# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# 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_Na2Mn3S4O16
_database_code_depnum_ccdc_archive 'CCDC 1470887'
_audit_update_record             
;
2016-03-28 deposited with the CCDC.
2016-06-22 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Mn3 Na2 O16 S4 '
_chemical_formula_weight         595.04

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mn Mn 0.3368 0.7283 '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'
Na Na 0.0362 0.0249 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   'C m c 21'

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

_cell_length_a                   14.8307(18)
_cell_length_b                   9.9107(18)
_cell_length_c                   8.6845(12)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1276.5(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    100
_cell_measurement_theta_min      2.47
_cell_measurement_theta_max      27.10

_exptl_crystal_description       plate-like
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.08
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    3.096
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1156
_exptl_absorpt_coefficient_mu    3.741
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.515
_exptl_absorpt_correction_T_max  0.741
_exptl_absorpt_process_details   ?

_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  'Bruker Smart CCD'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            3503
_diffrn_reflns_av_R_equivalents  0.0246
_diffrn_reflns_av_sigmaI/netI    0.0341
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_theta_min         2.47
_diffrn_reflns_theta_max         27.10
_reflns_number_total             1359
_reflns_number_gt                1318
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_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)+(0.0280P)²+3.6060P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   none
_refine_ls_hydrogen_treatment    none
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.0017(3)
_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   0.00
_refine_ls_number_reflns         1359
_refine_ls_number_parameters     125
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0274
_refine_ls_R_factor_gt           0.0264
_refine_ls_wR_factor_ref         0.0683
_refine_ls_wR_factor_gt          0.0668
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_restrained_S_all      1.095
_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
Mn1 Mn 1.14207(5) 1.08799(6) 0.75643(8) 0.01468(17) Uani 1 1 d . . .
Mn2 Mn 1.0000 0.56345(9) 1.09755(12) 0.0169(2) Uani 1 2 d S . .
S1 S 1.0000 0.86965(14) 0.95527(15) 0.0110(3) Uani 1 2 d S . .
S2 S 0.78174(7) 0.62214(10) 1.06111(11) 0.0118(2) Uani 1 1 d . . .
S3 S 1.0000 0.30290(14) 0.93631(16) 0.0126(3) Uani 1 2 d S . .
Na Na 1.36469(14) 1.2115(2) 0.7225(3) 0.0313(5) Uani 1 1 d . . .
O1 O 1.0818(2) 0.9212(3) 0.8817(4) 0.0197(7) Uani 1 1 d . . .
O2 O 1.0000 0.7208(4) 0.9387(5) 0.0191(10) Uani 1 2 d S . .
O3 O 0.85818(19) 0.5348(3) 1.1043(5) 0.0214(7) Uani 1 1 d . . .
O4 O 1.0818(2) 1.2262(3) 0.9072(4) 0.0267(8) Uani 1 1 d . . .
O5 O 1.2014(2) 1.2373(3) 0.6060(4) 0.0227(7) Uani 1 1 d . . .
O6 O 1.0000 1.0968(4) 0.6225(5) 0.0193(10) Uani 1 2 d S . .
O7 O 1.0000 0.3441(4) 1.1018(5) 0.0160(9) Uani 1 2 d S . .
O8 O 1.0000 0.4290(4) 0.8462(6) 0.0218(11) Uani 1 2 d S . .
O9 O 0.6999(2) 0.5765(3) 1.1412(4) 0.0197(8) Uani 1 1 d . . .
O10 O 0.7668(2) 0.6156(3) 0.8934(4) 0.0202(7) Uani 1 1 d . . .


