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_7158380
_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         'C19 H22 N4 O3'
_chemical_formula_sum            'C19 H22 N4 O3'
_chemical_formula_weight         354.40
_chemical_name_common
1,5-bis(2-methoxybenzyl)-2,4-dimethyl-carbohydrazide
_chemical_name_systematic
1,5-bis(2-methoxybenzyl)-2,4-dimethyl-carbohydrazide
_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     dual
_audit_creation_date             2020-09-04
_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                108.084(4)
_cell_angle_beta                 100.023(3)
_cell_angle_gamma                101.754(3)
_cell_formula_units_Z            2
_cell_length_a                   8.5045(3)
_cell_length_b                   9.7970(4)
_cell_length_c                   11.9453(5)
_cell_measurement_reflns_used    10860
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      73.0060
_cell_measurement_theta_min      4.9460
_cell_volume                     895.65(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      100.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.955
_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    0.24    --   46.20  77.00  60.00  188
  2  \w     90.00 176.00   0.50    1.00    --  102.41  37.00 116.00  172
  3  \w    141.00 167.00   0.50    1.00    --  102.41  45.00  60.00   52
  4  \w     80.00 105.00   0.50    1.00    --  102.41 -94.00   0.00   50
  5  \w     76.00 111.00   0.50    1.00    --  102.41-125.00  30.00   70
  6  \w     45.00 103.00   0.50    1.00    --  102.41 -94.00 150.00  116
  7  \w     40.00  88.00   0.50    1.00    --  102.41 -77.00  90.00   96
  8  \w     39.00 116.00   0.50    1.00    --  102.41-130.00 -17.13  154
  9  \w     58.00  99.00   0.50    1.00    --  102.41 -94.00-120.00   82
 10  \w     30.00  82.00   0.50    1.00    --  102.41 -77.00 -30.00  104
 11  \w     30.00  99.00   0.50    1.00    --  102.41 -94.00  60.00  138
 12  \w     34.00  72.00   0.50    1.00    --  102.41 -94.00   0.00   76
 13  \w     34.00 119.00   0.50    0.24    --   46.20  37.00 116.00  170
 14  \w     38.00 135.00   0.50    0.24    --   62.00  79.00  -8.53  194
 15  \w     41.00 135.00   0.50    0.24    --   62.00  72.00-119.49  188
 16  \w     42.00 129.00   0.50    0.24    --   66.00  79.00-104.43  174
 17  \w     34.00 119.00   0.50    0.24    --   46.20  38.00-180.00  170
 18  \w     36.00 131.00   0.50    0.24    --   58.00  75.00 -59.23  190
 19  \w     39.00 135.00   0.50    0.24    --   62.00  78.00  84.23  192
 20  \w     43.00  69.00   0.50    0.24    --   66.00  77.00 -51.75   52
 21  \w     43.00  69.00   0.50    0.24    --   66.00  78.00 -27.99   52
 22  \w     34.00 131.00   0.50    0.24    --   58.00  79.00  45.05  194
 23  \w     39.00 135.00   0.50    0.24    --   62.00  77.00 142.37  192
 24  \w     44.00  70.00   0.50    0.24    --   66.00  77.00 116.12   52
 25  \w     26.00 122.00   0.50    0.24    --   50.00  80.00 125.72  192
 26  \w     35.00 131.00   0.50    0.24    --   58.00  77.00 159.06  192
 27  \w     24.00 118.00   0.50    0.24    --   46.20  77.00   0.00  188
 28  \w     24.00 118.00   0.50    0.24    --   46.20  77.00-120.00  188
 29  \w     24.00 118.00   0.50    0.24    --   46.20  77.00 -90.00  188
 30  \w     24.00 118.00   0.50    0.24    --   46.20  77.00-180.00  188
 31  \w     34.00 131.00   0.50    0.24    --   58.00  79.00-164.01  194
 32  \w      7.00  34.00   0.50    0.24    --   38.00  94.00 -33.48   54
 33  \w    -21.00  34.00   0.50    0.24    --   10.00  94.00 -26.81  110
 34  \w    -17.00  14.00   0.50    0.24    --   18.00 102.00 -90.74   62
