Poly[μ-chlorido-[μ4-5-(4-pyrid­yl)tetra­zol­ato]dicopper(I)]

Wang, C.-K.; Li, X.-Y.

doi:10.1107/S1600536809006564

metal-organic compounds

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Volume 65| Part 4| April 2009| Page m363

doi:10.1107/S1600536809006564

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Poly[μ-chlorido-[μ₄-5-(4-pyridyl)tetrazolato]dicopper(I)]

Cun-Kuan Wang ^a ^* and Xiao-Yan Li ^b

^aYangming School, Ningbo University, Ningbo, Zhejiang 315211, People's Republic of China, and ^bDepartment of Biological Engineering, Zibo Vocational Institute, Zibo, Shandong 255314, People's Republic of China
^*Correspondence e-mail: wcklx@nbu.edu.cn

(Received 25 December 2008; accepted 23 February 2009; online 6 March 2009)

The title three-dimensional coordination polymer, [Cu₂Cl(C₆H₄N₅)]_n, is the product of the hydrothermal reaction of CuCl₂·2H₂O and 5-(4-pyridyl)-1H-tetrazole (4-Hptz). The two independent Cu^I ions are coordinated in distorted tetrahedral and distorted trigonal coordination environments. In the unique 5-(4-pyridyl)-1H-tetrazolate ligand, the dihedral angle between the pyridine and tetrazole rings is 17.3 (2)°.

Related literature

For related transition metals complexes of 5-(4-pyridyl)-1H-tetrazole, see: Xue et al. (2002 ); Jiang et al. (2004 ); Luo et al. (2005 ); Lin et al. (2005 ); Chen et al. (2008 ). For the applications of tetrazoles, see: Butler (1996 ).

Experimental

Crystal data

[Cu₂Cl(C₆H₄N₅)]
M_r = 308.67
Monoclinic, C c
a = 19.6899 (7) Å
b = 3.64790 (10) Å
c = 11.6337 (3) Å
β = 102.923 (2)°
V = 814.45 (4) Å³
Z = 4
Mo Kα radiation
μ = 5.50 mm⁻¹
T = 298 K
0.30 × 0.26 × 0.24 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.230, T_max = 0.269
3752 measured reflections
1572 independent reflections
1415 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.092
S = 1.11
1572 reflections
128 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.71 e Å⁻³
Absolute structure: Flack (1983 ), 621 Friedel pairs
Flack parameter: 0.19 (3)

Table 1
Selected geometric parameters (Å, °)

Cu1—N3ⁱ	1.958 (5)
Cu1—N1	2.038 (5)
Cu1—Cl1	2.4422 (15)
Cu1—Cl1ⁱⁱ	2.5090 (16)
Cu2—N2ⁱⁱⁱ	1.921 (5)
Cu2—N5^iv	1.931 (4)
Cu2—Cl1	2.4923 (18)

N3ⁱ—Cu1—N1	133.4 (2)
N3ⁱ—Cu1—Cl1	116.27 (15)
N1—Cu1—Cl1	97.70 (14)
N3ⁱ—Cu1—Cl1ⁱⁱ	106.89 (15)
N1—Cu1—Cl1ⁱⁱ	100.51 (13)
Cl1—Cu1—Cl1ⁱⁱ	94.90 (6)
N2ⁱⁱⁱ—Cu2—N5^iv	152.3 (2)
N2ⁱⁱⁱ—Cu2—Cl1	101.13 (17)
N5^iv—Cu2—Cl1	106.30 (16)
Cu1—Cl1—Cu2	123.48 (7)
Cu1—Cl1—Cu1ⁱⁱⁱ	94.90 (6)
Cu2—Cl1—Cu1ⁱⁱⁱ	78.17 (5)
Symmetry codes: (i) $[x, -y+2, z-{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) x, y-1, z; (iv) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2003 ) ; cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809006564/lh2752sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809006564/lh2752Isup2.hkl

checkCIF report

Comment top

Tetrazoles have found a wide range of applications in areas as diverse as coordination chemistry, medicinal chemistry and materials science (Butler, 1996). The study of complexes containing substituted tetrazole ligands is of interest to delineate the ways in which tetrazoles bind to metal centres. Recently, a series of 5-(4-pyridyl)-1H-tetrazole complexes of transition metals have been reported in which a range of coordination modes for the ligand were observed and extended two-dimensional and three-dimensional structures identified (Xue et al., 2002; Jiang et al., 2004; Luo et al., 2005; Lin et al., 2005; Chen et al., 2008). Herein, we report the crystal structure of a three-dimensional coordination polymer, [Cu^I₂Cl(4-ptz)]_n, derived from 5-(4-pyridyl)-1H-tetrazole and CuCl₂.2H₂O under hydrothermal reaction.

