A new two-dimensional luminescent Ag<sub>12</sub> cluster-assembled material and its catalytic activity for reduction of hexacyanoferrate(III).
Nakatani, Riki; Biswas, Sourav; Irie, Tsukasa; Sakai, Jin; Hirayama, Daisuke; Kawawaki, Tokuhisa; Niihori, Yoshiki; Das, Saikat; Negishi, Yuichi; Nanoscale 15 (2023) 16299–16306; doi:10.1039/d3nr03343k

data_1569861
_publ_section_title
;
 A new two-dimensional luminescent Ag<sub>12</sub> cluster-assembled
 material and its catalytic activity for reduction of
 hexacyanoferrate(III).
;
_journal_issue                   40
_journal_name_full               Nanoscale
_journal_page_first              16299
_journal_page_last               16306
_journal_paper_doi               10.1039/d3nr03343k
_journal_volume                  15
_journal_year                    2023
_chemical_formula_moiety         'C84 H84 Ag12 F18 N12 O18 S6, 6(C5 H6 N O)'
_chemical_formula_sum            'C114 H120 Ag12 F18 N18 O24 S6'
_chemical_formula_weight         3955.07
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_audit_block_doi                 10.5517/ccdc.csd.cc2gfl8s
_audit_creation_date             2023-07-07
_audit_creation_method
; 
Olex2 1.5 
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748) 
;
_audit_update_record
;
2023-07-07 deposited with the CCDC.	2023-09-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   24.1539(5)
_cell_length_b                   24.1539(5)
_cell_length_c                   20.9231(9)
_cell_measurement_reflns_used    9862
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      30.56
_cell_measurement_theta_min      2.75
_cell_volume                     10571.4(6)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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      273.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0482
_diffrn_reflns_av_unetI/netI     0.0251
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            47476
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.535
_diffrn_reflns_theta_min         2.177
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.809
_exptl_absorpt_correction_T_max  0.7462
_exptl_absorpt_correction_T_min  0.6614
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
; 
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 
wR2(int) was 0.0818 before and 0.0396 after correction. 
The Ratio of minimum to maximum transmission is 0.8864. 
The \l/2 correction factor is Not present. 
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.864
_exptl_crystal_description       block
_exptl_crystal_F_000             5832
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.639
_refine_diff_density_min         -1.300
_refine_diff_density_rms         0.121
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     352
_refine_ls_number_reflns         6329
_refine_ls_number_restraints     628
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0441
_refine_ls_R_factor_gt           0.0357
_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^)+(0.0462P)^2^+80.3244P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0888
_refine_ls_wR_factor_ref         0.0962
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5402
_reflns_number_total             6329
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nr03343k2.cif
_cod_data_source_block           TUS_3
_cod_depositor_comments          'Adding full bibliography for 1569861.cif.'
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               1569861
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.714
_shelx_estimated_absorpt_t_min   0.671
_olex2_refinement_description
; 
1. Fixed Uiso 
 At 1.2 times of: 
  All C(H) groups 
 At 1.5 times of: 
  All C(H,H,H) groups 
2. Restrained distances 
 O4_$1-N3 
 3 with sigma of 0.001 
 O4-C14 \\sim O4A-C14A 
 with sigma of 0.02 
 C14-C15 \\sim C14A-C15A 
 with sigma of 0.02 
 C14-N16 \\sim C14A-N16A 
 with sigma of 0.02 
 C15-C \\sim C15A-CA 
 with sigma of 0.02 
 N16-C17 \\sim N16A-C17A 
 with sigma of 0.02 
 N16-C18 \\sim N16A-C18A 
 with sigma of 0.02 
 C18-C \\sim C18A-CA 
 with sigma of 0.02 
 O4-C15 \\sim O4A-C15A 
 with sigma of 0.04 
 O4-N16 \\sim O4A-N16A 
 with sigma of 0.04 
 C14-C17 \\sim C14A-C17A 
 with sigma of 0.04 
 C14-C18 \\sim C14A-C18A 
 with sigma of 0.04 
 C14-C \\sim C14A-CA 
 with sigma of 0.04 
 C15-N16 \\sim C15A-N16A 
 with sigma of 0.04 
 C15-C18 \\sim C15A-C18A 
 with sigma of 0.04 
 N16-C \\sim N16A-CA 
 with sigma of 0.04 
 C17-C18 \\sim C17A-C18A 
 with sigma of 0.04 
3. Rigid bond restraints 
 All non-hydrogen atoms 
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01 
4. Uiso/Uaniso restraints and constraints 
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma 
for terminal atoms of 0.02 within 2A 
Uanis(C17A) \\sim Ueq, Uanis(O4) \\sim Ueq: with sigma of 0.001 and sigma for 
terminal atoms of 0.002 
Uanis(C17) \\sim Ueq: with sigma of 0.0001 and sigma for terminal atoms of 
0.0002 
Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C) \\sim Ueq, Uanis(C15A) 
\\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(N16A) \\sim Ueq, Uanis(N16) \\sim Ueq, 
Uanis(CA) \\sim Ueq, Uanis(C18A) \\sim Ueq, Uanis(O4A) \\sim Ueq: with sigma of 
0.01 and sigma for terminal atoms of 0.02 
Uanis(C17A) = Uanis(O4) 
5. Rigid body (RIGU) restrains 
 C17A, O4A, C14A, C15A, N16A, CA, C18A, O4, C14, C15, N16, C, C17, C18 
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001 
6. Others 
 Sof(O4A)=Sof(C14A)=Sof(C15A)=Sof(H15A)=Sof(CA)=Sof(HA)=Sof(C18A)=Sof(H18A)= 
 Sof(N16A)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=1-FVAR(1) 
 Sof(O4)=Sof(C14)=Sof(C15)=Sof(H15)=Sof(N16)=Sof(C17)=Sof(H17A)=Sof(H17B)= 
 Sof(H17C)=Sof(C18)=Sof(H18)=Sof(C)=Sof(H)=FVAR(1) 
7.a Aromatic/amide H refined with riding coordinates: 
 C6(H6), C7(H7), C9(H9), C10(H10), C13(H13), C15(H15), C18(H18), C(H), 
 C15A(H15A), CA(HA), C18A(H18A) 
7.b Idealised Me refined as rotating group: 
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C17(H17A,H17B,H17C), 
 C17A(H17D,H17E,H17F) 
;
_shelx_res_checksum              90400
_olex2_submission_special_instructions 'No special instructions were received'