# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2023

####################################################################### 
# 
# 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_K0590
_database_code_depnum_ccdc_archive 'CCDC 2232759'
loop_
_audit_author_name
_audit_author_address
'Saeed Ataie'
;University of Ottawa
Canada
;
_audit_update_record             
;
2022-12-25 deposited with the CCDC.	2023-08-04 downloaded from the CCDC.
;
#===============================================================================
# 5. CHEMICAL DATA

_chemical_name_systematic        
; 
;

_chemical_formula_sum            'C56 H48 Cu4 N4 S8'
_chemical_formula_moiety         'C56 H48 Cu4 N4 S8'
_chemical_formula_weight         1287.62
#=============================================================
# 6. CRYSTAL DATA

_space_group_crystal_system      tetragonal
_space_group_IT_number           142
_space_group_name_H-M_alt        'I 41/a c d'
_space_group_name_Hall           '-I 4bd 2c'

_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'
'-y+1/4, x+3/4, z+1/4'
'y+1/4, -x+1/4, z+3/4'
'-x+1/2, y, -z'
'x, -y, -z+1/2'
'y+1/4, x+3/4, -z+3/4'
'-y+1/4, -x+1/4, -z+1/4'
'x+1/2, y+1/2, z+1/2'
'-x+1, -y+1/2, z+1'
'-y+3/4, x+5/4, z+3/4'
'y+3/4, -x+3/4, z+5/4'
'-x+1, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1'
'y+3/4, x+5/4, -z+5/4'
'-y+3/4, -x+3/4, -z+3/4'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'y-1/4, -x-3/4, -z-1/4'
'-y-1/4, x-1/4, -z-3/4'
'x-1/2, -y, z'
'-x, y, z-1/2'
'-y-1/4, -x-3/4, z-3/4'
'y-1/4, x-1/4, z-1/4'
'-x+1/2, -y+1/2, -z+1/2'
'x, y+1/2, -z'
'y+1/4, -x-1/4, -z+1/4'
'-y+1/4, x+1/4, -z-1/4'
'x, -y+1/2, z+1/2'
'-x+1/2, y+1/2, z'
'-y+1/4, -x-1/4, z-1/4'
'y+1/4, x+1/4, z+1/4'

#------------------------------------------------
_cell_length_a                   24.1902(11)
_cell_length_b                   24.1902(11)
_cell_length_c                   22.8468(12)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     13369.2(14)
_cell_formula_units_Z            8
_cell_measurement_temperature    203(2)
_cell_measurement_reflns_used    8887
_cell_measurement_theta_min      2.38
_cell_measurement_theta_max      24.53

_exptl_crystal_description       needle
_exptl_crystal_colour            red
_exptl_crystal_size_min          0.036
_exptl_crystal_size_mid          0.039
_exptl_crystal_size_max          1.306

_exptl_crystal_density_diffrn    1.279
_exptl_crystal_F_000             5248
_exptl_absorpt_coefficient_mu    1.540
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5877
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_process_details   SADABS

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

_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_method       'ω and φ scans'
_diffrn_ambient_temperature      203(2)
_diffrn_reflns_number            38238
_diffrn_reflns_av_unetI/netI     0.0464
_diffrn_reflns_av_R_equivalents  0.1029
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         1.190
_diffrn_reflns_theta_max         25.081
_diffrn_reflns_theta_full        25.081
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999


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

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _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_number_total             3088
_reflns_number_gt                2317
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_refine_special_details          none

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details none
_refine_ls_abs_structure_Flack   .
_refine_ls_number_reflns         3088
_refine_ls_number_parameters     174
_refine_ls_number_restraints     152
_refine_ls_R_factor_all          0.1684
_refine_ls_R_factor_gt           0.1409
_refine_ls_wR_factor_ref         0.3352
_refine_ls_wR_factor_gt          0.3210
_refine_ls_goodness_of_fit_ref   1.134
_refine_ls_restrained_S_all      1.110
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0472P)²+1061.921387P] where P=(Fo²+2Fc²)/3'

