supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

gk2140 scheme

Acta Cryst. (2008). E64, m741-m742    [ doi:10.1107/S1600536808012026 ]

Bis[3-ethyl-4-(4-methoxyphenyl)-5-(2-pyridyl)-4H-1,2,4-triazole-[kappa]2N1,N5]bis(perchlorato-[kappa]O)copper(II) acetonitrile disolvate

L. Huang, Z. Wang, X. Zhang and P. Wu

Abstract top

In the title compound, [Cu(ClO4)2(C16H16N4O)2]·2CH3CN, the CuII atom, located on an inversion center, is in a tetragonally distorted octahedral environment, coordinated by four N atoms of two bidentate 3-ethyl-4-(4-methoxyphenyl)-5-(2-pyridyl)-4H-1,2,4-triazole ligands in equatorial positions and by the O atoms of two perchlorate groups in axial positions. The long axial Cu-O bond of 2.4743 (17) Å is the result of the Jahn-Teller effect.

Comment top

1,2,4-Triazole derivatives can be used as bridging ligands in transition metal coordination chemistry (Bencini et al., 1987; Koningsbruggen et al., 1995; Moliner et al., 1998, 2001; Klingele et al., 2005, 2006). Some spin-crossover complexes of 1,2,4-triazoles with iron(II) salts have been reported with potential applications 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). Recently we have reported synthesis of some new 3,4-disubstituted-5-(2-pyridyl)-1,2,4-triazole ligands and crystal structures of their transition-metal complexes (Wang et al., 2005; Zhou et al., 2006a,b). Here we report the crystal structure of the title compound (Fig. 1). The CuII atom is located on an inversion center. It shows a tetragonally distorted octahedral coordination geometry and is coordinated by two bis-chelating 3-ethyl-4-(4-methoxyphenyl)-5-(2-pyridyl)-1,2,4-triazole ligands with the CuN2N'2 chromophore in the equatorial plane and two O atoms of two perchlorate groups in axial positions.

Related literature top

For related literature, see: Bencini et al. (1987); Garcia et al. (1997); Kahn & Martinez (1998); Klingele et al. (2005, 2006); Koningsbruggen (2004); Koningsbruggen et al. (1995); Lavrenova & Larionov (1998); Matouzenko et al. (2004); Moliner et al. (1998, 2001); Wang et al. (2005); Zhou et al., (2006a,b).

