# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2021

####################################################################### 
# 
# 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_m1_a
_database_code_depnum_ccdc_archive 'CCDC 2095238'
loop_
_audit_author_name
_audit_author_address
'Alexey Dobrynin'
;Arbuzov Institute of Organic and Physical Chemistry of RAS
Russia
;
_audit_update_record             
;
2021-07-08 deposited with the CCDC.	2021-08-30 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
tetra-(μ3-iodo)-tetrakis(10-(4-chlorophenyl)-5,10-dihydro-5-methyl-phenarsazine)copper(I)
_chemical_name_common            ?
_chemical_melting_point          551
_chemical_formula_moiety         ?
_chemical_formula_sum            'C76 H60 As4 Cl4 Cu4 I4 N4'
_chemical_formula_weight         2232.52

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'
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'
As As 0.0499 2.0058 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
I I -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      tetragonal
_space_group_IT_number           88
_space_group_name_H-M_alt        'I 41/a'
_space_group_name_Hall           '-I 4ad'

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

_cell_length_a                   25.4392(13)
_cell_length_b                   25.4392(13)
_cell_length_c                   12.2009(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     7895.8(9)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    3787
_cell_measurement_theta_min      2.45
_cell_measurement_theta_max      27.05

_exptl_crystal_description       prismatic
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.878
_exptl_crystal_F_000             4288
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.10
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.09
_exptl_absorpt_coefficient_mu    4.469
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            14748
_diffrn_reflns_av_unetI/netI     0.0802
_diffrn_reflns_av_R_equivalents  0.1219
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         1.601
_diffrn_reflns_theta_max         25.510
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measured_fraction_theta_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_point_group_measured_fraction_full 0.987
_reflns_number_total             3613
_reflns_number_gt                2557
_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       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2017)'
_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)+(0.1000P)²+0.0737P] 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     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3613
_refine_ls_number_parameters     218
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0760
_refine_ls_R_factor_gt           0.0418
_refine_ls_wR_factor_ref         0.1647
_refine_ls_wR_factor_gt          0.1151
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_restrained_S_all      1.009
