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The title compound, [Cu(C2N3)(C3H10N2)2]ClO4, is made up of [Cu(tn)2{N(CN)2}]+ complex cations (tn is 1,3-diamino­propane) and ClO4- anions. The CuII atom is coordinated by four N atoms of two equatorial tn ligands, with an average distance of 2.041 (7) Å, and one nitrile N atom of the dicyanamide anion in an axial position, at a distance of 2.236 (3) Å, in a manner approaching square-planar coordination geometry. The complex has Cs symmetry, with the mirror plane lying through the central C atoms of both tn ligands and the dca ligand. The ClO4- anion might be considered as very weakly coordinated in the opposite axial position [Cu-O = 2.705 (3) Å], thus completing the CuII coordination to asymmetric elongated octa­hedral (4+1+1*). The Cu atom and the perchlorate anion both lie on mirror planes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105016768/sk1838sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105016768/sk1838Isup2.hkl
Contains datablock I

CCDC reference: 278546

Comment top

Understanding the shape of coordination polyhedra (SCP) in the case of five-coordination is a current problem in coordination chemistry. A number of different structural approaches have been used in the past to describe the geometries of five-coordinated compounds (Potočňák et al., 2001). With the aim of finding out possible reasons for different SCP in related compounds, we have previously studied the structures of five-coordinate CuII coordination compounds of the general formula [Cu(L)2X]Y, where L is a bidentate chelate ligand, such as 1,10-phenanthroline (phen) or 2,2'-bipyridine (bpy), X is an N-donor pseudohalide anion and Y is the tricyanomethanide anion, [C(CN)3]- (Potočňák et al., 2001). In more recent work, we have changed our focus from compounds with the same counter-anion to compounds with the same coordinated anionic ligand, having the general formula [Cu(L)2(dca)]Y, where dca is the dicyanamide anion [N(CN)2]- and Y is an anion of charge 1-. The SCP in these compounds, as well as that in compounds with the [C(CN)3]- counter-anion, is more or less distorted trigonal–bipyramidal, but we have observed that the SCP in compounds with bpy molecules is more distorted than in compounds with phen molecules. We suppose that the reason could be a different rigidity between the highly rigid phen and the less rigid bpy 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. To verify this idea, we have decided to use even more flexible ligands L than bpy, namely aliphatic diamines, such as ethylenediamine, 1,2-diaminepropane or 1,3-diaminepropane (tn), in the desired [Cu(L)2(dca)]Y compounds. To avoid the possible effect of anion Y on the SCP, we have used the same anion in our study, in this case a perchlorate anion. To date, we have succeeded in the preparation of the title compound with tn, [Cu(tn)2(dca)]ClO4, (I), the structure of which is presented here and compared with the previously prepared [Cu(L)2(dca)]ClO4 compounds containing bpy [(II)] or phen ligands [(III)].

Fig. 1 shows the structure and labelling scheme of one formula unit of (I). The Cu atom is mainly coordinated by two chelate-like bound tn molecules and by one terminal N atom of the dca ligand. The complex has Cs symmetry, with the mirror plane lying through the central C atoms of both tn ligands and the dca ligand. The four N atoms of the tn ligands are thus coplanar by symmetry and form the base of a distorted square pyramid [average Cu—N 2.041 (7) Å]. Owing to the Jahn–Teller effect, the axial bond to the dca ligand is elongated [2.236 (3) Å].

Using the criteria of Harrison & Hathaway (1980), the angles N1—Cu—N20, N1—Cu—N10 and N20—Cu—N10i [symmetry code: (i) x, 1/2 - y, z] can be labelled α1, α2 and α3, respectively (Table 2). The large angle α3, which is opposite to the Cu—N1 bond (N1 from the dca), and the small difference of 0.35° between α1 and α2, clearly classify the coordination polyhedron around the CuII atom as square pyramidal. The same result is obtained, of course, when using the τ parameter of Addison et al. (1984) as a criterion, which is zero by symmetry in (I) (the τ parameter is 100 for an ideal trigonal bipyramid and 0 for an ideal tetragonal pyramid). Table 2 also lists the values of selected bond distances and angles and the τ parameters for compounds (II) and (III). One can see from this table that the SCP gradually changes from distorted square pyramid in (I) through intermediate in (II) to a distorted trigonal bipyramid in (III). This may be seen as a confirmation of our hypothesis on the dependence of the SCP on the different rigidity of the chelate L ligands used.

