Organic Redox Systems Based on Pyridinium-Carbene Hybrids.
Antoni, Patrick W.; Bruckhoff, Tim; Hansmann, Max M.; Journal of the American Chemical Society 141 (2019) 9701–9711; doi:10.1021/jacs.9b04249

data_4127448
_publ_section_title
;
 Organic Redox Systems Based on Pyridinium-Carbene Hybrids.
;
_journal_issue                   24
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9701
_journal_page_last               9711
_journal_paper_doi               10.1021/jacs.9b04249
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         '2(F6 Sb), 3.5(C4 H8 O), C55 H62 N6'
_chemical_formula_sum            'C69 H90 F12 N6 O3.5 Sb2'
_chemical_formula_weight         1530.96
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-04-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                86.506(3)
_cell_angle_beta                 74.026(3)
_cell_angle_gamma                81.296(3)
_cell_formula_units_Z            2
_cell_length_a                   11.7476(8)
_cell_length_b                   16.1366(13)
_cell_length_c                   20.0336(17)
_cell_measurement_reflns_used    9240
_cell_measurement_temperature    100.01
_cell_measurement_theta_max      29.627
_cell_measurement_theta_min      2.392
_cell_volume                     3608.3(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.01
_diffrn_measured_fraction_theta_full 0.999
_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           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0331
_diffrn_reflns_av_unetI/netI     0.0215
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            137779
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.661
_diffrn_reflns_theta_min         2.340
_exptl_absorpt_coefficient_mu    0.828
_exptl_absorpt_correction_T_max  0.3237
_exptl_absorpt_correction_T_min  0.2631
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1455 before and 0.0528 after correction. The Ratio of minimum to maximum transmission is 0.8128. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'dark yellow'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.409
_exptl_crystal_description       block
_exptl_crystal_F_000             1568
_exptl_crystal_recrystallization_method
'The material was recrystallised from thf by slow evaporation'
_exptl_crystal_size_max          0.658
_exptl_crystal_size_mid          0.392
_exptl_crystal_size_min          0.098
_refine_diff_density_max         2.772
_refine_diff_density_min         -2.744
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1025
_refine_ls_number_reflns         20362
_refine_ls_number_restraints     340
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0645
_refine_ls_R_factor_gt           0.0579
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0657P)^2^+9.1325P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1529
_refine_ls_wR_factor_ref         0.1582
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18008
_reflns_number_total             20362
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04249_si_012.cif
_cod_data_source_block           0560_pa_0m
_cod_original_formula_sum        'C69 H90 F12 N6 O3.50 Sb2'
_cod_database_code               4127448
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.923
_shelx_estimated_absorpt_t_min   0.612
_olex2_refinement_description
;
1. 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
2. Restrained distances
 C66-C67
 1.54 with sigma of 0.02
 C67-C65
 2.35 with sigma of 0.02
 C64-C66
 2.35 with sigma of 0.02
 C64-C67
 2.35 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C72 \\sim C73 \\sim C74: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
O3 \\sim C64 \\sim C65 \\sim C66 \\sim C67: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
O4 \\sim C68 \\sim C69 \\sim C70 \\sim C71: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
Uanis(F5B) = Uanis(F1A)
4. Rigid body (RIGU) restrains
 Sb1A, F1A, F2A, F3A, F4A, F5A, F6A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Sb1B, F1B, F2B, F3B, F4B, F5B, F6B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2, C60, C61, C62, C63
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1, C56, C57, C58, C59
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3, C64, C65, C66, C67
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O5, C72, C73, C74, C75
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 O4, C68, C69, C70, C71
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F7B)=Sof(F8B)=Sof(F9B)=Sof(F10B)=Sof(F11B)=Sof(F12B)=Sof(F1A)=Sof(Sb1B)=
 Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=Sof(F6B)=1-FVAR(1)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(Sb1A)=Sof(F2A)=
 Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(F5B)=FVAR(1)
 Fixed Sof: O3(0.5) C64(0.5) H64A(0.5) H64B(0.5) C65(0.5) H65A(0.5) H65B(0.5)
 C66(0.5) H66A(0.5) H66B(0.5) C67(0.5) H67A(0.5) H67B(0.5) O4(0.5) C68(0.5)
 H68A(0.5) H68B(0.5) C69(0.5) H69A(0.5) H69B(0.5) C70(0.5) H70A(0.5) H70B(0.5)
 C71(0.5) H71A(0.5) H71B(0.5) O5(0.5) C72(0.5) H72A(0.5) H72B(0.5) C73(0.5)
 H73A(0.5) H73B(0.5) C74(0.5) H74A(0.5) H74B(0.5) C75(0.5) H75A(0.5) H75B(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B), C60(H60A,
 H60B), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B), C11(H11A,H11B),
 C12(H12A,H12B), C13(H13A,H13B), C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B),
  C67(H67A,H67B), C68(H68A,H68B), C69(H69A,H69B), C70(H70A,H70B), C71(H71A,
 H71B), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B), C75(H75A,H75B)
6.b Aromatic/amide H refined with riding coordinates:
 C0BA(H0BA), C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C9AA(H9AA), C10(H10),
 C14(H14), C15(H15), C18(H18), C20(H20), C27(H27), C29(H29), C38(H38), C40(H40),
  C45(H45), C46(H46), C49(H49), C51(H51)
6.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C31(H31A,H31B,
 H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C42(H42A,H42B,H42C), C43(H43A,
 H43B,H43C), C44(H44A,H44B,H44C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C),
 C55(H55A,H55B,H55C)
;
_shelx_res_checksum              32408
_shelx_hkl_checksum              28169
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 800'
_olex2_submission_special_instructions 'No special instructions were received'