Acta Cryst. (2010). E66, o1941 [ doi:10.1107/S1600536810025857 ]
In the title compound, C2H5N2+·BF4-, the cations and anions are connected via intermolecular N-H
F and C-HF hydrogen bonds, forming a three-dimensional network.
A mixture of aminoacetonitrile hydrochloride (0.095 g, 0.01 mol) and tetrafluoro-borate sodium (1.10 g, 0.01 mol) in water (20 ml) was stirred until clear. After several days, colourless prismatic crystals of the title compound were formed which were suitable for X-ray analysis.
The methylene H-atoms were positioned geometrically and refined using a riding model, with C—H = 0.97 Å and Uiso(H) = 1.2eq(C). The H-atoms bonded to the N-atom were located from a difference map and were allowed to refine freely.
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 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./pv2302fig1thm.gif)
| Fig. 1. Perspective structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./pv2302fig2thm.gif)
| Fig. 2. The crystal packing of the title compound viewed along the a axis showing the hydrogen bondings network. |
| C2H5N2+·BF4− | F(000) = 576 |
| Mr = 143.89 | Dx = 1.730 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 970 reflections |
| a = 9.790 (2) Å | θ = 2.6–25.0° |
| b = 10.204 (2) Å | µ = 0.20 mm−1 |
| c = 11.057 (2) Å | T = 293 K |
| V = 1104.6 (4) Å3 | Prism, colorless |
| Z = 8 | 0.20 × 0.20 × 0.20 mm |
| Rigaku Mercury2 (2x2 bin mode) diffractometer | 969 independent reflections |
| Radiation source: fine-focus sealed tube | 891 reflections with I > 2σ(I) |
| graphite | Rint = 0.046 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 25.0°, θmin = 3.4° |
| CCD_Profile_fitting scans | h = −11→11 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −12→12 |
| Tmin = 0.815, Tmax = 1.000 | l = −13→13 |
| 8605 measured reflections |
| 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)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0711P)2 + 0.9831P] where P = (Fo2 + 2Fc2)/3 |
| S = 0.74 | (Δ/σ)max < 0.001 |
| 969 reflections | Δρmax = 0.21 e Å−3 |
| 95 parameters | Δρmin = −0.19 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.034 (4) |
| C2H5N2+·BF4− | V = 1104.6 (4) Å3 |
| Mr = 143.89 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 9.790 (2) Å | µ = 0.20 mm−1 |
| b = 10.204 (2) Å | T = 293 K |
| c = 11.057 (2) Å | 0.20 × 0.20 × 0.20 mm |
| Rigaku Mercury2 (2x2 bin mode) diffractometer | 969 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 891 reflections with I > 2σ(I) |
| Tmin = 0.815, Tmax = 1.000 | Rint = 0.046 |
| 8605 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.097 | Δρmax = 0.21 e Å−3 |
| S = 0.74 | Δρmin = −0.19 e Å−3 |
| 969 reflections | Absolute structure: ? |
| 95 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 | ||
| F1 | 0.20443 (11) | 0.51691 (10) | 0.27959 (10) | 0.0507 (4) | |
| F3 | 0.25530 (11) | 0.69102 (10) | 0.39731 (9) | 0.0482 (4) | |
| F4 | 0.39397 (10) | 0.51360 (11) | 0.39567 (11) | 0.0536 (4) | |
| N2 | 0.11384 (16) | 0.80444 (15) | 0.59675 (13) | 0.0363 (4) | |
| F2 | 0.18692 (13) | 0.50016 (11) | 0.48270 (11) | 0.0586 (4) | |
| C1 | 0.05747 (17) | 0.69059 (16) | 0.66197 (16) | 0.0380 (4) | |
| H1A | −0.0034 | 0.6428 | 0.6086 | 0.046* | |
| H1B | 0.1315 | 0.6323 | 0.6844 | 0.046* | |
| C2 | −0.01713 (15) | 0.72917 (17) | 0.77058 (14) | 0.0363 (4) | |
| N1 | −0.07586 (17) | 0.75568 (18) | 0.85538 (14) | 0.0553 (5) | |
| B1 | 0.25945 (17) | 0.55466 (18) | 0.38936 (15) | 0.0305 (4) | |
| H2C | 0.052 (3) | 0.861 (3) | 0.574 (2) | 0.079 (8)* | |
| H2B | 0.170 (3) | 0.852 (2) | 0.645 (2) | 0.079 (8)* | |
| H2A | 0.165 (3) | 0.778 (2) | 0.535 (2) | 0.070 (7)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| F1 | 0.0617 (7) | 0.0499 (6) | 0.0406 (6) | −0.0010 (5) | −0.0146 (5) | −0.0072 (4) |
| F3 | 0.0601 (7) | 0.0311 (6) | 0.0535 (7) | 0.0006 (4) | 0.0087 (5) | −0.0054 (4) |