Experimental top

The title compound was prepared by the reaction of 3-ethyl-4-(4-methoxyphenyl)-5-(2-pyridyl)-1,2,4-triazole with copper(II) perchlorate in acetonitrile. To a warm solution of 3-ethyl-4-(4-methoxyphenyl)-5-(2-pyridyl)-1,2,4-triazole (1.120 g, 4.0 mmol) in 20 ml acetonitrile, copper(II) perchlorate (0.525 g, 2.0 mmol) was added. After several days blue single crystals suitable for X-ray analysis 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 0.93 Å(C—H aromatic), 0.97 Å(C—H methylene) and 0.96 Å(C—H methyl), and with Uiso(H) values of 1.2–1.5 times Ueq of the parent atoms.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids shown at the 30% probability level. Symmetry code (i):-x + 1,-y + 1,-z + 1
Bis[3-ethyl-4-(4-methoxyphenyl)-5-(2-pyridyl)-4H-1,2,4-triazole- κ2N1,N5]bis(perchlorato-κO)copper(II) acetonitrile disolvate top
Crystal data top
[Cu(ClO4)2(C16H16N4O)2]·2C2H3NZ = 1
Mr = 905.21F000 = 467
Triclinic, P1Dx = 1.469 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.3286 (11) ÅCell parameters from 2714 reflections
b = 9.1266 (14) Åθ = 3.1–27.5º
c = 14.225 (2) ŵ = 0.73 mm−1
α = 100.516 (7)ºT = 293 (2) K
β = 101.067 (4)ºPrism, blue
γ = 98.780 (4)º0.20 × 0.20 × 0.20 mm
V = 1023.4 (3) Å3
Data collection top
Rigaku Mercury2
diffractometer		3565 independent reflections
Radiation source: fine-focus sealed tube3170 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.031
Detector resolution: 13.6612 pixels mm-1θmax = 25.0º
T = 293(2) Kθmin = 2.3º
ω scansh = −9→9
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		k = −10→10
Tmin = 0.864, Tmax = 0.867l = −16→16
8302 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.120  w = 1/[σ2(Fo2) + (0.0739P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.16(Δ/σ)max < 0.001
3565 reflectionsΔρmax = 0.46 e Å−3
271 parametersΔρmin = −0.54 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(ClO4)2(C16H16N4O)2]·2C2H3Nγ = 98.780 (4)º
Mr = 905.21V = 1023.4 (3) Å3
Triclinic, P1Z = 1
a = 8.3286 (11) ÅMo Kα
b = 9.1266 (14) ŵ = 0.73 mm−1
c = 14.225 (2) ÅT = 293 (2) K
α = 100.516 (7)º0.20 × 0.20 × 0.20 mm
β = 101.067 (4)º
Data collection top
Rigaku Mercury2
diffractometer		3565 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		3170 reflections with I > 2σ(I)
Tmin = 0.864, Tmax = 0.867Rint = 0.031
8302 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.039271 parameters
wR(F2) = 0.120H-atom parameters constrained
S = 1.16Δρmax = 0.46 e Å−3
3565 reflectionsΔρmin = −0.54 e Å−3
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
Cu10.50000.50000.50000.03204 (16)
Cl10.54072 (7)0.50192 (6)0.25312 (4)0.04015 (18)
O1−0.0616 (2)−0.3362 (2)0.02788 (13)0.0619 (5)
O20.6082 (2)0.5545 (2)0.35718 (12)0.0508 (4)
O30.4928 (4)0.3415 (2)0.23080 (16)0.0795 (7)
O40.6656 (3)0.5460 (3)0.20330 (15)0.0827 (8)
O50.4003 (3)0.5667 (3)0.2258 (2)0.0942 (8)
N10.2619 (2)0.43579 (19)0.42008 (13)0.0325 (4)
N20.4977 (2)0.28147 (18)0.44924 (13)0.0329 (4)
N30.6125 (2)0.1869 (2)0.45117 (13)0.0370 (4)
N40.3825 (2)0.07416 (18)0.34047 (12)0.0315 (4)
N50.7131 (5)0.9957 (4)0.1193 (3)0.1093 (12)
C10.5401 (3)0.0628 (2)0.38456 (15)0.0354 (5)
C20.3617 (3)0.2129 (2)0.38257 (14)0.0302 (5)
C30.2210 (3)0.2907 (2)0.36606 (15)0.0305 (4)
C40.0646 (3)0.2305 (3)0.30709 (16)0.0401 (5)
H10.03980.13140.27030.048*
C5−0.0554 (3)0.3207 (3)0.30364 (18)0.0455 (6)
H2−0.16220.28250.26470.055*
