# Electronic Supplementary Material (ESI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2014

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_LaCo(CN)6_5H2O_neutron
_audit_creation_date             14-03-18
_audit_creation_method           'CRYSTALS_ver_14.30 + LaueG software'

_chemical_name_systematic        
'lanthanum(III) hexacyanidocobaltate(III) pentahydrate'
_chemical_name_common            
'lanthanum(III) hexacyanidocobaltate(III) pentahydrate'
_chemical_melting_point          ?

_cell_length_a                   7.4597(11)
_cell_length_b                   7.4597(11)
_cell_length_c                   14.293(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     688.8(2)

_symmetry_cell_setting           Hexagonal
_symmetry_space_group_name_H-M   'P 63/m '
_symmetry_space_group_name_Hall  ?
loop_
_symmetry_equiv_pos_as_xyz
x,y,z
-x,-y,-z
x-y,x,z+1/2
-x+y,-x,-z+1/2
-y,x-y,z
y,-x+y,-z
-x,-y,z+1/2
x,y,-z+1/2
-x+y,-x,z
x-y,x,-z
y,-x+y,z+1/2
-y,x-y,-z+1/2

loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_source
C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 6.6484
'International Tables Vol C 4.2.6.8 and 6.1.1.4'
Co 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 2.4900
'International Tables Vol C 4.2.6.8 and 6.1.1.4'
La 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 8.2400
'International Tables Vol C 4.2.6.8 and 6.1.1.4'
N 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 9.3600
'International Tables Vol C 4.2.6.8 and 6.1.1.4'
O 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 5.8050
'International Tables Vol C 4.2.6.8 and 6.1.1.4'
H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 -3.7409
'International Tables Vol C 4.2.6.8 and 6.1.1.4'


_cell_formula_units_Z            2

# Given Formula = C6 H10 Co1 La1 N6 O5.00 
# Dc =      2.14 Fooo =    192.00 Mu =     42.87 M =     74.00
# Found Formula = C6 H10 Co1 La1 N6 O5 
# Dc =      2.14 FOOO =    192.00 Mu =     42.87 M =     74.00

_chemical_formula_sum            'C6 H10 Co1 La1 N6 O5'
_chemical_formula_moiety         'C6 H10 Co1 La1 N6 O5'
_chemical_compound_source        ?
_chemical_formula_weight         444.02


_cell_measurement_reflns_used    0
_cell_measurement_theta_min      0
_cell_measurement_theta_max      0
_cell_measurement_temperature    300

_exptl_crystal_description       ?block
_exptl_crystal_colour            colourless
_exptl_crystal_size_min          2
_exptl_crystal_size_mid          2
_exptl_crystal_size_max          2

_exptl_crystal_density_diffrn    2.141
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
# Non-dispersive F(000): 
_exptl_crystal_F_000             192


# Sheldrick geometric approximatio 1.00 1.00 

_exptl_absorpt_correction_T_min  1.0000
_exptl_absorpt_correction_T_max  1.0000
_diffrn_measurement_details      '31 images, exposure time  100 minutes'
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_radiation_wavelength     0.85
_diffrn_reflns_theta_full        70.44
_diffrn_reflns_theta_max         70.53
_diffrn_reflns_resolution_max    1.43
_diffrn_measured_fraction_theta_full 0.850
_diffrn_measured_fraction_theta_max 0.850
_diffrn_reflns_av_R_equivalents  0.1789
_diffrn_reflns_av_unetI/netI     0.0885

_reflns_number_total             596
_reflns_number_gt                574
_reflns_threshold_expression     >2sigma(I)

_exptl_absorpt_coefficient_mu    0.0
_exptl_absorpt_correction_type   none

#===============================================================================
# LAUEG SPECIFIC

_reflns_special_details          
;
LAUEG SPECIFIC INFORMATION:
  HKL generation: wav = 0.850 to 1.700, d-space > 0.700
  Image scale factors: refined
  Wavelength spectra model:  10 point spline + non-param, gamma = 300.0
  Efficiency model: Quadratic in Y
  Extinction correction: Zach. Type 1 / SHELX
  Harmonics (wav/2) correction: off
  Absorption correction: off
  Friedel pairs are merged
  Merge statistics using final weights:
    R =17.1 ( 5.3)%  wR2 =30.9 ( 4.9)%  GOOF = 6.3  ( 13711 reflns > 4 sig)
    R =17.9 ( 7.0)%  wR2 =31.7 ( 6.6)%  GOOF = 4.8  (all 24710 reflns)
  Summary of refineable correction factors:
    File scale factor    min=-11.7%  max=242.1%  ave= 27.6%  st.dev.= 69.3%
    Wavelength spectra   min=-18.1%  max= 24.0%  ave= -2.5%  st.dev.=  5.9%
    Refined efficiency   min= -5.3%  max=  8.6%  ave= -0.0%  st.dev.=  3.9%
    Sample absorption    min=  0.0%  max=  0.0%  ave=  0.0%  st.dev.=  0.0%
    Sample extinction    min=  0.0%  max= 13.6%  ave=  0.2%  st.dev.=  0.4%
;

#===============================================================================
# SOFTWARE

_computing_data_collection       'MAATEL/ANSTO control program'
_computing_cell_refinement       'LaueG (Piltz, 2011)'
_computing_data_reduction        
'argonne_boxes (Wilkinson et al., 1988) & LaueG (Piltz, 2011)'

#===============================================================================
# REFERENCES






_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'

_diffrn_standards_interval_time  .
_diffrn_standards_interval_count .
_diffrn_standards_number         0
_diffrn_standards_decay_%        ?

_diffrn_ambient_temperature      300
_diffrn_reflns_number            596

# Number of reflections without Friedels Law is 0 
# Number of reflections with Friedels Law is 596 
# Theoretical number of reflections is about 1398 


_diffrn_reflns_theta_min         0.443








_oxford_diffrn_Wilson_B_factor   0.00
_oxford_diffrn_Wilson_scale      0.00

_atom_sites_solution_primary     geom
_atom_sites_solution_hydrogens   difmap

_refine_diff_density_min         -2.64
_refine_diff_density_max         1.75


# The current dictionary definitions do not cover the 
# situation where the reflections used for refinement were 
# selected by a user-defined sigma threshold 


# The values actually used during refinement 
_oxford_reflns_threshold_expression_ref I>3.0\s(I)
_refine_ls_number_reflns         558
_refine_ls_number_restraints     24
_refine_ls_number_parameters     50
_oxford_refine_ls_R_factor_ref   0.1153
_refine_ls_wR_factor_ref         0.0927
_refine_ls_goodness_of_fit_ref   0.9954
_refine_ls_shift/su_max          0.0000176
_refine_ls_shift/su_mean         0.0000038


# The values computed with all filters except I/sigma 
_oxford_reflns_number_all        594
_refine_ls_R_factor_all          0.1199
_refine_ls_wR_factor_all         0.0935

# The values computed with a 2 sigma cutoff - a la SHELX 

_refine_ls_R_factor_gt           0.1180
_refine_ls_wR_factor_gt          0.0931

# choose from: rm (reference molecule of known chirality), 
# ad (anomolous dispersion - Flack), rmad (rm and ad), 
# syn (from synthesis), unk (unknown) or . (not applicable). 
_chemical_absolute_configuration .


_refine_ls_structure_factor_coef F
_refine_ls_matrix_type           full
_refine_ls_hydrogen_treatment    mixed # none, undef, noref, refall,
# refxyz, refU, constr or mixed
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) 
 [weight] = 1.0/[A₀*T₀(x)+A₁*T₁(x) ... +Aₙ₋₁]*Tₙ₋₁(x)] 
 where Ai are the Chebychev coefficients listed below and x= Fcalc/Fmax 
 Method = Robust Weighting (Prince, 1982) 
 W = [weight] * [1-(deltaF/6*sigmaF)²]² 
 Ai are: 
 3.73 1.42 2.70 1.13 
;

# Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3

# Replace last . with number of unfound hydrogen atoms attached to an atom.

# ..._refinement_flags_... 
# . no refinement constraints           S special position constraint on site
# G rigid group refinement of site      R riding atom
# D distance or angle restraint on site T thermal displacement constraints
# U Uiso or Uij restraint (rigid bond)  P partial occupancy constraint


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_occupancy
_atom_site_adp_type
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
_atom_site_attached_hydrogens
Co1 Co 0.0000 0.0000 0.0000 0.0098 1.0000 Uani S T . . . .
C1 C 0.1339(3) -0.1022(3) 0.07565(15) 0.0206 1.0000 Uani . . . . . .
O1 O 0.5717(11) 0.0593(7) 0.2500 0.0583 1.0000 Uani S TU . . . .
N N 0.2153(3) -0.1667(3) 0.12136(15) 0.0396 1.0000 Uani . . . . . .
La1 La 0.3333 -0.3333 0.2500 0.0106 1.0000 Uani S T . . . .
O2 O 0.6667 0.3333 0.0844(6) 0.0612 1.0000 Uani S TU . . . .
H1 H 0.621(2) 0.1296(14) 0.1934(12) 0.1301 1.0000 Uani . U . . . .
H2 H 0.752(3) 0.337(4) 0.0388(13) 0.1056 0.6667 Uani . 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
Co1 0.010(2) 0.010(2) 0.010(4) 0.0000 0.0000 0.0049(11)
C1 0.0240(8) 0.0240(9) 0.0173(8) 0.0020(6) -0.0058(6) 0.0145(7)
O1 0.064(3) 0.0159(16) 0.077(4) 0.0000 0.0000 0.007(2)
N 0.0447(10) 0.0441(11) 0.0398(10) 0.0091(7) -0.0133(7) 0.0295(8)
La1 0.0108(7) 0.0108(7) 0.0100(12) 0.0000 0.0000 0.0054(4)
O2 0.071(3) 0.071(3) 0.042(3) 0.0000 0.0000 0.0354(14)
H1 0.144(9) 0.051(4) 0.139(10) 0.000(5) 0.074(8) 0.007(5)
H2 0.110(10) 0.112(9) 0.097(9) 0.009(8) 0.021(8) 0.057(9)

_refine_ls_extinction_method     None
_oxford_refine_ls_scale          0.714(8)
loop_
_geom_bond_atom_site_label_1
_geom_bond_site_symmetry_1
_geom_bond_atom_site_label_2
_geom_bond_site_symmetry_2
_geom_bond_distance
_geom_bond_publ_flag
Co1 . C1 10_555 1.8734(17) yes
Co1 . C1 6_555 1.8734(17) yes
Co1 . C1 2_555 1.8734(17) yes
Co1 . C1 9_555 1.8734(17) yes
Co1 . C1 5_555 1.8734(17) yes
Co1 . C1 . 1.8734(17) yes
C1 . N0 . 1.149(2) yes
O1 . H1 8_555 0.934(16) no
O1 . La1 . 2.556(5) yes
O1 . H1 . 0.934(16) no
N0 . La1 . 2.6065(17) yes
O2 . H2 5_655 0.90(2) no
O2 . H2 9_665 0.90(2) no
O2 . H2 . 0.90(2) no
loop_
_geom_angle_atom_site_label_1
_geom_angle_site_symmetry_1
_geom_angle_atom_site_label_2
_geom_angle_site_symmetry_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_3
_geom_angle
_geom_angle_publ_flag
C1 10_555 Co1 . C1 6_555 90.02(9) yes
C1 10_555 Co1 . C1 2_555 90.02(9) yes
C1 6_555 Co1 . C1 2_555 90.02(9) yes
C1 10_555 Co1 . C1 9_555 179.994 yes
C1 6_555 Co1 . C1 9_555 89.98(9) yes
C1 2_555 Co1 . C1 9_555 89.98(9) yes
C1 10_555 Co1 . C1 5_555 89.98(9) yes
C1 6_555 Co1 . C1 5_555 179.994 yes
C1 2_555 Co1 . C1 5_555 89.98(9) yes
C1 9_555 Co1 . C1 5_555 90.02(9) yes
C1 10_555 Co1 . C1 . 89.98(9) yes
C1 6_555 Co1 . C1 . 89.98(9) yes
C1 2_555 Co1 . C1 . 179.994 yes
C1 9_555 Co1 . C1 . 90.02(9) yes
C1 5_555 Co1 . C1 . 90.02(9) yes
Co1 . C1 . N0 . 179.21(19) yes
H1 8_555 O1 . La1 . 119.8(8) no
H1 8_555 O1 . H1 . 120.2(16) no
La1 . O1 . H1 . 119.8(8) no
C1 . N0 . La1 . 167.5(2) yes
N0 12_545 La1 . N0 8_555 75.74(8) yes
N0 12_545 La1 . N0 4_655 75.74(8) yes
N0 8_555 La1 . N0 4_655 75.74(8) yes
N0 12_545 La1 . N0 . 138.49(4) yes
N0 8_555 La1 . N0 . 89.72(10) yes
N0 4_655 La1 . N0 . 138.49(4) yes
N0 12_545 La1 . N0 9_655 138.49(4) yes
N0 8_555 La1 . N0 9_655 138.49(4) yes
N0 4_655 La1 . N0 9_655 89.72(10) yes
N0 . La1 . N0 9_655 75.74(8) yes
N0 12_545 La1 . N0 5_545 89.72(10) yes
N0 8_555 La1 . N0 5_545 138.49(4) yes
N0 4_655 La1 . N0 5_545 138.49(4) yes
N0 . La1 . N0 5_545 75.74(8) yes
N0 9_655 La1 . N0 5_545 75.74(8) yes
N0 12_545 La1 . O1 9_655 68.31(12) yes
N0 8_555 La1 . O1 9_655 135.12(5) yes
N0 4_655 La1 . O1 9_655 70.18(12) yes
N0 . La1 . O1 9_655 135.12(5) yes
N0 9_655 La1 . O1 9_655 70.18(12) yes
N0 12_545 La1 . O1 5_545 70.18(12) yes
N0 8_555 La1 . O1 5_545 68.31(12) yes
N0 4_655 La1 . O1 5_545 135.12(5) yes
N0 . La1 . O1 5_545 68.31(12) yes
N0 9_655 La1 . O1 5_545 135.12(5) yes
N0 12_545 La1 . O1 . 135.12(5) yes
N0 8_555 La1 . O1 . 70.18(12) yes
N0 4_655 La1 . O1 . 68.31(12) yes
N0 . La1 . O1 . 70.18(12) yes
N0 9_655 La1 . O1 . 68.31(12) yes
N0 5_545 La1 . O1 9_655 68.31(12) yes
N0 5_545 La1 . O1 5_545 70.18(12) yes
O1 9_655 La1 . O1 5_545 120.000(9) yes
N0 5_545 La1 . O1 . 135.12(5) yes
O1 9_655 La1 . O1 . 120.000(9) yes
O1 5_545 La1 . O1 . 120.000 yes
H2 5_655 O2 . H2 9_665 73.7(20) no
H2 5_655 O2 . H2 . 73.7(20) no
H2 9_665 O2 . H2 . 73.7(20) no
loop_
_geom_hbond_atom_site_label_D
_geom_hbond_site_symmetry_D
_geom_hbond_atom_site_label_H
_geom_hbond_site_symmetry_H
_geom_hbond_atom_site_label_A
_geom_hbond_site_symmetry_A
_geom_hbond_angle_DHA
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_publ_flag
O1 . H1 . O2 . 159.1(12) 0.934 2.081 2.972(3) yes


