Acta Cryst. (2007). E63, m2061 [ doi:10.1107/S1600536807031881 ]
The coordination geometry of the Re atom in the title compound, (CH6N3)[ReO4], is tetrahedral. The structure consists of alternating cationic and anionic layers parallel to the (1
0) plane; the layers are held in a three-dimensional structure by N-H
O hydrogen bonds.
Synthesis of (I) was carried out as a neutralization reaction by dissolution of stoichiometric quantity of guanidine under intensive stirring in 0.2 M water solution of HReO4 at room temperature, followed by evaporation of the resulting solution over P2O5. The compound was recrystallized from ethanol.
The H atoms of NH2 groups were refined in idealized geometrical positions with displacement parameters being equal to 1.2 times Ueq of the attached N atoms.
Largest electron density peak on the final difference Fourier-synthesis is 1.593 e Å−3 (0.94 Å from Re1), the deepest hole is −2.902 e Å−3 (0.69 Å from Re1).
Data collection: APEX2 (Bruker, 0000); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL97 (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL97.
![[Figure 1]](./ng2292fig1thm.gif)
| Fig. 1. A view of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by circles of arbitrary size. Dashed line indicates the hydrogen-bonding interaction. |
![[Figure 2]](./ng2292fig2thm.gif)
| Fig. 2. A pattern of the hydrogen-bonding of one guanidinium cation in (I). |
![[Figure 3]](./ng2292fig3thm.gif)
| Fig. 3. The packing of (I) showing three-dimensional net of hydrogen bonds. |
| (CH6N3)[ReO4] | Z = 2 |
| Mr = 310.29 | F(000) = 280 |
| Triclinic, P1 | Dx = 3.334 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 4.9657 (4) Å | Cell parameters from 8692 reflections |
| b = 7.7187 (7) Å | θ = 2.8–35.0° |
| c = 8.4423 (7) Å | µ = 19.61 mm−1 |
| α = 75.314 (4)° | T = 100 K |
| β = 88.707 (5)° | Plate, colourless |
| γ = 80.985 (5)° | 0.12 × 0.10 × 0.06 mm |
| V = 309.09 (5) Å3 |
| Bruker KappaAPEXII area-detector diffractometer | 2698 independent reflections |
| Radiation source: fine-focus sealed tube | 2506 reflections with I > 2σ(I) |
| graphite | Rint = 0.027 |
| ω and φ scans | θmax = 35.0°, θmin = 2.8° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→8 |
| Tmin = 0.192, Tmax = 0.346 | k = −12→12 |
| 11709 measured reflections | l = −13→13 |
| 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)] = 0.018 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.040 | H-atom parameters constrained |
| S = 1.11 | w = 1/[σ2(Fo2) + (0.0177P)2 + 0.58P] where P = (Fo2 + 2Fc2)/3 |
| 2698 reflections | (Δ/σ)max = 0.002 |
| 82 parameters | Δρmax = 1.59 e Å−3 |
| 0 restraints | Δρmin = −2.90 e Å−3 |
| (CH6N3)[ReO4] | γ = 80.985 (5)° |
| Mr = 310.29 | V = 309.09 (5) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 4.9657 (4) Å | Mo Kα radiation |
| b = 7.7187 (7) Å | µ = 19.61 mm−1 |
| c = 8.4423 (7) Å | T = 100 K |
| α = 75.314 (4)° | 0.12 × 0.10 × 0.06 mm |
| β = 88.707 (5)° |
| Bruker KappaAPEXII area-detector diffractometer | 2698 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2506 reflections with I > 2σ(I) |
