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Partial reduction of the CuII ions in the aqueous system CuII–en–[Ni(CN)4]2− (1/1/1) (en is 1,2-di­amino­ethane) yields a novel heterobimetallic mixed-valence compound, poly­[[aqua­bis(1,2-di­amino­ethane)copper(II)] [hexa-μ-cyano-tetra­cyano­bis(1,2-di­amino­ethane)­tricopper(I,II)­dinickel(II)] dihydrate], [Cu(C2H8N2)2(H2O)][Ni2Cu3(CN)10(C2H8N2)2]·2H2O or [Cu(en)2(H2O)][Cu(en)2Ni2Cu2(CN)10]·2H2O. The structure is formed by a negatively charged two-dimensional array of the cyano complex [Cu(en)2Ni2Cu2(CN)10]n2n, [Cu(en)2(H2O)]2+ complex cations and water mol­ecules of crystallization. These last are involved in a complicated hydrogen-bonding system. The cyano groups act as terminal, μ2-bridging or μ3-bridging ligands.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101021898/jz1484sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101021898/jz1484Isup2.hkl
Contains datablock I

CCDC reference: 182977

Comment top

Because of the tendency of a cyano group to bridge two metal centres, cyano complexes can be used as building blocks in the construction of compounds possessing varying degrees of dimensionality (Vahrenkamp et al., 1997; Iwamoto, 1996; Verdaguer et al., 1999; Ohba & Okawa, 2000; Černák et al., 2001). Compounds of this type containing paramagnetic central atoms are often the subject of magnetic investigations (Weihe & Güdel, 2000; Verdaguer et al., 1999; Dunbar & Heintz, 1997; Kitazawa et al., 1996; Ma et al., 2001; Trávníček et al., 2001). Such studies may contribute to the understanding of fundamental physical issues, e.g. the role of antiferromagnetic spin fluctuations in high-temperature superconductors (Affleck et al., 1987; Khurana, 1988) or the possible practical application of novel molecular devices (Kahn, 1994; Dagotto, 1996).

We are interested in the preparation, crystal structure and magnetic properties of low-dimensional compounds based on cyano complexes, which are used as bridges in linking paramagnetic centres (Černák et al., 2001). To date, starting from the aqueous system CuII-en-[Ni(CN)4]2-, only one product has been isolated, with composition [Cu(en)2Ni(CN)4] (Dunaj-Jurčo et al., 1976). This compound possesses a one-dimensional crystal structure (Lokaj et al., 1991; Seitz et al., 2001), but its spins behave as a two-dimensional magnet at low temperatures (Orendáč et al., 1995). On the other hand, numerous compounds have been isolated from the analogous systems containing NiII, ZnII or CdII, (Černák et al., 1989, 1993). In addition, the compound [Cu(H2O)2(en)SO4] was reported to be one-dimensional, with [Cu(en)(H2O)2]2+ cations linked by bridging sulfate anions (Healy et al., 1978). For the work reported here, our goal was to examine the possibility of replacing the sulfate group with a tetracyanonickelate anion. From the above-mentioned system with a Cu:en ratio of 1:1, we isolated the title mixed valence coordination polymeric compound, [Cu(en)2(H2O)][Cu(en)2Ni2Cu2(CN)10]·2H2O, (I). \sch

The formation of (I) from the aqueous system CuII-en-[Ni(CN)4]2- required partial reduction of CuII to CuI by the cyano groups, present in the initial solution in the form of the tetracyanonickellate anion (see Experimental). The formation of a CuII/CuI redox equilibrium is often observed in systems containing CuII, cyano groups and N-donor ligands (Dunaj-Jurčo et al., 1988). The fact that the first crystals appeared in the mother liquor after a week supports the synthetic route presented here and suggests that the equilibrium is achieved slowly.

The structure of (I) is formed of a negatively charged two-dimensional cyano complex array, [Cu(en)2Ni2Cu2(CN)10]n2n-, [Cu(en)2(H2O)]2+ complex cations and water molecules of crystallization (Fig. 1). In the complicated two-dimensional array can be distinguished a core part and side arms, which are directed to the upper and lower sides of the core (Fig. 2). The core is built up of CuI and NiII atoms linked by bridging cyano groups, while the side arms exhibit the composition -µ-NC—Ni1(CN)2-µ-CN—Cu(en)2 and are linked to the core via bridging cyano groups. The packing of neighbouring two-dimensional arrays leads to channels parallel to [010]. Enclosed in the channels are the [Cu(en)2(H2O)]2+ complex cations and water molecules of crystallization. Therefore, this structure can also be viewed as a host–guest system, with complex cations and water molecules as the guests placed between the host layers. This structure is unique among cyano complexes.

Atoms Ni1 and Ni2 are both coordinated by four cyano groups. They exhibit square-planar geometry and are thus diamagnetic. Two of the cyano groups, in trans positions in each anion, exhibit bridging character. The Ni—C (1.854–1.892 Å) and CN (1.132–1.155 Å) distances are close to the ideal values of 1.86 and 1.15 Å, respectively (Sharpe, 1986). The Ni—C—N angles deviate only slightly from linearity (maximum deviation 4.7°). On the other hand, the C11—N11—Cu3 angle from the bridging cyano group is bent considerably [135.2 (4)°], but such a situation is not uncommon for a bridging cyano group (Vahrenkamp et al., 1997; Janiak et al., 1999).

Atoms Cu1 and Cu2, as indicated by their distorted tetrahedral coordination geometry and charge balance, are in oxidation state I, and consequently they are diamagnetic. Atom Cu1 is coordinated by three ordered N-oriented bridging cyano groups (mean distance 1.992 Å). The fourth cyano group is disordered, as imposed by the symmetry, and is at the somewhat shorter distance of 1.945 Å. One of the cyano groups, C25—N25, acts as an unsymmetrical µ3-cyano ligand >CN–; the N atom coordinates to Cu1, while the C atom coordinates unsymmetrically (2.044 versus 2.142 Å) to two different Cu2 atoms related by a symmetry centre. Consequently, these are close together [2.444 (1) Å]. A similar situation was found in some cyanocuprate complexes, e.g. [Cu5(CN)6(dmf)4] (dmf is dimethylformamide; Peng & Liaw, 1986) or [Zn(NH3)0.7(H2O)0.3Cu(CN)3] (Černák et al., 1998). The geometric parameters are similar to those found in the above-mentioned examples.