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


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

_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'Bruker SAINT'
_computing_cell_refinement       'Bruker SAINT'
_computing_structure_solution    
; 
 SHELXT 2014/5 (Sheldrick, 2014)
;
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_shelx_SHELXL_version_number     2018/3

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

_atom_sites_solution_primary     direct
_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'
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

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
Cu1 Cu 0.56366(8) 0.21038(8) 0.15562(7) 0.0419(6) Uani 1 1 d . . . . .
S1 S 0.51777(19) 0.13113(17) 0.13916(15) 0.0454(11) Uani 1 1 d . . . . .
S2 S 0.6928(2) 0.1627(3) 0.3551(2) 0.0795(18) Uani 1 1 d D U . . .
N1 N 0.5552(5) 0.1958(5) 0.2450(5) 0.034(2) Uani 1 1 d . . . . .
C1 C 0.4901(7) 0.1245(6) 0.2107(6) 0.041(3) Uani 1 1 d . . . . .
C2 C 0.4510(9) 0.0872(8) 0.2232(8) 0.064(5) Uani 1 1 d . . . . .
H2 H 0.436858 0.064964 0.192980 0.077 Uiso 1 1 calc R U . . .
C3 C 0.4304(10) 0.0804(9) 0.2805(8) 0.080(7) Uani 1 1 d . . . . .
H3 H 0.405633 0.051458 0.288461 0.095 Uiso 1 1 calc R U . . .
C4 C 0.4459(8) 0.1154(8) 0.3250(8) 0.063(5) Uani 1 1 d . . . . .
H4 H 0.429217 0.113803 0.362130 0.075 Uiso 1 1 calc R U . . .
C5 C 0.4876(7) 0.1535(6) 0.3124(6) 0.042(3) Uani 1 1 d . . . . .
H5 H 0.499828 0.177011 0.342566 0.050 Uiso 1 1 calc R U . . .
C6 C 0.5120(6) 0.1585(6) 0.2573(6) 0.035(3) Uani 1 1 d . . . . .
C7 C 0.5946(6) 0.1974(7) 0.2839(6) 0.042(3) Uani 1 1 d . . . . .
H7 H 0.593599 0.171200 0.314252 0.051 Uiso 1 1 calc R U . . .
C8 C 0.6402(7) 0.2367(8) 0.2836(6) 0.045(3) Uani 1 1 d . . . . .
C9 C 0.6369(7) 0.2880(8) 0.2550(7) 0.053(4) Uani 1 1 d . . . . .
H9 H 0.605067 0.296297 0.233094 0.063 Uiso 1 1 calc R U . . .
C10 C 0.6787(8) 0.3264(9) 0.2580(7) 0.063(4) Uani 1 1 d . . . . .
H10 H 0.676037 0.360661 0.238765 0.076 Uiso 1 1 calc R U . . .
C11 C 0.7263(8) 0.3120(11) 0.2919(7) 0.073(5) Uani 1 1 d . . . . .
H11 H 0.755659 0.337354 0.294324 0.088 Uiso 1 1 calc R U . . .
C12 C 0.7306(8) 0.2642(10) 0.3198(7) 0.071(5) Uani 1 1 d . . . . .
H12 H 0.762857 0.256809 0.341503 0.085 Uiso 1 1 calc R U . . .
C13 C 0.6883(7) 0.2239(9) 0.3181(6) 0.054(4) Uani 1 1 d . . . . .
C14A C 0.719(4) 0.146(6) 0.428(2) 0.081(8) Uani 0.23(5) 1 d D U P A 1
H14A H 0.728407 0.106831 0.429825 0.121 Uiso 0.23(5) 1 calc R U P A 1
H14B H 0.690423 0.153532 0.457109 0.121 Uiso 0.23(5) 1 calc R U P A 1
H14C H 0.751300 0.167849 0.436559 0.121 Uiso 0.23(5) 1 calc R U P A 1
C14B C 0.7305(11) 0.1843(16) 0.4203(11) 0.082(7) Uani 0.77(5) 1 d D U P A 2
H14D H 0.727040 0.156137 0.450301 0.122 Uiso 0.77(5) 1 calc R U P A 2
H14E H 0.715346 0.218838 0.434610 0.122 Uiso 0.77(5) 1 calc R U P A 2
H14F H 0.769221 0.189332 0.410591 0.122 Uiso 0.77(5) 1 calc R U P A 2


