A Cationic Sulfur-Hydrocarbon Triradical with an Excited Quartet State
Tang, Shuxuan; Ruan, Huapeng; Hu, Zhao-Bo; Zhao, Yue; Song, You; Wang, Xinping; Chemical Communications  (2022) –; doi:10.1039/D1CC06904G

data_7129569
_publ_section_title
;
 A Cationic Sulfur-Hydrocarbon Triradical with an Excited Quartet State
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC06904G
_journal_year                    2022
_chemical_formula_moiety         'C38 H20 S6, 3(Al C16 F36 O4)'
_chemical_formula_sum            'C86 H20 Al3 F108 O12 S6'
_chemical_formula_weight         3570.32
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2021-05-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-07-22 deposited with the CCDC.	2022-01-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.191(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.8747(14)
_cell_length_b                   20.9396(11)
_cell_length_c                   21.1968(11)
_cell_measurement_reflns_used    9871
_cell_measurement_temperature    193(2)
_cell_measurement_theta_max      53.769
_cell_measurement_theta_min      2.300
_cell_volume                     12321.5(11)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      193.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0651
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            183106
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         53.981
_diffrn_reflns_theta_min         2.299
_diffrn_source_current           2.86
_diffrn_source_power             0.1993706
_diffrn_source_voltage           69.71
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.132
_exptl_absorpt_correction_T_max  0.7506
_exptl_absorpt_correction_T_min  0.5168
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1196 before and 0.0824 after correction.
The Ratio of minimum to maximum transmission is 0.6885.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.925
_exptl_crystal_description       block
_exptl_crystal_F_000             6956
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.853
_refine_diff_density_min         -1.583
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2481
_refine_ls_number_reflns         22554
_refine_ls_number_restraints     2614
_refine_ls_restrained_S_all      1.158
_refine_ls_R_factor_all          0.1377
_refine_ls_R_factor_gt           0.1179
_refine_ls_shift/su_max          0.049
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0500P)^2^+65.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2472
_refine_ls_wR_factor_ref         0.2583
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16997
_reflns_number_total             22554
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc06904g2.cif
_cod_data_source_block           a_a_CCDC1
_cod_database_code               7129569
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.815
_shelx_estimated_absorpt_t_min   0.784
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 F76-C70 \\sim F77-C70 \\sim F75-C70
 with sigma of 0.02
 F114-C82 \\sim F111-C81 \\sim F109-C81 \\sim F110-C81 \\sim F108-C80 \\sim