Two different paramagnetic Cu centres are present in the structure of (I). Both of them are penta coordinated. The calculated values of the τ parameters (Adison et al., 1984) are 9.2% for Cu3 and 5.3% for Cu4, indicating an almost ideal square-pyramidal form (ideal value τ = 0) of the coordination polyhedron. Atom Cu3 is linked to the anionic array by the bridging cyano group and exhibits a CuN4N chromophore, with four N atoms from two chelate-bonded en ligands in the basal plane (mean Cu—N 2.011 Å) and an N atom from the bridging cyano group in the apical position, with a longer Cu—N distance of 2.324 (5) Å. The central Cu atom is displaced from the mean plane of the four atoms N31, N32, N34 and N34 toward atom N11 by 0.159 (2) Å.

An interesting situation is observed around atom Cu4. This atom (chromophore CuN4O) is coordinated in the basal plane with two chelate-type en ligands, with four short Cu—N distances (mean 2.010 Å). The apical O atom from the water molecule is at a longer distance of 2.547 (4) Å. In the sixth direction of a very distorted tetragonal bipyramid is placed, almost perpendicularly, the disordered cyano group A1—A2, at a distance of 2.93 (2) Å to the middle of the cyano group. Moreover, the displacement of atom Cu4 toward the apical atom O1 from the mean plane formed by N41, N42, N43 and N44 is significantly smaller, at 0.054 (2) Å. Molecular orbital quantum chemical calculations for [Cu(NH3)4Cu4(CN)6] indicated the existence of a weak π-bonding interaction between Cu2+ and the triple bond, with a distance 2.97 (1) Å (Dunaj-Jurčo & Boča, 1983). A similar weak π-bonding interaction can be assumed in the present case. The geometric parameters in the chelate rings of both cations are close to those found in similar compounds (Williams et al., 1972; Lokaj et al., 1991).

Hydrogen bonds may play an important role in CuII compounds as possible exchange paths for magnetic interactions. In compound (I), several hydrogen bonds are possible, of the types O—H···O, O—H···N, N—H···O and N—H···N(C), with participation of water molecules, terminal cyano groups and amine groups from the [Cu(en)2]2+ and [Cu(H2O)(en)2]2+ paramagnetic cations. Details of the most important hydrogen bonds are given in Table 2.

In cyano complexes, the absorption bands due to the ν(CN) stretching vibrations of the cyano groups, which can be found in the wavenumber range 2000–2200 cm-1 (Sharpe, 1976), are very characteristic. There are three absorption bands at 2152 (m), 2128 (s) and 2096 (s) cm-1 in the spectrum of (I). The absorption bands at 2128 and 2152 cm-1 can be ascribed to the stretching vibrations of terminal and bridging cyano groups, respectively, of the tetracyanonickellate anion, while the remaining absorption band at 2096 cm-1 may be due to the presence of bridging cyano groups linking two CuI atoms. The presence of the en ligands manifests itself by various absorption bands due to ν(NH2), ν(CH2), δ(NH2) and other vibrations. These are presented in the Experimental section. Only one broad absorption band due to ν(OH) vibrations is present in the spectrum, at 3416 (m) cm-1, accompanied by a shoulder at 3390 (msh) cm-1; their position and shape is in line with the presence of the hydrogen-bonding system. The presence of water molecules is also shown by weak absorption bands at 1664 (w) and 1650 (wsh) cm-1, due to a deformation vibration, δ(H2O).

The thermodynamic and magnetic properties of (I) are under study (Kajňaková et al., 2001).

Experimental top

In a typical preparation procedure, a 0.1M solution of CuSO4 (20 ml, 2 mmol) was added to a 0.1M solution of K2[Ni(CN)4] (20 ml, 2 mmol) and water (60 ml). The resultant precipitate redissolved upon the addition of solid citric acid (1.8 g) and ethanolamine (1.6 ml). Finally, 1,2-ethanediamine (0.135 ml) was added. This solution was filtered and placed in a refrigerator for crystallization via slow evaporation. Within a week, blue-violet needles of (I) (approximate dimensions 0.1 mm in diameter and 5 mm in length) appeared, and these were separated by filtration and dried in air (yield 35%). Spectroscopic analyses were carried out using a Carlo Erba EA1108 and a Specord M40 spectrometer. Analysis calculated for C18H38Cu4N18Ni2O3 (Mr 926.19): C 23.34, H 4.14, N 27.22%; found: C 23.82, H 3.90, N 26.50%; IR (cm-1, KBr disc): ν(OH): 3416 (m), 3390 (msh); ν(NH2): 3328 (s), 3272 (s), 3150 (msh); ν(CH2): 2980 (wsh), 2968 (w), 2896 (w); ν(CN): 2152 (m), 2128 (s), 2096 (s); δ(OH2): 1664 (w), 1650 (wsh); δ(NH2): 1610 (msh), 1588 (s); ν(C—N): 1040 (versus); ρ(NH2): 696 (m); δ(NCCN): 420 (m); δ(Ni—CN): 404 (m).

Refinement top

The atom labelled A represents a C or N atom of the disordered cyano group. The site occupancy factors for atoms A1 and A2 were obtained by refining the relative contributions of the C and N atom (a common isotropic displacement parameter was used at this stage). The site occupancy factors were then fixed and both atoms A1 and A2 were refined anisotropically. The disordered cyano group (A1—A2) could also be modelled by two different cyano groups with site occupancy factors of 0.41 (4) and 0.59 (1), respectively, but the cyano groups in this case exhibit unusual bond distances of 1.04 and 1.20 Å. The largest peak in the final difference map is 0.92 Å from Ni2. During the localization and refinement of the O atoms from the water molecules, a peak was present in the difference map; at the same time, the displacement parameter of atom O3 was high. It was possible to interpret and refine the observed peak as a second position of the disordered water oxygen O3. The minor position was refined isotropically and its H atoms were not located. A riding model was used for the H atoms bound to C and N. The H atoms of the water molecules were found from a difference map and refined freely, with O—H distances restrained to 0.84 and H···H to 1.328 Å. Full data collection details are in the relevant _special_details section of the archived CIF and are also reported elsewhere (Abboud et al., 1997).

Structure description top

Because of the tendency of a cyano group to bridge two metal centres, cyano complexes can be used as building blocks in the construction of compounds possessing varying degrees of dimensionality (Vahrenkamp et al., 1997; Iwamoto, 1996; Verdaguer et al., 1999; Ohba & Okawa, 2000; Černák et al., 2001). Compounds of this type containing paramagnetic central atoms are often the subject of magnetic investigations (Weihe & Güdel, 2000; Verdaguer et al., 1999; Dunbar & Heintz, 1997; Kitazawa et al., 1996; Ma et al., 2001; Trávníček et al., 2001). Such studies may contribute to the understanding of fundamental physical issues, e.g. the role of antiferromagnetic spin fluctuations in high-temperature superconductors (Affleck et al., 1987; Khurana, 1988) or the possible practical application of novel molecular devices (Kahn, 1994; Dagotto, 1996).

