Poly[bis­[μ₂-5-(pyrimidin-2-yl)tetra­zol­ato]­zinc(II)]

The title compound, [Zn(C₅H₃N₆)₂]_n, has a neutral two-dimensional square grid-like network structure, in which the central Zn^II 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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.059
• wR factor = 0.081
• Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .      38.00 A   3 

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1         (2)       1.84

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

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 Zn^II atom is located on an inversion centre and exhibits a distorted octahedral coordination geometry around by six N atoms. Each Zn^II atom coordinates to four ligands and each ligand bonds to two Zn^II 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

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

S2. Experimental

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%.

S3. Refinement

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

Computing details

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

	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.]
	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)]

Crystal data

[Zn(C5H3N6)2]	F(000) = 720
Mr = 359.64	Dx = 1.694 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 10696 reflections
a = 8.3490 (17) Å	θ = 3.1–27.5°
b = 9.4760 (19) Å	µ = 1.76 mm^−1
c = 17.828 (4) Å	T = 293 K
V = 1410.5 (5) Å^3	Block, colourless
Z = 4	0.20 × 0.20 × 0.18 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	1619 independent reflections
Radiation source: fine-focus sealed tube	1162 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.085
φ and ω scans	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −10→10
Tmin = 0.720, Tmax = 0.742	k = −12→12
13281 measured reflections	l = −22→23

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters constrained
S = 1.19	w = 1/[σ^2(Fo^2) + (0.0173P)^2 + 1.2986P] where P = (Fo^2 + 2Fc^2)/3
1619 reflections	(Δ/σ)max < 0.001
106 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	1.0000	0.5000	0.5000	0.02321 (15)
N1	0.8536 (3)	0.3208 (3)	0.48306 (14)	0.0251 (6)
N2	0.7488 (3)	0.2405 (3)	0.51939 (13)	0.0293 (6)
N3	0.6979 (3)	0.1430 (3)	0.47237 (15)	0.0277 (7)
N4	0.7676 (3)	0.1574 (3)	0.40459 (15)	0.0286 (7)
N5	1.0407 (3)	0.4532 (3)	0.38246 (14)	0.0229 (6)
N6	0.9801 (4)	0.2806 (3)	0.28978 (16)	0.0442 (8)
C1	0.8634 (4)	0.2684 (3)	0.41356 (17)	0.0241 (7)
C2	0.9676 (4)	0.3365 (3)	0.35780 (18)	0.0264 (8)
C3	1.0735 (5)	0.3528 (4)	0.2425 (2)	0.0491 (11)
H3A	1.0860	0.3182	0.1940	0.059*
C4	1.1517 (5)	0.4744 (4)	0.2612 (2)	0.0435 (10)
H4A	1.2141	0.5230	0.2265	0.052*
C5	1.1340 (4)	0.5217 (4)	0.3333 (2)	0.0355 (9)
H5A	1.1878	0.6028	0.3484	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0251 (2)	0.0189 (2)	0.0256 (3)	−0.0015 (3)	−0.0001 (3)	−0.0023 (3)
N1	0.0259 (14)	0.0229 (14)	0.0264 (16)	−0.0039 (13)	0.0022 (12)	−0.0011 (12)
N2	0.0332 (14)	0.0247 (14)	0.0299 (15)	−0.0076 (13)	0.0055 (16)	−0.0035 (15)
N3	0.0261 (15)	0.0267 (15)	0.0303 (15)	−0.0067 (13)	0.0073 (13)	−0.0046 (13)
N4	0.0312 (16)	0.0278 (15)	0.0269 (15)	−0.0085 (13)	0.0058 (13)	−0.0063 (13)
N5	0.0237 (16)	0.0194 (13)	0.0256 (14)	−0.0004 (10)	0.0035 (12)	0.0043 (11)
N6	0.054 (2)	0.0475 (19)	0.0310 (17)	−0.0108 (18)	0.0148 (16)	−0.0130 (15)
C1	0.0259 (17)	0.0225 (17)	0.0239 (17)	−0.0016 (15)	0.0015 (15)	−0.0036 (15)
C2	0.026 (2)	0.0256 (18)	0.0276 (18)	−0.0002 (15)	0.0024 (14)	−0.0004 (14)
C3	0.064 (3)	0.056 (3)	0.027 (2)	−0.003 (2)	0.017 (2)	−0.010 (2)
C4	0.054 (3)	0.040 (2)	0.037 (2)	0.000 (2)	0.0209 (19)	0.0069 (18)
C5	0.038 (2)	0.026 (2)	0.043 (2)	−0.0001 (17)	0.0066 (17)	0.0049 (17)

Geometric parameters (Å, º)

