# Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.
# This journal is © the Owner Societies 2019

####################################################################### 
# 
# 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 1866815'
_audit_update_record             
;
2018-09-10 deposited with the CCDC.
2019-01-22 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C20 H19 Cl Cu N4 O S'
_chemical_formula_sum            'C20 H19 Cl Cu N4 O S'
_chemical_formula_weight         462.44

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'
Cl Cl 0.1484 0.1585 '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'
O O 0.0106 0.0060 '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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

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

_cell_length_a                   11.9790(3)
_cell_length_b                   14.0236(5)
_cell_length_c                   12.1193(3)
_cell_angle_alpha                90
_cell_angle_beta                 104.952(2)
_cell_angle_gamma                90
_cell_volume                     1966.97(10)
_cell_formula_units_Z            4
_cell_measurement_temperature    294(2)
_cell_measurement_reflns_used    16840
_cell_measurement_theta_min      2.579
_cell_measurement_theta_max      25.999
_cell_measurement_wavelength     0.71073
_exptl_crystal_description       prism
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    1.562
_exptl_crystal_size_max          0.325
_exptl_crystal_size_mid          0.310
_exptl_crystal_size_min          0.260
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             948

#----------------------------------------------------------------------------#
#                   ABSORPTION CORRECTION                                    #
#----------------------------------------------------------------------------#
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
0 -1 -1 0.1380
0 1 1 0.1720
0 1 -1 0.1300
0 -1 1 0.1300
0 -1 0 0.1300
5 0 0 0.1700
-5 0 0 0.1550
-3 -1 1 0.1440

_exptl_absorpt_coefficient_mu    1.371
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
a grid of  8 x  8 x  8 =   512 sampling points was used
;
_exptl_absorpt_correction_T_min  0.6731
_exptl_absorpt_correction_T_max  0.7333
_exptl_absorpt_correction_T_ave  0.7099

#----------------------------------------------------------------------------#
#                   DATA COLLECTION                                          #
#----------------------------------------------------------------------------#

_diffrn_source                   'Enraf Nonius FR590'
_diffrn_ambient_temperature      294(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_monochromator  'horizonally mounted graphite crystal'
_diffrn_radiation_probe          x-ray
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 9
_diffrn_orient_matrix_type       'by Bruker AXS Collect from scalepack cell'
_diffrn_measurement_device       '95mm CCD camera on κ-goniostat'
_diffrn_measurement_device_type  KappaCCD
_diffrn_measurement_method       'CCD rotation images, thick slices'


_diffrn_reflns_number            16840
_diffrn_reflns_av_unetI/netI     0.0562
_diffrn_reflns_av_R_equivalents  0.0931
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         2.579
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_full        25.242
_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
_reflns_number_total             3856
_reflns_number_gt                3134
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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.
;

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/6 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0821P)²+8.4778P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.018(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         3856
_refine_ls_number_parameters     256
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0791
_refine_ls_R_factor_gt           0.0656
_refine_ls_wR_factor_ref         0.1973
_refine_ls_wR_factor_gt          0.1888
_refine_ls_goodness_of_fit_ref   1.104
_refine_ls_restrained_S_all      1.104
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

