Enhanced synthesis of oxo-verdazyl radicals bearing sterically-and electronically-diverse C3-substituents.
Fuller, Rebecca O.; Taylor, Madeleine R.; Duggin, Margot; Bissember, Alex C.; Canty, Allan J.; Judd, Martyna M.; Cox, Nicholas; Moggach, Stephen A.; Turner, Gemma F.; Organic & biomolecular chemistry 19 (2021) 10120–10138; doi:10.1039/d1ob01946e

data_7158379
_publ_section_title
;
 Enhanced synthesis of oxo-verdazyl radicals bearing sterically-and
 electronically-diverse C3-substituents.
;
_journal_issue                   46
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              10120
_journal_page_last               10138
_journal_paper_doi               10.1039/d1ob01946e
_journal_volume                  19
_journal_year                    2021
_chemical_formula_moiety         'C13 H14 N4 O S2'
_chemical_formula_sum            'C13 H14 N4 O S2'
_chemical_formula_weight         306.40
_chemical_name_common            1,5-bis(thiophenyl)-2,4-dimethyl-carbohydrazide
_chemical_name_systematic        1,5-bis(thiophenyl)-2,4-dimethyl-carbohydrazide
_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     dual
_audit_creation_date             2020-09-03
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2021-09-30 deposited with the CCDC.	2021-11-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.845(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.32320(10)
_cell_length_b                   19.6029(2)
_cell_length_c                   10.4905(2)
_cell_measurement_reflns_used    13876
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      75.1310
_cell_measurement_theta_min      4.4860
_cell_volume                     1433.52(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Hybrid photon'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.983
_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     24.00 118.00   0.50    0.05    --   46.20  77.00  60.00  188
  2  \w     24.00 118.00   0.50    0.05    --   46.20  77.00 120.00  188
  3  \w     31.00 118.00   0.50    0.05    --   46.20  57.00  90.00  174
  4  \w     24.00 118.00   0.50    0.05    --   46.20  77.00   0.00  188
  5  \w     34.00 121.00   0.50    0.05    --   46.20  19.00  90.00  174
  6  \w     31.00 118.00   0.50    0.05    --   46.20  57.00   0.00  174
  7  \w     31.00 118.00   0.50    0.05    --   46.20  57.00 -60.00  174
  8  \w     31.00 118.00   0.50    0.05    --   46.20  57.00-120.00  174
  9  \w     24.00 118.00   0.50    0.05    --   46.20  77.00-150.00  188
 10  \w     56.00 118.00   0.50    0.05    --   46.20 151.00-133.00  124
 11  \w     56.00 164.00   0.50    0.08    --  102.41 151.00-133.00  216
 12  \w     86.00 175.00   0.50    0.08    --  102.41  61.00-150.00  178
 13  \w     76.00 175.00   0.50    0.08    --  102.41 122.00  65.00  198
 14  \w     74.00 175.00   0.50    0.08    --  102.41 125.00 120.00  202
 15  \w     90.00 177.00   0.50    0.08    --  102.41  30.00 150.00  174
 16  \w    -28.00  26.00   0.50    0.05    --   46.20 -19.00 120.00  108
 17  \w     30.00  71.00   0.50    0.08    --  102.41 -61.00 120.00   82
 18  \w     30.00  71.00   0.50    0.08    --  102.41 -61.00  30.00   82
 19  \w     30.00  71.00   0.50    0.08    --  102.41 -61.00   0.00   82
 20  \w     30.00  71.00   0.50    0.08    --  102.41 -61.00 -30.00   82
 21  \w     30.00 105.00   0.50    0.08    --  102.41 -77.00-180.00  150
 22  \w     30.00 105.00   0.50    0.08    --  102.41 -94.00-180.00  150
 23  \w     26.00 109.00   0.50    0.05    --   46.20-151.00-177.00  166
 24  \w     30.00 130.00   0.50    0.08    --  102.41-151.00-177.00  200
 25  \w     30.00 111.00   0.50    0.08    --  102.41-125.00-120.00  162
 26  \w     30.00 111.00   0.50    0.08    --  102.41-125.00  90.00  162
 27  \w     11.00  92.00   0.50    0.05    --   46.20-122.00 -15.00  162
 28  \w     30.00 109.00   0.50    0.08    --  102.41-122.00 -15.00  158
 29  \w     30.00 105.00   0.50    0.08    --  102.41 -94.00   0.00  150
 30  \w   -130.00 -30.00   0.50    0.08    -- -102.41 151.00-133.00  200
 31  \w   -111.00 -30.00   0.50    0.08    -- -102.41 125.00 150.00  162
