Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102015731/bm1508sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102015731/bm1508Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102015731/bm1508IIsup3.hkl |
CCDC references: 197326; 197327
Crystals of (I) were prepared by mixing a 0.1 M aqueous solution of Cu(ClO4)2 (5 ml) with a 0.1 M ethanol solution of bpy (10 ml). To the resulting blue solution, a 0.1 M aqueous ethanol solution of KN(CN)2 (6 ml) was added (all solutions were warmed before mixing). Blue sheet-like crystals appeared within 1 h. The crystals were filtered off and dissolved in a mixture of ethanol and water (1:1). After two weeks, blue hexagonal plate-like crystals of (I) were filtered off and dried in air. Crystals of (II) were prepared by mixing a 0.1 M aqueous solution of Cu(ClO4)2 (5 ml) with a 0.1 M ethanol solution of bpy (10 ml). To the resulting blue solution, a 0.1 M aqueous ethanol solution of KN(CN)2 (5 ml) was added (all solutions were warmed before mixing). Blue crystals of (II) appeared within one week. The crystals were filtered off and dried in air.
The aromatic H-atoms in (I) were placed in calculated positions and refined riding on their parent C atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). In (II), these H atoms were placed geometrically and refined as riding, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C), while the solvent H atoms were found in difference Fourier syntheses and refined as part of rigid rotating groups, with O—H = 0.84, methylene C—H = 0.99 and methyl C—H = 0.98 Å, and with Uiso(H) = 1.2Ueq(C, O). Please check these changes. Was the hydroxyl H atom in the ethanol located unambiguously?
The dicyanamide (dca) anion, [N(CN)2]-, exhibits a rich variety of bonding modes. It can coordinate either in a monodentate manner or, more typically, in a bidentate, tridentate or even tetradentate manner, with participation of two or three N donor atoms. Nevertheless, monodentate coordination of dca through the amide N atom is rather improbable and, to date, no crystal structure of such a compound is known (Kohout et al., 2000). 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 contain either 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), [Ni(4-Meim)4(dca)2] (4-Meim is 4-methylimidazole; Kožíšek et al., 1996), [Cu(phen)2(dca)2] (phen is 1,10-phenanthroline; Potočňák et al., 1995) and [Cu(NITpPy)2(H2O)2(dca)2] (NITpPy is the nitronyl nitroxide radical; Dasna et al., 2001), or exhibit five-coordination and have the general formula [ML4(dca)]X, e.g. [Cu(phen)2(dca)]C(CN)3 (Potočňák et al., 1996), [Cu(bpy)2(dca)]C(CN)3 (bpy is 2,2'-bipyridine; Potočňák, Dunaj-Jurčo, Mikloš & Jäger, 2001) and [Cu(bpy)2(dca)]BF4 (Potočňák, Dunaj-Jurčo, Mikloš, Massa & Jäger, 2001), in which L4 may be one tetradentate, two bidentate or four monodentate ligands, and X is a monoanion.
As a consequence of the possible bridging function of dca, there has been an unusual interest in this ligand during recent years, especially in connection with the preparation of magnetic materials. Among them, weak ferromagnets of the general formula α-[M(dca)2], with a three-dimensional rutile-type structure, have attracted much attention because of the ability of dca to act as a molecular-based magnet precursor, with several transition metal ions octahedrally coordinated by tridentate dca ligands (Batten et al., 1998; Jensen et al., 1999; Kurmoo & Kepert, 1998; Manson et al., 1998). If the two dca ligands are tetrahedrally coordinated only through the nitrile N atoms, β-isomers of these compounds occur in the form of sheet-like structures (Jensen et al., 1999). When two coordination sites of hexacoordinated metallic centres are occupied by additional blocking ligands, the dca acts as a bidentate bridging ligand coordinated through the nitrile N atoms and the resulting compounds contain [ML2(dca)2] units (L2 is one bidentate or two monodentate ligands; Manson et al., 1999; Escuer et al., 2000; van Albada et al., 2000; Jäger et al., 2001; Dasna et al., 2001; Sun et al., 2001). All these compounds are one-dimensional and contain chains in which two metallic centres are connected by a pair of dca ligands, forming double bridges. Moreover, if the ligands L can serve as additional bridges between central atoms, the above chains are connected by these ligands, giving two-dimensional sheets (Jensen et al., 1999, 2001).
The [ML2(dca)2] units are also present in another type of structure, which was previously observed in [M(bpym)(dca)2]·H2O (M is Mn, Fe or Co, and bpym is 2,2'-bipyrimidine; Marshall et al., 2000) and consists of chains in which two hexacoordinate metallic centres are connected by only one bridging dca ligand, while the second remains monodentate. The same type of one-dimensional structure, but with five-coordinate metal atoms, has been observed in the very recently published structures of [Cu(dmpbpy)(dca)2] (dmbpy is 5,5'-dimethyl-2,2'-bipyridine; Kooijman et al., 2002), [Cu(phen)(dca)2] (Luo et al., 2002) and [Cu(bpy)(dca)2] (Potočňák et al., 2002; Vangdal et al., 2002).
As part of our study on low dimensional magnetic materials (Černák et al., 2002), and with the aim of finding possible reasons for the different shapes of the coordination polyhedra in related five-coordinate compounds, we present here the structures of two new complexes containing dca which were prepared from reaction mixtures containing the same reagents. The [Cu(bpy)2(dca)]ClO4 complex, (I), belongs to the class of compounds with dca coordinated in a relatively unusual monodentate manner. On the other hand, the [Cu(bpy)2(dca)(bpy)2Cu](ClO4)3·0.5EtOH complex, (II), contains dca coordinated in a bidentate manner, which is the most common coordination mode of dca. However, the propagation of the polymeric structure is broken at the two neighbouring central atoms and, instead of a chain structure, only binuclear units arise. As far as we are aware, complex (II) represents the first example of this type of structure containing bridging dca. Structures (I) and (II) are both ionic. \sch
The structure of (I) (Fig. 1) consists of the [Cu(bpy)2N(CN)2]+ complex cation and a ClO4- anion which does not enter the inner coordination sphere. The copper centre is five-coordinate within a distorted trigonal bipyramid, by two bpy molecules and one dca ligand coordinated through one nitrile N atom in the equatorial plane. In the trigonal bipyramid, the two out-of-plane Cu1—N10 and Cu1—N30 bonds have nearly the same values and are almost collinear (Table 1). The two in-plane distances (Cu1—N20 and Cu1—N40) are, on average, longer by 0.096 Å than the out-of-plane Cu—N distances; this is a common feature for this kind of compound. The third in-plane Cu1—N2 [N from the N(CN)2 ligand] distance is shorter than the other two but is comparable with the out-of-plane distances. This is different from the compound where the non-coordinating out-of-sphere anion X is [C(CN)3]-, (III) (Potočňák, Dunaj-Jurčo, Mikloš & Jäger, 2001), where this is the shortest Cu—N bond, but the same trends in bond distances were observed in the compound where X is [BF4]-, (IV) (Potočňák, Dunaj-Jurčo, Mikloš, Massa & Jäger, 2001), and in the related compound [Cu(phen)2N(CN)2]C(CN)3, (V), where this bond has the same length (within 1σ) as the two out-of-plane bonds (Potočňák et al., 1996) (Table 2).
The out-of-plane angles in (I) lie within the range 78.78 (7)–96.84 (7)°, similar to the values observed in (III)-(V). The bond angles in the equatorial plane of (I) differ considerably from the ideal trigonal angle of 120°, with one wide angle of 146.66 (8)° (α1 = N2—Cu1—N40) and two narrow angles of 108.46 (8)° (α2 = N2—Cu1—N20) and 104.87 (8)° (α3 = N20—Cu1—N40). Corresponding values for (III)-(V) are given in Table 2. Thus the angle α3, which is opposite the Cu1—N2 bond, is narrower than the ideal angle of 120° by 15.13°, and there is a difference of 38.20° between α1 and α2.
According to the criteria of Harrison & Hathaway (1980), the coordination polyhedron around the Cu can be best described as distorted trigonal-bipyramidal with a distortion toward square-pyramidal, similar to (III) and (IV). On the other hand, according to the values of the angles α1, α2 and α3, the coordination polyhedron of (V) can be best described as trigonal-bipyramidal with near C2v symmetry. The difference in the shape of the coordination polyhedra is 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 tetragonal pyramid (Addison et al., 1984)]. This difference in the shape of the coordination polyhedron of (I), (III) and (IV) on one hand and of (V) on the other can be explained by the lower rigidity of the bpy ligand compared with the phen ligand. While the two pyridine rings in a phen molecule are connected by a phenyl ring and thus the molecule as a whole is planar, the two pyridine rings in a bpy molecule can rotate around their common C—C single bond.
The angles between the two pyridine rings are 2.54 (7) and 8.35 (7)° for the first (N10—N20) and the second (N30—N40) bpy molecule in (I), respectively. Consequently, the first bpy molecule is almost planar [the largest deviation of atoms from the mean plane is 0.036 (3) Å for atom C24], while the planarity of the second one is less [the largest deviation from the mean plane is 0.112 (3) Å for C43]. The sum of the bond angles in the equatorial plane of (I) (359.99°) indicates coplanarity of atom Cu1 with the three equatorial atoms [it is displaced from the N2/N20/N40 plane by 0.0092 (3) Å towards N10].
The dca anion in (I) is ligated in an unusual monodentate manner. Inspection of the bond lengths (Table 1) shows that none of the three possible canonical formulae (Golub et al., 1986) adequately describes the bonding mode of the dicyanamide. Both the nitrile N≡C and amide N═C distances have values close to those of N≡C (1.15 Å) and N═C bonds (1.27 Å), respectively. The N(amide)-C≡N(nitrile) angles are almost linear, while the C2—N1—C3 angle adopts a value of 119.4 (2)°, close to the ideal value of 120°. The dca ligand is planar, the largest deviation from the mean plane being 0.003 (2) Å for atom C2, and its bonding mode to atom Cu1 (C2≡N2—Cu1) can be considered as angular.
The asymmetric unit of (II) (Fig. 2) contains one binuclear [Cu(bpy)2N(CN)2(bpy)2Cu]3+ complex cation, the charge of which is balanced by three uncoordinated perchlorate anions, and half a molecule of ethanol. Formally, we can consider the cation as two [Cu(bpy)2N(CN)2]+ complex cations, in which both Cu centres are five-coordinate within a slightly distorted trigonal bipyramid by two bpy molecules and one bridging dca ligand, which is coordinated equatorially to the two Cu centres via different nitrile N atoms. Inspection of Tables 2 and 3 indicates that, from this point of view, there is no major difference between the complex cation in (I) and the `two cations' in (II).
The two out-of-plane bonds around the Cu1 and Cu2 centres have the same length to within 2σ and are almost collinear. The two in-plane Cu—Nphen distances are of almost the same value and are longer on average than the out-of-plane Cu—N distances by 0.093 Å for Cu1 and 0.100 Å for Cu2 Is this change OK?. The in-plane Cu—N(dca) distances are shorter than the other two, but, unlike the corresponding bond in (I), they are somewhat longer than the out-of-plane distances.
Although the corresponding bond distances around Cu1 and Cu2 in (II) are very similar and all equatorial angles are close to the ideal value of 120°, the equatorial angles around Cu1 and Cu2 are nevertheless quite different. The α1 angles are almost equal, but the α2 and α3 angles differ. Thus, there is a difference [of 8.54° for Cu1 and 1.49° for Cu2 Is this change OK?] between α1 and α2, and both polyhedra can, according to the criteria of Harrison & Hathaway (1980), be best described as trigonal-bipyramidal with near C2v symmetry. The high values of the τ parameter for the polyhedra around Cu1 and Cu2 confirm that the distortions of the polyhedra from the ideal trigonal-bipyramidal shape are small.
Although, in comparison with (I), the dicyanamide is differently ligated in (II), there are no significant differences in ligand molecular geometry in the two structures. Nevertheless, due to its bridging function in (II), the ligand is more symmetrical in this compound, and this manifests itself in almost identical values for the corresponding bond distances (Table 3). Moreover, probably due to internal repulsions within the dinuclear cation, both the C3—N1—C2 and the two C≡N(nitrile)-Cu angles adopt higher values in (II), increasing the distance between the two Cu centres in the cation and thus decreasing the intra-cation repulsion.
