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The title compound, catena-poly­[[μ-cyano-1:2κ2C:N-di­cyano-1κ2C-trans-bis­[N-(2-hydroxy­ethyl)­ethane-1,2-di­amine-2κ2N,N′]­cadmium(II)­nickel(II)]-μ-cyano-1:2′κ2C:N], [CdNi(CN)4(C4H12N2O)2], consists of alternating square-planar Ni(CN)4 fragments, formally dianionic, and Cd(hydet-en)2 moieties [hydet-en is N-(2-hydroxy­ethyl)­ethyl­ene­di­amine], with the two bridging cyanide ligands in a mutually trans disposition at the Ni atom and cis at the Cd atom. The resulting one-dimensional zigzag chain structure has the Ni atom on an inversion center, while the distorted octahedron centered on the Cd atom lies on a twofold axis. The polymer chains are connected into undulating sheets by weak interchain N—H...N, N—H...O and O—H...N hydrogen bonds, which are also present between successive sheets.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104021493/fa1079sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104021493/fa1079Isup2.hkl
Contains datablock I

CCDC reference: 256994

Comment top

The chemistry of cyano-bridged homo- and heteronuclear polymers involving transition metals is of current interest as these coordination polymers may have interesting properties and applications, for example, in adsorbtion or ion exchange, or as non-linear optical and magnetic materials. Such polymers may possess interesting one-, two- or three-dimensional topologies, including helical, diamondoid and honeycomb, T-shaped, and ladder (Goher et al., 2003; Kumar & Goldberg, 1999; Lin et al., 1998). For example, tetracyanonickelates are suitable model compounds for magnetic studies at low temperatures as the tetracyanonickelate anion may bridge paramagnetic ions partially coordinated with amine ligands and thus form molecular one-, two- and three-dimensional structures (Smékal et al., 2001; Smékal et al., 2003). In addition, a series of polymeric cyano-bridged cadmium and nickel compounds include organic molecules in a host–guest type of relationship (Zhang et al., 2000).

The crystal engineering of coordination polymers is usually achieved by the reaction of metal ions with bi- or multidentate ligands containing O-donors or mixed N/O-donors (Xia et al., 2004). In general, the construction of one-dimensional systems containing cyano complex anions as bridging species is achieved by the so-called `brick and mortar' method (Willet et al., 1993; Kahn, 1993). The CdII ion is well suited for construction of such materials, as its electronic configuration and size permit a wide variety of geometries and coordination numbers (Banerjee et al., 2003). In the present study, we have used a mixed N/O-donor ligand, N-(2-hydroxyethyl)ethylenediamine (hydet-en), to prepare a compound exhibiting a one-dimensional structure. The hydet-en ligand, which has three donor sites, has been the subject of few studies (Yılmaz et al., 2002; Karadaǧ et al., 2004), and its coordination behavior, therefore, is not well characterized. In this context, we have synthesized a CdII–NiII coordination polymer and determined its crystal structure.

In the literature, the expression `2,2-TT-type chain' is used for a one-dimensional structure with two bridging cyano groups in both the cation and the anion, and with both bridges in relative trans positions in their respective coordination polyhedra (Černák et al., 2002). In accordance with this definition, the title complex can be said to be of the 2,2-CT type. Cadmium complexes usually exhibit 2,2-TT (linear chain) topologies in one-dimensional systems. To our knowledge, there are only a few examples of zigzag-chain structures and there is no known cadmium coordination polymer exhibiting a 2,2-CT type zigzag chain in a one-dimensional system.

