Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103028385/fa1041sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103028385/fa1041Isup2.hkl |
CCDC reference: 233105
The dipm ligand was synthesized using the method of Yao et al. (2000). Metal salts and solvents were commercially available and used without further purification. The title compound was synthesized by mixing equimolar amounts of copper(II) trifluoromethylsulfonate, sodium dicyanamide and di-2-pyrimidylamine in an ethanol/water (Ratio?) mixture. After standing in air at room temperature for about two weeks, blue-green block-shaped crystals of (I) were formed, which were suitable for X-ray structure determination. IR analysis: the characteristic trifluoromethanesulfonate vibrations are observed at 1255, 1246, 1223, 1154 and 1026 cm-1 (van Albada et al., 1997, 1998). The characteristic IR vibrations for the dicyanamide anion are found in the 2400–2100 cm-1 region (Kohout et al., 2000). The νs + νas(C—N) is observed as two weak-to-medium bands at 2361 and 2294 cm-1, and the ν(C≡N) is observed as two medium-to-strong bands at 2238 and 2167 cm-1. These vibrations occur in the ranges found for other polymeric copper(II) dicyanamide compounds (Kohout et al., 2000; Riggio et al., 2001; van Albada, Quiroz-Castro et al., 2000; van Albada, Smeets et al., 2000).
An absorption correction based on multiple measurements of symmetry-related reflections had little influence on Rint, R1 and the residual density. The correction was therefore not considered necessary and was not applied to the reflection data. The amine H atoms were located in a difference Fourier map and their coordinates were refined. The other H atoms were placed in calculated positions, riding on their carrier atoms. Uiso(H) values were set to 1.5 or 1.2 times Ueq(parent atom) for amine H atoms and other H atoms, respectively. The unit cell contains two symmetry-related cavities located on the crystallographic inversion centres at (1/2,0,1/2) and (1/2,1/2,0), filled with disordered solvent, probably ethanol. The volume of each cavity is 81 Å3. Attempts to model an ethanol molecule into the solvent density did not result in an acceptable model. There are no groups lining the cavity which could accept a hydrogen bond from the solvent. The contribution of the disordered solvent to the scattering factors has been taken into account with PLATON/SQUEEZE (Spek, 2003; van der Sluis & Spek, 1990). A total of 24 e was found in each cavity, corresponding to approximately one ethanol molecule per cavity. Where relevant, the crystal data reported earlier in this paper are given without the contribution of the disordered solvent. Taking into account the presence of one ethanol molecule per cavity, the following values are obtained: C19H14CuF3N13O3S·0.5C2H6O, Mr = 648.05, µ = 1.065 mm-1, F(000) = 1312 and Dx = 1.708 Mg m-3.
In recent years, the anionic dicyanamide ligand has attracted much interest, in the form of MII(dca)2 [where M is Ni, Co or Cu, and dca N(CN)2], as a new class of molecule-based magnetic materials (Batten et al., 1998; Batten & Murray, 2001; Manson et al., 1999). In the field of crystal engineering, the number of X-ray crystal structures of compounds with the dca anion showing one-, two- and three-dimensional networks has increased enormously in the last few years (e.g. Kohout et al., 2000; Vangdal et al., 2002; Mohamadou et al., 2003; Kooijman et al., 2002; Shi et al., 2003).
Dicyanamide itself is an interesting anionic bridging ligand and can act as a monodentate, bidentate or even tridentate ligand (Mroziński et al., 1997; Escuer et al., 2000). Various coordination modes of the dicyanamide ligand and the metal can occur, such as monodentate bonding via the nitrile atom, coordination via the amide atom (Marshall et al., 2002; Mohamadou et al., 2003; Shi et al., 2003; Vangdal et al., 2002), and even µ4 and µ5 coordination, where nitrile atoms bridge two metal atoms (Chow & Britton, 1975; Shi et al., 2002). However, in most cases monodentate or bidentate coordination via the nitrile N atom is found.
In the field of supramolecular chemistry, not only are direct metal-ligand bonds of interest, but hydrogen bonding is also of great importance (Beatty, 2001; Rodríguez-Martin et al., 2002; Nedelcu et al., 2003; Kutasi et al., 2002; Riggio et al., 2001). One ligand with interesting hydrogen-bonding properties is the recently developed di-2-pyrimidylamine (abbreviated as dipm). The dipm molecule can both donate and accept hydrogen bonds, and has a more or less linear donor-acceptor array of type ADA. This type of array is capable of forming so-called Watson-Crick-type hydrogen bonds (van Albada et al., 2002), as was also shown in the literature with the first generation ligand 2-aminopyrimidine (van Albada, Quiroz-Castro et al., 2000; van Albada, Smeets et al., 2000).
To date, only one X-ray crystal structure determination of a dipm-containing complex has been published, [Cu(dipm)(CO3)(H2O)]·2H2O (van Albada et al., 2002). In this paper, we present the crystal structure of a new complex of copper with the dipm molecule as ligand, which has the formulation [Cu(dca)(dipm)2(tms)], (I), where tms is the trifluoromethylsulfonate anion. An atomic displacement ellipsoid plot of this complex is given in Fig. 1, together with the atomic labelling scheme. Selected geometric parameters are given in Table 1. \sch
The geometry around the CuII ion in (I) is distorted octahedral, with the basal plane formed by two pyrimidinyl N atoms of one of the coordinating dipm molecules (N111 and N121), one pyrimidinyl N atom of the second coordinating dipm molecule (N211) and a nitrile N atom (N2) of the dca ligand. The Cu—N distances are in the range 1.972 (2)–2.021 (2) Å. The trans-basal angles are 176.41 (8) (N111—Cu1—N211) and 165.33 (9)° (N2—Cu1—N121). The apical positions are occupied by a pyrimidinyl N atom (N221) of the second dipm ligand, at a distance of 2.208 (2) Å, and by an O atom (O1) of the trifluoromethylsulfonate anion, at a semi-coordination distance of 2.747 (2) Å.
The dipm molecules in (I) show a significant difference in conformation. The angle between the least-squares planes through the pyrimidine rings is 33.71 (12)° in the ligand containing atom N11 and 11.73 (13)° in the molecule containing atom N21. In the dipm-copper-carbonate complex reported previously, the dipm molecule is virtually planar, with a ring-ring angle of 1.80 (11)°.
