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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): m542.
Published online 2009 April 22. doi:  10.1107/S1600536809013567
PMCID: PMC2977593

trans-Diaqua­bis[5-(1H-imidazol-4-yl-κN 3)-1H-tetra­zolato-κN 1]zinc(II)

Abstract

In the title complex, [Zn(C4H3N6)2(H2O)2], the metal centre lies on an inversion centre and displays a distorted octa­hedral ZnN4O2 coordination geometry. The organic ligand is not planar; the dihedral angle between the imidazole and tetra­zole rings is 8.39 (9)°. An extended network of inter­molecular N—H(...)N and O—H(...)N hydrogen bonds stabilizes the crystal structure.

Related literature

For the synthesis and properties of tetra­zole compounds, see: Demko & Sharpless (2001 [triangle], 2002 [triangle]); Zhao et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0m542-scheme1.jpg

Experimental

Crystal data

  • [Zn(C4H3N6)2(H2O)2]
  • M r = 371.65
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m542-efi1.jpg
  • a = 5.9068 (10) Å
  • b = 17.408 (3) Å
  • c = 7.091 (2) Å
  • β = 110.70 (2)°
  • V = 682.1 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.84 mm−1
  • T = 291 K
  • 0.20 × 0.18 × 0.15 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.753, T max = 0.762
  • 6793 measured reflections
  • 1555 independent reflections
  • 1429 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.028
  • wR(F 2) = 0.113
  • S = 1.30
  • 1555 reflections
  • 106 parameters
  • H-atom parameters constrained
  • Δρmax = 0.59 e Å−3
  • Δρmin = −0.64 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL/PC (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL/PC.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809013567/rz2306sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809013567/rz2306Isup2.hkl

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

Acknowledgments

This work was supported by a start-up grant from Southeast University to HZ.

supplementary crystallographic information

Comment

Tetrazole ligands have found a wide range of applications in medicine chemistry, coordination chemistry and material chemistry (Demko & Sharpless, 2001). Recently, the tetrazole synthesis in water has attracted intense attention. For example, a safe, convenient, and environmentally friendly procedure for the synthesis of 5-substituted 1H-tetrazoles, which were prepared by the addition of azides to nitriles in water using zinc salts as catalysts, has been reported (Demko & Sharpless, 2002). Our group has been interested in the construction of novel supramolecular motifs through in situ hydrothermal reactions (Zhao et al., 2008). In particular, we have combined metal salts with potentially bridging organic ligands under hydrothermal conditions to produce a range of new materials in order to investigate the Demko-Sharpless reaction. Herein we report on the synthesis and structure of the title compound, which was obtained by the hydrothermal reaction of ZnCl2 with (4-cyano)-imidazole and NaN3 in water.

Figure 1 shows the monomeric complex molecule along with the atom-labelling scheme. The zinc(II) metal lies on an inversion centre, and displays a distorted octahedral coordination geometry provided by the N atoms of two chelating ligands at the equatorial plane and by the oxygen atoms of two trans-arranged water molecules at the axial positions. The bond distances and angles within the coordination octahedron have normal values. The organic ligand is not planar, the dihedral angle formed by the imidazole and tetrazole rings is 8.39 (9)°. The five-membered chelating ring assumes an approximately planar conformation (maximum deviation 0.030 (2) Å for atom C4). The crystal structure is stabilized by intermolecular N—H···N and O—H···N hydrogen bonds (Table 1), forming an extended three-dimensional network (Fig. 2).

Experimental

Colourless single crystals of title compound were obtained by hydrothermal treatment of ZnCl2 (1 mmol), NaN3 (3 mmol), (4-cyano)-imidazole (1 mmol) and water (7 ml) over 1 day at 398 K. Yield: 53% (based on ZnCl2).

Refinement

The water H atoms were located from a difference Fourier map but not refined [Uiso(H) = 1.5 Ueq(O)]. All other H atoms were placed at calculated positions and refined as riding, with C—H = 0.93 Å, N—H = 0.86 Å, and with Uiso(H) = 1.2 Ueq(C, N).

Figures

Fig. 1.
The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Atoms labelled with suffix A are generated by the symmetry operation (2-x, 1-y, 1-z).
Fig. 2.
Packing diagram of the title compound viewed along the b axis. Intermolecular hydrogen bonds are shown as dashed lines.

Crystal data

[Zn(C4H3N6)2(H2O)2]F(000) = 376
Mr = 371.65Dx = 1.809 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2098 reflections
a = 5.9068 (10) Åθ = 2.3–27.5°
b = 17.408 (3) ŵ = 1.84 mm1
c = 7.091 (2) ÅT = 291 K
β = 110.70 (2)°Prism, colourless
V = 682.1 (3) Å30.20 × 0.18 × 0.15 mm
Z = 2

Data collection

Rigaku SCXmini diffractometer1555 independent reflections
Radiation source: fine-focus sealed tube1429 reflections with I > 2σ(I)
graphiteRint = 0.025
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 2.3°
ω scansh = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −22→22
Tmin = 0.753, Tmax = 0.762l = −9→9
6793 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.30w = 1/[σ2(Fo2) + (0.0683P)2 + 0.021P] where P = (Fo2 + 2Fc2)/3
1555 reflections(Δ/σ)max < 0.001
106 parametersΔρmax = 0.59 e Å3
0 restraintsΔρmin = −0.64 e Å3

