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The title compound, [Cu(C2N3)(C12H8N2)2](CF3SO3), is formed by discrete [Cu(phen)2{N(CN)2)}]+ complex cations (phen is 1,10-phenanthroline) and uncoordinated CF3SO3- anions. The Cu centre is five-coordinated in the form of a distorted trigonal bipyramid to two phen mol­ecules and one dicyan­amide ligand, which is coordinated through one nitrile N atom in the equatorial plane at a distance of 1.990 (2) Å. The two axial Cu-N distances are similar (mean 1.993 Å) and are substantially shorter than the two equatorial Cu-N bonds (mean 2.125 Å).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103010187/tr1060sup1.cif
Contains datablocks V, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103010187/tr1060Vsup2.hkl
Contains datablock V

CCDC reference: 214384

Comment top

The dicyanamide anion, [N(CN)2]- (dca), can be coordinated to a central atom in a monodentate fashion, through a nitrile or amide N atom, or as a bidentate, tridentate or even tetradentate bridging ligand with the participation of two or three donor N atoms. Nevertheless, monodentate coordination of dca through an amide N atom is unlikely (Kohout et al., 2000), and up to now only one compound with such a dca coordination has been reported (Marshall et al., 2002). 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-coordinated central atoms and have the general formula [ML4(dca)2], for example, [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, for example, [Cu(bpy)2(dca)]BF4 (I) (bpy is 2,2'-bipyridine; Potočňák et al., 2001a), [Cu(bpy)2(dca)]ClO4 (II) (Potočňák et al., 2002), [Cu(bpy)2(dca)]C(CN)3 (III) (Potočňák et al., 2001b) and [Cu(phen)2(dca)]C(CN)3 (IV) (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 finding possible reasons for different SCPs in related compounds, we have previously studied the structures of five- coordinated copper(II) complexes of the general formula [Cu(L—L)2X]Y, where L—L is 1,10-phenanthroline or 2,2'-bipyridine, X is an N-donor pseudohalide anion and Y is the tricyanomethanide anion, [C(CN)3]- (Potočňák et al., 2001b). The SCP in those compounds with the same counter-anion is a more or less distorted trigonal bipyramidal. In more recent work, we have changed our focus from compounds with the same counter-anion to compounds with the same coordinated ligands, having a general formula [Cu(L—L)2(dca)]X, where X is a monoanion (I–IV). Here, we present the structure of the title compound, [Cu(phen)2(dca)]CF3SO3 (V).

Fig. 1 shows the labelling scheme of one formula unit of (V). The Cu atom is fivefold coordinated by two phen molecules and one [N(CN)2]- ligand (in the equatorial plane). The coordination polyhedron is a distorted trigonal bipyramid, and the [CF3SO3]- anion, which is in a staggered conformation, does not enter the inner coordination sphere. In the trigonal bipyramid, the two out-of-plane distances (Cu—N1 and Cu—N3) have nearly the same values and are almost collinear (Table 1). The two in-plane distances (Cu—N2 and Cu—N4) are, on average, 0.132 Å longer than the out-of-plane Cu—N distances, which is a feature generally observed for compounds containing the [Cu(L—L)2X] cation, where L—L is bpy and X is Cl-, Br- or I- (O'Sullivan et al., 1999); L—L is phen and X is Cl- (Murphy et al., 1998), Br- (Murphy et al., 1997a) or H2O (Murphy et al., 1997b); and L—L is phen or bpy and X is a pseudohalide(-1) anion (Potočňák et al., 2001b). The third in-plane distance (Cu—N5; atom N5 is from dca) is shorter than the other two in-plane distances and is comparable with the out-of-plane distances. The same trends in bond distances are observed in [Cu(bpy)2(dca)]X, where X is [BF4]-, (I) (Potočňák et al., 2001a), or [ClO4]-, (II) (Potočňák et al., 2002), and in the related compound [Cu(phen)2(dca)]C(CN)3, (IV) (Potočňák, et al., 1996). However, for [Cu(bpy)2(dca)]X where the non-coordinating out-of-sphere X anion is [C(CN)3]-, (III) (Potočňák et al., 2001b), the Cu—N5 bond is the shortest Cu—N bond. Table 2 gives details of these comparisons.

The out-of-plane angles in (V) lie in the range 80.40 (9)–97.22 (8)°, which is similar to the values observed in (I)–(IV). The bond angles in the equatorial plane of (V) differ considerably from the ideal trigonal angle of 120°, with one wide angle of 135.28 (9)° (α1 = N5—Cu—N4), one normal angle of 121.20 (10)° (α2 = N5—Cu—N2) and one narrow angle of 103.51 (8)° (α3 = N4—Cu—N2). Corresponding values for (I)–(IV) are given in Table 2. Thus, the angle α3, which is opposite the Cu—N5 bond, is 16.49° narrower than the ideal angle of 120°, and there is a difference of 14.08° between α1 and α2.

