Quantitative analysis of air-oxidation reactions of thiolate-protected gold nanoclusters.
Suzuki, Wataru; Takahata, Ryo; Mizuhata, Yoshiyuki; Tokitoh, Norihiro; Xue, Songlin; Teranishi, Toshiharu; Chemical science 15 (2024) 18896–18902; doi:10.1039/d4sc02995j

data_1572881
_publ_section_title
;
 Quantitative analysis of air-oxidation reactions of thiolate-protected
 gold nanoclusters.
;
_journal_issue                   45
_journal_name_full               'Chemical science'
_journal_page_first              18896
_journal_page_last               18902
_journal_paper_doi               10.1039/d4sc02995j
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety
'C108 H90 Au25 S18, C32 H68 N, 0.766(C7 H8), C2 H6 O'
_chemical_formula_sum            'C147.36 H170.13 Au25 N O S18'
_chemical_formula_weight         7472.59
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-10-05
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-10-06 deposited with the CCDC.	2024-10-07 downloaded from the CCDC.
;
_cell_angle_alpha                73.391(2)
_cell_angle_beta                 72.258(2)
_cell_angle_gamma                65.634(2)
_cell_formula_units_Z            2
_cell_length_a                   17.0841(8)
_cell_length_b                   20.5511(10)
_cell_length_c                   26.5333(12)
_cell_measurement_reflns_used    9981
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      27.47
_cell_measurement_theta_min      2.21
_cell_volume                     7943.6(7)
_computing_cell_refinement       'SAINT V8.40A (Bruker Nano, Inc., 2019)'
_computing_data_collection       'Bruker Instrument Service vV6.2.12'
_computing_data_reduction        'SAINT V8.40A (Bruker Nano, Inc., 2019)'
_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      90(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker D8 goniometer'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0589
_diffrn_reflns_av_unetI/netI     0.0433
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            193152
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.481
_diffrn_reflns_theta_min         1.855
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    23.262
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.5214
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1286 before and 0.0634 after correction.
The Ratio of minimum to maximum transmission is 0.6994.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    3.124
_exptl_crystal_description       block
_exptl_crystal_F_000             6665
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene/ethanol'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.06
_refine_diff_density_max         2.749
_refine_diff_density_min         -1.139
_refine_diff_density_rms         0.226
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1840
_refine_ls_number_reflns         36399
_refine_ls_number_restraints     34
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0444
_refine_ls_R_factor_gt           0.0306
_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^)+(0.0238P)^2^+21.3030P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0648
_refine_ls_wR_factor_ref         0.0703
_reflns_Friedel_coverage         0.000
_reflns_number_gt                28950
_reflns_number_total             36399
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02995j2.cif
_cod_data_source_block           Au25S18Ph18
_cod_depositor_comments          'Adding full bibliography for 1572881.cif.'
