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Acta Cryst. (2007). E63, m3060    [ doi:10.1107/S1600536807057686 ]

Bis[3-ethyl-4-(4-methylphenyl)-5-(2-pyridyl)-4H-1,2,4-triazole-[kappa]2N,N']copper(II) bis(perchlorate)

P. Wu, Z. Wang, B. Zhou and L. Huang

Abstract top

In the title compound, [Cu(C16H16N4)2](ClO4)2, the CuII atom lies on an inversion centre and has a distorted square-planar geometry. In each ligand, the dihedral angle between the triazole and pyridine rings is 9.1 (3)°, and that between the triazole and benzene rings is 85.01 (14)°.

Comment top

The coordination chemistry of 1,2,4-triazole derivatives has attracted great attention in recent years (Bencini et al., 1987; Koningsbruggen et al., 1995; Moliner et al., 1998; Moliner et al., 2001; Klingele & Brooker 2003; Klingele et al., 2005). Some spin-crossover complexes of 1,2,4-triazoles with iron(II) salts have been reported, which could be used as molecular-based memory devices, displays and optical switches (Garcia et al., 1997; Lavrenova & Larionov, 1998; Kahn & Martinez, 1998; Koningsbruggen, 2004; Matouzenko et al., 2004). We report here the crystal structure analysis of the title compound, (I).

The structure of (I) is shown in Fig.1. In the crystal structure, the CuII atom lies on an inversion centre and is coordinated by two 3-ethyl-4-(p-methylphenyl)-5-(2-pyridyl)-1,2,4-triazole ligands in a distorted square-planar geometry. In each ligand, the dihedral angle between the triazole and pyridine rings is 9.1 (3)°, and that between the triazole and benzene rings is 85.01 (14)°.

Related literature top

For related literature, see: Bencini et al. (1987); Garcia et al. (1997); Kahn & Martinez (1998); Klingele & Brooker (2003); Klingele et al. (2005); Koningsbruggen (2004); Koningsbruggen et al. (1995); Lavrenova & Larionov (1998); Matouzenko et al. (2004); Moliner et al. (1998, 2001).

Experimental top

The title compound was prepared by reaction of 3-ethyl-4-(p-methylphenyl)-5-(2-pyridyl)-1,2,4-triazole with copper(II) perchlorate in acetonitrile and water. To a warm solution of 1.06 grams of 3-ethyl-4-(p-methylphenyl)-5-(2-pyridyl)-1,2,4-triazole (4.0 mmol) in 20 ml acetonitrile-water (V/V = 1:1), 0.52 grams of copper(II) perchlorate (2.0 mmol) was added. The filtrate was left to stand at room temperature for several days, and single crystals suitable for X-ray diffraction were collected.

Refinement top

All H atoms were located in a difference Fourier map and allowed to ride on their parent atoms at distances of 0.93Å (aromatic), 0.96Å (methyl) and 0.97Å (methylene), and with Uiso(H) values of 1.2 or 1.5 times Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atomic labelling. Displacement ellipsoids are shown at the 30% probability level.
Bis[3-ethyl-4-(4-methylphenyl)-5-(2-pyridyl)-4H-1,2,4-triazole-\ κ2N,N']copper(II) bis(perchlorate) top
Crystal data top
[Cu(C16H16N4)2](ClO4)2Z = 1
Mr = 791.10F000 = 407
Triclinic, P1Dx = 1.534 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.0113 (14) ÅCell parameters from 1954 reflections
b = 8.3126 (14) Åθ = 2.6–25.9º
c = 14.215 (3) ŵ = 0.86 mm−1
α = 99.374 (3)ºT = 291 (2) K
β = 102.689 (3)ºBlock, blue
γ = 107.041 (2)º0.26 × 0.20 × 0.18 mm
V = 856.4 (3) Å3
Data collection top
Bruker SMART APEX CCD
diffractometer		3294 independent reflections
Radiation source: sealed tube2297 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.031
T = 291(2) Kθmax = 26.0º
φ and ω scansθmin = 2.6º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −9→9
Tmin = 0.808, Tmax = 0.861k = −10→4
4686 measured reflectionsl = −17→17
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.127  w = 1/[σ2(Fo2) + (0.0658P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
3294 reflectionsΔρmax = 0.82 e Å−3
234 parametersΔρmin = −0.47 e Å−3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Cu(C16H16N4)2](ClO4)2γ = 107.041 (2)º
Mr = 791.10V = 856.4 (3) Å3
Triclinic, P1Z = 1
a = 8.0113 (14) ÅMo Kα
b = 8.3126 (14) ŵ = 0.86 mm−1
c = 14.215 (3) ÅT = 291 (2) K
α = 99.374 (3)º0.26 × 0.20 × 0.18 mm
β = 102.689 (3)º
Data collection top
Bruker SMART APEX CCD
diffractometer		3294 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		2297 reflections with I > 2σ(I)
Tmin = 0.808, Tmax = 0.861Rint = 0.031
4686 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0581 restraint
wR(F2) = 0.127H-atom parameters constrained
S = 1.03Δρmax = 0.82 e Å−3
3294 reflectionsΔρmin = −0.47 e Å−3
234 parameters
Special details top

