Cyanomethanaminium tetra­fluoro­borate

Han, M.T.; Zhang, Y.

doi:10.1107/S1600536810025857

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o1941

https://doi.org/10.1107/S1600536810025857

Open

access

Cyanomethanaminium tetrafluoroborate

Meng Ting Han ^a and Yuan Zhang ^a ^*

^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 ); Homes et al. (2001 ). For thesynthesis of a variety of compounds with potential piezoelectric and ferroelectric properties, see: Fu et al. (2009 ); Hang et al. (2009 ). For comparison bond lengths and bond angles, see: Wishkerman & Bernstein (2006 ).

Experimental

Crystal data

C₂H₅N₂⁺·BF₄⁻
M_r = 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 ) T_min = 0.815, T_max = 1.000
8605 measured reflections
969 independent reflections
891 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯F4^iv	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); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810025857/pv2302sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810025857/pv2302Isup2.hkl

checkCIF report

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.

Structure description top

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

	Fig. 1. Perspective structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	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⁺·BF₄⁻	F(000) = 576
M_r = 143.89	D_x = 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

Data collection top

Rigaku Mercury2 (2x2 bin mode) diffractometer	969 independent reflections
Radiation source: fine-focus sealed tube	891 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 13.6612 pixels mm^-1	θ_max = 25.0°, θ_min = 3.4°
CCD_Profile_fitting scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
T_min = 0.815, T_max = 1.000	l = −13→13
8605 measured reflections

Refinement top

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(F_o²) + (0.0711P)² + 0.9831P] where P = (F_o² + 2F_c²)/3
S = 0.74	(Δ/σ)_max < 0.001
969 reflections	Δρ_max = 0.21 e Å⁻³
95 parameters	Δρ_min = −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)

Crystal data top

C₂H₅N₂⁺·BF₄⁻	V = 1104.6 (4) Å³
M_r = 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

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)
T_min = 0.815, T_max = 1.000	R_int = 0.046
8605 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 0.74	Δρ_max = 0.21 e Å⁻³
969 reflections	Δρ_min = −0.19 e Å⁻³
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

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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···F4^iv	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.

Experimental details

Crystal data
Chemical formula	C₂H₅N₂⁺·BF₄⁻
M_r	143.89
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	9.790 (2), 10.204 (2), 11.057 (2)
V (Å³)	1104.6 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 (2x2 bin mode)
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.815, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8605, 969, 891
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.097, 0.74
No. of reflections	969
No. of parameters	95
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···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···F4^iv	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.

Acknowledgements

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

References

Fu, 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
Haertling, G. H. (1999). J. Am. Ceram. Soc. A82, 797–810. CrossRef Google Scholar
Hang, T., Fu, D. W., Ye, Q. & Xiong, R. G. (2009). Cryst. Growth Des. A5, 2026–2029. Web of Science CSD CrossRef Google Scholar
Homes, C. C., Vogt, T., Shapiro, S. M., Wakimoto, S. & Ramirez, A. P. (2001). Science, A293, 673–676. Web of Science CrossRef Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wishkerman, S. & Bernstein, J. (2006). CrystEngComm, 8, 245–249. Web of Science CSD CrossRef CAS Google Scholar