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
Cu Cu 0.72916(5) 0.42378(5) 0.44735(5) 0.0317(3) Uani 1 1 d . . . . .
Cl Cl 0.78192(13) 0.57204(10) 0.54997(13) 0.0431(4) Uani 1 1 d . . . . .
S S 0.81022(13) 0.40303(11) 0.29562(12) 0.0409(4) Uani 1 1 d . . . . .
O O 0.5862(3) 0.4691(3) 0.3441(3) 0.0388(9) Uani 1 1 d . . . . .
N3 N 0.6374(4) 0.3431(3) 0.5384(4) 0.0338(10) Uani 1 1 d . . . . .
N4 N 0.8585(4) 0.3498(3) 0.5509(4) 0.0354(10) Uani 1 1 d . . . . .
N1 N 0.6482(4) 0.5361(4) 0.1943(4) 0.0386(11) Uani 1 1 d . . . . .
N2 N 0.8243(4) 0.5481(4) 0.1610(4) 0.0424(12) Uani 1 1 d . . . . .
C35 C 0.7037(5) 0.2876(4) 0.6204(5) 0.0354(12) Uani 1 1 d . . . . .
C1 C 0.5703(5) 0.5111(4) 0.2490(4) 0.0324(11) Uani 1 1 d . . . . .
C31 C 0.5232(5) 0.3466(4) 0.5284(5) 0.0392(13) Uani 1 1 d . . . . .
H31 H 0.4777 0.3864 0.4733 0.047 Uiso 1 1 calc R U . . .
C2 C 0.4481(5) 0.5391(4) 0.1904(5) 0.0338(11) Uani 1 1 d . . . . .
C3 C 0.3589(5) 0.5143(4) 0.2381(5) 0.0369(12) Uani 1 1 d . . . . .
H3 H 0.3749 0.4789 0.3053 0.044 Uiso 1 1 calc R U . . .
C4 C 0.2470(5) 0.5412(5) 0.1878(5) 0.0443(14) Uani 1 1 d . . . . .
H4 H 0.1877 0.5231 0.2199 0.053 Uiso 1 1 calc R U . . .
C8 C 0.7561(5) 0.5025(4) 0.2156(4) 0.0346(12) Uani 1 1 d . . . . .
C34 C 0.6568(6) 0.2334(4) 0.6932(5) 0.0460(14) Uani 1 1 d . . . . .
H34 H 0.7038 0.1950 0.7489 0.055 Uiso 1 1 calc R U . . .
C42 C 1.0548(6) 0.3029(5) 0.6210(6) 0.0509(16) Uani 1 1 d . . . . .
H42 H 1.1313 0.3082 0.6181 0.061 Uiso 1 1 calc R U . . .
C45 C 0.8279(5) 0.2891(4) 0.6258(5) 0.0363(12) Uani 1 1 d . . . . .
C5 C 0.2231(5) 0.5956(5) 0.0887(6) 0.0512(16) Uani 1 1 d . . . . .
H5 H 0.1479 0.6152 0.0550 0.061 Uiso 1 1 calc R U . . .
C32 C 0.4705(6) 0.2932(5) 0.5972(6) 0.0497(15) Uani 1 1 d . . . . .
H32 H 0.3908 0.2952 0.5865 0.060 Uiso 1 1 calc R U . . .
C10 C 0.9437(5) 0.5222(5) 0.1723(6) 0.0518(16) Uani 1 1 d . . . . .
H10A H 0.9784 0.5023 0.2493 0.078 Uiso 1 1 calc R U . . .
H10B H 0.9849 0.5763 0.1542 0.078 Uiso 1 1 calc R U . . .
H10C H 0.9471 0.4709 0.1208 0.078 Uiso 1 1 calc R U . . .
C44 C 0.9110(6) 0.2354(4) 0.6992(6) 0.0508(16) Uani 1 1 d . . . . .
H44 H 0.8897 0.1950 0.7511 0.061 Uiso 1 1 calc R U . . .
C7 C 0.4235(6) 0.5917(5) 0.0897(5) 0.0466(15) Uani 1 1 d . . . . .
H7 H 0.4820 0.6076 0.0553 0.056 Uiso 1 1 calc R U . . .
C9 C 0.7778(6) 0.6246(6) 0.0796(7) 0.0598(19) Uani 1 1 d . . . . .
H9A H 0.7111 0.6018 0.0236 0.090 Uiso 1 1 calc R U . . .
H9B H 0.8356 0.6444 0.0423 0.090 Uiso 1 1 calc R U . . .
H9C H 0.7564 0.6778 0.1196 0.090 Uiso 1 1 calc R U . . .
C41 C 0.9703(5) 0.3568(5) 0.5503(5) 0.0431(14) Uani 1 1 d . . . . .
H41 H 0.9910 0.3996 0.5004 0.052 Uiso 1 1 calc R U . . .
C43 C 1.0241(6) 0.2404(5) 0.6970(7) 0.0575(18) Uani 1 1 d . . . . .
H43 H 1.0796 0.2027 0.7454 0.069 Uiso 1 1 calc R U . . .
C33 C 0.5382(7) 0.2376(5) 0.6811(6) 0.0527(16) Uani 1 1 d . . . . .
H33 H 0.5050 0.2027 0.7298 0.063 Uiso 1 1 calc R U . . .
C6 C 0.3105(6) 0.6202(5) 0.0411(6) 0.0534(17) Uani 1 1 d . . . . .
H6 H 0.2941 0.6568 -0.0251 0.064 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
Cu O 1.948(4) . ?
Cu N4 2.013(4) . ?
Cu N3 2.081(5) . ?
Cu S 2.3088(15) . ?
Cu Cl 2.4215(16) . ?
S C8 1.727(6) . ?
O C1 1.264(6) . ?
N3 C31 1.343(7) . ?
N3 C35 1.347(7) . ?
N4 C41 1.345(7) . ?
N4 C45 1.361(7) . ?
N1 C1 1.323(7) . ?
N1 C8 1.337(7) . ?
N2 C8 1.339(7) . ?
N2 C10 1.448(8) . ?
N2 C9 1.467(8) . ?
C35 C34 1.389(8) . ?
C35 C45 1.473(8) . ?
C1 C2 1.505(7) . ?
C31 C32 1.388(9) . ?
C31 H31 0.9300 . ?
C2 C3 1.384(8) . ?
C2 C7 1.391(8) . ?
C3 C4 1.374(8) . ?
C3 H3 0.9300 . ?
C4 C5 1.389(10) . ?
C4 H4 0.9300 . ?
C34 C33 1.392(10) . ?
C34 H34 0.9300 . ?
C42 C41 1.372(9) . ?
C42 C43 1.387(11) . ?
C42 H42 0.9300 . ?
C45 C44 1.376(8) . ?
C5 C6 1.364(10) . ?
C5 H5 0.9300 . ?
C32 C33 1.369(10) . ?
C32 H32 0.9300 . ?
C10 H10A 0.9600 . ?
C10 H10B 0.9600 . ?
C10 H10C 0.9600 . ?
C44 C43 1.364(10) . ?
C44 H44 0.9300 . ?
C7 C6 1.387(9) . ?
C7 H7 0.9300 . ?
C9 H9A 0.9600 . ?
C9 H9B 0.9600 . ?
C9 H9C 0.9600 . ?
C41 H41 0.9300 . ?
C43 H43 0.9300 . ?
C33 H33 0.9300 . ?
C6 H6 0.9300 . ?

