2-(Eth­oxy­carbon­yl)pyridinium nitrate

Wang, Y.

doi:10.1107/S1600536810025407

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2025

https://doi.org/10.1107/S1600536810025407

Open

access

2-(Ethoxycarbonyl)pyridinium nitrate

Yingchun Wang ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: wyingchun0107@126.com

(Received 24 March 2010; accepted 28 June 2010; online 14 July 2010)

In the title compound, C₈H₁₀NO₂⁺·NO₃⁻, the cation is essentially planar with C—O—C—C and C—O—C—O torsion angles of −178.1 (2) and 2.1 (4)°, respectively. In the crystal, N—H⋯O and C—H⋯O hydrogen-bond interactions stabilize the structure.

Related literature

For phase transition of pyridinium salts studied by X-ray analysis and dielectric and heat capacity measurements, see: Asaji et al. (2007 ). For their ferroelecric properties, see: Wasicki et al. (1997 ).

Experimental

Crystal data

C₈H₁₀NO₂⁺·NO₃⁻
M_r = 214.18
Monoclinic, P 2₁ /n
a = 6.8221 (14) Å
b = 16.208 (3) Å
c = 9.2195 (18) Å
β = 106.55 (3)°
V = 977.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.976, T_max = 0.976
9694 measured reflections
2226 independent reflections
1287 reflections with I > 2σ(I)
R_int = 0.089

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.178
S = 1.04
2226 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4	0.86	1.91	2.759 (3)	170
C1—H1B⋯O3	0.93	2.38	3.078 (4)	131
C8—H8A⋯O3ⁱ	0.96	2.57	3.506 (4)	166
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810025407/fl2300sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810025407/fl2300Isup2.hkl

checkCIF report

Comment top

The study of seignette-electrics materials has received much attention. Some materials exhibit predominant dielectric-ferroelectric properties such as pyridine single salts of the PyHX type (X=ICl₄, ClO₄, IO₄, ReO_4,etc.) ( Asaji et al.(2007); Wasicki et al. (1997)). As one part of our continuing studies on looking for materials with these properties, we have used 2-ethyl picolinate as the ligand and synthesized salts similar to PyHX. The title compound (I) is one of these salts. It exhibits no phase-transition in dielectric measurement going from 93 K to 340 K (m.p 348 K).

The asymmetric unit of (I) contains one picolinate cation and one nitrate radical (Fig 1). The pyridine ring is planar and the carbethoxy is in the plane of the ring with an O2—C6—C5—C4 torsion angle of 0.1 (4)°. The torsion angles C7—O1—C6—C5 and C7—O1—C6—O2 at -178.1 (2)° and 2.1 (4)° respectively also show the overall planarity of the cation. Intramolecular N1—H···O4 and C1—H1B···O3 interactions link the cation and the anion while intermolecular C8—H8A···O3 interactions link the molecules into chains (Table 1, Fig 2).

Related literature top

For phase transition of pyridinium salts studied by X-ray analysis and dielectric and heat capacity measurements, see: Asaji et al. (2007). For their ferroelecric properties, see: Wasicki et al. (1997).

Experimental top

A solution of 2-ethyl picolinate (10 mmol) in ethanol (20 ml) was added to a solution of equimolar amount of aqua fortis aqueous solution (1 mol/L). Crystals suitable for structure determination were grown by slow evaporation of the mixture at room temperature.

Structure description top

For phase transition of pyridinium salts studied by X-ray analysis and dielectric and heat capacity measurements, see: Asaji et al. (2007). For their ferroelecric properties, see: Wasicki et al. (1997).

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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level, and all H atoms have been omitted for clarity.
	Fig. 2. A view of the packing of the title compound, stacking along the b axis. Dashed lines indicate hydrogen bonds.

2-(Ethoxycarbonyl)pyridinium nitrate top

Crystal data top

C₈H₁₀NO₂⁺·NO₃⁻	F(000) = 448
M_r = 214.18	D_x = 1.456 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3542 reflections
a = 6.8221 (14) Å	θ = 3.1–27.6°
b = 16.208 (3) Å	µ = 0.12 mm⁻¹
c = 9.2195 (18) Å	T = 293 K
β = 106.55 (3)°	Prism, colourless
V = 977.2 (3) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2226 independent reflections
Radiation source: fine-focus sealed tube	1287 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.089
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −21→21
T_min = 0.976, T_max = 0.976	l = −11→11
9694 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.072P)² + 0.2351P] where P = (F_o² + 2F_c²)/3
2226 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₈H₁₀NO₂⁺·NO₃⁻	V = 977.2 (3) Å³
M_r = 214.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.8221 (14) Å	µ = 0.12 mm⁻¹
b = 16.208 (3) Å	T = 293 K
c = 9.2195 (18) Å	0.20 × 0.20 × 0.20 mm
β = 106.55 (3)°

