# Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 2022

####################################################################### 
# 
# 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_1234rfv
_audit_block_doi                 10.5517/ccdc.csd.cc2bj3zz
_database_code_depnum_ccdc_archive 'CCDC 2160451'
loop_
_audit_author_name
_audit_author_address
'Xiao Xu'
;Dalian University of Technology
China
;
_audit_update_record             
;
2022-03-19 deposited with the CCDC.	2022-06-06 downloaded from the CCDC.
;
_audit_creation_date             2022-03-15
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelxl_version_number           2014-1
_chemical_name_common            ?
_chemical_name_systematic        Cu-TSP
_chemical_formula_moiety         '0.08(C240 H288 Cu12 N144 S48)'
_chemical_formula_sum            'C20 H16 Cu N12 S4'
_chemical_formula_weight         616.23
_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 0.0033 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'

_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      cubic
_space_group_IT_number           220
_space_group_name_H-M_alt        'I -4 3 d'
_space_group_name_Hall           'I -4bd 2c 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'
'z, x, y'
'z+1/2, -x+1/2, -y'
'-z+1/2, -x, y+1/2'
'-z, x+1/2, -y+1/2'
'y, z, x'
'-y, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x'
'-y+1/2, -z, x+1/2'
'y+1/4, x+1/4, z+1/4'
'-y+1/4, -x+3/4, z+3/4'
'y+3/4, -x+1/4, -z+3/4'
'-y+3/4, x+3/4, -z+1/4'
'x+1/4, z+1/4, y+1/4'
'-x+3/4, z+3/4, -y+1/4'
'-x+1/4, -z+3/4, y+3/4'
'x+3/4, -z+1/4, -y+3/4'
'z+1/4, y+1/4, x+1/4'
'z+3/4, -y+1/4, -x+3/4'
'-z+3/4, y+3/4, -x+1/4'
'-z+1/4, -y+3/4, x+3/4'
'x+1/2, y+1/2, z+1/2'
'-x+1, -y+1/2, z+1'
'-x+1/2, y+1, -z+1'
'x+1, -y+1, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1, -x+1, -y+1/2'
'-z+1, -x+1/2, y+1'
'-z+1/2, x+1, -y+1'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1, -x+1'
'y+1, -z+1, -x+1/2'
'-y+1, -z+1/2, x+1'
'y+3/4, x+3/4, z+3/4'
'-y+3/4, -x+5/4, z+5/4'
'y+5/4, -x+3/4, -z+5/4'
'-y+5/4, x+5/4, -z+3/4'
'x+3/4, z+3/4, y+3/4'
'-x+5/4, z+5/4, -y+3/4'
'-x+3/4, -z+5/4, y+5/4'
'x+5/4, -z+3/4, -y+5/4'
'z+3/4, y+3/4, x+3/4'
'z+5/4, -y+3/4, -x+5/4'
'-z+5/4, y+5/4, -x+3/4'
'-z+3/4, -y+5/4, x+5/4'