The O6···C11 distance in (II) is shorter than the sum of the corresponding van der Waals radii, and the O6···C11i—C15i, O6···C11i—C21i and O6···C11i—N10i [symmetry code: (i) 1 - x, 1 - y, -z] angles have values of 90.21 (1), 85.31 (1) and 93.96 (1)°, respectively, which are all close to 90°. The O6···C11 contact is therefore almost perpendicular to the plane of the bipyridine molecule and may be considered as an intermolecular interaction between a free electron pair on the O atom and the delocalized π-electron system of the bipyridine molecule.
Comments from the coeditor: Please confirm the data collection temperatures and ellipsoid probability levels for (I) and (II). Looking at your second structure, there is a close intermolecular contact O6···C11 of 2.86 Å. Such short contacts sometimes indicate hydrogen bonds but in a situation where the atom type (usually assigned as C) has been incorrectly assigned and is in fact N or O. I do not think that this is likely here, but it is an interestingly short contact and I wonder if you would be able to check whether this is a common phenomenon and include a sentence of two of description and analysis.
Data collection: EXPOSE in IPDS (Stoe & Cie, 1999) for (I); EXPOSE in IPDS (Stoe, 1999) for (II). For both compounds, cell refinement: CELL in IPDS; data reduction: INTEGRATE in IPDS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.
[Cu(C10H8N2)2(C2N3)]ClO4 | Dx = 1.598 Mg m−3 |
Mr = 541.41 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 8000 reflections |
a = 8.7343 (4) Å | θ = 14.3–28.0° |
b = 17.9450 (9) Å | µ = 1.14 mm−1 |
c = 28.7230 (17) Å | T = 293 K |
V = 4502.0 (4) Å3 | Hexagonal plate, blue |
Z = 8 | 0.60 × 0.46 × 0.22 mm |
F(000) = 2200 |
Stoe IPDS image-plate diffractometer | 5308 independent reflections |
Radiation source: fine-focus sealed tube | 3430 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
D = 60mm, φ 0–200°, Δφ 1.2°, 1 min/rec scans | θmax = 28.1°, θmin = 2.3° |
Absorption correction: numerical indexed faces | h = −10→11 |
Tmin = 0.627, Tmax = 0.792 | k = −23→23 |
40361 measured reflections | l = −37→37 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.05P)2] where P = (Fo2 + 2Fc2)/3 |
5308 reflections | (Δ/σ)max = 0.001 |
316 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
[Cu(C10H8N2)2(C2N3)]ClO4 | V = 4502.0 (4) Å3 |
Mr = 541.41 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 8.7343 (4) Å | µ = 1.14 mm−1 |
b = 17.9450 (9) Å | T = 293 K |
c = 28.7230 (17) Å | 0.60 × 0.46 × 0.22 mm |
Stoe IPDS image-plate diffractometer | 5308 independent reflections |
Absorption correction: numerical indexed faces | 3430 reflections with I > 2σ(I) |
Tmin = 0.627, Tmax = 0.792 | Rint = 0.062 |
40361 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.53 e Å−3 |
5308 reflections | Δρmin = −0.43 e Å−3 |
316 parameters |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.30387 (8) | 0.27579 (3) | 0.15764 (2) | 0.0438 (2) | |
O1 | 0.2975 (3) | 0.30780 (14) | 0.11289 (9) | 0.0894 (10) | |
O2 | 0.1895 (3) | 0.30149 (13) | 0.18853 (11) | 0.0958 (11) | |
O3 | 0.2929 (3) | 0.19614 (10) | 0.15371 (7) | 0.0668 (8) | |
O4 | 0.4494 (3) | 0.29272 (14) | 0.17746 (8) | 0.0736 (9) | |
Cu1 | 0.52177 (3) | 0.05962 (1) | 0.12751 (1) | 0.0312 (1) | |
N1 | 0.0416 (3) | 0.06184 (14) | 0.10884 (9) | 0.0530 (9) | |
N2 | 0.3086 (3) | 0.02478 (12) | 0.11532 (7) | 0.0407 (8) | |
N3 | −0.0563 (3) | 0.15526 (14) | 0.05380 (9) | 0.0582 (9) | |
N10 | 0.5332 (2) | 0.10238 (10) | 0.06321 (6) | 0.0318 (6) | |
N20 | 0.6778 (2) | −0.01626 (10) | 0.09462 (6) | 0.0318 (6) | |
N30 | 0.5200 (2) | 0.01971 (10) | 0.19221 (6) | 0.0338 (6) | |
N40 | 0.6580 (2) | 0.13695 (10) | 0.15901 (6) | 0.0313 (6) | |
C2 | 0.1849 (3) | 0.04457 (13) | 0.11080 (8) | 0.0357 (9) | |
C3 | −0.0047 (3) | 0.11266 (15) | 0.07858 (9) | 0.0421 (9) | |
C11 | 0.6236 (3) | 0.06758 (12) | 0.03207 (7) | 0.0309 (7) | |
C12 | 0.4526 (3) | 0.16228 (13) | 0.05013 (8) | 0.0410 (8) | |
C13 | 0.4626 (3) | 0.19159 (14) | 0.00596 (8) | 0.0450 (9) | |
C14 | 0.5552 (3) | 0.15686 (15) | −0.02596 (8) | 0.0463 (9) | |
C15 | 0.6357 (3) | 0.09453 (15) | −0.01310 (8) | 0.0421 (9) | |
C21 | 0.7072 (3) | 0.00161 (12) | 0.05000 (8) | 0.0323 (7) | |
C22 | 0.7511 (3) | −0.07424 (13) | 0.11352 (9) | 0.0395 (8) | |
C23 | 0.8558 (3) | −0.11649 (14) | 0.08952 (10) | 0.0495 (10) | |
C24 | 0.8854 (4) | −0.09851 (16) | 0.04377 (11) | 0.0557 (11) | |
C25 | 0.8111 (3) | −0.03933 (14) | 0.02369 (10) | 0.0465 (9) | |
C31 | 0.5937 (3) | 0.06138 (12) | 0.22422 (7) | 0.0318 (7) | |
C32 | 0.4489 (3) | −0.04304 (13) | 0.20536 (8) | 0.0404 (8) | |
C33 | 0.4501 (3) | −0.06746 (14) | 0.25087 (8) | 0.0451 (9) | |
C34 | 0.5212 (4) | −0.02376 (15) | 0.28399 (8) | 0.0495 (9) | |
C35 | 0.5930 (4) | 0.04114 (14) | 0.27077 (8) | 0.0442 (9) | |
C41 | 0.6758 (3) | 0.12655 (12) | 0.20532 (7) | 0.0337 (7) | |
C42 | 0.7350 (3) | 0.19240 (13) | 0.13865 (8) | 0.0383 (8) | |
C43 | 0.8338 (3) | 0.23801 (14) | 0.16282 (10) | 0.0471 (10) | |
C44 | 0.8512 (4) | 0.22814 (15) | 0.20980 (10) | 0.0532 (10) | |
C45 | 0.7697 (4) | 0.17169 (14) | 0.23156 (9) | 0.0459 (9) | |
H12 | 0.38770 | 0.18480 | 0.07160 | 0.0490* | |
H13 | 0.40770 | 0.23410 | −0.00210 | 0.0540* | |
H14 | 0.56330 | 0.17540 | −0.05610 | 0.0550* | |
H15 | 0.69810 | 0.07040 | −0.03460 | 0.0510* | |
H22 | 0.73030 | −0.08650 | 0.14430 | 0.0470* | |
H23 | 0.90540 | −0.15620 | 0.10380 | 0.0590* | |
H24 | 0.95530 | −0.12630 | 0.02660 | 0.0670* | |
H25 | 0.83000 | −0.02670 | −0.00720 | 0.0560* | |
H32 | 0.39720 | −0.07100 | 0.18310 | 0.0480* | |
H33 | 0.40400 | −0.11230 | 0.25910 | 0.0540* | |
H34 | 0.52070 | −0.03810 | 0.31510 | 0.0590* | |
H35 | 0.64060 | 0.07110 | 0.29290 | 0.0530* | |
H42 | 0.72130 | 0.20050 | 0.10690 | 0.0460* | |
H43 | 0.88810 | 0.27510 | 0.14740 | 0.0560* | |
H44 | 0.91650 | 0.25870 | 0.22680 | 0.0640* | |
H45 | 0.77830 | 0.16440 | 0.26350 | 0.0550* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0446 (4) | 0.0412 (3) | 0.0456 (3) | −0.0036 (3) | 0.0073 (3) | −0.0040 (3) |
O1 | 0.107 (2) | 0.0838 (17) | 0.0773 (16) | −0.0198 (16) | −0.0390 (15) | 0.0317 (13) |
O2 | 0.083 (2) | 0.0655 (15) | 0.139 (2) | 0.0185 (13) | 0.0615 (18) | −0.0061 (15) |
O3 | 0.103 (2) | 0.0405 (10) | 0.0570 (12) | −0.0114 (11) | 0.0199 (12) | −0.0117 (9) |
O4 | 0.0645 (17) | 0.0839 (16) | 0.0724 (15) | −0.0103 (13) | −0.0150 (12) | −0.0070 (12) |
Cu1 | 0.0402 (2) | 0.0326 (1) | 0.0209 (1) | 0.0011 (1) | −0.0002 (1) | 0.0022 (1) |
N1 | 0.0380 (16) | 0.0646 (15) | 0.0564 (14) | −0.0041 (12) | −0.0005 (11) | 0.0239 (12) |
N2 | 0.0441 (16) | 0.0448 (12) | 0.0332 (11) | −0.0011 (10) | −0.0023 (10) | 0.0052 (8) |
N3 | 0.0612 (19) | 0.0603 (15) | 0.0532 (14) | 0.0083 (13) | 0.0057 (12) | 0.0173 (12) |
N10 | 0.0401 (12) | 0.0311 (9) | 0.0241 (8) | 0.0026 (8) | 0.0000 (8) | 0.0021 (7) |
N20 | 0.0330 (12) | 0.0316 (9) | 0.0309 (9) | 0.0027 (8) | −0.0008 (8) | 0.0005 (8) |
N30 | 0.0425 (13) | 0.0348 (10) | 0.0241 (9) | 0.0003 (9) | −0.0019 (8) | 0.0000 (7) |
N40 | 0.0361 (13) | 0.0312 (9) | 0.0266 (9) | 0.0043 (8) | 0.0026 (8) | −0.0007 (7) |
C2 | 0.0437 (19) | 0.0399 (13) | 0.0236 (11) | −0.0047 (12) | −0.0004 (10) | 0.0038 (9) |