_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
Mn1 O4 2.095(3) . ?
Mn1 O9 2.096(3) 7_564 ?
Mn1 O5 2.161(3) . ?
Mn1 O1 2.172(3) . ?
Mn1 O10 2.216(3) 5 ?
Mn1 O6 2.408(2) . ?
Mn1 Na 3.534(2) . ?
Mn2 O2 2.082(4) . ?
Mn2 O3 2.123(3) . ?
Mn2 O3 2.123(3) 4_755 ?
Mn2 O8 2.161(5) 2_765 ?
Mn2 O7 2.174(4) . ?
Mn2 Na 3.554(2) 7_465 ?
Mn2 Na 3.554(2) 6_765 ?
S1 O1 1.463(3) 4_755 ?
S1 O1 1.463(3) . ?
S1 O2 1.482(4) . ?
S1 O6 1.490(5) 2_775 ?
S1 Na 3.251(3) 5_445 ?
S1 Na 3.251(3) 8_745 ?
S2 O5 1.468(3) 2_775 ?
S2 O9 1.470(3) . ?
S2 O3 1.475(3) . ?
S2 O10 1.475(3) . ?
S2 Na 3.066(2) 2_775 ?
S2 Na 3.309(2) 5_445 ?
S3 O4 1.453(3) 4_745 ?
S3 O4 1.453(3) 1_545 ?
S3 O8 1.474(5) . ?
S3 O7 1.494(5) . ?
S3 Na 3.197(2) 6_765 ?
S3 Na 3.197(2) 7_465 ?
Na O10 2.283(4) 5 ?
Na O7 2.330(3) 6_764 ?
Na O9 2.415(4) 2_774 ?
Na O1 2.620(4) 8_755 ?
Na O5 2.637(4) . ?
Na O3 2.650(4) 7_564 ?
Na O2 2.750(4) 5 ?
Na O4 2.917(4) 6_774 ?
Na S2 3.066(2) 2_774 ?
Na S3 3.197(2) 6_764 ?
Na S1 3.251(3) 5 ?
Na S2 3.309(2) 5 ?
O1 Na 2.620(4) 8_745 ?
O2 Na 2.750(4) 5_445 ?
O2 Na 2.750(4) 8_745 ?
O3 Na 2.650(4) 7_465 ?
O4 S3 1.453(3) 1_565 ?
O4 Na 2.917(4) 6_775 ?
O5 S2 1.468(3) 2_774 ?
O6 S1 1.490(5) 2_774 ?
O6 Mn1 2.408(2) 4_755 ?
O7 Na 2.330(3) 6_765 ?
O7 Na 2.330(3) 7_465 ?
O8 Mn2 2.161(5) 2_764 ?
O9 Mn1 2.096(3) 7_465 ?
O9 Na 2.415(4) 2_775 ?
O10 Mn1 2.216(3) 5_445 ?
O10 Na 2.283(4) 5_445 ?