The very weakly coordinated ClO4- anion [Cu—O 2.705 (3) Å] supplements the coordination sphere of the CuII atom to an asymmetrically elongated octahedron (4 + 1+1*). Atoms Cl, O2 and O3 lie on the same mirror plane as the CuII atom and the dca anion. Although the displacement ellipsoids of the O atoms are larger than the ellipsoids for other atoms, they are not disordered. The CuII atom is displaced 0.2556 (2) Å from the equatorial plane towards atom N1. To the best of our knowledge, only eight structures of copper(II) compounds with a comparable CuN5O chromophore containing coordinated perchlorate anions are known to date (Cambridge Structural Database, Version?; Allen, 2002). The Cu—Oaxial and Cu—Naxial bond distances in these compounds are in the ranges 2.383 (3)–2.732 (3) Å [mean 2.59 (11) Å] and 2.323 (3)–2.842 (61) Å [mean 2.51 (18) Å], respectively, which are close to the corresponding bond distances in (I). In contrast with (I), the maximum deviation of the Cu atoms from the equatorial plane in these compounds is only 0.088 (2) Å (Lee et al., 1997) and, moreover, the Cu—N and Cu—O bond distances are much more symmetric than in (I). In the title compound (I), the perchlorate anion is thus the weakest coordinated moiety and the coordination mode of the CuII atom is much closer to a deformed square pyramid than a distorted octahedron.

According to the definition of Zelewsky (1995), both tn molecules in (I) are in chair forms, as also observed in other copper compounds with two tn molecules [e.g. Wang et al. (2002) and Thetiot et al. (2003)]. The bond distances in both molecules are normal for single C—C and C—N bonds, while the C—C—C and C—C—N angles adopt slightly higher values than tetrahedral.

There are three canonical formulae describing the bonding mode in the dicyanamide ligand (Golub et al., 1986). Inspection of the bond lengths in (I) (Table 1) shows that the third canonical formula, with single and triple C—N bonds only, can be used for proper description of the bonding mode in this particular case. Both NcyanoC bonds (C1N1 and C2 N2) are normal for a NC triple bond and both Namide—C distances (N3—C1 and N3—C2) are only slightly shorter than a single bond between an N atom and an sp-hybridized C atom (Reference for standard values?). The N1—C1—N3 and N3—C2—N2 angles are slightly bent from linearity, while the value of the C1—N3—C2 angle is close to the expected 120°. Nevertheless, the reliability of the geometric parameters involving atoms N3, C1 and C2 may be reduced by the observed disorder over two positions related by the mirror plane [the distances from this plane are 0.43 (1), 0.20 (1) and 0.21 (1) Å, respectively]. In accordance with Golub et al. (1986), the bonding mode of dicyanamide to the CuII atom can be considered as almost linear [C1—N1—Cu 169.9 (4)°].

Besides ionic forces, the crystal structure of (I) is stabilized by weak N—H···X hydrogen bonds (X is O or N); those with an N—H···X angle greater than 120° and an H···X distance less than 2.6 Å are given in Table 3. Two of them, N10—H10A···O1 and another bond?, are `intramolecular' in the sense that the hydrogen bonds connect cation and anion within the asymmetric part of the structure. The others are intermolecular. The non-coordinated atom N2 of the dicyanamide ligand acts as fourfold acceptor for N—H···N hydrogen bonds. Through these intermolecular bonds, cations and anions are interconnected to form sheets along the (101) plane, as shown in Fig. 2.

Experimental top

Crystals of (I) were prepared by mixing a 0.1 M aqueous solution of Cu(ClO4)2 (5 ml) with a 0.1 M aqueous solution of NaN(CN)2 (10 ml). To the resulting solution, a 1 M aqueous solution of tn (1 ml) was added (all solutions were warmed before mixing). Blue crystals of the title complex appeared in two weeks. The crystals were filtered off and dried in air.

