Bis(3,5 di­methyl 1,2,4 triazolato κN4)bis­­(pivalic acid κO)copper(II) dihydrate

metal-organic papers

Acta Cryst.(2004). E60, m1889±m1891 doi: 10.1107/S1600536804028697 Zhouet al. [Cu(C₄H₆N₃)₂(C₅H₁₀O₂)₂]2H₂O

m1889

Structure Reports Online

ISSN 1600-5368

Bis(3,5-dimethyl-1,2,4-triazolato-

j

N

)bis(pivalic

acid-

j

O

)copper(II) dihydrate

Jian-Hao Zhou, Yi-Zhi Li, Bin Huang and Xue-Tai Chen*

Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, People's Republic of China

Correspondence e-mail: llyyjz@nju.edu.cn

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C±C) = 0.008 AÊ

Rfactor = 0.062

wRfactor = 0.164

Data-to-parameter ratio = 15.6

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 molecule of the title complex, [Cu(C4H6N3)2(C5H10O2)2]

-2H2O, is situated about a site of symmetry 2/mand shows a

trans-N2O2square-planar coordination geometry for the CuII

centre. The crystal structure exhibits a two-dimensional layer arrangement mediated by intermolecular hydrogen bonds.

Comment

Molecular materials exhibiting interesting magnetic and luminescent properties have received increasing attention in recent years (Kahn et al., 1992; Kahn, 1993; Haasnoot, 2000; Thompson, 2002). 1,2,4-Triazole and its derivatives are able to provide several bridging coordination modes to link metal(II) ions, an important consideration for molecular materials. Indeed, many structures of coordination complexes have been reported, showing a variety of coordination modes (Haasnoot, 2000). Rare examples of structures containing the bridging 3,5-dimethyl-1,2,4-triazole ligand includeN1_,N2_{bridging (Yiet}

al., 2004) andN1_,N2_,N4_{bridging (Drewet al., 1985; Zhanget}

al., 2004). Here, we report the title copper(II) complex, (I), with the 3,5-dimethyl-1,2,4-triazole ligand exhibiting a monodentateN4_{coordination mode.}

The molecule of (I) is disposed about a site of symmetry 2/m

(Fig. 1 and Table 1). The CuII_{atom is coordinated by twoN}4

atoms from two 3,5-dimethyl-1,2,4-triazole anions in a trans

con®guration. The CuÐN4_{bond distances [mean 1.994 (5) AÊ]}

are in the range of those reported for catena-[[3

-3,5-dimethyl-1,2,4-triazolato-3_N,N0_,N00_{]copper(I)] [1.963 (1)±}

2.016 (1) AÊ; Zhang et al., 2004]. The two remaining coordi-nation sites in the square-planar geometry are occupied by O atoms from two pivalic acid molecules.

The crystal structure of (I) features intermolecular hydrogen bonds, as shown in Fig. 2; geometric details are given in Table 2. The hydroxyl group of (I) forms a hydrogen bond with the O atom of the solvent water molecule (O1Ð H1B O3). The water molecule, in turn, links two N2 atoms, so that a two-dimensional layer structure results.

Experimental

3,5-Dimethyl-1,2,4-triazole (0.068 g, 0.7 mmol) was added to an ethanol solution (10 ml) of [Cu(Me3CCOO)2]2(0.15 g, 0.28 mmol) with stirring. The resulting solution was stirred at 276 K for 24 h and then ®ltered. Uncharacterized blue compounds, which formed on slow evaporation of the mother liquor, were ®ltered off several times, before red crystals of (I) suitable for X-ray diffraction analysis were obtained from the mother liquor (18% yield). Analysis calculated for C18H36Cu1N6O6: C 43.58, H 7.32, N 16.94%; found: C 43.83, H 7.61, N 16.74%; IR (KBr,, cmÿ1_{): 3375 (br), 3053 (w), 2966 (m), 2935 (w),} 2720 (w), 1596 (m), 1553 (vs), 1484 (m), 1439 (w), 1418 (s), 1378 (m),

1364 (m), 1322 (w), 1225 (m), 1146 (w), 1087 (w), 1051 (w), 902 (w), 754 (w), 619 (m).

