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_1554852
_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
'C28 H47 Cl N3 O2, 0.44(C4 H10 O), F6 P, 0.5(C1.12 H2.24 Cl2.24)'
_chemical_formula_sum            'C30.33 H52.53 Cl2.12 F6 N3 O2.44 P'
_chemical_formula_weight         718.30
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-02-21
_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                83.275(4)
_cell_angle_beta                 88.086(4)
_cell_angle_gamma                80.993(3)
_cell_formula_units_Z            4
_cell_length_a                   9.5322(4)
_cell_length_b                   18.6061(7)
_cell_length_c                   21.1198(11)
_cell_measurement_reflns_used    6650
_cell_measurement_temperature    150.00(14)
_cell_measurement_theta_max      24.7400
_cell_measurement_theta_min      2.3270
_cell_volume                     3673.7(3)
_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 0.996
_diffrn_measured_fraction_theta_max 0.990
_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    -38.00  37.00   1.00   10.00    --   -0.62  90.00 -38.00   75
  2  \w    -69.00  21.00   1.00   10.00    --   -0.62 -57.00-150.00   90
  3  \w    -20.00  22.00   1.00   10.00    --   24.00 104.00  46.13   42
  4  \w    -14.00  12.00   1.00  100.00    --   36.00 114.00-108.77   26
  5  \w     -3.00  23.00   1.00  100.00    --   40.00 101.00 179.27   26
  6  \w      5.00  32.00   1.00  100.00    --   44.00  93.00  67.07   27
  7  \w     12.00  39.00   1.00  100.00    --   48.00  87.00 -16.98   27
  8  \w     11.00  37.00   1.00  100.00    --   48.00  90.00-170.39   26
  9  \w     18.00  46.00   1.00  100.00    --   52.00  84.00  91.99   28
 10  \w    -13.00  77.00   1.00  100.00    --   55.51 -57.00  30.00   90
 11  \w     -3.00 113.00   1.00  100.00    --   55.51-125.00-120.00  116
 12  \w     25.00 126.00   1.00  100.00    --   55.51  78.00 163.71  101
 13  \w     24.00 125.00   1.00  100.00    --   55.51  79.00 -56.84  101
 14  \w    -13.00  74.00   1.00  100.00    --   55.51 -57.00  90.00   87
 15  \w      5.00  97.00   1.00  100.00    --   55.51 -99.00   0.00   92
 16  \w     24.00 125.00   1.00  100.00    --   55.51  79.00-110.52  101
 17  \w     25.00 125.00   1.00  100.00    --   55.51  77.00  60.00  100
 18  \w     73.00 126.00   1.00  100.00    --   55.51 125.00  60.00   53
 19  \w     25.00  53.00   1.00  100.00    --   55.51  77.00 120.00   28
;
_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      0.0327008000
_diffrn_orient_matrix_UB_12      -0.0363737000
_diffrn_orient_matrix_UB_13      -0.0032173000
_diffrn_orient_matrix_UB_21      -0.0295329000
_diffrn_orient_matrix_UB_22      0.0026600000
_diffrn_orient_matrix_UB_23      -0.0307254000
_diffrn_orient_matrix_UB_31      0.0611218000
_diffrn_orient_matrix_UB_32      0.0133811000
_diffrn_orient_matrix_UB_33      -0.0137652000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1134
_diffrn_reflns_av_unetI/netI     0.0774
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            65540
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.472
_diffrn_reflns_theta_min         2.127
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.291
_exptl_absorpt_correction_T_max  0.998
_exptl_absorpt_correction_T_min  0.986
_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    1.299
_exptl_crystal_description       'long plate'
_exptl_crystal_F_000             1520
_exptl_crystal_size_max          0.536
_exptl_crystal_size_mid          0.156
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.824
_refine_diff_density_min         -0.865
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.105
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     976
_refine_ls_number_reflns         15036
_refine_ls_number_restraints     179
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.1554
_refine_ls_R_factor_gt           0.1108
_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^)+(0.1051P)^2^+14.3851P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2715
_refine_ls_wR_factor_ref         0.2951
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9764
_reflns_number_total             15036
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00298g2.cif
_cod_data_source_block           1d
_cod_database_code               1554852
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'P1 F6 O5 N3 C40 H80'
_reflns_odcompleteness_completeness 99.33
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     22.44
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C51B-C52B = C51B-C54B = C51B-C53B
 1.5 with sigma of 0.02
 Cl6-C66 = Cl5-C66
 1.75 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C22 \\sim C23 \\sim C24 \\sim C22B \\sim C23B \\sim C24B: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02
F13 \\sim F14 \\sim F15 \\sim F16 \\sim F13B \\sim F14B \\sim F15B \\sim F16B:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
C51 \\sim C52 \\sim C53 \\sim C54 \\sim C51B \\sim C52B \\sim C53B \\sim C54B:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(Cl6) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(Cl5) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C22B)=Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C23B)=Sof(H23D)=Sof(H23E)=
 Sof(H23F)=Sof(C24B)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(1)
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(1)
 Sof(F13B)=Sof(F14B)=Sof(F15B)=Sof(F16B)=1-FVAR(2)
 Sof(F13)=Sof(F14)=Sof(F15)=Sof(F16)=FVAR(2)
 Sof(Cl5)=Sof(Cl6)=Sof(C66)=Sof(H66A)=Sof(H66B)=1-FVAR(3)
 Sof(O61)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=FVAR(3)
 Sof(C51B)=Sof(C52B)=Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C53B)=Sof(H53D)=
 Sof(H53E)=Sof(H53F)=Sof(C54B)=Sof(H54D)=Sof(H54E)=Sof(H54F)=1-FVAR(4)
 Sof(C51)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C53)=Sof(H53A)=Sof(H53B)=
 Sof(H53C)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=FVAR(4)
5.a Secondary CH2 refined with riding coordinates:
 C61(H61A,H61B), C63(H63A,H63B), C65(H65A,H65B), C66(H66A,H66B)
5.b Me refined with riding coordinates:
 C52B(H52D,H52E,H52F), C53B(H53D,H53E,H53F), C54B(H54D,H54E,H54F)
5.c Aromatic/amide H refined with riding coordinates:
 C43(H43), C45(H45), C13(H13), C15(H15)
5.d Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,
 H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C48(H48A,H48B,H48C), C49(H49A,
 H49B,H49C), C50(H50A,H50B,H50C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C),
 C58(H58A,H58B,H58C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,
 H54C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C),
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C),
 C20(H20A,H20B,H20C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C),
 C22B(H22D,H22E,H22F), C23B(H23D,H23E,H23F), C24B(H24D,H24E,H24F), C62(H62A,
 H62B,H62C), C64(H64A,H64B,H64C)
;
_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 1.087
_oxdiff_exptl_absorpt_empirical_full_min 0.906