We are interested in the preparation, crystal structure and magnetic properties of low-dimensional compounds based on cyano complexes, which are used as bridges in linking paramagnetic centres (Černák et al., 2001). To date, starting from the aqueous system CuII-en-[Ni(CN)4]2-, only one product has been isolated, with composition [Cu(en)2Ni(CN)4] (Dunaj-Jurčo et al., 1976). This compound possesses a one-dimensional crystal structure (Lokaj et al., 1991; Seitz et al., 2001), but its spins behave as a two-dimensional magnet at low temperatures (Orendáč et al., 1995). On the other hand, numerous compounds have been isolated from the analogous systems containing NiII, ZnII or CdII, (Černák et al., 1989, 1993). In addition, the compound [Cu(H2O)2(en)SO4] was reported to be one-dimensional, with [Cu(en)(H2O)2]2+ cations linked by bridging sulfate anions (Healy et al., 1978). For the work reported here, our goal was to examine the possibility of replacing the sulfate group with a tetracyanonickelate anion. From the above-mentioned system with a Cu:en ratio of 1:1, we isolated the title mixed valence coordination polymeric compound, [Cu(en)2(H2O)][Cu(en)2Ni2Cu2(CN)10]·2H2O, (I). \sch

The formation of (I) from the aqueous system CuII-en-[Ni(CN)4]2- required partial reduction of CuII to CuI by the cyano groups, present in the initial solution in the form of the tetracyanonickellate anion (see Experimental). The formation of a CuII/CuI redox equilibrium is often observed in systems containing CuII, cyano groups and N-donor ligands (Dunaj-Jurčo et al., 1988). The fact that the first crystals appeared in the mother liquor after a week supports the synthetic route presented here and suggests that the equilibrium is achieved slowly.

The structure of (I) is formed of a negatively charged two-dimensional cyano complex array, [Cu(en)2Ni2Cu2(CN)10]n2n-, [Cu(en)2(H2O)]2+ complex cations and water molecules of crystallization (Fig. 1). In the complicated two-dimensional array can be distinguished a core part and side arms, which are directed to the upper and lower sides of the core (Fig. 2). The core is built up of CuI and NiII atoms linked by bridging cyano groups, while the side arms exhibit the composition -µ-NC—Ni1(CN)2-µ-CN—Cu(en)2 and are linked to the core via bridging cyano groups. The packing of neighbouring two-dimensional arrays leads to channels parallel to [010]. Enclosed in the channels are the [Cu(en)2(H2O)]2+ complex cations and water molecules of crystallization. Therefore, this structure can also be viewed as a host–guest system, with complex cations and water molecules as the guests placed between the host layers. This structure is unique among cyano complexes.

Atoms Ni1 and Ni2 are both coordinated by four cyano groups. They exhibit square-planar geometry and are thus diamagnetic. Two of the cyano groups, in trans positions in each anion, exhibit bridging character. The Ni—C (1.854–1.892 Å) and CN (1.132–1.155 Å) distances are close to the ideal values of 1.86 and 1.15 Å, respectively (Sharpe, 1986). The Ni—C—N angles deviate only slightly from linearity (maximum deviation 4.7°). On the other hand, the C11—N11—Cu3 angle from the bridging cyano group is bent considerably [135.2 (4)°], but such a situation is not uncommon for a bridging cyano group (Vahrenkamp et al., 1997; Janiak et al., 1999).

Atoms Cu1 and Cu2, as indicated by their distorted tetrahedral coordination geometry and charge balance, are in oxidation state I, and consequently they are diamagnetic. Atom Cu1 is coordinated by three ordered N-oriented bridging cyano groups (mean distance 1.992 Å). The fourth cyano group is disordered, as imposed by the symmetry, and is at the somewhat shorter distance of 1.945 Å. One of the cyano groups, C25—N25, acts as an unsymmetrical µ3-cyano ligand >CN–; the N atom coordinates to Cu1, while the C atom coordinates unsymmetrically (2.044 versus 2.142 Å) to two different Cu2 atoms related by a symmetry centre. Consequently, these are close together [2.444 (1) Å]. A similar situation was found in some cyanocuprate complexes, e.g. [Cu5(CN)6(dmf)4] (dmf is dimethylformamide; Peng & Liaw, 1986) or [Zn(NH3)0.7(H2O)0.3Cu(CN)3] (Černák et al., 1998). The geometric parameters are similar to those found in the above-mentioned examples.

Two different paramagnetic Cu centres are present in the structure of (I). Both of them are penta coordinated. The calculated values of the τ parameters (Adison et al., 1984) are 9.2% for Cu3 and 5.3% for Cu4, indicating an almost ideal square-pyramidal form (ideal value τ = 0) of the coordination polyhedron. Atom Cu3 is linked to the anionic array by the bridging cyano group and exhibits a CuN4N chromophore, with four N atoms from two chelate-bonded en ligands in the basal plane (mean Cu—N 2.011 Å) and an N atom from the bridging cyano group in the apical position, with a longer Cu—N distance of 2.324 (5) Å. The central Cu atom is displaced from the mean plane of the four atoms N31, N32, N34 and N34 toward atom N11 by 0.159 (2) Å.

An interesting situation is observed around atom Cu4. This atom (chromophore CuN4O) is coordinated in the basal plane with two chelate-type en ligands, with four short Cu—N distances (mean 2.010 Å). The apical O atom from the water molecule is at a longer distance of 2.547 (4) Å. In the sixth direction of a very distorted tetragonal bipyramid is placed, almost perpendicularly, the disordered cyano group A1—A2, at a distance of 2.93 (2) Å to the middle of the cyano group. Moreover, the displacement of atom Cu4 toward the apical atom O1 from the mean plane formed by N41, N42, N43 and N44 is significantly smaller, at 0.054 (2) Å. Molecular orbital quantum chemical calculations for [Cu(NH3)4Cu4(CN)6] indicated the existence of a weak π-bonding interaction between Cu2+ and the triple bond, with a distance 2.97 (1) Å (Dunaj-Jurčo & Boča, 1983). A similar weak π-bonding interaction can be assumed in the present case. The geometric parameters in the chelate rings of both cations are close to those found in similar compounds (Williams et al., 1972; Lokaj et al., 1991).

