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

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_a
_database_code_depnum_ccdc_archive 'CCDC 2159551'
loop_
_audit_author_name
_audit_author_address
'Sheng-Ping Guo'
;Yangzhou University
China
;
_audit_update_record             
;
2022-03-17 deposited with the CCDC.	2022-06-01 downloaded from the CCDC.
;
_audit_creation_date             2021-11-15
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'Ag Ge In2 Li S6'
_chemical_formula_sum            'Ag Ge In2 Li S6'
_chemical_formula_weight         609.40
_chemical_absolute_configuration ?
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Li Li -0.0003 0.0001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ag Ag -0.8971 1.1015 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
In In -0.7276 1.3100 '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'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_H-M_alt        'C 1 c 1'
_space_group_name_Hall           'C -2yc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'x, -y, z+1/2'
'x+1/2, y+1/2, z'
'x+1/2, -y+1/2, z+1/2'

_cell_length_a                   12.1567(6)
_cell_length_b                   7.2525(4)
_cell_length_c                   12.1757(6)
_cell_angle_alpha                90
_cell_angle_beta                 109.9070(10)
_cell_angle_gamma                90
_cell_volume                     1009.34(9)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    7047
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.33
_cell_measurement_theta_min      3.33
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    10.539
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.4420
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1094 before and 0.0533 after correction.
The Ratio of minimum to maximum transmission is 0.5927.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    4.010
_exptl_crystal_density_meas      .
_exptl_crystal_density_method    ?
_exptl_crystal_description       bulk
_exptl_crystal_F_000             1104
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.18
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0262
_diffrn_reflns_av_unetI/netI     0.0298
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            6397
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.997
_diffrn_reflns_theta_min         3.327
_diffrn_ambient_temperature      293
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.996
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                1915
_reflns_number_total             1919
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.879
_refine_diff_density_min         -0.903
_refine_diff_density_rms         0.106
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.032(15)
_refine_ls_extinction_coef       0.00543(19)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     102
_refine_ls_number_reflns         1919
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0145
_refine_ls_R_factor_gt           0.0145
_refine_ls_restrained_S_all      1.051
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0019P)²+1.6638P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0342
_refine_ls_wR_factor_ref         0.0342
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.968(15)
 0.032(15)
2. Shared sites
{Ag2, Li2}
{Ag1, Li1}
3. Uiso/Uaniso restraints and constraints
Uanis(Ag2) = Uanis(Li2)
Uanis(Ag1) = Uanis(Li1)
4. Others
 Fixed Sof: Li1(0.25) Ag1(0.75) Li2(0.75) Ag2(0.25)
;
_atom_sites_solution_hydrogens   .
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Li1 Li 0.50574(7) 0.20918(11) 0.34851(7) 0.0393(2) Uani 0.25 1 d . . P . .
Ag1 Ag 0.50574(7) 0.20918(11) 0.34851(7) 0.0393(2) Uani 0.75 1 d . . P . .
Li2 Li 0.30045(18) 0.5848(2) 0.19676(18) 0.0309(4) Uani 0.75 1 d . . P . .
Ag2 Ag 0.30045(18) 0.5848(2) 0.19676(18) 0.0309(4) Uani 0.25 1 d . . P . .
In1 In 0.14274(3) 0.06730(5) 0.19690(3) 0.01617(12) Uani 1 1 d . . . . .
In2 In 0.32469(3) 0.09020(6) 0.00257(3) 0.01651(12) Uani 1 1 d . . . . .
Ge1 Ge 0.07557(5) 0.23480(7) 0.44125(5) 0.01053(14) Uani 1 1 d . . . . .
S1 S 0.31193(14) 0.2383(2) 0.17938(14) 0.0192(3) Uani 1 1 d . . . . .
S2 S 0.00019(13) 0.0054(2) -0.00171(13) 0.0176(3) Uani 1 1 d . . . . .
S3 S 0.00107(13) 0.2581(2) 0.25095(13) 0.0176(3) Uani 1 1 d . . . . .
S4 S 0.26638(14) 0.2411(2) 0.49525(15) 0.0197(3) Uani 1 1 d . . . . .
S5 S 0.69887(14) 0.2817(2) 0.31367(13) 0.0185(3) Uani 1 1 d . . . . .
S6 S 0.52859(12) 0.0165(2) 0.02006(12) 0.0154(3) Uani 1 1 d . . . . .

