Controlling Ag-Doping in [AgxAu25-x(SC6H11)18]‒ Nanoclusters, Cryogenic Optical, Electronic and Electrocatalytic Properties
Jin, Rongchao; Jin, Renxi; Zhao, Shuo; Liu, Chong; Zhou, Meng; Panapitiya, Gihan; Xing, Yan; Rosi, Nathaniel L.; Lewis, James P.; Nanoscale  (2017) –; doi:10.1039/C7NR05871C

data_1547946
_publ_section_title
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 Controlling Ag-Doping in [AgxAu25-x(SC6H11)18]-- Nanoclusters, Cryogenic
 Optical, Electronic and Electrocatalytic Properties
;
_journal_name_full               Nanoscale
_journal_paper_doi               10.1039/C7NR05871C
_journal_year                    2017
_chemical_formula_moiety
'2(C108 H198 Ag20.33 Au4.67 S18), 0.25(C24 H20 P)'
_chemical_formula_sum            'C221.98 H400.98 Ag40.77 Au9.23 P0.25 S36'
_chemical_formula_weight         10447.91
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-09-28
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2017-10-10 deposited with the CCDC.
2017-11-06 downloaded from the CCDC.
;
_cell_angle_alpha                89.303(2)
_cell_angle_beta                 84.834(2)
_cell_angle_gamma                86.718(2)
_cell_formula_units_Z            1
_cell_length_a                   17.6005(4)
_cell_length_b                   18.7929(5)
_cell_length_c                   26.8471(6)
_cell_measurement_reflns_used    9986
_cell_measurement_temperature    230.0
_cell_measurement_theta_max      68.268
_cell_measurement_theta_min      2.868
_cell_volume                     8829.3(4)
_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, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      230.0
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measurement_device_type  'Bruker X8 Prospector Ultra'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1301
_diffrn_reflns_av_unetI/netI     0.1184
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            117636
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.785
_diffrn_reflns_theta_min         1.652
_exptl_absorpt_coefficient_mu    26.899
_exptl_absorpt_correction_T_max  0.753
_exptl_absorpt_correction_T_min  0.349
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1628 before and 0.0735 after correction.
The Ratio of minimum to maximum transmission is 0.4635.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_density_diffrn    1.965
_exptl_crystal_description       plate
_exptl_crystal_F_000             4958
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.02
_refine_diff_density_max         3.080
_refine_diff_density_min         -1.697
_refine_diff_density_rms         0.334
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1347
_refine_ls_number_reflns         31597
_refine_ls_number_restraints     3462
_refine_ls_restrained_S_all      0.983
_refine_ls_R_factor_all          0.1354
_refine_ls_R_factor_gt           0.0758
_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^)+(0.1434P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2103
_refine_ls_wR_factor_ref         0.2579
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18116
_reflns_number_total             31597
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7nr05871c2.cif
_cod_data_source_block           lcau1016_0m
_cod_database_code               1547946
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.615
_shelx_estimated_absorpt_t_min   0.174
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Shared sites
{Au26, Ag26}
{Au25, Ag25}
{Au24, Ag24}
{Au23, Ag23}
{Au22, Ag22}
{Au21, Ag21}
{Au19, Ag19}
{Au18, Ag18}
{Au17, Ag17}
{Au16, Ag16}
{Au15, Ag15}
{Au13, Ag13}
{Au10, Ag10}
{Au8, Ag8}
{Au7, Ag7}
{Au6, Ag6}
{Au5, Ag5}
{Au4, Ag4}
{Au3, Ag3}
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(Au26) = Uanis(Ag26)
Uanis(Au25) = Uanis(Ag25)
Uanis(Au24) = Uanis(Ag24)
Uanis(Au23) = Uanis(Ag23)
Uanis(Au22) = Uanis(Ag22)
Uanis(Au21) = Uanis(Ag21)
