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The title compound, bis[di­aqua­bis­(ethyl­enedi­amine-κ2N,N′)copper(II)­] hexa­cyano­iron(II) tetrahydrate, [Cu(C2H8N2)2(H2O)1.935]2[Fe(CN)6]·4H2O, was crystallized from an aqueous reaction mixture initially containing CuSO4, K3[Fe(CN)6] and ethyl­enedi­amine (en) in a 3:2:6 molar ratio. Its structure is ionic and is built up of two crystallographically different cations, viz. [Cu(en)2(H2O)2]2+ and [Cu(en)2(H2O)1.87]2+, there being a deficiency of aqua ligands in the latter, [Fe(CN)6]4− anions and disordered solvent water mol­ecules. All the metal atoms lie on centres of inversion. The Cu atom is octahedrally coordinated by two chelate-bonded en mol­ecules [mean Cu—N = 2.016 (2) Å] in the equatorial plane, and by axial aqua ligands, showing very long distances due to the Jahn–Teller effect [mean Cu—O = 2.611 (2) Å]. In one of the cations, significant underoccupation of the O-atom site is observed, correlated with the appearance of a non-coordinated water mol­ecule. This is interpreted as the partial contribution of a hydrate isomer. The [Fe(CN)6]4− anions form quite regular octahedra, with a mean Fe—C distance of 1.913 (2) Å. The dominant intermolecular interactions are cation–anion O—H...N hydrogen bonds and these inter­actions form layers parallel to (001).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104014581/gd1319sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104014581/gd1319Isup2.hkl
Contains datablock I

CCDC reference: 248142

Comment top

Cyanocomplexes are often used as model compounds for studies of magneto-structural correlations (Dunbar & Heintz, 1997; Verdaguer et al., 1999; Ohba & Okawa, 2000; Černák et al., 2002). Previously, as part of our studies of magnetic materials, we have isolated and structurally characterized several compounds with the composition [Cu(LN)2Ni(CN)4], where LN is a bidentate N-donor ligand (Kuchár et al., 2003). Our original aim in the present work was to extend the class of compounds studied to include another coordination polymer in which the diamagnetic tetracyanonickelate(II) anion would be replaced by the paramagnetic cyanocomplex anion [Fe(CN)6]3-.

To date, several Cu—Fe bimetallic compounds with similar ligation of the Cu atom have been prepared and structurally characterized. Luo et al. (2002) synthesized and studied the compound K[Cu(en)2][Fe(CN)6], which is built up of [Fe(CN)6]3- anions, K+ cations, and [Cu(en)2]2+ cations which weakly interact with the anions via the cyano groups [Cu—N 2.861 (1) Å]. Using [Fe(CN)6]4-, Kou et al. (1996) studied the ferromagnetic complex [Cu(en)]3[Fe(CN)6]2·3H2O, which exhibits a polymeric structure. Suzuki & Uehara (1984) prepared and characterized the double complex salt [Cu(en)2]2[Fe(CN)6].nH2O. Moreover, Cu—Fe bimetallic compounds were found with other ligands, e.g. dien (diethylenetriamine; Kou et al., 1997), piperazine (Kundu et al., 1995) or tren [tris(2-aminoethyl)amine; Zou et al., 1997]. All these exhibit polymeric structures.

Our synthesis of the title compound, (I), was carried out in aqueous solution containing, as building blocks, [Cu(en)2]2+ cations and [Fe(CN)6]3- anions in the molar ratio 2:1. As confirmed by the crystal structure determination, compound (I), [Cu(en)2(H2O)1.935]2[Fe(CN)6]·4H2O, was formed. It is clear that during the synthesis and crystallization, reduction of [Fe(CN)6]3- to [Fe(CN)6]4- took place. The redox equilibrium can be complex, as Cu2+ cations, cyano groups and N-donor ligands were initially also present in the mixture. Moreover, the solution was in contact with air. Such systems often give rise to mixed-valence compounds (Dunaj-Jurčo et al., 1988). Compound (I) was also identified by chemical analysis (see Experimental). The measured IR spectrum indicates the presence of the respective ligands (CN, en and H2O) in (I). \sch

The structure of (I) is ionic (Figs. 1 and 2). The asymmetric unit contains two crystallographically independent Cu complex cations and one [Fe(CN)6]4- anion. Four solvate water molecules per formula unit are disordered over five independent sites in the space between the cations and anions, and most of their H atoms could not be located. Compound (I) is the first cyanocomplex containing the [Cu(en)2(H2O)2]2+ cation, although the same cation was found in, for example, [Cu(en)2(H2O)2]F2·4H2O (Emsley et al., 1990).

