# Electronic Supplementary Material for CrystEngComm
# This journal is (c) The Royal Society of Chemistry 2009

data_global
_journal_name_full               CrystEngComm

_journal_coden_Cambridge         1350
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Annie Powell'
_publ_contact_author_email       POWELL@AOC.UNI-KARLSRUHE.DE

_publ_section_title              
;
Photo- and Thermally-Enhanced Charge Separation
in Supramolecular Viologen-Hexacyanoferrate Complexes
;
loop_
_publ_author_name
'Annie Powell'
'Ahmed S. Abouelwafa'
'Christopher E. Anson'
'Teodor S. Balaban'
'Valeriu Mereacre'

# Attachment 'viologen.cif'

data_v1a
_database_code_depnum_ccdc_archive 'CCDC 692001'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '2(C22 H14 N6 O8), (C6 Fe N6), 20(H2 O)'
_chemical_formula_sum            'C50 H68 Fe N18 O36'
_chemical_formula_weight         1553.07

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 '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 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   'I b a m'
_symmetry_space_group_name_Hall  '-I 2 2c'

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

_cell_length_a                   26.3998(15)
_cell_length_b                   11.3528(6)
_cell_length_c                   22.2355(12)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     6664.2(6)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    8752
_cell_measurement_theta_min      2.39
_cell_measurement_theta_max      28.13

_exptl_crystal_description       block
_exptl_crystal_colour            green
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.18
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.548
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             3232
_exptl_absorpt_coefficient_mu    0.338
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.845
_exptl_absorpt_correction_T_max  0.951
_exptl_absorpt_process_details   'SADABS (Bruker AXS Inc., 2000)'

_exptl_special_details           
;
The crystal used had been freshly prepared and grown in the dark.
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'rotating anode'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker SMART Apex'
_diffrn_measurement_method       'CCD area detector'
_diffrn_detector_area_resol_mean 8.333
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            22965
_diffrn_reflns_av_R_equivalents  0.0232
_diffrn_reflns_av_sigmaI/netI    0.0162
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_theta_min         1.54
_diffrn_reflns_theta_max         28.13
_reflns_number_total             3955
_reflns_number_gt                3343
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART-NT 5.6 (Bruker AXS Inc., 2000)'
_computing_cell_refinement       'SMART-NT 5.6 (Bruker AXS Inc., 2000)'
_computing_data_reduction        'SAINT+ 6.0 (Bruker AXS Inc., 2000)'
_computing_structure_solution    'SHELXTL 5.1 (Bruker AXS Inc., 1997)'
_computing_structure_refinement  'SHELXTL 5.1 (Bruker AXS Inc., 1997)'
_computing_molecular_graphics    'SHELXTL 5.1 (Bruker AXS Inc., 1997)'
_computing_publication_material  'SHELXTL 5.1 (Bruker AXS Inc., 1997)'

_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.
Unlike most atoms of the viologen molecule, the thermal parameters of the
atoms of the hexacyanometallate complex anion are markedly anisotropic,
suggesting unresolved disorder between two closely separated sites.
Attempts to resolve this disorder, or twinned refinements of the structure
in lower-symmetry space groups, did not improve the structure.
Some of the of the lattice water molecules, those corresponding to O(15),
O(16) and O(17), were disordered over two or more sites.
The H-atoms bonded to O(11) and O(12) were located and refined with
restraints on the O-H distances.
;

