supplementary materials
trans-Diaquabis[5-(1H-imidazol-4-yl-![[kappa]](/logos/entities/kappa_rmgif.gif)
N3)-1H-tetrazolato-N1]zinc(II)
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-HN hydrogen bonds stabilizes the crystal structure.
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).
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).
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).
trans-Diaquabis[5-(1
H-imidazol-4-yl-
κN3)-1
H-
tetrazolato-
κN1]zinc(II)
top
Crystal data top
| [Zn(C4H3N6)2(H2O)2] | F(000) = 376 |
| Mr = 371.65 | Dx = 1.809 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2098 reflections |
| a = 5.9068 (10) Å | θ = 2.3–27.5° |
| b = 17.408 (3) Å | µ = 1.84 mm−1 |
| c = 7.091 (2) Å | T = 291 K |
| β = 110.70 (2)° | Prism, colourless |
| V = 682.1 (3) Å3 | 0.20 × 0.18 × 0.15 mm |
| Z = 2 | |
Data collection top
Rigaku SCXmini
diffractometer | 1555 independent reflections |
| Radiation source: fine-focus sealed tube | 1429 reflections with I > 2σ(I) |
| graphite | Rint = 0.025 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 2.3° |
| ω scans | h = −7→7 |
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005) | k = −22→22 |
| Tmin = 0.753, Tmax = 0.762 | l = −9→9 |
| 6793 measured reflections | |
Refinement top
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.113 | H-atom parameters constrained |
| S = 1.30 | w = 1/[σ2(Fo2) + (0.0683P)2 + 0.021P]
where P = (Fo2 + 2Fc2)/3 |
| 1555 reflections | (Δ/σ)max < 0.001 |
| 106 parameters | Δρmax = 0.59 e Å−3 |
| 0 restraints | Δρmin = −0.64 e Å−3 |
Crystal data top
| [Zn(C4H3N6)2(H2O)2] | V = 682.1 (3) Å3 |
| Mr = 371.65 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 5.9068 (10) Å | µ = 1.84 mm−1 |
| b = 17.408 (3) Å | T = 291 K |
| c = 7.091 (2) Å | 0.20 × 0.18 × 0.15 mm |
| β = 110.70 (2)° | |
Data collection top
Rigaku SCXmini
diffractometer | 1555 independent reflections |
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005) | 1429 reflections with I > 2σ(I) |
| Tmin = 0.753, Tmax = 0.762 | Rint = 0.025 |
| 6793 measured reflections | θmax = 27.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
| wR(F2) = 0.113 | Δρmax = 0.59 e Å−3 |
| S = 1.30 | Δρmin = −0.64 e Å−3 |
| 1555 reflections | Absolute structure: ? |
| 106 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | Uiso*/Ueq | |
| Zn1 | 1.0000 | 0.5000 | 0.5000 | 0.02202 (18) | |
| C1 | 0.9503 (4) | 0.34932 (12) | 0.3008 (3) | 0.0212 (4) | |
| C2 | 1.0396 (4) | 0.27845 (13) | 0.2890 (4) | 0.0287 (5) | |
| H2 | 0.9581 | 0.2376 | 0.2090 | 0.034* | |
| C3 | 1.3185 (4) | 0.34887 (13) | 0.5063 (4) | 0.0262 (5) | |
| H3 | 1.4657 | 0.3635 | 0.6021 | 0.031* | |
| C4 | 0.7145 (4) | 0.38475 (12) | 0.2122 (3) | 0.0207 (4) | |
| N1 | 1.1269 (3) | 0.39332 (10) | 0.4390 (3) | 0.0223 (4) | |
| N2 | 1.2733 (4) | 0.27947 (11) | 0.4186 (3) | 0.0292 (4) | |
| H2A | 1.3746 | 0.2421 | 0.4404 | 0.035* | |
| N3 | 0.6743 (3) | 0.45320 (10) | 0.2795 (3) | 0.0208 (4) | |
| N4 | 0.4411 (3) | 0.46893 (11) | 0.1772 (3) | 0.0242 (4) | |
| N5 | 0.3469 (3) | 0.41230 (11) | 0.0538 (3) | 0.0272 (4) | |
| N6 | 0.5162 (3) | 0.35808 (11) | 0.0704 (3) | 0.0258 (4) | |
| O1 | 1.0962 (3) | 0.56118 (9) | 0.2680 (2) | 0.0285 (4) | |
| H1B | 0.9793 | 0.5753 | 0.1617 | 0.043* | |
| H1A | 1.1972 | 0.5434 | 0.2327 | 0.043* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Zn1 | 0.0195 (3) | 0.0171 (2) | 0.0251 (3) | 0.00042 (11) | 0.00252 (17) | −0.00441 (12) |
| C1 | 0.0214 (10) | 0.0190 (10) | 0.0211 (10) | −0.0010 (7) | 0.0049 (8) | −0.0013 (8) |
