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Acta Cryst. (2007). E63, m2423    [ doi:10.1107/S1600536807041414 ]

Poly[bis[[mu]2-5-(pyrimidin-2-yl)tetrazolato]zinc(II)]

X.-L. Zhang, C.-L. Zhang, Y.-E. Qiu and N. An

Abstract top

The title compound, [Zn(C5H3N6)2]n, has a neutral two-dimensional square grid-like network structure, in which the central ZnII atom is located on an inversion centre and coordinated by six N atoms from four 5-(pyrimidin-2-yl)tetrazolate ligands in a distorted octahedral geometry [Zn-N = 2.114 (3)-2.193 (3) Å and N-Zn-N = 77.78 (9)-102.22 (9)°]. The tetrazolate ligand adopts an N,N':N''-tridentate chelating-bridging coordination mode. This complex is isostructural with the iron(II), cobalt(II) and nickel(II) analogues.

Comment top

Recently, several complexes of 5-(pyrimidin-2-yl)tetrazolato ligand have been reported containing iron(II), cobalt(II), nickel(II), zinc(II) and cadmium(II) metal ion [Rodríguez & Colacio (2006); Rodríguez et al., 2005, 2007; Liu & Fan, 2007]. The title compound poly[5-(pyrimidin-2-yl)tetrazolato]zinc(II)] (I, Fig. 1 and 2) is isostructural with the iron(II), cobalt(II) and nickel(II) analogs. The structure features a two-dimensional square-grid-like network with the grid side length of 6.315 (3) Å, in which ZnII atom is located on an inversion centre and exhibits a distorted octahedral coordination geometry around by six N atoms. Each ZnII atom coordinates to four ligands and each ligand bonds to two ZnII atoms through one of the pyrimidyl N atoms and the 1-positon tetrazole N for one, and one 3-position tetrazole N atom for the other. Selected bond distances and angles are listed in Table 1. In addition, in crystal structure such two-dimensional layers stack in an ABAB sequence.

Related literature top

For ligand preparation, see: Demko & Sharpless (2001). For related literature, see: Rodríguez & Colacio (2006); Rodríguez et al. (2005, 2007); Liu & Fan (2007).

Experimental top

The ligand, 2-(1H-tetrazol-5-yl)pyrimidine was synthesized by the literature method (Demko & Sharpless, 2001). A mixture of ZnCl2 (27 mg, 0.2 mmol) and the ligand (60 mg, 0.4 mmol) in N,N-dimethylformamide/ethanol (v/v = 3:1, 8 ml) in presence of a drop of triethylamine was placed in a Teflon-lined stainless-steel Parr bomb that was heated at 413 K for 36 h. Colorless crystals were collected after the bomb allowed to cool to room temperature during a period of 24 h. Yield, 30%.