Hydrogen bonds may play an important role in CuII compounds as possible exchange paths for magnetic interactions. In compound (I), several hydrogen bonds are possible, of the types O—H···O, O—H···N, N—H···O and N—H···N(C), with participation of water molecules, terminal cyano groups and amine groups from the [Cu(en)2]2+ and [Cu(H2O)(en)2]2+ paramagnetic cations. Details of the most important hydrogen bonds are given in Table 2.

In cyano complexes, the absorption bands due to the ν(CN) stretching vibrations of the cyano groups, which can be found in the wavenumber range 2000–2200 cm-1 (Sharpe, 1976), are very characteristic. There are three absorption bands at 2152 (m), 2128 (s) and 2096 (s) cm-1 in the spectrum of (I). The absorption bands at 2128 and 2152 cm-1 can be ascribed to the stretching vibrations of terminal and bridging cyano groups, respectively, of the tetracyanonickellate anion, while the remaining absorption band at 2096 cm-1 may be due to the presence of bridging cyano groups linking two CuI atoms. The presence of the en ligands manifests itself by various absorption bands due to ν(NH2), ν(CH2), δ(NH2) and other vibrations. These are presented in the Experimental section. Only one broad absorption band due to ν(OH) vibrations is present in the spectrum, at 3416 (m) cm-1, accompanied by a shoulder at 3390 (msh) cm-1; their position and shape is in line with the presence of the hydrogen-bonding system. The presence of water molecules is also shown by weak absorption bands at 1664 (w) and 1650 (wsh) cm-1, due to a deformation vibration, δ(H2O).

The thermodynamic and magnetic properties of (I) are under study (Kajňaková et al., 2001).

