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Bis(μ 1,2,4 triazole κ2N1:N2)­bis­­[di­aqua­(oxalato κ2O,O′)copper(II)]

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Acta Cryst.(2004). E60, m9±m11 DOI: 10.1107/S1600536803027119 Oscar Castilloet al. [Cu2(C2O4)2(C2H3N3)2(H2O)4]

m9

metal-organic papers

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

Bis(

l

-1,2,4-triazole-

j

2

N

1

:

N

2

)bis[diaqua-(oxalato-

j

2

O,O

000

)copper(II)]

Oscar Castillo,* Urko GarcõÂa-Couceiro, Antonio Luque, Juan P. GarcõÂa-TeraÂn and Pascual RomaÂn

Departamento de QuõÂmica InorgaÂnica, Facultad de Ciencia y TecnologõÂa, Universidad del PaõÂs Vasco, Apdo. 644, E-48080 Bilbao, Spain

Correspondence e-mail: qipcacao@lg.ehu.es

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C±C) = 0.005 AÊ

Rfactor = 0.041

wRfactor = 0.116

Data-to-parameter ratio = 18.6

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved

The crystal structure of the title compound,

[Cu2(C2O4)2(C2H3N3)2(H2O)4], consists of dimeric neutral

entities with D2 (222) point symmetry. The two CuII atoms

(site symmetry 2) are linked by two symmetry-relatedN1,N2

-bidentate 1,2,4-triazole bridges (one of the N atoms has site symmetry 2). The distorted octahedral coordination around each Cu atom is completed by two O donor atoms from a terminal bidentate oxalate ligand in the equatorial plane, and two trans-coordinated water molecules occupying the apical positions with longer metal±oxygen distances. The complete solid-state structure can be described as a three-dimensional supramolecular framework, stabilized by extensive hydrogen-bonding interactions involving the water molecules, the non-coordinated oxalate O atoms and the protonated N atom of the triazole ligands. The thermal degradation of the title compound was carried out in air between 298 and 873 K.

Comment

The design and synthesis of metal complexes with 1,2,4-tria-zole and its derivatives have attracted the interest of both physicists and chemists, due to their applications in the photographic (Berthaller, 1996) and anticorrosive industries

(Tsarenkoet al., 1997) and the multiple coordination modes of

these bridging ligands (through -2N1,N2, -2N1,N4 and

-3N1,N2,N4modes as anions) which have allowed the design

of a great diversity of homo- and heteropolymetallic frame-works (Haasnoot, 2000) with remarkable magnetic properties

(Tanget al., 2001). In the framework of our current research

on oxalate-containing ®rst-row transition metal complexes (Castillo, Luque, RomaÂnet al., 2001; Castilloet al., 2003), we have obtained the compound bis(-1,2,4-triazole-N1:N2

)bis-[diaqua(oxalato-2O,O0)copper(II)], (I).

The crystal structure of (I) consists of dinuclear complexes in which the metal atoms occupy special positions with site symmetry 2 and the overall cluster has 222 symmetry about its central point. As shown in Fig. 1, the two CuIIatoms are linked

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metal-organic papers

m10

Oscar Castilloet al. [Cu2(C2O4)2(C2H3N3)2(H2O)4] Acta Cryst.(2004). E60, m9±m11

by two bridging-1,2,4-triazole-2N1:N2ligands, with a CuÐ

NÐN bond angle of 129.9 (1). The Cu Cuiii [symmetry

code: (iii) 2ÿx,1

2ÿy,z] distance of 3.937 (1) AÊ is comparable

to those in polymeric copper complexes containing metal

centres linked by double triazole bridges (Liu et al., 1999,

2003). The copper centres are also attached to two O atoms from a terminal oxalato anion which acts as a bidentate ligand.

The O1ÐCuÐO1i bond angle of 83.7 (1) in the

®ve-membered ring is within the range reported for copper(II) complexes containing bidentate oxalate ligands (Castillo, Luque & RomaÂn, 2001). The donor atoms of triazole and oxalate ligands establish short bond distances [CuÐO1 1.975 (2) AÊ and CuÐN1 2.002 (3) AÊ] and form the equatorial plane [maximum deviation from the least-squares plane is

0.052 (2) AÊ for atom O1] of the elongated CuN2O4octahedron

around each metal atom. The apical positions are occupied by

the O atoms from twotrans-coordinated water molecules, with

a CuÐO3wbond distance of 2.483 (3) AÊ and an O3wÐCuÐ

O3wibond angle of 174.6 (1). The 1,2,4-triazole and oxalate

ligands are essentially planar [the maximum deviation is 0.049 (2) AÊ for atom O1]. The dihedral angle between the two

bridging triazole ligands is 6.51 (4), while the oxalate and

triazole ligands are tilted with respect to each other by

4.57 (3). The CÐO bond distances of the oxalate O atoms

attached to the Cu centres [1.259 (4) AÊ] are only slightly longer than those involving the non-coordinated O atoms [1.224 (4) AÊ], owing to the involvement of the free O atoms in an extensive network of hydrogen bonds.