Crystal data

[Cu(C4H6N3)2(C5H10O2)2]2H2O Mr= 496.07

Monoclinic, C2=m a= 13.270 (3) AÊ

b= 12.861 (3) AÊ

c= 8.770 (2) AÊ = 115.791 (4)

V= 1347.6 (5) AÊ3 Z= 2

Dx= 1.222 Mg mÿ3

MoKradiation Cell parameters from 709

re¯ections = 2.9±22.9 = 0.85 mmÿ1 T= 293 (2) K Block, red

0.330.280.23 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer 'and!scans

Absorption correction: multi-scan (SADABS; Bruker, 2000)

Tmin= 0.767,Tmax= 0.829

3525 measured re¯ections

1311 independent re¯ections 1141 re¯ections withI> 2(I)

Rint= 0.053

max= 25.5 h=ÿ16!15

k=ÿ15!15

l=ÿ10!9

Refinement

Re®nement onF2 R[F2_{> 2(F}2_{)] = 0.062} wR(F2_{) = 0.164} S= 1.09 1311 re¯ections 84 parameters

H atoms treated by a mixture of independent and constrained re®nement

w= 1/[2_(F

o2) + (0.09P)2

+ 1.95P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001 max= 0.38 e AÊÿ3 min=ÿ0.50 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_).

Cu1ÐO2 1.974 (4) Cu1ÐN1 1.994 (5) C1ÐC2 1.488 (6) C2ÐN2 1.306 (6) C2ÐN1 1.337 (5) C3ÐO1 1.251 (7)

C3ÐO2 1.253 (8) C3ÐC4 1.480 (7) C4ÐC5 1.501 (7) C4ÐC6 1.503 (10) N2ÐN2i _{1.399 (8)}

O1ÐC3ÐO2 120.7 (5)

O1ÐC3ÐC4 120.8 (6) Cu1ÐN1ÐC2Cu1ÐO2ÐC3 127.6 (3)103.3 (3)

O1ÐC3ÐC4ÐC6 180 O2ÐC3ÐC4ÐC6 0 N2ÐC2ÐN1ÐCu1 179.6 (3)

C1ÐC2ÐN1ÐCu1 1.1 (6) O2ÐCu1ÐN1ÐC2 120.2 (3) O2ii_{ÐCu1ÐN1ÐC2 ÿ59.8 (3)}

Symmetry codes: (i) 1ÿx;y;2ÿz; (ii) 1ÿx;ÿy;2ÿz.

Table 2

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

O1ÐH1B O3 0.85 1.86 2.637 (6) 151 O3ÐH3A N2i _{0.85 2.07 2.748 (5) 137}

Symmetry code: (i)1

2ÿx;12ÿy;2ÿz.

Atoms H1Band H3Awere found in a difference Fourier map and not re®ned. All other H atoms were positioned geometrically and re®ned in the riding-model approximation, with CÐH = 0.96 AÊ and

Uiso(H) = 1.2 (1.5 for methyl H) timesUeq(parent atom).

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

metal-organic papers

m1890

The two-dimensional layer structure of (I) [symmetry code: (i) 1 2ÿx, 1

2ÿy, 2ÿz]. Dashed lines indicate hydrogen bonds. Figure 1

This work was supported by a Measurement Grant of Nanjing University (grant No. 0205001333).

References

Bruker (2000).SMART(Version 5.625),SAINT(Version 6.01),SHELXTL

(Version 6.10) andSADABS(Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.

Drew, M. G. B., Yates, P. C., Trocha-Grimshaw, J., McKillop, K. P. & Nelson, S. M. (1985).J. Chem. Soc. Chem. Commun.pp. 262±263.

Haasnoot, J. G. (2000).Coord. Chem. Rev.200±202, 131±185. Kahn, O. (1993).Molecular Magnetism. New York: VCH. Kahn, O., KroÈber, J. & Jay, C. (1992).Adv. Mater.4, 718±728. Thompson, L. K. (2002).Coord. Chem. Rev.233±234, 193±206.

Yi, L., Ding, B., Zhao, B., Cheng, P., Liao, D. Z., Yan, S. P. & Jiang, Z. H. (2004).

Inorg. Chem.43, 33±43.

