Acta Cryst. (2011). E67, m113 [ doi:10.1107/S1600536810052992 ]
In the title compound, [Mg(H2O)6]Br2·2C6H5N5, the MgII atom, lying on an inversion center, is coordinated by six water molecules in a distorted octahedral geometry. The pyridine and tetrazole rings in the 5-(pyridinium-3-yl)tetrazol-1-ide zwitterion are nearly coplanar, twisted from each other by a dihedral angle of 5.70 (1)°. The zwitterions, Br anions and complex cations are connected by O-H
Br, O-HN and N-HBr hydrogen bonds, leading to the formation of a three-dimensional network.
MgBr2.6H2O (2 mmol) and 3-(1H-tetrazol-5-yl)pyridine (0.528 g, 2 mmol) were dissolved in 70% methanol aqueous solution, and then 2 ml HBr was added. Single crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of the solution at room temperature after two weeks. The crystals were colourless, block, and of average size 0.2×0.3×0.4 mm.
The permittivity measurement shows that there is no phase transition within temperature range from 100 to 400 K, and the permittivity is 9.1 at 1 MHz at room temperature.
H atoms attached to C and N atoms were positioned geometrically and treated as riding, with C—H = 0.93 and N—H = 0.86 Å and with Uiso(H) = 1.2Ueq(C, N). H atoms of water molecules were located in a difference Fourier map and refined using a riding model, with Uiso(H) = 1.5Ueq(O).
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./hy2389fig1thm.gif)
| Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (A) 1 - x, 1 - y, 2 - z.] |
![[Figure 2]](./hy2389fig2thm.gif)
| Fig. 2. The crystal packing of the title compound. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity. |
| [Mg(H2O)6]Br2·2C6H5N5 | Z = 1 |
| Mr = 586.53 | F(000) = 294 |
| Triclinic, P1 | Dx = 1.703 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.3439 (15) Å | Cell parameters from 2627 reflections |
| b = 8.7786 (18) Å | θ = 3.1–24.5° |
| c = 9.5863 (19) Å | µ = 3.62 mm−1 |
| α = 94.04 (3)° | T = 298 K |
| β = 90.94 (3)° | Block, colourless |
| γ = 111.75 (3)° | 0.40 × 0.05 × 0.05 mm |
| V = 572.0 (2) Å3 |
| Rigaku SCXmini CCD diffractometer | 2627 independent reflections |
| Radiation source: fine-focus sealed tube | 2172 reflections with I > 2σ(I) |
| graphite | Rint = 0.040 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
| ω scans | h = −9→9 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −11→11 |
| Tmin = 0.89, Tmax = 0.95 | l = −12→12 |
| 5933 measured reflections |
| 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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.097 | H-atom parameters constrained |
| S = 1.09 | w = 1/[σ2(Fo2) + (0.0426P)2 + 0.1011P] where P = (Fo2 + 2Fc2)/3 |
| 2627 reflections | (Δ/σ)max = 0.001 |
| 142 parameters | Δρmax = 0.32 e Å−3 |
