organic compounds
Cyanomethanaminium perchlorate
aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China
*Correspondence e-mail: quanjnjcc@126.com
In the crystal of the title salt, C2H5N2+·ClO4−, the cations and anions are connected via N—H⋯O and C—H⋯O hydrogen bonds, forming a three-dimensional network.
Related literature
For general background, see: Haertling (1999); Homes et al. (2001). For a related structure, see: Han & Zhang (2010).
Experimental
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536812047782/xu5654sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812047782/xu5654Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812047782/xu5654Isup3.cml
A mixture of aminoacetonitrile hydrochloride (0.095 g, 0.01 mol) and perchloric acid (1.40 g, 0.01 mol) in methanol (20 ml) was stirred until clear. After several days, the title compound was formed and recrystallized from solution to afford colourless prismatic crystals suitable for X-ray analysis.
H atoms were positioned geometrically and refined using a riding model with C—H = 0.97 and N—H = 0.89 Å, Uiso(H) = 1.2Ueq(C) and 1.5Ueq(N).
Data collection: CrystalClear (Rigaku, 2005); cell
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); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C2H5N2+·ClO4− | F(000) = 640 |
Mr = 156.53 | Dx = 1.806 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 1321 reflections |
a = 9.908 (2) Å | θ = 2.6–27.5° |
b = 10.398 (2) Å | µ = 0.61 mm−1 |
c = 11.176 (2) Å | T = 293 K |
V = 1151.4 (4) Å3 | Prism, colorless |
Z = 8 | 0.20 × 0.19 × 0.18 mm |
Rigaku Mercury2 diffractometer | 1321 independent reflections |
Radiation source: fine-focus sealed tube | 1151 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.4° |
CCD_Profile_fitting scans | h = −12→12 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −13→13 |
Tmin = 0.88, Tmax = 0.90 | l = −14→14 |
10965 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-atom parameters constrained |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.0373P)2 + 0.8373P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max = 0.002 |
1321 reflections | Δρmax = 0.40 e Å−3 |
84 parameters | Δρmin = −0.37 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.072 (3) |
C2H5N2+·ClO4− | V = 1151.4 (4) Å3 |
Mr = 156.53 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.908 (2) Å | µ = 0.61 mm−1 |
b = 10.398 (2) Å | T = 293 K |
c = 11.176 (2) Å | 0.20 × 0.19 × 0.18 mm |
Rigaku Mercury2 diffractometer | 1321 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1151 reflections with I > 2σ(I) |
Tmin = 0.88, Tmax = 0.90 | Rint = 0.044 |
10965 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.40 e Å−3 |
1321 reflections | Δρmin = −0.37 e Å−3 |
84 parameters |
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 | ||
Cl1 | 0.24234 (4) | 0.55298 (4) | 0.39030 (4) | 0.0262 (2) | |
N1 | 0.38874 (19) | 0.80122 (18) | 0.60010 (15) | 0.0338 (4) | |
H1C | 0.3343 | 0.8461 | 0.6478 | 0.051* | |
H1D | 0.3423 | 0.7726 | 0.5374 | 0.051* | |
H1E | 0.4558 | 0.8514 | 0.5750 | 0.051* | |
N2 | 0.5768 (2) | 0.7581 (2) | 0.85728 (18) | 0.0503 (6) | |
O1 | 0.30000 (17) | 0.51248 (16) | 0.27907 (14) | 0.0432 (4) | |
O2 | 0.10533 (16) | 0.50926 (18) | 0.39645 (16) | 0.0485 (5) | |
O3 | 0.31737 (19) | 0.50020 (19) | 0.48743 (16) | 0.0521 (5) | |
O4 | 0.24459 (16) | 0.69160 (15) | 0.39638 (15) | 0.0414 (5) | |
C1 | 0.4448 (2) | 0.6911 (2) | 0.6667 (2) | 0.0354 (5) | |
H1A | 0.3718 | 0.6343 | 0.6900 | 0.042* | |
H1B | 0.5049 | 0.6432 | 0.6147 | 0.042* | |
C2 | 0.5189 (2) | 0.7311 (2) | 0.77361 (19) | 0.0335 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0279 (3) | 0.0258 (3) | 0.0249 (3) | 0.00019 (17) | −0.00002 (18) | −0.00046 (17) |
N1 | 0.0368 (10) | 0.0363 (10) | 0.0283 (9) | −0.0023 (7) | −0.0062 (7) | −0.0005 (7) |
N2 | 0.0541 (12) | 0.0613 (15) | 0.0354 (11) | −0.0057 (11) | −0.0128 (9) | −0.0011 (10) |
O1 | 0.0516 (10) | 0.0449 (9) | 0.0331 (9) | 0.0040 (8) | 0.0122 (7) | −0.0064 (7) |