C3 | 0.0357 (17) | 0.0491 (14) | 0.0414 (13) | 0.0010 (11) | 0.0041 (11) | 0.0062 (11) |
C11 | 0.0329 (14) | 0.0346 (12) | 0.0252 (10) | −0.0040 (10) | 0.0010 (9) | −0.0020 (9) |
C12 | 0.0515 (18) | 0.0372 (12) | 0.0342 (12) | 0.0085 (11) | 0.0003 (11) | 0.0040 (10) |
C13 | 0.0548 (19) | 0.0401 (13) | 0.0402 (13) | −0.0006 (12) | −0.0050 (12) | 0.0113 (11) |
C14 | 0.054 (2) | 0.0546 (15) | 0.0302 (12) | −0.0076 (13) | −0.0035 (11) | 0.0152 (11) |
C15 | 0.0460 (18) | 0.0542 (15) | 0.0262 (11) | −0.0063 (12) | 0.0058 (10) | 0.0002 (11) |
C21 | 0.0313 (14) | 0.0335 (11) | 0.0320 (11) | −0.0048 (10) | 0.0028 (10) | −0.0032 (9) |
C22 | 0.0406 (16) | 0.0339 (13) | 0.0439 (13) | 0.0049 (10) | −0.0045 (11) | 0.0035 (10) |
C23 | 0.0452 (18) | 0.0371 (13) | 0.0661 (18) | 0.0107 (12) | −0.0027 (14) | 0.0022 (13) |
C24 | 0.047 (2) | 0.0480 (16) | 0.072 (2) | 0.0110 (13) | 0.0160 (15) | −0.0070 (14) |
C25 | 0.0475 (19) | 0.0466 (14) | 0.0454 (14) | 0.0018 (12) | 0.0128 (13) | −0.0059 (11) |
C31 | 0.0355 (14) | 0.0340 (11) | 0.0258 (10) | 0.0048 (10) | −0.0014 (9) | −0.0016 (9) |
C32 | 0.0540 (18) | 0.0367 (12) | 0.0305 (12) | −0.0045 (11) | −0.0035 (11) | 0.0044 (9) |
C33 | 0.058 (2) | 0.0444 (13) | 0.0329 (12) | −0.0040 (13) | −0.0005 (11) | 0.0100 (10) |
C34 | 0.068 (2) | 0.0566 (16) | 0.0238 (11) | −0.0026 (14) | −0.0026 (12) | 0.0086 (11) |
C35 | 0.0581 (19) | 0.0480 (14) | 0.0266 (12) | −0.0012 (12) | −0.0055 (11) | −0.0003 (10) |
C41 | 0.0393 (16) | 0.0327 (11) | 0.0290 (11) | 0.0036 (10) | −0.0008 (10) | −0.0023 (9) |
C42 | 0.0400 (16) | 0.0364 (12) | 0.0384 (13) | 0.0021 (11) | 0.0043 (11) | 0.0033 (10) |
C43 | 0.0476 (19) | 0.0405 (14) | 0.0531 (16) | −0.0070 (12) | 0.0026 (13) | 0.0037 (12) |
C44 | 0.057 (2) | 0.0456 (15) | 0.0569 (18) | −0.0120 (14) | −0.0086 (14) | −0.0059 (13) |
C45 | 0.056 (2) | 0.0437 (14) | 0.0379 (13) | −0.0030 (12) | −0.0083 (12) | −0.0035 (11) |
Cu1—N30 | 1.9916 (18) | C23—C24 | 1.378 (4) |
Cu1—N40 | 2.0396 (18) | C24—C25 | 1.372 (4) |
Cu1—N10 | 2.0025 (18) | C31—C35 | 1.386 (3) |
Cu1—N20 | 2.1457 (18) | C31—C41 | 1.475 (3) |
Cu1—N2 | 1.995 (3) | C32—C33 | 1.379 (3) |
Cl1—O3 | 1.4370 (19) | C33—C34 | 1.380 (4) |
Cl1—O4 | 1.426 (3) | C34—C35 | 1.376 (4) |
Cl1—O1 | 1.409 (3) | C41—C45 | 1.377 (4) |
Cl1—O2 | 1.413 (3) | C42—C43 | 1.377 (4) |
N1—C2 | 1.291 (4) | C43—C44 | 1.369 (4) |
N1—C3 | 1.323 (4) | C44—C45 | 1.387 (4) |
N2—C2 | 1.145 (4) | C12—H12 | 0.9300 |
N3—C3 | 1.138 (4) | C13—H13 | 0.9303 |
N10—C11 | 1.347 (3) | C14—H14 | 0.9301 |
N10—C12 | 1.339 (3) | C15—H15 | 0.9305 |
N20—C21 | 1.346 (3) | C22—H22 | 0.9290 |
N20—C22 | 1.337 (3) | C23—H23 | 0.9294 |
N30—C31 | 1.349 (3) | C24—H24 | 0.9299 |
N30—C32 | 1.340 (3) | C25—H25 | 0.9305 |
N40—C41 | 1.352 (3) | C32—H32 | 0.9298 |
N40—C42 | 1.336 (3) | C33—H33 | 0.9303 |
C11—C15 | 1.389 (3) | C34—H34 | 0.9299 |
C11—C21 | 1.483 (3) | C35—H35 | 0.9306 |
C12—C13 | 1.376 (3) | C42—H42 | 0.9312 |
C13—C14 | 1.372 (4) | C43—H43 | 0.9296 |
C14—C15 | 1.372 (4) | C44—H44 | 0.9298 |
C21—C25 | 1.391 (4) | C45—H45 | 0.9297 |
C22—C23 | 1.373 (4) | ||
N30—Cu1—N40 | 80.52 (7) | N30—C31—C35 | 120.7 (2) |
N2—Cu1—N30 | 92.51 (8) | N30—C31—C41 | 114.88 (18) |
N2—Cu1—N40 | 146.67 (8) | C35—C31—C41 | 124.4 (2) |
N10—Cu1—N20 | 78.78 (7) | N30—C32—C33 | 122.1 (2) |
N10—Cu1—N30 | 177.17 (7) | C32—C33—C34 | 118.4 (2) |
N10—Cu1—N40 | 96.85 (7) | C33—C34—C35 | 119.7 (2) |
N2—Cu1—N10 | 90.27 (8) | C31—C35—C34 | 119.3 (2) |
N2—Cu1—N20 | 108.46 (8) | N40—C41—C31 | 114.55 (19) |
N20—Cu1—N40 | 104.87 (7) | N40—C41—C45 | 121.7 (2) |
N20—Cu1—N30 | 100.81 (7) | C31—C41—C45 | 123.7 (2) |
O1—Cl1—O4 | 108.22 (15) | N40—C42—C43 | 122.5 (2) |
O1—Cl1—O3 | 109.34 (14) | C42—C43—C44 | 119.3 (2) |
O3—Cl1—O4 | 107.63 (15) | C43—C44—C45 | 118.8 (3) |
O2—Cl1—O3 | 109.07 (14) | C41—C45—C44 | 119.2 (2) |
O2—Cl1—O4 | 108.06 (15) | N10—C12—H12 | 118.90 |
O1—Cl1—O2 | 114.31 (16) | C13—C12—H12 | 118.94 |
C2—N1—C3 | 119.4 (2) | C12—C13—H13 | 120.67 |
Cu1—N2—C2 | 143.5 (2) | C14—C13—H13 | 120.66 |
Cu1—N10—C11 | 117.65 (14) | C13—C14—H14 | 120.28 |
Cu1—N10—C12 | 122.71 (15) | C15—C14—H14 | 120.22 |
C11—N10—C12 | 119.62 (19) | C11—C15—H15 | 120.17 |
Cu1—N20—C21 | 112.91 (14) | C14—C15—H15 | 120.06 |
Cu1—N20—C22 | 128.26 (16) | N20—C22—H22 | 118.50 |
C21—N20—C22 | 118.7 (2) | C23—C22—H22 | 118.50 |
Cu1—N30—C31 | 115.66 (14) | C22—C23—H23 | 120.81 |
Cu1—N30—C32 | 124.66 (15) | C24—C23—H23 | 120.87 |
C31—N30—C32 | 119.66 (19) | C23—C24—H24 | 120.23 |
Cu1—N40—C41 | 114.17 (14) | C25—C24—H24 | 120.19 |
Cu1—N40—C42 | 127.33 (15) | C21—C25—H25 | 120.34 |
C41—N40—C42 | 118.40 (19) | C24—C25—H25 | 120.37 |
N1—C2—N2 | 174.1 (3) | N30—C32—H32 | 118.99 |
N1—C3—N3 | 174.4 (3) | C33—C32—H32 | 118.96 |
N10—C11—C15 | 120.2 (2) | C32—C33—H33 | 120.83 |
N10—C11—C21 | 115.35 (18) | C34—C33—H33 | 120.73 |
C15—C11—C21 | 124.4 (2) | C33—C34—H34 | 120.19 |
N10—C12—C13 | 122.2 (2) | C35—C34—H34 | 120.10 |
C12—C13—C14 | 118.7 (2) | C31—C35—H35 | 120.38 |
C13—C14—C15 | 119.5 (2) | C34—C35—H35 | 120.27 |
C11—C15—C14 | 119.8 (2) | N40—C42—H42 | 118.71 |
N20—C21—C11 | 115.3 (2) | C43—C42—H42 | 118.78 |
N20—C21—C25 | 121.1 (2) | C42—C43—H43 | 120.34 |
C11—C21—C25 | 123.7 (2) | C44—C43—H43 | 120.36 |
N20—C22—C23 | 123.0 (2) | C43—C44—H44 | 120.62 |
C22—C23—C24 | 118.3 (3) | C45—C44—H44 | 120.60 |
C23—C24—C25 | 119.6 (3) | C41—C45—H45 | 120.35 |
C21—C25—C24 | 119.3 (3) | C44—C45—H45 | 120.40 |
[Cu2(C10H8N2)4(C2N3)](ClO4)3·0.5C2H6O | Z = 2 |
Mr = 1139.25 | F(000) = 1158 |
Triclinic, P1 | Dx = 1.645 Mg m−3 |
a = 10.2999 (9) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 14.3808 (12) Å | Cell parameters from 7998 reflections |
c = 16.4311 (16) Å | θ = 2.3–28.0° |
α = 74.12 (1)° | µ = 1.18 mm−1 |
β = 83.371 (11)° | T = 193 K |
γ = 80.046 (10)° | Block, blue |
V = 2299.7 (4) Å3 | 0.33 × 0.24 × 0.14 mm |
Stoe IPDS image-plate diffractometer | 10314 independent reflections |
Radiation source: fine-focus sealed tube | 5455 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.072 |
D = 60mm, φ 0–250°, Δφ 1.6°, 2 min/rec scans | θmax = 28.2°, θmin = 2.2° |
Absorption correction: numerical indexed faces | h = −13→13 |
Tmin = 0.790, Tmax = 0.869 | k = −17→17 |
27918 measured reflections | l = −21→21 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 0.84 | w = 1/[σ2(Fo2) + (0.0564P)2] where P = (Fo2 + 2Fc2)/3 |
10314 reflections | (Δ/σ)max = 0.001 |
658 parameters | Δρmax = 0.99 e Å−3 |
2 restraints | Δρmin = −0.67 e Å−3 |
[Cu2(C10H8N2)4(C2N3)](ClO4)3·0.5C2H6O | γ = 80.046 (10)° |
Mr = 1139.25 | V = 2299.7 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.2999 (9) Å | Mo Kα radiation |
b = 14.3808 (12) Å | µ = 1.18 mm−1 |
c = 16.4311 (16) Å | T = 193 K |
α = 74.12 (1)° | 0.33 × 0.24 × 0.14 mm |
β = 83.371 (11)° |
Stoe IPDS image-plate diffractometer | 10314 independent reflections |
Absorption correction: numerical indexed faces | 5455 reflections with I > 2σ(I) |
Tmin = 0.790, Tmax = 0.869 | Rint = 0.072 |
27918 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 2 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 0.84 | Δρmax = 0.99 e Å−3 |
10314 reflections | Δρmin = −0.67 e Å−3 |