The lattice of (I) is stabilized by two crystallographically independent hydrogen-bonding systems, both of the so-called Watson-Crick type (Fig. 2). The systems are formed by donation of a hydrogen bond by the amine N atom of a dipm molecule (either N11 or N21) to a non-coordinating pyrimidinyl N atom of an inversion-related dipm molecule (N113 or N213, respectively). Due to the crystallographic inversion symmetry, a hydrogen-bonded ring is formed with unitary graph-set R22(8) (Bernstein et al., 1995). The hydrogen-bonded system involving atom N11 is formed around the inversion centre at (1/2,1/2,1/2), while that involving atom N21 is formed around the centre at (0,1/2,0). Geometric details are given in Table 2.
The hydrogen-bonded systems link the copper complexes into an infinite one-dimensional chain running in the [101] direction. Within each chain, the copper complexes are linked alternately by hydrogen-bonded systems involving atoms N11 or N21 (Fig. 2). This arrangement of hydrogen-bonded dipm molecules may facilitate the formation of two C—H···N contacts adjacent to the N—H···N hydrogen bonds, resulting in the formation of a quadruply hydrogen-bonded array of type DADA (a review of quadruply hydrogen-bonded systems is given by Sijbesma & Meijer, 2003). Due to the deviations from planarity of the dipm molecules, the C—H···N contacts are somewhat long, especially that involving C114—H114 (Table 2). However, these contacts may still play a role in the stabilization of the hydrogen-bonded network of (I). The dipm-copper-carbonate complex reported previously displayed a similar hydrogen-bonded structure (van Albada et al., 2002).
The non-coordinating nitrile moiety of the dca anion in (I) does not accept any hydrogen bonds. There is a close contact [2.947 (4) Å, i.e. approximately 0.2 Å less than the sum of the Van der Waals radii] between atom N3 of the dca anion and atom C122(1 - x, y - 1/2, 1/2 - z) of a dipm molecule. Atom N3 also displays a short contact to atom C112 of the same dipm molecule, at 3.086 (3) Å. Contacts of the type C≡ N···C(sp2)X3, where X = C, N, O, P, S or halogen, are not unsual. The July 2003 update of the Cambridge Structural Database (Allen, 2002) contains approximately 150 examples with N···C distances in the range 2.8–3.2 Å, 23 of which display contact distances shorter than the value observed in the crystal structure of (I).
The electron paramagnetic resonance (EPR) spectrum for (I), measured as a polycrystalline powder at room temperature and at 77 K, shows an axial S = 1/2 signal, with g = 2.06, a value typical for CuII and in agreement with a dx2-y2 ground state.
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
[Cu(CF3SO3)(C2N3)(C8H7N5)2]·0.5C2H6O | F(000) = 1260 |
Mr = 625.05 | Quoted _cell_measurement_* data items refer to the initial cell determination. The cell parameters as reported in _cell_* are based on the complete data set. |
Monoclinic, P21/c | Dx = 1.648 Mg m−3 |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 9.972 (2) Å | Cell parameters from 304 reflections |
b = 13.751 (2) Å | θ = 2.0–25.0° |
c = 18.516 (4) Å | µ = 1.02 mm−1 |
β = 97.047 (8)° | T = 150 K |
V = 2519.8 (8) Å3 | Block, blue-green |
Z = 4 | 0.2 × 0.1 × 0.1 mm |
Nonius Kappa CCD area-detector diffractometer | 3766 reflections with I > 2σ(I) |
Radiation source: Rotating anode | Rint = 0.119 |
Graphite monochromator | θmax = 27.4°, θmin = 1.9° |
Detector resolution: 18.4 pixels mm-1 | h = −12→12 |
φ scans and ω scans with κ offset | k = −17→17 |
56102 measured reflections | l = −23→23 |
5712 independent reflections |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0468P)2] where P = (Fo2 + 2Fc2)/3 |
5712 reflections | (Δ/σ)max = 0.001 |
367 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
[Cu(CF3SO3)(C2N3)(C8H7N5)2]·0.5C2H6O | V = 2519.8 (8) Å3 |
Mr = 625.05 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.972 (2) Å | µ = 1.02 mm−1 |
b = 13.751 (2) Å | T = 150 K |
c = 18.516 (4) Å | 0.2 × 0.1 × 0.1 mm |
β = 97.047 (8)° |
Nonius Kappa CCD area-detector diffractometer | 3766 reflections with I > 2σ(I) |
56102 measured reflections | Rint = 0.119 |
5712 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.36 e Å−3 |
5712 reflections | Δρmin = −0.55 e Å−3 |
