Dichloridotetra-kis-(1H-1,2,4-triazole-κN(4))copper(II).

The central Cu(II) atom of the molecular title complex, [CuCl(2)(C(2)H(3)N(3))(4)], is situated on a site with symmetry 2.22. It is six-coordinated in an elongated octa-hedral 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 mol-ecules are connected via N-H⋯Cl hydrogen bonds and the crystal consists of two inter-penetrating 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 CuII complexes of pesticides, see: Kamiya & Kameyama (2001 ▶); Morillo et al. (2002 ▶).

Experimental

Crystal data

[CuCl2(C2H3N3)4]

M = 410.75

Tetragonal,

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[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.067

S = 1.10

952 reflections

59 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.26 e Å−3

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 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812008872/gk2463sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[CuCl2(C2H3N3)4]	Dx = 1.653 Mg m−3
Mr = 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

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

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(Fo2) + (0.0335P)2 + 1.7204P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.067	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 0.40 e Å−3
952 reflections	Δρmin = −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)

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1iv	0.80 (2)	2.28 (2)	3.0626 (16)	164 (2)

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) .