# Electronic Supplementary Material (ESI) for CrystEngComm.
# This journal is © The Royal Society of Chemistry 2020

####################################################################### 
# 
# 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_atu017
_database_code_depnum_ccdc_archive 'CCDC 2025030'
loop_
_audit_author_name
_audit_author_address
'Natalia Kuratieva'
;Nikolaev Institute of Inorganic Chemistry SB RAS
Russia
;
_audit_update_record             
;
2020-08-24 deposited with the CCDC.	2020-11-16 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_formula_moiety         'Cu1.94 S4 Sn Zn1.06'
_chemical_formula_sum            'Cu1.94 S4 Sn Zn1.06'
_chemical_melting_point          ?

_exptl_crystal_description       plate
_exptl_crystal_colour            black
_diffrn_ambient_temperature      293(2)
_chemical_formula_weight         439.49

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
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'
Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Sn Sn -0.6537 1.4246 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      tetragonal
_space_group_IT_number           121
_space_group_name_H-M_alt        'I -4 2 m'
_space_group_name_Hall           'I -4 2'

_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'
'y, -x, -z'
'-x, -y, z'
'-y, x, -z'
'x, -y, -z'
'-x, y, -z'
'-y, -x, z'
'y, x, z'
'x+1/2, y+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'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                   5.4383(2)
_cell_length_b                   5.4383(2)
_cell_length_c                   10.8455(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     320.76(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    1493
_cell_measurement_theta_min      3.76
_cell_measurement_theta_max      32.63
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    4.550
_exptl_crystal_F_000             404
_exptl_transmission_factor_min   0.487
_exptl_transmission_factor_max   0.746
_exptl_crystal_size_max          0.120
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.020
_exptl_absorpt_coefficient_mu    15.276
_shelx_estimated_absorpt_T_min   0.261
_shelx_estimated_absorpt_T_max   0.750

_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   'Bruker SADABS'
_exptl_absorpt_special_details   ?


_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker Apex DUO CCD area-detector'
_diffrn_measurement_method       'φ scans'
_diffrn_detector_area_resol_mean 25
_diffrn_reflns_number            1592
_diffrn_reflns_av_unetI/netI     0.0214
_diffrn_reflns_av_R_equivalents  0.0294
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         3.757
_diffrn_reflns_theta_max         32.630
_diffrn_reflns_theta_full        25.250
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measured_fraction_theta_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_point_group_measured_fraction_full 0.994
_reflns_number_total             335
_reflns_number_gt                335
_reflns_threshold_expression     >2σ(I)
_reflns_Friedel_coverage         0.649
_reflns_Friedel_fraction_max     1.000
_reflns_Friedel_fraction_full    1.000

_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    'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     'w=1/[σ²(Fo²)] where P=(Fo²+2Fc²)/3'

_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.02(4)
_symmetry_cell_setting           ?
_symmetry_space_group_name_h-m   ?
_symmetry_int_tables_number      ?
_chemical_absolute_configuration ?
_refine_ls_number_reflns         335
_refine_ls_number_parameters     15
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0092
_refine_ls_R_factor_gt           0.0092
_refine_ls_wR_factor_ref         0.0224
_refine_ls_wR_factor_gt          0.0224
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_restrained_S_all      1.053
_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
Sn1 Sn 0.0000 0.0000 0.5000 0.00844(7) Uani 1 8 d S T P . .
Cu1 Cu 0.0000 0.0000 0.0000 0.01629(10) Uani 1 8 d S T P . .
Cu2 Cu 0.0000 0.5000 0.2500 0.01354(9) Uani 0.47 4 d S T P . .
Zn2 Zn 0.0000 0.5000 0.2500 0.01354(9) Uani 0.53 4 d S T P . .
S1 S 0.75595(5) 0.24405(5) 0.12780(3) 0.00824(14) Uani 1 2 d S T P . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Sn1 0.00843(8) 0.00843(8) 0.00844(11) 0.000 0.000 0.000
Cu1 0.01636(14) 0.01636(14) 0.0161(2) 0.000 0.000 0.000
Cu2 0.01357(12) 0.01357(12) 0.01347(18) 0.000 0.000 0.000
Zn2 0.01357(12) 0.01357(12) 0.01347(18) 0.000 0.000 0.000
S1 0.00827(19) 0.00827(19) 0.0082(3) 0.00049(7) -0.00049(7) 0.00051(9)

_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
Sn1 S1 2.4075(4) 10_455 ?
Sn1 S1 2.4075(4) 12_545 ?
Sn1 S1 2.4075(3) 9_445 ?
Sn1 S1 2.4075(3) 11 ?
Cu1 S1 2.3333(3) 4_545 ?
Cu1 S1 2.3333(3) 1_455 ?
Cu1 S1 2.3333(3) 3_655 ?
Cu1 S1 2.3333(3) 2_565 ?
Cu2 S1 2.33569(18) 1_455 ?
Cu2 S1 2.33569(19) 12_545 ?
Cu2 S1 2.33569(18) 3_665 ?
Cu2 S1 2.33569(19) 10_465 ?
S1 Cu1 2.3333(3) 1_655 ?
S1 Zn2 2.33569(18) 1_655 ?
S1 Cu2 2.33569(18) 1_655 ?
S1 Zn2 2.33569(19) 13 ?
S1 Cu2 2.33569(19) 13 ?
S1 Sn1 2.4075(3) 9_554 ?