_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)+(0.0986P)²+27.7600P] 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         3955
_refine_ls_number_parameters     267
_refine_ls_number_restraints     4
_refine_ls_R_factor_all          0.0819
_refine_ls_R_factor_gt           0.0721
_refine_ls_wR_factor_ref         0.2023
_refine_ls_wR_factor_gt          0.1928
_refine_ls_goodness_of_fit_ref   0.991
_refine_ls_restrained_S_all      0.992
_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
Fe1 Fe 0.5000 0.5000 0.5000 0.0578(4) Uani 1 4 d S . .
C1 C 0.5000 0.5000 0.4141(2) 0.0470(11) Uani 1 2 d S . .
N1 N 0.5000 0.5000 0.36180(16) 0.0407(8) Uani 1 2 d S . .
C2 C 0.4348(2) 0.4280(5) 0.5000 0.0580(15) Uani 1 2 d S . .
N2 N 0.39496(19) 0.3830(4) 0.5000 0.0571(12) Uani 1 2 d S . .
C3 C 0.4691(3) 0.6509(7) 0.5000 0.067(2) Uani 1 2 d S . .
N3 N 0.4498(2) 0.7426(6) 0.5000 0.0747(19) Uani 1 2 d S . .
C4 C 0.45500(12) 0.7536(3) 0.33823(18) 0.0449(8) Uani 1 1 d . . .
H4A H 0.4631 0.6742 0.3287 0.054 Uiso 1 1 calc R . .
C5 C 0.49226(11) 0.8374(3) 0.33899(19) 0.0471(8) Uani 1 1 d . . .
H5A H 0.5263 0.8162 0.3303 0.057 Uiso 1 1 calc R . .
C6 C 0.48013(11) 0.9540(2) 0.35260(15) 0.0368(6) Uani 1 1 d . . .
C7 C 0.43018(11) 0.9814(2) 0.36674(15) 0.0385(7) Uani 1 1 d . . .
H7A H 0.4212 1.0598 0.3771 0.046 Uiso 1 1 calc R . .
C8 C 0.39396(11) 0.8952(2) 0.36579(14) 0.0366(6) Uani 1 1 d . . .
H8A H 0.3598 0.9136 0.3755 0.044 Uiso 1 1 calc R . .
N4 N 0.40702(9) 0.7837(2) 0.35097(11) 0.0326(5) Uani 1 1 d . . .
C9 C 0.36780(10) 0.6937(2) 0.34971(12) 0.0303(6) Uani 1 1 d . . .
C10 C 0.33263(10) 0.6859(2) 0.30339(12) 0.0278(5) Uani 1 1 d . . .
C11 C 0.29422(10) 0.6036(2) 0.30596(12) 0.0288(5) Uani 1 1 d . . .
H11A H 0.2695 0.5988 0.2750 0.035 Uiso 1 1 calc R . .
C12 C 0.29278(11) 0.5284(3) 0.35490(13) 0.0333(6) Uani 1 1 d . . .
C13 C 0.32799(12) 0.5311(3) 0.40022(13) 0.0401(7) Uani 1 1 d . . .
H13A H 0.3264 0.4770 0.4327 0.048 Uiso 1 1 calc R . .
C14 C 0.36609(12) 0.6154(3) 0.39715(13) 0.0386(7) Uani 1 1 d . . .
H14A H 0.3911 0.6192 0.4279 0.046 Uiso 1 1 calc R . .
N5 N 0.33502(9) 0.7615(2) 0.24929(11) 0.0325(5) Uani 1 1 d . . .
O1 O 0.36820(8) 0.83596(17) 0.24553(10) 0.0404(5) Uani 1 1 d . . .
O2 O 0.30315(8) 0.7434(2) 0.21036(10) 0.0435(5) Uani 1 1 d . . .
N6 N 0.25131(10) 0.4410(2) 0.35762(12) 0.0417(6) Uani 1 1 d . . .
O3 O 0.22149(8) 0.4380(2) 0.31539(11) 0.0438(5) Uani 1 1 d . . .
O4 O 0.24933(10) 0.3763(2) 0.40152(12) 0.0586(7) Uani 1 1 d . . .
O11 O 0.38963(11) 0.2600(2) 0.38494(14) 0.0564(7) Uani 1 1 d D . .
H111 H 0.396(2) 0.294(4) 0.4196(18) 0.085 Uiso 1 1 d D . .
H112 H 0.3586(15) 0.217(4) 0.399(2) 0.085 Uiso 1 1 d D . .
O12 O 0.42046(12) 0.4043(3) 0.28865(15) 0.0674(8) Uani 1 1 d D . .
H121 H 0.4487(16) 0.434(5) 0.304(3) 0.101 Uiso 1 1 d D . .
H122 H 0.408(2) 0.362(5) 0.322(2) 0.101 Uiso 1 1 d D . .
O13 O 0.19285(13) 0.6106(4) 0.41707(16) 0.0885(12) Uani 1 1 d . . .
O14 O 0.26540(17) 0.6945(4) 0.5000 0.0700(12) Uani 1 2 d S . .
O15A O 0.3448(6) 0.8764(16) 0.5000 0.082(4) Uiso 0.34 2 d SP A 1
O17A O 0.3852(10) 1.106(2) 0.5000 0.137(8) Uiso 0.34 2 d SP B 1
O15B O 0.3560(3) 0.8179(7) 0.5000 0.0556(16) Uiso 0.56 2 d SP C 2
O17B O 0.3640(5) 1.0474(11) 0.5000 0.098(3) Uiso 0.56 2 d SP D 2
O15C O 0.3813(5) 0.9712(12) 0.5000 0.029(3) Uiso 0.20 2 d SP E 3
O16A O 0.4750(5) 1.0713(12) 0.5000 0.089(3) Uiso 0.50 2 d SP F 1
O16B O 0.4596(4) 1.1143(10) 0.5000 0.073(3) Uiso 0.50 2 d SP G 2


