Atomically Precise Alkynyl-Protected Metal Nanoclusters as a Model Catalyst: Observation of Promoting Effect of Surface Ligands on Catalysis by Metal Nanoparticles.
Wang, Yu; Wan, Xian-Kai; Ren, Liting; Su, Haifeng; Li, Gang; Malola, Sami; Lin, Shuichao; Tang, Zichao; Häkkinen, Hannu; Teo, Boon K.; Wang, Quan-Ming; Zheng, Nanfeng; Journal of the American Chemical Society 138 (2016) 3278–3281; doi:10.1021/jacs.5b12730

data_4130013
_publ_section_title
;
 Atomically Precise Alkynyl-Protected Metal Nanoclusters as a Model
 Catalyst: Observation of Promoting Effect of Surface Ligands on Catalysis
 by Metal Nanoparticles.
;
_journal_issue                   10
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3278
_journal_page_last               3281
_journal_paper_doi               10.1021/jacs.5b12730
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         'C272 H170 Ag28 Au34, C7 H8'
_chemical_formula_sum            'C279 H178 Ag28 Au34'
_chemical_formula_weight         13247.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-07-18
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.2164(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   36.8939(6)
_cell_length_b                   22.0660(5)
_cell_length_c                   39.9832(7)
_cell_measurement_reflns_used    28629
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      70.4140
_cell_measurement_theta_min      3.6650
_cell_volume                     31813.3(11)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3415
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measurement_details
;
  1 omega  -47.00    9.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.4924   38.0000  150.0000 56

  2 omega -124.00  -79.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.4924  -99.0000  120.0000 45

  3 omega  -76.00   39.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.4924   19.0000   60.0000 115

  4 omega -109.00  -83.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.4924  -99.0000  -90.0000 26

  5 omega   81.00  164.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      102.9818   61.0000    0.0000 83

  6 omega   39.00   81.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      102.9818  -30.0000 -120.0000 42

  7 omega   27.00   91.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      102.9818  -30.0000   30.0000 64

  8 omega   32.00  131.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      102.9818  -61.0000  120.0000 99

  9 omega   80.00  163.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      102.9818   30.0000  -60.0000 83