The asymmetric unit of the title complex contains of two independent Cu^I ions, one Cl^-, and one 4-ptz ligand. As shown in Fig. 1, atom Cu1 adopts distorted tetrahedral geometry with a Cl₂N₂ donor set and atom Cu2 is in a disorted trigonal coordination geometry with an N₂Cl donor set. Atom Cl1 is bonded to three Cu^I atoms, and the 4-ptz ligand coordinates to four Cu^I ions. It is noteworthy that atoms N1, N2, and N3 bond to three Cu^I atoms, respectively, forming a µ₃-1,2,3-tetrazolyl coordination mode. The overall structure of title complex is a three-dimensional network (Fig. 2).

Related literature top

For related transition metals complexes of 5-(4-pyridyl)-1H-tetrazole, see: Xue et al. (2002); Jiang et al. (2004); Luo et al. (2005); Lin et al. (2005); Chen et al. (2008). For the applications of tetrazoles, see: Butler (1996).

Experimental top

A mixture of CuCl₂.2H₂O (0.172 g, 1 mmol), 5-(4-pyridyl)-1H-tetrazole (0.074 g, 0.5 mmol) in 8 ml deionized water was homogenized at room temperature for 30 minutes. Then the final solution was sealed in a 20 mL stainless-steelautoclave at 433 K for 72 h. A quantity of crystals was obtained after the solution was cooled to room temperature. The crystals were filtered, washed with deionized water and dried at room temperature. The yield is ca 64% based on CuCl₂.2H₂O.

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. View of the coordination environment around the Cu^I ions and 4-ptz ligand of title complex with labeling scheme and 30% thermal ellipsoids. Symmetry codes: (i) x, -y + 2, z - 1/2; (ii) x, y + 1, z; (iii) x, y - 1, z; (iv) x - 1/2, y - 1/2, z;(v) x, -y + 2, z + 1/2; (vi) x + 1/2, y + 1/2, z.
	Fig. 2. Part of the crystal structure of the title complex.

Poly[µ-chlorido-[µ₄-5-(4-pyridyl)tetrazolato]dicopper(I)] top

Crystal data top

[Cu₂Cl(C₆H₄N₅)]	F(000) = 600
M_r = 308.67	D_x = 2.517 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1367 reflections
a = 19.6899 (7) Å	θ = 2.1–27.8°
b = 3.6479 (1) Å	µ = 5.50 mm⁻¹
c = 11.6337 (3) Å	T = 298 K
β = 102.923 (2)°	Block, yellow
V = 814.45 (4) Å³	0.30 × 0.26 × 0.24 mm
Z = 4

Data collection top

Bruker SMART CCD APEXII diffractometer	1572 independent reflections
Radiation source: fine-focus sealed tube	1415 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 8.40 pixels mm^-1	θ_max = 27.8°, θ_min = 2.1°
ω scans	h = −21→25
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −4→4
T_min = 0.230, T_max = 0.269	l = −15→15
3752 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0547P)²] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
1572 reflections	Δρ_max = 0.71 e Å⁻³
128 parameters	Δρ_min = −0.71 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 621 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.19 (3)

Crystal data top

[Cu₂Cl(C₆H₄N₅)]	V = 814.45 (4) Å³
M_r = 308.67	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 19.6899 (7) Å	µ = 5.50 mm⁻¹
b = 3.6479 (1) Å	T = 298 K
c = 11.6337 (3) Å	0.30 × 0.26 × 0.24 mm
β = 102.923 (2)°

Data collection top

Bruker SMART CCD APEXII diffractometer	1572 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1415 reflections with I > 2σ(I)
T_min = 0.230, T_max = 0.269	R_int = 0.027
3752 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.092	Δρ_max = 0.71 e Å⁻³
S = 1.11	Δρ_min = −0.71 e Å⁻³
1572 reflections	Absolute structure: Flack (1983), 621 Friedel pairs
128 parameters	Absolute structure parameter: 0.19 (3)
2 restraints

Special details top

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.