_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
Fe1 C3 1.897(9) 9_666 ?
Fe1 C3 1.897(9) . ?
Fe1 C2 1.906(5) 9_666 ?
Fe1 C2 1.906(5) . ?
Fe1 C1 1.910(4) . ?
Fe1 C1 1.910(4) 9_666 ?
C1 N1 1.163(6) . ?
C2 N2 1.169(7) . ?
C3 N3 1.159(10) . ?
C4 N4 1.342(4) . ?
C4 C5 1.369(4) . ?
C4 H4A 0.9500 . ?
C5 C6 1.395(4) . ?
C5 H5A 0.9500 . ?
C6 C7 1.391(4) . ?
C6 C6 1.481(5) 2_675 ?
C7 C8 1.368(4) . ?
C7 H7A 0.9500 . ?
C8 N4 1.353(4) . ?
C8 H8A 0.9500 . ?
N4 C9 1.455(3) . ?
C9 C14 1.380(4) . ?
C9 C10 1.390(4) . ?
C10 C11 1.380(4) . ?
C10 N5 1.479(3) . ?
C11 C12 1.384(4) . ?
C11 H11A 0.9500 . ?
C12 C13 1.371(4) . ?
C12 N6 1.479(4) . ?
C13 C14 1.390(4) . ?
C13 H13A 0.9500 . ?
C14 H14A 0.9500 . ?
N5 O1 1.220(3) . ?
N5 O2 1.224(3) . ?
N6 O4 1.223(4) . ?
N6 O3 1.226(4) . ?
O11 H111 0.88(3) . ?
O11 H112 1.01(3) . ?
O12 H121 0.89(3) . ?
O12 H122 0.94(3) . ?