O2 | 0.0319 (9) | 0.0492 (10) | 0.0643 (12) | −0.0084 (7) | 0.0085 (8) | −0.0033 (8) |
O3 | 0.0638 (12) | 0.0515 (10) | 0.0409 (10) | 0.0079 (9) | −0.0182 (9) | 0.0077 (8) |
O4 | 0.0529 (11) | 0.0247 (9) | 0.0466 (11) | 0.0000 (6) | −0.0076 (8) | −0.0046 (6) |
C1 | 0.0415 (11) | 0.0306 (11) | 0.0341 (11) | −0.0017 (9) | −0.0089 (10) | −0.0009 (9) |
C2 | 0.0308 (10) | 0.0386 (11) | 0.0310 (11) | −0.0019 (9) | −0.0016 (8) | 0.0028 (9) |
Cl1—O3 | 1.4256 (17) | N1—H1D | 0.8900 |
Cl1—O1 | 1.4314 (16) | N1—H1E | 0.8900 |
Cl1—O2 | 1.4333 (17) | N2—C2 | 1.133 (3) |
Cl1—O4 | 1.4431 (16) | C1—C2 | 1.462 (3) |
N1—C1 | 1.475 (3) | C1—H1A | 0.9700 |
N1—H1C | 0.8900 | C1—H1B | 0.9700 |
O3—Cl1—O1 | 109.87 (11) | H1C—N1—H1E | 109.5 |
O3—Cl1—O2 | 109.59 (12) | H1D—N1—H1E | 109.5 |
O1—Cl1—O2 | 109.04 (11) | C2—C1—N1 | 112.37 (18) |
O3—Cl1—O4 | 109.92 (11) | C2—C1—H1A | 109.1 |
O1—Cl1—O4 | 109.18 (10) | N1—C1—H1A | 109.1 |
O2—Cl1—O4 | 109.22 (10) | C2—C1—H1B | 109.1 |
C1—N1—H1C | 109.5 | N1—C1—H1B | 109.1 |
C1—N1—H1D | 109.5 | H1A—C1—H1B | 107.9 |
H1C—N1—H1D | 109.5 | N2—C2—C1 | 177.8 (2) |
C1—N1—H1E | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···O1i | 0.89 | 2.10 | 2.920 (2) | 152 |
N1—H1D···O4 | 0.89 | 2.03 | 2.919 (2) | 175 |
N1—H1E···O2ii | 0.89 | 2.10 | 2.914 (3) | 152 |
C1—H1A···O1iii | 0.97 | 2.49 | 3.456 (3) | 172 |
C1—H1B···O3iv | 0.97 | 2.57 | 3.532 (3) | 169 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x+1/2, −y+3/2, −z+1; (iii) −x+1/2, −y+1, z+1/2; (iv) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C2H5N2+·ClO4− |
Mr | 156.53 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 9.908 (2), 10.398 (2), 11.176 (2) |
V (Å3) | 1151.4 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.61 |
Crystal size (mm) | 0.20 × 0.19 × 0.18 |
Data collection | |
Diffractometer | Rigaku Mercury2 diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.88, 0.90 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10965, 1321, 1151 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.096, 1.12 |
No. of reflections | 1321 |
No. of parameters | 84 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.37 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···O1i | 0.89 | 2.10 | 2.920 (2) | 152 |
N1—H1D···O4 | 0.89 | 2.03 | 2.919 (2) | 175 |
N1—H1E···O2ii | 0.89 | 2.10 | 2.914 (3) | 152 |
C1—H1A···O1iii | 0.97 | 2.49 | 3.456 (3) | 172 |
C1—H1B···O3iv | 0.97 | 2.57 | 3.532 (3) | 169 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x+1/2, −y+3/2, −z+1; (iii) −x+1/2, −y+1, z+1/2; (iv) −x+1, −y+1, −z+1. |
References
Haertling, G. H. (1999). J. Am. Ceram. Soc. 82, 797–810. CrossRef CAS Google Scholar
Han, M. T. & Zhang, Y. (2010). Acta Cryst. E66, o1941. Web of Science CSD CrossRef IUCr Journals Google Scholar
Homes, C. C., Vogt, T., Shapiro, S. M., Wakimoto, S. & Ramirez, A. P. (2001). Science, 293, 673–676. Web of Science CrossRef PubMed CAS 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
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
At present, much attention in ferroelectric material field is focused on developing ferroelectric pure organic or inorganic compounds (Haertling, 1999; Homes et al., 2001). In order to find more dielectric ferroelectric materials, we investigate the physical properties of the title compound (Fig. 1). The dielectric constant of the title compound as a function of temperature indicates that the permittivity is basically temperature-independent (dielectric constant equaling to 3.7 to 5.2), suggesting that this compound should be not a real ferroelectrics or there may be no distinct phase transition occurred 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 3.7 to 5.2). Herein, we report the synthesis and crystal structure of the title compound.
Molecules of the title compound have normal geometric parameters. The bond lengths and angles are within their normal ranges (Han & Zhang, 2010). As can be seen from the packing diagram (Fig. 2), molecules are connected via intermolecular N—H···O and C—H···O hydrogen bonds to form a three dimensional network.