_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
Cu1 N1 2.083(11) . ?
Cu1 S1 2.181(4) 20_656 ?
Cu1 S1 2.247(5) . ?
Cu1 Cu1 2.922(3) 20_656 ?
Cu1 Cu1 2.922(3) 27_565 ?
S1 C1 1.773(15) . ?
S2 C13 1.71(2) . ?
S2 C14B 1.82(2) . ?
S2 C14A 1.83(3) . ?
N1 C7 1.303(18) . ?
N1 C6 1.408(18) . ?
C1 C2 1.34(2) . ?
C1 C6 1.45(2) . ?
C2 C3 1.41(2) . ?
C2 H2 0.9400 . ?
C3 C4 1.37(3) . ?
C3 H3 0.9400 . ?
C4 C5 1.40(2) . ?
C4 H4 0.9400 . ?
C5 C6 1.40(2) . ?
C5 H5 0.9400 . ?
C7 C8 1.46(2) . ?
C7 H7 0.9400 . ?
C8 C9 1.40(2) . ?
C8 C13 1.44(2) . ?
C9 C10 1.38(2) . ?
C9 H9 0.9400 . ?
C10 C11 1.43(3) . ?
C10 H10 0.9400 . ?
C11 C12 1.33(3) . ?
C11 H11 0.9400 . ?
C12 C13 1.41(3) . ?
C12 H12 0.9400 . ?
C14A H14A 0.9700 . ?
C14A H14B 0.9700 . ?
C14A H14C 0.9700 . ?
C14B H14D 0.9700 . ?
C14B H14E 0.9700 . ?
C14B H14F 0.9700 . ?