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 (Å2)

xyzUiso*/Ueq
Zn11.00000.50000.50000.02202 (18)
C10.9503 (4)0.34932 (12)0.3008 (3)0.0212 (4)
C21.0396 (4)0.27845 (13)0.2890 (4)0.0287 (5)
H20.95810.23760.20900.034*
C31.3185 (4)0.34887 (13)0.5063 (4)0.0262 (5)
H31.46570.36350.60210.031*
C40.7145 (4)0.38475 (12)0.2122 (3)0.0207 (4)
N11.1269 (3)0.39332 (10)0.4390 (3)0.0223 (4)
N21.2733 (4)0.27947 (11)0.4186 (3)0.0292 (4)
H2A1.37460.24210.44040.035*
N30.6743 (3)0.45320 (10)0.2795 (3)0.0208 (4)
N40.4411 (3)0.46893 (11)0.1772 (3)0.0242 (4)
N50.3469 (3)0.41230 (11)0.0538 (3)0.0272 (4)
N60.5162 (3)0.35808 (11)0.0704 (3)0.0258 (4)
O11.0962 (3)0.56118 (9)0.2680 (2)0.0285 (4)
H1B0.97930.57530.16170.043*
H1A1.19720.54340.23270.043*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0195 (3)0.0171 (2)0.0251 (3)0.00042 (11)0.00252 (17)−0.00441 (12)
C10.0214 (10)0.0190 (10)0.0211 (10)−0.0010 (7)0.0049 (8)−0.0013 (8)
C20.0301 (12)0.0212 (11)0.0323 (12)0.0020 (9)0.0081 (9)−0.0019 (9)
C30.0198 (10)0.0270 (11)0.0287 (11)0.0035 (8)0.0045 (9)0.0030 (9)
C40.0210 (10)0.0175 (9)0.0216 (10)−0.0022 (7)0.0052 (8)0.0008 (8)
N10.0186 (9)0.0194 (8)0.0256 (9)0.0007 (7)0.0039 (7)−0.0019 (7)
N20.0271 (10)0.0233 (9)0.0356 (11)0.0098 (8)0.0089 (8)0.0035 (8)
N30.0169 (9)0.0214 (9)0.0217 (9)0.0030 (7)0.0037 (7)−0.0004 (7)
N40.0177 (9)0.0277 (10)0.0254 (10)0.0021 (7)0.0051 (7)0.0028 (8)
N50.0192 (9)0.0297 (10)0.0286 (10)−0.0008 (7)0.0031 (7)0.0028 (8)
N60.0215 (9)0.0214 (9)0.0282 (10)−0.0031 (7)0.0011 (7)−0.0021 (8)
O10.0226 (8)0.0344 (9)0.0259 (8)0.0058 (6)0.0055 (6)0.0016 (7)

Geometric parameters (Å, °)

Zn1—N1i2.1042 (18)C3—N11.313 (3)
Zn1—N12.1042 (18)C3—N21.342 (3)
Zn1—N3i2.1641 (19)C3—H30.9300
Zn1—N32.1641 (19)C4—N61.329 (3)
Zn1—O12.1966 (17)C4—N31.336 (3)
Zn1—O1i2.1966 (17)N2—H2A0.8600
C1—C21.356 (3)N3—N41.339 (3)
C1—N11.383 (3)N4—N51.305 (3)
C1—C41.448 (3)N5—N61.350 (3)
C2—N21.362 (3)O1—H1B0.8585
C2—H20.9300O1—H1A0.7874
N1i—Zn1—N1180.0N1—C3—N2110.9 (2)
N1i—Zn1—N3i79.02 (7)N1—C3—H3124.5
N1—Zn1—N3i100.98 (7)N2—C3—H3124.5
N1i—Zn1—N3100.98 (7)N6—C4—N3111.23 (19)
N1—Zn1—N379.02 (7)N6—C4—C1129.4 (2)
N3i—Zn1—N3180.00 (8)N3—C4—C1119.34 (19)
N1i—Zn1—O186.07 (7)C3—N1—C1105.58 (19)
N1—Zn1—O193.93 (7)C3—N1—Zn1140.26 (16)
N3i—Zn1—O187.66 (7)C1—N1—Zn1113.59 (14)
N3—Zn1—O192.34 (7)C3—N2—C2108.22 (18)
N1i—Zn1—O1i93.93 (7)C3—N2—H2A125.9
N1—Zn1—O1i86.07 (7)C2—N2—H2A125.9
N3i—Zn1—O1i92.34 (7)C4—N3—N4105.51 (17)
N3—Zn1—O1i87.66 (7)C4—N3—Zn1111.67 (14)
O1—Zn1—O1i180.00 (7)N4—N3—Zn1142.77 (14)
C2—C1—N1109.58 (19)N5—N4—N3108.77 (18)
C2—C1—C4134.1 (2)N4—N5—N6110.06 (17)
N1—C1—C4116.14 (18)C4—N6—N5104.42 (19)
C1—C2—N2105.7 (2)Zn1—O1—H1B117.1
C1—C2—H2127.2Zn1—O1—H1A118.2
N2—C2—H2127.2H1B—O1—H1A107.4

Symmetry codes: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···N6ii0.862.012.803 (3)153
O1—H1B···N5iii0.862.002.837 (3)164
O1—H1A···N4iv0.792.082.841 (2)164

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2306).

References

  • Demko, Z. P. & Sharpless, K. B. (2001). Org. Lett.3, 4091–4094. [PubMed]
  • Demko, Z. P. & Sharpless, K. B. (2002). Angew. Chem. Int. Ed.41, 2110–2113. [PubMed]
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhao, H., Qu, Z. R., Ye, H. Y. & Xiong, R. G. (2008). Chem. Soc. Rev.37, 84–100. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography