Doping Effect on the Magnetism of Thiolate-Capped 25-Atom Alloy Nanoclusters
Li, Yingwei; Biswas, Saborni; Luo, Tian-Yi; Juarez-Mosqueda, Rosalba; Taylor, Michael G.; Mpourmpakis, Giannis; Rosi, Nathaniel L.; Hendrich, Michael P.; Jin, Rongchao; Chemistry of Materials  (2020) –; doi:10.1021/acs.chemmater.0c02984

data_4003696
_publ_section_title
;
 Doping Effect on the Magnetism of Thiolate-Capped 25-Atom Alloy
 Nanoclusters
;
_journal_name_full               'Chemistry of Materials'
_journal_paper_doi               10.1021/acs.chemmater.0c02984
_journal_year                    2020
_chemical_formula_moiety         'C72 H81 Ag2.91 Au9.59 S9, C6'
_chemical_formula_sum            'C78 H81 Ag2.91 Au9.59 S9'
_chemical_formula_weight         3510.00
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-01-21
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.092(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.7728(14)
_cell_length_b                   24.4188(19)
_cell_length_c                   21.8661(17)
_cell_measurement_reflns_used    9876
_cell_measurement_temperature    230(2)
_cell_measurement_theta_max      68.36
_cell_measurement_theta_min      3.62
_cell_volume                     8954.1(12)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      230.0
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 8
_diffrn_detector_type            'APEX II CCD'
_diffrn_measured_fraction_theta_full 0.965
_diffrn_measured_fraction_theta_max 0.960
_diffrn_measurement_device_type  'Bruker X8 Prospector Ultra'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0550
_diffrn_reflns_av_unetI/netI     0.0535
_diffrn_reflns_Laue_measured_fraction_full 0.965
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            51847
_diffrn_reflns_point_group_measured_fraction_full 0.965
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.437
_diffrn_reflns_theta_min         2.713
_diffrn_source                   'IMuS micro-focus source'
_diffrn_source_target            Cu
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    35.943
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.3528
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1301 before and 0.0611 after correction.
The Ratio of minimum to maximum transmission is 0.4685.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.604
_exptl_crystal_description       block
_exptl_crystal_F_000             6350
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.02
_refine_diff_density_max         5.774
_refine_diff_density_min         -1.610
_refine_diff_density_rms         0.301
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     881
_refine_ls_number_reflns         15803
_refine_ls_number_restraints     339
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0507
_refine_ls_R_factor_gt           0.0417
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0550P)^2^+99.4433P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1111
_refine_ls_wR_factor_ref         0.1178
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13533
_reflns_number_total             15803
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm0c02984_si_002.cif
_cod_data_source_block           ltylyw20180616_0m_a
_cod_database_code               4003696
_shelxl_version_number           2014/6
_olex2_refinement_description
;
1. 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
2. Shared sites
{Au1, Ag1}
{Au3, Ag3}
{Au6, Ag6}
{Au9, Ag9}
{Au12, Ag12}
{Au13, Ag13}
3. Restrained distances
 C48-C47
 1.54 with sigma of 0.02
 C58-C57
 1.54 with sigma of 0.02
 C8-C7
 1.54 with sigma of 0.02
 C68-C67
 1.54 with sigma of 0.02
 C18-C17
 1.54 with sigma of 0.02
 C110-C111 \\sim C111-C112 \\sim C112-C113 \\sim C113-C114 \\sim C114-C115
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C17 \\sim C7 \\sim C8 \\sim C47 \\sim C48 \\sim C57 \\sim C58 \\sim C67 \\sim
C68: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C17 \\sim C18 \\sim C16: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28:
within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(Au1) = Uanis(Ag1)
Uanis(Au3) = Uanis(Ag3)
Uanis(Au6) = Uanis(Ag6)
Uanis(Au9) = Uanis(Ag9)
Uanis(Au12) = Uanis(Ag12)
Uanis(Au13) = Uanis(Ag13)
5. Rigid body (RIGU) restrains
 C21, C22, C23, C24, C25, C26, C27, C28
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, C2, C3, C4, C5, C6, C7, C8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C8, C7, C17, C67, C68, C47, C48, C57, C58
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11, C12, C13, C14, C15, C16, C17
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16, C17, C18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(Ag12)=1-FVAR(1)
 Sof(Au12)=FVAR(1)
 Sof(Ag13)=1-FVAR(2)
 Sof(Au13)=FVAR(2)
 Sof(Ag1)=1-FVAR(3)
 Sof(Au1)=FVAR(3)
 Sof(Ag3)=1-FVAR(4)
 Sof(Au3)=FVAR(4)
 Sof(Ag6)=1-FVAR(5)
 Sof(Au6)=FVAR(5)
 Sof(Ag9)=1-FVAR(6)
 Sof(Au9)=FVAR(6)
7.a Secondary CH2 refined with riding coordinates:
 C17(H17a,H17b), C27(H27a,H27b), C37(H37a,H37b), C47(H47a,H47b), C57(H57a,
 H57b), C67(H67a,H67b), C77(H77a,H77b), C87(H87a,H87b), C8(H8a,H8b)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C12(H12), C13(H13), C14(H14), C15(H15),
 C22(H22), C23(H23), C24(H24), C25(H25), C32(H32), C33(H33), C34(H34), C35(H35),
  C42(H42), C43(H43), C44(H44), C45(H45), C52(H52), C53(H53), C54(H54),
 C55(H55), C62(H62), C63(H63), C64(H64), C65(H65), C72(H72), C73(H73), C74(H74),
  C75(H75), C82(H82), C83(H83), C84(H84), C85(H85)
7.c Idealised Me refined with everything fixed:
 C48(H48a,H48b,H48c), C18(H18a,H18b,H18c)
7.d Idealised Me refined as rotating group:
 C7(H7a,H7b,H7c), C28(H28a,H28b,H28c), C38(H38a,H38b,H38c), C78(H78a,H78b,
 H78c), C88(H88a,H88b,H88c), C68(H68a,H68b,H68c), C58(H58a,H58b,H58c)
;
_olex2_submission_special_instructions 'No special instructions were received'