4-(3-Carb­oxy­phen­yl)pyridinium nitrate

Tang, L.; Wu, Y.-P.; Fu, F.; Zhang, Z.-L.; Guo, H.-K.

doi:10.1107/S1600536812013918

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1322

doi:10.1107/S1600536812013918

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4-(3-Carboxyphenyl)pyridinium nitrate

Long Tang,^a Ya-Pan Wu,^a Feng Fu,^a ^* Zhu-Lian Zhang ^a and Hai-Kang Guo ^a

^aDepartment of Chemistry and Chemical Engineering, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan'an University, Yan'an, Shaanxi 716000, People's Republic of China
^*Correspondence e-mail: yadxgncl@126.com

(Received 22 March 2012; accepted 30 March 2012; online 6 April 2012)

In the title salt, C₁₂H₁₀NO₂⁺·NO₃⁻, the dihedral angle between the pyridine ring and the benzene ring of the 4-(3-carboxyphenyl)pyridinium cation is 30.14 (2)°. Inversion-related pairs of cations are linked into dimers by pairs of O—H⋯O hydrogen bonds. Pairs of dimers are linked by N—H⋯O and C—H⋯O hydrogen bonds involving nitrate anions as acceptors, generating supramolecular chains along the diagonal of the bc plane.

Related literature

For structures of similar compounds, see: Jin et al. (2003 ); Bei et al. (2004 ); Rademeyer (2005 ); Wang (2006 ); Yu et al. (2006 ).

Experimental

Crystal data

C₁₂H₁₀NO₂⁺·NO₃⁻
M_r = 262.22
Triclinic, $[P \overline 1]$
a = 5.2545 (11) Å
b = 7.0617 (14) Å
c = 16.469 (3) Å
α = 97.39 (3)°
β = 92.96 (5)°
γ = 106.05 (3)°
V = 580.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.15 × 0.13 × 0.10 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.982, T_max = 0.988
4634 measured reflections
2255 independent reflections
1599 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.127
S = 1.00
2255 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.20 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
C10—H10⋯O4ⁱ	0.93	2.42	3.225 (3)	145
C11—H11⋯O5ⁱⁱ	0.93	2.49	3.122 (3)	125
O1—H1⋯O2ⁱⁱⁱ	0.82	1.82	2.624 (2)	167
N2—H2⋯O4ⁱⁱ	0.86	1.89	2.748 (3)	174
Symmetry codes: (i) x+1, y+1, z; (ii) -x+1, -y+1, -z; (iii) -x, -y+3, -z+1.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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: 10.1107/S1600536812013918/pk2401sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812013918/pk2401Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812013918/pk2401Isup3.cml

checkCIF report

Comment top

The title compound consists of a 3-(pyridin-4-yl)benzoic acid cation and a nitrate anion (Fig. 1). The nitric acid is deprotonated and the pyridine ring accepts the proton to produce the protonated organic cation, namely 3-(pyridin-4-yl)benzoic acid nitrate. The dihedral angle between pyridine ring and the benzene ring of the 3-(pyridin-4-yl)benzoic acid is 30.14 (2)°. The two components are linked by O—H···O [O1—H1···O2, 2.624 (2) Å] hydrogen bonds to form the cation dimers (Fig. 2), and further though N—H···O and C—H···O [N2—H2···O4, 2.748 (3) Å; C10—H10···O4, 3.225 (3) Å; C11—H11···O5, 3.122 (3)Å] hydrogen bonds. The cation dimers are thus connected by the nitrate anions into extended one-dimensional supramolecular chains (Fig. 2).

Related literature top

For structures of similar compounds, see: Jin et al. (2003); Bei et al. (2004); Rademeyer (2005); Wang (2006); Yu et al. (2006).

Experimental top

The title compound was prepared by a hydrothermal method. An aqueous solution (20 mL) containing 3-(pyridin-4-yl)benzoic acid (0.10 mmol) and samarium nitrate hexahydrate (0.10 mmol) was placed in a Parr Teflon-lined stainless steel vessel (25 mL) under autogenous pressure, and then heated to 433 K for 72 h and subsequently cooled to room temperature at a rate of 5 K an hour. The targeted Sm³⁺ complex was not synthesized. Unintentionally, colorless single crystals of the title compound suitable for X-ray analysis were obtained from the reaction mixture.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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. Thermal ellipsoid plot of the title compound (30% probability level), hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. The one-dimensional hydrogen-bonded supramolecular chains in the crystal structure. Dashed lines denote hydrogen bonds.