| 0 restraints | Δρmin = −0.52 e Å−3 |
| [Mg(H2O)6]Br2·2C6H5N5 | γ = 111.75 (3)° |
| Mr = 586.53 | V = 572.0 (2) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 7.3439 (15) Å | Mo Kα radiation |
| b = 8.7786 (18) Å | µ = 3.62 mm−1 |
| c = 9.5863 (19) Å | T = 298 K |
| α = 94.04 (3)° | 0.40 × 0.05 × 0.05 mm |
| β = 90.94 (3)° |
| Rigaku SCXmini CCD diffractometer | 2627 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 2172 reflections with I > 2σ(I) |
| Tmin = 0.89, Tmax = 0.95 | Rint = 0.040 |
| 5933 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
| wR(F2) = 0.097 | Δρmax = 0.32 e Å−3 |
| S = 1.09 | Δρmin = −0.52 e Å−3 |
| 2627 reflections | Absolute structure: ? |
| 142 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| x | y | z | Uiso*/Ueq | ||
| N4 | 0.3716 (3) | 0.6009 (3) | 0.6076 (3) | 0.0347 (6) | |
| N2 | 0.2637 (3) | 0.5318 (3) | 0.3932 (2) | 0.0315 (5) | |
| C6 | 0.1639 (4) | 0.4135 (3) | 0.4740 (3) | 0.0263 (6) | |
| N5 | 0.2266 (3) | 0.4528 (3) | 0.6073 (2) | 0.0328 (5) | |
| C2 | 0.0038 (4) | 0.2612 (3) | 0.4229 (3) | 0.0272 (6) | |
| C3 | −0.1073 (4) | 0.1506 (4) | 0.5142 (3) | 0.0319 (6) | |
| H3 | −0.0792 | 0.1730 | 0.6101 | 0.038* | |
| N1 | −0.1923 (4) | 0.0847 (4) | 0.2374 (3) | 0.0481 (7) | |
| H1A | −0.2202 | 0.0642 | 0.1489 | 0.058* | |
| N3 | 0.3947 (3) | 0.6479 (3) | 0.4800 (3) | 0.0360 (6) | |
| C1 | −0.0427 (5) | 0.2234 (4) | 0.2822 (3) | 0.0398 (7) | |
| H1 | 0.0296 | 0.2941 | 0.2180 | 0.048* | |
| C5 | −0.3000 (5) | −0.0234 (4) | 0.3232 (4) | 0.0464 (8) | |
| H5 | −0.4017 | −0.1188 | 0.2873 | 0.056* | |
| C4 | −0.2598 (4) | 0.0073 (4) | 0.4639 (4) | 0.0408 (7) | |
| H4 | −0.3335 | −0.0668 | 0.5253 | 0.049* | |
| Mg1 | 0.5000 | 0.5000 | 1.0000 | 0.0303 (3) | |
| O1W | 0.2634 (3) | 0.3471 (3) | 0.8692 (2) | 0.0497 (6) | |
| H1WA | 0.2453 | 0.3674 | 0.7906 | 0.075* | |
| H1WB | 0.1806 | 0.2467 | 0.8849 | 0.075* | |
| O2W | 0.5507 (3) | 0.6851 (2) | 0.8697 (2) | 0.0465 (6) | |
| H2WA | 0.5117 | 0.6602 | 0.7829 | 0.070* | |
| H2WB | 0.6098 | 0.7777 | 0.8780 | 0.070* | |
| O3W | 0.3123 (4) | 0.5786 (3) | 1.1155 (2) | 0.0532 (6) | |
| H3WA | 0.2760 | 0.6585 | 1.0834 | 0.080* | |
| H3WB | 0.3030 | 0.5606 | 1.2130 | 0.080* | |
| Br1 | 0.79518 (5) | 0.08632 (4) | 0.89951 (3) | 0.04481 (14) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N4 | 0.0315 (12) | 0.0309 (13) | 0.0353 (14) | 0.0055 (11) | −0.0054 (10) | −0.0025 (11) |
| N2 | 0.0307 (12) | 0.0285 (12) | 0.0293 (13) | 0.0041 (10) | 0.0010 (10) | 0.0027 (10) |
| C6 | 0.0242 (13) | 0.0277 (14) | 0.0257 (14) | 0.0080 (11) | 0.0012 (10) | 0.0028 (11) |
| N5 | 0.0325 (12) | 0.0336 (13) | 0.0262 (13) | 0.0053 (11) | −0.0038 (10) | 0.0027 (10) |