658 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.39715 (4) | 0.77460 (4) | 0.03948 (3) | 0.0332 (2) | |
Cu2 | −0.03369 (4) | 0.75098 (3) | 0.50717 (3) | 0.0249 (1) | |
N1 | 0.1089 (3) | 0.8554 (2) | 0.23858 (19) | 0.0350 (11) | |
N2 | 0.2946 (3) | 0.8135 (3) | 0.1415 (2) | 0.0385 (11) | |
N3 | 0.0356 (3) | 0.7768 (3) | 0.3837 (2) | 0.0381 (11) | |
N10 | 0.3096 (3) | 0.8937 (3) | −0.03844 (19) | 0.0364 (11) | |
N20 | 0.5622 (3) | 0.8340 (3) | −0.0210 (2) | 0.0391 (13) | |
N30 | 0.4884 (3) | 0.6556 (3) | 0.1147 (2) | 0.0359 (11) | |
N40 | 0.3231 (3) | 0.6692 (3) | 0.0015 (2) | 0.0373 (11) | |
N50 | −0.1724 (3) | 0.8667 (2) | 0.48242 (18) | 0.0245 (10) | |
N60 | 0.0134 (3) | 0.8272 (2) | 0.58837 (18) | 0.0269 (10) | |
N70 | 0.1015 (3) | 0.6346 (2) | 0.53880 (19) | 0.0293 (10) | |
N80 | −0.1542 (3) | 0.6470 (2) | 0.56497 (18) | 0.0254 (10) | |
C2 | 0.2096 (4) | 0.8274 (3) | 0.1908 (2) | 0.0296 (11) | |
C3 | 0.0769 (3) | 0.8086 (3) | 0.3153 (2) | 0.0292 (11) | |
C11 | 0.3901 (4) | 0.9532 (3) | −0.0889 (2) | 0.0392 (16) | |
C12 | 0.1785 (4) | 0.9196 (4) | −0.0404 (3) | 0.0495 (16) | |
C13 | 0.1221 (5) | 1.0047 (4) | −0.0946 (3) | 0.0586 (19) | |
C14 | 0.2020 (6) | 1.0657 (4) | −0.1456 (3) | 0.0633 (19) | |
C15 | 0.3382 (6) | 1.0412 (4) | −0.1435 (3) | 0.0557 (19) | |
C21 | 0.5315 (4) | 0.9180 (3) | −0.0823 (2) | 0.0384 (16) | |
C22 | 0.6891 (4) | 0.7970 (4) | −0.0124 (3) | 0.0533 (19) | |
C23 | 0.7904 (5) | 0.8412 (5) | −0.0626 (3) | 0.076 (2) | |
C24 | 0.7581 (5) | 0.9250 (5) | −0.1253 (3) | 0.075 (2) | |
C25 | 0.6296 (5) | 0.9638 (4) | −0.1355 (3) | 0.058 (2) | |
C31 | 0.4557 (4) | 0.5702 (3) | 0.1120 (2) | 0.0364 (14) | |
C32 | 0.5763 (4) | 0.6560 (4) | 0.1684 (2) | 0.0447 (16) | |
C33 | 0.6406 (4) | 0.5713 (4) | 0.2189 (3) | 0.0523 (18) | |
C34 | 0.6087 (5) | 0.4845 (4) | 0.2156 (3) | 0.0573 (19) | |
C35 | 0.5146 (4) | 0.4825 (3) | 0.1638 (3) | 0.0496 (17) | |
C41 | 0.3580 (4) | 0.5780 (3) | 0.0505 (3) | 0.0388 (14) | |
C42 | 0.2372 (4) | 0.6827 (4) | −0.0577 (3) | 0.0482 (19) | |
C43 | 0.1807 (5) | 0.6065 (5) | −0.0684 (4) | 0.066 (2) | |
C44 | 0.2155 (6) | 0.5140 (5) | −0.0160 (4) | 0.067 (2) | |
C45 | 0.3055 (5) | 0.4988 (4) | 0.0430 (3) | 0.0515 (17) | |
C51 | −0.1766 (3) | 0.9321 (3) | 0.5276 (2) | 0.0252 (11) | |
C52 | −0.2590 (3) | 0.8826 (3) | 0.4232 (2) | 0.0305 (11) | |
C53 | −0.3526 (3) | 0.9649 (3) | 0.4063 (3) | 0.0343 (14) | |
C54 | −0.3575 (4) | 1.0321 (3) | 0.4527 (3) | 0.0387 (16) | |
C55 | −0.2696 (4) | 1.0159 (3) | 0.5140 (3) | 0.0341 (12) | |
C61 | −0.0752 (3) | 0.9089 (3) | 0.5893 (2) | 0.0269 (11) | |
C62 | 0.1101 (4) | 0.8022 (3) | 0.6410 (2) | 0.0353 (14) | |
C63 | 0.1263 (4) | 0.8578 (3) | 0.6952 (3) | 0.0407 (14) | |
C64 | 0.0371 (4) | 0.9398 (3) | 0.6961 (3) | 0.0432 (16) | |
C65 | −0.0662 (4) | 0.9658 (3) | 0.6432 (3) | 0.0370 (14) | |
C71 | 0.0572 (3) | 0.5491 (3) | 0.5775 (2) | 0.0270 (11) | |
C72 | 0.2314 (3) | 0.6363 (3) | 0.5202 (3) | 0.0378 (14) | |
C73 | 0.3217 (4) | 0.5539 (4) | 0.5390 (3) | 0.0477 (18) | |
C74 | 0.2799 (4) | 0.4658 (4) | 0.5771 (3) | 0.0494 (18) | |
C75 | 0.1459 (4) | 0.4628 (3) | 0.5965 (2) | 0.0407 (16) | |
C81 | −0.0873 (4) | 0.5571 (3) | 0.5947 (2) | 0.0286 (11) | |
C82 | −0.2858 (3) | 0.6614 (3) | 0.5795 (2) | 0.0326 (14) | |
C83 | −0.3549 (4) | 0.5869 (3) | 0.6243 (3) | 0.0410 (16) | |
C84 | −0.2863 (4) | 0.4942 (4) | 0.6538 (3) | 0.0458 (16) | |
C85 | −0.1515 (4) | 0.4787 (3) | 0.6389 (2) | 0.0368 (14) | |
O13 | −0.0395 (7) | 0.4143 (5) | 0.2399 (4) | 0.070 (3) | 0.500 |
C4 | 0.1185 (11) | 0.3063 (11) | 0.1628 (9) | 0.171 (9) | 0.500 |
C5 | 0.0864 (6) | 0.3650 (6) | 0.2262 (5) | 0.026 (3) | 0.500 |
Cl1 | 0.53904 (8) | 0.22125 (7) | 0.64204 (6) | 0.0297 (3) | |
O1 | 0.4137 (3) | 0.2145 (3) | 0.6885 (2) | 0.0600 (13) | |
O2 | 0.5904 (3) | 0.3018 (3) | 0.6544 (2) | 0.0563 (12) | |
O3 | 0.5237 (3) | 0.2351 (3) | 0.55349 (18) | 0.0511 (10) | |
O4 | 0.6262 (4) | 0.1327 (3) | 0.6718 (2) | 0.0688 (14) | |
Cl2 | 0.48597 (13) | 0.20643 (9) | 0.25670 (8) | 0.0558 (4) | |
O5 | 0.4189 (6) | 0.2703 (3) | 0.1886 (4) | 0.146 (3) | |
O6 | 0.5860 (4) | 0.1415 (4) | 0.2232 (3) | 0.0993 (19) | |
O7 | 0.5524 (4) | 0.2582 (3) | 0.2979 (3) | 0.0798 (17) | |
O8 | 0.4017 (4) | 0.1518 (4) | 0.3150 (3) | 0.1074 (19) | |
Cl3 | 0.98479 (10) | 0.66642 (9) | 0.14780 (7) | 0.0447 (4) | |
O9 | 0.9225 (5) | 0.6119 (5) | 0.1125 (4) | 0.127 (3) | |
O10 | 1.1126 (4) | 0.6242 (4) | 0.1705 (3) | 0.0970 (18) | |
O11 | 1.0019 (4) | 0.7567 (3) | 0.0830 (2) | 0.0859 (16) | |
O12 | 0.9071 (3) | 0.6913 (3) | 0.2181 (2) | 0.0665 (12) | |
H12 | 0.12230 | 0.87810 | −0.00330 | 0.0590* | |
H13 | 0.02880 | 1.02030 | −0.09600 | 0.0700* | |
H14 | 0.16490 | 1.12510 | −0.18270 | 0.0760* | |
H15 | 0.39520 | 1.08360 | −0.17870 | 0.0670* | |
H22 | 0.71090 | 0.73790 | 0.02990 | 0.0640* | |
H23 | 0.88010 | 0.81420 | −0.05390 | 0.0910* | |
H24 | 0.82580 | 0.95580 | −0.16140 | 0.0900* | |
H25 | 0.60680 | 1.02190 | −0.17860 | 0.0700* | |
H32 | 0.59530 | 0.71700 | 0.17190 | 0.0540* | |
H33 | 0.70530 | 0.57360 | 0.25480 | 0.0620* | |
H34 | 0.65170 | 0.42500 | 0.24940 | 0.0690* | |
H35 | 0.48970 | 0.42220 | 0.16310 | 0.0600* | |
H42 | 0.21450 | 0.74640 | −0.09340 | 0.0580* | |
H43 | 0.11990 | 0.61740 | −0.11040 | 0.0790* | |
H44 | 0.17650 | 0.46080 | −0.02110 | 0.0810* | |
H45 | 0.33130 | 0.43520 | 0.07800 | 0.0620* | |
H52 | −0.25550 | 0.83560 | 0.39180 | 0.0370* | |
H53 | −0.41230 | 0.97510 | 0.36360 | 0.0410* | |
H54 | −0.42130 | 1.08950 | 0.44250 | 0.0460* | |
H55 | −0.27270 | 1.06160 | 0.54670 | 0.0410* | |
H62 | 0.17040 | 0.74410 | 0.64150 | 0.0420* | |
H63 | 0.19780 | 0.83920 | 0.73080 | 0.0480* | |
H64 | 0.04580 | 0.97880 | 0.73280 | 0.0520* | |
H65 | −0.12980 | 1.02200 | 0.64410 | 0.0450* | |
H72 | 0.26130 | 0.69700 | 0.49310 | 0.0460* | |
H73 | 0.41320 | 0.55740 | 0.52580 | 0.0570* | |
H74 | 0.34180 | 0.40760 | 0.59000 | 0.0600* | |
H75 | 0.11490 | 0.40230 | 0.62260 | 0.0490* | |
H82 | −0.33310 | 0.72490 | 0.55830 | 0.0390* | |
H83 | −0.44810 | 0.59920 | 0.63480 | 0.0490* | |
H84 | −0.33210 | 0.44170 | 0.68400 | 0.0540* | |
H85 | −0.10270 | 0.41540 | 0.65840 | 0.0440* | |
H4A | 0.06390 | 0.25380 | 0.17700 | 0.2050* | 0.500 |
H4B | 0.10060 | 0.34850 | 0.10620 | 0.2050* | 0.500 |
H4C | 0.21210 | 0.27780 | 0.16350 | 0.2050* | 0.500 |
H5A | 0.14700 | 0.41460 | 0.21130 | 0.0310* | 0.500 |
H5B | 0.11100 | 0.32060 | 0.28160 | 0.0310* | 0.500 |
H13A | −0.09610 | 0.38460 | 0.22920 | 0.0840* | 0.500 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0442 (3) | 0.0284 (3) | 0.0225 (2) | −0.0037 (2) | 0.0018 (2) | −0.0019 (2) |
Cu2 | 0.0263 (2) | 0.0200 (3) | 0.0265 (2) | −0.0011 (2) | 0.0010 (2) | −0.0056 (2) |
N1 | 0.0406 (18) | 0.031 (2) | 0.0233 (17) | 0.0069 (14) | 0.0009 (14) | 0.0011 (14) |
N2 | 0.0473 (19) | 0.041 (2) | 0.0229 (17) | −0.0027 (16) | 0.0014 (15) | −0.0050 (15) |
N3 | 0.0429 (18) | 0.029 (2) | 0.035 (2) | 0.0045 (15) | 0.0088 (15) | −0.0069 (15) |
N10 | 0.048 (2) | 0.037 (2) | 0.0204 (17) | −0.0002 (15) | 0.0002 (14) | −0.0060 (15) |
N20 | 0.048 (2) | 0.046 (3) | 0.0221 (17) | −0.0147 (16) | −0.0053 (14) | −0.0011 (15) |
