catena-Poly[[bis­[1-(2-hydroxy­ethyl)-1H-tetra­zole-κN4]copper(II)]-di-μ-chlorido]: a powder study

Ivashkevich, L.S.; Lyakhov, A.S.; Serebryanskaya, T.V.; Gaponik, P.N.

doi:10.1107/S1600536808022137

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Pages m1044-m1045

doi:10.1107/S1600536808022137

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catena-Poly[[bis[1-(2-hydroxyethyl)-1H-tetrazole-κN⁴]copper(II)]-di-μ-chlorido]: a powder study

Ludmila S. Ivashkevich,^a ^* Alexander S. Lyakhov,^a Tatiyana V. Serebryanskaya ^a and Pavel N. Gaponik ^a

^aResearch Institute for Physico-Chemical Problems, Belarusian State University, Leningradskaya Str. 14, Minsk 220030, Belarus
^*Correspondence e-mail: iva@bsu.by

(Received 20 June 2008; accepted 15 July 2008; online 19 July 2008)

The crystal structure of the title polymeric complex, [CuCl₂(C₃H₆N₄O)₂]_n, was obtained by the Rietveld refinement from laboratory X-ray powder diffraction data collected at room temperature. The unique Cu^II ion lies on an inversion center and is in a slightly distorted octahedral coordination environment. In the hydroxyethyl group, all H atoms, the O atom and its attached C atom are disordered over two positions; the site occupancy factors are ca 0.6 and 0.4. The OH group is involved in an intramolecular O—H⋯N hydrogen bond.

Related literature

For related literature, see: Ivashkevich et al. (2001 ); Ivashkevich, Lyakhov et al. (2005 ); Ivashkevich, Voitekhovich & Lyakhov (2005 ); Stassen et al. (2002 ); Werner et al. (1985 ); Allen (2002 ); Virovets et al. (1995 , 1996 ).

Experimental

Crystal data

[CuCl₂(C₃H₆N₄O)₂]
M_r = 362.69
Monoclinic, P 2₁ /c
a = 13.3349 (11) Å
b = 6.7406 (6) Å
c = 7.3419 (5) Å
β = 105.450 (8)°
V = 636.08 (9) Å³
Z = 2
Cu Kα radiation
T = 295 (2) K
Specimen shape: flat sheet
30 × 30 × 1 mm
Specimen prepared at 100 kPa
Specimen prepared at 295(2) K
Particle morphology: plate, green

Data collection

HZG-4A (Carl Zeiss, Jena) diffractometer
Specimen mounting: packed powder pellet
Specimen mounted in reflection mode
Scan method: step
2θ_min = 5.0, 2θ_max = 100.0°
Increment in 2θ = 0.02°

Refinement

R_p = 0.042
R_wp = 0.067
R_exp = 0.086
R_B = 0.029
S = 0.78
Wavelength of incident radiation: 1.5418 Å
Excluded region(s): none
Profile function: pseudo-Voigt
785 reflections
48 parameters
21 restraints
H-atom parameters constrained
Preferred orientation correction: Marsh–Dollase function (Marsh, 1932 ; Dollase, 1986 )

Table 1
Selected geometric parameters (Å, °)

Cu—Cl	2.234 (7)
Cu—N4	1.979 (10)
Cu—Clⁱ	3.008 (7)
Cu—Cuⁱⁱ	4.9835 (4)

Cl—Cu—N4	89.8 (7)
Cl—Cu—Clⁱ	90.8 (2)
Cl—Cu—Clⁱⁱⁱ	180
Cl—Cu—N4ⁱⁱⁱ	90.2 (7)
Cl—Cu—Cl^iv	89.2 (2)
Clⁱ—Cu—N4	92.6 (5)
N4—Cu—N4ⁱⁱⁱ	180
Cl^iv—Cu—N4	87.4 (5)
Cu—Cl—Cuⁱⁱ	143.5 (2)
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x, -y, -z+1; (iv) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2	0.82	2.35	3.08 (3)	149
O2—H2⋯N2	0.82	2.46	3.02 (3)	126
C5—H5⋯Clⁱⁱ	0.93	2.72	3.34 (2)	126
Symmetry code: (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: local program; cell refinement: FULLPROF (Rodríguez-Carvajal, 2001 ); data reduction: local program; program(s) used to refine structure: FULLPROF and SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: FULLPROF and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808022137/lh2648sup1.cif

