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_7158382
_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         'C20 H20 N4 O S, 0.5(H4 O2)'
_chemical_formula_sum            'C20 H22 N4 O2 S'
_chemical_formula_weight         382.49
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-09-30 deposited with the CCDC.	2021-11-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   4.93100(10)
_cell_length_b                   19.1334(6)
_cell_length_c                   20.4301(6)
_cell_measurement_reflns_used    4610
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      64.4070
_cell_measurement_theta_min      4.3070
_cell_volume                     1927.51(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.979
_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    -15.00  73.00   0.50    2.00    --   -2.66  22.00  61.00  176
  2  \w     11.00 108.00   0.50   30.00    --   83.35-111.00  64.00  194
  3  \w     82.00 155.00   0.50   30.00    --   83.35 111.00-108.00  146
  4  \w   -164.00 -76.00   0.50   30.00    --  -88.66 -22.00-104.00  176
  5  \w    -23.00  31.00   0.50    2.00    --   -2.66 -99.00 -90.00  108
  6  \w    -23.00  31.00   0.50    2.00    --   -2.66 -99.00-120.00  108
  7  \w     11.00  66.00   0.50   30.00    --   83.35 -57.00 150.00  110
  8  \w     11.00  43.00   0.50   30.00    --   83.35 -38.00-120.00   64
  9  \w     11.00  43.00   0.50   30.00    --   83.35 -38.00-150.00   64
 10  \w     11.00  43.00   0.50   30.00    --   83.35 -38.00 150.00   64
 11  \w     11.00  66.00   0.50   30.00    --   83.35 -57.00-150.00  110
 12  \w     11.00  43.00   0.50   30.00    --   83.35 -38.00 -30.00   64
 13  \w   -111.00 -16.00   0.50   30.00    --  -88.66 125.00  90.00  190
 14  \w    -66.00 -16.00   0.50   30.00    --  -88.66  57.00-180.00  100
 15  \w    -43.00 -16.00   0.50   30.00    --  -88.66  38.00  30.00   54
 16  \w    -43.00 -16.00   0.50   30.00    --  -88.66  38.00  60.00   54
 17  \w    -23.00  31.00   0.50    2.00    --   -2.66 -99.00  90.00  108
 18  \w    -74.00  12.00   0.50    2.00    --   -2.66 -57.00  90.00  172
 19  \w    -17.00  70.00   0.50    2.00    --   -2.66  57.00 -90.00  174
 20  \w     71.00 150.00   0.50   30.00    --   83.35  22.00  61.00  158
 21  \w     71.00 158.00   0.50   30.00    --   83.35  19.00 150.00  174
;
_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      0.0854417000
_diffrn_orient_matrix_UB_12      -0.0716726000
_diffrn_orient_matrix_UB_13      -0.0274885000
_diffrn_orient_matrix_UB_21      -0.0335089000
_diffrn_orient_matrix_UB_22      -0.0325794000
_diffrn_orient_matrix_UB_23      0.0684736000
_diffrn_orient_matrix_UB_31      -0.2987659000
_diffrn_orient_matrix_UB_32      -0.0168682000
_diffrn_orient_matrix_UB_33      -0.0154098000
_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  0.0703
_diffrn_reflns_av_unetI/netI     0.0410
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       3
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            13320
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.335
_diffrn_reflns_theta_max         67.335
_diffrn_reflns_theta_min         4.328
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.677
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84996
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.103a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.318
_exptl_crystal_description       block
_exptl_crystal_F_000             808
_exptl_crystal_size_max          0.228
_exptl_crystal_size_mid          0.056
_exptl_crystal_size_min          0.046
_refine_diff_density_max         0.583
_refine_diff_density_min         -0.405
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.279
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     121
_refine_ls_number_reflns         1736
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.268
_refine_ls_R_factor_all          0.1463
_refine_ls_R_factor_gt           0.1355
_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^)+18.5821P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2605
_refine_ls_wR_factor_ref         0.2648
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1534
_reflns_number_total             1736
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob01946e2.cif
_cod_data_source_block           bof21
_cod_depositor_comments
'Adding full bibliography for 7158376--7158384.cif.'
_cod_database_code               7158382
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C10 H10 N4 O2 S'
_chemical_oxdiff_usercomment     'Rebecca Fuller - Tasmania'
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     61.08
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C8) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C2) \\sim
Ueq, Uanis(S2) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(S2) = Uanis(C2) = Uanis(C5) = Uanis(C6) = Uanis(C8)
3. Others
 Fixed Sof: H16B(0.5) S2(0.5) C2(0.5) H2(0.5) C5(0.5) H5A(0.5) C6(0.5) H6(0.5)
 C8(0.5)
4.a Riding coordinates:
 N5(H5)
4.b Free rotating group:
 O16(H16A,H16B), S2(C2,C5,C6,C8)
4.c Ternary CH refined with riding coordinates:
 C4(H4)
4.d Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
4.e Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C2(H2), C5(H5A), C6(H6)
;
_shelx_res_checksum              48562
_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 2.360
_oxdiff_exptl_absorpt_empirical_full_min 0.567