According to the criteria of Harrison & Hathaway (1980), based on the values of the three equatorial angles and their differences, the coordination polyhedron around the Cu atom can be best described as trigonal-bipyramidal with approximate C2v symmetry, which is similar to conformation of (IV). On the other hand, according to the values of theα1, α2 and α3 angles, the coordination polyhedra of (I)—(III) can be best described as distorted trigonal-bipyramidal, with a distortion toward square-pyramidal. The differences in the SCPs are in accordance with the values of the τ parameter [Table 2; the τ parameter is 100 for an ideal trigonal bipyramid and 0 for an ideal square pyramid (Addison et al., 1984)]. This difference in the SCP of (IV) and (V) on the one hand and (I)—(III) on the other can be explained by the lower rigidity of the bpy ligand compared with the rigidity of the phen ligand. While the two outer pyridine rings in a phen molecule are connected by a phenyl ring, making the whole molecule planar, the two pyridine rings in a bpy molecule can rotate around their common C—C single bond.

Both phenanthroline molecules in (V) are almost planar [the largest deviation from the mean plane is 0.073 (3) Å for atom C24] and the bond distances and angles in these molecules are as expected. The dihedral angle between the two phenanthroline ligands is 83.59 (3)°.

There are three canonical formulae describing the mode of bonding in a dicyanamido ligand, including single and double Namide—C bonds, and double and triple Ncyano—C bonds (Golub et al., 1986). Inspection of the bond lengths (Table 1) shows that no canonical formula properly describes the bonding mode in this particular dicyanamide. The NcyanoC and NamideC distances are typical of NC triple (1.15 Å) and NC double bonds (1.27 Å), respectively. The N6—C1—N5 and N6—C2—N7 angles are almost linear, while the value of the C1—N6—C2 angle is close to 120°. The dicyanamido ligand is nearly planar, the largest deviation of atoms from the mean plane being 0.011 (3) Å. The coordination of the dicyanamide through the Ncyano atom results in an angular arrangement [C1—N5—-Cu = 151.6 (2)°].

Experimental top

Crystals of (V) were prepared by mixing an aqueous solution of Cu(CF3SO3)2 (0.1 M, 5 ml) with an ethanolic solution of phen (0.1 M, 10 ml). To the resulting green solution, an aqueous solution of NaN(CN)2 (0.1 M, 5 ml) was added (all solutions were warmed before mixing). Green crystals of the title complex appeared the next day, and these crystals were filtered off and dried in air.

Refinement top

Anisotropic displacement parameters were refined for all non-H atoms. All H-atom positions were calculated using the appropriate riding model, with Uiso values of 1.2Ueq of the parent C atom. Geometric analysis was performed using PARST (Nardelli, 1983) and SHELXL97 (Sheldrick, 1997).

Structure description top

The dicyanamide anion, [N(CN)2]- (dca), can be coordinated to a central atom in a monodentate fashion, through a nitrile or amide N atom, or as a bidentate, tridentate or even tetradentate bridging ligand with the participation of two or three donor N atoms. Nevertheless, monodentate coordination of dca through an amide N atom is unlikely (Kohout et al., 2000), and up to now only one compound with such a dca coordination has been reported (Marshall et al., 2002). 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-coordinated central atoms and have the general formula [ML4(dca)2], for example, [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, for example, [Cu(bpy)2(dca)]BF4 (I) (bpy is 2,2'-bipyridine; Potočňák et al., 2001a), [Cu(bpy)2(dca)]ClO4 (II) (Potočňák et al., 2002), [Cu(bpy)2(dca)]C(CN)3 (III) (Potočňák et al., 2001b) and [Cu(phen)2(dca)]C(CN)3 (IV) (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 finding possible reasons for different SCPs in related compounds, we have previously studied the structures of five- coordinated copper(II) complexes of the general formula [Cu(L—L)2X]Y, where L—L is 1,10-phenanthroline or 2,2'-bipyridine, X is an N-donor pseudohalide anion and Y is the tricyanomethanide anion, [C(CN)3]- (Potočňák et al., 2001b). The SCP in those compounds with the same counter-anion is a more or less distorted trigonal bipyramidal. In more recent work, we have changed our focus from compounds with the same counter-anion to compounds with the same coordinated ligands, having a general formula [Cu(L—L)2(dca)]X, where X is a monoanion (I–IV). Here, we present the structure of the title compound, [Cu(phen)2(dca)]CF3SO3 (V).

