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ISSN: 2056-9890

Cyanomethanaminium tetra­fluoro­borate

aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
*Correspondence e-mail: zhangshelley86@hotmail.com

(Received 19 June 2010; accepted 1 July 2010; online 7 July 2010)

In the title compound, C2H5N2+·BF4, the cations and anions are connected via inter­molecular N—H⋯F and C—H⋯F hydrogen bonds, forming a three-dimensional network.

Related literature

For background to the development of ferroelectric pure organic or inorganic compounds, see: Haertling (1999[Haertling, G. H. (1999). J. Am. Ceram. Soc. A82, 797-810.]); Homes et al. (2001[Homes, C. C., Vogt, T., Shapiro, S. M., Wakimoto, S. & Ramirez, A. P. (2001). Science, A293, 673-676.]). For thesynthesis of a variety of compounds with potential piezoelectric and ferroelectric properties, see: Fu et al. (2009[Fu, D. W., Ge, J. Z., Dai, J., Ye, H. Y. & Qu, Z. R. (2009). Inorg. Chem. Commun. 12, 994-997.]); Hang et al. (2009[Hang, T., Fu, D. W., Ye, Q. & Xiong, R. G. (2009). Cryst. Growth Des. A5, 2026-2029.]). For comparison bond lengths and bond angles, see: Wishkerman & Bernstein (2006[Wishkerman, S. & Bernstein, J. (2006). CrystEngComm, 8, 245-249.]).

[Scheme 1]

Experimental

Crystal data
  • C2H5N2+·BF4

  • Mr = 143.89

  • Orthorhombic, P b c a

  • a = 9.790 (2) Å

  • b = 10.204 (2) Å

  • c = 11.057 (2) Å

  • V = 1104.6 (4) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.20 mm−1

  • T = 293 K

  • 0.20 × 0.20 × 0.20 mm

Data collection
  • Rigaku Mercury2 diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.815, Tmax = 1.000

  • 8605 measured reflections

  • 969 independent reflections

  • 891 reflections with I > 2σ(I)

  • Rint = 0.046

Refinement
  • R[F2 > 2σ(F2)] = 0.034

  • wR(F2) = 0.097

  • S = 0.74

  • 969 reflections

  • 95 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.21 e Å−3

  • Δρmin = −0.19 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]; (iii) [x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]; (iv) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1].

Data collection: CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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).

Related literature top

For background literature, see: Haertling (1999); Homes et al. (2001). For related literature, see: Fu et al. (2009); Hang et al. (2009). For comparison of bond lengths and bond angles, see: Wishkerman & Bernstein (2006).

Experimental top

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.

Refinement top

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.

Structure description top

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).

