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_1573173
_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
'C147 H91 Cu17 F36 N13 O S24, 3(F6 P), C2 H6 O, 2(C7 H8)'
_chemical_formula_sum            'C163 H113 Cu17 F54 N13 O2 P3 S24'
_chemical_formula_weight         5254.19
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-23
_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                   24.8645(11)
_cell_length_b                   24.8645(11)
_cell_length_c                   66.598(6)
_cell_measurement_reflns_used    13680
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      26
_cell_measurement_theta_min      3
_cell_volume                     35658(4)
_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      150(2)
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker APEX4'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0640
_diffrn_reflns_av_unetI/netI     0.0456
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       79
_diffrn_reflns_limit_l_min       -78
_diffrn_reflns_number            95809
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         2.460
_exptl_absorpt_coefficient_mu    1.802
_exptl_absorpt_correction_T_max  1.023
_exptl_absorpt_correction_T_min  0.852
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            'clear dark brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.468
_exptl_crystal_description       block
_exptl_crystal_F_000             15636
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.814
_refine_diff_density_min         -1.685
_refine_diff_density_rms         0.122
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.049(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     965
_refine_ls_number_reflns         13680
_refine_ls_number_restraints     1080
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0767
_refine_ls_R_factor_gt           0.0554
_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^)+(0.1007P)^2^+84.1953P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1437
_refine_ls_wR_factor_ref         0.1587
_reflns_Friedel_coverage         0.975
_reflns_Friedel_fraction_full    0.967
_reflns_Friedel_fraction_max     0.967
_reflns_number_gt                11357
_reflns_number_total             13680
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nr03578j2.cif
_cod_data_source_block           shelx
_cod_depositor_comments
'Adding full bibliography for 1573171--1573173.cif.'
_cod_original_cell_volume        35657(4)
_cod_original_sg_symbol_H-M      'R 3 c'
_cod_database_code               1573173
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.840
_shelx_estimated_absorpt_t_min   0.840
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.951(19)
 0.049(19)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
3. Restrained distances
 C12A-F2A
 1.29 with sigma of 0.02
 C1-O1
 1.22 with sigma of 0.02
 C5-C4
 1.51 with sigma of 0.02
 C5-O2
 1.45 with sigma of 0.02
 C12A-F3A
 1.36 with sigma of 0.02
 C12A-F1A
 1.27 with sigma of 0.02
 N1-C2
 1.45 with sigma of 0.02
 N1-C3
 1.46 with sigma of 0.02
 C1-N1
 1.36 with sigma of 0.02
 C8T-C9T
 1.51 with sigma of 0.02
 C9T-C10T = C9T-C14T = C11T-C12T
 1.39 with sigma of 0.02
 C10T-C11T = C12T-C13T = C13T-C14T
 1.38 with sigma of 0.02
 C2T-C7T = C2T-C3T = C6T-C5T
 1.39 with sigma of 0.02
 C1T-C2T
 1.51 with sigma of 0.02
 C7T-C6T = C5T-C4T = C4T-C3T
 1.38 with sigma of 0.02
 C4-O2
 2.59 with sigma of 0.02
 C1-C3
 2.45 with sigma of 0.04
 C1-C2
 2.46 with sigma of 0.04
 C10T-C12T
 2.39 with sigma of 0.04
 C11T-C13T = C12T-C14T
 2.4 with sigma of 0.04
 C8T-C10T = C8T-C14T
 2.52 with sigma of 0.04
 C9T-C11T
 2.42 with sigma of 0.04
 C9T-C13T
 2.41 with sigma of 0.04
 C7T-C5T
 2.39 with sigma of 0.04
 C6T-C4T = C5T-C3T
 2.4 with sigma of 0.04
 C1T-C7T = C1T-C3T
 2.52 with sigma of 0.04
 C2T-C6T
 2.42 with sigma of 0.04
 C2T-C4T
 2.41 with sigma of 0.04
 F2D-C12D \\sim F5D-C12D
 with sigma of 0.02
