# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_33
_database_code_depnum_ccdc_archive 'CCDC 1540053'
_audit_update_record             
;
2017-03-24 deposited with the CCDC.
2017-06-01 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Ba Cu2 Se4 Si'
_chemical_formula_weight         608.35

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ba Ba -0.3244 2.2819 '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'
Se Se -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Si Si 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           154
_space_group_name_H-M_alt        'P 32 2 1'
_space_group_name_Hall           'P 32 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-y, z+2/3'
'-x+y, -x, z+1/3'
'y, x, -z'
'-x, -x+y, -z+2/3'
'x-y, -y, -z+1/3'

_cell_length_a                   6.4188(19)
_cell_length_b                   6.4188(19)
_cell_length_c                   16.083(10)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     573.9(5)
_cell_formula_units_Z            3
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    937
_cell_measurement_theta_min      3.67
_cell_measurement_theta_max      27.08

_exptl_crystal_description       block
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    5.281
_exptl_crystal_F_000             792
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.133
_exptl_crystal_size_mid          0.097
_exptl_crystal_size_min          0.043
_exptl_absorpt_coefficient_mu    29.673
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.4958
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'sealed tube'
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            3463
_diffrn_reflns_av_unetI/netI     0.0443
_diffrn_reflns_av_R_equivalents  0.0525
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         3.665
_diffrn_reflns_theta_max         27.295
_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 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             869
_reflns_number_gt                793
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.597
_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 SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_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)+(0.0129P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   ?
_refine_ls_hydrogen_treatment    ?
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_extinction_coef       0.0016(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.07(4)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         869
_refine_ls_number_parameters     40
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0310
_refine_ls_R_factor_gt           0.0264
_refine_ls_wR_factor_ref         0.0449
_refine_ls_wR_factor_gt          0.0437
_refine_ls_goodness_of_fit_ref   1.008
_refine_ls_restrained_S_all      1.008
_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
Se2 Se 1.02831(17) 0.51676(16) 0.72196(5) 0.0117(2) Uani 1 1 d . . . . .
Se1 Se 0.67479(16) 0.76707(17) 0.82764(5) 0.0118(2) Uani 1 1 d . . . . .
Cu1 Cu 0.9203(2) 0.5863(2) 0.57669(8) 0.0230(3) Uani 1 1 d . . . . .
Si1 Si 1.0000 0.7165(6) 0.8333 0.0093(8) Uani 1 2 d S T P . .
Ba1 Ba 0.54955(12) 1.0000 0.6667 0.0140(2) 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
Se2 0.0121(5) 0.0130(5) 0.0104(4) -0.0024(4) -0.0009(4) 0.0066(4)
Se1 0.0109(5) 0.0137(5) 0.0128(5) -0.0012(4) -0.0013(4) 0.0076(4)
Cu1 0.0198(7) 0.0216(8) 0.0262(7) 0.0038(6) 0.0061(7) 0.0092(6)
Si1 0.0088(17) 0.0101(13) 0.0084(18) -0.0005(7) -0.0010(14) 0.0044(9)
Ba1 0.0155(4) 0.0121(5) 0.0131(4) 0.0014(4) 0.00070(18) 0.0061(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
Se2 Si1 2.263(3) . ?
Se2 Cu1 2.4285(17) 6_666 ?
Se2 Cu1 2.539(2) . ?
Se2 Ba1 3.3232(13) 1_545 ?
Se2 Ba1 3.3508(14) 1_655 ?
Se1 Si1 2.269(3) . ?
Se1 Cu1 2.4286(18) 3_675 ?
Se1 Cu1 2.5045(17) 6_566 ?
Se1 Ba1 3.2843(16) . ?
Se1 Ba1 3.3108(18) 3_565 ?
Cu1 Se2 2.4285(17) 6_566 ?
Cu1 Se1 2.4286(18) 2_764 ?
Cu1 Se1 2.5045(17) 6_666 ?
Cu1 Ba1 3.6007(17) 1_545 ?
Cu1 Ba1 3.8382(18) 1_655 ?
Si1 Se2 2.263(3) 5_766 ?
Si1 Se1 2.269(3) 5_766 ?
Ba1 Se1 3.2843(16) 6_676 ?
Ba1 Se1 3.3108(18) 2_664 ?
Ba1 Se1 3.3108(18) 5_666 ?
Ba1 Se2 3.3232(14) 6_566 ?
Ba1 Se2 3.3232(14) 1_565 ?
Ba1 Se2 3.3508(14) 6_576 ?
Ba1 Se2 3.3508(14) 1_455 ?
Ba1 Cu1 3.6007(17) 1_565 ?
Ba1 Cu1 3.6007(17) 6_566 ?
Ba1 Cu1 3.8382(18) 1_455 ?
Ba1 Cu1 3.8382(18) 6_576 ?

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
Si1 Se2 Cu1 106.11(7) . 6_666 ?
Si1 Se2 Cu1 121.49(9) . . ?
Cu1 Se2 Cu1 126.02(5) 6_666 . ?
Si1 Se2 Ba1 118.77(4) . 1_545 ?
Cu1 Se2 Ba1 105.04(5) 6_666 1_545 ?
Cu1 Se2 Ba1 74.44(4) . 1_545 ?
Si1 Se2 Ba1 90.65(5) . 1_655 ?
Cu1 Se2 Ba1 75.19(4) 6_666 1_655 ?
Cu1 Se2 Ba1 80.04(4) . 1_655 ?
Ba1 Se2 Ba1 148.21(3) 1_545 1_655 ?
Si1 Se1 Cu1 119.95(8) . 3_675 ?
Si1 Se1 Cu1 109.77(9) . 6_566 ?
Cu1 Se1 Cu1 128.79(5) 3_675 6_566 ?
Si1 Se1 Ba1 123.30(5) . . ?
Cu1 Se1 Ba1 86.67(5) 3_675 . ?
Cu1 Se1 Ba1 75.59(4) 6_566 . ?
Si1 Se1 Ba1 91.57(5) . 3_565 ?
Cu1 Se1 Ba1 82.40(5) 3_675 3_565 ?
Cu1 Se1 Ba1 84.89(5) 6_566 3_565 ?
Ba1 Se1 Ba1 144.01(3) . 3_565 ?
Se2 Cu1 Se1 132.69(6) 6_566 2_764 ?
Se2 Cu1 Se1 108.47(6) 6_566 6_666 ?
Se1 Cu1 Se1 99.17(5) 2_764 6_666 ?
Se2 Cu1 Se2 95.36(5) 6_566 . ?
Se1 Cu1 Se2 117.98(7) 2_764 . ?
Se1 Cu1 Se2 98.53(6) 6_666 . ?
Se2 Cu1 Ba1 64.12(4) 6_566 1_545 ?
Se1 Cu1 Ba1 160.17(5) 2_764 1_545 ?
Se1 Cu1 Ba1 62.06(4) 6_666 1_545 ?
Se2 Cu1 Ba1 62.76(4) . 1_545 ?
Se2 Cu1 Ba1 136.20(5) 6_566 1_655 ?
Se1 Cu1 Ba1 58.76(5) 2_764 1_655 ?
Se1 Cu1 Ba1 110.17(5) 6_666 1_655 ?
Se2 Cu1 Ba1 59.30(4) . 1_655 ?
Ba1 Cu1 Ba1 119.25(4) 1_545 1_655 ?
Se2 Si1 Se2 105.26(16) 5_766 . ?
Se2 Si1 Se1 110.03(3) 5_766 . ?
Se2 Si1 Se1 112.92(4) . . ?
Se2 Si1 Se1 112.92(4) 5_766 5_766 ?
Se2 Si1 Se1 110.03(3) . 5_766 ?
Se1 Si1 Se1 105.84(17) . 5_766 ?
Se1 Ba1 Se1 123.62(5) 6_676 . ?
Se1 Ba1 Se1 69.44(4) 6_676 2_664 ?
Se1 Ba1 Se1 147.85(3) . 2_664 ?
Se1 Ba1 Se1 147.85(3) 6_676 5_666 ?
Se1 Ba1 Se1 69.44(4) . 5_666 ?
Se1 Ba1 Se1 116.75(5) 2_664 5_666 ?
Se1 Ba1 Se2 85.92(3) 6_676 6_566 ?
Se1 Ba1 Se2 70.67(4) . 6_566 ?
Se1 Ba1 Se2 82.26(3) 2_664 6_566 ?
Se1 Ba1 Se2 125.53(2) 5_666 6_566 ?
Se1 Ba1 Se2 70.67(4) 6_676 1_565 ?
Se1 Ba1 Se2 85.92(3) . 1_565 ?
Se1 Ba1 Se2 125.53(2) 2_664 1_565 ?
Se1 Ba1 Se2 82.26(3) 5_666 1_565 ?
Se2 Ba1 Se2 129.61(4) 6_566 1_565 ?
Se1 Ba1 Se2 74.20(2) 6_676 6_576 ?
Se1 Ba1 Se2 141.10(2) . 6_576 ?
Se1 Ba1 Se2 67.74(2) 2_664 6_576 ?
Se1 Ba1 Se2 79.46(3) 5_666 6_576 ?
Se2 Ba1 Se2 148.21(3) 6_566 6_576 ?
Se2 Ba1 Se2 66.799(15) 1_565 6_576 ?
Se1 Ba1 Se2 141.10(2) 6_676 1_455 ?
Se1 Ba1 Se2 74.20(2) . 1_455 ?
Se1 Ba1 Se2 79.46(3) 2_664 1_455 ?
Se1 Ba1 Se2 67.74(2) 5_666 1_455 ?
Se2 Ba1 Se2 66.798(15) 6_566 1_455 ?
Se2 Ba1 Se2 148.21(3) 1_565 1_455 ?
Se2 Ba1 Se2 115.23(4) 6_576 1_455 ?
Se1 Ba1 Cu1 42.35(2) 6_676 1_565 ?
Se1 Ba1 Cu1 127.47(3) . 1_565 ?
Se1 Ba1 Cu1 82.90(4) 2_664 1_565 ?
Se1 Ba1 Cu1 105.59(3) 5_666 1_565 ?
Se2 Ba1 Cu1 128.03(3) 6_566 1_565 ?
Se2 Ba1 Cu1 42.79(3) 1_565 1_565 ?
Se2 Ba1 Cu1 40.70(2) 6_576 1_565 ?
Se2 Ba1 Cu1 155.02(3) 1_455 1_565 ?
Se1 Ba1 Cu1 127.47(3) 6_676 6_566 ?
Se1 Ba1 Cu1 42.35(3) . 6_566 ?
Se1 Ba1 Cu1 105.59(3) 2_664 6_566 ?
Se1 Ba1 Cu1 82.90(3) 5_666 6_566 ?
Se2 Ba1 Cu1 42.79(3) 6_566 6_566 ?
Se2 Ba1 Cu1 128.02(3) 1_565 6_566 ?
Se2 Ba1 Cu1 155.02(3) 6_576 6_566 ?
Se2 Ba1 Cu1 40.69(2) 1_455 6_566 ?
Cu1 Ba1 Cu1 164.09(5) 1_565 6_566 ?
Se1 Ba1 Cu1 105.83(4) 6_676 1_455 ?
Se1 Ba1 Cu1 113.24(3) . 1_455 ?
Se1 Ba1 Cu1 38.84(3) 2_664 1_455 ?
Se1 Ba1 Cu1 92.18(4) 5_666 1_455 ?
Se2 Ba1 Cu1 71.45(2) 6_566 1_455 ?
Se2 Ba1 Cu1 156.84(3) 1_565 1_455 ?
Se2 Ba1 Cu1 90.11(3) 6_576 1_455 ?
Se2 Ba1 Cu1 40.66(3) 1_455 1_455 ?
Cu1 Ba1 Cu1 119.25(4) 1_565 1_455 ?
Cu1 Ba1 Cu1 72.96(3) 6_566 1_455 ?
Se1 Ba1 Cu1 113.24(3) 6_676 6_576 ?
Se1 Ba1 Cu1 105.82(4) . 6_576 ?
Se1 Ba1 Cu1 92.18(4) 2_664 6_576 ?
Se1 Ba1 Cu1 38.84(3) 5_666 6_576 ?
Se2 Ba1 Cu1 156.84(3) 6_566 6_576 ?
Se2 Ba1 Cu1 71.45(2) 1_565 6_576 ?
Se2 Ba1 Cu1 40.66(3) 6_576 6_576 ?
Se2 Ba1 Cu1 90.11(3) 1_455 6_576 ?
Cu1 Ba1 Cu1 72.96(3) 1_565 6_576 ?
Cu1 Ba1 Cu1 119.25(4) 6_566 6_576 ?
Cu1 Ba1 Cu1 90.12(4) 1_455 6_576 ?