367 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All s.u.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 on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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 | ||
Cu1 | 0.24153 (3) | 0.50090 (2) | 0.25102 (1) | 0.0184 (1) | |
S1 | 0.15554 (9) | 0.25256 (6) | 0.35456 (4) | 0.0410 (3) | |
F1 | 0.1753 (2) | 0.17557 (14) | 0.48504 (10) | 0.0562 (7) | |
F2 | 0.36370 (19) | 0.22129 (16) | 0.45168 (11) | 0.0663 (9) | |
F3 | 0.2260 (2) | 0.32628 (14) | 0.48366 (9) | 0.0538 (7) | |
O1 | 0.2312 (2) | 0.32820 (14) | 0.32466 (10) | 0.0386 (7) | |
O2 | 0.0182 (2) | 0.2769 (2) | 0.36276 (15) | 0.0836 (13) | |
O3 | 0.1737 (3) | 0.15685 (18) | 0.32620 (14) | 0.0829 (13) | |
N1 | 0.3835 (3) | 0.25713 (17) | 0.13134 (14) | 0.0363 (9) | |
N2 | 0.3122 (2) | 0.41020 (17) | 0.18235 (12) | 0.0260 (8) | |
N3 | 0.6131 (3) | 0.22466 (16) | 0.09952 (13) | 0.0330 (9) | |
N11 | 0.3461 (2) | 0.50682 (15) | 0.42174 (11) | 0.0171 (7) | |
N21 | 0.1101 (2) | 0.55680 (16) | 0.08638 (12) | 0.0218 (7) | |
N111 | 0.4262 (2) | 0.51345 (14) | 0.30691 (11) | 0.0173 (7) | |
N113 | 0.5737 (2) | 0.50088 (14) | 0.41791 (11) | 0.0187 (7) | |
N121 | 0.1662 (2) | 0.56215 (14) | 0.33589 (11) | 0.0178 (7) | |
N123 | 0.1623 (2) | 0.57220 (16) | 0.46456 (11) | 0.0231 (7) | |
N211 | 0.0578 (2) | 0.47928 (14) | 0.19397 (11) | 0.0183 (7) | |
N213 | −0.0622 (2) | 0.44870 (16) | 0.07676 (11) | 0.0225 (7) | |
N221 | 0.2523 (2) | 0.63107 (15) | 0.18212 (11) | 0.0208 (7) | |
N223 | 0.2380 (2) | 0.68547 (16) | 0.05900 (12) | 0.0252 (8) | |
C1 | 0.3509 (3) | 0.3393 (2) | 0.15861 (14) | 0.0256 (10) | |
C2 | 0.5080 (3) | 0.24374 (18) | 0.11442 (14) | 0.0239 (9) | |
C3 | 0.2345 (3) | 0.2428 (2) | 0.44805 (17) | 0.0336 (11) | |
C112 | 0.4503 (3) | 0.50744 (17) | 0.37992 (13) | 0.0162 (8) | |
C114 | 0.6788 (3) | 0.50861 (18) | 0.37973 (14) | 0.0228 (9) | |
C115 | 0.6640 (3) | 0.52306 (19) | 0.30534 (14) | 0.0245 (9) | |
C116 | 0.5348 (3) | 0.52276 (18) | 0.27052 (14) | 0.0211 (8) | |
C122 | 0.2201 (3) | 0.54849 (17) | 0.40552 (14) | 0.0182 (8) | |
C124 | 0.0482 (3) | 0.6226 (2) | 0.45290 (15) | 0.0287 (9) | |
C125 | −0.0101 (3) | 0.64883 (19) | 0.38402 (15) | 0.0272 (10) | |
C126 | 0.0514 (3) | 0.61543 (18) | 0.32654 (15) | 0.0222 (9) | |
C212 | 0.0344 (3) | 0.49427 (18) | 0.12168 (14) | 0.0182 (8) | |
C214 | −0.1451 (3) | 0.3900 (2) | 0.10746 (14) | 0.0268 (9) | |
C215 | −0.1360 (3) | 0.3762 (2) | 0.18219 (15) | 0.0270 (9) | |
C216 | −0.0309 (3) | 0.42104 (18) | 0.22321 (14) | 0.0227 (9) | |
C222 | 0.2038 (3) | 0.62727 (18) | 0.11168 (14) | 0.0209 (8) | |
C224 | 0.3304 (3) | 0.75317 (19) | 0.07920 (15) | 0.0279 (10) | |
C225 | 0.3864 (3) | 0.76385 (18) | 0.15084 (14) | 0.0256 (9) | |
C226 | 0.3431 (3) | 0.70199 (19) | 0.20041 (14) | 0.0246 (9) | |
H3 | 0.370 (3) | 0.5074 (17) | 0.4693 (14) | 0.0260* | |
H5 | 0.090 (3) | 0.555 (2) | 0.0395 (15) | 0.0330* | |
H114 | 0.76760 | 0.50390 | 0.40490 | 0.0270* | |
H115 | 0.73970 | 0.53270 | 0.27960 | 0.0290* | |
H116 | 0.52110 | 0.52930 | 0.21910 | 0.0250* | |
H124 | 0.00490 | 0.64150 | 0.49360 | 0.0340* | |
H125 | −0.08910 | 0.68810 | 0.37690 | 0.0330* | |
H126 | 0.01200 | 0.63020 | 0.27850 | 0.0270* | |
H214 | −0.21330 | 0.35620 | 0.07700 | 0.0320* | |
H215 | −0.19950 | 0.33750 | 0.20360 | 0.0320* | |
H216 | −0.01950 | 0.41100 | 0.27440 | 0.0270* | |
H224 | 0.35870 | 0.79530 | 0.04340 | 0.0330* | |
H225 | 0.45240 | 0.81230 | 0.16480 | 0.0310* | |
H226 | 0.37850 | 0.70920 | 0.25010 | 0.0290* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0180 (2) | 0.0234 (2) | 0.0129 (2) | 0.0009 (1) | −0.0021 (1) | −0.0014 (1) |
S1 | 0.0414 (5) | 0.0448 (5) | 0.0331 (5) | −0.0157 (4) | −0.0100 (4) | 0.0112 (4) |
F1 | 0.0609 (14) | 0.0579 (12) | 0.0464 (12) | −0.0185 (10) | −0.0071 (10) | 0.0251 (10) |
F2 | 0.0313 (12) | 0.1089 (18) | 0.0568 (14) | 0.0190 (11) | −0.0024 (10) | 0.0155 (12) |
F3 | 0.0728 (15) | 0.0511 (12) | 0.0391 (11) | −0.0087 (11) | 0.0136 (10) | −0.0051 (10) |
O1 | 0.0423 (13) | 0.0414 (12) | 0.0315 (12) | −0.0127 (10) | 0.0024 (10) | 0.0045 (10) |
O2 | 0.0257 (14) | 0.138 (3) | 0.083 (2) | −0.0064 (15) | −0.0095 (13) | 0.0698 (19) |
O3 | 0.147 (3) | 0.0470 (16) | 0.0524 (17) | −0.0349 (17) | 0.0033 (17) | −0.0130 (13) |
N1 | 0.0369 (16) | 0.0254 (14) | 0.0477 (17) | −0.0049 (12) | 0.0098 (13) | −0.0149 (12) |
