00  154
 58  \w    102.00 174.00   0.50    0.69    --  105.46  30.00  90.00  144
 59  \w     92.00 168.00   0.50    0.69    --  105.46  61.00 -90.00  152
 60  \w     97.00 174.00   0.50    0.69    --  105.46  15.00 150.00  154
 61  \w    102.00 174.00   0.50    0.69    --  105.46  30.00 -60.00  144
 62  \w     92.00 168.00   0.50    0.69    --  105.46  61.00 150.00  152
 63  \w     97.00 174.00   0.50    0.69    --  105.46  15.00-150.00  154
 64  \w     97.00 174.00   0.50    0.69    --  105.46  15.00  60.00  154
 65  \w     92.00 168.00   0.50    0.69    --  105.46  61.00  90.00  152
 66  \w    101.00 170.00   0.50    0.69    --  105.46  45.00-150.00  138
 67  \w     97.00 174.00   0.50    0.69    --  105.46  15.00  90.00  154
 68  \w     92.00 168.00   0.50    0.69    --  105.46  61.00 -30.00  152
 69  \w     97.00 174.00   0.50    0.69    --  105.46  15.00 -30.00  154
 70  \w    102.00 174.00   0.50    0.69    --  105.46  30.00   0.00  144
 71  \w    101.00 170.00   0.50    0.69    --  105.46  45.00 150.00  138
 72  \w    102.00 174.00   0.50    0.69    --  105.46  30.00  60.00  144
 73  \w     97.00 174.00   0.50    0.69    --  105.46  15.00 -60.00  154
 74  \w     92.00 168.00   0.50    0.69    --  105.46  61.00-120.00  152
 75  \w    -71.00  -1.00   0.50    0.50    --   -4.52 -38.00-150.00  140
 76  \w    -64.00  10.00   0.50    0.50    --    4.52 -19.00 -30.00  148
 77  \w      1.00  71.00   0.50    0.50    --    4.52  38.00   0.00  140
 78  \w    -64.00  10.00   0.50    0.50    --    4.52 -19.00 -90.00  148
 79  \w      1.00  71.00   0.50    0.50    --    4.52  38.00  30.00  140
 80  \w    -62.00   8.00   0.50    0.50    --    4.52 -38.00-180.00  140
 81  \w     37.00 109.00   0.50    0.69    --  105.46 -94.00   0.00  144
 82  \w     97.00 157.00   0.50    0.69    --  105.46  15.00 -90.00  120
 83  \w     92.00 168.00   0.50    0.69    --  105.46  61.00-150.00  152
;
_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      -0.0430079000
_diffrn_orient_matrix_UB_12      0.0199344000
_diffrn_orient_matrix_UB_13      0.0944012000
_diffrn_orient_matrix_UB_21      0.0716738000
_diffrn_orient_matrix_UB_22      -0.1547050000
_diffrn_orient_matrix_UB_23      0.0041580000
_diffrn_orient_matrix_UB_31      0.1921974000
_diffrn_orient_matrix_UB_32      0.1162879000
_diffrn_orient_matrix_UB_33      0.0351236000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0533
_diffrn_reflns_av_unetI/netI     0.0198
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            37748
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.493
_diffrn_reflns_theta_min         5.551
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.289
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42894
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41r (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.824
_exptl_crystal_description       plate
_exptl_crystal_F_000             528
_exptl_crystal_preparation
'Reduction of the corresponding dichloride with Ph3Sb in free-thaw degassed CH3CN.'
_exptl_crystal_recrystallization_method
'Crystals grown from the preparative reaction.'
_exptl_crystal_size_max          0.374
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.061
_refine_diff_density_max         0.511
_refine_diff_density_min         -0.484
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     320
_refine_ls_number_reflns         4013
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0398
_refine_ls_R_factor_gt           0.0385
_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^)+(0.0641P)^2^+0.8233P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1067
_refine_ls_wR_factor_ref         0.1076
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3874
_reflns_number_total             4013
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ao8b03211_si_002.cif
_cod_data_source_block           3
_cod_database_code               4516167
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C8 H4 F3 N3 S2'
_chemical_oxdiff_usercomment
'Judy Yip, small well-closed vial. Some hydrolysis evident.'
_shelx_estimated_absorpt_t_max   0.739
_shelx_estimated_absorpt_t_min   0.242
_reflns_odcompleteness_completeness 99.97
_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. Uiso/Uaniso restraints and constraints
F4 \\sim F5 \\sim F6 \\sim F4A \\sim F5A \\sim F6A: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
Uanis(C18) = Uanis(C18A)
3. Others
 Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(C18A)=1-FVAR(1)
 Sof(F4)=Sof(F5)=Sof(F6)=Sof(C18)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C6(H6), C7(H7), C13(H13), C15(H15), C16(H16), C17(H17)
;