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_4134952
_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(C378 H270 O153 Zr27)'
_chemical_formula_sum            'C42 H30 O17 Zr3'
_chemical_formula_weight         1080.32
_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
_audit_creation_date             2020-01-17
_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                   30.654(4)
_cell_length_b                   30.654(4)
_cell_length_c                   24.900(7)
_cell_measurement_reflns_used    3843
_cell_measurement_temperature    173
_cell_measurement_theta_max      41.653
_cell_measurement_theta_min      2.433
_cell_volume                     20263(7)
_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 0.342
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1952
_diffrn_reflns_av_unetI/netI     0.1220
_diffrn_reflns_Laue_measured_fraction_full 0.342
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            15456
_diffrn_reflns_point_group_measured_fraction_full 0.334
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         39.968
_diffrn_reflns_theta_min         6.063
_exptl_absorpt_coefficient_mu    3.103
_exptl_absorpt_correction_T_max  0.7488
_exptl_absorpt_correction_T_min  0.4552
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1221 before and 0.0928 after correction.
The Ratio of minimum to maximum transmission is 0.6079.
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    0.797
_exptl_crystal_description       block
_exptl_crystal_F_000             4842
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.930
_refine_diff_density_min         -0.628
_refine_diff_density_rms         0.108
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.45(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.931
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     160
_refine_ls_number_reflns         2731
_refine_ls_number_restraints     385
_refine_ls_restrained_S_all      0.882
_refine_ls_R_factor_all          0.0979
_refine_ls_R_factor_gt           0.0543
_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^)+(0.0682P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1178
_refine_ls_wR_factor_ref         0.1356
_reflns_Friedel_coverage         0.841
_reflns_Friedel_fraction_full    0.325
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                1669
_reflns_number_total             2731
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c00637_si_004.cif
_cod_data_source_block           ith-CMOF-1
_cod_depositor_comments
'Adding full bibliography for 4134951--4134954.cif.'
_cod_original_cell_volume        20263(8)
_cod_original_sg_symbol_H-M      'R 3 2'
_cod_database_code               4134952
_shelxl_version_number           2013-2
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.55(3)
 0.45(3)
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
 C21-C18
 1.5 with sigma of 0.02
 O4-C21
 1.27 with sigma of 0.02
 C11-C14
 1.5 with sigma of 0.02
 O2-C14 = O3-C14
 1.27 with sigma of 0.02
 C15-C3 = C21-C18
 1.5 with sigma of 0.02
 C11-C14 = C8-C5
 1.5 with sigma of 0.02
 O3-C14 = O2-C14 = O5-C21 = O4-C21
 1.27 with sigma of 0.02
 Zr2-O7
 2.1 with sigma of 0.02
 C12-C14
 2.48 with sigma of 0.04
 C3-C20
 2.48 with sigma of 0.04
 C16-C3
 2.48 with sigma of 0.04
 C21-C19
 2.48 with sigma of 0.04
 C21-C17
 2.48 with sigma of 0.04
 C14-C10
 2.48 with sigma of 0.04
 C14-C12
 2.48 with sigma of 0.04
 C9-C5
 2.48 with sigma of 0.04
 C13-C5
 2.48 with sigma of 0.04
 C8-C6
 2.48 with sigma of 0.04
 C8-C4
 2.48 with sigma of 0.04
4. Restrained planarity
 C9, C10, C11, C12, C13, C8, C14
 with sigma of 0.1
 O4, C18, C21, O5
 with sigma of 0.1
 C16, C17, C18, C19, C20, C15, C21
 with sigma of 0.1
 C16, C17, C18, C19, C20, C15, C3, C21
 with sigma of 0.1
 C5, C9, C10, C11, C12, C13, C8, C14
 with sigma of 0.1
 C11, O2, O3, C14
 with sigma of 0.1
5. Rigid bond restraints
 C13, C12
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Uiso/Uaniso restraints and constraints
O4 \\sim C7 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C15 \\sim
C6 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C9 \\sim C10 \\sim C11
\\sim C12 \\sim C13 \\sim C8 \\sim O2 \\sim O3 \\sim C21 \\sim C14 \\sim O5
\\sim O1 \\sim O9 \\sim O8 \\sim O6: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
O1W \\sim O6: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C21 \\sim C18 \\sim C17 \\sim C16 \\sim C15 \\sim C20 \\sim C19 \\sim C3 \\sim
C2 \\sim C1 \\sim C6 \\sim C7 \\sim C5 \\sim C4 \\sim C8 \\sim C9 \\sim C13
\\sim C12 \\sim C11 \\sim C10 \\sim C14: within 1.7A with sigma of 0.04 and
sigma for terminal atoms of 0.08
Uanis(O1W) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(Zr2) = Uanis(Zr1)
Uanis(C3) = Uanis(C2) = Uanis(C1) = Uanis(C7) = Uanis(C18) = Uanis(C14)
Uanis(C3) = Uanis(C10)
Uanis(O4) = Uanis(O5) = Uanis(O1) = Uanis(O2) = Uanis(O3) = Uanis(O6) =
Uanis(O8) = Uanis(O9)
Uanis(O8) = Uanis(O7)
Uanis(O8) = Uanis(O1W)
7. Rigid body (RIGU) restrains
 C10, C11, C13
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11, C12, C13
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C17, C18, C21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2, C3, C4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C18, C17, C16, C15, C20, C19, C3, C2, C1, C6, C5, C4, C7, C8, C9, C13,
 C12, C11, C10, C14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
8.a Rotating group:
 O1W(H1WA,H1WB)
8.b Me refined with riding coordinates:
 C7(H7A,H7B,H7C)
8.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C17(H17), C19(H19), C20(H20), C4(H4), C9(H9), C10(H10), C12(H12),
 C13(H13)
8.d Fitted hexagon refined as free rotating group:
 C16(C17,C18,C19,C20,C15), C6(C1,C2,C3,C4,C5), C9(C10,C11,C12,C13,C8)
8.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              99315
_shelx_hkl_checksum              24959
_shelx_fab_checksum              65154
_olex2_submission_special_instructions 'No special instructions were received'