For background literature, see: Haertling (1999); Homes et al. (2001). For related literature, see: Fu et al. (2009); Hang et al. (2009). For comparison of bond lengths and bond angles, see: Wishkerman & Bernstein (2006).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. Perspective structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The crystal packing of the title compound viewed along the a axis showing the hydrogen bondings network.
Cyanomethanaminium tetrafluoroborate top
Crystal data top
C2H5N2+·BF4F(000) = 576
Mr = 143.89Dx = 1.730 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 970 reflections
a = 9.790 (2) Åθ = 2.6–25.0°
b = 10.204 (2) ŵ = 0.20 mm1
c = 11.057 (2) ÅT = 293 K
V = 1104.6 (4) Å3Prism, colorless
Z = 80.20 × 0.20 × 0.20 mm
Data collection top
Rigaku Mercury2 (2x2 bin mode)
diffractometer
969 independent reflections
Radiation source: fine-focus sealed tube891 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
Detector resolution: 13.6612 pixels mm-1θmax = 25.0°, θmin = 3.4°
CCD_Profile_fitting scansh = 1111
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 1212
Tmin = 0.815, Tmax = 1.000l = 1313
8605 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H 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 reflectionsΔρmax = 0.21 e Å3
95 parametersΔρmin = 0.19 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.034 (4)
Crystal data top
C2H5N2+·BF4V = 1104.6 (4) Å3
Mr = 143.89Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 9.790 (2) ŵ = 0.20 mm1
b = 10.204 (2) ÅT = 293 K
c = 11.057 (2) Å0.20 × 0.20 × 0.20 mm
Data collection top
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 = 1.000Rint = 0.046
8605 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 0.74Δρmax = 0.21 e Å3
969 reflectionsΔρmin = 0.19 e Å3
95 parameters
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
xyzUiso*/Ueq
F10.20443 (11)0.51691 (10)0.27959 (10)0.0507 (4)
F30.25530 (11)0.69102 (10)0.39731 (9)0.0482 (4)
F40.39397 (10)0.51360 (11)0.39567 (11)0.0536 (4)
N20.11384 (16)0.80444 (15)0.59675 (13)0.0363 (4)
F20.18692 (13)0.50016 (11)0.48270 (11)0.0586 (4)
C10.05747 (17)0.69059 (16)0.66197 (16)0.0380 (4)
H1A0.00340.64280.60860.046*
H1B0.13150.63230.68440.046*
C20.01713 (15)0.72917 (17)0.77058 (14)0.0363 (4)
N10.07586 (17)0.75568 (18)0.85538 (14)0.0553 (5)
B10.25945 (17)0.55466 (18)0.38936 (15)0.0305 (4)
H2C0.052 (3)0.861 (3)0.574 (2)0.079 (8)*
H2B0.170 (3)0.852 (2)0.645 (2)0.079 (8)*
H2A0.165 (3)0.778 (2)0.535 (2)0.070 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F10.0617 (7)0.0499 (6)0.0406 (6)0.0010 (5)0.0146 (5)0.0072 (4)
F30.0601 (7)0.0311 (6)0.0535 (7)0.0006 (4)0.0087 (5)0.0054 (4)
F40.0367 (6)0.0529 (7)0.0713 (8)0.0075 (4)0.0063 (5)0.0017 (5)
N20.0375 (8)0.0398 (8)0.0314 (8)0.0024 (6)0.0054 (6)0.0001 (6)
F20.0686 (8)0.0589 (7)0.0483 (7)0.0096 (6)0.0185 (6)0.0086 (5)
C10.0442 (9)0.0329 (8)0.0369 (9)0.0026 (6)0.0089 (7)0.0006 (7)
C20.0333 (8)0.0423 (9)0.0333 (9)0.0022 (7)0.0001 (7)0.0032 (7)
N10.0533 (9)0.0722 (12)0.0404 (9)0.0060 (8)0.0127 (7)0.0008 (9)
B10.0320 (9)0.0299 (9)0.0296 (9)0.0005 (7)0.0005 (7)0.0006 (6)
Geometric parameters (Å, º) top
F1—B11.3828 (19)N2—H2A0.89 (3)
F3—B11.395 (2)F2—B11.371 (2)
F4—B11.384 (2)C1—C21.460 (2)
N2—C11.475 (2)C1—H1A0.9700
N2—H2C0.87 (3)C1—H1B0.9700
N2—H2B0.91 (3)C2—N11.133 (2)
C1—N2—H2C113.4 (17)N2—C1—H1B109.2
C1—N2—H2B111.3 (16)H1A—C1—H1B107.9
H2C—N2—H2B104 (2)N1—C2—C1178.16 (19)
C1—N2—H2A110.3 (16)F2—B1—F1110.25 (14)
H2C—N2—H2A112 (2)F2—B1—F4109.41 (14)
H2B—N2—H2A106 (2)F1—B1—F4109.31 (14)
C2—C1—N2112.16 (14)F2—B1—F3110.01 (13)
C2—C1—H1A109.2F1—B1—F3108.78 (13)
N2—C1—H1A109.2F4—B1—F3109.06 (13)
C2—C1—H1B109.2
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···F2i0.972.533.474 (2)166
C1—H1B···F1ii0.972.453.407 (2)169
N2—H2A···F30.89 (2)1.97 (2)2.850 (2)169 (2)
N2—H2B···F1iii0.91 (3)2.03 (3)2.863 (2)152 (2)
N2—H2C···F4iv0.87 (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) x1/2, y+3/2, z+1.

Experimental details

Crystal data
Chemical formulaC2H5N2+·BF4
Mr143.89
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)293
a, b, c (Å)9.790 (2), 10.204 (2), 11.057 (2)
V3)1104.6 (4)
Z8
Radiation typeMo Kα
µ (mm1)0.20
Crystal size (mm)0.20 × 0.20 × 0.20
Data collection
DiffractometerRigaku Mercury2 (2x2 bin mode)
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.815, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
8605, 969, 891
Rint0.046
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.097, 0.74
No. of reflections969
No. of parameters95
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.21, 0.19

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···F2i0.972.533.474 (2)166
C1—H1B···F1ii0.972.453.407 (2)169
N2—H2A···F30.89 (2)1.97 (2)2.850 (2)169 (2)
N2—H2B···F1iii0.91 (3)2.03 (3)2.863 (2)152 (2)
N2—H2C···F4iv0.87 (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) x1/2, y+3/2, z+1.
 

Acknowledgements

The authors are grateful to the Starter Fund of Southeast University for financial support to buy the X-ray diffractometer.

References

First citationFu, D. W., Ge, J. Z., Dai, J., Ye, H. Y. & Qu, Z. R. (2009). Inorg. Chem. Commun. 12, 994–997.  Web of Science CSD CrossRef CAS Google Scholar
First citationHaertling, G. H. (1999). J. Am. Ceram. Soc. A82, 797–810.  CrossRef Google Scholar
First citationHang, T., Fu, D. W., Ye, Q. & Xiong, R. G. (2009). Cryst. Growth Des. A5, 2026–2029.  Web of Science CSD CrossRef Google Scholar
First citationHomes, C. C., Vogt, T., Shapiro, S. M., Wakimoto, S. & Ramirez, A. P. (2001). Science, A293, 673–676.  Web of Science CrossRef Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWishkerman, S. & Bernstein, J. (2006). CrystEngComm, 8, 245–249.  Web of Science CSD CrossRef CAS Google Scholar

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ISSN: 2056-9890
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