Complex (I) has a cyanide-bridged polymeric structure in which the NiII ion is coordinated by four cyanide ligands (two cyano groups are terminal, while two cyano groups coordinated in a trans fashion about the Ni atom constitute the bridges) in a square-planar arrangement. The CdII ion is six-coordinated by four N atoms of the two chelating hydet-en ligands and two N atoms of the bridging cyanide ligands (Fig. 1). The cyanide groups act as ambidentate ligands, bridging the CdII and NiII centers and thus forming chains. The amine ligand acts as a bidentate N-donor ligand, and its ethanol group is not involved in coordination, as observed in the Cu and Cd complexes of saccharin with the hydet-en ligand (Yılmaz et al., 2002) and in the cyano-bridged ZnII–NiII complex (Karadaǧ et al., 2004). Selected bond lengths and angles for (I) are given in Table 1. While the Ni1—C1—N1 angle [178.96 (14)°] is essentially linear, the Cd1—N1—C1 bond angle [167.30 (12) Å] deviates from linearity. This deviation is greater than those observed in related structures (Zhan et al., 2000; Mukherjeee et al., 2001; Smékal et al., 2003; Černák et al., 2001). The Ni1—C2—N2 angle [178.53 (12)°] is effectively linear, as expected. The Cd—N bond lengths range from 2.3198 (12) to 2.3905 (11) Å. These values are longer than those in the Zn–Ni complex, as expected, but are in the same range as those found for the Cd complex of saccharin with the hydet-en ligand. The C1—Ni1, C2—Ni1, C1—N1 and C2—N2 bond distances of the square-planar Ni coordination environment are 1.8595 (13), 1.8680 (15), 1.1459 (17) and 1.146 (2) Å, respectively, comparable to those in related cyano-bridged tetracyanonickelates (Zhan et al., 2000; Smékal et al., 2001; Mukherjeee et al., 2001; Smékal et al., 2003).

In the extended structure, the NH, NH2 and OH groups of the hydet-en ligand are involved in interchain hydrogen bonding; the polymer chains are connected by interchain N3—H1B···O1(x + 1/2, y − 1/2, z), N3—H1B···N2(x + 1/2, y + 1/2,z) and O1—H11···N2(-x, y + 1,-z + 3/2) interactions (Fig. 2). These interactions are also effective in forming a layered structure, and the geometry of the interactions is given in Table 2. The intrachain Cd1···Cd1(- x, −y + 1, −z + 1) distance is 10.5839 (8) Å, whereas the shortest interchain Cd1···Cd1(x + 1/2, y − 1/2, z) distance is 7.5083 (6) Å.

Experimental top

Cadmium sulfate (3CdSO4·8H2O, Aldrich), nickel sulfate hexahydrate, (NiSO4·6H2O, Panreac), potassium cyanide (KCN, Merck) and [N-(2-hydroxyethyl)-ethylenediamine] (C4H12N2O, Aldrich) were used as received, and the dihydrate of potassium tetracyanonickellate(II) {K2[Ni(CN)4]·2H2O} was recrystallized as described by Fernelius (1946). To an aqueous solution (40 ml) of CdSO4.8/3H2O (1 mmol, 0.256 g) was added an aqueous solution (20 ml) of K2[Ni(CN)4]·2H2O (1 mmol, 0.241 g). The cream-colored precipitate that formed after 5 min of stirring was dissolved by pouring the mixture slowly into a bulb containing N-(2-hydroxyethyl)-ethylenediamine (0.208 g, 2 mmol). The resultant light-yellow solution was filtered to remove any solid impurities and left to crystallize at room temperature. Several days of standing led to the growth of light-yellow crystals suitable for X-ray analysis.

Refinement top

All H atoms were located in a difference Fourier map, and their coordinates and Uiso(H) valuers were freely refined. [O—H = 0.75 (2) Å, N—H = 0.82 (2)–0.862 (19) Å and C—H = 0.948 (19)–1.00 (2) Å].