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 Cu1 S1 128.9(4) . 20_656 ?
N1 Cu1 S1 88.4(3) . . ?
S1 Cu1 S1 140.09(9) 20_656 . ?
N1 Cu1 Cu1 126.5(3) . 20_656 ?
S1 Cu1 Cu1 49.68(14) 20_656 20_656 ?
S1 Cu1 Cu1 123.44(13) . 20_656 ?
N1 Cu1 Cu1 110.6(3) . 27_565 ?
S1 Cu1 Cu1 115.19(13) 20_656 27_565 ?
S1 Cu1 Cu1 47.75(12) . 27_565 ?
Cu1 Cu1 Cu1 76.75(6) 20_656 27_565 ?
C1 S1 Cu1 104.3(5) . 27_565 ?
C1 S1 Cu1 96.2(5) . . ?
Cu1 S1 Cu1 82.57(17) 27_565 . ?
C13 S2 C14B 100.8(14) . . ?
C13 S2 C14A 132(5) . . ?
C7 N1 C6 115.2(12) . . ?
C7 N1 Cu1 126.2(10) . . ?
C6 N1 Cu1 112.1(8) . . ?
C2 C1 C6 119.0(15) . . ?
C2 C1 S1 121.6(13) . . ?
C6 C1 S1 119.3(11) . . ?
C1 C2 C3 121.7(17) . . ?
C1 C2 H2 119.1 . . ?
C3 C2 H2 119.1 . . ?
C4 C3 C2 121.2(18) . . ?
C4 C3 H3 119.4 . . ?
C2 C3 H3 119.4 . . ?
C3 C4 C5 116.8(17) . . ?
C3 C4 H4 121.6 . . ?
C5 C4 H4 121.6 . . ?
C6 C5 C4 123.3(15) . . ?
C6 C5 H5 118.4 . . ?
C4 C5 H5 118.4 . . ?
C5 C6 N1 123.3(13) . . ?
C5 C6 C1 117.4(14) . . ?
N1 C6 C1 119.2(12) . . ?
N1 C7 C8 124.8(14) . . ?
N1 C7 H7 117.6 . . ?
C8 C7 H7 117.6 . . ?
C9 C8 C13 119.5(16) . . ?
C9 C8 C7 122.4(15) . . ?
C13 C8 C7 117.9(16) . . ?
C10 C9 C8 122.1(18) . . ?
C10 C9 H9 118.9 . . ?
C8 C9 H9 118.9 . . ?
C9 C10 C11 117(2) . . ?
C9 C10 H10 121.5 . . ?
C11 C10 H10 121.5 . . ?
C12 C11 C10 122(2) . . ?
C12 C11 H11 118.8 . . ?
C10 C11 H11 118.8 . . ?
C11 C12 C13 122.0(19) . . ?
C11 C12 H12 119.0 . . ?
C13 C12 H12 119.0 . . ?
C12 C13 C8 116.9(18) . . ?
C12 C13 S2 122.4(14) . . ?
C8 C13 S2 120.6(14) . . ?
S2 C14A H14A 109.5 . . ?
S2 C14A H14B 109.5 . . ?
H14A C14A H14B 109.5 . . ?
S2 C14A H14C 109.5 . . ?
H14A C14A H14C 109.5 . . ?
H14B C14A H14C 109.5 . . ?
S2 C14B H14D 109.5 . . ?
S2 C14B H14E 109.5 . . ?
H14D C14B H14E 109.5 . . ?
S2 C14B H14F 109.5 . . ?
H14D C14B H14F 109.5 . . ?
H14E C14B H14F 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Cu1 S1 C1 C2 85.3(16) 27_565 . . . ?
Cu1 S1 C1 C2 169.2(15) . . . . ?
Cu1 S1 C1 C6 -97.5(12) 27_565 . . . ?
Cu1 S1 C1 C6 -13.6(12) . . . . ?
C6 C1 C2 C3 0(3) . . . . ?
S1 C1 C2 C3 177.6(18) . . . . ?
C1 C2 C3 C4 6(4) . . . . ?
C2 C3 C4 C5 -7(3) . . . . ?
C3 C4 C5 C6 2(3) . . . . ?
C4 C5 C6 N1 -178.0(15) . . . . ?
C4 C5 C6 C1 4(2) . . . . ?
C7 N1 C6 C5 45(2) . . . . ?
Cu1 N1 C6 C5 -161.4(11) . . . . ?
C7 N1 C6 C1 -137.1(14) . . . . ?
Cu1 N1 C6 C1 16.6(16) . . . . ?
C2 C1 C6 C5 -5(2) . . . . ?
S1 C1 C6 C5 177.5(11) . . . . ?
C2 C1 C6 N1 176.7(16) . . . . ?
S1 C1 C6 N1 -0.6(19) . . . . ?
C6 N1 C7 C8 -173.1(14) . . . . ?
Cu1 N1 C7 C8 37(2) . . . . ?
N1 C7 C8 C9 23(2) . . . . ?
N1 C7 C8 C13 -162.2(15) . . . . ?
C13 C8 C9 C10 1(2) . . . . ?
C7 C8 C9 C10 175.8(15) . . . . ?
C8 C9 C10 C11 0(3) . . . . ?
C9 C10 C11 C12 -1(3) . . . . ?
C10 C11 C12 C13 0(3) . . . . ?
C11 C12 C13 C8 1(3) . . . . ?
C11 C12 C13 S2 -178.7(15) . . . . ?
C9 C8 C13 C12 -2(2) . . . . ?
C7 C8 C13 C12 -176.5(15) . . . . ?
C9 C8 C13 S2 178.2(12) . . . . ?
C7 C8 C13 S2 3(2) . . . . ?
C14B S2 C13 C12 34.4(19) . . . . ?
C14A S2 C13 C12 40(5) . . . . ?
C14B S2 C13 C8 -145.3(15) . . . . ?
C14A S2 C13 C8 -139(4) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
C14B^b H14F^b S1 0.97 2.94 3.89(3) 166.3 12_554 yes