 35  \w     10.00  43.00   0.50    0.24    --   38.00  88.00 106.31   66
 36  \w    -42.00  27.00   0.50    0.24    --  -46.20  37.00 116.00  138
 37  \w    -27.00  42.00   0.50    0.24    --   46.20 -37.00 -39.00  138
 38  \w    -25.00  69.00   0.50    0.24    --   46.20 -77.00-180.00  188
 39  \w     13.00  94.00   0.50    0.24    --   46.20-125.00-180.00  162
 40  \w    -65.00 -36.00   0.50    1.00    -- -102.41  61.00  30.00   58
 41  \w    -76.00 -50.00   0.50    1.00    -- -102.41 125.00  60.00   52
 42  \w    -69.00 -42.00   0.50    1.00    -- -102.41 125.00 150.00   54
 43  \w   -109.00 -81.00   0.50    1.00    -- -102.41 125.00  60.00   56
 44  \w   -111.00 -85.00   0.50    1.00    -- -102.41 125.00 150.00   52
 45  \w   -119.00 -34.00   0.50    0.24    --  -46.20 -37.00 -39.00  170
 46  \w    -80.00 -54.00   0.50    0.24    --  -74.00 -69.00  67.49   52
 47  \w    -77.00 -51.00   0.50    0.24    --  -74.00 -78.00  14.23   52
 48  \w    -82.00 -56.00   0.50    0.24    --  -74.00 -66.00  34.64   52
 49  \w    -85.00 -59.00   0.50    0.24    --  -74.00 -62.00  13.00   52
 50  \w    -86.00 -61.00   0.50    1.00    --  -82.00 -73.00  34.68   50
 51  \w    -92.00 -65.00   0.50    1.00    --  -82.00 -64.00  42.09   54
 52  \w    -90.00 -64.00   0.50    1.00    --  -82.00 -64.00  86.87   52
 53  \w    -85.00 -59.00   0.50    0.24    --  -74.00 -60.00 141.93   52
 54  \w    -82.00 -56.00   0.50    1.00    --  -78.00 -75.00 154.76   52
 55  \w    -87.00 -61.00   0.50    1.00    --  -82.00 -72.00 134.80   52
 56  \w    -90.00 -65.00   0.50    1.00    --  -86.00 -72.00 163.20   50
 57  \w    -94.00 -65.00   0.50    1.00    --  -82.00 -61.00 173.61   58
 58  \w    -93.00 -67.00   0.50    1.00    --  -90.00 -79.00 101.69   52
 59  \w   -108.00 -80.00   0.50    1.00    --  -90.00 -64.00  20.06   56
 60  \w    -95.00 -69.00   0.50    1.00    --  -90.00 -73.00   2.34   52
 61  \w    -93.00 -68.00   0.50    1.00    --  -90.00 -74.00 -39.25   50
 62  \w    -98.00 -64.00   0.50    1.00    --  -78.00 -58.00 -63.84   68
 63  \w    -87.00 -62.00   0.50    1.00    --  -78.00 -59.00-111.11   50
 64  \w    -92.00 -67.00   0.50    1.00    --  -82.00 -61.00-138.41   50
 65  \w    -93.00 -62.00   0.50    1.00    --  -82.00 -71.00-104.07   62
 66  \w    -94.00 -68.00   0.50    1.00    --  -86.00 -65.00-151.40   52
 67  \w   -106.00 -75.00   0.50    1.00    --  -94.00 -67.00 -64.48   62
 68  \w   -104.00 -68.00   0.50    1.00    --  -90.00 -74.00  -8.16   72
 69  \w   -103.00 -77.00   0.50    1.00    --  -94.00 -64.00  30.81   52
 70  \w   -113.00 -83.00   0.50    1.00    -- -102.41 -69.00  28.56   60
 71  \w   -114.00 -80.00   0.50    1.00    -- -102.41 -77.00 -60.00   68
 72  \w   -109.00 -80.00   0.50    1.00    -- -102.41 -77.00 -90.00   58
 73  \w   -115.00 -72.00   0.50    1.00    --  -94.00 -76.00-115.70   86
 74  \w   -126.00 -31.00   0.50    0.24    --  -54.00 -78.00-126.47  190
 75  \w   -123.00 -83.00   0.50    1.00    -- -102.41 -76.00 -11.82   80
 76  \w   -139.00 -79.00   0.50    1.00    --  -94.00 -58.00-108.60  120
 77  \w   -134.00 -72.00   0.50    1.00    --  -94.00 -76.00-160.20  124
 78  \w   -151.00-125.00   0.50    1.00    --  -90.00 -74.00  -8.16   52
 79  \w   -130.00 -79.00   0.50    1.00    --  -94.00 -61.00   3.82  102
 80  \w   -129.00 -82.00   0.50    1.00    -- -102.41 -70.00  91.45   94
 81  \w   -101.00 -69.00   0.50    1.00    --  -90.00 -72.00 143.10   64
 82  \w   -113.00 -73.00   0.50    1.00    --  -94.00 -72.00 169.78   80
 83  \w   -113.00 -71.00   0.50    1.00    --  -94.00 -76.00 138.58   84
 84  \w   -139.00 -47.00   0.50    0.24    --  -66.00 -67.00 164.08  184
