Bifunctional carbenium dications as metal-free catalysts for the reduction of oxygen.
Karimi, Mohammadjavad; Borthakur, Rosmita; Dorsey, Christopher L.; Chen, Chang-Hong; Lajeune, Sébastien; Gabbai, Francois P.; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c04841

data_4135142
_publ_section_title
;
 Bifunctional carbenium dications as metal-free catalysts for the
 reduction of oxygen.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c04841
_journal_year                    2020
_chemical_formula_moiety         '2(B F4), C41 H28 O3, C4 H10 O, C2 H3 N'
_chemical_formula_sum            'C47 H41 B2 F8 N O4'
_chemical_formula_weight         857.43
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-04-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.688(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.1316(12)
_cell_length_b                   9.3794(8)
_cell_length_c                   23.3395(16)
_cell_measurement_reflns_used    2555
_cell_measurement_temperature    163
_cell_measurement_theta_max      58.3010
_cell_measurement_theta_min      3.7660
_cell_volume                     3964.8(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      163
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    177.08 272.08   1.00   20.00    -- -104.11 -59.25-179.92   95
  2  \w    177.08 272.08   1.00   20.00    -- -104.11 -59.25  20.08   95
  3  \w    177.08 272.08   1.00   20.00    -- -104.11 -59.25 100.08   95
  4  \w   -135.74 -24.74   1.00   20.00    -- -104.11  83.74 -29.95  111
  5  \w    177.08 272.08   1.00   20.00    -- -104.11 -59.25 140.08   95
  6  \f   -114.17 -84.17   1.00   20.00  -3.01 -11.57 -30.17    --    30
  7  \w   -135.74 -24.74   1.00   20.00    -- -104.11  83.74-149.95  111
  8  \w    177.08 272.08   1.00   20.00    -- -104.11 -59.25  60.08   95
  9  \w    177.08 272.08   1.00   20.00    -- -104.11 -59.25 -19.92   95
 10  \w    -14.62  80.38   1.00   20.00    --    2.13  59.25 123.92   95
 11  \f   -340.18  19.82   1.00   20.00 -87.29-104.11 -58.55    --   360
 12  \w   -135.74 -24.74   1.00   20.00    -- -104.11  83.74-109.95  111
 13  \w   -135.74 -24.74   1.00   20.00    -- -104.11  83.74  90.05  111
 14  \w   -135.74 -24.74   1.00   20.00    -- -104.11  83.74 -69.95  111
 15  \f   -192.33 124.67   1.00   20.00 -24.61-104.11  30.17    --   317
 16  \w   -135.74 -24.74   1.00   20.00    -- -104.11  83.74 130.05  111
 17  \f    -42.17 196.83   1.00   20.00 -95.55-104.11 -30.17    --   239
 18  \w   -135.74 -24.74   1.00   20.00    -- -104.11  83.74  50.05  111
 19  \f   -340.18  19.82   1.00   20.00 -72.29 -89.11 -58.55    --   360
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0640187000
_diffrn_orient_matrix_UB_12      -0.0755295000
_diffrn_orient_matrix_UB_13      -0.0334590000
_diffrn_orient_matrix_UB_21      -0.0554808000
_diffrn_orient_matrix_UB_22      0.0693933000
_diffrn_orient_matrix_UB_23      0.0394388000
_diffrn_orient_matrix_UB_31      -0.0075975000
_diffrn_orient_matrix_UB_32      0.1282887000
_diffrn_orient_matrix_UB_33      -0.0411372000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.2493
_diffrn_reflns_av_unetI/netI     0.0765
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            70109
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        58.999
_diffrn_reflns_theta_max         58.999
_diffrn_reflns_theta_min         3.792
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.979
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.24428
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.436
_exptl_crystal_description       block
_exptl_crystal_F_000             1776
_exptl_crystal_preparation
'Obtained by dehydration of the corresponding carbinol with HBF4'
_exptl_crystal_recrystallization_method
'Crystalized from MeCN by diffusion of Et2O'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.467
_refine_diff_density_min         -0.480
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.002
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     611
_refine_ls_number_reflns         5676
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.003
_refine_ls_R_factor_all          0.1496
_refine_ls_R_factor_gt           0.1056
_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^)+(0.1000P)^2^+9.5000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2500
_refine_ls_wR_factor_ref         0.2827
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3365
_reflns_number_total             5676
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c04841_si_003.cif
_cod_data_source_block           data
_cod_database_code               4135142
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C45H38O4B2F8
_shelx_estimated_absorpt_t_max   0.953
_shelx_estimated_absorpt_t_min   0.828
_reflns_odcompleteness_completeness 99.35
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Uiso/Uaniso restraints and constraints
F6 \\sim F7 \\sim F8 \\sim F11 \\sim F12 \\sim F13: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
3. Others
 Sof(F9)=Sof(F10)=1-FVAR(1)
 Sof(F1)=Sof(F2)=FVAR(1)
 Sof(F11)=Sof(F12)=Sof(F13)=1-FVAR(2)
 Sof(F6)=Sof(F7)=Sof(F8)=FVAR(2)
4.a Secondary CH2 refined with riding coordinates:
 C42(H42A,H42B), C44(H44A,H44B)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C18(H18), C19(H19), C20(H20),
 C21(H21), C24(H24), C25(H25), C26(H26), C27(H27), C31(H31), C32(H32), C33(H33),
  C34(H34), C37(H37), C38(H38), C39(H39), C40(H40)
4.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C43(H43A,H43B,H43C), C45(H45A,H45B,
 H45C), C47(H47A,H47B,H47C)
;
_shelx_res_checksum              40032
_shelx_hkl_checksum              8911
_olex2_exptl_crystal_mounting_method Loop
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.851
_oxdiff_exptl_absorpt_empirical_full_min 0.462