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
Li1 0.0289(4) 0.0443(5) 0.0419(5) 0.0164(3) 0.0084(3) -0.0030(3)
Ag1 0.0289(4) 0.0443(5) 0.0419(5) 0.0164(3) 0.0084(3) -0.0030(3)
Li2 0.0342(11) 0.0254(10) 0.0316(11) -0.0012(7) 0.0092(8) 0.0050(8)
Ag2 0.0342(11) 0.0254(10) 0.0316(11) -0.0012(7) 0.0092(8) 0.0050(8)
In1 0.0158(2) 0.0211(2) 0.0131(2) -0.00034(16) 0.00686(16) 0.00071(17)
In2 0.0130(2) 0.0235(2) 0.0142(2) -0.00109(16) 0.00611(16) -0.00139(17)
Ge1 0.0093(3) 0.0126(3) 0.0101(3) 0.0002(2) 0.0038(2) 0.0008(2)
S1 0.0172(8) 0.0255(8) 0.0167(7) -0.0035(6) 0.0080(6) -0.0035(6)
S2 0.0173(7) 0.0182(8) 0.0150(7) -0.0032(6) 0.0026(5) 0.0064(6)
S3 0.0184(8) 0.0245(8) 0.0100(7) 0.0028(5) 0.0048(6) 0.0077(6)
S4 0.0087(7) 0.0212(8) 0.0281(8) -0.0009(6) 0.0048(6) 0.0000(6)
S5 0.0179(8) 0.0207(7) 0.0152(7) 0.0013(6) 0.0035(6) -0.0003(6)
S6 0.0125(7) 0.0156(7) 0.0187(7) 0.0056(6) 0.0060(5) 0.0008(5)

