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Acta Cryst. (2004). C60, m601-m604
https://doi.org/10.1107/S0108270104018244
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Low-dimensional compounds containing cyano groups. X. (Dicyan­amido-κN1)­bis(1,10-phenanthroline-κ2N,N′)copper(II) perchlorate

M. Burčák, I. Potočňák, P. Baran and L. Jäger
The title compound, [Cu(C2N3)(C12H8N2)2]ClO4, represents a relatively rare class of compounds with dicyan­amide coordinated in a monodentate manner. The structure is formed by the [Cu{N(CN)2}(phen)2]+ complex cation (phen is 1,10-phenanthroline) and an uncoordinated ClO4− anion. The Cu atom is five-coordinate, with a slightly distorted trigonal–bipyramidal environment. The dicyan­amide ligand is coordinated through one nitrile N atom in the equatorial plane, at a distance of 2.033 (6) Å from the metal. The two axial Cu—N distances are similar [mean 1.999 (4) Å] and are substantially shorter than the remaining two equatorial Cu—N bonds [mean 2.087 (1) Å].
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Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104018244/fa1074sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104018244/fa1074Isup2.hkl
Contains datablock I

CCDC reference: 259007

Comment top

The dicyanamide anion, [N(CN)2]- (dca), can coordinate either as a monodentate ligand through the nitrile or amide N atom, or as a bidentate, tridentate, tetradentate or even pentadentate bridging ligand with participation of two or three donor N atoms. Nevertheless, monodentate coordination of dca through the amide N atom is rather improbable (Kohout et al., 2000) and to date only two compounds with this type of dca coordination are known (Marshall et al., 2002; Montgomery et al., 1993). On the other hand, the structures of several molecular and ionic compounds with dca coordinated in a monodentate manner through a nitrile N atom have been reported. These compounds either contain six-coordinate central atoms and are of the general formula [ML4(dca)2], e.g. [Ni(teta)(dca)2] (teta is triethylenetetramine; Březina et al., 1999), [Cu(phen)2(dca)2] (phen is 1,10-phenanthroline; Potočňák et al., 1995), [Cu(NITpPy)2(H2O)2(dca)2] (NITpPy is the nitronyl nitroxide radical; Dasna et al., 2001) and [Ni(4-Meim)4(dca)2] (4-Meim is 4-methylimidazole; Kožíšek et al., 1996), or exhibit five-coordination and have the general formula [ML4(dca)]X, e.g. [Cu(bpy)2(dca)]BF4 (bpy is 2,2'-bipyridine; Potočňák Dunaj-Jurčo Mikloš Massa & Jäger, 2001), and [Cu(phen)2(dca)]C(CN)3 (Potočňák et al., 1996), in which L4 may be one tetradentate, two bidentate or four monodentate ligands, and X is a monoanion.

Understanding the shape of coordination polyhedra (SCP) in the case of five-coordination is one of the current problems in coordination chemistry. With the aim of elucidating the factors which determine the SCP in related compounds, we have previously studied structures of five-coordinate copper(II) complexes of the general formula [Cu(L)2X]C(CN)3, where L is phen or bpy and X is an N-donor pseudohalide anion (Potočňák Dunaj-Jurčo Mikloš & Jäger, 2001). More or less distorted trigonal bipyramids were found in those compounds. Recently, we have focused on compounds with the same inner coordination sphere and studied the influence of the counter-anion in complexes with the general formula [Cu(L)2(dca)]Y, where L is phen and Y is CF3SO3-, (II) or C(CN)3-, (III), and where L is bpy and Y is ClO4-, (IV), CF3SO3-, (V), C(CN)3-, (VI) or BF4- (VII), (Potočňák et al., 2003). This paper is a continuation of that work and we present here the structure of [Cu(phen)2(dca)]ClO4, (I). \sch

Fig. 1 shows the labelling scheme of one formula unit of (I). The Cu atom is pentacoordinated by two phen molecules and one [N(CN)2]- ligand. The coordination polyhedron is a distorted trigonal bipyramid (TBP). The two axial distances involving phen (Cu1—N10 and Cu1—N30) are almost equal and are essentially collinear. The two equatorial distances (Cu1—N20 and Cu1—N40) are of the same length (within 1 σ) and their average is 0.088 Å longer than the axial Cu—N distances, which is a feature generally observed for compounds with the [Cu(L)2X] cation, where L is bpy and X is Cl-, Br- or I- (O'Sullivan et al., 1999), where L is phen and X is Cl- (Murphy et al., 1998), Br- (Murphy Nagle et al., 1997) or H2O (Murphy Murphy et al., 1997), or where L is phen or bpy and X is a pseudohalide (-1) anion (Potočňák Dunaj-Jurčo Mikloš & Jäger, 2001). The third equatorial distance, Cu1—N1 [2.033 (6) Å, N from dca], is shorter than the other two but is 0.035 Å longer than the two axial bonds. This differs from compounds (II)-(VII), in which the Cu—Ndca bond length is comparable with the two axial bonds and in some cases is the shortest Cu—N bond. Table 2 gives details for the purpose of comparison.

