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_4127284
_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         'C84 H68 O25 S4 Zn4'
_chemical_formula_sum            'C84 H68 O25 S4 Zn4'
_chemical_formula_weight         1867.10
_space_group_crystal_system      tetragonal
_space_group_IT_number           75
_space_group_name_Hall           'P 4'
_space_group_name_H-M_alt        'P 4'
_symmetry_space_group_name_Hall  'P 4'
_symmetry_space_group_name_H-M   'P 4'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-07-15
_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            1
_cell_length_a                   14.1506(13)
_cell_length_b                   14.1506(13)
_cell_length_c                   14.793(3)
_cell_measurement_reflns_used    203
_cell_measurement_temperature    260.84
_cell_measurement_theta_max      55.034
_cell_measurement_theta_min      3.984
_cell_volume                     2962.1(7)
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      260.84
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0683
_diffrn_reflns_av_unetI/netI     0.0760
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            27063
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.517
_diffrn_reflns_theta_min         1.992
_exptl_absorpt_coefficient_mu    0.925
_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    1.047
_exptl_crystal_description       block
_exptl_crystal_F_000             956
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_platon_squeeze_details
;
TITL N in P4
CELL   14.1506   14.1506   14.7930     90.00     90.00     90.00
SPGR P4
Q101 1.000 1.007 0.719 !       3.67 eA-3
C102 0.500 0.499 0.030 !       2.01 eA-3
C103 0.221 0.516 0.486 !       1.93 eA-3
C104 0.079 0.530 0.469 !       1.65 eA-3
C105 0.142 0.525 0.461 !       1.53 eA-3
C106 0.262 0.549 0.436 !       1.49 eA-3
C107 0.206 0.474 0.515 !       1.46 eA-3
C108 0.290 0.451 0.549 !       1.42 eA-3
C109 0.243 0.503 0.548 !       1.39 eA-3
C110 0.525 0.739 0.486 !       1.36 eA-3
C111 0.937 0.107 0.830 !       1.22 eA-3
C112 0.542 0.254 0.499 !       1.19 eA-3
C113 0.545 0.889 0.423 !       1.18 eA-3
C114 0.249 0.604 0.388 !       1.18 eA-3
C115 0.968 0.118 0.815 !       1.18 eA-3
C116 0.188 0.571 0.432 !       1.17 eA-3
C117 0.340 0.426 0.450 !       1.13 eA-3
C118 0.062 0.515 0.429 !       1.13 eA-3
C119 0.307 0.404 0.593 !       1.10 eA-3
C120 0.840 0.031 0.829 !       1.09 eA-3
C121 0.353 0.453 0.565 !       1.09 eA-3
C122 0.984 0.949 0.786 !       1.08 eA-3
C123 1.000 1.008 0.858 !       1.06 eA-3
C124 0.419 0.464 0.590 !       1.06 eA-3
C125 0.219 0.549 0.361 !       1.06 eA-3
C126 0.307 0.503 0.530 !       1.06 eA-3
C127 0.529 1.009 0.395 !       1.05 eA-3
C128 0.482 0.469 0.589 !       1.05 eA-3
C129 0.422 0.422 0.550 !       1.03 eA-3
C130 0.169 0.455 0.457 !       1.03 eA-3
C131 0.777 0.016 0.840 !       1.02 eA-3
C132 0.798 0.910 0.855 !       1.01 eA-3
C133 0.163 0.582 0.367 !       0.99 eA-3
Q134 0.831 0.201 0.000 !       0.98 eA-3
C135 0.499 0.504 0.514 !       0.98 eA-3
C136 0.500 1.005 0.455 !       0.98 eA-3
C137 0.458 0.511 0.630 !       0.97 eA-3
C138 0.939 0.948 0.769 !       0.96 eA-3
C139 0.579 0.984 0.430 !       0.96 eA-3
C140 0.498 0.493 0.093 !       0.96 eA-3
Q141 0.202 0.610 0.342 !       0.95 eA-3
C142 0.353 0.424 0.372 !       0.92 eA-3
C143 0.398 0.515 0.317 !       0.90 eA-3
C144 0.853 0.077 0.846 !       0.90 eA-3
C145 0.284 0.567 0.343 !       0.89 eA-3
C146 0.403 0.760 0.554 !       0.88 eA-3
C147 0.517 0.716 0.563 !       0.88 eA-3
C148 0.347 0.553 0.342 !       0.88 eA-3
C149 0.325 0.504 0.363 !       0.87 eA-3
C150 0.392 0.488 0.360 !       0.86 eA-3
C151 0.133 0.621 0.413 !       0.86 eA-3
C152 0.337 0.530 0.451 !       0.86 eA-3
C153 0.296 0.618 0.499 !       0.86 eA-3
C154 0.334 0.614 0.374 !       0.86 eA-3
C155 0.380 0.524 0.393 !       0.85 eA-3
C156 0.452 0.498 0.354 !       0.85 eA-3
C157 0.970 0.031 0.824 !       0.83 eA-3
C158 0.999 0.991 0.203 !       0.81 eA-3
C159 0.425 0.308 0.496 !       0.80 eA-3
C160 0.894 0.097 0.901 !       0.80 eA-3
C161 0.909 0.051 0.776 !       0.80 eA-3
C162 0.291 0.355 0.547 !       0.79 eA-3
C163 0.376 0.523 0.582 !       0.78 eA-3
Q164 0.858 0.174 0.820 !       0.78 eA-3
Q165 0.073 0.427 0.516 !       0.77 eA-3
C166 0.803 0.106 0.827 !       0.77 eA-3
C167 0.155 0.515 0.378 !       0.76 eA-3
Q168 0.104 0.437 0.471 !       0.74 eA-3
C169 0.365 0.388 0.564 !       0.74 eA-3
C170 0.397 0.605 0.595 !       0.73 eA-3
Q171 0.189 0.530 0.604 !       0.72 eA-3
C172 0.359 0.356 0.604 !       0.72 eA-3
Q173 0.124 0.477 0.513 !       0.72 eA-3
C174 0.334 0.356 0.485 !       0.72 eA-3
C175 0.468 0.465 0.318 !       0.71 eA-3
Q176 0.157 0.565 0.320 !       0.71 eA-3
C177 0.358 0.593 0.456 !       0.71 eA-3
C178 0.381 0.594 0.418 !       0.71 eA-3
C179 0.916 0.051 0.853 !       0.70 eA-3
C180 0.433 0.487 0.137 !       0.70 eA-3
C181 0.872 0.905 0.989 !       0.70 eA-3
Q182 0.149 0.427 0.529 !       0.70 eA-3
C183 0.813 0.951 0.827 !       0.69 eA-3
C184 0.347 0.624 0.534 !       0.69 eA-3
C185 0.330 0.558 0.283 !       0.68 eA-3
