Boosting Enantioselectivity of Chiral Organocatalysts with Ultrathin Two-Dimensional Metal-Organic Framework Nanosheets.
Tan, Chunxia; Yang, Kuiwei; Dong, Jinqiao; Liu, Yuhao; Liu, Yan; Jiang, Jianwen; Cui, Yong; Journal of the American Chemical Society  (2019) –; doi:10.1021/jacs.9b07633

data_4127283
_publ_section_title
;
 Boosting Enantioselectivity of Chiral Organocatalysts with Ultrathin
 Two-Dimensional Metal-Organic Framework Nanosheets.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b07633
_journal_year                    2019
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C76 H76 O25 S4 Zn4, C2 H3 N, C3 H7 N O'
_chemical_formula_sum            'C81 H86 N2 O26 S4 Zn4'
_chemical_formula_weight         1893.23
_chemical_name_systematic        T3145
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-06-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                112.7680(10)
_cell_angle_beta                 103.6510(10)
_cell_angle_gamma                91.1570(10)
_cell_formula_units_Z            1
_cell_length_a                   13.9028(3)
_cell_length_b                   14.2795(3)
_cell_length_c                   16.7217(4)
_cell_measurement_reflns_used    9959
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      21.85
_cell_measurement_theta_min      2.26
_cell_volume                     2951.40(12)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.942
_diffrn_measured_fraction_theta_max 0.942
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0184
_diffrn_reflns_av_unetI/netI     0.0439
_diffrn_reflns_Laue_measured_fraction_full 0.942
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            32839
_diffrn_reflns_point_group_measured_fraction_full 0.936
_diffrn_reflns_point_group_measured_fraction_max 0.936
_diffrn_reflns_theta_full        61.695
_diffrn_reflns_theta_max         61.695
_diffrn_reflns_theta_min         4.544
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.054
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.065
_exptl_crystal_description       block
_exptl_crystal_F_000             978
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.01
_platon_squeeze_details
;
TITL T3145-a_0m_a.res in P1
CELL   13.9028   14.2795   16.7217    112.77    103.65     91.16
SPGR P1
C101 0.152 0.728 0.184 !       6.37 eA-3
C102 0.015 0.387 0.904 !       4.30 eA-3
C103 0.156 0.535 0.027 !       3.49 eA-3
C104 0.029 0.276 0.064 !       3.35 eA-3
C105 0.982 0.612 0.466 !       3.21 eA-3
C106 0.957 0.579 0.522 !       3.14 eA-3
C107 0.015 0.328 0.239 !       3.12 eA-3
C108 0.302 0.733 0.611 !       2.65 eA-3
C109 0.608 0.582 0.510 !       2.58 eA-3
C110 0.140 0.139 0.940 !       2.52 eA-3
C111 0.046 0.595 0.575 !       2.45 eA-3
C112 0.948 0.506 0.325 !       2.41 eA-3
C113 0.392 0.899 0.455 !       2.40 eA-3
C114 0.873 0.556 0.539 !       2.39 eA-3
C115 0.173 0.245 0.029 !       2.36 eA-3
C116 0.336 0.781 0.314 !       2.30 eA-3
C117 0.997 0.548 0.397 !       2.29 eA-3
C118 0.784 0.553 0.473 !       2.25 eA-3
C119 0.095 0.378 0.970 !       2.23 eA-3
C120 0.094 0.454 0.970 !       2.22 eA-3
C121 0.893 0.616 0.479 !       2.12 eA-3
C122 0.256 0.273 0.487 !       2.10 eA-3
C123 0.621 0.518 0.581 !       2.07 eA-3
C124 0.108 0.306 0.058 !       2.03 eA-3
C125 0.280 0.512 0.717 !       2.03 eA-3
C126 0.582 0.511 0.534 !       1.99 eA-3
C127 0.206 0.373 0.343 !       1.99 eA-3
C128 0.360 0.654 0.828 !       1.98 eA-3
C129 0.286 0.200 0.455 !       1.89 eA-3
C130 0.344 0.030 0.458 !       1.78 eA-3
C131 0.286 0.150 0.580 !       1.74 eA-3
C132 0.448 0.846 0.486 !       1.71 eA-3
C133 0.415 0.346 0.643 !       1.66 eA-3
C134 0.533 0.511 0.454 !       1.64 eA-3
C135 0.184 0.465 0.655 !       1.63 eA-3
C136 0.341 0.842 0.596 !       1.60 eA-3
C137 0.303 0.133 0.503 !       1.60 eA-3
C138 0.107 0.266 0.968 !       1.57 eA-3
C139 0.349 0.871 0.373 !       1.56 eA-3
C140 0.281 0.270 0.063 !       1.54 eA-3
C141 0.309 0.203 0.563 !       1.51 eA-3
C142 0.393 0.848 0.565 !       1.50 eA-3
C143 0.339 0.292 0.596 !       1.46 eA-3
C144 0.377 0.456 0.705 !       1.44 eA-3
