# Electronic Supplementary Material (ESI) for ChemComm.
# 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_444
_database_code_depnum_ccdc_archive 'CCDC 1509054'
_audit_update_record             
;
2016-10-09 deposited with the CCDC.
2017-01-19 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Ge2 Hg Li4 S7'
_chemical_formula_weight         597.95

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'
Ge Ge 0.1547 1.8001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Hg Hg -2.3894 9.2266 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   'Cc '

loop_
_symmetry_equiv_pos_as_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                   16.876(2)
_cell_length_b                   6.7764(8)
_cell_length_c                   10.1613(13)
_cell_angle_alpha                90.00
_cell_angle_beta                 93.360(7)
_cell_angle_gamma                90.00
_cell_volume                     1160.0(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    5480
_cell_measurement_theta_min      2.42
_cell_measurement_theta_max      27.46

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.189
_exptl_crystal_size_mid          0.157
_exptl_crystal_size_min          0.116
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    3.424
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1072
_exptl_absorpt_coefficient_mu    19.549
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5451
_exptl_absorpt_correction_T_max  0.7456
_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            8929
_diffrn_reflns_av_R_equivalents  0.0312
_diffrn_reflns_av_sigmaI/netI    0.0461
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         2.42
_diffrn_reflns_theta_max         27.51
_reflns_number_total             2556
_reflns_number_gt                2460
_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)+(0.0000P)²+0.0000P] 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     SHELXL
_refine_ls_extinction_coef       0.00582(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.007(5)
_refine_ls_number_reflns         2556
_refine_ls_number_parameters     128
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0204
_refine_ls_R_factor_gt           0.0191
_refine_ls_wR_factor_ref         0.0390
_refine_ls_wR_factor_gt          0.0386
_refine_ls_goodness_of_fit_ref   0.876
_refine_ls_restrained_S_all      0.875
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Hg1 Hg 0.37684(3) 0.13196(2) 0.55249(4) 0.02356(7) Uani 1 1 d . . .
Ge1 Ge 0.73122(3) 0.33681(13) 0.32823(5) 0.0117(2) Uani 1 1 d . . .
Ge2 Ge 0.52106(3) 0.17674(15) 0.26207(5) 0.01157(17) Uani 1 1 d . . .
S1 S 0.62756(8) 0.16956(17) 0.41222(14) 0.0136(3) Uani 1 1 d . . .
S2 S 0.69919(8) 0.64292(17) 0.29509(14) 0.0164(3) Uani 1 1 d . . .
S3 S 0.54733(9) 0.33162(19) 0.08392(14) 0.0185(3) Uani 1 1 d . . .
S4 S 0.76545(9) 0.16862(18) 0.15481(14) 0.0162(3) Uani 1 1 d . . .
S5 S 0.42236(8) 0.32600(18) 0.35394(15) 0.0163(3) Uani 1 1 d . . .
S6 S 0.49300(9) -0.13766(17) 0.22323(15) 0.0160(3) Uani 1 1 d . . .
S7 S 0.82574(8) 0.29490(19) 0.48651(13) 0.0158(3) Uani 1 1 d . . .
Li1 Li 0.6572(8) -0.194(2) 0.4851(13) 0.016(2) Uani 1 1 d . . .
Li2 Li 0.8025(11) 0.165(2) 0.7056(19) 0.024(3) Uani 1 1 d . . .
Li3 Li 0.4455(10) 0.6790(19) 0.4055(18) 0.017(2) Uani 1 1 d . . .