| Tmin = 0.192, Tmax = 0.346 | Rint = 0.027 |
| 11709 measured reflections | θmax = 35.0° |
| R[F2 > 2σ(F2)] = 0.018 | H-atom parameters constrained |
| wR(F2) = 0.040 | Δρmax = 1.59 e Å−3 |
| S = 1.11 | Δρmin = −2.90 e Å−3 |
| 2698 reflections | Absolute structure: ? |
| 82 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| Re1 | 0.00024 (2) | 0.252412 (14) | 0.685859 (11) | 0.00754 (3) | |
| O1 | −0.1246 (5) | 0.3316 (3) | 0.4871 (2) | 0.0164 (4) | |
| O2 | −0.0731 (5) | 0.0363 (3) | 0.7671 (3) | 0.0185 (4) | |
| O3 | 0.3487 (5) | 0.2424 (3) | 0.6862 (3) | 0.0150 (4) | |
| O4 | −0.1391 (5) | 0.3927 (3) | 0.8075 (3) | 0.0139 (4) | |
| N1 | 0.4480 (5) | 0.1966 (4) | 0.0569 (3) | 0.0129 (4) | |
| H1A | 0.5021 | 0.2371 | −0.0438 | 0.015* | |
| H1B | 0.3283 | 0.1212 | 0.0769 | 0.015* | |
| N2 | 0.4610 (5) | 0.1881 (4) | 0.3302 (3) | 0.0125 (4) | |
| H2A | 0.5238 | 0.2229 | 0.4119 | 0.015* | |
| H2B | 0.3413 | 0.1127 | 0.3486 | 0.015* | |
| N3 | 0.7270 (5) | 0.3627 (3) | 0.1487 (3) | 0.0117 (4) | |
| H3A | 0.7809 | 0.4031 | 0.0479 | 0.014* | |
| H3B | 0.7927 | 0.3977 | 0.2294 | 0.014* | |
| C1 | 0.5471 (5) | 0.2493 (3) | 0.1790 (3) | 0.0087 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Re1 | 0.00736 (5) | 0.00912 (5) | 0.00673 (4) | −0.00250 (3) | 0.00081 (3) | −0.00245 (3) |
| O1 | 0.0142 (10) | 0.0288 (12) | 0.0075 (8) | −0.0076 (9) | −0.0017 (7) | −0.0042 (8) |
| O2 | 0.0139 (10) | 0.0106 (9) | 0.0292 (12) | −0.0040 (8) | 0.0018 (8) | −0.0004 (8) |
| O3 | 0.0097 (9) | 0.0179 (10) | 0.0179 (9) | −0.0032 (8) | 0.0006 (7) | −0.0046 (8) |
| O4 | 0.0161 (10) | 0.0155 (9) | 0.0112 (8) | −0.0009 (8) | 0.0026 (7) | −0.0066 (7) |
| N1 | 0.0165 (11) | 0.0169 (11) | 0.0075 (8) | −0.0088 (9) | −0.0008 (8) | −0.0033 (8) |
| N2 | 0.0154 (11) | 0.0157 (11) | 0.0075 (8) | −0.0073 (9) | 0.0022 (7) | −0.0021 (8) |
| N3 | 0.0148 (11) | 0.0119 (10) | 0.0100 (9) | −0.0064 (8) | 0.0005 (7) | −0.0028 (7) |
| C1 | 0.0092 (11) | 0.0081 (10) | 0.0083 (9) | −0.0006 (8) | −0.0008 (8) | −0.0016 (8) |
| Re1—O1 | 1.727 (2) | C1—N2 | 1.330 (3) |
| Re1—O2 | 1.728 (2) | N2—H2A | 0.8800 |
| Re1—O3 | 1.720 (2) | N2—H2B | 0.8800 |
| Re1—O4 | 1.733 (2) | C1—N3 | 1.323 (3) |
| C1—N1 | 1.330 (3) | N3—H3A | 0.8800 |
| N1—H1A | 0.8800 | N3—H3B | 0.8800 |
| N1—H1B | 0.8800 | ||
| O1—Re1—O2 | 109.53 (12) | C1—N2—H2A | 120.0 |
| O1—Re1—O3 | 109.35 (11) | C1—N2—H2B | 120.0 |
| O1—Re1—O4 | 111.43 (11) | H2A—N2—H2B | 120.0 |
| O2—Re1—O3 | 108.35 (11) | C1—N3—H3A | 120.0 |
| O2—Re1—O4 | 109.43 (11) | C1—N3—H3B | 120.0 |
| O3—Re1—O4 | 108.69 (11) | H3A—N3—H3B | 120.0 |
| C1—N1—H1A | 120.0 | N1—C1—N2 | 119.1 (2) |
| C1—N1—H1B | 120.0 | N1—C1—N3 | 119.9 (2) |
| H1A—N1—H1B | 120.0 | N2—C1—N3 | 120.9 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O3i | 0.88 | 2.41 | 3.101 (3) | 136 |
| N1—H1A···O4ii | 0.88 | 2.45 | 3.177 (3) | 140 |
| N1—H1B···O2iii | 0.88 | 2.10 | 2.911 (3) | 153 |
| N2—H2A···O1iv | 0.88 | 2.22 | 2.966 (3) | 142 |
| N2—H2A···O3 | 0.88 | 2.49 | 3.164 (3) | 134 |
