Alkynyl and Halogen Co-protected (AuAg)44 Nanoclusters: A Comparative Study on Optical Absorbance, Structure Analysis, and Hydrogen Evolution Performance
Tang, Yun; Sun, Fang; Ma, Xiaoshuang; Qin, Lubing; Ma, Guanyu; Tang, Qing; Tang, Zhenghua; Dalton Transactions  (2022) –; doi:10.1039/D2DT00634K

data_7710117
_publ_section_title
;
 Alkynyl and Halogen Co-protected (AuAg)44 Nanoclusters: A Comparative
 Study on Optical Absorbance, Structure Analysis, and Hydrogen Evolution
 Performance
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00634K
_journal_year                    2022
_chemical_formula_moiety         'C288 H312 Ag20 Au24 Cl2, H2 O'
_chemical_formula_sum            'C288 H314 Ag20 Au24 Cl2 O'
_chemical_formula_weight         10746.87
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-04
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-04-22 deposited with the CCDC.	2022-04-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.5530(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.06600(10)
_cell_length_b                   32.5271(2)
_cell_length_c                   45.5844(3)
_cell_measurement_reflns_used    91927
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.2960
_cell_measurement_theta_min      2.3880
_cell_volume                     30887.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.948
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -77.00  25.00   0.50    0.47    --  -46.00  95.00 108.00  204
  2  \w    -23.00  28.00   0.50    0.47    --  -46.00  19.00  30.00  102
  3  \w     40.00  67.00   0.50    0.47    --   46.00 -95.00  -1.00   54
  4  \w     34.00 105.00   0.50    2.74    --  106.06 -95.00  -1.00  142
  5  \w     70.00  96.00   0.50    2.74    --  106.06 -77.00   0.00   52
  6  \w     42.00  67.00   0.50    2.74    --  106.06 -61.00   0.00   50
  7  \w     38.00  64.00   0.50    2.74    --  106.06 -61.00  60.00   52
  8  \w     33.00  64.00   0.50    2.74    --  106.06 -77.00   0.00   62
  9  \w     33.00  73.00   0.50    2.74    --  106.06 -61.00 -90.00   80
 10  \w     37.00  69.00   0.50    2.74    --  106.06 -61.00-150.00   64
 11  \w    -20.00  38.00   0.50    0.47    --   46.00 -95.00  -1.00  116
 12  \w    -29.00  28.00   0.50    0.47    --   46.00 -19.00   0.00  114
 13  \w     33.00  73.00   0.50    2.74    --  106.06 -61.00 120.00   80
 14  \w     34.00  70.00   0.50    2.74    --  106.06 -61.00 150.00   72
 15  \w     91.00 146.00   0.50    2.74    --  106.06  95.00 108.00  110
 16  \w    -62.00 -37.00   0.50    2.74    -- -102.00  61.00  60.00   50
 17  \w    -68.00 -31.00   0.50    2.74    -- -102.00  61.00  90.00   74
 18  \w   -103.00 -40.00   0.50    2.74    -- -102.00  95.00 108.00  126
 19  \w    -76.00 -31.00   0.50    2.74    -- -102.00  77.00 -60.00   90
 20  \w    -69.00 -29.00   0.50    2.74    -- -102.00  61.00-120.00   80
 21  \w    -68.00 -33.00   0.50    2.74    -- -102.00  61.00-180.00   70
 22  \w   -154.00-129.00   0.50    2.74    -- -102.00 -95.00  -1.00   50
 23  \w   -172.00 -87.00   0.50    2.74    -- -102.00 -45.00  60.00  170
 24  \w   -119.00 -78.00   0.50    0.47    --  -46.00-125.00 120.00   82
 25  \w   -135.00-110.00   0.50    2.74    -- -102.00 -45.00  90.00   50
 26  \w   -166.00-141.00   0.50    2.74    -- -102.00 -45.00  90.00   50
 27  \w   -162.00-112.00   0.50    2.74    -- -102.00 -15.00-180.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0178864000
_diffrn_orient_matrix_UB_12      -0.0261840000
_diffrn_orient_matrix_UB_13      0.0281806000
_diffrn_orient_matrix_UB_21      0.0196194000
_diffrn_orient_matrix_UB_22      -0.0356563000
_diffrn_orient_matrix_UB_23      -0.0190259000
_diffrn_orient_matrix_UB_31      0.0689952000
_diffrn_orient_matrix_UB_32      0.0169192000