Zn1—N1^i	2.114 (3)	N4—C1	1.331 (4)
Zn1—N1	2.114 (3)	N5—C2	1.338 (4)
Zn1—N5	2.169 (3)	N5—C5	1.340 (4)
Zn1—N5^i	2.169 (3)	N6—C2	1.327 (4)
Zn1—N3^ii	2.193 (3)	N6—C3	1.337 (5)
Zn1—N3^iii	2.193 (3)	C1—C2	1.470 (4)
N1—N2	1.329 (3)	C3—C4	1.366 (5)
N1—C1	1.337 (4)	C3—H3A	0.9300
N2—N3	1.318 (4)	C4—C5	1.370 (5)
N3—N4	1.348 (3)	C4—H4A	0.9300
N3—Zn1^iv	2.193 (3)	C5—H5A	0.9300
N1^i—Zn1—N1	180.0	N4—N3—Zn1^iv	126.1 (2)
N1^i—Zn1—N5	102.22 (9)	C1—N4—N3	103.4 (2)
N1—Zn1—N5	77.78 (9)	C2—N5—C5	116.8 (3)
N1^i—Zn1—N5^i	77.78 (9)	C2—N5—Zn1	114.5 (2)
N1—Zn1—N5^i	102.22 (9)	C5—N5—Zn1	128.6 (2)
N5—Zn1—N5^i	180.00 (3)	C2—N6—C3	114.7 (3)
N1^i—Zn1—N3^ii	91.63 (11)	N4—C1—N1	111.6 (3)
N1—Zn1—N3^ii	88.37 (11)	N4—C1—C2	128.4 (3)
N5—Zn1—N3^ii	88.44 (10)	N1—C1—C2	120.0 (3)
N5^i—Zn1—N3^ii	91.56 (10)	N6—C2—N5	126.5 (3)
N1^i—Zn1—N3^iii	88.37 (11)	N6—C2—C1	119.3 (3)
N1—Zn1—N3^iii	91.63 (11)	N5—C2—C1	114.2 (3)
N5—Zn1—N3^iii	91.56 (10)	N6—C3—C4	123.8 (4)
N5^i—Zn1—N3^iii	88.44 (10)	N6—C3—H3A	118.1
N3^ii—Zn1—N3^iii	180.00 (14)	C4—C3—H3A	118.1
N2—N1—C1	106.2 (3)	C3—C4—C5	117.0 (3)
N2—N1—Zn1	140.5 (2)	C3—C4—H4A	121.5
C1—N1—Zn1	113.3 (2)	C5—C4—H4A	121.5
N3—N2—N1	107.7 (2)	N5—C5—C4	121.2 (3)
N2—N3—N4	111.1 (2)	N5—C5—H5A	119.4
N2—N3—Zn1^iv	122.2 (2)	C4—C5—H5A	119.4
N5—Zn1—N1—N2	−176.3 (4)	N3—N4—C1—N1	−0.2 (4)
N5^i—Zn1—N1—N2	3.7 (4)	N3—N4—C1—C2	−178.3 (3)
N3^ii—Zn1—N1—N2	95.0 (3)	N2—N1—C1—N4	0.2 (4)
N3^iii—Zn1—N1—N2	−85.0 (3)	Zn1—N1—C1—N4	−178.9 (2)
N5—Zn1—N1—C1	2.3 (2)	N2—N1—C1—C2	178.4 (3)
N5^i—Zn1—N1—C1	−177.7 (2)	Zn1—N1—C1—C2	−0.6 (4)
N3^ii—Zn1—N1—C1	−86.5 (2)	C3—N6—C2—N5	−1.4 (5)
N3^iii—Zn1—N1—C1	93.5 (2)	C3—N6—C2—C1	177.9 (3)
C1—N1—N2—N3	0.0 (3)	C5—N5—C2—N6	1.0 (5)
Zn1—N1—N2—N3	178.6 (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—Zn1^iv	−171.9 (2)	Zn1—N5—C2—C1	4.6 (3)
N2—N3—N4—C1	0.2 (4)	N4—C1—C2—N6	−4.2 (5)
Zn1^iv—N3—N4—C1	171.6 (2)	N1—C1—C2—N6	177.8 (3)
N1^i—Zn1—N5—C2	176.1 (2)	N4—C1—C2—N5	175.2 (3)
N1—Zn1—N5—C2	−3.9 (2)	N1—C1—C2—N5	−2.8 (4)
N3^ii—Zn1—N5—C2	84.8 (2)	C2—N6—C3—C4	0.2 (6)
N3^iii—Zn1—N5—C2	−95.2 (2)	N6—C3—C4—C5	1.3 (6)
N1^i—Zn1—N5—C5	−0.5 (3)	C2—N5—C5—C4	0.7 (5)
N1—Zn1—N5—C5	179.5 (3)	Zn1—N5—C5—C4	177.2 (3)
N3^ii—Zn1—N5—C5	−91.8 (3)	C3—C4—C5—N5	−1.7 (6)
N3^iii—Zn1—N5—C5	88.2 (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.