Synthesis of spirocyclic 1,2-diamines by dearomatising intramolecular diamination of phenols.
Aimon, Anthony; Dow, Mark J.; Hanby, Abigail R.; Okolo, Ephraim A.; Pask, Christopher M.; Nelson, Adam; Marsden, Stephen P.; Chemical communications (Cambridge, England) 59 (2023) 607–610; doi:10.1039/d2cc06137f

data_7131092
_publ_section_title
;
 Synthesis of spirocyclic 1,2-diamines by dearomatising intramolecular
 diamination of phenols.
;
_journal_issue                   5
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              607
_journal_page_last               610
_journal_paper_doi               10.1039/d2cc06137f
_journal_volume                  59
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H20 N2 O4 S'
_chemical_formula_sum            'C17 H20 N2 O4 S'
_chemical_formula_weight         348.41
_space_group_crystal_system      tetragonal
_space_group_IT_number           76
_space_group_name_Hall           'P 4w'
_space_group_name_H-M_alt        'P 41'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-05-25 deposited with the CCDC.	2022-12-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.51937(12)
_cell_length_b                   8.51937(12)
_cell_length_c                   22.6198(5)
_cell_measurement_reflns_used    2898
_cell_measurement_temperature    125.01(10)
_cell_measurement_theta_max      73.2990
_cell_measurement_theta_min      5.1570
_cell_volume                     1641.74(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      125.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3095
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.986
_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    -28.00  27.00   1.00    1.00    --  -41.04  37.00 -60.00   55
  2  \w   -104.00 -14.00   1.00    1.00    --  -41.04 -57.00   0.00   90
  3  \w     45.00 102.00   1.00    1.00    --   41.04  37.00 -90.00   57
  4  \w     82.00 178.00   1.00    2.00    --  106.02  45.00  30.00   96
  5  \w     81.00 160.00   1.00    2.00    --  106.02  45.00 -60.00   79
  6  \w     80.00 108.00   1.00    2.00    --  106.02  45.00 -90.00   28
  7  \w     58.00  89.00   1.00    2.00    --  106.02 -45.00-180.00   31
  8  \w    116.00 141.00   1.00    2.00    --  106.02  45.00 -90.00   25
  9  \w    111.00 169.00   1.00    2.00    --  106.02  45.00-180.00   58
 10  \w     39.00 131.00   1.00    2.00    --  106.02 -30.00  90.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1729003000
_diffrn_orient_matrix_UB_12      -0.0490013000
_diffrn_orient_matrix_UB_13      -0.0081079000
_diffrn_orient_matrix_UB_21      0.0138361000
_diffrn_orient_matrix_UB_22      0.1111170000
_diffrn_orient_matrix_UB_23      -0.0535120000
_diffrn_orient_matrix_UB_31      0.0516927000
_diffrn_orient_matrix_UB_32      0.1336374000
_diffrn_orient_matrix_UB_33      0.0414023000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0412
_diffrn_reflns_av_unetI/netI     0.0545
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            6158
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.446
_diffrn_reflns_theta_min         5.192
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.967
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.673
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.43c (Rigaku Oxford Diffraction, 2018)
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_colour_primary    colourless
_exptl_crystal_density_diffrn    1.410
_exptl_crystal_description       block
_exptl_crystal_F_000             736
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.221
_refine_diff_density_min         -0.207
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1214 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.004(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         3188
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0440
_refine_ls_R_factor_gt           0.0378
_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^)+(0.0419P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0852
_refine_ls_wR_factor_ref         0.0892
_reflns_Friedel_coverage         0.909
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.945
_reflns_number_gt                2868
_reflns_number_total             3188
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc06137f2.cif
_cod_data_source_block           eo200p_a
_cod_depositor_comments
'Adding full bibliography for 7131091--7131095.cif.'
_cod_original_cell_volume        1641.74(6)
_cod_database_code               7131092
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C68  H80  N8  O16  S4  '
_shelx_estimated_absorpt_t_max   0.891
_shelx_estimated_absorpt_t_min   0.731
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C8(H8A,H8B)
2.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C15(H15), C16(H16)
2.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C)
;
_olex2_date_sample_data_collection 2019-01-11
_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 1.207
_oxdiff_exptl_absorpt_empirical_full_min 0.928