_refine_diff_density_max         1.075
_refine_diff_density_min         -0.970
_refine_diff_density_rms         0.236



# start Validation Reply Form
_vrf_PLAT341_K0590               
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............    0.02615 Ang.  
RESPONSE: Relatively poor crystal quality is responsible for the relatively
low bond precision.
;
# end Validation Reply Form
####################################################################### 
# 
# 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_S0726
_database_code_depnum_ccdc_archive 'CCDC 2232760'
loop_
_audit_author_name
_audit_author_address
'Saeed Ataie'
;University of Ottawa
Canada
;
_audit_update_record             
;
2022-12-25 deposited with the CCDC.	2023-08-04 downloaded from the CCDC.
;
#===============================================================================
# 5. CHEMICAL DATA

_chemical_name_systematic        
; 
;

_chemical_formula_sum            'C60 H64 Cu4 N4 S8'
_chemical_formula_moiety         'C60 H64 Cu4 N4 S8'
_chemical_formula_weight         1351.79
#=============================================================
# 6. CRYSTAL DATA

_space_group_crystal_system      tetragonal
_space_group_IT_number           114
_space_group_name_H-M_alt        'P -4 21 c'
_space_group_name_Hall           'P -4 2n'

_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, -y, z'
'y, -x, -z'
'-y, x, -z'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, x+1/2, z+1/2'

#------------------------------------------------
_cell_length_a                   14.4406(12)
_cell_length_b                   14.4406(12)
_cell_length_c                   14.0771(12)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2935.5(5)
_cell_formula_units_Z            2
_cell_measurement_temperature    203(2)
_cell_measurement_reflns_used    9843
_cell_measurement_theta_min      2.89
_cell_measurement_theta_max      27.43

_exptl_crystal_description       needle
_exptl_crystal_colour            gold
_exptl_crystal_size_min          0.075
_exptl_crystal_size_mid          0.092
_exptl_crystal_size_max          0.358

_exptl_crystal_density_diffrn    1.529
_exptl_crystal_F_000             1392
_exptl_absorpt_coefficient_mu    1.757
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6857
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_process_details   SADABS

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

_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_method       'ω and φ scans'
_diffrn_ambient_temperature      203(2)
_diffrn_reflns_number            69134
_diffrn_reflns_av_unetI/netI     0.0368
_diffrn_reflns_av_R_equivalents  0.0782
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         1.994
_diffrn_reflns_theta_max         30.521
_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 0.999
_diffrn_reflns_point_group_measured_fraction_full 1.000


#==========================================================================
# 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_number_total             4484
_reflns_number_gt                3550
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.802
_reflns_Friedel_fraction_max     0.998
_reflns_Friedel_fraction_full    1.000

_refine_special_details          none

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 1385 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(6)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         4484
_refine_ls_number_parameters     174
_refine_ls_number_restraints     42
_refine_ls_R_factor_all          0.0608
_refine_ls_R_factor_gt           0.0373
_refine_ls_wR_factor_ref         0.0949
_refine_ls_wR_factor_gt          0.0841
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_restrained_S_all      1.055
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0446P)²+1.5779P] where P=(Fo²+2Fc²)/3'

_refine_diff_density_max         0.642
_refine_diff_density_min         -0.258
_refine_diff_density_rms         0.076

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


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

_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'Bruker SAINT'
_computing_cell_refinement       'Bruker SAINT'
_computing_structure_solution    
; 
 SHELXT 2014/5 (Sheldrick, 2014)
;
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_shelx_SHELXL_version_number     2018/3

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

_atom_sites_solution_primary     direct
_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'
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'
Cu Cu 0.3201 1.2651 '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