| N2—H2B···O2iii | 0.88 | 2.27 | 3.037 (3) | 145 |
| N3—H3A···O4ii | 0.88 | 2.08 | 2.901 (3) | 155 |
| N3—H3B···O1iv | 0.88 | 2.14 | 2.907 (3) | 146 |
| N3—H3B···O4v | 0.88 | 2.50 | 3.080 (3) | 124 |
| Symmetry codes: (i) x, y, z−1; (ii) x+1, y, z−1; (iii) −x, −y, −z+1; (iv) x+1, y, z; (v) −x+1, −y+1, −z+1. |
| Re1—O1 | 1.727 (2) | Re1—O3 | 1.720 (2) |
| Re1—O2 | 1.728 (2) | Re1—O4 | 1.733 (2) |
| O1—Re1—O2 | 109.53 (12) | O2—Re1—O3 | 108.35 (11) |
| O1—Re1—O3 | 109.35 (11) | O2—Re1—O4 | 109.43 (11) |
| O1—Re1—O4 | 111.43 (11) | O3—Re1—O4 | 108.69 (11) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O3i | 0.88 | 2.41 | 3.101 (3) | 136 |
| N1—H1A···O4ii | 0.88 | 2.45 | 3.177 (3) | 140 |
| N1—H1B···O2iii | 0.88 | 2.10 | 2.911 (3) | 153 |
| N2—H2A···O1iv | 0.88 | 2.22 | 2.966 (3) | 142 |
| N2—H2A···O3 | 0.88 | 2.49 | 3.164 (3) | 134 |
| N2—H2B···O2iii | 0.88 | 2.27 | 3.037 (3) | 145 |
| N3—H3A···O4ii | 0.88 | 2.08 | 2.901 (3) | 155 |
| N3—H3B···O1iv | 0.88 | 2.14 | 2.907 (3) | 146 |
| N3—H3B···O4v | 0.88 | 2.50 | 3.080 (3) | 124 |
| Symmetry codes: (i) x, y, z−1; (ii) x+1, y, z−1; (iii) −x, −y, −z+1; (iv) x+1, y, z; (v) −x+1, −y+1, −z+1. |
Bruker (0000?). APEX2. Bruker AXS Inc., Madison,
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Bruker (1998). SAINT-Plus. Version 6.01. Bruker AXS Inc., Madison, Wisconsin, USA.
Kozak, A., Grottel, M., Koziol, A. E. & Pajak, Z. (1987). J. Phys. C: Solid State Phys. 20, 5433–5447.
Koziol, A. E. (1984). Z. Kristallogr. 168, 313–316.
Leibnitz, P., Reck, G., Pietzsch, H.-J. & Spies, H. (2001). Report FZR-311, pp. 36-40. Forschungszentrum Rossendorf, Berlin, Germany.
Sheldrick, G. M. (1996). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Sheldrick, G. M. (1997b). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.
Tamm, M. S., Beer, S. & Herdtweck, E. (2004). Z. Naturforsch. B, 59, 1497–1504.
The title compound, (I) (Fig. 1), contains slightly distorted tetrahedral ReO4− anions with Re—O distances from 1.720 (2) to 1.733 (2) Å (Table 1).
Guanidinium cations act as proton donors in a number of weak hydrogen bonds (Fig. 2, Table 2). In contrast to the structure of 2,2,8,8-tetraallyl-3,4,6,7,8,9-hexahydro-2H-pyrimidino(1,2 − a)pyrimidinium tetraoxorhenate(VII) (Leibnitz et al., 2001), only one O atom of each tetraoxoanion is bonded to the same cation.
The structure of (I) can be described as alternating cationic and anionic layers parallel to the (120) plane (Fig. 3). Similar alternating layers are present in the structures of C(NH2)3ClO4 (Koziol, 1984) and C(NH2)3BF4 (Kozak et al., 1987), but there is an essential difference in the orientation of tetrahedral anions between cationic layers. In (I), two O atoms of each anion participate in hydrogen bonding with one cationic layer and two - with another cationic layer. In C(NH2)3ClO4 and isostructural C(NH2)3BF4, three O or F atoms of tetrahedral anion are connected with one cationic layer and one atom - with another layer. The resulting hydrogen bond net in (I) is three-dimensional.