N30 | 0.0446 (19) | 0.034 (2) | 0.0250 (18) | −0.0052 (15) | 0.0059 (14) | −0.0045 (14) |
N40 | 0.0420 (18) | 0.041 (2) | 0.0290 (18) | −0.0046 (15) | 0.0057 (15) | −0.0136 (16) |
N50 | 0.0261 (15) | 0.0196 (19) | 0.0282 (17) | −0.0052 (12) | 0.0001 (12) | −0.0064 (13) |
N60 | 0.0314 (16) | 0.024 (2) | 0.0251 (16) | −0.0053 (13) | −0.0003 (13) | −0.0062 (13) |
N70 | 0.0288 (15) | 0.030 (2) | 0.0265 (17) | 0.0032 (13) | 0.0001 (13) | −0.0085 (14) |
N80 | 0.0308 (16) | 0.0220 (19) | 0.0235 (16) | −0.0046 (12) | 0.0008 (12) | −0.0069 (13) |
C2 | 0.042 (2) | 0.025 (2) | 0.0197 (19) | −0.0020 (16) | −0.0061 (16) | −0.0025 (15) |
C3 | 0.0333 (19) | 0.025 (2) | 0.027 (2) | 0.0046 (15) | −0.0013 (16) | −0.0088 (16) |
C11 | 0.072 (3) | 0.024 (3) | 0.023 (2) | −0.008 (2) | −0.0054 (19) | −0.0069 (17) |
C12 | 0.058 (3) | 0.053 (3) | 0.030 (2) | 0.008 (2) | 0.001 (2) | −0.010 (2) |
C13 | 0.069 (3) | 0.060 (4) | 0.035 (3) | 0.024 (3) | −0.007 (2) | −0.012 (2) |
C14 | 0.102 (4) | 0.037 (3) | 0.043 (3) | 0.021 (3) | −0.021 (3) | −0.010 (2) |
C15 | 0.105 (4) | 0.026 (3) | 0.035 (3) | −0.010 (3) | −0.012 (3) | −0.003 (2) |
C21 | 0.063 (3) | 0.032 (3) | 0.025 (2) | −0.022 (2) | −0.0057 (18) | −0.0052 (18) |
C22 | 0.050 (3) | 0.068 (4) | 0.035 (3) | −0.016 (2) | −0.009 (2) | 0.005 (2) |
C23 | 0.051 (3) | 0.119 (6) | 0.051 (3) | −0.038 (3) | −0.004 (2) | 0.003 (3) |
C24 | 0.066 (3) | 0.101 (5) | 0.054 (3) | −0.051 (3) | −0.001 (3) | 0.010 (3) |
C25 | 0.083 (4) | 0.061 (4) | 0.034 (3) | −0.046 (3) | −0.004 (2) | 0.004 (2) |
C31 | 0.040 (2) | 0.033 (3) | 0.028 (2) | −0.0042 (18) | 0.0132 (17) | −0.0016 (17) |
C32 | 0.055 (3) | 0.049 (3) | 0.024 (2) | −0.006 (2) | −0.0022 (19) | −0.0005 (19) |
C33 | 0.052 (3) | 0.062 (4) | 0.031 (2) | −0.003 (2) | 0.000 (2) | 0.003 (2) |
C34 | 0.056 (3) | 0.059 (4) | 0.036 (3) | 0.007 (2) | 0.006 (2) | 0.009 (2) |
C35 | 0.061 (3) | 0.029 (3) | 0.050 (3) | −0.007 (2) | 0.017 (2) | −0.004 (2) |
C41 | 0.048 (2) | 0.033 (3) | 0.035 (2) | −0.0083 (19) | 0.0184 (19) | −0.0157 (19) |
C42 | 0.049 (3) | 0.056 (4) | 0.043 (3) | −0.005 (2) | 0.003 (2) | −0.023 (2) |
C43 | 0.066 (3) | 0.091 (5) | 0.058 (3) | −0.014 (3) | −0.005 (3) | −0.048 (3) |
C44 | 0.080 (4) | 0.059 (4) | 0.076 (4) | −0.024 (3) | 0.016 (3) | −0.041 (3) |
C45 | 0.063 (3) | 0.044 (3) | 0.053 (3) | −0.014 (2) | 0.011 (2) | −0.024 (2) |
C51 | 0.0279 (18) | 0.020 (2) | 0.0259 (19) | −0.0061 (14) | 0.0051 (14) | −0.0044 (15) |
C52 | 0.0309 (19) | 0.026 (2) | 0.033 (2) | −0.0041 (15) | −0.0033 (16) | −0.0044 (16) |
C53 | 0.0285 (19) | 0.029 (3) | 0.040 (2) | −0.0027 (16) | −0.0077 (16) | 0.0010 (18) |
C54 | 0.035 (2) | 0.026 (3) | 0.046 (3) | 0.0030 (16) | 0.0006 (18) | −0.0003 (19) |
C55 | 0.041 (2) | 0.021 (2) | 0.038 (2) | −0.0013 (16) | 0.0054 (18) | −0.0094 (17) |
C61 | 0.0343 (19) | 0.021 (2) | 0.026 (2) | −0.0080 (15) | 0.0043 (15) | −0.0075 (15) |
C62 | 0.037 (2) | 0.032 (3) | 0.036 (2) | −0.0048 (17) | −0.0031 (17) | −0.0075 (18) |
C63 | 0.041 (2) | 0.050 (3) | 0.034 (2) | −0.012 (2) | −0.0059 (18) | −0.011 (2) |
C64 | 0.056 (3) | 0.046 (3) | 0.037 (2) | −0.015 (2) | −0.001 (2) | −0.023 (2) |
C65 | 0.044 (2) | 0.034 (3) | 0.038 (2) | −0.0074 (18) | 0.0014 (18) | −0.0184 (19) |
C71 | 0.037 (2) | 0.022 (2) | 0.0215 (18) | 0.0025 (16) | −0.0044 (15) | −0.0080 (15) |
C72 | 0.029 (2) | 0.044 (3) | 0.038 (2) | 0.0029 (17) | 0.0034 (17) | −0.014 (2) |
C73 | 0.039 (2) | 0.059 (4) | 0.043 (3) | 0.013 (2) | −0.0057 (19) | −0.021 (2) |
C74 | 0.053 (3) | 0.054 (4) | 0.034 (2) | 0.031 (2) | −0.011 (2) | −0.020 (2) |
C75 | 0.068 (3) | 0.024 (3) | 0.025 (2) | 0.0108 (19) | −0.0083 (19) | −0.0065 (17) |
C81 | 0.046 (2) | 0.022 (2) | 0.0177 (18) | −0.0033 (16) | −0.0032 (15) | −0.0059 (15) |
C82 | 0.031 (2) | 0.033 (3) | 0.034 (2) | −0.0064 (16) | −0.0004 (16) | −0.0090 (18) |
C83 | 0.040 (2) | 0.046 (3) | 0.042 (3) | −0.019 (2) | 0.0074 (19) | −0.016 (2) |
C84 | 0.067 (3) | 0.040 (3) | 0.036 (2) | −0.030 (2) | 0.014 (2) | −0.013 (2) |
C85 | 0.063 (3) | 0.019 (2) | 0.028 (2) | −0.0103 (18) | 0.0012 (18) | −0.0044 (16) |
O13 | 0.110 (6) | 0.065 (6) | 0.047 (4) | −0.041 (4) | −0.016 (4) | −0.015 (4) |
C4 | 0.058 (8) | 0.146 (17) | 0.26 (2) | −0.070 (10) | −0.071 (12) | 0.085 (17) |
C5 | 0.027 (4) | 0.031 (5) | 0.025 (4) | −0.009 (3) | −0.001 (3) | −0.014 (3) |
Cl1 | 0.0339 (5) | 0.0261 (6) | 0.0291 (5) | −0.0057 (4) | −0.0036 (4) | −0.0058 (4) |
O1 | 0.0526 (18) | 0.080 (3) | 0.058 (2) | −0.0323 (17) | 0.0161 (15) | −0.0297 (19) |
O2 | 0.078 (2) | 0.050 (2) | 0.054 (2) | −0.0377 (17) | 0.0071 (16) | −0.0227 (16) |
O3 | 0.0613 (18) | 0.065 (2) | 0.0287 (16) | −0.0222 (16) | −0.0127 (14) | −0.0030 (15) |
O4 | 0.090 (2) | 0.052 (3) | 0.059 (2) | 0.0314 (19) | −0.0303 (19) | −0.0209 (18) |
Cl2 | 0.0887 (9) | 0.0289 (7) | 0.0499 (7) | −0.0038 (6) | −0.0246 (6) | −0.0056 (5) |
O5 | 0.235 (6) | 0.049 (3) | 0.157 (5) | −0.035 (3) | −0.152 (5) | 0.032 (3) |
O6 | 0.109 (3) | 0.126 (4) | 0.091 (3) | −0.015 (3) | −0.003 (3) | −0.078 (3) |
O7 | 0.114 (3) | 0.048 (3) | 0.093 (3) | 0.012 (2) | −0.054 (2) | −0.040 (2) |
O8 | 0.088 (3) | 0.117 (4) | 0.100 (3) | −0.041 (3) | −0.008 (3) | 0.017 (3) |
Cl3 | 0.0433 (6) | 0.0533 (8) | 0.0366 (6) | −0.0046 (5) | −0.0012 (4) | −0.0126 (5) |
O9 | 0.113 (3) | 0.172 (6) | 0.153 (5) | −0.073 (4) | 0.025 (3) | −0.120 (5) |
O10 | 0.062 (2) | 0.133 (4) | 0.076 (3) | 0.021 (2) | −0.014 (2) | −0.012 (3) |
O11 | 0.104 (3) | 0.076 (3) | 0.056 (2) | −0.014 (2) | 0.012 (2) | 0.012 (2) |
O12 | 0.088 (2) | 0.053 (2) | 0.052 (2) | −0.0065 (18) | 0.0263 (18) | −0.0180 (17) |
Cu1—N2 | 2.034 (4) | C42—C43 | 1.386 (9) |
Cu1—N10 | 1.980 (4) | C43—C44 | 1.385 (10) |
Cu1—N20 | 2.063 (3) | C44—C45 | 1.367 (8) |
Cu1—N30 | 1.973 (4) | C51—C61 | 1.473 (5) |
Cu1—N40 | 2.073 (4) | C51—C55 | 1.387 (6) |
Cu2—N3 | 2.027 (3) | C52—C53 | 1.377 (6) |
Cu2—N50 | 1.979 (3) | C53—C54 | 1.377 (6) |
Cu2—N60 | 2.086 (3) | C54—C55 | 1.378 (6) |
Cu2—N70 | 1.974 (3) | C61—C65 | 1.380 (6) |
Cu2—N80 | 2.067 (3) | C62—C63 | 1.389 (6) |
Cl1—O2 | 1.424 (4) | C63—C64 | 1.366 (6) |
Cl1—O3 | 1.437 (3) | C64—C65 | 1.388 (6) |
Cl1—O1 | 1.426 (3) | C71—C81 | 1.473 (5) |
Cl1—O4 | 1.425 (4) | C71—C75 | 1.391 (6) |
Cl2—O6 | 1.433 (5) | C72—C73 | 1.360 (7) |
Cl2—O7 | 1.428 (5) | C73—C74 | 1.369 (8) |
Cl2—O5 | 1.403 (6) | C74—C75 | 1.386 (6) |
Cl2—O8 | 1.386 (5) | C81—C85 | 1.391 (6) |
Cl3—O9 | 1.368 (7) | C82—C83 | 1.381 (6) |
Cl3—O10 | 1.398 (5) | C83—C84 | 1.382 (7) |
Cl3—O12 | 1.420 (4) | C84—C85 | 1.372 (6) |
Cl3—O11 | 1.459 (4) | C12—H12 | 0.9496 |
O13—C5 | 1.392 (10) | C13—H13 | 0.9498 |
O13—H13A | 0.8391 | C14—H14 | 0.9504 |
N1—C2 | 1.302 (5) | C15—H15 | 0.9505 |
N1—C3 | 1.291 (4) | C22—H22 | 0.9501 |
N2—C2 | 1.152 (5) | C23—H23 | 0.9492 |
N3—C3 | 1.153 (5) | C24—H24 | 0.9496 |
N10—C12 | 1.339 (6) | C25—H25 | 0.9495 |
N10—C11 | 1.344 (5) | C32—H32 | 0.9490 |
N20—C21 | 1.360 (5) | C33—H33 | 0.9498 |
N20—C22 | 1.331 (6) | C34—H34 | 0.9500 |
N30—C31 | 1.342 (6) | C35—H35 | 0.9492 |
N30—C32 | 1.337 (5) | C42—H42 | 0.9495 |
N40—C42 | 1.343 (6) | C43—H43 | 0.9485 |
N40—C41 | 1.350 (6) | C44—H44 | 0.9502 |
N50—C52 | 1.343 (4) | C45—H45 | 0.9494 |
N50—C51 | 1.341 (5) | C52—H52 | 0.9500 |
N60—C62 | 1.332 (5) | C53—H53 | 0.9508 |
