# Electronic Supplementary Material (ESI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2020

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_Au3Ag3
_database_code_depnum_ccdc_archive 'CCDC 1899711'
loop_
_audit_author_name
_audit_author_address
'Xiaoping Wang'
;Oak Ridge National Laboratory
United States of America
;
_audit_update_record             
;
2019-02-26 deposited with the CCDC.	2020-09-11 downloaded from the CCDC.
;
_audit_creation_date             2019-02-05
_audit_creation_method           
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         '1(C51 H45 Ag3 Au3 F42 N15), 1(C6 H6)'
_chemical_formula_sum            'C57 H51 Ag3 Au3 F42 N15'
_chemical_formula_weight         2658.58
_chemical_absolute_configuration ?
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0030 0.0020 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ag Ag -0.8970 1.1010 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Au Au -2.0130 8.8020 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0170 0.0100 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0060 0.0030 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      trigonal
_space_group_IT_number           160
_space_group_name_H-M_alt        'R 3 m'
_space_group_name_Hall           'R 3 -2"'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'-x+y, y, z'
'x, x-y, z'
'-y, -x, z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'-x+y+2/3, y+1/3, z+1/3'
'x+2/3, x-y+1/3, z+1/3'
'-y+2/3, -x+1/3, z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'-x+y+1/3, y+2/3, z+2/3'
'x+1/3, x-y+2/3, z+2/3'
'-y+1/3, -x+2/3, z+2/3'

_cell_length_a                   25.7253(8)
_cell_length_b                   25.7253(8)
_cell_length_c                   10.2918(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     5898.5(5)
_cell_formula_units_Z            3.00006
_cell_measurement_reflns_used    6803
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.62
_cell_measurement_theta_min      2.18
_shelx_estimated_absorpt_T_max   0.465
_shelx_estimated_absorpt_T_min   0.187
_exptl_absorpt_coefficient_mu    6.455
_exptl_absorpt_correction_T_max  0.4695
_exptl_absorpt_correction_T_min  0.1874
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_description       plate
_exptl_crystal_density_diffrn    2.245
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             3762
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.14
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0305
_diffrn_reflns_av_unetI/netI     0.0390
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            18891
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.708
_diffrn_reflns_theta_min         1.583
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker SMART APEX II CCD'
_diffrn_measurement_method       'ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.977
_reflns_Friedel_fraction_full    0.986
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                2558
_reflns_number_total             2661
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       ?
_computing_data_collection       ?
_computing_data_reduction        ?
_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    ?
_refine_diff_density_max         1.543
_refine_diff_density_min         -4.080
_refine_diff_density_rms         0.157
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.010(17)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     213
_refine_ls_number_reflns         2661
_refine_ls_number_restraints     117
_refine_ls_R_factor_all          0.0459
_refine_ls_R_factor_gt           0.0432
_refine_ls_restrained_S_all      1.049
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0262P)²+186.0520P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1049
_refine_ls_wR_factor_ref         0.1069
_refine_special_details          'Refined as a 2-component inversion twin.,Twin'
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.990(17)
 0.010(17)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C1S-C1S_$1 = C1S-C1S_$2
 1.39 with sigma of 0.01
4. Rigid bond restraints
 C2, C3, C4, F1, F2, F5, F6, F7, F4, F3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1S
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C8, C9, C10
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C11, C12, C13
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Uiso/Uaniso restraints and constraints
C2 \\sim C3 \\sim C4 \\sim F1 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F7
\\sim F2: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C1S: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C8 \\sim C9 \\sim C10: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
C11 \\sim C12 \\sim C13: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
C1S \\sim Ag1 \\sim Au1: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(C1S) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(N3) = Uanis(N4) = Uanis(C5) = Uanis(C6) = Uanis(C7) = Uanis(C8)
6. Others
 Fixed Sof: Au1(0.5) N3(0.5) N4(0.5) C5(0.5) C6(0.5) H6(0.5) C7(0.5) C8(0.5)
 H8(0.5) C9(0.5) H9A(0.5) H9B(0.5) H9C(0.5) C10(0.5) H10A(0.5) H10B(0.5)
 H10C(0.5) C11(0.5) H11(0.5) C12(0.5) H12A(0.5) H12B(0.5) H12C(0.5) C13(0.5)
 H13A(0.5) H13B(0.5) H13C(0.5)
7.a Ternary CH refined with riding coordinates:
 C8(H8), C11(H11)
7.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C1S(H1S)
7.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Ag1 Ag 0.04527(4) 0.09054(7) 0.30888(14) 0.0410(4) Uani 1 2 d S TU P A .
