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_1554847
_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 N3 O2, 1(F6 P1), 1(C F3 O3 S), 1.5(C2 H3 N)'
_chemical_formula_sum            'C26 H39.5 F9 N4.5 O5 P S'
_chemical_formula_weight         729.15
_chemical_name_common            6c
_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     dual
_audit_creation_date             2018-07-26
_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                107.620(4)
_cell_angle_beta                 93.413(3)
_cell_angle_gamma                109.731(4)
_cell_formula_units_Z            2
_cell_length_a                   10.7516(4)
_cell_length_b                   12.0558(6)
_cell_length_c                   14.8348(6)
_cell_measurement_reflns_used    4273
_cell_measurement_temperature    150.00(14)
_cell_measurement_theta_max      29.2870
_cell_measurement_theta_min      2.9270
_cell_volume                     1696.80(14)
_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, 2008)'
_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 0.982
_diffrn_measured_fraction_theta_max 0.983
_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    -68.00  22.00   1.00   10.00    --   -0.62 -64.00 177.00   90
  2  \w    -13.00  77.00   1.00   60.00    --   55.51 -57.00-120.00   90
  3  \w    -13.00  77.00   1.00   60.00    --   55.51 -57.00  90.00   90
  4  \w     25.00 126.00   1.00   60.00    --   55.51  77.00   0.00  101
  5  \w    -16.00  97.00   1.00   60.00    --   55.51 -99.00  60.00  113
  6  \w     -3.00 113.00   1.00   60.00    --   55.51-125.00-120.00  116
  7  \w    -17.00 128.00   1.00   60.00    --   55.51   0.00   0.00  145
  8  \w    -77.00 -47.00   1.00   10.00    --   -0.62 178.00 -60.00   30
;
_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      -0.0191430000
_diffrn_orient_matrix_UB_12      0.0525933000
_diffrn_orient_matrix_UB_13      0.0157348000
_diffrn_orient_matrix_UB_21      -0.0320110000
_diffrn_orient_matrix_UB_22      -0.0231831000
_diffrn_orient_matrix_UB_23      0.0346078000
_diffrn_orient_matrix_UB_31      0.0607126000
_diffrn_orient_matrix_UB_32      0.0335579000
_diffrn_orient_matrix_UB_33      0.0339997000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0356
_diffrn_reflns_av_unetI/netI     0.0333
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            19002
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.366
_diffrn_reflns_theta_min         2.046
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.233
_exptl_absorpt_correction_T_max  0.994
_exptl_absorpt_correction_T_min  0.972
_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 light yellow'
_exptl_crystal_density_diffrn    1.427
_exptl_crystal_description       plate
_exptl_crystal_F_000             758
_exptl_crystal_size_max          0.542
_exptl_crystal_size_mid          0.348
_exptl_crystal_size_min          0.096
_refine_diff_density_max         0.499
_refine_diff_density_min         -0.446
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     693
_refine_ls_number_reflns         6815
_refine_ls_number_restraints     632
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0828
_refine_ls_R_factor_gt           0.0612
_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^)+(0.0837P)^2^+1.4357P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1572
_refine_ls_wR_factor_ref         0.1736
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5151
_reflns_number_total             6815
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00298g2.cif
_cod_data_source_block           6c
_cod_original_cell_volume        1696.78(13)
_cod_original_formula_sum        'C26 H39.50 F9 N4.50 O5 P S'
_cod_database_code               1554847
_chemical_oxdiff_formula         'C30 H50 N3 O2 P F6'
_reflns_odcompleteness_completeness 98.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Uiso/Uaniso restraints and constraints
N31 \\sim C31 \\sim N32 \\sim C32 \\sim C33 \\sim N33 \\sim C35 \\sim C36:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.01
P1 \\sim F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim S3 \\sim F1S3
\\sim F2S3 \\sim F3S3 \\sim O1S3 \\sim O2S3 \\sim O3S3 \\sim C3S: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.01
S2 \\sim O1S2 \\sim O2S2 \\sim O3S2 \\sim C2S \\sim F1S2 \\sim F2S2 \\sim F3S2
\\sim S1 \\sim O1S1 \\sim O2S1 \\sim O3S1 \\sim C1S \\sim F1S1 \\sim F2S1 \\sim
F3S1 \\sim P2 \\sim F11 \\sim F12 \\sim F13 \\sim F14 \\sim F15 \\sim F16:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.01
3. Others
 1*[Sof(S1)+Sof(F1S1)+Sof(F2S1)+Sof(F3S1)+Sof(O1S1)+Sof(O2S1)+Sof(O3S1)+
 Sof(C1S)]+1*[Sof(S2)+Sof(F1S2)+Sof(F2S2)+Sof(F3S2)+Sof(O1S2)+Sof(O2S2)+
 Sof(O3S2)+Sof(C2S)]+1*[Sof(P2)+Sof(F11)+Sof(F12)+Sof(F13)+Sof(F14)+Sof(F15)+
 Sof(F16)]=1 with esd of 0.000001
 1*[Sof(P1)+Sof(F1)+Sof(F2)+Sof(F3)+Sof(F4)+Sof(F5)+Sof(F6)+Sof(S3)+Sof(F1S3)+
 Sof(F2S3)+Sof(F3S3)+Sof(O1S3)+Sof(O2S3)+Sof(O3S3)+Sof(C3S)]+1*[Sof(P2)+
 Sof(F11)+Sof(F12)+Sof(F13)+Sof(F14)+Sof(F15)+Sof(F16)]=1 with esd of 0.000001
 Sof(S1)=Sof(F1S1)=Sof(F2S1)=Sof(F3S1)=Sof(O1S1)=Sof(O2S1)=Sof(O3S1)=Sof(C1S)=
 FVAR(1)
 Sof(S3)=Sof(F1S3)=Sof(F2S3)=Sof(F3S3)=Sof(O1S3)=Sof(O2S3)=Sof(O3S3)=Sof(C3S)=
 1-FVAR(2)
 Sof(P1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(2)
 Sof(N31)=Sof(C31)=Sof(H33D)=Sof(H33E)=Sof(H33F)=1-FVAR(3)
 Sof(N32)=Sof(C32)=Sof(H33A)=Sof(H33B)=Sof(H33C)=FVAR(3)
 Sof(S2)=Sof(F1S2)=Sof(F2S2)=Sof(F3S2)=Sof(O1S2)=Sof(O2S2)=Sof(O3S2)=Sof(C2S)=
 FVAR(4)
 Sof(P2)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(F16)=FVAR(5)
 Fixed Sof: N33(0.5) C35(0.5) C36(0.5) H36A(0.5) H36B(0.5) H36C(0.5)
4.a :
 P1(F1,F2,F3,F4,F5,F6), S3(F1S3,F2S3,F3S3,O1S3,O2S3,O3S3,C3S), S1(F1S1,F2S1,
 F3S1,O1S1,O2S1,O3S1,C1S), S2(F1S2,F2S2,F3S2,O1S2,O2S2,O3S2,C2S), P2(F11,F12,
 F13,F14,F15,F16)
4.b Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C33(H33D,H33E,H33F), C33(H33A,H33B,H33C), C36(H36A,H36B,
 H36C), C20(H20A,H20B,H20C), C19(H19A,H19B,H19C)
;
_shelx_shelxl_version_number     2016/6
_olex2_date_sample_data_collection 2018-07-25
_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 1.078
_oxdiff_exptl_absorpt_empirical_full_min 0.930