 F3D-C12D \\sim F6D-C12D
 with sigma of 0.02
 C12D-F1D \\sim C12D-F4D
 with sigma of 0.02
 F2A-F3A \\sim F3A-F1A \\sim F1A-F2A
 with sigma of 0.03
 C12A-F2A \\sim C12A-F3A \\sim C12A-F1A
 with sigma of 0.02
 C12A-F2A \\sim C12A-F5A
 with sigma of 0.02
 C12A-F1A \\sim C12A-F4A
 with sigma of 0.02
 C12A-F3A \\sim C12A-F6A
 with sigma of 0.02
 C12B-F2B \\sim C12B-F6B
 with sigma of 0.02
 F3B-C12B \\sim F4B-C12B
 with sigma of 0.02
 F2C-C12C \\sim F4C-C12C
 with sigma of 0.02
 C12C-F3C \\sim C12C-F5C
 with sigma of 0.02
 C12C-F1C \\sim C12C-F6C
 with sigma of 0.02
 F1B-C12B \\sim F5B-C12B
 with sigma of 0.02
 N1-C2 \\sim N1-C3
 with sigma of 0.02
 C9T-C13T \\sim C9T-C11T \\sim C14T-C12T \\sim C10T-C14T \\sim C11T-C13T \\sim
C10T-C12T
 with sigma of 0.04
 C9T-C10T \\sim C10T-C11T \\sim C11T-C12T \\sim C12T-C13T \\sim C13T-C14T \\sim
C14T-C9T
 with sigma of 0.02
 C8T-C14T \\sim C8T-C10T
 with sigma of 0.04
 C2T-C7T \\sim C7T-C6T \\sim C6T-C5T \\sim C5T-C4T \\sim C4T-C3T \\sim C3T-C2T
 with sigma of 0.02
 C2T-C4T \\sim C2T-C6T \\sim C3T-C5T \\sim C7T-C3T \\sim C6T-C4T \\sim C7T-C5T
 with sigma of 0.04
 C1T-C3T \\sim C1T-C7T
 with sigma of 0.04
4. Restrained planarity
 O1, N1, C1, C2, C3
 with sigma of 0.1
 C8T, C9T, C10T, C11T, C12T, C13T, C14T
 with sigma of 0.1
 C1T, C2T, C3T, C4T, C5T, C6T, C7T
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
O1 \\sim N1 \\sim C1 \\sim C2 \\sim C3: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
C8T \\sim C9T \\sim C10T \\sim C11T \\sim C12T \\sim C13T \\sim C14T: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C1T \\sim C2T \\sim C3T \\sim C4T \\sim C5T \\sim C6T \\sim C7T: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(F2A) = Uanis(F5A)
Uanis(F6A) = Uanis(F3A)
Uanis(F6D) = Uanis(F1D)
Uanis(F5B) = Uanis(F2B)
6. 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
 C1T, C2T, C3T, H3T, C4T, H4T, C5T, H5T, C6T, H6T, C7T, H7T
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 F1A, F2A, F3A, F4A, F5A, F6A, C12A
 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
7. Others
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(1)
 Sof(F4C)=Sof(F5C)=Sof(F6C)=1-FVAR(2)
 Sof(F1C)=Sof(F2C)=Sof(F3C)=FVAR(2)
 Sof(F4D)=Sof(F5D)=Sof(F6D)=1-FVAR(3)
 Sof(F1D)=Sof(F2D)=Sof(F3D)=FVAR(3)
 Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(4)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=FVAR(4)
 Fixed Sof: O1(0.333333) N1(0.333333) C1(0.333333) H1(0.333333) C2(0.333333)
 H2A(0.333333) H2B(0.333333) H2C(0.333333) C3(0.333333) H3A(0.333333)
 H3B(0.333333) H3C(0.333333) O2(0.333333) H2(0.333333) C4(0.333333)
 H4A(0.333333) H4B(0.333333) H4C(0.333333) C5(0.333333) H5E(0.333333)
 H5F(0.333333) C1T(0.333333) H1TA(0.333333) H1TB(0.333333) H1TC(0.333333)
 C2T(0.333333) C3T(0.333333) H3T(0.333333) C4T(0.333333) H4T(0.333333)
 C5T(0.333333) H5T(0.333333) C6T(0.333333) H6T(0.333333) C7T(0.333333)
 H7T(0.333333) C8T(0.333333) H8TA(0.333333) H8TB(0.333333) H8TC(0.333333)
 C9T(0.333333) C10T(0.333333) H10T(0.333333) C11T(0.333333) H11T(0.333333)
 C12T(0.333333) H12T(0.333333) C13T(0.333333) H13T(0.333333) C14T(0.333333)
 H14T(0.333333)
8.a Riding coordinates:
 O2(H2)
8.b Secondary CH2 refined with riding coordinates:
 C5(H5E,H5F)
8.c Me refined with riding coordinates:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C1T(H1TA,H1TB,H1TC),
 C8T(H8TA,H8TB,H8TC)
8.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C1A(H1A), C1B(H1B), C1C(H1C), C1D(H1D), C2A(H2AA), C2B(H2BA),
 C2C(H2CA), C2D(H2D), C3A(H3AA), C3B(H3BA), C3C(H3CA), C3D(H3D), C5A(H5A),
 C5B(H5B), C5C(H5C), C5D(H5D), C8A(H8A), C8B(H8B), C8C(H8C), C8D(H8D), C9A(H9A),
  C9B(H9B), C9C(H9C), C9D(H9D), C11A(H11A), C11B(H11B), C11C(H11C), C11D(H11D),
 C3T(H3T), C4T(H4T), C5T(H5T), C6T(H6T), C7T(H7T), C10T(H10T), C11T(H11T),
 C12T(H12T), C13T(H13T), C14T(H14T)
;
_shelx_res_checksum              45878
_olex2_submission_special_instructions 'No special instructions were received'