_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
Li1 S1 2.5558(18) . ?
Li1 S2 2.7748(18) 4 ?
Li1 S5 2.5782(17) . ?
Li1 S6 2.5931(17) 2 ?
Li2 S1 2.530(2) . ?
Li2 S3 2.621(3) 3 ?
Li2 S4 2.663(3) 2_564 ?
Li2 S5 2.605(3) 3_455 ?
In1 S1 2.4724(16) . ?
In1 S2 2.4897(15) . ?
In1 S3 2.4671(15) . ?
In1 S5 2.4734(15) 3_445 ?
In2 S1 2.4576(16) . ?
In2 S4 2.4980(16) 2_554 ?
In2 S5 2.4693(16) 4_454 ?
In2 S6 2.4730(15) . ?
Ge1 S2 2.1886(15) 2 ?
Ge1 S3 2.1884(16) . ?
Ge1 S4 2.1856(17) . ?
Ge1 S6 2.2075(15) 4_455 ?
S2 Li1 2.7747(18) 4_454 ?
S2 Ag1 2.7747(18) 4_454 ?
S2 Ge1 2.1886(15) 2_554 ?
S3 Li2 2.621(3) 3_445 ?
S3 Ag2 2.621(3) 3_445 ?
S4 Li2 2.663(3) 2_565 ?
S4 Ag2 2.663(3) 2_565 ?
S4 In2 2.4980(16) 2 ?
S5 Li2 2.605(3) 3_545 ?
S5 Ag2 2.605(3) 3_545 ?
S5 In1 2.4734(15) 3 ?
S5 In2 2.4693(16) 4 ?
S6 Li1 2.5931(17) 2_554 ?
S6 Ag1 2.5931(17) 2_554 ?
S6 Ge1 2.2074(15) 4_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 Li1 S2 104.23(5) . 4 ?
S1 Li1 S5 119.47(6) . . ?
S1 Li1 S6 121.18(5) . 2 ?
S5 Li1 S2 100.56(5) . 4 ?
S5 Li1 S6 114.05(5) . 2 ?
S6 Li1 S2 87.79(5) 2 4 ?
S1 Li2 S3 115.12(9) . 3 ?
S1 Li2 S4 112.93(9) . 2_564 ?
S1 Li2 S5 129.79(10) . 3_455 ?
S3 Li2 S4 81.03(7) 3 2_564 ?
S5 Li2 S3 99.98(8) 3_455 3 ?
S5 Li2 S4 106.84(8) 3_455 2_564 ?
S1 In1 S2 109.33(5) . . ?
S1 In1 S5 113.26(6) . 3_445 ?
S3 In1 S1 114.73(5) . . ?
S3 In1 S2 92.41(5) . . ?
S3 In1 S5 113.43(5) . 3_445 ?
S5 In1 S2 111.83(5) 3_445 . ?
S1 In2 S4 110.48(6) . 2_554 ?
S1 In2 S5 116.59(6) . 4_454 ?
S1 In2 S6 112.29(5) . . ?
S5 In2 S4 104.51(5) 4_454 2_554 ?
S5 In2 S6 116.51(5) 4_454 . ?
S6 In2 S4 93.39(5) . 2_554 ?
S2 Ge1 S6 108.31(6) 2 4_455 ?
S3 Ge1 S2 109.30(6) . 2 ?
S3 Ge1 S6 108.78(6) . 4_455 ?
S4 Ge1 S2 115.93(6) . 2 ?
S4 Ge1 S3 109.34(6) . . ?
S4 Ge1 S6 104.92(6) . 4_455 ?
Li2 S1 Li1 94.40(7) . . ?
In1 S1 Li1 117.05(7) . . ?
In1 S1 Li2 114.83(8) . . ?
In2 S1 Li1 110.72(6) . . ?
In2 S1 Li2 121.95(8) . . ?
In2 S1 In1 99.14(6) . . ?
Li1 S2 Ag1 0.00(3) 4_454 4_454 ?
In1 S2 Li1 109.83(6) . 4_454 ?
In1 S2 Ag1 109.83(6) . 4_454 ?
Ge1 S2 Li1 106.19(6) 2_554 4_454 ?
Ge1 S2 Ag1 106.19(6) 2_554 4_454 ?
Ge1 S2 In1 102.92(6) 2_554 . ?
Ag2 S3 Li2 0.0 3_445 3_445 ?
In1 S3 Li2 109.76(7) . 3_445 ?
In1 S3 Ag2 109.76(7) . 3_445 ?
Ge1 S3 Li2 104.10(7) . 3_445 ?
Ge1 S3 Ag2 104.10(7) . 3_445 ?
Ge1 S3 In1 99.45(6) . . ?
Li2 S4 Ag2 0.00(9) 2_565 2_565 ?
In2 S4 Li2 118.03(8) 2 2_565 ?
In2 S4 Ag2 118.03(8) 2 2_565 ?
Ge1 S4 Li2 95.93(7) . 2_565 ?
Ge1 S4 Ag2 95.93(7) . 2_565 ?
Ge1 S4 In2 104.47(6) . 2 ?
Li1 S5 Li2 127.29(8) . 3_545 ?
Li1 S5 Ag2 127.29(8) . 3_545 ?
Li2 S5 Ag2 0.00(9) 3_545 3_545 ?
In1 S5 Li1 100.19(6) 3 . ?
In1 S5 Li2 103.54(7) 3 3_545 ?
In1 S5 Ag2 103.54(7) 3 3_545 ?
In2 S5 Li1 103.50(6) 4 . ?
In2 S5 Li2 117.17(8) 4 3_545 ?
In2 S5 Ag2 117.17(8) 4 3_545 ?
In2 S5 In1 100.51(5) 4 3 ?
Li1 S6 Ag1 0.00(3) 2_554 2_554 ?
In2 S6 Li1 103.75(6) . 2_554 ?
In2 S6 Ag1 103.75(6) . 2_554 ?
Ge1 S6 Li1 97.95(6) 4_554 2_554 ?
Ge1 S6 Ag1 97.95(6) 4_554 2_554 ?
Ge1 S6 In2 100.73(6) 4_554 . ?

_shelx_res_file                  
;
    a.res created by SHELXL-2014/7

TITL a_a.res in Cc LiAgIn2GeS6
REM Old TITL a in Cc
REM SHELXT solution in Cc
REM R1 0.059, Rweak 0.022, Alpha 0.001, Orientation as input
REM Flack x = 0.244 ( 0.010 ) from Parsons' quotients
REM Formula found by SHELXT: S7 Ge2 Ag In
CELL 0.71073 12.1567 7.2525 12.1757 90 109.907 90
ZERR 4 0.0006 0.0004 0.0006 0 0.001 0
LATT -7
SYMM +X,-Y,0.5+Z
SFAC Li Ag In Ge S
UNIT 4 4 8 4 24
EADP Ag2 Li2
EADP Ag1 Li1
EXYZ Ag2 Li2
EXYZ Ag1 Li1