4-(3-Carboxyphenyl)pyridinium nitrate top

Crystal data top

C₁₂H₁₀NO₂⁺·NO₃⁻	Z = 2
M_r = 262.22	F(000) = 272
Triclinic, P1	D_x = 1.502 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.2545 (11) Å	Cell parameters from 2373 reflections
b = 7.0617 (14) Å	θ = 3.0–27.5°
c = 16.469 (3) Å	µ = 0.12 mm⁻¹
α = 97.39 (3)°	T = 293 K
β = 92.96 (5)°	Block, colourless
γ = 106.05 (3)°	0.15 × 0.13 × 0.10 mm
V = 580.0 (2) Å³

Data collection top

Bruker SMART diffractometer	2255 independent reflections
Radiation source: fine-focus sealed tube	1599 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ϕ and ω scans	θ_max = 26.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→6
T_min = 0.982, T_max = 0.988	k = −8→8
4634 measured reflections	l = −20→17

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)] = 0.050	H-atom parameters constrained
wR(F²) = 0.127	w = 1/[σ²(F_o²) + (0.063P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2255 reflections	Δρ_max = 0.20 e Å⁻³
174 parameters	Δρ_min = −0.22 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: 0.039 (7)

Crystal data top

C₁₂H₁₀NO₂⁺·NO₃⁻	γ = 106.05 (3)°
M_r = 262.22	V = 580.0 (2) Å³
Triclinic, P1	Z = 2
a = 5.2545 (11) Å	Mo Kα radiation
b = 7.0617 (14) Å	µ = 0.12 mm⁻¹
c = 16.469 (3) Å	T = 293 K
α = 97.39 (3)°	0.15 × 0.13 × 0.10 mm
β = 92.96 (5)°

