Tethered CAAC-CAAC dimers: oxidation to persistent radical cations and bridging-unit dependent reactivity/stability of the dications.
Nayak, Mithilesh Kumar; Suhr, Simon; Chrysochos, Nicolas; Rawat, Hemant; Schulzke, Carola; Chandrasekhar, Vadapalli; Sarkar, Biprajit; Jana, Anukul; Chemical communications (Cambridge, England) 57 (2021) 1210–1213; doi:10.1039/d0cc07385g

data_7127661
_publ_section_title
;
 Tethered CAAC-CAAC dimers: oxidation to persistent radical cations and
 bridging-unit dependent reactivity/stability of the dications.
;
_journal_issue                   10
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              1210
_journal_page_last               1213
_journal_paper_doi               10.1039/d0cc07385g
_journal_volume                  57
_journal_year                    2021
_chemical_formula_moiety         '2(C F3 O3 S), C22 H36 N2'
_chemical_formula_sum            'C24 H36 F6 N2 O6 S2'
_chemical_formula_weight         626.67
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-05-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-05-19 deposited with the CCDC.	2020-12-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.041(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.0963(7)
_cell_length_b                   12.0415(5)
_cell_length_c                   14.8878(6)
_cell_measurement_reflns_used    13012
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      28.0060
_cell_measurement_theta_min      3.3000
_cell_volume                     2883.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_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_temperature      173.00
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.917
_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    -81.00  14.00   0.50   29.77    --    7.10 -57.00 120.00  190
  2  \w     51.00  86.00   0.50   29.77    --    7.10  77.00-120.00   70
  3  \w    -89.00   6.00   0.50   29.77    --   -7.50 -57.00-180.00  190
  4  \w     41.00  81.00   0.50   29.77    --   -7.50  57.00 -60.00   80
  5  \w    -28.00   9.00   0.50   29.77    --   -7.50  57.00  60.00   74
  6  \w     45.00  80.00   0.50   29.77    --   -7.50  57.00  60.00   70
  7  \w      5.00  30.00   0.50   29.77    --   -7.50  57.00 -60.00   50
  8  \w    -63.00   3.00   0.50   29.77    --   -7.50 -82.00-180.00  132
  9  \w    -64.00 -13.00   0.50   29.77    --   -7.50 -77.00  30.00  102
 10  \w    -62.00  35.00   0.50   29.77    --   -7.50 -82.00 -30.00  194
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0446
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.917
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            6920
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.917
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.876
_diffrn_reflns_theta_min         2.493
_exptl_absorpt_coefficient_mu    0.264
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76315
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29d (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.443
_exptl_crystal_description       block
_exptl_crystal_F_000             1312
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.694
_refine_diff_density_min         -0.592
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     422
_refine_ls_number_reflns         6920
_refine_ls_number_restraints     99
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.1140
_refine_ls_R_factor_gt           0.0954
_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^)+(0.0664P)^2^+9.5346P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2351
_refine_ls_wR_factor_ref         0.2437
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5336
_reflns_number_total             6920
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc07385g2.cif
_cod_data_source_block           aj0779r
_cod_depositor_comments
'Adding full bibliography for 7127659--7127670.cif.'
_cod_database_code               7127661
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.964
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.645(4)
 0.355(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 O3-N1
 2.9 with sigma of 0.002
 F5-C24 \\sim F5A-C24
 with sigma of 0.02
 F4-C24 \\sim F4A-C24
 with sigma of 0.02
 F6-C24 \\sim F6A-C24
 with sigma of 0.02
 S2-O6 \\sim S2A-O6A
 with sigma of 0.02
 S2-O5 \\sim S2A-O5A
 with sigma of 0.02
 S2-O4 \\sim S2A-O4A
 with sigma of 0.02
 S2-C24 \\sim S2A-C24
 with sigma of 0.02
 O6-O5 \\sim O6A-O5A
 with sigma of 0.04
 O6-O4 \\sim O6A-O4A
 with sigma of 0.04
 O6-C24 \\sim O6A-C24
 with sigma of 0.04
 O5-O4 \\sim O5A-O4A
 with sigma of 0.04
 O5-C24 \\sim O5A-C24
 with sigma of 0.04
 O4-C24 \\sim O4A-C24
 with sigma of 0.04
 F1-C23 \\sim F1A-C23
 with sigma of 0.02
 F2-C23 \\sim F2A-C23
 with sigma of 0.02
 F3-C23 \\sim F3A-C23
 with sigma of 0.02
 S1-O3 \\sim S1A-O3A
 with sigma of 0.02
 S1-O1 \\sim S1A-O1A
 with sigma of 0.02
 S1-O2 \\sim S1A-O2A
 with sigma of 0.02
 S1-C23 \\sim S1A-C23
 with sigma of 0.02
 O3-O1 \\sim O3A-O1A
 with sigma of 0.04
 O3-O2 \\sim O3A-O2A
 with sigma of 0.04
 O3-C23 \\sim O3A-C23
 with sigma of 0.04
 O1-O2 \\sim O1A-O2A
 with sigma of 0.04
 O1-C23 \\sim O1A-C23
 with sigma of 0.04
 O2-C23 \\sim O2A-C23
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
Uanis(F6) = Uanis(F4A)
Uanis(F5A) = Uanis(F5)
Uanis(F4) = Uanis(F6A)
Uanis(O4A) = Uanis(O5)
Uanis(O6) = Uanis(O6A)
Uanis(O4) = Uanis(O5A)
Uanis(F1) = Uanis(F1A)
Uanis(F3) = Uanis(F3A)
Uanis(F2) = Uanis(F2A)
Uanis(O3A) = Uanis(O3)
Uanis(O2A) = Uanis(O2)
Uanis(O1A) = Uanis(O1)
Uanis(S1A) = Uanis(S1)
5. Rigid body (RIGU) restrains
 F5, F4, F6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F5A, F4A, F6A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S2, O6, O5, O4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S2A, O4A, O6A, O5A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1, F2, F3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F3A, F2A, F1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1, O3, O1, O2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1A, O3A, O2A, O1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F5A)=Sof(F4A)=Sof(F6A)=1-FVAR(1)
 Sof(F5)=Sof(F4)=Sof(F6)=FVAR(1)
 Sof(S2A)=Sof(O4A)=Sof(O6A)=Sof(O5A)=1-FVAR(2)
 Sof(S2)=Sof(O6)=Sof(O5)=Sof(O4)=FVAR(2)
 Sof(F3A)=Sof(F2A)=Sof(F1A)=1-FVAR(3)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(3)
 Sof(S1A)=Sof(O3A)=Sof(O2A)=Sof(O1A)=1-FVAR(4)
 Sof(S1)=Sof(O3)=Sof(O1)=Sof(O2)=FVAR(4)
7.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C17(H17A,H17B), C8(H8A,H8B), C6(H6A,H6B), C5(H5A,H5B), C7(H7A,
 H7B)
7.b Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C19(H19A,H19B,H19C), C13(H13A,H13B,
 H13C), C21(H21A,H21B,H21C), C20(H20A,H20B,H20C), C12(H12A,H12B,H12C), C22(H22A,
 H22B,H22C)
;
_shelx_res_checksum              70106
_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
;