N60—C61 | 1.360 (5) | C54—H54 | 0.9505 |
N70—C72 | 1.341 (5) | C55—H55 | 0.9506 |
N70—C71 | 1.350 (5) | C62—H62 | 0.9497 |
N80—C82 | 1.339 (5) | C63—H63 | 0.9496 |
N80—C81 | 1.345 (5) | C64—H64 | 0.9493 |
C11—C21 | 1.463 (6) | C65—H65 | 0.9507 |
C11—C15 | 1.396 (7) | C72—H72 | 0.9506 |
C12—C13 | 1.380 (7) | C73—H73 | 0.9492 |
C13—C14 | 1.355 (8) | C74—H74 | 0.9495 |
C14—C15 | 1.388 (9) | C75—H75 | 0.9503 |
C21—C25 | 1.389 (6) | C82—H82 | 0.9507 |
C22—C23 | 1.384 (7) | C83—H83 | 0.9499 |
C23—C24 | 1.373 (8) | C84—H84 | 0.9502 |
C24—C25 | 1.355 (8) | C85—H85 | 0.9504 |
C31—C35 | 1.397 (6) | C4—C5 | 1.487 (17) |
C31—C41 | 1.477 (6) | C4—H4C | 0.9803 |
C32—C33 | 1.380 (7) | C4—H4B | 0.9794 |
C33—C34 | 1.361 (8) | C4—H4A | 0.9802 |
C34—C35 | 1.370 (7) | C5—H5B | 0.9898 |
C41—C45 | 1.382 (7) | C5—H5A | 0.9906 |
N2—Cu1—N10 | 90.91 (15) | C52—C53—C54 | 118.3 (4) |
N2—Cu1—N20 | 123.00 (15) | C53—C54—C55 | 119.8 (4) |
N2—Cu1—N30 | 90.56 (15) | C51—C55—C54 | 119.3 (4) |
N2—Cu1—N40 | 114.49 (14) | N60—C61—C51 | 115.0 (3) |
N10—Cu1—N20 | 80.70 (14) | C51—C61—C65 | 123.7 (4) |
N10—Cu1—N30 | 178.42 (14) | N60—C61—C65 | 121.3 (3) |
N10—Cu1—N40 | 99.58 (15) | N60—C62—C63 | 122.6 (4) |
N20—Cu1—N30 | 98.01 (14) | C62—C63—C64 | 118.5 (4) |
N20—Cu1—N40 | 122.51 (14) | C63—C64—C65 | 119.7 (4) |
N30—Cu1—N40 | 80.31 (15) | C61—C65—C64 | 119.0 (4) |
N3—Cu2—N50 | 91.82 (14) | N70—C71—C81 | 114.5 (3) |
N3—Cu2—N60 | 122.38 (14) | C75—C71—C81 | 125.4 (4) |
N3—Cu2—N70 | 91.44 (14) | N70—C71—C75 | 120.1 (3) |
N3—Cu2—N80 | 123.90 (14) | N70—C72—C73 | 122.0 (4) |
N50—Cu2—N60 | 80.24 (12) | C72—C73—C74 | 119.6 (4) |
N50—Cu2—N70 | 176.73 (12) | C73—C74—C75 | 119.0 (5) |
N50—Cu2—N80 | 98.27 (12) | C71—C75—C74 | 119.4 (4) |
N60—Cu2—N70 | 97.73 (12) | N80—C81—C71 | 115.0 (3) |
N60—Cu2—N80 | 113.71 (12) | C71—C81—C85 | 123.3 (4) |
N70—Cu2—N80 | 80.15 (12) | N80—C81—C85 | 121.7 (4) |
O2—Cl1—O3 | 110.1 (2) | N80—C82—C83 | 122.0 (4) |
O2—Cl1—O4 | 110.2 (2) | C82—C83—C84 | 119.0 (4) |
O3—Cl1—O4 | 109.0 (2) | C83—C84—C85 | 119.4 (4) |
O1—Cl1—O4 | 109.1 (2) | C81—C85—C84 | 118.9 (4) |
O1—Cl1—O2 | 108.8 (2) | N10—C12—H12 | 118.99 |
O1—Cl1—O3 | 109.52 (19) | C13—C12—H12 | 118.79 |
O5—Cl2—O6 | 108.0 (3) | C14—C13—H13 | 120.57 |
O7—Cl2—O8 | 110.0 (3) | C12—C13—H13 | 120.50 |
O5—Cl2—O7 | 111.3 (3) | C15—C14—H14 | 120.07 |
O5—Cl2—O8 | 111.8 (3) | C13—C14—H14 | 120.11 |
O6—Cl2—O7 | 106.7 (3) | C14—C15—H15 | 120.57 |
O6—Cl2—O8 | 109.0 (3) | C11—C15—H15 | 120.52 |
O9—Cl3—O11 | 107.2 (3) | C23—C22—H22 | 118.76 |
O9—Cl3—O12 | 111.3 (3) | N20—C22—H22 | 118.61 |
O9—Cl3—O10 | 114.6 (4) | C22—C23—H23 | 120.78 |
O11—Cl3—O12 | 108.2 (2) | C24—C23—H23 | 120.76 |
O10—Cl3—O11 | 104.8 (3) | C25—C24—H24 | 120.04 |
O10—Cl3—O12 | 110.3 (3) | C23—C24—H24 | 120.01 |
C5—O13—H13A | 109.44 | C24—C25—H25 | 120.26 |
C2—N1—C3 | 125.3 (3) | C21—C25—H25 | 120.27 |
Cu1—N2—C2 | 161.4 (3) | C33—C32—H32 | 118.68 |
Cu2—N3—C3 | 167.0 (4) | N30—C32—H32 | 118.65 |
Cu1—N10—C11 | 116.0 (3) | C34—C33—H33 | 121.03 |
C11—N10—C12 | 119.5 (4) | C32—C33—H33 | 120.92 |
Cu1—N10—C12 | 124.4 (3) | C33—C34—H34 | 119.91 |
C21—N20—C22 | 118.4 (4) | C35—C34—H34 | 119.80 |
Cu1—N20—C21 | 112.6 (3) | C34—C35—H35 | 120.41 |
Cu1—N20—C22 | 128.8 (3) | C31—C35—H35 | 120.32 |
C31—N30—C32 | 119.4 (4) | N40—C42—H42 | 119.03 |
Cu1—N30—C32 | 124.1 (4) | C43—C42—H42 | 118.94 |
Cu1—N30—C31 | 116.5 (3) | C44—C43—H43 | 120.97 |
C41—N40—C42 | 118.8 (4) | C42—C43—H43 | 120.92 |
Cu1—N40—C41 | 112.8 (3) | C43—C44—H44 | 119.76 |
Cu1—N40—C42 | 128.0 (4) | C45—C44—H44 | 119.81 |
Cu2—N50—C52 | 123.6 (3) | C41—C45—H45 | 120.82 |
C51—N50—C52 | 119.7 (3) | C44—C45—H45 | 120.65 |
Cu2—N50—C51 | 116.7 (2) | N50—C52—H52 | 118.97 |
Cu2—N60—C61 | 112.5 (2) | C53—C52—H52 | 118.85 |
C61—N60—C62 | 118.8 (3) | C54—C53—H53 | 120.84 |
Cu2—N60—C62 | 128.6 (3) | C52—C53—H53 | 120.82 |
C71—N70—C72 | 119.8 (3) | C55—C54—H54 | 120.07 |
Cu2—N70—C72 | 123.4 (3) | C53—C54—H54 | 120.15 |
Cu2—N70—C71 | 116.7 (2) | C51—C55—H55 | 120.32 |
Cu2—N80—C82 | 127.4 (3) | C54—C55—H55 | 120.40 |
C81—N80—C82 | 119.0 (3) | C63—C62—H62 | 118.68 |
Cu2—N80—C81 | 113.6 (3) | N60—C62—H62 | 118.73 |
N1—C2—N2 | 171.6 (4) | C62—C63—H63 | 120.71 |
N1—C3—N3 | 171.2 (4) | C64—C63—H63 | 120.78 |
N10—C11—C15 | 120.6 (4) | C65—C64—H64 | 120.16 |
C15—C11—C21 | 124.2 (4) | C63—C64—H64 | 120.09 |
N10—C11—C21 | 115.3 (3) | C64—C65—H65 | 120.45 |
N10—C12—C13 | 122.2 (4) | C61—C65—H65 | 120.53 |
C12—C13—C14 | 118.9 (5) | C73—C72—H72 | 119.01 |
C13—C14—C15 | 119.8 (5) | N70—C72—H72 | 118.96 |
C11—C15—C14 | 118.9 (5) | C74—C73—H73 | 120.15 |
N20—C21—C11 | 115.2 (3) | C72—C73—H73 | 120.22 |
N20—C21—C25 | 121.1 (4) | C75—C74—H74 | 120.47 |
C11—C21—C25 | 123.7 (4) | C73—C74—H74 | 120.51 |
N20—C22—C23 | 122.6 (5) | C74—C75—H75 | 120.28 |
C22—C23—C24 | 118.5 (5) | C71—C75—H75 | 120.30 |
C23—C24—C25 | 120.0 (5) | N80—C82—H82 | 118.94 |
C21—C25—C24 | 119.5 (5) | C83—C82—H82 | 119.02 |
N30—C31—C41 | 115.0 (4) | C84—C83—H83 | 120.51 |
C35—C31—C41 | 124.8 (4) | C82—C83—H83 | 120.51 |
N30—C31—C35 | 120.3 (4) | C83—C84—H84 | 120.32 |
N30—C32—C33 | 122.7 (5) | C85—C84—H84 | 120.32 |
C32—C33—C34 | 118.0 (4) | C84—C85—H85 | 120.57 |
C33—C34—C35 | 120.3 (5) | C81—C85—H85 | 120.49 |
C31—C35—C34 | 119.3 (4) | O13—C5—C4 | 122.8 (7) |
N40—C41—C45 | 122.0 (4) | C5—C4—H4A | 109.43 |
N40—C41—C31 | 114.8 (4) | C5—C4—H4B | 109.47 |
C31—C41—C45 | 123.2 (4) | C5—C4—H4C | 109.53 |
N40—C42—C43 | 122.0 (5) | H4A—C4—H4B | 109.48 |
C42—C43—C44 | 118.1 (5) | H4A—C4—H4C | 109.41 |
C43—C44—C45 | 120.4 (6) | H4B—C4—H4C | 109.50 |
C41—C45—C44 | 118.5 (5) | O13—C5—H5B | 106.64 |
N50—C51—C61 | 115.3 (3) | H5A—C5—H5B | 106.53 |
C55—C51—C61 | 124.0 (4) | C4—C5—H5A | 106.65 |
N50—C51—C55 | 120.7 (3) | C4—C5—H5B | 106.69 |
N50—C52—C53 | 122.2 (4) | O13—C5—H5A | 106.56 |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Cu(C10H8N2)2(C2N3)]ClO4 | [Cu2(C10H8N2)4(C2N3)](ClO4)3·0.5C2H6O |
Mr | 541.41 | 1139.25 |
Crystal system, space group | Orthorhombic, Pbca | Triclinic, P1 |
Temperature (K) | 293 | 193 |
a, b, c (Å) | 8.7343 (4), 17.9450 (9), 28.7230 (17) | 10.2999 (9), 14.3808 (12), 16.4311 (16) |
α, β, γ (°) | 90, 90, 90 | 74.12 (1), 83.371 (11), 80.046 (10) |
V (Å3) | 4502.0 (4) | 2299.7 (4) |
Z | 8 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.14 | 1.18 |
Crystal size (mm) | 0.60 × 0.46 × 0.22 | 0.33 × 0.24 × 0.14 |
Data collection | ||
Diffractometer | Stoe IPDS image-plate | Stoe IPDS image-plate |
Absorption correction | Numerical indexed faces | Numerical indexed faces |
Tmin, Tmax | 0.627, 0.792 | 0.790, 0.869 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 40361, 5308, 3430 | 27918, 10314, 5455 |
Rint | 0.062 | 0.072 |
(sin θ/λ)max (Å−1) | 0.662 | 0.665 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.091, 0.97 | 0.046, 0.113, 0.84 |
No. of reflections | 5308 | 10314 |
No. of parameters | 316 | 658 |
No. of restraints | 0 | 2 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.43 | 0.99, −0.67 |
Computer programs: EXPOSE in IPDS (Stoe & Cie, 1999), EXPOSE in IPDS (Stoe, 1999), CELL in IPDS, INTEGRATE in IPDS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1999), SHELXL97.