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
C3 Fe1 C3 180.0 9_666 . ?
C3 Fe1 C2 89.9(3) 9_666 9_666 ?
C3 Fe1 C2 90.1(3) . 9_666 ?
C3 Fe1 C2 90.1(3) 9_666 . ?
C3 Fe1 C2 89.9(3) . . ?
C2 Fe1 C2 180.0 9_666 . ?
C3 Fe1 C1 90.0 9_666 . ?
C3 Fe1 C1 90.0 . . ?
C2 Fe1 C1 90.0 9_666 . ?
C2 Fe1 C1 90.0 . . ?
C3 Fe1 C1 90.0 9_666 9_666 ?
C3 Fe1 C1 90.0 . 9_666 ?
C2 Fe1 C1 90.0 9_666 9_666 ?
C2 Fe1 C1 90.0 . 9_666 ?
C1 Fe1 C1 180.0 . 9_666 ?
N1 C1 Fe1 180.0 . . ?
N2 C2 Fe1 179.5(6) . . ?
N3 C3 Fe1 179.4(5) . . ?
N4 C4 C5 119.9(3) . . ?
N4 C4 H4A 120.1 . . ?
C5 C4 H4A 120.1 . . ?
C4 C5 C6 119.8(3) . . ?
C4 C5 H5A 120.1 . . ?
C6 C5 H5A 120.1 . . ?
C7 C6 C5 118.6(3) . . ?
C7 C6 C6 120.9(3) . 2_675 ?
C5 C6 C6 120.4(3) . 2_675 ?
C8 C7 C6 120.0(3) . . ?
C8 C7 H7A 120.0 . . ?
C6 C7 H7A 120.0 . . ?
N4 C8 C7 119.7(3) . . ?
N4 C8 H8A 120.2 . . ?
C7 C8 H8A 120.2 . . ?
C4 N4 C8 122.0(2) . . ?
C4 N4 C9 119.2(2) . . ?
C8 N4 C9 118.7(2) . . ?
C14 C9 C10 120.3(2) . . ?
C14 C9 N4 117.4(3) . . ?
C10 C9 N4 122.3(3) . . ?
C11 C10 C9 120.2(2) . . ?
C11 C10 N5 117.2(2) . . ?
C9 C10 N5 122.5(2) . . ?
C10 C11 C12 118.1(3) . . ?
C10 C11 H11A 121.0 . . ?
C12 C11 H11A 121.0 . . ?
C13 C12 C11 123.1(3) . . ?
C13 C12 N6 119.1(3) . . ?
C11 C12 N6 117.8(3) . . ?
C12 C13 C14 118.0(3) . . ?
C12 C13 H13A 121.0 . . ?
C14 C13 H13A 121.0 . . ?
C9 C14 C13 120.3(3) . . ?
C9 C14 H14A 119.8 . . ?
C13 C14 H14A 119.8 . . ?
O1 N5 O2 124.1(3) . . ?
O1 N5 C10 119.2(2) . . ?
O2 N5 C10 116.7(2) . . ?
O4 N6 O3 124.6(3) . . ?
O4 N6 C12 117.9(3) . . ?
O3 N6 C12 117.6(3) . . ?
H111 O11 H112 96(5) . . ?
H121 O12 H122 100(5) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N4 C4 C5 C6 -0.5(6) . . . . ?
C4 C5 C6 C7 1.7(6) . . . . ?
C4 C5 C6 C6 -179.0(3) . . . 2_675 ?
C5 C6 C7 C8 -1.5(5) . . . . ?
C6 C6 C7 C8 179.2(2) 2_675 . . . ?
C6 C7 C8 N4 -0.1(5) . . . . ?
C5 C4 N4 C8 -1.2(5) . . . . ?
C5 C4 N4 C9 179.7(3) . . . . ?
C7 C8 N4 C4 1.4(5) . . . . ?
C7 C8 N4 C9 -179.4(3) . . . . ?
C4 N4 C9 C14 75.3(4) . . . . ?
C8 N4 C9 C14 -103.9(3) . . . . ?
C4 N4 C9 C10 -105.5(4) . . . . ?
C8 N4 C9 C10 75.4(4) . . . . ?
C14 C9 C10 C11 3.2(4) . . . . ?
N4 C9 C10 C11 -176.0(2) . . . . ?
C14 C9 C10 N5 -175.3(2) . . . . ?
N4 C9 C10 N5 5.6(4) . . . . ?
C9 C10 C11 C12 -1.5(4) . . . . ?
N5 C10 C11 C12 177.0(2) . . . . ?
C10 C11 C12 C13 -0.8(4) . . . . ?
C10 C11 C12 N6 179.6(2) . . . . ?
C11 C12 C13 C14 1.5(5) . . . . ?
N6 C12 C13 C14 -178.9(3) . . . . ?
C10 C9 C14 C13 -2.5(4) . . . . ?
N4 C9 C14 C13 176.7(3) . . . . ?
C12 C13 C14 C9 0.2(5) . . . . ?
C11 C10 N5 O1 179.4(2) . . . . ?
C9 C10 N5 O1 -2.1(4) . . . . ?
C11 C10 N5 O2 -1.3(3) . . . . ?
C9 C10 N5 O2 177.1(2) . . . . ?
C13 C12 N6 O4 2.1(4) . . . . ?
C11 C12 N6 O4 -178.3(3) . . . . ?
C13 C12 N6 O3 -177.5(3) . . . . ?
C11 C12 N6 O3 2.1(4) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O11 H111 N2 0.88(3) 2.05(4) 2.918(4) 167(5) .
O11 H112 O13 1.01(3) 1.86(4) 2.851(4) 168(5) 12_655
O12 H121 N1 0.89(3) 2.01(4) 2.869(3) 163(6) .
O12 H122 O11 0.94(3) 1.88(4) 2.816(5) 172(6) .
C4 H4A N1 0.95 2.32 3.158(3) 146.2 .
C13 H13A N2 0.95 2.58 3.298(5) 132.7 .
C14 H14A N2 0.95 3.13 3.574(5) 110.7 .
C14 H14A N3 0.95 2.63 3.492(5) 150.5 .
C8 H8A O3 0.95 2.54 3.283(4) 134.9 12_665