Li4 Li 0.5919(11) 0.653(2) 0.1260(19) 0.028(4) 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
Hg1 0.02209(11) 0.02591(10) 0.02252(12) -0.00139(15) -0.00005(7) -0.00191(14)
Ge1 0.0108(4) 0.0120(3) 0.0123(4) 0.0002(3) 0.0003(3) -0.0001(2)
Ge2 0.0109(4) 0.0134(3) 0.0104(4) 0.0002(3) 0.0007(3) -0.0005(3)
S1 0.0123(6) 0.0165(6) 0.0119(7) 0.0020(5) 0.0001(5) -0.0026(4)
S2 0.0176(8) 0.0135(6) 0.0181(7) 0.0005(5) 0.0007(6) 0.0014(5)
S3 0.0190(8) 0.0219(7) 0.0145(7) 0.0042(5) 0.0006(6) -0.0022(5)
S4 0.0177(7) 0.0156(6) 0.0154(7) -0.0033(5) 0.0031(6) 0.0001(4)
S5 0.0140(7) 0.0171(6) 0.0183(7) -0.0004(5) 0.0036(6) 0.0013(4)
S6 0.0168(7) 0.0134(6) 0.0177(7) -0.0012(5) -0.0007(6) -0.0005(4)
S7 0.0143(7) 0.0182(6) 0.0145(7) 0.0003(5) -0.0030(5) 0.0000(4)
Li1 0.009(6) 0.035(7) 0.005(5) -0.005(5) 0.003(4) -0.007(5)
Li2 0.015(6) 0.034(6) 0.023(8) -0.002(6) 0.000(5) -0.008(5)
Li3 0.020(6) 0.007(5) 0.023(6) -0.001(5) -0.002(5) -0.006(4)
Li4 0.025(7) 0.023(6) 0.035(9) 0.003(5) -0.003(6) 0.005(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
Hg1 S7 2.5184(13) 3_445 ?
Hg1 S6 2.5408(15) 2 ?
Hg1 S5 2.5635(15) . ?
Hg1 S4 2.5826(15) 4_455 ?
Ge1 S2 2.1650(14) . ?
Ge1 S4 2.2039(16) . ?
Ge1 S7 2.2161(16) . ?
Ge1 S1 2.2909(14) . ?
Ge2 S3 2.1607(15) . ?
Ge2 S5 2.2026(15) . ?
Ge2 S6 2.2129(17) . ?
Ge2 S1 2.2889(16) . ?
S1 Li4 2.584(18) 2_565 ?
S1 Li1 2.610(16) . ?
S2 Li1 2.370(13) 1_565 ?
S2 Li2 2.396(17) 2_564 ?
S2 Li4 2.423(18) . ?
S3 Li4 2.338(15) . ?
S3 Li1 2.353(13) 2_554 ?
S3 Li3 2.425(17) 2_564 ?
S4 Li2 2.396(14) 2_554 ?
S4 Li1 2.444(13) 2_554 ?
S4 Hg1 2.5826(15) 4_554 ?
S5 Li2 2.451(19) 4_454 ?
S5 Li3 2.475(13) . ?
S6 Li3 2.407(16) 1_545 ?
S6 Li4 2.441(17) 1_545 ?
S6 Hg1 2.5408(15) 2_554 ?
S7 Li3 2.360(17) 3_545 ?
S7 Li2 2.446(19) . ?
S7 Hg1 2.5184(13) 3 ?
Li1 S3 2.353(13) 2 ?
Li1 S2 2.370(13) 1_545 ?
Li1 S4 2.444(13) 2 ?
Li2 S4 2.396(14) 2 ?
Li2 S2 2.396(17) 2_565 ?
Li2 S5 2.451(19) 4 ?
Li3 S7 2.360(17) 3_455 ?
Li3 S6 2.407(16) 1_565 ?
Li3 S3 2.425(17) 2_565 ?
Li4 S6 2.441(17) 1_565 ?
Li4 S1 2.584(18) 2_564 ?

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
S7 Hg1 S6 115.72(4) 3_445 2 ?
S7 Hg1 S5 111.68(5) 3_445 . ?
S6 Hg1 S5 105.95(5) 2 . ?
S7 Hg1 S4 109.62(4) 3_445 4_455 ?
S6 Hg1 S4 105.53(5) 2 4_455 ?
S5 Hg1 S4 107.89(4) . 4_455 ?
S2 Ge1 S4 116.48(6) . . ?
S2 Ge1 S7 113.47(6) . . ?
S4 Ge1 S7 107.63(6) . . ?
S2 Ge1 S1 110.05(6) . . ?
S4 Ge1 S1 106.48(5) . . ?
S7 Ge1 S1 101.48(6) . . ?
S3 Ge2 S5 109.23(6) . . ?
S3 Ge2 S6 111.75(6) . . ?
S5 Ge2 S6 111.00(6) . . ?
S3 Ge2 S1 112.16(6) . . ?
S5 Ge2 S1 108.12(6) . . ?
S6 Ge2 S1 104.47(6) . . ?
Ge2 S1 Ge1 109.15(6) . . ?
Ge2 S1 Li4 109.8(4) . 2_565 ?