Fig. 1 shows the labelling scheme of one formula unit of (V). The Cu atom is fivefold coordinated by two phen molecules and one [N(CN)2]- ligand (in the equatorial plane). The coordination polyhedron is a distorted trigonal bipyramid, and the [CF3SO3]- anion, which is in a staggered conformation, does not enter the inner coordination sphere. In the trigonal bipyramid, the two out-of-plane distances (Cu—N1 and Cu—N3) have nearly the same values and are almost collinear (Table 1). The two in-plane distances (Cu—N2 and Cu—N4) are, on average, 0.132 Å longer than the out-of-plane Cu—N distances, which is a feature generally observed for compounds containing the [Cu(L—L)2X] cation, where L—L is bpy and X is Cl-, Br- or I- (O'Sullivan et al., 1999); L—L is phen and X is Cl- (Murphy et al., 1998), Br- (Murphy et al., 1997a) or H2O (Murphy et al., 1997b); and L—L is phen or bpy and X is a pseudohalide(-1) anion (Potočňák et al., 2001b). The third in-plane distance (Cu—N5; atom N5 is from dca) is shorter than the other two in-plane distances and is comparable with the out-of-plane distances. The same trends in bond distances are observed in [Cu(bpy)2(dca)]X, where X is [BF4]-, (I) (Potočňák et al., 2001a), or [ClO4]-, (II) (Potočňák et al., 2002), and in the related compound [Cu(phen)2(dca)]C(CN)3, (IV) (Potočňák, et al., 1996). However, for [Cu(bpy)2(dca)]X where the non-coordinating out-of-sphere X anion is [C(CN)3]-, (III) (Potočňák et al., 2001b), the Cu—N5 bond is the shortest Cu—N bond. Table 2 gives details of these comparisons.

The out-of-plane angles in (V) lie in the range 80.40 (9)–97.22 (8)°, which is similar to the values observed in (I)–(IV). The bond angles in the equatorial plane of (V) differ considerably from the ideal trigonal angle of 120°, with one wide angle of 135.28 (9)° (α1 = N5—Cu—N4), one normal angle of 121.20 (10)° (α2 = N5—Cu—N2) and one narrow angle of 103.51 (8)° (α3 = N4—Cu—N2). Corresponding values for (I)–(IV) are given in Table 2. Thus, the angle α3, which is opposite the Cu—N5 bond, is 16.49° narrower than the ideal angle of 120°, and there is a difference of 14.08° between α1 and α2.

According to the criteria of Harrison & Hathaway (1980), based on the values of the three equatorial angles and their differences, the coordination polyhedron around the Cu atom can be best described as trigonal-bipyramidal with approximate C2v symmetry, which is similar to conformation of (IV). On the other hand, according to the values of theα1, α2 and α3 angles, the coordination polyhedra of (I)—(III) can be best described as distorted trigonal-bipyramidal, with a distortion toward square-pyramidal. The differences in the SCPs are in accordance with the values of the τ parameter [Table 2; the τ parameter is 100 for an ideal trigonal bipyramid and 0 for an ideal square pyramid (Addison et al., 1984)]. This difference in the SCP of (IV) and (V) on the one hand and (I)—(III) on the other can be explained by the lower rigidity of the bpy ligand compared with the rigidity of the phen ligand. While the two outer pyridine rings in a phen molecule are connected by a phenyl ring, making the whole molecule planar, the two pyridine rings in a bpy molecule can rotate around their common C—C single bond.

Both phenanthroline molecules in (V) are almost planar [the largest deviation from the mean plane is 0.073 (3) Å for atom C24] and the bond distances and angles in these molecules are as expected. The dihedral angle between the two phenanthroline ligands is 83.59 (3)°.

There are three canonical formulae describing the mode of bonding in a dicyanamido ligand, including single and double Namide—C bonds, and double and triple Ncyano—C bonds (Golub et al., 1986). Inspection of the bond lengths (Table 1) shows that no canonical formula properly describes the bonding mode in this particular dicyanamide. The NcyanoC and NamideC distances are typical of NC triple (1.15 Å) and NC double bonds (1.27 Å), respectively. The N6—C1—N5 and N6—C2—N7 angles are almost linear, while the value of the C1—N6—C2 angle is close to 120°. The dicyanamido ligand is nearly planar, the largest deviation of atoms from the mean plane being 0.011 (3) Å. The coordination of the dicyanamide through the Ncyano atom results in an angular arrangement [C1—N5—-Cu = 151.6 (2)°].

Computing details top

Data collection: IPDS EXPOSE (Stoe & Cie, 1999); cell refinement: IPDS CELL (Stoe & Cie, 1999); data reduction: IPDS INTEGRATE (Stoe & Cie, 1999); program(s) used to solve structure: SIR97 (Altomare et al., 1998); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the structure of (V), showing the atom-labelling scheme. Displacement ellipsoids have been drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
Bis(1,10-phenanthroline)(dicyanamido)copper(II) trifluoromethanesulfonate top
Crystal data top
[Cu(C2N3)(C12H8N2)2](CF3SO3)Z = 2
Mr = 639.07F(000) = 646
Triclinic, P1Dx = 1.638 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71069 Å
a = 8.6026 (19) ÅCell parameters from 8000 reflections
b = 9.957 (2) Åθ = 1.7–26.1°
c = 15.664 (4) ŵ = 0.99 mm1
α = 79.05 (3)°T = 220 K
β = 87.01 (3)°Prism, green
γ = 79.64 (3)°0.33 × 0.12 × 0.11 mm
V = 1295.6 (5) Å3
Data collection top
IPDS Stoe
diffractometer
4678 independent reflections
Radiation source: fine-focus sealed tube3840 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
φ scanθmax = 26.0°, θmin = 2.3°
Absorption correction: numerical
IPDS FACE (Stoe & Cie, 1999)
h = 1010
Tmin = 0.793, Tmax = 0.913k = 1212
10138 measured reflectionsl = 1919
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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0547P)2 + 0.6424P]
where P = (Fo2 + 2Fc2)/3
4678 reflections(Δ/σ)max = 0.001
379 parametersΔρmax = 0.45 e Å3
0 restraintsΔρmin = 0.40 e Å3
Crystal data top
[Cu(C2N3)(C12H8N2)2](CF3SO3)γ = 79.64 (3)°
Mr = 639.07V = 1295.6 (5) Å3
Triclinic, P1Z = 2
a = 8.6026 (19) ÅMo Kα radiation
b = 9.957 (2) ŵ = 0.99 mm1
c = 15.664 (4) ÅT = 220 K
α = 79.05 (3)°0.33 × 0.12 × 0.11 mm
β = 87.01 (3)°
Data collection top
IPDS Stoe
diffractometer
4678 independent reflections
Absorption correction: numerical
IPDS FACE (Stoe & Cie, 1999)
3840 reflections with I > 2σ(I)
Tmin = 0.793, Tmax = 0.913Rint = 0.037
10138 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.100H-atom parameters constrained
S = 1.06Δρmax = 0.45 e Å3
4678 reflectionsΔρmin = 0.40 e Å3
379 parameters
Special details top