_iucr_refine_instruction_details_constraints 
;
#
# Punched on 18/03/14 at 17:57:25
#
#LIST     12                                                                    
FULL FIRST( X'S, U'S ) UNTIL LAST 
END                                                                             
;


_iucr_refine_instruction_details_restraints 
;
#
# Punched on 18/03/14 at 17:57:25
#
#LIST     16                                                                    
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
REM   THERMSIM   START (DO NOT REMOVE THIS LINE) 
U(IJ) .0, 0.02000 = O(2) TO H(2) 
U(IJ) .0, 0.02000 = O(2) TO H(2,5,1,1,1) 
U(IJ) .0, 0.02000 = O(2) TO H(2,3,1,1) 
U(IJ) .0, 0.02 = O(1) TO H(1) 
REM   THERMSIM   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;

# start Validation Reply Form
_vrf_PLAT029_LaCoCN6_5H2O_neutron 
;
PROBLEM: _diffrn_measured_fraction_theta_full Low .......      0.850 Note  
RESPONSE: Laue neutron data - this is an acceptable value.
;
_vrf_PLAT420_LaCoCN6_5H2O_neutron 
;
PROBLEM: D-H Without Acceptor       O2     -  >H2     ...     Please Check 
RESPONSE: This H2O molecule is an H-bond acceptor to the coordinated water but there are no available H-bond acceptors for this molecule.
;
# end Validation Reply Form
_database_code_depnum_ccdc_archive 'CCDC 992298'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_KLaFe(CN)6_4H2O

_audit_creation_method           SHELXL-97

_chemical_name_systematic        
; 
 potassium lanthanum(III) hexacyanidoferrate(II) tetrahydrate
;
_chemical_name_common            
'potassium lanthanum(III) hexacyanidoferrate(II) tetrahydrate'
_chemical_melting_point          ?
_chemical_formula_moiety         'C6 H8 Fe K La N6 O4'
_chemical_formula_sum            'C6 H8 Fe K La N6 O4'
_chemical_formula_weight         462.04

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'
K K 0.2009 0.2494 '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'
La La -0.2871 2.4523 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Hexagonal
_symmetry_space_group_name_H-M   P63/m
_symmetry_Int_Tables_number      176

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

_cell_length_a                   7.3829(8)
_cell_length_b                   7.3829(8)
_cell_length_c                   13.871(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     654.76(14)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       'needle fragment'
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.344
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             440
_exptl_absorpt_coefficient_mu    4.662
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.514080
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_process_details   'SADABS, Sheldrick 1996'

_exptl_special_details           
; 
Mounted inside an evacuated, flame-sealed glass capillary with glass wool.
;

_diffrn_ambient_temperature      150(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-AXS SMART 1000 CCD'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            553
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_sigmaI/netI    0.0126
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       0
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         2.94
_diffrn_reflns_theta_max         28.01
_reflns_number_total             553
_reflns_number_gt                517
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART (BrukerAXS, 1997)'
_computing_cell_refinement       'SMART (BrukerAXS, 1997)'
_computing_data_reduction        'SAINT+ (BrukerAXS, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 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. 
;

_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)+(0.1000P)²+0.0000P] 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         553
_refine_ls_number_parameters     38
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0156
_refine_ls_R_factor_gt           0.0145
_refine_ls_wR_factor_ref         0.0659
_refine_ls_wR_factor_gt          0.0621
_refine_ls_goodness_of_fit_ref   0.615
_refine_ls_restrained_S_all      0.615
_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
La1 La 0.3333 0.6667 0.2500 0.00750(16) Uani 1 6 d S . .
Fe1 Fe 0.0000 1.0000 0.0000 0.00813(19) Uani 1 6 d S . .
N1 N 0.2724(2) 0.8886(2) 0.12391(16) 0.0263(4) Uani 1 1 d . . .
C1 C 0.1691(2) 0.9322(2) 0.07800(12) 0.0147(4) Uani 1 1 d . . .
O1 O 0.4216(3) 0.3517(3) 0.2500 0.0192(4) Uani 1 2 d SD . .
K1 K 0.6667 0.3333 0.08827(11) 0.0249(4) Uani 0.50 3 d SP . .
O2 O 0.6667 0.3333 0.08827(11) 0.0249(4) Uani 0.50 3 d SP . .
H1A H 0.325(6) 0.221(4) 0.2500 0.078(16) Uiso 1 2 d SD . .
H1B H 0.560(4) 0.401(15) 0.2500 0.22(4) Uiso 1 2 d SD . .

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
La1 0.00725(18) 0.00725(18) 0.0080(2) 0.000 0.000 0.00363(9)
Fe1 0.0085(2) 0.0085(2) 0.0074(3) 0.000 0.000 0.00424(12)
N1 0.0193(7) 0.0165(7) 0.0363(9) 0.0097(8) -0.0116(8) 0.0038(5)
C1 0.0130(8) 0.0089(7) 0.0168(8) 0.0018(6) 0.0002(6) 0.0015(6)
O1 0.0174(9) 0.0167(9) 0.0262(10) 0.000 0.000 0.0106(8)
K1 0.0252(5) 0.0252(5) 0.0243(8) 0.000 0.000 0.0126(3)
O2 0.0252(5) 0.0252(5) 0.0243(8) 0.000 0.000 0.0126(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
La1 N1 2.5854(16) 10_556 ?
La1 N1 2.5854(16) . ?
La1 N1 2.5854(16) 3_665 ?
La1 N1 2.5854(16) 8_566 ?
La1 N1 2.5854(16) 12_666 ?
La1 N1 2.5854(16) 5_565 ?
La1 O1 2.7110(17) 8_566 ?
La1 O1 2.7110(17) 3_665 ?
La1 O1 2.7110(17) . ?
Fe1 C1 1.8986(17) 9_455 ?
Fe1 C1 1.8986(17) 3_675 ?
Fe1 C1 1.8986(17) 7_575 ?
Fe1 C1 1.8986(17) . ?
Fe1 C1 1.8986(17) 11_665 ?
Fe1 C1 1.8986(17) 5_465 ?
N1 C1 1.156(2) . ?
N1 K1 3.1527(14) 1_565 ?
C1 K1 3.3771(15) 1_565 ?
O1 K1 2.9272(16) 8_666 ?
O1 K1 2.9272(16) . ?
K1 O1 2.9272(16) 8_666 ?
K1 O1 2.9272(16) 3_655 ?
K1 N1 3.1527(14) 3_765 ?
K1 N1 3.1527(14) 1_545 ?
K1 N1 3.1527(14) 5_565 ?
K1 C1 3.3771(15) 3_765 ?
K1 C1 3.3771(16) 1_545 ?
K1 C1 3.3771(15) 5_565 ?
K1 K1 4.487(3) 8_666 ?
K1 K1 4.9158(16) 7_655 ?
K1 K1 4.9158(16) 7_765 ?

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
N1 La1 N1 85.14(9) 10_556 . ?
N1 La1 N1 136.79(3) 10_556 3_665 ?
N1 La1 N1 79.25(7) . 3_665 ?
N1 La1 N1 79.25(7) 10_556 8_566 ?
N1 La1 N1 136.79(3) . 8_566 ?
N1 La1 N1 136.79(3) 3_665 8_566 ?
N1 La1 N1 79.25(7) 10_556 12_666 ?
N1 La1 N1 136.79(3) . 12_666 ?
N1 La1 N1 85.14(9) 3_665 12_666 ?
N1 La1 N1 79.25(7) 8_566 12_666 ?
N1 La1 N1 136.79(3) 10_556 5_565 ?
N1 La1 N1 79.25(7) . 5_565 ?
N1 La1 N1 79.25(7) 3_665 5_565 ?
N1 La1 N1 85.14(9) 8_566 5_565 ?
N1 La1 N1 136.79(3) 12_666 5_565 ?
N1 La1 O1 68.54(4) 10_556 8_566 ?
N1 La1 O1 68.54(4) . 8_566 ?
N1 La1 O1 68.25(4) 3_665 8_566 ?
N1 La1 O1 137.43(5) 8_566 8_566 ?
N1 La1 O1 68.25(4) 12_666 8_566 ?
N1 La1 O1 137.43(5) 5_565 8_566 ?
N1 La1 O1 68.25(4) 10_556 3_665 ?
N1 La1 O1 68.25(4) . 3_665 ?
N1 La1 O1 137.43(5) 3_665 3_665 ?
N1 La1 O1 68.54(4) 8_566 3_665 ?
N1 La1 O1 137.43(5) 12_666 3_665 ?
N1 La1 O1 68.54(4) 5_565 3_665 ?
O1 La1 O1 120.0 8_566 3_665 ?
N1 La1 O1 137.43(5) 10_556 . ?
N1 La1 O1 137.43(5) . . ?
N1 La1 O1 68.54(4) 3_665 . ?
N1 La1 O1 68.25(4) 8_566 . ?
N1 La1 O1 68.54(4) 12_666 . ?
N1 La1 O1 68.25(4) 5_565 . ?
O1 La1 O1 120.000(1) 8_566 . ?
O1 La1 O1 120.0 3_665 . ?
C1 Fe1 C1 180.00(8) 9_455 3_675 ?
C1 Fe1 C1 90.74(7) 9_455 7_575 ?
C1 Fe1 C1 89.26(7) 3_675 7_575 ?
C1 Fe1 C1 89.26(7) 9_455 . ?
C1 Fe1 C1 90.74(7) 3_675 . ?
C1 Fe1 C1 180.00(8) 7_575 . ?
C1 Fe1 C1 90.74(7) 9_455 11_665 ?
C1 Fe1 C1 89.26(7) 3_675 11_665 ?
C1 Fe1 C1 90.74(7) 7_575 11_665 ?
C1 Fe1 C1 89.26(7) . 11_665 ?
C1 Fe1 C1 89.26(7) 9_455 5_465 ?
C1 Fe1 C1 90.74(7) 3_675 5_465 ?
C1 Fe1 C1 89.26(7) 7_575 5_465 ?
C1 Fe1 C1 90.74(7) . 5_465 ?
C1 Fe1 C1 180.0 11_665 5_465 ?
C1 N1 La1 153.81(13) . . ?
C1 N1 K1 91.02(11) . 1_565 ?
La1 N1 K1 113.80(5) . 1_565 ?
N1 C1 Fe1 178.58(16) . . ?
N1 C1 K1 68.97(10) . 1_565 ?
Fe1 C1 K1 111.30(6) . 1_565 ?
La1 O1 K1 117.32(4) . 8_666 ?
La1 O1 K1 117.32(4) . . ?
K1 O1 K1 100.06(6) 8_666 . ?
O1 K1 O1 67.60(5) 8_666 3_655 ?
O1 K1 O1 67.60(5) 8_666 . ?
O1 K1 O1 67.60(5) 3_655 . ?
O1 K1 N1 58.41(5) 8_666 3_765 ?
O1 K1 N1 69.99(5) 3_655 3_765 ?
O1 K1 N1 120.37(7) . 3_765 ?
O1 K1 N1 120.37(7) 8_666 1_545 ?
O1 K1 N1 58.41(5) 3_655 1_545 ?
O1 K1 N1 69.99(5) . 1_545 ?
N1 K1 N1 117.59(3) 3_765 1_545 ?
O1 K1 N1 69.99(5) 8_666 5_565 ?
O1 K1 N1 120.37(7) 3_655 5_565 ?
O1 K1 N1 58.41(5) . 5_565 ?
N1 K1 N1 117.59(3) 3_765 5_565 ?
N1 K1 N1 117.59(3) 1_545 5_565 ?
O1 K1 C1 77.35(5) 8_666 3_765 ?
O1 K1 C1 69.30(4) 3_655 3_765 ?
O1 K1 C1 132.02(6) . 3_765 ?
N1 K1 C1 20.01(4) 3_765 3_765 ?
N1 K1 C1 103.73(4) 1_545 3_765 ?
N1 K1 C1 136.23(4) 5_565 3_765 ?
O1 K1 C1 132.02(6) 8_666 1_545 ?
O1 K1 C1 77.35(5) 3_655 1_545 ?
O1 K1 C1 69.30(4) . 1_545 ?
N1 K1 C1 136.23(4) 3_765 1_545 ?
N1 K1 C1 20.01(4) 1_545 1_545 ?
N1 K1 C1 103.73(4) 5_565 1_545 ?
C1 K1 C1 119.824(6) 3_765 1_545 ?
O1 K1 C1 69.30(4) 8_666 5_565 ?
O1 K1 C1 132.02(6) 3_655 5_565 ?
O1 K1 C1 77.35(5) . 5_565 ?
N1 K1 C1 103.73(4) 3_765 5_565 ?
N1 K1 C1 136.23(4) 1_545 5_565 ?
N1 K1 C1 20.01(4) 5_565 5_565 ?
C1 K1 C1 119.824(6) 3_765 5_565 ?
C1 K1 C1 119.824(6) 1_545 5_565 ?
O1 K1 K1 39.97(3) 8_666 8_666 ?
O1 K1 K1 39.97(3) 3_655 8_666 ?
O1 K1 K1 39.97(3) . 8_666 ?
N1 K1 K1 80.98(5) 3_765 8_666 ?
N1 K1 K1 80.98(5) 1_545 8_666 ?
N1 K1 K1 80.98(5) 5_565 8_666 ?
C1 K1 K1 92.42(4) 3_765 8_666 ?
C1 K1 K1 92.42(4) 1_545 8_666 ?
C1 K1 K1 92.42(4) 5_565 8_666 ?
O1 K1 K1 147.76(5) 8_666 7_655 ?
O1 K1 K1 83.28(3) 3_655 7_655 ?
O1 K1 K1 114.61(4) . 7_655 ?
N1 K1 K1 99.60(3) 3_765 7_655 ?
N1 K1 K1 45.26(4) 1_545 7_655 ?
N1 K1 K1 140.48(5) 5_565 7_655 ?
C1 K1 K1 79.67(3) 3_765 7_655 ?
C1 K1 K1 47.20(3) 1_545 7_655 ?
C1 K1 K1 142.73(6) 5_565 7_655 ?
K1 K1 K1 119.88(3) 8_666 7_655 ?
O1 K1 K1 83.28(3) 8_666 7_765 ?
O1 K1 K1 114.61(4) 3_655 7_765 ?
O1 K1 K1 147.76(5) . 7_765 ?
N1 K1 K1 45.26(4) 3_765 7_765 ?
N1 K1 K1 140.48(5) 1_545 7_765 ?
N1 K1 K1 99.60(3) 5_565 7_765 ?
C1 K1 K1 47.20(3) 3_765 7_765 ?
C1 K1 K1 142.73(6) 1_545 7_765 ?
C1 K1 K1 79.67(3) 5_565 7_765 ?
K1 K1 K1 119.88(3) 8_666 7_765 ?
K1 K1 K1 97.34(4) 7_655 7_765 ?

