[Cu61(StBu)26S6Cl6H14]+: A Core‒Shell Superatom Nanocluster with a Quasi-J36 Cu19 Core and an “18-Crown-6” Metal-Sulfide-like Stabilizing Belt
Ghosh, Atanu; Huang, Ren-Wu; Alamer, Badriah; Abou-Hamad, Edy; Hedhili, Mohamed Nejib; Mohammed, Omar F.; Bakr, Osman M.; ACS Materials Letters 1 (2019) 297–; doi:10.1021/acsmaterialslett.9b00122

data_4515201
_publ_section_title
;
 [Cu61(StBu)26S6Cl6H14]+: A Core--Shell Superatom Nanocluster with a
 Quasi-J36 Cu19 Core and an &#x201C;18-Crown-6&#x201D; Metal-Sulfide-like
 Stabilizing Belt
;
_journal_issue                   3
_journal_name_full               'ACS Materials Letters'
_journal_page_first              297
_journal_paper_doi               10.1021/acsmaterialslett.9b00122
_journal_volume                  1
_journal_year                    2019
_chemical_formula_moiety         'C104 H234 Cl6 Cu61 S32, 6(C H Cl3)'
_chemical_formula_sum            'C110 H240 Cl24 Cu61 S32'
_chemical_formula_weight         7315.67
_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'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.412(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   35.762(13)
_cell_length_b                   21.040(9)
_cell_length_c                   29.441(10)
_cell_measurement_reflns_used    22717
_cell_measurement_temperature    130(2)
_cell_measurement_theta_max      26.449
_cell_measurement_theta_min      1.936
_cell_volume                     22087(14)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      130.04
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1232
_diffrn_reflns_av_unetI/netI     0.0878
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            132301
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.449
_diffrn_reflns_theta_min         1.936
_exptl_absorpt_coefficient_mu    6.351
_exptl_absorpt_correction_T_max  0.881
_exptl_absorpt_correction_T_min  0.639
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.200
_exptl_crystal_description       plate
_exptl_crystal_F_000             14356
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.146
_refine_diff_density_min         -1.191
_refine_diff_density_rms         0.190
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1095
_refine_ls_number_reflns         22717
_refine_ls_number_restraints     217
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.1167
_refine_ls_R_factor_gt           0.0616
_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^)+(0.0731P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1367
_refine_ls_wR_factor_ref         0.1539
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14076
_reflns_number_total             22717
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            tz9b00122_si_002.cif
_cod_data_source_block           funl_cu61
_cod_original_cell_volume        22087(15)
_cod_database_code               4515201
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.883
_shelx_estimated_absorpt_t_min   0.631
_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
 Cl14-C56 \\sim Cl13-C56 \\sim Cl15-C56
 with sigma of 0.01
 Cl5-C53 \\sim Cl6-C53 \\sim Cl4-C53
 with sigma of 0.01
 Cl9-C55 \\sim Cl7-C55 \\sim Cl8-C55
 with sigma of 0.01
 Cl7-Cl9 \\sim Cl9-Cl8
 with sigma of 0.01
 Cl9-Cl8 \\sim Cl8-Cl7
 with sigma of 0.01
 Cl12-Cl11 \\sim Cl11-Cl10
 with sigma of 0.01
 Cl10-C54 \\sim Cl11-C54 \\sim Cl12-C54
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Cl7 \\sim Cl8 \\sim Cl9 \\sim C55: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
Cl10 \\sim Cl11 \\sim Cl12 \\sim C54: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01
Uanis(Cl15) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(Cl14) \\sim Ueq, Uanis(Cl13)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(Cl10) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C5, C6, C7, C8, C21, C22, C23, C24, C29, C30, C31, C32, C45, C46, C47, C48,
 C49, C50, C51, C52
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 Cl13, Cl14, Cl15, C56
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 Cl7, Cl8, Cl9, C55
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl10, Cl11, Cl12, C54
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Fixed Sof: Cl7(0.5) Cl8(0.5) Cl9(0.5) H55(0.5) Cl10(0.5) Cl11(0.5) Cl12(0.5)
 C54(0.5) H54(0.5)
6.a Ternary CH refined with riding coordinates:
 C53(H53), C55(H55), C54(H54), C56(H56)
6.b Idealised Me refined as rotating group:
 C2(H2a,H2b,H2c), C3(H3a,H3b,H3c), C4(H4a,H4b,H4c), C6(H6a,H6b,H6c), C7(H7a,
 H7b,H7c), C8(H8a,H8b,H8c), C10(H10a,H10b,H10c), C11(H11a,H11b,H11c), C12(H12a,
 H12b,H12c), C14(H14a,H14b,H14c), C15(H15a,H15b,H15c), C16(H16a,H16b,H16c),
 C18(H18a,H18b,H18c), C19(H19a,H19b,H19c), C20(H20a,H20b,H20c), C22(H22a,H22b,
 H22c), C23(H23a,H23b,H23c), C24(H24a,H24b,H24c), C26(H26a,H26b,H26c), C27(H27a,
 H27b,H27c), C28(H28a,H28b,H28c), C30(H30a,H30b,H30c), C31(H31a,H31b,H31c),
 C32(H32a,H32b,H32c), C34(H34a,H34b,H34c), C35(H35a,H35b,H35c), C36(H36a,H36b,
 H36c), C38(H38a,H38b,H38c), C39(H39a,H39b,H39c), C40(H40a,H40b,H40c), C42(H42a,
 H42b,H42c), C43(H43a,H43b,H43c), C44(H44a,H44b,H44c), C46(H46a,H46b,H46c),
 C47(H47a,H47b,H47c), C48(H48a,H48b,H48c), C50(H50a,H50b,H50c), C51(H51a,H51b,
 H51c), C52(H52a,H52b,H52c)
commets: Some C atoms in t-butyl groups and all the free CHCl3 molecules
 were observed to be disordered. The geometry and ADP of the disordered 
moieties were restrained using the "SADI", "RIGU" and "SIMU" commands 
in order to achieve a better refinement result. ISORs with different values 
were applied to make thermal parameters of C56, Cl10, Cl14, Cl13 and 
Cl15 reasonable. Two CHCl3 molecules were fixed to have 0.5 occupancy 
because of symmetry requirements. "PART -1" was applied to suppress
 the symmetry for consistency with chemically reasonable modelling.
;
_olex2_submission_special_instructions 'No special instructions were received'