Cu1—N30 | 1.9916 (18) | N2—C2 | 1.145 (4) |
Cu1—N40 | 2.0396 (18) | N3—C3 | 1.138 (4) |
Cu1—N10 | 2.0025 (18) | N10—C11 | 1.347 (3) |
Cu1—N20 | 2.1457 (18) | N10—C12 | 1.339 (3) |
Cu1—N2 | 1.995 (3) | N20—C21 | 1.346 (3) |
Cl1—O3 | 1.4370 (19) | N20—C22 | 1.337 (3) |
Cl1—O4 | 1.426 (3) | N30—C31 | 1.349 (3) |
Cl1—O1 | 1.409 (3) | N30—C32 | 1.340 (3) |
Cl1—O2 | 1.413 (3) | N40—C41 | 1.352 (3) |
N1—C2 | 1.291 (4) | N40—C42 | 1.336 (3) |
N1—C3 | 1.323 (4) | ||
N30—Cu1—N40 | 80.52 (7) | Cu1—N20—C22 | 128.26 (16) |
N2—Cu1—N30 | 92.51 (8) | C21—N20—C22 | 118.7 (2) |
N2—Cu1—N40 | 146.67 (8) | Cu1—N30—C31 | 115.66 (14) |
N10—Cu1—N20 | 78.78 (7) | Cu1—N30—C32 | 124.66 (15) |
N10—Cu1—N30 | 177.17 (7) | C31—N30—C32 | 119.66 (19) |
N10—Cu1—N40 | 96.85 (7) | Cu1—N40—C41 | 114.17 (14) |
N2—Cu1—N10 | 90.27 (8) | Cu1—N40—C42 | 127.33 (15) |
N2—Cu1—N20 | 108.46 (8) | C41—N40—C42 | 118.40 (19) |
N20—Cu1—N40 | 104.87 (7) | N1—C2—N2 | 174.1 (3) |
N20—Cu1—N30 | 100.81 (7) | N1—C3—N3 | 174.4 (3) |
O1—Cl1—O4 | 108.22 (15) | N10—C11—C15 | 120.2 (2) |
O1—Cl1—O3 | 109.34 (14) | N10—C11—C21 | 115.35 (18) |
O3—Cl1—O4 | 107.63 (15) | N10—C12—C13 | 122.2 (2) |
O2—Cl1—O3 | 109.07 (14) | N20—C21—C11 | 115.3 (2) |
O2—Cl1—O4 | 108.06 (15) | N20—C21—C25 | 121.1 (2) |
O1—Cl1—O2 | 114.31 (16) | N20—C22—C23 | 123.0 (2) |
C2—N1—C3 | 119.4 (2) | N30—C31—C35 | 120.7 (2) |
Cu1—N2—C2 | 143.5 (2) | N30—C31—C41 | 114.88 (18) |
Cu1—N10—C11 | 117.65 (14) | N30—C32—C33 | 122.1 (2) |
Cu1—N10—C12 | 122.71 (15) | N40—C41—C31 | 114.55 (19) |
C11—N10—C12 | 119.62 (19) | N40—C41—C45 | 121.7 (2) |
Cu1—N20—C21 | 112.91 (14) | N40—C42—C43 | 122.5 (2) |
Parametera | (I) | (II)/Cu1 | (II)/Cu2 | (III) | (IV) | (V) |
Cu1-N10 | 2.0024 (17) | 1.979 (3) | 1.979 (3) | 1.998 (4) | 2.006 (3) | 1.981 (3) |
Cu1-N30 | 1.9916 (17) | 1.973 (3) | 1.974 (3) | 1.975 (4) | 1.998 (3) | 1.977 (4) |
Cu1-N20 | 2.1456 (19) | 2.063 (3) | 2.086 (3) | 2.116 (4) | 2.142 (3) | 2.112 (4) |
Cu1-N40 | 2.0395 (19) | 2.074 (4) | 2.067 (3) | 2.027 (4) | 2.043 (3) | 2.064 (3) |
Cu1-N2 | 1.995 (2) | 2.034 (3) | 2.027 (3) | 1.973 (5) | 2.015 (3) | 1.982 (4) |
N10-Cu1-N30 | 177.16 (9) | 178.41 (13) | 176.73 (12) | 175.3 (2) | 177.52 (12) | 175.12 (14) |
α1 | 146.66 (8) | 123.02 (15) | 123.88 (13) | 140.0 (2) | 145.00 (13) | 133.6 (2) |
α2 | 108.46 (8) | 114.48 (13) | 122.39 (13) | 112.4 (2) | 108.54 (12) | 115.7 (2) |
α3 | 104.87 (8) | 122.50 (13) | 113.72 (11) | 107.6 (2) | 106.45 (11) | 110.70 (13) |
τ | 50.8 | 92.3 | 88.1 | 58.8 | 54.2 | 69.2 |
(I) [Cu(bpy)2(dca)]ClO4 (this work);
(II) [Cu(bpy)2(dca)(bpy)2Cu](ClO4)3.1/2 EtOH (this work);
(III) [Cu(bpy)2(dca)]C(CN)3 (Potočňák, Dunaj-Jurčo, Mikloš &
Jäger, 2001);
(IV) [Cu(bpy)2(dca)]BF4 (Potočňák, Dunaj-Jurčo, Mikloš, Massa &
Jäger, 2001);
(V) [Cu(phen)2N(CN)2]C(CN)3 (Potočňák et al., 1996). a Numbering schemes have been standarised as for (I) |
Cu1—N2 | 2.034 (4) | O13—C5 | 1.392 (10) |
Cu1—N10 | 1.980 (4) | N1—C2 | 1.302 (5) |
Cu1—N20 | 2.063 (3) | N1—C3 | 1.291 (4) |
Cu1—N30 | 1.973 (4) | N2—C2 | 1.152 (5) |
Cu1—N40 | 2.073 (4) | N3—C3 | 1.153 (5) |
Cu2—N3 | 2.027 (3) | N10—C12 | 1.339 (6) |
Cu2—N50 | 1.979 (3) | N10—C11 | 1.344 (5) |
Cu2—N60 | 2.086 (3) | N20—C21 | 1.360 (5) |
Cu2—N70 | 1.974 (3) | N20—C22 | 1.331 (6) |
Cu2—N80 | 2.067 (3) | N30—C31 | 1.342 (6) |
Cl1—O2 | 1.424 (4) | N30—C32 | 1.337 (5) |
Cl1—O3 | 1.437 (3) | N40—C42 | 1.343 (6) |
Cl1—O1 | 1.426 (3) | N40—C41 | 1.350 (6) |
Cl1—O4 | 1.425 (4) | N50—C52 | 1.343 (4) |
Cl2—O6 | 1.433 (5) | N50—C51 | 1.341 (5) |
Cl2—O7 | 1.428 (5) | N60—C62 | 1.332 (5) |
Cl2—O5 | 1.403 (6) | N60—C61 | 1.360 (5) |
Cl2—O8 | 1.386 (5) | N70—C72 | 1.341 (5) |
Cl3—O9 | 1.368 (7) | N70—C71 | 1.350 (5) |
Cl3—O10 | 1.398 (5) | N80—C82 | 1.339 (5) |
Cl3—O12 | 1.420 (4) | N80—C81 | 1.345 (5) |
Cl3—O11 | 1.459 (4) | ||
N2—Cu1—N10 | 90.91 (15) | Cu1—N20—C22 | 128.8 (3) |
N2—Cu1—N20 | 123.00 (15) | C31—N30—C32 | 119.4 (4) |
N2—Cu1—N30 | 90.56 (15) | Cu1—N30—C32 | 124.1 (4) |
N2—Cu1—N40 | 114.49 (14) | Cu1—N30—C31 | 116.5 (3) |
N10—Cu1—N20 | 80.70 (14) | C41—N40—C42 | 118.8 (4) |
N10—Cu1—N30 | 178.42 (14) | Cu1—N40—C41 | 112.8 (3) |
N10—Cu1—N40 | 99.58 (15) | Cu1—N40—C42 | 128.0 (4) |
N20—Cu1—N30 | 98.01 (14) | Cu2—N50—C52 | 123.6 (3) |
N20—Cu1—N40 | 122.51 (14) | C51—N50—C52 | 119.7 (3) |
N30—Cu1—N40 | 80.31 (15) | Cu2—N50—C51 | 116.7 (2) |
N3—Cu2—N50 | 91.82 (14) | Cu2—N60—C61 | 112.5 (2) |
N3—Cu2—N60 | 122.38 (14) | C61—N60—C62 | 118.8 (3) |
N3—Cu2—N70 | 91.44 (14) | Cu2—N60—C62 | 128.6 (3) |
N3—Cu2—N80 | 123.90 (14) | C71—N70—C72 | 119.8 (3) |
N50—Cu2—N60 | 80.24 (12) | Cu2—N70—C72 | 123.4 (3) |
N50—Cu2—N70 | 176.73 (12) | Cu2—N70—C71 | 116.7 (2) |
N50—Cu2—N80 | 98.27 (12) | Cu2—N80—C82 | 127.4 (3) |
N60—Cu2—N70 | 97.73 (12) | C81—N80—C82 | 119.0 (3) |
N60—Cu2—N80 | 113.71 (12) | Cu2—N80—C81 | 113.6 (3) |
N70—Cu2—N80 | 80.15 (12) | N1—C2—N2 | 171.6 (4) |
O2—Cl1—O3 | 110.1 (2) | N1—C3—N3 | 171.2 (4) |
O2—Cl1—O4 | 110.2 (2) | N10—C11—C15 | 120.6 (4) |
O3—Cl1—O4 | 109.0 (2) | N10—C11—C21 | 115.3 (3) |
O1—Cl1—O4 | 109.1 (2) | N10—C12—C13 | 122.2 (4) |
O1—Cl1—O2 | 108.8 (2) | N20—C21—C11 | 115.2 (3) |
O1—Cl1—O3 | 109.52 (19) | N20—C21—C25 | 121.1 (4) |
O5—Cl2—O6 | 108.0 (3) | N20—C22—C23 | 122.6 (5) |
O7—Cl2—O8 | 110.0 (3) | N30—C31—C41 | 115.0 (4) |
O5—Cl2—O7 | 111.3 (3) | N30—C31—C35 | 120.3 (4) |
O5—Cl2—O8 | 111.8 (3) | N30—C32—C33 | 122.7 (5) |
O6—Cl2—O7 | 106.7 (3) | N40—C41—C45 | 122.0 (4) |
O6—Cl2—O8 | 109.0 (3) | N40—C41—C31 | 114.8 (4) |
O9—Cl3—O11 | 107.2 (3) | N40—C42—C43 | 122.0 (5) |
O9—Cl3—O12 | 111.3 (3) | N50—C51—C61 | 115.3 (3) |
O9—Cl3—O10 | 114.6 (4) | N50—C51—C55 | 120.7 (3) |
O11—Cl3—O12 | 108.2 (2) | N50—C52—C53 | 122.2 (4) |
O10—Cl3—O11 | 104.8 (3) | N60—C61—C51 | 115.0 (3) |
O10—Cl3—O12 | 110.3 (3) | N60—C61—C65 | 121.3 (3) |
C2—N1—C3 | 125.3 (3) | N60—C62—C63 | 122.6 (4) |
Cu1—N2—C2 | 161.4 (3) | N70—C71—C81 | 114.5 (3) |
Cu2—N3—C3 | 167.0 (4) | N70—C71—C75 | 120.1 (3) |
Cu1—N10—C11 | 116.0 (3) | N70—C72—C73 | 122.0 (4) |
C11—N10—C12 | 119.5 (4) | N80—C81—C71 | 115.0 (3) |
Cu1—N10—C12 | 124.4 (3) | N80—C81—C85 | 121.7 (4) |
C21—N20—C22 | 118.4 (4) | N80—C82—C83 | 122.0 (4) |
Cu1—N20—C21 | 112.6 (3) | O13—C5—C4 | 122.8 (7) |
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The dicyanamide (dca) anion, [N(CN)2]-, exhibits a rich variety of bonding modes. It can coordinate either in a monodentate manner or, more typically, in a bidentate, tridentate or even tetradentate manner, with participation of two or three N donor atoms. Nevertheless, monodentate coordination of dca through the amide N atom is rather improbable and, to date, no crystal structure of such a compound is known (Kohout et al., 2000). 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 contain either 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), [Ni(4-Meim)4(dca)2] (4-Meim is 4-methylimidazole; Kožíšek et al., 1996), [Cu(phen)2(dca)2] (phen is 1,10-phenanthroline; Potočňák et al., 1995) and [Cu(NITpPy)2(H2O)2(dca)2] (NITpPy is the nitronyl nitroxide radical; Dasna et al., 2001), or exhibit five-coordination and have the general formula [ML4(dca)]X, e.g. [Cu(phen)2(dca)]C(CN)3 (Potočňák et al., 1996), [Cu(bpy)2(dca)]C(CN)3 (bpy is 2,2'-bipyridine; Potočňák, Dunaj-Jurčo, Mikloš & Jäger, 2001) and [Cu(bpy)2(dca)]BF4 (Potočňák, Dunaj-Jurčo, Mikloš, Massa & Jäger, 2001), in which L4 may be one tetradentate, two bidentate or four monodentate ligands, and X is a monoanion.