Refinement top

H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997; molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures top
[Figure 1] Fig. 1. Displacement ellipsoid plot (30% probability) of a fragment of the layer structure of (I) showing the coordination environment of the metal and ligands. [symmetry codes: (A) 2 − x, 1 − y, 1 − z; (B) 1/2 + x, 1/2 − y, 1 − z; (C) 3/2 − x, 1/2 + y, z.]
[Figure 2] Fig. 2. Two-dimensional layer of (I). For clarity, all H atoms have been omitted.
Poly[bis[µ2-5-(pyrimidin-2-yl)tetrazolato]zinc(II)] top
Crystal data top
[Zn(C5H3N6)2]F000 = 720
Mr = 359.64Dx = 1.694 Mg m−3
Orthorhombic, PbcaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 10696 reflections
a = 8.3490 (17) Åθ = 3.1–27.5º
b = 9.4760 (19) ŵ = 1.76 mm−1
c = 17.828 (4) ÅT = 293 (2) K
V = 1410.5 (5) Å3Block, colourless
Z = 40.20 × 0.20 × 0.18 mm
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1619 independent reflections
Radiation source: fine-focus sealed tube1162 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.085
T = 293(2) Kθmax = 27.5º
φ and ω scansθmin = 3.3º
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		h = −10→10
Tmin = 0.720, Tmax = 0.742k = −12→12
13281 measured reflectionsl = −22→23
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.081  w = 1/[σ2(Fo2) + (0.0173P)2 + 1.2986P]
where P = (Fo2 + 2Fc2)/3
S = 1.19(Δ/σ)max < 0.001
1619 reflectionsΔρmax = 0.28 e Å−3
106 parametersΔρmin = −0.25 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Zn(C5H3N6)2]V = 1410.5 (5) Å3
Mr = 359.64Z = 4
Orthorhombic, PbcaMo Kα
a = 8.3490 (17) ŵ = 1.76 mm−1
b = 9.4760 (19) ÅT = 293 (2) K
c = 17.828 (4) Å0.20 × 0.20 × 0.18 mm
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1619 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		1162 reflections with I > 2σ(I)
Tmin = 0.720, Tmax = 0.742Rint = 0.085
13281 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.059106 parameters
wR(F2) = 0.081H-atom parameters constrained
S = 1.19Δρmax = 0.28 e Å−3
1619 reflectionsΔρmin = −0.25 e Å−3
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
xyzUiso*/Ueq
Zn11.00000.50000.50000.02321 (15)
N10.8536 (3)0.3208 (3)0.48306 (14)0.0251 (6)
N20.7488 (3)0.2405 (3)0.51939 (13)0.0293 (6)
N30.6979 (3)0.1430 (3)0.47237 (15)0.0277 (7)
N40.7676 (3)0.1574 (3)0.40459 (15)0.0286 (7)
N51.0407 (3)0.4532 (3)0.38246 (14)0.0229 (6)
N60.9801 (4)0.2806 (3)0.28978 (16)0.0442 (8)
C10.8634 (4)0.2684 (3)0.41356 (17)0.0241 (7)
C20.9676 (4)0.3365 (3)0.35780 (18)0.0264 (8)
C31.0735 (5)0.3528 (4)0.2425 (2)0.0491 (11)
H3A1.08600.31820.19400.059*
C41.1517 (5)0.4744 (4)0.2612 (2)0.0435 (10)
H4A1.21410.52300.22650.052*
C51.1340 (4)0.5217 (4)0.3333 (2)0.0355 (9)
H5A1.18780.60280.34840.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0251 (2)0.0189 (2)0.0256 (3)−0.0015 (3)−0.0001 (3)−0.0023 (3)
N10.0259 (14)0.0229 (14)0.0264 (16)−0.0039 (13)0.0022 (12)−0.0011 (12)
N20.0332 (14)0.0247 (14)0.0299 (15)−0.0076 (13)0.0055 (16)−0.0035 (15)
N30.0261 (15)0.0267 (15)0.0303 (15)−0.0067 (13)0.0073 (13)−0.0046 (13)
N40.0312 (16)0.0278 (15)0.0269 (15)−0.0085 (13)0.0058 (13)−0.0063 (13)
N50.0237 (16)0.0194 (13)0.0256 (14)−0.0004 (10)0.0035 (12)0.0043 (11)
N60.054 (2)0.0475 (19)0.0310 (17)−0.0108 (18)0.0148 (16)−0.0130 (15)
C10.0259 (17)0.0225 (17)0.0239 (17)−0.0016 (15)0.0015 (15)−0.0036 (15)
C20.026 (2)0.0256 (18)0.0276 (18)−0.0002 (15)0.0024 (14)−0.0004 (14)
