# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_CuAuDMS
_database_code_depnum_ccdc_archive 'CCDC 1537965'
_audit_update_record             
;
2017-03-14 deposited with the CCDC.
2017-05-24 downloaded from the CCDC.
;
#===============================================================================
# 5. CHEMICAL DATA

_chemical_name_systematic        
; 
;

_chemical_formula_sum            'C4 H6 Au Cu N2 S'
_chemical_formula_moiety         'C4 H6 Au Cu N2 S'
_chemical_formula_weight         374.67
#=============================================================
# 6. CRYSTAL DATA

_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'

_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.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'x+1/2, -y+1/2, -z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'-x-1/2, y-1/2, z'
'x, -y-1/2, z-1/2'

#------------------------------------------------
_cell_length_a                   15.764(2)
_cell_length_b                   6.7092(10)
_cell_length_c                   16.818(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1778.7(4)
_cell_formula_units_Z            8
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    9954
_cell_measurement_theta_min      2.422
_cell_measurement_theta_max      30.592

_exptl_crystal_description       Needle
_exptl_crystal_colour            Colourless
_exptl_crystal_size_max          0.093
_exptl_crystal_size_mid          0.037
_exptl_crystal_size_min          0.028

_exptl_crystal_density_diffrn    2.798
_exptl_crystal_F_000             1344
_exptl_absorpt_coefficient_mu    19.025
_shelx_estimated_absorpt_T_min   0.271
_shelx_estimated_absorpt_T_max   0.618
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6570
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   SADABS

#=============================================================================
# 7. EXPERIMENTAL DATA

_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_measurement_device_type  'Bruker APEX-II DUO CCD'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_method       'φ and ω scans'
_diffrn_ambient_temperature      150(2)
_diffrn_reflns_number            45396
_diffrn_reflns_av_unetI/netI     0.0254
_diffrn_reflns_av_R_equivalents  0.0694
_diffrn_reflns_theta_min         2.422
_diffrn_reflns_theta_max         30.652
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_limit_l_max       23


#==========================================================================
# 8. REFINEMENT DATA

_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.
;

_reflns_threshold_expression     'I > 2σ(I)'
_reflns_number_total             2754
_reflns_number_gt                2163
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_hydrogen_treatment    constr
_refine_ls_number_reflns         2754
_refine_ls_number_parameters     84
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0411
_refine_ls_R_factor_gt           0.0226
_refine_ls_wR_factor_ref         0.0460
_refine_ls_wR_factor_gt          0.0405
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_restrained_S_all      1.051
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000

_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .


_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 w=1/[σ²(Fo²)+(0.0172P)²+2.7490P]
 where P=(Fo²+2Fc²)/3
;

_refine_diff_density_max         2.682
_refine_diff_density_min         -1.110
_refine_diff_density_rms         0.217

#---------------------------------------------------------


#========================================================== 
# 9. General computing 

_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_cell_refinement       'Bruker SAINT'
_computing_structure_solution    
; 
Bruker Intrinsic Phasing (Sheldrick, 2012) 
;
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'

#===================================================================
# 10.  ATOMIC COORDINATES AND THERMAL PARAMETERS

_atom_sites_solution_primary     ?
_atom_sites_solution_hydrogens   Geom

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 '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'
Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

#==============================================================================
# Uequiv = arithmetic mean of Ui
# i.e. Ueqiv = (U1+U2+U3)/3

# Replace trailing . with the number of unfound
# hydrogen atoms attached to relavent atom
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
Au1 Au 0.24258(2) 1.03989(2) -0.00889(2) 0.02002(5) Uani 1 1 d . . . . .
Cu1 Cu 0.07513(3) 0.91353(7) 0.24212(3) 0.01672(10) Uani 1 1 d . . . . .
S1 S -0.04878(5) 1.07323(13) 0.27664(6) 0.01648(18) Uani 1 1 d . . . . .
N1 N 0.1315(2) 0.9960(5) 0.1439(2) 0.0228(7) Uani 1 1 d . . . . .
N2 N 0.3550(2) 1.0688(5) -0.1619(2) 0.0215(7) Uani 1 1 d . . . . .
C1 C 0.1713(3) 1.0153(6) 0.0880(3) 0.0228(8) Uani 1 1 d . . . . .
C2 C 0.3146(2) 1.0589(6) -0.1058(2) 0.0207(8) Uani 1 1 d . . . . .
C11 C -0.0626(3) 1.0206(6) 0.3810(3) 0.0297(10) Uani 1 1 d . . . . .
H11A H -0.116287 1.072137 0.398396 0.045 Uiso 1 1 calc R U . . .
H11B H -0.017811 1.082618 0.410699 0.045 Uiso 1 1 calc R U . . .
H11C H -0.061064 0.879144 0.389338 0.045 Uiso 1 1 calc R U . . .
C12 C -0.1415(3) 0.9559(6) 0.2356(3) 0.0347(11) Uani 1 1 d . . . . .
H12A H -0.142576 0.975774 0.179130 0.052 Uiso 1 1 calc R U . . .
H12B H -0.191388 1.013447 0.258941 0.052 Uiso 1 1 calc R U . . .
H12C H -0.140004 0.815656 0.246975 0.052 Uiso 1 1 calc R U . . .


