The study of the photochemical behavior of 5-aryl-2,3-dihydropyrazine 1,4-dioxides.
Bakuleva, Nadezhda A.; Lichitskii, Boris V.; Komogortsev, Andrey N.; Tretyakov, Evgeny V.; Organic & biomolecular chemistry 23 (2025) 369–376; doi:10.1039/d4ob01570c

data_7160242
_publ_section_title
;
 The study of the photochemical behavior of 5-aryl-2,3-dihydropyrazine
 1,4-dioxides.
;
_journal_issue                   2
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              369
_journal_page_last               376
_journal_paper_doi               10.1039/d4ob01570c
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C14 H17 Br N2 O'
_chemical_formula_sum            'C14 H17 Br N2 O'
_chemical_formula_weight         309.20
_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             2024-03-02
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-06-27 deposited with the CCDC.	2024-11-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.5849(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.47732(7)
_cell_length_b                   10.43720(5)
_cell_length_c                   11.94409(6)
_cell_measurement_reflns_used    34417
_cell_measurement_temperature    99.97(16)
_cell_measurement_theta_max      79.7980
_cell_measurement_theta_min      3.8930
_cell_volume                     1414.449(14)
_computing_cell_refinement       'CrysAlisPro 1.171.43.104a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.104a 64-bit (release 22-12-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.104a (Rigaku OD, 2023)'
_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    'XT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.97(16)
_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 0.999
_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   -101.00 -20.00   0.50    0.19    --  -93.75  76.00  57.00  162
  2  \w    -71.00 -20.00   0.50    0.19    --  -93.75  61.00-120.00  102
  3  \w    -51.00 -20.00   0.50    0.19    --  -93.75  45.00 -90.00   62
  4  \w    -70.00  29.00   0.50    0.05    --  -44.88  76.00  57.00  198
  5  \w    -27.00  33.00   0.50    0.05    --  -44.88  19.00  60.00  120
  6  \w     34.00  94.00   0.50    0.05    --   44.88-125.00 120.00  120
  7  \w     45.00 111.00   0.50    0.19    --  115.25-125.00 120.00  132
  8  \w     45.00 111.00   0.50    0.19    --  115.25-125.00  60.00  132
  9  \w     45.00 111.00   0.50    0.19    --  115.25-125.00  60.00  132
 10  \w     45.00 111.00   0.50    0.19    --  115.25-125.00  30.00  132
 11  \w     45.00 111.00   0.50    0.19    --  115.25-125.00   0.00  132
 12  \w     45.00 111.00   0.50    0.19    --  115.25-125.00   0.00  132
 13  \w     45.00 111.00   0.50    0.19    --  115.25-125.00 -30.00  132
 14  \w     45.00 111.00   0.50    0.19    --  115.25-125.00 -90.00  132
 15  \w     45.00 111.00   0.50    0.19    --  115.25-125.00 -60.00  132
 16  \w     43.00 105.00   0.50    0.19    --  115.25 -95.00 -30.00  124
 17  \w     43.00 105.00   0.50    0.19    --  115.25 -95.00 -60.00  124
 18  \w     43.00 105.00   0.50    0.19    --  115.25 -95.00  30.00  124
 19  \w     43.00 105.00   0.50    0.19    --  115.25 -95.00  60.00  124
 20  \w     43.00 105.00   0.50    0.19    --  115.25 -95.00 150.00  124
 21  \w     43.00 105.00   0.50    0.19    --  115.25 -77.00 150.00  124
 22  \w     43.00  94.00   0.50    0.19    --  115.25 -77.00  90.00  102
 23  \w     43.00  71.00   0.50    0.19    --  115.25 -61.00 -30.00   56
 24  \w     43.00  71.00   0.50    0.19    --  115.25 -61.00 -60.00   56
 25  \w     43.00 105.00   0.50    0.19    --  115.25 -77.00 -60.00  124
 26  \w     43.00 101.00   0.50    0.19    --  115.25 -76.00 -69.00  116
