Acta Cryst. (2007). E63, m1955 [ doi:10.1107/S1600536807029297 ]
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N1)zinc(II) perchlorateThe title compound, [Zn(C2H3N4)(H2O)3]ClO4, consists of one ZnII complex cation and one uncoordinated perchlorate anion. Both anion and cation lie on mirror planes. The ZnII ion displays a distorted tetrahedral geometry and is coordinated by three O atoms and one N atom. Classical O-H
O and O-HN hydrogen-bond interactions connect cations and anions to form a one-dimensional chain along [010].
The hydrothermal treatment of acetonitrile (8.2 mg, 0.2 mmol), Zn(ClO4)2 (26.4 mg, 0.1 mmol), and NaN3 (32.5 mg, 0.5 mmol) in water (2 ml) for 1 day at 1473 K afforded colourless crystals of the title complex.
H atoms bonded to O atoms were located in a difference map and refined with free coordinates and Uiso(H) = 1.2Ueq(carrier O). The methyl H atoms were positioned geometrically and refined using a riding model, with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C2).
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
![[Figure 1]](./bh2109fig1thm.gif)
| Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Symmetry codes: (i) x, −1/2 − y, z; (ii) x, 1/2 − y, z. |
![[Figure 2]](./bh2109fig2thm.gif)
| Fig. 2. View of the hydrogen bond interactions in the crystal structure. Symmetry codes: (iii) x + 1, y − 1, z; (iv) x + 1, y, z; (v) x, y − 1, z. |
![[Figure 3]](./bh2109fig3thm.gif)
| Fig. 3. View of the one-dimensional helix chain along axis [010]. |
| [Zn(C2H3N4)(H2O)3]ClO4 | F000 = 304 |
| Mr = 301.95 | Dx = 1.880 Mg m−3 |
| Monoclinic, P21/m | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yb | Cell parameters from 746 reflections |
| a = 6.1055 (5) Å | θ = 2.1–23.6º |
| b = 7.6413 (6) Å | µ = 2.58 mm−1 |
| c = 11.6547 (9) Å | T = 291 (2) K |
| β = 101.220 (2)º | Block, colourless |
| V = 533.35 (7) Å3 | 0.18 × 0.14 × 0.12 mm |
| Z = 2 |
| Bruker SMART APEX CCD diffractometer | 1133 independent reflections |
| Radiation source: sealed tube | 1034 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.035 |
| T = 291(2) K | θmax = 26.0º |
| φ and ω scans | θmin = 3.2º |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −7→7 |
| Tmin = 0.66, Tmax = 0.73 | k = −9→9 |
| 3060 measured reflections | l = −14→10 |
| 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)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.06P)2 + 0.88P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.10 | (Δ/σ)max < 0.001 |
| 1133 reflections | Δρmax = 0.70 e Å−3 |
| 94 parameters | Δρmin = −0.61 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [Zn(C2H3N4)(H2O)3]ClO4 | V = 533.35 (7) Å3 |
| Mr = 301.95 | Z = 2 |
| Monoclinic, P21/m | Mo Kα |
| a = 6.1055 (5) Å | µ = 2.58 mm−1 |
| b = 7.6413 (6) Å | T = 291 (2) K |
| c = 11.6547 (9) Å | 0.18 × 0.14 × 0.12 mm |
| β = 101.220 (2)º |
| Bruker SMART APEX CCD diffractometer | 1133 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1034 reflections with I > 2σ(I) |
| Tmin = 0.66, Tmax = 0.73 | Rint = 0.035 |
| 3060 measured reflections |