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
Cu1 Cu 0.38605(3) 0.55109(3) 0.51025(3) 0.02622(12) Uani 1 1 d . . . . .
S1 S 0.40952(9) 0.66820(9) 0.64219(8) 0.0392(3) Uani 1 1 d . . . . .
S2 S 0.42602(11) 0.63946(12) 0.12389(9) 0.0604(4) Uani 1 1 d . . . . .
N1 N 0.4325(2) 0.6552(2) 0.4382(2) 0.0246(7) Uani 1 1 d . . . . .
C1 C 0.3993(5) 0.7163(5) 0.7585(3) 0.0595(15) Uani 1 1 d . . . . .
H1A H 0.452752 0.754921 0.771649 0.089 Uiso 1 1 calc R U . . .
H1B H 0.396131 0.666714 0.804821 0.089 Uiso 1 1 calc R U . . .
H1C H 0.343461 0.753483 0.762164 0.089 Uiso 1 1 calc R U . . .
C2 C 0.4095(3) 0.7658(3) 0.5669(3) 0.0356(10) Uani 1 1 d . . . . .
C3 C 0.4013(4) 0.8564(4) 0.5993(4) 0.0525(14) Uani 1 1 d . . . . .
H3 H 0.396027 0.868248 0.664784 0.063 Uiso 1 1 calc R U . . .
C4 C 0.4009(5) 0.9290(4) 0.5355(5) 0.0668(18) Uani 1 1 d . . . . .
H4 H 0.396044 0.990069 0.557974 0.080 Uiso 1 1 calc R U . . .
C5 C 0.4075(4) 0.9130(4) 0.4403(5) 0.0561(14) Uani 1 1 d . . . . .
H5 H 0.406592 0.963024 0.397555 0.067 Uiso 1 1 calc R U . . .
C6 C 0.4156(3) 0.8232(3) 0.4064(4) 0.0382(10) Uani 1 1 d . . . . .
H6 H 0.418877 0.812981 0.340496 0.046 Uiso 1 1 calc R U . . .
C7 C 0.4190(3) 0.7479(3) 0.4681(3) 0.0294(9) Uani 1 1 d . . . . .
C8 C 0.4274(3) 0.6405(3) 0.3347(3) 0.0289(9) Uani 1 1 d . . . . .
H8A H 0.451422 0.578501 0.320621 0.035 Uiso 1 1 calc R U . . .
H8AB H 0.468480 0.685305 0.303740 0.035 Uiso 1 1 calc R U . . .
C9 C 0.3315(3) 0.6492(3) 0.2907(3) 0.0317(8) Uani 1 1 d . . . . .
C10 C 0.2526(3) 0.6538(4) 0.3446(4) 0.0441(11) Uani 1 1 d . . . . .
H10 H 0.257303 0.654006 0.411160 0.053 Uiso 1 1 calc R U . . .
C11 C 0.1650(4) 0.6581(5) 0.3019(5) 0.0611(13) Uani 1 1 d . . . . .
H11 H 0.111033 0.660626 0.339160 0.073 Uiso 1 1 calc R U . . .
C12 C 0.1596(5) 0.6584(5) 0.2048(5) 0.0677(14) Uani 1 1 d . . . . .
H12 H 0.100936 0.661145 0.176007 0.081 Uiso 1 1 calc R U . . .
C13 C 0.2364(4) 0.6550(4) 0.1484(5) 0.0606(12) Uani 1 1 d . . . . .
H13 H 0.230488 0.656143 0.081942 0.073 Uiso 1 1 calc R U . . .
C14 C 0.3240(4) 0.6497(3) 0.1906(3) 0.0416(9) Uani 1 1 d . . . . .
C15 C 0.3873(6) 0.6569(5) 0.0031(4) 0.082(2) Uani 1 1 d . . . . .
H15A H 0.370410 0.721286 -0.005905 0.122 Uiso 1 1 calc R U . . .
H15B H 0.333837 0.617922 -0.009211 0.122 Uiso 1 1 calc R U . . .
H15C H 0.436715 0.640675 -0.040503 0.122 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
Cu1 N1 1.934(3) . ?
Cu1 N1 1.953(3) 4_656 ?
Cu1 S1 2.5347(12) . ?
Cu1 Cu1 2.5665(7) 4_656 ?
Cu1 Cu1 2.5666(7) 3_566 ?
S1 C2 1.764(5) . ?
S1 C1 1.784(5) . ?
S2 C14 1.753(6) . ?
S2 C15 1.808(6) . ?
N1 C7 1.417(5) . ?
N1 C8 1.474(5) . ?
C1 H1A 0.9700 . ?
C1 H1B 0.9700 . ?
C1 H1C 0.9700 . ?
C2 C3 1.391(7) . ?
C2 C7 1.421(6) . ?
C3 C4 1.380(9) . ?
C3 H3 0.9400 . ?
C4 C5 1.363(9) . ?
C4 H4 0.9400 . ?
C5 C6 1.387(7) . ?
C5 H5 0.9400 . ?
C6 C7 1.393(6) . ?
C6 H6 0.9400 . ?
C8 C9 1.522(6) . ?
C8 H8A 0.9800 . ?
C8 H8AB 0.9800 . ?
C9 C10 1.370(7) . ?
C9 C14 1.414(6) . ?
C10 C11 1.402(7) . ?
C10 H10 0.9400 . ?
C11 C12 1.368(9) . ?
C11 H11 0.9400 . ?
C12 C13 1.365(10) . ?
C12 H12 0.9400 . ?
C13 C14 1.400(7) . ?
C13 H13 0.9400 . ?
C15 H15A 0.9700 . ?
C15 H15B 0.9700 . ?
C15 H15C 0.9700 . ?