_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
I1 I 0.07377(2) 0.20060(2) 0.24960(4) 0.0435(2) Uani 1 1 d . . . . .
As1 As 0.07290(3) 0.35840(3) 0.31475(6) 0.0358(3) Uani 1 1 d . . . . .
Cu1 Cu 0.02998(4) 0.29327(4) 0.20983(9) 0.0460(3) Uani 1 1 d . . . . .
Cl16 Cl 0.31191(11) 0.40133(15) 0.1660(3) 0.0874(10) Uani 1 1 d . . . . .
C2 C 0.0794(3) 0.3065(3) 0.5248(7) 0.044(2) Uani 1 1 d . . . . .
H2 H 0.0695 0.2765 0.4864 0.052 Uiso 1 1 calc R U . . .
C13 C 0.1455(3) 0.3745(3) 0.2730(6) 0.0384(19) Uani 1 1 d . . . . .
N1 N 0.0993(3) 0.4485(3) 0.4740(6) 0.0506(19) Uani 1 1 d . . . . .
C1 C 0.0835(3) 0.3545(3) 0.4690(7) 0.0358(18) Uani 1 1 d . . . . .
C16 C 0.2481(3) 0.3913(4) 0.2087(7) 0.051(2) Uani 1 1 d . . . . .
C6 C 0.0965(3) 0.4001(3) 0.5273(6) 0.0400(19) Uani 1 1 d . . . . .
C3 C 0.0897(4) 0.3027(4) 0.6351(8) 0.054(2) Uani 1 1 d . . . . .
H3 H 0.0869 0.2707 0.6714 0.065 Uiso 1 1 calc R U . . .
C17 C 0.2363(4) 0.3467(4) 0.2661(8) 0.061(3) Uani 1 1 d . . . . .
H17 H 0.2625 0.3227 0.2845 0.073 Uiso 1 1 calc R U . . .
C18 C 0.1850(4) 0.3380(4) 0.2962(8) 0.056(2) Uani 1 1 d . . . . .
H18 H 0.1763 0.3072 0.3328 0.067 Uiso 1 1 calc R U . . .
C5 C 0.1074(3) 0.3951(4) 0.6383(7) 0.053(2) Uani 1 1 d . . . . .
H5 H 0.1170 0.4246 0.6782 0.064 Uiso 1 1 calc R U . . .
C12 C 0.0435(3) 0.4270(3) 0.3179(7) 0.0407(19) Uani 1 1 d . . . . .
C7 C 0.0621(3) 0.4628(3) 0.3945(7) 0.045(2) Uani 1 1 d . . . . .
C4 C 0.1042(4) 0.3474(4) 0.6903(8) 0.053(2) Uani 1 1 d . . . . .
H4 H 0.1120 0.3453 0.7647 0.064 Uiso 1 1 calc R U . . .
C14 C 0.1587(4) 0.4186(4) 0.2168(8) 0.067(3) Uani 1 1 d . . . . .
H14 H 0.1330 0.4434 0.2001 0.080 Uiso 1 1 calc R U . . .
C9 C 0.0067(4) 0.5290(4) 0.3102(9) 0.065(3) Uani 1 1 d . . . . .
H9 H -0.0047 0.5637 0.3069 0.079 Uiso 1 1 calc R U . . .
C8 C 0.0432(4) 0.5154(4) 0.3873(9) 0.062(3) Uani 1 1 d . . . . .
H8 H 0.0558 0.5407 0.4356 0.075 Uiso 1 1 calc R U . . .
C15 C 0.2098(4) 0.4271(5) 0.1841(10) 0.076(3) Uani 1 1 d . . . . .
H15 H 0.2183 0.4574 0.1452 0.092 Uiso 1 1 calc R U . . .
C11 C 0.0053(4) 0.4427(4) 0.2410(8) 0.059(3) Uani 1 1 d . . . . .
H11 H -0.0075 0.4182 0.1911 0.070 Uiso 1 1 calc R U . . .
C10 C -0.0135(4) 0.4935(4) 0.2379(9) 0.064(3) Uani 1 1 d . . . . .
H10 H -0.0393 0.5033 0.1880 0.077 Uiso 1 1 calc R U . . .
C19 C 0.1302(6) 0.4901(4) 0.5254(10) 0.088(4) Uani 1 1 d . . . . .
H19A H 0.1103 0.5057 0.5838 0.131 Uiso 1 1 calc R U . . .
H19B H 0.1385 0.5165 0.4718 0.131 Uiso 1 1 calc R U . . .
H19C H 0.1621 0.4755 0.5543 0.131 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
I1 Cu1 2.6522(12) . ?
I1 Cu1 2.6878(12) 6_454 ?
I1 Cu1 2.7157(12) 15 ?
As1 C12 1.900(8) . ?
As1 C1 1.904(8) . ?
As1 C13 1.959(8) . ?
As1 Cu1 2.3614(12) . ?
Cu1 Cu1 2.678(2) 6_454 ?
Cu1 I1 2.6878(12) 6_454 ?
Cu1 I1 2.7156(12) 12_666 ?
Cu1 Cu1 2.8056(18) 15 ?
Cu1 Cu1 2.8057(18) 12_666 ?
Cl16 C16 1.724(9) . ?
C2 C3 1.374(13) . ?
C2 C1 1.402(11) . ?
C2 H2 0.9300 . ?
C13 C14 1.358(12) . ?
C13 C18 1.395(12) . ?
N1 C6 1.393(11) . ?
N1 C7 1.402(11) . ?
N1 C19 1.460(11) . ?
C1 C6 1.402(11) . ?
