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_7127667
_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         'C22 H38 N2, F3.97 Sb, 2.03(F)'
_chemical_formula_sum            'C22 H38 F6 N2 Sb'
_chemical_formula_weight         566.29
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-04-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-11-28 deposited with the CCDC.	2020-12-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.5683(14)
_cell_length_b                   15.5783(14)
_cell_length_c                   10.020(2)
_cell_measurement_reflns_used    7107
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.7570
_cell_measurement_theta_min      3.5250
_cell_volume                     2430.1(6)
_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      293(2)
_diffrn_detector_area_resol_mean 7.9
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.847
_diffrn_measurement_device_type  'Bruker SMART CCD 1K area detector'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0925
_diffrn_reflns_av_unetI/netI     0.0467
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.847
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            25957
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.845
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.030
_diffrn_reflns_theta_min         2.615
_exptl_absorpt_coefficient_mu    1.192
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64597
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.548
_exptl_crystal_description       block
_exptl_crystal_F_000             1156
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.742
_refine_diff_density_min         -0.732
_refine_diff_density_rms         0.095
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.50(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.984
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     513
_refine_ls_number_reflns         5714
_refine_ls_number_restraints     1208
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0606
_refine_ls_R_factor_gt           0.0396
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0639P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0980
_refine_ls_wR_factor_ref         0.1079
_reflns_Friedel_coverage         0.786
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.843
_reflns_number_gt                4059
_reflns_number_total             5714
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc07385g2.cif
_cod_data_source_block           shelx
_cod_depositor_comments
'Adding full bibliography for 7127659--7127670.cif.'
_cod_original_cell_volume        2430.2(6)
_cod_database_code               7127667
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.851
_shelx_estimated_absorpt_t_min   0.771
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.50(6)
 0.50(6)
2. 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
3. Restrained distances
 Sb1-F1 \\sim Sb1-F2 \\sim Sb1-F3 \\sim Sb1-F4 \\sim Sb1-F5 \\sim Sb1-F6 \\sim
Sb1-F1' \\sim Sb1-F2' \\sim Sb1-
 F3' \\sim Sb1-F4'
 with sigma of 0.02
 Sb1-F1 \\sim Sb1-F5' \\sim Sb1-F6' \\sim Sb1-F1'' \\sim Sb1-F2'' \\sim
Sb1-F3'' \\sim Sb1-F4'' \\sim Sb1-
 F5''
 with sigma of 0.02
 Sb1-F1 \\sim Sb1-F6''
 with sigma of 0.02
 F1-F2 \\sim F1'-F2' \\sim F3-F5 \\sim F3'-F5' \\sim F4-F6 \\sim F4'-F6' \\sim
F3''-F5'' \\sim F4''-F6''
 with sigma of 0.02
 F1-F3 \\sim F1-F4 \\sim F1-F5 \\sim F1-F6 \\sim F1'-F3' \\sim F1'-F4' \\sim
F1'-F5' \\sim F1'-F6' \\sim F2-F3
 \\sim F2-F4 \\sim F2-F5
 with sigma of 0.02
 F1-F3 \\sim F2-F6 \\sim F2'-F3' \\sim F2'-F4' \\sim F2'-F5' \\sim F2'-F6'
\\sim F1''-F3'' \\sim F1''-F4''
 \\sim F1''-F5''
 with sigma of 0.02
 F1-F3 \\sim F1''-F6'' \\sim F2''-F3'' \\sim F2''-F4'' \\sim F2''-F5'' \\sim
F2''-F6''
 with sigma of 0.02
 N2-C3 \\sim N2-C3A
 with sigma of 0.02
4. Rigid bond restraints
 C12, C14, C13, C13A, C15, C15A, C16, C16A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C5, C7, C6, C6A, C9, C9A, C8, C8A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C3, C3A, C4, C4A, C22, C22A, C21, C21A, C20, C20A, C19, C19A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F1' \\sim F2' \\sim F3'
\\sim F4' \\sim F5' \\sim F6' \\sim F2'': within 2.9A with sigma of 0.01 and
sigma for terminal atoms of 0.02
F1'' \\sim F2'' \\sim F3'' \\sim F4'' \\sim F5'' \\sim F6'': within 3.5A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C12 \\sim C14 \\sim C13 \\sim C13A \\sim C15 \\sim C15A \\sim C16 \\sim C16A:
within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
C5 \\sim C7 \\sim C6 \\sim C6A \\sim C9 \\sim C9A \\sim C8 \\sim C8A: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C3 \\sim C3A \\sim C4 \\sim C4A \\sim C22 \\sim C22A \\sim C21 \\sim C21A \\sim
C20 \\sim C20A \\sim C19 \\sim C19A: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.02
6. Same fragment restrains
{C3A, C4A, C22A, C21A, C20A, C19A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C3, C4, C22, C21, C20, C19}
7. Others
 Sof(F1')=Sof(F2')=Sof(F3')=Sof(F4')=Sof(F5')=Sof(F6')=0.7*(1-FVAR(2))
 Sof(F1'')=Sof(F2'')=Sof(F3'')=Sof(F4'')=Sof(F5'')=Sof(F6'')=0.3*(1-FVAR(2))
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1)
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C8A)=
 Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=1-FVAR(2)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C8)=Sof(H8A)=
 Sof(H8B)=Sof(H8C)=FVAR(2)
 Sof(C13A)=Sof(H13C)=Sof(H13D)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=
 Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(3)
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16)=
 Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(3)
 Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C22A)=Sof(H22C)=Sof(H22D)=Sof(C21A)=
 Sof(H21C)=Sof(H21D)=Sof(C20A)=Sof(H20C)=Sof(H20D)=Sof(C19A)=Sof(H19C)=
 Sof(H19D)=1-FVAR(4)
 Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C21)=
 Sof(H21A)=Sof(H21B)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(C19)=Sof(H19A)=Sof(H19B)=
 FVAR(4)
8.a Ternary CH refined with riding coordinates:
 C3(H3), C4(H4), C3A(H3A), C4A(H4A)
8.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C6A(H6AA,H6AB), C13(H13A,H13B), C13A(H13C,H13D), C22(H22A,H22B),
 C21(H21A,H21B), C20(H20A,H20B), C19(H19A,H19B), C22A(H22C,H22D), C21A(H21C,
 H21D), C20A(H20C,H20D), C19A(H19C,H19D)
8.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C10(H10A,H10B,H10C), C18(H18A,H18B,H18C), C17(H17A,H17B,
 H17C), C9(H9A,H9B,H9C), C8(H8A,H8B,H8C), C9A(H9AA,H9AB,H9AC), C8A(H8AA,H8AB,
 H8AC), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C15A(H15D,H15E,H15F),
 C16A(H16D,H16E,H16F)
;
_shelx_res_checksum              13907
_olex2_submission_special_instructions 'No special instructions were received'