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_1573172
_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
'C156 H108 Cu16 F36 N12 S25, Cl O4, 4(C7 H8), 4[C7H8]'
_chemical_formula_sum            'C212 H172 Cl Cu16 F36 N12 O4 S25'
_chemical_formula_weight         5489.20
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-15
_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                 113.044(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   39.487(9)
_cell_length_b                   20.216(3)
_cell_length_c                   31.428(5)
_cell_measurement_reflns_used    9432
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30
_cell_measurement_theta_min      3
_cell_volume                     23086(7)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Bruker APEX4'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1614
_diffrn_reflns_av_unetI/netI     0.1922
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       46
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            85171
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.206
_exptl_absorpt_coefficient_mu    1.761
_exptl_crystal_colour            'metallic reddish brown'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.579
_exptl_crystal_description       block
_exptl_crystal_F_000             11060
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.585
_refine_diff_density_min         -1.260
_refine_diff_density_rms         0.197
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1293
_refine_ls_number_reflns         20081
_refine_ls_number_restraints     485
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.2096
_refine_ls_R_factor_gt           0.1103
_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^)+(0.1826P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2912
_refine_ls_wR_factor_ref         0.3271
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9432
_reflns_number_total             20081
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nr03578j2.cif
_cod_data_source_block           test5
_cod_depositor_comments
'Adding full bibliography for 1573171--1573173.cif.'
_cod_database_code               1573172
_shelx_shelxl_version_number     2019/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H13P,H13Q,H13R} of C13F, {H13A,H13B,H13C} of C13A
 At 1.5 times of:
  {H1TA,H1TB,H1TC} of C1T, {H13M,H13N,H13O} of C13E, {H8TA,H8TB,H8TC} of C8T,
  {H13J,H13K,H13L} of C13D, {H13D,H13E,H13F} of C13B, {H13G,H13H,H13I} of C13C
2. Restrained distances
 Cl1-O2 = Cl1-O4 = Cl1-O1 = Cl1-O3
 1.5 with sigma of 0.02
 C8T-C9T
 1.51 with sigma of 0.02
 C9T-C14T = C9T-C10T = C13T-C12T
 1.39 with sigma of 0.02
 C14T-C13T = C12T-C11T = C11T-C10T
 1.38 with sigma of 0.02
 C1T-C2T
 1.51 with sigma of 0.02
 C2T-C7T = C2T-C3T = C6T-C5T
 1.39 with sigma of 0.02
 C7T-C6T = C5T-C4T = C4T-C3T
 1.38 with sigma of 0.02
 C8T-C14T = C8T-C10T
 2.52 with sigma of 0.04
 C9T-C13T
 2.42 with sigma of 0.04
 C9T-C11T
 2.41 with sigma of 0.04
 C14T-C12T
 2.39 with sigma of 0.04
 C13T-C11T = C12T-C10T
 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
 C7T-C5T
 2.39 with sigma of 0.04
 C6T-C4T = C5T-C3T
 2.4 with sigma of 0.04
 Cl1-O2 \\sim Cl1-O4 \\sim Cl1-O1 \\sim Cl1-O3
 with sigma of 0.02
 F2B-C12B \\sim F5B-C12B
 with sigma of 0.02
 O2-O1 \\sim O4-O3 \\sim O2-O3 \\sim O4-O1 \\sim O2-O4 \\sim O1-O3
 with sigma of 0.04
 F1B-C12B \\sim F4B-C12B
 with sigma of 0.02
 C12B-F3B \\sim C12B-F6B
 with sigma of 0.02
 C9T-C14T \\sim C14T-C13T \\sim C13T-C12T \\sim C12T-C11T \\sim C11T-C10T \\sim
C10T-C9T
 with sigma of 0.02
 C9T-C11T \\sim C9T-C13T \\sim C10T-C12T \\sim C14T-C10T \\sim C13T-C11T \\sim
C14T-C12T
 with sigma of 0.04
 C8T-C10T \\sim C8T-C14T
 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
 F2D-C12D \\sim F5D-C12D
 with sigma of 0.02
 F1D-C12D \\sim F4D-C12D
 with sigma of 0.02
 F3D-C12D \\sim F6D-C12D
 with sigma of 0.02
 F3C-C12C \\sim F4C-C12C
 with sigma of 0.02
 F2C-C12C \\sim F6C-C12C
 with sigma of 0.02
 F1C-C12C \\sim F5C-C12C
 with sigma of 0.02
3. Restrained planarity
 C8T, C9T, C10T, C11T, C12T, C13T, C14T
 with sigma of 0.1
 C1T, C2T, C3T, C4T, C5T, C6T, C7T
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Cl1 \\sim O1 \\sim O2 \\sim O3 \\sim O4: 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(C5F) = Uanis(C5E)
Uanis(C6B) = Uanis(C6A)
Uanis(C5D) = Uanis(C5E)
Uanis(F2D) = Uanis(F4D)
Uanis(F3D) = Uanis(F5D)
Uanis(F1D) = Uanis(F6D)
Uanis(C2B) = Uanis(C2A)
Uanis(C6E) = Uanis(C6A)
Uanis(C3B) = Uanis(C3A)
Uanis(C13A) = Uanis(C13B)
Uanis(C10B) = Uanis(C10C)
Uanis(F6C) = Uanis(F2C)
5. Rigid body (RIGU) restrains
 Cl1, O1, O2, O3, O4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C8T, C9T, C10T, C11T, C12T, C13T, C14T
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1T, C2T, C3T, C4T, C5T, C6T, C7T
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1T, C2T, C3T, C4T, C5T, C6T, C7T, C8T, C9T, C10T, C11T, C12T, C13T, C14T
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1B, F2B, F3B, F4B, F5B, F6B, C12B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1D, F2D, F3D, F4D, F5D, F6D, C12D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1C, F2C, F3C, F4C, F5C, F6C, C10C, C12C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(1)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=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)
 Fixed Sof: Cl1(0.5) O1(0.5) O2(0.5) O3(0.5) O4(0.5)
7.a Riding coordinates:
 C1A(H1A), C1B(H1B), C1C(H1C), C1D(H1D), C1F(H1F), C2A(H2A), C2C(H2C),
 C2D(H2D), C2E(H2E), C5A(H5A), C5C(H5C), C5D(H5D), C5E(H5E), C5F(H5F), C8A(H8A),
  C8B(H8B), C8C(H8C), C8D(H8D), C8F(H8F), C9A(H9A), C9C(H9C), C9D(H9D),
 C9F(H9F), C11B(H11B), C11C(H11C), C11E(H11E), C13A(H13A,H13B,H13C), C13F(H13P,
 H13Q,H13R)
7.b Aromatic/amide H refined with riding coordinates:
 C1E(H1E), C2B(H2B), C2F(H2F), C5B(H5B), C8E(H8E), C9B(H9B), C9E(H9E),
 C11A(H11A), C11D(H11D), C11F(H11F), C3T(H3T), C4T(H4T), C5T(H5T), C6T(H6T),
 C7T(H7T), C10T(H10T), C11T(H11T), C12T(H12T), C13T(H13T), C14T(H14T)
7.c Idealised Me refined as rotating group:
 C13B(H13D,H13E,H13F), C13C(H13G,H13H,H13I), C13D(H13J,H13K,H13L), C13E(H13M,
 H13N,H13O), C1T(H1TA,H1TB,H1TC), C8T(H8TA,H8TB,H8TC)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 760 electrons were 
found in a volume of 5234\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 4[C7H8] per Asymmetric Unit 
which account for 800 electrons per unit cell.
;
_shelx_res_checksum              34930
_shelx_fab_checksum              91013
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'