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) top

	x	y	z	U_iso*/U_eq
Cu1	0.17283 (4)	0.9867 (2)	0.16168 (5)	0.0302 (2)
Cu2	0.07924 (5)	0.1504 (3)	0.34304 (8)	0.0341 (2)
Cl1	0.08796 (8)	0.4991 (4)	0.16267 (13)	0.0264 (3)
N1	0.2207 (2)	0.9667 (13)	0.3361 (4)	0.0188 (9)
N2	0.1753 (3)	1.0294 (14)	0.4064 (5)	0.0209 (9)
N3	0.2072 (3)	0.9615 (14)	0.5171 (4)	0.0219 (10)
N4	0.2723 (3)	0.8552 (15)	0.5223 (4)	0.0232 (10)
N5	0.4827 (2)	0.6742 (14)	0.3528 (4)	0.0215 (10)
C1	0.4640 (3)	0.5674 (16)	0.4514 (6)	0.0234 (12)
H1A	0.4971	0.4535	0.5101	0.028*
C2	0.3980 (3)	0.6184 (16)	0.4700 (5)	0.0203 (11)
H2A	0.3876	0.5450	0.5407	0.024*
C3	0.4326 (3)	0.8253 (16)	0.2677 (5)	0.0230 (11)
H3A	0.4446	0.9003	0.1985	0.028*
C4	0.3644 (3)	0.8755 (16)	0.2771 (5)	0.0203 (11)
H4A	0.3312	0.9704	0.2145	0.024*
C5	0.3469 (3)	0.7798 (14)	0.3829 (5)	0.0176 (10)
C6	0.2791 (3)	0.8611 (16)	0.4091 (5)	0.0173 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0279 (4)	0.0496 (4)	0.0144 (3)	−0.0021 (4)	0.0076 (3)	0.0018 (3)
Cu2	0.0125 (3)	0.0561 (5)	0.0334 (4)	0.0066 (4)	0.0042 (3)	0.0033 (4)
Cl1	0.0223 (7)	0.0274 (6)	0.0276 (8)	−0.0018 (5)	0.0016 (6)	0.0035 (5)
N1	0.012 (2)	0.032 (2)	0.012 (2)	0.0020 (18)	0.0023 (17)	0.0003 (18)
N2	0.013 (2)	0.036 (2)	0.014 (2)	0.0013 (19)	0.0042 (16)	−0.001 (2)
N3	0.017 (2)	0.038 (3)	0.011 (2)	0.0014 (19)	0.0038 (18)	−0.0001 (18)
N4	0.018 (2)	0.040 (3)	0.011 (2)	0.004 (2)	0.0035 (18)	0.001 (2)
N5	0.014 (2)	0.028 (2)	0.022 (2)	0.0037 (19)	0.0043 (19)	−0.0005 (19)
C1	0.016 (3)	0.028 (3)	0.025 (3)	0.006 (2)	0.001 (2)	0.006 (2)
C2	0.019 (3)	0.030 (3)	0.012 (3)	0.002 (2)	0.003 (2)	0.002 (2)
C3	0.017 (3)	0.034 (3)	0.018 (3)	0.002 (2)	0.005 (2)	−0.001 (2)
C4	0.021 (3)	0.028 (3)	0.012 (3)	0.004 (2)	0.002 (2)	−0.002 (2)
C5	0.012 (2)	0.023 (2)	0.017 (3)	0.002 (2)	0.002 (2)	−0.0028 (19)
C6	0.014 (2)	0.024 (2)	0.012 (2)	0.000 (2)	0.0001 (19)	−0.002 (2)

Geometric parameters (Å, º) top

Cu1—N3ⁱ	1.958 (5)	N4—C6	1.354 (7)
Cu1—N1	2.038 (5)	N5—C1	1.339 (8)
Cu1—Cl1	2.4422 (15)	N5—C3	1.349 (7)
Cu1—Cl1ⁱⁱ	2.5090 (16)	N5—Cu2^vi	1.931 (4)
Cu2—N2ⁱⁱⁱ	1.921 (5)	C1—C2	1.377 (8)
Cu2—N5^iv	1.931 (4)	C1—H1A	0.9300
Cu2—Cl1	2.4923 (18)	C2—C5	1.389 (8)
Cl1—Cu1ⁱⁱⁱ	2.5090 (16)	C2—H2A	0.9300
N1—C6	1.325 (7)	C3—C4	1.383 (8)
N1—N2	1.360 (7)	C3—H3A	0.9300
N2—N3	1.323 (7)	C4—C5	1.395 (8)
N2—Cu2ⁱⁱ	1.921 (5)	C4—H4A	0.9300
N3—N4	1.327 (7)	C5—C6	1.464 (7)
N3—Cu1^v	1.958 (5)