_diffrn_measured_fraction_theta_max 0.996
_diffrn_reflns_theta_full        28.01
_diffrn_measured_fraction_theta_full 0.996
_refine_diff_density_max         0.509
_refine_diff_density_min         -0.568
_refine_diff_density_rms         0.087


# start Validation Reply Form
_vrf_PLAT420_KLaFeCN6_4H2O       
;
PROBLEM: D-H Without Acceptor       O1     -   H1A    ...     Please Check 
RESPONSE: The determined H2O orientation is reasonable, with these H atoms maximising their distance from the K+ ions.
;
# end Validation Reply Form
_database_code_depnum_ccdc_archive 'CCDC 992299'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_KLaFe(CN)6_anhydrous

_audit_creation_method           SHELXL-97

_chemical_name_systematic        
; 
 potassium lanthanum(III) hexacyanidoferrate(II)
;
_chemical_name_common            
'potassium lanthanum(III) hexacyanidoferrate(II)'
_chemical_melting_point          ?
_chemical_formula_moiety         'C6 Fe K La N6'
_chemical_formula_sum            'C6 Fe K La N6'
_chemical_formula_weight         389.98

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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
K K 0.2009 0.2494 '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'
La La -0.2871 2.4523 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Trigonal
_symmetry_space_group_name_H-M   'P -3 1 c'
_symmetry_space_group_name_Hall  '-P 3 2c'
_symmetry_Int_Tables_number      163

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

_cell_length_a                   7.1852(10)
_cell_length_b                   7.1852(10)
_cell_length_c                   12.238(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     547.2(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       'needle fragment'
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.367
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             360
_exptl_absorpt_coefficient_mu    5.529
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.347499
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_process_details   'SADABS, Sheldrick 1996'

_exptl_special_details           
; 
Mounted inside an evacuated, flame-sealed glass capillary with glass wool.
;

_diffrn_ambient_temperature      150(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-AXS SMART 1000 CCD'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            1444
_diffrn_reflns_av_R_equivalents  0.0607
_diffrn_reflns_av_sigmaI/netI    0.0325
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         3.27
_diffrn_reflns_theta_max         21.26
_reflns_number_total             209
_reflns_number_gt                197
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART (BrukerAXS, 1997)'
_computing_cell_refinement       'SMART (BrukerAXS, 1997)'
_computing_data_reduction        'SAINT+ (BrukerAXS, 1997)'
_computing_structure_solution    'SHELXTL (BrukerAXS, 2000)'
_computing_structure_refinement  'SHELXTL (BrukerAXS, 2000)'

_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+98.2436P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         209
_refine_ls_number_parameters     16
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.1053
_refine_ls_R_factor_gt           0.1006
_refine_ls_wR_factor_ref         0.2446
_refine_ls_wR_factor_gt          0.2426
_refine_ls_goodness_of_fit_ref   1.434
_refine_ls_restrained_S_all      1.434
_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
La1 La 0.6667 0.3333 0.2500 0.0160(17) Uani 1 6 d S . .
Fe1 Fe 1.0000 0.0000 0.0000 0.022(3) Uani 1 6 d S . .
K1 K 0.3333 -0.3333 0.2500 0.035(6) Uani 1 6 d S . .
N1 N 0.663(7) 0.038(6) 0.139(3) 0.016(7) Uiso 1 1 d U . .
C1 C 0.798(7) 0.031(7) 0.084(3) 0.011(8) Uiso 1 1 d 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
La1 0.0093(19) 0.0093(19) 0.029(3) 0.000 0.000 0.0047(10)
Fe1 0.010(4) 0.010(4) 0.046(9) 0.000 0.000 0.005(2)
K1 0.019(6) 0.019(6) 0.069(16) 0.000 0.000 0.009(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
La1 N1 2.50(3) 4_665 ?
La1 N1 2.50(3) . ?
La1 N1 2.50(3) 2_655 ?
La1 N1 2.50(3) 5_655 ?
La1 N1 2.50(3) 6 ?
La1 N1 2.50(3) 3_665 ?
La1 K1 4.1484(6) 1_665 ?
La1 K1 4.1484(6) . ?
La1 K1 4.1484(6) 1_565 ?
Fe1 C1 1.88(4) 9_545 ?
Fe1 C1 1.88(4) 3_765 ?
Fe1 C1 1.88(4) 7_755 ?
Fe1 C1 1.88(4) 2_645 ?
Fe1 C1 1.88(4) . ?
Fe1 C1 1.88(4) 8_665 ?
K1 N1 2.87(4) 5_655 ?
K1 N1 2.87(4) 2_545 ?
K1 N1 2.87(4) . ?
K1 N1 2.87(4) 4 ?
K1 N1 2.87(4) 3_655 ?
K1 N1 2.87(4) 6_545 ?
K1 La1 4.1484(6) 1_445 ?
K1 La1 4.1484(6) 1_545 ?
N1 C1 1.21(5) . ?

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
N1 La1 N1 87.2(17) 4_665 . ?
N1 La1 N1 85.7(17) 4_665 2_655 ?
N1 La1 N1 93.6(10) . 2_655 ?
N1 La1 N1 93.6(10) 4_665 5_655 ?
N1 La1 N1 85.7(17) . 5_655 ?
N1 La1 N1 178.9(19) 2_655 5_655 ?
N1 La1 N1 93.6(10) 4_665 6 ?
N1 La1 N1 178.9(19) . 6 ?
N1 La1 N1 87.2(17) 2_655 6 ?
N1 La1 N1 93.6(10) 5_655 6 ?
N1 La1 N1 178.9(19) 4_665 3_665 ?
N1 La1 N1 93.6(10) . 3_665 ?
N1 La1 N1 93.6(10) 2_655 3_665 ?
N1 La1 N1 87.2(17) 5_655 3_665 ?
N1 La1 N1 85.7(17) 6 3_665 ?
N1 La1 K1 42.8(8) 4_665 1_665 ?
N1 La1 K1 90.5(9) . 1_665 ?
N1 La1 K1 42.8(8) 2_655 1_665 ?
N1 La1 K1 136.4(9) 5_655 1_665 ?
N1 La1 K1 90.5(9) 6 1_665 ?
N1 La1 K1 136.4(9) 3_665 1_665 ?
N1 La1 K1 90.5(9) 4_665 . ?
N1 La1 K1 42.8(8) . . ?
N1 La1 K1 136.4(9) 2_655 . ?
N1 La1 K1 42.8(8) 5_655 . ?
N1 La1 K1 136.4(9) 6 . ?
N1 La1 K1 90.5(9) 3_665 . ?
K1 La1 K1 120.0 1_665 . ?
N1 La1 K1 136.4(9) 4_665 1_565 ?
N1 La1 K1 136.4(9) . 1_565 ?
N1 La1 K1 90.5(9) 2_655 1_565 ?
N1 La1 K1 90.5(9) 5_655 1_565 ?
N1 La1 K1 42.8(8) 6 1_565 ?
N1 La1 K1 42.8(8) 3_665 1_565 ?
K1 La1 K1 120.0 1_665 1_565 ?
K1 La1 K1 120.0 . 1_565 ?
C1 Fe1 C1 180.0(18) 9_545 3_765 ?
C1 Fe1 C1 93.1(15) 9_545 7_755 ?
C1 Fe1 C1 86.9(15) 3_765 7_755 ?
C1 Fe1 C1 86.9(15) 9_545 2_645 ?
C1 Fe1 C1 93.1(15) 3_765 2_645 ?
C1 Fe1 C1 86.9(15) 7_755 2_645 ?
C1 Fe1 C1 86.9(15) 9_545 . ?
C1 Fe1 C1 93.1(15) 3_765 . ?
C1 Fe1 C1 180(2) 7_755 . ?
C1 Fe1 C1 93.1(15) 2_645 . ?
C1 Fe1 C1 93.1(15) 9_545 8_665 ?
C1 Fe1 C1 86.9(15) 3_765 8_665 ?
C1 Fe1 C1 93.1(15) 7_755 8_665 ?
C1 Fe1 C1 180(3) 2_645 8_665 ?
C1 Fe1 C1 86.9(15) . 8_665 ?
N1 K1 N1 88.8(15) 5_655 2_545 ?
N1 K1 N1 72.7(13) 5_655 . ?
N1 K1 N1 99.6(8) 2_545 . ?
N1 K1 N1 99.6(8) 5_655 4 ?
N1 K1 N1 72.7(13) 2_545 4 ?
N1 K1 N1 169.6(14) . 4 ?
N1 K1 N1 169.6(14) 5_655 3_655 ?
N1 K1 N1 99.6(8) 2_545 3_655 ?
N1 K1 N1 99.6(8) . 3_655 ?
N1 K1 N1 88.8(15) 4 3_655 ?
N1 K1 N1 99.6(8) 5_655 6_545 ?
N1 K1 N1 169.6(14) 2_545 6_545 ?
N1 K1 N1 88.8(15) . 6_545 ?
N1 K1 N1 99.6(8) 4 6_545 ?
N1 K1 N1 72.7(13) 3_655 6_545 ?
N1 K1 La1 95.2(7) 5_655 1_445 ?
N1 K1 La1 36.4(6) 2_545 1_445 ?
N1 K1 La1 135.6(7) . 1_445 ?
N1 K1 La1 36.4(6) 4 1_445 ?
N1 K1 La1 95.2(7) 3_655 1_445 ?
N1 K1 La1 135.6(7) 6_545 1_445 ?
N1 K1 La1 36.4(6) 5_655 . ?
N1 K1 La1 95.2(7) 2_545 . ?
N1 K1 La1 36.4(6) . . ?
N1 K1 La1 135.6(7) 4 . ?
N1 K1 La1 135.6(7) 3_655 . ?
N1 K1 La1 95.2(7) 6_545 . ?
La1 K1 La1 120.0 1_445 . ?
N1 K1 La1 135.6(7) 5_655 1_545 ?
N1 K1 La1 135.6(7) 2_545 1_545 ?
N1 K1 La1 95.2(7) . 1_545 ?
N1 K1 La1 95.2(7) 4 1_545 ?
N1 K1 La1 36.4(6) 3_655 1_545 ?
N1 K1 La1 36.4(6) 6_545 1_545 ?
La1 K1 La1 120.0 1_445 1_545 ?
La1 K1 La1 120.0 . 1_545 ?
C1 N1 La1 132(3) . . ?
C1 N1 K1 122(3) . . ?
La1 N1 K1 100.8(11) . . ?
N1 C1 Fe1 176(4) . . ?