 27  \w     43.00  71.00   0.50    0.19    --  115.25 -61.00-180.00   56
 28  \w    -27.00  70.00   0.50    0.05    --   44.88 -76.00 -69.00  194
 29  \w     43.00  71.00   0.50    0.19    --  115.25 -61.00 120.00   56
 30  \w     44.00  69.00   0.50    0.19    --  115.25 -61.00 150.00   50
 31  \w    -32.00  27.00   0.50    0.05    --   44.88 -19.00 120.00  118
 32  \w     16.00  43.00   0.50    0.05    --   44.88  84.00 148.06   54
 33  \w     95.00 178.00   0.50    0.19    --  115.25 125.00 150.00  166
 34  \w     95.00 178.00   0.50    0.19    --  115.25 125.00 120.00  166
 35  \w     95.00 178.00   0.50    0.19    --  115.25 125.00  90.00  166
 36  \w     95.00 178.00   0.50    0.19    --  115.25 125.00-120.00  166
 37  \w    121.00 147.00   0.50    0.19    --  115.25 125.00-180.00   52
 38  \w    138.00 177.00   0.50    0.19    --  115.25   8.00 -65.50   78
 39  \w    111.00 144.00   0.50    0.19    --  115.25  77.00 -60.00   66
 40  \w    153.00 178.00   0.50    0.19    --  115.25  77.00 -60.00   50
 41  \w     89.00 178.00   0.50    0.19    --  115.25  77.00   0.00  178
 42  \w    111.00 137.00   0.50    0.19    --  115.25  77.00  60.00   52
 43  \w     20.00 118.00   0.50    0.05    --   44.88  76.00  57.00  196
 44  \w     89.00 178.00   0.50    0.19    --  115.25  77.00 150.00  178
 45  \w     96.00 178.00   0.50    0.19    --  115.25  61.00 150.00  164
 46  \w     96.00 178.00   0.50    0.19    --  115.25  61.00 150.00  164
 47  \w     99.00 136.00   0.50    0.19    --  115.25  61.00  60.00   74
 48  \w     90.00 178.00   0.50    0.19    --  115.25  76.00  57.00  176
 49  \w     96.00 178.00   0.50    0.19    --  115.25  61.00 120.00  164
 50  \w     96.00 178.00   0.50    0.19    --  115.25  61.00   0.00  164
 51  \w     96.00 178.00   0.50    0.19    --  115.25  61.00   0.00  164
 52  \w     96.00 178.00   0.50    0.19    --  115.25  61.00  30.00  164
 53  \w     99.00 176.00   0.50    0.19    --  115.25  61.00  90.00  154
 54  \w     97.00 178.00   0.50    0.19    --  115.25  45.00   0.00  162
 55  \w     97.00 178.00   0.50    0.19    --  115.25  45.00  30.00  162
 56  \w     97.00 178.00   0.50    0.19    --  115.25  45.00  90.00  162
 57  \w     97.00 178.00   0.50    0.19    --  115.25  45.00  90.00  162
 58  \w     97.00 178.00   0.50    0.19    --  115.25  45.00 -30.00  162
 59  \w     97.00 149.00   0.50    0.19    --  115.25  45.00 -60.00  104
 60  \w    112.00 138.00   0.50    0.19    --  115.25  45.00-120.00   52
 61  \w    128.00 154.00   0.50    0.19    --  115.25  45.00-180.00   52
 62  \w     96.00 178.00   0.50    0.19    --  115.25  61.00-150.00  164
 63  \w     96.00 178.00   0.50    0.19    --  115.25  61.00-180.00  164
 64  \w     97.00 178.00   0.50    0.19    --  115.25  45.00-150.00  162
 65  \w    145.00 172.00   0.50    0.19    --  115.25  45.00 -30.00   54
 66  \w    100.00 145.00   0.50    0.19    --  115.25  30.00   0.00   90
 67  \w     97.00 178.00   0.50    0.19    --  115.25  45.00  30.00  162
 68  \w     90.00 178.00   0.50    0.19    --  115.25  15.00  60.00  176
 69  \w     90.00 178.00   0.50    0.19    --  115.25  15.00  60.00  176
 70  \w     90.00 178.00   0.50    0.19    --  115.25  15.00 150.00  176
 71  \w     90.00 178.00   0.50    0.19    --  115.25  15.00 150.00  176
 72  \w     62.00 178.00   0.50    0.19    --  115.25   8.00 -65.50  232
 73  \w   -117.00 -19.00   0.50    0.05    --  -44.88 -76.00 -69.00  196
 74  \w   -170.00 -75.00   0.50    0.19    --  -93.75 -30.00-180.00  190
 75  \w   -167.00 -68.00   0.50    0.19    --  -93.75 -76.00 -69.00  198
 76  \w   -167.00 -74.00   0.50    0.19    --  -93.75 -59.00 165.73  186