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2672 (5)0.8169 (5)0.4734 (3)0.0436 (8)
H10.28710.87530.42420.052*
C20.3614 (5)0.7036 (5)0.4944 (3)0.0464 (9)
H20.44790.69200.46200.056*
C30.3255 (6)0.6094 (5)0.5632 (3)0.0517 (10)
H30.38000.52690.57410.062*
C40.2066 (5)0.6394 (5)0.6158 (3)0.0439 (8)
H40.18490.58290.66550.053*
C50.1218 (4)0.7550 (4)0.5924 (2)0.0346 (7)
C6−0.0067 (5)0.8021 (4)0.6396 (2)0.0331 (7)
C7−0.1790 (6)0.8482 (5)0.7319 (3)0.0514 (9)
C8−0.2685 (6)0.8364 (6)0.8112 (3)0.0594 (11)
H8A−0.17710.84510.87110.071*
H8B−0.35780.72060.79380.071*
C9−0.3609 (7)0.9592 (7)0.8374 (4)0.0722 (14)
H9A−0.31161.01530.90700.108*
H9B−0.48890.89750.82320.108*
H9C−0.34251.04480.79930.108*
C100.0172 (5)0.6772 (5)0.7884 (2)0.0405 (7)
C110.1746 (6)0.7618 (6)0.8615 (3)0.0551 (10)
H110.23710.87830.86740.066*
C120.2433 (6)0.6748 (6)0.9279 (3)0.0574 (11)
H120.34850.73460.98000.069*
C130.1561 (6)0.5013 (5)0.9166 (3)0.0473 (9)
C140.0003 (6)0.4204 (6)0.8422 (3)0.0560 (10)
H14−0.05820.30250.83420.067*
C15−0.0762 (6)0.5021 (5)0.7780 (3)0.0563 (11)
H15−0.18620.44310.72930.068*
C160.2347 (6)0.4050 (6)0.9865 (4)0.0607 (11)
H16A0.31070.35350.95810.091*
H16B0.13730.31580.99650.091*
H16C0.30570.48481.04920.091*
Cl1−0.35945 (13)0.75087 (13)0.28048 (7)0.0529 (3)
Cu10.00001.00000.50000.03407 (19)
N10.1517 (4)0.8428 (4)0.5214 (2)0.0366 (6)
N2−0.0939 (4)0.8995 (4)0.6031 (2)0.0387 (6)
N3−0.2055 (5)0.9288 (5)0.6598 (2)0.0503 (8)
N4−0.0578 (4)0.7672 (4)0.7204 (2)0.0428 (7)
O11−0.4876 (4)0.8173 (4)0.3132 (2)0.0591 (8)
O12−0.2782 (4)0.8561 (4)0.2241 (2)0.0564 (7)
O13−0.2264 (4)0.7560 (4)0.3667 (2)0.0594 (8)
O14−0.4462 (4)0.5766 (4)0.2267 (2)0.0740 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.058 (2)0.050 (2)0.0445 (19)0.0306 (18)0.0273 (18)0.0285 (17)
C20.055 (2)0.057 (2)0.050 (2)0.0327 (19)0.0264 (17)0.0321 (18)
C30.066 (3)0.060 (2)0.060 (2)0.046 (2)0.029 (2)0.036 (2)
C40.0469 (19)0.047 (2)0.055 (2)0.0257 (17)0.0234 (17)0.0300 (18)
C50.0441 (17)0.0351 (17)0.0335 (15)0.0162 (15)0.0167 (14)0.0193 (14)
C60.0402 (15)0.0269 (15)0.0345 (16)0.0145 (13)0.0089 (13)0.0101 (12)
C70.066 (2)0.054 (2)0.061 (2)0.034 (2)0.037 (2)0.0349 (19)
C80.060 (2)0.073 (3)0.049 (2)0.017 (2)0.026 (2)0.024 (2)
C90.075 (3)0.074 (3)0.069 (3)0.021 (3)0.033 (3)0.015 (3)
C100.0628 (18)0.0398 (18)0.0293 (14)0.0239 (16)0.0186 (12)0.0169 (13)
C110.059 (2)0.050 (2)0.056 (2)0.0147 (18)0.0140 (14)0.0198 (18)
C120.058 (2)0.067 (3)0.052 (2)0.026 (2)0.0083 (19)0.029 (2)
C130.060 (2)0.055 (2)0.0360 (18)0.0219 (19)0.0214 (17)0.0206 (17)
C140.066 (2)0.051 (2)0.057 (2)0.024 (2)0.012 (2)0.028 (2)
C150.066 (2)0.041 (2)0.056 (2)0.0145 (19)0.0016 (19)0.0248 (19)
C160.068 (3)0.058 (3)0.071 (3)0.032 (2)0.024 (2)0.031 (2)
Cl10.0524 (5)0.0504 (6)0.0511 (5)0.0100 (4)0.0129 (4)0.0157 (4)
Cu10.0445 (3)0.0388 (3)0.0348 (3)0.0229 (3)0.0183 (2)0.0261 (3)
N10.0407 (15)0.0344 (14)0.0394 (15)0.0156 (13)0.0090 (12)0.0198 (12)