Rietveld powder data: contains datablock I. DOI: 10.1107/S1600536808022137/lh2648Isup2.rtv

checkCIF report

Comment top

Complexes of copper(II) chloride with substituted tetrazoles attract attention because of their magnetic bahaviour at low temperatures. Among them, there are layered coordination polymers with square grids of only Cu and Cl atoms, of the composition CuCl₂L₂, where L = 1-ethyltetrazole (Virovets et al., 1995), 1-allyltetrazole (Virovets et al., 1996), 1-(2-azidoethyl)terazole (Ivashkevich et al., 2001), 1-(2-chloroethyl)tetrazole (Stassen et al., 2002), 1-benzyltetrazole (Ivashkevich, Voitekhovich & Lyakhov, 2005), and 1-methyltetrazole (Ivashkevich, Lyakhov, Ivashkevich, Degtyarik & Gaponik, 2005). These compounds crystallize in the space group P2₁/c and are isotypic. Here, we present another example, poly[[bis(1-(2-hydroxyethyl)tetrazole-N⁴)copper(II)]-di-µ-chloro], (I), (Fig. 1). As it is difficult to obtain single crystals for structural analysis, the compound (I) was investigated by X-ray powder diffraction.

The Cu atom lies on inversion center and shows a slightly distorted octahedral coordination environment. Equatorial sites are occupied by two trans positioned N atoms and two Cl atoms; Cl atoms lying in axial positions are essentially more distant from the Cu atom (Table 1). Each Cl atom is a bridge between the neighbouring Cu atoms, forming two different in length Cu—Cl bonds, with Cu—Cl—Cu angle of 143.4 (2)°. These bonds are responsible for the formation of polymeric layers parallel to the yz plane (Fig. 2). Within a layer, the shortest Cu···Cu distance is 4.9835 (4) Å, whereas between two neighbouring layers, the closest Cu centers are separated by cell dimension a. Only van der Waals interactions are between the layers.

The 2-hydroxyethyl substituent at the tetrazole ring atom N1 was found to be disordered over two positions, with almost equal occupancies of 0.562 (12) for C71—O1 and 0.438 (12) for C72—O2 (Fig. 1). For both positions, OH groups are involved in intramolecular hydrogen bonds O—H···N. There are also hydrogen bonds C—H···Cl (Table 2).

Related literature top

For related literature, see: Ivashkevich et al. (2001); Ivashkevich, Lyakhov, et al. (2005); Ivashkevich, Voitekhovich & Lyakhov (2005); Stassen et al. (2002); Werner et al. (1985).

For related literature, see: Allen (2002); Virovets et al. (1995, 1996).

Experimental top

A solution, containing 2.13 g (0.0125 mol) of CuCl₂.2H₂O in 75 ml of ethanol, was added to a slightly heated solution of 1-(2-hydroxyethyl)tetrazole (2.85 g, 0.025 mol) in a solvent mixture (45 ml of ethanol and 30 ml of n-buthanol), with stirring at room temperature. After stirring the reaction mixture for 10 min, the obtained green crystals of (I) were filtered off, air dried and recrystallized from (ethanol—n-buthanol) mixture (v/v = 4:1) [3.55 g, yield 78.3%]. Calc.(%): Cu 17.52, Cl 19.59. Found (%): Cu 18.2, Cl 20.1.

Computing details top

Data collection: local program; cell refinement: FULLPROF (Rodríguez-Carvajal, 2001); data reduction: local program; program(s) used to refine structure: FULLPROF (Rodríguez-Carvajal, 2001) and SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: FULLPROF (Rodríguez-Carvajal, 2001) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The asymmetric unit of (I) with the atomic numbering scheme. 2-hydroxyethyl substituent is shown as disordered over two positions.
	Fig. 2. Layered structure of (I), viewed along the b axis. Disordered 2-hydroxyethyl substituent is shown only in position with occupancy factor of 0.562 (12).
	Fig. 3. The Rietveld plot, showing the observed (circles), calculated (line) and difference patterns for (I). The reflection positions are shown above the difference pattern.

catena-Poly[[bis[1-(2-hydroxyethyl)-1H-tetrazole-κN⁴]copper(II)]- di-µ-chlorido] top

Crystal data top

[CuCl₂(C₃H₆N₄O)₂]	Z = 2
M_r = 362.69	F(000) = 366.0
Monoclinic, P2₁/c	D_x = 1.894 Mg m⁻³
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.5418 Å
a = 13.3349 (11) Å	T = 295 K
b = 6.7406 (6) Å	Particle morphology: plate
c = 7.3419 (5) Å	green
β = 105.450 (8)°	flat sheet, 30 × 30 mm
V = 636.08 (9) Å³	Specimen preparation: Prepared at 295 K and 100 kPa

Data collection top

HZG-4A (Carl Zeiss, Jena) diffractometer	Data collection mode: reflection
Radiation source: fine-focus sealed X-ray tube, BSV-29	Scan method: step
Ni filtered monochromator	2θ_min = 5.000°, 2θ_max = 100.000°, 2θ_step = 0.020°
Specimen mounting: packed powder pellet