C30.064 (3)0.056 (3)0.027 (2)−0.003 (2)0.017 (2)−0.010 (2)
C40.054 (3)0.040 (2)0.037 (2)0.000 (2)0.0209 (19)0.0069 (18)
C50.038 (2)0.026 (2)0.043 (2)−0.0001 (17)0.0066 (17)0.0049 (17)
Geometric parameters (Å, °) top
Zn1—N1i2.114 (3)N4—C11.331 (4)
Zn1—N12.114 (3)N5—C21.338 (4)
Zn1—N52.169 (3)N5—C51.340 (4)
Zn1—N5i2.169 (3)N6—C21.327 (4)
Zn1—N3ii2.193 (3)N6—C31.337 (5)
Zn1—N3iii2.193 (3)C1—C21.470 (4)
N1—N21.329 (3)C3—C41.366 (5)
N1—C11.337 (4)C3—H3A0.9300
N2—N31.318 (4)C4—C51.370 (5)
N3—N41.348 (3)C4—H4A0.9300
N3—Zn1iv2.193 (3)C5—H5A0.9300
N1i—Zn1—N1180.0N4—N3—Zn1iv126.1 (2)
N1i—Zn1—N5102.22 (9)C1—N4—N3103.4 (2)
N1—Zn1—N577.78 (9)C2—N5—C5116.8 (3)
N1i—Zn1—N5i77.78 (9)C2—N5—Zn1114.5 (2)
N1—Zn1—N5i102.22 (9)C5—N5—Zn1128.6 (2)
N5—Zn1—N5i180.00 (3)C2—N6—C3114.7 (3)
N1i—Zn1—N3ii91.63 (11)N4—C1—N1111.6 (3)
N1—Zn1—N3ii88.37 (11)N4—C1—C2128.4 (3)
N5—Zn1—N3ii88.44 (10)N1—C1—C2120.0 (3)
N5i—Zn1—N3ii91.56 (10)N6—C2—N5126.5 (3)
N1i—Zn1—N3iii88.37 (11)N6—C2—C1119.3 (3)
N1—Zn1—N3iii91.63 (11)N5—C2—C1114.2 (3)
N5—Zn1—N3iii91.56 (10)N6—C3—C4123.8 (4)
N5i—Zn1—N3iii88.44 (10)N6—C3—H3A118.1
N3ii—Zn1—N3iii180.00 (14)C4—C3—H3A118.1
N2—N1—C1106.2 (3)C3—C4—C5117.0 (3)
N2—N1—Zn1140.5 (2)C3—C4—H4A121.5
C1—N1—Zn1113.3 (2)C5—C4—H4A121.5
N3—N2—N1107.7 (2)N5—C5—C4121.2 (3)
N2—N3—N4111.1 (2)N5—C5—H5A119.4
N2—N3—Zn1iv122.2 (2)C4—C5—H5A119.4
N5—Zn1—N1—N2−176.3 (4)N3—N4—C1—N1−0.2 (4)
N5i—Zn1—N1—N23.7 (4)N3—N4—C1—C2−178.3 (3)
N3ii—Zn1—N1—N295.0 (3)N2—N1—C1—N40.2 (4)
N3iii—Zn1—N1—N2−85.0 (3)Zn1—N1—C1—N4−178.9 (2)
N5—Zn1—N1—C12.3 (2)N2—N1—C1—C2178.4 (3)
N5i—Zn1—N1—C1−177.7 (2)Zn1—N1—C1—C2−0.6 (4)
N3ii—Zn1—N1—C1−86.5 (2)C3—N6—C2—N5−1.4 (5)
N3iii—Zn1—N1—C193.5 (2)C3—N6—C2—C1177.9 (3)
C1—N1—N2—N30.0 (3)C5—N5—C2—N61.0 (5)
Zn1—N1—N2—N3178.6 (3)Zn1—N5—C2—N6−176.1 (3)
N1—N2—N3—N4−0.2 (4)C5—N5—C2—C1−178.3 (3)
N1—N2—N3—Zn1iv−171.9 (2)Zn1—N5—C2—C14.6 (3)
N2—N3—N4—C10.2 (4)N4—C1—C2—N6−4.2 (5)
Zn1iv—N3—N4—C1171.6 (2)N1—C1—C2—N6177.8 (3)
N1i—Zn1—N5—C2176.1 (2)N4—C1—C2—N5175.2 (3)
N1—Zn1—N5—C2−3.9 (2)N1—C1—C2—N5−2.8 (4)
N3ii—Zn1—N5—C284.8 (2)C2—N6—C3—C40.2 (6)
N3iii—Zn1—N5—C2−95.2 (2)N6—C3—C4—C51.3 (6)
N1i—Zn1—N5—C5−0.5 (3)C2—N5—C5—C40.7 (5)
N1—Zn1—N5—C5179.5 (3)Zn1—N5—C5—C4177.2 (3)
N3ii—Zn1—N5—C5−91.8 (3)C3—C4—C5—N5−1.7 (6)
N3iii—Zn1—N5—C588.2 (3)
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1/2, −y+1/2, −z+1; (iii) −x+3/2, y+1/2, z; (iv) x−1/2, −y+1/2, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Zn1—N12.114 (3)Zn1—N5i2.169 (3)
Zn1—N52.169 (3)
N1i—Zn1—N5102.22 (9)N5—Zn1—N3ii88.44 (10)
N1—Zn1—N577.78 (9)N1—Zn1—N3iii91.63 (11)
N1—Zn1—N3ii88.37 (11)N5—Zn1—N3iii91.56 (10)
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1/2, −y+1/2, −z+1; (iii) −x+3/2, y+1/2, z.
Acknowledgements top

The authors thank Dezhou University for supporting this work.

references
References top

Bruker (1998). SMART (Version 5.051), SAINT (Version 5.01), SADABS (Version 2.03) and SHELXTL (Version 6.1). Bruker AXS Inc., Madison, Wisconsin, USA.

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Rodríguez, A., Kivekäsb, R. & Colacio, E. (2005). Chem. Commun. pp. 5228–5230.

Rodríguez, A., Salinas-Castillo, A., Galli, A. S., Masciocchi, N., Gutíerrez-Zorrilla, J. M., Vitoriad, P. & Colacio, E. (2007). Dalton Trans. pp. 1821–1828.

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Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.