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 Cu1 N1 169.26(9) . 4_656 ?
N1 Cu1 S1 79.59(10) . . ?
N1 Cu1 S1 110.70(10) 4_656 . ?
N1 Cu1 Cu1 122.71(10) . 4_656 ?
N1 Cu1 Cu1 48.36(10) 4_656 4_656 ?
S1 Cu1 Cu1 130.90(4) . 4_656 ?
N1 Cu1 Cu1 49.01(10) . 3_566 ?
N1 Cu1 Cu1 129.43(10) 4_656 3_566 ?
S1 Cu1 Cu1 73.88(4) . 3_566 ?
Cu1 Cu1 Cu1 89.275(5) 4_656 3_566 ?
C2 S1 C1 103.9(3) . . ?
C2 S1 Cu1 95.33(15) . . ?
C1 S1 Cu1 157.1(2) . . ?
C14 S2 C15 103.4(3) . . ?
C7 N1 C8 115.1(3) . . ?
C7 N1 Cu1 122.0(3) . . ?
C8 N1 Cu1 112.9(3) . . ?
C7 N1 Cu1 107.4(3) . 3_566 ?
C8 N1 Cu1 111.5(2) . 3_566 ?
Cu1 N1 Cu1 82.63(12) . 3_566 ?
S1 C1 H1A 109.5 . . ?
S1 C1 H1B 109.5 . . ?
H1A C1 H1B 109.5 . . ?
S1 C1 H1C 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
C3 C2 C7 120.1(5) . . ?
C3 C2 S1 123.7(4) . . ?
C7 C2 S1 116.2(3) . . ?
C4 C3 C2 120.0(5) . . ?
C4 C3 H3 120.0 . . ?
C2 C3 H3 120.0 . . ?
C5 C4 C3 120.8(5) . . ?
C5 C4 H4 119.6 . . ?
C3 C4 H4 119.6 . . ?
C4 C5 C6 120.2(5) . . ?
C4 C5 H5 119.9 . . ?
C6 C5 H5 119.9 . . ?
C5 C6 C7 121.2(5) . . ?
C5 C6 H6 119.4 . . ?
C7 C6 H6 119.4 . . ?
C6 C7 N1 123.8(4) . . ?
C6 C7 C2 117.7(4) . . ?
N1 C7 C2 118.5(4) . . ?
N1 C8 C9 115.8(3) . . ?
N1 C8 H8A 108.3 . . ?
C9 C8 H8A 108.3 . . ?
N1 C8 H8AB 108.3 . . ?
C9 C8 H8AB 108.3 . . ?
H8A C8 H8AB 107.4 . . ?
C10 C9 C14 119.2(4) . . ?
C10 C9 C8 122.4(4) . . ?
C14 C9 C8 118.4(4) . . ?
C9 C10 C11 121.0(5) . . ?
C9 C10 H10 119.5 . . ?
C11 C10 H10 119.5 . . ?
C12 C11 C10 118.6(7) . . ?
C12 C11 H11 120.7 . . ?
C10 C11 H11 120.7 . . ?
C13 C12 C11 122.3(7) . . ?
C13 C12 H12 118.8 . . ?