Computing details top

Data collection: SMART (Bruker 1998); cell refinement: SMART and SAINT (Bruker 1998); data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity.
[Figure 2] Fig. 2. A packing diagram for (I) viewed approximatively along the b axis. The [Cu(en)2(H2O)]2+ complex cations and water molecules are shown only in the central channel. H atoms have been omitted for clarity.
poly[[aquabis(1,2-diaminoethane)copper(II)] [bis(1,2-diaminoethane)hexa-µ-cyano-tetracyanotricopper(II)dinickel(II) dihydrate] top
Crystal data top
[Cu(C2H8N2)2(H2O)][Ni2Cu3(CN)10(C2H8N2)2]·2H2OF(000) = 1872
Mr = 926.24Dx = 1.838 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 19.476 (2) ÅCell parameters from 80 reflections
b = 8.2737 (4) Åθ = 2.0–28.0°
c = 21.786 (2) ŵ = 3.65 mm1
β = 107.583 (2)°T = 173 K
V = 3346.4 (3) Å3Needle, blue
Z = 40.24 × 0.23 × 0.11 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
7643 independent reflections
Radiation source: normal-focus sealed tube4511 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.068
ω scansθmax = 27.5°, θmin = 2.0°
Absorption correction: analytical
based on measured indexed crystal faces (SHELXTL; Sheldrick, 1997)
h = 2524
Tmin = 0.532, Tmax = 0.930k = 1010
20433 measured reflectionsl = 2825
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 0.92Calculated w = 1/[σ2(Fo2) + (0.0492P)2]
where P = (Fo2 + 2Fc2)/3
7643 reflections(Δ/σ)max = 0.001
429 parametersΔρmax = 2.14 e Å3
9 restraintsΔρmin = 1.35 e Å3
Crystal data top
[Cu(C2H8N2)2(H2O)][Ni2Cu3(CN)10(C2H8N2)2]·2H2OV = 3346.4 (3) Å3
Mr = 926.24Z = 4
Monoclinic, P21/nMo Kα radiation
a = 19.476 (2) ŵ = 3.65 mm1
b = 8.2737 (4) ÅT = 173 K
c = 21.786 (2) Å0.24 × 0.23 × 0.11 mm
β = 107.583 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
7643 independent reflections
Absorption correction: analytical
based on measured indexed crystal faces (SHELXTL; Sheldrick, 1997)
4511 reflections with I > 2σ(I)
Tmin = 0.532, Tmax = 0.930Rint = 0.068
20433 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0449 restraints
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 0.92Δρmax = 2.14 e Å3
7643 reflectionsΔρmin = 1.35 e Å3
429 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*/UeqOcc. (<1)
Cu11.01893 (3)0.08110 (8)0.35366 (3)0.02285 (15)
Ni11.22999 (3)0.20910 (9)0.27921 (3)0.02244 (16)
O11.3137 (2)0.1773 (6)0.5563 (2)0.0494 (12)
H1A1.319 (4)0.200 (8)0.5948 (17)0.074*
H1B1.340 (4)0.099 (6)0.557 (3)0.074*
Ni20.76634 (4)0.08074 (10)0.20830 (3)0.03145 (18)
Cu21.02232 (3)0.41648 (8)0.54820 (3)0.02174 (15)
O21.6200 (3)0.1409 (7)0.4468 (2)0.0598 (14)
H2A1.644 (3)0.149 (10)0.4879 (16)0.090*
H2B1.583 (3)0.197 (9)0.450 (3)0.090*
Cu31.49228 (3)0.21849 (8)0.32174 (3)0.02206 (15)
O30.5851 (3)0.2389 (9)0.5090 (2)0.078 (3)0.887 (12)
H3A0.587 (7)0.137 (5)0.501 (4)0.117*0.887 (12)
H3B0.601 (5)0.233 (11)0.5499 (14)0.117*0.887 (12)
O3'0.539 (3)0.109 (6)0.523 (2)0.062 (17)*0.113 (12)
Cu41.18323 (3)0.19942 (7)0.48614 (3)0.01995 (15)
N111.3742 (2)0.2303 (6)0.2546 (2)0.0302 (11)
C111.3186 (3)0.2261 (6)0.2619 (2)0.0240 (12)
N121.1424 (3)0.2987 (6)0.1446 (2)0.0344 (12)
C121.1769 (3)0.2624 (7)0.1955 (2)0.0246 (12)
N131.0929 (2)0.1456 (5)0.3112 (2)0.0250 (10)
C131.1441 (3)0.1759 (6)0.2980 (2)0.0240 (12)
N141.3076 (3)0.1425 (6)0.4190 (2)0.0347 (12)
C141.2787 (3)0.1659 (7)0.3652 (2)0.0257 (12)
A11.0364 (3)0.1361 (6)0.3915 (2)0.0232 (11)0.57
A21.0286 (2)0.2561 (6)0.4154 (2)0.0239 (11)0.57
A1'1.0364 (3)0.1361 (6)0.3915 (2)0.0232 (11)0.43
A2'1.0286 (2)0.2561 (6)0.4154 (2)0.0239 (11)0.43
N210.9196 (2)0.0878 (6)0.2933 (2)0.0281 (10)
C210.8606 (3)0.0868 (7)0.2620 (2)0.0268 (12)
C220.8049 (3)0.0696 (8)0.1384 (3)0.0367 (14)
N220.8266 (3)0.0676 (7)0.0958 (2)0.0417 (13)
N230.6199 (2)0.0575 (5)0.1111 (2)0.0240 (10)
C230.6751 (3)0.0652 (7)0.1494 (2)0.0261 (12)
C240.7285 (3)0.1120 (8)0.2761 (3)0.0388 (15)
N240.7061 (3)0.1422 (8)0.3178 (2)0.0537 (16)
N251.0256 (2)0.2476 (5)0.42128 (19)0.0213 (10)
C251.0218 (3)0.3447 (6)0.4583 (2)0.0207 (11)
N311.4600 (2)0.2479 (5)0.40021 (19)0.0261 (10)
H31A1.49650.22010.43660.031*
H31B1.42090.18260.39760.031*
C311.4400 (3)0.4203 (7)0.4036 (3)0.0369 (14)
H31C1.39230.44240.37220.044*
H31D1.43780.44680.44730.044*
N321.5058 (3)0.4610 (5)0.3262 (2)0.0326 (11)
H32A1.47210.50930.29220.039*
H32B1.55090.48700.32390.039*
C321.4973 (3)0.5192 (7)0.3880 (3)0.0390 (15)
H32C1.54350.50830.42280.047*
H32D1.48330.63470.38420.047*
N331.5363 (2)0.1832 (6)0.2506 (2)0.0283 (11)
H33A1.58510.20130.26520.034*
H33B1.51630.25270.21700.034*
C331.5214 (3)0.0133 (7)0.2291 (3)0.0342 (14)
H33C1.47020.00050.20370.041*
H33D1.55160.01840.20190.041*
N341.4997 (2)0.0233 (5)0.3319 (2)0.0255 (10)
H34A1.45430.06760.32180.031*
H34B1.52390.04910.37400.031*
C341.5388 (3)0.0907 (7)0.2887 (3)0.0311 (13)
