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_1554846
_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         '2(F6 P), C32 H46 N6 O4, C2 H3 N'
_chemical_formula_sum            'C34 H49 F12 N7 O4 P2'
_chemical_formula_weight         909.74
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_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                90
_cell_angle_beta                 105.666(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.915(2)
_cell_length_b                   8.8562(7)
_cell_length_c                   19.8464(18)
_cell_measurement_reflns_used    1186
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      21.3690
_cell_measurement_theta_min      2.4430
_cell_volume                     4216.5(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9653
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.996
_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   -100.00  17.00   1.00    8.00    --  -26.81 -19.00-120.00  117
  2  \w    -97.00   3.00   1.00    8.00    --  -26.81 -77.00  60.00  100
  3  \w    -47.00  -1.00   1.00    8.00    --   25.41 -37.00 -60.00   46
;
_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      -0.0246387000
_diffrn_orient_matrix_UB_12      0.0292233000
_diffrn_orient_matrix_UB_13      0.0065443000
_diffrn_orient_matrix_UB_21      -0.0163549000
_diffrn_orient_matrix_UB_22      -0.0432340000
_diffrn_orient_matrix_UB_23      -0.0282263000
_diffrn_orient_matrix_UB_31      -0.0002018000
_diffrn_orient_matrix_UB_32      -0.0607219000
_diffrn_orient_matrix_UB_33      0.0231945000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0462
_diffrn_reflns_av_unetI/netI     0.0773
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            9639
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.370
_diffrn_reflns_theta_min         2.132
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.202
_exptl_absorpt_correction_T_max  0.996
_exptl_absorpt_correction_T_min  0.994
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (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    1.433
_exptl_crystal_description       block
_exptl_crystal_F_000             1888
_exptl_crystal_size_max          0.353
_exptl_crystal_size_mid          0.203
_exptl_crystal_size_min          0.157
_refine_diff_density_max         0.414
_refine_diff_density_min         -0.445
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     387
_refine_ls_number_reflns         4280
_refine_ls_number_restraints     174
_refine_ls_restrained_S_all      1.101
_refine_ls_R_factor_all          0.1380
_refine_ls_R_factor_gt           0.0803
_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^)+(0.0657P)^2^+9.7135P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1669
_refine_ls_wR_factor_ref         0.1960
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2597
_reflns_number_total             4280
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00298g2.cif
_cod_data_source_block           8ameso
_cod_original_cell_volume        4216.6(7)
_cod_database_code               1554846
_chemical_oxdiff_formula         'N4 C30 H30 P F6'
_reflns_odcompleteness_completeness 66.97
_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
C1 \\sim C11 \\sim C11' \\sim C16 \\sim C16' \\sim C15 \\sim C15' \\sim C14
\\sim C14' \\sim C13 \\sim C13' \\sim C12 \\sim C12': within 1.7A with sigma of
0.01 and sigma for terminal atoms of 0.02
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F1B \\sim F2B \\sim F3B
\\sim F4B \\sim F5B \\sim F6B: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02
P1 \\sim P1B: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
Uanis(C22) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(N21) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
3. Others
 Sof(P1B)=Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(1)
 Sof(P1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1)
 Sof(C1')=Sof(C11')=Sof(C16')=Sof(H16')=Sof(C15')=Sof(H15')=Sof(C14')=
 Sof(H14')=Sof(C13')=Sof(H13')=Sof(C12')=Sof(H12')=1-FVAR(2)
 Sof(C1)=Sof(C11)=Sof(C16)=Sof(H16)=Sof(C15)=Sof(H15)=Sof(C14)=Sof(H14)=
 Sof(C13)=Sof(H13)=Sof(C12)=Sof(H12)=FVAR(2)
 Fixed Sof: N21(0.5) C21(0.5) C22(0.5) H22A(0.5) H22B(0.5) H22C(0.5)
4.a :
 P1(F1,F2,F3,F4,F5,F6), P1B(F1B,F2B,F3B,F4B,F5B,F6B)
4.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C16'(H16'), C15(H15), C15'(H15'), C14(H14), C14'(H14'), C13(H13),
 C13'(H13'), C12(H12), C12'(H12')
4.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C5(H5A,H5B,H5C), C4(H4A,H4B,H4C), C22(H22A,H22B,H22C)
;
_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 1.052
_oxdiff_exptl_absorpt_empirical_full_min 0.957