_refine_diff_density_max         0.846
_refine_diff_density_min         -0.809
_refine_diff_density_rms         0.207

_shelx_res_file                  
;

    33.res created by SHELXL-2014/7

TITL 33 in P3(2)21               New: P3221
CELL  0.71073    6.4188    6.4188   16.0830    90.000    90.000   120.000
ZERR  3           0.0019    0.0019    0.0100     0.000     0.000     0.000
LATT -1
SYMM             - Y ,          X - Y ,    0.66667 + Z
SYMM         - X + Y ,            - X ,    0.33333 + Z
SYMM               Y ,              X ,            - Z
SYMM             - X ,        - X + Y ,    0.66667 - Z
SYMM           X - Y ,            - Y ,    0.33333 - Z
SFAC Ba Cu Se Si
UNIT 3 6 12 3
L.S. 20
ACTA
BOND $H
FMAP 2
PLAN 5
TWIN
CONF
WGHT    0.012900
EXTI    0.001645
BASF   0.07311
FVAR       0.10818
SE2   3    1.028313    0.516756    0.721955    11.00000    0.01214    0.01301 =
         0.01043   -0.00236   -0.00090    0.00665
Se1   3    0.674791    0.767069    0.827643    11.00000    0.01089    0.01366 =
         0.01281   -0.00118   -0.00133    0.00757
Cu1   2    0.920332    0.586325    0.576695    11.00000    0.01978    0.02164 =
         0.02616    0.00383    0.00609    0.00918
Si1   4    1.000000    0.716547    0.833333    10.50000    0.00881    0.01015 =
         0.00840   -0.00048   -0.00096    0.00441
BA1   1    0.549545    1.000000    0.666667    10.50000    0.01548    0.01211 =
         0.01314    0.00140    0.00070    0.00605
HKLF 4 1 -1.0000  0.0000  0.0000  0.0000 -1.0000  0.0000  0.0000  0.0000  1.0000

REM  33 in P3(2)21               New: P3221
REM R1 =  0.0264 for     793 Fo > 4sig(Fo)  and  0.0310 for all     869 data
REM     40 parameters refined using      0 restraints

END

WGHT      0.0129      0.0000

REM Highest difference peak  0.846,  deepest hole -0.809,  1-sigma level  0.207
Q1    1   0.9280  0.6136  0.7481  11.00000  0.05    0.85
Q2    1   0.7830  0.7405  0.4800  11.00000  0.05    0.78
Q3    1   0.7179  0.5127  0.5898  11.00000  0.05    0.77
Q4    1   0.4693  0.8762  0.6989  11.00000  0.05    0.73
Q5    1   0.5757  0.7082  0.8557  11.00000  0.05    0.71
;
_shelx_res_checksum              91539
####################################################################### 
# 
# 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_22
_database_code_depnum_ccdc_archive 'CCDC 1540057'
_audit_update_record             
;
2017-03-24 deposited with the CCDC.
2017-06-01 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Ba Cu2 Se4 Sn'
_chemical_formula_weight         698.95

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ba Ba -0.3244 2.2819 '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'
Se Se -0.0929 2.2259 '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      orthorhombic
_space_group_IT_number           40
_space_group_name_H-M_alt        'A m a 2'
_space_group_name_Hall           'A 2 -2a'

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

_cell_length_a                   11.101(10)
_cell_length_b                   11.189(10)
_cell_length_c                   6.728(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     835.7(13)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    1268
_cell_measurement_theta_min      3.53
_cell_measurement_theta_max      27.66

_exptl_crystal_description       block
_exptl_crystal_colour            black
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    5.555
_exptl_crystal_F_000             1200
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.206
_exptl_crystal_size_mid          0.145
_exptl_crystal_size_min          0.093
_exptl_absorpt_coefficient_mu    29.945
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.2704
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'sealed tube'
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            2497
_diffrn_reflns_av_unetI/netI     0.0466
_diffrn_reflns_av_R_equivalents  0.0343
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_theta_min         3.534
_diffrn_reflns_theta_max         27.687
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             992
_reflns_number_gt                952
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.843
_reflns_Friedel_fraction_max     0.998
_reflns_Friedel_fraction_full    0.997

_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 SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_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)+(0.0146P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   ?
_refine_ls_hydrogen_treatment    ?
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.06(3)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         992
_refine_ls_number_parameters     43
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0265
_refine_ls_R_factor_gt           0.0251
_refine_ls_wR_factor_ref         0.0532
_refine_ls_wR_factor_gt          0.0527
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_restrained_S_all      1.017
_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
Sn1 Sn 0.2500 0.14760(9) 0.58646(15) 0.0119(2) Uani 1 2 d S T P . .
Se1 Se 0.2500 0.10955(13) 0.2189(2) 0.0133(3) Uani 1 2 d S T P . .
Se2 Se 0.2500 -0.05877(12) 0.7456(2) 0.0134(3) Uani 1 2 d S T P . .
Se3 Se 0.07169(8) 0.25248(9) 0.7415(2) 0.0132(2) Uani 1 1 d . . . . .
Cu1 Cu 0.12851(12) 0.28525(13) 0.0862(2) 0.0229(3) Uani 1 1 d . . . . .
Ba1 Ba 0.0000 0.5000 0.49921(16) 0.0152(2) 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 0.0104(5) 0.0142(5) 0.0109(4) -0.0005(4) 0.000 0.000
Se1 0.0133(7) 0.0151(7) 0.0115(7) -0.0002(6) 0.000 0.000
Se2 0.0138(7) 0.0118(7) 0.0147(7) -0.0003(6) 0.000 0.000
Se3 0.0112(5) 0.0161(5) 0.0124(5) 0.0005(4) -0.0004(5) 0.0024(4)
Cu1 0.0206(7) 0.0258(7) 0.0225(7) -0.0037(7) -0.0040(7) -0.0025(6)
Ba1 0.0136(4) 0.0132(4) 0.0186(4) 0.000 0.000 -0.0012(3)

