Cyano­methanaminium perchlorate

Quan, J.

doi:10.1107/S1600536812047782

organic compounds

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Volume 68| Part 12| December 2012| Page o3480

doi:10.1107/S1600536812047782

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Cyanomethanaminium perchlorate

Jing Quan ^a ^*

^aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China
^*Correspondence e-mail: quanjnjcc@126.com

(Received 18 November 2012; accepted 21 November 2012; online 30 November 2012)

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

C₂H₅N₂⁺·ClO₄⁻
M_r = 156.53
Orthorhombic, P b c a
a = 9.908 (2) Å
b = 10.398 (2) Å
c = 11.176 (2) Å
V = 1151.4 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.61 mm⁻¹
T = 293 K
0.20 × 0.19 × 0.18 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.88, T_max = 0.90
10965 measured reflections
1321 independent reflections
1151 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.096
S = 1.12
1321 reflections
84 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯O3^iv	0.97	2.57	3.532 (3)	169
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iii) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z+1.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812047782/xu5654sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812047782/xu5654Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812047782/xu5654Isup3.cml

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). 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.

Related literature top

For background, see: Haertling (1999); Homes et al. (2001). For a related structure, see: Han & Zhang (2010).

Experimental top

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.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: 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).

Figures top

	Fig. 1. Perspective structure of the title compound with displacement ellipsoids drawn at the 50% probability level. The dashed line indicates N—H···O hydrogen bond.
	Fig. 2. The crystal packing of the title compound viewed along thea axis showing the hydrogen bondings network.

Cyanomethanaminium perchlorate top

Crystal data top

C₂H₅N₂⁺·ClO₄⁻	F(000) = 640
M_r = 156.53	D_x = 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

Data collection top

Rigaku Mercury2 diffractometer	1321 independent reflections
Radiation source: fine-focus sealed tube	1151 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.4°
CCD_Profile_fitting scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→13
T_min = 0.88, T_max = 0.90	l = −14→14
10965 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-atom parameters constrained
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0373P)² + 0.8373P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max = 0.002
1321 reflections	Δρ_max = 0.40 e Å⁻³
84 parameters	Δρ_min = −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)

Crystal data top

C₂H₅N₂⁺·ClO₄⁻	V = 1151.4 (4) Å³
M_r = 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

Data collection top

Rigaku Mercury2 diffractometer	1321 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1151 reflections with I > 2σ(I)
T_min = 0.88, T_max = 0.90	R_int = 0.044
10965 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.12	Δρ_max = 0.40 e Å⁻³
1321 reflections	Δρ_min = −0.37 e Å⁻³
84 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
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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···O3^iv	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⁻
M_r	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)
T_min, T_max	0.88, 0.90
No. of measured, independent and observed [I > 2σ(I)] reflections	10965, 1321, 1151
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.37

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

Hydrogen-bond geometry (Å, º) top

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···O3^iv	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

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3480

doi:10.1107/S1600536812047782

Open

access