In the crystal structure, the protonated N atoms of the

dimeric entities form symmetric bifurcated NÐH Oox

hydrogen bonds with an adjacent unit to form square-grid sheets which extend parallel to theabplane (Fig. 2). The holes generated by this packing are occupied by the coordinated water molecules belonging to dimeric units from adjacent sheets. These molecules are connected to each other and to

the free oxalate O2 atom by means of OwÐHw Ow and

OwÐHw Ooxhydrogen bonds, respectively.

The thermal degradation of (I) in air starts with an endo-thermic process in the temperature range 373±423 K, which is attributable to the loss of the coordinated water molecules (experimental 14.3%, calculated 14.0%). Subsequently, two exothermic processes in the temperature range 433±473 K

lead to the intermediate compound CuCO3 (experimental

51.6%, calculated 51.8%), which is stable up to 513 K. Finally, it undergoes successive exothermic processes to give CuO as the ®nal product above 783 K (experimental 69.5%, calculated 69.3%).

Experimental

A methanolic solution (15 ml) of 1,2,4-triazole (0.082 g, 1.2 mmol) was slowly diffused into an aqueous solution (15 ml) of K2[Cu(

-C2O4)2(H2O)2] (Kirschner, 1960) (0.106 g, 0.3 mmol) and

K2(C2O4).H2O (0.05 g, 0.27 mmol) using a test tube. Blue crystals of

(I) were formed over a period of 3 weeks. Analysis calculated for C8H14Cu2N6O12: C 18.7, H 2.8, N 16.4, Cu 24.8%; found: C 18.5, H 2.9,

N 16.5, Cu 24.8%.

Figure 1

The dimeric unit of (I), showing the atom-numbering scheme, with 50% probability displacement ellipsoids. Symmetry codes as in Table 1; additionally (ii)5

4ÿy,54ÿx,14ÿz; (iii) 2ÿx,12ÿy,z.

Figure 2

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Crystal data

[Cu2(C2O4)2(C2H3N3)2(H2O)4]

Mr= 513.35

Tetragonal,I41=acd

a= 16.596 (1) AÊ

c= 11.996 (2) AÊ

V= 3304.0 (6) AÊ3

Z= 8

Dx= 2.064 Mg mÿ3

Dm= 2.05 (1) Mg mÿ3

Dmmeasured by ¯otation in a

mixture of carbon tetrachloride and bromoform

MoKradiation

Cell parameters from 13778 re¯ections

= 2.5±25.8

= 2.66 mmÿ1

T= 293 (2) K

Prism, blue

0.420.200.08 mm

Data collection

Oxford Diffraction Xcalibur diffractometer

!scans

Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2003)

Tmin= 0.534,Tmax= 0.809

13778 measured re¯ections

1212 independent re¯ections 652 re¯ections withI> 2(I)

Rint= 0.070

max= 30.0

h=ÿ23!23

k=ÿ23!23

l=ÿ16!16

Re®nement

Re®nement onF2

R[F2> 2(F2)] = 0.041

wR(F2) = 0.116

S= 0.98

1212 re¯ections 65 parameters

H-atom parameters not re®ned

w= 1/[2(F

o2) + (0.0549P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001

max= 0.50 e AÊÿ3

min=ÿ0.55 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,).

Cu1ÐO1 1.975 (2)

Cu1ÐN1 2.002 (3) Cu1ÐO3w 2.483 (3)

O1ÐCu1ÐO1i 83.7 (1)

O1ÐCu1ÐN1 171.4 (1)

O1ÐCu1ÐN1i 88.3 (1)

O1ÐCu1ÐO3w 94.0 (1)

O1ÐCu1ÐO3wi 90.1 (1)

N1ÐCu1ÐN1i 100.0 (1)

N1ÐCu1ÐO3w 89.1 (1)

N1ÐCu1ÐO3wi 87.5 (1)

O3wÐCu1ÐO3wi 174.6 (1)

Symmetry code: (i)3

4‡y;xÿ34;14ÿz.

Table 2

Hydrogen-bonding geometry (AÊ,).