_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 Se1 2.509(3) . ?
Sn1 Se3 2.527(2) . ?
Sn1 Se3 2.527(2) 3 ?
Sn1 Se2 2.545(3) . ?
Se1 Cu1 2.546(2) 3 ?
Se1 Cu1 2.546(2) . ?
Se1 Ba1 3.375(2) 5_544 ?
Se1 Ba1 3.375(2) 7_544 ?
Se2 Cu1 2.453(2) 5_545 ?
Se2 Cu1 2.453(2) 7_545 ?
Se2 Ba1 3.323(2) 7_545 ?
Se2 Ba1 3.323(2) 5_545 ?
Se3 Cu1 2.431(3) 1_556 ?
Se3 Cu1 2.492(3) 6 ?
Se3 Ba1 3.311(3) . ?
Se3 Ba1 3.409(3) 5_545 ?
Cu1 Se3 2.431(3) 1_554 ?
Cu1 Se2 2.453(2) 5_554 ?
Cu1 Se3 2.492(3) 6_554 ?
Cu1 Cu1 2.697(4) 3 ?
Cu1 Ba1 3.545(3) 5_544 ?
Cu1 Ba1 3.941(3) . ?
Ba1 Se3 3.311(3) 2_565 ?
Ba1 Se2 3.323(2) 6_554 ?
Ba1 Se2 3.323(2) 5_554 ?
Ba1 Se1 3.375(2) 5 ?
Ba1 Se1 3.375(2) 6 ?
Ba1 Se3 3.409(3) 6_554 ?
Ba1 Se3 3.409(3) 5_554 ?
Ba1 Cu1 3.545(3) 5 ?
Ba1 Cu1 3.545(3) 6 ?
Ba1 Cu1 3.941(3) 2_565 ?

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
Se1 Sn1 Se3 119.06(5) . . ?
Se1 Sn1 Se3 119.06(5) . 3 ?
Se3 Sn1 Se3 103.15(9) . 3 ?
Se1 Sn1 Se2 105.11(7) . . ?
Se3 Sn1 Se2 104.34(6) . . ?
Se3 Sn1 Se2 104.34(6) 3 . ?
Sn1 Se1 Cu1 102.40(7) . 3 ?
Sn1 Se1 Cu1 102.40(7) . . ?
Cu1 Se1 Cu1 63.97(9) 3 . ?
Sn1 Se1 Ba1 119.55(4) . 5_544 ?
Cu1 Se1 Ba1 124.22(7) 3 5_544 ?
Cu1 Se1 Ba1 72.01(6) . 5_544 ?
Sn1 Se1 Ba1 119.55(4) . 7_544 ?
Cu1 Se1 Ba1 72.01(6) 3 7_544 ?
Cu1 Se1 Ba1 124.22(7) . 7_544 ?
Ba1 Se1 Ba1 110.64(8) 5_544 7_544 ?
Cu1 Se2 Cu1 66.71(10) 5_545 7_545 ?
Cu1 Se2 Sn1 117.48(8) 5_545 . ?
Cu1 Se2 Sn1 117.48(8) 7_545 . ?
Cu1 Se2 Ba1 145.54(6) 5_545 7_545 ?
Cu1 Se2 Ba1 84.62(6) 7_545 7_545 ?
Sn1 Se2 Ba1 92.09(4) . 7_545 ?
Cu1 Se2 Ba1 84.62(6) 5_545 5_545 ?
Cu1 Se2 Ba1 145.54(6) 7_545 5_545 ?
Sn1 Se2 Ba1 92.09(4) . 5_545 ?
Ba1 Se2 Ba1 113.24(8) 7_545 5_545 ?
Cu1 Se3 Cu1 131.08(7) 1_556 6 ?
Cu1 Se3 Sn1 105.10(7) 1_556 . ?
Cu1 Se3 Sn1 116.54(9) 6 . ?
Cu1 Se3 Ba1 113.95(7) 1_556 . ?
Cu1 Se3 Ba1 73.79(5) 6 . ?
Sn1 Se3 Ba1 111.93(6) . . ?
Cu1 Se3 Ba1 72.57(6) 1_556 5_545 ?
Cu1 Se3 Ba1 82.23(5) 6 5_545 ?
Sn1 Se3 Ba1 90.46(6) . 5_545 ?
Ba1 Se3 Ba1 152.57(4) . 5_545 ?
Se3 Cu1 Se2 131.86(8) 1_554 5_554 ?
Se3 Cu1 Se3 98.23(7) 1_554 6_554 ?
Se2 Cu1 Se3 115.30(8) 5_554 6_554 ?
Se3 Cu1 Se1 110.83(8) 1_554 . ?
Se2 Cu1 Se1 96.01(9) 5_554 . ?
Se3 Cu1 Se1 101.21(8) 6_554 . ?
Se3 Cu1 Cu1 105.04(5) 1_554 3 ?
Se2 Cu1 Cu1 56.64(5) 5_554 3 ?
Se3 Cu1 Cu1 153.10(6) 6_554 3 ?
Se1 Cu1 Cu1 58.01(5) . 3 ?
Se3 Cu1 Ba1 66.57(4) 1_554 5_544 ?
Se2 Cu1 Ba1 159.10(7) 5_554 5_544 ?
Se3 Cu1 Ba1 63.75(4) 6_554 5_544 ?
Se1 Cu1 Ba1 64.90(7) . 5_544 ?
Cu1 Cu1 Ba1 113.73(4) 3 5_544 ?
Se3 Cu1 Ba1 132.12(7) 1_554 . ?
Se2 Cu1 Ba1 57.09(6) 5_554 . ?
Se3 Cu1 Ba1 58.98(5) 6_554 . ?
Se1 Cu1 Ba1 114.53(8) . . ?
Cu1 Cu1 Ba1 111.22(3) 3 . ?
Ba1 Cu1 Ba1 121.31(6) 5_544 . ?
Se3 Ba1 Se3 121.00(8) 2_565 . ?
Se3 Ba1 Se2 83.49(5) 2_565 6_554 ?
Se3 Ba1 Se2 128.24(3) . 6_554 ?
Se3 Ba1 Se2 128.24(3) 2_565 5_554 ?
Se3 Ba1 Se2 83.49(5) . 5_554 ?
Se2 Ba1 Se2 118.23(8) 6_554 5_554 ?
Se3 Ba1 Se1 71.23(5) 2_565 5 ?
Se3 Ba1 Se1 83.71(6) . 5 ?
Se2 Ba1 Se1 147.11(5) 6_554 5 ?
Se2 Ba1 Se1 67.04(7) 5_554 5 ?
Se3 Ba1 Se1 83.71(6) 2_565 6 ?
Se3 Ba1 Se1 71.23(5) . 6 ?
Se2 Ba1 Se1 67.04(7) 6_554 6 ?
Se2 Ba1 Se1 147.11(5) 5_554 6 ?
Se1 Ba1 Se1 128.05(8) 5 6 ?
Se3 Ba1 Se3 152.57(4) 2_565 6_554 ?
Se3 Ba1 Se3 67.25(6) . 6_554 ?
Se2 Ba1 Se3 73.02(5) 6_554 6_554 ?
Se2 Ba1 Se3 76.70(5) 5_554 6_554 ?
Se1 Ba1 Se3 135.70(3) 5 6_554 ?
Se1 Ba1 Se3 74.32(5) 6 6_554 ?
Se3 Ba1 Se3 67.25(6) 2_565 5_554 ?
Se3 Ba1 Se3 152.57(4) . 5_554 ?
Se2 Ba1 Se3 76.70(5) 6_554 5_554 ?
Se2 Ba1 Se3 73.02(5) 5_554 5_554 ?
Se1 Ba1 Se3 74.32(5) 5 5_554 ?
Se1 Ba1 Se3 135.70(3) 6 5_554 ?
Se3 Ba1 Se3 118.86(8) 6_554 5_554 ?
Se3 Ba1 Cu1 42.46(5) 2_565 5 ?
Se3 Ba1 Cu1 125.11(6) . 5 ?
Se2 Ba1 Cu1 104.04(5) 6_554 5 ?
Se2 Ba1 Cu1 85.80(5) 5_554 5 ?
Se1 Ba1 Cu1 43.09(3) 5 5 ?
Se1 Ba1 Cu1 125.86(5) 6 5 ?
Se3 Ba1 Cu1 157.54(5) 6_554 5 ?
Se3 Ba1 Cu1 40.87(5) 5_554 5 ?
Se3 Ba1 Cu1 125.11(6) 2_565 6 ?
Se3 Ba1 Cu1 42.46(5) . 6 ?
Se2 Ba1 Cu1 85.80(5) 6_554 6 ?
Se2 Ba1 Cu1 104.04(5) 5_554 6 ?
Se1 Ba1 Cu1 125.86(5) 5 6 ?
Se1 Ba1 Cu1 43.09(3) 6 6 ?
Se3 Ba1 Cu1 40.87(5) 6_554 6 ?
Se3 Ba1 Cu1 157.54(5) 5_554 6 ?
Cu1 Ba1 Cu1 161.00(7) 5 6 ?
Se3 Ba1 Cu1 75.53(7) 2_565 2_565 ?
Se3 Ba1 Cu1 160.78(4) . 2_565 ?
Se2 Ba1 Cu1 38.29(3) 6_554 2_565 ?
Se2 Ba1 Cu1 93.49(6) 5_554 2_565 ?
Se1 Ba1 Cu1 112.65(5) 5 2_565 ?
Se1 Ba1 Cu1 103.45(6) 6 2_565 ?
Se3 Ba1 Cu1 93.56(7) 6_554 2_565 ?
Se3 Ba1 Cu1 38.79(4) 5_554 2_565 ?
Cu1 Ba1 Cu1 73.33(6) 5 2_565 ?
Cu1 Ba1 Cu1 121.31(6) 6 2_565 ?
Se3 Ba1 Cu1 160.78(4) 2_565 . ?
Se3 Ba1 Cu1 75.53(7) . . ?
Se2 Ba1 Cu1 93.49(6) 6_554 . ?
Se2 Ba1 Cu1 38.29(3) 5_554 . ?
Se1 Ba1 Cu1 103.45(6) 5 . ?
Se1 Ba1 Cu1 112.65(5) 6 . ?
Se3 Ba1 Cu1 38.79(4) 6_554 . ?
Se3 Ba1 Cu1 93.56(7) 5_554 . ?
Cu1 Ba1 Cu1 121.31(6) 5 . ?
Cu1 Ba1 Cu1 73.33(6) 6 . ?
Cu1 Ba1 Cu1 90.32(8) 2_565 . ?


