Acridine Photocatalysis: Insights into the Mechanism and Development of a Dual-Catalytic Direct Decarboxylative Conjugate Addition
Dang, Hang T.; Haug, Graham C.; Nguyen, Vu T.; Vuong, Ngan T. H.; Nguyen, Viet D.; Arman, Hadi D.; Larionov, Oleg V.; ACS Catalysis 10 (2020) 11448–11457; doi:10.1021/acscatal.0c03440

data_4518057
_publ_section_title
;
 Acridine Photocatalysis: Insights into the Mechanism and Development of a
 Dual-Catalytic Direct Decarboxylative Conjugate Addition
;
_journal_issue                   19
_journal_name_full               'ACS Catalysis'
_journal_page_first              11448
_journal_page_last               11457
_journal_paper_doi               10.1021/acscatal.0c03440
_journal_volume                  10
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         '0.5(H4 O2), 2(C64 H104 O6)'
_chemical_formula_sum            'C128 H210 O13'
_chemical_formula_weight         1956.95
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-02-22
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.10.09 svn.r3662 for Rigaku Oxford Diffraction, GUI svn.r5959)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.0090(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   27.5054(2)
_cell_length_b                   7.15900(10)
_cell_length_c                   28.9864(2)
_cell_measurement_reflns_used    22129
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.5830
_cell_measurement_theta_min      3.0510
_cell_volume                     5706.86(10)
_computing_cell_refinement       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.958
_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    -25.00  67.00   0.50    1.50    --   46.87 -68.00  47.00  184
  2  \w     34.00  82.00   0.50    6.00    --  106.69 -68.00  47.00   96
  3  \w     43.00  69.00   0.50    6.00    --  106.69 -61.00  90.00   52
  4  \w     39.00  69.00   0.50    6.00    --  106.69 -61.00 120.00   60
  5  \w     35.00  71.00   0.50    6.00    --  106.69 -61.00  60.00   72
  6  \w     36.00 100.00   0.50    6.00    --  106.69 -77.00   0.00  128
  7  \w     34.00 101.00   0.50    6.00    --  106.69 -77.00-150.00  134
  8  \w     34.00  59.00   0.50    6.00    --  106.69 -61.00-150.00   50
  9  \w     27.00 120.00   0.50    1.50    --   46.87  68.00-179.00  186
 10  \w     83.00 120.00   0.50    1.50    --   46.87  57.00-120.00   74
 11  \w     87.00 178.00   0.50    6.00    --  106.69  68.00-179.00  182
 12  \w    101.00 168.00   0.50    6.00    --  106.69  77.00-120.00  134
 13  \w     94.00 178.00   0.50    6.00    --  106.69  61.00 -60.00  168
 14  \w    -51.00 -16.00   0.50    6.00    --  -88.50  45.00  30.00   70
 15  \w    -51.00 -16.00   0.50    6.00    --  -88.50  45.00   0.00   70
 16  \w    -51.00 -16.00   0.50    6.00    --  -88.50  45.00 -30.00   70
 17  \w    -67.00  26.00   0.50    1.50    --  -46.87  68.00-179.00  186
 18  \w    -51.00 -16.00   0.50    6.00    --  -88.50  45.00-180.00   70
 19  \w    -82.00 -15.00   0.50    6.00    --  -88.50  68.00-179.00  134
 20  \w   -120.00 -27.00   0.50    1.50    --  -46.87 -68.00  47.00  186
 21  \w   -120.00 -87.00   0.50    1.50    --  -46.87-125.00-180.00   66
 22  \w   -160.00 -68.00   0.50    6.00    --  -88.50 -68.00  47.00  184
 23  \w   -160.00-101.00   0.50    6.00    --  -88.50 -77.00 120.00  118
 24  \w   -160.00-101.00   0.50    6.00    --  -88.50 -77.00 150.00  118
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0527657000
_diffrn_orient_matrix_UB_12      0.0674642000
_diffrn_orient_matrix_UB_13      0.0072458000
_diffrn_orient_matrix_UB_21      0.0177001000
_diffrn_orient_matrix_UB_22      -0.1521586000
_diffrn_orient_matrix_UB_23      -0.0333540000
_diffrn_orient_matrix_UB_31      -0.0064573000
_diffrn_orient_matrix_UB_32      0.1364347000
_diffrn_orient_matrix_UB_33      -0.0407307000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0268
_diffrn_reflns_av_unetI/netI     0.0245
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            29583
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.631
_diffrn_reflns_theta_min         3.050
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.547
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.608
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.63a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.139
_exptl_crystal_description       plank
_exptl_crystal_F_000             2164
_exptl_crystal_size_max          0.186
_exptl_crystal_size_mid          0.119
_exptl_crystal_size_min          0.043
_refine_diff_density_max         0.208
_refine_diff_density_min         -0.274
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Refined as a perfect inversion twin.