L.S. 20
PLAN  4
TEMP 0
list 4
fmap 2 53
acta
TWIN -1 0 0 0 -1 0 0 0 -1 2
OMIT -3 52
REM <olex2.extras>
REM <HklSrc "%.\\a.hkl">
REM </olex2.extras>

WGHT    0.001900    1.663800
EXTI    0.005429
BASF   0.03194
FVAR       0.28137
LI1   1    0.505740    0.209183    0.348510    10.25000    0.02890    0.04431 =
         0.04186    0.01636    0.00838   -0.00303
AG1   2    0.505740    0.209183    0.348510    10.75000    0.02890    0.04431 =
         0.04186    0.01636    0.00838   -0.00303
LI2   1    0.300454    0.584832    0.196762    10.75000    0.03419    0.02539 =
         0.03165   -0.00118    0.00922    0.00504
AG2   2    0.300454    0.584832    0.196762    10.25000    0.03419    0.02539 =
         0.03165   -0.00118    0.00922    0.00504
IN1   3    0.142741    0.067302    0.196898    11.00000    0.01579    0.02112 =
         0.01308   -0.00034    0.00686    0.00071
IN2   3    0.324689    0.090196    0.002570    11.00000    0.01297    0.02349 =
         0.01420   -0.00109    0.00611   -0.00139
GE1   4    0.075569    0.234800    0.441254    11.00000    0.00933    0.01255 =
         0.01009    0.00018    0.00380    0.00084
S1    5    0.311931    0.238297    0.179383    11.00000    0.01715    0.02548 =
         0.01674   -0.00347    0.00804   -0.00353
S2    5    0.000189    0.005392   -0.001707    11.00000    0.01727    0.01819 =
         0.01504   -0.00319    0.00264    0.00641
S3    5    0.001071    0.258149    0.250946    11.00000    0.01837    0.02447 =
         0.01001    0.00277    0.00481    0.00773
S4    5    0.266384    0.241083    0.495254    11.00000    0.00868    0.02121 =
         0.02808   -0.00090    0.00485   -0.00005
S5    5    0.698873    0.281676    0.313671    11.00000    0.01787    0.02074 =
         0.01515    0.00135    0.00350   -0.00029
S6    5    0.528590    0.016519    0.020060    11.00000    0.01251    0.01556 =
         0.01875    0.00564    0.00602    0.00076
HKLF 4

REM  a_a.res in Cc LiAgIn2GeS6
REM R1 =  0.0145 for    1915 Fo > 4sig(Fo)  and  0.0145 for all    1919 data
REM    102 parameters refined using      2 restraints

END

WGHT      0.0019      1.6638

REM Highest difference peak  0.879,  deepest hole -0.903,  1-sigma level  0.106
Q1    1   0.5053  0.1317  0.2992  11.00000  0.05    0.88
Q2    1   0.2446  0.5625  0.1896  11.00000  0.05    0.42
Q3    1   0.2750  0.6329  0.0898  11.00000  0.05    0.40
Q4    1   0.3141  0.3835  0.1218  11.00000  0.05    0.38
;
_shelx_res_checksum              23331
_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.968(15)
2 0.032(15)

####################################################################### 
# 
# 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_zwf1299y1_0m
_database_code_depnum_ccdc_archive 'CCDC 2159552'
loop_
_audit_author_name
_audit_author_address
'Sheng-Ping Guo'
;Yangzhou University
China
;
_audit_update_record             
;
2022-03-17 deposited with the CCDC.	2022-06-01 downloaded from the CCDC.
;
_audit_creation_date             2021-11-15
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'Ag Ge In2 Na S6'
_chemical_formula_sum            'Ag Ge In2 Na S6'
_chemical_formula_weight         625.45
_chemical_absolute_configuration ?
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Na Na 0.0362 0.0249 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ag Ag -0.8971 1.1015 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
In In -0.7276 1.3100 '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'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_H-M_alt        'C 1 c 1'
_space_group_name_Hall           'C -2yc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'x, -y, z+1/2'
'x+1/2, y+1/2, z'
'x+1/2, -y+1/2, z+1/2'