Data collection top

Rigaku SCXmini diffractometer	2226 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1287 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.976	R_int = 0.089
9694 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.178	H-atom parameters constrained
S = 1.04	Δρ_max = 0.22 e Å⁻³
2226 reflections	Δρ_min = −0.22 e Å⁻³
136 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
O1	0.2450 (3)	0.15158 (11)	0.4900 (2)	0.0500 (6)
O5	0.1957 (4)	−0.10679 (14)	0.7615 (2)	0.0641 (7)
N1	0.2593 (3)	0.01904 (14)	0.3286 (2)	0.0410 (6)
H1A	0.2558	0.0168	0.4210	0.049*
O4	0.2397 (4)	−0.00834 (13)	0.6195 (3)	0.0730 (8)
O3	0.2805 (4)	−0.13303 (14)	0.5588 (2)	0.0727 (7)
N2	0.2370 (3)	−0.08353 (15)	0.6463 (3)	0.0445 (6)
C6	0.2474 (4)	0.16983 (18)	0.3508 (3)	0.0445 (7)
C5	0.2573 (4)	0.09338 (17)	0.2627 (3)	0.0406 (7)
O2	0.2430 (3)	0.23734 (13)	0.2988 (2)	0.0611 (7)
C3	0.2670 (5)	0.0251 (2)	0.0360 (3)	0.0540 (8)
H3A	0.2693	0.0270	−0.0643	0.065*
C4	0.2621 (4)	0.09761 (19)	0.1144 (3)	0.0503 (8)
H4A	0.2621	0.1485	0.0677	0.060*
C1	0.2664 (4)	−0.05092 (18)	0.2550 (3)	0.0472 (8)
H1B	0.2701	−0.1012	0.3043	0.057*
C7	0.2289 (5)	0.22041 (19)	0.5875 (3)	0.0567 (9)
H7A	0.1064	0.2522	0.5417	0.068*
H7B	0.3465	0.2565	0.6026	0.068*
C2	0.2684 (5)	−0.04929 (19)	0.1065 (4)	0.0513 (8)
H2A	0.2707	−0.0982	0.0544	0.062*
C8	0.2201 (6)	0.1856 (2)	0.7339 (4)	0.0611 (9)
H8A	0.2077	0.2297	0.8004	0.092*
H8B	0.3429	0.1550	0.7788	0.092*
H8C	0.1040	0.1497	0.7175	0.092*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0731 (15)	0.0370 (11)	0.0431 (11)	−0.0019 (9)	0.0217 (10)	−0.0039 (9)
O5	0.0931 (17)	0.0609 (14)	0.0470 (12)	−0.0035 (12)	0.0340 (12)	0.0060 (10)
N1	0.0460 (14)	0.0425 (14)	0.0376 (12)	−0.0003 (11)	0.0172 (11)	0.0002 (10)
O4	0.124 (2)	0.0409 (13)	0.0617 (14)	−0.0030 (12)	0.0388 (14)	0.0056 (11)
O3	0.116 (2)	0.0547 (14)	0.0573 (14)	0.0149 (13)	0.0415 (14)	0.0021 (12)
N2	0.0493 (15)	0.0443 (15)	0.0406 (14)	−0.0017 (11)	0.0138 (11)	0.0039 (11)
C6	0.0479 (18)	0.0420 (16)	0.0449 (16)	−0.0037 (13)	0.0154 (14)	0.0046 (13)
C5	0.0422 (16)	0.0431 (17)	0.0384 (15)	−0.0007 (12)	0.0145 (12)	0.0033 (12)
O2	0.0861 (17)	0.0428 (13)	0.0580 (14)	0.0003 (11)	0.0261 (12)	0.0106 (10)
C3	0.059 (2)	0.066 (2)	0.0412 (17)	−0.0029 (16)	0.0199 (15)	−0.0040 (15)
C4	0.058 (2)	0.0517 (18)	0.0442 (16)	−0.0006 (15)	0.0188 (14)	0.0087 (14)
C1	0.0542 (19)	0.0420 (18)	0.0474 (17)	0.0005 (13)	0.0176 (14)	−0.0042 (13)
C7	0.082 (2)	0.0418 (17)	0.0463 (18)	−0.0006 (16)	0.0181 (16)	−0.0061 (14)
C2	0.053 (2)	0.0539 (19)	0.0464 (17)	0.0032 (15)	0.0139 (14)	−0.0073 (14)
C8	0.086 (2)	0.0526 (19)	0.0507 (18)	−0.0035 (17)	0.0289 (17)	−0.0091 (15)