C16 C17 1.366(14) . ?
C16 C15 1.368(15) . ?
C6 C5 1.388(12) . ?
C3 C4 1.371(13) . ?
C3 H3 0.9300 . ?
C17 C18 1.375(13) . ?
C17 H17 0.9300 . ?
C18 H18 0.9300 . ?
C5 C4 1.372(13) . ?
C5 H5 0.9300 . ?
C12 C7 1.389(11) . ?
C12 C11 1.407(13) . ?
C7 C8 1.424(12) . ?
C4 H4 0.9300 . ?
C14 C15 1.376(14) . ?
C14 H14 0.9300 . ?
C9 C10 1.364(14) . ?
C9 C8 1.366(14) . ?
C9 H9 0.9300 . ?
C8 H8 0.9300 . ?
C15 H15 0.9300 . ?
C11 C10 1.379(14) . ?
C11 H11 0.9300 . ?
C10 H10 0.9300 . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 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
Cu1 I1 Cu1 60.20(4) . 6_454 ?
Cu1 I1 Cu1 63.01(4) . 15 ?
Cu1 I1 Cu1 62.56(4) 6_454 15 ?
C12 As1 C1 94.8(3) . . ?
C12 As1 C13 100.6(3) . . ?
C1 As1 C13 97.7(3) . . ?
C12 As1 Cu1 118.3(2) . . ?
C1 As1 Cu1 124.3(2) . . ?
C13 As1 Cu1 116.2(2) . . ?
As1 Cu1 I1 109.29(5) . . ?
As1 Cu1 Cu1 147.15(3) . 6_454 ?
I1 Cu1 Cu1 60.56(4) . 6_454 ?
As1 Cu1 I1 108.39(4) . 6_454 ?
I1 Cu1 I1 115.53(4) . 6_454 ?
Cu1 Cu1 I1 59.24(4) 6_454 6_454 ?
As1 Cu1 I1 103.03(4) . 12_666 ?
I1 Cu1 I1 110.46(4) . 12_666 ?
Cu1 Cu1 I1 109.78(2) 6_454 12_666 ?
I1 Cu1 I1 109.39(4) 6_454 12_666 ?
As1 Cu1 Cu1 144.12(6) . 15 ?
I1 Cu1 Cu1 59.60(3) . 15 ?
Cu1 Cu1 Cu1 61.49(2) 6_454 15 ?
I1 Cu1 Cu1 106.86(4) 6_454 15 ?
I1 Cu1 Cu1 58.23(4) 12_666 15 ?
As1 Cu1 Cu1 142.34(6) . 12_666 ?
I1 Cu1 Cu1 107.87(4) . 12_666 ?
Cu1 Cu1 Cu1 61.49(2) 6_454 12_666 ?
I1 Cu1 Cu1 59.21(3) 6_454 12_666 ?
I1 Cu1 Cu1 57.39(4) 12_666 12_666 ?
Cu1 Cu1 Cu1 57.02(5) 15 12_666 ?
C3 C2 C1 121.5(9) . . ?
C3 C2 H2 119.3 . . ?
C1 C2 H2 119.3 . . ?
C14 C13 C18 118.3(8) . . ?
C14 C13 As1 122.5(7) . . ?
C18 C13 As1 119.1(6) . . ?
C6 N1 C7 121.2(7) . . ?
C6 N1 C19 117.9(8) . . ?
C7 N1 C19 118.2(8) . . ?
C2 C1 C6 119.5(8) . . ?
C2 C1 As1 121.1(6) . . ?
C6 C1 As1 119.4(6) . . ?
C17 C16 C15 120.6(9) . . ?
C17 C16 Cl16 119.0(8) . . ?
C15 C16 Cl16 120.3(8) . . ?
C5 C6 N1 121.8(8) . . ?
C5 C6 C1 117.7(8) . . ?
N1 C6 C1 120.5(7) . . ?
C4 C3 C2 118.3(9) . . ?
C4 C3 H3 120.8 . . ?
C2 C3 H3 120.8 . . ?
C16 C17 C18 118.6(9) . . ?
C16 C17 H17 120.7 . . ?
C18 C17 H17 120.7 . . ?
C17 C18 C13 121.5(9) . . ?
C17 C18 H18 119.2 . . ?
C13 C18 H18 119.2 . . ?
C4 C5 C6 121.5(9) . . ?
C4 C5 H5 119.3 . . ?
C6 C5 H5 119.3 . . ?
C7 C12 C11 119.9(8) . . ?
C7 C12 As1 118.8(6) . . ?
C11 C12 As1 121.3(6) . . ?
C12 C7 N1 121.7(7) . . ?
C12 C7 C8 117.2(8) . . ?
N1 C7 C8 121.0(8) . . ?
C3 C4 C5 121.4(9) . . ?
C3 C4 H4 119.3 . . ?
C5 C4 H4 119.3 . . ?
C13 C14 C15 120.7(10) . . ?
C13 C14 H14 119.7 . . ?
C15 C14 H14 119.7 . . ?
C10 C9 C8 122.2(9) . . ?
C10 C9 H9 118.9 . . ?
C8 C9 H9 118.9 . . ?
C9 C8 C7 120.8(9) . . ?
C9 C8 H8 119.6 . . ?
C7 C8 H8 119.6 . . ?
C16 C15 C14 120.3(10) . . ?
C16 C15 H15 119.9 . . ?
C14 C15 H15 119.9 . . ?
C10 C11 C12 121.6(9) . . ?
C10 C11 H11 119.2 . . ?
C12 C11 H11 119.2 . . ?
C9 C10 C11 118.2(9) . . ?
C9 C10 H10 120.9 . . ?
C11 C10 H10 120.9 . . ?
N1 C19 H19A 109.5 . . ?
N1 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
N1 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?