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. [Symmetry code: (i) −x,1 − y,2 − z; (ii) −x,y,3/2 − z.]
[Figure 2] Fig. 2. The zigzag chain structure of the Cd–Ni complex, with intra- and interchain interactions shown as broken lines.
catena-poly[[µ-cyano-1:2κ2C:N-dicyano-1κ2C-trans-bis[N-(2- hydroxyethyl)ethane-1,2-diamine-2κ2N,N']cadmium(II)nickel(II)]-µ-cyano- 1:2'κ2C:N] top
Crystal data top
[CdNi(CN)4(C4H12N2O)2]F(000) = 976
Mr = 483.50Dx = 1.679 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 26673 reflections
a = 10.0637 (5) Åθ = 2.4–28.9°
b = 11.1455 (8) ŵ = 2.12 mm1
c = 17.5089 (9) ÅT = 293 K
β = 103.046 (4)°Prism, light-yellow
V = 1913.20 (19) Å30.58 × 0.40 × 0.14 mm
Z = 4
Data collection top
STOE IPDS-II
diffractometer
2457 independent reflections
Radiation source: fine-focus sealed tube2292 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.059
Detector resolution: 6.67 pixels mm-1θmax = 28.7°, θmin = 2.4°
rotation method scansh = 1313
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)
k = 1414
Tmin = 0.376, Tmax = 0.744l = 2323
14985 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.016Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.036All H-atom parameters refined
S = 1.05 w = 1/[σ2(Fo2) + (0.0096P)2 + 1.3234P]
where P = (Fo2 + 2Fc2)/3
2457 reflections(Δ/σ)max = 0.020
159 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.79 e Å3
Crystal data top
[CdNi(CN)4(C4H12N2O)2]V = 1913.20 (19) Å3
Mr = 483.50Z = 4
Monoclinic, C2/cMo Kα radiation
a = 10.0637 (5) ŵ = 2.12 mm1
b = 11.1455 (8) ÅT = 293 K
c = 17.5089 (9) Å0.58 × 0.40 × 0.14 mm
β = 103.046 (4)°
Data collection top
STOE IPDS-II
diffractometer
2457 independent reflections
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)
2292 reflections with I > 2σ(I)
Tmin = 0.376, Tmax = 0.744Rint = 0.059
14985 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0160 restraints
wR(F2) = 0.036All H-atom parameters refined
S = 1.05Δρmax = 0.30 e Å3
2457 reflectionsΔρmin = 0.79 e Å3
159 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. 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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.01262 (14)0.58290 (13)0.90974 (7)0.0202 (3)
C20.00962 (15)0.35512 (13)0.94788 (7)0.0227 (3)
C30.29852 (16)0.85117 (16)0.73504 (9)0.0285 (3)
C40.20362 (16)0.88556 (16)0.65842 (8)0.0255 (3)
C50.02385 (16)0.95032 (14)0.59495 (7)0.0242 (3)
C60.15755 (17)0.99701 (14)0.60717 (8)0.0267 (3)
N10.01837 (15)0.63355 (12)0.85362 (7)0.0271 (3)
N20.01536 (17)0.26755 (13)0.91443 (7)0.0336 (3)
N30.24045 (14)0.74985 (13)0.77032 (7)0.0249 (2)
N40.06834 (12)0.91869 (11)0.67036 (6)0.0185 (2)
O10.13789 (13)1.09084 (11)0.66356 (6)0.0297 (2)
Ni10.00000.50001.00000.01617 (6)
Cd10.00000.766835 (12)0.75000.01520 (4)
H3A0.3116 (19)0.9192 (19)0.7711 (9)0.029 (5)*
H3B0.384 (2)0.8294 (19)0.7247 (10)0.034 (5)*
H4A0.243 (2)0.953 (2)0.6340 (10)0.034 (5)*
H4B0.1885 (19)0.8193 (19)0.6236 (9)0.028 (5)*
H5A0.0411 (19)0.8809 (18)0.5624 (9)0.027 (4)*
H5B0.0169 (18)1.0126 (17)0.5682 (9)0.023 (4)*
H6A0.210 (2)0.9326 (19)0.6276 (10)0.032 (5)*
H6B0.212 (2)1.025 (2)0.5585 (10)0.035 (5)*
H1A0.250 (2)0.686 (2)0.7474 (11)0.039 (6)*
H1B0.282 (2)0.742 (2)0.8161 (12)0.038 (6)*
H20.075 (2)0.9811 (18)0.7001 (9)0.027 (5)*
H110.107 (2)1.142 (2)0.6454 (11)0.038 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0243 (7)0.0167 (6)0.0201 (5)0.0021 (5)0.0061 (5)0.0004 (5)
