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_7158381
_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         'C9 H13 N5 O'
_chemical_formula_sum            'C9 H13 N5 O'
_chemical_formula_weight         207.24
_chemical_name_common            1,5-dimethyl-3-pyridyl-oxoverdazyl
_chemical_name_systematic        1,5-dimethyl-3-pyridyl-oxoverdazyl
_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   mixed
_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                 124.601(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.7981(3)
_cell_length_b                   7.60210(10)
_cell_length_c                   16.1604(3)
_cell_measurement_reflns_used    17950
_cell_measurement_temperature    99.9(3)
_cell_measurement_theta_max      74.0140
_cell_measurement_theta_min      3.2810
_cell_volume                     2002.05(7)
_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      99.9(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.979
_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 -90.00  188
  2  \w     24.00 118.00   0.50    0.05    --   46.20  77.00-150.00  188
  3  \w     24.00 118.00   0.50    0.05    --   46.20  77.00 -60.00  188
  4  \w     24.00 118.00   0.50    0.05    --   46.20  77.00   0.00  188
  5  \w     34.00 119.00   0.50    0.05    --   46.20  38.00 -60.00  170
  6  \w     24.00 118.00   0.50    0.05    --   46.20  77.00  60.00  188
  7  \w     31.00 118.00   0.50    0.05    --   46.20  57.00 120.00  174
  8  \w     24.00 118.00   0.50    0.05    --   46.20  77.00 150.00  188
  9  \w     34.00 119.00   0.50    0.05    --   46.20  38.00  90.00  170
 10  \w     34.00 121.00   0.50    0.05    --   46.20  19.00-120.00  174
 11  \w    -71.00 -30.00   0.50    0.17    -- -102.41  61.00   0.00   82
 12  \w    -71.00 -30.00   0.50    0.17    -- -102.41  61.00-120.00   82
 13  \w    -71.00 -30.00   0.50    0.17    -- -102.41  61.00-180.00   82
 14  \w     90.00 174.00   0.50    0.17    --  102.41  45.00-180.00  168
 15  \w     80.00 175.00   0.50    0.17    --  102.41 115.00-151.00  190
 16  \w     46.00 118.00   0.50    0.05    --   46.20 168.00  -7.00  144
 17  \w    -28.00  26.00   0.50    0.05    --   46.20 -19.00 -90.00  108
 18  \w     30.00 105.00   0.50    0.17    --  102.41 -77.00 -90.00  150
 19  \w    -28.00  26.00   0.50    0.05    --   46.20 -19.00  90.00  108
 20  \w    -28.00  26.00   0.50    0.05    --   46.20 -19.00 150.00  108
 21  \w     30.00  71.00   0.50    0.17    --  102.41 -61.00 120.00   82
 22  \w     30.00 105.00   0.50    0.17    --  102.41 -94.00 120.00  150
 23  \w     30.00 108.00   0.50    0.17    --  102.41-115.00 119.00  156
 24  \w      6.00  89.00   0.50    0.05    --   46.20-115.00 119.00  166
 25  \w     35.00 142.00   0.50    0.17    --  102.41-168.00 -25.00  214
 26  \w     30.00 105.00   0.50    0.17    --  102.41 -94.00-180.00  150
 27  \w   -141.00 -34.00   0.50    0.17    -- -102.41 168.00  -7.00  214
 28  \w   -111.00 -30.00   0.50    0.17    -- -102.41 125.00   0.00  162
 29  \w   -108.00 -30.00   0.50    0.17    -- -102.41 115.00-151.00  156
 30  \w   -108.00 -30.00   0.50    0.17    -- -102.41 110.00 -70.58  156
 31  \w    -89.00  -6.00   0.50    0.05    --  -46.20 115.00-151.00  166
 32  \w   -174.00 -90.00   0.50    0.17    -- -102.41 -45.00 -60.00  168
 33  \w   -175.00 -80.00   0.50    0.17    -- -102.41 -77.00 -60.00  190
 34  \w   -175.00 -80.00   0.50    0.17    -- -102.41 -77.00-150.00  190
 35  \w   -175.00 -80.00   0.50    0.17    -- -102.41 -75.00  34.71  190
 36  \w   -175.00 -81.00   0.50    0.17    -- -102.41 -74.00-127.16  188
 37  \w   -175.00 -83.00   0.50    0.17    -- -102.41 -68.00 150.46  184