;
_refine_ls_abs_structure_Flack   0.5
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     658
_refine_ls_number_reflns         10160
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0354
_refine_ls_R_factor_gt           0.0343
_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^)+(0.0577P)^2^+1.9461P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0922
_refine_ls_wR_factor_ref         0.0931
_reflns_Friedel_coverage         0.843
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.955
_reflns_number_gt                9802
_reflns_number_total             10160
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c03440_si_006.cif
_cod_data_source_block           hpd095
_cod_depositor_comments
'Adding full bibliography for 4518056--4518062.cif.'
_cod_database_code               4518057
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         O6C32H54
_chemical_oxdiff_usercomment     972
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.905
_reflns_odcompleteness_completeness 99.53
_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, All O(H) groups, All O(H,H) groups
2. Restrained distances
 H1B-O3_$1
 2.05 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O1A) = Uanis(O1B) = Uanis(O2A) = Uanis(O2B)
4. Others
 Fixed Sof: H7C(0.5) H7D(0.5) O2A(0.8) O1A(0.8) H1A(0.8) O1B(0.2) H1B(0.2)
 O2B(0.2)
5.a Free rotating group:
 O7(H7C,H7D)
5.b Ternary CH refined with riding coordinates:
 C46(H46), C42(H42), C40(H40), C18(H18), C50(H50), C14(H14), C8(H8), C10(H10)
5.c Secondary CH2 refined with riding coordinates:
 C43(H43A,H43B), C55(H55A,H55B), C47(H47A,H47B), C44(H44A,H44B), C35(H35A,
 H35B), C39(H39A,H39B), C34(H34A,H34B), C38(H38A,H38B), C12(H12A,H12B),
 C22(H22A,H22B), C15(H15A,H15B), C56(H56A,H56B), C53(H53A,H53B), C19(H19A,H19B),
  C2(H2A,H2B), C21(H21A,H21B), C23(H23A,H23B), C54(H54A,H54B), C51(H51A,H51B),
 C6(H6A,H6B), C7(H7A,H7B), C11(H11A,H11B), C3(H3A,H3B), C24(H24A,H24B)
5.d Aromatic/amide H refined with riding coordinates:
 C48(H48), C16(H16)
5.e Idealised Me refined as rotating group:
 C59(H59A,H59B,H59C), C62(H62A,H62B,H62C), C58(H58A,H58B,H58C), C27(H27A,H27B,
 H27C), C30(H30A,H30B,H30C), C61(H61A,H61B,H61C), C26(H26A,H26B,H26C), C60(H60A,
 H60B,H60C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C28(H28A,H28B,H28C),
 C64(H64A,H64B,H64C), C63(H63A,H63B,H63C), C29(H29A,H29B,H29C)
5.f Idealised tetrahedral OH refined as rotating group:
 O6(H6), O5(H5), O3(H3), O1A(H1A), O1B(H1B)
;
_olex2_exptl_crystal_mounting_method 'nylon 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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.449
_oxdiff_exptl_absorpt_empirical_full_min 0.778