_refine_diff_density_max         0.826
_refine_diff_density_min         -2.308
_refine_diff_density_rms         0.463



_exptl_crystal_preparation       Luminescent
####################################################################### 
# 
# 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_Milya13_01_a
_database_code_depnum_ccdc_archive 'CCDC 2095239'
loop_
_audit_author_name
_audit_author_address
'Alexey Dobrynin'
;Arbuzov Institute of Organic and Physical Chemistry of RAS
Russia
;
_audit_update_record             
;
2021-07-08 deposited with the CCDC.	2021-08-30 downloaded from the CCDC.
;



_audit_creation_method           SHELXL-2017/1
_shelx_SHELXL_version_number     2017/1
_chemical_name_systematic        
tetra-(μ3-iodo)-tetrakis(10-(4-bromophenyl)-5,10-dihydro-5-methyl-phenarsazine)copper(I)

_chemical_name_common            ?
_chemical_melting_point          535
_chemical_formula_moiety         ?
_chemical_formula_sum            'C152 H120 As8 Br8 Cu8 I8 N8'
_chemical_formula_weight         4820.71

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'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
As As 0.0499 2.0058 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
I I -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      tetragonal
_space_group_IT_number           88
_space_group_name_H-M_alt        'I 41/a'
_space_group_name_Hall           '-I 4ad'

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

_cell_length_a                   25.383(2)
_cell_length_b                   25.383(2)
_cell_length_c                   12.2628(9)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     7900.9(14)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    4794
_cell_measurement_theta_min      2.44
_cell_measurement_theta_max      27.78