Experimental. _diffrn_measurement_method D=70 mm, Φ 0–199.5°, ΔΦ 1.5°, 6 min/rec

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu0.05086 (4)0.05276 (3)0.73277 (2)0.02581 (11)
S0.34251 (9)0.47479 (7)0.79106 (5)0.03632 (18)
N20.0737 (2)0.1642 (2)0.80255 (15)0.0276 (5)
O10.3730 (4)0.6085 (2)0.82816 (19)0.0684 (8)
N40.1229 (2)0.0287 (2)0.64756 (15)0.0271 (5)
C310.0053 (3)0.1835 (2)0.55914 (17)0.0256 (5)
N30.0964 (2)0.2007 (2)0.62756 (14)0.0264 (5)
N60.5571 (3)0.0981 (3)0.7160 (2)0.0529 (8)
N10.0146 (2)0.0950 (2)0.83531 (15)0.0272 (5)
C210.1412 (3)0.0793 (3)0.87425 (17)0.0271 (5)
O30.4004 (4)0.4223 (3)0.70628 (18)0.0917 (12)
C110.1053 (3)0.0587 (3)0.89376 (17)0.0253 (5)
O20.1845 (3)0.4572 (3)0.8036 (3)0.0854 (10)
C350.0020 (3)0.2804 (3)0.48113 (18)0.0306 (6)
F30.6134 (3)0.3651 (3)0.8529 (2)0.0927 (9)
C450.2328 (3)0.0355 (3)0.50211 (19)0.0328 (6)
C10.4092 (3)0.0771 (3)0.73515 (18)0.0303 (6)
F20.4493 (4)0.2300 (2)0.8298 (3)0.1111 (11)
C410.1237 (3)0.0592 (3)0.56975 (17)0.0261 (5)
N70.6747 (3)0.2967 (3)0.6066 (2)0.0534 (7)
C320.2099 (3)0.3141 (3)0.61998 (19)0.0320 (6)
H320.27980.32570.66640.038*
C330.2255 (4)0.4149 (3)0.5442 (2)0.0375 (7)
H330.30500.49260.54040.045*
C340.1232 (4)0.3989 (3)0.4755 (2)0.0377 (7)
H340.13310.46580.42500.045*
N50.2797 (3)0.0477 (2)0.75549 (17)0.0381 (6)
C140.1177 (3)0.2822 (3)0.9860 (2)0.0375 (7)
H140.15060.34561.03600.045*
C260.2956 (3)0.0255 (3)1.0076 (2)0.0415 (7)
H260.35910.05281.04500.050*
C150.1619 (3)0.1499 (3)0.96976 (18)0.0305 (6)
C250.2394 (3)0.1209 (3)0.9301 (2)0.0354 (6)
C30.4613 (4)0.3609 (4)0.8569 (3)0.0531 (9)
C130.0256 (4)0.3163 (3)0.9272 (2)0.0382 (7)
H130.00360.40350.93730.046*
C220.1049 (3)0.2923 (3)0.7833 (2)0.0353 (6)
H220.05780.35230.73510.042*
C230.2069 (4)0.3404 (3)0.8333 (2)0.0446 (8)
H230.22810.43020.81720.054*
C440.3459 (3)0.0886 (3)0.5172 (2)0.0392 (7)
H440.41990.10950.47410.047*
C460.2259 (4)0.1379 (3)0.4233 (2)0.0392 (7)
H460.29920.12440.37860.047*
C240.2746 (4)0.2558 (3)0.9054 (2)0.0447 (8)
H240.34350.28680.93800.054*
C360.1128 (4)0.2547 (3)0.4137 (2)0.0393 (7)
H360.11000.31920.36220.047*
C430.3461 (3)0.1766 (3)0.5947 (2)0.0415 (7)
H430.41990.25820.60520.050*
C20.6145 (3)0.2071 (3)0.6577 (2)0.0371 (7)
C120.0246 (3)0.2205 (3)0.85234 (19)0.0329 (6)
H120.08720.24540.81330.039*
C160.2580 (3)0.1027 (3)1.0270 (2)0.0412 (7)
H160.29450.16171.07810.049*
C420.2336 (3)0.1432 (3)0.6588 (2)0.0339 (6)
H420.23610.20390.71200.041*
F10.4189 (5)0.3915 (4)0.93808 (19)0.1249 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.02389 (17)0.02479 (17)0.0271 (2)0.00222 (11)0.00330 (13)0.00163 (12)
S0.0406 (4)0.0285 (3)0.0378 (4)0.0019 (3)0.0002 (3)0.0050 (3)
N20.0242 (10)0.0279 (11)0.0310 (13)0.0033 (8)0.0004 (10)0.0079 (9)
