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_4127444
_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         'F6 Sb, C48 H51 N3, 0.5(C4 H8 O)'
_chemical_formula_sum            'C50 H55 F6 N3 O0.5 Sb'
_chemical_formula_weight         941.72
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-04-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.596(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.130(9)
_cell_length_b                   18.914(7)
_cell_length_c                   13.580(5)
_cell_measurement_reflns_used    9134
_cell_measurement_temperature    99.97
_cell_measurement_theta_max      27.85
_cell_measurement_theta_min      2.45
_cell_volume                     4463(3)
_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      99.97
_diffrn_measured_fraction_theta_full 0.999
_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           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0508
_diffrn_reflns_av_unetI/netI     0.0327
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_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            62328
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.933
_diffrn_reflns_theta_min         2.344
_exptl_absorpt_coefficient_mu    0.682
_exptl_absorpt_correction_T_max  0.3884
_exptl_absorpt_correction_T_min  0.3522
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0898 before and 0.0548 after correction. The Ratio of minimum to maximum transmission is 0.8978. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.402
_exptl_crystal_description       needle
_exptl_crystal_F_000             1940
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of thf and Diethylether  by slow evaporation'
_exptl_crystal_size_max          0.536
_exptl_crystal_size_mid          0.036
_exptl_crystal_size_min          0.022
_refine_diff_density_max         0.605
_refine_diff_density_min         -0.625
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     608
_refine_ls_number_reflns         10665
_refine_ls_number_restraints     558
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.0436
_refine_ls_R_factor_gt           0.0304
_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^)+(0.0274P)^2^+3.2501P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0652
_refine_ls_wR_factor_ref         0.0705
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8714
_reflns_number_total             10665
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04249_si_013.cif
_cod_data_source_block           p21c
_cod_original_formula_sum        'C50 H55 F6 N3 O0.50 Sb'
_cod_database_code               4127444
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.711
_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
 C52-C51 \\sim C51-C50 \\sim C50-C49
 with sigma of 0.02
 O1-C52 \\sim O1-C49
 with sigma of 0.02
 O1-C51 \\sim O1-C50
 with sigma of 0.04
 C51-C49 \\sim C52-C50
 with sigma of 0.04
 C5AA-C8B \\sim C5AA-C8A
 with sigma of 0.02
 C5AA-C9B \\sim C5AA-C9A
 with sigma of 0.02
 C5AA-C10B \\sim C5AA-C10A
 with sigma of 0.02
 C8B-H8BA \\sim C8A-H8AA
 with sigma of 0.02
 C8B-H8BB \\sim C8A-H8AB
 with sigma of 0.02
 C8B-H8BC \\sim C8A-H8AC
 with sigma of 0.02
 C9B-H9BA \\sim C9A-H9AA
 with sigma of 0.02
 C9B-H9BB \\sim C9A-H9AB
 with sigma of 0.02
 C9B-H9BC \\sim C9A-H9AC
 with sigma of 0.02
 C10B-H10A \\sim C10A-H10D
 with sigma of 0.02
 C10B-H10B \\sim C10A-H10E
 with sigma of 0.02
 C10B-H10C \\sim C10A-H10F
 with sigma of 0.02
 C5AA-H8BA \\sim C5AA-H8AA
 with sigma of 0.04
 C5AA-H8BB \\sim C5AA-H8AB
 with sigma of 0.04
 C5AA-H8BC \\sim C5AA-H8AC
 with sigma of 0.04
 C5AA-H9BA \\sim C5AA-H9AA
 with sigma of 0.04
 C5AA-H9BB \\sim C5AA-H9AB
 with sigma of 0.04
 C5AA-H9BC \\sim C5AA-H9AC
 with sigma of 0.04
 C5AA-H10A \\sim C5AA-H10D
 with sigma of 0.04
 C5AA-H10B \\sim C5AA-H10E
 with sigma of 0.04
 C5AA-H10C \\sim C5AA-H10F
 with sigma of 0.04
 H8BA-H8BB \\sim H8AA-H8AB
 with sigma of 0.04
 H8BA-H8BC \\sim H8AA-H8AC
 with sigma of 0.04
 H8BB-H8BC \\sim H8AB-H8AC
 with sigma of 0.04
 H9BA-H9BB \\sim H9AA-H9AB
 with sigma of 0.04
 H9BA-H9BC \\sim H9AA-H9AC
 with sigma of 0.04
 H9BB-H9BC \\sim H9AB-H9AC
 with sigma of 0.04
 H10A-H10B \\sim H10D-H10E
 with sigma of 0.04
 H10A-H10C \\sim H10D-H10F
 with sigma of 0.04
 H10B-H10C \\sim H10E-H10F
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O1 \\sim C49 \\sim C50 \\sim C51 \\sim C52: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
C9B \\sim C9A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.001
C8B \\sim C8A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.001
C10B \\sim C10A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.001
4. Rigid body (RIGU) restrains
 O1, C49, C50, C51, C52
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1, N2, N3, C1, C2, C3, C4, C5, C5AA, C6, C7, C8, C9, C10, C11, C12, C17, C18,
  C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33,
 C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45, C46, C47, C48, C8B,
  C9B, C10B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C5AA, C8B, C9B, C10B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C5AA, C8A, C9A, C10A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=
 Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=1-FVAR(1)
 Sof(C8B)=Sof(H8BA)=Sof(H8BB)=Sof(H8BC)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=Sof(H9BC)=
 Sof(C10B)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(1)
 Fixed Sof: O1(0.5) C49(0.5) H49A(0.5) H49B(0.5) C50(0.5) H50A(0.5) H50B(0.5)
 C51(0.5) H51A(0.5) H51B(0.5) C52(0.5) H52A(0.5) H52B(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C30(H30A,H30B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,
 H51B), C52(H52A,H52B)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28),
  C33(H33), C35(H35), C42(H42), C44(H44)
6.c Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C46(H46A,H46B,
 H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C8B(H8BA,H8BB,H8BC), C9B(H9BA,
 H9BB,H9BC), C10B(H10A,H10B,H10C), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC),
 C10A(H10D,H10E,H10F)
;
_shelx_res_checksum              30596
_shelx_hkl_checksum              75347
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 800'
_olex2_submission_special_instructions 'No special instructions were received'