_exptl_crystal_description       prismatic
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.026
_exptl_crystal_F_000             4576
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.10
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.08
_exptl_absorpt_coefficient_mu    6.354
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            17373
_diffrn_reflns_av_unetI/netI     0.0922
_diffrn_reflns_av_R_equivalents  0.1471
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         1.605
_diffrn_reflns_theta_max         25.997
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measured_fraction_theta_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_point_group_measured_fraction_full 0.984
_reflns_number_total             3805
_reflns_number_gt                2851
_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       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2017)'
_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)+(0.1000P)²-0.0494P] 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     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3805
_refine_ls_number_parameters     218
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0719
_refine_ls_R_factor_gt           0.0466
_refine_ls_wR_factor_ref         0.1617
_refine_ls_wR_factor_gt          0.1356
_refine_ls_goodness_of_fit_ref   0.995
_refine_ls_restrained_S_all      0.995
_refine_ls_shift/su_max          0.001
_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
I1 I -0.04935(2) 0.32416(2) 0.50059(5) 0.0183(2) Uani 1 1 d . . . . .
As1 As 0.10783(3) 0.32131(3) 0.43745(7) 0.0158(2) Uani 1 1 d . . . . .
Br16 Br 0.15458(4) 0.56744(4) 0.58254(9) 0.0336(3) Uani 1 1 d . . . . .
Cu1 Cu 0.04273(4) 0.27925(4) 0.54272(9) 0.0183(3) Uani 1 1 d . . . . .
N1 N 0.1983(3) 0.3459(3) 0.2759(6) 0.0235(17) Uani 1 1 d . . . . .
C13 C 0.1243(3) 0.3938(3) 0.4762(7) 0.0194(19) Uani 1 1 d . . . . .
C3 C 0.0492(3) 0.3397(3) 0.1189(7) 0.0210(19) Uani 1 1 d . . . . .
H3 H 0.016982 0.337779 0.083116 0.025 Uiso 1 1 calc R U . . .
C6 C 0.1483(3) 0.3443(3) 0.2231(7) 0.0166(18) Uani 1 1 d . . . . .
C12 C 0.1775(3) 0.2910(3) 0.4350(7) 0.0208(19) Uani 1 1 d . . . . .
C2 C 0.0533(3) 0.3290(3) 0.2295(8) 0.021(2) Uani 1 1 d . . . . .
H2 H 0.023271 0.319980 0.268744 0.025 Uiso 1 1 calc R U . . .
C16 C 0.1423(4) 0.4963(3) 0.5374(7) 0.0207(19) Uani 1 1 d . . . . .
C5 C 0.1434(3) 0.3552(3) 0.1144(8) 0.022(2) Uani 1 1 d . . . . .
H5 H 0.173316 0.363776 0.074228 0.027 Uiso 1 1 calc R U . . .
C17 C 0.0966(4) 0.4848(4) 0.4837(8) 0.026(2) Uani 1 1 d . . . . .
