Inorg. Chem. 2006, 45, 7665−7670
An Unprecedented Asymmetric End-On Azido-Bridged Copper(II) Imino Nitroxide Complex: Structure, Magnetic Properties, and Density Functional Theory Analysis Licun Li,*,† Daizheng Liao,† Zonghui Jiang,† Jean-Marie Mouesca,‡ and Paul Rey*,‡ Department of Chemistry, Nankai UniVersity, Tianjin 300071, People’s Republic of China, and CEA-Grenoble, De´ partement de Recherche Fondamentale sur la Matie` re Condense´ e, Laboratoire de Chimie Inorganique et Biologique (UMR-E3, CEA-UJF), 17 rue des Martyrs, 38054 Grenoble Cedex 9, France Received April 14, 2006
The dinuclear copper(II) complex [Cu2(µ1,1-N3)2(im-2py)2(N3)2] [im-2py ) 2-(2-pyridyl)-4,4,5,5-tetramethylimidazolinyl1-oxy] has been prepared and structurally characterized. The crystal structure consists of a dinuclear unit in which the CuII ions are bridged by two azido ions in a end-on asymmetric fashion and the imino nitroxide radicals are chelating by the two imino N atoms. Accordingly, the magnetic susceptibility data were analyzed considering a linear spin-coupling scheme rad(1)−Cu(2)−Cu(3)−rad(4) (with Si ) 1/2, i ) 1−4), where the Heisenberg spin Hamiltonian assumes the general form −2∑i +190 cm-1), as is expected for copper imino nitroxide species, and the copper−copper (rad)−Cu−Cu−(rad) coupling through the asymmetric double end-on azide bridges appeared antiferromagnetic and rather large [J23 ) J2 ) −43(2) cm-1]. By contrast, a density functional theory analysis of the system through the computation of broken-symmetry-state energies resulted in J2 ≈ 0 cm-1. This apparent paradox is resolved by introducing a second-neighbor rad−(Cu)−Cu− (rad)t(rad)−Cu−(Cu)−rad spin-coupling constant J13 ) J24 ) J3, which turns out to be antiferromagnetic both experimentally (when J2 is set equal to zero) and computationally.
Introduction Metal-nitroxide magnetic interactions are generally antiferromagnetic except in a few cases when the geometry of the coordination sphere results in an orthogonal arrangement of the magnetic orbitals.1 This happens in copper(II) nitronyl nitroxide complexes; when the radical ligand is axially bound by the O atom to a square-pyramidal or octahedral Cu ion, * To whom correspondence should be addressed. E-mail: llicun@ nankai.edu.cn (L.L.),
[email protected] (P.R.). † Nankai University. ‡ CEA-Grenoble. (1) (a) Bencini, A.; Benelli, C.; Gatteschi, D.; Zanchini, C. J. Am. Chem. Soc. 1984, 106, 5813. (b) Grand, A.; Rey, P.; Subra, R. Inorg. Chem. 1983, 22, 391. (c) Caneschi, A.; Gatteschi, D.; Laugier, J.; Rey, P. J. Am. Chem. Soc. 1987, 109, 2191. (d) Caneschi, A.; Gatteschi, D.; Grand, A.; Laugier, J.; Parch, L.; Rey, P. Inorg. Chem. 1988, 27, 1031. (e) Laugier, J.; Rey, P.; Benelli, C.; Gatteschi, D.; Zanchini, C. J. Am. Chem. Soc. 1986, 108, 6931. (f) Gatteschi, D.; Laugier, J.; Rey, P.; Zanchini, C. Inorg. Chem. 1987, 26, 938. (g) Lanfranc de Panthou, F.; Belorizky, E.; Calemezuk, R.; Luneau, D.; Marcenat, C.; Ressouche, E.; Turek, Ph.; Rey, P. J. Am. Chem. Soc. 1995, 117, 11247.
10.1021/ic0606429 CCC: $33.50 Published on Web 08/19/2006
© 2006 American Chemical Society
the metal-radical magnetic coupling is weakly ferromagnetic, in contrast to the equatorial situation, which results in strong spin pairing.2 More interestingly, strong ferromagnetic couplings (J ≈ +200 cm-1; H ) -2∑i 2σ(I)] and R1 ) ∑(||Fo| - |Fc||)/∑|F0|, wR2 ) (∑w(|Fo|2 - |Fc|2)2/∑w|Fo|2)2, w ) 1/[σ2(Fo2) + (0.0602P)2 + 0.0102P] where P ) (Fo2 + 2Fc2)/3. Maximum and minimum peaks in the final difference Fourier synthesis were 0.313 and -0.367 e Å-3.