Both Cu atoms in (I) exhibit centrosymmetric axially elongated octahedral coordination, due to the presence of the Jahn-Teller effect. The environment around both Cu atoms is very similar, with slight differences in bond lengths and angles. The four N atoms from two en ligands occupy the equatorial plane of a deformed CuN4O2 octahedron [mean Cu—Neq 2.016 (2) Å] and water O atoms occupy the axial positions [mean Cu—Oax 2.611 (2) Å]. These geometric parameters are comparable with the corresponding values in [Cu(en)2(H2O)2]F2·4H2O [Cu—Neq 2.021 (2) and Cu—Oax 2.572 (2) Å].

Interestingly, at Cu2 the H2O ligands (O2) are only 93.4 (5)% occupied. The remaining 6.6% are in a more remote position, O2A [Cu2···O2A 4.29 (2) and O2···O2A 2.39 (1) Å]. The close distance between O2 and O2A, observed only in very strong symmetrical hydrogen bonds in acid systems, rules out an occupation of both sites at the same time in this structure. Refinement of a model with a fully occupied O2 position and omitting O2A gives a small but significant deterioration of the refinement results: wR2 = 0.0752, R1 = 0.0296, and a residual electron density of 0.57 e Å-3 at the site of O2A. This is an example, therefore, of disorder of an elongated octahedron, [Cu(en)2(H2O)2]2+, and its `hydrate isomer', [Cu(en)2(H2O)]2+·H2O, which has square-pyramidal coordination, or [Cu(en)2]2+·2H2O, which has square-planar coordination. Both coordination geometries are well known for the Jahn-Teller-sensitive Cu2+ ion.

The en molecules in (I) behave as bidentate N-donor chelate type ligands, and are in gauche conformations of the δ and λ types. One of them (at Cu2) shows disorder of the C atoms, with 24 (1)% occupancy of the alternative positions (Fig. 1). Such disorder is not uncommon for bis(en) complexes (Černák et al., 2003). The geometrical characteristics of the organic ligand are normal (Table 1) and are similar to those found in K[Cu(en)2][Fe(CN)6] (Luo et al., 2002).

The Fe central atom of (I) has an almost ideal octahedral geometry. The average Fe—C and CN distances are 1.913 (2) and 1.160 (3) Å, respectively, which are similar to the values found in K4[Fe(CN)6]·3H2O [1.925 (4) and 1.165 (1) Å, respectively; Razak et al., 2000].

The coordinated water molecules, the cyano N atoms and some of the solvate water molecules are involved in O—H···N(C) and O—H···O hydrogen bonds (Table 2, Fig. 2). Owing to severe disorder, not all of these involving solvate water can be localized clearly. As shown in Fig. 3, the dominating feature is a two-dimensional hydrogen-bonding net of Cu1 cations and Fe(CN)6 anions in layers parallel to the ab plane. Each cation is surrounded by four anions and vice versa. The Cu2 cations and disordered water molecules, O2A, O4A and O4B, are located between these layers (Fig. 2), and are connected by the weaker O2—H21···N6 hydrogen bond and the disordered water molecules O4A and O4B. Possible hydrogen-bond interactions involving the NH2 groups of the en ligands are all very weak (D···A > 3.0 Å, low angles) and are therefore not discussed further. The distances between the neighbouring Fe and Cu1 and Fe and Cu2 atoms are 5.380 (2) and 5.476 (2) Å, respectively.

Table 2. Hydrogen bonds (Å, °) with D···A distances up to 3.0 Å.

Experimental top

Single crystals of (I), in the form of dark-brownish needles suitable for single-crystal X-ray diffraction, were crystallized from a solution formed by the following procedure. To a warm solution of 0.1 M CuSO4 (30 ml, 3 mmol) was added a solution of ethylenediamine (0.39 ml, 6 mmol) in water (10 ml), followed by addition of a warm solution of 0.1 M K3[Fe(CN)6] (20 ml, 2 mmol). The resulting solution was filtered and set aside for crystallization at room temperature. The first crystals appeared after 1 d. IR spectroscopy, cm-1: ν(NH) 3309 (versus) and 3218 (versus), ν(CH) 2964 (w), 2945 (w) and 2885 (w), ν(CN) 2040 (versus), δ(NH2) 1584 (s), δ(CH2) 1452 (m), ν(Fe—C) 584 (m), δ(Fe—CN) 421 (s). CHN analysis (found/calculated): C 23.5/23.2, H 6.4/6.7, N 27.4/27.1%.