 38  \w   -175.00 -85.00   0.50    0.17    -- -102.41 -63.00 -96.71  180
 39  \w   -175.00 -86.00   0.50    0.17    -- -102.41 -62.00   9.94  178
 40  \w   -175.00 -86.00   0.50    0.17    -- -102.41 -61.00  60.00  178
 41  \w   -175.00 -86.00   0.50    0.17    -- -102.41 -61.00 120.00  178
 42  \w   -175.00 -86.00   0.50    0.17    -- -102.41 -61.00 -30.00  178
 43  \w   -175.00 -86.00   0.50    0.17    -- -102.41 -61.00-180.00  178
 44  \w   -175.00-143.00   0.50    0.17    -- -102.41 -58.00  80.01   64
 45  \w   -175.00 -89.00   0.50    0.17    -- -102.41 -50.00 140.24  172
 46  \w   -175.00 -88.00   0.50    0.17    -- -102.41 -48.00 -24.21  174
 47  \w   -175.00 -90.00   0.50    0.17    -- -102.41 -46.00  81.89  170
 48  \w   -174.00 -90.00   0.50    0.17    -- -102.41 -45.00  30.00  168
 49  \w   -174.00 -90.00   0.50    0.17    -- -102.41 -45.00-130.87  168
 50  \w   -118.00 -46.00   0.50    0.05    --  -46.20-168.00 -25.00  144
 51  \w   -118.00 -73.00   0.50    0.05    --  -46.20-125.00 -30.00   90
 52  \w   -118.00 -73.00   0.50    0.05    --  -46.20-125.00-150.00   90
 53  \w   -118.00 -73.00   0.50    0.05    --  -46.20-125.00-180.00   90
 54  \w   -175.00 -80.00   0.50    0.17    -- -102.41-115.00 119.00  190
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0169793000
_diffrn_orient_matrix_UB_12      0.1921504000
_diffrn_orient_matrix_UB_13      -0.0130707000
_diffrn_orient_matrix_UB_21      0.0036337000
_diffrn_orient_matrix_UB_22      -0.0551930000
_diffrn_orient_matrix_UB_23      -0.0891551000
_diffrn_orient_matrix_UB_31      -0.0929207000
_diffrn_orient_matrix_UB_32      0.0329782000
_diffrn_orient_matrix_UB_33      -0.0727806000
_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  0.0641
_diffrn_reflns_av_unetI/netI     0.0199
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            28970
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.623
_diffrn_reflns_theta_min         5.429
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.794
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68333
_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    1.375
_exptl_crystal_description       block
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.171
_exptl_crystal_size_min          0.113
_refine_diff_density_max         0.275
_refine_diff_density_min         -0.277
_refine_diff_density_rms         0.047
_refine_ls_extinction_coef       0.00074(15)
_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   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     139
_refine_ls_number_reflns         2042
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0401
_refine_ls_R_factor_gt           0.0388
_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^)+(0.0534P)^2^+1.7124P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1038
_refine_ls_wR_factor_ref         0.1050
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1937
_reflns_number_total             2042
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob01946e2.cif
_cod_data_source_block           9c
_cod_depositor_comments
'Adding full bibliography for 7158376--7158384.cif.'
_cod_database_code               7158381
_chemical_oxdiff_formula         'C9 H13 N5 O'
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Riding coordinates:
 N003(H003), N005(H005)
2.b Ternary CH refined with riding coordinates:
 C00A(H00A)
2.c Aromatic/amide H refined with riding coordinates:
 C008(H008), C00B(H00B), C00C(H00C), C00D(H00D)
2.d Idealised Me refined as rotating group:
 C00E(H00E,H00F,H00G), C00F(H00H,H00I,H00J)
;
_shelx_res_checksum              53912
_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 1.601
_oxdiff_exptl_absorpt_empirical_full_min 0.699