# 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_VNU-15
_database_code_depnum_ccdc_archive 'CCDC 1443413'
_audit_update_record             
;
2015-12-20 deposited with the CCDC.
2016-01-20 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        VNU-15
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C18 H21 Fe2 N2 O14 S2'
_chemical_formula_weight         665.19

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe -1.1336 3.1974 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           orthorhombic

_symmetry_space_group_name_H-M   Fddd

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+3/4, -y+3/4, z'
'-x+3/4, y, -z+3/4'
'x, -y+3/4, -z+3/4'
'x, y+1/2, z+1/2'
'-x+3/4, -y+5/4, z+1/2'
'-x+3/4, y+1/2, -z+5/4'
'x, -y+5/4, -z+5/4'
'x+1/2, y, z+1/2'
'-x+5/4, -y+3/4, z+1/2'
'-x+5/4, y, -z+5/4'
'x+1/2, -y+3/4, -z+5/4'
'x+1/2, y+1/2, z'
'-x+5/4, -y+5/4, z'
'-x+5/4, y+1/2, -z+3/4'
'x+1/2, -y+5/4, -z+3/4'
'-x, -y, -z'
'x-3/4, y-3/4, -z'
'x-3/4, -y, z-3/4'
'-x, y-3/4, z-3/4'
'-x, -y+1/2, -z+1/2'
'x-3/4, y-1/4, -z+1/2'
'x-3/4, -y+1/2, z-1/4'
'-x, y-1/4, z-1/4'
'-x+1/2, -y, -z+1/2'
'x-1/4, y-3/4, -z+1/2'
'x-1/4, -y, z-1/4'
'-x+1/2, y-3/4, z-1/4'
'-x+1/2, -y+1/2, -z'
'x-1/4, y-1/4, -z'
'x-1/4, -y+1/2, z-3/4'
'-x+1/2, y-1/4, z-3/4'

_cell_length_a                   16.7581(7)
_cell_length_b                   18.8268(9)
_cell_length_c                   38.9998(18)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     12304.5(10)
_cell_formula_units_Z            16
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    300
_cell_measurement_theta_min      3.6931\%
_cell_measurement_theta_max      67.9142\%