DÐH A DÐH H A D A DÐH A

N3ÐH3 O2iv 0.78 2.18 2.838 (4) 142

N3ÐH3 O2v 0.78 2.18 2.838 (4) 142

O3wÐH32 O2vi 0.89 1.91 2.724 (3) 152

O3wÐH31 O3wvii 0.99 1.88 2.822 (4) 157

Symmetry codes: (iv) 1

2‡x;ÿy;z; (v) 54‡y;34ÿx;14ÿz; (vi) 32ÿx;y;ÿz; (vii) 5

4ÿy;xÿ34;ÿ14ÿz.

All the H atoms were located in difference Fourier maps and were included in the structure-factor calculations with ®xed positional parameters and a displacement parameter ofUiso= 0.05 AÊ2.

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell re®nement: CrysAlis CCD; data reduction:CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure:SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication:WinGX(Farrugia, 1999).

This work was supported by the Ministerio de Ciencia y TecnologõÂa (MAT2002-03166) and the Universidad del PaõÂs Vasco/Euskal Herriko Unibertsitatea (9/UPV 00169.310-15329/2003). UG thanks the latter institution for a predoctoral fellowship.

References

Berthaller, P. (1996).Sulfur Rep.18, 337±359.

Castillo, O., Alonso, J., GarcõÂa-Couceiro, U., Luque, A. & RomaÂn, P. (2003).

Inorg. Chem. Commun.6, 803±806.

Castillo, O., Luque, A., RomaÂn, P., Lloret, F. & Julve, M. (2001).Inorg. Chem.

40, 5526±5535.

Castillo, O., Luque, A. & RomaÂn, P. (2001).J. Mol. Struct.570, 181±188. Farrugia, L. J. (1997).J. Appl. Cryst.30, 565.

Farrugia, L. J. (1999).J. Appl. Cryst.32, 837±838.

Haasnoot, J. G. (2000).Coord. Chem. Rev.200±202, 131±185.

Kirschner, S. (1960).Inorganic Synthesis, Vol. 6, edited by E. D. Rochow. New

York: McGraw-Hill.

Liu, J. C., Fu, D. G., Zhuang, J. Z., Duan, C. Y. & You, X. Z. (1999).J. Chem. Soc. Dalton Trans.pp. 2337±2342.

Liu, J. C., Guo, G. C., Huang, J. S. & You, X. Z. (2003).Inorg. Chem.42, 235± 243.

Oxford Diffraction (2003).CrysAlis CCDandCrysAlis RED. Versions 1.170.

Oxford Diffraction, Wrocøaw, Poland.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

GoÈttingen, Germany.

Tang, J. K., Wang, H. M., Cheng, P., Lu, X., Liao, D. Z., Jiang, Z. H. & Yan, S. P.

(2001).Polyhedron,20, 675±680.

Tsarenko, I. V., Makarevich, A. V., Kofman, T. P. (1997).Protection of Metals,

33, 374±376.

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supporting information

sup-1

Acta Cryst. (2004). E60, m9–m11

supporting information

Acta Cryst. (2004). E60, m9–m11 [https://doi.org/10.1107/S1600536803027119]

Bis(

µ

-1,2,4-triazole-

κ

2

N

1

:

N

2

)bis[diaqua(oxalato-

κ

2

O,O

)copper(II)]

Oscar Castillo, Urko Garc

í

a-Couceiro, Antonio Luque, Juan P. Garc

í

a-Ter

á

n and Pascual Rom

á

n

Bis(µ-1,2,4-triazole-κ2N1:N2)bis[aqua(oxalato-κ2O,O)copper(II)]

Crystal data

[Cu2(C2O4)2(C2H3N3)2(H2O)4] Mr = 513.35

Tetragonal, I41/acd Hall symbol: -I 4bd 2c

a = 16.596 (1) Å

c = 11.996 (2) Å

V = 3304.0 (6) Å3 Z = 8

F(000) = 2064

Dx = 2.064 Mg m−3 Dm = 2.05 (1) Mg m−3

Dm measured by flotation in a mixture of carbon tetrachloride and bromoform

Mo radiation, λ = 0.71073 Å Cell parameters from 13778 reflections

θ = 2.5–25.8°

µ = 2.66 mm−1 T = 293 K Prism, blue

0.42 × 0.20 × 0.08 mm

Data collection

Xcalibur diffractometer

Radiation source: fine-focus sealed tube

ω scans

Absorption correction: numerical

CrysAlis RED (Oxford Diffraction, 2003)

Tmin = 0.534, Tmax = 0.809 13778 measured reflections

1212 independent reflections 652 reflections with I > 2σ(I)

Rint = 0.070

θmax = 30.0°, θmin = 3.2° h = −23→23

k = −23→23

l = −16→16

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 > 2σ(F2)] = 0.041 wR(F2) = 0.116 S = 0.98 1212 reflections 65 parameters 0 restraints

