# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# 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_srini43neu
_database_code_depnum_ccdc_archive 'CCDC 1873857'
_audit_update_record             
;
2018-10-17 deposited with the CCDC.
2018-11-27 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'H10 N4 S4 W'
_chemical_formula_weight         378.21

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 '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'
W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'

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

_cell_length_a                   6.6033(8)
_cell_length_b                   7.4965(8)
_cell_length_c                   18.663(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     923.8(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    3372
_cell_measurement_theta_min      2.18
_cell_measurement_theta_max      29.99

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.719
_exptl_crystal_F_000             704
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.14
_exptl_absorpt_coefficient_mu    13.341
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   Numerical
_exptl_absorpt_correction_T_min  0.1401
_exptl_absorpt_correction_T_max  0.2348
_exptl_absorpt_process_details   'Stadi-4 program package (STOE, 2014)'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'STOE Stadi-4 4-circle diffractometer'
_diffrn_measurement_method       'Phi scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            3372
_diffrn_reflns_av_unetI/netI     0.0274
_diffrn_reflns_av_R_equivalents  0.0254
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       1
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_limit_l_max       3
_diffrn_reflns_theta_min         2.183
_diffrn_reflns_theta_max         29.993
_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 0.946
_diffrn_reflns_point_group_measured_fraction_full 0.976
_reflns_number_total             2544
_reflns_number_gt                2396
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.612
_reflns_Friedel_fraction_max     0.869
_reflns_Friedel_fraction_full    0.940

_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       'Stadi-4 program package (STOE, 2014)'
_computing_cell_refinement       'Stadi-4 program package(STOE, 2014)'
_computing_data_reduction        'Stadi-4 program package(STOE, 2014)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 ?
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0219P)²+0.2248P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.0020(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Flack x determined using 899 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(9)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         2544
_refine_ls_number_parameters     83
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0233
_refine_ls_R_factor_gt           0.0186
_refine_ls_wR_factor_ref         0.0442
_refine_ls_wR_factor_gt          0.0431
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_restrained_S_all      1.046
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
W1 W 0.07330(3) 0.51138(2) 0.87053(2) 0.01902(7) Uani 1 1 d . . . . .
S1 S -0.2269(2) 0.4793(3) 0.91789(8) 0.0328(3) Uani 1 1 d . . . . .
S2 S 0.0483(2) 0.55159(19) 0.75504(8) 0.0285(3) Uani 1 1 d . . . . .
S3 S 0.2286(3) 0.7428(2) 0.91783(9) 0.0305(3) Uani 1 1 d . . . . .
S4 S 0.2551(2) 0.2722(2) 0.89342(9) 0.0276(3) Uani 1 1 d . . . . .
N1 N 0.8642(8) 1.0316(7) 0.9457(3) 0.0349(12) Uani 1 1 d . . . . .
H1N1 H 0.9335 0.9327 0.9578 0.052 Uiso 1 1 d R U . . .
H2N1 H 0.8515 1.1027 0.9843 0.052 Uiso 1 1 d R U . . .
H3N1 H 0.9319 1.0919 0.9115 0.052 Uiso 1 1 d R U . . .
N2 N 0.6694(8) 0.9806(9) 0.9196(3) 0.0388(13) Uani 1 1 d . . . . .
H1N2 H 0.6154 0.8984 0.9491 0.047 Uiso 1 1 d R U . . .
H2N2 H 0.5884 1.0771 0.9177 0.047 Uiso 1 1 d R U . . .
N3 N 0.5858(9) 0.7736(6) 0.7807(3) 0.0294(10) Uani 1 1 d . . . . .
H1N3 H 0.7070 0.8095 0.7641 0.044 Uiso 1 1 d R U . . .
H2N3 H 0.5628 0.6596 0.7679 0.044 Uiso 1 1 d R U . . .
H3N3 H 0.5836 0.7795 0.8289 0.044 Uiso 1 1 d R U . . .
N4 N 0.4297(9) 0.8839(7) 0.7525(3) 0.0366(12) Uani 1 1 d . . . . .
H1N4 H 0.3175 0.8725 0.7795 0.044 Uiso 1 1 d R U . . .
H2N4 H 0.4027 0.8520 0.7070 0.044 Uiso 1 1 d R U . . .

