Tunable synthesis of heteroleptic zirconium-based porous coordination cages.
Morey, Merissa N.; Montone, Christine M.; Dworzak, Michael R.; Yap, Glenn P. A.; Bloch, Eric D.; Chemical science 16 (2025) 816–823; doi:10.1039/d4sc06023g

data_1573223
_publ_section_title
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 Tunable synthesis of heteroleptic zirconium-based porous coordination
 cages.
;
_journal_issue                   2
_journal_name_full               'Chemical science'
_journal_page_first              816
_journal_page_last               823
_journal_paper_doi               10.1039/d4sc06023g
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C58 H64 N2 O22 Zr6, 2(Cl), 4[C3H7NO]'
_chemical_formula_sum            'C70 H92 Cl2 N6 O26 Zr6'
_chemical_formula_weight         2051.71
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-01-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.12.01 svn.r5f60950 for OlexSys, GUI svn.r6408)
;
_audit_update_record
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2023-12-22 deposited with the CCDC.	2024-11-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.0277(6)
_cell_length_b                   31.9593(12)
_cell_length_c                   20.8847(8)
_cell_measurement_reflns_used    9700
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      56.91
_cell_measurement_theta_min      3.80
_cell_volume                     9362.9(6)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      120.0
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0490
_diffrn_reflns_av_unetI/netI     0.0294
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            43756
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        56.960
_diffrn_reflns_theta_max         56.960
_diffrn_reflns_theta_min         2.527
_diffrn_source_current           1.2
_diffrn_source_power             0.06
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.390
_exptl_absorpt_correction_T_max  0.7512
_exptl_absorpt_correction_T_min  0.5299
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.0855 before and 0.0530 after correction.
The Ratio of minimum to maximum transmission is 0.7054.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.456
_exptl_crystal_description       block
_exptl_crystal_F_000             4144
_exptl_crystal_size_max          0.204
_exptl_crystal_size_mid          0.123
_exptl_crystal_size_min          0.072
_refine_diff_density_max         1.183
_refine_diff_density_min         -1.586
_refine_diff_density_rms         0.192
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.170
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     473
_refine_ls_number_reflns         6412
_refine_ls_number_restraints     414
_refine_ls_restrained_S_all      1.143
_refine_ls_R_factor_all          0.1161
_refine_ls_R_factor_gt           0.1118
_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^)+323.8655P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2385
_refine_ls_wR_factor_ref         0.2408
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6002
_reflns_number_total             6412
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06023g2.cif
_cod_data_source_block           eric635
_cod_depositor_comments          'Adding full bibliography for 1573223.cif.'
_cod_database_code               1573223
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.656
_shelx_estimated_absorpt_t_min   0.356
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C26-C23 \\sim C25-C23 \\sim C24-C23 \\sim C34-C33 \\sim C35-C33 \\sim C33-C36
 with sigma of 0.02
 C26-C24 \\sim C24-C25 \\sim C25-C26 \\sim C34-C35 \\sim C35-C36 \\sim C36-C34
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.004 and sigma
for terminal atoms of 0.008 within 2A
Uanis(C2) = Uanis(C2A)
Uanis(C3) = Uanis(C3A)
Uanis(C4) = Uanis(C4A)
Uanis(C5) = Uanis(C5A)
Uanis(C1) = Uanis(C1A)
4. Others
 Sof(C1A)=Sof(H1AA)=Sof(C2A)=Sof(H2AA)=Sof(C3A)=Sof(H3AA)=Sof(C4A)=Sof(H4A)=
 Sof(C5A)=Sof(H5A)=1-FVAR(1)
 Sof(C1)=Sof(H1B)=Sof(C2)=Sof(H2B)=Sof(C3)=Sof(H3A)=Sof(C4)=Sof(H4)=Sof(C5)=
 Sof(H5)=FVAR(1)
 Fixed Sof: O9(0.5) O12(0.5) N1(0.5) H1A(0.5) N2(0.5) H2A(0.5) C22(0.5)
 C23(0.5) C24(0.5) H24A(0.5) H24B(0.5) H24C(0.5) C25(0.5) H25A(0.5) H25B(0.5)
 H25C(0.5) C26(0.5) H26A(0.5) H26B(0.5) H26C(0.5) C32(0.5) C33(0.5) C34(0.5)
 H34A(0.5) H34B(0.5) H34C(0.5) C35(0.5) H35A(0.5) H35B(0.5) H35C(0.5) C36(0.5)
 H36A(0.5) H36B(0.5) H36C(0.5)
5.a Ternary CH refined with riding coordinates:
 C1(H1B), C2(H2B), C3(H3A), C4(H4), C5(H5), C1A(H1AA), C5A(H5A)
5.b Me refined with riding coordinates:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C34(H34A,H34B,
 H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C)
5.c Aromatic/amide H refined with riding coordinates:
 O1(H1), O2(H2), O3(H3), N1(H1A), N2(H2A), C2A(H2AA), C3A(H3AA), C4A(H4A),
 C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16), C18(H18), C20(H20), C28(H28), C30(H30)
5.d Fitted pentagon refined as free rotating group:
 C1(C2,C3,C4,C5), C1A(C2A,C3A,C4A,C5A)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 614 electrons were 
found in a volume of 3451\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
4[C3H7NO] per Asymmetric Unit 
which account for 640 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              53001
_shelx_hkl_checksum              41118
_shelx_fab_checksum              32260
_olex2_submission_special_instructions 'No special instructions were received'