N2 | 0.0253 (14) | 0.0300 (14) | 0.0222 (13) | 0.0004 (11) | 0.0006 (10) | −0.0066 (11) |
N3 | 0.0386 (17) | 0.0266 (14) | 0.0332 (15) | 0.0068 (12) | 0.0023 (13) | 0.0001 (11) |
N11 | 0.0161 (11) | 0.0242 (12) | 0.0104 (11) | 0.0018 (10) | −0.0010 (9) | 0.0009 (10) |
N21 | 0.0249 (13) | 0.0293 (13) | 0.0098 (11) | −0.0080 (10) | −0.0034 (10) | 0.0018 (10) |
N111 | 0.0181 (12) | 0.0205 (12) | 0.0130 (11) | 0.0007 (9) | 0.0007 (9) | −0.0007 (9) |
N113 | 0.0169 (11) | 0.0220 (12) | 0.0163 (11) | −0.0003 (10) | −0.0013 (9) | −0.0010 (9) |
N121 | 0.0180 (12) | 0.0165 (11) | 0.0178 (12) | −0.0006 (9) | −0.0018 (9) | 0.0004 (9) |
N123 | 0.0185 (13) | 0.0327 (13) | 0.0181 (12) | 0.0005 (10) | 0.0020 (10) | −0.0023 (10) |
N211 | 0.0196 (12) | 0.0234 (12) | 0.0114 (11) | 0.0002 (9) | −0.0003 (9) | 0.0004 (9) |
N213 | 0.0228 (13) | 0.0278 (13) | 0.0159 (12) | −0.0058 (10) | −0.0018 (10) | −0.0004 (10) |
N221 | 0.0242 (13) | 0.0243 (12) | 0.0128 (12) | −0.0028 (10) | −0.0022 (9) | −0.0002 (9) |
N223 | 0.0271 (14) | 0.0278 (13) | 0.0195 (12) | −0.0070 (11) | −0.0014 (10) | 0.0006 (10) |
C1 | 0.0215 (16) | 0.0317 (18) | 0.0225 (16) | −0.0063 (13) | −0.0011 (12) | −0.0009 (13) |
C2 | 0.0362 (19) | 0.0167 (15) | 0.0178 (15) | −0.0001 (13) | −0.0004 (13) | 0.0000 (11) |
C3 | 0.0284 (18) | 0.0366 (19) | 0.0352 (19) | −0.0027 (14) | 0.0016 (14) | 0.0067 (15) |
C112 | 0.0193 (14) | 0.0149 (13) | 0.0138 (13) | −0.0022 (11) | 0.0001 (10) | −0.0004 (11) |
C114 | 0.0171 (14) | 0.0259 (16) | 0.0245 (15) | 0.0003 (12) | −0.0014 (11) | −0.0004 (12) |
C115 | 0.0169 (15) | 0.0321 (17) | 0.0247 (16) | −0.0007 (12) | 0.0031 (12) | −0.0011 (12) |
C116 | 0.0212 (15) | 0.0265 (15) | 0.0154 (14) | 0.0001 (12) | 0.0018 (12) | 0.0018 (11) |
C122 | 0.0185 (15) | 0.0153 (14) | 0.0198 (15) | −0.0027 (11) | −0.0016 (12) | −0.0001 (11) |
C124 | 0.0248 (16) | 0.0369 (17) | 0.0253 (16) | 0.0042 (14) | 0.0069 (13) | −0.0037 (13) |
C125 | 0.0211 (16) | 0.0307 (17) | 0.0290 (17) | 0.0049 (12) | −0.0003 (13) | −0.0010 (13) |
C126 | 0.0213 (15) | 0.0238 (15) | 0.0197 (15) | 0.0017 (12) | −0.0044 (12) | 0.0005 (11) |
C212 | 0.0179 (13) | 0.0191 (14) | 0.0172 (14) | 0.0025 (12) | 0.0005 (11) | −0.0006 (11) |
C214 | 0.0237 (16) | 0.0303 (16) | 0.0255 (17) | −0.0057 (13) | −0.0007 (13) | −0.0018 (13) |
C215 | 0.0247 (16) | 0.0331 (17) | 0.0238 (16) | −0.0080 (13) | 0.0056 (12) | 0.0013 (13) |
C216 | 0.0280 (16) | 0.0266 (15) | 0.0136 (14) | 0.0010 (12) | 0.0030 (12) | 0.0008 (11) |
C222 | 0.0212 (15) | 0.0234 (15) | 0.0171 (14) | −0.0004 (12) | −0.0018 (11) | −0.0013 (12) |
C224 | 0.0360 (18) | 0.0242 (16) | 0.0231 (16) | −0.0072 (13) | 0.0023 (13) | 0.0034 (12) |
C225 | 0.0325 (17) | 0.0196 (15) | 0.0231 (16) | −0.0045 (12) | −0.0032 (13) | −0.0016 (12) |
C226 | 0.0316 (17) | 0.0225 (15) | 0.0173 (15) | −0.0017 (12) | −0.0064 (12) | −0.0035 (12) |
Cu1—O1 | 2.747 (2) | N123—C124 | 1.327 (4) |
Cu1—N2 | 1.972 (2) | N211—C212 | 1.346 (3) |
Cu1—N111 | 2.006 (2) | N211—C216 | 1.354 (3) |
Cu1—N121 | 2.008 (2) | N213—C212 | 1.348 (3) |
Cu1—N211 | 2.021 (2) | N213—C214 | 1.332 (4) |
Cu1—N221 | 2.208 (2) | N221—C226 | 1.346 (3) |
S1—O1 | 1.435 (2) | N221—C222 | 1.335 (3) |
S1—O2 | 1.436 (2) | N223—C222 | 1.338 (3) |
S1—O3 | 1.437 (3) | N223—C224 | 1.331 (4) |
S1—C3 | 1.817 (3) | C114—C115 | 1.382 (4) |
F1—C3 | 1.331 (4) | C115—C116 | 1.368 (4) |
F2—C3 | 1.316 (4) | C124—C125 | 1.383 (4) |
F3—C3 | 1.332 (3) | C125—C126 | 1.371 (4) |
N1—C1 | 1.295 (4) | C214—C215 | 1.389 (4) |
N1—C2 | 1.330 (4) | C114—H114 | 0.9509 |
N2—C1 | 1.155 (4) | C215—C216 | 1.364 (4) |
N3—C2 | 1.146 (4) | C115—H115 | 0.9502 |
N11—C112 | 1.370 (3) | C116—H116 | 0.9494 |
N11—C122 | 1.380 (4) | C124—H124 | 0.9496 |
N21—C212 | 1.363 (3) | C224—C225 | 1.383 (4) |
N21—C222 | 1.387 (3) | C225—C226 | 1.360 (4) |
N111—C112 | 1.346 (3) | C125—H125 | 0.9508 |
N111—C116 | 1.350 (4) | C126—H126 | 0.9493 |
N11—H3 | 0.88 (3) | C214—H214 | 0.9500 |
N113—C114 | 1.338 (4) | C215—H215 | 0.9502 |
N113—C112 | 1.343 (4) | C216—H216 | 0.9508 |
N121—C122 | 1.348 (3) | C224—H224 | 0.9490 |
N121—C126 | 1.352 (3) | C225—H225 | 0.9498 |
N21—H5 | 0.87 (3) | C226—H226 | 0.9493 |
N123—C122 | 1.337 (3) | ||
Cu1···N11 | 3.206 (2) | N211···C126 | 3.094 (3) |
Cu1···N21 | 3.259 (2) | N213···N21x | 3.001 (3) |