The Nax—Cu—Neq angles span the range 80.74 (18)–99.04 (18)° in (I), as they do in (II)-(VII). The Neq—Cu—Neq bond angles in (I) are not ideal trigonal angles of 120°. One of them is slightly greater [N40—Cu1—N20 (α3) 126.40 (17)°], one has a normal value [N1—Cu1—N40 (α1) 118.41 (19)°] and one is slightly smaller [N1—Cu1—N20 (α2) 115.19 (19)°]. The corresponding values for (II)-(VII) are given in Table 2. For complexes (II)-(VII), α1 is the second largest angle in the Cu coordination polyhedron, while in (I), the second largest angle is α3. In a putative square-pyramidal distortion of the TBP arrangement of donor atoms, atom N20 from phen or bpy would become an apical atom in (II)-(VII), but in (I), the apical atom would be N1 from dca. Because the differences between the observed and ideal values are not great in (I), the SCP around Cu can be considered as TBP, with atom Cu1 lying in the trigonal plane. This is in accord with the value of the τ parameter [Table 2; τ = 100 for an ideal TBP or 0 for an ideal square pyramid (SP); Addison et al., 1984]. We have shown in our previous work (Potočňák & Burčák, 2003), that the τ parameter does not always describe the SCP correctly. Therefore, besides τ, another, more reliable, criterion is presented in Table 2, to describe the actual SCP in five-coordinate compounds, namely the sum of the angle deviations for a TBP, Σ(TBP) (Holmes & Deiters, 1977). According to this criterion, a larger value of Σ(TBP) represents a greater deviation of the SCP from the ideal TBP. The data in Table 2 show that compounds (I)-(III) (all containing phen ligands), achieve lower Σ(TBP) values than compounds (IV)-(VII), which contain bpy ligands, which corresponds to a greater distortion of the TBP of the latter group compared with the former. We believe that the observed difference can be explained by the lower rigidity of bpy compared with phen. While the two outer pyridine rings in a phen molecule are connected by a phenyl ring, making the whole molecule planar and rigid, the two pyridine rings in a bpy molecule can rotate around their common C—C single bond. Our results indicate that compounds with rigid chelating ligands prefer a TBP SCP, while those with more flexible chelating ligands have an SCP more distorted towards square pyramidal.

Both phen moieties in (I) are nearly planar [the largest deviation from the mean plane is 0.067 (6) Å for atom C14] and exhibit the expected bond lengths and angles. The two phen ligands form a dihedral angle of 54.48 (8)°.

There are three canonical forms describing the mode of bonding in the dicyanamide ligand, including single and double Namide—C bonds, and double and triple Ncyano—C bonds (Golub et al., 1986). Inspection of the bond lengths in (I) (Table 1) shows that no canonical form properly describes the bonding mode in this particular dicyanamide. The Namide═C distances (N3═C1 and N3═C2) are typical for N═C double bonds (1.27 Å; Reference?), but Ncyano≡C (C1≡N1 and C2≡N2) are shorter than typical N≡C triple bonds (1.15 Å; Jolly, 1991). The N3—C1—N1 and N3—C2—N2 angles are almost linear, while the C1—N3—C2 angle is close to 120°. The dicyanamide ligand is nearly planar, with the largest deviation from the mean plane being 0.021 (7) Å For which atom?. According to Golub et al. (1986), the bonding mode of the dicyanamide to the Cu atom can be considered as linear [C1—N1—Cu1 173.1 (6)°].

The ClO4- anion does not enter the inner coordination sphere of the Cu atom in (I). Atoms O2, O3 and O4 are disordered over two positions, but their displacement ellipsoids are still quite large, indicating possible rotational disorder, with the rotation axis passing through atoms Cl1 and O1.

Besides ionic forces, the structure of (I) is stabilized by weak C—H···X hydrogen bonds (X is O or N); those with C—H···X angles greater than 120° and H···X distances less than 2.6 Å are given in Table 3. There was no hydrogen-bond table in the CIF - do you wish to add one? Further stabilization may come from possible π–π interactions between stacked phen entities. There is a stacking interaction involving one of the phen ligands [that containing atoms N30 and N40 and its symmetry relative at (-x, 1 - y, 1 - z)], with the shortest distance of 3.514 (7) Å being between atoms C36 and C31(-x, 1 - y, 1 - z). There is another stacking interaction involving the phen ligand containing atoms N10 and N20, and that containing N30 and N40, with the latter at symmetry position (1/2 + x, 1/2 - y, 1 - z). The shortest distance of 3.314 (7) Å involves atoms C26 and C34(1/2 + x, 1/2 - y, 1 - z). Because the angle between the mean planes of these two phen ligands is 13.2 (6)°, the other C···C(1/2 + x, 1/2 - y, 1 - z) distances are longer and, moreover, this second interaction seems to have less overlap than the first.