Ge1 S1 Li4 107.7(4) . 2_565 ?
Ge2 S1 Li1 109.8(3) . . ?
Ge1 S1 Li1 115.8(3) . . ?
Li4 S1 Li1 104.4(6) 2_565 . ?
Ge1 S2 Li1 113.9(4) . 1_565 ?
Ge1 S2 Li2 113.5(4) . 2_564 ?
Li1 S2 Li2 108.4(5) 1_565 2_564 ?
Ge1 S2 Li4 107.9(3) . . ?
Li1 S2 Li4 108.5(6) 1_565 . ?
Li2 S2 Li4 104.2(6) 2_564 . ?
Ge2 S3 Li4 112.3(5) . . ?
Ge2 S3 Li1 111.7(3) . 2_554 ?
Li4 S3 Li1 101.3(7) . 2_554 ?
Ge2 S3 Li3 116.1(4) . 2_564 ?
Li4 S3 Li3 111.8(5) . 2_564 ?
Li1 S3 Li3 102.2(5) 2_554 2_564 ?
Ge1 S4 Li2 113.2(4) . 2_554 ?
Ge1 S4 Li1 107.9(3) . 2_554 ?
Li2 S4 Li1 113.1(6) 2_554 2_554 ?
Ge1 S4 Hg1 106.40(5) . 4_554 ?
Li2 S4 Hg1 113.2(4) 2_554 4_554 ?
Li1 S4 Hg1 102.2(3) 2_554 4_554 ?
Ge2 S5 Li2 111.6(4) . 4_454 ?
Ge2 S5 Li3 114.8(4) . . ?
Li2 S5 Li3 102.8(5) 4_454 . ?
Ge2 S5 Hg1 111.53(6) . . ?
Li2 S5 Hg1 102.8(4) 4_454 . ?
Li3 S5 Hg1 112.3(4) . . ?
Ge2 S6 Li3 115.9(3) . 1_545 ?
Ge2 S6 Li4 119.1(4) . 1_545 ?
Li3 S6 Li4 106.2(5) 1_545 1_545 ?
Ge2 S6 Hg1 104.81(5) . 2_554 ?
Li3 S6 Hg1 104.8(4) 1_545 2_554 ?
Li4 S6 Hg1 104.5(4) 1_545 2_554 ?
Ge1 S7 Li3 112.6(4) . 3_545 ?
Ge1 S7 Li2 124.0(4) . . ?
Li3 S7 Li2 112.6(6) 3_545 . ?
Ge1 S7 Hg1 107.32(6) . 3 ?
Li3 S7 Hg1 96.2(3) 3_545 3 ?
Li2 S7 Hg1 98.9(3) . 3 ?
S3 Li1 S2 116.3(6) 2 1_545 ?
S3 Li1 S4 107.6(5) 2 2 ?
S2 Li1 S4 111.1(5) 1_545 2 ?
S3 Li1 S1 110.7(5) 2 . ?
S2 Li1 S1 105.7(5) 1_545 . ?
S4 Li1 S1 104.9(5) 2 . ?
S4 Li2 S2 114.0(7) 2 2_565 ?
S4 Li2 S7 101.3(6) 2 . ?
S2 Li2 S7 108.0(7) 2_565 . ?
S4 Li2 S5 110.5(7) 2 4 ?
S2 Li2 S5 110.3(7) 2_565 4 ?
S7 Li2 S5 112.4(7) . 4 ?
S7 Li3 S6 115.3(6) 3_455 1_565 ?
S7 Li3 S3 109.5(7) 3_455 2_565 ?
S6 Li3 S3 109.7(6) 1_565 2_565 ?
S7 Li3 S5 105.5(6) 3_455 . ?
S6 Li3 S5 113.0(7) 1_565 . ?
S3 Li3 S5 103.0(6) 2_565 . ?
S3 Li4 S2 108.7(6) . . ?
S3 Li4 S6 113.3(7) . 1_565 ?
S2 Li4 S6 103.3(7) . 1_565 ?
S3 Li4 S1 111.6(7) . 2_564 ?
S2 Li4 S1 114.1(7) . 2_564 ?
S6 Li4 S1 105.6(5) 1_565 2_564 ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        27.51
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         1.081
_refine_diff_density_min         -0.665
_refine_diff_density_rms         0.140