_diffrn_measured_fraction_theta_max 0.972
_diffrn_reflns_theta_full        21.26
_diffrn_measured_fraction_theta_full 0.972
_refine_diff_density_max         3.039
_refine_diff_density_min         -6.812
_refine_diff_density_rms         0.450


# start Validation Reply Form
_vrf_THETM01_KLaFeCN6_anhydrous  
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: Weak scattering at high angle was seen, due to the crystal quality being unavoidably affected by the significant strain undergone during the dehydration process and associated 16% volume reduction.
;
_vrf_DIFMN02_KLaFeCN6_anhydrous  
;
PROBLEM: The minimum difference density is < -0.1*ZMAX*1.00
RESPONSE: The crystal quality was unavoidably affected by the significant strain undergone during the dehydration process and associated 16% volume reduction.
;
_vrf_PLAT098_KLaFeCN6_anhydrous  
;
PROBLEM: Large Reported Min.  (Negative) Residual Density      -6.81 eA-3  
RESPONSE: The crystal quality was unavoidably affected by the significant strain undergone during the dehydration process and associated 16% volume reduction.
;
# end Validation Reply Form
_database_code_depnum_ccdc_archive 'CCDC 992300'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_PrCo(CN)6_4.5H2O

_audit_creation_method           SHELXL-97

_chemical_name_systematic        
'praseodymium(III) hexacyanidocobaltate(III) tetrahemihydrate'
_chemical_name_common            
'praseodymium(III) hexacyanidocobaltate(III) tetrahemihydrate'
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C6 H9 Co N6 O4.50 Pr'
_chemical_formula_weight         437.016

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'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pr Pr -0.2180 2.8214 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Cmcm

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

_cell_length_a                   7.431(7)
_cell_length_b                   12.815(11)
_cell_length_c                   14.298(13)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1362(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    940
_cell_measurement_theta_min      3.475
_cell_measurement_theta_max      27.868

_exptl_crystal_description       'hexagonal capped prism'
_exptl_crystal_colour            green
_exptl_crystal_size_max          0.267
_exptl_crystal_size_mid          0.230
_exptl_crystal_size_min          0.226
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.127
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             832
_exptl_absorpt_coefficient_mu    4.773
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.822016
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_process_details   'SADABS, Sheldrick 1996'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      100(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 1000 CCD'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         102
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        0.00
_diffrn_reflns_number            3789
_diffrn_reflns_av_R_equivalents  0.2413
_diffrn_reflns_av_sigmaI/netI    0.1152
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         3.47
_diffrn_reflns_theta_max         26.37
_reflns_number_total             805
_reflns_number_gt                723
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART (BrukerAXS, 1997)'
_computing_cell_refinement       'SMART (BrukerAXS, 1997)'
_computing_data_reduction        'SAINT+ (BrukerAXS, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'XPMA/ZORTEP, WebLab Viewer 3.7'
_computing_publication_material  XCIF

_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)+(0.0475P)²+102.1499P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         805
_refine_ls_number_parameters     29
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0787
_refine_ls_R_factor_gt           0.0733
_refine_ls_wR_factor_ref         0.1885
_refine_ls_wR_factor_gt          0.1836
_refine_ls_goodness_of_fit_ref   1.123
_refine_ls_restrained_S_all      1.123
_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
Pr1A Pr 0.0000 0.3443(4) 0.7500 0.0008(5) Uiso 0.50 4 d SPD . 1
Pr1B Pr 0.0000 0.3228(4) 0.7500 0.0008(5) Uiso 0.50 4 d SPD . 2
Co1 Co 0.0000 0.0000 0.5000 0.0059(7) Uiso 1 4 d S . .
N1 N 0.0000 0.2129(17) 0.6072(14) 0.014(5) Uiso 1 2 d S . .
C1 C 0.0000 0.135(2) 0.5664(17) 0.007(4) Uiso 1 2 d S . .
N2 N 0.239(3) 0.3886(14) 0.6278(10) 0.026(3) Uiso 1 1 d . . .
C2 C 0.338(2) 0.4290(15) 0.5787(10) 0.011(3) Uiso 1 1 d . . .
O1 O 0.306(2) 0.2526(16) 0.7500 0.024(5) Uiso 1 2 d SD . .
O1B O 0.0000 0.5221(15) 0.7500 0.039(18) Uiso 0.50 4 d SPD A 2
O2 O 0.0000 0.6681(16) 0.5850(8) 0.020(3) Uiso 1 2 d S . .

_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
Pr1A N2 2.556(17) 10_557 ?
Pr1A N2 2.556(17) 11 ?
Pr1A N2 2.556(17) . ?
Pr1A N2 2.556(17) 4_556 ?
Pr1A O1 2.558(17) 11 ?
Pr1A O1 2.558(17) . ?
Pr1A N1 2.65(2) . ?
Pr1A N1 2.65(2) 10_557 ?
Pr1B O1 2.443(17) 11 ?
Pr1B O1 2.443(17) . ?
Pr1B N1 2.48(2) . ?
Pr1B N1 2.48(2) 10_557 ?
Pr1B O1B 2.554(19) . ?
Pr1B N2 2.631(17) 10_557 ?
Pr1B N2 2.631(17) 11 ?
Pr1B N2 2.631(17) . ?
Pr1B N2 2.631(17) 4_556 ?
Co1 C2 1.884(17) 15_545 ?
Co1 C2 1.884(17) 7_456 ?
Co1 C2 1.884(17) 13_556 ?
Co1 C2 1.884(17) 5_445 ?
Co1 C1 1.97(3) . ?
Co1 C1 1.97(3) 9_556 ?
N1 C1 1.16(4) . ?
N2 C2 1.14(2) . ?
C2 Co1 1.884(17) 5 ?

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
N2 Pr1A N2 154.3(8) 10_557 11 ?
N2 Pr1A N2 86.2(8) 10_557 . ?
N2 Pr1A N2 88.1(8) 11 . ?
N2 Pr1A N2 88.1(8) 10_557 4_556 ?
N2 Pr1A N2 86.2(8) 11 4_556 ?
N2 Pr1A N2 154.3(8) . 4_556 ?
N2 Pr1A O1 136.0(4) 10_557 11 ?
N2 Pr1A O1 59.0(5) 11 11 ?
N2 Pr1A O1 136.0(4) . 11 ?
N2 Pr1A O1 59.0(5) 4_556 11 ?
N2 Pr1A O1 59.0(5) 10_557 . ?
N2 Pr1A O1 136.0(4) 11 . ?
N2 Pr1A O1 59.0(5) . . ?
N2 Pr1A O1 136.0(4) 4_556 . ?
O1 Pr1A O1 125.3(10) 11 . ?
N2 Pr1A N1 132.0(5) 10_557 . ?
N2 Pr1A N1 67.3(5) 11 . ?
N2 Pr1A N1 67.3(5) . . ?
N2 Pr1A N1 132.0(5) 4_556 . ?
O1 Pr1A N1 73.0(4) 11 . ?
O1 Pr1A N1 73.0(4) . . ?
N2 Pr1A N1 67.3(5) 10_557 10_557 ?
N2 Pr1A N1 132.0(5) 11 10_557 ?
N2 Pr1A N1 132.0(5) . 10_557 ?
N2 Pr1A N1 67.3(5) 4_556 10_557 ?
O1 Pr1A N1 73.0(4) 11 10_557 ?
O1 Pr1A N1 73.0(4) . 10_557 ?
N1 Pr1A N1 101.0(9) . 10_557 ?
O1 Pr1B O1 136.8(11) 11 . ?
O1 Pr1B N1 77.9(3) 11 . ?
O1 Pr1B N1 77.9(3) . . ?
O1 Pr1B N1 77.9(3) 11 10_557 ?
O1 Pr1B N1 77.9(3) . 10_557 ?
N1 Pr1B N1 110.8(10) . 10_557 ?
O1 Pr1B O1B 111.6(5) 11 . ?
O1 Pr1B O1B 111.6(5) . . ?
N1 Pr1B O1B 124.6(5) . . ?
N1 Pr1B O1B 124.6(5) 10_557 . ?
O1 Pr1B N2 138.3(4) 11 10_557 ?
O1 Pr1B N2 59.3(5) . 10_557 ?
N1 Pr1B N2 136.8(4) . 10_557 ?
N1 Pr1B N2 68.6(5) 10_557 10_557 ?
O1B Pr1B N2 71.3(4) . 10_557 ?
O1 Pr1B N2 59.3(5) 11 11 ?
O1 Pr1B N2 138.3(4) . 11 ?
N1 Pr1B N2 68.6(5) . 11 ?
N1 Pr1B N2 136.8(4) 10_557 11 ?
O1B Pr1B N2 71.3(4) . 11 ?
N2 Pr1B N2 142.6(8) 10_557 11 ?
O1 Pr1B N2 138.3(4) 11 . ?
O1 Pr1B N2 59.3(5) . . ?
N1 Pr1B N2 68.6(5) . . ?
N1 Pr1B N2 136.8(4) 10_557 . ?
O1B Pr1B N2 71.3(4) . . ?
N2 Pr1B N2 83.2(7) 10_557 . ?
N2 Pr1B N2 85.0(8) 11 . ?
O1 Pr1B N2 59.3(5) 11 4_556 ?
O1 Pr1B N2 138.3(4) . 4_556 ?
N1 Pr1B N2 136.8(4) . 4_556 ?
N1 Pr1B N2 68.6(5) 10_557 4_556 ?
O1B Pr1B N2 71.3(4) . 4_556 ?
N2 Pr1B N2 85.0(8) 10_557 4_556 ?
N2 Pr1B N2 83.2(7) 11 4_556 ?
N2 Pr1B N2 142.6(8) . 4_556 ?
C2 Co1 C2 180.0(7) 15_545 7_456 ?
C2 Co1 C2 100.4(11) 15_545 13_556 ?
C2 Co1 C2 79.6(11) 7_456 13_556 ?
C2 Co1 C2 79.6(11) 15_545 5_445 ?
C2 Co1 C2 100.4(11) 7_456 5_445 ?
C2 Co1 C2 180.000(2) 13_556 5_445 ?
C2 Co1 C1 97.8(7) 15_545 . ?
C2 Co1 C1 82.2(7) 7_456 . ?
C2 Co1 C1 82.2(7) 13_556 . ?
C2 Co1 C1 97.8(7) 5_445 . ?
C2 Co1 C1 82.2(7) 15_545 9_556 ?
C2 Co1 C1 97.8(7) 7_456 9_556 ?
C2 Co1 C1 97.8(7) 13_556 9_556 ?
C2 Co1 C1 82.2(7) 5_445 9_556 ?
C1 Co1 C1 180.000(2) . 9_556 ?
C1 N1 Pr1B 155(2) . . ?
C1 N1 Pr1A 160(2) . . ?
Pr1B N1 Pr1A 4.92(18) . . ?
N1 C1 Co1 179(2) . . ?
C2 N2 Pr1A 165.8(16) . . ?
C2 N2 Pr1B 171.7(16) . . ?
Pr1A N2 Pr1B 5.9(2) . . ?
N2 C2 Co1 178.0(17) . 5 ?
Pr1B O1 Pr1A 5.8(2) . . ?

_diffrn_measured_fraction_theta_max 0.997
_diffrn_reflns_theta_full        26.37
_diffrn_measured_fraction_theta_full 0.996
_refine_diff_density_max         3.089
_refine_diff_density_min         -2.523
_refine_diff_density_rms         0.386


# start Validation Reply Form
_vrf_ATOM007_PrCoCN6_4.5H2O      
;
PROBLEM: _atom_site_aniso_label is missing
RESPONSE: The ADPs could not be satisfactorily refined anisotropically due to the twinning and disorder at the Pr site.
;
_vrf_RINTA01_PrCoCN6_4.5H2O      
;
PROBLEM: The value of Rint is greater than 0.18
RESPONSE: The high value of Rint is a consequence of the pseudo-merohedral twinning discussed in the article.
;
_vrf_PLAT020_PrCoCN6_4.5H2O      
;
PROBLEM: The value of Rint is greater than 0.12 .........      0.241       
RESPONSE: The high value of Rint is a consequence of the pseudo-merohedral twinning discussed in the article.
;
_vrf_PLAT043_PrCoCN6_4.5H2O      
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..      18.11 Check 
RESPONSE: The 18 H atoms per unit cell were not refined or modelled.
;
_vrf_PLAT201_PrCoCN6_4.5H2O      
;
PROBLEM: Isotropic non-H Atoms in Main Residue(s) .......          6 Why ? 
RESPONSE: The ADPs could not be satisfactorily refined anisotropically due to the twinning and disorder at the Pr site.
;
_vrf_PLAT306_PrCoCN6_4.5H2O      
;
PROBLEM: Isolated Oxygen Atom (H-atoms Missing ?) .......         O1 Check 
RESPONSE: The H atoms of this unbound water molecule are disordered and were not refined or modelled (see the accompanying single crystal neutron structure for LaCo(CN)6.5H2O).
;
# end Validation Reply Form
_database_code_depnum_ccdc_archive 'CCDC 992301'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_PrFe(CN)6_4.5H2O