O10.095 (2)0.0323 (12)0.0772 (19)0.0179 (12)0.0029 (17)0.0017 (12)
N40.0220 (10)0.0276 (10)0.0322 (13)0.0030 (8)0.0011 (10)0.0082 (9)
C310.0245 (12)0.0278 (12)0.0270 (14)0.0080 (10)0.0023 (11)0.0073 (10)
N30.0256 (10)0.0251 (10)0.0280 (12)0.0025 (8)0.0020 (10)0.0055 (8)
N60.0281 (13)0.0477 (15)0.075 (2)0.0071 (11)0.0087 (14)0.0122 (14)
N10.0227 (10)0.0280 (10)0.0298 (13)0.0026 (8)0.0003 (10)0.0042 (9)
C210.0196 (11)0.0353 (13)0.0274 (15)0.0030 (10)0.0031 (11)0.0108 (11)
O30.128 (3)0.084 (2)0.0402 (16)0.0396 (19)0.0115 (18)0.0055 (14)
C110.0177 (11)0.0324 (13)0.0239 (14)0.0005 (9)0.0021 (11)0.0055 (10)
O20.0394 (14)0.0704 (18)0.154 (3)0.0079 (12)0.0079 (17)0.0439 (19)
C350.0338 (14)0.0308 (13)0.0299 (15)0.0113 (11)0.0022 (12)0.0065 (11)
F30.0486 (13)0.117 (2)0.122 (2)0.0151 (13)0.0322 (14)0.0537 (19)
C450.0244 (13)0.0408 (15)0.0388 (17)0.0086 (11)0.0008 (12)0.0184 (12)
C10.0304 (14)0.0308 (13)0.0278 (15)0.0059 (11)0.0035 (12)0.0011 (10)
F20.111 (2)0.0406 (13)0.187 (3)0.0083 (13)0.029 (2)0.0478 (17)
C410.0225 (12)0.0285 (12)0.0303 (15)0.0079 (10)0.0022 (11)0.0095 (10)
N70.0461 (16)0.0554 (17)0.0527 (19)0.0006 (13)0.0124 (15)0.0008 (14)
C320.0338 (14)0.0250 (12)0.0361 (16)0.0003 (10)0.0015 (13)0.0072 (11)
C330.0404 (16)0.0252 (13)0.0438 (18)0.0024 (11)0.0089 (15)0.0038 (11)
C340.0499 (18)0.0268 (13)0.0349 (17)0.0085 (12)0.0115 (15)0.0029 (11)
N50.0280 (13)0.0435 (13)0.0378 (15)0.0042 (10)0.0042 (11)0.0045 (10)
C140.0346 (15)0.0386 (15)0.0296 (16)0.0051 (12)0.0033 (13)0.0061 (12)
C260.0299 (14)0.066 (2)0.0315 (17)0.0060 (14)0.0047 (13)0.0163 (14)
C150.0223 (12)0.0417 (15)0.0222 (14)0.0034 (11)0.0055 (11)0.0027 (11)
C250.0251 (13)0.0493 (16)0.0352 (17)0.0055 (11)0.0015 (13)0.0179 (13)
C30.0485 (19)0.058 (2)0.059 (2)0.0100 (16)0.0025 (18)0.0263 (17)
C130.0389 (15)0.0298 (14)0.0408 (18)0.0032 (11)0.0057 (14)0.0019 (12)
C220.0372 (15)0.0297 (13)0.0399 (17)0.0057 (11)0.0008 (13)0.0095 (12)
C230.0469 (17)0.0386 (16)0.055 (2)0.0187 (13)0.0051 (16)0.0177 (14)
C440.0249 (13)0.0485 (17)0.050 (2)0.0044 (12)0.0042 (14)0.0260 (15)
C460.0347 (15)0.0563 (18)0.0320 (17)0.0156 (13)0.0072 (13)0.0165 (13)
C240.0419 (17)0.0544 (18)0.047 (2)0.0176 (14)0.0004 (15)0.0245 (15)
C360.0426 (16)0.0487 (17)0.0299 (16)0.0189 (13)0.0007 (14)0.0051 (12)
C430.0273 (14)0.0386 (15)0.059 (2)0.0046 (12)0.0062 (15)0.0191 (14)
C20.0252 (13)0.0417 (16)0.0450 (18)0.0030 (12)0.0034 (14)0.0117 (13)
C120.0310 (14)0.0300 (13)0.0365 (17)0.0066 (11)0.0000 (13)0.0021 (11)
C160.0288 (14)0.063 (2)0.0273 (16)0.0032 (13)0.0029 (13)0.0064 (13)
C420.0276 (13)0.0309 (13)0.0412 (17)0.0020 (11)0.0056 (13)0.0066 (12)
F10.170 (3)0.151 (3)0.0596 (18)0.007 (2)0.016 (2)0.0620 (19)
Geometric parameters (Å, º) top
Cu—N11.990 (2)N7—C21.145 (4)
Cu—N51.990 (2)C32—C331.397 (4)
