3-Carb­oxy­pyridinium nitrate

Abstract

In the crystal structure of the title compound, C₆H₆NO₂ ⁺·NO₃ ⁻, the protonated cations are linked by N—H⋯O hydrogen bonds into chains along the b axis. The cations and anions are also linked by N—H⋯O and O—H⋯O hydrogen bonds. C—H⋯O inter­actions also occur. In the cation, the ring makes a dihedral angle of 10.1 (3)° with the carboxylate group.

Related literature  

For related structures, see: Athimoolam & Rajaram (2005 ▶); Athimoolam & Natarajan (2007 ▶); Kutoglu & Scheringer (1983 ▶); Jebas et al. (2006 ▶); Slouf (2001 ▶); Ye et al. (2010 ▶). For graph-set descriptors, see: Etter (1990 ▶); Bernstein et al. (1995 ▶); Motherwell et al. (2000 ▶).

Experimental  

Crystal data  

• C₆H₆NO₂ ⁺·NO₃ ⁻

• M _r = 186.13

• Triclinic,

• a = 6.7530 (4) Å

• b = 7.5024 (4) Å

• c = 8.4439 (5) Å

• α = 81.895 (2)°

• β = 82.215 (1)°

• γ = 66.769 (2)°

• V = 387.69 (4) ų

• Z = 2

• Mo Kα radiation

• μ = 0.14 mm⁻¹

• T = 293 K

• 0.40 × 0.20 × 0.10 mm

Data collection  

• Rigaku R-AXIS RAPID diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ▶) T _min = 0.946, T _max = 0.986

• 15468 measured reflections

• 1760 independent reflections

• 1102 reflections with I > 2σ(I)

• R _int = 0.046

Refinement  

• R[F ² > 2σ(F ²)] = 0.050

• wR(F ²) = 0.145

• S = 1.13

• 1760 reflections

• 127 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.19 e Å⁻³

• Δρ_min = −0.35 e Å⁻³

Data collection: CrystalClear (Rigaku, 2007 ▶); 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: DIAMOND (Brandenburg, 2004 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812028565/lx2240Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O4i	0.92 (3)	1.67 (3)	2.5833 (19)	169 (2)
N1—H1N⋯O2ii	0.96 (3)	2.08 (3)	2.824 (2)	133 (2)
N1—H1N⋯O4	0.96 (3)	2.12 (3)	2.921 (2)	139 (2)
C3—H3⋯O3	0.93	2.45	3.330 (3)	158
C6—H6⋯O5iii	0.93	2.37	3.259 (2)	160
C5—H5⋯O3iv	0.93	2.47	3.142 (2)	129

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

Previously, the crystal structures of nicotinium derivatives containing diverse anions have been reported (Athimoolam & Rajaram, 2005; Athimoolam & Natarajan, 2007; Kutoglu & Scheringer, 1983; Jebas et al., 2006; Slouf, 2001; Ye et al., 2010). We report herein the crystal structure of the title compound.

In the title molecule (Fig. 1), the nicotinium cation is planar with a maximum deviation for the carboxylate oxygen atom (O1) being 0.265 (2) Å. In the crystal structure (Fig. 2), the cations are linked by N—H···O hydrogen bonds (Table 1) into infinite chains along the [010] vector. Regarding the graph set descriptors (Etter, 1990; Bernstein et al., 1995; Motherwell et al., 2000), this N—H···O chain motif is described as C(6). The bifurcated N—H···O with O—H···O interactions (Table 1) are connecting the nicotinium with nitrates, thus defining a third-level discrete D³₃(13) hydrogen bond motif in the bc-plane (Fig. 2).

Experimental

The title compound was unintentionally obtained during a microwave irradiation (300 W, 150 ^oC, 10 min., MicroSynth, Milestone) reaction of Ce(OH)₄ in diluted nitric acid with aqueous solution of nicotinic acid. After cooling, the solution was left undisturbed and colourless crystals were collected by filtration after one week.

Refinement

Aromatic carbon–bound H–atoms were placed in ideal calculated positions [C—H 0.93 Å, U_iso(H) = 1.2U_eq(C)] and refined as riding atoms. Amine and hydroxyl hydrogen atoms were located from difference Fourier map and refined freely.

Figures

Fig. 1.

The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.

Fig. 2.

A view of the O—H···O, N—H···O and C—H···O interactions (dotted lines) in the crystal structure of the title compound. [Symmetry codes: (i) x,y - 1, z; (ii) x, y + 1, z; (iii) x,y + 1, z - 1; (iv) x, y, z - 1.]

Crystal data

C6H6NO2+·NO3−	Z = 2
Mr = 186.13	F(000) = 192
Triclinic, P1	Dx = 1.594 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 6.7530 (4) Å	Cell parameters from 963 reflections
b = 7.5024 (4) Å	θ = 3.3–27.5°
c = 8.4439 (5) Å	µ = 0.14 mm−1
α = 81.895 (2)°	T = 293 K
β = 82.215 (1)°	Block, colourless
γ = 66.769 (2)°	0.40 × 0.20 × 0.10 mm
V = 387.69 (4) Å3

Data collection

Rigaku R-AXIS RAPID diffractometer	1760 independent reflections
Radiation source: fine-focus sealed tube	1102 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 10.0 pixels mm-1	θmax = 27.5°, θmin = 3.3°
ω scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	k = −9→9
Tmin = 0.946, Tmax = 0.986	l = −10→10
15468 measured reflections

Refinement

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)] = 0.050	Hydrogen site location: difference Fourier map
wR(F2) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ2(Fo2) + (0.0739P)2 + 0.025P] where P = (Fo2 + 2Fc2)/3
1760 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.19 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

