Analogous copper nanoclusters (Cu<sub>16/17</sub>) with two electron superatomic and mixed valence copper(II)/copper(I) and copper(I)/copper(0) characters.
Kumar, Shibaditya; Mishra, Saikat; Das, Aniruddha; Mahiya, Kuldeep; Laha, Sourav; Maji, Milan; Patra, Apurba K.; Nanoscale 17 (2025) 982–991; doi:10.1039/d4nr03578j

data_1573171
_publ_section_title
;
 Analogous copper nanoclusters (Cu<sub>16/17</sub>) with two electron
 superatomic and mixed valence copper(II)/copper(I) and
 copper(I)/copper(0) characters.
;
_journal_issue                   2
_journal_name_full               Nanoscale
_journal_page_first              982
_journal_page_last               991
_journal_paper_doi               10.1039/d4nr03578j
_journal_volume                  17
_journal_year                    2025
_chemical_formula_moiety         'C144 H84 Cu16 F36 N12 S25, 3(F6 P)'
_chemical_formula_sum            'C144 H84 Cu16 F54 N12 P3 S25'
_chemical_formula_weight         4919.28
_space_group_crystal_system      trigonal
_space_group_IT_number           161
_space_group_name_Hall           'R 3 -2"c'
_space_group_name_H-M_alt        'R 3 c :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-04-28
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-06-15 deposited with the CCDC.	2024-11-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   24.8150(6)
_cell_length_b                   24.8150(6)
_cell_length_c                   66.157(3)
_cell_measurement_reflns_used    9908
_cell_measurement_temperature    140.00
_cell_measurement_theta_max      43.40
_cell_measurement_theta_min      4.01
_cell_volume                     35281(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      140.00
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.971
_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  0.1003
_diffrn_reflns_av_unetI/netI     0.0853
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       76
_diffrn_reflns_limit_l_min       -67
_diffrn_reflns_number            71375
_diffrn_reflns_point_group_measured_fraction_full 0.900
_diffrn_reflns_point_group_measured_fraction_max 0.900
_diffrn_reflns_theta_full        63.403
_diffrn_reflns_theta_max         63.403
_diffrn_reflns_theta_min         4.009
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.513
_exptl_absorpt_correction_T_max  0.7523
_exptl_absorpt_correction_T_min  0.5943
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0991 before and 0.0833 after correction.
The Ratio of minimum to maximum transmission is 0.7900.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'metallic dark red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.389
_exptl_crystal_description       block
_exptl_crystal_F_000             14562
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.701
_refine_diff_density_min         -0.922
_refine_diff_density_rms         0.094
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.08(5)
_refine_ls_extinction_coef       0.000107(13)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   0.984
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     841
_refine_ls_number_reflns         11546
_refine_ls_number_restraints     273
_refine_ls_restrained_S_all      0.984
_refine_ls_R_factor_all          0.1364
_refine_ls_R_factor_gt           0.0687
_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^)+(0.1439P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1748
_refine_ls_wR_factor_ref         0.2248
_reflns_Friedel_coverage         0.852
_reflns_Friedel_fraction_full    0.830
_reflns_Friedel_fraction_max     0.830
_reflns_number_gt                6458
_reflns_number_total             11546
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nr03578j2.cif
_cod_data_source_block           cu_skmx_0m
_cod_depositor_comments
'Adding full bibliography for 1573171--1573173.cif.'
