3-Carb­oxy­pyridinium nitrate

Al-Farhan, K.; Khair, M.; Ghazzali, M.

doi:10.1107/S1600536812028565

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2246

https://doi.org/10.1107/S1600536812028565

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3-Carboxypyridinium nitrate

Khalid Al-Farhan,^a Miftahul Khair ^a and Mohamed Ghazzali ^a ^*

^aDepartment of Chemistry, College of Science, King Saud University, PO Box 2455, Riyadh 11451, Saudi Arabia
^*Correspondence e-mail: mghazzali@ksu.edu.sa

(Received 11 April 2012; accepted 23 June 2012; online 30 June 2012)

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, $[P \overline 1]$
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) Å³
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[F² > 2σ(F²)] = 0.050
wR(F²) = 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

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⋯O3^iv	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.

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812028565/lx2240sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812028565/lx2240Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812028565/lx2240Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Structure description top

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).

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); 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).

Figures top

	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.]

3-Carboxypyridinium nitrate top

Crystal data top

C₆H₆NO₂⁺·NO₃⁻	Z = 2
M_r = 186.13	F(000) = 192
Triclinic, P1	D_x = 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 top

Rigaku R-AXIS RAPID diffractometer	1760 independent reflections
Radiation source: fine-focus sealed tube	1102 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 10.0 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	k = −9→9
T_min = 0.946, T_max = 0.986	l = −10→10
15468 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)] = 0.050	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(F_o²) + (0.0739P)² + 0.025P] where P = (F_o² + 2F_c²)/3
1760 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₆H₆NO₂⁺·NO₃⁻	γ = 66.769 (2)°
M_r = 186.13	V = 387.69 (4) Å³
Triclinic, P1	Z = 2
a = 6.7530 (4) Å	Mo Kα radiation
b = 7.5024 (4) Å	µ = 0.14 mm⁻¹
c = 8.4439 (5) Å	T = 293 K
α = 81.895 (2)°	0.40 × 0.20 × 0.10 mm
β = 82.215 (1)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1760 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	1102 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.986	R_int = 0.046
15468 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.19 e Å⁻³
1760 reflections	Δρ_min = −0.35 e Å⁻³
127 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 > 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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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···O3^iv	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.

Experimental details

Crystal data
Chemical formula	C₆H₆NO₂⁺·NO₃⁻
M_r	186.13
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.7530 (4), 7.5024 (4), 8.4439 (5)
α, β, γ (°)	81.895 (2), 82.215 (1), 66.769 (2)
V (Å³)	387.69 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.40 × 0.20 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2007)
T_min, T_max	0.946, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	15468, 1760, 1102
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.145, 1.13
No. of reflections	1760
No. of parameters	127
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.35

Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2004), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

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)	157.7
C6—H6···O5ⁱⁱⁱ	0.93	2.37	3.259 (2)	159.9
C5—H5···O3^iv	0.93	2.47	3.142 (2)	128.9

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

Acknowledgements

The authors are thankful for the National Plan for Science and Technology, KSU (NPST grant 09-ENE909–02) for funding this work.

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