_audit_creation_method           SHELXL-97

_chemical_name_systematic        
'praseodymium(III) hexacyanidoferrate(III) tetrahemihydrate'
_chemical_name_common            
'praseodymium(III) hexacyanidoferrate(III) tetrahemihydrate'
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C6 H9 Fe N6 O4.50 Pr'
_chemical_formula_weight         432.94

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'
Pr Pr -0.2180 2.8214 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Cmcm

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

_cell_length_a                   7.523(8)
_cell_length_b                   13.117(14)
_cell_length_c                   14.476(15)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1428(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    886
_cell_measurement_theta_min      2.8225
_cell_measurement_theta_max      27.7075

_exptl_crystal_description       'hexagonal capped prism'
_exptl_crystal_colour            red-brown
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.24
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.013
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             828
_exptl_absorpt_coefficient_mu    4.404
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.714080
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_process_details   'SADABS, Sheldrick 1996'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      100(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 1000 CCD'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        0.00
_diffrn_reflns_number            2492
_diffrn_reflns_av_R_equivalents  0.1538
_diffrn_reflns_av_sigmaI/netI    0.0883
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_theta_min         1.41
_diffrn_reflns_theta_max         27.88
_reflns_number_total             916
_reflns_number_gt                800
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART (BrukerAXS, 1997)'
_computing_cell_refinement       'SMART (BrukerAXS, 1997)'
_computing_data_reduction        'SAINT+ (BrukerAXS, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'XPMA/ZORTEP, WebLab Viewer 3.7'
_computing_publication_material  XCIF

_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)+(0.0742P)²+87.6496P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         916
_refine_ls_number_parameters     29
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0812
_refine_ls_R_factor_gt           0.0733
_refine_ls_wR_factor_ref         0.1869
_refine_ls_wR_factor_gt          0.1803
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_restrained_S_all      1.096
_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
Pr1A Pr 0.0000 0.3348(7) 0.7500 0.0080(4) Uiso 0.50 4 d SPD . 1
Pr1B Pr 0.0000 0.3322(8) 0.7500 0.0080(4) Uiso 0.50 4 d SPD . 2
Fe1 Fe 0.0000 0.0000 0.5000 0.0078(6) Uiso 1 4 d S . .
N1 N 0.0000 0.2101(16) 0.6102(14) 0.015(4) Uiso 1 2 d S . .
C1 C 0.0000 0.128(3) 0.565(3) 0.035(8) Uiso 1 2 d S . .
N2 N 0.243(2) 0.3933(13) 0.6312(11) 0.032(3) Uiso 1 1 d . . .
C2 C 0.307(2) 0.4473(14) 0.5778(11) 0.018(3) Uiso 1 1 d . . .
O1 O 0.303(2) 0.2541(15) 0.7500 0.032(5) Uiso 1 2 d SD . .
O1B O 0.0000 0.5235(14) 0.7500 0.042(19) Uiso 0.50 4 d SPD A 2
O2 O 0.0000 0.6509(11) 0.5897(8) 0.012(3) Uiso 1 2 d S . .

_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
Pr1A O1 2.511(17) 11 ?
Pr1A O1 2.511(17) . ?
Pr1A N2 2.623(18) 10_557 ?
Pr1A N2 2.623(18) 11 ?
Pr1A N2 2.623(18) . ?
Pr1A N2 2.623(18) 4_556 ?
Pr1A N1 2.60(2) . ?
Pr1A N1 2.60(2) 10_557 ?
Pr1B O1B 2.510(19) . ?
Pr1B O1 2.497(17) 11 ?
Pr1B O1 2.497(17) . ?
Pr1B N1 2.58(2) . ?
Pr1B N1 2.58(2) 10_557 ?
Pr1B N2 2.634(18) 10_557 ?
Pr1B N2 2.634(18) 11 ?
Pr1B N2 2.634(18) . ?
Pr1B N2 2.634(18) 4_556 ?
Fe1 C1 1.92(4) 9_556 ?
Fe1 C1 1.92(4) . ?
Fe1 C2 1.961(17) 15_545 ?
Fe1 C2 1.961(17) 13_556 ?
Fe1 C2 1.961(17) 7_456 ?
Fe1 C2 1.961(17) 5_445 ?
N1 C1 1.26(5) . ?
N2 C2 1.16(2) . ?
C2 Fe1 1.961(17) 5 ?

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
O1 Pr1A O1 130.1(11) 11 . ?
O1 Pr1A N2 139.0(4) 11 10_557 ?
O1 Pr1A N2 59.5(5) . 10_557 ?
O1 Pr1A N2 59.5(5) 11 11 ?
O1 Pr1A N2 139.0(4) . 11 ?
N2 Pr1A N2 146.0(8) 10_557 11 ?
O1 Pr1A N2 139.0(4) 11 . ?
O1 Pr1A N2 59.5(5) . . ?
N2 Pr1A N2 81.9(8) 10_557 . ?
N2 Pr1A N2 88.2(8) 11 . ?
O1 Pr1A N2 59.5(5) 11 4_556 ?
O1 Pr1A N2 139.0(4) . 4_556 ?
N2 Pr1A N2 88.2(8) 10_557 4_556 ?
N2 Pr1A N2 81.9(8) 11 4_556 ?
N2 Pr1A N2 146.0(8) . 4_556 ?
O1 Pr1A N1 74.6(4) 11 . ?
O1 Pr1A N1 74.6(4) . . ?
N2 Pr1A N1 133.9(5) 10_557 . ?
N2 Pr1A N1 71.0(5) 11 . ?
N2 Pr1A N1 71.0(5) . . ?
N2 Pr1A N1 133.9(5) 4_556 . ?
O1 Pr1A N1 74.6(4) 11 10_557 ?
O1 Pr1A N1 74.6(4) . 10_557 ?
N2 Pr1A N1 71.0(5) 10_557 10_557 ?
N2 Pr1A N1 133.9(5) 11 10_557 ?
N2 Pr1A N1 133.9(5) . 10_557 ?
N2 Pr1A N1 71.0(5) 4_556 10_557 ?
N1 Pr1A N1 102.1(10) . 10_557 ?
O1B Pr1B O1 114.2(5) . 11 ?
O1B Pr1B O1 114.2(5) . . ?
O1 Pr1B O1 131.6(11) 11 . ?
O1B Pr1B N1 128.3(5) . . ?
O1 Pr1B N1 75.3(4) 11 . ?
O1 Pr1B N1 75.3(4) . . ?
O1B Pr1B N1 128.3(5) . 10_557 ?
O1 Pr1B N1 75.3(4) 11 10_557 ?
O1 Pr1B N1 75.3(4) . 10_557 ?
N1 Pr1B N1 103.3(10) . 10_557 ?
O1B Pr1B N2 72.3(4) . 10_557 ?
O1 Pr1B N2 139.2(4) 11 10_557 ?
O1 Pr1B N2 59.5(5) . 10_557 ?
N1 Pr1B N2 134.5(5) . 10_557 ?
N1 Pr1B N2 71.1(5) 10_557 10_557 ?
O1B Pr1B N2 72.3(4) . 11 ?
O1 Pr1B N2 59.5(5) 11 11 ?
O1 Pr1B N2 139.2(4) . 11 ?
N1 Pr1B N2 71.1(5) . 11 ?
N1 Pr1B N2 134.5(5) 10_557 11 ?
N2 Pr1B N2 144.6(8) 10_557 11 ?
O1B Pr1B N2 72.3(4) . . ?
O1 Pr1B N2 139.2(4) 11 . ?
O1 Pr1B N2 59.5(5) . . ?
N1 Pr1B N2 71.1(5) . . ?
N1 Pr1B N2 134.5(5) 10_557 . ?
N2 Pr1B N2 81.6(8) 10_557 . ?
N2 Pr1B N2 87.8(8) 11 . ?
O1B Pr1B N2 72.3(4) . 4_556 ?
O1 Pr1B N2 59.5(5) 11 4_556 ?
O1 Pr1B N2 139.2(4) . 4_556 ?
N1 Pr1B N2 134.5(5) . 4_556 ?
N1 Pr1B N2 71.1(5) 10_557 4_556 ?
N2 Pr1B N2 87.8(8) 10_557 4_556 ?
N2 Pr1B N2 81.6(8) 11 4_556 ?
N2 Pr1B N2 144.6(8) . 4_556 ?
C1 Fe1 C1 180.000(2) 9_556 . ?
C1 Fe1 C2 88.6(9) 9_556 15_545 ?
C1 Fe1 C2 91.4(9) . 15_545 ?
C1 Fe1 C2 91.4(9) 9_556 13_556 ?
C1 Fe1 C2 88.6(9) . 13_556 ?
C2 Fe1 C2 84.8(11) 15_545 13_556 ?
C1 Fe1 C2 91.4(9) 9_556 7_456 ?
C1 Fe1 C2 88.6(9) . 7_456 ?
C2 Fe1 C2 180.0(8) 15_545 7_456 ?
C2 Fe1 C2 95.2(11) 13_556 7_456 ?
C1 Fe1 C2 88.6(9) 9_556 5_445 ?
C1 Fe1 C2 91.4(9) . 5_445 ?
C2 Fe1 C2 95.2(11) 15_545 5_445 ?
C2 Fe1 C2 180.000(1) 13_556 5_445 ?
C2 Fe1 C2 84.8(11) 7_456 5_445 ?
C1 N1 Pr1B 159(2) . . ?
C1 N1 Pr1A 160(2) . . ?
Pr1B N1 Pr1A 0.6(3) . . ?
N1 C1 Fe1 178(3) . . ?
C2 N2 Pr1A 155.6(16) . . ?
C2 N2 Pr1B 156.2(16) . . ?
Pr1A N2 Pr1B 0.7(4) . . ?
N2 C2 Fe1 155.7(18) . 5 ?
Pr1B O1 Pr1A 0.7(4) . . ?

_diffrn_measured_fraction_theta_max 0.927
_diffrn_reflns_theta_full        27.88
_diffrn_measured_fraction_theta_full 0.927
_refine_diff_density_max         4.548
_refine_diff_density_min         -4.330
_refine_diff_density_rms         0.407

# start Validation Reply Form
_vrf_ATOM007_PrFeCN6_4.5H2O      
;
PROBLEM: _atom_site_aniso_label is missing
RESPONSE: The ADPs could not be satisfactorily refined anisotropically due to the twinning and disorder at the Pr site.
;
_vrf_PLAT029_PrFeCN6_4.5H2O      
;
PROBLEM: _diffrn_measured_fraction_theta_full Low .......      0.927 Note  
RESPONSE: Some high angle data were discarded to aid the refinement for this twinned crystal.
;
_vrf_PLAT043_PrFeCN6_4.5H2O      
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..      18.10 Check 
RESPONSE: The 18 H atoms per unit cell were not refined or modelled.
;
_vrf_PLAT201_PrFeCN6_4.5H2O      
;
PROBLEM: Isotropic non-H Atoms in Main Residue(s) .......          6 Why ? 
RESPONSE: The ADPs could not be satisfactorily refined anisotropically due to the twinning and disorder at the Pr site.
;
_vrf_PLAT306_PrFeCN6_4.5H2O      
;
PROBLEM: Isolated Oxygen Atom (H-atoms Missing ?) .......         O1 Check 
RESPONSE: The H atoms of this unbound water molecule are disordered and were not refined or modelled (see the accompanying single crystal neutron structure for LaCo(CN)6.5H2O).
;
# end Validation Reply Form
_database_code_depnum_ccdc_archive 'CCDC 992302'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_SmCo(CN)6_4H2O

_audit_creation_method           SHELXL-97

_chemical_name_systematic        
'samarium(III) hexacyanidocobaltate(III) tetrahydrate'
_chemical_name_common            
'samarium(III) hexacyanidocobaltate(III) tetrahydrate'
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C6 H8 Co N6 O4 Sm'
_chemical_formula_weight         437.46

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'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Sm Sm -0.1638 3.4418 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Cmcm

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

_cell_length_a                   7.375(4)
_cell_length_b                   12.742(6)
_cell_length_c                   13.653(7)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1283.1(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    841
_cell_measurement_theta_min      2.9835
_cell_measurement_theta_max      28.0215

_exptl_crystal_description       needle
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.11
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.265
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             828
_exptl_absorpt_coefficient_mu    5.840
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.813348
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_process_details   'SADABS, Sheldrick 1996'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         125
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        0.00
_diffrn_reflns_number            4277
_diffrn_reflns_av_R_equivalents  0.1376
_diffrn_reflns_av_sigmaI/netI    0.0675
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         1.49
_diffrn_reflns_theta_max         28.11
_reflns_number_total             884
_reflns_number_gt                880
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART (BrukerAXS, 1997)'
_computing_cell_refinement       'SMART (BrukerAXS, 1997)'
_computing_data_reduction        'SAINT+ (BrukerAXS, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'XPMA/ZORTEP, WebLab Viewer 3.7'
_computing_publication_material  XCIF

_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+25.5770P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         884
_refine_ls_number_parameters     53
_refine_ls_number_restraints     12
_refine_ls_R_factor_all          0.0350
_refine_ls_R_factor_gt           0.0348
_refine_ls_wR_factor_ref         0.0859
_refine_ls_wR_factor_gt          0.0858
_refine_ls_goodness_of_fit_ref   1.124
_refine_ls_restrained_S_all      1.116
_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
Sm1 Sm 0.0000 0.32472(6) 0.7500 0.00506(17) Uani 1 4 d S . .
Co1 Co 0.0000 0.0000 0.5000 0.0055(3) Uani 1 4 d S . .
N1 N 0.0000 0.2189(8) 0.5939(6) 0.0096(18) Uani 1 2 d SU . .
C1 C 0.0000 0.1356(10) 0.5573(7) 0.012(2) Uani 1 2 d S . .
N2 N 0.2047(8) 0.4269(5) 0.6388(4) 0.0119(12) Uani 1 1 d . . .
C2 C 0.3184(10) 0.4552(6) 0.5871(4) 0.0069(12) Uani 1 1 d U . .
O1 O 0.2647(12) 0.2156(7) 0.7500 0.0187(18) Uani 1 2 d S . .
O2 O 0.0000 0.6541(6) 0.6004(4) 0.0127(13) Uani 1 2 d S . .