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
O Cu N4 167.55(19) . . ?
O Cu N3 91.21(17) . . ?
N4 Cu N3 79.38(18) . . ?
O Cu S 90.59(12) . . ?
N4 Cu S 91.00(14) . . ?
N3 Cu S 137.91(13) . . ?
O Cu Cl 96.85(13) . . ?
N4 Cu Cl 93.76(14) . . ?
N3 Cu Cl 107.33(13) . . ?
S Cu Cl 114.18(6) . . ?
C8 S Cu 99.88(19) . . ?
C1 O Cu 129.7(4) . . ?
C31 N3 C35 118.7(5) . . ?
C31 N3 Cu 126.7(4) . . ?
C35 N3 Cu 114.5(4) . . ?
C41 N4 C45 119.3(5) . . ?
C41 N4 Cu 124.5(4) . . ?
C45 N4 Cu 116.2(4) . . ?
C1 N1 C8 125.6(5) . . ?
C8 N2 C10 123.2(5) . . ?
C8 N2 C9 120.5(5) . . ?
C10 N2 C9 116.2(5) . . ?
N3 C35 C34 121.9(6) . . ?
N3 C35 C45 114.9(5) . . ?
C34 C35 C45 123.3(5) . . ?
O C1 N1 128.3(5) . . ?
O C1 C2 116.8(5) . . ?
N1 C1 C2 114.8(5) . . ?
N3 C31 C32 122.4(6) . . ?
N3 C31 H31 118.8 . . ?
C32 C31 H31 118.8 . . ?
C3 C2 C7 119.2(5) . . ?
C3 C2 C1 119.9(5) . . ?
C7 C2 C1 120.9(5) . . ?
C4 C3 C2 121.0(6) . . ?
C4 C3 H3 119.5 . . ?
C2 C3 H3 119.5 . . ?
C3 C4 C5 119.6(6) . . ?
C3 C4 H4 120.2 . . ?
C5 C4 H4 120.2 . . ?
N1 C8 N2 114.8(5) . . ?
N1 C8 S 126.6(4) . . ?
N2 C8 S 118.4(4) . . ?
C35 C34 C33 118.6(6) . . ?
C35 C34 H34 120.7 . . ?
C33 C34 H34 120.7 . . ?
C41 C42 C43 118.9(6) . . ?
C41 C42 H42 120.5 . . ?
C43 C42 H42 120.5 . . ?
N4 C45 C44 119.9(6) . . ?
N4 C45 C35 115.0(5) . . ?
C44 C45 C35 125.1(6) . . ?
C6 C5 C4 119.7(6) . . ?
C6 C5 H5 120.2 . . ?
C4 C5 H5 120.2 . . ?
C33 C32 C31 118.7(6) . . ?
C33 C32 H32 120.6 . . ?
C31 C32 H32 120.6 . . ?
N2 C10 H10A 109.5 . . ?
N2 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
N2 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
C43 C44 C45 121.1(6) . . ?
C43 C44 H44 119.5 . . ?
C45 C44 H44 119.5 . . ?
C6 C7 C2 119.2(6) . . ?
C6 C7 H7 120.4 . . ?
C2 C7 H7 120.4 . . ?
N2 C9 H9A 109.5 . . ?
N2 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
N2 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
N4 C41 C42 122.1(6) . . ?
N4 C41 H41 119.0 . . ?
C42 C41 H41 119.0 . . ?
C44 C43 C42 118.7(6) . . ?
C44 C43 H43 120.7 . . ?
C42 C43 H43 120.7 . . ?
C32 C33 C34 119.6(6) . . ?
C32 C33 H33 120.2 . . ?
C34 C33 H33 120.2 . . ?
C5 C6 C7 121.2(6) . . ?
C5 C6 H6 119.4 . . ?
C7 C6 H6 119.4 . . ?