 32  \w   -109.00 -30.00   0.50    0.08    -- -102.41 122.00  65.00  158
 33  \w    -92.00 -11.00   0.50    0.05    --  -46.20 122.00  65.00  162
 34  \w   -107.00 -30.00   0.50    0.08    -- -102.41 107.00-152.30  154
 35  \w   -175.00-123.00   0.50    0.08    -- -102.41 -80.00 120.37  104
 36  \w   -175.00 -79.00   0.50    0.08    -- -102.41 -79.00  18.53  192
 37  \w   -175.00 -80.00   0.50    0.08    -- -102.41 -77.00   0.00  190
 38  \w   -118.00 -23.00   0.50    0.05    --  -46.20 -77.00 -90.00  190
 39  \w   -175.00 -80.00   0.50    0.08    -- -102.41 -77.00-180.00  190
 40  \w   -118.00 -23.00   0.50    0.05    --  -46.20 -77.00-180.00  190
 41  \w   -175.00 -80.00   0.50    0.08    -- -102.41 -75.00 143.81  190
 42  \w   -175.00 -81.00   0.50    0.08    -- -102.41 -74.00 -62.19  188
 43  \w   -175.00 -84.00   0.50    0.08    -- -102.41 -65.00-158.59  182
 44  \w   -175.00 -86.00   0.50    0.08    -- -102.41 -62.00  24.34  178
 45  \w   -175.00 -86.00   0.50    0.08    -- -102.41 -61.00  60.00  178
 46  \w   -175.00 -89.00   0.50    0.08    -- -102.41 -51.00  72.72  172
 47  \w   -174.00 -90.00   0.50    0.08    -- -102.41 -45.00  90.00  168
 48  \w   -174.00 -90.00   0.50    0.08    -- -102.41 -45.00 -60.00  168
 49  \w   -177.00 -90.00   0.50    0.08    -- -102.41 -30.00-120.00  174
 50  \w   -118.00 -55.00   0.50    0.05    --  -46.20-151.00-177.00  126
 51  \w   -164.00 -55.00   0.50    0.08    -- -102.41-151.00-177.00  218
 52  \w   -118.00 -73.00   0.50    0.05    --  -46.20-125.00  30.00   90
 53  \w   -118.00 -73.00   0.50    0.05    --  -46.20-125.00-150.00   90
 54  \w   -175.00 -75.00   0.50    0.08    -- -102.41-122.00 -15.00  200
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0912886000
_diffrn_orient_matrix_UB_12      0.0709547000
_diffrn_orient_matrix_UB_13      -0.0372384000
_diffrn_orient_matrix_UB_21      0.2007438000
_diffrn_orient_matrix_UB_22      0.0328367000
_diffrn_orient_matrix_UB_23      0.0453401000
_diffrn_orient_matrix_UB_31      0.0144310000
_diffrn_orient_matrix_UB_32      -0.0080908000
_diffrn_orient_matrix_UB_33      -0.1426495000
_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  0.0754
_diffrn_reflns_av_unetI/netI     0.0225
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            21491
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.509
_diffrn_reflns_theta_min         4.511
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.380
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64386
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.420
_exptl_crystal_description       block
_exptl_crystal_F_000             640
_exptl_crystal_size_max          0.262
_exptl_crystal_size_mid          0.117
_exptl_crystal_size_min          0.086
_refine_diff_density_max         0.282
_refine_diff_density_min         -0.394
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.137
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     93
_refine_ls_number_reflns         1468
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.137
_refine_ls_R_factor_all          0.0323
_refine_ls_R_factor_gt           0.0317
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1202
_refine_ls_wR_factor_ref         0.1228
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1426
_reflns_number_total             1468
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob01946e2.cif
_cod_data_source_block           11b
_cod_depositor_comments
'Adding full bibliography for 7158376--7158384.cif.'
_cod_database_code               7158379
_chemical_oxdiff_formula         'C13 H14 N4 O S2'
_chemical_oxdiff_usercomment     'Becky UTas'
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_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
2.a Aromatic/amide H refined with riding coordinates:
 C005(H005), C008(H008), C00A(H00D), C00B(H00E)
2.b Idealised Me refined as rotating group:
 C009(H00A,H00B,H00C)
;
_shelx_res_checksum              93504
_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 2.385
_oxdiff_exptl_absorpt_empirical_full_min 0.653