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
Sm1 0.0022(3) 0.0096(4) 0.0034(2) 0.000 0.000 0.000
Co1 0.0036(8) 0.0086(10) 0.0042(6) 0.0004(6) 0.000 0.000
N1 0.010(2) 0.009(2) 0.0095(19) -0.0003(10) 0.000 0.000
C1 0.005(4) 0.023(5) 0.007(4) 0.011(4) 0.000 0.000
N2 0.006(3) 0.020(3) 0.009(2) -0.002(2) -0.001(2) -0.002(3)
C2 0.0064(14) 0.0072(15) 0.0072(14) -0.0004(9) -0.0002(9) -0.0001(9)
O1 0.011(4) 0.033(5) 0.012(3) 0.000 0.000 0.008(4)
O2 0.009(4) 0.020(5) 0.010(2) 0.000(2) 0.000 0.000

_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
Sm1 O1 2.397(8) . ?
Sm1 O1 2.397(8) 11 ?
Sm1 N2 2.506(6) 10_557 ?
Sm1 N2 2.506(6) 11 ?
Sm1 N2 2.506(6) 4_556 ?
Sm1 N2 2.506(6) . ?
Sm1 N1 2.522(9) 10_557 ?
Sm1 N1 2.522(9) . ?
Co1 C2 1.880(7) 15_545 ?
Co1 C2 1.880(7) 7_456 ?
Co1 C2 1.880(7) 13_556 ?
Co1 C2 1.880(7) 5_445 ?
Co1 C1 1.896(13) 9_556 ?
Co1 C1 1.896(13) . ?
N1 C1 1.174(16) . ?
N2 C2 1.153(9) . ?
C2 Co1 1.880(7) 5 ?

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
O1 Sm1 O1 109.1(5) . 11 ?
O1 Sm1 N2 79.1(2) . 10_557 ?
O1 Sm1 N2 142.39(12) 11 10_557 ?
O1 Sm1 N2 142.39(12) . 11 ?
O1 Sm1 N2 79.1(2) 11 11 ?
N2 Sm1 N2 117.4(3) 10_557 11 ?
O1 Sm1 N2 142.39(12) . 4_556 ?
O1 Sm1 N2 79.1(2) 11 4_556 ?
N2 Sm1 N2 74.1(3) 10_557 4_556 ?
N2 Sm1 N2 74.6(2) 11 4_556 ?
O1 Sm1 N2 79.1(2) . . ?
O1 Sm1 N2 142.39(12) 11 . ?
N2 Sm1 N2 74.6(2) 10_557 . ?
N2 Sm1 N2 74.1(3) 11 . ?
N2 Sm1 N2 117.4(3) 4_556 . ?
O1 Sm1 N1 71.94(16) . 10_557 ?
O1 Sm1 N1 71.93(16) 11 10_557 ?
N2 Sm1 N1 76.5(2) 10_557 10_557 ?
N2 Sm1 N1 142.17(14) 11 10_557 ?
N2 Sm1 N1 76.5(2) 4_556 10_557 ?
N2 Sm1 N1 142.17(14) . 10_557 ?
O1 Sm1 N1 71.94(16) . . ?
O1 Sm1 N1 71.94(16) 11 . ?
N2 Sm1 N1 142.17(14) 10_557 . ?
N2 Sm1 N1 76.5(2) 11 . ?
N2 Sm1 N1 142.17(14) 4_556 . ?
N2 Sm1 N1 76.4(2) . . ?
N1 Sm1 N1 115.4(4) 10_557 . ?
C2 Co1 C2 180.000(1) 15_545 7_456 ?
C2 Co1 C2 89.2(4) 15_545 13_556 ?
C2 Co1 C2 90.8(4) 7_456 13_556 ?
C2 Co1 C2 90.8(4) 15_545 5_445 ?
C2 Co1 C2 89.2(4) 7_456 5_445 ?
C2 Co1 C2 180.000(1) 13_556 5_445 ?
C2 Co1 C1 89.1(3) 15_545 9_556 ?
C2 Co1 C1 90.9(3) 7_456 9_556 ?
C2 Co1 C1 90.9(3) 13_556 9_556 ?
C2 Co1 C1 89.1(3) 5_445 9_556 ?
C2 Co1 C1 90.9(3) 15_545 . ?
C2 Co1 C1 89.1(3) 7_456 . ?
C2 Co1 C1 89.1(3) 13_556 . ?
C2 Co1 C1 90.9(3) 5_445 . ?
C1 Co1 C1 180.000(1) 9_556 . ?
C1 N1 Sm1 147.5(8) . . ?
N1 C1 Co1 179.2(9) . . ?
C2 N2 Sm1 166.1(6) . . ?
N2 C2 Co1 178.4(6) . 5 ?

_diffrn_measured_fraction_theta_max 0.972
_diffrn_reflns_theta_full        28.11
_diffrn_measured_fraction_theta_full 0.972
_refine_diff_density_max         1.583
_refine_diff_density_min         -3.132
_refine_diff_density_rms         0.233


# start Validation Reply Form
_vrf_PLAT043_SmCoCN6_4H2O        
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..       8.05 Check 
RESPONSE: The 8 H atoms per formula unit were not refined or modelled.
;
_vrf_PLAT213_SmCoCN6_4H2O        
;
PROBLEM: Atom C1              has ADP max/min Ratio .....        4.5 prolat
RESPONSE: C is a weak scatterer in comparison to Sm and Fe, which, in addition to the pseudo-merohedral twinning, may lead to this anomalous ADP ratio.
;
_vrf_PLAT306_SmCoCN6_4H2O        
;
PROBLEM: Isolated Oxygen Atom (H-atoms Missing ?) .......         O2 Check 
RESPONSE: The H atoms of this unbound water molecule are disordered and were not refined or modelled (see the accompanying single crystal neutron structure for LaCo(CN)6.5H2O).
;
# end Validation Reply Form
_database_code_depnum_ccdc_archive 'CCDC 992303'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_EuCo(CN)6_4H2O

_audit_creation_method           SHELXL-97

_chemical_name_systematic        
'europium(III) hexacyanidocobaltate(III) tetrahydrate'
_chemical_name_common            
'europium(III) hexacyanidocobaltate(III) tetrahydrate'
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C6 H8 Co Eu N6 O4'
_chemical_formula_weight         439.07

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'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Eu Eu -0.1578 3.6682 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Cmcm

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

_cell_length_a                   7.3394(12)
_cell_length_b                   12.750(2)
_cell_length_c                   13.617(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1274.3(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    3883
_cell_measurement_theta_min      2.992
_cell_measurement_theta_max      28.0585

_exptl_crystal_description       needle
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.289
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             832
_exptl_absorpt_coefficient_mu    6.194
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.767629
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_process_details   'SADABS, Sheldrick 1996'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      100(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 1000 CCD'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            4011
_diffrn_reflns_av_R_equivalents  0.1378
_diffrn_reflns_av_sigmaI/netI    0.0684
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         1.50
_diffrn_reflns_theta_max         28.06
_reflns_number_total             885
_reflns_number_gt                878
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART (BrukerAXS, 1997)'
_computing_cell_refinement       'SMART (BrukerAXS, 1997)'
_computing_data_reduction        'SAINT+ (BrukerAXS, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'XPMA/ZORTEP, WebLab Viewer 3.7'
_computing_publication_material  XCIF

_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)+(0.0491P)²+6.7292P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         885
_refine_ls_number_parameters     53
_refine_ls_number_restraints     12
_refine_ls_R_factor_all          0.0370
_refine_ls_R_factor_gt           0.0368
_refine_ls_wR_factor_ref         0.1010
_refine_ls_wR_factor_gt          0.1009
_refine_ls_goodness_of_fit_ref   1.193
_refine_ls_restrained_S_all      1.187
_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
Eu1 Eu 0.0000 0.32458(5) 0.7500 0.0052(2) Uani 1 4 d S . .
Co1 Co 0.0000 0.0000 0.5000 0.0053(3) Uani 1 4 d S . .
N1 N 0.0000 0.2187(8) 0.5949(6) 0.0126(18) Uani 1 2 d S . .
C1 C 0.0000 0.1351(9) 0.5573(8) 0.0120(19) Uani 1 2 d SU . .
N2 N 0.2037(9) 0.4268(5) 0.6394(4) 0.0146(12) Uani 1 1 d . . .
C2 C 0.3178(9) 0.4547(6) 0.5872(4) 0.0073(12) Uani 1 1 d U . .
O1 O 0.2636(10) 0.2157(7) 0.7500 0.0169(15) Uani 1 2 d S . .
O2 O 0.0000 0.6536(6) 0.6007(5) 0.0146(12) Uani 1 2 d S . .

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
Eu1 0.0085(4) 0.0014(4) 0.0057(3) 0.000 0.000 0.000
Co1 0.0072(8) 0.0020(10) 0.0068(6) 0.0005(6) 0.000 0.000
N1 0.022(5) 0.004(4) 0.012(4) -0.005(3) 0.000 0.000
C1 0.012(4) 0.012(4) 0.012(3) 0.007(3) 0.000 0.000
N2 0.016(3) 0.017(3) 0.011(2) 0.002(2) -0.001(2) -0.001(2)
C2 0.010(3) 0.003(3) 0.009(2) 0.001(2) -0.003(2) 0.001(2)
O1 0.010(4) 0.023(4) 0.018(3) 0.000 0.000 0.010(3)
O2 0.019(4) 0.013(4) 0.012(2) 0.005(2) 0.000 0.000

_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
Eu1 O1 2.381(7) 11 ?
Eu1 O1 2.381(7) . ?
Eu1 N2 2.490(6) . ?
Eu1 N2 2.490(6) 10_557 ?
Eu1 N2 2.490(6) 11 ?
Eu1 N2 2.490(6) 4_556 ?
Eu1 N1 2.507(9) . ?
Eu1 N1 2.507(9) 10_557 ?
Co1 C2 1.879(7) 15_545 ?
Co1 C2 1.879(7) 7_456 ?
Co1 C2 1.879(7) 13_556 ?
Co1 C2 1.879(7) 5_445 ?
Co1 C1 1.891(12) 9_556 ?
Co1 C1 1.891(12) . ?
N1 C1 1.182(16) . ?
N2 C2 1.155(9) . ?
C2 Co1 1.879(7) 5 ?

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
O1 Eu1 O1 108.7(5) 11 . ?
O1 Eu1 N2 142.43(14) 11 . ?
O1 Eu1 N2 79.5(2) . . ?
O1 Eu1 N2 142.43(14) 11 10_557 ?
O1 Eu1 N2 79.5(2) . 10_557 ?
N2 Eu1 N2 74.5(3) . 10_557 ?
O1 Eu1 N2 79.5(2) 11 11 ?
O1 Eu1 N2 142.43(14) . 11 ?
N2 Eu1 N2 73.8(3) . 11 ?
N2 Eu1 N2 116.9(3) 10_557 11 ?
O1 Eu1 N2 79.5(2) 11 4_556 ?
O1 Eu1 N2 142.43(14) . 4_556 ?
N2 Eu1 N2 116.9(3) . 4_556 ?
N2 Eu1 N2 73.8(3) 10_557 4_556 ?
N2 Eu1 N2 74.5(3) 11 4_556 ?
O1 Eu1 N1 71.70(16) 11 . ?
O1 Eu1 N1 71.70(16) . . ?
N2 Eu1 N1 76.8(2) . . ?
N2 Eu1 N1 142.33(15) 10_557 . ?
N2 Eu1 N1 76.8(2) 11 . ?
N2 Eu1 N1 142.33(15) 4_556 . ?
O1 Eu1 N1 71.70(16) 11 10_557 ?
O1 Eu1 N1 71.70(16) . 10_557 ?
N2 Eu1 N1 142.33(15) . 10_557 ?
N2 Eu1 N1 76.8(2) 10_557 10_557 ?
N2 Eu1 N1 142.33(15) 11 10_557 ?
N2 Eu1 N1 76.8(2) 4_556 10_557 ?
N1 Eu1 N1 114.8(5) . 10_557 ?
C2 Co1 C2 180.000(1) 15_545 7_456 ?
C2 Co1 C2 89.3(4) 15_545 13_556 ?
C2 Co1 C2 90.7(4) 7_456 13_556 ?
C2 Co1 C2 90.7(4) 15_545 5_445 ?
C2 Co1 C2 89.3(4) 7_456 5_445 ?
C2 Co1 C2 180.000(1) 13_556 5_445 ?
C2 Co1 C1 88.9(3) 15_545 9_556 ?
C2 Co1 C1 91.1(3) 7_456 9_556 ?
C2 Co1 C1 91.1(3) 13_556 9_556 ?
C2 Co1 C1 88.9(3) 5_445 9_556 ?
C2 Co1 C1 91.1(3) 15_545 . ?
C2 Co1 C1 88.9(3) 7_456 . ?
C2 Co1 C1 88.9(3) 13_556 . ?
C2 Co1 C1 91.1(3) 5_445 . ?
C1 Co1 C1 179.999(1) 9_556 . ?
C1 N1 Eu1 148.2(9) . . ?
N1 C1 Co1 178.8(10) . . ?
C2 N2 Eu1 165.7(6) . . ?
N2 C2 Co1 178.8(6) . 5 ?