_diffrn_measured_fraction_theta_max 0.947
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.996
_refine_diff_density_max         0.819
_refine_diff_density_min         -1.488
_refine_diff_density_rms         0.080

#############################################################

data_108
_database_code_depnum_ccdc_archive 'CCDC 692002'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '2(C22 H14 N6 O8), (C6 Fe N6), 20(H2 O)'
_chemical_formula_sum            'C50 H68 Fe N18 O36'
_chemical_formula_weight         1553.07

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 '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 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   'I b a m'
_symmetry_space_group_name_Hall  '-I 2 2c'

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

_cell_length_a                   26.442(3)
_cell_length_b                   11.3715(12)
_cell_length_c                   22.311(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     6708.8(12)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    8025
_cell_measurement_theta_min      2.39
_cell_measurement_theta_max      27.99

_exptl_crystal_description       needle
_exptl_crystal_colour            green-black
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.538
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             3232
_exptl_absorpt_coefficient_mu    0.336
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.948
_exptl_absorpt_correction_T_max  0.989
_exptl_absorpt_process_details   'SADABS (Bruker AXS Inc., 2000)'

_exptl_special_details           
;
The crystal used had been irradiated with sunlight until the
colour had changed from pale greenish-blue to dark greenish-black.
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'rotating anode'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker SMART Apex'
_diffrn_measurement_method       'CCD area detector'
_diffrn_detector_area_resol_mean 8.333
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            16154
_diffrn_reflns_av_R_equivalents  0.0222
_diffrn_reflns_av_sigmaI/netI    0.0186
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_theta_min         2.39
_diffrn_reflns_theta_max         27.98
_reflns_number_total             3935
_reflns_number_gt                3122
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART-NT 5.6 (Bruker AXS Inc., 2000)'
_computing_cell_refinement       'SMART-NT 5.6 (Bruker AXS Inc., 2000)'
_computing_data_reduction        'SAINT+ 6.0 (Bruker AXS Inc., 2000)'
_computing_structure_solution    'SHELXTL 5.1 (Bruker AXS Inc., 1997)'
_computing_structure_refinement  'SHELXTL 5.1 (Bruker AXS Inc., 1997)'
_computing_molecular_graphics    'SHELXTL 5.1 (Bruker AXS Inc., 1997)'
_computing_publication_material  'SHELXTL 5.1 (Bruker AXS Inc., 1997)'

_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.
Unlike most atoms of the viologen molecule, the thermal parameters of the
atoms of the hexacyanometallate complex anion are markedly anisotropic,
suggesting unresolved disorder between two closely separated sites.
Attempts to resolve this disorder, or twinned refinements of the structure
in lower-symmetry space groups, did not improve the structure.
Some of the of the lattice water molecules, those corresponding to O(15),
O(16) and O(17), were disordered over two or more sites.
The H-atoms bonded to O(11) and O(12) were located and refined with
restraints on the O-H distances.
;