| R[F2 > 2σ(F2)] = 0.049 | 94 parameters |
| wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.10 | Δρmax = 0.70 e Å−3 |
| 1133 reflections | Δρmin = −0.61 e Å−3 |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.4977 (10) | 0.2500 | 0.5068 (6) | 0.0331 (13) | |
| C2 | 0.7244 (10) | 0.2500 | 0.5742 (5) | 0.0360 (15) | |
| H2A | 0.8278 | 0.2500 | 0.5218 | 0.054* | |
| H2B | 0.7477 | 0.3526 | 0.6227 | 0.054* | |
| Cl1 | 0.2413 (2) | 0.7500 | 0.08687 (14) | 0.0362 (4) | |
| N1 | 0.4385 (9) | 0.2500 | 0.3991 (5) | 0.0353 (12) | |
| N2 | 0.2200 (8) | 0.2500 | 0.3701 (4) | 0.0345 (12) | |
| N3 | 0.1563 (9) | 0.2500 | 0.4728 (5) | 0.0404 (14) | |
| N4 | 0.3248 (9) | 0.2500 | 0.5603 (4) | 0.0334 (12) | |
| O1 | 0.7816 (6) | 0.0291 (5) | 0.2642 (4) | 0.0466 (9) | |
| H1B | 0.840 (10) | 0.025 (9) | 0.203 (6) | 0.056* | |
| H1A | 0.885 (10) | 0.032 (9) | 0.325 (5) | 0.056* | |
| O2 | 0.3480 (8) | 0.2500 | 0.1219 (4) | 0.0449 (12) | |
| H2C | 0.291 (9) | 0.152 (9) | 0.091 (5) | 0.054* | |
| O3 | 0.1365 (6) | 0.8932 (5) | 0.1446 (3) | 0.0489 (9) | |
| O4 | 0.4596 (8) | 0.7500 | 0.1194 (4) | 0.0454 (12) | |
| O5 | 0.1834 (8) | 0.7500 | −0.0279 (5) | 0.0467 (12) | |
| Zn1 | 0.59689 (11) | 0.2500 | 0.25880 (6) | 0.0268 (2) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.024 (3) | 0.041 (4) | 0.034 (3) | 0.000 | 0.005 (2) | 0.000 |
| C2 | 0.035 (3) | 0.048 (4) | 0.022 (3) | 0.000 | −0.004 (2) | 0.000 |
| Cl1 | 0.0311 (7) | 0.0386 (9) | 0.0352 (8) | 0.000 | −0.0024 (6) | 0.000 |
| N1 | 0.041 (3) | 0.039 (3) | 0.027 (3) | 0.000 | 0.011 (2) | 0.000 |
| N2 | 0.029 (2) | 0.050 (3) | 0.022 (2) | 0.000 | 0.000 (2) | 0.000 |
| N3 | 0.034 (3) | 0.054 (4) | 0.038 (3) | 0.000 | 0.019 (2) | 0.000 |
| N4 | 0.032 (3) | 0.045 (3) | 0.024 (2) | 0.000 | 0.007 (2) | 0.000 |
| O1 | 0.0413 (19) | 0.042 (2) | 0.058 (2) | 0.0146 (16) | 0.0145 (16) | −0.0136 (18) |
| O2 | 0.031 (2) | 0.068 (4) | 0.034 (3) | 0.000 | 0.002 (2) | 0.000 |
| O3 | 0.053 (2) | 0.049 (2) | 0.051 (2) | −0.0228 (17) | 0.0246 (17) | −0.0069 (17) |
| O4 | 0.052 (3) | 0.042 (3) | 0.047 (3) | 0.000 | 0.022 (2) | 0.000 |
| O5 | 0.043 (3) | 0.052 (3) | 0.045 (3) | 0.000 | 0.007 (2) | 0.000 |
| Zn1 | 0.0265 (4) | 0.0311 (4) | 0.0236 (4) | 0.000 | 0.0071 (2) | 0.000 |
| C1—N1 | 1.237 (8) | N1—Zn1 | 2.055 (5) |
| C1—N4 | 1.326 (8) | N2—N3 | 1.330 (8) |
| C1—C2 | 1.453 (8) | N3—N4 | 1.300 (8) |
| C2—H2A | 0.9600 | O1—Zn1 | 2.024 (3) |
| C2—H2B | 0.9600 | O1—H1B | 0.86 (7) |
| Cl1—O4 | 1.313 (5) | O1—H1A | 0.85 (6) |
| Cl1—O5 | 1.315 (5) | O2—Zn1 | 1.977 (5) |
| Cl1—O3 | 1.493 (4) | O2—H2C | 0.87 (6) |
| Cl1—O3i | 1.493 (4) | Zn1—O1ii | 2.024 (3) |
| N1—N2 | 1.311 (7) | ||
| N1—C1—N4 | 112.0 (6) | N2—N1—Zn1 | 114.1 (4) |
| N1—C1—C2 | 127.5 (6) | N1—N2—N3 | 103.2 (5) |
| N4—C1—C2 | 120.5 (6) | N4—N3—N2 | 112.4 (5) |
| C1—C2—H2A | 109.3 | N3—N4—C1 | 102.3 (5) |
| C1—C2—H2B | 109.5 | Zn1—O1—H1B | 109 (5) |
| H2A—C2—H2B | 109.5 | Zn1—O1—H1A | 109 (5) |
| O4—Cl1—O5 | 110.5 (3) | H1B—O1—H1A | 109 (6) |
| O4—Cl1—O3 | 111.7 (2) | Zn1—O2—H2C | 121 (4) |