N3ⁱ—Cu1—N1	133.4 (2)	C1—N5—C3	116.8 (5)
N3ⁱ—Cu1—Cl1	116.27 (15)	C1—N5—Cu2^vi	120.1 (4)
N1—Cu1—Cl1	97.70 (14)	C3—N5—Cu2^vi	122.9 (4)
N3ⁱ—Cu1—Cl1ⁱⁱ	106.89 (15)	N5—C1—C2	123.1 (5)
N1—Cu1—Cl1ⁱⁱ	100.51 (13)	N5—C1—H1A	118.5
Cl1—Cu1—Cl1ⁱⁱ	94.90 (6)	C2—C1—H1A	118.5
N2ⁱⁱⁱ—Cu2—N5^iv	152.3 (2)	C1—C2—C5	119.8 (5)
N2ⁱⁱⁱ—Cu2—Cl1	101.13 (17)	C1—C2—H2A	120.1
N5^iv—Cu2—Cl1	106.30 (16)	C5—C2—H2A	120.1
Cu1—Cl1—Cu2	123.48 (7)	N5—C3—C4	124.0 (5)
Cu1—Cl1—Cu1ⁱⁱⁱ	94.90 (6)	N5—C3—H3A	118.0
Cu2—Cl1—Cu1ⁱⁱⁱ	78.17 (5)	C4—C3—H3A	118.0
C6—N1—N2	104.9 (5)	C3—C4—C5	118.2 (5)
C6—N1—Cu1	142.2 (4)	C3—C4—H4A	120.9
N2—N1—Cu1	111.9 (4)	C5—C4—H4A	120.9
N3—N2—N1	108.7 (5)	C2—C5—C4	117.9 (5)
N3—N2—Cu2ⁱⁱ	128.9 (4)	C2—C5—C6	118.6 (5)
N1—N2—Cu2ⁱⁱ	122.1 (4)	C4—C5—C6	123.4 (5)
N2—N3—N4	110.1 (4)	N1—C6—N4	111.5 (5)
N2—N3—Cu1^v	129.6 (4)	N1—C6—C5	128.8 (5)
N4—N3—Cu1^v	120.3 (4)	N4—C6—C5	119.6 (5)
N3—N4—C6	104.8 (4)

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

Experimental details

Crystal data
Chemical formula	[Cu₂Cl(C₆H₄N₅)]
M_r	308.67
Crystal system, space group	Monoclinic, Cc
Temperature (K)	298
a, b, c (Å)	19.6899 (7), 3.6479 (1), 11.6337 (3)
β (°)	102.923 (2)
V (Å³)	814.45 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.50
Crystal size (mm)	0.30 × 0.26 × 0.24

Data collection
Diffractometer	Bruker SMART CCD APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.230, 0.269
No. of measured, independent and observed [I > 2σ(I)] reflections	3752, 1572, 1415
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.655

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.092, 1.11
No. of reflections	1572
No. of parameters	128
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.71
Absolute structure	Flack (1983), 621 Friedel pairs
Absolute structure parameter	0.19 (3)

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cu1—N3ⁱ	1.958 (5)	Cu2—N2ⁱⁱⁱ	1.921 (5)
Cu1—N1	2.038 (5)	Cu2—N5^iv	1.931 (4)
Cu1—Cl1	2.4422 (15)	Cu2—Cl1	2.4923 (18)
Cu1—Cl1ⁱⁱ	2.5090 (16)

N3ⁱ—Cu1—N1	133.4 (2)	N2ⁱⁱⁱ—Cu2—N5^iv	152.3 (2)
N3ⁱ—Cu1—Cl1	116.27 (15)	N2ⁱⁱⁱ—Cu2—Cl1	101.13 (17)
N1—Cu1—Cl1	97.70 (14)	N5^iv—Cu2—Cl1	106.30 (16)
N3ⁱ—Cu1—Cl1ⁱⁱ	106.89 (15)	Cu1—Cl1—Cu2	123.48 (7)
N1—Cu1—Cl1ⁱⁱ	100.51 (13)	Cu1—Cl1—Cu1ⁱⁱⁱ	94.90 (6)
Cl1—Cu1—Cl1ⁱⁱ	94.90 (6)	Cu2—Cl1—Cu1ⁱⁱⁱ	78.17 (5)

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

Acknowledgements

This work was supported by the K. C. Wong Magna Fund in Ningbo University.

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