_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)+(0.1131P)²+14.3861P] 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         3935
_refine_ls_number_parameters     267
_refine_ls_number_restraints     10
_refine_ls_R_factor_all          0.0829
_refine_ls_R_factor_gt           0.0692
_refine_ls_wR_factor_ref         0.2028
_refine_ls_wR_factor_gt          0.1904
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_restrained_S_all      1.047
_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
Fe1 Fe 0.5000 0.5000 0.5000 0.0591(4) Uani 1 4 d S . .
C1 C 0.5000 0.5000 0.41404(19) 0.0477(11) Uani 1 2 d S . .
N1 N 0.5000 0.5000 0.36218(15) 0.0418(8) Uani 1 2 d S . .
C2 C 0.4346(2) 0.4276(5) 0.5000 0.0591(14) Uani 1 2 d S . .
N2 N 0.39478(18) 0.3826(4) 0.5000 0.0586(12) Uani 1 2 d S . .
C3 C 0.4694(3) 0.6498(7) 0.5000 0.0662(18) Uani 1 2 d S . .
N3 N 0.4497(2) 0.7417(6) 0.5000 0.0757(17) Uani 1 2 d S . .
C4 C 0.45489(11) 0.7537(2) 0.33827(17) 0.0459(7) Uani 1 1 d . . .
H4A H 0.4629 0.6745 0.3287 0.055 Uiso 1 1 calc R . .
C5 C 0.49228(11) 0.8376(2) 0.33906(18) 0.0477(8) Uani 1 1 d . . .
H5A H 0.5262 0.8165 0.3303 0.057 Uiso 1 1 calc R . .
C6 C 0.48008(10) 0.9540(2) 0.35287(14) 0.0368(6) Uani 1 1 d . . .
C7 C 0.43006(10) 0.9814(2) 0.36677(14) 0.0384(6) Uani 1 1 d . . .
H7A H 0.4211 1.0599 0.3768 0.046 Uiso 1 1 calc R . .
C8 C 0.39392(10) 0.8951(2) 0.36590(13) 0.0371(6) Uani 1 1 d . . .
H8A H 0.3598 0.9133 0.3757 0.045 Uiso 1 1 calc R . .
N4 N 0.40700(8) 0.78391(18) 0.35107(11) 0.0329(5) Uani 1 1 d . . .
C9 C 0.36773(9) 0.6937(2) 0.34979(11) 0.0311(5) Uani 1 1 d . . .
C10 C 0.33269(9) 0.6860(2) 0.30341(11) 0.0290(5) Uani 1 1 d . . .
C11 C 0.29440(9) 0.6035(2) 0.30592(12) 0.0300(5) Uani 1 1 d . . .
H11A H 0.2698 0.5983 0.2750 0.036 Uiso 1 1 calc R . .
C12 C 0.29279(10) 0.5286(2) 0.35469(12) 0.0337(6) Uani 1 1 d . . .
C13 C 0.32806(12) 0.5312(3) 0.40006(12) 0.0400(6) Uani 1 1 d . . .
H13A H 0.3265 0.4769 0.4324 0.048 Uiso 1 1 calc R . .
C14 C 0.36600(11) 0.6155(3) 0.39726(12) 0.0391(6) Uani 1 1 d . . .
H14A H 0.3908 0.6194 0.4280 0.047 Uiso 1 1 calc R . .
N5 N 0.33505(9) 0.76146(19) 0.24952(10) 0.0334(5) Uani 1 1 d . . .
O1 O 0.36823(8) 0.83597(16) 0.24571(10) 0.0407(5) Uani 1 1 d . . .
O2 O 0.30320(8) 0.74343(19) 0.21055(10) 0.0441(5) Uani 1 1 d . . .
N6 N 0.25140(10) 0.4409(2) 0.35747(11) 0.0418(6) Uani 1 1 d . . .
O3 O 0.22160(8) 0.43815(19) 0.31519(10) 0.0444(5) Uani 1 1 d . . .
O4 O 0.24933(10) 0.3765(2) 0.40114(12) 0.0586(7) Uani 1 1 d . . .
O11 O 0.38954(10) 0.2604(2) 0.38478(13) 0.0567(6) Uani 1 1 d D . .
H111 H 0.3971(19) 0.292(4) 0.4177(18) 0.085 Uiso 1 1 d D . .
H112 H 0.3601(15) 0.216(4) 0.399(2) 0.085 Uiso 1 1 d D . .
O12 O 0.42055(12) 0.4045(3) 0.28882(14) 0.0695(8) Uani 1 1 d D . .
H121 H 0.4480(16) 0.432(5) 0.303(3) 0.104 Uiso 1 1 d D . .
H122 H 0.407(2) 0.358(5) 0.320(2) 0.104 Uiso 1 1 d D . .
O13 O 0.19294(12) 0.6114(3) 0.41657(14) 0.0869(11) Uani 1 1 d . . .
O14 O 0.26516(16) 0.6945(4) 0.5000 0.0718(11) Uani 1 2 d S . .
O15A O 0.3452(5) 0.8776(13) 0.5000 0.075(3) Uiso 0.34 2 d SPU A 1
O17A O 0.3856(6) 1.1119(15) 0.5000 0.087(3) Uiso 0.34 2 d SPU B 1
O15B O 0.3561(3) 0.8176(7) 0.5000 0.0571(15) Uiso 0.56 2 d SPU C 2
O17B O 0.3642(4) 1.0477(10) 0.5000 0.088(2) Uiso 0.56 2 d SPU D 2
O15C O 0.3808(7) 0.9716(18) 0.5000 0.059(3) Uiso 0.20 2 d SPU E 3
O16A O 0.4753(5) 1.0718(10) 0.5000 0.086(3) Uiso 0.50 2 d SPU F 1
O16B O 0.4589(4) 1.1154(9) 0.5000 0.077(2) Uiso 0.50 2 d SPU G 2


