Chiral FLPs-Catalyzed Asymmetric Hydrogenation of 3-Fluorinated Chromones
Dai, Yun; Meng, Wei; Feng, Xiangqing; Du, Haifeng; Chemical Communications  (2022) –; doi:10.1039/D1CC06964K

data_7129465
_publ_section_title
;
 Chiral FLPs-Catalyzed Asymmetric Hydrogenation of 3-Fluorinated Chromones
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC06964K
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C13 H9 F O2 S'
_chemical_formula_sum            'C13 H9 F O2 S'
_chemical_formula_weight         248.26
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-31
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-10-11 deposited with the CCDC.	2021-12-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.30320(10)
_cell_length_b                   8.3138(2)
_cell_length_c                   24.4770(7)
_cell_measurement_reflns_used    13268
_cell_measurement_temperature    170.00(10)
_cell_measurement_theta_max      30.9920
_cell_measurement_theta_min      1.6380
_cell_volume                     1079.18(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45i (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45i (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45i (Rigaku OD, 2018)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      170.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.933
_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    -42.00 -16.00   0.50    2.00    --    5.00  45.00 150.00   52
  2  \w    -42.00 -16.00   0.50    2.00    --    5.00  45.00 120.00   52
  3  \w   -101.00  58.00   0.50    2.00    --  -11.60  45.00  90.00  318
  4  \w      1.00  27.00   0.50    2.00    --  -11.60  45.00 -19.45   52
  5  \w   -101.00  75.00   0.50    2.00    --  -11.60  45.00  30.00  352
  6  \w    -19.00  77.00   0.50    2.00    --  -11.60  45.00 177.58  192
  7  \w    -82.00 -49.00   0.50    2.00    --  -11.60  45.00 177.58   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC10 (RCD3): fixed-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1177354000
_diffrn_orient_matrix_UB_12      0.0199796000
_diffrn_orient_matrix_UB_13      -0.0119722000
_diffrn_orient_matrix_UB_21      0.0631411000
_diffrn_orient_matrix_UB_22      -0.0457748000
_diffrn_orient_matrix_UB_23      0.0202862000
_diffrn_orient_matrix_UB_31      -0.0073096000
_diffrn_orient_matrix_UB_32      -0.0691320000
_diffrn_orient_matrix_UB_33      -0.0168775000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0199
_diffrn_reflns_av_unetI/netI     0.0140
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.933
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            17206
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.908
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.833
_diffrn_reflns_theta_min         1.664
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.298
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72892
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.45i (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.528
_exptl_crystal_description       block
_exptl_crystal_F_000             512
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.255
_refine_diff_density_min         -0.207
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 1153 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     191
_refine_ls_number_reflns         3076
_refine_ls_number_restraints     124
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0270
_refine_ls_R_factor_gt           0.0257
_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^)+(0.0494P)^2^+0.0913P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0722
_refine_ls_wR_factor_ref         0.0729
_reflns_Friedel_coverage         0.658
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.872
_reflns_number_gt                2951
_reflns_number_total             3076
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc06964k2.cif
_cod_data_source_block           mx9580
_cod_database_code               7129465
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHOFS
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 S1-C4 = S1-C1 = S1A-C1 = S1A-C4A
 1.72 with sigma of 0.01
 C2-C1 = C4-C3 = C4A-C3A = C2A-C1
 1.38 with sigma of 0.01
 C3A-C2A = C3-C2
 1.42 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
S1 \\sim C2 \\sim C3 \\sim C4 \\sim C2A \\sim C3A \\sim C4A \\sim S1A: within
1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
Uanis(S1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim
Ueq, Uanis(C2A) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C4A) \\sim Ueq,
Uanis(S1A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(S1A)=1-FVAR(1)
 Sof(S1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C10(H10)
5.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C6(H6), C7(H7), C13(H13), C2A(H2A), C3A(H3A), C4A(H4A)
;
_shelx_res_checksum              17410
_shelx_hkl_checksum              87570
_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 1.508
_oxdiff_exptl_absorpt_empirical_full_min 0.660