_cell_length_a                   12.0762(9)
_cell_length_b                   7.6256(5)
_cell_length_c                   12.1838(9)
_cell_angle_alpha                90
_cell_angle_beta                 110.004(2)
_cell_angle_gamma                90
_cell_volume                     1054.29(13)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    7224
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.68
_cell_measurement_theta_min      3.22
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    10.133
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.3462
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1242 before and 0.0579 after correction.
The Ratio of minimum to maximum transmission is 0.4641.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    3.940
_exptl_crystal_density_meas      .
_exptl_crystal_density_method    ?
_exptl_crystal_description       bulk
_exptl_crystal_F_000             1136
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.18
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0342
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            6402
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.993
_diffrn_reflns_theta_min         3.219
_diffrn_ambient_temperature      293
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.996
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                1872
_reflns_number_total             1887
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         1.668
_refine_diff_density_min         -1.887
_refine_diff_density_rms         0.175
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.05(3)
_refine_ls_extinction_coef       0.0046(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     102
_refine_ls_number_reflns         1887
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0228
_refine_ls_R_factor_gt           0.0226
_refine_ls_restrained_S_all      1.062
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0253P)²+9.1884P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0577
_refine_ls_wR_factor_ref         0.0578
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.95(3)
 0.05(3)
;
_atom_sites_solution_hydrogens   .
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Na1 Na 0.2892(4) 0.5631(5) 0.1972(4) 0.0211(9) Uani 1 1 d . . . . .
Ag1 Ag 0.50826(10) 0.21561(15) 0.36131(10) 0.0451(3) Uani 1 1 d . . . . .
In1 In 0.14061(5) 0.05561(9) 0.19685(5) 0.01636(19) Uani 1 1 d . . . . .
In2 In 0.32745(5) 0.07385(9) 0.00472(5) 0.01654(19) Uani 1 1 d . . . . .
Ge1 Ge 0.07755(9) 0.23536(12) 0.43706(9) 0.0112(2) Uani 1 1 d . . . . .
S1 S 0.3152(2) 0.2082(3) 0.1822(2) 0.0201(5) Uani 1 1 d . . . . .
S2 S -0.0006(2) -0.0104(3) -0.0024(2) 0.0174(5) Uani 1 1 d . . . . .
S3 S 0.0023(2) 0.2521(3) 0.2464(2) 0.0186(5) Uani 1 1 d . . . . .
S4 S 0.2695(2) 0.2403(3) 0.4903(3) 0.0208(5) Uani 1 1 d . . . . .
S5 S 0.6977(2) 0.2937(3) 0.3211(2) 0.0183(5) Uani 1 1 d . . . . .
S6 S 0.5344(2) 0.0239(3) 0.0180(2) 0.0152(5) Uani 1 1 d . . . . .