N1 N -0.0360(8) 0.0901(8) 0.3354(12) 0.058(4) Uani 1 1 d . . . . .
N2 N -0.1111(5) 0.1111(5) 0.356(2) 0.096(12) Uani 1 2 d S T P . .
C1 C -0.0508(12) 0.1327(10) 0.3479(16) 0.067(6) Uani 1 1 d . . . . .
C2 C -0.0064(17) 0.1989(12) 0.359(2) 0.098(7) Uani 1 1 d . U . . .
C3 C -0.0018(17) 0.2172(15) 0.497(2) 0.112(6) Uani 1 1 d . U . . .
C4 C 0.0295(18) 0.2778(17) 0.527(4) 0.126(7) Uani 1 1 d . U . . .
F1 F -0.0251(10) 0.2304(7) 0.2904(13) 0.124(7) Uani 1 1 d . U . . .
F2 F 0.0438(9) 0.2070(5) 0.3054(16) 0.105(5) Uani 1 1 d . U . . .
F3 F -0.0603(11) 0.1967(11) 0.5667(19) 0.182(10) Uani 1 1 d . U . . .
F4 F 0.0292(14) 0.1914(9) 0.5618(18) 0.173(9) Uani 1 1 d . U . . .
F5 F -0.0074(15) 0.2999(15) 0.479(3) 0.217(12) Uani 1 1 d . U . . .
F6 F 0.0272(10) 0.2757(13) 0.671(2) 0.185(10) Uani 1 1 d . U . . .
F7 F 0.0777(9) 0.2942(7) 0.4685(16) 0.115(5) Uani 1 1 d . U . . .
Au1 Au 0.00663(4) 0.07845(5) 0.02553(11) 0.0238(3) Uani 0.5 1 d . U . . .
N3 N 0.0947(14) 0.1143(17) 0.019(3) 0.040(3) Uani 0.5 1 d . . . A -1
N4 N 0.1212(10) 0.0835(12) 0.023(2) 0.040(3) Uani 0.5 1 d . . . A -1
C5 C 0.1388(13) 0.1754(15) 0.006(3) 0.040(3) Uani 0.5 1 d . . . A -1
C6 C 0.1962(13) 0.1778(15) 0.002(3) 0.040(3) Uani 0.5 1 d . . . A -1
H6 H 0.234907 0.212553 -0.002339 0.048 Uiso 0.5 1 calc R . . A -1
C7 C 0.1821(13) 0.1179(15) 0.007(3) 0.040(3) Uani 0.5 1 d . . . A -1
C8 C 0.2216(12) 0.0937(13) -0.002(3) 0.040(3) Uani 0.5 1 d . U . A -1
H8 H 0.202744 0.056340 0.051836 0.048 Uiso 0.5 1 calc R . . A -1
C9 C 0.2857(13) 0.1297(15) 0.044(3) 0.049(8) Uani 0.5 1 d . U . A -1
H9A H 0.305563 0.168631 -0.000207 0.073 Uiso 0.5 1 calc GR . . A -1
H9B H 0.306885 0.107858 0.024082 0.073 Uiso 0.5 1 calc GR . . A -1
H9C H 0.286233 0.135905 0.138014 0.073 Uiso 0.5 1 calc GR . . A -1
C10 C 0.2246(14) 0.0732(17) -0.141(3) 0.053(7) Uani 0.5 1 d . U . A -1
H10A H 0.185006 0.040122 -0.165564 0.080 Uiso 0.5 1 calc GR . . A -1