Data collection top

Bruker SMART diffractometer	2255 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1599 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.988	R_int = 0.042
4634 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.00	Δρ_max = 0.20 e Å⁻³
2255 reflections	Δρ_min = −0.22 e Å⁻³
174 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2σ(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
N2	0.5337 (3)	0.8423 (2)	0.07114 (11)	0.0357 (4)
H2	0.6254	0.8387	0.0295	0.043*
O2	0.1639 (3)	1.3909 (2)	0.43108 (10)	0.0541 (5)
O1	−0.2183 (3)	1.2586 (2)	0.48279 (11)	0.0555 (5)
H1	−0.1765	1.3685	0.5113	0.083*
C4	0.0785 (4)	0.8582 (3)	0.27490 (12)	0.0316 (5)
C8	0.2414 (4)	0.8503 (3)	0.20449 (13)	0.0306 (5)
C12	0.1417 (4)	0.7172 (3)	0.13261 (13)	0.0352 (5)
H12	−0.0275	0.6284	0.1292	0.042*
C10	0.6380 (4)	0.9746 (3)	0.13859 (13)	0.0370 (5)
H10	0.8073	1.0623	0.1400	0.044*
C9	0.4953 (4)	0.9804 (3)	0.20526 (13)	0.0341 (5)
H9	0.5685	1.0726	0.2519	0.041*
C3	0.1074 (4)	1.0373 (3)	0.32576 (12)	0.0332 (5)
H3	0.2408	1.1501	0.3185	0.040*
C1	−0.0351 (4)	1.2460 (3)	0.43713 (14)	0.0394 (5)
C5	−0.1169 (4)	0.6893 (3)	0.28921 (14)	0.0384 (5)
H5	−0.1356	0.5674	0.2568	0.046*
C11	0.2897 (4)	0.7157 (3)	0.06729 (14)	0.0384 (5)
H11	0.2208	0.6260	0.0196	0.046*
C7	−0.2581 (4)	0.8815 (3)	0.39976 (14)	0.0410 (5)
H7	−0.3726	0.8898	0.4404	0.049*
C2	−0.0603 (4)	1.0497 (3)	0.38714 (13)	0.0349 (5)
C6	−0.2820 (5)	0.7011 (3)	0.35072 (14)	0.0454 (6)
H6	−0.4108	0.5872	0.3595	0.054*
O3	0.2280 (3)	0.3289 (2)	0.18749 (10)	0.0466 (4)
O5	0.5525 (3)	0.3893 (2)	0.10947 (10)	0.0513 (5)
N1	0.3185 (4)	0.3064 (2)	0.12032 (11)	0.0355 (4)
O4	0.1696 (3)	0.1940 (2)	0.05948 (10)	0.0479 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0348 (10)	0.0396 (9)	0.0369 (11)	0.0138 (7)	0.0154 (8)	0.0091 (8)
O2	0.0551 (11)	0.0408 (9)	0.0583 (11)	0.0013 (7)	0.0264 (9)	−0.0027 (7)
O1	0.0538 (11)	0.0479 (10)	0.0593 (12)	0.0076 (8)	0.0287 (9)	−0.0062 (8)
C4	0.0293 (11)	0.0351 (11)	0.0310 (12)	0.0097 (8)	0.0049 (9)	0.0057 (8)
C8	0.0289 (11)	0.0306 (10)	0.0345 (12)	0.0104 (8)	0.0059 (9)	0.0075 (8)
C12	0.0317 (11)	0.0327 (10)	0.0390 (13)	0.0057 (8)	0.0102 (10)	0.0017 (9)
C10	0.0311 (12)	0.0372 (11)	0.0440 (14)	0.0093 (9)	0.0066 (10)	0.0102 (10)
C9	0.0304 (11)	0.0353 (10)	0.0354 (12)	0.0077 (8)	0.0055 (9)	0.0038 (9)
C3	0.0312 (11)	0.0341 (10)	0.0318 (12)	0.0051 (8)	0.0053 (9)	0.0047 (9)
C1	0.0409 (13)	0.0431 (12)	0.0346 (12)	0.0113 (10)	0.0125 (10)	0.0052 (9)
C5	0.0415 (13)	0.0315 (11)	0.0394 (13)	0.0054 (9)	0.0124 (10)	0.0032 (9)
C11	0.0383 (13)	0.0349 (11)	0.0398 (13)	0.0077 (9)	0.0090 (10)	0.0015 (9)
C7	0.0411 (13)	0.0458 (12)	0.0350 (13)	0.0081 (10)	0.0160 (10)	0.0068 (10)
C2	0.0353 (12)	0.0375 (11)	0.0316 (12)	0.0097 (9)	0.0064 (10)	0.0041 (9)
C6	0.0453 (14)	0.0393 (12)	0.0457 (14)	−0.0001 (10)	0.0159 (11)	0.0071 (10)
O3	0.0551 (11)	0.0481 (9)	0.0378 (10)	0.0147 (7)	0.0171 (8)	0.0054 (7)
O5	0.0345 (10)	0.0517 (9)	0.0570 (11)	−0.0034 (7)	0.0119 (8)	0.0011 (8)
N1	0.0376 (11)	0.0296 (9)	0.0397 (11)	0.0085 (7)	0.0093 (9)	0.0061 (8)
O4	0.0348 (9)	0.0587 (10)	0.0393 (9)	0.0008 (7)	0.0076 (7)	−0.0064 (7)

Geometric parameters (Å, º) top

N2—C11	1.338 (3)	C9—H9	0.9300
N2—C10	1.339 (3)	C3—C2	1.385 (3)
N2—H2	0.8600	C3—H3	0.9300
O2—C1	1.263 (3)	C1—C2	1.487 (3)
O1—C1	1.267 (3)	C5—C6	1.377 (3)
O1—H1	0.8200	C5—H5	0.9300
C4—C3	1.391 (3)	C11—H11	0.9300
C4—C5	1.398 (3)	C7—C6	1.388 (3)
C4—C8	1.481 (3)	C7—C2	1.393 (3)
C8—C12	1.392 (3)	C7—H7	0.9300
C8—C9	1.393 (3)	C6—H6	0.9300
C12—C11	1.360 (3)	O3—N1	1.235 (2)
C12—H12	0.9300	O5—N1	1.240 (2)
C10—C9	1.364 (3)	N1—O4	1.272 (2)
C10—H10	0.9300