 10 omega   46.00  103.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      102.9818  -94.0000   90.0000 57
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0391182000
_diffrn_orient_matrix_UB_12      0.0034187000
_diffrn_orient_matrix_UB_13      -0.0231354000
_diffrn_orient_matrix_UB_21      0.0131974000
_diffrn_orient_matrix_UB_22      -0.0389150000
_diffrn_orient_matrix_UB_23      -0.0271461000
_diffrn_orient_matrix_UB_31      -0.0111122000
_diffrn_orient_matrix_UB_32      -0.0577467000
_diffrn_orient_matrix_UB_33      0.0168839000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0586
_diffrn_reflns_av_unetI/netI     0.0778
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            129151
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.699
_diffrn_reflns_theta_min         3.182
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    42.365
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.16996
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    2.766
_exptl_crystal_description
;
;
_exptl_crystal_F_000             23416
_refine_diff_density_max         3.244
_refine_diff_density_min         -2.447
_refine_diff_density_rms         0.304
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2873
_refine_ls_number_reflns         60204
_refine_ls_number_restraints     347
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0935
_refine_ls_R_factor_gt           0.0604
_refine_ls_shift/su_max          0.103
_refine_ls_shift/su_mean         0.005
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0731P)^2^+215.2500P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1484
_refine_ls_wR_factor_ref         0.1666
_reflns_Friedel_coverage         0.000
_reflns_number_gt                41811
_reflns_number_total             60204
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b12730_si_002.cif
_cod_data_source_block           wy140916-2
_cod_original_cell_volume        31813.2(11)
_cod_database_code               4130013
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_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
 C9BA-C210
 1.45 with sigma of 0.02
 C36-C18
 1.21 with sigma of 0.02
 C27-C71
 1.2 with sigma of 0.02
 C71-C164
 1.4 with sigma of 0.02
 C107-C189
 1.4 with sigma of 0.02
 C69-C179
 1.45 with sigma of 0.02
 C69-C179
 1.4 with sigma of 0.02
 C112-C69
 2.45 with sigma of 0.04
 C69-C300
 2.45 with sigma of 0.04
3. Rigid bond restraints
 C142, C310, C330, C421, C256, C264, C361, C483, C7, C7BA, C0BA, C42
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C265, C306
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C358, C290
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C83, C421
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C268, C275
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C275, C286
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C18, C36
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C165, C176
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C297, C338
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C122, C338
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C57, C3CA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C248, C89
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Au0X, C36
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C0DA, C69
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C12, C107
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C27, C71
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C71, C164
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C252, C271, C134, C189, C280, C345, C364, C298, C187, C290, C72, C90, C10, C43
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C96, C279, C334, C118, C229, C320, C408, C144, C144, C159, C166, C205, C208,
 C295, C210, C210, C343, C343, C361, C314, C255, C8BA, C9BA, C9BA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C107, C189
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C310, C421, C113, C176, C197, C215, C118, C305, C320, C296, C163, C207, C221,
 C254, C247, C266, C277, C304, C483, C314
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C106, C110, C279, C306, C117, C165, C125, C201, C204, C268, C274, C274, C189,
 C296, C136, C140, C159, C183, C191, C205, C207, C130, C0AA, C256, C285, C303,
 C104, C298, C187, C1AA, C14, C16
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C179, C112
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C112, C200
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C200, C5AA, C5DA, C0BA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C74, C300, C46, C72
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C69, C179
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C139) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C204) \\sim Ueq, Uanis(C268) \\sim Ueq, Uanis(C275) \\sim Ueq,
Uanis(C286) \\sim Ueq, Uanis(C125) \\sim Ueq, Uanis(C201) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
Uanis(C343) \\sim Ueq, Uanis(C255) \\sim Ueq, Uanis(C314) \\sim Ueq,
Uanis(C210) \\sim Ueq, Uanis(C361) \\sim Ueq, Uanis(C483) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
Uanis(C36) \\sim Ueq, Uanis(C338) \\sim Ueq, Uanis(C361) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
Uanis(C86) \\sim Ueq, Uanis(C297) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C83) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C197) \\sim Ueq, Uanis(C338)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C179) \\sim Ueq, Uanis(C421) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C200) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C36) \\sim Ueq, Uanis(C1CA) \\sim Ueq, Uanis(C5AA) \\sim Ueq, Uanis(C9BA)
\\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C208) \\sim Ueq,
Uanis(C223) \\sim Ueq, Uanis(C252) \\sim Ueq, Uanis(C290) \\sim Ueq,
Uanis(C336) \\sim Ueq, Uanis(C358) \\sim Ueq, Uanis(C364) \\sim Ueq,
Uanis(C421) \\sim Ueq, Uanis(C483) \\sim Ueq, Uanis(C104) \\sim Ueq,
Uanis(C142) \\sim Ueq, Uanis(C187) \\sim Ueq, Uanis(C210) \\sim Ueq,
Uanis(C238) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C36) \\sim Ueq, Uanis(C139) \\sim Ueq, Uanis(C197) \\sim Ueq, Uanis(C338)
\\sim Ueq, Uanis(C179) \\sim Ueq, Uanis(C189) \\sim Ueq, Uanis(C271) \\sim Ueq,
Uanis(C320) \\sim Ueq, Uanis(C7BA) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C197) = Uanis(C164)
Uanis(C134) = Uanis(C189)
Uanis(C179) = Uanis(C112)
5.a Aromatic/amide H refined with riding coordinates:
 C9AA(H9AA), C49(H49), C51(H51), C52(H52), C3CA(H3CA), C128(H128), C182(H182),
 C327(H327), C213(H213), C64(H64), C66(H66), C73(H73), C76(H76), C78(H78),
 C5CA(H5CA), C80(H80), C83(H83), C223(H223), C310(H310), C330(H330), C421(H421),
  C91(H91), C94(H94), C96(H96), C102(H102), C103(H103), C105(H105), C220(H220),
 C225(H225), C236(H236), C246(H246), C336(H336), C108(H108), C110(H110),
 C111(H111), C112(H112), C200(H200), C5AA(H5AA), C74(H74), C300(H300),
 C126(H126), C279(H279), C334(H334), C265(H265), C306(H306), C114(H114),
 C117(H117), C165(H165), C176(H176), C197(H197), C215(H215), C118(H118),
 C229(H229), C252(H252), C271(H271), C283(H283), C119(H119), C170(H170),
 C185(H185), C238(H238), C297(H297), C338(H338), C123(H123), C124(H124),
 C125(H125), C204(H204), C268(H268), C275(H275), C286(H286), C132(H132),
 C133(H133), C320(H320), C408(H408), C274(H274), C134(H134), C296(H296),
 C136(H136), C137(H137), C139(H139), C141(H141), C143(H143), C144(H144),
 C145(H145), C148(H148), C0CA(H0CA), C150(H150), C153(H153), C154(H154),
 C157(H157), C158(H158), C159(H159), C161(H161), C163(H163), C166(H166),
 C167(H167), C168(H168), C169(H169), C172(H172), C173(H173), C177(H177),
 C178(H178), C181(H181), C183(H183), C184(H184), C186(H186), C188(H188),
 C191(H191), C192(H192), C194(H194), C195(H195), C196(H196), C199(H199),
 C205(H205), C207(H207), C208(H208), C214(H214), C218(H218), C221(H221),
 C63(H63), C130(H130), C0AA(H0AA), C254(H254), C222(H222), C224(H224),
 C226(H226), C228(H228), C232(H232), C233(H233), C241(H241), C245(H245),
 C247(H247), C256(H256), C264(H264), C266(H266), C272(H272), C277(H277),
 C280(H280), C282(H282), C285(H285), C288(H288), C295(H295), C302(H302),
 C248(H248), C89(H89), C58(H58), C237(H237), C303(H303), C304(H304), C321(H321),
  C343(H343), C361(H361), C483(H483), C314(H314), C255(H255), C345(H345),
 C358(H358), C364(H364), C298(H298), C187(H187), C290(H290), C7(H7), C44(H44),
 C46(H46), C72(H72), C90(H90), C19(H19), C22(H22), C5DA(H5DA), C0BA(H0BA),
 C42(H42), C10(H10), C14(H14), C17(H17), C39(H39), C43(H43)
5.b Fitted hexagon refined as free rotating group:
 C57(C3CA,C128,C182,C327,C213), C83(C142,C223,C310,C330,C421), C106(C220,C225,
 C236,C246,C336), C113(C126,C279,C334,C265,C306), C117(C164,C165,C176,C197,
 C215), C118(C229,C252,C271,C283,C305), C122(C170,C185,C238,C297,C338),
 C125(C201,C204,C268,C275,C286), C221(C6DA,C63,C130,C0AA,C254), C302(C248,C89,
 C58,C3BA,C237), C210(C343,C361,C483,C314,C255), C358(C104,C364,C298,C187,C290),
  C7(C7BA,C44,C46,C72,C90), C19(C6AA,C22,C5DA,C0BA,C42), C10(C14,C16,C17,C39,
 C43)
5.c Idealised Me refined as rotating group:
 C60(H60A,H60B,H60C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'
_platon_squeeze_void_probe_radius 1.20