C145 0.296 0.809 0.661 !       1.44 eA-3
C146 0.375 0.546 0.253 !       1.44 eA-3
C147 0.341 0.950 0.390 !       1.43 eA-3
C148 0.320 0.323 0.629 !       1.42 eA-3
C149 0.236 0.377 0.610 !       1.39 eA-3
C150 0.247 0.549 0.652 !       1.38 eA-3
C151 0.287 0.588 0.785 !       1.34 eA-3
C152 0.066 0.680 0.546 !       1.34 eA-3
C153 0.576 0.623 0.624 !       1.32 eA-3
C154 0.597 0.441 0.568 !       1.29 eA-3
C155 0.454 0.544 0.150 !       1.27 eA-3
C156 0.407 0.925 0.533 !       1.24 eA-3
C157 0.402 0.528 0.207 !       1.21 eA-3
C158 0.504 0.726 0.572 !       1.18 eA-3
C159 0.386 0.291 0.280 !       1.16 eA-3
C160 0.056 0.314 0.923 !       1.16 eA-3
C161 0.384 0.025 0.497 !       1.14 eA-3
C162 0.171 0.560 0.280 !       1.14 eA-3
C163 0.276 0.346 0.392 !       1.12 eA-3
C164 0.307 0.492 0.345 !       1.07 eA-3
C165 0.586 0.644 0.574 !       1.06 eA-3
C166 0.470 0.798 0.544 !       1.06 eA-3
C167 0.274 0.640 0.224 !       1.05 eA-3
C168 0.280 0.683 0.518 !       1.05 eA-3
C169 0.499 0.436 0.455 !       1.04 eA-3
C170 0.287 0.648 0.283 !       1.03 eA-3
C171 0.361 0.688 0.655 !       1.02 eA-3
C172 0.325 0.311 0.508 !       1.01 eA-3
C173 0.390 0.812 0.390 !       1.01 eA-3
C174 0.194 0.531 0.097 !       1.00 eA-3
C175 0.361 0.359 0.076 !       0.99 eA-3
C176 0.298 0.592 0.476 !       0.99 eA-3
C177 0.458 0.441 0.377 !       0.96 eA-3
C178 0.313 0.415 0.659 !       0.93 eA-3
C179 0.300 0.894 0.309 !       0.90 eA-3
C180 0.070 0.579 0.387 !       0.90 eA-3
C181 0.065 0.238 0.017 !       0.87 eA-3
C182 0.524 0.682 0.635 !       0.85 eA-3
C183 0.346 0.748 0.691 !       0.85 eA-3
C184 0.363 0.846 0.493 !       0.84 eA-3
C185 0.261 0.557 0.498 !       0.83 eA-3
C186 0.267 0.474 0.644 !       0.82 eA-3
Q187 0.028 0.081 0.893 !       0.81 eA-3
C188 0.248 0.800 0.574 !       0.79 eA-3
Q189 0.067 0.233 0.902 !       0.76 eA-3
C190 0.152 0.599 0.587 !       0.75 eA-3
C191 0.123 0.471 0.278 !       0.75 eA-3
C192 0.340 0.639 0.708 !       0.73 eA-3
C193 0.328 0.353 0.199 !       0.71 eA-3
Q194 0.070 0.109 0.931 !       0.71 eA-3
C195 0.285 0.273 0.165 !       0.70 eA-3
C196 0.317 0.568 0.318 !       0.70 eA-3
C197 0.286 0.486 0.502 !       0.69 eA-3
C198 0.533 0.598 0.448 !       0.68 eA-3
Q199 0.205 0.061 0.593 !       0.67 eA-3
;
_refine_diff_density_max         0.398
_refine_diff_density_min         -0.346
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 7560 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.032(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1056
_refine_ls_number_reflns         17236
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.0262
_refine_ls_R_factor_gt           0.0243
_refine_ls_shift/su_max          0.019
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0289P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0603
_refine_ls_wR_factor_ref         0.0608
_reflns_Friedel_coverage         0.988
_reflns_Friedel_fraction_full    0.930
_reflns_Friedel_fraction_max     0.930
_reflns_number_gt                16173
_reflns_number_total             17236
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07633_si_002.cif
_cod_data_source_block           t3145-a_0m_sq
_cod_database_code               4127283
_shelx_shelxl_version_number     2016/4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C72(H72), C31(H31), C21(H21), C5(H5), C25(H25), C11(H11), C35(H35),
 C61(H61), C15(H15), C44(H44), C54(H54), C80(H80)
2.b Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C65(H65A,H65B,H65C), C78(H78A,H78B,
 H78C), C38(H38A,H38B,H38C), C10(H10A,H10B,H10C), C8(H8A,H8B,H8C), C63(H63A,
 H63B,H63C), C74(H74A,H74B,H74C), C9(H9A,H9B,H9C), C76(H76A,H76B,H76C),
 C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C29(H29A,H29B,H29C), C28(H28A,H28B,
 H28C), C19(H19A,H19B,H19C), C47(H47A,H47B,H47C), C46(H46A,H46B,H46C), C57(H57A,
 H57B,H57C), C58(H58A,H58B,H58C), C81(H81A,H81B,H81C), C82(H82A,H82B,H82C),
 C30(H30A,H30B,H30C)
2.c Idealised tetrahedral OH refined as rotating group:
 O16(H16), O17(H17), O22(H22), O23(H23)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'