Refinement top

All H atom positions were calculated using the appropriate riding model, with C—H distances of 0.99 Å and N—H distances of 0.92 Å [Please check added text] and with Uiso(H) = 1.2Ueq(C,N). Geometric analysis was performed using PARST (Nardelli, 1983) and SHELXL97 (Sheldrick, 1997a).

Structure description top

Understanding the shape of coordination polyhedra (SCP) in the case of five-coordination is a current problem in coordination chemistry. A number of different structural approaches have been used in the past to describe the geometries of five-coordinated compounds (Potočňák et al., 2001). With the aim of finding out possible reasons for different SCP in related compounds, we have previously studied the structures of five-coordinate CuII coordination compounds of the general formula [Cu(L)2X]Y, where L is a bidentate chelate ligand, such as 1,10-phenanthroline (phen) or 2,2'-bipyridine (bpy), X is an N-donor pseudohalide anion and Y is the tricyanomethanide anion, [C(CN)3]- (Potočňák et al., 2001). In more recent work, we have changed our focus from compounds with the same counter-anion to compounds with the same coordinated anionic ligand, having the general formula [Cu(L)2(dca)]Y, where dca is the dicyanamide anion [N(CN)2]- and Y is an anion of charge 1-. The SCP in these compounds, as well as that in compounds with the [C(CN)3]- counter-anion, is more or less distorted trigonal–bipyramidal, but we have observed that the SCP in compounds with bpy molecules is more distorted than in compounds with phen molecules. We suppose that the reason could be a different rigidity between the highly rigid phen and the less rigid bpy 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. To verify this idea, we have decided to use even more flexible ligands L than bpy, namely aliphatic diamines, such as ethylenediamine, 1,2-diaminepropane or 1,3-diaminepropane (tn), in the desired [Cu(L)2(dca)]Y compounds. To avoid the possible effect of anion Y on the SCP, we have used the same anion in our study, in this case a perchlorate anion. To date, we have succeeded in the preparation of the title compound with tn, [Cu(tn)2(dca)]ClO4, (I), the structure of which is presented here and compared with the previously prepared [Cu(L)2(dca)]ClO4 compounds containing bpy [(II)] or phen ligands [(III)].

Fig. 1 shows the structure and labelling scheme of one formula unit of (I). The Cu atom is mainly coordinated by two chelate-like bound tn molecules and by one terminal N atom of the dca ligand. The complex has Cs symmetry, with the mirror plane lying through the central C atoms of both tn ligands and the dca ligand. The four N atoms of the tn ligands are thus coplanar by symmetry and form the base of a distorted square pyramid [average Cu—N 2.041 (7) Å]. Owing to the Jahn–Teller effect, the axial bond to the dca ligand is elongated [2.236 (3) Å].

Using the criteria of Harrison & Hathaway (1980), the angles N1—Cu—N20, N1—Cu—N10 and N20—Cu—N10i [symmetry code: (i) x, 1/2 - y, z] can be labelled α1, α2 and α3, respectively (Table 2). The large angle α3, which is opposite to the Cu—N1 bond (N1 from the dca), and the small difference of 0.35° between α1 and α2, clearly classify the coordination polyhedron around the CuII atom as square pyramidal. The same result is obtained, of course, when using the τ parameter of Addison et al. (1984) as a criterion, which is zero by symmetry in (I) (the τ parameter is 100 for an ideal trigonal bipyramid and 0 for an ideal tetragonal pyramid). Table 2 also lists the values of selected bond distances and angles and the τ parameters for compounds (II) and (III). One can see from this table that the SCP gradually changes from distorted square pyramid in (I) through intermediate in (II) to a distorted trigonal bipyramid in (III). This may be seen as a confirmation of our hypothesis on the dependence of the SCP on the different rigidity of the chelate L ligands used.