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 Sn1 S1 109.700(15) 10_455 12_545 ?
S1 Sn1 S1 109.357(8) 10_455 9_445 ?
S1 Sn1 S1 109.357(7) 12_545 9_445 ?
S1 Sn1 S1 109.357(8) 10_455 11 ?
S1 Sn1 S1 109.357(7) 12_545 11 ?
S1 Sn1 S1 109.700(15) 9_445 11 ?
S1 Cu1 S1 110.664(8) 4_545 1_455 ?
S1 Cu1 S1 110.664(8) 4_545 3_655 ?
S1 Cu1 S1 107.111(17) 1_455 3_655 ?
S1 Cu1 S1 107.111(17) 4_545 2_565 ?
S1 Cu1 S1 110.664(8) 1_455 2_565 ?
S1 Cu1 S1 110.664(8) 3_655 2_565 ?
S1 Cu2 S1 108.782(6) 1_455 12_545 ?
S1 Cu2 S1 110.859(13) 1_455 3_665 ?
S1 Cu2 S1 108.782(6) 12_545 3_665 ?
S1 Cu2 S1 108.782(6) 1_455 10_465 ?
S1 Cu2 S1 110.859(13) 12_545 10_465 ?
S1 Cu2 S1 108.782(6) 3_665 10_465 ?
Cu1 S1 Zn2 110.661(10) 1_655 1_655 ?
Cu1 S1 Cu2 110.661(10) 1_655 1_655 ?
Zn2 S1 Cu2 0.0 1_655 1_655 ?
Cu1 S1 Zn2 110.661(10) 1_655 13 ?
Zn2 S1 Zn2 110.812(13) 1_655 13 ?
Cu2 S1 Zn2 110.812(13) 1_655 13 ?
Cu1 S1 Cu2 110.661(10) 1_655 13 ?
Zn2 S1 Cu2 110.8 1_655 13 ?
Cu2 S1 Cu2 110.812(13) 1_655 13 ?
Zn2 S1 Cu2 0.0 13 13 ?
Cu1 S1 Sn1 108.405(12) 1_655 9_554 ?
Zn2 S1 Sn1 108.099(10) 1_655 9_554 ?
Cu2 S1 Sn1 108.099(10) 1_655 9_554 ?
Zn2 S1 Sn1 108.099(10) 13 9_554 ?
Cu2 S1 Sn1 108.099(10) 13 9_554 ?

_refine_diff_density_max         0.352
_refine_diff_density_min         -0.488
_refine_diff_density_rms         0.092

_shelx_res_file                  
;

    D:\Job\PERVUH~1\Atuchin\atu017\atu017.res created by SHELXL-2014/7

TITL atu017 in I-42m
CELL 0.71073 5.4383 5.4383 10.8455 90.000 90.000 90.000
ZERR 2.0000 0.0002 0.0002 0.0005 0.000 0.000 0.000
LATT -2
SYMM Y, -X, -Z
SYMM -X, -Y, Z
SYMM -Y, X, -Z
SYMM X, -Y, -Z
SYMM -X, Y, -Z
SYMM -Y, -X, Z
SYMM Y, X, Z
SFAC S CU ZN SN
UNIT 8 3.88 2.12 2
MERG 2
OMIT 0 180
FMAP 2
GRID
PLAN 5
TEMP 20
SIZE 0.12 0.1 0.02
EADP CU2 ZN2
EXYZ CU2 ZN2
BOND
TWIN
OMIT  0 2 14
OMIT  2 2 0
L.S. 20
ACTA 50.5
WGHT    0.000000
BASF   0.02475
FVAR       0.11547   0.00000
SN1   4    0.000000    0.000000    0.500000    10.12500    0.00843    0.00843 =
         0.00844    0.00000    0.00000    0.00000
CU1   2    0.000000    0.000000    0.000000    10.12500    0.01636    0.01636 =
         0.01615    0.00000    0.00000    0.00000
CU2   2    0.000000    0.500000    0.250000    10.11750    0.01357    0.01357 =
         0.01347    0.00000    0.00000    0.00000
ZN2   3    0.000000    0.500000    0.250000    10.13250    0.01357    0.01357 =
         0.01347    0.00000    0.00000    0.00000
S1    1    0.755951    0.244049    0.127801    10.50000    0.00827    0.00827 =
         0.00818    0.00049   -0.00049    0.00051
HKLF 4

REM  atu017 in I-42m
REM R1 =  0.0092 for     335 Fo > 4sig(Fo)  and  0.0092 for all     335 data
REM     15 parameters refined using      0 restraints

END

WGHT      0.0000      0.0000

REM Highest difference peak  0.352,  deepest hole -0.488,  1-sigma level  0.092
Q1    1   0.0000  0.5000  0.4027  10.50000  0.05    0.22
Q2    1   0.5845 -0.0266  0.0391  11.00000  0.05    0.20
Q3    1  -0.1078  0.1078  0.3096  10.50000  0.05    0.20
Q4    1   0.0000  0.0000  0.1574  10.25000  0.05    0.20
Q5    1   0.0000  0.0000  0.3433  10.25000  0.05    0.20
;
_shelx_res_checksum              87714
_diffrn_radiation_monochromator  graphite
_diffrn_standards_number         0
_diffrn_standards_decay_%        0


# start Validation Reply Form
_vrf_PLAT113_atu017              
;
PROBLEM: ADDSYM Suggests Possible Pseudo/New  Space Group      P-4m2 Check 
RESPONSE: This ADDSYM test doesn't take into account disordered atoms. 
The structure contain the disordering in one site occupied simultaneously 
by Cu and Zn atoms.
;

# end Validation Reply Form