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
Na1 0.024(2) 0.0112(18) 0.024(2) -0.0033(15) 0.0034(18) 0.0082(15)
Ag1 0.0324(6) 0.0509(7) 0.0493(7) 0.0208(5) 0.0105(5) -0.0042(5)
In1 0.0160(4) 0.0201(3) 0.0138(3) -0.0003(3) 0.0062(3) 0.0005(3)
In2 0.0134(3) 0.0221(4) 0.0150(4) -0.0018(3) 0.0059(3) -0.0020(3)
Ge1 0.0095(5) 0.0131(4) 0.0108(5) 0.0003(4) 0.0033(4) 0.0008(4)
S1 0.0178(13) 0.0273(13) 0.0174(12) -0.0052(10) 0.0088(10) -0.0045(10)
S2 0.0158(12) 0.0186(11) 0.0164(12) -0.0024(9) 0.0038(10) 0.0048(9)
S3 0.0190(13) 0.0265(12) 0.0091(11) 0.0026(9) 0.0031(10) 0.0090(10)
S4 0.0106(12) 0.0190(11) 0.0305(15) -0.0013(10) 0.0040(10) -0.0005(9)
S5 0.0174(13) 0.0205(12) 0.0152(11) -0.0004(9) 0.0031(10) -0.0002(10)
S6 0.0124(11) 0.0149(10) 0.0184(12) 0.0036(9) 0.0052(10) 0.0000(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
Na1 S1 2.738(4) . ?
Na1 S3 2.829(5) 3 ?
Na1 S4 2.872(5) 2_564 ?
Na1 S5 2.781(5) 3_455 ?
Na1 S6 3.119(5) 3_455 ?
Ag1 S1 2.593(3) . ?
Ag1 S2 2.818(3) 4 ?
Ag1 S5 2.568(3) . ?
Ag1 S6 2.582(3) 2 ?
In1 S1 2.467(3) . ?
In1 S2 2.494(3) . ?
In1 S3 2.468(3) . ?
In1 S5 2.458(3) 3_445 ?
In2 S1 2.442(3) . ?
In2 S4 2.485(3) 2_554 ?
In2 S5 2.466(3) 4_454 ?
In2 S6 2.478(2) . ?
Ge1 S2 2.203(2) 2 ?
Ge1 S3 2.189(3) . ?
Ge1 S4 2.183(3) . ?
Ge1 S6 2.228(2) 4_455 ?
S2 Ag1 2.818(3) 4_454 ?
S2 Ge1 2.203(2) 2_554 ?
S3 Na1 2.829(5) 3_445 ?
S4 Na1 2.872(5) 2_565 ?
S4 In2 2.485(3) 2 ?
S5 Na1 2.781(5) 3_545 ?
S5 In1 2.458(3) 3 ?
S5 In2 2.466(3) 4 ?
S6 Na1 3.119(5) 3_545 ?
S6 Ag1 2.582(3) 2_554 ?
S6 Ge1 2.228(2) 4_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 Na1 S3 113.65(16) . 3 ?
S1 Na1 S4 115.74(16) . 2_564 ?
S1 Na1 S5 137.51(18) . 3_455 ?
S1 Na1 S6 88.10(13) . 3_455 ?
S3 Na1 S4 73.52(12) 3 2_564 ?
S3 Na1 S6 143.61(16) 3 3_455 ?
S4 Na1 S6 70.71(12) 2_564 3_455 ?
S5 Na1 S3 93.67(13) 3_455 3 ?
S5 Na1 S4 102.55(13) 3_455 2_564 ?
S5 Na1 S6 87.74(13) 3_455 3_455 ?
S1 Ag1 S2 108.00(8) . 4 ?
S5 Ag1 S1 116.60(9) . . ?
S5 Ag1 S2 98.23(8) . 4 ?
S5 Ag1 S6 114.42(9) . 2 ?
S6 Ag1 S1 117.01(9) 2 . ?
S6 Ag1 S2 98.53(8) 2 4 ?
S1 In1 S2 109.94(9) . . ?
S1 In1 S3 113.46(9) . . ?
S3 In1 S2 93.78(8) . . ?
S5 In1 S1 111.18(9) 3_445 . ?
S5 In1 S2 112.95(8) 3_445 . ?
S5 In1 S3 114.41(9) 3_445 . ?
S1 In2 S4 111.47(9) . 2_554 ?
S1 In2 S5 114.78(9) . 4_454 ?
S1 In2 S6 111.84(9) . . ?
S5 In2 S4 104.73(9) 4_454 2_554 ?
S5 In2 S6 115.83(8) 4_454 . ?
S6 In2 S4 96.31(9) . 2_554 ?
S2 Ge1 S6 107.56(10) 2 4_455 ?
S3 Ge1 S2 109.31(11) . 2 ?
S3 Ge1 S6 110.26(10) . 4_455 ?
S4 Ge1 S2 116.53(10) . 2 ?
S4 Ge1 S3 109.12(11) . . ?
S4 Ge1 S6 103.86(10) . 4_455 ?
Ag1 S1 Na1 90.73(12) . . ?
In1 S1 Na1 109.93(13) . . ?
In1 S1 Ag1 119.59(11) . . ?
In2 S1 Na1 121.13(14) . . ?
In2 S1 Ag1 116.42(11) . . ?
In2 S1 In1 100.29(9) . . ?
In1 S2 Ag1 105.17(9) . 4_454 ?
Ge1 S2 Ag1 108.47(9) 2_554 4_454 ?
Ge1 S2 In1 104.75(10) 2_554 . ?
In1 S3 Na1 106.35(12) . 3_445 ?
Ge1 S3 Na1 102.28(13) . 3_445 ?
Ge1 S3 In1 98.85(10) . . ?
In2 S4 Na1 120.29(13) 2 2_565 ?
Ge1 S4 Na1 91.74(13) . 2_565 ?
Ge1 S4 In2 104.43(10) . 2 ?
Ag1 S5 Na1 120.13(13) . 3_545 ?
In1 S5 Na1 105.03(12) 3 3_545 ?
In1 S5 Ag1 103.04(10) 3 . ?
In1 S5 In2 100.57(9) 3 4 ?
In2 S5 Na1 120.28(13) 4 3_545 ?
In2 S5 Ag1 104.66(9) 4 . ?
Ag1 S6 Na1 115.28(11) 2_554 3_545 ?
In2 S6 Na1 139.67(12) . 3_545 ?
In2 S6 Ag1 101.24(9) . 2_554 ?
Ge1 S6 Na1 84.67(11) 4_554 3_545 ?
Ge1 S6 Ag1 104.10(10) 4_554 2_554 ?
Ge1 S6 In2 103.17(9) 4_554 . ?