The very weakly coordinated ClO4- anion [Cu—O 2.705 (3) Å] supplements the coordination sphere of the CuII atom to an asymmetrically elongated octahedron (4 + 1+1*). Atoms Cl, O2 and O3 lie on the same mirror plane as the CuII atom and the dca anion. Although the displacement ellipsoids of the O atoms are larger than the ellipsoids for other atoms, they are not disordered. The CuII atom is displaced 0.2556 (2) Å from the equatorial plane towards atom N1. To the best of our knowledge, only eight structures of copper(II) compounds with a comparable CuN5O chromophore containing coordinated perchlorate anions are known to date (Cambridge Structural Database, Version?; Allen, 2002). The Cu—Oaxial and Cu—Naxial bond distances in these compounds are in the ranges 2.383 (3)–2.732 (3) Å [mean 2.59 (11) Å] and 2.323 (3)–2.842 (61) Å [mean 2.51 (18) Å], respectively, which are close to the corresponding bond distances in (I). In contrast with (I), the maximum deviation of the Cu atoms from the equatorial plane in these compounds is only 0.088 (2) Å (Lee et al., 1997) and, moreover, the Cu—N and Cu—O bond distances are much more symmetric than in (I). In the title compound (I), the perchlorate anion is thus the weakest coordinated moiety and the coordination mode of the CuII atom is much closer to a deformed square pyramid than a distorted octahedron.

According to the definition of Zelewsky (1995), both tn molecules in (I) are in chair forms, as also observed in other copper compounds with two tn molecules [e.g. Wang et al. (2002) and Thetiot et al. (2003)]. The bond distances in both molecules are normal for single C—C and C—N bonds, while the C—C—C and C—C—N angles adopt slightly higher values than tetrahedral.

There are three canonical formulae describing the bonding mode in the dicyanamide ligand (Golub et al., 1986). Inspection of the bond lengths in (I) (Table 1) shows that the third canonical formula, with single and triple C—N bonds only, can be used for proper description of the bonding mode in this particular case. Both NcyanoC bonds (C1N1 and C2 N2) are normal for a NC triple bond and both Namide—C distances (N3—C1 and N3—C2) are only slightly shorter than a single bond between an N atom and an sp-hybridized C atom (Reference for standard values?). The N1—C1—N3 and N3—C2—N2 angles are slightly bent from linearity, while the value of the C1—N3—C2 angle is close to the expected 120°. Nevertheless, the reliability of the geometric parameters involving atoms N3, C1 and C2 may be reduced by the observed disorder over two positions related by the mirror plane [the distances from this plane are 0.43 (1), 0.20 (1) and 0.21 (1) Å, respectively]. In accordance with Golub et al. (1986), the bonding mode of dicyanamide to the CuII atom can be considered as almost linear [C1—N1—Cu 169.9 (4)°].

Besides ionic forces, the crystal structure of (I) is stabilized by weak N—H···X hydrogen bonds (X is O or N); those with an N—H···X angle greater than 120° and an H···X distance less than 2.6 Å are given in Table 3. Two of them, N10—H10A···O1 and another bond?, are `intramolecular' in the sense that the hydrogen bonds connect cation and anion within the asymmetric part of the structure. The others are intermolecular. The non-coordinated atom N2 of the dicyanamide ligand acts as fourfold acceptor for N—H···N hydrogen bonds. Through these intermolecular bonds, cations and anions are interconnected to form sheets along the (101) plane, as shown in Fig. 2.

Computing details top

Data collection: WinXPOSE in X-AREA (Stoe & Cie, 2002); cell refinement: RECIPE in X-AREA; data reduction: INTEGRATE in X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97.

