Dichloridotetra­kis­(1H-1,2,4-triazole-κN4)copper(II)

Vidmar, M.; Kobal, T.; Kozlevčar, B.; Šegedin, P.; Golobič, A.

doi:10.1107/S1600536812008872

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m375-m376

doi:10.1107/S1600536812008872

Open

access

Dichloridotetrakis(1H-1,2,4-triazole-κN⁴)copper(II)

Maja Vidmar,^a ^* Tatjana Kobal,^a Bojan Kozlevčar,^a Primož Šegedin ^a and Amalija Golobič ^a

^aFaculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, 1000 Ljubljana, Slovenia
^*Correspondence e-mail: maja.vidmar@fkkt.uni-lj.si

(Received 22 February 2012; accepted 28 February 2012; online 3 March 2012)

The central Cu^II atom of the molecular title complex, [CuCl₂(C₂H₃N₃)₄], is situated on a site with symmetry 2.22. It is six-coordinated in an elongated octahedral geometry, with the equatorial plane defined by four N atoms of four 1,2,4-triazole ligands and the axial positions occupied by two Cl atoms situated on a twofold axis. The molecules are connected via N—H⋯Cl hydrogen bonds and the crystal consists of two interpenetrating three-dimensional hydrogen-bonded frameworks.

Related literature

For the synthesis and structure of copper(II) coordination compounds with 1,2,4-triazole derivatives, see: Zhang et al. (2003 ); Zhang & Wu (2005 ); Zhao et al. (2009 ); Haasnoot (2000 ). For the synthesis and structure of 1,2,4-triazole with other metal ions, see: Arion et al. (2003 ), Haasnoot (2000). For properties of some Cu^II complexes of pesticides, see: Kamiya & Kameyama (2001 ); Morillo et al. (2002 ).

Experimental

Crystal data

[CuCl₂(C₂H₃N₃)₄]
M_r = 410.75
Tetragonal, I 4₁ /a c d
a = 14.4471 (3) Å
c = 15.8181 (3) Å
V = 3301.53 (12) Å³
Z = 8
Mo Kα radiation
μ = 1.67 mm⁻¹
T = 294 K
0.30 × 0.24 × 0.22 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997 ) T_min = 0.635, T_max = 0.711
21092 measured reflections
952 independent reflections
776 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.067
S = 1.10
952 reflections
59 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	2.0049 (12)
Cu1—Cl1	2.8296 (6)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Cl1ⁱ	0.80 (2)	2.28 (2)	3.0626 (16)	164 (2)
Symmetry code: (i) $[x, y+{\script{1\over 2}}, -z]$ .

Data collection: COLLECT (Nonius, 2000 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SIR08 (Burla et al., 2007 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812008872/gk2463sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008872/gk2463Isup2.hkl

checkCIF report

Comment top

The 1,2,4-triazoles are being widely used as pharmaceutical and as agricultural chemicals (Haasnoot, 2000). There has also been considerable research on complexation of pesticides with metal ions since it influences their pharmacological and toxicological properties (Arion et al., 2003; Zhang et al., 2003; Kamiya & Kameyama, 2001; Morillo et al., 2002). We report here the preparation and structure of the novel Cu^IIcomplex, (I), containing the 1-H-1,2,4-triazole ligands.

The title compound [CuCl₂(C₂H₃N₃)₄] is mononuclear complex, where central Cu^II atom has a distorted (4 + 2) octahedral coordination environment with four N atoms of 1-H-1,2,4-triazole ligands in the equatorial plane and two axial trans positioned chlorido ligands. The Cu—N and Cu—Cl bond distances (Table 1) indicate Jahn-Teller elongation of the coordination octahedron. Similar coordination bond lengths and elongation were observed also in all three known structures of analogous mononuclear Cu^II complexes containing four coordinated triazolo derivatives and two choride ions at axial position (Zhang & Wu, 2005; Zhang et al., 2003; Zhao et al., 2009). Figure 1 shows the ORTEP drawing of complex molecule of (I). The Cu atom lies on a cross-section of three twofold rotation axes (Wyckoff position b) and both Cl atoms from the molecule lie on one of these twofold axes (Wyckoff position f). Conformation of the molecule is a propeller like. N2 atom is a donor of intermolecular hydrogen bond accepted by Cl atom (symmetry code: x, y + 1/2, -z) from neighbouring molecule. This way molecules are linked into a three-dimensional hydrogen-bonding framework (Figure 2, Table 2). The crystal of (I) consists of two interpenetrating three-dimesional hydrogen-bond frameworks.