H34C1.59130.09030.31060.037*
H34D1.52330.20350.27690.037*
N411.1470 (2)0.1632 (5)0.56263 (18)0.0210 (9)
H41A1.18270.18710.60010.025*
H41B1.10820.22930.55990.025*
C411.1253 (3)0.0099 (6)0.5627 (2)0.0256 (12)
H41C1.07630.02610.53260.031*
H41D1.12520.04250.60630.031*
N421.1830 (2)0.0418 (5)0.47991 (19)0.0218 (10)
H42A1.14420.07580.44660.026*
H42B1.22440.07680.47200.026*
C421.1789 (3)0.1093 (6)0.5419 (2)0.0224 (11)
H42C1.22670.10420.57480.027*
H42D1.16320.22360.53620.027*
N431.2115 (2)0.2366 (5)0.40524 (19)0.0240 (10)
H43A1.24970.17110.40520.029*
H43B1.17350.21240.36950.029*
C431.2320 (3)0.4088 (7)0.4037 (3)0.0347 (14)
H43C1.28240.42500.43060.042*
H43D1.22800.44130.35900.042*
N441.1812 (2)0.4404 (5)0.49109 (19)0.0266 (10)
H44A1.14010.47360.49990.032*
H44B1.22040.47670.52360.032*
C441.1829 (3)0.5079 (7)0.4285 (3)0.0343 (14)
H44C1.13390.50670.39740.041*
H44D1.20000.62110.43420.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0193 (3)0.0273 (4)0.0224 (3)0.0017 (3)0.0070 (3)0.0028 (3)
Ni10.0167 (4)0.0321 (4)0.0198 (3)0.0017 (3)0.0073 (3)0.0003 (3)
O10.036 (3)0.075 (4)0.037 (2)0.001 (2)0.011 (2)0.005 (2)
Ni20.0199 (4)0.0427 (5)0.0263 (4)0.0005 (3)0.0012 (3)0.0014 (3)
Cu20.0206 (4)0.0228 (4)0.0196 (3)0.0004 (3)0.0028 (3)0.0005 (3)
O20.069 (4)0.066 (4)0.028 (2)0.002 (3)0.008 (2)0.002 (2)
Cu30.0199 (4)0.0241 (4)0.0219 (3)0.0003 (3)0.0059 (3)0.0030 (3)
O30.041 (4)0.164 (8)0.026 (3)0.019 (4)0.004 (3)0.012 (3)
Cu40.0229 (4)0.0195 (3)0.0191 (3)0.0005 (3)0.0088 (3)0.0008 (3)
N110.024 (3)0.041 (3)0.026 (2)0.001 (2)0.008 (2)0.006 (2)
C110.025 (3)0.029 (3)0.017 (2)0.003 (2)0.005 (2)0.003 (2)
N120.026 (3)0.048 (3)0.027 (3)0.003 (2)0.005 (2)0.005 (2)
C120.013 (3)0.035 (3)0.026 (3)0.001 (2)0.007 (2)0.001 (2)
N130.023 (3)0.029 (3)0.025 (2)0.002 (2)0.009 (2)0.0005 (19)
C130.028 (3)0.024 (3)0.020 (3)0.002 (2)0.007 (2)0.002 (2)
N140.024 (3)0.053 (3)0.027 (3)0.002 (2)0.008 (2)0.006 (2)
C140.016 (3)0.035 (3)0.027 (3)0.001 (2)0.008 (2)0.000 (2)
A10.019 (3)0.024 (3)0.020 (2)0.002 (2)0.004 (2)0.002 (2)
A20.017 (3)0.034 (3)0.016 (2)0.003 (2)0.0021 (19)0.000 (2)
A1'0.019 (3)0.024 (3)0.020 (2)0.002 (2)0.004 (2)0.002 (2)
A2'0.017 (3)0.034 (3)0.016 (2)0.003 (2)0.0021 (19)0.000 (2)
N210.020 (3)0.037 (3)0.026 (2)0.001 (2)0.005 (2)0.005 (2)
C210.022 (3)0.039 (3)0.020 (3)0.002 (3)0.007 (2)0.005 (2)
C220.028 (3)0.042 (4)0.034 (3)0.000 (3)0.001 (3)0.002 (3)
N220.032 (3)0.066 (4)0.030 (3)0.002 (3)0.014 (2)0.005 (3)
N230.017 (2)0.031 (3)0.020 (2)0.0036 (19)0.0007 (19)0.0037 (19)
C230.028 (3)0.035 (3)0.017 (3)0.000 (3)0.009 (2)0.000 (2)
C240.024 (3)0.048 (4)0.038 (3)0.003 (3)0.000 (3)0.001 (3)
N240.024 (3)0.099 (5)0.035 (3)0.006 (3)0.004 (2)0.004 (3)
N250.022 (2)0.023 (2)0.017 (2)0.0009 (18)0.0023 (18)0.0009 (18)
C250.020 (3)0.017 (3)0.026 (3)0.002 (2)0.009 (2)0.003 (2)
N310.026 (3)0.029 (3)0.023 (2)0.001 (2)0.0064 (19)0.0013 (19)
C310.033 (4)0.037 (4)0.042 (3)0.001 (3)0.013 (3)0.008 (3)
N320.026 (3)0.029 (3)0.039 (3)0.002 (2)0.004 (2)0.007 (2)
C320.025 (3)0.031 (4)0.059 (4)0.003 (3)0.010 (3)0.012 (3)
N330.022 (3)0.035 (3)0.028 (2)0.001 (2)0.008 (2)0.008 (2)
C330.030 (3)0.043 (4)0.028 (3)0.000 (3)0.007 (3)0.002 (3)
N340.024 (3)0.027 (3)0.026 (2)0.002 (2)0.009 (2)0.0020 (19)
C340.031 (3)0.028 (3)0.035 (3)0.003 (3)0.011 (3)0.002 (3)
N410.022 (2)0.021 (2)0.021 (2)0.0014 (19)0.0080 (19)0.0031 (18)
C410.029 (3)0.022 (3)0.030 (3)0.005 (2)0.015 (3)0.002 (2)
N420.022 (2)0.022 (2)0.022 (2)0.0006 (18)0.0068 (19)0.0018 (18)
C420.026 (3)0.018 (3)0.023 (3)0.001 (2)0.008 (2)0.003 (2)
N430.028 (3)0.023 (3)0.022 (2)0.0021 (19)0.009 (2)0.0021 (18)
C430.052 (4)0.025 (3)0.034 (3)0.004 (3)0.023 (3)0.003 (3)
N440.033 (3)0.030 (3)0.018 (2)0.003 (2)0.009 (2)0.0035 (19)
C440.049 (4)0.020 (3)0.040 (3)0.003 (3)0.021 (3)0.003 (3)
Geometric parameters (Å, º) top
Cu1—A1'1.963 (5)C24—N241.147 (7)
Cu1—A11.963 (5)N25—C251.156 (6)
Cu1—N211.984 (5)C25—Cu2iii2.142 (5)
Cu1—N251.992 (4)N31—C311.486 (7)
Cu1—N132.005 (4)N31—H31A0.9200
Ni1—C121.858 (5)N31—H31B0.9200
Ni1—C131.860 (5)C31—C321.503 (8)
Ni1—C141.860 (5)C31—H31C0.9900
Ni1—C111.881 (5)C31—H31D0.9900
O1—H1A0.83 (3)N32—C321.485 (7)
O1—H1B0.82 (3)N32—H32A0.9200
Ni2—C211.855 (6)N32—H32B0.9200
Ni2—C231.856 (6)C32—H32C0.9900
Ni2—C241.858 (6)C32—H32D0.9900
Ni2—C221.891 (6)N33—C331.481 (7)
Cu2—A2'i1.962 (5)N33—H33A0.9200
Cu2—A2i1.962 (5)N33—H33B0.9200
Cu2—N23ii1.991 (4)C33—C341.507 (7)
Cu2—C252.044 (5)C33—H33C0.9900
Cu2—C25iii2.142 (5)C33—H33D0.9900
Cu2—Cu2iii2.4440 (12)N34—C341.487 (6)
O2—H2A0.88 (3)N34—H34A0.9200
O2—H2B0.87 (3)N34—H34B0.9200
Cu3—N332.007 (4)C34—H34C0.9900
Cu3—N312.007 (4)C34—H34D0.9900
Cu3—N342.013 (4)N41—C411.494 (6)
Cu3—N322.022 (5)N41—H41A0.9200
Cu3—N112.325 (5)N41—H41B0.9200
O3—H3A0.87 (3)C41—C421.501 (7)