Refinement top

The H atoms of the coordinated water molecules (O1, O2) were refined with restraints in bond lengths (0.85 Å) and a common Uiso(H). The H atoms at N of the ordered en ligand (N1, N2) were also refined with common Uiso by groups. H atoms of the CH2 groups and all H atoms of the second disordered en ligand (N4, N5) were treated as riding on idealized positions, with C—H distances of 0.99 Å and N—H distances of 0.92 Å. The solvate water molecules (O3, O4) are disordered over two positions and a centre of symmetry. Only some of these H atoms could be localized. Both C atoms of the en ligand at Cu2 are disordered over two positions. The aqua ligand O2 at Cu2 is disordered over two positions, the alternative one (O2A) having no bond to Cu and belonging to the region of solvate water (O4a, O4b). Free refinement of site occupancies for O2A, O4A and O4B sums to 1.00.

Structure description top

Cyanocomplexes are often used as model compounds for studies of magneto-structural correlations (Dunbar & Heintz, 1997; Verdaguer et al., 1999; Ohba & Okawa, 2000; Černák et al., 2002). Previously, as part of our studies of magnetic materials, we have isolated and structurally characterized several compounds with the composition [Cu(LN)2Ni(CN)4], where LN is a bidentate N-donor ligand (Kuchár et al., 2003). Our original aim in the present work was to extend the class of compounds studied to include another coordination polymer in which the diamagnetic tetracyanonickelate(II) anion would be replaced by the paramagnetic cyanocomplex anion [Fe(CN)6]3-.

To date, several Cu—Fe bimetallic compounds with similar ligation of the Cu atom have been prepared and structurally characterized. Luo et al. (2002) synthesized and studied the compound K[Cu(en)2][Fe(CN)6], which is built up of [Fe(CN)6]3- anions, K+ cations, and [Cu(en)2]2+ cations which weakly interact with the anions via the cyano groups [Cu—N 2.861 (1) Å]. Using [Fe(CN)6]4-, Kou et al. (1996) studied the ferromagnetic complex [Cu(en)]3[Fe(CN)6]2·3H2O, which exhibits a polymeric structure. Suzuki & Uehara (1984) prepared and characterized the double complex salt [Cu(en)2]2[Fe(CN)6].nH2O. Moreover, Cu—Fe bimetallic compounds were found with other ligands, e.g. dien (diethylenetriamine; Kou et al., 1997), piperazine (Kundu et al., 1995) or tren [tris(2-aminoethyl)amine; Zou et al., 1997]. All these exhibit polymeric structures.

Our synthesis of the title compound, (I), was carried out in aqueous solution containing, as building blocks, [Cu(en)2]2+ cations and [Fe(CN)6]3- anions in the molar ratio 2:1. As confirmed by the crystal structure determination, compound (I), [Cu(en)2(H2O)1.935]2[Fe(CN)6]·4H2O, was formed. It is clear that during the synthesis and crystallization, reduction of [Fe(CN)6]3- to [Fe(CN)6]4- took place. The redox equilibrium can be complex, as Cu2+ cations, cyano groups and N-donor ligands were initially also present in the mixture. Moreover, the solution was in contact with air. Such systems often give rise to mixed-valence compounds (Dunaj-Jurčo et al., 1988). Compound (I) was also identified by chemical analysis (see Experimental). The measured IR spectrum indicates the presence of the respective ligands (CN, en and H2O) in (I). \sch

The structure of (I) is ionic (Figs. 1 and 2). The asymmetric unit contains two crystallographically independent Cu complex cations and one [Fe(CN)6]4- anion. Four solvate water molecules per formula unit are disordered over five independent sites in the space between the cations and anions, and most of their H atoms could not be located. Compound (I) is the first cyanocomplex containing the [Cu(en)2(H2O)2]2+ cation, although the same cation was found in, for example, [Cu(en)2(H2O)2]F2·4H2O (Emsley et al., 1990).

Both Cu atoms in (I) exhibit centrosymmetric axially elongated octahedral coordination, due to the presence of the Jahn-Teller effect. The environment around both Cu atoms is very similar, with slight differences in bond lengths and angles. The four N atoms from two en ligands occupy the equatorial plane of a deformed CuN4O2 octahedron [mean Cu—Neq 2.016 (2) Å] and water O atoms occupy the axial positions [mean Cu—Oax 2.611 (2) Å]. These geometric parameters are comparable with the corresponding values in [Cu(en)2(H2O)2]F2·4H2O [Cu—Neq 2.021 (2) and Cu—Oax 2.572 (2) Å].

