Multiple stable redox states and tunable ground states <i>via</i> the marriage of viologens and Chichibabin's hydrocarbon.
Dai, Yuyang; Xie, Zhuofeng; Bao, Manling; Liu, Chunmeng; Su, Yuanting; Chemical science 14 (2023) 3548–3553; doi:10.1039/d3sc00102d

data_1568625
_publ_section_title
;
 Multiple stable redox states and tunable ground states <i>via</i> the
 marriage of viologens and Chichibabin's hydrocarbon.
;
_journal_issue                   13
_journal_name_full               'Chemical science'
_journal_page_first              3548
_journal_page_last               3553
_journal_paper_doi               10.1039/d3sc00102d
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         '2(Al C16 F36 O4), C62 H80 B2 N6, 2(C7 H8)'
_chemical_formula_sum            'C108 H96 Al2 B2 F72 N6 O8'
_chemical_formula_weight         3049.48
_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             2021-12-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-09-07 deposited with the CCDC.	2023-02-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.219(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.7100(12)
_cell_length_b                   21.2756(10)
_cell_length_c                   24.7191(12)
_cell_measurement_reflns_used    9867
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      54.01
_cell_measurement_theta_min      3.31
_cell_volume                     12861.9(11)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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      120.0
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.995
_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  0.0815
_diffrn_reflns_av_unetI/netI     0.0432
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            204947
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.083
_diffrn_reflns_theta_min         1.571
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.067
_exptl_absorpt_correction_T_max  0.7240
_exptl_absorpt_correction_T_min  0.5766
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1388 before and 0.1088 after correction.
The Ratio of minimum to maximum transmission is 0.7964.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.575
_exptl_crystal_description       plate
_exptl_crystal_F_000             6136
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.20
_refine_diff_density_max         1.480
_refine_diff_density_min         -0.899
_refine_diff_density_rms         0.140
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1950
_refine_ls_number_reflns         23898
_refine_ls_number_restraints     1967
_refine_ls_restrained_S_all      1.127
_refine_ls_R_factor_all          0.1491
_refine_ls_R_factor_gt           0.1444
_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^)+(0.1003P)^2^+100.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3288
_refine_ls_wR_factor_ref         0.3316
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22252
_reflns_number_total             23898
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc00102d2.cif
_cod_data_source_block           1dication
_cod_depositor_comments
'Adding full bibliography for 1568622--1568625.cif.'
_cod_original_cell_volume        12861.8(11)
_cod_database_code               1568625
_shelx_shelxl_version_number     2018/1
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5765(17)
 0.4235(17)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C73-C71
 1.54 with sigma of 0.01
 C90-C87
 1.54 with sigma of 0.01
 C8S-C9S
 1.54 with sigma of 0.01
 C15S-C16S
 1.54 with sigma of 0.01
 C91-C97
 1.54 with sigma of 0.01
 C1S-C2S
 1.54 with sigma of 0.01
 C93-C91
 1.54 with sigma of 0.01
 C15S-C17S \\sim C15S-C21S
 with sigma of 0.02
 C15S-C18S \\sim C15S-C20S
 with sigma of 0.02
 C14S-C8S \\sim C8S-C10S
 with sigma of 0.02
 C13S-C8S \\sim C11S-C8S
 with sigma of 0.02
 C83-C85 \\sim C83-C86 \\sim C83-C84