O3—H3B0.85 (3)C41—H41C0.9900
Cu4—N441.998 (4)C41—H41D0.9900
Cu4—N422.000 (4)N42—C421.486 (6)
Cu4—N412.019 (4)N42—H42A0.9200
Cu4—N432.022 (4)N42—H42B0.9200
N11—C111.142 (6)C42—H42C0.9900
N12—C121.149 (6)C42—H42D0.9900
N13—C131.145 (6)N43—C431.482 (7)
N14—C141.155 (6)N43—H43A0.9200
A1—A2'1.153 (6)N43—H43B0.9200
A1—A21.153 (6)C43—C441.479 (7)
A2—A1'1.153 (6)C43—H43C0.9900
A2—Cu2i1.962 (5)C43—H43D0.9900
A1'—A2'1.153 (6)N44—C441.483 (6)
A2'—Cu2i1.962 (5)N44—H44A0.9200
N21—C211.146 (6)N44—H44B0.9200
C22—N221.132 (7)C44—H44C0.9900
N23—C231.146 (6)C44—H44D0.9900
N23—Cu2iv1.991 (4)
A1'—Cu1—A10.0 (4)N31—C31—C32106.8 (5)
A1'—Cu1—N21108.33 (19)N31—C31—H31C110.4
A1—Cu1—N21108.33 (19)C32—C31—H31C110.4
A1'—Cu1—N25111.00 (18)N31—C31—H31D110.4
A1—Cu1—N25111.00 (18)C32—C31—H31D110.4
N21—Cu1—N25107.66 (18)H31C—C31—H31D108.6
A1'—Cu1—N13112.30 (19)C32—N32—Cu3108.5 (3)
A1—Cu1—N13112.30 (19)C32—N32—H32A110.0
N21—Cu1—N13112.27 (17)Cu3—N32—H32A110.0
N25—Cu1—N13105.18 (17)C32—N32—H32B110.0
C12—Ni1—C1388.9 (2)Cu3—N32—H32B110.0
C12—Ni1—C14175.7 (2)H32A—N32—H32B108.4
C13—Ni1—C1488.2 (2)N32—C32—C31108.8 (5)
C12—Ni1—C1193.3 (2)N32—C32—H32C109.9
C13—Ni1—C11175.6 (2)C31—C32—H32C109.9
C14—Ni1—C1189.8 (2)N32—C32—H32D109.9
H1A—O1—H1B105 (4)C31—C32—H32D109.9
C21—Ni2—C23175.0 (2)H32C—C32—H32D108.3
C21—Ni2—C2492.8 (2)C33—N33—Cu3107.1 (3)
C23—Ni2—C2491.8 (2)C33—N33—H33A110.3
C21—Ni2—C2287.2 (2)Cu3—N33—H33A110.3
C23—Ni2—C2288.3 (2)C33—N33—H33B110.3
C24—Ni2—C22174.8 (3)Cu3—N33—H33B110.3
A2'i—Cu2—A2i0.0 (4)H33A—N33—H33B108.6
A2'i—Cu2—N23ii106.80 (18)N33—C33—C34107.4 (4)
A2i—Cu2—N23ii106.80 (18)N33—C33—H33C110.2
A2'i—Cu2—C25109.49 (19)C34—C33—H33C110.2
A2i—Cu2—C25109.49 (19)N33—C33—H33D110.2
N23ii—Cu2—C25114.76 (18)C34—C33—H33D110.2
A2'i—Cu2—C25iii114.16 (19)H33C—C33—H33D108.5
A2i—Cu2—C25iii114.16 (19)C34—N34—Cu3109.6 (3)
N23ii—Cu2—C25iii103.05 (19)C34—N34—H34A109.7
C25—Cu2—C25iii108.60 (16)Cu3—N34—H34A109.7
A2'i—Cu2—Cu2iii129.63 (13)C34—N34—H34B109.7
A2i—Cu2—Cu2iii129.63 (13)Cu3—N34—H34B109.7
N23ii—Cu2—Cu2iii123.24 (13)H34A—N34—H34B108.2
C25—Cu2—Cu2iii56.17 (14)N34—C34—C33107.9 (4)
C25iii—Cu2—Cu2iii52.43 (13)N34—C34—H34C110.1
H2A—O2—H2B94 (3)C33—C34—H34C110.1
N33—Cu3—N31173.15 (18)N34—C34—H34D110.1
N33—Cu3—N3484.68 (17)C33—C34—H34D110.1
N31—Cu3—N3493.27 (17)H34C—C34—H34D108.4
N33—Cu3—N3295.87 (18)C41—N41—Cu4108.2 (3)
N31—Cu3—N3284.74 (18)C41—N41—H41A110.1
N34—Cu3—N32167.64 (19)Cu4—N41—H41A110.1
N33—Cu3—N1195.24 (17)C41—N41—H41B110.1
N31—Cu3—N1191.51 (17)Cu4—N41—H41B110.1
N34—Cu3—N1197.78 (18)H41A—N41—H41B108.4
N32—Cu3—N1194.47 (18)N41—C41—C42107.6 (4)
H3A—O3—H3B98 (4)N41—C41—H41C110.2
N44—Cu4—N42178.75 (18)C42—C41—H41C110.2
N44—Cu4—N4194.93 (16)N41—C41—H41D110.2
N42—Cu4—N4185.08 (16)C42—C41—H41D110.2
N44—Cu4—N4384.84 (16)H41C—C41—H41D108.5
N42—Cu4—N4395.06 (16)C42—N42—Cu4108.2 (3)
N41—Cu4—N43175.57 (18)C42—N42—H42A110.1
C11—N11—Cu3135.2 (4)Cu4—N42—H42A110.1
N11—C11—Ni1175.8 (5)C42—N42—H42B110.1
N12—C12—Ni1177.5 (5)Cu4—N42—H42B110.1
C13—N13—Cu1167.1 (4)H42A—N42—H42B108.4
N13—C13—Ni1175.4 (5)N42—C42—C41107.6 (4)
N14—C14—Ni1178.0 (5)N42—C42—H42C110.2
A2'—A1—A20.0 (7)C41—C42—H42C110.2
A2'—A1—Cu1161.5 (4)N42—C42—H42D110.2
A2—A1—Cu1161.5 (4)C41—C42—H42D110.2
A1'—A2—A10.0 (7)H42C—C42—H42D108.5
A1'—A2—Cu2i156.6 (4)C43—N43—Cu4108.2 (3)
A1—A2—Cu2i156.6 (4)C43—N43—H43A110.1
A2'—A1'—A20.0 (7)Cu4—N43—H43A110.1
A2'—A1'—Cu1161.5 (4)C43—N43—H43B110.1
A2—A1'—Cu1161.5 (4)Cu4—N43—H43B110.1
A1'—A2'—A10.0 (7)H43A—N43—H43B108.4
A1'—A2'—Cu2i156.6 (4)C44—C43—N43108.4 (4)
A1—A2'—Cu2i156.6 (4)C44—C43—H43C110.0
C21—N21—Cu1174.9 (4)N43—C43—H43C110.0
N21—C21—Ni2177.3 (5)C44—C43—H43D110.0
N22—C22—Ni2177.6 (6)N43—C43—H43D110.0
C23—N23—Cu2iv170.2 (4)H43C—C43—H43D108.4
N23—C23—Ni2177.2 (4)C44—N44—Cu4108.6 (3)
N24—C24—Ni2175.4 (6)C44—N44—H44A110.0
C25—N25—Cu1172.9 (4)Cu4—N44—H44A110.0
N25—C25—Cu2152.5 (4)C44—N44—H44B110.0
N25—C25—Cu2iii134.7 (4)Cu4—N44—H44B110.0
Cu2—C25—Cu2iii71.40 (16)H44A—N44—H44B108.3
C31—N31—Cu3108.2 (3)C43—C44—N44108.9 (5)
C31—N31—H31A110.1C43—C44—H44C109.9
Cu3—N31—H31A110.1N44—C44—H44C109.9
C31—N31—H31B110.1C43—C44—H44D109.9
Cu3—N31—H31B110.1N44—C44—H44D109.9
H31A—N31—H31B108.4H44C—C44—H44D108.3
Symmetry codes: (i) x+2, y, z+1; (ii) x+1/2, y1/2, z+1/2; (iii) x+2, y1, z+1; (iv) x1/2, y1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N24i0.83 (3)2.16 (5)2.898 (7)148 (7)
O1—H1B···O2v0.82 (3)2.14 (3)2.942 (7)165 (8)
O2—H2A···N14v0.88 (3)1.96 (3)2.835 (6)174 (8)
O2—H2B···O3i0.87 (3)2.72 (8)3.37 (5)132 (7)
O3—H3A···O1i0.87 (3)2.62 (12)2.803 (7)93 (8)
O3—H3B···N12vi0.85 (3)1.99 (3)2.843 (7)174 (9)
N31—H31A···O3vii0.921.962.841 (7)160
N31—H31A···O3vii0.922.042.90 (4)155
N34—H34B···O20.922.193.026 (7)151
Symmetry codes: (i) x+2, y, z+1; (v) x+3, y, z+1; (vi) x1/2, y1/2, z+1/2; (vii) x+1, y, z.