_diffrn_orient_matrix_UB_33      0.0035365000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0609
_diffrn_reflns_av_unetI/netI     0.0510
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.948
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       57
_diffrn_reflns_limit_l_min       -56
_diffrn_reflns_number            237255
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.948
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.903
_diffrn_reflns_theta_min         2.385
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    31.190
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.11353
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    2.311
_exptl_crystal_F_000             19680
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.07
_refine_diff_density_max         5.600
_refine_diff_density_min         -2.914
_refine_diff_density_rms         0.348
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2895
_refine_ls_number_reflns         61867
_refine_ls_number_restraints     1015
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0869
_refine_ls_R_factor_gt           0.0735
_refine_ls_shift/su_max          0.016
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0711P)^2^+1189.7517P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1810
_refine_ls_wR_factor_ref         0.1913
_reflns_Friedel_coverage         0.000
_reflns_number_gt                51211
_reflns_number_total             61867
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00634k2.cif
_cod_data_source_block           hg-ty-1
_cod_database_code               7710117
_shelx_shelxl_version_number     2018/3
_diffrn_oxdiff_digest_frames
;
0161262c23501f96dcd16128c9f55ea4c802346b35d
;
_diffrn_oxdiff_digest_hkl
;
01eb8ad56b7211b9fabf2f85f7cc7d50118395
;
_reflns_odcompleteness_completeness 99.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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, All O(H,H) groups
2. Restrained distances
 C147-C89 = C234-C167 = C231-C190 = C195-C48 = C144-C29 = C248-C126 = C177-C57
 = C207-C166 = C197-C102 = C146-C94 = C249-C220 = C129-C79 = C259-C17 = C229-
 C74 = C110-C186 = C237-C62 = C209-C139 = C264-C132
 1.5 with sigma of 0.02
 C295-C200
 1.5 with sigma of 0.02
 C13-C5
 1.17 with sigma of 0.02
 C255-C234 = C253-C234 = C251-C234
 1.52 with sigma of 0.02
 C275-C274 = C276-C274 = C274-C273
 1.52 with sigma of 0.02
 H181-H23P
 2.1 with sigma of 0.02
 H27R-H92
 2.1 with sigma of 0.02
 C265-C266 \\sim C265-C267 \\sim C265-C268
 with sigma of 0.02
 C266-C267 \\sim C266-C268 \\sim C267-C268
 with sigma of 0.04
 C153-C265 \\sim C265-C149
 with sigma of 0.02
 C269-C270 \\sim C269-C271 \\sim C269-C272
 with sigma of 0.02
 C270-C271 \\sim C270-C272 \\sim C271-C272
 with sigma of 0.04
 C155-C269 \\sim C269-C157
 with sigma of 0.02
 C106-C274 \\sim C274-C92
 with sigma of 0.02
 C277-C278 \\sim C277-C279 \\sim C278-C279
 with sigma of 0.04
 C119-C256 \\sim C256-C115
 with sigma of 0.02
 C213-C281 \\sim C281-C217
 with sigma of 0.02
 C292-C293 \\sim C292-C294 \\sim C292-C291
 with sigma of 0.02
 C291-C293 \\sim C291-C294
 with sigma of 0.04
 C295-C296 \\sim C295-C297 \\sim C295-C298
 with sigma of 0.02
 C296-C297 \\sim C296-C298 \\sim C297-C298
 with sigma of 0.04
 C201-C295 \\sim C295-C205
 with sigma of 0.02
 C281-C282 \\sim C281-C283 \\sim C281-C280
 with sigma of 0.02
 C280-C282 \\sim C280-C283
 with sigma of 0.04
 C253-C255 \\sim C255-C251
 with sigma of 0.02
 C255-C251 \\sim C251-C253
 with sigma of 0.02
 C251-C253 \\sim C253-C255
 with sigma of 0.02
 C274-C275 \\sim C274-C276 \\sim C274-C273
 with sigma of 0.02
 C273-C275 \\sim C273-C276
 with sigma of 0.04
3. Restrained planarity
 C201, C202, C203, C204, C205, C200
 with sigma of 0.01
