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_4127442
_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         'C43 H55 N3, C4 H10 O'
_chemical_formula_sum            'C47 H65 N3 O'
_chemical_formula_weight         688.02
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 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                 91.294(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.636(8)
_cell_length_b                   9.669(3)
_cell_length_c                   15.648(6)
_cell_measurement_reflns_used    9954
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      27.970
_cell_measurement_theta_min      2.950
_cell_volume                     4180(2)
_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      100.0
_diffrn_measured_fraction_theta_full 0.937
_diffrn_measured_fraction_theta_max 0.924
_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  0.0228
_diffrn_reflns_av_unetI/netI     0.0387
_diffrn_reflns_Laue_measured_fraction_full 0.937
_diffrn_reflns_Laue_measured_fraction_max 0.924
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            15276
_diffrn_reflns_point_group_measured_fraction_full 0.802
_diffrn_reflns_point_group_measured_fraction_max 0.747
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.712
_diffrn_reflns_theta_min         2.949
_exptl_absorpt_coefficient_mu    0.064
_exptl_absorpt_correction_T_max  0.9144
_exptl_absorpt_correction_T_min  0.7703
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0813 before and 0.0369 after correction. The Ratio of minimum to maximum transmission is 0.8424. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.093
_exptl_crystal_description       plate
_exptl_crystal_F_000             1504
_exptl_crystal_recrystallization_method
'The material was recrystallised from Diethylether by slow evaporation'
_exptl_crystal_size_max          0.255
_exptl_crystal_size_mid          0.158
_exptl_crystal_size_min          0.083
_refine_diff_density_max         0.529
_refine_diff_density_min         -0.295
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 2691 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -1.1(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     519
_refine_ls_number_reflns         8887
_refine_ls_number_restraints     97
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0715
_refine_ls_R_factor_gt           0.0682
_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^)+(0.1099P)^2^+4.0407P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1856
_refine_ls_wR_factor_ref         0.1886
_reflns_Friedel_coverage         0.532
_reflns_Friedel_fraction_full    0.647
_reflns_Friedel_fraction_max     0.549
_reflns_number_gt                8327
_reflns_number_total             8887
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04249_si_002.cif
_cod_data_source_block           0505_cg_0m
_cod_database_code               4127442
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.984
_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
 C47-C46 \\sim C44-C45
 with sigma of 0.02
 O1-C46 \\sim O1-C44
 with sigma of 0.02
 C47-O1 \\sim O1-C45
 with sigma of 0.04
 C49-C48 \\sim C50-C51
 with sigma of 0.02
 O2-C48 \\sim O2-C50
 with sigma of 0.02
 C49-O2 \\sim O2-C51
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O1 \\sim C44 \\sim C45 \\sim C46 \\sim C47: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
O2 \\sim C48 \\sim C49 \\sim C50 \\sim C51: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 O1, C44, C45, C46, C47
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2, C48, C49, C50, C51
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: O1(0.5) C44(0.5) H44A(0.5) H44B(0.5) C45(0.5) H45A(0.5) H45B(0.5)
 H45C(0.5) C46(0.5) H46A(0.5) H46B(0.5) C47(0.5) H47A(0.5) H47B(0.5) H47C(0.5)
 O2(0.5) C48(0.5) H48A(0.5) H48B(0.5) C49(0.5) H49A(0.5) H49B(0.5) H49C(0.5)
 C50(0.5) H50A(0.5) H50B(0.5) C51(0.5) H51A(0.5) H51B(0.5) H51C(0.5)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C18(H18)
6.b Secondary CH2 refined with riding coordinates:
 C44(H44A,H44B), C46(H46A,H46B), C48(H48A,H48B), C50(H50A,H50B)
6.c Me refined with riding coordinates:
 C45(H45A,H45B,H45C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C), C51(H51A,H51B,
 H51C)
6.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C7(H7), C9(H9), C20(H20), C21(H21), C28(H28), C30(H30),
 C37(H37), C39(H39)
6.e Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C24(H24A,H24B,H24C), C25(H25A,
 H25B,H25C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C),
 C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C)
;
_shelx_res_checksum              30216
_shelx_hkl_checksum              43450
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 800'
_olex2_submission_special_instructions 'No special instructions were received'