Experimental top

Crystals of (I) were prepared by mixing a solution of Cu(ClO4)2 (5 ml, 0.1M in dimethylformamide) with a solution of phen (10 ml, 0.1M in ethanol). To the resulting green solution was added a solution of NaN(CN)2 (5 ml, 0.1M in water) (all solutions were warmed before mixing). Green crystals of (I) appeared after a week. The crystals were filtered off and dried in air.

Refinement top

All H-atom positions were calculated and then refined using a riding model, with Uiso(H) = 1.2Ueq(C). Geometrical analysis was performed using PARST (Nardelli, 1983) and SHELXL97 (Sheldrick, 1997).

Structure description top

The dicyanamide anion, [N(CN)2]- (dca), can coordinate either as a monodentate ligand through the nitrile or amide N atom, or as a bidentate, tridentate, tetradentate or even pentadentate bridging ligand with participation of two or three donor N atoms. Nevertheless, monodentate coordination of dca through the amide N atom is rather improbable (Kohout et al., 2000) and to date only two compounds with this type of dca coordination are known (Marshall et al., 2002; Montgomery et al., 1993). On the other hand, the structures of several molecular and ionic compounds with dca coordinated in a monodentate manner through a nitrile N atom have been reported. These compounds either contain six-coordinate central atoms and are of the general formula [ML4(dca)2], e.g. [Ni(teta)(dca)2] (teta is triethylenetetramine; Březina et al., 1999), [Cu(phen)2(dca)2] (phen is 1,10-phenanthroline; Potočňák et al., 1995), [Cu(NITpPy)2(H2O)2(dca)2] (NITpPy is the nitronyl nitroxide radical; Dasna et al., 2001) and [Ni(4-Meim)4(dca)2] (4-Meim is 4-methylimidazole; Kožíšek et al., 1996), or exhibit five-coordination and have the general formula [ML4(dca)]X, e.g. [Cu(bpy)2(dca)]BF4 (bpy is 2,2'-bipyridine; Potočňák Dunaj-Jurčo Mikloš Massa & Jäger, 2001), and [Cu(phen)2(dca)]C(CN)3 (Potočňák et al., 1996), in which L4 may be one tetradentate, two bidentate or four monodentate ligands, and X is a monoanion.

Understanding the shape of coordination polyhedra (SCP) in the case of five-coordination is one of the current problems in coordination chemistry. With the aim of elucidating the factors which determine the SCP in related compounds, we have previously studied structures of five-coordinate copper(II) complexes of the general formula [Cu(L)2X]C(CN)3, where L is phen or bpy and X is an N-donor pseudohalide anion (Potočňák Dunaj-Jurčo Mikloš & Jäger, 2001). More or less distorted trigonal bipyramids were found in those compounds. Recently, we have focused on compounds with the same inner coordination sphere and studied the influence of the counter-anion in complexes with the general formula [Cu(L)2(dca)]Y, where L is phen and Y is CF3SO3-, (II) or C(CN)3-, (III), and where L is bpy and Y is ClO4-, (IV), CF3SO3-, (V), C(CN)3-, (VI) or BF4- (VII), (Potočňák et al., 2003). This paper is a continuation of that work and we present here the structure of [Cu(phen)2(dca)]ClO4, (I). \sch

Fig. 1 shows the labelling scheme of one formula unit of (I). The Cu atom is pentacoordinated by two phen molecules and one [N(CN)2]- ligand. The coordination polyhedron is a distorted trigonal bipyramid (TBP). The two axial distances involving phen (Cu1—N10 and Cu1—N30) are almost equal and are essentially collinear. The two equatorial distances (Cu1—N20 and Cu1—N40) are of the same length (within 1 σ) and their average is 0.088 Å longer than the axial Cu—N distances, which is a feature generally observed for compounds with the [Cu(L)2X] cation, where L is bpy and X is Cl-, Br- or I- (O'Sullivan et al., 1999), where L is phen and X is Cl- (Murphy et al., 1998), Br- (Murphy Nagle et al., 1997) or H2O (Murphy Murphy et al., 1997), or where L is phen or bpy and X is a pseudohalide (-1) anion (Potočňák Dunaj-Jurčo Mikloš & Jäger, 2001). The third equatorial distance, Cu1—N1 [2.033 (6) Å, N from dca], is shorter than the other two but is 0.035 Å longer than the two axial bonds. This differs from compounds (II)-(VII), in which the Cu—Ndca bond length is comparable with the two axial bonds and in some cases is the shortest Cu—N bond. Table 2 gives details for the purpose of comparison.