_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
Fe1 C3 1.887(9) 9_666 ?
Fe1 C3 1.887(9) . ?
Fe1 C2 1.914(5) . ?
Fe1 C2 1.914(5) 9_666 ?
Fe1 C1 1.918(4) 9_666 ?
Fe1 C1 1.918(4) . ?
C1 N1 1.157(6) . ?
C2 N2 1.172(6) . ?
C3 N3 1.167(9) . ?
C4 N4 1.343(4) . ?
C4 C5 1.374(4) . ?
C4 H4A 0.9500 . ?
C5 C6 1.397(4) . ?
C5 H5A 0.9500 . ?
C6 C7 1.394(4) . ?
C6 C6 1.485(5) 2_675 ?
C7 C8 1.370(4) . ?
C7 H7A 0.9500 . ?
C8 N4 1.352(3) . ?
C8 H8A 0.9500 . ?
N4 C9 1.460(3) . ?
C9 C14 1.384(4) . ?
C9 C10 1.392(4) . ?
C10 C11 1.382(3) . ?
C10 N5 1.478(3) . ?
C11 C12 1.382(4) . ?
C11 H11A 0.9500 . ?
C12 C13 1.377(4) . ?
C12 N6 1.481(3) . ?
C13 C14 1.389(4) . ?
C13 H13A 0.9500 . ?
C14 H14A 0.9500 . ?
N5 O1 1.223(3) . ?
N5 O2 1.228(3) . ?
N6 O4 1.220(3) . ?
N6 O3 1.230(3) . ?
O11 H111 0.84(3) . ?
O11 H112 0.98(3) . ?
O12 H121 0.85(3) . ?
O12 H122 0.95(3) . ?

