Extraordinary Redox Activities in Ladder-Type Conjugated Molecules Enabled by B ←N Coordination-Promoted Delocalization and Hyperconjugation.
Zhu, Congzhi; Ji, Xiaozhou; You, Di; Chen, Teresa L.; Mu, Anthony U.; Barker, Kayla P.; Klivansky, Liana M.; Liu, Yi; Fang, Lei; Journal of the American Chemical Society 140 (2018) 18173–18182; doi:10.1021/jacs.8b11337

data_4133579
_publ_section_title
;
 Extraordinary Redox Activities in Ladder-Type Conjugated Molecules
 Enabled by B \\leftarrow N Coordination-Promoted Delocalization and
 Hyperconjugation.
;
_journal_issue                   51
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              18173
_journal_page_last               18182
_journal_paper_doi               10.1021/jacs.8b11337
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety
'Cl6 Sb, 1.75(C H2 Cl2), C64 H52 B2 N4 S2, C5 H12'
_chemical_formula_sum            'C70.75 H67.5 B2 Cl9.5 N4 S2 Sb'
_chemical_formula_weight         1518.05
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-06-28
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.9213(9)
_cell_length_b                   17.9210(7)
_cell_length_c                   32.1974(13)
_cell_measurement_reflns_used    9017
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      70.137
_cell_measurement_theta_min      3.309
_cell_volume                     13802.8(9)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1312
_diffrn_reflns_av_unetI/netI     0.0517
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            99462
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        49.998
_diffrn_reflns_theta_max         49.998
_diffrn_reflns_theta_min         2.745
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    7.471
_exptl_absorpt_correction_T_max  0.3841
_exptl_absorpt_correction_T_min  0.2098
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1421 before and 0.0958 after correction. The Ratio of minimum to maximum transmission is 0.5462. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            gray
_exptl_crystal_colour_primary    gray
_exptl_crystal_density_diffrn    1.461
_exptl_crystal_description       plate
_exptl_crystal_F_000             6196
_exptl_crystal_size_max          0.267
_exptl_crystal_size_mid          0.139
_exptl_crystal_size_min          0.038
_refine_diff_density_max         1.948
_refine_diff_density_min         -1.071
_refine_diff_density_rms         0.127
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     824
_refine_ls_number_reflns         7083
_refine_ls_number_restraints     192
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.1131
_refine_ls_R_factor_gt           0.0921
_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^)+(0.0375P)^2^+308.6752P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1843
_refine_ls_wR_factor_ref         0.1960
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5574
_reflns_number_total             7083
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b11337_si_004.cif
_cod_data_source_block           ta
_cod_original_formula_sum        'C70.75 H67.50 B2 Cl9.50 N4 S2 Sb'
_cod_database_code               4133579
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.764
_shelx_estimated_absorpt_t_min   0.240
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C71-C70 = C70-C71A
 1.54 with sigma of 0.01
 C68-C67 \\sim C68-C69 \\sim C70-C69 \\sim C70-C71A
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
C71A \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01
C27 \\sim C28 \\sim C23 \\sim C22 \\sim N2 \\sim C9 \\sim C8 \\sim C36 \\sim N3
\\sim C38 \\sim S2: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02
C53 \\sim C52 \\sim C51: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C71A) = Uanis(C71)
Uanis(C71) = Uanis(C71A)
Uanis(Cl10) = Uanis(ClA)
4. Rigid body (RIGU) restrains
 C71A, C67, C68, C69, C70, C71
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C27, C28, C23, C22, N2, C9, C8, C36, N3, C38, S2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C53, C52, C51
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(C71A)=Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(H70C)=Sof(H70D)=1-FVAR(1)
 Sof(ClA)=Sof(H66C)=Sof(H66D)=0.75*(1-FVAR(2))
 Sof(Cl10)=Sof(H66A)=Sof(H66B)=0.75*FVAR(2)
 Sof(H70A)=Sof(H70B)=Sof(C71)=Sof(H71D)=Sof(H71E)=Sof(H71F)=FVAR(1)
 Fixed Sof: Cl9(0.75) C66(0.75)
6.a Secondary CH2 refined with riding coordinates:
 C65(H65A,H65B), C66(H66A,H66B), C66(H66C,H66D), C68(H68A,H68B), C69(H69A,
 H69B), C70(H70C,H70D), C70(H70A,H70B)
6.b Me refined with riding coordinates:
 C71A(H71A,H71B,H71C), C67(H67A,H67B,H67C), C71(H71D,H71E,H71F)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C11(H11), C12(H12), C13(H13), C14(H14),
 C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C25(H25), C26(H26),
  C28(H28), C39(H39), C40(H40), C41(H41), C42(H42), C44(H44), C45(H45),
 C46(H46), C47(H47), C48(H48), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54),
  C57(H57), C58(H58), C60(H60)
6.d Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C62(H62A,H62B,
 H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C)
;
_shelx_res_checksum              89543
_shelx_hkl_checksum              2168
_olex2_submission_special_instructions 'No special instructions were received'