S1···C216 | 3.692 (3) | N113···H3viii | 2.10 (3) |
S1···H216 | 3.0595 | N121···H216 | 2.9203 |
F1···O2 | 2.941 (3) | N221···C212 | 2.986 (3) |
F1···O3 | 2.950 (3) | N221···C116 | 3.421 (4) |
F2···O1 | 2.946 (3) | N221···N111 | 3.159 (3) |
F2···O3 | 2.948 (3) | N221···N121 | 3.216 (3) |
F2···C224i | 3.202 (4) | N221···N2 | 3.095 (3) |
F2···C225i | 3.364 (4) | N221···N211 | 2.876 (3) |
F2···C2ii | 3.212 (3) | N123···H224xi | 2.9300 |
F3···O1 | 2.951 (3) | N223···C214x | 3.276 (3) |
F3···O2 | 2.937 (3) | N123···H114viii | 2.6479 |
F3···N11 | 3.041 (3) | N211···H126 | 2.6722 |
F3···C124iii | 3.184 (4) | N213···H5x | 2.14 (3) |
F3···N1ii | 3.195 (3) | N223···H214x | 2.5648 |
F3···H124iii | 2.4317 | C2···C112i | 3.276 (3) |
O1···F2 | 2.946 (3) | C2···F2v | 3.212 (3) |
O1···F3 | 2.951 (3) | C2···H226i | 2.6651 |
O1···N2 | 3.064 (3) | C112···N3ix | 3.086 (3) |
O1···N11 | 3.174 (3) | C112···C2ix | 3.276 (3) |
O1···N111 | 3.246 (3) | C114···C224i | 3.598 (4) |
O1···C112 | 3.369 (3) | C114···C225i | 3.461 (4) |
O1···C122 | 3.387 (3) | C114···N123viii | 3.307 (3) |
O1···C216 | 3.284 (3) | C116···C226 | 3.287 (4) |
O2···C216 | 3.246 (4) | C122···N3ix | 2.947 (4) |
O2···F1 | 2.941 (3) | C124···F3iii | 3.184 (4) |
O2···F3 | 2.937 (3) | C126···C216 | 3.331 (4) |
O2···C222iv | 3.101 (4) | C112···H225i | 3.0041 |
O3···F2 | 2.948 (3) | C212···O3xii | 3.275 (4) |
O3···F1 | 2.950 (3) | C114···H225i | 3.0682 |
O3···C212iv | 3.275 (4) | C214···N3xiii | 3.304 (4) |
O1···H216 | 2.8003 | C114···H3viii | 2.90 (3) |
O2···H216 | 2.4632 | C214···N223x | 3.276 (3) |
O3···H115i | 2.8130 | C216···S1 | 3.692 (3) |
O3···H126iv | 2.5379 | C116···H226 | 3.0001 |
N1···F3v | 3.195 (3) | C216···C126 | 3.331 (4) |
N2···O1 | 3.064 (3) | C216···O2 | 3.246 (4) |
N2···N21 | 3.226 (3) | C222···O2xii | 3.101 (4) |
N2···N111 | 2.826 (3) | C224···N3vii | 3.438 (4) |
N2···N211 | 2.742 (3) | C224···F2ix | 3.202 (4) |
N2···N221 | 3.095 (3) | C224···C114ix | 3.598 (4) |
N2···C116 | 3.017 (4) | C225···F2ix | 3.364 (4) |
N2···C212 | 3.084 (4) | C225···C114ix | 3.461 (4) |
N2···C222 | 3.383 (3) | C125···H114xiii | 3.0407 |
N3···N11i | 3.055 (3) | C126···H216 | 3.0277 |
N3···C214vi | 3.304 (4) | C226···C116 | 3.287 (4) |
N3···C112i | 3.086 (3) | C214···H5x | 2.94 (3) |
N3···C122i | 2.947 (4) | C216···H115xiii | 3.0441 |
N3···N121i | 3.259 (3) | C216···H126 | 3.0653 |
N3···C224vii | 3.438 (4) | C226···H116 | 2.9595 |
N11···N113viii | 2.981 (3) | C226···H215xii | 3.0506 |
N11···Cu1 | 3.206 (2) | H3···N113viii | 2.10 (3) |
N11···F3 | 3.041 (3) | H3···C114viii | 2.90 (3) |
N11···O1 | 3.174 (3) | H5···N213x | 2.14 (3) |
N11···N3ix | 3.055 (3) | H5···C214x | 2.94 (3) |
N21···N213x | 3.001 (3) | H114···C125vi | 3.0407 |
N21···N2 | 3.226 (3) | H114···N123viii | 2.6479 |
N21···Cu1 | 3.259 (2) | H115···C216vi | 3.0441 |
N2···H116 | 2.6715 | H115···O3ix | 2.8130 |
N3···H226i | 2.7835 | H116···N2 | 2.6715 |
N3···H224vii | 2.7092 | H116···C226 | 2.9595 |
N3···H214vi | 2.5729 | H124···F3iii | 2.4317 |
N111···O1 | 3.246 (3) | H126···N211 | 2.6722 |
N111···N2 | 2.826 (3) | H126···C216 | 3.0653 |
N111···N121 | 2.793 (3) | H126···O3xii | 2.5379 |
N111···N221 | 3.159 (3) | H214···N3xiii | 2.5729 |
N111···C122 | 2.951 (4) | H214···N223x | 2.5648 |
N111···C226 | 3.301 (3) | H215···C226iv | 3.0506 |
N113···N11viii | 2.981 (3) | H216···S1 | 3.0595 |
N121···C216 | 3.313 (3) | H216···O1 | 2.8003 |
N121···N3ix | 3.259 (3) | H216···O2 | 2.4632 |
N121···N111 | 2.793 (3) | H216···N121 | 2.9203 |
N121···N211 | 2.945 (3) | H216···C126 | 3.0277 |
N121···N221 | 3.216 (3) | H224···N3vii | 2.7092 |
N121···C112 | 2.948 (4) | H224···N123xiv | 2.9300 |
N123···C114viii | 3.307 (3) | H225···C112ix | 3.0041 |
N211···N221 | 2.876 (3) | H225···C114ix | 3.0682 |
N211···C222 | 3.021 (3) | H226···N111 | 2.9078 |
N111···H226 | 2.9078 | H226···C116 | 3.0001 |
N211···N121 | 2.945 (3) | H226···N3ix | 2.7835 |
N211···N2 | 2.742 (3) | H226···C2ix | 2.6651 |
O1—Cu1—N2 | 79.13 (8) | S1—C3—F2 | 111.9 (2) |
O1—Cu1—N111 | 84.62 (7) | F2—C3—F3 | 106.9 (2) |
O1—Cu1—N121 | 86.20 (7) | S1—C3—F3 | 111.2 (2) |
O1—Cu1—N211 | 92.61 (7) | N11—C112—N111 | 120.9 (2) |
O1—Cu1—N221 | 174.31 (7) | N11—C112—N113 | 114.4 (2) |
N2—Cu1—N111 | 90.52 (8) | N111—C112—N113 | 124.7 (2) |
N2—Cu1—N121 | 165.33 (9) | N113—C114—C115 | 122.9 (3) |