F107-C80 \\sim F106-C80 ~
 F113-C82 \\sim F112-C82
 with sigma of 0.02
 C81A-C78 \\sim C80-C78 \\sim C80A-C78 \\sim C82-C78 \\sim C82A-C78 \\sim
C81-C78
 with sigma of 0.02
 F1D-C82A \\sim F1F-C82A \\sim F1E-C82A \\sim F21-C80A \\sim F1G-C80A \\sim
F1A-C80A \\sim F1H-C81A ~
 F1B-C81A \\sim F1C-C81A
 with sigma of 0.02
 F50A-C62A \\sim F49A-C62A \\sim F48A-C62A \\sim F54A-C61A \\sim F55A-C61A
\\sim F68A-C61A \\sim F66A-
 C63A \\sim F67A-C63A \\sim F65A-C63A
 with sigma of 0.02
 F47A-C54A \\sim F46A-C54A \\sim F40A-C53A \\sim F41A-C53A \\sim F44A-C55A
\\sim F62-C55A \\sim F43A-
 C55A
 with sigma of 0.02
 C54A-C52 \\sim C55A-C52 \\sim C53A-C52
 with sigma of 0.02
 F64-C53A \\sim F41A-C53A \\sim F40A-C53A
 with sigma of 0.02
 F43A-C55A \\sim F62-C55A \\sim F44A-C55A
 with sigma of 0.02
 C65-C51 \\sim C65-C64 \\sim C65-C50
 with sigma of 0.02
 F115-C51 \\sim F28-C51 \\sim F29-C51 \\sim F27-C50 \\sim F26-C50 \\sim F25-C50
\\sim F71-C64 \\sim F70-
 C64 \\sim F69-C64
 with sigma of 0.02
 F29A-C51A \\sim F102-C51A \\sim F28A-C51A \\sim F69A-C64A \\sim F71A-C64A
\\sim F70A-C64A \\sim F26A-
 C50A \\sim F25A-C50A \\sim F27A-C50A
 with sigma of 0.02
 F82-C69 \\sim F83-C69 \\sim F81-C69 \\sim F79-C68 \\sim F80-C68 \\sim F78-C68
\\sim F77-C70 \\sim F75-C70
 \\sim F76-C70
 with sigma of 0.02
 C68-C67 \\sim F68A-F54A \\sim F68A-F55A \\sim F55A-F54A
 with sigma of 0.02
 F50A-F48A \\sim F50A-F49A \\sim F49A-F48A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Al1 \\sim O4: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C03F \\sim C39 \\sim
C40 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim
C48 \\sim C50 \\sim C51 \\sim C64 \\sim C65 \\sim C66 \\sim C02E \\sim C67
\\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75
\\sim C76 \\sim C77 \\sim C78 \\sim C80 \\sim C81 \\sim C82 \\sim C01Q \\sim
C02O \\sim C03Z \\sim C036 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56
\\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim
C61A \\sim C62A \\sim C63A \\sim C80A \\sim C81A \\sim C82A \\sim C53A \\sim
C54A \\sim C55A \\sim C50A \\sim C51A \\sim C64A \\sim C69A \\sim C70A \\sim
C68A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F7 \\sim F8 \\sim F9
\\sim F10 \\sim F11 \\sim F12 \\sim F13 \\sim F14 \\sim F15 \\sim F16 \\sim F17
\\sim F18 \\sim F19 \\sim F20 \\sim F22 \\sim F23 \\sim F24 \\sim F25 \\sim F26
\\sim F27 \\sim F28 \\sim F29 \\sim F69 \\sim F70 \\sim F71 \\sim F72 \\sim F73
\\sim F74 \\sim F115 \\sim F116 \\sim F75 \\sim F76 \\sim F77 \\sim F78 \\sim
F79 \\sim F80 \\sim F81 \\sim F82 \\sim F83 \\sim F84 \\sim F85 \\sim F86 \\sim
F87 \\sim F88 \\sim F89 \\sim F90 \\sim F91 \\sim F92 \\sim F93 \\sim F94 \\sim
F95 \\sim F96 \\sim F97 \\sim F98 \\sim F99 \\sim F100 \\sim F101 \\sim F106
\\sim F107 \\sim F108 \\sim F109 \\sim F110 \\sim F111 \\sim F112 \\sim F113
\\sim F114 \\sim F30 \\sim F31 \\sim F32 \\sim F33 \\sim F34 \\sim F35 \\sim
F36 \\sim F37 \\sim F38 \\sim F39 \\sim F40 \\sim F41 \\sim F42 \\sim F43 \\sim
F44 \\sim F45 \\sim F46 \\sim F47 \\sim F48 \\sim F49 \\sim F50 \\sim F51 \\sim