Special details

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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.2671 (2)	−0.1191 (2)	0.48174 (17)	0.0528 (4)
H1O	0.277 (4)	−0.232 (4)	0.443 (3)	0.079 (8)*
N1	0.2399 (3)	0.3328 (2)	0.7169 (2)	0.0461 (5)
H1N	0.245 (4)	0.449 (4)	0.654 (3)	0.086 (9)*
C1	0.2321 (3)	−0.1404 (3)	0.6385 (2)	0.0405 (5)
O2	0.2000 (3)	−0.2778 (2)	0.71433 (17)	0.0570 (5)
N2	0.2859 (3)	0.5132 (2)	0.2675 (2)	0.0461 (4)
C2	0.2350 (3)	0.0215 (2)	0.7207 (2)	0.0366 (4)
O3	0.2861 (3)	0.3523 (2)	0.2502 (2)	0.0723 (6)
C3	0.2385 (3)	0.1913 (3)	0.6360 (2)	0.0416 (5)
H3	0.2399	0.2079	0.5247	0.050*
O4	0.2781 (3)	0.5540 (2)	0.40863 (18)	0.0698 (5)
C4	0.2393 (3)	0.3167 (3)	0.8764 (3)	0.0483 (5)
H4	0.2410	0.4182	0.9273	0.058*
C5	0.2361 (3)	0.1507 (3)	0.9645 (2)	0.0497 (5)
H5	0.2348	0.1381	1.0758	0.060*
O5	0.2917 (3)	0.6324 (3)	0.1555 (2)	0.0817 (6)
C6	0.2350 (3)	0.0018 (3)	0.8862 (2)	0.0439 (5)
H6	0.2341	−0.1126	0.9449	0.053*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0802 (11)	0.0451 (9)	0.0395 (9)	−0.0309 (8)	0.0008 (7)	−0.0094 (6)
N1	0.0598 (11)	0.0313 (9)	0.0518 (11)	−0.0232 (8)	−0.0029 (8)	−0.0032 (7)
C1	0.0501 (11)	0.0346 (10)	0.0389 (11)	−0.0185 (9)	−0.0027 (8)	−0.0052 (8)
O2	0.0937 (12)	0.0416 (8)	0.0482 (9)	−0.0412 (8)	−0.0003 (8)	−0.0045 (7)
N2	0.0578 (11)	0.0445 (10)	0.0380 (9)	−0.0205 (8)	−0.0065 (7)	−0.0053 (7)
C2	0.0447 (10)	0.0304 (9)	0.0364 (10)	−0.0171 (8)	−0.0010 (8)	−0.0033 (7)
O3	0.1120 (14)	0.0623 (11)	0.0602 (11)	−0.0464 (10)	−0.0100 (9)	−0.0208 (8)
C3	0.0533 (12)	0.0346 (10)	0.0390 (10)	−0.0202 (9)	−0.0018 (8)	−0.0025 (8)
O4	0.1353 (15)	0.0522 (10)	0.0359 (9)	−0.0481 (10)	−0.0118 (9)	−0.0077 (7)
C4	0.0580 (13)	0.0421 (11)	0.0514 (13)	−0.0237 (10)	−0.0038 (9)	−0.0126 (9)
C5	0.0660 (14)	0.0477 (12)	0.0408 (12)	−0.0264 (11)	−0.0052 (10)	−0.0077 (9)
O5	0.1135 (15)	0.0740 (12)	0.0513 (10)	−0.0380 (11)	−0.0075 (9)	0.0208 (9)
C6	0.0585 (12)	0.0352 (10)	0.0419 (11)	−0.0230 (9)	−0.0024 (9)	−0.0031 (8)

Geometric parameters (Å, º)

O1—C1	1.311 (2)	N2—O4	1.261 (2)
O1—H1O	0.92 (3)	C2—C3	1.377 (2)
N1—C4	1.335 (3)	C2—C6	1.385 (3)
N1—C3	1.344 (3)	C3—H3	0.9300
N1—H1N	0.96 (3)	C4—C5	1.364 (3)
C1—O2	1.213 (2)	C4—H4	0.9300
C1—C2	1.489 (3)	C5—C6	1.379 (3)
N2—O5	1.214 (2)	C5—H5	0.9300
N2—O3	1.236 (2)	C6—H6	0.9300
C1—O1—H1O	107.7 (16)	N1—C3—C2	118.93 (18)
C4—N1—C3	123.13 (17)	N1—C3—H3	120.5
C4—N1—H1N	120.2 (16)	C2—C3—H3	120.5
C3—N1—H1N	116.7 (16)	N1—C4—C5	119.72 (18)
O2—C1—O1	124.77 (18)	N1—C4—H4	120.1
O2—C1—C2	121.11 (18)	C5—C4—H4	120.1
O1—C1—C2	114.11 (16)	C4—C5—C6	119.0 (2)
O5—N2—O3	123.04 (18)	C4—C5—H5	120.5
O5—N2—O4	119.22 (18)	C6—C5—H5	120.5
O3—N2—O4	117.74 (17)	C5—C6—C2	120.39 (18)
C3—C2—C6	118.80 (17)	C5—C6—H6	119.8
C3—C2—C1	121.64 (17)	C2—C6—H6	119.8
C6—C2—C1	119.56 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O4i	0.92 (3)	1.67 (3)	2.5833 (19)	169 (2)
N1—H1N···O2ii	0.96 (3)	2.08 (3)	2.824 (2)	133 (2)
N1—H1N···O4	0.96 (3)	2.12 (3)	2.921 (2)	139 (2)
C3—H3···O3	0.93	2.45	3.330 (3)	158
C6—H6···O5iii	0.93	2.37	3.259 (2)	160
C5—H5···O3iv	0.93	2.47	3.142 (2)	129

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