Interestingly, at Cu2 the H2O ligands (O2) are only 93.4 (5)% occupied. The remaining 6.6% are in a more remote position, O2A [Cu2···O2A 4.29 (2) and O2···O2A 2.39 (1) Å]. The close distance between O2 and O2A, observed only in very strong symmetrical hydrogen bonds in acid systems, rules out an occupation of both sites at the same time in this structure. Refinement of a model with a fully occupied O2 position and omitting O2A gives a small but significant deterioration of the refinement results: wR2 = 0.0752, R1 = 0.0296, and a residual electron density of 0.57 e Å-3 at the site of O2A. This is an example, therefore, of disorder of an elongated octahedron, [Cu(en)2(H2O)2]2+, and its `hydrate isomer', [Cu(en)2(H2O)]2+·H2O, which has square-pyramidal coordination, or [Cu(en)2]2+·2H2O, which has square-planar coordination. Both coordination geometries are well known for the Jahn-Teller-sensitive Cu2+ ion.

The en molecules in (I) behave as bidentate N-donor chelate type ligands, and are in gauche conformations of the δ and λ types. One of them (at Cu2) shows disorder of the C atoms, with 24 (1)% occupancy of the alternative positions (Fig. 1). Such disorder is not uncommon for bis(en) complexes (Černák et al., 2003). The geometrical characteristics of the organic ligand are normal (Table 1) and are similar to those found in K[Cu(en)2][Fe(CN)6] (Luo et al., 2002).

The Fe central atom of (I) has an almost ideal octahedral geometry. The average Fe—C and CN distances are 1.913 (2) and 1.160 (3) Å, respectively, which are similar to the values found in K4[Fe(CN)6]·3H2O [1.925 (4) and 1.165 (1) Å, respectively; Razak et al., 2000].

The coordinated water molecules, the cyano N atoms and some of the solvate water molecules are involved in O—H···N(C) and O—H···O hydrogen bonds (Table 2, Fig. 2). Owing to severe disorder, not all of these involving solvate water can be localized clearly. As shown in Fig. 3, the dominating feature is a two-dimensional hydrogen-bonding net of Cu1 cations and Fe(CN)6 anions in layers parallel to the ab plane. Each cation is surrounded by four anions and vice versa. The Cu2 cations and disordered water molecules, O2A, O4A and O4B, are located between these layers (Fig. 2), and are connected by the weaker O2—H21···N6 hydrogen bond and the disordered water molecules O4A and O4B. Possible hydrogen-bond interactions involving the NH2 groups of the en ligands are all very weak (D···A > 3.0 Å, low angles) and are therefore not discussed further. The distances between the neighbouring Fe and Cu1 and Fe and Cu2 atoms are 5.380 (2) and 5.476 (2) Å, respectively.

Table 2. Hydrogen bonds (Å, °) with D···A distances up to 3.0 Å.

Computing details top

Data collection: EXPOSE in IPDS (Stoe & Cie, 1999); cell refinement: CELL in IPDS; data reduction: INTEGRATE in IPDS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: Please provide missing details.

Figures top
[Figure 1] Fig. 1. Plots of the two crystallographically independent cations and the anion of (I), along with atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A packing diagram for (I). Hydrogen bonds are shown as dashed lines (for D···A < 3 Å). For the sake of clarity, the methylene groups and the H atoms of the en ligands have been omitted. Atom O1' is at the symmetry position (x, 1 + y, z) and atom O2' is at the symmetry position (x, y, 1 + z).
[Figure 3] Fig. 3. The two-dimensional hydrogen-bond system in (I) (dashed lines), in (001) layers.
diaquabis(ethylenediamine-κ2N,N')copper(II)hexacyanoiron(II) tetrahydrate top
Crystal data top
[Cu(C2H8N2)2(H2O)1.935]2[Fe(CN)6]·4H2OZ = 1
Mr = 721.07F(000) = 376.7
Triclinic, P1Dx = 1.564 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71069 Å
a = 7.9407 (6) ÅCell parameters from 7673 reflections
b = 8.9815 (7) Åθ = 2.7–25.9°
c = 10.9523 (10) ŵ = 1.90 mm1
α = 91.072 (10)°T = 193 K
β = 91.061 (10)°Needle, brown
γ = 101.290 (9)°0.38 × 0.10 × 0.06 mm
V = 765.67 (11) Å3
Data collection top
Stoe IPDS
diffractometer
2774 independent reflections
Radiation source: fine-focus sealed tube2408 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
Detector resolution: 150 pixels mm-1θmax = 25.9°, θmin = 2.6°
φ scansh = 99
Absorption correction: multi-scan
(XPREP in SHELXTL; Siemens 1996)
k = 1011
Tmin = 0.462, Tmax = 0.892l = 1313
7571 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)] = 0.029Hydrogen site location: mixed
wR(F2) = 0.073H atoms treated by a mixture of independent and constrained refinement
S = 0.99 w = 1/[σ2(Fo2) + (0.0504P)2]
where P = (Fo2 + 2Fc2)/3
2774 reflections(Δ/σ)max < 0.001
243 parametersΔρmax = 0.39 e Å3
6 restraintsΔρmin = 0.66 e Å3
Crystal data top
[Cu(C2H8N2)2(H2O)1.935]2[Fe(CN)6]·4H2Oγ = 101.290 (9)°
Mr = 721.07V = 765.67 (11) Å3
Triclinic, P1Z = 1
a = 7.9407 (6) ÅMo Kα radiation
b = 8.9815 (7) ŵ = 1.90 mm1
c = 10.9523 (10) ÅT = 193 K
α = 91.072 (10)°0.38 × 0.10 × 0.06 mm
β = 91.061 (10)°
Data collection top
Stoe IPDS
diffractometer
2774 independent reflections
Absorption correction: multi-scan
(XPREP in SHELXTL; Siemens 1996)
2408 reflections with I > 2σ(I)
Tmin = 0.462, Tmax = 0.892Rint = 0.033
7571 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0296 restraints
wR(F2) = 0.073H atoms treated by a mixture of independent and constrained refinement
S = 0.99Δρmax = 0.39 e Å3
2774 reflectionsΔρmin = 0.66 e Å3
243 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. Split-atom refinement for disordered en ligand at Cu2 (C3, C4). For aqua ligand O2 and alternative remote water molecule O2A sum of SOF restraint to 1. Disorder of O3 and O4. Positions of O4a, O4b, and O2A alternative. Free refinement of SOFs of O4a and O4b gives, together with that of O2A a SOF sum of 1.00.