The Nax—Cu—Neq angles span the range 80.74 (18)–99.04 (18)° in (I), as they do in (II)-(VII). The Neq—Cu—Neq bond angles in (I) are not ideal trigonal angles of 120°. One of them is slightly greater [N40—Cu1—N20 (α3) 126.40 (17)°], one has a normal value [N1—Cu1—N40 (α1) 118.41 (19)°] and one is slightly smaller [N1—Cu1—N20 (α2) 115.19 (19)°]. The corresponding values for (II)-(VII) are given in Table 2. For complexes (II)-(VII), α1 is the second largest angle in the Cu coordination polyhedron, while in (I), the second largest angle is α3. In a putative square-pyramidal distortion of the TBP arrangement of donor atoms, atom N20 from phen or bpy would become an apical atom in (II)-(VII), but in (I), the apical atom would be N1 from dca. Because the differences between the observed and ideal values are not great in (I), the SCP around Cu can be considered as TBP, with atom Cu1 lying in the trigonal plane. This is in accord with the value of the τ parameter [Table 2; τ = 100 for an ideal TBP or 0 for an ideal square pyramid (SP); Addison et al., 1984]. We have shown in our previous work (Potočňák & Burčák, 2003), that the τ parameter does not always describe the SCP correctly. Therefore, besides τ, another, more reliable, criterion is presented in Table 2, to describe the actual SCP in five-coordinate compounds, namely the sum of the angle deviations for a TBP, Σ(TBP) (Holmes & Deiters, 1977). According to this criterion, a larger value of Σ(TBP) represents a greater deviation of the SCP from the ideal TBP. The data in Table 2 show that compounds (I)-(III) (all containing phen ligands), achieve lower Σ(TBP) values than compounds (IV)-(VII), which contain bpy ligands, which corresponds to a greater distortion of the TBP of the latter group compared with the former. We believe that the observed difference can be explained by the lower rigidity of bpy compared with phen. While the two outer pyridine rings in a phen molecule are connected by a phenyl ring, making the whole molecule planar and rigid, the two pyridine rings in a bpy molecule can rotate around their common C—C single bond. Our results indicate that compounds with rigid chelating ligands prefer a TBP SCP, while those with more flexible chelating ligands have an SCP more distorted towards square pyramidal.

Both phen moieties in (I) are nearly planar [the largest deviation from the mean plane is 0.067 (6) Å for atom C14] and exhibit the expected bond lengths and angles. The two phen ligands form a dihedral angle of 54.48 (8)°.

There are three canonical forms describing the mode of bonding in the dicyanamide ligand, including single and double Namide—C bonds, and double and triple Ncyano—C bonds (Golub et al., 1986). Inspection of the bond lengths in (I) (Table 1) shows that no canonical form properly describes the bonding mode in this particular dicyanamide. The Namide═C distances (N3═C1 and N3═C2) are typical for N═C double bonds (1.27 Å; Reference?), but Ncyano≡C (C1≡N1 and C2≡N2) are shorter than typical N≡C triple bonds (1.15 Å; Jolly, 1991). The N3—C1—N1 and N3—C2—N2 angles are almost linear, while the C1—N3—C2 angle is close to 120°. The dicyanamide ligand is nearly planar, with the largest deviation from the mean plane being 0.021 (7) Å For which atom?. According to Golub et al. (1986), the bonding mode of the dicyanamide to the Cu atom can be considered as linear [C1—N1—Cu1 173.1 (6)°].

The ClO4- anion does not enter the inner coordination sphere of the Cu atom in (I). Atoms O2, O3 and O4 are disordered over two positions, but their displacement ellipsoids are still quite large, indicating possible rotational disorder, with the rotation axis passing through atoms Cl1 and O1.

Besides ionic forces, the structure of (I) is stabilized by weak C—H···X hydrogen bonds (X is O or N); those with C—H···X angles greater than 120° and H···X distances less than 2.6 Å are given in Table 3. There was no hydrogen-bond table in the CIF - do you wish to add one? Further stabilization may come from possible π–π interactions between stacked phen entities. There is a stacking interaction involving one of the phen ligands [that containing atoms N30 and N40 and its symmetry relative at (-x, 1 - y, 1 - z)], with the shortest distance of 3.514 (7) Å being between atoms C36 and C31(-x, 1 - y, 1 - z). There is another stacking interaction involving the phen ligand containing atoms N10 and N20, and that containing N30 and N40, with the latter at symmetry position (1/2 + x, 1/2 - y, 1 - z). The shortest distance of 3.314 (7) Å involves atoms C26 and C34(1/2 + x, 1/2 - y, 1 - z). Because the angle between the mean planes of these two phen ligands is 13.2 (6)°, the other C···C(1/2 + x, 1/2 - y, 1 - z) distances are longer and, moreover, this second interaction seems to have less overlap than the first.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXTL (Bruker, 1999).