_refine_diff_density_max         1.041
_refine_diff_density_min         -1.691
_refine_diff_density_rms         0.235

_shelx_res_file                  
;

    22.res created by SHELXL-2014/7

TITL 22 in Ama2                  New: Ama2
CELL  0.71073   11.1010   11.1890    6.7280    90.000    90.000    90.000
ZERR  4           0.0100    0.0100    0.0060     0.000     0.000     0.000
LATT -5
SYMM             - X ,            - Y ,              Z
SYMM     0.50000 - X ,              Y ,              Z
SYMM     0.50000 + X ,            - Y ,              Z
SFAC Ba Cu Se Sn
UNIT 4 8 16 4
L.S. 20
ACTA
BOND $H
FMAP 2
PLAN 5
CONF
TWIN
WGHT    0.014600
BASF   0.05872
FVAR       0.06148
SN1   4    0.250000    0.147597    0.586461    10.50000    0.01042    0.01423 =
         0.01093   -0.00046    0.00000    0.00000
SE1   3    0.250000    0.109546    0.218901    10.50000    0.01333    0.01514 =
         0.01152   -0.00021    0.00000    0.00000
SE2   3    0.250000   -0.058771    0.745633    10.50000    0.01381    0.01175 =
         0.01472   -0.00029    0.00000    0.00000
SE3   3    0.071686    0.252483    0.741520    11.00000    0.01125    0.01607 =
         0.01243    0.00055   -0.00039    0.00236
CU1   2    0.128513    0.285247    0.086156    11.00000    0.02059    0.02576 =
         0.02249   -0.00373   -0.00402   -0.00250
BA1   1    0.000000    0.500000    0.499208    10.50000    0.01362    0.01324 =
         0.01865    0.00000    0.00000   -0.00115
HKLF 4

REM  22 in Ama2                  New: Ama2
REM R1 =  0.0251 for     952 Fo > 4sig(Fo)  and  0.0265 for all     992 data
REM     43 parameters refined using      1 restraints

END

WGHT      0.0146      0.0000

REM Highest difference peak  1.041,  deepest hole -1.691,  1-sigma level  0.235
Q1    1   0.2500  0.0924  0.4964  10.50000  0.05    1.04
Q2    1   0.2500  0.1913  0.5141  10.50000  0.05    0.90
Q3    1   0.2500  0.0937  0.6669  10.50000  0.05    0.90
Q4    1   0.0135  0.5641  0.4077  11.00000  0.05    0.89
Q5    1   0.2500  0.2122  0.6833  10.50000  0.05    0.86
;
_shelx_res_checksum              7050
####################################################################### 
# 
# 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_1
_database_code_depnum_ccdc_archive 'CCDC 1540056'
_audit_update_record             
;
2017-03-24 deposited with the CCDC.
2017-06-01 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Ba Cu2 S4 Sn'
_chemical_formula_weight         511.35

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ba Ba -0.3244 2.2819 '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'
S S 0.1246 0.1234 '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      trigonal
_space_group_IT_number           154
_space_group_name_H-M_alt        'P 32 2 1'
_space_group_name_Hall           'P 32 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-y, z+2/3'
'-x+y, -x, z+1/3'
'y, x, -z'
'-x, -x+y, -z+2/3'
'x-y, -y, -z+1/3'

_cell_length_a                   6.353(3)
_cell_length_b                   6.353(3)
_cell_length_c                   15.788(14)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     551.8(7)
_cell_formula_units_Z            3
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    1042
_cell_measurement_theta_min      3.70
_cell_measurement_theta_max      27.05

_exptl_crystal_description       block
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    4.616
_exptl_crystal_F_000             684
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_absorpt_coefficient_mu    15.357
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.4592
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'sealed tube'
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            2808
_diffrn_reflns_av_unetI/netI     0.0471
_diffrn_reflns_av_R_equivalents  0.0470
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         3.703
_diffrn_reflns_theta_max         27.511
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measured_fraction_theta_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_point_group_measured_fraction_full 0.994
_reflns_number_total             842
_reflns_number_gt                740
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.598
_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 SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_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)+(0.0224P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   ?
_refine_ls_hydrogen_treatment    ?
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_extinction_coef       0.0076(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -0.04(6)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         842
_refine_ls_number_parameters     40
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0316
_refine_ls_R_factor_gt           0.0258
_refine_ls_wR_factor_ref         0.0595
_refine_ls_wR_factor_gt          0.0569
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_restrained_S_all      1.070
_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
Sn1 Sn 0.70953(16) 1.0000 0.1667 0.0110(2) Uani 1 2 d S T P . .
Cu1 Cu 0.0728(2) 0.6536(2) 0.08934(8) 0.0227(4) Uani 1 1 d . . . . .
S1 S 0.4575(5) 0.9522(5) 0.04777(15) 0.0131(5) Uani 1 1 d . . . . .
S2 S 0.7650(5) 0.6548(5) 0.16697(16) 0.0131(6) Uani 1 1 d . . . . .
Ba1 Ba 0.43236(14) 0.43236(14) 0.0000 0.0137(2) 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 0.0111(4) 0.0112(5) 0.0108(4) -0.0005(4) -0.00024(19) 0.0056(2)
Cu1 0.0190(7) 0.0246(8) 0.0239(7) 0.0027(6) 0.0052(6) 0.0105(6)
S1 0.0134(12) 0.0131(13) 0.0112(11) 0.0010(11) -0.0013(10) 0.0055(11)
S2 0.0153(13) 0.0129(13) 0.0139(12) 0.0007(10) 0.0015(11) 0.0091(10)
Ba1 0.0152(3) 0.0152(3) 0.0129(4) -0.00076(19) 0.00076(19) 0.0093(4)

_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 2.386(3) . ?
Sn1 S1 2.386(3) 6_675 ?
Sn1 S2 2.389(3) . ?
Sn1 S2 2.389(3) 6_675 ?
Cu1 S2 2.311(3) 1_455 ?
Cu1 S1 2.316(3) . ?
Cu1 S2 2.416(3) 6_565 ?
Cu1 S1 2.423(3) 4_455 ?
Cu1 Ba1 3.847(2) 1_455 ?
Cu1 Ba1 3.886(4) 3_565 ?
S1 Cu1 2.423(3) 4_565 ?
S1 Ba1 3.223(3) 1_565 ?
S1 Ba1 3.313(3) . ?
S2 Cu1 2.311(3) 1_655 ?
S2 Cu1 2.416(3) 6_665 ?
S2 Ba1 3.203(3) 3_665 ?
S2 Ba1 3.229(3) . ?
Ba1 S2 3.203(3) 2_654 ?
Ba1 S2 3.203(3) 6_565 ?
Ba1 S1 3.223(3) 4_455 ?
Ba1 S1 3.223(3) 1_545 ?
Ba1 S2 3.229(3) 4 ?
Ba1 S1 3.313(3) 4 ?
Ba1 Cu1 3.520(2) 4 ?
Ba1 Cu1 3.847(2) 1_655 ?
Ba1 Cu1 3.847(2) 4_565 ?
Ba1 Cu1 3.886(4) 2_664 ?