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*/UeqOcc. (<1)
Cu10.50000.00000.50000.02193 (12)
O10.3494 (2)0.0444 (2)0.70509 (18)0.0359 (4)
H110.280 (3)0.0403 (19)0.709 (3)0.068 (8)*
H120.290 (4)0.113 (3)0.697 (3)0.068 (8)*
N10.2795 (2)0.0760 (2)0.4048 (2)0.0262 (4)
H1B0.311 (4)0.119 (3)0.343 (3)0.042 (5)*
H1A0.209 (4)0.142 (4)0.444 (3)0.042 (5)*
C10.2014 (3)0.0540 (3)0.3700 (2)0.0296 (5)
H1D0.13290.08290.43800.035 (5)*
H1C0.12430.02620.29760.035 (5)*
C20.3436 (3)0.1846 (3)0.3413 (2)0.0294 (5)
H2D0.39930.16250.26470.039 (5)*
H2C0.29680.27800.33030.039 (5)*
N20.4699 (2)0.2062 (2)0.44402 (19)0.0237 (4)
H2A0.434 (4)0.244 (3)0.497 (3)0.037 (5)*
H2B0.566 (4)0.256 (3)0.425 (3)0.037 (5)*
Cu20.00000.50000.00000.02740 (12)
O20.2907 (3)0.6428 (4)0.0821 (3)0.0640 (9)0.934 (5)
H210.329 (6)0.727 (3)0.115 (5)0.111 (14)*0.934 (5)
H220.361 (5)0.587 (5)0.102 (5)0.111 (14)*0.934 (5)
N30.0342 (3)0.6779 (2)0.11970 (19)0.0364 (5)
H3A0.03330.65350.18660.044*0.766 (12)
H3B0.14710.70190.14600.044*0.766 (12)
H3A10.01200.64380.19760.044*0.234 (12)
H3A20.14600.73010.11820.044*0.234 (12)
C30.0135 (8)0.8078 (5)0.0579 (4)0.0390 (12)0.766 (12)
H3C0.08480.86120.01110.047*0.766 (12)
H3D0.04350.88010.11920.047*0.766 (12)
C40.1642 (7)0.7527 (5)0.0268 (4)0.0345 (12)0.766 (12)
H4A0.26860.71720.02090.041*0.766 (12)
H4B0.18480.83630.07910.041*0.766 (12)
N40.1268 (3)0.6277 (2)0.10253 (18)0.0311 (4)
H4C0.06090.66580.16720.037*0.766 (12)
H4D0.22760.56930.13310.037*0.766 (12)
H4A30.09270.62620.18230.037*0.234 (12)
H4A40.24320.59010.10080.037*0.234 (12)
C3A0.0865 (19)0.7813 (16)0.0846 (12)0.031 (3)*0.234 (12)
H3A30.20340.74160.11430.037*0.234 (12)
H3A40.04550.88470.11980.037*0.234 (12)
C4A0.088 (2)0.7841 (15)0.0521 (12)0.030 (3)*0.234 (12)
H4A10.17490.84080.08150.036*0.234 (12)
H4A20.02610.83660.08020.036*0.234 (12)
Fe0.00000.50000.50000.01833 (12)
C50.1953 (3)0.5553 (2)0.3987 (2)0.0250 (5)
N50.3088 (3)0.5906 (3)0.3337 (2)0.0414 (5)
C60.0938 (2)0.6545 (3)0.6184 (2)0.0227 (5)
N60.1493 (2)0.7474 (2)0.69162 (18)0.0322 (4)
C70.1095 (3)0.3585 (3)0.5839 (2)0.0242 (5)
N70.1713 (3)0.2714 (2)0.6365 (2)0.0356 (5)
O3A0.5787 (3)0.1005 (3)0.9074 (3)0.0719 (8)0.962 (4)
H3OA0.501 (4)0.096 (5)0.853 (3)0.086*0.962 (4)
O3B0.50000.00001.00000.072*0.076 (8)
O2A0.424 (5)0.531 (5)0.246 (5)0.072*0.066 (5)
O4B0.4267 (10)0.4325 (10)0.1847 (10)0.068 (3)0.401 (15)
H4OB0.34960.40400.23970.082*0.401 (15)
O4A0.5106 (10)0.4380 (6)0.1318 (6)0.050 (2)0.529 (15)
H4O0.516 (8)0.426 (6)0.221 (6)0.100*0.93