Related literature top

For the synthesis and structure of copper(II) coordination compounds with 1,2,4-triazole derivatives, see: Zhang et al. (2003); Zhang & Wu ( 2005); Zhao et al. (2009); Haasnoot (2000). For the synthesis and structure of 1,2,4-triazole with other metal ions, see: Arion et al. (2003), Haasnoot (2000). For properties of some Cu^II complexes of pesticides, see: Kamiya & Kameyama (2001); Morillo et al. (2002).

Experimental top

To a solution of hydrated copper(II) nitrate(V) (0.196 g, 0.81 mmol) in distilled water (40.0 ml) was added a solution of 37% hydrochloric acid (4.0 ml). The pale blue solution was heated till boiling and the colour changed into green. To a cooled solution was added borax (0.400 g, 1.05 mmol) and 1,2,4-triazole (9.600 g, 0.140 mol). The dark blue solution was obtained and at the end NaCl (7.00 g, 0.120 mol) was added. The solution was left for 48 h and the blue crystals suitable for X-ray analysis were obtained.

Structure description top

For the synthesis and structure of copper(II) coordination compounds with 1,2,4-triazole derivatives, see: Zhang et al. (2003); Zhang & Wu ( 2005); Zhao et al. (2009); Haasnoot (2000). For the synthesis and structure of 1,2,4-triazole with other metal ions, see: Arion et al. (2003), Haasnoot (2000). For properties of some Cu^II complexes of pesticides, see: Kamiya & Kameyama (2001); Morillo et al. (2002).

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR08 (Burla et al., 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are drawn as small spheres of arbitrary radii. [Symmetry codes: (i) -x, -y + 1/2, z; (ii) -y + 1/4, -x + 1/4, -z + 1/4; (iii) y - 1/4, x + 1/4, -z + 1/4.]
	Fig. 2. Fragment of a three-dimensional hydrogen-bond framework formed via N—H···Cl intermolecular interactions.

Dichloridotetrakis(1H-1,2,4-triazole-κN⁴)copper(II) top

Crystal data top

[CuCl₂(C₂H₃N₃)₄]	D_x = 1.653 Mg m⁻³
M_r = 410.75	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/acd	Cell parameters from 1966 reflections
Hall symbol: -I 4bd 2c	θ = 2.6–27.5°
a = 14.4471 (3) Å	µ = 1.67 mm⁻¹
c = 15.8181 (3) Å	T = 294 K
V = 3301.53 (12) Å³	Prism, dark blue
Z = 8	0.30 × 0.24 × 0.22 mm
F(000) = 1656

Data collection top

Nonius KappaCCD diffractometer	952 independent reflections
Radiation source: fine-focus sealed tube	776 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
φ and ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −13→13
T_min = 0.635, T_max = 0.711	k = −18→18
21092 measured reflections	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.025	w = 1/[σ²(F_o²) + (0.0335P)² + 1.7204P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.067	(Δ/σ)_max < 0.001
S = 1.10	Δρ_max = 0.40 e Å⁻³
952 reflections	Δρ_min = −0.26 e Å⁻³
59 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0043 (3)

Crystal data top

[CuCl₂(C₂H₃N₃)₄]	Z = 8
M_r = 410.75	Mo Kα radiation
Tetragonal, I4₁/acd	µ = 1.67 mm⁻¹
a = 14.4471 (3) Å	T = 294 K
c = 15.8181 (3) Å	0.30 × 0.24 × 0.22 mm
V = 3301.53 (12) Å³