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 105.19(14) . 6_675 ?
S1 Sn1 S2 106.41(10) . . ?
S1 Sn1 S2 117.02(9) 6_675 . ?
S1 Sn1 S2 117.03(9) . 6_675 ?
S1 Sn1 S2 106.41(10) 6_675 6_675 ?
S2 Sn1 S2 105.32(14) . 6_675 ?
S2 Cu1 S1 134.06(12) 1_455 . ?
S2 Cu1 S2 99.33(8) 1_455 6_565 ?
S1 Cu1 S2 108.39(10) . 6_565 ?
S2 Cu1 S1 115.15(12) 1_455 4_455 ?
S1 Cu1 S1 95.79(8) . 4_455 ?
S2 Cu1 S1 99.60(11) 6_565 4_455 ?
S2 Cu1 Ba1 56.88(8) 1_455 1_455 ?
S1 Cu1 Ba1 133.26(8) . 1_455 ?
S2 Cu1 Ba1 113.77(8) 6_565 1_455 ?
S1 Cu1 Ba1 58.66(8) 4_455 1_455 ?
S2 Cu1 Ba1 55.47(7) 1_455 3_565 ?
S1 Cu1 Ba1 113.50(8) . 3_565 ?
S2 Cu1 Ba1 55.96(7) 6_565 3_565 ?
S1 Cu1 Ba1 145.96(8) 4_455 3_565 ?
Ba1 Cu1 Ba1 106.39(4) 1_455 3_565 ?
Cu1 S1 Sn1 104.32(11) . . ?
Cu1 S1 Cu1 132.63(12) . 4_565 ?
Sn1 S1 Cu1 117.15(12) . 4_565 ?
Cu1 S1 Ba1 108.08(10) . 1_565 ?
Sn1 S1 Ba1 114.29(10) . 1_565 ?
Cu1 S1 Ba1 75.68(8) 4_565 1_565 ?
Cu1 S1 Ba1 75.09(9) . . ?
Sn1 S1 Ba1 90.03(9) . . ?
Cu1 S1 Ba1 82.69(8) 4_565 . ?
Ba1 S1 Ba1 152.86(8) 1_565 . ?
Cu1 S2 Sn1 121.02(12) 1_655 . ?
Cu1 S2 Cu1 133.79(12) 1_655 6_665 ?
Sn1 S2 Cu1 104.70(10) . 6_665 ?
Cu1 S2 Ba1 88.06(10) 1_655 3_665 ?
Sn1 S2 Ba1 117.11(9) . 3_665 ?
Cu1 S2 Ba1 76.15(8) 6_665 3_665 ?
Cu1 S2 Ba1 86.29(9) 1_655 . ?
Sn1 S2 Ba1 92.03(8) . . ?
Cu1 S2 Ba1 85.72(10) 6_665 . ?
Ba1 S2 Ba1 148.59(9) 3_665 . ?
S2 Ba1 S2 132.11(10) 2_654 6_565 ?
S2 Ba1 S1 88.53(7) 2_654 4_455 ?
S2 Ba1 S1 70.23(8) 6_565 4_455 ?
S2 Ba1 S1 70.23(8) 2_654 1_545 ?
S2 Ba1 S1 88.53(7) 6_565 1_545 ?
S1 Ba1 S1 126.71(9) 4_455 1_545 ?
S2 Ba1 S2 144.61(6) 2_654 . ?
S2 Ba1 S2 68.16(6) 6_565 . ?
S1 Ba1 S2 126.73(6) 4_455 . ?
S1 Ba1 S2 83.79(6) 1_545 . ?
S2 Ba1 S2 68.16(6) 2_654 4 ?
S2 Ba1 S2 144.61(6) 6_565 4 ?
S1 Ba1 S2 83.79(6) 4_455 4 ?
S1 Ba1 S2 126.73(6) 1_545 4 ?
S2 Ba1 S2 113.81(11) . 4 ?
S2 Ba1 S1 136.92(6) 2_654 . ?
S2 Ba1 S1 72.17(6) 6_565 . ?
S1 Ba1 S1 65.09(3) 4_455 . ?
S1 Ba1 S1 152.86(8) 1_545 . ?
S2 Ba1 S1 71.53(6) . . ?
S2 Ba1 S1 75.30(7) 4 . ?
S2 Ba1 S1 72.17(6) 2_654 4 ?
S2 Ba1 S1 136.92(6) 6_565 4 ?
S1 Ba1 S1 152.86(8) 4_455 4 ?
S1 Ba1 S1 65.09(3) 1_545 4 ?
S2 Ba1 S1 75.30(7) . 4 ?
S2 Ba1 S1 71.53(6) 4 4 ?
S1 Ba1 S1 116.99(9) . 4 ?
S2 Ba1 Cu1 41.79(5) 2_654 4 ?
S2 Ba1 Cu1 130.11(6) 6_565 4 ?
S1 Ba1 Cu1 129.29(6) 4_455 4 ?
S1 Ba1 Cu1 41.82(6) 1_545 4 ?
S2 Ba1 Cu1 102.99(6) . 4 ?
S2 Ba1 Cu1 84.92(6) 4 4 ?
S1 Ba1 Cu1 154.45(6) . 4 ?
S1 Ba1 Cu1 39.49(5) 4 4 ?
S2 Ba1 Cu1 110.32(6) 2_654 1_655 ?
S2 Ba1 Cu1 103.31(7) 6_565 1_655 ?
S1 Ba1 Cu1 157.23(5) 4_455 1_655 ?
S1 Ba1 Cu1 73.51(5) 1_545 1_655 ?
S2 Ba1 Cu1 36.83(5) . 1_655 ?
S2 Ba1 Cu1 91.34(6) 4 1_655 ?
S1 Ba1 Cu1 92.14(5) . 1_655 ?
S1 Ba1 Cu1 38.65(6) 4 1_655 ?
Cu1 Ba1 Cu1 72.03(3) 4 1_655 ?
S2 Ba1 Cu1 103.31(7) 2_654 4_565 ?
S2 Ba1 Cu1 110.32(6) 6_565 4_565 ?
S1 Ba1 Cu1 73.51(5) 4_455 4_565 ?
S1 Ba1 Cu1 157.23(5) 1_545 4_565 ?
S2 Ba1 Cu1 91.34(6) . 4_565 ?
S2 Ba1 Cu1 36.83(5) 4 4_565 ?
S1 Ba1 Cu1 38.65(6) . 4_565 ?
S1 Ba1 Cu1 92.14(5) 4 4_565 ?
Cu1 Ba1 Cu1 119.09(5) 4 4_565 ?
Cu1 Ba1 Cu1 89.29(5) 1_655 4_565 ?
S2 Ba1 Cu1 36.47(6) 2_654 2_664 ?
S2 Ba1 Cu1 137.60(6) 6_565 2_664 ?
S1 Ba1 Cu1 69.07(5) 4_455 2_664 ?
S1 Ba1 Cu1 106.54(5) 1_545 2_664 ?
S2 Ba1 Cu1 150.81(6) . 2_664 ?
S2 Ba1 Cu1 38.32(6) 4 2_664 ?
S1 Ba1 Cu1 100.56(5) . 2_664 ?
S1 Ba1 Cu1 84.34(5) 4 2_664 ?
Cu1 Ba1 Cu1 71.72(4) 4 2_664 ?
Cu1 Ba1 Cu1 118.87(3) 1_655 2_664 ?
Cu1 Ba1 Cu1 68.43(3) 4_565 2_664 ?


_refine_diff_density_max         0.864
_refine_diff_density_min         -0.880
_refine_diff_density_rms         0.212

_shelx_res_file                  
;

    1.res created by SHELXL-2014/7

TITL 1 in P3(2)                  New: P3221
CELL  0.71073    6.3530    6.3530   15.7880    90.000    90.000   120.000
ZERR        3    0.0030    0.0030    0.0140     0.000     0.000     0.000
LATT -1
SYMM             - Y ,          X - Y ,    0.66667 + Z
SYMM         - X + Y ,            - X ,    0.33333 + Z
SYMM               Y ,              X ,            - Z
SYMM             - X ,        - X + Y ,    0.66667 - Z
SYMM           X - Y ,            - Y ,    0.33333 - Z
SFAC Ba Cu S  Sn
UNIT 3 6 12 3
L.S. 20
ACTA
BOND $H
FMAP 2
PLAN 5
TWIN
CONF
FREE Cu1  Ba1
WGHT    0.022400
EXTI    0.007634
BASF  -0.04001
FVAR       0.11448
SN1   4    0.709530    1.000000    0.166667    10.50000    0.01115    0.01121 =
         0.01076   -0.00048   -0.00024    0.00560
CU1   2    0.072824    0.653590    0.089335    11.00000    0.01904    0.02465 =
         0.02395    0.00270    0.00515    0.01047
S1    3    0.457487    0.952245    0.047766    11.00000    0.01338    0.01311 =
         0.01124    0.00097   -0.00133    0.00549
S2    3    0.764994    0.654752    0.166975    11.00000    0.01526    0.01290 =
         0.01393    0.00067    0.00147    0.00915
BA1   1    0.432363    0.432363    0.000000    10.50000    0.01524    0.01524 =
         0.01290   -0.00076    0.00076    0.00931
HKLF 4 1 -1.0000  0.0000  0.0000  0.0000 -1.0000  0.0000  0.0000  0.0000  1.0000

REM  1 in P3(2)                  New: P3221
REM R1 =  0.0258 for     740 Fo > 4sig(Fo)  and  0.0316 for all     842 data
REM     40 parameters refined using      0 restraints

END

WGHT      0.0226      0.0000

REM Highest difference peak  0.864,  deepest hole -0.880,  1-sigma level  0.212
Q1    1   0.3397  0.2368  0.0029  11.00000  0.05    0.86
Q2    1   0.3003  0.2405  0.0999  11.00000  0.05    0.78
Q3    1   0.5786  1.0040  0.0633  11.00000  0.05    0.71
Q4    1   0.3260  0.5208  0.0023  11.00000  0.05    0.71
Q5    1   0.6215  1.0968  0.1657  11.00000  0.05    0.67
;
_shelx_res_checksum              23239
####################################################################### 
# 
# 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_22
_database_code_depnum_ccdc_archive 'CCDC 1540054'
_audit_update_record             
;
2017-03-24 deposited with the CCDC.
2017-06-01 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Ba Cu2 Ge S4'
_chemical_formula_weight         465.25

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ba Ba -0.3244 2.2819 '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'
Ge Ge 0.1547 1.8001 '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      trigonal
_space_group_IT_number           152
_space_group_name_H-M_alt        'P 31 2 1'
_space_group_name_Hall           'P 31 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-y, z+1/3'
'-x+y, -x, z+2/3'
'y, x, -z'
'-x, -x+y, -z+1/3'
'x-y, -y, -z+2/3'

_cell_length_a                   6.2092(8)
_cell_length_b                   6.2092(8)
_cell_length_c                   15.520(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     518.20(19)
_cell_formula_units_Z            3
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    1368
_cell_measurement_theta_min      3.79
_cell_measurement_theta_max      27.34