N2—Cu1—N211 | 86.72 (8) | C114—C115—C116 | 116.7 (3) |
N2—Cu1—N221 | 95.38 (9) | N111—C116—C115 | 122.1 (2) |
N111—Cu1—N121 | 88.17 (8) | N11—C122—N123 | 113.3 (2) |
N111—Cu1—N211 | 176.41 (8) | N121—C122—N123 | 125.9 (3) |
N111—Cu1—N221 | 96.99 (8) | N11—C122—N121 | 120.8 (2) |
N121—Cu1—N211 | 93.93 (8) | N123—C124—C125 | 122.8 (3) |
N121—Cu1—N221 | 99.29 (8) | C124—C125—C126 | 116.8 (3) |
N211—Cu1—N221 | 85.56 (8) | N121—C126—C125 | 122.3 (3) |
O1—S1—O2 | 115.16 (15) | N21—C212—N213 | 113.2 (2) |
O1—S1—O3 | 115.28 (15) | N211—C212—N213 | 124.5 (2) |
O1—S1—C3 | 103.54 (13) | N21—C212—N211 | 122.3 (2) |
O2—S1—O3 | 114.63 (17) | N213—C214—C215 | 122.7 (3) |
O2—S1—C3 | 102.94 (15) | C115—C114—H114 | 118.53 |
O3—S1—C3 | 102.78 (14) | N113—C114—H114 | 118.57 |
Cu1—O1—S1 | 150.64 (12) | C214—C215—C216 | 116.4 (3) |
C1—N1—C2 | 119.9 (3) | C114—C115—H115 | 121.73 |
Cu1—N2—C1 | 160.3 (2) | C116—C115—H115 | 121.62 |
C112—N11—C122 | 127.4 (2) | C115—C116—H116 | 118.92 |
C212—N21—C222 | 132.0 (2) | N111—C116—H116 | 118.95 |
Cu1—N111—C112 | 123.52 (18) | N211—C216—C215 | 122.7 (2) |
Cu1—N111—C116 | 119.51 (17) | N221—C222—N223 | 126.5 (2) |
C112—N111—C116 | 116.9 (2) | N21—C222—N223 | 113.2 (2) |
C122—N11—H3 | 109.9 (19) | N21—C222—N221 | 120.4 (2) |
C112—N11—H3 | 115.6 (19) | N223—C224—C225 | 121.9 (3) |
C112—N113—C114 | 116.4 (2) | C125—C124—H124 | 118.67 |
Cu1—N121—C126 | 121.27 (17) | N123—C124—H124 | 118.56 |
C122—N121—C126 | 115.5 (2) | C126—C125—H125 | 121.63 |
Cu1—N121—C122 | 123.13 (17) | C224—C225—C226 | 117.2 (3) |
C212—N21—H5 | 112.9 (19) | C124—C125—H125 | 121.56 |
C222—N21—H5 | 114.9 (19) | N221—C226—C225 | 122.9 (2) |
C122—N123—C124 | 116.2 (2) | N121—C126—H126 | 118.85 |
Cu1—N211—C212 | 122.18 (18) | C125—C126—H126 | 118.85 |
Cu1—N211—C216 | 118.20 (17) | N213—C214—H214 | 118.67 |
C212—N211—C216 | 116.5 (2) | C215—C214—H214 | 118.64 |
C212—N213—C214 | 116.9 (2) | C214—C215—H215 | 121.79 |
Cu1—N221—C222 | 119.68 (16) | C216—C215—H215 | 121.79 |
C222—N221—C226 | 115.2 (2) | N211—C216—H216 | 118.71 |
Cu1—N221—C226 | 121.40 (17) | C215—C216—H216 | 118.64 |
C222—N223—C224 | 116.3 (2) | N223—C224—H224 | 119.06 |
N1—C1—N2 | 175.0 (3) | C225—C224—H224 | 119.05 |
N1—C2—N3 | 174.7 (3) | C224—C225—H225 | 121.37 |
F1—C3—F2 | 108.1 (2) | C226—C225—H225 | 121.46 |
F1—C3—F3 | 106.5 (2) | N221—C226—H226 | 118.58 |
S1—C3—F1 | 112.0 (2) | C225—C226—H226 | 118.53 |
N2—Cu1—O1—S1 | −114.7 (2) | C122—N11—C112—N111 | −28.0 (4) |
N111—Cu1—O1—S1 | 153.8 (2) | C122—N11—C112—N113 | 152.5 (2) |
N121—Cu1—O1—S1 | 65.2 (2) | C112—N11—C122—N121 | 26.3 (4) |
N211—Cu1—O1—S1 | −28.5 (2) | C112—N11—C122—N123 | −153.6 (2) |
O1—Cu1—N111—C112 | −54.09 (18) | C222—N21—C212—N211 | −12.3 (4) |
O1—Cu1—N111—C116 | 121.85 (18) | C222—N21—C212—N213 | 169.0 (3) |
N2—Cu1—N111—C112 | −133.11 (19) | C212—N21—C222—N221 | 12.6 (4) |
N2—Cu1—N111—C116 | 42.82 (19) | C212—N21—C222—N223 | −168.5 (3) |
N121—Cu1—N111—C112 | 32.27 (19) | C216—N211—C212—N213 | −6.4 (4) |
N121—Cu1—N111—C116 | −151.80 (18) | Cu1—N211—C212—N21 | −25.3 (3) |
N221—Cu1—N111—C112 | 131.41 (19) | Cu1—N211—C212—N213 | 153.2 (2) |
N221—Cu1—N111—C116 | −52.66 (19) | Cu1—N211—C216—C215 | −158.0 (2) |
O1—Cu1—N121—C122 | 51.13 (19) | C212—N211—C216—C215 | 2.5 (4) |
O1—Cu1—N121—C126 | −124.55 (19) | C112—N111—C116—H116 | −177.98 |
N111—Cu1—N121—C122 | −33.6 (2) | C216—N211—C212—N21 | 175.1 (2) |
N111—Cu1—N121—C126 | 150.72 (19) | Cu1—N111—C116—H116 | 5.81 |
N211—Cu1—N121—C122 | 143.5 (2) | C214—N213—C212—N211 | 4.7 (4) |
N211—Cu1—N121—C126 | −32.2 (2) | C214—N213—C212—N21 | −176.7 (2) |
N221—Cu1—N121—C122 | −130.38 (19) | C212—N213—C214—C215 | 1.0 (4) |
N221—Cu1—N121—C126 | 53.9 (2) | C112—N113—C114—H114 | −179.63 |
O1—Cu1—N211—C212 | −134.19 (19) | Cu1—N221—C222—N21 | 21.0 (3) |
O1—Cu1—N211—C216 | 25.09 (18) | Cu1—N221—C222—N223 | −157.7 (2) |
N2—Cu1—N211—C212 | −55.24 (19) | Cu1—N121—C126—H126 | −7.39 |
N2—Cu1—N211—C216 | 104.04 (19) | C122—N121—C126—H126 | 176.61 |
N121—Cu1—N211—C212 | 139.45 (19) | C226—N221—C222—N223 | 0.9 (4) |
N121—Cu1—N211—C216 | −61.28 (19) | Cu1—N221—C226—C225 | 156.2 (2) |
N221—Cu1—N211—C212 | 40.41 (19) | C226—N221—C222—N21 | 179.6 (2) |
N221—Cu1—N211—C216 | −160.31 (19) | C222—N221—C226—C225 | −2.0 (4) |
N2—Cu1—N221—C222 | 47.4 (2) | C122—N123—C124—H124 | −179.16 |