_diffrn_measured_fraction_theta_max 0.977
_diffrn_reflns_theta_full        28.06
_diffrn_measured_fraction_theta_full 0.977
_refine_diff_density_max         3.398
_refine_diff_density_min         -2.603
_refine_diff_density_rms         0.321


# start Validation Reply Form
_vrf_PLAT043_EuCoCN6_4H2O        
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..       8.05 Check 
RESPONSE: The 8 H atoms per formula unit were not refined or modelled.
;
_vrf_PLAT306_SmCoCN6_4H2O        
;
PROBLEM: Isolated Oxygen Atom (H-atoms Missing ?) .......         O2 Check 
RESPONSE: The H atoms of this unbound water molecule are disordered and were not refined or modelled (see the accompanying single crystal neutron structure for LaCo(CN)6.5H2O).
;
# end Validation Reply Form
_database_code_depnum_ccdc_archive 'CCDC 992304'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_NaLuFe(CN)6_3H2O

_audit_creation_method           SHELXL-97

_chemical_name_systematic        
'sodium lutetium(III) hexacyanidoferrate(II) trihydrate'
_chemical_name_common            
'sodium lutetium(III) hexacyanidoferrate(II) trihydrate'
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C6 H6 Fe Lu N6 Na O3'
_chemical_formula_weight         463.96

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'
Lu Lu -0.4720 5.8584 '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   Cmcm

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

_cell_length_a                   7.242(3)
_cell_length_b                   12.578(5)
_cell_length_c                   13.361(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1216.9(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    990
_cell_measurement_theta_min      6.098
_cell_measurement_theta_max      55.789

_exptl_crystal_description       'needle fragment'
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.631
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             904
_exptl_absorpt_coefficient_mu    9.311
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.2762
_exptl_absorpt_correction_T_max  0.4309
_exptl_absorpt_process_details   'SADABS, Sheldrick 1996'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      150(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  ?
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            5596
_diffrn_reflns_av_R_equivalents  0.0307
_diffrn_reflns_av_sigmaI/netI    0.0182
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         3.24
_diffrn_reflns_theta_max         26.72
_reflns_number_total             757
_reflns_number_gt                752
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART (BrukerAXS, 1997)'
_computing_cell_refinement       'SMART (BrukerAXS, 1997)'
_computing_data_reduction        'SAINT+ (BrukerAXS, 1997)'
_computing_structure_solution    'SHELXTL (BrukerAXS, 2000)'
_computing_structure_refinement  'SHELXTL (BrukerAXS, 2000)'

_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)+(0.0304P)²+72.9368P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         757
_refine_ls_number_parameters     53
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0549
_refine_ls_R_factor_gt           0.0542
_refine_ls_wR_factor_ref         0.1317
_refine_ls_wR_factor_gt          0.1306
_refine_ls_goodness_of_fit_ref   1.310
_refine_ls_restrained_S_all      1.310
_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
Lu1 Lu 0.0000 0.32752(11) 0.7500 0.0242(3) Uani 1 4 d S . .
Fe1 Fe 0.0000 0.0000 0.5000 0.0321(8) Uani 1 4 d S . .
N1 N 0.0000 0.202(3) 0.626(3) 0.12(3) Uani 1 2 d S . .
C1 C 0.0000 0.129(3) 0.571(4) 0.11(3) Uani 1 2 d S . .
N2 N 0.201(4) 0.409(3) 0.6387(15) 0.092(12) Uani 1 1 d . . .
C2 C 0.316(3) 0.443(3) 0.5854(16) 0.052(6) Uani 1 1 d . . .
O1 O 0.259(4) 0.208(3) 0.7500 0.103(12) Uani 1 2 d S . .
O2 O 0.0000 0.664(3) 0.5856(13) 0.116(10) Uani 0.50 2 d SP . .
Na1 Na 0.0000 0.664(3) 0.5856(13) 0.116(10) Uani 0.50 2 d SP . .

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
Lu1 0.0322(10) 0.0243(9) 0.0162(4) 0.000 0.000 0.000
Fe1 0.034(3) 0.033(3) 0.0294(17) 0.002(2) 0.000 0.000
N1 0.28(9) 0.034(17) 0.05(2) -0.021(16) 0.000 0.000
C1 0.26(9) 0.04(2) 0.05(2) -0.010(19) 0.000 0.000
N2 0.08(3) 0.16(3) 0.033(9) 0.022(15) 0.005(11) -0.07(3)
C2 0.022(11) 0.100(19) 0.034(9) 0.016(13) -0.006(9) -0.002(12)
O1 0.07(2) 0.17(3) 0.060(13) 0.000 0.000 0.04(2)
O2 0.062(19) 0.22(4) 0.071(10) 0.006(17) 0.000 0.000
Na1 0.062(19) 0.22(4) 0.071(10) 0.006(17) 0.000 0.000

_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
Lu1 N1 2.29(3) . ?
Lu1 N1 2.29(3) 10_557 ?
Lu1 N2 2.317(18) . ?
Lu1 N2 2.317(18) 10_557 ?
Lu1 N2 2.317(18) 11 ?
Lu1 N2 2.317(18) 4_556 ?
Lu1 O1 2.40(3) . ?
Lu1 O1 2.40(3) 11 ?
Fe1 C1 1.88(4) . ?
Fe1 C1 1.88(4) 9_556 ?
Fe1 C2 1.90(2) 15_545 ?
Fe1 C2 1.90(2) 7_456 ?
Fe1 C2 1.90(2) 5_445 ?
Fe1 C2 1.90(2) 13_556 ?
N1 C1 1.17(5) . ?
N2 C2 1.18(3) . ?
C2 Fe1 1.90(2) 5 ?
O1 Na1 2.86(2) 14_547 ?
O1 Na1 2.86(2) 5_545 ?

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
N1 Lu1 N1 92(2) . 10_557 ?
N1 Lu1 N2 80.9(10) . . ?
N1 Lu1 N2 140.2(9) 10_557 . ?
N1 Lu1 N2 140.2(9) . 10_557 ?
N1 Lu1 N2 80.9(10) 10_557 10_557 ?
N2 Lu1 N2 79.8(11) . 10_557 ?
N1 Lu1 N2 80.9(10) . 11 ?
N1 Lu1 N2 140.2(9) 10_557 11 ?
N2 Lu1 N2 77.8(16) . 11 ?
N2 Lu1 N2 128(2) 10_557 11 ?
N1 Lu1 N2 140.2(9) . 4_556 ?
N1 Lu1 N2 80.9(10) 10_557 4_556 ?
N2 Lu1 N2 128(2) . 4_556 ?
N2 Lu1 N2 77.8(16) 10_557 4_556 ?
N2 Lu1 N2 79.8(11) 11 4_556 ?
N1 Lu1 O1 64.4(8) . . ?
N1 Lu1 O1 64.4(8) 10_557 . ?
N2 Lu1 O1 77.5(13) . . ?
N2 Lu1 O1 77.5(13) 10_557 . ?
N2 Lu1 O1 139.9(6) 11 . ?
N2 Lu1 O1 139.9(6) 4_556 . ?
N1 Lu1 O1 64.4(8) . 11 ?
N1 Lu1 O1 64.4(8) 10_557 11 ?
N2 Lu1 O1 139.9(6) . 11 ?
N2 Lu1 O1 139.9(6) 10_557 11 ?
N2 Lu1 O1 77.5(13) 11 11 ?
N2 Lu1 O1 77.5(13) 4_556 11 ?
O1 Lu1 O1 103(2) . 11 ?
C1 Fe1 C1 179.999(3) . 9_556 ?
C1 Fe1 C2 91.4(13) . 15_545 ?
C1 Fe1 C2 88.6(13) 9_556 15_545 ?
C1 Fe1 C2 88.6(13) . 7_456 ?
C1 Fe1 C2 91.4(13) 9_556 7_456 ?
C2 Fe1 C2 180.0(10) 15_545 7_456 ?
C1 Fe1 C2 91.4(13) . 5_445 ?
C1 Fe1 C2 88.6(13) 9_556 5_445 ?
C2 Fe1 C2 89.2(14) 15_545 5_445 ?
C2 Fe1 C2 90.8(14) 7_456 5_445 ?
C1 Fe1 C2 88.6(13) . 13_556 ?
C1 Fe1 C2 91.4(13) 9_556 13_556 ?
C2 Fe1 C2 90.8(14) 15_545 13_556 ?
C2 Fe1 C2 89.2(14) 7_456 13_556 ?
C2 Fe1 C2 180.000(2) 5_445 13_556 ?
C1 N1 Lu1 173(4) . . ?
N1 C1 Fe1 171(5) . . ?
C2 N2 Lu1 173(3) . . ?
N2 C2 Fe1 179(4) . 5 ?
Lu1 O1 Na1 126.8(8) . 14_547 ?
Lu1 O1 Na1 126.8(8) . 5_545 ?
Na1 O1 Na1 100.4(10) 14_547 5_545 ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        26.72
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         2.971
_refine_diff_density_min         -2.758
_refine_diff_density_rms         0.318


# start Validation Reply Form
_vrf_PLAT043_NaLuFeCN6_3H2O      
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..       6.03 Check 
RESPONSE: The 6 H atoms per formula unit were not refined or modelled.
;
_vrf_PLAT241_NaLuFeCN6_3H2O      
;
PROBLEM: High      Ueq as Compared to Neighbors for .....         N2 Check 
RESPONSE: The N atom has some minor disorder.
;
_vrf_PLAT242_NaLuFeCN6_3H2O      
;
PROBLEM: Low       Ueq as Compared to Neighbors for .....        Lu1 Check 
RESPONSE: The neighbouring N atom has some minor disorder.
;
# end Validation Reply Form
_database_code_depnum_ccdc_archive 'CCDC 992305'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_LiLaFe(CN)6_4H2O

_audit_creation_method           SHELXL-97

_chemical_name_systematic        
; 
 lithium lanthanum(III) hexacyanidoferrate(II) tetrahydrate
;
_chemical_name_common            
'lithium lanthanum(III) hexacyanidoferrate(II) tetrahydrate'
_chemical_melting_point          ?
_chemical_formula_moiety         'C6 H8 Fe La Li N6 O4'
_chemical_formula_sum            'C6 H8 Fe La Li N6 O4'
_chemical_formula_weight         429.86

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'
Li Li -0.0003 0.0001 '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'
La La -0.2871 2.4523 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Hexagonal
_symmetry_space_group_name_H-M   P63/m
_symmetry_Int_Tables_number      176

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

_cell_length_a                   7.2338(5)
_cell_length_b                   7.2338(5)
_cell_length_c                   14.2923(9)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     647.69(8)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    3865
_cell_measurement_theta_min      6.494
_cell_measurement_theta_max      55.973

_exptl_crystal_description       'needle fragment'
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.3
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.204
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             408
_exptl_absorpt_coefficient_mu    4.389
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.3176
_exptl_absorpt_correction_T_max  0.4309
_exptl_absorpt_process_details   'SADABS, Sheldrick 1996'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      150(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-AXS SMART 1000 CCD'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            4649
_diffrn_reflns_av_R_equivalents  0.0242
_diffrn_reflns_av_sigmaI/netI    0.0108
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         3.25
_diffrn_reflns_theta_max         26.37
_reflns_number_total             458
_reflns_number_gt                449
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART (BrukerAXS, 1997)'
_computing_cell_refinement       'SMART (BrukerAXS, 1997)'
_computing_data_reduction        'SAINT+ (BrukerAXS, 1997)'
_computing_structure_solution    'SHELXTL (BrukerAXS, 2000)'
_computing_structure_refinement  'SHELXTL (BrukerAXS, 2000)'

_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)+(0.0704P)²+8.8484P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         458
_refine_ls_number_parameters     32
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0465
_refine_ls_R_factor_gt           0.0461
_refine_ls_wR_factor_ref         0.1417
_refine_ls_wR_factor_gt          0.1414
_refine_ls_goodness_of_fit_ref   1.281
_refine_ls_restrained_S_all      1.281
_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
La1 La 0.3333 0.6667 0.2500 0.0106(4) Uani 1 6 d S . .
Fe1 Fe 0.0000 1.0000 0.0000 0.0248(7) Uani 1 6 d S . .
N1 N 0.2832(12) 0.8947(12) 0.1242(6) 0.0348(19) Uani 1 1 d . . .
C1 C 0.1732(15) 0.9384(15) 0.0792(7) 0.030(2) Uani 1 1 d . . .
O1 O 0.4050(17) 0.3401(16) 0.2500 0.038(2) Uani 1 2 d S . .
Li1 Li 0.6667 0.3333 0.0724(13) 0.037(4) Uani 0.50 3 d SP . .
O2 O 0.6667 0.3333 0.0724(13) 0.037(4) Uani 0.50 3 d SP . .