| C2 | 0.0270 (13) | 0.0270 (14) | 0.0269 (14) | 0.0097 (11) | 0.0010 (11) | 0.0009 (11) |
| C3 | 0.0309 (14) | 0.0311 (15) | 0.0313 (15) | 0.0083 (12) | 0.0010 (11) | 0.0051 (12) |
| N1 | 0.0513 (16) | 0.0464 (17) | 0.0333 (15) | 0.0059 (14) | −0.0096 (12) | −0.0124 (13) |
| N3 | 0.0332 (13) | 0.0292 (13) | 0.0411 (15) | 0.0063 (11) | 0.0026 (11) | 0.0039 (11) |
| C1 | 0.0410 (16) | 0.0376 (17) | 0.0297 (16) | 0.0025 (14) | 0.0027 (13) | −0.0010 (13) |
| C5 | 0.0369 (17) | 0.0301 (17) | 0.061 (2) | 0.0016 (14) | −0.0041 (16) | −0.0084 (16) |
| C4 | 0.0344 (16) | 0.0307 (16) | 0.052 (2) | 0.0049 (13) | 0.0049 (14) | 0.0061 (15) |
| Mg1 | 0.0387 (7) | 0.0245 (7) | 0.0216 (7) | 0.0047 (6) | 0.0004 (5) | 0.0022 (5) |
| O1W | 0.0520 (13) | 0.0454 (14) | 0.0302 (12) | −0.0069 (11) | −0.0088 (10) | 0.0073 (10) |
| O2W | 0.0710 (15) | 0.0213 (10) | 0.0310 (12) | −0.0015 (10) | −0.0103 (10) | 0.0041 (9) |
| O3W | 0.0792 (17) | 0.0629 (17) | 0.0342 (13) | 0.0432 (15) | 0.0173 (12) | 0.0161 (12) |
| Br1 | 0.0546 (2) | 0.03047 (19) | 0.0402 (2) | 0.00473 (15) | 0.00206 (14) | 0.00592 (14) |
| N4—N3 | 1.312 (4) | C5—H5 | 0.9300 |
| N4—N5 | 1.341 (3) | C4—H4 | 0.9300 |
| N2—N3 | 1.336 (3) | Mg1—O2Wi | 2.048 (2) |
| N2—C6 | 1.336 (3) | Mg1—O2W | 2.048 (2) |
| C6—N5 | 1.329 (3) | Mg1—O3Wi | 2.061 (2) |
| C6—C2 | 1.460 (4) | Mg1—O3W | 2.061 (2) |
| C2—C1 | 1.373 (4) | Mg1—O1W | 2.087 (2) |
| C2—C3 | 1.390 (4) | Mg1—O1Wi | 2.087 (2) |
| C3—C4 | 1.386 (4) | O1W—H1WA | 0.8068 |
| C3—H3 | 0.9300 | O1W—H1WB | 0.8907 |
| N1—C5 | 1.333 (4) | O2W—H2WA | 0.8615 |
| N1—C1 | 1.339 (4) | O2W—H2WB | 0.7636 |
| N1—H1A | 0.8600 | O3W—H3WA | 0.9085 |
| C1—H1 | 0.9300 | O3W—H3WB | 0.9576 |
| C5—C4 | 1.363 (5) | ||
| N3—N4—N5 | 110.0 (2) | O2Wi—Mg1—O2W | 180.000 (1) |
| N3—N2—C6 | 105.2 (2) | O2Wi—Mg1—O3Wi | 91.93 (10) |
| N5—C6—N2 | 111.4 (2) | O2W—Mg1—O3Wi | 88.07 (10) |
| N5—C6—C2 | 124.2 (2) | O2Wi—Mg1—O3W | 88.07 (10) |
| N2—C6—C2 | 124.4 (2) | O2W—Mg1—O3W | 91.93 (10) |
| C6—N5—N4 | 104.5 (2) | O3Wi—Mg1—O3W | 180.000 (1) |
| C1—C2—C3 | 117.8 (3) | O2Wi—Mg1—O1W | 89.55 (9) |
| C1—C2—C6 | 120.7 (3) | O2W—Mg1—O1W | 90.45 (9) |
| C3—C2—C6 | 121.5 (3) | O3Wi—Mg1—O1W | 90.10 (11) |
| C4—C3—C2 | 120.7 (3) | O3W—Mg1—O1W | 89.90 (11) |
| C4—C3—H3 | 119.6 | O2Wi—Mg1—O1Wi | 90.45 (9) |
| C2—C3—H3 | 119.6 | O2W—Mg1—O1Wi | 89.55 (9) |
| C5—N1—C1 | 123.3 (3) | O3Wi—Mg1—O1Wi | 89.90 (11) |
| C5—N1—H1A | 118.3 | O3W—Mg1—O1Wi | 90.10 (11) |
| C1—N1—H1A | 118.3 | O1W—Mg1—O1Wi | 180.000 (1) |
| N4—N3—N2 | 108.8 (2) | Mg1—O1W—H1WA | 122.5 |
| N1—C1—C2 | 119.9 (3) | Mg1—O1W—H1WB | 126.6 |
| N1—C1—H1 | 120.1 | H1WA—O1W—H1WB | 110.2 |
| C2—C1—H1 | 120.1 | Mg1—O2W—H2WA | 119.0 |
| N1—C5—C4 | 119.4 (3) | Mg1—O2W—H2WB | 133.7 |
| N1—C5—H5 | 120.3 | H2WA—O2W—H2WB | 107.0 |