_exptl_crystal_description       Octahedral
_exptl_crystal_colour            red
_exptl_crystal_size_max          0.234
_exptl_crystal_size_mid          0.143
_exptl_crystal_size_min          0.13
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.436
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             5424
_exptl_absorpt_coefficient_mu    9.385
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.4790
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  BrukerD8Venturediffractometer
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            18293
_diffrn_reflns_av_R_equivalents  0.1476
_diffrn_reflns_av_sigmaI/netI    0.0651
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_theta_min         3.71
_diffrn_reflns_theta_max         63.66
_reflns_number_total             2535
_reflns_number_gt                1984
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          SQUEEZE
# SQUEEZE RESULTS (APPEND TO CIF)
# Note: Data are Listed for all Voids in the P1 Unit Cell
# i.e. Centre of Gravity, Solvent Accessible Volume,
# Recovered number of Electrons in the Void and
# Details about the Squeezed Material
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.011 -0.010 0.125 754 233 ' '
2 -0.005 0.252 0.375 754 233 ' '
3 -0.013 0.486 0.625 754 233 ' '
4 -0.005 0.752 0.875 754 233 ' '
_platon_squeeze_details          
;
;
_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)+(0.0633P)²+31.0633P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2535
_refine_ls_number_parameters     196
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0768
_refine_ls_R_factor_gt           0.0547
_refine_ls_wR_factor_ref         0.1324
_refine_ls_wR_factor_gt          0.1226
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_restrained_S_all      1.070
_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
C1 C 0.6153(14) 0.1109(12) 0.1893(2) 0.026(5) Uani 0.50 1 d P A -1
C2 C 0.6194(5) 0.0401(6) 0.1747(2) 0.020(2) Uani 0.50 1 d P A -1
H2 H 0.6249 -0.0001 0.1893 0.024 Uiso 0.50 1 calc PR A -1
C3 C 0.6153(5) 0.0313(4) 0.1400(2) 0.0188(18) Uani 0.50 1 d P A -1
C4 C 0.6132(5) 0.1595(4) 0.13171(19) 0.019(2) Uiso 0.50 1 d P A -1
C5 C 0.6129(6) 0.1674(6) 0.1687(3) 0.023(2) Uani 0.50 1 d P A -1
H5 H 0.6109 0.2136 0.1784 0.027 Uiso 0.50 1 calc PR A -1
Fe2 Fe 0.3750 0.3750 0.20508(2) 0.0213(3) Uani 1 2 d S . .
N1 N 0.4743(3) 0.5501(3) 0.24571(13) 0.0544(13) Uani 1 1 d . . .
HN1A H 0.4221 0.5616 0.2505 0.065 Uiso 0.50 1 calc PR . .
HN1B H 0.4750 0.5050 0.2367 0.065 Uiso 0.50 1 calc PR . .
C8 C 0.4235(3) 0.1067(2) 0.15932(11) 0.0309(11) Uani 1 1 d . . .
H8 H 0.4246 0.0939 0.1829 0.037 Uiso 1 1 calc R . .
Fe1 Fe 0.5000 0.2500 0.2500 0.0217(3) Uani 1 2 d S . .
C9 C 0.6250 0.1250 0.22704(15) 0.0257(15) Uani 1 2 d S . .
S1 S 0.56956(8) 0.39589(7) 0.20846(4) 0.0474(4) Uani 1 1 d . . .
O5 O 0.60037(17) 0.17851(15) 0.24403(7) 0.0256(7) Uani 1 1 d . . .
O6 O 0.48723(18) 0.42304(16) 0.20864(8) 0.0356(8) Uani 1 1 d . . .
H1 H 0.6250 -0.015(4) 0.1250 0.05(2) Uiso 1 2 d S . .
O7 O 0.40760(19) 0.29728(16) 0.16945(7) 0.0338(8) Uani 1 1 d . . .
O8 O 0.4441(2) 0.21393(16) 0.20721(8) 0.0355(8) Uani 1 1 d . . .
O9 O 0.57243(19) 0.32575(18) 0.22430(10) 0.0481(10) Uani 1 1 d . . .
C11 C 0.4256(3) 0.2345(2) 0.17740(11) 0.0265(10) Uani 1 1 d . . .
O10 O 0.5946(3) 0.3878(3) 0.17277(13) 0.101(2) Uani 1 1 d . . .
C12 C 0.4232(3) 0.1785(2) 0.15001(11) 0.0284(11) Uani 1 1 d . . .
C13 C 0.4223(3) 0.1957(2) 0.11555(11) 0.0325(11) Uani 1 1 d . . .
H13 H 0.4208 0.2442 0.1088 0.039 Uiso 1 1 calc R . .
O11 O 0.6220(3) 0.4437(3) 0.2255(2) 0.128(3) Uani 1 1 d . . .
C14 C 0.5054(4) 0.6001(4) 0.2201(2) 0.083(2) Uani 1 1 d . . .
H14A H 0.4724 0.5979 0.1994 0.125 Uiso 1 1 calc R . .
H14B H 0.5605 0.5873 0.2144 0.125 Uiso 1 1 calc R . .
H14C H 0.5041 0.6484 0.2295 0.125 Uiso 1 1 calc R . .
C15 C 0.5200(5) 0.5509(5) 0.2772(2) 0.096(3) Uani 1 1 d . . .
H15D H 0.5735 0.5319 0.2728 0.144 Uiso 1 1 calc R . .
H15E H 0.4931 0.5215 0.2944 0.144 Uiso 1 1 calc R . .
H15G H 0.5242 0.5998 0.2856 0.144 Uiso 1 1 calc R . .


_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
C1 C5 1.33(2) . ?
C1 C2 1.45(2) . ?
C1 C9 1.504(11) . ?
C2 C3 1.366(12) . ?
C4 C5 1.449(13) . ?
Fe2 O7 2.091(3) . ?
Fe2 O7 2.091(3) 2 ?
Fe2 O6 2.091(3) 2 ?
Fe2 O6 2.091(3) . ?
Fe2 O5 2.264(3) 26_565 ?
Fe2 O5 2.264(3) 21_655 ?
N1 C15 1.446(9) . ?
N1 C14 1.466(8) . ?
C8 C13 1.384(6) 8_544 ?
C8 C12 1.398(6) . ?
Fe1 O8 2.030(3) 21_655 ?
Fe1 O8 2.030(3) . ?
Fe1 O9 2.124(3) 21_655 ?
Fe1 O9 2.124(3) . ?
Fe1 O5 2.167(3) 21_655 ?
Fe1 O5 2.167(3) . ?
C9 O5 1.274(4) . ?
C9 O5 1.274(4) 14_545 ?
C9 C1 1.505(11) 14_545 ?
S1 O11 1.422(5) . ?
S1 O9 1.459(3) . ?
S1 O10 1.462(5) . ?
S1 O6 1.471(3) . ?
O5 Fe2 2.264(3) 21_655 ?
O7 C11 1.259(5) . ?
O8 C11 1.264(5) . ?
C11 C12 1.502(6) . ?
C12 C13 1.383(6) . ?
C13 C8 1.384(6) 8_544 ?