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
O4 Mn1 O9 168.91(14) . 7_564 ?
O4 Mn1 O5 95.94(13) . . ?
O9 Mn1 O5 94.44(13) 7_564 . ?
O4 Mn1 O1 90.51(14) . . ?
O9 Mn1 O1 79.40(12) 7_564 . ?
O5 Mn1 O1 172.63(14) . . ?
O4 Mn1 O10 86.56(13) . 5 ?
O9 Mn1 O10 90.60(13) 7_564 5 ?
O5 Mn1 O10 84.26(13) . 5 ?
O1 Mn1 O10 99.73(13) . 5 ?
O4 Mn1 O6 84.54(14) . . ?
O9 Mn1 O6 98.96(14) 7_564 . ?
O5 Mn1 O6 92.26(14) . . ?
O1 Mn1 O6 84.79(13) . . ?
O10 Mn1 O6 170.06(13) 5 . ?
O4 Mn1 Na 102.96(10) . . ?
O9 Mn1 Na 81.20(10) 7_564 . ?
O5 Mn1 Na 48.09(10) . . ?
O1 Mn1 Na 133.65(10) . . ?
O10 Mn1 Na 38.92(10) 5 . ?
O6 Mn1 Na 139.88(11) . . ?
O2 Mn2 O3 96.80(9) . . ?
O2 Mn2 O3 96.80(9) . 4_755 ?
O3 Mn2 O3 164.31(17) . 4_755 ?
O2 Mn2 O8 129.49(18) . 2_765 ?
O3 Mn2 O8 88.68(11) . 2_765 ?
O3 Mn2 O8 88.68(11) 4_755 2_765 ?
O2 Mn2 O7 139.48(17) . . ?
O3 Mn2 O7 82.30(9) . . ?
O3 Mn2 O7 82.30(9) 4_755 . ?
O8 Mn2 O7 91.03(17) 2_765 . ?
O2 Mn2 Na 140.96(7) . 7_465 ?
O3 Mn2 Na 47.91(9) . 7_465 ?
O3 Mn2 Na 116.64(9) 4_755 7_465 ?
O8 Mn2 Na 73.83(11) 2_765 7_465 ?
O7 Mn2 Na 39.48(6) . 7_465 ?
O2 Mn2 Na 140.96(7) . 6_765 ?
O3 Mn2 Na 116.64(9) . 6_765 ?
O3 Mn2 Na 47.91(9) 4_755 6_765 ?
O8 Mn2 Na 73.83(11) 2_765 6_765 ?
O7 Mn2 Na 39.48(6) . 6_765 ?
Na Mn2 Na 68.75(7) 7_465 6_765 ?
O1 S1 O1 112.0(3) 4_755 . ?
O1 S1 O2 107.78(16) 4_755 . ?
O1 S1 O2 107.78(16) . . ?
O1 S1 O6 110.34(17) 4_755 2_775 ?
O1 S1 O6 110.34(17) . 2_775 ?
O2 S1 O6 108.5(3) . 2_775 ?
O1 S1 Na 52.06(14) 4_755 5_445 ?
O1 S1 Na 114.12(16) . 5_445 ?
O2 S1 Na 57.32(13) . 5_445 ?
O6 S1 Na 135.54(10) 2_775 5_445 ?
O1 S1 Na 114.12(16) 4_755 8_745 ?
O1 S1 Na 52.06(13) . 8_745 ?
O2 S1 Na 57.32(13) . 8_745 ?
O6 S1 Na 135.54(10) 2_775 8_745 ?
Na S1 Na 76.23(8) 5_445 8_745 ?
O5 S2 O9 107.9(2) 2_775 . ?
O5 S2 O3 111.0(2) 2_775 . ?
O9 S2 O3 109.48(19) . . ?
O5 S2 O10 109.2(2) 2_775 . ?
O9 S2 O10 109.3(2) . . ?
O3 S2 O10 109.9(2) . . ?
O5 S2 Na 59.28(14) 2_775 2_775 ?
O9 S2 Na 50.55(13) . 2_775 ?
O3 S2 Na 138.05(17) . 2_775 ?
O10 S2 Na 111.65(14) . 2_775 ?
O5 S2 Na 85.33(16) 2_775 5_445 ?
O9 S2 Na 144.09(15) . 5_445 ?
O3 S2 Na 95.60(15) . 5_445 ?
O10 S2 Na 35.87(14) . 5_445 ?
Na S2 Na 121.72(5) 2_775 5_445 ?
O4 S3 O4 113.1(3) 4_745 1_545 ?
O4 S3 O8 110.53(18) 4_745 . ?
O4 S3 O8 110.53(18) 1_545 . ?
O4 S3 O7 108.07(18) 4_745 . ?
O4 S3 O7 108.07(18) 1_545 . ?
O8 S3 O7 106.2(3) . . ?
O4 S3 Na 129.46(17) 4_745 6_765 ?
O4 S3 Na 65.67(15) 1_545 6_765 ?
O8 S3 Na 116.77(15) . 6_765 ?
O7 S3 Na 42.66(7) . 6_765 ?
O4 S3 Na 65.67(15) 4_745 7_465 ?
O4 S3 Na 129.46(17) 1_545 7_465 ?
O8 S3 Na 116.77(15) . 7_465 ?
O7 S3 Na 42.66(7) . 7_465 ?
Na S3 Na 77.74(9) 6_765 7_465 ?
O10 Na O7 137.85(17) 5 6_764 ?
O10 Na O9 107.46(15) 5 2_774 ?
O7 Na O9 114.58(16) 6_764 2_774 ?
O10 Na O1 100.36(14) 5 8_755 ?
O7 Na O1 99.45(14) 6_764 8_755 ?
O9 Na O1 65.44(11) 2_774 8_755 ?
O10 Na O5 72.89(12) 5 . ?
O7 Na O5 129.89(16) 6_764 . ?
O9 Na O5 55.88(11) 2_774 . ?
O1 Na O5 113.82(12) 8_755 . ?