Figures top
[Figure 1] Fig. 1. The structure of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii. Only one position of the disordered perchlorate anion is shown.
(Dicyanamido-κN1)bis(1,10-phenanthroline-κ2N,N')copper(II) perchlorate top
Crystal data top
[Cu(C12H8N2)2(C2N3)]ClO4Dx = 1.618 Mg m−3
Mr = 589.45Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 878 reflections
a = 14.9903 (17) Åθ = 2.7–16.8°
b = 15.3555 (18) ŵ = 1.06 mm−1
c = 21.022 (3) ÅT = 300 K
V = 4838.8 (10) Å3Prism, green
Z = 80.10 × 0.05 × 0.04 mm
F(000) = 2392
Data collection top
Bruker SMART CCD area-detector
diffractometer		4527 independent reflections
Radiation source: fine-focus sealed tube2150 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.089
Detector resolution: 512 pixels mm-1θmax = 25.6°, θmin = 1.9°
φ and ω scansh = −16→18
Absorption correction: multi-scan
(XPREP; Sheldrick, 1990)		k = −17→18
Tmin = 0.820, Tmax = 0.924l = −25→24
23973 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.169 w = 1/[σ2(Fo2) + (0.0798P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max < 0.001
4527 reflectionsΔρmax = 0.40 e Å−3
381 parametersΔρmin = −0.57 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0009 (2)
Crystal data top
[Cu(C12H8N2)2(C2N3)]ClO4V = 4838.8 (10) Å3
Mr = 589.45Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 14.9903 (17) ŵ = 1.06 mm−1
b = 15.3555 (18) ÅT = 300 K
c = 21.022 (3) Å0.10 × 0.05 × 0.04 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		4527 independent reflections
Absorption correction: multi-scan
(XPREP; Sheldrick, 1990)		2150 reflections with I > 2σ(I)
Tmin = 0.820, Tmax = 0.924Rint = 0.089
23973 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0570 restraints
wR(F2) = 0.169H-atom parameters constrained
S = 0.99Δρmax = 0.40 e Å−3
4527 reflectionsΔρmin = −0.57 e Å−3
381 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)
C10.0983 (3)0.0730 (4)0.5407 (3)0.0648 (15)
C110.2191 (3)0.1718 (3)0.3554 (2)0.0569 (13)
C120.0873 (4)0.0948 (4)0.3574 (3)0.0801 (17)
C130.1157 (5)0.0406 (4)0.3089 (3)0.0832 (18)
C140.1972 (4)0.0531 (4)0.2828 (3)0.0777 (17)
C150.2519 (4)0.1210 (4)0.3050 (2)0.0613 (14)
C160.3389 (4)0.1408 (5)0.2804 (3)0.0776 (18)
C20.1391 (5)−0.0446 (5)0.5991 (3)0.0823 (19)
C210.2726 (3)0.2387 (3)0.3822 (2)0.0543 (12)
C220.2877 (4)0.3436 (4)0.4594 (3)0.0784 (17)
C230.3716 (4)0.3652 (4)0.4370 (3)0.0856 (19)
C240.4064 (4)0.3227 (4)0.3862 (3)0.0824 (18)
C250.3570 (3)0.2568 (4)0.3572 (3)0.0663 (15)
C260.3877 (4)0.2063 (5)0.3048 (3)0.0759 (17)
C310.0048 (3)0.3617 (3)0.5207 (2)0.0592 (14)
C320.1277 (4)0.3280 (4)0.5805 (3)0.0818 (18)
C330.1008 (5)0.3830 (5)0.6286 (3)0.088 (2)
C340.0249 (5)0.4302 (4)0.6221 (3)0.0859 (19)
C35−0.0273 (4)0.4196 (4)0.5670 (3)0.0651 (15)
C36−0.1103 (4)0.4626 (4)0.5556 (3)0.0731 (17)
C41−0.0464 (3)0.3463 (3)0.4646 (2)0.0566 (13)
C42−0.0552 (4)0.2747 (4)0.3683 (3)0.0702 (15)
C43−0.1365 (4)0.3150 (4)0.3553 (3)0.0769 (17)
C44−0.1726 (4)0.3715 (4)0.3978 (3)0.0761 (17)
C45−0.1274 (3)0.3890 (4)0.4553 (3)0.0619 (14)
C46−0.1578 (4)0.4472 (4)0.5027 (3)0.0739 (16)
Cl10.11751 (10)0.36436 (11)0.25378 (8)0.0766 (5)
Cu10.10960 (4)0.23744 (5)0.45430 (3)0.0658 (3)
N10.1049 (3)0.1330 (4)0.5136 (3)0.0849 (15)
N100.1373 (3)0.1593 (3)0.3807 (2)0.0649 (12)
N20.1841 (4)−0.0932 (4)0.6237 (3)0.113 (2)
N200.2375 (3)0.2823 (3)0.4327 (2)0.0642 (12)
N30.0801 (4)0.0022 (5)0.5704 (3)0.122 (2)
N300.0817 (3)0.3169 (3)0.5268 (2)0.0678 (13)
N40−0.0103 (3)0.2893 (3)0.4212 (2)0.0596 (11)
O10.0961 (4)0.2751 (4)0.2506 (3)0.140 (2)
O20.049 (2)0.406 (2)0.2354 (17)0.251 (19)0.52 (2)
O30.1346 (16)0.3858 (15)0.3195 (7)0.151 (10)0.52 (2)
O40.1967 (13)0.3814 (16)0.2236 (14)0.188 (11)0.52 (2)
