# Supplementary Material (ESI) for Dalton Transactions
# This journal is (c) The Royal Society of Chemistry 2009

data_global

_journal_coden_Cambridge         222

loop_
_publ_author_name
'Oscar Castillo'
'Garikoitz Beobide'
'Javier Cepeda'
'Antonio Luque'
'Sonia Perez-Yanez'
'Pascual Roman'

_publ_contact_author_name        'Oscar Castillo'
_publ_contact_author_email       QIPCACAO@LG.EHU.ES

_publ_section_title              
;
Condensed heterometallic bidimensional mixed valence CuI/CuII/NiII
cyanidometallate
;

# Attachment 'Castillo_CIF.cif'

data_compound_1
_database_code_depnum_ccdc_archive 'CCDC 742537'

_audit_creation_method           SHELXL97

_chemical_name_systematic        
;
poly-(pentakis(mu-cyanido)-(diethylenetriamine-k3N,N',N'')
dicopper(I/II)-nickel(II)
;
_chemical_formula_moiety         'C9 H13 Cu2 N8 Ni'
_chemical_formula_structural     'C9 H13 Cu2 N8 Ni'
_chemical_formula_sum            'C9 H13 Cu2 N8 Ni'
_chemical_formula_weight         419.06
_chemical_compound_source        'synthesis as described'

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'
Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   'P n m a'
_symmetry_space_group_name_Hall  '-P 2ac 2n'
_symmetry_Int_Tables_number      62

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

_cell_length_a                   12.8823(3)
_cell_length_b                   8.6820(2)
_cell_length_c                   13.3457(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1492.64(6)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    15003
_cell_measurement_theta_min      2.80
_cell_measurement_theta_max      28.15

_exptl_crystal_description       prism
_exptl_crystal_colour            violet
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.06
_exptl_crystal_density_diffrn    1.865
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             836
_exptl_absorpt_coefficient_mu    4.073
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details   
;
CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.33.41 (release 06-05-2009 CrysAlis171 .NET)
(compiled May 6 2009,17:20:42)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_absorpt_correction_T_min  0.638
_exptl_absorpt_correction_T_max  0.806

_diffrn_ambient_temperature      293(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  Xcalibur
_diffrn_measurement_method       \w
_diffrn_standards_number         0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_decay_%        0
_diffrn_reflns_number            15003
_diffrn_reflns_av_R_equivalents  0.0356
_diffrn_reflns_av_sigmaI/netI    0.0277
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.80
_diffrn_reflns_theta_max         28.15
_reflns_number_total             1907
_reflns_number_gt                1462
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'CrysAlis CCD (Oxford Diffraction, 2003)'
_computing_cell_refinement       'CrysAlis CCD (Oxford Diffraction, 2003)'
_computing_data_reduction        'CrysAlis RED (Oxford Diffraction, 2003)'
_computing_structure_solution    'Sir92 (Altamore et al., 1993)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Ortep-3 (Farrugia, 1997)'
_computing_publication_material  'WinGX (Farrugia, 1999)'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ 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/[\s^2^(Fo^2^)+(0.0404P)^2^]'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    none
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         1907
_refine_ls_number_parameters     112
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0379
_refine_ls_R_factor_gt           0.0267
_refine_ls_wR_factor_ref         0.0636
_refine_ls_wR_factor_gt          0.0621
_refine_ls_goodness_of_fit_ref   0.943
_refine_ls_restrained_S_all      0.943
_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
Ni1 Ni 0.20527(3) 0.2500 0.54221(3) 0.03083(12) Uani 1 2 d S . .
Cu1 Cu 0.82655(3) 0.2500 0.60390(3) 0.05308(15) Uani 1 2 d S . .
Cu2 Cu 0.54798(3) 0.2500 0.34936(3) 0.03581(13) Uani 1 2 d S . .
C1 C 0.1771(2) 0.2500 0.4057(2) 0.0457(8) Uani 1 2 d S . .
N1 N 0.1639(2) 0.2500 0.3211(2) 0.0666(10) Uani 1 2 d S . .
C2 C 0.3448(2) 0.2500 0.5119(2) 0.0302(6) Uani 1 2 d S . .
N2 N 0.43124(19) 0.2500 0.4944(2) 0.0439(7) Uani 1 2 d S . .
C3 C 0.7284(2) 0.2500 0.4985(3) 0.0525(10) Uani 1 2 d S . .
N3 N 0.6696(2) 0.2500 0.4360(2) 0.0528(8) Uani 1 2 d S . .
C4 C 0.7463(2) 0.2500 0.8234(2) 0.0323(7) Uani 1 2 d S . .
N4 N 0.7808(2) 0.2500 0.74463(19) 0.0449(7) Uani 1 2 d S . .
C5 C 1.0630(2) 0.2500 0.5687(2) 0.0445(8) Uani 1 2 d S . .
N5 N 0.9764(2) 0.2500 0.5843(2) 0.0610(9) Uani 1 2 d S . .
N11 N 0.54148(15) 0.0226(2) 0.32929(15) 0.0468(5) Uani 1 1 d . . .
H11B H 0.5932 -0.0077 0.2884 0.056 Uiso 1 1 calc R . .
H11A H 0.5492 -0.0258 0.3885 0.056 Uiso 1 1 calc R . .
C12 C 0.4403(2) -0.0183(2) 0.2847(2) 0.0529(7) Uani 1 1 d . . .
H12A H 0.3878 -0.0256 0.3366 0.064 Uiso 1 1 calc R . .
H12B H 0.4450 -0.1170 0.2510 0.064 Uiso 1 1 calc R . .
C13 C 0.41209(18) 0.1054(2) 0.21125(17) 0.0422(5) Uani 1 1 d . . .
H13B H 0.4603 0.1061 0.1554 0.051 Uiso 1 1 calc R . .
H13A H 0.3425 0.0894 0.1856 0.051 Uiso 1 1 calc R . .
N14 N 0.41811(18) 0.2500 0.26703(17) 0.0281(5) Uani 1 2 d S . .
H14 H 0.3640 0.2500 0.3109 0.034 Uiso 1 2 calc SR . .