_exptl_crystal_description       block
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    4.473
_exptl_crystal_F_000             630
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.312
_exptl_crystal_size_mid          0.225
_exptl_crystal_size_min          0.185
_exptl_absorpt_coefficient_mu    17.089
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5528
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'sealed tube'
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            3149
_diffrn_reflns_av_unetI/netI     0.0306
_diffrn_reflns_av_R_equivalents  0.0333
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       4
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         3.789
_diffrn_reflns_theta_max         27.411
_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 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             784
_reflns_number_gt                729
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.587
_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 SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_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)+(0.0124P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_extinction_coef       0.0008(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.05(3)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         784
_refine_ls_number_parameters     40
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0214
_refine_ls_R_factor_gt           0.0185
_refine_ls_wR_factor_ref         0.0373
_refine_ls_wR_factor_gt          0.0366
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_restrained_S_all      1.031
_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
Ge1 Ge 0.71419(16) 0.71419(16) 0.0000 0.00870(19) Uani 1 2 d S T P . .
Cu1 Cu 0.41042(16) 0.07492(15) 0.07655(5) 0.0208(2) Uani 1 1 d . . . . .
S1 S 0.5178(3) 0.4805(3) 0.11312(9) 0.0110(3) Uani 1 1 d . . . . .
S2 S 0.7628(3) 1.0930(3) 0.00349(9) 0.0109(3) Uani 1 1 d . . . . .
Ba1 Ba 0.0000 0.43609(8) 0.1667 0.01174(15) 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
Ge1 0.0080(3) 0.0080(3) 0.0102(4) -0.00010(16) 0.00010(16) 0.0040(3)
Cu1 0.0188(5) 0.0166(4) 0.0252(4) -0.0052(4) -0.0026(4) 0.0076(4)
S1 0.0117(8) 0.0108(7) 0.0112(6) 0.0010(5) 0.0018(6) 0.0061(7)
S2 0.0104(8) 0.0078(7) 0.0143(7) -0.0004(6) 0.0009(6) 0.0044(6)
Ba1 0.0091(3) 0.0122(2) 0.0130(2) -0.00077(11) -0.0015(2) 0.00455(14)

_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
Ge1 S1 2.2147(16) 4 ?
Ge1 S1 2.2147(16) . ?
Ge1 S2 2.2173(16) 4 ?
Ge1 S2 2.2173(16) . ?
Cu1 S2 2.3161(17) 4_445 ?
Cu1 S1 2.3300(17) . ?
Cu1 S2 2.4165(17) 1_545 ?
Cu1 S1 2.4426(17) 5_655 ?
Cu1 Ba1 3.4896(9) 1_655 ?
Cu1 Ba1 3.7518(10) 1_545 ?
Cu1 Ba1 3.8163(13) 3_554 ?
S1 Cu1 2.4427(17) 5_665 ?
S1 Ba1 3.1967(17) . ?
S1 Ba1 3.2489(17) 1_655 ?
S2 Cu1 2.3162(17) 4_665 ?
S2 Cu1 2.4164(17) 1_565 ?
S2 Ba1 3.1597(16) 1_665 ?
S2 Ba1 3.2016(16) 3_564 ?
Ba1 S2 3.1597(16) 5_655 ?
Ba1 S2 3.1598(16) 1_445 ?
Ba1 S1 3.1967(17) 5 ?
Ba1 S2 3.2016(16) 4_455 ?
Ba1 S2 3.2016(16) 2_665 ?
Ba1 S1 3.2489(17) 5_665 ?
Ba1 S1 3.2489(17) 1_455 ?
Ba1 Cu1 3.4895(9) 1_455 ?
Ba1 Cu1 3.4896(9) 5_665 ?
Ba1 Cu1 3.7518(10) 1_565 ?
Ba1 Cu1 3.7518(10) 5_565 ?

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 Ge1 S1 105.85(9) 4 . ?
S1 Ge1 S2 114.46(5) 4 4 ?
S1 Ge1 S2 107.91(6) . 4 ?
S1 Ge1 S2 107.91(6) 4 . ?
S1 Ge1 S2 114.46(5) . . ?
S2 Ge1 S2 106.49(9) 4 . ?
S2 Cu1 S1 134.35(6) 4_445 . ?
S2 Cu1 S2 99.15(4) 4_445 1_545 ?
S1 Cu1 S2 107.51(6) . 1_545 ?
S2 Cu1 S1 116.81(6) 4_445 5_655 ?
S1 Cu1 S1 95.26(4) . 5_655 ?
S2 Cu1 S1 98.72(6) 1_545 5_655 ?
S2 Cu1 Ba1 158.92(5) 4_445 1_655 ?
S1 Cu1 Ba1 64.30(4) . 1_655 ?
S2 Cu1 Ba1 61.56(4) 1_545 1_655 ?
S1 Cu1 Ba1 62.30(4) 5_655 1_655 ?
S2 Cu1 Ba1 58.08(4) 4_445 1_545 ?
S1 Cu1 Ba1 136.71(5) . 1_545 ?
S2 Cu1 Ba1 110.16(4) 1_545 1_545 ?
S1 Cu1 Ba1 58.83(4) 5_655 1_545 ?
Ba1 Cu1 Ba1 118.02(3) 1_655 1_545 ?
S2 Cu1 Ba1 55.77(4) 4_445 3_554 ?
S1 Cu1 Ba1 111.46(4) . 3_554 ?
S2 Cu1 Ba1 56.60(4) 1_545 3_554 ?
S1 Cu1 Ba1 147.50(5) 5_655 3_554 ?
Ba1 Cu1 Ba1 112.36(2) 1_655 3_554 ?
Ba1 Cu1 Ba1 106.71(2) 1_545 3_554 ?
Ge1 S1 Cu1 106.34(6) . . ?
Ge1 S1 Cu1 120.35(7) . 5_665 ?
Cu1 S1 Cu1 127.92(7) . 5_665 ?
Ge1 S1 Ba1 117.59(6) . . ?
Cu1 S1 Ba1 103.77(6) . . ?
Cu1 S1 Ba1 75.13(4) 5_665 . ?
Ge1 S1 Ba1 91.70(5) . 1_655 ?
Cu1 S1 Ba1 75.44(5) . 1_655 ?
Cu1 S1 Ba1 81.14(5) 5_665 1_655 ?
Ba1 S1 Ba1 148.87(5) . 1_655 ?
Ge1 S2 Cu1 120.11(7) . 4_665 ?
Ge1 S2 Cu1 108.81(6) . 1_565 ?
Cu1 S2 Cu1 130.10(7) 4_665 1_565 ?
Ge1 S2 Ba1 120.34(6) . 1_665 ?
Cu1 S2 Ba1 86.93(5) 4_665 1_665 ?
Cu1 S2 Ba1 76.19(4) 1_565 1_665 ?
Ge1 S2 Ba1 92.90(5) . 3_564 ?
Cu1 S2 Ba1 84.04(5) 4_665 3_564 ?
Cu1 S2 Ba1 84.34(5) 1_565 3_564 ?
Ba1 S2 Ba1 145.33(5) 1_665 3_564 ?
S2 Ba1 S2 127.65(6) 5_655 1_445 ?
S2 Ba1 S1 87.68(4) 5_655 5 ?
S2 Ba1 S1 70.91(4) 1_445 5 ?
S2 Ba1 S1 70.91(4) 5_655 . ?
S2 Ba1 S1 87.68(4) 1_445 . ?
S1 Ba1 S1 130.75(5) 5 . ?
S2 Ba1 S2 146.90(3) 5_655 4_455 ?
S2 Ba1 S2 69.00(3) 1_445 4_455 ?
S1 Ba1 S2 125.23(4) 5 4_455 ?
S1 Ba1 S2 82.87(4) . 4_455 ?
S2 Ba1 S2 69.00(3) 5_655 2_665 ?
S2 Ba1 S2 146.90(3) 1_445 2_665 ?
S1 Ba1 S2 82.87(4) 5 2_665 ?
S1 Ba1 S2 125.23(4) . 2_665 ?
S2 Ba1 S2 114.17(6) 4_455 2_665 ?
S2 Ba1 S1 73.35(4) 5_655 5_665 ?
S2 Ba1 S1 140.17(4) 1_445 5_665 ?
S1 Ba1 S1 148.87(5) 5 5_665 ?
S1 Ba1 S1 66.34(2) . 5_665 ?
S2 Ba1 S1 77.87(4) 4_455 5_665 ?
S2 Ba1 S1 67.49(4) 2_665 5_665 ?
S2 Ba1 S1 140.17(4) 5_655 1_455 ?
S2 Ba1 S1 73.35(4) 1_445 1_455 ?
S1 Ba1 S1 66.34(2) 5 1_455 ?
S1 Ba1 S1 148.87(5) . 1_455 ?
S2 Ba1 S1 67.49(4) 4_455 1_455 ?
S2 Ba1 S1 77.87(4) 2_665 1_455 ?
S1 Ba1 S1 113.87(5) 5_665 1_455 ?
S2 Ba1 Cu1 129.49(3) 5_655 1_455 ?
S2 Ba1 Cu1 42.26(3) 1_445 1_455 ?
S1 Ba1 Cu1 42.57(3) 5 1_455 ?
S1 Ba1 Cu1 129.64(3) . 1_455 ?
S2 Ba1 Cu1 82.85(3) 4_455 1_455 ?
S2 Ba1 Cu1 104.65(3) 2_665 1_455 ?
S1 Ba1 Cu1 153.13(3) 5_665 1_455 ?
S1 Ba1 Cu1 40.26(3) 1_455 1_455 ?
S2 Ba1 Cu1 42.26(3) 5_655 5_665 ?
S2 Ba1 Cu1 129.49(3) 1_445 5_665 ?
S1 Ba1 Cu1 129.64(3) 5 5_665 ?
S1 Ba1 Cu1 42.57(3) . 5_665 ?
S2 Ba1 Cu1 104.65(3) 4_455 5_665 ?
S2 Ba1 Cu1 82.85(3) 2_665 5_665 ?
S1 Ba1 Cu1 40.26(3) 5_665 5_665 ?
S1 Ba1 Cu1 153.13(3) 1_455 5_665 ?
Cu1 Ba1 Cu1 166.43(3) 1_455 5_665 ?
S2 Ba1 Cu1 112.20(3) 5_655 1_565 ?
S2 Ba1 Cu1 104.79(3) 1_445 1_565 ?
S1 Ba1 Cu1 155.28(3) 5 1_565 ?
S1 Ba1 Cu1 71.92(3) . 1_565 ?
S2 Ba1 Cu1 37.88(3) 4_455 1_565 ?
S2 Ba1 Cu1 90.54(3) 2_665 1_565 ?
S1 Ba1 Cu1 40.04(3) 5_665 1_565 ?
S1 Ba1 Cu1 89.00(3) 1_455 1_565 ?
Cu1 Ba1 Cu1 118.02(3) 1_455 1_565 ?
Cu1 Ba1 Cu1 72.526(17) 5_665 1_565 ?
S2 Ba1 Cu1 104.79(3) 5_655 5_565 ?
S2 Ba1 Cu1 112.20(3) 1_445 5_565 ?
S1 Ba1 Cu1 71.92(3) 5 5_565 ?
S1 Ba1 Cu1 155.28(3) . 5_565 ?
S2 Ba1 Cu1 90.54(3) 4_455 5_565 ?
S2 Ba1 Cu1 37.88(3) 2_665 5_565 ?
S1 Ba1 Cu1 89.00(3) 5_665 5_565 ?
S1 Ba1 Cu1 40.04(3) 1_455 5_565 ?
Cu1 Ba1 Cu1 72.527(17) 1_455 5_565 ?
Cu1 Ba1 Cu1 118.02(3) 5_665 5_565 ?
Cu1 Ba1 Cu1 88.28(3) 1_565 5_565 ?