 C148, C153, C152, C151, C150, C149, C265
 with sigma of 0.01
 C156, C157, C158, C159, C154, C155, C269
 with sigma of 0.01
 C274, C128, C106, C67, C71, C85, C92
 with sigma of 0.01
 C256, C120, C119, C118, C117, C116, C115
 with sigma of 0.01
 C217, C212, C213, C281
 with sigma of 0.01
 C295, C200, C201, C205
 with sigma of 0.01
4. Rigid bond restraints
 C203, C204, C205, C200, C295, C297, C296, C298, C201, C202
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C265 \\sim C266 \\sim C267 \\sim C268: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C269 \\sim C270 \\sim C271 \\sim C272: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C277 \\sim C278 \\sim C279: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C291 \\sim C292 \\sim C293 \\sim C294: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C295 \\sim C296 \\sim C297 \\sim C298: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C203 \\sim C204 \\sim C205 \\sim C200 \\sim C201 \\sim C202 \\sim C295 \\sim
C296 \\sim C297 \\sim C298: within 1.7A with sigma of 0.02 and sigma for
terminal atoms of 0.04
C280 \\sim C281 \\sim C282 \\sim C283: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C273 \\sim C274 \\sim C275 \\sim C276: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(C295) \\sim Ueq, Uanis(C296) \\sim Ueq, Uanis(C297) \\sim Ueq,
Uanis(C298) \\sim Ueq, Uanis(C200) \\sim Ueq, Uanis(C205) \\sim Ueq,
Uanis(C204) \\sim Ueq, Uanis(C203) \\sim Ueq, Uanis(C202) \\sim Ueq,
Uanis(C201) \\sim Ueq: with sigma of 0.04 and sigma for terminal atoms of 0.1
Uanis(Au15) = Uanis(C5)
6. Rigid body (RIGU) restrains
 C265, C266, C267, C268
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C269, C270, C271, C272
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C277, C278, C279
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C120, C279, C256, C278, C277
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C226, C207, C242, C239, C161, C162, C166, C165, C164, C163
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C240, C231, C233, C235, C190, C191, C192, C193, C194, C189
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C250, C248, C252, C243, C125, C126, C121, C122, C123, C124
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C291, C292, C293, C294
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C291, C292, C294, C293, C284, C289, C288, C287, C286, C285
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C295, C296, C297, C298
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C201, C202, C203, C204, C205, C200, C297, C296, C295, C298
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C280, C281, C282, C283
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C58, C99, C214, C215, C216, C217, C212, C213, C280, C281, C283, C282
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C8, C44, C222, C223, C218, C219, C220, C221, C249, C290, C246, C244
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C253, C234, C255, C251, C167, C172, C168, C171, C169, C170
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C273, C274, C275, C276
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Fixed Sof: C218(0.5) H218(0.5) C219(0.5) H219(0.5) C220(0.5) C221(0.5)
 H221(0.5) C222(0.5) H222(0.5) C223(0.5) C244(0.5) H24M(0.5) H24N(0.5)
 H24O(0.5) C246(0.5) H24S(0.5) H24T(0.5) H24U(0.5) C249(0.5) C284(0.5)
 C285(0.5) H285(0.5) C286(0.5) H286(0.5) C287(0.5) C288(0.5) H288(0.5)
 C289(0.5) H289(0.5) C290(0.5) H29A(0.5) H29B(0.5) H29C(0.5) C291(0.5)
 H29D(0.5) H29E(0.5) H29F(0.5) C292(0.5) C293(0.5) H29G(0.5) H29H(0.5)
 H29I(0.5) C294(0.5) H29J(0.5) H29K(0.5) H29L(0.5)
8.a Riding coordinates:
 C175(H17G,H17H,H17I), C244(H24M,H24N,H24O), C260(H26A,H26B,H26C), C283(H28G,
 H28H,H28I), O1(HB,HC)