Primary atom site location: heavy-atom method

Secondary atom site location: difference Fourier map

Hydrogen site location: difference Fourier map H-atom parameters not refined

w = 1/[σ2(F

o2) + (0.0549P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001

Δρmax = 0.50 e Å−3 Δρmin = −0.55 e Å−3

Special details

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supporting information

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Acta Cryst. (2004). E60, m9–m11

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)

x y z Uiso*/Ueq

Cu1 0.91613 (2) 0.16613 (2) 0.1250 0.0264 (2)

O1 0.7976 (1) 0.1593 (1) 0.1352 (2) 0.0290 (6)

O2 0.7013 (1) 0.0664 (1) 0.1278 (2) 0.0309 (6)

O3w 0.9167 (2) 0.1755 (2) −0.0816 (2) 0.0336 (6)

N1 1.0363 (2) 0.1557 (2) 0.1219 (3) 0.0208 (6)

N3 1.1525 (2) 0.0975 (2) 0.1250 0.0250 (9)

C1 0.7718 (2) 0.0882 (2) 0.1279 (3) 0.0245 (7)

C2 1.0740 (2) 0.0864 (2) 0.1199 (3) 0.0286 (8)

H2 1.047 0.041 0.127 0.05*

H3 1.186 0.064 0.1250 0.05*

H31 0.969 0.157 −0.112 0.05*

H32 0.892 0.129 −0.095 0.05*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

Cu1 0.0157 (2) 0.0157 (2) 0.0477 (4) −0.0014 (3) 0.0003 (2) −0.0003 (2) O1 0.018 (1) 0.017 (1) 0.052 (2) −0.000 (1) 0.001 (1) 0.001 (1) O2 0.018 (1) 0.023 (1) 0.051 (2) −0.004 (1) −0.002 (1) 0.002 (1) O3w 0.029 (2) 0.032 (2) 0.040 (2) −0.002 (1) 0.000 (1) 0.001 (1) N1 0.017 (1) 0.013 (1) 0.033 (2) −0.002 (1) 0.001 (1) 0.000 (1) N3 0.019 (1) 0.019 (1) 0.037 (2) 0.010 (2) −0.003 (2) −0.003 (2) C1 0.023 (2) 0.021 (2) 0.029 (2) −0.002 (1) 0.000 (2) 0.005 (2) C2 0.024 (2) 0.018 (2) 0.044 (2) 0.002 (1) −0.005 (2) −0.003 (2)

Geometric parameters (Å, º)

Cu1—O1 1.975 (2) O3w—H32 0.89

Cu1—N1 2.002 (3) N1—N1ii 1.364 (5)

Cu1—O3w 2.483 (3) N1—C2 1.309 (4)

Cu1—O1i 1.975 (2) N3—C2 1.318 (4)

Cu1—N1i 2.002 (3) N3—C2ii 1.318 (4)

Cu1—O3wi 2.483 (3) C1—C1i 1.560 (7)

O1—C1 1.259 (4) C2—H2 0.88

O2—C1 1.224 (4) N3—H3 0.78

O3w—H31 0.99

O1—Cu1—O1i 83.7 (1) N1i—Cu1—O3wi 89.1 (1)

O1—Cu1—N1 171.4 (1) N1i—Cu1—O3w 87.5 (1)

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supporting information

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Acta Cryst. (2004). E60, m9–m11

O1—Cu1—O3w 94.0 (1) O1—C1—O2 127.0 (3)

O1—Cu1—O3wi 90.1 (1) O1—C1—C1i 115.2 (2)

N1—Cu1—N1i 100.0 (1) O2—C1—C1i 117.8 (2)

N1—Cu1—O3w 89.1 (1) N1—C2—N3 110.5 (3)

N1—Cu1—O3wi 87.5 (1) C2—N1—N1ii 106.5 (2)

O3w—Cu1—O3wi 174.6 (1) C2—N3—C2ii 106.1 (4)

O1i—Cu1—N1i 171.4 (1) N1—C2—H2 121.0

O1i—Cu1—N1 88.3 (1) C2—N3—H3 127.0

O1i—Cu1—O3wi 94.0 (1) C2ii—N3—H3 127.0

O1i—Cu1—O3w 90.1 (1) N3—C2—H2 127.6

Symmetry codes: (i) y+3/4, x−3/4, −z+1/4; (ii) −y+5/4, −x+5/4, −z+1/4.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N3—H3···O2iii 0.78 2.18 2.838 (4) 142

N3—H3···O2iv 0.78 2.18 2.838 (4) 142

O3w—H32···O2v 0.89 1.91 2.724 (3) 152

O3w—H31···O3wvi 0.99 1.88 2.822 (4) 157

References

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