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
C3 Fe1 C3 180.0 9_666 . ?
C3 Fe1 C2 89.9(3) 9_666 . ?
C3 Fe1 C2 90.1(3) . . ?
C3 Fe1 C2 90.1(3) 9_666 9_666 ?
C3 Fe1 C2 89.9(3) . 9_666 ?
C2 Fe1 C2 180.0 . 9_666 ?
C3 Fe1 C1 90.0 9_666 9_666 ?
C3 Fe1 C1 90.0 . 9_666 ?
C2 Fe1 C1 90.0 . 9_666 ?
C2 Fe1 C1 90.0 9_666 9_666 ?
C3 Fe1 C1 90.0 9_666 . ?
C3 Fe1 C1 90.0 . . ?
C2 Fe1 C1 90.0 . . ?
C2 Fe1 C1 90.0 9_666 . ?
C1 Fe1 C1 180.0 9_666 . ?
N1 C1 Fe1 180.0 . . ?
N2 C2 Fe1 179.6(6) . . ?
N3 C3 Fe1 179.0(5) . . ?
N4 C4 C5 119.9(2) . . ?
N4 C4 H4A 120.1 . . ?
C5 C4 H4A 120.1 . . ?
C4 C5 C6 119.6(3) . . ?
C4 C5 H5A 120.2 . . ?
C6 C5 H5A 120.2 . . ?
C7 C6 C5 118.7(2) . . ?
C7 C6 C6 121.0(3) . 2_675 ?
C5 C6 C6 120.3(3) . 2_675 ?
C8 C7 C6 119.9(2) . . ?
C8 C7 H7A 120.1 . . ?
C6 C7 H7A 120.1 . . ?
N4 C8 C7 119.7(2) . . ?
N4 C8 H8A 120.2 . . ?
C7 C8 H8A 120.2 . . ?
C4 N4 C8 122.2(2) . . ?
C4 N4 C9 119.1(2) . . ?
C8 N4 C9 118.7(2) . . ?
C14 C9 C10 120.4(2) . . ?
C14 C9 N4 117.4(2) . . ?
C10 C9 N4 122.1(2) . . ?
C11 C10 C9 120.0(2) . . ?
C11 C10 N5 117.3(2) . . ?
C9 C10 N5 122.7(2) . . ?
C10 C11 C12 118.2(2) . . ?
C10 C11 H11A 120.9 . . ?
C12 C11 H11A 120.9 . . ?
C13 C12 C11 123.0(2) . . ?
C13 C12 N6 119.0(2) . . ?
C11 C12 N6 118.0(2) . . ?
C12 C13 C14 118.1(3) . . ?
C12 C13 H13A 120.9 . . ?
C14 C13 H13A 120.9 . . ?
C9 C14 C13 120.1(3) . . ?
C9 C14 H14A 119.9 . . ?
C13 C14 H14A 119.9 . . ?
O1 N5 O2 124.0(2) . . ?
O1 N5 C10 119.3(2) . . ?
O2 N5 C10 116.8(2) . . ?
O4 N6 O3 124.6(2) . . ?
O4 N6 C12 118.1(3) . . ?
O3 N6 C12 117.3(2) . . ?
H111 O11 H112 97(5) . . ?
H121 O12 H122 105(5) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N4 C4 C5 C6 -0.4(6) . . . . ?
C4 C5 C6 C7 1.3(5) . . . . ?
C4 C5 C6 C6 -178.9(3) . . . 2_675 ?
C5 C6 C7 C8 -0.9(5) . . . . ?
C6 C6 C7 C8 179.4(2) 2_675 . . . ?
C6 C7 C8 N4 -0.5(5) . . . . ?
C5 C4 N4 C8 -1.1(5) . . . . ?
C5 C4 N4 C9 179.8(3) . . . . ?
C7 C8 N4 C4 1.5(5) . . . . ?
C7 C8 N4 C9 -179.3(3) . . . . ?
C4 N4 C9 C14 75.5(3) . . . . ?
C8 N4 C9 C14 -103.7(3) . . . . ?
C4 N4 C9 C10 -105.3(3) . . . . ?
C8 N4 C9 C10 75.6(3) . . . . ?
C14 C9 C10 C11 3.0(4) . . . . ?
N4 C9 C10 C11 -176.2(2) . . . . ?
C14 C9 C10 N5 -175.3(2) . . . . ?
N4 C9 C10 N5 5.4(4) . . . . ?
C9 C10 C11 C12 -1.2(3) . . . . ?
N5 C10 C11 C12 177.2(2) . . . . ?
C10 C11 C12 C13 -1.3(4) . . . . ?
C10 C11 C12 N6 179.4(2) . . . . ?
C11 C12 C13 C14 1.9(4) . . . . ?
N6 C12 C13 C14 -178.8(3) . . . . ?
C10 C9 C14 C13 -2.4(4) . . . . ?
N4 C9 C14 C13 176.9(2) . . . . ?
C12 C13 C14 C9 -0.1(4) . . . . ?
C11 C10 N5 O1 179.7(2) . . . . ?
C9 C10 N5 O1 -1.9(3) . . . . ?
C11 C10 N5 O2 -1.2(3) . . . . ?
C9 C10 N5 O2 177.2(2) . . . . ?
C13 C12 N6 O4 2.2(4) . . . . ?
C11 C12 N6 O4 -178.4(3) . . . . ?
C13 C12 N6 O3 -177.5(3) . . . . ?
C11 C12 N6 O3 1.9(4) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O11 H111 N2 0.84(3) 2.10(4) 2.926(3) 164(5) .
O11 H112 O13 0.98(3) 1.88(3) 2.851(4) 170(5) 12_655
O12 H121 N1 0.85(3) 2.06(4) 2.876(3) 161(6) .
O12 H122 O11 0.95(3) 1.88(4) 2.818(4) 172(5) .
C4 H4A N1 0.95 2.34 3.167(3) 145.8 .
C13 H13A N2 0.95 2.59 3.307(5) 133.0 .
C14 H14A N2 0.95 3.14 3.584(5) 110.6 .
C14 H14A N3 0.95 2.63 3.495(4) 150.8 .
C8 H8A O3 0.95 2.56 3.294(3) 134.6 12_665

_diffrn_measured_fraction_theta_max 0.950
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.991
_refine_diff_density_max         0.613
_refine_diff_density_min         -1.672
_refine_diff_density_rms         0.088