N2—Cu1—N221—C226 | −109.9 (2) | C222—N223—C224—C225 | −1.0 (4) |
N111—Cu1—N221—C222 | 138.6 (2) | C224—N223—C222—N21 | −178.2 (2) |
N111—Cu1—N221—C226 | −18.7 (2) | C224—N223—C222—N221 | 0.6 (4) |
N121—Cu1—N221—C222 | −132.2 (2) | N113—C114—C115—H115 | 175.74 |
N121—Cu1—N221—C226 | 70.6 (2) | H114—C114—C115—C116 | 175.66 |
N211—Cu1—N221—C222 | −38.9 (2) | N213—C214—C215—C216 | −4.4 (4) |
N211—Cu1—N221—C226 | 163.8 (2) | H114—C114—C115—H115 | −4.31 |
O2—S1—O1—Cu1 | −16.6 (3) | C114—C115—C116—H116 | −176.96 |
O3—S1—O1—Cu1 | 120.4 (2) | H115—C115—C116—N111 | −177.00 |
C3—S1—O1—Cu1 | −128.2 (2) | C214—C215—C216—N211 | 2.5 (4) |
O1—S1—C3—F1 | 179.3 (2) | H115—C115—C116—H116 | 3.01 |
O1—S1—C3—F2 | −59.2 (2) | N223—C224—C225—C226 | 0.0 (4) |
O1—S1—C3—F3 | 60.2 (2) | H124—C124—C125—H125 | 3.54 |
O2—S1—C3—F1 | 59.0 (2) | N123—C124—C125—H125 | −176.37 |
O2—S1—C3—F2 | −179.4 (2) | H124—C124—C125—C126 | −176.40 |
O2—S1—C3—F3 | −60.0 (2) | C224—C225—C226—N221 | 1.6 (4) |
O3—S1—C3—F1 | −60.4 (2) | C124—C125—C126—H126 | 177.75 |
O3—S1—C3—F2 | 61.2 (2) | H125—C125—C126—N121 | 177.83 |
O3—S1—C3—F3 | −179.4 (2) | H125—C125—C126—H126 | −2.20 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x, −y+1, −z+1; (iv) −x, y−1/2, −z+1/2; (v) x, −y+1/2, z−1/2; (vi) x+1, y, z; (vii) −x+1, −y+1, −z; (viii) −x+1, −y+1, −z+1; (ix) −x+1, y+1/2, −z+1/2; (x) −x, −y+1, −z; (xi) x, −y+3/2, z+1/2; (xii) −x, y+1/2, −z+1/2; (xiii) x−1, y, z; (xiv) x, −y+3/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H3···N113viii | 0.88 (3) | 2.10 (3) | 2.981 (3) | 176 (2) |
N21—H5···N213x | 0.87 (3) | 2.14 (3) | 3.001 (3) | 174 (3) |
C114—H114···N123viii | 0.95 | 2.65 | 3.307 (3) | 127 |
C214—H214···N223x | 0.95 | 2.56 | 3.276 (3) | 132 |
C124—H124···F3iii | 0.95 | 2.43 | 3.184 (4) | 136 |
C216—H216···O2 | 0.95 | 2.46 | 3.246 (4) | 140 |
Symmetry codes: (iii) −x, −y+1, −z+1; (viii) −x+1, −y+1, −z+1; (x) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(CF3SO3)(C2N3)(C8H7N5)2]·0.5C2H6O |
Mr | 625.05 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 9.972 (2), 13.751 (2), 18.516 (4) |
β (°) | 97.047 (8) |
V (Å3) | 2519.8 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.02 |
Crystal size (mm) | 0.2 × 0.1 × 0.1 |
Data collection | |
Diffractometer | Nonius Kappa CCD area-detector |
Absorption correction | ? |
No. of measured, independent and observed [I > 2σ(I)] reflections | 56102, 5712, 3766 |
Rint | 0.119 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.104, 1.04 |
No. of reflections | 5712 |
No. of parameters | 367 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.36, −0.55 |
Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), DENZO, SHELXS86 (Sheldrick, 1985), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PLATON.
Cu1—O1 | 2.747 (2) | Cu1—N121 | 2.008 (2) |
Cu1—N2 | 1.972 (2) | Cu1—N211 | 2.021 (2) |
Cu1—N111 | 2.006 (2) | Cu1—N221 | 2.208 (2) |
O1—Cu1—N2 | 79.13 (8) | N111—Cu1—N121 | 88.17 (8) |
O1—Cu1—N111 | 84.62 (7) | N111—Cu1—N211 | 176.41 (8) |
O1—Cu1—N121 | 86.20 (7) | N111—Cu1—N221 | 96.99 (8) |
O1—Cu1—N211 | 92.61 (7) | N121—Cu1—N211 | 93.93 (8) |
O1—Cu1—N221 | 174.31 (7) | N121—Cu1—N221 | 99.29 (8) |
N2—Cu1—N111 | 90.52 (8) | N211—Cu1—N221 | 85.56 (8) |
N2—Cu1—N121 | 165.33 (9) | C1—N1—C2 | 119.9 (3) |
N2—Cu1—N211 | 86.72 (8) | C112—N11—C122 | 127.4 (2) |
N2—Cu1—N221 | 95.38 (9) | C212—N21—C222 | 132.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H3···N113i | 0.88 (3) | 2.10 (3) | 2.981 (3) | 176 (2) |
N21—H5···N213ii | 0.87 (3) | 2.14 (3) | 3.001 (3) | 174 (3) |
C114—H114···N123i | 0.95 | 2.65 | 3.307 (3) | 127 |
C214—H214···N223ii | 0.95 | 2.56 | 3.276 (3) | 132 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z. |
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In recent years, the anionic dicyanamide ligand has attracted much interest, in the form of MII(dca)2 [where M is Ni, Co or Cu, and dca N(CN)2], as a new class of molecule-based magnetic materials (Batten et al., 1998; Batten & Murray, 2001; Manson et al., 1999). In the field of crystal engineering, the number of X-ray crystal structures of compounds with the dca anion showing one-, two- and three-dimensional networks has increased enormously in the last few years (e.g. Kohout et al., 2000; Vangdal et al., 2002; Mohamadou et al., 2003; Kooijman et al., 2002; Shi et al., 2003).