Results and Discussion Crystal Structure. An ORTEP drawing of the molecular structure with the atom-labeling scheme is shown in Figure 1. Selected bond distances and bond angles are summarized in Table 1. The crystal structure consists of centrosymmetric dinuclear units [Cu2(µ1,1-N3)2(im-2py)2(N3)2] in which the CuII ions are bridged by two azido ligands in an end-on fashion. Each metal ion has a 4 + 1 distorted square-pyramidal environment (Figure 1) whose basal plane [N(1), N(2), N(4A), and N(7)] comprises two N atoms [N(1) and N(2)] belonging to the chelating imino nitroxide ligand and two N atoms from a bridging azido [N(4A)] and a terminal azido [N(7)] anions. (12) (a) Koner, S.; Saha, S.; Mallah, T.; Okamoto, K.-I. Inorg. Chem. 2004, 43, 840. (b) Triki, S.; Gomez-Garcia, C. J.; Ruiz, E.; Sala-Pala, J. Inorg. Chem. 2005, 44, 5501 and references cited therein. (13) Helbert, J. N.; Kopf, P. W.; Poindexter E. H.; Wagner, B. E. J. Chem. Soc., Dalton Trans. 1975, 998. (14) Sheldrick, G. M. SHELXS 97, Program for the Solution of Crystal Structure; University of Go¨ttingen: Go¨ttingen, Germany, 1997. (15) Sheldrick, G. M. SHELXL 97, Program for the Refinement of Crystal Structure; University of Go¨ttingen: Go¨ttingen, Germany, 1997.
Azido-Bridged Copper(II) Imino Nitroxide Complex
Figure 2. View of the packing of dinuclear units [Cu2(µ1,1-N3)2(im-2py)2(N3)2]. Figure 1. ORTEP drawing with 30% thermal ellipsoid probability showing the atom labeling of [Cu2(µ1,1-N3)2(im-2py)2(N3)2]. Table 1. Selected Bond Lengths (Å) and Angles (deg) for [Cu2(µ1,1-N3)2(im-2py)2(N3)2]a Cu(1)-N(2) Cu(1)-N(7) Cu(1)-N(4)
2.016(3) 1.935(4) 2.434(4)
Cu(1)-N(1) Cu(1)-N(4A) O(1)-N(3)
2.059(3) 1.948(4) 1.268(4)
N(7)-Cu(1)-N(2) N(4A)-Cu(1)-N(2) N(4A)-Cu(1)-N(1) C(5)-N(1)-Cu(1) O(1)-N(3)-C(6) Cu(1A)-N(4)-Cu(1) N(7)-N(8)-N(9)
95.02(16) 167.69(15) 90.95(15) 115.4(3) 126.1(3) 95.15(15) 174.6(5)
N(7)-Cu(1)-N(4A) N(7)-Cu(1)-N(1) N(2)-Cu(1)-N(1) C(6)-N(2)-Cu(1) O(1)-N(3)-C(10) N(6)-N(5)-N(4)
96.26(17) 164.36(19) 79.34(13) 114.0(3) 123.5(3) 176.8(5)
Figure 3. Plots of χM (4) and χMT (O) vs T for [Cu2(µ1,1-N3)2(im-2py)2(N3)2]. The solid lines correspond to the best theoretical fit.
a Symmetry transformations used to generate equivalent atoms: -x + 1, -y, -z + 2.
The Cu(1)-N(1), Cu(1)-N(2), Cu(1)-N(7), and CuN(4A) in-plane distances are 2.059(3), 2.016(3), 1.935(4), and 1.948(4) Å, respectively. One N atom [N(4)] from the second azido bridge occupies the axial position at a distance of 2.434(4) Å, with the Cu atom being displaced toward this apical site by 0.0695 Å from the basal plane. The bridging azido anion is quasi-linear [176.8(5)° for N(4)-N(5)-N(6)], the bond angle Cu(1)-N(4)-Cu(1A) is 95.1(1)°, and the Cu-Cu separation is 3.252 Å. In the radical ligand, the oxyl bond length, N(3)-O(1) ) 1.268(4) Å, is similar to N-O distances already reported in analogous complexes,3-5,16 and the O(1)-N(3)-C(6)-N(2) plane of the free-radical ligand makes angles of 12.4° and 8.9° with the metal basal plane and the pyridyl ring, respectively. A stacking diagram is shown in Figure 2. The dinuclear units are linked by fairly weak bonds [Cu(1)-N(6A) ) 3.441 Å] to form one-dimensional chains along the z axis and completing the metal coordination sphere to pseudooctahedral. Therefore, the complex may be viewed as chains of binuclear units in which the end-on bridging azido ligands of a molecule are also end-to-end bridging for another unit along the chain. Other intermolecular contacts (3.656 Å) are (16) Oshio, H.; Watanabe, T.; Ohto, A.; Ito, T.; Masuda, H. Inorg. Chem. 1996, 35, 472.