N20.0468 (15)0.0495 (18)0.0299 (13)0.0191 (13)0.0173 (12)0.0234 (12)
N30.065 (2)0.066 (2)0.0453 (18)0.0412 (18)0.0238 (16)0.0341 (16)
N40.0607 (18)0.0420 (16)0.0392 (15)0.0266 (14)0.0190 (14)0.0224 (13)
O110.0631 (17)0.0517 (17)0.0564 (17)0.0120 (14)0.0141 (14)0.0147 (14)
O120.0551 (15)0.0517 (17)0.0565 (16)0.0090 (13)0.0131 (13)0.0177 (14)
O130.0586 (16)0.0471 (16)0.0525 (18)0.0096 (13)0.0075 (14)0.0152 (14)
O140.068 (2)0.0549 (19)0.066 (2)−0.0070 (16)0.0069 (17)−0.0063 (16)
Geometric parameters (Å, °) top
C1—N11.310 (5)C10—N41.449 (4)
C1—C21.398 (5)C11—C121.395 (5)
C1—H10.930C11—H110.930
C2—C31.376 (5)C12—C131.371 (6)
C2—H20.930C12—H120.930
C3—C41.387 (5)C13—C141.351 (6)
C3—H30.930C13—C161.518 (5)
C4—C51.372 (4)C14—C151.367 (5)
C4—H40.930C14—H140.930
C5—N11.361 (4)C15—H150.930
C5—C61.456 (4)C16—H16A0.960
C6—N21.312 (4)C16—H16B0.960
C6—N41.348 (4)C16—H16C0.960
C7—N31.325 (4)Cl1—O121.398 (3)
C7—N41.356 (5)Cl1—O141.407 (3)
C7—C81.464 (5)Cl1—O131.422 (3)
C8—C91.474 (6)Cl1—O111.426 (3)
C8—H8A0.970Cl1—Cu13.5736 (11)
C8—H8B0.970Cu1—N21.982 (3)
C9—H9A0.960Cu1—N2i1.982 (3)
C9—H9B0.960Cu1—N1i2.043 (3)
C9—H9C0.960Cu1—N12.043 (3)
C10—C111.353 (6)N2—N31.374 (4)
C10—C151.394 (5)
N1—C1—C2121.6 (3)C14—C13—C16121.7 (4)
N1—C1—H1119.2C12—C13—C16120.1 (4)
C2—C1—H1119.2C13—C14—C15123.7 (4)
C3—C2—C1119.6 (3)C13—C14—H14118.1
C3—C2—H2120.2C15—C14—H14118.1
C1—C2—H2120.2C14—C15—C10117.4 (4)
C2—C3—C4118.8 (3)C14—C15—H15121.3
C2—C3—H3120.6C10—C15—H15121.3
C4—C3—H3120.6C13—C16—H16A109.5
C5—C4—C3118.0 (3)C13—C16—H16B109.5
C5—C4—H4121.0H16A—C16—H16B109.5
C3—C4—H4121.0C13—C16—H16C109.5
N1—C5—C4123.0 (3)H16A—C16—H16C109.5
N1—C5—C6111.5 (3)H16B—C16—H16C109.5
C4—C5—C6125.5 (3)O12—Cl1—O14112.3 (2)
N2—C6—N4108.3 (3)O12—Cl1—O13110.27 (18)
N2—C6—C5119.5 (3)O14—Cl1—O13108.0 (2)
N4—C6—C5132.2 (3)O12—Cl1—O11108.75 (19)
N3—C7—N4109.7 (3)O14—Cl1—O11110.0 (2)
N3—C7—C8127.6 (4)O13—Cl1—O11107.42 (19)
N4—C7—C8122.7 (3)O12—Cl1—Cu190.71 (12)
C7—C8—C9120.8 (4)O14—Cl1—Cu1138.86 (16)
C7—C8—H8A107.1O11—Cl1—Cu192.63 (13)
C9—C8—H8A107.1N2—Cu1—N2i180
C7—C8—H8B107.1N2—Cu1—N1i99.18 (12)
C9—C8—H8B107.1N2i—Cu1—N1i80.82 (12)
H8A—C8—H8B106.8N2—Cu1—N180.82 (12)
C8—C9—H9A109.5N2i—Cu1—N199.18 (12)
C8—C9—H9B109.5N1i—Cu1—N1180
H9A—C9—H9B109.5N2—Cu1—Cl1101.05 (9)
C8—C9—H9C109.5N2i—Cu1—Cl178.95 (9)
H9A—C9—H9C109.5N1i—Cu1—Cl176.99 (8)
H9B—C9—H9C109.5N1—Cu1—Cl1103.01 (8)
C11—C10—C15120.4 (4)C1—N1—C5118.7 (3)
C11—C10—N4120.6 (3)C1—N1—Cu1127.2 (2)
C15—C10—N4119.0 (3)C5—N1—Cu1114.1 (2)
C10—C11—C12120.1 (4)C6—N2—N3109.5 (3)
C10—C11—H11120.0C6—N2—Cu1113.3 (2)
C12—C11—H11120.0N3—N2—Cu1136.0 (2)
C13—C12—C11120.1 (4)C7—N3—N2105.7 (3)
C13—C12—H12120.0C6—N4—C7106.8 (3)
C11—C12—H12120.0C6—N4—C10126.5 (3)
C14—C13—C12118.2 (4)C7—N4—C10126.3 (3)
Symmetry codes: (i) −x, −y+2, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Cu1—N21.982 (3)Cu1—N12.043 (3)
N2—Cu1—N180.82 (12)
Acknowledgements top