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
W1 0.01792(10) 0.01915(9) 0.01999(9) 0.00056(8) -0.00028(7) 0.00010(8)
S1 0.0222(6) 0.0420(8) 0.0341(7) 0.0004(7) 0.0058(6) 0.0002(7)
S2 0.0312(8) 0.0307(6) 0.0238(6) 0.0033(5) -0.0014(6) 0.0029(6)
S3 0.0324(9) 0.0253(6) 0.0337(7) -0.0039(6) -0.0003(7) -0.0057(6)
S4 0.0258(9) 0.0242(6) 0.0327(7) 0.0030(5) -0.0016(7) 0.0050(5)
N1 0.031(3) 0.035(3) 0.039(3) 0.000(2) 0.006(2) -0.006(2)
N2 0.034(3) 0.048(3) 0.035(3) 0.003(3) -0.001(2) 0.000(3)
N3 0.031(3) 0.029(2) 0.028(2) 0.0058(18) 0.002(2) 0.000(2)
N4 0.030(3) 0.033(2) 0.046(3) 0.010(2) -0.004(3) 0.002(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
W1 S2 2.1826(14) . ?
W1 S1 2.1839(15) . ?
W1 S4 2.1997(15) . ?
W1 S3 2.2000(16) . ?
N1 N2 1.427(8) . ?
N3 N4 1.423(7) . ?

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 W1 S1 110.26(6) . . ?
S2 W1 S4 110.21(6) . . ?
S1 W1 S4 109.09(7) . . ?
S2 W1 S3 108.82(6) . . ?
S1 W1 S3 110.34(7) . . ?
S4 W1 S3 108.10(6) . . ?

_refine_diff_density_max         1.017
_refine_diff_density_min         -0.586
_refine_diff_density_rms         0.130

_shelxl_version_number           2014-3

_shelx_res_file                  
;
TITL H2N-NH3)2 WS4 in P2(1)2(1)2(1) (Srini43)
CELL 0.71073   6.6033   7.4965  18.6625  90.000  90.000  90.000
ZERR    4.00   0.0008   0.0008   0.0030   0.000   0.000   0.000
LATT -1
SYMM 0.5-X, -Y, 0.5+Z
SYMM -X, 0.5+Y, 0.5-Z
SYMM 0.5+X, 0.5-Y, -Z
SFAC N H S W
UNIT 16 40 16 4
L.S. 10
ACTA
HTAB
WGHT    0.021900    0.224800
EXTI    0.001976
FVAR       0.33524
W1    4    0.073300    0.511385    0.870535    11.00000    0.01792    0.01915 =
         0.01999    0.00056   -0.00028    0.00010
S1    3   -0.226941    0.479301    0.917889    11.00000    0.02216    0.04204 =
         0.03405    0.00042    0.00579    0.00024
S2    3    0.048337    0.551589    0.755043    11.00000    0.03120    0.03068 =
         0.02376    0.00327   -0.00138    0.00287
S3    3    0.228578    0.742800    0.917833    11.00000    0.03244    0.02533 =
         0.03365   -0.00389   -0.00034   -0.00572
S4    3    0.255065    0.272173    0.893419    11.00000    0.02580    0.02418 =
         0.03274    0.00295   -0.00164    0.00502
N1    1    0.864233    1.031551    0.945652    11.00000    0.03087    0.03479 =
         0.03902    0.00036    0.00561   -0.00602
AFIX   3
H1N1  2    0.933523    0.932711    0.957823    11.00000   -1.50000
H2N1  2    0.851483    1.102671    0.984252    11.00000   -1.50000
H3N1  2    0.931873    1.091913    0.911522    11.00000   -1.50000
AFIX   0
N2    1    0.669398    0.980629    0.919593    11.00000    0.03378    0.04798 =
         0.03460    0.00320   -0.00126   -0.00024
AFIX   3
H1N2  2    0.615378    0.898389    0.949073    11.00000   -1.20000
H2N2  2    0.588388    1.077069    0.917733    11.00000   -1.20000
AFIX   0
N3    1    0.585813    0.773580    0.780743    11.00000    0.03112    0.02889 =
         0.02821    0.00581    0.00211   -0.00033
AFIX   3
H1N3  2    0.707023    0.809530    0.764063    11.00000   -1.50000
H2N3  2    0.562823    0.659610    0.767943    11.00000   -1.50000
H3N3  2    0.583583    0.779480    0.828903    11.00000   -1.50000
AFIX   0
N4    1    0.429673    0.883871    0.752514    11.00000    0.03031    0.03313 =
         0.04622    0.00998   -0.00428    0.00167
AFIX   3
H1N4  2    0.317472    0.872491    0.779504    11.00000   -1.20000
H2N4  2    0.402732    0.852001    0.707004    11.00000   -1.20000