 85  \w   -158.00-100.00   0.50    1.00    --  -86.00 -72.00 163.20  116
 86  \w   -160.00-123.00   0.50    1.00    --  -90.00 -79.00 101.69   74
 87  \w   -162.00-112.00   0.50    1.00    --  -90.00 -64.00  20.06  100
 88  \w   -161.00-116.00   0.50    1.00    --  -90.00 -74.00 -39.25   90
 89  \w   -167.00-115.00   0.50    1.00    --  -94.00 -67.00 -64.48  104
 90  \w   -167.00-121.00   0.50    1.00    --  -94.00 -76.00-115.70   92
 91  \w   -156.00 -77.00   0.50    1.00    --  -94.00 -63.00-155.74  158
 92  \w   -175.00 -90.00   0.50    1.00    -- -102.41 -37.00 -39.00  170
 93  \w   -173.00-130.00   0.50    1.00    -- -102.41 -76.00 -11.82   86
 94  \w   -174.00-115.00   0.50    1.00    -- -102.41 -77.00 -90.00  118
 95  \w   -174.00-117.00   0.50    1.00    -- -102.41 -69.00  28.56  114
 96  \w   -163.00-118.00   0.50    1.00    --  -94.00 -76.00 138.58   90
 97  \w   -175.00-134.00   0.50    1.00    -- -102.41 -70.00  91.45   82
 98  \w   -167.00 -83.00   0.50    1.00    -- -102.41 -69.00  69.43  168
 99  \w   -173.00-138.00   0.50    1.00    -- -102.41 -77.00 -60.00   70
100  \w   -105.00 -37.00   0.50    1.00    -- -102.41  77.00 -90.00  136
;
_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      -0.1807026000
_diffrn_orient_matrix_UB_12      -0.0038875000
_diffrn_orient_matrix_UB_13      -0.0513994000
_diffrn_orient_matrix_UB_21      -0.0512697000
_diffrn_orient_matrix_UB_22      -0.1716119000
_diffrn_orient_matrix_UB_23      -0.0406752000
_diffrn_orient_matrix_UB_31      -0.0365037000
_diffrn_orient_matrix_UB_32      0.0119366000
_diffrn_orient_matrix_UB_33      0.1240538000
_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  0.1264
_diffrn_reflns_av_unetI/netI     0.0481
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            31657
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.621
_diffrn_reflns_theta_min         4.026
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.743
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49823
_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    1.314
_exptl_crystal_description       block
_exptl_crystal_F_000             376
_exptl_crystal_size_max          0.163
_exptl_crystal_size_mid          0.093
_exptl_crystal_size_min          0.062
_refine_diff_density_max         0.460
_refine_diff_density_min         -0.483
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     239
_refine_ls_number_reflns         3558
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0754
_refine_ls_R_factor_gt           0.0668
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1462P)^2^+0.0814P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1822
_refine_ls_wR_factor_ref         0.2014
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2984
_reflns_number_total             3558
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob01946e2.cif
_cod_data_source_block           1b
_cod_depositor_comments
'Adding full bibliography for 7158376--7158384.cif.'
_cod_database_code               7158380
_chemical_oxdiff_formula         'C19 H22 N4 O3'
_chemical_oxdiff_usercomment     'UTas Becky'
_reflns_odcompleteness_completeness 99.87
_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:
 C009(H009), C00B(H00B), C00D(H00D), C00E(H00E), C00I(H00I), C00J(H00J),
 C00K(H00K), C00L(H00L), C00N(H00N), C00P(H00R)
2.b Idealised Me refined as rotating group:
 C00H(H00A,H00C,H00F), C00M(H00G,H00H,H00M), C00O(H00O,H00P,H00Q), C00Q(H00S,
 H00T,H00U)
;
_shelx_res_checksum              2397
_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 3.300
_oxdiff_exptl_absorpt_empirical_full_min 0.441