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
La1 0.0111(5) 0.0111(5) 0.0096(6) 0.000 0.000 0.0055(2)
Fe1 0.0248(10) 0.0248(10) 0.0248(16) 0.000 0.000 0.0124(5)
N1 0.030(4) 0.028(4) 0.037(4) 0.015(4) -0.013(4) 0.007(3)
C1 0.030(5) 0.029(4) 0.028(5) 0.002(4) 0.001(4) 0.011(4)
O1 0.047(6) 0.032(5) 0.049(6) 0.000 0.000 0.030(5)
Li1 0.046(7) 0.046(7) 0.019(9) 0.000 0.000 0.023(3)
O2 0.046(7) 0.046(7) 0.019(9) 0.000 0.000 0.023(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
La1 N1 2.585(7) 10_556 ?
La1 N1 2.585(7) . ?
La1 N1 2.585(7) 3_665 ?
La1 N1 2.585(7) 12_666 ?
La1 N1 2.585(7) 8_566 ?
La1 N1 2.585(7) 5_565 ?
La1 O1 2.660(9) 8_566 ?
La1 O1 2.660(9) 3_665 ?
La1 O1 2.660(9) . ?
Fe1 C1 1.900(10) 3_675 ?
Fe1 C1 1.900(10) 9_455 ?
Fe1 C1 1.900(10) . ?
Fe1 C1 1.900(10) 5_465 ?
Fe1 C1 1.900(10) 11_665 ?
Fe1 C1 1.900(10) 7_575 ?
N1 C1 1.182(12) . ?

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
N1 La1 N1 88.1(4) 10_556 . ?
N1 La1 N1 137.88(16) 10_556 3_665 ?
N1 La1 N1 77.0(3) . 3_665 ?
N1 La1 N1 77.0(3) 10_556 12_666 ?
N1 La1 N1 137.88(16) . 12_666 ?
N1 La1 N1 88.1(4) 3_665 12_666 ?
N1 La1 N1 77.0(3) 10_556 8_566 ?
N1 La1 N1 137.88(16) . 8_566 ?
N1 La1 N1 137.88(16) 3_665 8_566 ?
N1 La1 N1 77.0(3) 12_666 8_566 ?
N1 La1 N1 137.88(16) 10_556 5_565 ?
N1 La1 N1 77.0(3) . 5_565 ?
N1 La1 N1 77.0(3) 3_665 5_565 ?
N1 La1 N1 137.88(16) 12_666 5_565 ?
N1 La1 N1 88.1(4) 8_566 5_565 ?
N1 La1 O1 68.9(2) 10_556 8_566 ?
N1 La1 O1 68.9(2) . 8_566 ?
N1 La1 O1 69.0(2) 3_665 8_566 ?
N1 La1 O1 69.0(2) 12_666 8_566 ?
N1 La1 O1 135.9(2) 8_566 8_566 ?
N1 La1 O1 135.9(2) 5_565 8_566 ?
N1 La1 O1 69.0(2) 10_556 3_665 ?
N1 La1 O1 69.0(2) . 3_665 ?
N1 La1 O1 135.9(2) 3_665 3_665 ?
N1 La1 O1 135.9(2) 12_666 3_665 ?
N1 La1 O1 68.9(2) 8_566 3_665 ?
N1 La1 O1 68.9(2) 5_565 3_665 ?
O1 La1 O1 120.000(1) 8_566 3_665 ?
N1 La1 O1 135.9(2) 10_556 . ?
N1 La1 O1 135.9(2) . . ?
N1 La1 O1 68.9(2) 3_665 . ?
N1 La1 O1 68.9(2) 12_666 . ?
N1 La1 O1 69.0(2) 8_566 . ?
N1 La1 O1 69.0(2) 5_565 . ?
O1 La1 O1 120.000(3) 8_566 . ?
O1 La1 O1 120.000(3) 3_665 . ?
C1 Fe1 C1 180.0(5) 3_675 9_455 ?
C1 Fe1 C1 88.1(4) 3_675 . ?
C1 Fe1 C1 91.9(4) 9_455 . ?
C1 Fe1 C1 88.1(4) 3_675 5_465 ?
C1 Fe1 C1 91.9(4) 9_455 5_465 ?
C1 Fe1 C1 88.1(4) . 5_465 ?
C1 Fe1 C1 91.9(4) 3_675 11_665 ?
C1 Fe1 C1 88.1(4) 9_455 11_665 ?
C1 Fe1 C1 91.9(4) . 11_665 ?
C1 Fe1 C1 180.000(1) 5_465 11_665 ?
C1 Fe1 C1 91.9(4) 3_675 7_575 ?
C1 Fe1 C1 88.1(4) 9_455 7_575 ?
C1 Fe1 C1 180.000(1) . 7_575 ?
C1 Fe1 C1 91.9(4) 5_465 7_575 ?
C1 Fe1 C1 88.1(4) 11_665 7_575 ?
C1 N1 La1 151.3(7) . . ?
N1 C1 Fe1 176.2(9) . . ?

_diffrn_measured_fraction_theta_max 0.991
_diffrn_reflns_theta_full        26.37
_diffrn_measured_fraction_theta_full 0.991
_refine_diff_density_max         3.429
_refine_diff_density_min         -3.586
_refine_diff_density_rms         0.329


# start Validation Reply Form
_vrf_PLAT043_LiLaFeCN6_4H2O      
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..       8.04 Check 
RESPONSE: The 8 H atoms per formula unit were not refined or modelled.
;
# end Validation Reply Form
_database_code_depnum_ccdc_archive 'CCDC 992306'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_LiLuFe(CN)6_3H2O

_audit_creation_method           SHELXL-97

_chemical_name_systematic        
'lithium lutetium(III) hexacyanidoferrate(II) trihydrate'
_chemical_name_common            
'lithium lutetium(III) hexacyanidoferrate(II) trihydrate'
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C6 H6 Fe Li Lu N6 O3'
_chemical_formula_weight         447.91

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'
Lu Lu -0.4720 5.8584 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Li Li -0.0003 0.0001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Cmcm

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

_cell_length_a                   7.2309(7)
_cell_length_b                   12.5358(12)
_cell_length_c                   13.2519(13)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1201.2(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    3343
_cell_measurement_theta_min      6.149
_cell_measurement_theta_max      55.866

_exptl_crystal_description       'needle fragment'
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.576
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             872
_exptl_absorpt_coefficient_mu    9.395
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.3131
_exptl_absorpt_correction_T_max  0.4309
_exptl_absorpt_process_details   'SADABS, Sheldrick 1996'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      150(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-AXS SMART 1000 CCD'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            5495
_diffrn_reflns_av_R_equivalents  0.0260
_diffrn_reflns_av_sigmaI/netI    0.0146
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         3.25
_diffrn_reflns_theta_max         26.72
_reflns_number_total             736
_reflns_number_gt                722
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART (BrukerAXS, 1997)'
_computing_cell_refinement       'SMART (BrukerAXS, 1997)'
_computing_data_reduction        'SAINT+ (BrukerAXS, 1997)'
_computing_structure_solution    'SHELXTL (BrukerAXS, 2000)'
_computing_structure_refinement  'SHELXTL (BrukerAXS, 2000)'

_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)+(0.0602P)²+44.6256P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         736
_refine_ls_number_parameters     47
_refine_ls_number_restraints     38
_refine_ls_R_factor_all          0.0538
_refine_ls_R_factor_gt           0.0529
_refine_ls_wR_factor_ref         0.1427
_refine_ls_wR_factor_gt          0.1421
_refine_ls_goodness_of_fit_ref   1.285
_refine_ls_restrained_S_all      1.268
_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
Lu1 Lu 0.0000 0.32977(11) 0.7500 0.0300(4) Uani 1 4 d S . .
Fe1 Fe 0.0000 0.0000 0.5000 0.0404(12) Uani 1 4 d S . .
O1 O 0.250(5) 0.200(3) 0.7500 0.070 Uiso 0.79(5) 2 d SP . .
O2 O 0.0000 0.6499(17) 0.5880(14) 0.035(5) Uiso 0.50 2 d SP . .
Li1 Li 0.0000 0.6499(17) 0.5880(14) 0.035(5) Uiso 0.50 2 d SP . .
C2 C 0.278(4) 0.457(2) 0.583(2) 0.073(6) Uani 1 1 d DU . .
C1 C 0.0000 0.1220(16) 0.5834(18) 0.029(4) Uani 1 2 d SDU . .
N2 N 0.163(3) 0.4311(18) 0.6373(18) 0.071(5) Uani 1 1 d DU . .
N1 N 0.0000 0.1975(17) 0.6297(19) 0.047(5) Uani 1 2 d SDU . .

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
Lu1 0.0474(19) 0.0261(13) 0.0164(4) 0.000 0.000 0.000
Fe1 0.071(6) 0.017(3) 0.0333(16) 0.004(2) 0.000 0.000
C2 0.074(6) 0.073(6) 0.073(6) 0.0002(10) 0.0001(10) -0.0003(10)
C1 0.029(4) 0.029(4) 0.029(4) -0.0001(10) 0.000 0.000
N2 0.071(5) 0.071(5) 0.071(5) 0.0001(10) 0.0003(10) -0.0005(10)
N1 0.047(5) 0.047(5) 0.047(5) -0.0005(10) 0.000 0.000

_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
Lu1 N1 2.30(2) . ?
Lu1 N1 2.30(2) 10_557 ?
Lu1 N2 2.29(2) 10_557 ?
Lu1 N2 2.29(2) . ?
Lu1 N2 2.29(2) 4_556 ?
Lu1 N2 2.29(2) 11 ?
Lu1 O1 2.43(3) 11 ?
Lu1 O1 2.43(3) . ?
Fe1 C1 1.886(19) 9_556 ?
Fe1 C1 1.886(19) . ?
Fe1 C2 2.01(2) 15_545 ?
Fe1 C2 2.01(2) 7_456 ?
Fe1 C2 2.01(2) 5_445 ?
Fe1 C2 2.01(2) 13_556 ?
C2 N2 1.154(17) . ?
C2 Fe1 2.01(2) 5 ?
C1 N1 1.128(18) . ?

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
N1 Lu1 N1 87.7(13) . 10_557 ?
N1 Lu1 N2 148.6(6) . 10_557 ?
N1 Lu1 N2 87.0(7) 10_557 10_557 ?
N1 Lu1 N2 87.0(7) . . ?
N1 Lu1 N2 148.6(6) 10_557 . ?
N2 Lu1 N2 81.6(12) 10_557 . ?
N1 Lu1 N2 148.6(6) . 4_556 ?
N1 Lu1 N2 87.0(7) 10_557 4_556 ?
N2 Lu1 N2 61.9(12) 10_557 4_556 ?
N2 Lu1 N2 112.5(11) . 4_556 ?
N1 Lu1 N2 87.0(7) . 11 ?
N1 Lu1 N2 148.6(6) 10_557 11 ?
N2 Lu1 N2 112.5(11) 10_557 11 ?
N2 Lu1 N2 61.9(12) . 11 ?
N2 Lu1 N2 81.6(12) 4_556 11 ?
N1 Lu1 O1 61.2(6) . 11 ?
N1 Lu1 O1 61.2(6) 10_557 11 ?
N2 Lu1 O1 138.9(6) 10_557 11 ?
N2 Lu1 O1 138.9(6) . 11 ?
N2 Lu1 O1 89.3(8) 4_556 11 ?
N2 Lu1 O1 89.3(8) 11 11 ?
N1 Lu1 O1 61.2(6) . . ?
N1 Lu1 O1 61.2(6) 10_557 . ?
N2 Lu1 O1 89.3(8) 10_557 . ?
N2 Lu1 O1 89.3(8) . . ?
N2 Lu1 O1 138.9(6) 4_556 . ?
N2 Lu1 O1 138.9(6) 11 . ?
O1 Lu1 O1 96.3(15) 11 . ?
C1 Fe1 C1 180.0(12) 9_556 . ?
C1 Fe1 C2 95.9(8) 9_556 15_545 ?
C1 Fe1 C2 84.1(8) . 15_545 ?
C1 Fe1 C2 84.1(8) 9_556 7_456 ?
C1 Fe1 C2 95.9(8) . 7_456 ?
C2 Fe1 C2 180.000(3) 15_545 7_456 ?
C1 Fe1 C2 95.9(8) 9_556 5_445 ?
C1 Fe1 C2 84.1(8) . 5_445 ?
C2 Fe1 C2 105.6(16) 15_545 5_445 ?
C2 Fe1 C2 74.4(16) 7_456 5_445 ?
C1 Fe1 C2 84.1(8) 9_556 13_556 ?
C1 Fe1 C2 95.9(8) . 13_556 ?
C2 Fe1 C2 74.4(16) 15_545 13_556 ?
C2 Fe1 C2 105.6(16) 7_456 13_556 ?
C2 Fe1 C2 180.000(2) 5_445 13_556 ?
N2 C2 Fe1 174(3) . 5 ?
N1 C1 Fe1 177(3) . . ?
C2 N2 Lu1 160(2) . . ?
C1 N1 Lu1 169(3) . . ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        26.72
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         2.394
_refine_diff_density_min         -2.327
_refine_diff_density_rms         0.336


# start Validation Reply Form
_vrf_PLAT043_LiLuFeCN6_3H2O      
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PROBLEM: Calculated and Reported Mol. Weight Differ by ..      51.00 Check 
RESPONSE: H atoms were not modelled. Some H2O disorder means that not all O is modelled. However, the water content is known from thermogravimetric measurements.
;
_vrf_PLAT201_LiLuFeCN6_3H2O      
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PROBLEM: Isotropic non-H Atoms in Main Residue(s) .......          1 Why ? 
RESPONSE: Li is a weak scatterer and also the 50:50 Li:O site is disordered.
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# end Validation Reply Form
_database_code_depnum_ccdc_archive 'CCDC 992307'
