Enhanced organic dye adsorption and photocatalytic activity through a metal–organic framework featuring heptanuclear/binuclear clusters and cage cavities
Chen, Xi; Chen, Zi-tong; Zhu, Feng; Chen, Yuan; Liu, Ao-gang; Yin, Xue; Chen, Zi-ke; Li, Bao; CrystEngComm 26 (2024) 4489–4497; doi:10.1039/D4CE00484A

data_7249075
_publ_section_title
;
 Enhanced organic dye adsorption and photocatalytic activity through a
 metal--organic framework featuring heptanuclear/binuclear clusters and
 cage cavities
;
_journal_issue                   33
_journal_name_full               CrystEngComm
_journal_page_first              4489
_journal_page_last               4497
_journal_paper_doi               10.1039/D4CE00484A
_journal_volume                  26
_journal_year                    2024
_chemical_formula_moiety         'C120 H60 Cu9 N40 O22'
_chemical_formula_sum            'C120 H60 Cu9 N40 O22'
_chemical_formula_weight         2986.00
_space_group_crystal_system      orthorhombic
_space_group_IT_number           58
_space_group_name_Hall           '-P 2 2n'
_space_group_name_H-M_alt        'P n n m'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2024-07-16
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-07-16 deposited with the CCDC.	2024-07-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   29.618(2)
_cell_length_b                   15.2128(13)
_cell_length_c                   24.2347(11)
_cell_measurement_reflns_used    2994
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      0.790
_cell_measurement_theta_min      0.762
_cell_volume                     10919.5(13)
_computing_data_collection       'Bruker APEX-II CCD'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.710
_diffrn_reflns_av_R_equivalents  0.0779
_diffrn_reflns_av_unetI/netI     0.0831
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            26740
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.214
_diffrn_reflns_theta_max         25.747
_diffrn_reflns_theta_min         1.503
_exptl_absorpt_coefficient_mu    0.907
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    0.908
_exptl_crystal_description       block
_exptl_crystal_F_000             2994
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.26
_refine_diff_density_max         2.739
_refine_diff_density_min         -0.894
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     642
_refine_ls_number_reflns         10577
_refine_ls_number_restraints     249
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.1321
_refine_ls_R_factor_gt           0.0952
_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^)+(0.1925P)^2^+5.0025P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2646
_refine_ls_wR_factor_ref         0.3274
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6262
_reflns_number_total             10577
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce00484a2.cif
_cod_data_source_block           p
_cod_depositor_comments          'Adding full bibliography for 7249075.cif.'
_cod_original_cell_volume        10919.6(13)
_cod_database_code               7249075
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.798
_shelx_estimated_absorpt_t_min   0.766
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 Cu5C-O5C
 2 with sigma of 0.04
 C11B-O1B = C11B-O2B
 1.25 with sigma of 0.02
 C2B-C11B
 1.48 with sigma of 0.02
 C11C-O1C = C11C-O2C
 1.25 with sigma of 0.02
 C2C-C11C
 1.48 with sigma of 0.02
 C12C-C9C
 1.5 with sigma of 0.02
 C10C-C9C
 1.45 with sigma of 0.02
 C10C-C12C
 2.45 with sigma of 0.02
 C8C-C10C
 2.45 with sigma of 0.02
 C9C-C10C = C9C-C8C = C8C-C7C = C7C-C6C = C6C-C5C = C5C-C10C
 1.45 with sigma of 0.02
 C5C-C7C
 2.45 with sigma of 0.02
 C10C-C8C
 2.45 with sigma of 0.02
 C9C-C7C
 2.45 with sigma of 0.02
 C10C-C6C
 2.45 with sigma of 0.02
 Cu5D-O5D
 2.3 with sigma of 0.02
 C6B-C1B \\sim C5-C10
 with sigma of 0.02
 C6B-C5B \\sim C5-C6
 with sigma of 0.02
 C6B-C7B \\sim C5-C4
 with sigma of 0.02
 C7B-C8B \\sim C4-C3
 with sigma of 0.02
 C8B-C9B \\sim C3-C1
 with sigma of 0.02
 C6B-C2B \\sim C5-C9
 with sigma of 0.04
 C6B-C4B \\sim C5-C7
 with sigma of 0.04
 C6B-C10B \\sim C5-C2
 with sigma of 0.04
 C6B-C8B \\sim C5-C3
 with sigma of 0.04
 C1B-C7B \\sim C10-C4
 with sigma of 0.04
 C5B-C7B \\sim C6-C4
 with sigma of 0.04
 C10B-C8B \\sim C2-C3
 with sigma of 0.04