Zhang, J. P., Zheng, S. L., Huang, X. C. & Chen, X. M. (2004).Angew. Chem. Int. Ed. Engl.43, 206±209.

metal-organic papers

supporting information

sup-1 Acta Cryst. (2004). E60, m1889–m1891

supporting information

Acta Cryst. (2004). E60, m1889–m1891 [https://doi.org/10.1107/S1600536804028697]

Bis(3,5-dimethyl-1,2,4-triazolato-

κ

N

_{)bis(pivalic acid-}

_κ

_O

_{)copper(II) dihydrate}

Jian-Hao Zhou, Yi-Zhi Li, Bin Huang and Xue-Tai Chen

Bis(3,5-dimethyl-1,2,4-triazolato-κN4_{)bis(pivalic acid-κO)copper(II) dihydrate}

Crystal data

[Cu(C4H6N3)2(C5H10O2)2]·2H2O

Mr = 496.07

Monoclinic, C2/m

Hall symbol: -C 2y

a = 13.270 (3) Å

b = 12.861 (3) Å

c = 8.770 (2) Å

β = 115.791 (4)°

V = 1347.6 (5) Å3

Z = 2

F(000) = 526

Dx = 1.222 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 709 reflections

θ = 2.9–22.9°

µ = 0.85 mm−1

T = 293 K Block, red

0.33 × 0.28 × 0.23 mm

Data collection

Bruker SMART Apex CCD area detector diffractometer

Radiation source: sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Bruker, 2000)

Tmin = 0.767, Tmax = 0.829

3525 measured reflections 1311 independent reflections 1141 reflections with I > 2σ(I)

Rint = 0.053

θmax = 25.5°, θmin = 2.3°

h = −16→15

k = −15→15

l = −10→9

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.062}

wR(F2_{) = 0.164}

S = 1.09 1311 reflections 84 parameters 3 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + (0.09P)2 + 1.95P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.38 e Å−3

supporting information

sup-2 Acta Cryst. (2004). E60, m1889–m1891

Special details

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 13.2662 (0.0031) x - 0.0000 (0.0001) y - 4.0044 (0.0172) z = 2.6286 (0.0175)

* 0.0000 (0.0000) Cu1 * 0.0000 (0.0000) O2 * 0.0000 (0.0000) O2_$1 * 0.0000 (0.0000) N1 * 0.0000 (0.0000) N1_$1 Rms deviation of fitted atoms = 0.0000

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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 0.5000 0.0000 1.0000 0.0312 (3) C1 0.3898 (4) 0.1839 (4) 1.1669 (6) 0.0540 (12) H1D 0.3643 0.2436 1.2059 0.081* H1E 0.4382 0.1430 1.2623 0.081* H1F 0.3266 0.1427 1.0949 0.081* C2 0.4522 (4) 0.2185 (4) 1.0702 (6) 0.0467 (10) C3 0.3227 (6) 0.0000 0.7173 (6) 0.0542 (17) C4 0.2394 (4) 0.0000 0.5375 (6) 0.0540 (17) C5 0.1606 (4) 0.0904 (4) 0.4994 (7) 0.0623 (14) H5A 0.1247 0.0885 0.5737 0.093* H5B 0.1050 0.0862 0.3840 0.093* H5C 0.2017 0.1541 0.5162 0.093* C6 0.2913 (6) 0.0000 0.4155 (9) 0.0616 (19) H6A 0.2348 0.0000 0.3005 0.092* H6B 0.3370 0.0610 0.4353 0.092* N1 0.5000 0.1551 (4) 1.0000 0.0449 (12) N2 0.4691 (4) 0.3161 (3) 1.0473 (6) 0.0575 (11) O1 0.2924 (4) 0.0000 0.8337 (5) 0.0418 (10) H1B 0.2247 0.0000 0.8191 0.050* O2 0.4246 (4) 0.0000 0.7501 (5) 0.0468 (11) O3 0.1184 (5) 0.0000 0.9043 (8) 0.0671 (15) H3A 0.0793 0.0540 0.8626 0.081*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

supporting information

sup-3 Acta Cryst. (2004). E60, m1889–m1891

C6 0.064 (5) 0.064 (5) 0.069 (5) 0.000 0.040 (4) 0.000 N1 0.056 (3) 0.036 (3) 0.052 (3) 0.000 0.033 (3) 0.000 N2 0.066 (3) 0.044 (2) 0.075 (3) 0.0006 (19) 0.043 (2) −0.003 (2) O1 0.052 (2) 0.050 (3) 0.042 (2) 0.000 0.038 (2) 0.000 O2 0.057 (3) 0.047 (3) 0.045 (2) 0.000 0.031 (2) 0.000 O3 0.079 (4) 0.052 (3) 0.094 (4) 0.000 0.060 (3) 0.000