O60.144 (2)0.3921 (14)0.1965 (10)0.217 (12)0.48 (2)
O70.0395 (19)0.413 (2)0.2601 (16)0.188 (14)0.48 (2)
O80.171 (3)0.3755 (17)0.300 (2)0.28 (2)0.48 (2)
H120.03090.08580.37450.096*
H130.0791−0.00390.29430.100*
H140.21700.01690.25030.093*
H160.36190.10780.24710.093*
H220.26550.37320.49460.094*
H230.40420.40890.45690.103*
H240.46270.33730.37090.099*
H260.44300.21890.28700.091*
H320.18050.29710.58580.098*
H330.13470.38780.66540.105*
H340.00760.46920.65360.103*
H36−0.13180.50200.58540.088*
H42−0.03180.23620.33860.084*
H43−0.16620.30320.31740.092*
H44−0.22670.39850.38910.091*
H46−0.21200.47560.49700.089*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.054 (3)0.073 (4)0.068 (4)−0.002 (3)0.001 (3)0.002 (3)
C110.055 (3)0.067 (4)0.048 (3)0.012 (3)−0.004 (3)0.008 (3)
C120.072 (4)0.088 (5)0.081 (4)−0.016 (3)0.004 (3)0.000 (4)
C130.102 (5)0.069 (4)0.079 (4)−0.005 (4)−0.011 (4)−0.013 (3)
C140.090 (5)0.079 (4)0.065 (4)0.011 (4)−0.006 (4)−0.002 (3)
C150.068 (4)0.066 (4)0.050 (3)0.015 (3)−0.008 (3)0.005 (3)
C160.067 (4)0.111 (5)0.056 (4)0.025 (4)0.007 (3)0.000 (3)
C20.085 (5)0.075 (5)0.087 (5)−0.001 (4)0.017 (4)0.011 (4)
C210.052 (3)0.061 (3)0.050 (3)0.006 (3)−0.005 (2)0.007 (3)
C220.070 (4)0.090 (5)0.074 (4)−0.004 (3)−0.005 (3)−0.017 (3)
C230.060 (4)0.094 (5)0.103 (5)−0.010 (3)0.001 (3)−0.020 (4)
C240.048 (3)0.102 (5)0.097 (5)−0.008 (3)−0.001 (3)0.005 (4)
C250.051 (3)0.091 (5)0.057 (4)0.011 (3)0.001 (3)0.014 (3)
C260.058 (3)0.110 (5)0.060 (4)0.002 (4)0.004 (3)0.005 (3)
C310.057 (3)0.066 (4)0.055 (3)−0.008 (3)0.011 (3)0.003 (3)
C320.069 (4)0.103 (5)0.074 (4)−0.005 (3)−0.009 (3)−0.003 (4)
C330.087 (5)0.120 (6)0.056 (4)−0.018 (4)0.001 (4)−0.010 (4)
C340.092 (5)0.103 (5)0.063 (4)−0.018 (4)0.023 (4)−0.013 (3)
C350.069 (4)0.073 (4)0.053 (3)−0.013 (3)0.014 (3)0.001 (3)
C360.070 (4)0.065 (4)0.084 (5)−0.009 (3)0.025 (3)−0.011 (3)
C410.057 (3)0.061 (3)0.051 (3)−0.006 (3)0.006 (3)0.004 (2)
C420.064 (4)0.083 (4)0.063 (4)0.003 (3)0.000 (3)−0.014 (3)
C430.070 (4)0.087 (5)0.073 (4)0.004 (3)−0.014 (3)−0.006 (3)
C440.057 (3)0.083 (4)0.088 (5)0.002 (3)0.001 (3)0.001 (4)
C450.053 (3)0.069 (4)0.064 (3)−0.003 (3)0.008 (3)0.004 (3)
C460.058 (3)0.074 (4)0.090 (5)0.006 (3)0.012 (3)−0.008 (3)
Cl10.0638 (9)0.0811 (11)0.0847 (11)0.0020 (8)−0.0066 (10)0.0127 (9)
Cu10.0578 (4)0.0773 (5)0.0625 (5)0.0015 (3)0.0024 (3)−0.0032 (3)
N10.085 (4)0.095 (4)0.075 (4)0.006 (3)0.006 (3)0.013 (3)
N100.055 (3)0.072 (3)0.068 (3)−0.004 (2)0.003 (2)−0.001 (2)
N20.119 (5)0.105 (5)0.114 (5)0.017 (4)0.026 (4)0.030 (4)
N200.063 (3)0.071 (3)0.059 (3)0.005 (2)−0.004 (2)−0.003 (2)
N30.089 (4)0.119 (5)0.159 (6)−0.024 (4)−0.020 (4)0.058 (5)
N300.057 (3)0.089 (4)0.058 (3)−0.005 (3)−0.004 (2)0.000 (2)
N400.055 (3)0.068 (3)0.056 (3)−0.001 (2)0.005 (2)−0.001 (2)
O10.159 (5)0.106 (4)0.156 (5)−0.023 (4)−0.015 (4)−0.017 (4)
O20.19 (3)0.26 (3)0.30 (4)0.11 (2)−0.15 (3)0.02 (2)
O30.22 (2)0.166 (15)0.067 (8)−0.012 (12)0.021 (12)−0.066 (9)
O40.090 (11)0.212 (17)0.26 (2)−0.063 (10)0.113 (13)−0.128 (18)
O60.17 (2)0.28 (2)0.203 (17)0.027 (16)0.102 (15)0.184 (17)
O70.17 (2)0.158 (17)0.24 (3)0.094 (14)0.09 (2)−0.001 (15)
O80.30 (3)0.16 (2)0.38 (4)−0.07 (2)−0.30 (3)0.09 (3)
Geometric parameters (Å, º) top
Cu1—N301.996 (5)C15—C141.406 (8)
Cu1—N102.001 (5)C15—C161.435 (8)
Cu1—N12.033 (6)C16—C261.345 (8)
Cu1—N402.086 (4)C16—H160.9300
Cu1—N202.087 (5)C32—C331.377 (8)
Cl1—O21.271 (19)C32—H320.9300
Cl1—O81.273 (19)C44—C431.357 (7)
Cl1—O61.337 (13)C44—H440.9300
Cl1—O41.371 (12)C43—C421.394 (7)
Cl1—O71.39 (2)C43—H430.9300
Cl1—O11.409 (5)C24—C231.356 (8)
Cl1—O31.443 (14)C24—H240.9300
N40—C421.319 (6)C1—N11.088 (7)
N40—C411.374 (6)C1—N31.282 (8)
C31—N301.349 (6)C46—C361.341 (7)
C31—C351.403 (7)C46—H460.9300
