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_4127453
_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(C27 H31 N3), C4 H8 O1'
_chemical_formula_sum            'C58 H70 N6 O'
_chemical_formula_weight         867.20
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 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                 100.960(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.9721(18)
_cell_length_b                   18.650(2)
_cell_length_c                   17.0396(17)
_cell_measurement_reflns_used    9074
_cell_measurement_temperature    100.04
_cell_measurement_theta_max      30.515
_cell_measurement_theta_min      2.542
_cell_volume                     4983.2(9)
_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      99.95
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.986
_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  0.0332
_diffrn_reflns_av_unetI/netI     0.0228
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            98398
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.528
_diffrn_reflns_theta_min         2.184
_exptl_absorpt_coefficient_mu    0.069
_exptl_absorpt_correction_T_max  0.9011
_exptl_absorpt_correction_T_min  0.8445
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0698 before and 0.0516 after correction. The Ratio of minimum to maximum transmission is 0.9372. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.156
_exptl_crystal_description       block
_exptl_crystal_F_000             1872
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of thf and Diethylether  by slow evaporation'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.390
_refine_diff_density_min         -0.290
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     681
_refine_ls_number_reflns         15030
_refine_ls_number_restraints     65
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0595
_refine_ls_R_factor_gt           0.0469
_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^)+(0.0761P)^2^+1.5245P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1354
_refine_ls_wR_factor_ref         0.1472
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12048
_reflns_number_total             15030
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04249_si_005.cif
_cod_data_source_block           0542_cg_0m
_cod_original_cell_volume        4983.3(10)
_cod_database_code               4127453
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.993
_shelx_estimated_absorpt_t_min   0.980
_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
 O1B-C55B \\sim O1A-C55A
 with sigma of 0.02
 O1B-C58B \\sim O1A-C58A
 with sigma of 0.02
 C57B-C58B \\sim C57A-C58A
 with sigma of 0.02
 C57B-C56B \\sim C57A-C56A
 with sigma of 0.02
 C55B-C56B \\sim C55A-C56A
 with sigma of 0.02
 C29A-C28 \\sim C29B-C28
 with sigma of 0.02
 C29A-C33A \\sim C29B-C30B
 with sigma of 0.02
 C29A-C30A \\sim C29B-C33B
 with sigma of 0.02
 N6A-C32A \\sim N6B-C31B
 with sigma of 0.02
 N6A-C31A \\sim N6B-C32B
 with sigma of 0.02
 C33A-C32A \\sim C30B-C31B
 with sigma of 0.02
 C30A-C31A \\sim C33B-C32B
 with sigma of 0.02
 C29A-C32A \\sim C29B-C31B
 with sigma of 0.04
 C29A-C31A \\sim C29B-C32B
 with sigma of 0.04
 N6A-C33A \\sim N6B-C30B
 with sigma of 0.04
 N6A-C30A \\sim N6B-C33B
 with sigma of 0.04
 C28-C33A \\sim C28-C30B
 with sigma of 0.04
 C28-C30A \\sim C28-C33B
 with sigma of 0.04
 C33A-C30A \\sim C30B-C33B
 with sigma of 0.04
 C32A-C31A \\sim C31B-C32B
 with sigma of 0.04
 N6A-C34A \\sim N6B-C34B
 with sigma of 0.02
 C32A-C34A \\sim C31B-C34B
 with sigma of 0.04
 C31A-C34A \\sim C32B-C34B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
N6B \\sim C34B: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.001
N6A \\sim C34A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.001
Uanis(C31A) = Uanis(C31B)
Uanis(C30A) = Uanis(C30B)
Uanis(C29A) = Uanis(C29B)
Uanis(C33A) = Uanis(C33B)
Uanis(C32A) = Uanis(C32B)
4. Rigid body (RIGU) restrains
 O1B, C55B, C56B, C57B, C58B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O1B)=Sof(C55B)=Sof(H55C)=Sof(H55D)=Sof(C56B)=Sof(H56C)=Sof(H56D)=
 Sof(C57B)=Sof(H57C)=Sof(H57D)=Sof(C58B)=Sof(H58C)=Sof(H58D)=1-FVAR(1)
 Sof(O1A)=Sof(C55A)=Sof(H55A)=Sof(H55B)=Sof(C56A)=Sof(H56A)=Sof(H56B)=
 Sof(C57A)=Sof(H57A)=Sof(H57B)=Sof(C58A)=Sof(H58A)=Sof(H58B)=FVAR(1)
 Sof(N6B)=Sof(C29B)=Sof(C30B)=Sof(H30B)=Sof(C31B)=Sof(H31B)=Sof(C32B)=
 Sof(H32B)=Sof(C33B)=Sof(H33B)=Sof(C34B)=Sof(H34D)=Sof(H34E)=Sof(H34F)=1-FVAR(2)
 Sof(N6A)=Sof(C29A)=Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=Sof(C32A)=
 Sof(H32A)=Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C55A(H55A,H55B), C56A(H56A,H56B), C57A(H57A,H57B), C58A(H58A,H58B), C55B(H55C,
 H55D), C56B(H56C,H56D), C57B(H57C,H57D), C58B(H58C,H58D)
6.b Aromatic/amide H refined with riding coordinates:
 C0AA(H0AA), C3(H3), C4(H4), C6(H6), C8(H8), C9(H9), C12(H12), C14(H14),
 C21(H21), C23(H23), C35(H35), C36(H36), C39(H39), C41(H41), C48(H48), C50(H50),
  C30A(H30A), C31A(H31A), C32A(H32A), C33A(H33A), C30B(H30B), C31B(H31B),
 C32B(H32B), C33B(H33B)
6.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C43(H43A,
 H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C52(H52A,H52B,H52C),
 C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C34A(H34A,H34B,H34C), C34B(H34D,H34E,
 H34F)
;
_shelx_res_checksum              45536
_shelx_hkl_checksum              37323
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 800'
_olex2_submission_special_instructions 'No special instructions were received'