Data collection top

Nonius KappaCCD diffractometer	952 independent reflections
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	776 reflections with I > 2σ(I)
T_min = 0.635, T_max = 0.711	R_int = 0.035
21092 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.40 e Å⁻³
952 reflections	Δρ_min = −0.26 e Å⁻³
59 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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

	x	y	z	U_iso*/U_eq
Cu1	0.0000	0.2500	0.1250	0.03175 (17)
Cl1	0.13849 (3)	0.11151 (3)	0.1250	0.0453 (2)
N1	0.07460 (8)	0.31410 (8)	0.03559 (8)	0.0329 (3)
N3	0.16037 (11)	0.33828 (11)	−0.07999 (9)	0.0488 (4)
N2	0.13429 (10)	0.41905 (11)	−0.04391 (10)	0.0436 (4)
C2	0.12290 (12)	0.27712 (13)	−0.02974 (10)	0.0435 (4)
H2A	0.1288	0.2137	−0.0380	0.052*
C3	0.08400 (11)	0.40417 (11)	0.02389 (10)	0.0386 (4)
H3	0.0589	0.4499	0.0583	0.046*
H2	0.1460 (16)	0.4665 (16)	−0.0679 (13)	0.059 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03525 (19)	0.03525 (19)	0.0247 (2)	−0.01284 (14)	0.000	0.000
Cl1	0.0398 (2)	0.0398 (2)	0.0562 (4)	0.0036 (2)	−0.01066 (18)	−0.01066 (18)
N1	0.0358 (7)	0.0325 (6)	0.0305 (6)	−0.0064 (5)	0.0031 (5)	−0.0016 (5)
N3	0.0550 (9)	0.0519 (9)	0.0395 (8)	0.0014 (7)	0.0144 (7)	0.0045 (7)
N2	0.0465 (8)	0.0386 (8)	0.0457 (8)	−0.0059 (6)	0.0072 (7)	0.0109 (7)
C2	0.0573 (11)	0.0370 (8)	0.0362 (8)	−0.0013 (8)	0.0102 (8)	−0.0021 (7)
C3	0.0410 (9)	0.0337 (8)	0.0411 (9)	−0.0021 (7)	0.0060 (7)	0.0019 (7)

Geometric parameters (Å, º) top

Cu1—N1	2.0049 (12)	N3—N2	1.353 (2)
Cu1—Cl1	2.8296 (6)	N2—C3	1.313 (2)
N1—C3	1.321 (2)	N2—H2	0.80 (2)
N1—C2	1.357 (2)	C2—H2A	0.9300
N3—C2	1.306 (2)	C3—H3	0.9300

N1ⁱ—Cu1—N1ⁱⁱ	173.87 (7)	Cl1ⁱ—Cu1—Cl1	180.0
N1ⁱ—Cu1—N1	90.27 (7)	C3—N1—C2	103.20 (13)
N1ⁱⁱ—Cu1—N1	90.06 (7)	C3—N1—Cu1	127.51 (10)
N1ⁱ—Cu1—N1ⁱⁱⁱ	90.06 (7)	C2—N1—Cu1	129.20 (11)
N1ⁱⁱ—Cu1—N1ⁱⁱⁱ	90.27 (7)	C2—N3—N2	102.21 (13)
N1—Cu1—N1ⁱⁱⁱ	173.87 (7)	C3—N2—N3	110.94 (14)
N1ⁱ—Cu1—Cl1ⁱ	86.93 (3)	C3—N2—H2	130.1 (16)
N1ⁱⁱ—Cu1—Cl1ⁱ	86.93 (3)	N3—N2—H2	118.6 (15)
N1—Cu1—Cl1ⁱ	93.07 (3)	N3—C2—N1	114.23 (15)
N1ⁱⁱⁱ—Cu1—Cl1ⁱ	93.07 (3)	N3—C2—H2A	122.9
N1ⁱ—Cu1—Cl1	93.07 (3)	N1—C2—H2A	122.9
N1ⁱⁱ—Cu1—Cl1	93.07 (3)	N2—C3—N1	109.42 (14)
N1—Cu1—Cl1	86.93 (3)	N2—C3—H3	125.3
N1ⁱⁱⁱ—Cu1—Cl1	86.93 (3)	N1—C3—H3	125.3