Experimental details

Crystal data
Chemical formula[Cu(C2H8N2)2(H2O)][Ni2Cu3(CN)10(C2H8N2)2]·2H2O
Mr926.24
Crystal system, space groupMonoclinic, P21/n
Temperature (K)173
a, b, c (Å)19.476 (2), 8.2737 (4), 21.786 (2)
β (°) 107.583 (2)
V3)3346.4 (3)
Z4
Radiation typeMo Kα
µ (mm1)3.65
Crystal size (mm)0.24 × 0.23 × 0.11
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionAnalytical
based on measured indexed crystal faces (SHELXTL; Sheldrick, 1997)
Tmin, Tmax0.532, 0.930
No. of measured, independent and
observed [I > 2σ(I)] reflections
20433, 7643, 4511
Rint0.068
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.108, 0.92
No. of reflections7643
No. of parameters429
No. of restraints9
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)2.14, 1.35

Computer programs: SMART (Bruker 1998), SMART and SAINT (Bruker 1998), SHELXTL (Sheldrick, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
Cu1—A11.963 (5)Cu4—N412.019 (4)
Cu1—N211.984 (5)Cu4—N432.022 (4)
Cu1—N251.992 (4)N11—C111.142 (6)
Cu1—N132.005 (4)N12—C121.149 (6)
Ni1—C121.858 (5)N13—C131.145 (6)
Ni1—C131.860 (5)N14—C141.155 (6)
Ni1—C141.860 (5)A1—A21.153 (6)
Ni1—C111.881 (5)N21—C211.146 (6)
Ni2—C211.855 (6)C22—N221.132 (7)
Ni2—C231.856 (6)N23—C231.146 (6)
Ni2—C241.858 (6)C24—N241.147 (7)
Ni2—C221.891 (6)N25—C251.156 (6)
Cu2—A2i1.962 (5)N31—C311.486 (7)
Cu2—N23ii1.991 (4)C31—C321.503 (8)
Cu2—C252.044 (5)N32—C321.485 (7)
Cu2—C25iii2.142 (5)N33—C331.481 (7)
Cu2—Cu2iii2.4440 (12)C33—C341.507 (7)
Cu3—N332.007 (4)N34—C341.487 (6)
Cu3—N312.007 (4)N41—C411.494 (6)
Cu3—N342.013 (4)C41—C421.501 (7)
Cu3—N322.022 (5)N42—C421.486 (6)
Cu3—N112.325 (5)N43—C431.482 (7)
Cu4—N441.998 (4)C43—C441.479 (7)
Cu4—N422.000 (4)N44—C441.483 (6)
A1—Cu1—N21108.33 (19)N34—Cu3—N1197.78 (18)
A1—Cu1—N25111.00 (18)N32—Cu3—N1194.47 (18)
N21—Cu1—N25107.66 (18)N44—Cu4—N4194.93 (16)
A1—Cu1—N13112.30 (19)N42—Cu4—N4185.08 (16)
N21—Cu1—N13112.27 (17)N44—Cu4—N4384.84 (16)
N25—Cu1—N13105.18 (17)N42—Cu4—N4395.06 (16)
C12—Ni1—C1388.9 (2)C11—N11—Cu3135.2 (4)
C13—Ni1—C1488.2 (2)N11—C11—Ni1175.8 (5)
C12—Ni1—C1193.3 (2)N12—C12—Ni1177.5 (5)
C14—Ni1—C1189.8 (2)C13—N13—Cu1167.1 (4)
C21—Ni2—C2492.8 (2)N13—C13—Ni1175.4 (5)
C23—Ni2—C2491.8 (2)N14—C14—Ni1178.0 (5)
C21—Ni2—C2287.2 (2)A2—A1—Cu1161.5 (4)
C23—Ni2—C2288.3 (2)A1—A2—Cu2i156.6 (4)
A2i—Cu2—N23ii106.80 (18)C21—N21—Cu1174.9 (4)
A2i—Cu2—C25109.49 (19)N21—C21—Ni2177.3 (5)
N23ii—Cu2—C25114.76 (18)N22—C22—Ni2177.6 (6)
C25—Cu2—C25iii108.60 (16)C23—N23—Cu2iv170.2 (4)
N33—Cu3—N3484.68 (17)N23—C23—Ni2177.2 (4)
N31—Cu3—N3493.27 (17)N24—C24—Ni2175.4 (6)
N33—Cu3—N3295.87 (18)C25—N25—Cu1172.9 (4)
N31—Cu3—N3284.74 (18)N25—C25—Cu2152.5 (4)
N33—Cu3—N1195.24 (17)N25—C25—Cu2iii134.7 (4)
N31—Cu3—N1191.51 (17)Cu2—C25—Cu2iii71.40 (16)
Symmetry codes: (i) x+2, y, z+1; (ii) x+1/2, y1/2, z+1/2; (iii) x+2, y1, z+1; (iv) x1/2, y1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N24i0.83 (3)2.16 (5)2.898 (7)148 (7)
O1—H1B···O2v0.82 (3)2.14 (3)2.942 (7)165 (8)
O2—H2A···N14v0.88 (3)1.96 (3)2.835 (6)174 (8)
O2—H2B···O3'i0.87 (3)2.72 (8)3.37 (5)132 (7)
O3—H3A···O1i0.87 (3)2.62 (12)2.803 (7)93 (8)
O3—H3B···N12vi0.85 (3)1.99 (3)2.843 (7)174 (9)
N31—H31A···O3vii0.921.962.841 (7)160
N31—H31A···O3'vii0.922.042.90 (4)155
N34—H34B···O20.922.193.026 (7)151
Symmetry codes: (i) x+2, y, z+1; (v) x+3, y, z+1; (vi) x1/2, y1/2, z+1/2; (vii) x+1, y, z.
 

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