AFIX   0
HKLF 4

REM  H2N-NH3)2 WS4 in P2(1)2(1)2(1) (Srini43)
REM R1 =  0.0186 for    2396 Fo > 4sig(Fo)  and  0.0233 for all    2544 data
REM     83 parameters refined using      0 restraints

END

WGHT      0.0219      0.2248

REM Instructions for potential hydrogen bonds
EQIV $1 x+1, y, z
HTAB N1 S3_$1
EQIV $2 x+1/2, -y+3/2, -z+2
HTAB N1 S4_$2
EQIV $3 x+1, y+1, z
HTAB N1 S4_$3
HTAB N2 S3
HTAB N2 S3_$2
EQIV $4 x, y+1, z
HTAB N2 S4_$4
HTAB N3 S2_$1
EQIV $5 -x+1, y+1/2, -z+3/2
HTAB N3 S2_$5
HTAB N3 S4_$5
EQIV $6 -x+1, y-1/2, -z+3/2
HTAB N3 N4_$6
HTAB N3 S3
HTAB N3 N2
HTAB N4 S2
EQIV $7 -x, y+1/2, -z+3/2
HTAB N4 S2_$7
HTAB N4 S3
HTAB N4 S1_$7
HTAB N4 S4_$5

REM Highest difference peak  1.017,  deepest hole -0.586,  1-sigma level  0.130
Q1    1  -0.1495  0.5195  0.8680  11.00000  0.05    1.02
Q2    1   0.3013  0.5400  0.8748  11.00000  0.05    0.85
Q3    1   0.1489  0.3628  0.8738  11.00000  0.05    0.81
Q4    1   0.0404  0.6241  0.8720  11.00000  0.05    0.75
Q5    1   0.0179  0.3764  0.8708  11.00000  0.05    0.74
Q6    1  -0.0442  0.5116  0.8967  11.00000  0.05    0.55
Q7    1   0.3278  1.0130  0.8791  11.00000  0.05    0.50
Q8    1   0.0014  0.7295  0.8870  11.00000  0.05    0.45
Q9    1   0.2997  0.5259  0.7598  11.00000  0.05    0.45
Q10   1   0.6661  1.2366  0.8685  11.00000  0.05    0.45
Q11   1   0.6018  0.9926  0.8884  11.00000  0.05    0.44
Q12   1   1.0044  1.2541  0.9091  11.00000  0.05    0.42
Q13   1   1.0571  1.0614  1.0223  11.00000  0.05    0.40
Q14   1   0.3513  0.2682  0.8272  11.00000  0.05    0.40
Q15   1   0.6827  0.7784  0.8686  11.00000  0.05    0.40
Q16   1   0.5049  0.7628  0.8885  11.00000  0.05    0.40
Q17   1   0.6183  0.8550  0.8164  11.00000  0.05    0.39
Q18   1   0.6876  1.0789  0.8738  11.00000  0.05    0.39
Q19   1   0.6323  0.6816  0.8678  11.00000  0.05    0.38
Q20   1   0.6566  0.9044  0.8773  11.00000  0.05    0.38
;
_shelx_res_checksum              85419
####################################################################### 
# 
# 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_AHTT
_database_code_depnum_ccdc_archive 'CCDC 1873859'
_audit_update_record             
;
2018-10-17 deposited with the CCDC.
2018-11-27 downloaded from the CCDC.
;
_chemical_name_mineral           ?(NH4)(N2H5)WS4?
_chemical_formula_sum            N3H9W1S4
_chemical_formula_weight         363.2056
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_H-M_alt        'P n m a'
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z '
'-x, y+1/2, -z '
'-x+1/2, -y, z+1/2 '
'-x+1/2, y+1/2, z+1/2 '
'x, -y+1/2, z '
'-x, -y, -z '
'x+1/2, -y+1/2, -z+1/2 '
'x+1/2, y, -z+1/2 '
_cell_length_a                   10.53537(17)
_cell_length_b                   7.07583(11)
_cell_length_c                   11.75952(17)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     876.63(2)
_cell_formula_units_Z            4