C11 C12 H12 118.8 . . ?
C12 C13 C14 119.3(6) . . ?
C12 C13 H13 120.3 . . ?
C14 C13 H13 120.3 . . ?
C13 C14 C9 119.5(5) . . ?
C13 C14 S2 122.5(4) . . ?
C9 C14 S2 118.0(4) . . ?
S2 C15 H15A 109.5 . . ?
S2 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
S2 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C1 S1 C2 C3 -1.0(5) . . . . ?
Cu1 S1 C2 C3 166.4(4) . . . . ?
C1 S1 C2 C7 178.7(4) . . . . ?
Cu1 S1 C2 C7 -13.9(4) . . . . ?
C7 C2 C3 C4 1.0(8) . . . . ?
S1 C2 C3 C4 -179.3(5) . . . . ?
C2 C3 C4 C5 0.7(10) . . . . ?
C3 C4 C5 C6 -0.6(11) . . . . ?
C4 C5 C6 C7 -1.3(9) . . . . ?
C5 C6 C7 N1 -176.3(5) . . . . ?
C5 C6 C7 C2 2.9(7) . . . . ?
C8 N1 C7 C6 -9.8(6) . . . . ?
Cu1 N1 C7 C6 -152.9(4) . . . . ?
Cu1 N1 C7 C6 115.0(4) 3_566 . . . ?
C8 N1 C7 C2 171.1(4) . . . . ?
Cu1 N1 C7 C2 28.0(5) . . . . ?
Cu1 N1 C7 C2 -64.1(4) 3_566 . . . ?
C3 C2 C7 C6 -2.7(7) . . . . ?
S1 C2 C7 C6 177.5(3) . . . . ?
C3 C2 C7 N1 176.4(4) . . . . ?
S1 C2 C7 N1 -3.3(6) . . . . ?
C7 N1 C8 C9 -70.9(5) . . . . ?
Cu1 N1 C8 C9 75.5(4) . . . . ?
Cu1 N1 C8 C9 166.5(3) 3_566 . . . ?
N1 C8 C9 C10 -11.3(6) . . . . ?
N1 C8 C9 C14 170.6(4) . . . . ?
C14 C9 C10 C11 0.6(8) . . . . ?
C8 C9 C10 C11 -177.4(5) . . . . ?
C9 C10 C11 C12 -0.6(9) . . . . ?
C10 C11 C12 C13 -0.2(11) . . . . ?
C11 C12 C13 C14 0.8(10) . . . . ?
C12 C13 C14 C9 -0.8(8) . . . . ?
C12 C13 C14 S2 176.9(5) . . . . ?
C10 C9 C14 C13 0.1(8) . . . . ?
C8 C9 C14 C13 178.2(4) . . . . ?
C10 C9 C14 S2 -177.7(4) . . . . ?
C8 C9 C14 S2 0.4(6) . . . . ?
C15 S2 C14 C13 8.8(5) . . . . ?
C15 S2 C14 C9 -173.5(4) . . . . ?

