Topology-Based Functionalization of Robust Chiral Zr-Based Metal-Organic Frameworks for Catalytic Enantioselective Hydrogenation.
Jiang, Hong; Zhang, Wenqiang; Kang, Xing; Cao, Ziping; Chen, Xu; Liu, Yan; Cui, Yong; Journal of the American Chemical Society 142 (2020) 9642–9652; doi:10.1021/jacs.0c00637

data_4134953
_publ_section_title
;
 Topology-Based Functionalization of Robust Chiral Zr-Based Metal-Organic
 Frameworks for Catalytic Enantioselective Hydrogenation.
;
_journal_issue                   21
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9642
_journal_page_last               9652
_journal_paper_doi               10.1021/jacs.0c00637
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         '0.13(C448 H240 O160 Zr24)'
_chemical_formula_sum            'C56 H30 O20 Zr3'
_chemical_formula_weight         1296.46
_space_group_crystal_system      orthorhombic
_space_group_IT_number           69
_space_group_name_Hall           '-F 2 2'
_space_group_name_H-M_alt        'F m m m'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-01-07
_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            8
_cell_length_a                   16.031(2)
_cell_length_b                   36.971(5)
_cell_length_c                   44.102(5)
_cell_measurement_reflns_used    9904
_cell_measurement_temperature    173
_cell_measurement_theta_max      27.410
_cell_measurement_theta_min      2.483
_cell_volume                     26138(6)
_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  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      173
_diffrn_measured_fraction_theta_full 0.435
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0968
_diffrn_reflns_av_unetI/netI     0.0408
_diffrn_reflns_Laue_measured_fraction_full 0.435
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            31094
_diffrn_reflns_point_group_measured_fraction_full 0.435
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         18.840
_diffrn_reflns_theta_min         2.135
_exptl_absorpt_coefficient_mu    0.267
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.4062
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1237 before and 0.0811 after correction.
The Ratio of minimum to maximum transmission is 0.5449.
The \l/2 correction factor is Not present.
;
_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    0.659
_exptl_crystal_description       octahedral
_exptl_crystal_F_000             5168
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.016
_refine_diff_density_min         -0.570
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     163
_refine_ls_number_reflns         2761
_refine_ls_number_restraints     262
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.1093
_refine_ls_R_factor_gt           0.0764
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0923P)^2^+702.6301P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1983
_refine_ls_wR_factor_ref         0.2325
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1868
_reflns_number_total             2761
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c00637_si_003.cif
_cod_data_source_block           flu-CMOF-2
_cod_depositor_comments
'Adding full bibliography for 4134951--4134954.cif.'
_cod_database_code               4134953
_shelxl_version_number           2013-2
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 C8-C17 = C17-C12 = C6-C12
 1.39 with sigma of 0.02
 C7-C17
 1.5 with sigma of 0.02
 C17-C19
 2.48 with sigma of 0.04
 C17-C20
 2.48 with sigma of 0.04
 C7-C8
 2.48 with sigma of 0.04
 C7-C12
 2.48 with sigma of 0.04
3. Restrained planarity
 O4, C6, C8, C12, C17
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
O4 \\sim C6 \\sim C8 \\sim C11 \\sim C16 \\sim C13 \\sim C22 \\sim C15 \\sim
C25 \\sim C24 \\sim C19 \\sim C7 \\sim C20 \\sim C12 \\sim C17 \\sim C18 \\sim
O0AA \\sim O9: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
Uanis(Zr1) = Uanis(Zr2)
5. Rigid body (RIGU) restrains
 O4, C6, C8, C11, C16, C13, C22, C15, C25, C24, C19, C7, C20, C12, C17, C18,
 O0AA, O9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C11(H11), C13(H13), C22(H22), C24(H24), C19(H19), C20(H20)
6.b Naphthalene refined as free rotating group:
 C11(C16,C13,C22,C15,C25,C24,C19,C7,C20)
6.c Idealised tetrahedral OH refined as rotating group:
 O4(H4)
;
_shelx_res_checksum              73787
_shelx_hkl_checksum              12192
_shelx_fab_checksum              40744
_olex2_submission_special_instructions 'No special instructions were received'