_refine_diff_density_max         0.695
_refine_diff_density_min         -0.535
_refine_diff_density_rms         0.136

_shelx_res_file                  
;

    22.res created by SHELXL-2014/7

TITL 22 in P3(1)                 New: P3121
CELL  0.71073    6.2092    6.2092   15.5200    90.000    90.000   120.000
ZERR  3           0.0008    0.0008    0.0040     0.000     0.000     0.000
LATT -1
SYMM             - Y ,          X - Y ,    0.33333 + Z
SYMM         - X + Y ,            - X ,    0.66667 + Z
SYMM               Y ,              X ,            - Z
SYMM             - X ,        - X + Y ,    0.33333 - Z
SYMM           X - Y ,            - Y ,    0.66667 - Z
SFAC Ba Cu Ge S
UNIT 3 6 3 12
L.S. 20
ACTA
BOND $H
FMAP 2
PLAN 5
TWIN
CONF
WGHT    0.012400
EXTI    0.000756
BASF   0.05244
FVAR       0.11593
GE1   3    0.714189    0.714189    0.000000    10.50000    0.00799    0.00799 =
         0.01019   -0.00010    0.00010    0.00403
CU1   2    0.410420    0.074921    0.076551    11.00000    0.01884    0.01657 =
         0.02525   -0.00519   -0.00263    0.00756
S1    4    0.517835    0.480492    0.113115    11.00000    0.01170    0.01080 =
         0.01117    0.00097    0.00177    0.00614
S2    4    0.762762    1.092987    0.003490    11.00000    0.01044    0.00776 =
         0.01430   -0.00037    0.00086    0.00439
BA1   1    0.000000    0.436088    0.166667    10.50000    0.00909    0.01215 =
         0.01297   -0.00077   -0.00154    0.00455
HKLF 4 1 -1.0000  0.0000  0.0000  0.0000 -1.0000  0.0000  0.0000  0.0000  1.0000

REM  22 in P3(1)                 New: P3121
REM R1 =  0.0185 for     729 Fo > 4sig(Fo)  and  0.0214 for all     784 data
REM     40 parameters refined using      0 restraints

END

WGHT      0.0124      0.0000

REM Highest difference peak  0.695,  deepest hole -0.535,  1-sigma level  0.136
Q1    1  -0.1200  0.3853  0.1200  11.00000  0.05    0.69
Q2    1   0.0551  0.3872  0.1129  11.00000  0.05    0.69
Q3    1   0.6087  0.5910  0.1787  11.00000  0.05    0.65
Q4    1   0.4806  0.0682  0.0181  11.00000  0.05    0.61
Q5    1   0.0816  0.5420  0.1293  11.00000  0.05    0.58
;
_shelx_res_checksum              10917
####################################################################### 
# 
# 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_33
_database_code_depnum_ccdc_archive 'CCDC 1540055'
_audit_update_record             
;
2017-03-24 deposited with the CCDC.
2017-06-01 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Ba Cu2 Ge Se4'
_chemical_formula_weight         652.85

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ba Ba -0.3244 2.2819 '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'
Ge Ge 0.1547 1.8001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Se Se -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           152
_space_group_name_H-M_alt        'P 31 2 1'
_space_group_name_Hall           'P 31 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-y, z+1/3'
'-x+y, -x, z+2/3'
'y, x, -z'
'-x, -x+y, -z+1/3'
'x-y, -y, -z+2/3'

_cell_length_a                   6.5014(6)
_cell_length_b                   6.5014(6)
_cell_length_c                   16.266(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     595.42(16)
_cell_formula_units_Z            3
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2114
_cell_measurement_theta_min      3.62
_cell_measurement_theta_max      27.49

_exptl_crystal_description       block
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    5.462
_exptl_crystal_F_000             846
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.314
_exptl_crystal_size_mid          0.226
_exptl_crystal_size_min          0.156
_exptl_absorpt_coefficient_mu    32.160
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.2368
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'sealed tube'
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            3659
_diffrn_reflns_av_unetI/netI     0.0518
_diffrn_reflns_av_R_equivalents  0.0601
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -4
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         3.619
_diffrn_reflns_theta_max         27.597
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_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
_reflns_number_total             928
_reflns_number_gt                898
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.599
_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 SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_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)+(0.0249P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_extinction_coef       0.0072(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.09(4)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         928
_refine_ls_number_parameters     40
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0287
_refine_ls_R_factor_gt           0.0281
_refine_ls_wR_factor_ref         0.0663
_refine_ls_wR_factor_gt          0.0659
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_restrained_S_all      1.054
_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
Se1 Se 0.96694(16) 0.47818(15) 0.05239(5) 0.0099(2) Uani 1 1 d . . . . .
Se2 Se 0.66625(15) 0.76750(16) 0.17105(5) 0.0101(3) Uani 1 1 d . . . . .
Ge1 Ge 1.0000 0.7149(2) 0.1667 0.0078(3) Uani 1 2 d S T P . .
Cu1 Cu 0.6608(2) 0.0797(2) 0.08999(7) 0.0207(3) Uani 1 1 d . . . . .
Ba1 Ba 0.44972(12) 0.44972(12) 0.0000 0.0119(2) 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
Se1 0.0110(5) 0.0106(4) 0.0069(4) -0.0010(3) 0.0013(3) 0.0045(4)
Se2 0.0109(5) 0.0124(5) 0.0095(5) 0.0019(3) 0.0023(3) 0.0078(4)
Ge1 0.0088(6) 0.0091(5) 0.0055(6) 0.0000(2) -0.0001(4) 0.0044(3)
Cu1 0.0214(7) 0.0183(6) 0.0223(7) 0.0060(5) 0.0027(5) 0.0099(6)
Ba1 0.0144(3) 0.0144(3) 0.0092(4) 0.00079(14) -0.00079(14) 0.0090(3)

_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
Se1 Ge1 2.3537(12) . ?
Se1 Cu1 2.4272(15) . ?
Se1 Cu1 2.5379(16) 4_655 ?
Se1 Ba1 3.3456(10) 1_655 ?
Se1 Ba1 3.3831(10) . ?
Se2 Ge1 2.3604(12) . ?
Se2 Cu1 2.4352(15) 1_565 ?
Se2 Cu1 2.4945(15) 5_665 ?
Se2 Ba1 3.3108(10) 2_665 ?
Se2 Ba1 3.3291(10) . ?
Ge1 Se1 2.3536(12) 5_765 ?
Ge1 Se2 2.3604(12) 5_765 ?
Cu1 Se2 2.4352(15) 1_545 ?
Cu1 Se2 2.4945(15) 5_655 ?
Cu1 Se1 2.5378(16) 4_545 ?
Cu1 Ba1 3.8960(14) 1_545 ?
Ba1 Se2 3.3108(10) 3_564 ?
Ba1 Se2 3.3107(10) 5_655 ?
Ba1 Se2 3.3292(10) 4 ?
Ba1 Se1 3.3456(10) 4_545 ?
Ba1 Se1 3.3456(10) 1_455 ?
Ba1 Se1 3.3831(10) 4 ?
Ba1 Cu1 3.6217(13) 4 ?
Ba1 Cu1 3.8960(14) 1_565 ?
Ba1 Cu1 3.8960(14) 4_655 ?

