# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2019

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

data_1
_database_code_depnum_ccdc_archive 'CCDC 1879891'
loop_
_audit_author_name
_audit_author_address
Wu
;hebei university
China
;
_audit_update_record             
;
2019-02-21 deposited with the CCDC.	2019-02-25 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Ge Li2 S4 Zn'
_chemical_formula_weight         280.08

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ge Ge 0.1547 1.8001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   Pn

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'x+1/2, -y, z+1/2'

_cell_length_a                   6.213(5)
_cell_length_b                   6.525(5)
_cell_length_c                   7.830(6)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.70
_cell_angle_gamma                90.00
_cell_volume                     317.4(5)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    445
_cell_measurement_theta_min      4.07
_cell_measurement_theta_max      27.23

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.158
_exptl_crystal_size_mid          0.142
_exptl_crystal_size_min          0.117
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.931
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             264
_exptl_absorpt_coefficient_mu    9.687
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6014
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            1548
_diffrn_reflns_av_R_equivalents  0.0386
_diffrn_reflns_av_sigmaI/netI    0.0728
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -4
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         3.12
_diffrn_reflns_theta_max         24.97
_reflns_number_total             976
_reflns_number_gt                736
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0733P)²+0.8973P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   ?
_refine_ls_hydrogen_treatment    ?
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.04(5)
_refine_ls_number_reflns         976
_refine_ls_number_parameters     43
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0795
_refine_ls_R_factor_gt           0.0580
_refine_ls_wR_factor_ref         0.1617
_refine_ls_wR_factor_gt          0.1404
_refine_ls_goodness_of_fit_ref   1.166
_refine_ls_restrained_S_all      1.165
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Ge1 Ge -0.1892(3) 0.3221(2) 0.0222(2) 0.0055(6) Uani 1 1 d . . .
Zn1 Zn 0.3098(4) 0.1776(3) -0.2333(3) 0.0202(12) Uani 1 1 d . . .
S1 S 0.1709(6) 0.3152(7) 0.0132(6) 0.0093(9) Uiso 1 1 d . . .
S2 S -0.3176(7) 0.1812(7) -0.2169(6) 0.0139(10) Uiso 1 1 d . . .
S3 S -0.3055(7) 0.6480(7) 0.0291(6) 0.0092(9) Uiso 1 1 d . . .
S4 S -0.3035(7) 0.1572(7) 0.2561(6) 0.0116(10) Uiso 1 1 d . . .
Li2 Li 0.307(6) 0.173(4) 0.287(5) 0.000(10) Uiso 1 1 d . . .
Li1 Li 0.314(6) 0.672(3) -0.005(4) 0.000(8) Uiso 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
Ge1 0.0052(8) 0.0026(8) 0.0087(9) 0.0002(8) -0.0014(6) 0.0003(7)
Zn1 0.0220(16) 0.0212(16) 0.0175(16) 0.0017(10) 0.0022(10) 0.0000(10)

_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 S2 2.224(5) . ?
Ge1 S1 2.238(4) . ?
Ge1 S3 2.246(5) . ?
Ge1 S4 2.251(5) . ?
Zn1 S1 2.306(5) . ?
Zn1 S4 2.296(6) 2_554 ?
Zn1 S3 2.288(5) 2_564 ?
Zn1 S2 2.318(5) 1_655 ?
S1 Li2 2.49(4) . ?
S1 Li1 2.50(2) . ?
S2 Zn1 2.318(5) 1_455 ?
S2 Li2 2.44(2) 2_454 ?
S2 Li1 2.59(3) 2_464 ?
S3 Zn1 2.284(5) 2_465 ?
S3 Li2 2.35(3) 2_464 ?
S3 Li1 2.38(3) 1_455 ?
S4 Li1 2.28(3) 2_465 ?
S4 Zn1 2.298(6) 2_455 ?
S4 Li2 2.44(4) 1_455 ?
Li2 S3 2.32(3) 2_565 ?
Li2 S4 2.44(4) 1_655 ?
Li2 S2 2.44(2) 2 ?
Li1 S4 2.31(3) 2_564 ?
Li1 S3 2.38(3) 1_655 ?
Li1 S2 2.57(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
S2 Ge1 S1 108.26(18) . . ?
S2 Ge1 S3 107.41(18) . . ?
S1 Ge1 S3 109.94(17) . . ?
S2 Ge1 S4 112.0(2) . . ?
S1 Ge1 S4 109.99(18) . . ?
S3 Ge1 S4 109.19(18) . . ?
S1 Zn1 S4 106.44(18) . 2_554 ?
S1 Zn1 S3 111.78(19) . 2_564 ?
S4 Zn1 S3 110.54(19) 2_554 2_564 ?
S1 Zn1 S2 109.48(18) . 1_655 ?
S4 Zn1 S2 108.49(18) 2_554 1_655 ?
S3 Zn1 S2 110.04(19) 2_564 1_655 ?
Ge1 S1 Zn1 114.7(2) . . ?
Ge1 S1 Li2 108.6(9) . . ?
Zn1 S1 Li2 116.8(8) . . ?
Ge1 S1 Li1 109.8(8) . . ?
Zn1 S1 Li1 100.0(9) . . ?
Li2 S1 Li1 106.6(11) . . ?
Ge1 S2 Zn1 113.5(2) . 1_455 ?
Ge1 S2 Li2 105.0(9) . 2_454 ?
Zn1 S2 Li2 107.9(9) 1_455 2_454 ?
Ge1 S2 Li1 117.8(6) . 2_464 ?
Zn1 S2 Li1 105.7(8) 1_455 2_464 ?
Li2 S2 Li1 105.6(11) 2_454 2_464 ?
Ge1 S3 Zn1 113.1(2) . 2_465 ?
Ge1 S3 Li2 111.4(7) . 2_464 ?
Zn1 S3 Li2 108.5(7) 2_465 2_464 ?
Ge1 S3 Li1 112.4(6) . 1_455 ?
Zn1 S3 Li1 111.7(7) 2_465 1_455 ?
Li2 S3 Li1 99.7(11) 2_464 1_455 ?
Ge1 S4 Li1 109.4(8) . 2_465 ?
Ge1 S4 Zn1 112.7(2) . 2_455 ?
Li1 S4 Zn1 109.8(7) 2_465 2_455 ?
Ge1 S4 Li2 111.9(7) . 1_455 ?
Li1 S4 Li2 102.6(13) 2_465 1_455 ?
Zn1 S4 Li2 109.9(6) 2_455 1_455 ?
S3 Li2 S4 113.5(13) 2_565 1_655 ?
S3 Li2 S2 112.5(14) 2_565 2 ?
S4 Li2 S2 105.9(11) 1_655 2 ?
S3 Li2 S1 114.3(12) 2_565 . ?
S4 Li2 S1 105.5(14) 1_655 . ?
S2 Li2 S1 104.3(12) 2 . ?
S4 Li1 S3 116.1(14) 2_564 1_655 ?
S4 Li1 S1 113.1(12) 2_564 . ?
S3 Li1 S1 106.5(10) 1_655 . ?
S4 Li1 S2 115.6(11) 2_564 2_565 ?
S3 Li1 S2 104.0(11) 1_655 2_565 ?
S1 Li1 S2 99.9(11) . 2_565 ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        24.97
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         1.960
_refine_diff_density_min         -1.170
_refine_diff_density_rms         0.368