C6−0.0147 (3)0.4656 (3)0.35806 (19)0.0470 (6)
H3−0.09400.52720.35660.056*
C70.1451 (3)0.5213 (2)0.41562 (17)0.0410 (5)
H40.17160.62080.45210.049*
C80.2691 (3)−0.0342 (2)0.25825 (15)0.0317 (5)
C90.2728 (3)−0.0173 (3)0.16435 (16)0.0419 (6)
H50.34840.06130.15430.050*
C100.1638 (3)−0.1176 (3)0.08535 (17)0.0467 (6)
H10A0.1665−0.10730.02180.056*
C110.0513 (3)−0.2327 (3)0.10070 (17)0.0425 (6)
C120.0493 (3)−0.2497 (3)0.19559 (19)0.0491 (6)
H12A−0.0261−0.32810.20590.059*
C130.1592 (3)−0.1503 (3)0.27446 (17)0.0433 (6)
H13A0.1589−0.16180.33810.052*
C14−0.0529 (5)−0.3328 (4)−0.0708 (2)0.0801 (11)
H14A−0.1345−0.4146−0.11480.120*
H14B0.0564−0.3439−0.07950.120*
H14C−0.0748−0.2377−0.08450.120*
C150.6135 (3)−0.0739 (3)0.3591 (2)0.0476 (6)
H15A0.6122−0.09320.28960.057*
H15B0.5440−0.16090.37100.057*
C160.7893 (3)−0.0596 (3)0.4159 (2)0.0558 (7)
H16A0.8271−0.15280.39780.084*
H16B0.7922−0.03920.48490.084*
H16C0.86060.02210.40130.084*
C170.6382 (5)0.8821 (5)0.0784 (3)0.0736 (9)
C180.5389 (5)0.7344 (4)0.0255 (3)0.0826 (10)
H18A0.46340.69870.06330.124*
H18B0.61130.66360.01500.124*
H18C0.47660.7434−0.03670.124*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0291 (2)0.0242 (2)0.0355 (2)0.00483 (15)−0.00289 (16)−0.00093 (16)
Cl10.0357 (3)0.0382 (3)0.0421 (3)0.0009 (2)0.0040 (2)0.0079 (3)
O10.0567 (12)0.0558 (11)0.0491 (11)−0.0125 (9)−0.0083 (9)−0.0088 (9)
O20.0526 (11)0.0506 (10)0.0418 (9)0.0000 (8)0.0062 (8)0.0047 (8)
O30.135 (2)0.0369 (10)0.0564 (12)−0.0054 (12)0.0259 (13)−0.0023 (9)
O40.0610 (14)0.126 (2)0.0611 (12)−0.0114 (13)0.0182 (11)0.0415 (14)
O50.0570 (14)0.0994 (18)0.1069 (19)0.0306 (13)−0.0222 (13)0.0044 (16)
N10.0316 (9)0.0288 (9)0.0332 (9)0.0056 (7)0.0016 (7)0.0032 (7)
N20.0332 (10)0.0277 (9)0.0323 (9)0.0052 (7)−0.0005 (8)0.0016 (7)
N30.0376 (10)0.0279 (9)0.0399 (10)0.0092 (8)−0.0005 (8)0.0008 (8)
N40.0342 (10)0.0241 (8)0.0312 (9)0.0021 (7)0.0023 (7)0.0014 (7)
N50.121 (3)0.095 (3)0.104 (3)−0.002 (2)0.036 (2)0.009 (2)
C10.0390 (12)0.0282 (11)0.0342 (11)0.0045 (9)0.0036 (9)0.0016 (9)
C20.0335 (11)0.0241 (9)0.0294 (10)0.0017 (8)0.0044 (9)0.0027 (8)
C30.0315 (11)0.0270 (10)0.0290 (10)0.0018 (8)0.0023 (8)0.0041 (8)
C40.0364 (12)0.0352 (12)0.0407 (12)0.0016 (10)0.0008 (10)0.0012 (10)
C50.0300 (12)0.0494 (14)0.0483 (14)0.0028 (10)−0.0041 (10)0.0062 (12)
C60.0347 (12)0.0467 (13)0.0552 (14)0.0142 (11)−0.0007 (11)0.0062 (12)
C70.0379 (13)0.0329 (11)0.0475 (13)0.0090 (10)0.0033 (11)0.0021 (10)
C80.0346 (11)0.0238 (10)0.0308 (10)0.0027 (9)0.0023 (9)−0.0011 (8)
C90.0464 (13)0.0348 (12)0.0366 (12)−0.0056 (10)0.0059 (10)0.0023 (10)
C100.0569 (16)0.0456 (13)0.0295 (11)−0.0004 (12)0.0035 (11)0.0031 (10)
C110.0409 (13)0.0345 (11)0.0393 (12)0.0012 (10)−0.0031 (10)−0.0064 (10)
C120.0502 (15)0.0362 (12)0.0514 (14)−0.0105 (11)0.0104 (12)0.0022 (11)
C130.0509 (14)0.0363 (12)0.0359 (12)−0.0048 (11)0.0089 (11)0.0028 (10)
C140.093 (3)0.072 (2)0.0437 (16)−0.0080 (19)−0.0183 (16)−0.0116 (15)
C150.0515 (15)0.0332 (12)0.0524 (14)0.0174 (11)0.0020 (12)−0.0022 (11)
C160.0468 (15)0.0451 (14)0.0750 (19)0.0169 (12)0.0103 (14)0.0091 (13)
C170.078 (2)0.085 (2)0.0633 (19)0.016 (2)0.0250 (18)0.0214 (19)
C180.092 (3)0.087 (3)0.069 (2)0.019 (2)0.0183 (19)0.0167 (19)
Geometric parameters (Å, °) top
Cu1—N2i1.9892 (16)C6—C71.387 (3)
Cu1—N21.9892 (16)C6—H30.9300
Cu1—N12.0261 (18)C7—H40.9300
Cu1—N1i2.0261 (18)C8—C131.375 (3)
Cu1—O22.4743 (17)C8—C91.378 (3)