_cod_database_code               1572881
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.336
_shelx_estimated_absorpt_t_min   0.090
_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, All O(H) groups
2. Restrained distances
 C154-C155
 1.54 with sigma of 0.02
 C102-C111 \\sim C102-C108 \\sim C102-C103 \\sim C102-C107
 with sigma of 0.02
 C103-C104 \\sim C107-C106 \\sim C108-C109 \\sim C111-C110
 with sigma of 0.02
 C109-C105 \\sim C110-C105 \\sim C104-C105 \\sim C105-C106
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C115) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C153, C154, C162, C163, C127, C128
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C118)=Sof(C119)=Sof(H119)=Sof(C120)=Sof(H120)=Sof(C121)=Sof(H121)=
 Sof(C122)=Sof(H122)=Sof(C123)=Sof(H123)=1-FVAR(1)
 Sof(C112)=Sof(C113)=Sof(H113)=Sof(C114)=Sof(H114)=Sof(C115)=Sof(H115)=
 Sof(C116)=Sof(H116)=Sof(C117)=Sof(H117)=Sof(C124)=Sof(C125)=Sof(H125)=
 Sof(C126)=Sof(H126)=Sof(C127)=Sof(H127)=Sof(C128)=Sof(H128)=Sof(C129)=
 Sof(H129)=Sof(C130)=Sof(H13O)=Sof(H13P)=Sof(H13Q)=FVAR(1)
 Sof(Au15)=1-FVAR(2)
 Sof(Au14)=FVAR(2)
 Sof(Au24)=1-FVAR(3)
 Sof(Au23)=FVAR(3)
 Sof(Au17)=1-FVAR(4)
 Sof(Au18)=FVAR(4)
 Sof(H10A)=Sof(C108)=Sof(H108)=Sof(C109)=Sof(H109)=Sof(C110)=Sof(H110)=
 Sof(C111)=Sof(H111)=1-FVAR(5)
 Sof(C103)=Sof(H103)=Sof(C104)=Sof(H104)=Sof(H105)=Sof(C106)=Sof(H106)=
 Sof(C107)=Sof(H107)=FVAR(5)
 Sof(C67)=Sof(H67)=Sof(C68)=Sof(H68)=Sof(C69)=Sof(H69)=Sof(C70)=Sof(H70)=
 Sof(C71)=Sof(H71)=1-FVAR(6)
 Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=Sof(C65)=Sof(H65)=
 Sof(C66)=Sof(H66)=FVAR(6)
6.a Secondary CH2 refined with riding coordinates:
 C131(H13R,H13S), C133(H13A,H13B), C134(H13C,H13D), C135(H13E,H13F), C136(H13G,
 H13H), C137(H13I,H13J), C138(H13K,H13L), C139(H13M,H13N), C141(H14D,H14E),
 C142(H14F,H14G), C143(H14H,H14I), C144(H14J,H14K), C145(H14L,H14M), C146(H14N,
 H14O), C147(H14P,H14Q), C149(H14U,H14V), C150(H15A,H15B), C151(H15C,H15D),
 C152(H15E,H15F), C153(H15G,H15H), C154(H15I,H15J), C155(H15K,H15L), C157(H15P,
 H15Q), C158(H15R,H15S), C159(H15T,H15U), C160(H16A,H16B), C161(H16C,H16D),
 C162(H16E,H16F), C163(H16G,H16H)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21),
  C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29),
 C30(H30), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C38(H38), C39(H39),
  C40(H40), C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47),
 C48(H48), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57),
  C58(H58), C59(H59), C60(H60), C62(H62), C63(H63), C64(H64), C65(H65),
 C66(H66), C67(H67), C68(H68), C69(H69), C70(H70), C71(H71), C73(H73), C74(H74),
  C75(H75), C76(H76), C77(H77), C79(H79), C80(H80), C81(H81), C82(H82),
 C83(H83), C85(H85), C86(H86), C87(H87), C88(H88), C89(H89), C91(H91), C92(H92),
  C93(H93), C94(H94), C95(H95), C97(H97), C98(H98), C99(H99), C100(H100),
 C101(H101), C103(H103), C104(H104), C105(H105), C105(H10A), C106(H106),
 C107(H107), C108(H108), C109(H109), C110(H110), C111(H111), C113(H113),
 C114(H114), C115(H115), C116(H116), C117(H117), C119(H119), C120(H120),
 C121(H121), C122(H122), C123(H123), C125(H125), C126(H126), C127(H127),
 C128(H128), C129(H129)
6.c Fitted hexagon refined as free rotating group:
 C124(C125,C126,C127,C128,C129)
6.d Idealised Me refined as rotating group:
 C130(H13O,H13P,H13Q), C132(H13T,H13U,H13V), C140(H14A,H14B,H14C), C148(H14R,
 H14S,H14T), C156(H15M,H15N,H15O), C164(H16I,H16J,H16K)
6.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              4416
_shelx_hkl_checksum              27110
_olex2_submission_special_instructions 'No special instructions were received'