H10B H 0.253996 0.059655 -0.143732 0.080 Uiso 0.5 1 calc GR . . A -1
H10C H 0.236611 0.106834 -0.200824 0.080 Uiso 0.5 1 calc GR . . A -1
C11 C 0.1265(16) 0.2240(12) 0.002(3) 0.049(8) Uani 0.5 1 d . U . A -1
H11 H 0.094319 0.214146 0.067829 0.059 Uiso 0.5 1 calc R . . A -1
C12 C 0.0984(15) 0.2263(13) -0.134(3) 0.056(9) Uani 0.5 1 d . U . A -1
H12A H 0.130510 0.253179 -0.192693 0.084 Uiso 0.5 1 calc GR . . A -1
H12B H 0.070363 0.241166 -0.120663 0.084 Uiso 0.5 1 calc GR . . A -1
H12C H 0.076918 0.185872 -0.171092 0.084 Uiso 0.5 1 calc GR . . A -1
C13 C 0.1754(18) 0.2848(17) 0.035(4) 0.073(10) Uani 0.5 1 d . U . A -1
H13A H 0.200491 0.282153 0.102956 0.110 Uiso 0.5 1 calc GR . . A -1
H13B H 0.158348 0.309151 0.065278 0.110 Uiso 0.5 1 calc GR . . A -1
H13C H 0.199949 0.303486 -0.042857 0.110 Uiso 0.5 1 calc GR . . A -1
C1S C 0.0538(4) 0.0539(4) 0.642(3) 0.17(2) Uani 1 1 d D U . . .
H1S H 0.090768 0.090856 0.641713 0.203 Uiso 1 1 calc R . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ag1 N1 2.104(16) 4 ?
Ag1 N1 2.104(16) . ?
Ag1 Au1 3.0462(18) . ?
Ag1 Au1 3.0462(18) 4 ?
N1 N1 1.39(4) 6 ?
N1 C1 1.33(2) . ?
N2 C1 1.36(3) 6 ?
N2 C1 1.36(3) . ?
C1 C2 1.51(4) . ?
C2 C3 1.48(3) . ?
C2 F1 1.33(2) . ?
C2 F2 1.32(4) . ?
C3 C4 1.39(4) . ?
C3 F3 1.51(4) . ?
C3 F4 1.43(3) . ?
C4 F5 1.41(4) . ?
C4 F6 1.48(4) . ?
C4 F7 1.25(4) . ?
Au1 Au1 3.3578(18) 3 ?
Au1 Au1 1.6770(19) 4 ?
Au1 Au1 2.189(2) 6 ?
Au1 Au1 3.3578(18) 2 ?
Au1 N3 1.97(3) . ?
N3 N4 1.28(4) . ?
N3 C5 1.41(5) . ?
N4 C7 1.37(4) . ?
C5 C6 1.45(4) . ?
C5 C11 1.44(5) . ?
C6 C7 1.40(4) . ?
C7 C8 1.44(4) . ?
C8 C9 1.51(4) . ?
C8 C10 1.53(4) . ?
C11 C12 1.58(4) . ?
C11 C13 1.48(4) . ?
C1S C1S 1.390(15) 5 ?
C1S C1S 1.383(15) 4 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Ag1 N1 165.1(7) 4 . ?
N1 Ag1 Au1 81.4(3) . . ?
N1 Ag1 Au1 81.4(3) 4 4 ?
N1 Ag1 Au1 113.4(3) 4 . ?
N1 Ag1 Au1 113.4(3) . 4 ?
Au1 Ag1 Au1 31.96(4) . 4 ?
N1 N1 Ag1 120.0(5) 6 . ?
C1 N1 Ag1 134.4(17) . . ?