F52 \\sim F53 \\sim F54 \\sim F55 \\sim F56 \\sim F57 \\sim F58 \\sim F59 \\sim
F60 \\sim F61 \\sim F65 \\sim F66 \\sim F67 \\sim F68 \\sim F49A \\sim F50A
\\sim F54A \\sim F65A \\sim F67A \\sim F68A \\sim F48A \\sim F55A \\sim F66A
\\sim F21 \\sim F1A \\sim F1B \\sim F1C \\sim F1D \\sim F1E \\sim F1F \\sim F1G
\\sim F1H \\sim F40A \\sim F41A \\sim F43A \\sim F44A \\sim F46A \\sim F47A
\\sim F62 \\sim F63 \\sim F64 \\sim F25A \\sim F26A \\sim F27A \\sim F28A \\sim
F29A \\sim F69A \\sim F70A \\sim F71A \\sim F102 \\sim F75A \\sim F76A \\sim
F77A \\sim F80A \\sim F82A \\sim F83A \\sim F79A \\sim F81A \\sim F78A: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O6 \\sim C78: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
Uanis(F1) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F4) \\sim
Ueq, Uanis(F5) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F8)
\\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F11) \\sim Ueq,
Uanis(F12) \\sim Ueq, Uanis(F13) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F15)
\\sim Ueq, Uanis(F16) \\sim Ueq, Uanis(F17) \\sim Ueq, Uanis(F18) \\sim Ueq,
Uanis(F19) \\sim Ueq, Uanis(F20) \\sim Ueq, Uanis(F22) \\sim Ueq, Uanis(F23)
\\sim Ueq, Uanis(F24) \\sim Ueq, Uanis(F25) \\sim Ueq, Uanis(F26) \\sim Ueq,
Uanis(F27) \\sim Ueq, Uanis(F28) \\sim Ueq, Uanis(F29) \\sim Ueq, Uanis(F69)
\\sim Ueq, Uanis(F70) \\sim Ueq, Uanis(F71) \\sim Ueq, Uanis(F72) \\sim Ueq,
Uanis(F73) \\sim Ueq, Uanis(F74) \\sim Ueq, Uanis(F115) \\sim Ueq, Uanis(F116)
\\sim Ueq, Uanis(F75) \\sim Ueq, Uanis(F76) \\sim Ueq, Uanis(F77) \\sim Ueq,
Uanis(F78) \\sim Ueq, Uanis(F79) \\sim Ueq, Uanis(F80) \\sim Ueq, Uanis(F81)
\\sim Ueq, Uanis(F82) \\sim Ueq, Uanis(F83) \\sim Ueq, Uanis(F84) \\sim Ueq,
Uanis(F85) \\sim Ueq, Uanis(F86) \\sim Ueq, Uanis(F87) \\sim Ueq, Uanis(F88)
\\sim Ueq, Uanis(F89) \\sim Ueq, Uanis(F90) \\sim Ueq, Uanis(F91) \\sim Ueq,
Uanis(F92) \\sim Ueq, Uanis(F93) \\sim Ueq, Uanis(F94) \\sim Ueq, Uanis(F95)
\\sim Ueq, Uanis(F96) \\sim Ueq, Uanis(F97) \\sim Ueq, Uanis(F98) \\sim Ueq,
Uanis(F99) \\sim Ueq, Uanis(F100) \\sim Ueq, Uanis(F101) \\sim Ueq, Uanis(F106)
\\sim Ueq, Uanis(F107) \\sim Ueq, Uanis(F108) \\sim Ueq, Uanis(F109) \\sim Ueq,
Uanis(F110) \\sim Ueq, Uanis(F111) \\sim Ueq, Uanis(F112) \\sim Ueq,
Uanis(F113) \\sim Ueq, Uanis(F114) \\sim Ueq, Uanis(F30) \\sim Ueq, Uanis(F31)
\\sim Ueq, Uanis(F32) \\sim Ueq, Uanis(F33) \\sim Ueq, Uanis(F34) \\sim Ueq,
Uanis(F35) \\sim Ueq, Uanis(F36) \\sim Ueq, Uanis(F37) \\sim Ueq, Uanis(F38)
\\sim Ueq, Uanis(F39) \\sim Ueq, Uanis(F40) \\sim Ueq, Uanis(F41) \\sim Ueq,
Uanis(F42) \\sim Ueq, Uanis(F43) \\sim Ueq, Uanis(F44) \\sim Ueq, Uanis(F45)
\\sim Ueq, Uanis(F46) \\sim Ueq, Uanis(F47) \\sim Ueq, Uanis(F48) \\sim Ueq,
Uanis(F49) \\sim Ueq, Uanis(F50) \\sim Ueq, Uanis(F51) \\sim Ueq, Uanis(F52)
\\sim Ueq, Uanis(F53) \\sim Ueq, Uanis(F54) \\sim Ueq, Uanis(F55) \\sim Ueq,
Uanis(F56) \\sim Ueq, Uanis(F57) \\sim Ueq, Uanis(F58) \\sim Ueq, Uanis(F59)
\\sim Ueq, Uanis(F60) \\sim Ueq, Uanis(F61) \\sim Ueq, Uanis(F65) \\sim Ueq,