C186 0.470 0.048 0.355 !       0.68 eA-3
C187 0.484 0.422 0.420 !       0.68 eA-3
C188 0.497 0.497 0.780 !       0.68 eA-3
C189 0.500 0.487 0.374 !       0.67 eA-3
Q190 0.266 0.543 0.233 !       0.67 eA-3
Q191 0.738 0.138 0.877 !       0.67 eA-3
Q192 0.081 0.474 0.357 !       0.66 eA-3
C193 0.373 0.558 0.522 !       0.66 eA-3
Q194 0.851 0.154 0.744 !       0.65 eA-3
Q195 0.827 0.945 0.986 !       0.65 eA-3
Q196 0.287 0.457 0.325 !       0.65 eA-3
C197 0.945 1.003 0.156 !       0.65 eA-3
Q198 0.312 0.649 0.298 !       0.65 eA-3
C199 0.334 0.531 0.144 !       0.64 eA-3
;
_refine_diff_density_max         0.333
_refine_diff_density_min         -0.215
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 1408 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.040(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.925
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     254
_refine_ls_number_reflns         6828
_refine_ls_number_restraints     203
_refine_ls_restrained_S_all      0.969
_refine_ls_R_factor_all          0.0993
_refine_ls_R_factor_gt           0.0453
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0660P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1062
_refine_ls_wR_factor_ref         0.1278
_reflns_Friedel_coverage         0.922
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                3873
_reflns_number_total             6828
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07633_si_001.cif
_cod_data_source_block           n_sq
_cod_original_cell_volume        2962.1(8)
_cod_database_code               4127284
_shelx_shelxl_version_number     2016/4
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.982
_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. Restrained distances
 C18-C17
 1.5 with sigma of 0.02
 C19-C17
 2.5 with sigma of 0.02
 C17-C21
 2.5 with sigma of 0.02
 C19-C21
 2.5 with sigma of 0.02
 C17-C20
 2.5 with sigma of 0.02
 C19-C20
 2.5 with sigma of 0.02
 C21-C20
 2.5 with sigma of 0.02
 C17-C18 = C19-C18 = C20-C18 = C21-C18
 1.5 with sigma of 0.02
 C19-C18 = C17-C18 = C20-C18 = C21-C18
 1.48 with sigma of 0.02
 C19-C20 \\sim C20-C21
 with sigma of 0.02
 C20-C21 \\sim C21-C19
 with sigma of 0.02
 C21-C19 \\sim C19-C20
 with sigma of 0.02
3. Restrained planarity
 C18, C17, C16, C12, C13, C15, C14
 with sigma of 0.1
4. Rigid bond restraints
 C16, C18, C12
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C10, C11, C2, C4, C9, C3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C10, C11
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O7, C11, C10, C9, C4, C3, C2, C1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C21, C17, C19
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C19, C17, C20
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C20, C17, C21
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C18, C20, C21, C19, C17, C12, C13, C14, C15, C16
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C20, C18, C21, C19, C17, C12, C13, C14, C15, C16
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C21, C19, C20
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C19, C21, C20
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C19, C20, C21
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C16 \\sim C18 \\sim C12: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C10 \\sim C11 \\sim C2 \\sim C3 \\sim C4 \\sim C9: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
C10 \\sim C11: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
O7 \\sim C11 \\sim C10 \\sim C9 \\sim C4 \\sim C3 \\sim C2: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C21 \\sim C17 \\sim C19: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C19 \\sim C17 \\sim C20: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C20 \\sim C17 \\sim C21: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C15 \\sim C14 \\sim C13 \\sim C12 \\sim C17 \\sim C16 \\sim C18 \\sim C21 \\sim
C20 \\sim C19: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C20 \\sim C21 \\sim C19 \\sim C18 \\sim C17 \\sim C12 \\sim C13 \\sim C14 \\sim
C15 \\sim C16: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C19 \\sim C20 \\sim C21: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C21 \\sim C19 \\sim C20: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C19 \\sim C21 \\sim C20: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Uanis(C16) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C17) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C18) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C19) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C21) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C20) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
6.a Me refined with riding coordinates:
 C21(H21A,H21B,H21C), C20(H20A,H20B,H20C), C19(H19A,H19B,H19C)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C8(H8), C6(H6), C5(H5), C7(H7), C16(H16), C12(H12)
6.c Fitted hexagon refined as free rotating group:
 C14(C15,C16,C17,C12,C13)
6.d Idealised tetrahedral OH refined as rotating group:
 O7(H7A)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'