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_1554843
_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         'C16 H23 Cl N3 O2, F6 P'
_chemical_formula_sum            'C16 H23 Cl F6 N3 O2 P'
_chemical_formula_weight         469.79
_chemical_name_common            1a
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-12-04
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2019-02-21 deposited with the CCDC.	2019-03-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.991(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.7226(3)
_cell_length_b                   12.3939(3)
_cell_length_c                   15.6108(4)
_cell_measurement_reflns_used    1918
_cell_measurement_temperature    123(40)
_cell_measurement_theta_max      31.3980
_cell_measurement_theta_min      2.5090
_cell_volume                     2071.77(9)
_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, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123(40)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9653
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_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     35.00 101.00   1.00   10.00    --   25.56 178.00  30.00   66
  2  \w    -22.00  67.00   1.00   10.00    --   25.56 -99.00  30.00   89
  3  \w    -30.00  71.00   1.00   10.00    --   25.56   0.00-150.00  101
;
_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      -0.0206072000
_diffrn_orient_matrix_UB_12      -0.0537240000
_diffrn_orient_matrix_UB_13      0.0059167000
_diffrn_orient_matrix_UB_21      -0.0444154000
_diffrn_orient_matrix_UB_22      0.0186442000
_diffrn_orient_matrix_UB_23      0.0286972000
_diffrn_orient_matrix_UB_31      -0.0446429000
_diffrn_orient_matrix_UB_32      0.0062604000
_diffrn_orient_matrix_UB_33      -0.0348105000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0207
_diffrn_reflns_av_unetI/netI     0.0347
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            6369
_diffrn_reflns_point_group_measured_fraction_full 0.690
_diffrn_reflns_point_group_measured_fraction_max 0.646
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.507
_diffrn_reflns_theta_min         2.514
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.332
_exptl_absorpt_correction_T_max  0.936
_exptl_absorpt_correction_T_min  0.887
_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 colourless'
_exptl_crystal_density_diffrn    1.506
_exptl_crystal_description       block
_exptl_crystal_F_000             968
_exptl_crystal_size_max          0.405
_exptl_crystal_size_mid          0.204
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.453
_refine_diff_density_min         -0.311
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 783 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     312
_refine_ls_number_reflns         4090
_refine_ls_number_restraints     140
_refine_ls_restrained_S_all      1.138
_refine_ls_R_factor_all          0.0509
_refine_ls_R_factor_gt           0.0434
_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^)+(0.0543P)^2^+1.6642P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1061
_refine_ls_wR_factor_ref         0.1107
_reflns_Friedel_coverage         0.294
_reflns_Friedel_fraction_full    0.379
_reflns_Friedel_fraction_max     0.294
_reflns_number_gt                3656
_reflns_number_total             4090
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00298g2.cif
_cod_data_source_block           1a
_cod_original_cell_volume        2071.75(10)
_cod_database_code               1554843
_chemical_oxdiff_formula         'C10 H10 N4 P F6'
_reflns_odcompleteness_completeness 99.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_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. Uiso/Uaniso restraints and constraints
F6B \\sim F3B \\sim F2B \\sim F1B \\sim F2 \\sim F4 \\sim F5B \\sim F6 \\sim F3
\\sim F5 \\sim F1 \\sim F4B: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.01
Uanis(F6B) \\sim Ueq, Uanis(F3B) \\sim Ueq, Uanis(F2B) \\sim Ueq, Uanis(F1B)
\\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F5B) \\sim Ueq,
Uanis(F6) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F1) \\sim
Ueq, Uanis(F4B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of
0.01
3. Others
 Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1)
4.a :
 F1B(F2B,F3B,F4B,F5B,F6B)
4.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16)
4.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,
 H8B,H8C), C9(H9A,H9B,H9C)
;
_shelx_shelxl_version_number     2016/6
_olex2_date_sample_data_collection 2017-12-01
_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 1.044
_oxdiff_exptl_absorpt_empirical_full_min 0.970