Cu—N31.995 (2)C32—H320.9300
Cu—N42.108 (2)C33—C341.369 (5)
Cu—N22.141 (2)C33—H330.9300
S—O11.412 (2)C34—H340.9300
S—O31.413 (3)C14—C131.372 (4)
S—O21.430 (3)C14—C151.409 (4)
S—C31.819 (4)C14—H140.9300
N2—C221.326 (3)C26—C161.348 (5)
N2—C211.358 (3)C26—C251.437 (4)
N4—C421.337 (3)C26—H260.9300
N4—C411.359 (3)C15—C161.444 (4)
C31—N31.365 (4)C25—C241.408 (4)
C31—C351.402 (4)C3—F11.306 (5)
C31—C411.444 (3)C13—C121.397 (4)
N3—C321.344 (3)C13—H130.9300
N6—C11.294 (4)C22—C231.408 (4)
N6—C21.316 (4)C22—H220.9300
N1—C121.328 (3)C23—C241.361 (5)
N1—C111.370 (3)C23—H230.9300
C21—C251.411 (4)C44—C431.356 (5)
C21—C111.436 (4)C44—H440.9300
C11—C151.404 (4)C46—C361.365 (4)
C35—C341.419 (4)C46—H460.9300
C35—C361.434 (4)C24—H240.9300
F3—C31.322 (4)C36—H360.9300
C45—C411.404 (4)C43—C421.402 (4)
C45—C441.418 (4)C43—H430.9300
C45—C461.441 (4)C12—H120.9300
C1—N51.145 (3)C16—H160.9300
F2—C31.313 (4)C42—H420.9300
N1—Cu—N593.14 (10)C33—C34—H34119.9
N1—Cu—N3174.98 (9)C35—C34—H34119.9
N5—Cu—N391.87 (10)C1—N5—Cu151.6 (2)
N1—Cu—N495.12 (9)C13—C14—C15119.3 (3)
N5—Cu—N4135.28 (9)C13—C14—H14120.3
N3—Cu—N481.09 (9)C15—C14—H14120.3
N1—Cu—N280.40 (9)C16—C26—C25121.4 (3)
N5—Cu—N2121.20 (10)C16—C26—H26119.3
N3—Cu—N297.22 (8)C25—C26—H26119.3
N4—Cu—N2103.51 (8)C11—C15—C14117.1 (2)
O1—S—O3115.1 (2)C11—C15—C16118.8 (3)
O1—S—O2113.39 (19)C14—C15—C16124.1 (3)
O3—S—O2115.1 (3)C24—C25—C21116.5 (3)
O1—S—C3104.22 (19)C24—C25—C26124.5 (3)
O3—S—C3103.61 (18)C21—C25—C26119.0 (3)
O2—S—C3103.45 (17)F1—C3—F2106.3 (3)
C22—N2—C21117.9 (2)F1—C3—F3109.3 (4)
C22—N2—Cu131.23 (19)F2—C3—F3105.1 (3)
C21—N2—Cu110.59 (16)F1—C3—S112.0 (3)
C42—N4—C41117.0 (2)F2—C3—S112.4 (3)
C42—N4—Cu131.7 (2)F3—C3—S111.4 (2)
C41—N4—Cu111.10 (16)C14—C13—C12120.3 (3)
N3—C31—C35122.7 (2)C14—C13—H13119.9
N3—C31—C41117.1 (2)C12—C13—H13119.9
C35—C31—C41120.2 (2)N2—C22—C23122.2 (3)
C32—N3—C31119.0 (2)N2—C22—H22118.9
C32—N3—Cu126.7 (2)C23—C22—H22118.9
C31—N3—Cu114.19 (16)C24—C23—C22120.2 (3)
C1—N6—C2119.2 (3)C24—C23—H23119.9
C12—N1—C11118.6 (2)C22—C23—H23119.9
C12—N1—Cu126.29 (18)C43—C44—C45119.8 (3)
C11—N1—Cu115.08 (17)C43—C44—H44120.1
N2—C21—C25123.7 (2)C45—C44—H44120.1
N2—C21—C11116.8 (2)C36—C46—C45120.6 (3)
C25—C21—C11119.5 (2)C36—C46—H46119.7
N1—C11—C15122.8 (2)C45—C46—H46119.7
N1—C11—C21116.9 (2)C23—C24—C25119.5 (3)
C15—C11—C21120.3 (2)C23—C24—H24120.3
C31—C35—C34116.7 (3)C25—C24—H24120.3
C31—C35—C36118.6 (2)C46—C36—C35121.7 (3)
C34—C35—C36124.8 (3)C46—C36—H36119.2
C41—C45—C44116.9 (3)C35—C36—H36119.2
C41—C45—C46119.0 (2)C44—C43—C42119.2 (3)
C44—C45—C46124.1 (3)C44—C43—H43120.4
N5—C1—N6174.3 (3)C42—C43—H43120.4
N4—C41—C45123.6 (2)N7—C2—N6174.4 (3)
N4—C41—C31116.4 (2)N1—C12—C13121.9 (3)
C45—C41—C31120.0 (2)N1—C12—H12119.1
N3—C32—C33121.7 (3)C13—C12—H12119.1