Dicyanamide itself is an interesting anionic bridging ligand and can act as a monodentate, bidentate or even tridentate ligand (Mroziński et al., 1997; Escuer et al., 2000). Various coordination modes of the dicyanamide ligand and the metal can occur, such as monodentate bonding via the nitrile atom, coordination via the amide atom (Marshall et al., 2002; Mohamadou et al., 2003; Shi et al., 2003; Vangdal et al., 2002), and even µ4 and µ5 coordination, where nitrile atoms bridge two metal atoms (Chow & Britton, 1975; Shi et al., 2002). However, in most cases monodentate or bidentate coordination via the nitrile N atom is found.
In the field of supramolecular chemistry, not only are direct metal-ligand bonds of interest, but hydrogen bonding is also of great importance (Beatty, 2001; Rodríguez-Martin et al., 2002; Nedelcu et al., 2003; Kutasi et al., 2002; Riggio et al., 2001). One ligand with interesting hydrogen-bonding properties is the recently developed di-2-pyrimidylamine (abbreviated as dipm). The dipm molecule can both donate and accept hydrogen bonds, and has a more or less linear donor-acceptor array of type ADA. This type of array is capable of forming so-called Watson-Crick-type hydrogen bonds (van Albada et al., 2002), as was also shown in the literature with the first generation ligand 2-aminopyrimidine (van Albada, Quiroz-Castro et al., 2000; van Albada, Smeets et al., 2000).
To date, only one X-ray crystal structure determination of a dipm-containing complex has been published, [Cu(dipm)(CO3)(H2O)]·2H2O (van Albada et al., 2002). In this paper, we present the crystal structure of a new complex of copper with the dipm molecule as ligand, which has the formulation [Cu(dca)(dipm)2(tms)], (I), where tms is the trifluoromethylsulfonate anion. An atomic displacement ellipsoid plot of this complex is given in Fig. 1, together with the atomic labelling scheme. Selected geometric parameters are given in Table 1. \sch
The geometry around the CuII ion in (I) is distorted octahedral, with the basal plane formed by two pyrimidinyl N atoms of one of the coordinating dipm molecules (N111 and N121), one pyrimidinyl N atom of the second coordinating dipm molecule (N211) and a nitrile N atom (N2) of the dca ligand. The Cu—N distances are in the range 1.972 (2)–2.021 (2) Å. The trans-basal angles are 176.41 (8) (N111—Cu1—N211) and 165.33 (9)° (N2—Cu1—N121). The apical positions are occupied by a pyrimidinyl N atom (N221) of the second dipm ligand, at a distance of 2.208 (2) Å, and by an O atom (O1) of the trifluoromethylsulfonate anion, at a semi-coordination distance of 2.747 (2) Å.
The dipm molecules in (I) show a significant difference in conformation. The angle between the least-squares planes through the pyrimidine rings is 33.71 (12)° in the ligand containing atom N11 and 11.73 (13)° in the molecule containing atom N21. In the dipm-copper-carbonate complex reported previously, the dipm molecule is virtually planar, with a ring-ring angle of 1.80 (11)°.
The lattice of (I) is stabilized by two crystallographically independent hydrogen-bonding systems, both of the so-called Watson-Crick type (Fig. 2). The systems are formed by donation of a hydrogen bond by the amine N atom of a dipm molecule (either N11 or N21) to a non-coordinating pyrimidinyl N atom of an inversion-related dipm molecule (N113 or N213, respectively). Due to the crystallographic inversion symmetry, a hydrogen-bonded ring is formed with unitary graph-set R22(8) (Bernstein et al., 1995). The hydrogen-bonded system involving atom N11 is formed around the inversion centre at (1/2,1/2,1/2), while that involving atom N21 is formed around the centre at (0,1/2,0). Geometric details are given in Table 2.
The hydrogen-bonded systems link the copper complexes into an infinite one-dimensional chain running in the [101] direction. Within each chain, the copper complexes are linked alternately by hydrogen-bonded systems involving atoms N11 or N21 (Fig. 2). This arrangement of hydrogen-bonded dipm molecules may facilitate the formation of two C—H···N contacts adjacent to the N—H···N hydrogen bonds, resulting in the formation of a quadruply hydrogen-bonded array of type DADA (a review of quadruply hydrogen-bonded systems is given by Sijbesma & Meijer, 2003). Due to the deviations from planarity of the dipm molecules, the C—H···N contacts are somewhat long, especially that involving C114—H114 (Table 2). However, these contacts may still play a role in the stabilization of the hydrogen-bonded network of (I). The dipm-copper-carbonate complex reported previously displayed a similar hydrogen-bonded structure (van Albada et al., 2002).
The non-coordinating nitrile moiety of the dca anion in (I) does not accept any hydrogen bonds. There is a close contact [2.947 (4) Å, i.e. approximately 0.2 Å less than the sum of the Van der Waals radii] between atom N3 of the dca anion and atom C122(1 - x, y - 1/2, 1/2 - z) of a dipm molecule. Atom N3 also displays a short contact to atom C112 of the same dipm molecule, at 3.086 (3) Å. Contacts of the type C≡ N···C(sp2)X3, where X = C, N, O, P, S or halogen, are not unsual. The July 2003 update of the Cambridge Structural Database (Allen, 2002) contains approximately 150 examples with N···C distances in the range 2.8–3.2 Å, 23 of which display contact distances shorter than the value observed in the crystal structure of (I).
The electron paramagnetic resonance (EPR) spectrum for (I), measured as a polycrystalline powder at room temperature and at 77 K, shows an axial S = 1/2 signal, with g = 2.06, a value typical for CuII and in agreement with a dx2-y2 ground state.