_cell_measurement_radiation      'Cu K\a'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_wavelength     1.5418
_diffrn_ambient_temperature      298
_diffrn_source                   'sealed X-ray tube'
_diffrn_measurement_device_type  'Panalytical Empyrean'
_diffrn_detector                 'PIXcel 1D'



_exptl_crystal_description       powder
_exptl_absorpt_correction_type   none

_pd_meas_2theta_range_min        2.5
_pd_meas_2theta_range_max        50
_cell_measurement_temperature    298

_pd_proc_ls_prof_R_factor        0.0305
_pd_proc_ls_prof_wR_factor       0.0415
_pd_proc_ls_prof_wR_expected     0.0198
_refine_ls_R_I_factor            0.0194
_refine_ls_goodness_of_fit_all   2.095


loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_symmetry_multiplicity
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_B_iso_or_equiv
W1 W 4 0.279(3) 0.25 0.9209(8) 1 0.13(16)
S1 S 4 0.287(4) 0.25 1.1137(9) 1 2.97(8)
S2 S 4 0.079(3) 0.25 0.8647(8) 1 2.97(8)
S3 S 8 0.373(3) -0.0031(5) 0.8546(11) 1 2.97(8)
N1 N 4 -0.849(16) 0.25 0.583(18) 1 1.0(2)
N2 N 4 -0.714(16) 0.25 0.585(16) 1 1.0(2)
N3 N 4 -0.074(18) 0.25 -0.87(7) 1 1.0(2)
H1 H 4 -0.879(17) 0.25 0.655(18) 1 2
H2 H 8 -0.864(16) 0.1376853 0.550(18) 1 2
H5 H 8 -0.685(17) 0.3573958 0.617(16) 1 2
H6 H 4 -0.1(2) 0.25 -0.94(7) 1 2
H7 H 4 0.0(2) 0.25 -0.88(7) 1 2
H8 H 8 -0.1(2) 0.1510907 -0.84(7) 1 2

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_1
_geom_bond_site_symmetry_2
W1 S1 2.270(5) 1_555 1_555
W1 S2 2.205(5) 1_555 1_555
W1 S3 2.190(3) 1_555 1_555
W1 S3 2.190(3) 1_555 5_555


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_2
_geom_angle_site_symmetry_3
S1 W1 S2 109.60(18) 1_555 1_555 1_555
S1 W1 S3 109.75(12) 1_555 1_555 1_555
S2 W1 S3 109.00(15) 1_555 1_555 1_555
S3 W1 S3 109.7(2) 5_555 1_555 1_555