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02177 (18)0.0183 (2)0.0254 (2)0.00344 (14)0.00560 (14)0.00411 (14)
O10.0345 (8)0.0245 (10)0.0501 (11)0.0086 (7)0.0013 (8)0.0061 (8)
N10.0257 (9)0.0214 (11)0.0312 (11)0.0043 (8)0.0043 (8)0.0006 (8)
C10.0288 (10)0.0286 (14)0.0333 (13)0.0118 (10)0.0113 (9)0.0039 (10)
C20.0390 (12)0.0264 (13)0.0251 (12)0.0126 (10)0.0077 (9)0.0026 (9)
N20.0249 (9)0.0217 (11)0.0250 (10)0.0054 (8)0.0005 (8)0.0022 (8)
Cu20.0395 (2)0.0269 (2)0.0164 (2)0.00894 (17)0.00746 (15)0.00011 (15)
O20.0551 (14)0.086 (2)0.0598 (17)0.0313 (14)0.0200 (12)0.0288 (14)
N30.0514 (12)0.0361 (13)0.0230 (10)0.0134 (10)0.0101 (9)0.0049 (9)
C30.051 (3)0.031 (2)0.035 (2)0.0123 (19)0.0121 (19)0.0056 (15)
C40.037 (2)0.035 (2)0.034 (2)0.0128 (17)0.0016 (16)0.0025 (15)
N40.0385 (10)0.0338 (13)0.0215 (10)0.0084 (9)0.0063 (8)0.0018 (8)
Fe0.0213 (2)0.0178 (2)0.0166 (2)0.00559 (16)0.00248 (15)0.00059 (15)
C50.0294 (10)0.0186 (12)0.0271 (12)0.0049 (9)0.0025 (9)0.0033 (8)
N50.0426 (11)0.0327 (14)0.0464 (14)0.0002 (10)0.0213 (10)0.0053 (10)
C60.0240 (9)0.0222 (12)0.0226 (11)0.0051 (9)0.0069 (8)0.0052 (9)
N60.0383 (10)0.0278 (12)0.0276 (11)0.0000 (9)0.0013 (8)0.0039 (9)
C70.0279 (10)0.0245 (13)0.0209 (11)0.0071 (9)0.0026 (8)0.0010 (9)
N70.0433 (11)0.0338 (13)0.0334 (12)0.0167 (10)0.0016 (9)0.0043 (9)
O3A0.0604 (14)0.089 (2)0.0627 (18)0.0081 (13)0.0182 (12)0.0157 (15)
O4B0.021 (3)0.127 (7)0.052 (5)0.007 (3)0.004 (3)0.046 (4)
O4A0.047 (4)0.062 (3)0.041 (3)0.014 (2)0.009 (3)0.001 (2)
Geometric parameters (Å, º) top
Cu1—N12.0138 (19)N3—H3A20.9200
Cu1—N1i2.0139 (19)C3—C41.499 (6)
Cu1—N22.0183 (18)C3—H3C0.9900
Cu1—N2i2.0184 (18)C3—H3D0.9900
Cu1—O12.6244 (19)C4—N41.463 (4)
O1—H110.85 (3)C4—H4A0.9900
O1—H120.85 (3)C4—H4B0.9900
N1—C11.478 (3)N4—C4A1.473 (12)
N1—H1B0.84 (3)N4—H4C0.9200
N1—H1A0.86 (3)N4—H4D0.9200
C1—C21.502 (4)N4—H4A30.9200
C1—H1D0.9900N4—H4A40.9200
C1—H1C0.9900C3A—C4A1.50 (2)
C2—N21.478 (3)C3A—H3A30.9900
C2—H2D0.9900C3A—H3A40.9900
C2—H2C0.9900C4A—H4A10.9900
N2—H2A0.75 (3)C4A—H4A20.9900
N2—H2B0.84 (3)Fe—C61.911 (2)
Cu2—N42.0125 (18)Fe—C6iii1.911 (2)
Cu2—N4ii2.0125 (18)Fe—C7iii1.914 (2)
Cu2—N32.021 (2)Fe—C71.914 (2)
Cu2—N3ii2.021 (2)Fe—C5iii1.915 (2)
Cu2—O22.597 (3)Fe—C51.915 (2)
O2—H210.847 (5)C5—N51.158 (3)
O2—H220.848 (5)C6—N61.162 (3)
N3—C31.468 (4)C7—N71.158 (3)
N3—C3A1.509 (12)O3A—H3OA0.847 (5)
N3—H3A0.9200O4B—H4OB0.8499
N3—H3B0.9200O4B—H4O0.83 (6)
N3—H3A10.9200O4A—H4O0.98 (6)
N1—Cu1—N1i180.0C3A—N3—H3A2109.9