Geometric parameters (Å, º)

Cu1—O2 1.974 (4) C4—C5ii _{1.501 (7)}

Cu1—O2i _{1.974 (4) C4—C5 1.501 (7)}

Cu1—N1i _{1.994 (5) C4—C6 1.503 (10)}

Cu1—N1 1.994 (5) C5—H5A 0.9600

C1—C2 1.488 (6) C5—H5B 0.9600

C1—H1D 0.9600 C5—H5C 0.9600

C1—H1E 0.9600 C6—H6A 0.9599

C1—H1F 0.9600 C6—H6B 0.9600

C2—N2 1.306 (6) N1—C2iii _{1.337 (5)}

C2—N1 1.337 (5) N2—N2iii _{1.399 (8)}

C3—O1 1.251 (7) O1—H1B 0.8501

C3—O2 1.253 (8) O3—H3A 0.8482

C3—C4 1.480 (7)

O2—Cu1—O2i _{180.000 (1) C5}ii_{—C4—C5 101.5 (5)}

O2—Cu1—N1i _{90.000 (1) C3—C4—C6 113.4 (5)}

O2i_—Cu1—N1i _{90.000 (1) C5}ii_{—C4—C6 109.4 (3)}

O2—Cu1—N1 90.00 (1) C5—C4—C6 109.4 (3) O2i_{—Cu1—N1 90.000 (1) C4—C5—H5A 109.5}

N1i_{—Cu1—N1 180.000 (1) C4—C5—H5B 109.5}

C2—C1—H1D 109.5 H5A—C5—H5B 109.5

C2—C1—H1E 109.5 C4—C5—H5C 109.5

H1D—C1—H1E 109.5 H5A—C5—H5C 109.5

C2—C1—H1F 109.5 H5B—C5—H5C 109.5

H1D—C1—H1F 109.5 C4—C6—H6A 110.9

H1E—C1—H1F 109.5 C4—C6—H6B 108.7

N2—C2—N1 111.6 (4) H6A—C6—H6B 109.5 N2—C2—C1 123.4 (4) C2—N1—C2iii _{104.8 (5)}

N1—C2—C1 125.0 (4) Cu1—N1—C2 127.6 (3) O1—C3—O2 120.7 (5) Cu1iii_{—N1—C2 127.6 (3)}

O1—C3—C4 120.8 (6) C2—N2—N2iii _{106.0 (3)}

O2—C3—C4 118.4 (5) C3—O1—H1B 124.8 C3—C4—C5ii _{111.2 (4) Cu1—O2—C3 103.3 (3)}

C3—C4—C5 111.2 (4)

O1—C3—C4—C5ii _{−56.2 (3) O2—Cu1—N1—C2 120.2 (3)}

O2—C3—C4—C5ii _{123.8 (3) O2}i_{—Cu1—N1—C2 −59.8 (3)}

O1—C3—C4—C5 56.2 (3) O2—Cu1—N1—C2iii _{−59.8 (3)}

supporting information

sup-4 Acta Cryst. (2004). E60, m1889–m1891

O1—C3—C4—C6 180.000 (2) N1—C2—N2—N2iii _{1.1 (7)}

O2—C3—C4—C6 0.000 (2) C1—C2—N2—N2iii _{179.5 (5)}

N2—C2—N1—C2iii _{−0.4 (3) O1—C3—O2—Cu1 0.000 (1)}

C1—C2—N1—C2iii _{−178.9 (6) C4—C3—O2—Cu1 180.000 (1)}

N2—C2—N1—Cu1 179.6 (3) N1i_{—Cu1—O2—C3 90.00 (1)}

C1—C2—N1—Cu1 1.1 (6) N1—Cu1—O2—C3 −90.00 (2)

Symmetry codes: (i) −x+1, −y, −z+2; (ii) x, −y, z; (iii) −x+1, y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O1—H1B···O3 0.85 1.86 2.637 (6) 151 O3—H3A···N2iv _{0.85 2.07 2.748 (5) 137}