Rapid Post-Synthetic Modification of Porous Coordination Cages with Copper-Catalyzed Click Chemistry
Dworzak, Michael; Montone, Christine M.; Halaszynski, Nicole Irene; Yap, Glenn P. A.; Kloxin, Christopher; Bloch, Eric D.; Chemical Communications  (2023) –; doi:10.1039/D3CC02015K

data_7131718
_publ_section_title
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 Rapid Post-Synthetic Modification of Porous Coordination Cages with
 Copper-Catalyzed Click Chemistry
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_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC02015K
_journal_year                    2023
_chemical_formula_moiety         'C248 H228 Co16 O92 S16, 40[C3H7NO]'
_chemical_formula_sum            'C368 H508 Co16 N40 O132 S16'
_chemical_formula_weight         9059.95
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.12.01 svn.r5f60950 for OlexSys, GUI svn.r6408)
;
_audit_update_record
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2022-07-18 deposited with the CCDC.	2023-05-26 downloaded from the CCDC.
;
_cell_angle_alpha                92.828(6)
_cell_angle_beta                 96.711(6)
_cell_angle_gamma                111.522(5)
_cell_formula_units_Z            1
_cell_length_a                   20.642(2)
_cell_length_b                   20.651(3)
_cell_length_c                   28.167(4)
_cell_measurement_reflns_used    9706
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      48.00
_cell_measurement_theta_min      2.62
_cell_volume                     11038(3)
_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 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 0.963
_diffrn_measured_fraction_theta_max 0.963
_diffrn_measurement_device_type  'Bruker Venture Photon'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1038
_diffrn_reflns_av_unetI/netI     0.0946
_diffrn_reflns_Laue_measured_fraction_full 0.963
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            103251
_diffrn_reflns_point_group_measured_fraction_full 0.963
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        48.126
_diffrn_reflns_theta_max         48.126
_diffrn_reflns_theta_min         1.587
_diffrn_source_current           1.2
_diffrn_source_power             0.06
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.001
_exptl_absorpt_correction_T_max  0.7494
_exptl_absorpt_correction_T_min  0.4906
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.1514 before and 0.1042 after correction.
The Ratio of minimum to maximum transmission is 0.6547.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.363
_exptl_crystal_description       block
_exptl_crystal_F_000             4740
_exptl_crystal_size_max          0.127
_exptl_crystal_size_mid          0.091
_exptl_crystal_size_min          0.013
_refine_diff_density_max         1.659
_refine_diff_density_min         -1.839
_refine_diff_density_rms         0.192
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.746
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1612
_refine_ls_number_reflns         20055
_refine_ls_number_restraints     3300
_refine_ls_restrained_S_all      1.720
_refine_ls_R_factor_all          0.1871
_refine_ls_R_factor_gt           0.1579
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_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          0.4143
_refine_ls_wR_factor_ref         0.4364
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14607
_reflns_number_total             20055
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc02015k2.cif
_cod_data_source_block           eric542a
_cod_original_cell_volume        11038(2)
_cod_database_code               7131718
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.926
_shelx_estimated_absorpt_t_min   0.516
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O2-H2
 0.82 with sigma of 0.02
 C7_12-C8_12 = C7_12-C9_12 = C7_12-C10_12
 1.534 with sigma of 0.011
 C5_8-O5_8
 1.37 with sigma of 0.011
 O1-H1
 0.82 with sigma of 0.02
 C11_2-C12
 -2 with sigma of 0.02
 O5_1-C10_1 \\sim O5_2-C10_2 \\sim O5_7-C10_7 \\sim O5_8-C10_8
 with sigma of 0.02
 C8_12-C9_12 \\sim C9_12-C10_12 \\sim C10_12-C8_12
 with sigma of 0.02
 C5_1-C9_1 \\sim C5_2-C9_2 \\sim C5_7-C9_7 \\sim C5_8-C9_8
 with sigma of 0.02
 H2-Co5 \\sim H2-Co8 \\sim H2-Co7 \\sim H2-Co6
 with sigma of 0.02
 C1_7-C3_7 \\sim C8_7-C7_7
 with sigma of 0.02
 C1_8-C3_8 \\sim C8_8-C7_8
 with sigma of 0.02
 C7_3-C12_3 \\sim C7_3-C9_3 \\sim C7_3-C10_3 \\sim C7_4-C12_4 \\sim C7_4-C9_4
\\sim C7_4-C10_4 ~
 C7_5-C12_5 \\sim C7_5-C9_5 \\sim C7_5-C10_5 \\sim C7_6-C9_6 \\sim C7_6-C10_6
\\sim C7_6-C12_6
 with sigma of 0.002
 C12_3-C9_3 \\sim C9_3-C10_3 \\sim C10_3-C12_3 \\sim C12_4-C9_4 \\sim
C9_4-C10_4 \\sim C10_4-C12_4
 \\sim C12_5-C9_5 \\sim C9_5-C10_5 \\sim C10_5-C12_5 \\sim C9_6-C10_6 \\sim
C10_6-C12_6 \\sim C12_6-C9_6
 with sigma of 0.002
 H1-Co1 \\sim H1-Co4 \\sim H1-Co3 \\sim H1-Co2
 with sigma of 0.02
 C7_9-C12 \\sim C7_9-C9_9 \\sim C7_9-C10_9
 with sigma of 0.02
 C12-C9_9 \\sim C9_9-C10_9 \\sim C10_9-C12
 with sigma of 0.02
3. Restrained planarity
 O5_8, C2_8, C3_8, C4_8, C5_8, C6_8, C7_8
 with sigma of 0.1
4. 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(O2) \\sim Ueq, Uanis(O1_9) \\sim Ueq, Uanis(O1_3) \\sim Ueq: with sigma
of 0.002 and sigma for terminal atoms of 0.004
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Free rotating group:
 O5(C9,C10,C11), O5(C9,C10,C11), O5(C9,C10,C11), C9(C10,C11)
6.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C9(H9A,H9B), C9(H9A,H9B), C9(H9A,H9B)
6.c Me refined with riding coordinates:
 C12(H12A,H12B,H12C), C12(H12A,H12B,H12C), C9(H9A,H9B,H9C), C10(H10A,H10B,
 H10C), C12(H12A,H12B,H12C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,
 H12B,H12C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C9(H9A,
 H9B,H9C), C10(H10A,H10B,H10C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,
 H12B,H12C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C9(H9A,
 H9B,H9C), C10(H10A,H10B,H10C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,
 H10C)
6.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C2(H2), C4(H4), C6(H6), C3(H3), C5(H5), C3(H3),
 C5(H5), C3(H3), C5(H5), C3(H3), C5(H5), C2(H2), C4(H4), C6(H6), C2(H2), C4(H4),
  C6(H6), C3(H3), C5(H5), C3(H3), C5(H5), C3(H3), C5(H5), C3(H3), C5(H5)
6.e Fitted hexagon refined as free rotating group:
 C2(C3,C4,C5,C6,C7), C2(C3,C4,C5,C6,C7), C2(C3,C4,C5,C6,C7), C2(C3,C4,C5,C6,C7)
6.f :
 C11(H11), C11(H11), C11(H11), C11(H11)
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_smtbx_masks_special_details
;
A solvent mask was calculated and 1673 electrons were 
found in a volume of 5852\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
40[C3H7NO] per Asymmetric Unit 
which account for 1600 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              64157
_shelx_hkl_checksum              3819
_shelx_fab_checksum              57259
_olex2_submission_special_instructions 'No special instructions were received'