N3—C32—H32119.1C26—C16—C15121.0 (3)
C33—C32—H32119.1C26—C16—H16119.5
C34—C33—C32119.6 (3)C15—C16—H16119.5
C34—C33—H33120.2N4—C42—C43123.4 (3)
C32—C33—H33120.2N4—C42—H42118.3
C33—C34—C35120.3 (3)C43—C42—H42118.3
N1—Cu—N2—C22177.8 (3)N3—C31—C41—C45179.6 (2)
N5—Cu—N2—C2294.3 (3)C35—C31—C41—C450.5 (3)
N3—Cu—N2—C222.3 (3)C31—N3—C32—C330.5 (4)
N4—Cu—N2—C2284.8 (3)Cu—N3—C32—C33176.52 (19)
N1—Cu—N2—C214.46 (17)N3—C32—C33—C340.0 (4)
N5—Cu—N2—C2192.31 (19)C32—C33—C34—C350.1 (4)
N3—Cu—N2—C21171.07 (18)C31—C35—C34—C330.3 (4)
N4—Cu—N2—C2188.54 (18)C36—C35—C34—C33178.9 (3)
N1—Cu—N4—C422.4 (2)N1—Cu—N5—C1168.7 (5)
N5—Cu—N4—C4297.4 (2)N3—Cu—N5—C111.1 (5)
N3—Cu—N4—C42179.0 (2)N4—Cu—N5—C168.2 (5)
N2—Cu—N4—C4283.7 (2)N2—Cu—N5—C1110.7 (5)
N1—Cu—N4—C41173.12 (16)N1—C11—C15—C141.9 (4)
N5—Cu—N4—C4187.17 (19)C21—C11—C15—C14178.0 (2)
N3—Cu—N4—C413.56 (15)N1—C11—C15—C16179.4 (2)
N2—Cu—N4—C4191.79 (16)C21—C11—C15—C160.7 (4)
C35—C31—N3—C320.9 (3)C13—C14—C15—C111.2 (4)
C41—C31—N3—C32179.1 (2)C13—C14—C15—C16179.8 (3)
C35—C31—N3—Cu176.47 (18)N2—C21—C25—C243.9 (4)
C41—C31—N3—Cu3.6 (3)C11—C21—C25—C24177.7 (3)
N5—Cu—N3—C3243.4 (2)N2—C21—C25—C26175.6 (3)
N4—Cu—N3—C32179.0 (2)C11—C21—C25—C262.8 (4)
N2—Cu—N3—C3278.3 (2)C16—C26—C25—C24179.6 (3)
N5—Cu—N3—C31139.46 (17)C16—C26—C25—C210.9 (4)
N4—Cu—N3—C313.85 (16)O1—S—C3—F161.8 (3)
N2—Cu—N3—C3198.77 (17)O3—S—C3—F1177.5 (3)
N5—Cu—N1—C1254.6 (2)O2—S—C3—F157.0 (4)
N4—Cu—N1—C1281.4 (2)O1—S—C3—F2178.7 (3)
N2—Cu—N1—C12175.7 (2)O3—S—C3—F257.9 (3)
N5—Cu—N1—C11123.56 (19)O2—S—C3—F262.5 (3)
N4—Cu—N1—C11100.44 (18)O1—S—C3—F361.0 (3)
N2—Cu—N1—C112.43 (17)O3—S—C3—F359.8 (4)
C22—N2—C21—C251.4 (4)O2—S—C3—F3179.8 (3)
Cu—N2—C21—C25175.8 (2)C15—C14—C13—C120.4 (4)
C22—N2—C21—C11179.9 (2)C21—N2—C22—C231.3 (4)
Cu—N2—C21—C115.8 (3)Cu—N2—C22—C23171.6 (2)
C12—N1—C11—C151.7 (4)N2—C22—C23—C241.5 (5)
Cu—N1—C11—C15179.99 (19)C41—C45—C44—C430.8 (4)
C12—N1—C11—C21178.2 (2)C46—C45—C44—C43177.8 (3)
Cu—N1—C11—C210.1 (3)C41—C45—C46—C361.5 (4)
N2—C21—C11—N14.1 (3)C44—C45—C46—C36179.8 (3)
C25—C21—C11—N1177.4 (2)C22—C23—C24—C251.1 (5)
N2—C21—C11—C15175.8 (2)C21—C25—C24—C233.6 (5)
C25—C21—C11—C152.7 (4)C26—C25—C24—C23175.9 (3)
N3—C31—C35—C340.8 (4)C45—C46—C36—C350.4 (4)
C41—C31—C35—C34179.1 (2)C31—C35—C36—C461.1 (4)
N3—C31—C35—C36178.5 (2)C34—C35—C36—C46179.7 (3)
C41—C31—C35—C361.6 (3)C45—C44—C43—C420.0 (4)
C42—N4—C41—C450.2 (3)C11—N1—C12—C130.8 (4)
Cu—N4—C41—C45176.37 (18)Cu—N1—C12—C13178.9 (2)
C42—N4—C41—C31178.9 (2)C14—C13—C12—N10.2 (5)
Cu—N4—C41—C312.7 (2)C25—C26—C16—C151.1 (5)
C44—C45—C41—N40.7 (4)C11—C15—C16—C261.2 (4)
C46—C45—C41—N4178.0 (2)C14—C15—C16—C26179.8 (3)
C44—C45—C41—C31179.8 (2)C41—N4—C42—C431.0 (4)
C46—C45—C41—C311.1 (3)Cu—N4—C42—C43176.30 (19)
N3—C31—C41—N40.4 (3)C44—C43—C42—N41.0 (4)
C35—C31—C41—N4179.6 (2)