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. [Symmetry code: (i) x, 1/2 - y, z.]
[Figure 2] Fig. 2. Hydrogen bonds (dashed lines) connecting the cations and anions of (I) to form layers parallel to (101). [Symmetry codes: (i) -x, -y, 2 - z; (ii) -x, y - 1/2, 2 - z; (iii) 1 - x, y - 1/2, 1 - z.]
Bis(1,3-diaminopropane-κ2N,N')(dicyanamido-κN')copper(II) perchlorate top
Crystal data top
[Cu(C3H10N2)2N(CN)2]ClO4F(000) = 390
Mr = 377.30Dx = 1.637 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 9435 reflections
a = 8.4715 (17) Åθ = 1.7–29.4°
b = 7.5679 (15) ŵ = 1.63 mm1
c = 11.953 (2) ÅT = 193 K
β = 92.56 (3)°Platelet, blue
V = 765.5 (3) Å30.24 × 0.22 × 0.06 mm
Z = 2
Data collection top
Stoe IPDS-II
diffractometer
2268 independent reflections
Radiation source: fine-focus sealed tube2018 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.048
Detector resolution: 150 pixels mm-1θmax = 29.5°, θmin = 1.7°
ω scansh = 1111
Absorption correction: numerical
(XPREP in SHELXTL; Sheldrick, 1997b)
k = 1010
Tmin = 0.722, Tmax = 0.900l = 1616
9279 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)] = 0.039H-atom parameters constrained
wR(F2) = 0.109 w = 1/[σ2(Fo2) + (0.067P)2 + 0.3495P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
2268 reflectionsΔρmax = 0.51 e Å3
122 parametersΔρmin = 0.54 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.030 (6)
Crystal data top
[Cu(C3H10N2)2N(CN)2]ClO4V = 765.5 (3) Å3
Mr = 377.30Z = 2
Monoclinic, P21/mMo Kα radiation
a = 8.4715 (17) ŵ = 1.63 mm1
b = 7.5679 (15) ÅT = 193 K
c = 11.953 (2) Å0.24 × 0.22 × 0.06 mm
β = 92.56 (3)°
Data collection top
Stoe IPDS-II
diffractometer
2268 independent reflections
Absorption correction: numerical
(XPREP in SHELXTL; Sheldrick, 1997b)
2018 reflections with I > 2σ(I)
Tmin = 0.722, Tmax = 0.900Rint = 0.048
9279 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.109H-atom parameters constrained
S = 1.03Δρmax = 0.51 e Å3
2268 reflectionsΔρmin = 0.54 e Å3
122 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)
Cu0.18744 (4)0.25000.74822 (3)0.03173 (14)
N100.3178 (2)0.0581 (3)0.83008 (15)0.0377 (4)
H10A0.28080.04700.90090.045*
H10B0.29820.04720.79360.045*
N200.0325 (2)0.0535 (3)0.70494 (17)0.0430 (4)
H20A0.09010.03510.67340.052*
H20B0.00400.00890.77060.052*
C110.4914 (2)0.0819 (3)0.84124 (19)0.0419 (5)
H11B0.53480.08550.76570.050*
H11A0.53890.02050.88170.050*
C120.5365 (4)0.25000.9035 (3)0.0454 (7)
H12B0.65220.25000.91940.055*
H12A0.48510.25000.97630.055*
C210.1080 (3)0.0842 (5)0.6288 (3)0.0606 (7)
H21A0.18060.01790.63310.073*
H21B0.07410.09280.55080.073*
C220.1944 (4)0.25000.6580 (3)0.0467 (8)
H22A0.29930.25000.61800.056*
H22B0.21190.25000.73940.056*
Cl0.07245 (9)0.25001.05703 (7)0.0430 (2)
O10.1624 (2)0.0945 (3)1.0821 (2)0.0687 (6)
O20.0286 (4)0.25000.9396 (2)0.0690 (9)
O30.0692 (3)0.25001.1195 (2)0.0484 (6)
C10.3869 (4)0.2764 (11)0.5118 (3)0.036 (2)0.50
N10.3200 (3)0.25000.5906 (2)0.0469 (6)
N30.4479 (6)0.3065 (13)0.4176 (4)0.107 (5)0.50
C20.5885 (5)0.2771 (11)0.3895 (3)0.040 (2)0.50