| O5—Cl1—O3 | 113.9 (2) | O2—Zn1—O1ii | 111.18 (13) |
| O4—Cl1—O3i | 111.7 (2) | O2—Zn1—O1 | 111.18 (13) |
| O5—Cl1—O3i | 113.9 (2) | O1ii—Zn1—O1 | 113.0 (2) |
| O3—Cl1—O3i | 94.3 (3) | O2—Zn1—N1 | 103.6 (2) |
| C1—N1—N2 | 110.1 (5) | O1ii—Zn1—N1 | 108.70 (14) |
| C1—N1—Zn1 | 135.9 (5) | O1—Zn1—N1 | 108.70 (14) |
| Symmetry codes: (i) x, −y+3/2, z; (ii) x, −y+1/2, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2C···O3iii | 0.87 (6) | 2.33 (6) | 3.050 (4) | 140 (5) |
| O1—H1A···N2iv | 0.85 (6) | 2.61 (6) | 3.202 (6) | 127 (5) |
| O1—H1B···O3v | 0.86 (7) | 2.29 (7) | 2.982 (5) | 138 (5) |
| Symmetry codes: (iii) x, y−1, z; (iv) x+1, y, z; (v) x+1, y−1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2C···O3i | 0.87 (6) | 2.33 (6) | 3.050 (4) | 140 (5) |
| O1—H1A···N2ii | 0.85 (6) | 2.61 (6) | 3.202 (6) | 127 (5) |
| O1—H1B···O3iii | 0.86 (7) | 2.29 (7) | 2.982 (5) | 138 (5) |
| Symmetry codes: (i) x, y−1, z; (ii) x+1, y, z; (iii) x+1, y−1, z. |
The authors are grateful to the Starter Fund of Southeast University for financial support to buy the CCD X-ray diffractometer.
Bruker (2000). SMART (Version 5.625), SAINT (Version 6.22), SHELXTL (Version 6.10) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.
Carlucci, L., Ciani, G. & Proserpio, D. M. (1999). Angew. Chem. Int. Ed. 38, 3488–3492.
Demko, Z. P. & Sharpless, K. B. (2001). J. Org. Chem. 66, 7945–7950.
Xiong, R.-G., Xue, X., Zhao, H., You, X.-Z., Abrahams, B. F. & Xue, Z. (2002). Angew. Chem. Int. Ed. 41, 3800–3803.
The tetrazole functional group has found a wide range of applications as ligand in coordination chemistry, in medicinal chemistry as a metabolically stable surrogate for a carboxylic acid group, and in material sciences as high density energy materials (Carlucci et al., 1999; Demko & Sharpless, 2001). Recently, we have successfully trapped and structurally characterized many intermediates in which organic part contains one or two cyano groups, affording mono-tetrazolyl or bi-tetrazolyl organic ligands (Xiong et al., 2002). Herein, we report the crystal structure of a simple tetrazole coordination compound, (I), synthesized in-situ by hydrothermal method.
The crystal structure shows that the title compound presents a novel structure consisting of two distinct units: the coordination ZnII complex cation and the perchlorate anion, both lying on a mirror plane. For the cation, atoms in special positions are C1/C2/N1/N2/N3/N4/Zn1/O2, while O1 is in general position. The ZnII ion is in a distorted tetrahedral geometry and is coordinated to three O atoms from water molecules and one N atom from the tetrazolate ring (Fig.1). It should be noted that there are classical O—H···O and O—H···N hydrogen bond interactions in the crystal structure (Table 1, Fig. 2). Owning to the intermolecular hydrogen bonding interactions, the cations and the anions are linked into a one-dimensional (one-dimensional) backbone chain along [010] axis (Fig, 3). Finally, adjacent chains are further extended into a three-dimensional (three-dimensional) network structure through weak contacts.