Uanis(F66) \\sim Ueq, Uanis(F67) \\sim Ueq, Uanis(F68) \\sim Ueq, Uanis(F49A)
\\sim Ueq, Uanis(F50A) \\sim Ueq, Uanis(F54A) \\sim Ueq, Uanis(F65A) \\sim Ueq,
Uanis(F67A) \\sim Ueq, Uanis(F68A) \\sim Ueq, Uanis(F48A) \\sim Ueq,
Uanis(F55A) \\sim Ueq, Uanis(F66A) \\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(F1A)
\\sim Ueq, Uanis(F1B) \\sim Ueq, Uanis(F1C) \\sim Ueq, Uanis(F1D) \\sim Ueq,
Uanis(F1E) \\sim Ueq, Uanis(F1F) \\sim Ueq, Uanis(F1G) \\sim Ueq, Uanis(F1H)
\\sim Ueq, Uanis(F40A) \\sim Ueq, Uanis(F41A) \\sim Ueq, Uanis(F43A) \\sim Ueq,
Uanis(F44A) \\sim Ueq, Uanis(F46A) \\sim Ueq, Uanis(F47A) \\sim Ueq, Uanis(F62)
\\sim Ueq, Uanis(F63) \\sim Ueq, Uanis(F64) \\sim Ueq, Uanis(F25A) \\sim Ueq,
Uanis(F26A) \\sim Ueq, Uanis(F27A) \\sim Ueq, Uanis(F28A) \\sim Ueq,
Uanis(F29A) \\sim Ueq, Uanis(F69A) \\sim Ueq, Uanis(F70A) \\sim Ueq,
Uanis(F71A) \\sim Ueq, Uanis(F102) \\sim Ueq, Uanis(F75A) \\sim Ueq,
Uanis(F76A) \\sim Ueq, Uanis(F77A) \\sim Ueq, Uanis(F80A) \\sim Ueq,
Uanis(F82A) \\sim Ueq, Uanis(F83A) \\sim Ueq, Uanis(F79A) \\sim Ueq,
Uanis(F81A) \\sim Ueq, Uanis(F78A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C81A) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C82A) \\sim Ueq, Uanis(C81)
\\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C80A) \\sim Ueq, Uanis(C78) \\sim Ueq:
with sigma of 0.008 and sigma for terminal atoms of 0.016
4. Others
 Sof(F49A)=Sof(F50A)=Sof(F54A)=Sof(F65A)=Sof(F67A)=Sof(F68A)=Sof(C61A)=
 Sof(C62A)=Sof(C63A)=Sof(F48A)=Sof(F55A)=Sof(F66A)=1-FVAR(1)
 Sof(F48)=Sof(F49)=Sof(F50)=Sof(F54)=Sof(F55)=Sof(F65)=Sof(F66)=Sof(F67)=
 Sof(F68)=Sof(C61)=Sof(C62)=Sof(C63)=FVAR(1)
 Sof(F21)=Sof(F1A)=Sof(F1B)=Sof(F1C)=Sof(F1D)=Sof(F1E)=Sof(F1F)=Sof(C80A)=
 Sof(C81A)=Sof(C82A)=Sof(F1G)=Sof(F1H)=1-FVAR(2)
 Sof(F106)=Sof(F107)=Sof(F108)=Sof(F109)=Sof(F110)=Sof(F111)=Sof(F112)=
 Sof(F113)=Sof(F114)=Sof(C80)=Sof(C81)=Sof(C82)=FVAR(2)
 Sof(F40A)=Sof(F41A)=Sof(F43A)=Sof(F44A)=Sof(F46A)=Sof(F47A)=Sof(C53A)=
 Sof(C54A)=Sof(C55A)=Sof(F62)=Sof(F63)=Sof(F64)=1-FVAR(3)
 Sof(F39)=Sof(F40)=Sof(F41)=Sof(F42)=Sof(F43)=Sof(F44)=Sof(F45)=Sof(F46)=
 Sof(F47)=Sof(C53)=Sof(C54)=Sof(C55)=FVAR(3)
 Sof(F25A)=Sof(F26A)=Sof(F27A)=Sof(F28A)=Sof(F29A)=Sof(F69A)=Sof(F70A)=
 Sof(F71A)=Sof(F102)=Sof(C50A)=Sof(C51A)=Sof(C64A)=1-FVAR(4)
 Sof(F25)=Sof(F26)=Sof(F27)=Sof(F28)=Sof(F29)=Sof(F69)=Sof(F70)=Sof(F71)=
 Sof(F115)=Sof(C50)=Sof(C51)=Sof(C64)=FVAR(4)
 Sof(F75A)=Sof(F76A)=Sof(F77A)=Sof(F80A)=Sof(F82A)=Sof(F83A)=Sof(C69A)=
 Sof(C70A)=Sof(F79A)=Sof(F81A)=Sof(C68A)=Sof(F78A)=1-FVAR(5)
 Sof(F75)=Sof(F76)=Sof(F77)=Sof(F78)=Sof(F79)=Sof(F80)=Sof(F81)=Sof(F82)=
 Sof(F83)=Sof(C68)=Sof(C69)=Sof(C70)=FVAR(5)
5.a Ternary CH refined with riding coordinates:
 C13(H13), C14(H14)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C9(H9), C12(H12), C17(H17), C20(H20),
 C23(H23), C24(H24), C25(H25), C26(H26), C29(H29), C32(H32), C35(H35), C36(H36),
  C37(H37), C38(H38)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              15380
_shelx_fab_checksum              85922
_olex2_submission_special_instructions 'No special instructions were received'