_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
Au1 C1 1.985(4) . ?
Au1 C2 1.989(4) . ?
Au1 Au1 3.3627(5) 7_665 ?
Au1 Au1 3.3628(5) 7_655 ?
Cu1 N1 1.955(3) . ?
Cu1 N2 1.958(3) 2_575 ?
Cu1 S1 2.3023(10) . ?
Cu1 S1 2.3420(10) 4_545 ?
S1 C12 1.798(4) . ?
S1 C11 1.803(4) . ?
N1 C1 1.139(5) . ?
N2 C2 1.141(5) . ?
C11 H11A 0.9600 . ?
C11 H11B 0.9600 . ?
C11 H11C 0.9600 . ?
C12 H12A 0.9600 . ?
C12 H12B 0.9600 . ?
C12 H12C 0.9600 . ?

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
C1 Au1 C2 178.88(16) . . ?
C1 Au1 Au1 97.03(11) . 7_665 ?
C2 Au1 Au1 84.04(11) . 7_665 ?
C1 Au1 Au1 87.50(11) . 7_655 ?
C2 Au1 Au1 91.40(11) . 7_655 ?
Au1 Au1 Au1 172.025(9) 7_665 7_655 ?
N1 Cu1 N2 115.09(15) . 2_575 ?
N1 Cu1 S1 117.82(10) . . ?
N2 Cu1 S1 103.94(10) 2_575 . ?
N1 Cu1 S1 104.05(10) . 4_545 ?
N2 Cu1 S1 105.64(10) 2_575 4_545 ?
S1 Cu1 S1 109.71(3) . 4_545 ?
C12 S1 C11 100.9(2) . . ?
C12 S1 Cu1 112.90(16) . . ?
C11 S1 Cu1 104.89(15) . . ?
C12 S1 Cu1 103.37(14) . 4 ?
C11 S1 Cu1 107.49(14) . 4 ?
Cu1 S1 Cu1 124.76(4) . 4 ?
C1 N1 Cu1 168.7(3) . . ?
C2 N2 Cu1 179.7(4) . 2_574 ?
N1 C1 Au1 178.1(4) . . ?
N2 C2 Au1 179.1(4) . . ?
S1 C11 H11A 109.5 . . ?
S1 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
S1 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
S1 C12 H12A 109.5 . . ?
S1 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
S1 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?




# start Validation Reply Form
_vrf_PLAT094_CuAuDMS             
;
PROBLEM: Ratio of Maximum / Minimum Residual Density ....       2.42 Report
RESPONSE: This refers to a Q peak next to the Au1 atom. It is probably due to the crystal being poorly diffracting.
;
_vrf_PLAT601_CuAuDMS             
;
PROBLEM: Structure Contains Solvent Accessible VOIDS of .         51 Ang3  
RESPONSE: These solvent-accessible voids are actually quite narrow. SQUEEZE reports an electron count of 3 per unit cell. 
;
_vrf_PLAT905_CuAuDMS             
;
PROBLEM: Negative K value in the Analysis of Variance ...     -0.124 Report
RESPONSE: Low angle data was collected using a lower exposure time.
;
_vrf_PLAT971_CuAuDMS             
;
PROBLEM: Check Calcd Residual Density  0.62A From     Au1       2.14 eA-3  
RESPONSE: Crystal diffracts poorly. This is likely not due to unaccounted for solvent, since SQUEEZE reports an electron count of 3 per unit cell.
;
_vrf_PLAT977_CuAuDMS             
;
PROBLEM: Check the Negative Difference Density on    H11A      -0.32 eA-3  
RESPONSE: ...
;
_vrf_PLAT978_CuAuDMS             
;
PROBLEM: Number C-C Bonds with Positive Residual Density.          0 Note  
RESPONSE: ...
;
# end Validation Reply Form
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: acetonitrile'
_exptl_crystal_preparation       ', Luminescent'
