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_4134951
_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         '0.11(C522 H342 O153 Zr27)'
_chemical_formula_sum            'C58 H38 I0 N0 O17 Zr3'
_chemical_formula_weight         1280.54
_space_group_crystal_system      trigonal
_space_group_IT_number           155
_space_group_name_Hall           'R 3 2"'
_space_group_name_H-M_alt        'R 3 2 :H'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-01-02
_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                120
_cell_formula_units_Z            9
_cell_length_a                   30.5594(14)
_cell_length_b                   30.5594(14)
_cell_length_c                   25.331(3)
_cell_measurement_reflns_used    9799
_cell_measurement_temperature    173.0
_cell_measurement_theta_max      3.76
_cell_measurement_theta_min      59.27
_cell_volume                     20487(3)
_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)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173.0
_diffrn_measured_fraction_theta_full 0.801
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0813
_diffrn_reflns_av_unetI/netI     0.0489
_diffrn_reflns_Laue_measured_fraction_full 0.801
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            44425
_diffrn_reflns_point_group_measured_fraction_full 0.798
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         59.368
_diffrn_reflns_theta_min         2.414
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.133
_exptl_absorpt_correction_T_max  0.7516
_exptl_absorpt_correction_T_min  0.6231
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1282 before and 0.0906 after correction.
The Ratio of minimum to maximum transmission is 0.8290.
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    0.934
_exptl_crystal_description       block
_exptl_crystal_F_000             5778
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         2.457
_refine_diff_density_min         -0.962
_refine_diff_density_rms         0.129
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.51(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         6587
_refine_ls_number_restraints     460
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0845
_refine_ls_R_factor_gt           0.0685
_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^)+(0.1273P)^2^+146.1787P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1814
_refine_ls_wR_factor_ref         0.2040
_reflns_Friedel_coverage         0.879
_reflns_Friedel_fraction_full    0.795
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                5266
_reflns_number_total             6587
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c00637_si_006.cif
_cod_data_source_block           ith-CMOF-3
_cod_depositor_comments
'Adding full bibliography for 4134951--4134954.cif.'
_cod_original_sg_symbol_H-M      'R 3 2'
_cod_database_code               4134951
_shelxl_version_number           2013-2
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.49(2)
 0.51(2)
2. 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, All O(H,H) groups
3. Restrained distances
 O5-C29 = O4-C29 = O3-C18 = O2-C18
 1.27 with sigma of 0.02
 C18-C11 = C3-C8 = C5-C19 = C29-C22
 1.5 with sigma of 0.02
 C1-C2
 1.38 with sigma of 0.02
 C29-C21
 2.48 with sigma of 0.04
 C29-C23
 2.48 with sigma of 0.04
 C19-C4
 2.48 with sigma of 0.04
 C19-C6
 2.48 with sigma of 0.04
 C13-C3
 2.48 with sigma of 0.04
 C9-C3
 2.48 with sigma of 0.04
 C8-C2
 2.48 with sigma of 0.04
 C4-C8
 2.48 with sigma of 0.04
 C18-C12
 2.48 with sigma of 0.04
 C18-C10
 2.48 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
C29 \\sim C22 \\sim C23 \\sim C28 \\sim C27 \\sim C26 \\sim C25 \\sim C24 \\sim
C19 \\sim C20 \\sim C21 \\sim C5 \\sim C6 \\sim C0AA \\sim C2 \\sim C3 \\sim C4
\\sim O7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C18 \\sim C12 \\sim C14
\\sim C13 \\sim C15 \\sim C16 \\sim C17: within 1.7A with sigma of 0.04 and
sigma for terminal atoms of 0.08
O3 \\sim O2 \\sim O5 \\sim O9 \\sim O4 \\sim O6 \\sim O0AA \\sim O8: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(O5) = Uanis(O4) = Uanis(O6) = Uanis(O3) = Uanis(O2)
Uanis(C22) = Uanis(C29)
5. Rigid body (RIGU) restrains
 C28, C27, C26, C25, C24, C23, C22, C21, C20, C19, C13, C14, C15, C16, C17,
 C12, C11, C18, C10, C9, C8, H20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29, C22, C21, C20, C19, C24, C23, C28, C27, C26, C25, C5, C6, C0AA, C2, C4,
 C3, C1, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Rotating group:
 O1W(H1WA,H1WB)
6.b Me refined with riding coordinates:
 C1(H1A,H1B,H1C)
6.c Aromatic/amide H refined with riding coordinates:
 C21(H21), C20(H20), C28(H28), C27(H27), C26(H26), C25(H25), C4(H4), C10(H10),
 C9(H9), C17(H17), C16(H16), C15(H15), C14(H14)
6.d Fitted hexagon refined as free rotating group:
 C3(C4,C5,C6,C0AA,C2)
6.e Naphthalene refined as free rotating group:
 C22(C21,C20,C19,C24,C23,C28,C27,C26,C25), C11(C10,C9,C8,C13,C12,C17,C16,C15,
 C14)
6.f Idealised tetrahedral OH refined as rotating group:
 O7(H7)
;
_shelx_res_checksum              77016
_shelx_hkl_checksum              59530
_shelx_fab_checksum              68468
_olex2_submission_special_instructions 'No special instructions were received'