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_1554853
_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         'C22 H35 Cl N3 O2, F6 P'
_chemical_formula_sum            'C22 H35 Cl F6 N3 O2 P'
_chemical_formula_weight         553.95
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-02-20
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2018.12.18 svn.r3554 for Rigaku Oxford Diffraction, GUI svn.r1)
;
_audit_update_record
;
2019-02-21 deposited with the CCDC.	2019-03-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.051(7)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.7678(13)
_cell_length_b                   11.6389(10)
_cell_length_c                   36.278(3)
_cell_measurement_reflns_used    602
_cell_measurement_temperature    150.00(14)
_cell_measurement_theta_max      19.4960
_cell_measurement_theta_min      2.3620
_cell_volume                     5377.6(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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      150.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9653
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.3681
_diffrn_measured_fraction_theta_max 0.9948
_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    -22.00  68.00   1.00   60.00    --   -0.62  57.00-150.00   90
  2  \w    -15.00  86.00   1.00  270.00    --   55.51 -77.00-150.00  101
  3  \w     34.00 124.00   1.00  270.00    --   55.51  57.00   0.00   90
  4  \w     25.00 126.00   1.00  270.00    --   55.51  77.00  90.00  101
  5  \w    -77.00 -32.00   1.00   60.00    --   -0.62 178.00 -60.00   45
  6  \w     30.00  67.00   1.00  270.00    --   55.51  37.00 -90.00   37
;
_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      -0.0472204000
_diffrn_orient_matrix_UB_12      0.0253998000
_diffrn_orient_matrix_UB_13      0.0052283000
_diffrn_orient_matrix_UB_21      -0.0295448000
_diffrn_orient_matrix_UB_22      -0.0414882000
_diffrn_orient_matrix_UB_23      -0.0106230000
_diffrn_orient_matrix_UB_31      0.0006424000
_diffrn_orient_matrix_UB_32      -0.0367017000
_diffrn_orient_matrix_UB_33      0.0156168000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.2429
_diffrn_reflns_av_unetI/netI     0.2667
_diffrn_reflns_Laue_measured_fraction_full 0.997
_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       14
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            36736
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         2.242
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.267
_exptl_absorpt_correction_T_max  0.999
_exptl_absorpt_correction_T_min  0.996
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (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    1.368
_exptl_crystal_description       plate
_exptl_crystal_F_000             2320
_exptl_crystal_size_max          0.141
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.017
_refine_diff_density_max         0.602
_refine_diff_density_min         -0.411
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.929
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     692
_refine_ls_number_reflns         10955
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      0.934
_refine_ls_R_factor_all          0.2373
_refine_ls_R_factor_gt           0.0847
_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^)] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1418
_refine_ls_wR_factor_ref         0.2095
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3964
_reflns_number_total             10955
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00298g2.cif
_cod_data_source_block           1c
_cod_database_code               1554853
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C30 H50 N3 O2 P F6 Cl'
_reflns_odcompleteness_completeness 36.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     45.18
_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
C20 \\sim C21 \\sim C20B \\sim C21B: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.01
F16B \\sim F15 \\sim F15B \\sim F16: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.01
3. Others
 Sof(C20B)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21B)=Sof(H21D)=Sof(H21E)=
 Sof(H21F)=1-FVAR(1)
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=
 FVAR(1)
 Fixed Sof: F15(0.5) F16(0.5) F15B(0.5) F16B(0.5)
4.a Aromatic/amide H refined with riding coordinates:
 C13(H13), C15(H15), C43(H43), C45(H45)
4.b 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), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C22(H22A,
 H22B,H22C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C20B(H20D,H20E,H20F),
 C21B(H21D,H21E,H21F), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,
 H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C47(H47A,
 H47B,H47C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C),
 C52(H52A,H52B,H52C)
;
_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 1.054
_oxdiff_exptl_absorpt_empirical_full_min 0.967