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
Ge1 Se1 Cu1 104.90(5) . . ?
Ge1 Se1 Cu1 120.28(5) . 4_655 ?
Cu1 Se1 Cu1 128.33(5) . 4_655 ?
Ge1 Se1 Ba1 117.12(3) . 1_655 ?
Cu1 Se1 Ba1 107.24(4) . 1_655 ?
Cu1 Se1 Ba1 74.57(4) 4_655 1_655 ?
Ge1 Se1 Ba1 89.88(3) . . ?
Cu1 Se1 Ba1 75.11(4) . . ?
Cu1 Se1 Ba1 80.93(4) 4_655 . ?
Ba1 Se1 Ba1 150.13(3) 1_655 . ?
Ge1 Se2 Cu1 120.12(5) . 1_565 ?
Ge1 Se2 Cu1 108.08(5) . 5_665 ?
Cu1 Se2 Cu1 130.66(5) 1_565 5_665 ?
Ge1 Se2 Ba1 121.73(4) . 2_665 ?
Cu1 Se2 Ba1 87.12(4) 1_565 2_665 ?
Cu1 Se2 Ba1 75.75(4) 5_665 2_665 ?
Ge1 Se2 Ba1 91.09(3) . . ?
Cu1 Se2 Ba1 83.50(4) 1_565 . ?
Cu1 Se2 Ba1 85.77(4) 5_665 . ?
Ba1 Se2 Ba1 145.85(3) 2_665 . ?
Se1 Ge1 Se1 105.07(7) 5_765 . ?
Se1 Ge1 Se2 109.18(3) 5_765 5_765 ?
Se1 Ge1 Se2 114.00(3) . 5_765 ?
Se1 Ge1 Se2 114.00(3) 5_765 . ?
Se1 Ge1 Se2 109.18(3) . . ?
Se2 Ge1 Se2 105.62(7) 5_765 . ?
Se1 Cu1 Se2 132.86(6) . 1_545 ?
Se1 Cu1 Se2 109.01(6) . 5_655 ?
Se2 Cu1 Se2 99.19(4) 1_545 5_655 ?
Se1 Cu1 Se1 95.38(4) . 4_545 ?
Se2 Cu1 Se1 116.94(6) 1_545 4_545 ?
Se2 Cu1 Se1 99.06(5) 5_655 4_545 ?
Se1 Cu1 Ba1 134.21(5) . 1_545 ?
Se2 Cu1 Ba1 58.11(3) 1_545 1_545 ?
Se2 Cu1 Ba1 111.97(4) 5_655 1_545 ?
Se1 Cu1 Ba1 59.04(3) 4_545 1_545 ?
Se2 Ba1 Se2 125.74(4) 3_564 5_655 ?
Se2 Ba1 Se2 146.780(19) 3_564 . ?
Se2 Ba1 Se2 68.856(17) 5_655 . ?
Se2 Ba1 Se2 68.855(17) 3_564 4 ?
Se2 Ba1 Se2 146.780(19) 5_655 4 ?
Se2 Ba1 Se2 117.10(4) . 4 ?
Se2 Ba1 Se1 86.32(2) 3_564 4_545 ?
Se2 Ba1 Se1 70.22(2) 5_655 4_545 ?
Se2 Ba1 Se1 126.19(2) . 4_545 ?
Se2 Ba1 Se1 82.54(2) 4 4_545 ?
Se2 Ba1 Se1 70.22(2) 3_564 1_455 ?
Se2 Ba1 Se1 86.32(2) 5_655 1_455 ?
Se2 Ba1 Se1 82.54(2) . 1_455 ?
Se2 Ba1 Se1 126.19(2) 4 1_455 ?
Se1 Ba1 Se1 127.61(4) 4_545 1_455 ?
Se2 Ba1 Se1 73.54(2) 3_564 4 ?
Se2 Ba1 Se1 139.60(2) 5_655 4 ?
Se2 Ba1 Se1 78.33(2) . 4 ?
Se2 Ba1 Se1 69.83(2) 4 4 ?
Se1 Ba1 Se1 150.13(3) 4_545 4 ?
Se1 Ba1 Se1 66.156(11) 1_455 4 ?
Se2 Ba1 Se1 139.60(2) 3_564 . ?
Se2 Ba1 Se1 73.54(2) 5_655 . ?
Se2 Ba1 Se1 69.83(2) . . ?
Se2 Ba1 Se1 78.33(2) 4 . ?
Se1 Ba1 Se1 66.156(11) 4_545 . ?
Se1 Ba1 Se1 150.13(3) 1_455 . ?
Se1 Ba1 Se1 116.76(4) 4 . ?
Se2 Ba1 Cu1 41.88(2) 3_564 4 ?
Se2 Ba1 Cu1 127.91(3) 5_655 4 ?
Se2 Ba1 Cu1 104.92(3) . 4 ?
Se2 Ba1 Cu1 83.76(3) 4 4 ?
Se1 Ba1 Cu1 127.69(3) 4_545 4 ?
Se1 Ba1 Cu1 42.49(3) 1_455 4 ?
Se1 Ba1 Cu1 40.37(2) 4 4 ?
Se1 Ba1 Cu1 155.72(3) . 4 ?
Se2 Ba1 Cu1 112.35(2) 3_564 1_565 ?
Se2 Ba1 Cu1 105.06(3) 5_655 1_565 ?
Se2 Ba1 Cu1 38.39(2) . 1_565 ?
Se2 Ba1 Cu1 92.95(3) 4 1_565 ?
Se1 Ba1 Cu1 157.86(3) 4_545 1_565 ?
Se1 Ba1 Cu1 72.14(2) 1_455 1_565 ?
Se1 Ba1 Cu1 40.03(2) 4 1_565 ?
Se1 Ba1 Cu1 91.71(3) . 1_565 ?
Cu1 Ba1 Cu1 72.85(2) 4 1_565 ?
Se2 Ba1 Cu1 105.06(3) 3_564 4_655 ?
Se2 Ba1 Cu1 112.35(2) 5_655 4_655 ?
Se2 Ba1 Cu1 92.95(3) . 4_655 ?
Se2 Ba1 Cu1 38.39(2) 4 4_655 ?
Se1 Ba1 Cu1 72.14(2) 4_545 4_655 ?
Se1 Ba1 Cu1 157.86(3) 1_455 4_655 ?
Se1 Ba1 Cu1 91.71(3) 4 4_655 ?
Se1 Ba1 Cu1 40.04(2) . 4_655 ?
Cu1 Ba1 Cu1 119.68(3) 4 4_655 ?
Cu1 Ba1 Cu1 90.87(4) 1_565 4_655 ?


_refine_diff_density_max         1.135
_refine_diff_density_min         -1.207
_refine_diff_density_rms         0.278

_shelx_res_file                  
;

    33.res created by SHELXL-2014/7

TITL 33 in P3(1)                 New: P3121
CELL  0.71073    6.5014    6.5014   16.2660    90.000    90.000   120.000
ZERR  3           0.0006    0.0006    0.0030     0.000     0.000     0.000
LATT -1
SYMM             - Y ,          X - Y ,    0.33333 + Z
SYMM         - X + Y ,            - X ,    0.66667 + Z
SYMM               Y ,              X ,            - Z
SYMM             - X ,        - X + Y ,    0.33333 - Z
SYMM           X - Y ,            - Y ,    0.66667 - Z
SFAC Ba Cu Ge Se
UNIT 3 6 3 12
L.S. 20
ACTA
BOND $H
FMAP 2
PLAN 5
CONF
TWIN
FREE Cu1  Ba1
WGHT    0.024900
EXTI    0.007153
BASF   0.08752
FVAR       0.11006
SE1   4    0.966938    0.478179    0.052390    11.00000    0.01096    0.01056 =
         0.00691   -0.00099    0.00127    0.00449
SE2   4    0.666255    0.767503    0.171051    11.00000    0.01092    0.01244 =
         0.00955    0.00187    0.00232    0.00777
GE1   3    1.000000    0.714929    0.166667    10.50000    0.00883    0.00909 =
         0.00548   -0.00005   -0.00010    0.00441
CU1   2    0.660824    0.079666    0.089993    11.00000    0.02138    0.01835 =
         0.02231    0.00598    0.00268    0.00993
BA1   1    0.449721    0.449721    0.000000    10.50000    0.01442    0.01442 =
         0.00918    0.00079   -0.00079    0.00896
HKLF 4 1 -1.0000  0.0000  0.0000  0.0000 -1.0000  0.0000  0.0000  0.0000  1.0000

REM  33 in P3(1)                 New: P3121
REM R1 =  0.0281 for     898 Fo > 4sig(Fo)  and  0.0287 for all     928 data
REM     40 parameters refined using      0 restraints

END

WGHT      0.0249      0.0000

REM Highest difference peak  1.135,  deepest hole -1.207,  1-sigma level  0.278
Q1    1   0.5997  0.5997  0.0000  10.50000  0.05    1.13
Q2    1   0.4557  0.6021 -0.0002  11.00000  0.05    1.13
Q3    1   0.8578  0.2672  0.1007  11.00000  0.05    1.12
Q4    1   0.3370  0.2285  0.0513  11.00000  0.05    1.06
Q5    1   0.3016  0.3016  0.0000  10.50000  0.05    1.04
;
_shelx_res_checksum              99691