As a consequence of the possible bridging function of dca, there has been an unusual interest in this ligand during recent years, especially in connection with the preparation of magnetic materials. Among them, weak ferromagnets of the general formula α-[M(dca)2], with a three-dimensional rutile-type structure, have attracted much attention because of the ability of dca to act as a molecular-based magnet precursor, with several transition metal ions octahedrally coordinated by tridentate dca ligands (Batten et al., 1998; Jensen et al., 1999; Kurmoo & Kepert, 1998; Manson et al., 1998). If the two dca ligands are tetrahedrally coordinated only through the nitrile N atoms, β-isomers of these compounds occur in the form of sheet-like structures (Jensen et al., 1999). When two coordination sites of hexacoordinated metallic centres are occupied by additional blocking ligands, the dca acts as a bidentate bridging ligand coordinated through the nitrile N atoms and the resulting compounds contain [ML2(dca)2] units (L2 is one bidentate or two monodentate ligands; Manson et al., 1999; Escuer et al., 2000; van Albada et al., 2000; Jäger et al., 2001; Dasna et al., 2001; Sun et al., 2001). All these compounds are one-dimensional and contain chains in which two metallic centres are connected by a pair of dca ligands, forming double bridges. Moreover, if the ligands L can serve as additional bridges between central atoms, the above chains are connected by these ligands, giving two-dimensional sheets (Jensen et al., 1999, 2001).
The [ML2(dca)2] units are also present in another type of structure, which was previously observed in [M(bpym)(dca)2]·H2O (M is Mn, Fe or Co, and bpym is 2,2'-bipyrimidine; Marshall et al., 2000) and consists of chains in which two hexacoordinate metallic centres are connected by only one bridging dca ligand, while the second remains monodentate. The same type of one-dimensional structure, but with five-coordinate metal atoms, has been observed in the very recently published structures of [Cu(dmpbpy)(dca)2] (dmbpy is 5,5'-dimethyl-2,2'-bipyridine; Kooijman et al., 2002), [Cu(phen)(dca)2] (Luo et al., 2002) and [Cu(bpy)(dca)2] (Potočňák et al., 2002; Vangdal et al., 2002).
As part of our study on low dimensional magnetic materials (Černák et al., 2002), and with the aim of finding possible reasons for the different shapes of the coordination polyhedra in related five-coordinate compounds, we present here the structures of two new complexes containing dca which were prepared from reaction mixtures containing the same reagents. The [Cu(bpy)2(dca)]ClO4 complex, (I), belongs to the class of compounds with dca coordinated in a relatively unusual monodentate manner. On the other hand, the [Cu(bpy)2(dca)(bpy)2Cu](ClO4)3·0.5EtOH complex, (II), contains dca coordinated in a bidentate manner, which is the most common coordination mode of dca. However, the propagation of the polymeric structure is broken at the two neighbouring central atoms and, instead of a chain structure, only binuclear units arise. As far as we are aware, complex (II) represents the first example of this type of structure containing bridging dca. Structures (I) and (II) are both ionic. \sch
The structure of (I) (Fig. 1) consists of the [Cu(bpy)2N(CN)2]+ complex cation and a ClO4- anion which does not enter the inner coordination sphere. The copper centre is five-coordinate within a distorted trigonal bipyramid, by two bpy molecules and one dca ligand coordinated through one nitrile N atom in the equatorial plane. In the trigonal bipyramid, the two out-of-plane Cu1—N10 and Cu1—N30 bonds have nearly the same values and are almost collinear (Table 1). The two in-plane distances (Cu1—N20 and Cu1—N40) are, on average, longer by 0.096 Å than the out-of-plane Cu—N distances; this is a common feature for this kind of compound. The third in-plane Cu1—N2 [N from the N(CN)2 ligand] distance is shorter than the other two but is comparable with the out-of-plane distances. This is different from the compound where the non-coordinating out-of-sphere anion X is [C(CN)3]-, (III) (Potočňák, Dunaj-Jurčo, Mikloš & Jäger, 2001), where this is the shortest Cu—N bond, but the same trends in bond distances were observed in the compound where X is [BF4]-, (IV) (Potočňák, Dunaj-Jurčo, Mikloš, Massa & Jäger, 2001), and in the related compound [Cu(phen)2N(CN)2]C(CN)3, (V), where this bond has the same length (within 1σ) as the two out-of-plane bonds (Potočňák et al., 1996) (Table 2).
The out-of-plane angles in (I) lie within the range 78.78 (7)–96.84 (7)°, similar to the values observed in (III)-(V). The bond angles in the equatorial plane of (I) differ considerably from the ideal trigonal angle of 120°, with one wide angle of 146.66 (8)° (α1 = N2—Cu1—N40) and two narrow angles of 108.46 (8)° (α2 = N2—Cu1—N20) and 104.87 (8)° (α3 = N20—Cu1—N40). Corresponding values for (III)-(V) are given in Table 2. Thus the angle α3, which is opposite the Cu1—N2 bond, is narrower than the ideal angle of 120° by 15.13°, and there is a difference of 38.20° between α1 and α2.
According to the criteria of Harrison & Hathaway (1980), the coordination polyhedron around the Cu can be best described as distorted trigonal-bipyramidal with a distortion toward square-pyramidal, similar to (III) and (IV). On the other hand, according to the values of the angles α1, α2 and α3, the coordination polyhedron of (V) can be best described as trigonal-bipyramidal with near C2v symmetry. The difference in the shape of the coordination polyhedra is 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 tetragonal pyramid (Addison et al., 1984)]. This difference in the shape of the coordination polyhedron of (I), (III) and (IV) on one hand and of (V) on the other can be explained by the lower rigidity of the bpy ligand compared with the phen ligand. While the two pyridine rings in a phen molecule are connected by a phenyl ring and thus the molecule as a whole is planar, the two pyridine rings in a bpy molecule can rotate around their common C—C single bond.
The angles between the two pyridine rings are 2.54 (7) and 8.35 (7)° for the first (N10—N20) and the second (N30—N40) bpy molecule in (I), respectively. Consequently, the first bpy molecule is almost planar [the largest deviation of atoms from the mean plane is 0.036 (3) Å for atom C24], while the planarity of the second one is less [the largest deviation from the mean plane is 0.112 (3) Å for C43]. The sum of the bond angles in the equatorial plane of (I) (359.99°) indicates coplanarity of atom Cu1 with the three equatorial atoms [it is displaced from the N2/N20/N40 plane by 0.0092 (3) Å towards N10].
The dca anion in (I) is ligated in an unusual monodentate manner. Inspection of the bond lengths (Table 1) shows that none of the three possible canonical formulae (Golub et al., 1986) adequately describes the bonding mode of the dicyanamide. Both the nitrile N≡C and amide N═C distances have values close to those of N≡C (1.15 Å) and N═C bonds (1.27 Å), respectively. The N(amide)-C≡N(nitrile) angles are almost linear, while the C2—N1—C3 angle adopts a value of 119.4 (2)°, close to the ideal value of 120°. The dca ligand is planar, the largest deviation from the mean plane being 0.003 (2) Å for atom C2, and its bonding mode to atom Cu1 (C2≡N2—Cu1) can be considered as angular.
The asymmetric unit of (II) (Fig. 2) contains one binuclear [Cu(bpy)2N(CN)2(bpy)2Cu]3+ complex cation, the charge of which is balanced by three uncoordinated perchlorate anions, and half a molecule of ethanol. Formally, we can consider the cation as two [Cu(bpy)2N(CN)2]+ complex cations, in which both Cu centres are five-coordinate within a slightly distorted trigonal bipyramid by two bpy molecules and one bridging dca ligand, which is coordinated equatorially to the two Cu centres via different nitrile N atoms. Inspection of Tables 2 and 3 indicates that, from this point of view, there is no major difference between the complex cation in (I) and the `two cations' in (II).
The two out-of-plane bonds around the Cu1 and Cu2 centres have the same length to within 2σ and are almost collinear. The two in-plane Cu—Nphen distances are of almost the same value and are longer on average than the out-of-plane Cu—N distances by 0.093 Å for Cu1 and 0.100 Å for Cu2 Is this change OK?. The in-plane Cu—N(dca) distances are shorter than the other two, but, unlike the corresponding bond in (I), they are somewhat longer than the out-of-plane distances.
Although the corresponding bond distances around Cu1 and Cu2 in (II) are very similar and all equatorial angles are close to the ideal value of 120°, the equatorial angles around Cu1 and Cu2 are nevertheless quite different. The α1 angles are almost equal, but the α2 and α3 angles differ. Thus, there is a difference [of 8.54° for Cu1 and 1.49° for Cu2 Is this change OK?] between α1 and α2, and both polyhedra can, according to the criteria of Harrison & Hathaway (1980), be best described as trigonal-bipyramidal with near C2v symmetry. The high values of the τ parameter for the polyhedra around Cu1 and Cu2 confirm that the distortions of the polyhedra from the ideal trigonal-bipyramidal shape are small.
Although, in comparison with (I), the dicyanamide is differently ligated in (II), there are no significant differences in ligand molecular geometry in the two structures. Nevertheless, due to its bridging function in (II), the ligand is more symmetrical in this compound, and this manifests itself in almost identical values for the corresponding bond distances (Table 3). Moreover, probably due to internal repulsions within the dinuclear cation, both the C3—N1—C2 and the two C≡N(nitrile)-Cu angles adopt higher values in (II), increasing the distance between the two Cu centres in the cation and thus decreasing the intra-cation repulsion.
The O6···C11 distance in (II) is shorter than the sum of the corresponding van der Waals radii, and the O6···C11i—C15i, O6···C11i—C21i and O6···C11i—N10i [symmetry code: (i) 1 - x, 1 - y, -z] angles have values of 90.21 (1), 85.31 (1) and 93.96 (1)°, respectively, which are all close to 90°. The O6···C11 contact is therefore almost perpendicular to the plane of the bipyridine molecule and may be considered as an intermolecular interaction between a free electron pair on the O atom and the delocalized π-electron system of the bipyridine molecule.
Comments from the coeditor: Please confirm the data collection temperatures and ellipsoid probability levels for (I) and (II). Looking at your second structure, there is a close intermolecular contact O6···C11 of 2.86 Å. Such short contacts sometimes indicate hydrogen bonds but in a situation where the atom type (usually assigned as C) has been incorrectly assigned and is in fact N or O. I do not think that this is likely here, but it is an interestingly short contact and I wonder if you would be able to check whether this is a common phenomenon and include a sentence of two of description and analysis.