Enantioselective Intermolecular Excited-State Photoreactions Using a Chiral Ir Triplet Sensitizer: Separating Association from Energy Transfer in Asymmetric Photocatalysis.
Zheng, Jian; Swords, Wesley B.; Jung, Hoimin; Skubi, Kazimer L.; Kidd, Jesse B.; Meyer, Gerald J.; Baik, Mu-Hyun; Yoon, Tehshik P.; Journal of the American Chemical Society 141 (2019) 13625–13634; doi:10.1021/jacs.9b06244

data_4128905
_publ_section_title
;
 Enantioselective Intermolecular Excited-State Photoreactions Using a
 Chiral Ir Triplet Sensitizer: Separating Association from Energy Transfer
 in Asymmetric Photocatalysis.
;
_journal_issue                   34
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13625
_journal_page_last               13634
_journal_paper_doi               10.1021/jacs.9b06244
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C18 H21 N O6'
_chemical_formula_sum            'C18 H21 N O6'
_chemical_formula_weight         347.36
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   8.605(4)
_cell_length_b                   19.697(7)
_cell_length_c                   30.793(12)
_cell_measurement_reflns_used    9920
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.195
_cell_measurement_theta_min      2.171
_cell_volume                     5219(4)
_computing_cell_refinement       'SAINT+ Ver. 2018.1-0. (Bruker-AXS, 2018)'
_computing_data_collection       'APEX3 Ver. 2018.1-0. (Bruker-AXS, 2018)'
_computing_data_reduction        'SAINT+ Ver. 2018.1-0. (Bruker-AXS, 2018)'
_computing_molecular_graphics    'OLEX2 (Dolomanov et al., 2009)'
_computing_publication_material  'OLEX2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      99.97
_diffrn_detector                 'charge-coupled device (CCD) area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker APEX II'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II Quazar'
_diffrn_measurement_method       '0.5\% \w and 0.5\% \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_detector       'Bruker APEX II'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0459
_diffrn_reflns_av_unetI/netI     0.0359
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            55373
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         26.396
_diffrn_reflns_theta_min         1.227
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.100
_exptl_absorpt_correction_T_max  0.9585
_exptl_absorpt_correction_T_min  0.9110
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Krause et al., 2015) was used for absorption correction.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.326
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2208
_exptl_crystal_size_max          0.161
_exptl_crystal_size_mid          0.104
_exptl_crystal_size_min          0.041
_refine_diff_density_max         0.507
_refine_diff_density_min         -0.526
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 3486 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     793
_refine_ls_number_reflns         10690
_refine_ls_number_restraints     221
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0588
_refine_ls_R_factor_gt           0.0467
_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^)+(0.0469P)^2^+3.3052P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1095
_refine_ls_wR_factor_ref         0.1161
_reflns_Friedel_coverage         0.793
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                9076
_reflns_number_total             10690
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b06244_si_003.cif