_cod_original_cell_volume        35280(2)
_cod_original_sg_symbol_H-M      'R 3 c'
_cod_database_code               1573171
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.571
_shelx_estimated_absorpt_t_min   0.387
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.92(5)
 0.08(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3. Restrained distances
 C12C-F2C
 1.29 with sigma of 0.02
 C12C-F1C
 1.36 with sigma of 0.02
 C12C-F3C
 1.27 with sigma of 0.02
 C12D-F3D
 1.29 with sigma of 0.02
 C12D-F1D
 1.36 with sigma of 0.02
 C12D-F2D
 1.27 with sigma of 0.02
 C12A-F3A
 1.29 with sigma of 0.02
 C12A-F1A
 1.36 with sigma of 0.02
 C12A-F2A
 1.27 with sigma of 0.02
 C12D-C10D
 1.51 with sigma of 0.02
 C12C-C10C
 1.51 with sigma of 0.02
 C12B-F1B
 1.29 with sigma of 0.02
 C12B-F2B
 1.36 with sigma of 0.02
 C12B-F3B
 1.27 with sigma of 0.02
 C12C-F2C \\sim C12C-F1C \\sim C12C-F3C
 with sigma of 0.02
 F2C-F1C \\sim F1C-F3C \\sim F3C-F2C
 with sigma of 0.03
 C12D-F3D \\sim C12D-F1D \\sim C12D-F2D
 with sigma of 0.02
 F3D-F1D \\sim F1D-F2D \\sim F2D-F3D
 with sigma of 0.03
 C12A-F3A \\sim C12A-F1A \\sim C12A-F2A
 with sigma of 0.02
 F3A-F1A \\sim F1A-F2A \\sim F2A-F3A
 with sigma of 0.03
 C12A-F3A \\sim C12A-F4A
 with sigma of 0.02
 C12A-F1A \\sim C12A-F5A
 with sigma of 0.02
 C12A-F2A \\sim C12A-F6A
 with sigma of 0.02
 C12D-F3D \\sim C12D-F4D
 with sigma of 0.02
 C12D-F1D \\sim C12D-F5D
 with sigma of 0.02
 C12D-F2D \\sim C12D-F6D
 with sigma of 0.02
 C12C-F2C \\sim C12C-F5C
 with sigma of 0.02
 C12C-F1C \\sim C12C-F4C
 with sigma of 0.02
 C12C-F3C \\sim C12C-F6C
 with sigma of 0.02
 C12B-F1B \\sim C12B-F2B \\sim C12B-F3B
 with sigma of 0.02
 F1B-F2B \\sim F2B-F3B \\sim F3B-F1B
 with sigma of 0.03
 C12B-F1B \\sim C12B-F4B
 with sigma of 0.02
 C12B-F2B \\sim C12B-F5B
 with sigma of 0.02
 C12B-F3B \\sim C12B-F6B
 with sigma of 0.02
4. Restrained planarity
 C6D, C7D, C8D, C9D, C10D, C11D
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
Cu1 \\sim S1: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
Uanis(Cu1) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(F1A) = Uanis(F6A)
Uanis(F5D) = Uanis(F6D)
6. Rigid body (RIGU) restrains
 F1A, F1C, F1D, F2A, F2C, F2D, F3A, F3C, F3D, F4A, F4C, F4D, F5A, F5C, F5D,
 F6A, F6C, F6D, C12A, C12C, C12D
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 F1B, F2B, F3B, C12B
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 F1B, F2B, F3B, F4B, F5B, F6B, C12B
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 C9B, C10B, C11B
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 C9A, C10A, C11A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C8D, C9D, C10D, C11D
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
7. Others
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(1)
 Sof(F4D)=Sof(F5D)=Sof(F6D)=1-FVAR(2)
 Sof(F1D)=Sof(F2D)=Sof(F3D)=FVAR(2)
 Sof(F4C)=Sof(F5C)=Sof(F6C)=1-FVAR(3)
 Sof(F1C)=Sof(F2C)=Sof(F3C)=FVAR(3)
 Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(4)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=FVAR(4)
8.a Aromatic/amide H refined with riding coordinates:
 C1A(H1A), C1B(H1B), C1C(H1C), C1D(H1D), C2A(H2A), C2B(H2B), C2C(H2C),
 C2D(H2D), C3A(H3A), C3B(H3B), C3C(H3C), C3D(H3D), C5A(H5A), C5B(H5B), C5C(H5C),
  C5D(H5D), C8A(H8A), C9A(H9A), C11A(H11A), C8B(H8B), C8C(H8C), C9B(H9B),
 C9C(H9C), C11D(H11D), C8D(H8D), C9D(H9D), C11B(H11B), C11C(H11C)
8.b Fitted hexagon refined as free rotating group:
 C6A(C7A,C8A,C9A,C10A,C11A), C10D(C11D,C6D,C7D,C8D,C9D)
;
_shelx_res_checksum              62188
_olex2_submission_special_instructions 'No special instructions were received'