Reconstructing the Surface of Gold Nanoclusters by Cadmium Doping.
Li, Qi; Lambright, Kelly J.; Taylor, Michael G.; Kirschbaum, Kristin; Luo, Tian-Yi; Zhao, Jianbo; Mpourmpakis, Giannis; Mokashi-Punekar, Soumitra; Rosi, Nathaniel L.; Jin, Rongchao; Journal of the American Chemical Society 139 (2017) 17779–17782; doi:10.1021/jacs.7b11491

data_4131829
_publ_section_title
;
 Reconstructing the Surface of Gold Nanoclusters by Cadmium Doping.
;
_journal_issue                   49
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              17779
_journal_page_last               17782
_journal_paper_doi               10.1021/jacs.7b11491
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety
'2(C48 H88 Au10.66 Cu0.84 S8), C7 N0.5, C9 N0.5'
_chemical_formula_sum            'C112 H176 Au21.34 Cu1.66 N S16'
_chemical_formula_weight         6358.56
_space_group_crystal_system      orthorhombic
_space_group_IT_number           68
_space_group_name_Hall           '-C 2a 2ac'
_space_group_name_H-M_alt        'C c c a :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-11-27
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   33.0713(12)
_cell_length_b                   63.499(3)
_cell_length_c                   32.3807(11)
_cell_measurement_reflns_used    9869
_cell_measurement_temperature    230.01
_cell_measurement_theta_max      51.19
_cell_measurement_theta_min      2.73
_cell_volume                     67999(5)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      230.01
_diffrn_detector                 'CCD area detector'
_diffrn_detector_type            'APEX II CCD'
_diffrn_measured_fraction_theta_full 0.600
_diffrn_measured_fraction_theta_max 0.999
_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  0.1338
_diffrn_reflns_av_unetI/netI     0.0764
_diffrn_reflns_Laue_measured_fraction_full 0.600
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       64
_diffrn_reflns_limit_k_min       -63
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            150560
_diffrn_reflns_point_group_measured_fraction_full 0.600
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         51.277
_diffrn_reflns_theta_min         1.391
_diffrn_source                   'IMuS micro-focus source'
_diffrn_source_target            Cu
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    35.924
_exptl_absorpt_correction_T_max  0.7501
_exptl_absorpt_correction_T_min  0.1809
_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 0.0744 after correction.
The Ratio of minimum to maximum transmission is 0.2412.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'metallic brownish'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_density_diffrn    2.484
_exptl_crystal_description       rectangular
_exptl_crystal_F_000             45522
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.06
_refine_diff_density_max         2.421
_refine_diff_density_min         -2.209
_refine_diff_density_rms         0.384
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1381
_refine_ls_number_reflns         18456
_refine_ls_number_restraints     1386
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.1072
_refine_ls_R_factor_gt           0.0702
_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^)+(0.0619P)^2^+6977.9121P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1685
_refine_ls_wR_factor_ref         0.1974
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12762
_reflns_number_total             18456
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b11491_si_004.cif
_cod_data_source_block           ltylq20161014_0m_a
_cod_original_cell_volume        67999(4)
_cod_original_sg_symbol_Hall     '-C 2b 2bc'
_cod_original_sg_symbol_H-M      'C c c e'
_cod_database_code               4131829
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.222
_shelx_estimated_absorpt_t_min   0.035
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Shared sites
{Au1, Cu1}
{Au10, Cu10}
{Au11, Cu11}
{Au12, Cu12}
{Au13, Cu13}
{Au15, Cu15}
{Au17, Cu17}
{Au24, Cu24}
3. Restrained distances
 C142-C146 \\sim C143-C145
 with sigma of 0.02
 C22-C26 \\sim C23-C25
 with sigma of 0.02
 C66-C64 \\sim C62-C64
 with sigma of 0.02
 C83-C84 \\sim C85-C84
 with sigma of 0.02
 C201-C202 \\sim C202-C203 \\sim C203-C204 \\sim C204-C205
 with sigma of 0.02
 C301-C302 \\sim C302-C303
 with sigma of 0.02
 C21-C22 \\sim C21-C26
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
S1 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
S2 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
S3 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
S4 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
S5 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
S6 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
S7 \\sim C61 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
S8 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
S9 \\sim C91 \\sim C92 \\sim C93 \\sim C94 \\sim C95 \\sim C96: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