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
C5 C1 C2 119.9(10) . . ?
C5 C1 C9 116.9(15) . . ?
C2 C1 C9 122.6(14) . . ?
C3 C2 C1 119.7(10) . . ?
C1 C5 C4 121.2(12) . . ?
O7 Fe2 O7 96.69(17) . 2 ?
O7 Fe2 O6 88.66(12) . 2 ?
O7 Fe2 O6 96.42(13) 2 2 ?
O7 Fe2 O6 96.42(13) . . ?
O7 Fe2 O6 88.65(12) 2 . ?
O6 Fe2 O6 172.37(18) 2 . ?
O7 Fe2 O5 160.37(11) . 26_565 ?
O7 Fe2 O5 102.92(11) 2 26_565 ?
O6 Fe2 O5 88.29(12) 2 26_565 ?
O6 Fe2 O5 85.02(12) . 26_565 ?
O7 Fe2 O5 102.92(11) . 21_655 ?
O7 Fe2 O5 160.37(11) 2 21_655 ?
O6 Fe2 O5 85.02(12) 2 21_655 ?
O6 Fe2 O5 88.29(12) . 21_655 ?
O5 Fe2 O5 57.49(14) 26_565 21_655 ?
C15 N1 C14 112.5(6) . . ?
C13 C8 C12 120.5(4) 8_544 . ?
O8 Fe1 O8 180.00(16) 21_655 . ?
O8 Fe1 O9 95.76(14) 21_655 21_655 ?
O8 Fe1 O9 84.24(14) . 21_655 ?
O8 Fe1 O9 84.24(14) 21_655 . ?
O8 Fe1 O9 95.76(14) . . ?
O9 Fe1 O9 179.998(1) 21_655 . ?
O8 Fe1 O5 93.55(12) 21_655 21_655 ?
O8 Fe1 O5 86.45(12) . 21_655 ?
O9 Fe1 O5 85.57(12) 21_655 21_655 ?
O9 Fe1 O5 94.43(12) . 21_655 ?
O8 Fe1 O5 86.45(12) 21_655 . ?
O8 Fe1 O5 93.54(12) . . ?
O9 Fe1 O5 94.43(12) 21_655 . ?
O9 Fe1 O5 85.57(12) . . ?
O5 Fe1 O5 180.00(12) 21_655 . ?
O5 C9 O5 117.4(5) . 14_545 ?
O5 C9 C1 127.8(12) . . ?
O5 C9 C1 113.9(11) 14_545 . ?
O5 C9 C1 113.9(11) . 14_545 ?
O5 C9 C1 127.8(12) 14_545 14_545 ?
C1 C9 C1 23.8(10) . 14_545 ?
O11 S1 O9 110.8(3) . . ?
O11 S1 O10 109.4(4) . . ?
O9 S1 O10 107.4(3) . . ?
O11 S1 O6 110.9(3) . . ?
O9 S1 O6 110.09(19) . . ?
O10 S1 O6 108.1(2) . . ?
C9 O5 Fe1 143.0(2) . . ?
C9 O5 Fe2 92.6(3) . 21_655 ?
Fe1 O5 Fe2 108.88(11) . 21_655 ?
S1 O6 Fe2 133.8(2) . . ?
C11 O7 Fe2 123.8(3) . . ?
C11 O8 Fe1 140.0(3) . . ?
S1 O9 Fe1 142.1(2) . . ?
O7 C11 O8 125.0(4) . . ?
O7 C11 C12 118.6(4) . . ?
O8 C11 C12 116.4(4) . . ?
C13 C12 C8 118.6(4) . . ?
C13 C12 C11 121.8(4) . . ?
C8 C12 C11 119.6(4) . . ?
C12 C13 C8 120.9(4) . 8_544 ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        63.66
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.651
_refine_diff_density_min         -0.401
_refine_diff_density_rms         0.085
_exptl_crystal_preparation       'proton conductivity'