 with sigma of 0.02
 C85-C86 \\sim C86-C84 \\sim C84-C85
 with sigma of 0.02
 C85-F50 \\sim C85-F51 \\sim C85-F49
 with sigma of 0.02
 F50-F51 \\sim F51-F49 \\sim F49-F50
 with sigma of 0.02
 C86-F52 \\sim C86-F54 \\sim C86-F53
 with sigma of 0.02
 F52-F54 \\sim F54-F53 \\sim F53-F52
 with sigma of 0.02
 C84-F47 \\sim C84-F46 \\sim C84-F48
 with sigma of 0.02
 F47-F46 \\sim F46-F48 \\sim F48-F47
 with sigma of 0.02
 C63-C66 \\sim C63-C64 \\sim C63-C65
 with sigma of 0.02
 C66-C64 \\sim C64-C65 \\sim C65-C66
 with sigma of 0.02
 C66-F9 \\sim C66-F8 \\sim C66-F7
 with sigma of 0.02
 F9-F8 \\sim F8-F7 \\sim F7-F9
 with sigma of 0.02
 C64-F2 \\sim C64-F1 \\sim C64-F3
 with sigma of 0.02
 F2-F1 \\sim F1-F3 \\sim F3-F2
 with sigma of 0.02
 C65-F4 \\sim C65-F5 \\sim C65-F6
 with sigma of 0.02
 F4-F5 \\sim F5-F6 \\sim F6-F4
 with sigma of 0.02
 C71-C73 \\sim C71-C74 \\sim C71-C72
 with sigma of 0.02
 C73-C74 \\sim C74-C72 \\sim C72-C73
 with sigma of 0.02
 C73-F23 \\sim C73-F22 \\sim C73-F24
 with sigma of 0.02
 F23-F22 \\sim F22-F24 \\sim F24-F23
 with sigma of 0.02
 C74-F25 \\sim C74-F27 \\sim C74-F26
 with sigma of 0.02
 F25-F27 \\sim F27-F26 \\sim F26-F25
 with sigma of 0.02
 C72-F21 \\sim C72-F20 \\sim C72-F19
 with sigma of 0.02
 F21-F20 \\sim F20-F19 \\sim F19-F21
 with sigma of 0.02
 C75-C78 \\sim C75-C77 \\sim C75-C76
 with sigma of 0.02
 C78-C77 \\sim C77-C76 \\sim C76-C78
 with sigma of 0.02
 C78-F34 \\sim C78-F35 \\sim C78-F36
 with sigma of 0.02
 F34-F35 \\sim F35-F36 \\sim F36-F34
 with sigma of 0.02
 C77-F33 \\sim C77-F31 \\sim C77-F32
 with sigma of 0.02
 F33-F31 \\sim F31-F32 \\sim F32-F33
 with sigma of 0.02
 C67-C69 \\sim C67-C68 \\sim C67-C70
 with sigma of 0.02
 C69-C68 \\sim C68-C70 \\sim C70-C69
 with sigma of 0.02
 C69-F13 \\sim C69-F14 \\sim C69-F15
 with sigma of 0.02
 F13-F14 \\sim F14-F15 \\sim F15-F13
 with sigma of 0.02
 C68-F10 \\sim C68-F12 \\sim C68-F11
 with sigma of 0.02
 F10-F12 \\sim F12-F11 \\sim F11-F10
 with sigma of 0.02
 C76-F29 \\sim C76-F30 \\sim C76-F28
 with sigma of 0.02
 F29-F30 \\sim F30-F28 \\sim F28-F29
 with sigma of 0.02
 C70-F16 \\sim C70-F18 \\sim C70-F17
 with sigma of 0.02
 F16-F18 \\sim F18-F17 \\sim F17-F16
 with sigma of 0.02
 C79-C81 \\sim C79-C80 \\sim C79-C82
 with sigma of 0.02
 C81-C80 \\sim C80-C82 \\sim C82-C81
 with sigma of 0.02
 C81-F41 \\sim C81-F42 \\sim C81-F40
 with sigma of 0.02
 F41-F42 \\sim F42-F40 \\sim F40-F41
 with sigma of 0.02
 C80-F37 \\sim C80-F39 \\sim C80-F38
 with sigma of 0.02
 F37-F39 \\sim F39-F38 \\sim F38-F37
 with sigma of 0.02
 C82-F43 \\sim C82-F44 \\sim C82-F45
 with sigma of 0.02
 F43-F44 \\sim F44-F45 \\sim F45-F43
 with sigma of 0.02
 C94-C92 \\sim C92-C93 \\sim C93-C94
 with sigma of 0.02
 C94-F72 \\sim C94-F71 \\sim C94-F70
 with sigma of 0.02
 F72-F71 \\sim F71-F70 \\sim F70-F72
 with sigma of 0.02
 C92-F64 \\sim C92-F65 \\sim C92-F66
 with sigma of 0.02
 F64-F65 \\sim F65-F66 \\sim F66-F64
 with sigma of 0.02
 C93-F68 \\sim C93-F67 \\sim C93-F69
 with sigma of 0.02
 F68-F67 \\sim F67-F69 \\sim F69-F68
 with sigma of 0.02
 C87-C88 \\sim C87-C89 \\sim C87-C90
 with sigma of 0.02
 C88-C89 \\sim C89-C90 \\sim C90-C88
 with sigma of 0.02
 C88-F55 \\sim C88-F57 \\sim C88-F56
 with sigma of 0.02
 F55-F57 \\sim F57-F56 \\sim F56-F55
 with sigma of 0.02
 C89-F59 \\sim C89-F58 \\sim C89-F60
 with sigma of 0.02
 F59-F58 \\sim F58-F60 \\sim F60-F59
 with sigma of 0.02
 C90-F63 \\sim C90-F62 \\sim C90-F61
 with sigma of 0.02
 F63-F62 \\sim F62-F61 \\sim F61-F63
 with sigma of 0.02
 C9S-C14S \\sim C14S-C13S \\sim C13S-C12S \\sim C12S-C11S \\sim C11S-C10S \\sim
C10S-C9S
 with sigma of 0.02
 C9S-C13S \\sim C9S-C11S \\sim C14S-C12S \\sim C14S-C10S \\sim C12S-C10S \\sim
C13S-C11S
 with sigma of 0.02
 C1S-C3S \\sim C1S-C7S
 with sigma of 0.02
 C1S-C4S \\sim C1S-C6S
 with sigma of 0.02
 C91-C94 \\sim C91-C92 \\sim C91-C93