We are grateful to Jingye Pharmochemical Pilot Plant for financial assistance though project 8507041056.

references
References top

Bencini, A., Gatteschi, D., Zanchini, C., Haasnoot, J. G., Prins, R. & Reedijk, J. (1987). J. Am. Chem. Soc. 109, 2926–2931.

Bruker (2000). SMART (Version 5.625), SAINT (Version 6.01), SHELXTL (Version 6.10) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.

Garcia, Y., Koningsbruggen, P. J., Codjovi, E., Lapouyade, R., Kahn, O. & Rabardel, L. (1997). J. Mater. Chem. 7, 857–858.

Kahn, O. & Martinez, C. J. (1998). Science, 279, 44–48.

Klingele, M. H., Boyd, P. D. W., Moubaraki, B., Murray, K. S. & Brooker, S. (2005). Eur. J. Inorg. Chem. pp. 910–918.

Klingele, M. H. & Brooker, S. (2003). Coord. Chem. Rev. 241, 119–132.

Koningsbruggen, P. J. (2004). Top. Curr. Chem. 233, 123–149.

Koningsbruggen, P. J., Gatteshi, D., Graaff, R. A. G., Hassnoot, J. G., Reedijk, J. & Zanchini, C. (1995). Inorg. Chem. 34, 5175–5182.

Lavrenova, L. G. & Larionov, S. V. (1998). Russ. J. Coord. Chem. 24, 379–395.

Matouzenko, G. S., Bousseksou, A., Borshch, S. A., Perrin, M., Zein, S., Salmon, L., Molnar, G. & Lecocq, S. (2004). Inorg. Chem. 43, 227–236.

Moliner, N., Gaspar, A. B., Munoz, M. C., Niel, V., Cano, J. & Real, J. A. (2001). Inorg. Chem. 40, 3986–3991.

Moliner, N., Munoz, M. C., Koningsbruggen, P. J. & Real, J. A. (1998). Inorg. Chim. Acta, 274, 1–6.