N1ⁱ—Cu1—N1—C3	120.99 (15)	C2—N3—N2—C3	−0.10 (19)
N1ⁱⁱ—Cu1—N1—C3	−52.88 (12)	N2—N3—C2—N1	0.2 (2)
Cl1ⁱ—Cu1—N1—C3	34.05 (13)	C3—N1—C2—N3	−0.22 (19)
Cl1—Cu1—N1—C3	−145.95 (13)	Cu1—N1—C2—N3	176.42 (12)
N1ⁱ—Cu1—N1—C2	−54.89 (12)	N3—N2—C3—N1	0.0 (2)
N1ⁱⁱ—Cu1—N1—C2	131.24 (15)	C2—N1—C3—N2	0.14 (18)
Cl1ⁱ—Cu1—N1—C2	−141.83 (13)	Cu1—N1—C3—N2	−176.58 (11)
Cl1—Cu1—N1—C2	38.17 (13)

Symmetry codes: (i) −x, −y+1/2, z; (ii) y−1/4, x+1/4, −z+1/4; (iii) −y+1/4, −x+1/4, −z+1/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1^iv	0.80 (2)	2.28 (2)	3.0626 (16)	164 (2)

Symmetry code: (iv) x, y+1/2, −z.

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₂H₃N₃)₄]
M_r	410.75
Crystal system, space group	Tetragonal, I4₁/acd
Temperature (K)	294
a, c (Å)	14.4471 (3), 15.8181 (3)
V (Å³)	3301.53 (12)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.67
Crystal size (mm)	0.30 × 0.24 × 0.22

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)
T_min, T_max	0.635, 0.711
No. of measured, independent and observed [I > 2σ(I)] reflections	21092, 952, 776
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.067, 1.10
No. of reflections	952
No. of parameters	59
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.26

Computer programs: COLLECT (Nonius, 2000), DENZO-SMN (Otwinowski & Minor, 1997), SIR08 (Burla et al., 2007), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Cu1—N1

2.0049 (12)

Cu1—Cl1

2.8296 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1ⁱ	0.80 (2)	2.28 (2)	3.0626 (16)	164 (2)

Symmetry code: (i) x, y+1/2, −z.

Acknowledgements

This work was supported by the Ministry of Education, Science, Culture and Sport of the Republic of Slovenia (grants P1–0175 and MR-33158).

References

Arion, V. B., Reisner, E., Fremuth, M., Jakupec, M. A., Keppler, B. K., Kukushkin, V. Y. & Pombeiro, A. J. L. (2003). Inorg. Chem. 42, 6024–6031. Web of Science CSD CrossRef PubMed CAS Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G., Siliqi, D. & Spagna, R. (2007). J. Appl. Cryst. 40, 609–613. Web of Science CrossRef CAS IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Haasnoot, J. G. (2000). Coord. Chem. Rev. 200–202, 131–185. Web of Science CrossRef CAS Google Scholar
Kamiya, M. & Kameyama, K. (2001). Chemosphere, 45, 231–235. Web of Science CrossRef PubMed CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Morillo, E., Undabeytia, T., Maqueda, C. & Ramos, A. (2002). Chemosphere, 47, 747–752. Web of Science CrossRef PubMed CAS Google Scholar
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, P.-Z. & Wu, J. (2005). Acta Cryst. E61, m560–m562. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, P.-Z., Wu, J., Gong, Y.-O., Hu, X.-R. & Gu, J.-M. (2003). Chin. J. Inorg. Chem. 19, 909–912. CAS Google Scholar
Zhao, X.-X., Ma, J.-P., Shen, D.-Z., Dong, Y.-B. & Huang, R.-Q. (2009). CrystEngComm, 11, 1281–1290. Web of Science CSD CrossRef CAS Google Scholar