Refinement top

Refinement on I_net	Profile function: psevdo-Voigt
Least-squares matrix: full with fixed elements per cycle	48 parameters
R_p = 0.042	21 restraints
R_wp = 0.067	0 constraints
R_exp = 0.086	H-atom parameters constrained
R_Bragg = 0.029	Weighting scheme based on measured s.u.'s
χ² = 0.608	(Δ/σ)_max = 0.02
4751 data points	Background function: Fourier filtering
Excluded region(s): none	Preferred orientation correction: Marsh–Dollase function (Marsh, 1932; Dollase, 1986)

Crystal data top

[CuCl₂(C₃H₆N₄O)₂]	β = 105.450 (8)°
M_r = 362.69	V = 636.08 (9) Å³
Monoclinic, P2₁/c	Z = 2
a = 13.3349 (11) Å	Cu Kα radiation, λ = 1.5418 Å
b = 6.7406 (6) Å	T = 295 K
c = 7.3419 (5) Å	flat sheet, 30 × 30 mm

Data collection top

HZG-4A (Carl Zeiss, Jena) diffractometer	Scan method: step
Specimen mounting: packed powder pellet	2θ_min = 5.000°, 2θ_max = 100.000°, 2θ_step = 0.020°
Data collection mode: reflection

Refinement top

R_p = 0.042	4751 data points
R_wp = 0.067	48 parameters
R_exp = 0.086	21 restraints
R_Bragg = 0.029	H-atom parameters constrained
χ² = 0.608

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu	0.00000	0.00000	0.50000	0.0309 (10)*
Cl	−0.0624 (4)	0.2048 (11)	0.2569 (10)	0.0309 (10)*
N1	0.24708 (16)	0.3706 (2)	0.583 (4)	0.0309 (10)*
N2	0.2982 (2)	0.19676 (13)	0.595 (3)	0.0309 (10)*
N3	0.2308 (2)	0.05581 (18)	0.577 (3)	0.0309 (10)*
N4	0.1358 (4)	0.1377 (3)	0.553 (4)	0.0309 (10)*
C5	0.14654 (16)	0.3314 (4)	0.545 (5)	0.0309 (10)*
H5	0.09292	0.42403	0.51621	0.0309 (10)*
C6	0.3006 (6)	0.5643 (10)	0.5973 (16)	0.0309 (10)*
H61A	0.24602	0.66346	0.56434	0.0309 (10)*	0.562 (12)
H61B	0.33551	0.56618	0.49731	0.0309 (10)*	0.562 (12)
C71	0.3778 (18)	0.641 (2)	0.768 (3)	0.0309 (10)*	0.562 (12)
H71A	0.41791	0.74586	0.73283	0.0309 (10)*	0.562 (12)
H71B	0.34071	0.69633	0.85467	0.0309 (10)*	0.562 (12)
O1	0.4451 (15)	0.489 (3)	0.862 (5)	0.0309 (10)*	0.562 (12)
H1	0.42627	0.38207	0.81168	0.0309 (10)*	0.562 (12)
H62A	0.31564	0.60902	0.72756	0.0309 (10)*	0.438 (12)
H62B	0.25331	0.65967	0.52039	0.0309 (10)*	0.438 (12)
C72	0.3987 (12)	0.565 (7)	0.539 (4)	0.0309 (10)*	0.438 (12)
H72A	0.38957	0.48960	0.42321	0.0309 (10)*	0.438 (12)
H72B	0.41727	0.69967	0.51599	0.0309 (10)*	0.438 (12)
O2	0.479 (2)	0.480 (6)	0.684 (5)	0.0309 (10)*	0.438 (12)
H2	0.46854	0.35907	0.68929	0.0309 (10)*	0.438 (12)

Geometric parameters (Å, º) top

Cu—Cl	2.234 (7)	N3—N4	1.350 (11)
Cu—N4	1.979 (10)	N4—C5	1.316 (4)
Cu—Clⁱ	3.008 (7)	C6—C71	1.49 (2)
Cu—Clⁱⁱ	2.234 (7)	C6—C72	1.48 (2)
Cu—N4ⁱⁱ	1.979 (10)	C5—H5	0.9300
Cu—Clⁱⁱⁱ	3.008 (7)	C6—H61B	0.9700
O1—C71	1.41 (3)	C6—H62A	0.9700
O2—C72	1.42 (5)	C6—H61A	0.9700
O1—H1	0.8200	C6—H62B	0.9700
O2—H2	0.8200	C71—H71A	0.9700
N1—N2	1.346 (6)	C71—H71B	0.9700
N1—C5	1.321 (15)	C72—H72A	0.9700
N1—C6	1.478 (8)	C72—H72B	0.9700
N2—N3	1.291 (7)	Cu—Cu^iv	4.9835 (4)