_cell_length_a                   29.0808(19)
_cell_length_b                   29.0808(19)
_cell_length_c                   29.0808(19)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     24593(5)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    7089
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      22.71
_cell_measurement_theta_min      2.21
_shelx_estimated_absorpt_T_max   0.981
_shelx_estimated_absorpt_T_min   0.970
_exptl_absorpt_coefficient_mu    0.380
_exptl_absorpt_correction_T_max  0.7449
_exptl_absorpt_correction_T_min  0.5610
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details   
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1276 before and 0.0730 after correction. The Ratio of minimum to maximum transmission is 0.7531. The λ/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.499
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             3756
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0984
_diffrn_reflns_av_unetI/netI     0.0489
_diffrn_reflns_Laue_measured_fraction_full 0.803
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            34109
_diffrn_reflns_point_group_measured_fraction_full 0.799
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         23.279
_diffrn_reflns_theta_min         2.215
_diffrn_ambient_temperature      120.0
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.803
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.869
_reflns_Friedel_fraction_full    0.794
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                2223
_reflns_number_total             2965
_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_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_refine_diff_density_max         0.338
_refine_diff_density_min         -0.399
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details 
;
 Flack x determined using 878 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.052(17)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.136
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     85
_refine_ls_number_reflns         2965
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0944
_refine_ls_R_factor_gt           0.0721
_refine_ls_restrained_S_all      1.136
_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)+(0.1365P)²+7.1035P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2112
_refine_ls_wR_factor_ref         0.2257
_refine_special_details          
;
 ?
;
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C1(H1)
2.b X=CH2 refined with riding coordinates:
 N3(H3a,H3b)
2.c Idealised Me refined as rotating group:
 C4(H4a,H4b,H4c)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_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
Cu1 Cu 0.5000 0.7500 0.3750 0.0590(7) Uani 1 4 d S T P . .
S1 S 0.56765(8) 0.76243(8) 0.41575(8) 0.0655(7) Uani 1 1 d . . . . .
N2 N 0.5157(3) 0.8241(3) 0.4555(3) 0.070(2) Uani 1 1 d . . . . .
N1 N 0.5055(3) 0.8600(3) 0.4853(3) 0.075(2) Uani 1 1 d . . . . .
N3 N 0.5895(3) 0.8266(4) 0.4772(3) 0.098(3) Uani 1 1 d . . . . .
H3A H 0.5826 0.8491 0.4962 0.118 Uiso 1 1 calc R . . . .
H3B H 0.6180 0.8166 0.4753 0.118 Uiso 1 1 calc R . . . .
C3 C 0.4656(4) 0.8754(4) 0.4850(3) 0.073(3) Uani 1 1 d . . . . .
C5 C 0.5571(4) 0.8080(4) 0.4513(3) 0.072(3) Uani 1 1 d . . . . .
C4 C 0.4276(5) 0.8592(5) 0.4562(5) 0.108(4) Uani 1 1 d . . . . .
H4A H 0.4195 0.8830 0.4338 0.163 Uiso 1 1 calc GR . . . .
H4B H 0.4009 0.8524 0.4755 0.163 Uiso 1 1 calc GR . . . .
H4C H 0.4370 0.8312 0.4399 0.163 Uiso 1 1 calc GR . . . .
C2 C 0.4568(4) 0.9135(4) 0.5173(4) 0.086(3) Uani 1 1 d . . . . .
C1 C 0.4217(4) 0.9457(4) 0.5121(4) 0.098(4) Uani 1 1 d . . . . .
H1 H 0.4020 0.9428 0.4862 0.118 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
Cu1 S1 2.325(2) 15_465 ?
Cu1 S1 2.325(2) 40_545 ?
Cu1 S1 2.325(2) . ?
Cu1 S1 2.325(2) 26_564 ?
S1 C5 1.709(10) . ?
N2 N1 1.390(11) . ?
N2 C5 1.298(12) . ?
N1 C3 1.244(12) . ?
N3 C5 1.321(12) . ?
C3 C4 1.464(16) . ?
C3 C2 1.476(14) . ?
C2 C1 1.427(14) 8_656 ?
C2 C1 1.393(15) . ?
C1 C2 1.427(14) 11_466 ?

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
S1 Cu1 S1 105.06(6) 15_465 26_564 ?
S1 Cu1 S1 118.71(12) 26_564 . ?
S1 Cu1 S1 118.71(12) 15_465 40_545 ?
S1 Cu1 S1 105.06(6) 40_545 . ?
S1 Cu1 S1 105.06(6) 15_465 . ?
S1 Cu1 S1 105.06(6) 26_564 40_545 ?
C5 S1 Cu1 106.1(3) . . ?
C5 N2 N1 121.8(8) . . ?
C3 N1 N2 117.7(8) . . ?
N1 C3 C4 126.3(9) . . ?
N1 C3 C2 115.3(10) . . ?
C4 C3 C2 118.4(9) . . ?
N2 C5 S1 120.1(7) . . ?
N2 C5 N3 117.4(9) . . ?
N3 C5 S1 122.3(8) . . ?
C1 C2 C3 119.7(10) 8_656 . ?
C1 C2 C3 124.2(10) . . ?
C1 C2 C1 115.9(11) . 8_656 ?
C2 C1 C2 124.0(11) . 11_466 ?

_smtbx_masks_special_details     ?
loop_
_smtbx_masks_void_nr
_smtbx_masks_void_average_x
_smtbx_masks_void_average_y
_smtbx_masks_void_average_z
_smtbx_masks_void_volume
_smtbx_masks_void_count_electrons
_smtbx_masks_void_content
1 -0.822 -0.038 -0.777 18440.6 452.6 ?

_olex2_submission_special_instructions 'No special instructions were received'
