Enantioselective Excited-State Photoreactions Controlled by a Chiral Hydrogen-Bonding Iridium Sensitizer.
Skubi, Kazimer L.; Kidd, Jesse B.; Jung, Hoimin; Guzei, Ilia A.; Baik, Mu-Hyun; Yoon, Tehshik P.; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b10586

data_4126743
_publ_section_title
;
 Enantioselective Excited-State Photoreactions Controlled by a Chiral
 Hydrogen-Bonding Iridium Sensitizer.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b10586
_journal_year                    2017
_chemical_formula_moiety
'C32 H17 F10 Ir N5, C H2 Cl2, C32 H12 B F24, 1.33(O)'
_chemical_formula_sum            'C65 H31 B Cl2 F34 Ir N5 O1.34'
_chemical_formula_weight         1823.26
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-06-08
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2016.05.11 svn.r3296 for OlexSys, GUI svn.r5177)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.629(9)
_cell_length_b                   18.192(7)
_cell_length_c                   14.314(4)
_cell_measurement_reflns_used    9968
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.59
_cell_measurement_theta_min      2.38
_cell_volume                     6674(4)
_computing_cell_refinement       'SAINT+ Ver. 2015.9-0 (Bruker-AXS, 2015)'
_computing_data_collection       'APEX3 Ver. 2015.9-0 (Bruker-AXS, 2015)'
_computing_data_reduction        'SAINT+ Ver. 2015.9-0 (Bruker-AXS, 2015)'
_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      100.01
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '0.5\% \w and 0.5\% \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_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  0.0504
_diffrn_reflns_av_unetI/netI     0.0423
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            126769
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.573
_diffrn_reflns_theta_min         1.373
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    2.225
_exptl_absorpt_correction_T_max  0.4330
_exptl_absorpt_correction_T_min  0.3923
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Krause et al., 2015) was used for absorption correction.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.815
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3555
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.769
_refine_diff_density_min         -1.606
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.048(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1070
_refine_ls_number_reflns         20454
_refine_ls_number_restraints     808
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0427
_refine_ls_R_factor_gt           0.0321
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0371P)^2^+2.6538P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0740
_refine_ls_wR_factor_ref         0.0763
_reflns_Friedel_coverage         0.930
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                17018
_reflns_number_total             20454
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            5f.cif
_cod_data_source_block           yoon45
_cod_database_code               4126743
_shelx_estimated_absorpt_t_max   0.916
_shelx_estimated_absorpt_t_min   0.690
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.952(5) 0.048(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
3. Restrained distances
 C47-F17 \\sim C47-F18 \\sim C47-F19 \\sim C47-F17A \\sim C47-F18A \\sim
C47-F19A \\sim C48-F20 \\sim C48-
 F21 \\sim C48-F22 \\sim C48-F20A \\sim C48-F21A \\sim C48-F22A \\sim C64-F32
\\sim C64-F33 \\sim C64-F34 ~
 C64-F32A \\sim C64-F33A \\sim C64-F34A
 with sigma of 0.004
 F17-F18 \\sim F17-F18 \\sim F18-F19 \\sim F17A-F18A \\sim F17A-F18A \\sim
F18A-F19A \\sim F20-F21 ~
 F20-F22 \\sim F21-F22 \\sim F20A-F21A \\sim F20A-F22A \\sim F21A-F22A \\sim
F32-F33 \\sim F32-F34 ~
 F33-F34 \\sim F32A-F33A \\sim F32A-F34A \\sim F33A-F34A
 with sigma of 0.008
4. Uiso/Uaniso restraints and constraints
Uanis(F34) \\sim Ueq, Uanis(F33A) \\sim Ueq, Uanis(F34A) \\sim Ueq, Uanis(F32)
\\sim Ueq, Uanis(F19) \\sim Ueq, Uanis(F19A) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(F18) \\sim Ueq, Uanis(F18A) \\sim Ueq: with sigma of 0.006 and sigma for
terminal atoms of 0.012
Uanis(F21A) = Uanis(F22)
Uanis(F21) = Uanis(F20A)
Uanis(F20) = Uanis(F22A)
Uanis(F17A) = Uanis(F17)
Uanis(O1) = Uanis(O1A)
Uanis(N3A) = Uanis(N4A) = Uanis(N5A) = Uanis(C25A) = Uanis(C26A) = Uanis(C27A)
= Uanis(C28A) = Uanis(C29A) = Uanis(C30A) = Uanis(C31A) = Uanis(C32A)
5. Rigid body (RIGU) restrains
 F34A, F11, C39, F12, F13, C35, C34, C36, C33, C37, C38, B1, C40, C41, C49,
 C57, F14, F15, F16, C42, C46, C50, C54, C58, C62, C43, C45, C51, C53, C59, C61,
  C44, C47, C48, C52, C55, C56, C60, C63, C64, F17A, F18A, F19A, F20A, F21A,
 F22A, F23, F24, F25, F26, F27, F28, F29, F30, F31, F32A, F33A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(N3A)=Sof(N4A)=Sof(H4A)=Sof(N5A)=Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=
 Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(C30A)=Sof(C31A)=
 Sof(H31A)=Sof(C32A)=Sof(H32A)=1-FVAR(1)
 Sof(N3)=Sof(N4)=Sof(N5)=Sof(H5)=Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26)=Sof(C27)=
 Sof(H27)=Sof(C28)=Sof(H28)=Sof(C29)=Sof(C30)=Sof(C31)=Sof(H31)=Sof(C32)=
 Sof(H32)=FVAR(1)
 Sof(F17A)=Sof(F18A)=Sof(F19A)=1-FVAR(2)
 Sof(F17)=Sof(F18)=Sof(F19)=FVAR(2)
 Sof(F32A)=Sof(F33A)=Sof(F34A)=1-FVAR(3)
 Sof(F32)=Sof(F33)=Sof(F34)=FVAR(3)
 Sof(F20A)=Sof(F21A)=Sof(F22A)=1-FVAR(4)
 Sof(F20)=Sof(F21)=Sof(F22)=FVAR(4)
 Sof(O1A)=1-FVAR(5)
 Sof(O1)=FVAR(5)
7.a Free rotating group:
 N3A(N4A,N5A,C25A,C26A,C27A,C28A,C29A,C30A,C31A,C32A)
7.b Secondary CH2 refined with riding coordinates:
 C65(H65A,H65B)
7.c Aromatic/amide H refined with riding coordinates:
 N5(H5), C25(H25), C26(H26), C27(H27), C28(H28), C31(H31), C32(H32), N4A(H4A),
 C25A(H25A), C26A(H26A), C27A(H27A), C28A(H28A), C31A(H31A), C32A(H32A), C2(H2),
  C4(H4), C8(H8), C9(H9), C11(H11), C14(H14), C16(H16), C20(H20), C21(H21),
 C23(H23), C34(H34), C36(H36), C38(H38), C42(H42), C44(H44), C46(H46), C50(H50),
  C52(H52), C54(H54), C58(H58), C60(H60), C62(H62)
;
_shelx_res_checksum              82985
_shelx_hkl_checksum              89245
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'