O10 Na O3 81.08(13) 5 7_564 ?
O7 Na O3 68.85(13) 6_764 7_564 ?
O9 Na O3 132.38(14) 2_774 7_564 ?
O1 Na O3 161.14(13) 8_755 7_564 ?
O5 Na O3 84.69(11) . 7_564 ?
O10 Na O2 91.95(13) 5 5 ?
O7 Na O2 71.75(14) 6_764 5 ?
O9 Na O2 117.38(14) 2_774 5 ?
O1 Na O2 52.52(11) 8_755 5 ?
O5 Na O2 158.26(14) . 5 ?
O3 Na O2 108.78(13) 7_564 5 ?
O10 Na O4 150.60(15) 5 6_774 ?
O7 Na O4 52.65(13) 6_764 6_774 ?
O9 Na O4 69.48(11) 2_774 6_774 ?
O1 Na O4 104.20(12) 8_755 6_774 ?
O5 Na O4 82.49(12) . 6_774 ?
O3 Na O4 80.87(13) 7_564 6_774 ?
O2 Na O4 115.81(11) 5 6_774 ?
O10 Na S2 94.05(11) 5 2_774 ?
O7 Na S2 122.11(13) 6_764 2_774 ?
O9 Na S2 28.04(8) 2_774 2_774 ?
O1 Na S2 91.69(9) 8_755 2_774 ?
O5 Na S2 28.58(7) . 2_774 ?
O3 Na S2 107.02(10) 7_564 2_774 ?
O2 Na S2 144.20(12) 5 2_774 ?
O4 Na S2 69.51(8) 6_774 2_774 ?
O10 Na S3 152.33(13) 5 6_764 ?
O7 Na S3 25.74(11) 6_764 6_764 ?
O9 Na S3 93.48(11) 2_774 6_764 ?
O1 Na S3 104.81(10) 8_755 6_764 ?
O5 Na S3 106.41(11) . 6_764 ?
O3 Na S3 71.38(9) 7_564 6_764 ?
O2 Na S3 94.27(9) 5 6_764 ?
O4 Na S3 27.01(6) 6_774 6_764 ?
S2 Na S3 96.50(6) 2_774 6_764 ?
O10 Na S1 100.89(11) 5 5 ?
O7 Na S1 82.08(12) 6_764 5 ?
O9 Na S1 90.42(10) 2_774 5 ?
O1 Na S1 26.13(7) 8_755 5 ?
O5 Na S1 139.34(11) . 5 ?
O3 Na S1 135.02(10) 7_564 5 ?
O2 Na S1 26.97(9) 5 5 ?
O4 Na S1 108.29(9) 6_774 5 ?
S2 Na S1 117.53(7) 2_774 5 ?
S3 Na S1 96.75(6) 6_764 5 ?
O10 Na S2 22.24(8) 5 5 ?
O7 Na S2 131.06(13) 6_764 5 ?
O9 Na S2 110.20(11) 2_774 5 ?
O1 Na S2 81.71(10) 8_755 5 ?
O5 Na S2 91.46(10) . 5 ?
O3 Na S2 94.81(10) 7_564 5 ?
O2 Na S2 70.93(9) 5 5 ?
O4 Na S2 172.84(11) 6_774 5 ?
S2 Na S2 106.67(6) 2_774 5 ?
S3 Na S2 155.82(8) 6_764 5 ?
S1 Na S2 78.81(6) 5 5 ?
S1 O1 Mn1 145.7(2) . . ?
S1 O1 Na 101.81(16) . 8_745 ?
Mn1 O1 Na 102.38(14) . 8_745 ?
S1 O2 Mn2 133.0(3) . . ?
S1 O2 Na 95.71(15) . 5_445 ?
Mn2 O2 Na 115.29(12) . 5_445 ?
S1 O2 Na 95.71(16) . 8_745 ?
Mn2 O2 Na 115.29(12) . 8_745 ?
Na O2 Na 93.72(16) 5_445 8_745 ?
S2 O3 Mn2 132.54(19) . . ?
S2 O3 Na 131.84(17) . 7_465 ?
Mn2 O3 Na 95.61(11) . 7_465 ?
S3 O4 Mn1 143.8(2) 1_565 . ?
S3 O4 Na 87.33(17) 1_565 6_775 ?
Mn1 O4 Na 127.50(14) . 6_775 ?
S2 O5 Mn1 151.6(2) 2_774 . ?
S2 O5 Na 92.13(15) 2_774 . ?
Mn1 O5 Na 94.33(13) . . ?
S1 O6 Mn1 118.60(10) 2_774 . ?
S1 O6 Mn1 118.60(10) 2_774 4_755 ?
Mn1 O6 Mn1 122.1(2) . 4_755 ?
S3 O7 Mn2 104.9(2) . . ?
S3 O7 Na 111.60(13) . 6_765 ?
Mn2 O7 Na 104.13(13) . 6_765 ?
S3 O7 Na 111.60(14) . 7_465 ?
Mn2 O7 Na 104.13(13) . 7_465 ?
Na O7 Na 118.9(2) 6_765 7_465 ?
S3 O8 Mn2 124.1(3) . 2_764 ?
S2 O9 Mn1 143.4(2) . 7_465 ?
S2 O9 Na 101.42(16) . 2_775 ?
Mn1 O9 Na 112.00(16) 7_465 2_775 ?
S2 O10 Mn1 131.3(2) . 5_445 ?
S2 O10 Na 121.9(2) . 5_445 ?
Mn1 O10 Na 103.49(14) 5_445 5_445 ?

_diffrn_measured_fraction_theta_max 0.988
_diffrn_reflns_theta_full        27.10
_diffrn_measured_fraction_theta_full 0.988
_refine_diff_density_max         0.387
_refine_diff_density_min         -0.389
_refine_diff_density_rms         0.092