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
C31 N3 C35 C34 0.9(8) . . . . ?
Cu N3 C35 C34 176.4(4) . . . . ?
C31 N3 C35 C45 -179.3(5) . . . . ?
Cu N3 C35 C45 -3.9(6) . . . . ?
Cu O C1 N1 -0.4(9) . . . . ?
Cu O C1 C2 -178.8(4) . . . . ?
C8 N1 C1 O 16.6(10) . . . . ?
C8 N1 C1 C2 -165.0(5) . . . . ?
C35 N3 C31 C32 -1.9(8) . . . . ?
Cu N3 C31 C32 -176.7(4) . . . . ?
O C1 C2 C3 -3.3(8) . . . . ?
N1 C1 C2 C3 178.1(5) . . . . ?
O C1 C2 C7 175.3(5) . . . . ?
N1 C1 C2 C7 -3.3(8) . . . . ?
C7 C2 C3 C4 -0.3(9) . . . . ?
C1 C2 C3 C4 178.3(5) . . . . ?
C2 C3 C4 C5 -1.3(9) . . . . ?
C1 N1 C8 N2 -170.6(5) . . . . ?
C1 N1 C8 S 14.7(9) . . . . ?
C10 N2 C8 N1 -179.7(6) . . . . ?
C9 N2 C8 N1 -3.6(9) . . . . ?
C10 N2 C8 S -4.5(8) . . . . ?
C9 N2 C8 S 171.6(5) . . . . ?
Cu S C8 N1 -43.1(5) . . . . ?
Cu S C8 N2 142.5(4) . . . . ?
N3 C35 C34 C33 -0.6(9) . . . . ?
C45 C35 C34 C33 179.7(5) . . . . ?
C41 N4 C45 C44 -0.4(8) . . . . ?
Cu N4 C45 C44 179.6(5) . . . . ?
C41 N4 C45 C35 179.3(5) . . . . ?
Cu N4 C45 C35 -0.7(6) . . . . ?
N3 C35 C45 N4 3.1(7) . . . . ?
C34 C35 C45 N4 -177.2(5) . . . . ?
N3 C35 C45 C44 -177.2(6) . . . . ?
C34 C35 C45 C44 2.5(9) . . . . ?
C3 C4 C5 C6 1.3(10) . . . . ?
N3 C31 C32 C33 2.5(9) . . . . ?
N4 C45 C44 C43 -1.2(10) . . . . ?
C35 C45 C44 C43 179.1(6) . . . . ?
C3 C2 C7 C6 1.7(9) . . . . ?
C1 C2 C7 C6 -176.8(6) . . . . ?
C45 N4 C41 C42 1.7(9) . . . . ?
Cu N4 C41 C42 -178.4(5) . . . . ?
C43 C42 C41 N4 -1.2(10) . . . . ?
C45 C44 C43 C42 1.7(11) . . . . ?
C41 C42 C43 C44 -0.5(11) . . . . ?
C31 C32 C33 C34 -2.1(10) . . . . ?
C35 C34 C33 C32 1.2(10) . . . . ?
C4 C5 C6 C7 0.1(11) . . . . ?
C2 C7 C6 C5 -1.6(11) . . . . ?

_refine_diff_density_max         1.023
_refine_diff_density_min         -0.657
_refine_diff_density_rms         0.132

_shelxl_version_number           2014/6