Experimental details

Crystal data
Chemical formula[Cu(C2N3)(C12H8N2)2](CF3SO3)
Mr639.07
Crystal system, space groupTriclinic, P1
Temperature (K)220
a, b, c (Å)8.6026 (19), 9.957 (2), 15.664 (4)
α, β, γ (°)79.05 (3), 87.01 (3), 79.64 (3)
V3)1295.6 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.99
Crystal size (mm)0.33 × 0.12 × 0.11
Data collection
DiffractometerIPDS Stoe
Absorption correctionNumerical
IPDS FACE (Stoe & Cie, 1999)
Tmin, Tmax0.793, 0.913
No. of measured, independent and
observed [I > 2σ(I)] reflections
10138, 4678, 3840
Rint0.037
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.100, 1.06
No. of reflections4678
No. of parameters379
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.45, 0.40

Computer programs: IPDS EXPOSE (Stoe & Cie, 1999), IPDS CELL (Stoe & Cie, 1999), IPDS INTEGRATE (Stoe & Cie, 1999), SIR97 (Altomare et al., 1998), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2000), SHELXL97.

Selected geometric parameters (Å, º) top
Cu—N11.990 (2)N6—C11.294 (4)
Cu—N51.990 (2)N6—C21.316 (4)
Cu—N31.995 (2)C1—N51.145 (3)
Cu—N42.108 (2)N7—C21.145 (4)
Cu—N22.141 (2)
N1—Cu—N593.14 (10)N5—Cu—N2121.20 (10)
N1—Cu—N3174.98 (9)N3—Cu—N297.22 (8)
N5—Cu—N391.87 (10)N4—Cu—N2103.51 (8)
N1—Cu—N495.12 (9)C1—N6—C2119.2 (3)
N5—Cu—N4135.28 (9)N5—C1—N6174.3 (3)
N3—Cu—N481.09 (9)C1—N5—Cu151.6 (2)
N1—Cu—N280.40 (9)N7—C2—N6174.4 (3)
A comparison of molecular geometry parameters (Å, °) for some [CuL4(dca)]+ species. top
Parametera(I)(II)(III)(IV)(V)
Cu-N12.006 (3)2.0024 (17)1.998 (4)1.981 (3)1.990 (2)
Cu-N31.998 (3)1.9916 (17)1.975 (4)1.977 (4)1.995 (2)
Cu-N22.142 (3)2.1456 (19)2.116 (4)2.112 (4)2.141 (2)
Cu-N42.043 (3)2.0395 (19)2.027 (4)2.064 (3)2.108 (2)
Cu-N52.015 (3)1.995 (2)1.973 (5)1.982 (4)1.990 (2)
N1-Cu-N3177.52 (12)177.16 (9)175.3 (2)175.12 (14)174.98 (9)
α1145.00 (13)146.66 (8)140.0 (2)133.6 (2)135.28 (9)
α2108.54 (12)108.46 (8)112.4 (2)115.7 (2)121.20 (10)
α3106.45 (11)104.87 (8)107.6 (2)110.70 (13)103.51 (8)
τ54.250.858.869.266.2
(I) [Cu(bpy)2(dca)]BF4 (Potočňák et al., 2001a); (II) [Cu(bpy)2(dca)]ClO4 (Potočňák et al., 2002); (III) [Cu(bpy)2(dca)]C(CN)3 (Potočňák et al., 2001b); (IV) [Cu(phen)2(dca)]C(CN)3 (Potočňák et al., 1996); (V) [Cu(phen)2(dca)]CF3SO3 (this work)

a Numbering schemes have been standardised as for (V)
 

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