_shelx_res_file                  
;
    zwf1299y1_0m.res created by SHELXL-2014/7

TITL zwf1299y1_0m_a.res in Cc NaAgIn2GeS6
REM Old TITL ZWF1299Y1_0m in Cc
REM SHELXT solution in Cc
REM R1 0.073, Rweak 0.026, Alpha 0.002, Orientation as input
REM Flack x = 0.275 ( 0.011 ) from Parsons' quotients
REM Formula found by SHELXT: S7 Ge2 Ag2
CELL 0.71073 12.0762 7.6256 12.1838 90 110.004 90
ZERR 4 0.0009 0.0005 0.0009 0 0.002 0
LATT -7
SYMM +X,-Y,0.5+Z
SFAC Na Ag In Ge S
UNIT 4 4 8 4 24

L.S. 20
PLAN  4
TEMP 0
FREE Ag1 Na1
FREE In1 Ag1
list 4
fmap 2 53
acta
TWIN -1 0 0 0 -1 0 0 0 -1 2
OMIT -3 52
REM <olex2.extras>
REM <HklSrc "%.\\ZWF1299Y1_0m.hkl">
REM </olex2.extras>

WGHT    0.025300    9.188400
EXTI    0.004625
BASF   0.04630
FVAR       0.28209
NA1   1    0.289180    0.563051    0.197193    11.00000    0.02388    0.01121 =
         0.02431   -0.00325    0.00340    0.00819
AG1   2    0.508262    0.215607    0.361307    11.00000    0.03239    0.05093 =
         0.04927    0.02079    0.01048   -0.00417
IN1   3    0.140610    0.055609    0.196852    11.00000    0.01597    0.02012 =
         0.01383   -0.00031    0.00620    0.00050
IN2   3    0.327450    0.073854    0.004719    11.00000    0.01336    0.02207 =
         0.01501   -0.00185    0.00593   -0.00202
GE1   4    0.077548    0.235362    0.437057    11.00000    0.00946    0.01308 =
         0.01077    0.00027    0.00327    0.00076
S1    5    0.315170    0.208178    0.182154    11.00000    0.01780    0.02733 =
         0.01745   -0.00521    0.00882   -0.00451
S2    5   -0.000573   -0.010352   -0.002378    11.00000    0.01577    0.01855 =
         0.01643   -0.00245    0.00381    0.00481
S3    5    0.002253    0.252119    0.246418    11.00000    0.01902    0.02648 =
         0.00913    0.00256    0.00312    0.00897
S4    5    0.269480    0.240298    0.490273    11.00000    0.01061    0.01899 =
         0.03048   -0.00129    0.00404   -0.00050
S5    5    0.697682    0.293746    0.321115    11.00000    0.01738    0.02049 =
         0.01516   -0.00036    0.00309   -0.00022
S6    5    0.534414    0.023939    0.017973    11.00000    0.01236    0.01485 =
         0.01841    0.00356    0.00515    0.00004
HKLF 4

REM  zwf1299y1_0m_a.res in Cc NaAgIn2GeS6
REM R1 =  0.0226 for    1872 Fo > 4sig(Fo)  and  0.0228 for all    1887 data
REM    102 parameters refined using      2 restraints

END

WGHT      0.0253      9.1883

REM Highest difference peak  1.668,  deepest hole -1.887,  1-sigma level  0.175
Q1    1   0.5152  0.1373  0.3166  11.00000  0.05    1.67
Q2    1   0.2883  0.5269  0.2379  11.00000  0.05    0.81
Q3    1   0.5696  0.2214  0.4110  11.00000  0.05    0.54
Q4    1   0.4033  0.1204  0.0419  11.00000  0.05    0.52
;
_shelx_res_checksum              30738
_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.95(3)
2 0.05(3)