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
Ni1 0.01695(19) 0.0569(3) 0.01868(18) 0.000 -0.00029(14) 0.000
Cu1 0.0206(2) 0.1156(4) 0.0230(2) 0.000 -0.00313(15) 0.000
Cu2 0.0285(2) 0.0405(2) 0.0385(2) 0.000 -0.01660(16) 0.000
C1 0.0204(15) 0.090(3) 0.0268(17) 0.000 -0.0006(12) 0.000
N1 0.0411(18) 0.130(3) 0.0284(17) 0.000 -0.0047(13) 0.000
C2 0.0292(16) 0.0460(17) 0.0153(13) 0.000 -0.0016(12) 0.000
N2 0.0258(14) 0.076(2) 0.0300(14) 0.000 0.0030(12) 0.000
C3 0.0211(16) 0.108(3) 0.0286(17) 0.000 -0.0007(14) 0.000
N3 0.0261(14) 0.100(2) 0.0325(15) 0.000 -0.0091(12) 0.000
C4 0.0161(13) 0.0563(18) 0.0245(15) 0.000 -0.0045(11) 0.000
N4 0.0263(14) 0.084(2) 0.0243(14) 0.000 -0.0025(11) 0.000
C5 0.0217(16) 0.090(3) 0.0216(15) 0.000 -0.0014(12) 0.000
N5 0.0235(15) 0.132(3) 0.0270(14) 0.000 0.0003(12) 0.000
N11 0.0587(13) 0.0422(10) 0.0395(11) 0.0046(9) 0.0001(9) 0.0206(10)
C12 0.0752(19) 0.0348(12) 0.0488(15) -0.0071(11) -0.0034(13) -0.0101(13)
C13 0.0485(14) 0.0417(12) 0.0364(12) -0.0080(11) -0.0109(11) -0.0098(11)
N14 0.0209(12) 0.0379(13) 0.0254(12) 0.000 -0.0024(10) 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
Ni1 C2 1.842(3) . ?
Ni1 C1 1.858(3) . ?
Ni1 C5 1.866(3) 1_455 ?
Ni1 C4 1.869(3) 6_557 ?
Cu1 C3 1.892(3) . ?
Cu1 N5 1.948(3) . ?
Cu1 N4 1.968(3) . ?
Cu2 N3 1.947(3) . ?
Cu2 N11 1.9941(18) 8_565 ?
Cu2 N11 1.9941(18) . ?
Cu2 N14 2.002(2) . ?
Cu2 N2 2.452(3) . ?
C1 N1 1.142(4) . ?
C2 N2 1.138(4) . ?
C3 N3 1.127(4) . ?
C4 N4 1.142(4) . ?
C4 Ni1 1.869(3) 6_657 ?
C5 N5 1.135(4) . ?
C5 Ni1 1.866(3) 1_655 ?
N11 C12 1.476(3) . ?
C12 C13 1.499(3) . ?
C13 N14 1.461(2) . ?
N14 C13 1.461(2) 8_565 ?

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
C2 Ni1 C1 88.60(13) . . ?
C2 Ni1 C5 178.24(12) . 1_455 ?
C1 Ni1 C5 89.64(13) . 1_455 ?
C2 Ni1 C4 86.25(12) . 6_557 ?
C1 Ni1 C4 174.84(13) . 6_557 ?
C5 Ni1 C4 95.52(13) 1_455 6_557 ?
C3 Cu1 N5 124.24(12) . . ?
C3 Cu1 N4 120.64(12) . . ?
N5 Cu1 N4 115.12(11) . . ?
N3 Cu2 N11 96.52(6) . 8_565 ?
N3 Cu2 N11 96.52(6) . . ?
N11 Cu2 N11 163.82(11) 8_565 . ?
N3 Cu2 N14 176.86(11) . . ?
N11 Cu2 N14 83.75(6) 8_565 . ?
N11 Cu2 N14 83.75(6) . . ?
N3 Cu2 N2 91.40(11) . . ?
N11 Cu2 N2 94.61(6) 8_565 . ?
N11 Cu2 N2 94.61(6) . . ?
N14 Cu2 N2 85.46(9) . . ?
N1 C1 Ni1 177.3(3) . . ?
N2 C2 Ni1 179.2(3) . . ?
C2 N2 Cu2 139.7(2) . . ?
N3 C3 Cu1 179.7(3) . . ?
C3 N3 Cu2 168.7(3) . . ?
N4 C4 Ni1 173.5(3) . 6_657 ?
C4 N4 Cu1 174.5(3) . . ?
N5 C5 Ni1 179.7(3) . 1_655 ?
C5 N5 Cu1 177.1(3) . . ?
C12 N11 Cu2 109.23(13) . . ?
N11 C12 C13 107.77(18) . . ?
N14 C13 C12 105.63(18) . . ?
C13 N14 C13 118.4(2) 8_565 . ?
C13 N14 Cu2 108.91(13) 8_565 . ?
C13 N14 Cu2 108.91(13) . . ?

_diffrn_measured_fraction_theta_max 0.976
_diffrn_reflns_theta_full        28.15
_diffrn_measured_fraction_theta_full 0.976
_refine_diff_density_max         0.507
_refine_diff_density_min         -0.650
_refine_diff_density_rms         0.146