Catalysts Confined in Programmed Framework Pores Enable New Transformations and Tune Reaction Efficiency and Selectivity.
Zhou, Tian-You; Auer, Bernhard; Lee, Seok J.; Telfer, Shane G.; Journal of the American Chemical Society 141 (2019) 1577–1582; doi:10.1021/jacs.8b11221

data_4128099
_publ_section_title
;
 Catalysts Confined in Programmed Framework Pores Enable New
 Transformations and Tune Reaction Efficiency and Selectivity.
;
_journal_issue                   4
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1577
_journal_page_last               1582
_journal_paper_doi               10.1021/jacs.8b11221
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         '0.33(C627 H723 N6 O81 Zn24)'
_chemical_formula_sum            'C209 H241 N2 O27 Zn8'
_chemical_formula_weight         3735.98
_space_group_crystal_system      cubic
_space_group_IT_number           200
_space_group_name_Hall           '-P 2 2 3'
_space_group_name_H-M_alt        'P m -3'
_symmetry_space_group_name_Hall  '-P 2 2 3'
_symmetry_space_group_name_H-M   'P m -3'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
????
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            3
_cell_length_a                   29.8348(4)
_cell_length_b                   29.8348(4)
_cell_length_c                   29.8348(4)
_cell_measurement_reflns_used    22443
_cell_measurement_temperature    153.0
_cell_measurement_theta_max      72.0
_cell_measurement_theta_min      2.6
_cell_volume                     26556.4(6)
_computing_cell_refinement       'FSProcess in Process-Auto (Rigaku, 1998)'
_computing_data_collection       'CrystalClear (Rigaku, 2005)'
_computing_data_reduction        'FSProcess in Process-Auto (Rigaku, 1998)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      153.0
_diffrn_detector                 'Image plate'
_diffrn_detector_area_resol_mean 10
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_device_type  'Rigaku Spider'
_diffrn_measurement_method       \w-scans
_diffrn_radiation_monochromator  'Rigaku VariMax-HF Confocal Optical System'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0552
_diffrn_reflns_av_unetI/netI     0.0509
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            24709
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        63.662
_diffrn_reflns_theta_max         63.662
_diffrn_reflns_theta_min         5.548
_diffrn_source                   'Rigaku MM007 rotating anode'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.879
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.327
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   '(ABSCOR; Higashi, 1995)'
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.701
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Prism
_exptl_crystal_F_000             5895
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.732
_refine_diff_density_min         -1.334
_refine_diff_density_rms         0.147
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.776
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     373
_refine_ls_number_reflns         7627
_refine_ls_number_restraints     547
_refine_ls_restrained_S_all      1.811
_refine_ls_R_factor_all          0.1806
_refine_ls_R_factor_gt           0.1660
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4414
_refine_ls_wR_factor_ref         0.4553
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5604
_reflns_number_total             7627
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b11221_si_003.cif
_cod_data_source_block           ba1133_hhtt
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_crystal_density_meas' value 'not measured' was changed to '?'
- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 
;
_cod_original_cell_volume        26556.4(11)
_cod_database_code               4128099
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.720
_shelx_estimated_absorpt_t_min   0.668
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-C3
 1.41 with sigma of 0.005
 C6-C5 = C7-C6 = C8-C7
 1.51 with sigma of 0.02
 N2-C8
 1.46 with sigma of 0.01
 N2-C5
 1.48 with sigma of 0.01
 C4-N1
 1.385 with sigma of 0.001
 O6-C4
 1.228 with sigma of 0.001
 C5-C4
 1.541 with sigma of 0.001
 C16-C15 = C17-C16 = C17-C18
 1.39 with sigma of 0.01
 O6-N1
 2.324 with sigma of 0.001
 N1-C5
 2.433 with sigma of 0.001
 O6-C5
 2.428 with sigma of 0.001
 C5-C7
 2.416 with sigma of 0.01
 C5-C8
 2.358 with sigma of 0.01
 C6-C8
 2.379 with sigma of 0.01
 N2-C7
 2.327 with sigma of 0.01
 N2-C6
 2.411 with sigma of 0.01
 C3-C4
 2.489 with sigma of 0.001
 C35-C26 \\sim C36-C35 \\sim C37-C36 \\sim C37-C38 \\sim C39-C38 \\sim C39-C40
\\sim C29-C26 \\sim C30-C29
 \\sim C31-C32 \\sim C31-C30 \\sim C33-C32 \\sim C33-C34
 with sigma of 0.0001
 C26-C30 \\sim C29-C31 \\sim C30-C32 \\sim C31-C33 \\sim C32-C34 \\sim C26-C36
\\sim C35-C37 \\sim C36-C38
 \\sim C37-C39 \\sim C38-C40
 with sigma of 0.001
 C16-C15 \\sim C17-C16 \\sim C17-C18
 with sigma of 0.02
 C15-C17 \\sim C16-C18
 with sigma of 0.02
 C15-C18 \\sim C16-C17_$1 \\sim C17-C16_$1
 with sigma of 0.02
3. Restrained planarity
 C17_$1, C16_$1, C15, C16, C18, C17
 with sigma of 0.0001
4. Uiso/Uaniso restraints and constraints
Uanis(C7) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32)
\\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C37) \\sim Ueq,
Uanis(C38) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C40) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.02
Uanis(N1) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(C5) \\sim
Ueq, Uanis(N2) \\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C17) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C12) \\sim Ueq, : with sigma of 0.05 and
sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 O2, C2, C1, C3, H3, N1
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C20, C20, C20, C25, C25, C25, C28, C28, C28, C27, C27, C27, C24, C24, C24,
 C26, C26, C26, C23, C23, C23, C21, C21, C21, C35, C35, C35, C29, C29, C29, C22,
  C22, C22, C30, C30, C30, C31, C31, C31, C36, C36, C36, C37, C37, C37
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 O4, C19, C20, C25, C28, C27, C24, C26, C23, C21, C35, C29, C22, C30, C31, C36,
  C37, O3
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 O4, C19, C20, C25, C28, C27, C24, C26, C23, C21, C35, C29, C22, C30, C31, C36,
  C37, C38, C39, C40, C32, C33, C34, O3
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C4, O6, C5, C6, C7, C8, N2, N1
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 O5, C10, C13, C12, H12, C14, C15, C18, C17, C16, C9
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.00001
6. Others
 Fixed Sof: H3(0.375) C14(0.25) C15(0.25) C18(0.25) H18(0.25) C17(0.5)
 H17(0.5) C16(0.5) H16(0.5) C33(0.5) H33A(0.5) H33B(0.5) C34(0.5) H34A(0.5)
 H34B(0.5) H34C(0.5) N1(0.125) H1(0.125) C4(0.125) O6(0.125) C5(0.125)
 H5(0.125) C6(0.125) H6A(0.125) H6B(0.125) C7(0.125) H7A(0.125) H7B(0.125)
 C8(0.125) H8A(0.0625) H8B(0.0625) N2(0.125) H2A(0.0625) H2B(0.0625)
 Fixed X: H3(0.43316) C40(0.786099) H40A(0.782729) H40B(0.808701)
 H40C(0.795609) C34(0.536129) H34A(0.504069) H34B(0.5535) H34C(0.54276)
 Fixed Y: H3(0.53772) C40(0.96087) H40A(0.969729) H40B(0.937149)
 H40C(0.986829) C34(0.635961) H34A(0.63567) H34B(0.631041) H34C(0.612101)
 Fixed Z: H3(0) C40(0.07584) H40A(0.04439) H40B(0.07817) H40C(0.09357)
 C34(0.395881) H34A(0.40302) H34B(0.423321) H34C(0.3743)
7.a Ternary CH refined with riding coordinates:
 C5(H5)
7.b Secondary CH2 refined with riding coordinates:
 C35(H35A,H35B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C36(H36A,
 H36B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C32(H32A,H32B),
 C33(H33A,H33B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), N2(H2A,H2B)
7.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C11(H11), C28(H28), C22(H22), C21(H21), C18(H18), C17(H17),
 C16(H16), N1(H1)
7.d Fitted hexagon refined as free rotating group:
 C20(C28,C27,C23,C22,C21)
;
_olex2_exptl_crystal_mounting_method
'The MOF crystal was mounted on a nylon loop with aid of fomblin oil under a cold stream.'
_olex2_submission_original_sample_id BA1133_hhtt
_olex2_submission_special_instructions 'No special instructions were received'