Geometric parameters (Å, º) top

O1—C6	1.321 (3)	C3—C4	1.385 (4)
O1—C7	1.457 (3)	C3—H3A	0.9300
O5—N2	1.233 (3)	C4—H4A	0.9300
N1—C1	1.329 (3)	C1—C2	1.373 (4)
N1—C5	1.348 (3)	C1—H1B	0.9300
N1—H1A	0.8600	C7—C8	1.480 (4)
O4—N2	1.245 (3)	C7—H7A	0.9700
O3—N2	1.232 (3)	C7—H7B	0.9700
C6—O2	1.192 (3)	C2—H2A	0.9300
C6—C5	1.494 (4)	C8—H8A	0.9600
C5—C4	1.378 (4)	C8—H8B	0.9600
C3—C2	1.369 (4)	C8—H8C	0.9600

C6—O1—C7	116.9 (2)	N1—C1—C2	120.3 (3)
C1—N1—C5	122.0 (2)	N1—C1—H1B	119.8
C1—N1—H1A	119.0	C2—C1—H1B	119.8
C5—N1—H1A	119.0	O1—C7—C8	107.5 (2)
O3—N2—O5	121.4 (2)	O1—C7—H7A	110.2
O3—N2—O4	119.2 (2)	C8—C7—H7A	110.2
O5—N2—O4	119.4 (2)	O1—C7—H7B	110.2
O2—C6—O1	126.2 (3)	C8—C7—H7B	110.2
O2—C6—C5	122.9 (3)	H7A—C7—H7B	108.5
O1—C6—C5	110.9 (2)	C3—C2—C1	119.3 (3)
N1—C5—C4	119.4 (3)	C3—C2—H2A	120.3
N1—C5—C6	119.5 (2)	C1—C2—H2A	120.3
C4—C5—C6	121.0 (2)	C7—C8—H8A	109.5
C2—C3—C4	119.8 (3)	C7—C8—H8B	109.5
C2—C3—H3A	120.1	H8A—C8—H8B	109.5
C4—C3—H3A	120.1	C7—C8—H8C	109.5
C5—C4—C3	119.1 (3)	H8A—C8—H8C	109.5
C5—C4—H4A	120.4	H8B—C8—H8C	109.5
C3—C4—H4A	120.4

C7—O1—C6—O2	2.1 (4)	N1—C5—C4—C3	0.6 (4)
C7—O1—C6—C5	−178.1 (2)	C6—C5—C4—C3	−178.7 (3)
C1—N1—C5—C4	0.2 (4)	C2—C3—C4—C5	−0.4 (4)
C1—N1—C5—C6	179.5 (3)	C5—N1—C1—C2	−1.2 (4)
O2—C6—C5—N1	−179.2 (3)	C6—O1—C7—C8	177.6 (3)
O1—C6—C5—N1	1.0 (4)	C4—C3—C2—C1	−0.5 (5)
O2—C6—C5—C4	0.1 (4)	N1—C1—C2—C3	1.3 (4)
O1—C6—C5—C4	−179.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4	0.86	1.91	2.759 (3)	170
C1—H1B···O3	0.93	2.38	3.078 (4)	131
C8—H8A···O3ⁱ	0.96	2.57	3.506 (4)	166

Symmetry code: (i) −x+1/2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₈H₁₀NO₂⁺·NO₃⁻
M_r	214.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.8221 (14), 16.208 (3), 9.2195 (18)
β (°)	106.55 (3)
V (Å³)	977.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.976, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	9694, 2226, 1287
R_int	0.089
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.178, 1.04
No. of reflections	2226
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.22

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
N1—H1A···O4	0.86	1.91	2.759 (3)	170.0
C1—H1B···O3	0.93	2.38	3.078 (4)	131.3
C8—H8A···O3ⁱ	0.96	2.57	3.506 (4)	166.4

Symmetry code: (i) −x+1/2, y+1/2, −z+3/2.

Acknowledgements

This work was supported by a start-up grant from Southeast University.

References

Asaji, T., Eda, K., Fujimori, H., Adachi, T., Shibusawa, T. & Oguni, M. (2007). J. Mol. Struct. 826, 24–28. Web of Science CSD CrossRef 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
Wasicki, J., Czarnecki, P., Pajak, Z., Nawrocik, W. & Szepanski, W. (1997). J. Chem. Phys. 107, 576–578. CrossRef CAS Google Scholar