 C7B-C9B \\sim C4-C1
 with sigma of 0.04
 C8B-C12B \\sim C3-C12B
 with sigma of 0.04
 C1B-C2B \\sim C10-C9
 with sigma of 0.02
 C11C-C1C \\sim C11B-C1B \\sim C11B-C3B
 with sigma of 0.02
 C2C-O1C \\sim C2B-O1B \\sim C2B-O2B
 with sigma of 0.02
 C2B-C3B \\sim C9-C8
 with sigma of 0.02
 C2B-C11B \\sim C9-C11
 with sigma of 0.02
 C3B-C4B \\sim C8-C7
 with sigma of 0.02
 C4B-C5B \\sim C7-C6
 with sigma of 0.02
 C5B-C10B \\sim C6-C2
 with sigma of 0.02
 C10B-C9B \\sim C2-C1
 with sigma of 0.02
 C11C-C1C \\sim C11C-C3C
 with sigma of 0.02
 C9B-C12B \\sim C1-C12B
 with sigma of 0.02
 C11B-O1B \\sim C11-O1
 with sigma of 0.02
 C2C-O1C \\sim C2C-O2C
 with sigma of 0.02
 C11B-O2B \\sim C11-O2
 with sigma of 0.02
 C1B-C3B \\sim C10-C8
 with sigma of 0.04
 C1B-C5B \\sim C10-C6
 with sigma of 0.04
 C1B-C11B \\sim C10-C11
 with sigma of 0.04
 C2B-C4B \\sim C9-C7
 with sigma of 0.04
 C2B-O1B \\sim C9-O1
 with sigma of 0.04
 C2B-O2B \\sim C9-O2
 with sigma of 0.04
 C3B-C5B \\sim C8-C6
 with sigma of 0.04
 C12C-C8C \\sim C12C-C10C
 with sigma of 0.02
 C3B-C11B \\sim C8-C11
 with sigma of 0.04
 C4B-C10B \\sim C7-C2
 with sigma of 0.04
 C5B-C9B \\sim C6-C1
 with sigma of 0.04
 C10B-C12B \\sim C2-C12B
 with sigma of 0.04
 O1B-O2B \\sim O1-O2
 with sigma of 0.04
 O1B-Cu5C \\sim O1B-Cu5D
 with sigma of 0.02
 Cu5C-O5C \\sim Cu5D-O5D
 with sigma of 0.02
 Cu5C-O2 \\sim Cu5D-O2
 with sigma of 0.02
 O1B-O5C \\sim O1B-O5D
 with sigma of 0.04
 O5C-O2 \\sim O5D-O2
 with sigma of 0.04
3. Restrained planarity
 C2C, C11C, O1C, O2C
 with sigma of 0.1
 C2B, C11B, O1B, O2B
 with sigma of 0.1
4. Rigid bond restraints
 Cu5C, O5C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C4, C5B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C11, C11B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C11, C9
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cu5C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cu5C, Cu5D
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cu5D, O5D, Cu5C, O5C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
Cu5C: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within
2A
C9 \\sim C10 \\sim C11 \\sim C8: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Cu5D \\sim Cu5C: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
O5D \\sim O5C: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(O5C) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(Cu5C) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C3A) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C1) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C6) \\sim
Ueq, Uanis(C2) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(O2) \\sim Ueq,
Uanis(O1) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C12C) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O5D) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
6. Rigid body (RIGU) restrains
 C7B, C6B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11, C9, C10, C8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Same fragment restrains
{C6B, C1B} sigma for 1-2: 0.02, 1-3: 0.04
{C5B, C10B} sigma for 1-2: 0.02, 1-3: 0.04
{C6C, C1C} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C5C, C6C}
8. Others
 Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(C6)=
 Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(O1)=
 Sof(O2)=1-FVAR(1)
 Sof(Cu5D)=Sof(O5D)=0.5*(1-FVAR(2))
 Sof(Cu5C)=Sof(O5C)=0.5*FVAR(2)
 Sof(C6B)=Sof(C1B)=Sof(H1B)=Sof(C2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(H4B)=
 Sof(C5B)=Sof(C10B)=Sof(H10B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(H8B)=Sof(C9B)=
 Sof(C11B)=Sof(O1B)=Sof(O2B)=FVAR(1)
 Fixed Sof: C5C(0.5) C6C(0.5) C1C(0.5) H1C(0.5) C2C(0.5) C3C(0.5) H3C(0.5)
 C4C(0.5) H4C(0.5) C7C(0.5) H7C(0.5) C8C(0.5) H8C(0.5) C9C(0.5) C10C(0.5)
 H10C(0.5) C11C(0.5) O1C(0.5) O2C(0.5) C12C(0.5)
9.a Riding coordinates:
 C1C(H1C), C3C(H3C), C4C(H4C), C7C(H7C), C8C(H8C), C10C(H10C), C10(H10)
9.b Aromatic/amide H refined with riding coordinates:
 C1A(H1A), C3A(H3A), C4A(H4A), C7A(H7A), C8A(H8A), C10A(H10A), C1B(H1B),
 C3B(H3B), C4B(H4B), C10B(H10B), C7B(H7B), C8B(H8B), C2(H2), C3(H3), C4(H4),
 C7(H7), C8(H8)
;
_shelx_res_checksum              25395
_shelx_hkl_checksum              56955
_shelx_fab_checksum              19990
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'