| C4—C5—H5 | 120.3 | Mg1—O3W—H3WA | 118.6 |
| C5—C4—C3 | 119.0 (3) | Mg1—O3W—H3WB | 118.7 |
| C5—C4—H4 | 120.5 | H3WA—O3W—H3WB | 119.2 |
| C3—C4—H4 | 120.5 |
| Symmetry codes: (i) −x+1, −y+1, −z+2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···Br1ii | 0.86 | 2.41 | 3.240 (3) | 161 |
| O1W—H1WA···N5 | 0.81 | 1.98 | 2.780 (3) | 171 |
| O1W—H1WB···Br1iii | 0.89 | 2.66 | 3.382 (3) | 138 |
| O2W—H2WA···N4 | 0.86 | 1.89 | 2.738 (3) | 167 |
| O2W—H2WB···Br1iv | 0.76 | 2.53 | 3.296 (2) | 178 |
| O3W—H3WA···Br1i | 0.91 | 2.48 | 3.328 (2) | 156 |
| O3W—H3WB···N2v | 0.96 | 1.78 | 2.730 (3) | 174 |
| Symmetry codes: (ii) x−1, y, z−1; (iii) x−1, y, z; (iv) x, y+1, z; (i) −x+1, −y+1, −z+2; (v) x, y, z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···Br1i | 0.86 | 2.41 | 3.240 (3) | 161 |
| O1W—H1WA···N5 | 0.81 | 1.98 | 2.780 (3) | 171 |
| O1W—H1WB···Br1ii | 0.89 | 2.66 | 3.382 (3) | 138 |
| O2W—H2WA···N4 | 0.86 | 1.89 | 2.738 (3) | 167 |
| O2W—H2WB···Br1iii | 0.76 | 2.53 | 3.296 (2) | 178 |
| O3W—H3WA···Br1iv | 0.91 | 2.48 | 3.328 (2) | 156 |
| O3W—H3WB···N2v | 0.96 | 1.78 | 2.730 (3) | 174 |
| Symmetry codes: (i) x−1, y, z−1; (ii) x−1, y, z; (iii) x, y+1, z; (iv) −x+1, −y+1, −z+2; (v) x, y, z+1. |
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Tetrazole compounds have attracted more attention as phase transition dielectric materials for its applications in micro-electronics, memory storage. With the purpose of obtaining phase transition crystals of 3-(1H-tetrazol-5-yl)pyridine compounds, its interaction with various metal ions has been studied and a series of new materials have been elaborated with this organic molecule (Fu et al., 2007, 2008; Fu & Xiong 2008; Zhao et al., 2008). In this paper, we describe the crystal structure of the title compound.
The asymmetric unit of the title compound (Fig. 1) is composed of one zwitterionic organic molecule, half [Mg(H2O)6]2+ cation and one Br anion. In the zwitterionic organic molecule, the pyridine N atom is protonated. The pyridine and tetrazole rings are nearly coplanar and only twisted from each other by a dihedral angle of 5.70 (1)°. The geometric parameters of the tetrazole ring are comparable to those in related molecules (Fu et al., 2009; Zhao et al., 2008).
In the crystal structure, the intermolecular hydrogen bonds are formed by all H atoms of the water molecules and pyridine N atoms with the tetrazole N atoms or Br anions. The complex cations [Mg(H2O)6]2+ and Br anions are linked in the crystal through O—H···Br hydrogen bonds into an infinite cation–anion sheet parallel to (0 0 1). The two-dimensional sheets are linked by organic molecules through O—H···N and N—H···Br hydrogen bonds into a three-dimensional network (Table 1 and Fig. 2).