N1—Cu1—N284.34 (8)Cu2—N3—H3A2109.9
N1i—Cu1—N295.66 (8)H3A1—N3—H3A2108.3
N1—Cu1—N2i95.66 (8)N3—C3—C4109.4 (4)
N1i—Cu1—N2i84.34 (8)N3—C3—H3C109.8
N2—Cu1—N2i179.999 (1)C4—C3—H3C109.8
N1—Cu1—O194.96 (7)N3—C3—H3D109.8
N1i—Cu1—O185.05 (7)C4—C3—H3D109.8
N2—Cu1—O189.76 (7)H3C—C3—H3D108.2
N2i—Cu1—O190.24 (7)N4—C4—C3108.5 (3)
Cu1—O1—H11100 (2)N4—C4—H4A110.0
Cu1—O1—H12110 (3)C3—C4—H4A110.0
H11—O1—H12108 (3)N4—C4—H4B110.0
C1—N1—Cu1109.59 (15)C3—C4—H4B110.0
C1—N1—H1B111 (2)H4A—C4—H4B108.4
Cu1—N1—H1B104 (2)C4—N4—Cu2108.97 (16)
C1—N1—H1A111.5 (19)C4A—N4—Cu2108.0 (4)
Cu1—N1—H1A113 (2)C4—N4—H4C109.9
H1B—N1—H1A108 (3)Cu2—N4—H4C109.9
N1—C1—C2108.17 (17)C4—N4—H4D109.9
N1—C1—H1D110.1Cu2—N4—H4D109.9
C2—C1—H1D110.1H4C—N4—H4D108.3
N1—C1—H1C110.1C4A—N4—H4A3110.1
C2—C1—H1C110.1Cu2—N4—H4A3110.1
H1D—C1—H1C108.4C4A—N4—H4A4110.1
N2—C2—C1108.16 (18)Cu2—N4—H4A4110.1
N2—C2—H2D110.1H4A3—N4—H4A4108.4
C1—C2—H2D110.1C4A—C3A—N3105.7 (10)
N2—C2—H2C110.1C4A—C3A—H3A3110.6
C1—C2—H2C110.1N3—C3A—H3A3110.6
H2D—C2—H2C108.4C4A—C3A—H3A4110.6
C2—N2—Cu1108.47 (14)N3—C3A—H3A4110.6
C2—N2—H2A109 (2)H3A3—C3A—H3A4108.7
Cu1—N2—H2A107 (2)N4—C4A—C3A109.8 (11)
C2—N2—H2B113 (2)N4—C4A—H4A1109.7
Cu1—N2—H2B108.7 (18)C3A—C4A—H4A1109.7
H2A—N2—H2B111 (3)N4—C4A—H4A2109.7
N4—Cu2—N4ii180.0C3A—C4A—H4A2109.7
N4—Cu2—N384.68 (8)H4A1—C4A—H4A2108.2
N4ii—Cu2—N395.32 (8)C6—Fe—C6iii180.0
N4—Cu2—N3ii95.32 (8)C6—Fe—C7iii89.98 (9)
N4ii—Cu2—N3ii84.68 (8)C6iii—Fe—C7iii90.02 (9)
N3—Cu2—N3ii180.0C6—Fe—C790.03 (9)
N4—Cu2—O290.35 (8)C6iii—Fe—C789.97 (9)
N4ii—Cu2—O289.65 (8)C7iii—Fe—C7180.00 (9)
N3—Cu2—O282.89 (10)C6—Fe—C5iii88.53 (9)
N3ii—Cu2—O297.11 (10)C6iii—Fe—C5iii91.47 (9)
Cu2—O2—H21138 (3)C7iii—Fe—C5iii90.68 (9)
Cu2—O2—H22116 (4)C7—Fe—C5iii89.32 (9)
H21—O2—H22104 (5)C6—Fe—C591.47 (9)
C3—N3—Cu2108.37 (18)C6iii—Fe—C588.53 (9)
C3A—N3—Cu2108.8 (5)C7iii—Fe—C589.32 (9)
C3—N3—H3A110.0C7—Fe—C590.68 (9)
Cu2—N3—H3A110.0C5iii—Fe—C5180.0
C3—N3—H3B110.0N5—C5—Fe177.1 (2)
Cu2—N3—H3B110.0N6—C6—Fe179.0 (2)
H3A—N3—H3B108.4N7—C7—Fe178.0 (2)
C3A—N3—H3A1109.9H4OB—O4B—H4O102.6
Cu2—N3—H3A1109.9
Symmetry codes: (i) x+1, y, z+1; (ii) x, y+1, z; (iii) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H11···N6iv0.85 (2)1.99 (2)2.825 (2)168 (3)
O1—H12···N70.85 (3)1.97 (3)2.804 (3)166 (3)
O2—H21···N6v0.85 (3)2.56 (5)2.947 (4)109 (4)
O2—H22···O4A0.85 (3)1.98 (5)2.826 (14)172 (4)
O2—H22···O4B0.85 (3)1.81 (5)2.600 (16)154 (4)
O3A—H3OA···O10.84 (3)1.99 (3)2.816 (4)165 (4)
Symmetry codes: (iv) x, y1, z; (v) x, y, z1.