 with sigma of 0.02
 C91-C97 \\sim C91-C96 \\sim C91-C95
 with sigma of 0.02
 C97-C96 \\sim C96-C95 \\sim C95-C97
 with sigma of 0.02
 C97-F81 \\sim C97-F80 \\sim C97-F79
 with sigma of 0.02
 F81-F80 \\sim F80-F79 \\sim F79-F81
 with sigma of 0.02
 C96-F76 \\sim C96-F78 \\sim C96-F77
 with sigma of 0.02
 F76-F78 \\sim F78-F77 \\sim F77-F76
 with sigma of 0.02
 C95-F73 \\sim C95-F74 \\sim C95-F75
 with sigma of 0.02
 F73-F74 \\sim F74-F75 \\sim F75-F73
 with sigma of 0.02
4. Restrained planarity
 C8S, C9S, C10S, C11S, C12S, C13S, C14S
 with sigma of 0.01
5. Uiso/Uaniso restraints and constraints
N1 \\sim N2 \\sim N3 \\sim N4 \\sim N5 \\sim N6 \\sim 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 C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim
C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim
C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim
C60 \\sim C61 \\sim C62 \\sim B1 \\sim B2: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
Al1 \\sim 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 F21 \\sim F22 \\sim F23 \\sim F24
\\sim F25 \\sim F26 \\sim F27 \\sim F28 \\sim F29 \\sim F30 \\sim F31 \\sim F32
\\sim F33 \\sim F34 \\sim F35 \\sim F36 \\sim O1 \\sim O2 \\sim O3 \\sim O4
\\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70
\\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim
C78: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C91 \\sim Al2 \\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 F62 \\sim F63 \\sim F64 \\sim F65 \\sim F66 \\sim
F67 \\sim F68 \\sim F69 \\sim F70 \\sim F71 \\sim F72 \\sim O5 \\sim O6 \\sim
O7 \\sim O8 \\sim C79 \\sim C80 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim
C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89 \\sim C90 \\sim C92 \\sim C93 \\sim
C94 \\sim F73 \\sim F74 \\sim F75 \\sim F76 \\sim F77 \\sim F78 \\sim F79 \\sim
F80 \\sim F81 \\sim C95 \\sim C96 \\sim C97: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C1S \\sim C2S \\sim C3S \\sim C4S \\sim C5S \\sim C6S \\sim C7S: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C8S \\sim C9S \\sim C10S \\sim C11S \\sim C12S \\sim C13S \\sim C14S \\sim C15S
\\sim C16S \\sim C17S \\sim C18S \\sim C19S \\sim C20S \\sim C21S: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
6. Others
 Fixed Sof: F64(0.5) F65(0.5) F66(0.5) F67(0.5) F68(0.5) F69(0.5) F70(0.5)
 F71(0.5) F72(0.5) C92(0.5) C93(0.5) C94(0.5) F73(0.5) F74(0.5) F75(0.5)
 F76(0.5) F77(0.5) F78(0.5) F79(0.5) F80(0.5) F81(0.5) C95(0.5) C96(0.5)
 C97(0.5) C8S(0.5) H8SA(0.5) H8SB(0.5) H8SC(0.5) C9S(0.5) C10S(0.5) H10S(0.5)
 C11S(0.5) H11S(0.5) C12S(0.5) H12S(0.5) C13S(0.5) H13S(0.5) C14S(0.5)
 H14S(0.5) C15S(0.5) H15D(0.5) H15E(0.5) H15F(0.5) C21S(0.5) H21S(0.5)
 C16S(0.5) C17S(0.5) H17S(0.5) C18S(0.5) H18S(0.5) C19S(0.5) H19S(0.5)
 C20S(0.5) H20S(0.5)
7.a Ternary CH refined with riding coordinates:
 C14(H14), C17(H17), C26(H26), C29(H29), C45(H45), C48(H48), C57(H57), C60(H60)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C10(H10), C11(H11), C12(H12),
 C22(H22), C23(H23), C24(H24), C33(H33), C34(H34), C35(H35), C36(H36), C37(H37),
  C38(H38), C41(H41), C42(H42), C43(H43), C53(H53), C54(H54), C55(H55),
 C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S), C7S(H7S), C10S(H10S), C11S(H11S),
 C12S(H12S), C13S(H13S), C14S(H14S), C21S(H21S), C17S(H17S), C18S(H18S),
 C19S(H19S), C20S(H20S)
7.c Fitted hexagon refined as free rotating group:
 C9S(C10S,C11S,C12S,C13S,C14S), C21S(C16S,C17S,C18S,C19S,C20S)
7.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C),
 C50(H50A,H50B,H50C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C61(H61A,H61B,
 H61C), C62(H62A,H62B,H62C), C1S(H1SA,H1SB,H1SC), C8S(H8SA,H8SB,H8SC),
 C15S(H15D,H15E,H15F)
;
_shelx_res_checksum              65941
_shelx_hkl_checksum              90877
_olex2_submission_special_instructions 'No special instructions were received'