Cl1—O51.410 (2)C9—C101.380 (3)
Cl1—O41.416 (2)C9—H50.9300
Cl1—O31.416 (2)C10—C111.376 (3)
Cl1—O21.4409 (18)C10—H10A0.9300
O1—C111.359 (3)C11—C121.389 (4)
O1—C141.425 (4)C12—C131.378 (3)
N1—C71.336 (3)C12—H12A0.9300
N1—C31.360 (3)C13—H13A0.9300
N2—C21.315 (3)C14—H14A0.9600
N2—N31.382 (2)C14—H14B0.9600
N3—C11.313 (3)C14—H14C0.9600
N4—C21.349 (2)C15—C161.504 (4)
N4—C11.370 (3)C15—H15A0.9700
N4—C81.451 (2)C15—H15B0.9700
N5—C171.116 (5)C16—H16A0.9600
C1—C151.488 (3)C16—H16B0.9600
C2—C31.463 (3)C16—H16C0.9600
C3—C41.377 (3)C17—C181.455 (5)
C4—C51.387 (3)C18—H18A0.9600
C4—H10.9300C18—H18B0.9600
C5—C61.361 (3)C18—H18C0.9600
C5—H20.9300
N2i—Cu1—N2180.0N1—C7—C6121.7 (2)
N2i—Cu1—N199.31 (7)N1—C7—H4119.1
N2—Cu1—N180.69 (7)C6—C7—H4119.1
N2i—Cu1—N1i80.69 (7)C13—C8—C9120.95 (19)
N2—Cu1—N1i99.31 (7)C13—C8—N4120.21 (18)
N1—Cu1—N1i180.0C9—C8—N4118.83 (18)
N2i—Cu1—O292.07 (7)C8—C9—C10119.6 (2)
N2—Cu1—O287.93 (7)C8—C9—H5120.2
N1—Cu1—O292.61 (7)C10—C9—H5120.2
N1i—Cu1—O287.39 (7)C11—C10—C9119.9 (2)
O5—Cl1—O4110.60 (17)C11—C10—H10A120.0
O5—Cl1—O3109.64 (17)C9—C10—H10A120.0
O4—Cl1—O3109.77 (15)O1—C11—C10124.3 (2)
O5—Cl1—O2109.11 (14)O1—C11—C12115.6 (2)
O4—Cl1—O2108.51 (12)C10—C11—C12120.0 (2)
O3—Cl1—O2109.19 (12)C13—C12—C11120.0 (2)
C11—O1—C14117.6 (2)C13—C12—H12A120.0
Cl1—O2—Cu1131.53 (10)C11—C12—H12A120.0
C7—N1—C3118.35 (18)C8—C13—C12119.4 (2)
C7—N1—Cu1126.54 (14)C8—C13—H13A120.3
C3—N1—Cu1115.11 (14)C12—C13—H13A120.3
C2—N2—N3109.04 (16)O1—C14—H14A109.5
C2—N2—Cu1112.95 (14)O1—C14—H14B109.5
N3—N2—Cu1136.71 (14)H14A—C14—H14B109.5
C1—N3—N2105.81 (18)O1—C14—H14C109.5
C2—N4—C1105.79 (17)H14A—C14—H14C109.5
C2—N4—C8127.23 (18)H14B—C14—H14C109.5
C1—N4—C8126.67 (17)C1—C15—C16113.9 (2)
N3—C1—N4110.41 (18)C1—C15—H15A108.8
N3—C1—C15126.3 (2)C16—C15—H15A108.8
N4—C1—C15123.28 (19)C1—C15—H15B108.8
N2—C2—N4108.94 (18)C16—C15—H15B108.8
N2—C2—C3119.51 (17)H15A—C15—H15B107.7
N4—C2—C3131.54 (18)C15—C16—H16A109.5
N1—C3—C4122.13 (19)C15—C16—H16B109.5
N1—C3—C2110.79 (17)H16A—C16—H16B109.5
C4—C3—C2127.06 (18)C15—C16—H16C109.5
C3—C4—C5118.8 (2)H16A—C16—H16C109.5
C3—C4—H1120.6H16B—C16—H16C109.5
C5—C4—H1120.6N5—C17—C18179.4 (5)
C6—C5—C4119.1 (2)C17—C18—H18A109.5
C6—C5—H2120.4C17—C18—H18B109.5
C4—C5—H2120.4H18A—C18—H18B109.5
C5—C6—C7119.9 (2)C17—C18—H18C109.5
C5—C6—H3120.0H18A—C18—H18C109.5
C7—C6—H3120.0H18B—C18—H18C109.5
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Cu1—N21.9892 (16)Cu1—O22.4743 (17)
Cu1—N12.0261 (18)
N2i—Cu1—N2180.0N2i—Cu1—O292.07 (7)
N2i—Cu1—N199.31 (7)N2—Cu1—O287.93 (7)
N2—Cu1—N180.69 (7)N1—Cu1—O292.61 (7)
N1—Cu1—N1i180.0N1i—Cu1—O287.39 (7)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Acknowledgements top

We are grateful to Jingye Pharmochemical Pilot Plant for financial assistance through 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.

Garcia, Y., Kkoningsbruggen, 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., Boyd, P. D. W., Moubaraki, B., Murray, K. S. & Brooker, S. (2006). Eur. J. Inorg. Chem. pp. 573–589.

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.

Rigaku/MSC (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Wang, Z.-X., Lan, Y., Yuan, L.-T. & Liu, C.-Y. (2005). Acta Cryst. E61, o2033–o2034.

Zhou, A.-Y., Wang, Z.-X., Lan, Y., Yuan, L.-T. & Liu, C.-Y. (2006a). Acta Cryst. E62, m591–m592.

Zhou, B.-G., Wang, Z.-X., Qiao, X.-Y. & Liu, C.-Y. (2006b). Acta Cryst. E62, m3176–m3177.