C1 N1 N1 105.6(14) . 6 ?
C1 N2 C1 101(2) 6 . ?
N1 C1 N2 114(2) . . ?
N1 C1 C2 125(2) . . ?
N2 C1 C2 121.4(18) . . ?
C3 C2 C1 109(2) . . ?
F1 C2 C1 110(3) . . ?
F1 C2 C3 108(2) . . ?
F2 C2 C1 106.0(16) . . ?
F2 C2 C3 116(3) . . ?
F2 C2 F1 108(2) . . ?
C2 C3 F3 116(3) . . ?
C4 C3 C2 119(3) . . ?
C4 C3 F3 102(3) . . ?
C4 C3 F4 106(3) . . ?
F4 C3 C2 106(2) . . ?
F4 C3 F3 108(2) . . ?
C3 C4 F5 104(3) . . ?
C3 C4 F6 101(3) . . ?
F5 C4 F6 110(3) . . ?
F7 C4 C3 101(3) . . ?
F7 C4 F5 117(4) . . ?
F7 C4 F6 121(3) . . ?
Ag1 Au1 Au1 79.79(3) . 3 ?
Ag1 Au1 Au1 96.27(3) . 2 ?
Au1 Au1 Ag1 74.02(2) 4 . ?
Au1 Au1 Ag1 102.37(3) 6 . ?
Au1 Au1 Au1 85.63(3) 6 3 ?
Au1 Au1 Au1 94.37(3) 4 2 ?
Au1 Au1 Au1 60.0 3 2 ?
Au1 Au1 Au1 25.63(3) 6 2 ?
Au1 Au1 Au1 120.0 4 6 ?
Au1 Au1 Au1 34.37(3) 4 3 ?
Au1 Au1 N3 23.9(10) 4 . ?
N3 Au1 Ag1 75.3(8) . . ?
N3 Au1 Au1 58.2(10) . 3 ?
N3 Au1 Au1 143.8(10) . 6 ?
N3 Au1 Au1 118.2(10) . 2 ?
N4 N3 Au1 124(3) . . ?
N4 N3 C5 108(3) . . ?
C5 N3 Au1 128(2) . . ?
N3 N4 C7 113(3) . . ?
N3 C5 C6 107(3) . . ?
N3 C5 C11 125(3) . . ?
C11 C5 C6 129(3) . . ?
C7 C6 C5 105(3) . . ?
N4 C7 C6 107(3) . . ?
N4 C7 C8 124(3) . . ?
C6 C7 C8 129(3) . . ?
C7 C8 C9 120(3) . . ?
C7 C8 C10 112(3) . . ?
C9 C8 C10 106(2) . . ?
C5 C11 C12 111(3) . . ?
C5 C11 C13 118(4) . . ?
C13 C11 C12 109(3) . . ?
C1S C1S C1S 120.000(10) 4 5 ?

# start Validation Reply Form
_vrf_PLAT972_Au3Ag3              
;
PROBLEM: Check Calcd Resid. Dens.  1.88A   From Au1            -4.15 eA-3  
RESPONSE: The hole at 3a site is within 2.0 A from the tree gold atoms 
in the crystal structure. It is a featureless ghost peak comes from the 
ripple effects of difference Fourier (abrupt truncation of the series 
because of limited data resolution) near the three heavy Au atoms in 
the crystal structure.
;
_vrf_PLAT260_Au3Ag3              
;
PROBLEM: Large Average Ueq of Residue Including       C1S      0.166 Check 
RESPONSE: C1S is carbon atom on a benzene solvate.
;
_vrf_PLAT342_Au3Ag3              
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............     0.0312 Ang.  
RESPONSE: The X-ray scattering density is dominated by Au and Ag atoms in 
the crystal structure. Low bond C-C bond precision is expected due to disorder 
of the TzF ligand.
;
# end Validation Reply Form

_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.990(17)
2 0.010(17)

_exptl_crystal_preparation       Luminescent