Figure 4. Low-temperature magnetic data (20 K). Accordingly, the system was first modeled as a linear array of spins S ) 1/2 (Chart 1). Only first-neighbor interactions were considered, and the corresponding Heisenberg spin Hamiltonian (H ˆ ) 1JSˆ 1Sˆ 2 2J2Sˆ 2Sˆ 3 - 2J1Sˆ 3Sˆ 4, S1 ) S2 ) S3 ) S4 ) 1/2) was diagonalized numerically using a homemade program including the Minuit subroutine for fitting of the data.17 It soon appeared that g was strongly correlated with the J’s, and to minimize problems, the g value (g ) 2.065) was determined by electron paramagnetic resonance and entered in the fitting process as a fixed parameter. The best-fit values were as follows: g ) 2.065 (fixed), J1 ) +190(51) cm-1, J2 ) -43(2) cm-1, R ) 6 × 10-4 (R ) ∑[(χM)obs - (χM)calc]2/ ∑[(χM)obs]2). It is worth noting that the experimental hightemperature data could not be reproduced by considering negative values of both interactions or by reversing the sign of the coupling constants. These values reproduced fairly well the high-temperature data including the maximum observed in the temperature dependence of χM, but attempts to fit the low-temperature data were unsuccessful. In particular, modeling of the intercluster interaction in the frame of the mean-field approximation did slightly improve the fit, but a large zJ value (zJ ) -13 cm-1) was obtained. Moreover, the slower than expected decrease of χ below 15 K was never reproduced. As usual for ferromagnetic interactions, J1 is not accurately determined;18 fitting the data as χ or χT afforded different J1 values, +170 and +210 cm-1, respectively (mean value 190 cm-1), without a significant change of the R factor value. Note that g ) 2.065 at room temperature is consistent with J1 > +200 cm-1 because for a quartet state one expects gQ ) (gNO + gCu)/2. Taking gNO ) 2, one obtained gCu ) 2.13, a value close to that reported in related complexes involving diamagnetic ligands.12 Accordingly, the smaller (1.85 cm3 K mol-1) than 2 (for two independent spins S ) 1) of χT at room temperature is the signature of rather large antiferromagnetic interactions showing up even at high temperature, in agreement with the fairly large value of J2 (-43 cm-1). Upon examination of the structural data, close contacts have been mentioned, which suggest that the magnetic data should be analyzed as chains of four-spin systems rather than isolated clusters. Indeed, along the z axis, the CuII ions might be viewed as linked alternatively by end-on and end-to-end (17) Belorizky, E.; Friess, P. H.; Gojon, E.; Latour, J.-M. Mol. Phys. 1987, 61, 661. (18) Kahn, O. Molecular Magnetism; VCH: New York, 1993.
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azido bridges, while along the y axis, owing to contacts between uncoordinated NO groups of adjacent molecules, one should consider chains of antiferromagnetically coupled four-spin systems. Calculations of χM for such chains including three different ferro- and antiferromagnetic coupling constants are an intractable problem that we solved approximatively considering the following features. Along the z axis, the end-to-end pattern occurs with a very long Cu-N(6A) bond of 3.441 Å, a situation which, according to a recent study, should result in a very weak antiferromagnetic interaction.12 In contrast, along the y axis, uncoordinated oxyl groups are arranged at the corners of a distorted parallelogram [O(1)-N(3) ) 1.268 Å, N(3)-O(1B) ) 4.24 Å, O(1B)-N(3B) ) 1.268 Å, N(3B)-O(1) ) 4.21 Å, O(1)-O(1B) ) 3.67 Å; O(1)-N(3)-O(1B) ) 113°] and the π* magnetic orbitals make an angle of 41°. In this situation, the inter-N-oxyl interaction is expected to be antiferromagnetic with a magnitude as large as -30 cm-1.2 Therefore, considering the large J1 ferromagnetic metalradical coupling, the low-temperature data (
