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_4133578
_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         '2(C1 H1 Cl3), C64 H52 B2 N4 S2'
_chemical_formula_sum            'C66 H54 B2 Cl6 N4 S2'
_chemical_formula_weight         1201.57
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-06-25
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.2800(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.3742(3)
_cell_length_b                   20.3276(5)
_cell_length_c                   14.6088(4)
_cell_measurement_reflns_used    9795
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      69.944
_cell_measurement_theta_min      3.817
_cell_volume                     2971.84(14)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.996
_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  0.0491
_diffrn_reflns_av_unetI/netI     0.0159
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            108854
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.220
_diffrn_reflns_theta_min         3.817
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.642
_exptl_absorpt_correction_T_max  0.4684
_exptl_absorpt_correction_T_min  0.2743
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1191 before and 0.0702 after correction. The Ratio of minimum to maximum transmission is 0.5856. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.343
_exptl_crystal_description       block
_exptl_crystal_F_000             1244
_exptl_crystal_size_max          0.278
_exptl_crystal_size_mid          0.097
_exptl_crystal_size_min          0.058
_refine_diff_density_max         0.861
_refine_diff_density_min         -0.926
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     383
_refine_ls_number_reflns         5645
_refine_ls_number_restraints     126
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0604
_refine_ls_R_factor_gt           0.0545
_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^)+(0.0848P)^2^+4.7420P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1519
_refine_ls_wR_factor_ref         0.1577
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4996
_reflns_number_total             5645
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b11337_si_002.cif
_cod_data_source_block           bthbph2
_cod_database_code               4133578
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.817
_shelx_estimated_absorpt_t_min   0.431
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl1-C33 \\sim Cl1A-C33A
 with sigma of 0.01
 Cl2-C33 \\sim Cl2A-C33A
 with sigma of 0.01
 Cl3-C33 \\sim Cl3A-C33A
 with sigma of 0.01
 Cl1-Cl2 \\sim Cl1A-Cl2A
 with sigma of 0.01
 Cl1-Cl3 \\sim Cl1A-Cl3A
 with sigma of 0.01
 Cl2-Cl3 \\sim Cl2A-Cl3A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Cl3 \\sim Cl1 \\sim C33 \\sim Cl2 \\sim Cl3A \\sim C33A \\sim Cl1A \\sim Cl2A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl1) = Uanis(Cl1A)
Uanis(Cl2) = Uanis(Cl2A)
Uanis(Cl3) = Uanis(Cl3A)
4. Rigid body (RIGU) restrains
 Cl3, Cl1, C33, Cl2, Cl3A, C33A, Cl1A, Cl2A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(C33A)=Sof(H33A)=Sof(Cl1A)=Sof(Cl2A)=Sof(Cl3A)=1-FVAR(1)
 Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=Sof(C33)=Sof(H33)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C33(H33), C33A(H33A)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C13(H13), C15(H15), C16(H16), C22(H22),
 C23(H23), C24(H24), C25(H25), C26(H26), C28(H28), C29(H29), C30(H30), C31(H31),
  C32(H32)
6.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              53293
_shelx_hkl_checksum              43859
_olex2_submission_special_instructions 'No special instructions were received'