| C2 | 0.0301 (12) | 0.0212 (11) | 0.0323 (12) | 0.0020 (9) | 0.0081 (9) | −0.0019 (9) |
| C3 | 0.0198 (10) | 0.0270 (11) | 0.0287 (11) | 0.0035 (8) | 0.0045 (9) | 0.0030 (9) |
| C4 | 0.0210 (10) | 0.0175 (9) | 0.0216 (10) | −0.0022 (7) | 0.0052 (8) | 0.0008 (8) |
| N1 | 0.0186 (9) | 0.0194 (8) | 0.0256 (9) | 0.0007 (7) | 0.0039 (7) | −0.0019 (7) |
| N2 | 0.0271 (10) | 0.0233 (9) | 0.0356 (11) | 0.0098 (8) | 0.0089 (8) | 0.0035 (8) |
| N3 | 0.0169 (9) | 0.0214 (9) | 0.0217 (9) | 0.0030 (7) | 0.0037 (7) | −0.0004 (7) |
| N4 | 0.0177 (9) | 0.0277 (10) | 0.0254 (10) | 0.0021 (7) | 0.0051 (7) | 0.0028 (8) |
| N5 | 0.0192 (9) | 0.0297 (10) | 0.0286 (10) | −0.0008 (7) | 0.0031 (7) | 0.0028 (8) |
| N6 | 0.0215 (9) | 0.0214 (9) | 0.0282 (10) | −0.0031 (7) | 0.0011 (7) | −0.0021 (8) |
| O1 | 0.0226 (8) | 0.0344 (9) | 0.0259 (8) | 0.0058 (6) | 0.0055 (6) | 0.0016 (7) |
Geometric parameters (Å, °) top
| Zn1—N1i | 2.1042 (18) | C3—N1 | 1.313 (3) |
| Zn1—N1 | 2.1042 (18) | C3—N2 | 1.342 (3) |
| Zn1—N3i | 2.1641 (19) | C3—H3 | 0.9300 |
| Zn1—N3 | 2.1641 (19) | C4—N6 | 1.329 (3) |
| Zn1—O1 | 2.1966 (17) | C4—N3 | 1.336 (3) |
| Zn1—O1i | 2.1966 (17) | N2—H2A | 0.8600 |
| C1—C2 | 1.356 (3) | N3—N4 | 1.339 (3) |
| C1—N1 | 1.383 (3) | N4—N5 | 1.305 (3) |
| C1—C4 | 1.448 (3) | N5—N6 | 1.350 (3) |
| C2—N2 | 1.362 (3) | O1—H1B | 0.8585 |
| C2—H2 | 0.9300 | O1—H1A | 0.7874 |
| | | |
| N1i—Zn1—N1 | 180.0 | N1—C3—N2 | 110.9 (2) |
| N1i—Zn1—N3i | 79.02 (7) | N1—C3—H3 | 124.5 |
| N1—Zn1—N3i | 100.98 (7) | N2—C3—H3 | 124.5 |
| N1i—Zn1—N3 | 100.98 (7) | N6—C4—N3 | 111.23 (19) |
| N1—Zn1—N3 | 79.02 (7) | N6—C4—C1 | 129.4 (2) |
| N3i—Zn1—N3 | 180.00 (8) | N3—C4—C1 | 119.34 (19) |
| N1i—Zn1—O1 | 86.07 (7) | C3—N1—C1 | 105.58 (19) |
| N1—Zn1—O1 | 93.93 (7) | C3—N1—Zn1 | 140.26 (16) |
| N3i—Zn1—O1 | 87.66 (7) | C1—N1—Zn1 | 113.59 (14) |
| N3—Zn1—O1 | 92.34 (7) | C3—N2—C2 | 108.22 (18) |
| N1i—Zn1—O1i | 93.93 (7) | C3—N2—H2A | 125.9 |
| N1—Zn1—O1i | 86.07 (7) | C2—N2—H2A | 125.9 |
| N3i—Zn1—O1i | 92.34 (7) | C4—N3—N4 | 105.51 (17) |
| N3—Zn1—O1i | 87.66 (7) | C4—N3—Zn1 | 111.67 (14) |
| O1—Zn1—O1i | 180.00 (7) | N4—N3—Zn1 | 142.77 (14) |
| C2—C1—N1 | 109.58 (19) | N5—N4—N3 | 108.77 (18) |
| C2—C1—C4 | 134.1 (2) | N4—N5—N6 | 110.06 (17) |
| N1—C1—C4 | 116.14 (18) | C4—N6—N5 | 104.42 (19) |
| C1—C2—N2 | 105.7 (2) | Zn1—O1—H1B | 117.1 |
| C1—C2—H2 | 127.2 | Zn1—O1—H1A | 118.2 |
| N2—C2—H2 | 127.2 | H1B—O1—H1A | 107.4 |
| Symmetry codes: (i) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···N6ii | 0.86 | 2.01 | 2.803 (3) | 153 |
| O1—H1B···N5iii | 0.86 | 2.00 | 2.837 (3) | 164 |
| O1—H1A···N4iv | 0.79 | 2.08 | 2.841 (2) | 164 |
| Symmetry codes: (ii) x+1, −y+1/2, z+1/2; (iii) −x+1, −y+1, −z; (iv) x+1, y, z. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···N6i | 0.86 | 2.01 | 2.803 (3) | 153 |
| O1—H1B···N5ii | 0.86 | 2.00 | 2.837 (3) | 164 |
| O1—H1A···N4iii | 0.79 | 2.08 | 2.841 (2) | 164 |
| Symmetry codes: (i) x+1, −y+1/2, z+1/2; (ii) −x+1, −y+1, −z; (iii) x+1, y, z. |
This work was supported by a start-up grant from Southeast University to HZ.
Demko, Z. P. & Sharpless, K. B. (2001). Org. Lett. 3, 4091–4094
Demko, Z. P. & Sharpless, K. B. (2002). Angew. Chem. Int. Ed. 41, 2110–2113
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Zhao, H., Qu, Z. R., Ye, H. Y. & Xiong, R. G. (2008). Chem. Soc. Rev. 37, 84–100
![[Figure 1]](./rz2306fig1thm.gif)
![[Figure 2]](./rz2306fig2thm.gif)
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).