C20.0294 (7)0.0213 (7)0.0181 (5)0.0008 (6)0.0068 (5)0.0033 (5)
C30.0206 (7)0.0347 (9)0.0314 (7)0.0018 (6)0.0083 (6)0.0027 (6)
C40.0247 (7)0.0282 (7)0.0276 (6)0.0005 (6)0.0142 (6)0.0014 (6)
C50.0359 (8)0.0211 (7)0.0166 (5)0.0030 (6)0.0081 (5)0.0034 (5)
C60.0297 (8)0.0253 (8)0.0236 (6)0.0016 (6)0.0032 (6)0.0068 (5)
N10.0361 (7)0.0244 (7)0.0224 (5)0.0028 (5)0.0096 (5)0.0064 (5)
N20.0479 (9)0.0229 (7)0.0310 (6)0.0019 (6)0.0111 (6)0.0024 (5)
N30.0257 (6)0.0266 (6)0.0217 (5)0.0052 (5)0.0037 (5)0.0005 (5)
N40.0231 (6)0.0167 (5)0.0175 (5)0.0007 (4)0.0081 (4)0.0002 (4)
O10.0365 (6)0.0231 (6)0.0337 (5)0.0049 (5)0.0168 (5)0.0040 (5)
Ni10.02214 (12)0.01380 (12)0.01306 (9)0.00100 (8)0.00501 (8)0.00259 (7)
Cd10.02117 (7)0.01314 (7)0.01215 (6)0.0000.00559 (4)0.000
Geometric parameters (Å, º) top
C1—N11.1459 (17)C6—O11.4211 (19)
C1—Ni11.8595 (13)C6—H6A1.00 (2)
C2—N21.146 (2)C6—H6B0.952 (19)
C2—Ni11.8680 (15)N1—Cd12.3198 (12)
C3—N31.470 (2)N3—Cd12.3726 (13)
C3—C41.510 (2)N3—H1A0.83 (2)
C3—H3A0.977 (19)N3—H1B0.82 (2)
C3—H3B0.95 (2)N4—Cd12.3905 (11)
C4—N41.4704 (18)N4—H20.862 (19)
C4—H4A0.99 (2)O1—H110.75 (2)
C4—H4B0.948 (19)Ni1—C1i1.8595 (13)
C5—N41.4750 (17)Ni1—C2i1.8680 (15)
C5—C61.502 (2)Cd1—N1ii2.3198 (12)
C5—H5A0.953 (19)Cd1—N3ii2.3726 (14)
C5—H5B0.978 (18)Cd1—N4ii2.3905 (11)
N1—C1—Ni1178.95 (14)C3—N3—Cd1111.37 (9)
N2—C2—Ni1178.53 (12)C3—N3—H1A110.5 (14)
N3—C3—C4109.67 (13)Cd1—N3—H1A102.9 (15)
N3—C3—H3A109.5 (10)C3—N3—H1B109.2 (16)
C4—C3—H3A110.1 (11)Cd1—N3—H1B115.9 (15)
N3—C3—H3B110.3 (13)H1A—N3—H1B107 (2)
C4—C3—H3B108.3 (10)C4—N4—C5110.38 (10)
H3A—C3—H3B109.1 (16)C4—N4—Cd1107.62 (9)
N4—C4—C3110.95 (11)C5—N4—Cd1119.06 (9)
N4—C4—H4A110.3 (12)C4—N4—H2110.1 (13)
C3—C4—H4A109.9 (11)C5—N4—H2107.0 (12)
N4—C4—H4B105.5 (11)Cd1—N4—H2102.2 (12)
C3—C4—H4B110.5 (11)C6—O1—H11105.5 (16)
H4A—C4—H4B109.5 (14)C1i—Ni1—C1180.000 (1)
N4—C5—C6110.96 (11)C1—Ni1—C289.62 (6)
N4—C5—H5A109.5 (11)C2i—Ni1—C2180.000 (1)
C6—C5—H5A108.6 (11)N1—Cd1—N1ii100.36 (7)
N4—C5—H5B110.6 (10)N1—Cd1—N386.16 (5)
C6—C5—H5B108.0 (11)N1ii—Cd1—N387.98 (5)
H5A—C5—H5B109.1 (13)N3ii—Cd1—N3170.84 (7)
O1—C6—C5111.42 (13)N1—Cd1—N4ii88.84 (4)
O1—C6—H6A106.3 (10)N3—Cd1—N4ii112.77 (4)
C5—C6—H6A111.3 (11)N1—Cd1—N4157.96 (5)
O1—C6—H6B110.3 (13)N1ii—Cd1—N488.84 (4)
C5—C6—H6B109.5 (12)N3ii—Cd1—N4112.77 (4)
H6A—C6—H6B108.0 (17)N3—Cd1—N474.10 (4)
C1—N1—Cd1167.30 (12)N4ii—Cd1—N489.86 (6)
N3—C3—C4—N458.78 (17)C3—N3—Cd1—N1ii98.98 (10)
N4—C5—C6—O151.80 (17)C3—N3—Cd1—N4ii73.36 (10)
C4—C3—N3—Cd137.56 (15)C3—N3—Cd1—N49.61 (9)
C3—C4—N4—C5179.16 (13)C4—N4—Cd1—N147.18 (16)
C3—C4—N4—Cd147.74 (15)C5—N4—Cd1—N1173.65 (11)
C6—C5—N4—C4173.91 (13)C4—N4—Cd1—N1ii68.26 (9)
C6—C5—N4—Cd160.94 (14)C5—N4—Cd1—N1ii58.22 (10)
C1—N1—Cd1—N1ii141.5 (6)C4—N4—Cd1—N3ii153.61 (9)
C1—N1—Cd1—N3ii55.8 (6)C5—N4—Cd1—N3ii27.13 (11)
C1—N1—Cd1—N3131.3 (6)C4—N4—Cd1—N319.97 (9)
C1—N1—Cd1—N4ii18.3 (6)C5—N4—Cd1—N3146.44 (10)
C1—N1—Cd1—N4105.1 (6)C4—N4—Cd1—N4ii133.74 (10)
C3—N3—Cd1—N1160.49 (10)C5—N4—Cd1—N4ii99.78 (10)
Symmetry codes: (i) x, y+1, z+2; (ii) x, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H1A···O1iii0.83 (2)2.30 (2)3.0276 (17)146 (2)
N3—H1B···N2iv0.82 (2)2.59 (2)3.303 (2)145.4 (19)
O1—H11···N2v0.75 (2)2.09 (2)2.8328 (18)173 (2)
Symmetry codes: (iii) x+1/2, y1/2, z; (iv) x+1/2, y+1/2, z; (v) x, y+1, z+3/2.