C31—C411.427 (7)C26—H260.9300
C11—N101.351 (6)C36—H360.9300
C11—C151.405 (7)C12—C131.383 (8)
C11—C211.421 (7)C12—H120.9300
C25—C241.395 (8)C23—C221.383 (8)
C25—C211.397 (7)C23—H230.9300
C25—C261.424 (8)C13—C141.352 (8)
C45—C411.394 (7)C13—H130.9300
C45—C441.411 (7)C42—H420.9300
C45—C461.414 (7)C34—C331.356 (8)
N30—C321.335 (7)C34—H340.9300
N20—C221.330 (6)C22—H220.9300
N20—C211.360 (6)C33—H330.9300
N10—C121.336 (7)C2—N21.130 (8)
C35—C341.407 (8)C2—N31.290 (9)
C35—C361.429 (8)C14—H140.9300
N30—Cu1—N10179.14 (19)N20—C21—C25123.1 (5)
N30—Cu1—N190.4 (2)N20—C21—C11116.5 (5)
N10—Cu1—N190.4 (2)C25—C21—C11120.4 (5)
N30—Cu1—N4080.82 (18)C26—C16—C15121.0 (6)
N10—Cu1—N4098.64 (18)C26—C16—H16119.5
N1—Cu1—N40118.41 (19)C15—C16—H16119.5
N30—Cu1—N2099.04 (18)N30—C32—C33123.3 (6)
N10—Cu1—N2080.74 (18)N30—C32—H32118.4
N1—Cu1—N20115.19 (19)C33—C32—H32118.4
N40—Cu1—N20126.40 (17)C43—C44—C45119.6 (5)
O8—Cl1—O6117.8 (19)C43—C44—H44120.2
O2—Cl1—O4118 (2)C45—C44—H44120.2
O8—Cl1—O7112 (2)C44—C43—C42120.1 (6)
O6—Cl1—O799.6 (15)C44—C43—H43119.9
O2—Cl1—O1106.6 (17)C42—C43—H43119.9
O8—Cl1—O1108.0 (11)C23—C24—C25119.3 (6)
O6—Cl1—O1109.6 (12)C23—C24—H24120.4
O4—Cl1—O1111.2 (9)C25—C24—H24120.4
O7—Cl1—O1109.3 (15)N1—C1—N3172.7 (7)
O2—Cl1—O3108.7 (17)C36—C46—C45121.6 (6)
O4—Cl1—O3104.2 (13)C36—C46—H46119.2
O1—Cl1—O3107.9 (10)C45—C46—H46119.2
C42—N40—C41117.8 (5)C16—C26—C25121.8 (6)
C42—N40—Cu1131.0 (4)C16—C26—H26119.1
C41—N40—Cu1111.2 (3)C25—C26—H26119.1
N30—C31—C35123.5 (5)C46—C36—C35121.3 (5)
N30—C31—C41116.9 (5)C46—C36—H36119.3
C35—C31—C41119.6 (5)C35—C36—H36119.3
N10—C11—C15122.4 (5)N10—C12—C13123.0 (6)
N10—C11—C21117.4 (5)N10—C12—H12118.5
C15—C11—C21120.2 (5)C13—C12—H12118.5
C24—C25—C21117.4 (5)C24—C23—C22120.2 (6)
C24—C25—C26124.2 (5)C24—C23—H23119.9
C21—C25—C26118.4 (6)C22—C23—H23119.9
C41—C45—C44116.6 (5)C14—C13—C12119.4 (6)
C41—C45—C46118.7 (5)C14—C13—H13120.3
C44—C45—C46124.7 (5)C12—C13—H13120.3
C32—N30—C31117.1 (5)N40—C42—C43122.4 (5)
C32—N30—Cu1128.1 (4)N40—C42—H42118.8
C31—N30—Cu1114.8 (4)C43—C42—H42118.8
C22—N20—C21117.2 (5)C33—C34—C35119.2 (6)
C22—N20—Cu1131.4 (4)C33—C34—H34120.4
C21—N20—Cu1111.3 (3)C35—C34—H34120.4
C12—N10—C11118.0 (5)C1—N1—Cu1173.1 (6)
C12—N10—Cu1127.8 (4)N20—C22—C23122.8 (6)
C11—N10—Cu1114.1 (4)N20—C22—H22118.6
C31—C35—C34117.0 (6)C23—C22—H22118.6
C31—C35—C36118.3 (5)C34—C33—C32120.0 (6)
C34—C35—C36124.7 (6)C34—C33—H33120.0
N40—C41—C45123.3 (5)C32—C33—H33120.0
N40—C41—C31116.3 (5)N2—C2—N3172.2 (8)
C45—C41—C31120.4 (5)C13—C14—C15119.9 (6)
C11—C15—C14117.2 (5)C13—C14—H14120.1
C11—C15—C16118.2 (5)C15—C14—H14120.1
C14—C15—C16124.6 (6)C1—N3—C2123.6 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C43—H43···O4i0.932.533.17 (2)126
C26—H26···O1ii0.932.583.498 (8)171
C12—H12···N3iii0.932.443.289 (9)153
C13—H13···O2iv0.932.453.35 (2)165
C13—H13···O7iv0.932.473.37 (3)164
C14—H14···O4v0.932.513.32 (2)146
Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) x+1/2, y, −z+1/2; (iii) −x, −y, −z+1; (iv) −x, y−1/2, −z+1/2; (v) −x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula[Cu(C12H8N2)2(C2N3)]ClO4
Mr589.45
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)300
a, b, c (Å)14.9903 (17), 15.3555 (18), 21.022 (3)
V (Å3)4838.8 (10)
Z8
Radiation typeMo Kα
µ (mm−1)1.06
Crystal size (mm)0.10 × 0.05 × 0.04
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(XPREP; Sheldrick, 1990)
Tmin, Tmax0.820, 0.924
No. of measured, independent and
observed [I > 2σ(I)] reflections		23973, 4527, 2150
Rint0.089
(sin θ/λ)max (Å−1)0.609
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.169, 0.99
No. of reflections4527
No. of parameters381
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.40, −0.57

Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2000), SHELXTL (Bruker, 1999).

Selected geometric parameters (Å, º) top
Cu1—N301.996 (5)C1—N11.088 (7)
Cu1—N102.001 (5)C1—N31.282 (8)
Cu1—N12.033 (6)C2—N21.130 (8)
Cu1—N402.086 (4)C2—N31.290 (9)
Cu1—N202.087 (5)
N30—Cu1—N10179.14 (19)N10—Cu1—N2080.74 (18)
N30—Cu1—N190.4 (2)N1—Cu1—N20115.19 (19)
N10—Cu1—N190.4 (2)N40—Cu1—N20126.40 (17)
N30—Cu1—N4080.82 (18)N1—C1—N3172.7 (7)
N10—Cu1—N4098.64 (18)C1—N1—Cu1173.1 (6)
N1—Cu1—N40118.41 (19)N2—C2—N3172.2 (8)
N30—Cu1—N2099.04 (18)C1—N3—C2123.6 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C43—H43···O4i0.932.533.17 (2)126
C26—H26···O1ii0.932.583.498 (8)171
C12—H12···N3iii0.932.443.289 (9)153
C13—H13···O2iv0.932.453.35 (2)165
C13—H13···O7iv0.932.473.37 (3)164
C14—H14···O4v0.932.513.32 (2)146
Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) x+1/2, y, −z+1/2; (iii) −x, −y, −z+1; (iv) −x, y−1/2, −z+1/2; (v) −x+1/2, y−1/2, z.
 

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