| F4 | 0.0367 (6) | 0.0529 (7) | 0.0713 (8) | 0.0075 (4) | −0.0063 (5) | −0.0017 (5) |
| N2 | 0.0375 (8) | 0.0398 (8) | 0.0314 (8) | 0.0024 (6) | 0.0054 (6) | 0.0001 (6) |
| F2 | 0.0686 (8) | 0.0589 (7) | 0.0483 (7) | −0.0096 (6) | 0.0185 (6) | 0.0086 (5) |
| C1 | 0.0442 (9) | 0.0329 (8) | 0.0369 (9) | 0.0026 (6) | 0.0089 (7) | −0.0006 (7) |
| C2 | 0.0333 (8) | 0.0423 (9) | 0.0333 (9) | 0.0022 (7) | 0.0001 (7) | 0.0032 (7) |
| N1 | 0.0533 (9) | 0.0722 (12) | 0.0404 (9) | 0.0060 (8) | 0.0127 (7) | −0.0008 (9) |
| B1 | 0.0320 (9) | 0.0299 (9) | 0.0296 (9) | −0.0005 (7) | 0.0005 (7) | −0.0006 (6) |
| F1—B1 | 1.3828 (19) | N2—H2A | 0.89 (3) |
| F3—B1 | 1.395 (2) | F2—B1 | 1.371 (2) |
| F4—B1 | 1.384 (2) | C1—C2 | 1.460 (2) |
| N2—C1 | 1.475 (2) | C1—H1A | 0.9700 |
| N2—H2C | 0.87 (3) | C1—H1B | 0.9700 |
| N2—H2B | 0.91 (3) | C2—N1 | 1.133 (2) |
| C1—N2—H2C | 113.4 (17) | N2—C1—H1B | 109.2 |
| C1—N2—H2B | 111.3 (16) | H1A—C1—H1B | 107.9 |
| H2C—N2—H2B | 104 (2) | N1—C2—C1 | 178.16 (19) |
| C1—N2—H2A | 110.3 (16) | F2—B1—F1 | 110.25 (14) |
| H2C—N2—H2A | 112 (2) | F2—B1—F4 | 109.41 (14) |
| H2B—N2—H2A | 106 (2) | F1—B1—F4 | 109.31 (14) |
| C2—C1—N2 | 112.16 (14) | F2—B1—F3 | 110.01 (13) |
| C2—C1—H1A | 109.2 | F1—B1—F3 | 108.78 (13) |
| N2—C1—H1A | 109.2 | F4—B1—F3 | 109.06 (13) |
| C2—C1—H1B | 109.2 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C1—H1A···F2i | 0.97 | 2.53 | 3.474 (2) | 166 |
| C1—H1B···F1ii | 0.97 | 2.45 | 3.407 (2) | 169 |
| N2—H2A···F3 | 0.89 (2) | 1.97 (2) | 2.850 (2) | 169 (2) |
| N2—H2B···F1iii | 0.91 (3) | 2.03 (3) | 2.863 (2) | 152 (2) |
| N2—H2C···F4iv | 0.87 (3) | 2.04 (3) | 2.844 (2) | 154 (2) |
| Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, −y+1, z+1/2; (iii) x, −y+3/2, z+1/2; (iv) x−1/2, −y+3/2, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C1—H1A···F2i | 0.97 | 2.53 | 3.474 (2) | 166 |
| C1—H1B···F1ii | 0.97 | 2.45 | 3.407 (2) | 169 |
| N2—H2A···F3 | 0.89 (2) | 1.97 (2) | 2.850 (2) | 169 (2) |
| N2—H2B···F1iii | 0.91 (3) | 2.03 (3) | 2.863 (2) | 152 (2) |
| N2—H2C···F4iv | 0.87 (3) | 2.04 (3) | 2.844 (2) | 154 (2) |
| Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, −y+1, z+1/2; (iii) x, −y+3/2, z+1/2; (iv) x−1/2, −y+3/2, −z+1. |
The authors are grateful to the Starter Fund of Southeast University for financial support to buy the X-ray diffractometer.
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Wishkerman, S. & Bernstein, J. (2006). CrystEngComm, 8, 245–249.
At present, much attention in ferroelectric material field is focused on developing ferroelectric pure organic or inorganic compounds (Haertling, 1999; Homes et al., 2001). Recently we have reported the synthesis of a variety of compounds (Fu et al., 2009; Hang et al., 2009), which have potential piezoelectric and ferroelectric properties. In order to find more dielectric ferroelectric materials, we have investigate the physical properties of the title compound. The dielectric constant of the title compound as a function of temperature indicates that the permittivity is basically temperature-independent (dielectric constant equaling to 3.6 to 4.7), suggesting that this compound should not be ferroelectric or there may be no distinct phase transition within the measured temperature range. Similarly, below the melting point (453 K) of the compound, the dielectric constant as a function of temperature also goes smoothly, and there is no dielectric anomaly observed (dielectric constant equaling to 3.6 to 4.7). Herein, we report the synthesis and crystal structure of the title compound.
The molecular structure of the title compund is presented in Fig. 1. The bond lengths and angles are within their normal ranges (Wishkerman & Bernstein, 2006). The cations and anions are connected via intermolecular N—H···F and C—H···F hydrogen bonds, forming a three dimensional network (Tab. 1 & Fig. 2).