N20.7103 (4)0.25000.3529 (3)0.0480 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.02362 (19)0.0403 (2)0.03119 (19)0.0000.00082 (12)0.000
N100.0292 (8)0.0445 (9)0.0394 (8)0.0017 (7)0.0021 (6)0.0052 (7)
N200.0334 (9)0.0476 (10)0.0476 (10)0.0038 (8)0.0046 (7)0.0039 (8)
C110.0286 (9)0.0539 (12)0.0433 (10)0.0057 (9)0.0007 (8)0.0036 (9)
C120.0299 (13)0.066 (2)0.0403 (14)0.0000.0049 (11)0.000
C210.0449 (13)0.0721 (18)0.0630 (15)0.0038 (12)0.0176 (11)0.0204 (14)
C220.0263 (13)0.072 (2)0.0411 (15)0.0000.0010 (11)0.000
Cl0.0331 (3)0.0518 (4)0.0447 (4)0.0000.0107 (3)0.000
O10.0527 (11)0.0682 (13)0.0858 (15)0.0205 (10)0.0117 (10)0.0115 (11)
O20.0627 (18)0.103 (3)0.0427 (13)0.0000.0147 (12)0.000
O30.0401 (12)0.0600 (15)0.0464 (12)0.0000.0173 (10)0.000
C10.0327 (15)0.037 (6)0.0396 (16)0.0027 (16)0.0046 (12)0.0067 (18)
N10.0400 (14)0.0616 (18)0.0397 (13)0.0000.0093 (11)0.000
N30.053 (2)0.216 (14)0.053 (2)0.052 (5)0.0227 (19)0.066 (5)
C20.0446 (18)0.040 (6)0.0362 (15)0.0022 (18)0.0088 (13)0.009 (2)
N20.0462 (15)0.0510 (16)0.0480 (15)0.0000.0165 (12)0.000
Geometric parameters (Å, º) top
Cu—N202.0349 (19)C12—H12B0.9900
Cu—N20i2.0349 (19)C12—H12A0.9900
Cu—N10i2.0468 (18)C21—C221.502 (4)
Cu—N102.0468 (18)C21—H21A0.9900
Cu—N12.236 (3)C21—H21B0.9900
Cu—O22.705 (3)C22—C21i1.502 (4)
N10—C111.481 (3)C22—H22A0.9900
N10—H10A0.9200C22—H22B0.9900
N10—H10B0.9200Cl—O1i1.427 (2)
N20—C211.484 (3)Cl—O11.427 (2)
N20—H20A0.9200Cl—O21.436 (3)
N20—H20B0.9200Cl—O31.441 (2)
C11—C121.514 (3)C1—N11.139 (5)
C11—H11B0.9900C1—N31.280 (6)
C11—H11A0.9900N3—C21.272 (6)
C12—C11i1.514 (3)C2—N21.157 (5)
N20—Cu—N20i93.91 (12)C12—C11—H11A109.2
N20—Cu—N10i165.49 (8)H11B—C11—H11A107.9
N20i—Cu—N10i86.06 (8)C11—C12—C11i114.3 (3)
N20—Cu—N1086.06 (8)C11—C12—H12B108.7
N20i—Cu—N10165.49 (8)C11i—C12—H12B108.7
N10i—Cu—N1090.37 (11)C11—C12—H12A108.7
N20—Cu—N197.37 (8)C11i—C12—H12A108.7
N20i—Cu—N197.37 (8)H12B—C12—H12A107.6
N10i—Cu—N197.02 (8)N20—C21—C22112.0 (2)
N10—Cu—N197.02 (8)N20—C21—H21A109.2
N20—Cu—O282.84 (8)C22—C21—H21A109.2
N20i—Cu—O282.84 (8)N20—C21—H21B109.2
N10i—Cu—O282.76 (7)C22—C21—H21B109.2
N10—Cu—O282.76 (7)H21A—C21—H21B107.9
N1—Cu—O2179.70 (10)C21i—C22—C21113.3 (3)
C11—N10—Cu117.97 (14)C21i—C22—H22A108.9
C11—N10—H10A107.8C21—C22—H22A108.9
Cu—N10—H10A107.8C21i—C22—H22B108.9
C11—N10—H10B107.8C21—C22—H22B108.9
Cu—N10—H10B107.8H22A—C22—H22B107.7
H10A—N10—H10B107.2O1i—Cl—O1111.2 (2)
C21—N20—Cu122.15 (19)O1i—Cl—O2108.52 (13)
C21—N20—H20A106.8O1—Cl—O2108.52 (13)
Cu—N20—H20A106.8O1i—Cl—O3109.92 (11)
C21—N20—H20B106.8O1—Cl—O3109.92 (11)
Cu—N20—H20B106.8O2—Cl—O3108.72 (18)
H20A—N20—H20B106.6Cl—O2—Cu135.20 (19)
N10—C11—C12112.0 (2)N1—C1—N3173.9 (5)
N10—C11—H11B109.2C1—N1—Cu169.9 (4)
C12—C11—H11B109.2C2—N3—C1128.3 (5)
N10—C11—H11A109.2N2—C2—N3173.0 (5)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N10—H10A···O10.922.453.352 (3)166
N20—H20B···O1ii0.922.393.292 (3)166
N20—H20B···O3iii0.922.423.117 (3)132
N20—H20A···N2iv0.922.383.261 (3)161
N10—H10B···N2iv0.922.333.198 (3)158
Symmetry codes: (ii) x, y, z+2; (iii) x, y1/2, z+2; (iv) x+1, y1/2, z+1.