Uanis(Au19) = Uanis(Ag19)
Uanis(Au18) = Uanis(Ag18)
Uanis(Au17) = Uanis(Ag17)
Uanis(Au16) = Uanis(Ag16)
Uanis(Au15) = Uanis(Ag15)
Uanis(Au13) = Uanis(Ag13)
Uanis(Au10) = Uanis(Ag10)
Uanis(Au8) = Uanis(Ag8)
Uanis(Au7) = Uanis(Ag7)
Uanis(Au6) = Uanis(Ag6)
Uanis(Au5) = Uanis(Ag5)
Uanis(Au4) = Uanis(Ag4)
Uanis(Au3) = Uanis(Ag3)
4. 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
5. Others
 Sof(Ag3)=1-FVAR(1)
 Sof(Au3)=FVAR(1)
 Sof(Ag4)=1-FVAR(2)
 Sof(Au4)=FVAR(2)
 Sof(Ag5)=1-FVAR(3)
 Sof(Au5)=FVAR(3)
 Sof(Ag6)=1-FVAR(4)
 Sof(Au6)=FVAR(4)
 Sof(Ag7)=1-FVAR(5)
 Sof(Au7)=FVAR(5)
 Sof(Ag8)=1-FVAR(6)
 Sof(Au8)=FVAR(6)
 Sof(Ag10)=1-FVAR(7)
 Sof(Au10)=FVAR(7)
 Sof(Ag13)=1-FVAR(8)
 Sof(Au13)=FVAR(8)
 Sof(Ag15)=1-FVAR(9)
 Sof(Au15)=FVAR(9)
 Sof(Ag16)=1-FVAR(10)
 Sof(Au16)=FVAR(10)
 Sof(Ag17)=1-FVAR(11)
 Sof(Au17)=FVAR(11)
 Sof(Ag18)=1-FVAR(12)
 Sof(Au18)=FVAR(12)
 Sof(Ag19)=1-FVAR(13)
 Sof(Au19)=FVAR(13)
 Sof(Ag21)=1-FVAR(14)
 Sof(Au21)=FVAR(14)
 Sof(Ag22)=1-FVAR(15)
 Sof(Au22)=FVAR(15)
 Sof(Ag23)=1-FVAR(16)
 Sof(Au23)=FVAR(16)
 Sof(Ag24)=1-FVAR(17)
 Sof(Au24)=FVAR(17)
 Sof(Ag25)=1-FVAR(18)
 Sof(Au25)=FVAR(18)
 Sof(Ag26)=1-FVAR(19)
 Sof(Au26)=FVAR(19)
 Sof(P1)=Sof(C109)=Sof(C110)=Sof(H110)=Sof(C111)=Sof(H111)=Sof(C112)=Sof(H112)=
 Sof(C113)=Sof(H113)=Sof(C114)=Sof(H114)=Sof(C115)=Sof(C116)=Sof(H116)=
 Sof(C117)=Sof(H117)=Sof(C118)=Sof(H118)=Sof(C119)=Sof(H119)=Sof(C120)=
 Sof(H120)=Sof(C121)=Sof(C122)=Sof(H122)=Sof(C123)=Sof(H123)=Sof(C124)=
 Sof(H124)=Sof(C125)=Sof(H125)=Sof(C126)=Sof(H126)=Sof(C127)=Sof(C128)=
 Sof(H128)=Sof(C129)=Sof(H129)=Sof(C130)=Sof(H130)=Sof(C131)=Sof(H131)=
 Sof(C132)=Sof(H132)=FVAR(20)
6.a Everything fixed:
 C109, C110, C111, C112, C113, C114, C115, C116, C117, C118, C119, C120, C121,
 C122, C123, C124, C125, C126, C127, C128, C129, C130, C131, C132
6.b Free rotating group:
 C92(C93,C94,C95,C96,C91,C97,C98,C99,C100,C101,C102), C103(C104,C105,C106,C107,
 C108,P1)
6.c Ternary CH refined with riding coordinates:
 C1(H1), C7(H7), C13(H13), C19(H19), C25(H25), C31(H31), C37(H37), C43(H43),
 C49(H49), C55(H55), C61(H61), C67(H67), C73(H73), C79(H79), C85(H85), C91(H91),
  C97(H97), C103(H103)
6.d Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C8(H8A,H8B),
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C14(H14A,H14B),
 C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C20(H20A,H20B),
  C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C26(H26A,
 H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B),
 C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B),
  C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,
 H42B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B), C47(H47A,H47B),
 C48(H48A,H48B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B),
  C54(H54A,H54B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,
 H59B), C60(H60A,H60B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B),
 C65(H65A,H65B), C66(H66A,H66B), C68(H68A,H68B), C69(H69A,H69B), C70(H70A,H70B),
  C71(H71A,H71B), C72(H72A,H72B), C74(H74A,H74B), C75(H75A,H75B), C76(H76A,
 H76B), C77(H77A,H77B), C78(H78A,H78B), C80(H80A,H80B), C81(H81A,H81B),
 C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B), C86(H86A,H86B), C87(H87A,H87B),
  C88(H88A,H88B), C89(H89A,H89B), C90(H90A,H90B), C92(H92A,H92B), C93(H93A,
 H93B), C94(H94A,H94B), C95(H95A,H95B), C96(H96A,H96B), C98(H98A,H98B),
 C99(H99A,H99B), C100(H10C,H10D), C101(H10E,H10F), C102(H10G,H10H), C104(H10I,
 H10J), C105(H10K,H10L), C106(H10M,H10N), C107(H10O,H10P), C108(H10Q,H10R)
6.e Aromatic/amide H refined with riding coordinates:
 C110(H110), C111(H111), C112(H112), C113(H113), C114(H114), C116(H116),
 C117(H117), C118(H118), C119(H119), C120(H120), C122(H122), C123(H123),
 C124(H124), C125(H125), C126(H126), C128(H128), C129(H129), C130(H130),
 C131(H131), C132(H132)
;
_olex2_submission_special_instructions 'No special instructions were received'