C11—N2—C10	121.3 (2)	O2—C1—O1	123.68 (19)
C11—N2—H2	119.4	O2—C1—C2	118.7 (2)
C10—N2—H2	119.4	O1—C1—C2	117.61 (19)
C1—O1—H1	109.5	C6—C5—C4	120.80 (19)
C3—C4—C5	118.4 (2)	C6—C5—H5	119.6
C3—C4—C8	120.40 (18)	C4—C5—H5	119.6
C5—C4—C8	121.07 (17)	N2—C11—C12	120.49 (19)
C12—C8—C9	116.8 (2)	N2—C11—H11	119.8
C12—C8—C4	121.07 (18)	C12—C11—H11	119.8
C9—C8—C4	122.08 (18)	C6—C7—C2	119.0 (2)
C11—C12—C8	120.60 (19)	C6—C7—H7	120.5
C11—C12—H12	119.7	C2—C7—H7	120.5
C8—C12—H12	119.7	C3—C2—C7	120.33 (18)
N2—C10—C9	119.82 (19)	C3—C2—C1	119.46 (18)
N2—C10—H10	120.1	C7—C2—C1	120.2 (2)
C9—C10—H10	120.1	C5—C6—C7	120.6 (2)
C10—C9—C8	121.00 (19)	C5—C6—H6	119.7
C10—C9—H9	119.5	C7—C6—H6	119.7
C8—C9—H9	119.5	O3—N1—O5	122.40 (18)
C2—C3—C4	120.76 (18)	O3—N1—O4	119.71 (18)
C2—C3—H3	119.6	O5—N1—O4	117.89 (19)
C4—C3—H3	119.6

C3—C4—C8—C12	−147.6 (2)	C8—C4—C5—C6	−174.7 (2)
C5—C4—C8—C12	28.9 (3)	C10—N2—C11—C12	−0.6 (3)
C3—C4—C8—C9	29.6 (3)	C8—C12—C11—N2	0.0 (3)
C5—C4—C8—C9	−154.0 (2)	C4—C3—C2—C7	1.1 (3)
C9—C8—C12—C11	0.5 (3)	C4—C3—C2—C1	−176.26 (19)
C4—C8—C12—C11	177.82 (19)	C6—C7—C2—C3	0.9 (3)
C11—N2—C10—C9	0.6 (3)	C6—C7—C2—C1	178.2 (2)
N2—C10—C9—C8	0.0 (3)	O2—C1—C2—C3	−10.7 (3)
C12—C8—C9—C10	−0.6 (3)	O1—C1—C2—C3	168.3 (2)
C4—C8—C9—C10	−177.83 (18)	O2—C1—C2—C7	172.0 (2)
C5—C4—C3—C2	−2.4 (3)	O1—C1—C2—C7	−9.0 (3)
C8—C4—C3—C2	174.15 (18)	C4—C5—C6—C7	0.1 (4)
C3—C4—C5—C6	1.8 (3)	C2—C7—C6—C5	−1.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O4ⁱ	0.93	2.42	3.225 (3)	145
C11—H11···O5ⁱⁱ	0.93	2.49	3.122 (3)	125
O1—H1···O2ⁱⁱⁱ	0.82	1.82	2.624 (2)	167
N2—H2···O4ⁱⁱ	0.86	1.89	2.748 (3)	174

Symmetry codes: (i) x+1, y+1, z; (ii) −x+1, −y+1, −z; (iii) −x, −y+3, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀NO₂⁺·NO₃⁻
M_r	262.22
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.2545 (11), 7.0617 (14), 16.469 (3)
α, β, γ (°)	97.39 (3), 92.96 (5), 106.05 (3)
V (Å³)	580.0 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.15 × 0.13 × 0.10

Data collection
Diffractometer	Bruker SMART diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.982, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	4634, 2255, 1599
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.127, 1.00
No. of reflections	2255
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.22

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), 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
C10—H10···O4ⁱ	0.93	2.42	3.225 (3)	145.2
C11—H11···O5ⁱⁱ	0.93	2.49	3.122 (3)	124.9
O1—H1···O2ⁱⁱⁱ	0.82	1.82	2.624 (2)	166.8
N2—H2···O4ⁱⁱ	0.86	1.89	2.748 (3)	174.2

Symmetry codes: (i) x+1, y+1, z; (ii) −x+1, −y+1, −z; (iii) −x, −y+3, −z+1.

Acknowledgements

This project was supported by the Natural Scientific Research Foundation of Shaanxi Provincial Education Office of China (Nos. 2010 JK905, 2010JK903).

References

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