Experimental details

Crystal data
Chemical formula[Cu(C2H8N2)2(H2O)1.935]2[Fe(CN)6]·4H2O
Mr721.07
Crystal system, space groupTriclinic, P1
Temperature (K)193
a, b, c (Å)7.9407 (6), 8.9815 (7), 10.9523 (10)
α, β, γ (°)91.072 (10), 91.061 (10), 101.290 (9)
V3)765.67 (11)
Z1
Radiation typeMo Kα
µ (mm1)1.90
Crystal size (mm)0.38 × 0.10 × 0.06
Data collection
DiffractometerStoe IPDS
Absorption correctionMulti-scan
(XPREP in SHELXTL; Siemens 1996)
Tmin, Tmax0.462, 0.892
No. of measured, independent and
observed [I > 2σ(I)] reflections
7571, 2774, 2408
Rint0.033
(sin θ/λ)max1)0.614
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.073, 0.99
No. of reflections2774
No. of parameters243
No. of restraints6
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.39, 0.66

Computer programs: EXPOSE in IPDS (Stoe & Cie, 1999), CELL in IPDS, INTEGRATE in IPDS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2000), Please provide missing details.

Selected geometric parameters (Å, º) top
Cu1—N12.0138 (19)N3—C31.468 (4)
Cu1—N22.0183 (18)C3—C41.499 (6)
Cu1—O12.6244 (19)C4—N41.463 (4)
N1—C11.478 (3)Fe—C61.911 (2)
C1—C21.502 (4)Fe—C71.914 (2)
C2—N21.478 (3)Fe—C51.915 (2)
Cu2—N42.0125 (18)C5—N51.158 (3)
Cu2—N32.021 (2)C6—N61.162 (3)
Cu2—O22.597 (3)C7—N71.158 (3)
N1—Cu1—N284.34 (8)C3—N3—Cu2108.37 (18)
N1—Cu1—O194.96 (7)N3—C3—C4109.4 (4)
N2—Cu1—O189.76 (7)N4—C4—C3108.5 (3)
N1—C1—C2108.17 (17)C6—Fe—C790.03 (9)
N2—C2—C1108.16 (18)C6—Fe—C591.47 (9)
C2—N2—Cu1108.47 (14)C7—Fe—C590.68 (9)
N4—Cu2—N384.68 (8)N5—C5—Fe177.1 (2)
N4—Cu2—O290.35 (8)N6—C6—Fe179.0 (2)
N3—Cu2—O282.89 (10)N7—C7—Fe178.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H11···N6i0.850 (19)1.988 (18)2.825 (2)168 (3)
O1—H12···N70.85 (3)1.97 (3)2.804 (3)166 (3)
O2—H21···N6ii0.85 (3)2.56 (5)2.947 (4)109 (4)
O2—H22···O4A0.85 (3)1.98 (5)2.826 (14)172 (4)
O2—H22···O4B0.85 (3)1.81 (5)2.600 (16)154 (4)
O3A—H3OA···O10.84 (3)1.99 (3)2.816 (4)165 (4)
Symmetry codes: (i) x, y1, z; (ii) x, y, z1.
 

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