Stable dicationic dioxoliums and fate of their dioxolyl radicals
Devillard, Marc; Regnier, Vianney; Pecaut, Jacques; Martin, David; Organic Chemistry Frontiers 6 (2019) 3184–; doi:10.1039/C9QO00298G

data_1554854
_publ_section_title
;
 Stable dicationic dioxoliums and fate of their dioxolyl radicals
;
_journal_issue                   18
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              3184
_journal_paper_doi               10.1039/C9QO00298G
_journal_volume                  6
_journal_year                    2019
_chemical_formula_moiety
'C32 H46 N6 O4, 2(F6 P), 0.5(C2 H3 N), 0.08(H2 O)'
_chemical_formula_sum            'C33 H47.66 F12 N6.5 O4.08 P2'
_chemical_formula_weight         890.65
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-02-11
_audit_creation_method
;
Olex2 1.2-ac21
(compiled 2015.09.16 svn.r134, GUI svn.r4998)
;
_audit_update_record
;
2019-02-21 deposited with the CCDC.	2019-03-18 downloaded from the CCDC.
;
_cell_angle_alpha                95.650(2)
_cell_angle_beta                 102.392(2)
_cell_angle_gamma                94.7722(19)
_cell_formula_units_Z            4
_cell_length_a                   12.1931(3)
_cell_length_b                   15.3991(4)
_cell_length_c                   22.7102(5)
_cell_measurement_reflns_used    17228
_cell_measurement_temperature    149.95(10)
_cell_measurement_theta_max      29.6870
_cell_measurement_theta_min      2.4030
_cell_volume                     4120.61(18)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41r (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41r (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41r (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.95(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9653
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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    -43.00  -1.00   1.00    5.00    --   18.00 131.00 -58.44   42
  2  \w      9.00  39.00   1.00   15.00    --   45.45  88.00-147.44   30
  3  \w    -23.00  67.00   1.00   15.00    --   45.45 -57.00 150.00   90
  4  \w     -3.00 103.00   1.00   15.00    --   45.45-125.00 150.00  106
  5  \w      9.00  38.00   1.00   15.00    --   45.45  89.00  -8.21   29
  6  \w    -25.00  76.00   1.00   15.00    --   45.45 -77.00-120.00  101
  7  \w     20.00 118.00   1.00   15.00    --   45.45  37.00 -30.00   98
  8  \w      7.00  33.00   1.00   15.00    --   45.45  92.00 131.66   26
  9  \w      9.00  39.00   1.00   15.00    --   45.45  88.00  66.42   30
 10  \w     25.00 114.00   1.00   15.00    --   45.45  57.00-120.00   89
 11  \w     20.00 118.00   1.00   15.00    --   45.45  37.00  60.00   98
 12  \w      9.00  38.00   1.00   15.00    --   45.45  89.00 -89.01   29
 13  \w     25.00 114.00   1.00   15.00    --   45.45  57.00-180.00   89
 14  \w     20.00 118.00   1.00   15.00    --   45.45  37.00 150.00   98
 15  \w    -77.00  23.00   1.00   15.00    --  -46.70  77.00  30.00  100
 16  \w   -118.00 -73.00   1.00   15.00    --  -46.70-125.00 150.00   45
 17  \w   -118.00 -73.00   1.00   15.00    --  -46.70-125.00-150.00   45
 18  \w    -32.00   7.00   1.00    5.00    --   22.00 120.00 158.06   39
 19  \w      9.00  38.00   1.00   15.00    --   45.45  89.00 -29.75   29
 20  \w   -118.00 -73.00   1.00   15.00    --  -46.70-125.00  60.00   45
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0256379000
_diffrn_orient_matrix_UB_12      -0.0395276000
_diffrn_orient_matrix_UB_13      0.0028334000
_diffrn_orient_matrix_UB_21      -0.0514061000
_diffrn_orient_matrix_UB_22      -0.0243168000
_diffrn_orient_matrix_UB_23      -0.0161792000
_diffrn_orient_matrix_UB_31      0.0169955000
_diffrn_orient_matrix_UB_32      0.0036904000
_diffrn_orient_matrix_UB_33      -0.0277054000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0604
_diffrn_reflns_av_unetI/netI     0.0398
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            88692
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.149
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.205
_exptl_absorpt_correction_T_max  0.997
_exptl_absorpt_correction_T_min  0.996
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41r (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'translucent pale yellow'
_exptl_crystal_density_diffrn    1.436
_exptl_crystal_description       block
_exptl_crystal_F_000             1847
_exptl_crystal_size_max          0.287
_exptl_crystal_size_mid          0.252
_exptl_crystal_size_min          0.176
_refine_diff_density_max         0.728
_refine_diff_density_min         -0.467
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1122
_refine_ls_number_reflns         16766
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0807
_refine_ls_R_factor_gt           0.0581
_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^)+(0.0497P)^2^+4.7619P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1262
_refine_ls_wR_factor_ref         0.1370
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12757
_reflns_number_total             16766
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00298g2.cif
_cod_data_source_block           8adl
_cod_original_cell_volume        4120.62(17)
_cod_original_formula_sum        'C33 H47.66 F12 N6.50 O4.08 P2'
_cod_database_code               1554854
_chemical_oxdiff_formula         'C11 H10 N O'
_reflns_odcompleteness_completeness 48.42
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     40.15
_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, All O(H,H) groups
2. Uiso/Uaniso restraints and constraints
F13B \\sim F14B \\sim F15B \\sim F16B \\sim F13 \\sim F14 \\sim F15 \\sim F16:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.01
C42B \\sim N41 \\sim C41 \\sim C42: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.01
3. Others
 Sof(F13)=Sof(F14)=Sof(F15)=Sof(F16)=1-FVAR(1)
 Sof(F13B)=Sof(F14B)=Sof(F15B)=Sof(F16B)=FVAR(1)
 Sof(C42B)=Sof(H42A)=Sof(H42B)=Sof(H42C)=1-FVAR(2)
 Sof(C42)=Sof(H42D)=Sof(H42E)=Sof(H42F)=FVAR(2)
 Sof(O1W)=Sof(H1WA)=Sof(H1WB)=FVAR(3)
4.a Free rotating group:
 O1W(H1WA,H1WB)
4.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C15(H15), C14(H14), C13(H13), C12(H12), C16'(H16'), C15'(H15'),
 C14'(H14'), C13'(H13'), C12'(H12'), C32(H32), C33(H33), C34(H34), C35(H35),
 C36(H36), C36'(H36'), C35'(H35'), C34'(H34'), C33'(H33'), C32'(H32')
4.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C8(H8A,H8B,H8C), C7(H7A,H7B,H7C), C4'(H4'A,H4'B,H4'C), C5'(H5'A,H5'B,H5'C),
 C10'(H10D,H10E,H10F), C9'(H9'A,H9'B,H9'C), C8'(H8'A,H8'B,H8'C), C7'(H7'A,H7'B,
 H7'C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C30(H30A,H30B,H30C), C29(H29A,
 H29B,H29C), C28(H28A,H28B,H28C), C27(H27A,H27B,H27C), C24'(H24D,H24E,H24F),
 C25'(H25D,H25E,H25F), C30'(H30D,H30E,H30F), C29'(H29D,H29E,H29F), C28'(H28D,
 H28E,H28F), C27'(H27D,H27E,H27F), C42B(H42A,H42B,H42C), C42(H42D,H42E,H42F)
;
_shelx_shelxl_version_number     2016/6
_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 1.073
_oxdiff_exptl_absorpt_empirical_full_min 0.981