;
_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      -0.0608677000
_diffrn_orient_matrix_UB_12      0.1217812000
_diffrn_orient_matrix_UB_13      -0.0709317000
_diffrn_orient_matrix_UB_21      0.0689430000
_diffrn_orient_matrix_UB_22      -0.0122159000
_diffrn_orient_matrix_UB_23      -0.0806473000
_diffrn_orient_matrix_UB_31      -0.0998666000
_diffrn_orient_matrix_UB_32      -0.0824846000
_diffrn_orient_matrix_UB_33      -0.0926907000
_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  0.0310
_diffrn_reflns_av_unetI/netI     0.0133
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            43942
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.001
_diffrn_reflns_theta_min         3.896
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.880
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.328
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.104a (Rigaku Oxford Diffraction, 2023)
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            colourless
_exptl_crystal_density_diffrn    1.452
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             632
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.470
_refine_diff_density_min         -0.425
_refine_diff_density_rms         0.053
_refine_ls_extinction_coef       0.00268(14)
_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   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     191
_refine_ls_number_reflns         3082
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0255
_refine_ls_R_factor_gt           0.0255
_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^)+(0.0242P)^2^+1.0043P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0609
_refine_ls_wR_factor_ref         0.0610
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3065
_reflns_number_total             3082
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01570c2.cif
_cod_data_source_block           hydrs
_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 7160239--7160242.cif.
;
_cod_original_cell_volume        1414.450(14)
_cod_database_code               7160242
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C14 H17 N2 O Br'
_chemical_oxdiff_usercomment     HYDRS
_shelx_estimated_absorpt_t_max   0.558
_shelx_estimated_absorpt_t_min   0.320
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C8-C12 \\sim C8A-C12A
 with sigma of 0.02
 C9A-C13A \\sim C9-C13
 with sigma of 0.02
 C8A-C9A \\sim C8-C9
 with sigma of 0.02
 C9A-C14 \\sim C14-C9
 with sigma of 0.02
 C8-C11 \\sim C11-C8A
 with sigma of 0.02
 O1A-N1 \\sim N1-O1
 with sigma of 0.02
 C9A-C14A \\sim C9-C14
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C12) = Uanis(C12A)
Uanis(C13A) = Uanis(C13)
Uanis(C8A) = Uanis(C8)
Uanis(C9) = Uanis(C9A)
Uanis(O1A) = Uanis(O1)
Uanis(C14A) = Uanis(C14)
4. Others
 Sof(O1A)=Sof(C8A)=Sof(C9A)=Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C12A)=Sof(H12D)=
 Sof(H12E)=Sof(H12F)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=1-FVAR(1)
 Sof(O1)=Sof(C8)=Sof(C9)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C12)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=FVAR(1)
 Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=1-FVAR(2)
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C10(H10)
5.b Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C11(H11D,H11E,H11F), C12(H12A,H12B,H12C), C12A(H12D,H12E,
 H12F), C13(H13A,H13B,H13C), C13A(H13D,H13E,H13F), C14(H14A,H14B,H14C),
 C14A(H14D,H14E,H14F)
;
_shelx_res_checksum              49069
_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 1.203
_oxdiff_exptl_absorpt_empirical_full_min 0.825