Experimental details

Crystal data
Chemical formula[Cu(C3H10N2)2N(CN)2]ClO4
Mr377.30
Crystal system, space groupMonoclinic, P21/m
Temperature (K)193
a, b, c (Å)8.4715 (17), 7.5679 (15), 11.953 (2)
β (°) 92.56 (3)
V3)765.5 (3)
Z2
Radiation typeMo Kα
µ (mm1)1.63
Crystal size (mm)0.24 × 0.22 × 0.06
Data collection
DiffractometerStoe IPDS-II
Absorption correctionNumerical
(XPREP in SHELXTL; Sheldrick, 1997b)
Tmin, Tmax0.722, 0.900
No. of measured, independent and
observed [I > 2σ(I)] reflections
9279, 2268, 2018
Rint0.048
(sin θ/λ)max1)0.692
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.109, 1.03
No. of reflections2268
No. of parameters122
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.51, 0.54

Computer programs: WinXPOSE in X-AREA (Stoe & Cie, 2002), RECIPE in X-AREA, INTEGRATE in X-AREA, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), DIAMOND (Brandenburg, 2000), SHELXL97.

Selected geometric parameters (Å, º) top
Cu—N202.0349 (19)C1—N11.139 (5)
Cu—N102.0468 (18)C1—N31.280 (6)
Cu—N12.236 (3)N3—C21.272 (6)
Cu—O22.705 (3)C2—N21.157 (5)
N20—Cu—N20i93.91 (12)N10—Cu—O282.76 (7)
N20—Cu—N10i165.49 (8)N1—Cu—O2179.70 (10)
N20—Cu—N1086.06 (8)N1—C1—N3173.9 (5)
N10i—Cu—N1090.37 (11)C1—N1—Cu169.9 (4)
N20—Cu—N197.37 (8)C2—N3—C1128.3 (5)
N10—Cu—N197.02 (8)N2—C2—N3173.0 (5)
N20—Cu—O282.84 (8)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N10—H10A···O10.922.453.352 (3)166
N20—H20B···O1ii0.922.393.292 (3)166
N20—H20B···O3iii0.922.423.117 (3)132
N20—H20A···N2iv0.922.383.261 (3)161
N10—H10B···N2iv0.922.333.198 (3)158
Symmetry codes: (ii) x, y, z+2; (iii) x, y1/2, z+2; (iv) x+1, y1/2, z+1.
A comparison of molecular geometry parameters (Å, °) for some [CuL4(dca)]+ species. top
Parametera(I)(II)(III)
Cu-N102.0468 (18)2.0024 (17)2.001 (5)
Cu-N302.0468 (18)1.9916 (17)1.996 (5)
Cu-N202.0349 (19)2.1456 (19)2.087 (5)
Cu-N402.0349 (19)2.0395 (19)2.086 (4)
Cu-N12.236 (3)1.995 (2)2.033 (6)
N10-Cu-N30165.5 (8)177.16 (9)179.14 (19)
α197.37 (8)146.66 (8)118.41 (19)
α297.02 (8)108.46 (8)115.19 (1)
α3165.49 (8)104.87 (8)126.40 (1)
τ0.050.887.9
(I) [Cu(tn)2(dca)]ClO4 (this work); (II) [Cu(bpy)2(dca)]ClO4 (Potočňák et al., 2002); (III) [Cu(phen)2(dca)]ClO4 (Burčák et al., 2004).

a Numbering schemes have been standardized as for (II)
 

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