Cl—Cu—N4	89.8 (7)	N1—C6—C72	115 (2)
Cl—Cu—Clⁱ	90.8 (2)	N1—C6—C71	125.5 (14)
Cl—Cu—Clⁱⁱ	180	O1—C71—C6	111.5 (15)
Cl—Cu—N4ⁱⁱ	90.2 (7)	O2—C72—C6	110 (2)
Cl—Cu—Clⁱⁱⁱ	89.2 (2)	N1—C5—H5	126.00
Clⁱ—Cu—N4	92.6 (5)	N4—C5—H5	126.00
Clⁱⁱ—Cu—N4	90.2 (7)	N1—C6—H61B	106.00
N4—Cu—N4ⁱⁱ	180	N1—C6—H62A	108.00
Clⁱⁱⁱ—Cu—N4	87.4 (5)	N1—C6—H62B	108.00
Clⁱ—Cu—Clⁱⁱ	89.2 (2)	C71—C6—H61A	106.00
Clⁱ—Cu—N4ⁱⁱ	87.4 (5)	C71—C6—H61B	106.00
Clⁱ—Cu—Clⁱⁱⁱ	180.00	H61A—C6—H61B	106.00
Clⁱⁱ—Cu—N4ⁱⁱ	89.8 (7)	C72—C6—H62A	109.00
Clⁱⁱ—Cu—Clⁱⁱⁱ	90.8 (2)	C72—C6—H62B	109.00
Clⁱⁱⁱ—Cu—N4ⁱⁱ	92.6 (5)	H62A—C6—H62B	107.00
Cu—Cl—Cu^iv	143.5 (2)	N1—C6—H61A	106.00
C71—O1—H1	109.00	O1—C71—H71A	109.00
C72—O2—H2	109.00	O1—C71—H71B	109.00
N2—N1—C6	122.6 (7)	C6—C71—H71B	109.00
C5—N1—C6	129.4 (6)	H71A—C71—H71B	108.00
N2—N1—C5	107.9 (5)	C6—C71—H71A	109.00
N1—N2—N3	107.9 (6)	C6—C72—H72A	110.00
N2—N3—N4	108.4 (3)	C6—C72—H72B	110.00
Cu—N4—N3	127.6 (3)	O2—C72—H72A	110.00
N3—N4—C5	107.5 (8)	O2—C72—H72B	109.00
Cu—N4—C5	124.1 (9)	H72A—C72—H72B	108.00
N1—C5—N4	107.8 (9)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.8200	2.3500	3.08 (3)	149.00
O2—H2···N2	0.8200	2.4600	3.02 (3)	126.00
C5—H5···Cl^iv	0.9300	2.7200	3.34 (2)	126.00

Symmetry code: (iv) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₃H₆N₄O)₂]
M_r	362.69
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	13.3349 (11), 6.7406 (6), 7.3419 (5)
β (°)	105.450 (8)
V (Å³)	636.08 (9)
Z	2
Radiation type	Cu Kα, λ = 1.5418 Å
Specimen shape, size (mm)	Flat sheet, 30 × 30

Data collection
Diffractometer	HZG-4A (Carl Zeiss, Jena) diffractometer
Specimen mounting	Packed powder pellet
Data collection mode	Reflection
Scan method	Step
2θ values (°)	2θ_min = 5.000 2θ_max = 100.000 2θ_step = 0.020

Refinement
R factors and goodness of fit	R_p = 0.042, R_wp = 0.067, R_exp = 0.086, R_Bragg = 0.029, χ² = 0.608
No. of data points	4751
No. of parameters	48
No. of restraints	21
H-atom treatment	H-atom parameters constrained

Computer programs: local program, FULLPROF (Rodríguez-Carvajal, 2001) and SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), FULLPROF (Rodríguez-Carvajal, 2001) and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top

Cu—Cl	2.234 (7)	Cu—Clⁱ	3.008 (7)
Cu—N4	1.979 (10)	Cu—Cuⁱⁱ	4.9835 (4)

Cl—Cu—N4	89.8 (7)	Clⁱ—Cu—N4	92.6 (5)
Cl—Cu—Clⁱ	90.8 (2)	N4—Cu—N4ⁱⁱⁱ	180
Cl—Cu—Clⁱⁱⁱ	180	Cl^iv—Cu—N4	87.4 (5)
Cl—Cu—N4ⁱⁱⁱ	90.2 (7)	Cu—Cl—Cuⁱⁱ	143.5 (2)
Cl—Cu—Cl^iv	89.2 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.8200	2.3500	3.08 (3)	149.00
O2—H2···N2	0.8200	2.4600	3.02 (3)	126.00
C5—H5···Clⁱⁱ	0.9300	2.7200	3.34 (2)	126.00

Symmetry code: (ii) −x, y+1/2, −z+1/2.

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