8.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C16(H16), C18(H18), C19(H19), C28(H28), C30(H30), C31(H31),
 C33(H33), C46(H46), C47(H47), C49(H49), C50(H50), C52(H52), C53(H53), C55(H55),
  C56(H56), C60(H60), C61(H61), C63(H63), C64(H64), C67(H67), C72(H72),
 C73(H73), C75(H75), C76(H76), C78(H78), C80(H80), C81(H81), C83(H83), C85(H85),
  C87(H87), C88(H88), C90(H90), C91(H91), C92(H92), C93(H93), C95(H95),
 C96(H96), C98(H98), C100(H100), C101(H101), C103(H103), C104(H104), C106(H106),
  C115(H115), C116(H116), C118(H118), C119(H119), C121(H121), C122(H122),
 C124(H124), C125(H125), C131(H131), C133(H133), C134(H134), C136(H136),
 C138(H138), C140(H140), C141(H141), C143(H143), C149(H149), C150(H150),
 C152(H152), C153(H153), C154(H154), C155(H155), C157(H157), C158(H158),
 C161(H161), C162(H162), C164(H164), C165(H165), C168(H168), C169(H169),
 C171(H171), C172(H172), C181(H181), C182(H182), C184(H184), C185(H185),
 C189(H189), C191(H191), C192(H192), C194(H194), C201(H201), C202(H202),
 C204(H204), C205(H205), C213(H213), C214(H214), C216(H216), C217(H217),
 C218(H218), C219(H219), C221(H221), C222(H222), C285(H285), C286(H286),
 C288(H288), C289(H289)
8.c Fitted hexagon refined as free rotating group:
 C14(C15,C16,C17,C18,C19), C28(C29,C30,C31,C32,C33), C46(C47,C48,C49,C50,C51),
 C52(C53,C54,C55,C56,C57), C60(C61,C62,C63,C64,C65), C72(C73,C74,C75,C76,C77),
 C78(C79,C80,C81,C82,C83), C86(C87,C88,C89,C90,C91), C93(C94,C95,C96,C97,C98),
 C100(C101,C102,C103,C104,C105), C115(C116,C117,C118,C119,C120), C121(C122,C123,
 C124,C125,C126), C131(C132,C133,C134,C135,C136), C138(C139,C140,C141,C142,
 C143), C148(C149,C150,C151,C152,C153), C154(C155,C156,C157,C158,C159),
 C161(C162,C163,C164,C165,C166), C167(C168,C169,C170,C171,C172), C189(C190,C191,
 C192,C193,C194), C200(C201,C202,C203,C204,C205), C212(C213,C214,C215,C216,
 C217), C218(C219,C220,C221,C222,C223), C284(C285,C286,C287,C288,C289)
8.d Idealised Me refined as rotating group:
 C111(H11A,H11B,H11C), C113(H11D,H11E,H11F), C130(H13A,H13B,H13C), C137(H13D,
 H13E,H13F), C145(H14A,H14B,H14C), C160(H16A,H16B,H16C), C173(H17A,H17B,H17C),
 C174(H17D,H17E,H17F), C176(H17J,H17K,H17L), C178(H17M,H17N,H17O), C179(H17P,
 H17Q,H17R), C180(H18A,H18B,H18C), C187(H18D,H18E,H18F), C188(H18G,H18H,H18I),
 C196(H19A,H19B,H19C), C198(H19D,H19E,H19F), C199(H19G,H19H,H19I), C206(H20A,
 H20B,H20C), C210(H21A,H21B,H21C), C211(H21D,H21E,H21F), C224(H22A,H22B,H22C),
 C225(H22D,H22E,H22F), C226(H22G,H22H,H22I), C227(H22J,H22K,H22L), C228(H22M,
 H22N,H22O), C230(H23A,H23B,H23C), C232(H23D,H23E,H23F), C233(H23G,H23H,H23I),
 C235(H23J,H23K,H23L), C236(H23M,H23N,H23O), C238(H23P,H23Q,H23R), C239(H23S,
 H23T,H23U), C240(H24A,H24B,H24C), C241(H24D,H24E,H24F), C242(H24G,H24H,H24I),
 C243(H24J,H24K,H24L), C245(H24P,H24Q,H24R), C246(H24S,H24T,H24U), C247(H24V,
 H24W,H24X), C250(H25A,H25B,H25C), C251(H25D,H25E,H25F), C252(H25G,H25H,H25I),
 C253(H25J,H25K,H25L), C254(H25M,H25N,H25O), C255(H25P,H25Q,H25R), C257(H25S,
 H25T,H25U), C258(H25V,H25W,H25X), C261(H26D,H26E,H26F), C262(H26G,H26H,H26I),
 C263(H26J,H26K,H26L), C266(H26M,H26N,H26O), C267(H26P,H26Q,H26R), C268(H26S,
 H26T,H26U), C270(H27A,H27B,H27C), C271(H27D,H27E,H27F), C272(H27G,H27H,H27I),
 C273(H27J,H27K,H27L), C275(H27M,H27N,H27O), C276(H27P,H27Q,H27R), C277(H27S,
 H27T,H27U), C278(H27V,H27W,H27X), C279(H27Y,H,HA), C280(H28A,H28B,H28C),
 C282(H28D,H28E,H28F), C290(H29A,H29B,H29C), C291(H29D,H29E,H29F), C293(H29G,
 H29H,H29I), C294(H29J,H29K,H29L), C296(H29M,H29N,H29O), C297(H29P,H29Q,H29R),
 C298(H29S,H29T,H29U)
;
_shelx_res_checksum              74027
_shelx_fab_checksum              26396
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 8.594
_oxdiff_exptl_absorpt_empirical_full_min 0.591