Experimental details

Crystal data
Chemical formula[CdNi(CN)4(C4H12N2O)2]
Mr483.50
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)10.0637 (5), 11.1455 (8), 17.5089 (9)
β (°) 103.046 (4)
V3)1913.20 (19)
Z4
Radiation typeMo Kα
µ (mm1)2.12
Crystal size (mm)0.58 × 0.40 × 0.14
Data collection
DiffractometerSTOE IPDS-II
diffractometer
Absorption correctionIntegration
(X-RED32; Stoe & Cie, 2002)
Tmin, Tmax0.376, 0.744
No. of measured, independent and
observed [I > 2σ(I)] reflections
14985, 2457, 2292
Rint0.059
(sin θ/λ)max1)0.675
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.016, 0.036, 1.05
No. of reflections2457
No. of parameters159
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.30, 0.79

Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
C1—N11.1459 (17)N1—Cd12.3198 (12)
C1—Ni11.8595 (13)N3—Cd12.3726 (13)
C2—N21.146 (2)N4—Cd12.3905 (11)
C2—Ni11.8680 (15)
N1—C1—Ni1178.95 (14)C1—Ni1—C289.62 (6)
N2—C2—Ni1178.53 (12)N1—Cd1—N386.16 (5)
C1—N1—Cd1167.30 (12)N1—Cd1—N4157.96 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H1A···O1i0.83 (2)2.30 (2)3.0276 (17)146 (2)
N3—H1B···N2ii0.82 (2)2.59 (2)3.303 (2)145.4 (19)
O1—H11···N2iii0.75 (2)2.09 (2)2.8328 (18)173 (2)
Symmetry codes: (i) x+1/2, y1/2, z; (ii) x+1/2, y+1/2, z; (iii) x, y+1, z+3/2.
 

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