H17 H 0.072047 0.510909 0.467967 0.031 Uiso 1 1 calc R U . . .
C18 C 0.0878(4) 0.4326(3) 0.4533(7) 0.0222(19) Uani 1 1 d . . . . .
H18 H 0.056924 0.423761 0.416862 0.027 Uiso 1 1 calc R U . . .
C4 C 0.0951(4) 0.3536(3) 0.0629(8) 0.025(2) Uani 1 1 d . . . . .
H4 H 0.093055 0.361958 -0.010846 0.030 Uiso 1 1 calc R U . . .
C10 C 0.2434(4) 0.2353(4) 0.5172(8) 0.030(2) Uani 1 1 d . . . . .
H10 H 0.253633 0.210198 0.568203 0.035 Uiso 1 1 calc R U . . .
C1 C 0.1026(3) 0.3316(3) 0.2837(7) 0.0156(17) Uani 1 1 d . . . . .
C9 C 0.2792(3) 0.2554(4) 0.4425(8) 0.030(2) Uani 1 1 d . . . . .
H9 H 0.314106 0.244596 0.446996 0.035 Uiso 1 1 calc R U . . .
C7 C 0.2128(3) 0.3088(3) 0.3569(7) 0.0209(19) Uani 1 1 d . . . . .
C19 C 0.2393(3) 0.3755(4) 0.2208(9) 0.033(2) Uani 1 1 d . . . . .
H19A H 0.267493 0.382580 0.270906 0.049 Uiso 1 1 calc R U . . .
H19B H 0.225076 0.408197 0.194599 0.049 Uiso 1 1 calc R U . . .
H19C H 0.252486 0.355371 0.160425 0.049 Uiso 1 1 calc R U . . .
C11 C 0.1919(3) 0.2537(3) 0.5138(8) 0.026(2) Uani 1 1 d . . . . .
H11 H 0.167103 0.241327 0.563520 0.031 Uiso 1 1 calc R U . . .
C8 C 0.2653(3) 0.2905(4) 0.3621(8) 0.028(2) Uani 1 1 d . . . . .
H8 H 0.290117 0.301966 0.311683 0.033 Uiso 1 1 calc R U . . .
C15 C 0.1797(4) 0.4593(4) 0.5592(9) 0.034(3) Uani 1 1 d . . . . .
H15 H 0.211215 0.468842 0.592431 0.040 Uiso 1 1 calc R U . . .
C14 C 0.1704(4) 0.4074(4) 0.5317(9) 0.034(2) Uani 1 1 d . . . . .
H14 H 0.194743 0.381554 0.549994 0.041 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
I1 Cu1 2.6512(11) . ?
I1 Cu1 2.6803(11) 6_454 ?
I1 Cu1 2.7058(12) 12_667 ?
As1 C1 1.908(9) . ?
As1 C12 1.929(8) . ?
As1 C13 1.946(8) . ?
As1 Cu1 2.3532(13) . ?
Br16 C16 1.913(8) . ?
Cu1 Cu1 2.628(2) 6_454 ?
Cu1 Cu1 2.7435(18) 12_667 ?
Cu1 Cu1 2.7435(18) 15_556 ?
N1 C7 1.417(11) . ?
N1 C6 1.424(10) . ?
N1 C19 1.452(11) . ?
C13 C18 1.379(12) . ?
C13 C14 1.397(12) . ?
C3 C2 1.388(13) . ?
C3 C4 1.397(12) . ?
C3 H3 0.9300 . ?
C6 C5 1.367(12) . ?
C6 C1 1.415(11) . ?
C12 C7 1.387(12) . ?
C12 C11 1.402(13) . ?
C2 C1 1.419(11) . ?
C2 H2 0.9300 . ?
C16 C15 1.362(13) . ?
C16 C17 1.367(12) . ?
C5 C4 1.380(12) . ?
C5 H5 0.9300 . ?
C17 C18 1.394(12) . ?
C17 H17 0.9300 . ?
C18 H18 0.9300 . ?
C4 H4 0.9300 . ?
C10 C9 1.386(13) . ?
C10 C11 1.389(12) . ?
C10 H10 0.9300 . ?
C9 C8 1.375(14) . ?
C9 H9 0.9300 . ?
C7 C8 1.412(12) . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?
C11 H11 0.9300 . ?
C8 H8 0.9300 . ?
C15 C14 1.379(13) . ?
C15 H15 0.9300 . ?
C14 H14 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
Cu1 I1 Cu1 59.07(4) . 6_454 ?
Cu1 I1 Cu1 61.60(4) . 12_667 ?