_cod_data_source_block           yoon56
_cod_database_code               4128905
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.996
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O4A-C15A \\sim O3A-C19A
 with sigma of 0.005
 O3A-C14A \\sim O4A-C14A
 with sigma of 0.005
 N1B-H1BB \\sim N1A-H1A \\sim N1-H1
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uiso(O7) = Uiso(C19) = Uiso(C20) = Uiso(C21)
Uanis(O6A) = Uanis(C16A) = Uanis(C17A) = Uanis(C18A) = Uanis(C20A) =
Uanis(C21A) = Uanis(C22A)
Uiso(C25B) = Uiso(C23B) = Uiso(O11B) = Uiso(C24B)
4. Rigid body (RIGU) restrains
 C1B, O1B, O2B, C12B, C13B, O7B, O8B, C19B, C20B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C11, O7, C19, C20, C21} sigma for 1-2: 0.01, 1-3: 0.02
{C11A, O6A, C16A, C17A, C18A} sigma for 1-2: 0.01, 1-3: 0.02
{C11A, O6A, C20A, C21A, C22A} sigma for 1-2: 0.01, 1-3: 0.02
{C11B, O6B, C16B, C17B, C18B} sigma for 1-2: 0.01, 1-3: 0.02
{C11B, O11B, C23B, C24B, C25B} sigma for 1-2: 0.01, 1-3: 0.02
as
{C11, O6, C16, C17, C18}
{C1B, O7B, O8B, C19B, C20B} sigma for 1-2: 0.01, 1-3: 0.02
{C2B, O3B, O4B, C14B, C15B} sigma for 1-2: 0.01, 1-3: 0.02
{C2B, O9B, O10B, C21B, C22B} sigma for 1-2: 0.01, 1-3: 0.02
as
{C1B, O1B, O2B, C12B, C13B}
6. Others
 Sof(O7)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20E)=Sof(H20F)=Sof(H20G)=Sof(C21)=
 Sof(H21D)=Sof(H21E)=Sof(H21F)=1-FVAR(1)
 Sof(O6)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17G)=Sof(H17H)=Sof(H17I)=Sof(C18)=
 Sof(H18G)=Sof(H18H)=Sof(H18I)=FVAR(1)
 Sof(C19A)=Sof(H19A)=Sof(H19B)=Sof(H19C)=1-FVAR(2)
 Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=FVAR(2)
 Sof(C20A)=Sof(H20D)=Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22A)=
 Sof(H22D)=Sof(H22E)=Sof(H22F)=1-FVAR(3)
 Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C18A)=
 Sof(H18D)=Sof(H18E)=Sof(H18F)=FVAR(3)
 Sof(H1BA)=Sof(O7B)=Sof(O8B)=Sof(C19B)=Sof(C20B)=Sof(H20A)=Sof(H20B)=Sof(H20C)=
 1-FVAR(4)
 Sof(H1B)=Sof(O1B)=Sof(O2B)=Sof(C12B)=Sof(C13B)=Sof(H13A)=Sof(H13B)=Sof(H13C)=
 FVAR(4)
 Sof(O9B)=Sof(O10B)=Sof(C21B)=Sof(C22B)=Sof(H22A)=Sof(H22B)=Sof(H22C)=
 Sof(H2BA)=1-FVAR(5)
 Sof(O3B)=Sof(O4B)=Sof(C14B)=Sof(C15B)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(H2B)=
 FVAR(5)
 Sof(C23B)=Sof(H23B)=Sof(C24B)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25B)=
 Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(O11B)=1-FVAR(6)
 Sof(O6B)=Sof(C16B)=Sof(H16B)=Sof(C17B)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 Sof(C18B)=Sof(H18A)=Sof(H18B)=Sof(H18C)=FVAR(6)
7.a Ternary CH refined with riding coordinates:
 C16(H16), C19(H19), C1(H1C), C2(H2), C3(H3), C1A(H1AA), C2A(H2A), C16A(H16A),
 C20A(H20D), C1B(H1B), C1B(H1BA), C16B(H16B), C23B(H23B), C2B(H2B), C2B(H2BA),
 C3B(H3B)
7.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C5A(H5A), C6A(H6A), C7A(H7A), C8A(H8A),
 C5B(H5B), C6B(H6B), C7B(H7B), C8B(H8B)
7.c Idealised Me refined as rotating group:
 C17(H17G,H17H,H17I), C18(H18G,H18H,H18I), C20(H20E,H20F,H20G), C21(H21D,H21E,
 H21F), C13(H13G,H13H,H13I), C15(H15G,H15H,H15I), C13A(H13D,H13E,H13F),
 C15A(H15D,H15E,H15F), C19A(H19A,H19B,H19C), C17A(H17D,H17E,H17F), C18A(H18D,
 H18E,H18F), C21A(H21A,H21B,H21C), C22A(H22D,H22E,H22F), C13B(H13A,H13B,H13C),
 C20B(H20A,H20B,H20C), C15B(H15A,H15B,H15C), C22B(H22A,H22B,H22C), C17B(H17A,
 H17B,H17C), C18B(H18A,H18B,H18C), C24B(H24A,H24B,H24C), C25B(H25A,H25B,H25C)
;
_shelx_res_checksum              50477
_shelx_hkl_checksum              77308
_olex2_submission_special_instructions 'No special instructions were received'