S10 \\sim C101 \\sim C102 \\sim C103 \\sim C104 \\sim C105 \\sim C106: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
S11 \\sim C111 \\sim C112 \\sim C113 \\sim C114 \\sim C115 \\sim C116: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
S12 \\sim C121 \\sim C122 \\sim C123 \\sim C124 \\sim C125 \\sim C126: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
S13 \\sim C131 \\sim C132 \\sim C133 \\sim C134 \\sim C135 \\sim C136: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
S14 \\sim C141 \\sim C142 \\sim C143 \\sim C144 \\sim C145 \\sim C146: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
S15 \\sim C151 \\sim C152 \\sim C153 \\sim C154 \\sim C155 \\sim C156: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
S16 \\sim C161 \\sim C162 \\sim C163 \\sim C164 \\sim C165 \\sim C166: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C312 \\sim C311 \\sim C310 \\sim C309 \\sim N1 \\sim C301 \\sim C302 \\sim
C303: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
N2 \\sim C201 \\sim C202 \\sim C203 \\sim C204 \\sim C205: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(Au1) = Uanis(Cu1)
Uanis(Au10) = Uanis(Cu10)
Uanis(Au11) = Uanis(Cu11)
Uanis(Au12) = Uanis(Cu12)
Uanis(Au13) = Uanis(Cu13)
Uanis(Au15) = Uanis(Cu15)
Uanis(Au17) = Uanis(Cu17)
Uanis(Au24) = Uanis(Cu24)
5. Rigid body (RIGU) restrains
 S1, C11, C12, C13, C14, C15, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S2, C21, C22, C23, C24, C25, C26
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S3, C31, C32, C33, C34, C35, C36
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S4, C41, C42, C43, C44, C45, C46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S5, C51, C52, C53, C54, C55, C56
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S6, C61, C62, C63, C64, C65, C66
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S7, C61, C72, C73, C74, C75, C76
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S8, C81, C82, C83, C84, C85, C86
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S9, C91, C92, C93, C94, C95, C96
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S10, C101, C102, C103, C104, C105, C106
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S11, C111, C112, C113, C114, C115, C116
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S12, C121, C122, C123, C124, C125, C126
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S13, C131, C132, C133, C134, C135, C136
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S14, C141, C142, C143, C144, C145, C146
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S15, C151, C152, C153, C154, C155, C156
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S16, C161, C162, C163, C164, C165, C166
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C312, C311, C310, C309, N1, C301, C302, C303
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N2, C201, C202, C203, C204, C205
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(Au12)=1-FVAR(1)
 Sof(Cu12)=FVAR(1)
 Sof(Au24)=1-FVAR(2)
 Sof(Cu24)=FVAR(2)
 Sof(Au1)=1-FVAR(3)
 Sof(Cu1)=FVAR(3)
 Sof(Au10)=1-FVAR(4)
 Sof(Cu10)=FVAR(4)
 Sof(Au11)=1-FVAR(5)
 Sof(Cu11)=FVAR(5)
 Sof(Au13)=1-FVAR(6)
 Sof(Cu13)=FVAR(6)
 Sof(Au15)=1-FVAR(7)
 Sof(Cu15)=FVAR(7)
 Sof(Au17)=1-FVAR(8)
 Sof(Cu17)=FVAR(8)
7.a Ternary CH refined with riding coordinates:
 C11(H11), C21(H21), C31(H31), C41(H41), C51(H51), C61(H61), C71(H71),
 C81(H81), C91(H91), C101(H101), C111(H111), C121(H121), C131(H131), C141(H141),
  C151(H151), C161(H161)
7.b Secondary CH2 refined with riding coordinates:
 C12(H12a,H12b), C13(H13a,H13b), C14(H14a,H14b), C15(H15a,H15b), C16(H16a,
 H16b), C22(H22a,H22b), C23(H23a,H23b), C24(H24a,H24b), C25(H25a,H25b),
 C26(H26a,H26b), C32(H32a,H32b), C33(H33a,H33b), C34(H34a,H34b), C35(H35a,H35b),
  C36(H36a,H36b), C42(H42a,H42b), C43(H43a,H43b), C44(H44a,H44b), C45(H45a,
 H45b), C46(H46a,H46b), C52(H52a,H52b), C53(H53a,H53b), C54(H54a,H54b),
 C55(H55a,H55b), C56(H56a,H56b), C62(H62a,H62b), C63(H63a,H63b), C64(H64a,H64b),
  C65(H65a,H65b), C66(H66a,H66b), C72(H72a,H72b), C73(H73a,H73b), C74(H74a,
 H74b), C75(H75a,H75b), C76(H76a,H76b), C82(H82a,H82b), C83(H83a,H83b),
 C84(H84a,H84b), C85(H85a,H85b), C86(H86a,H86b), C92(H92a,H92b), C93(H93a,H93b),
  C94(H94a,H94b), C95(H95a,H95b), C96(H96a,H96b), C102(H10a,H10b), C103(H10c,
 H10d), C104(H10e,H10f), C105(H10g,H10h), C106(H10i,H10j), C112(H11a,H11b),
 C113(H11c,H11d), C114(H11e,H11f), C115(H11g,H11h), C116(H11i,H11j), C122(H12c,
 H12d), C123(H12e,H12f), C124(H12g,H12h), C125(H12i,H12j), C126(H12k,H12l),
 C132(H13c,H13d), C133(H13e,H13f), C134(H13g,H13h), C135(H13i,H13j), C136(H13k,
 H13l), C142(H14c,H14d), C143(H14e,H14f), C144(H14g,H14h), C145(H14i,H14j),
 C146(H14k,H14l), C152(H15c,H15d), C153(H15e,H15f), C154(H15g,H15h), C155(H15i,
 H15j), C156(H15k,H15l), C162(H16c,H16d), C163(H16e,H16f), C164(H16g,H16h),
 C165(H16i,H16j), C166(H16k,H16l)
;
_shelx_res_checksum              16033
_shelx_hkl_checksum              1994
_olex2_submission_special_instructions 'No special instructions were received'