Cu1 I1 Cu1 61.24(4) 6_454 12_667 ?
C1 As1 C12 95.9(4) . . ?
C1 As1 C13 97.3(4) . . ?
C12 As1 C13 100.6(3) . . ?
C1 As1 Cu1 123.7(2) . . ?
C12 As1 Cu1 118.1(3) . . ?
C13 As1 Cu1 116.5(3) . . ?
As1 Cu1 Cu1 146.70(3) . 6_454 ?
As1 Cu1 I1 108.49(4) . . ?
Cu1 Cu1 I1 61.02(4) 6_454 . ?
As1 Cu1 I1 107.13(4) . 6_454 ?
Cu1 Cu1 I1 59.91(4) 6_454 6_454 ?
I1 Cu1 I1 116.03(4) . 6_454 ?
As1 Cu1 I1 102.78(4) . 15_556 ?
Cu1 Cu1 I1 110.48(2) 6_454 15_556 ?
I1 Cu1 I1 111.18(4) . 15_556 ?
I1 Cu1 I1 110.29(4) 6_454 15_556 ?
As1 Cu1 Cu1 144.54(6) . 12_667 ?
Cu1 Cu1 Cu1 61.38(2) 6_454 12_667 ?
I1 Cu1 Cu1 60.18(3) . 12_667 ?
I1 Cu1 Cu1 107.80(3) 6_454 12_667 ?
I1 Cu1 Cu1 58.92(4) 15_556 12_667 ?
As1 Cu1 Cu1 142.49(5) . 15_556 ?
Cu1 Cu1 Cu1 61.38(2) 6_454 15_556 ?
I1 Cu1 Cu1 108.64(3) . 15_556 ?
I1 Cu1 Cu1 59.84(3) 6_454 15_556 ?
I1 Cu1 Cu1 58.22(4) 15_556 15_556 ?
Cu1 Cu1 Cu1 57.24(5) 12_667 15_556 ?
C7 N1 C6 122.1(7) . . ?
C7 N1 C19 118.9(7) . . ?
C6 N1 C19 116.2(7) . . ?
C18 C13 C14 119.0(8) . . ?
C18 C13 As1 118.7(6) . . ?
C14 C13 As1 122.2(7) . . ?
C2 C3 C4 117.9(8) . . ?
C2 C3 H3 121.1 . . ?
C4 C3 H3 121.1 . . ?
C5 C6 C1 119.0(8) . . ?
C5 C6 N1 121.3(7) . . ?
C1 C6 N1 119.8(7) . . ?
C7 C12 C11 121.9(8) . . ?
C7 C12 As1 118.3(7) . . ?
C11 C12 As1 119.8(6) . . ?
C3 C2 C1 120.9(8) . . ?
C3 C2 H2 119.5 . . ?
C1 C2 H2 119.5 . . ?
C15 C16 C17 122.5(8) . . ?
C15 C16 Br16 118.8(7) . . ?
C17 C16 Br16 118.7(7) . . ?
C6 C5 C4 121.4(8) . . ?
C6 C5 H5 119.3 . . ?
C4 C5 H5 119.3 . . ?
C16 C17 C18 117.9(8) . . ?
C16 C17 H17 121.0 . . ?
C18 C17 H17 121.0 . . ?
C13 C18 C17 121.1(8) . . ?
C13 C18 H18 119.5 . . ?
C17 C18 H18 119.5 . . ?
C5 C4 C3 121.6(9) . . ?
C5 C4 H4 119.2 . . ?
C3 C4 H4 119.2 . . ?
C9 C10 C11 118.3(9) . . ?
C9 C10 H10 120.9 . . ?
C11 C10 H10 120.9 . . ?
C6 C1 C2 119.2(8) . . ?
C6 C1 As1 119.6(6) . . ?
C2 C1 As1 121.1(6) . . ?
C8 C9 C10 123.0(8) . . ?
C8 C9 H9 118.5 . . ?
C10 C9 H9 118.5 . . ?
C12 C7 C8 118.1(9) . . ?
C12 C7 N1 122.1(8) . . ?
C8 C7 N1 119.8(8) . . ?
N1 C19 H19A 109.5 . . ?
N1 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
N1 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
C10 C11 C12 119.5(9) . . ?
C10 C11 H11 120.3 . . ?
C12 C11 H11 120.3 . . ?
C9 C8 C7 119.2(9) . . ?
C9 C8 H8 120.4 . . ?
C7 C8 H8 120.4 . . ?
C16 C15 C14 119.4(9) . . ?
C16 C15 H15 120.3 . . ?
C14 C15 H15 120.3 . . ?
C15 C14 C13 119.9(9) . . ?
C15 C14 H14 120.0 . . ?
C13 C14 H14 120.0 . . ?

_refine_diff_density_max         1.041
_refine_diff_density_min         -2.083
_refine_diff_density_rms         0.378



_exptl_crystal_preparation       Luminescent
