4-Amino­pyridinium isonicotinate monohydrate

Kennedy, A.R.; Kittner, M.

doi:10.1107/S1600536805000887

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 2| February 2005| Pages o333-o334

https://doi.org/10.1107/S1600536805000887

4-Aminopyridinium isonicotinate monohydrate

Alan R. Kennedy ^a ^* and Madeleine Kittner ^a

^aDepartment of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL, Scotland
^*Correspondence e-mail: a.r.kennedy@strath.ac.uk

(Received 5 January 2005; accepted 10 January 2005; online 22 January 2005)

The 4-aminopyridinium isonicotinate salt was isolated as a monohydrate, C₅H₇N $[{}_{2}^{\,+}]$ ·C₆H₄NO $[{}_{2}^{\,- }]$ ·H₂O, with a layered cation–water–anion structure. Hydrogen-bonding between layers utilizes all hydrogen-bonding donors and acceptors, whilst π stacking dominates interactions within the organic layers.

Comment

The isonicotinate anion is well known as a ligand capable of forming supramolecular metal–organic structures. Here, the serendipitous isolation of the title compound, (I), highlights that it is also capable of supporting organic supramolecular architectures. Isolated with the 4-aminopyridinium cation [itself well known in studies of organic supramolecular structures; see for example Cowan et al. (2001 ) and Teulon et al. (1985 )], (I) is found as a monohydrate (Fig. 1) with, in the c direction, alternating layers of cations and anions separated by water molecules (Fig. 2). These layers are held together by the participation of all the molecular fragments in a three-dimensional hydrogen-bonding network. Each cation acts as a threefold donor using all its N—H bonds, each anion acts as a fourfold acceptor with atom O1 accepting two hydrogen bonds and atoms O2 and N1 accepting one each, and the water molecule both accepts a single hydrogen-bond and acts as a twofold donor. Within each organic layer, π stacking interactions are observed. The shortest such contacts appear between antiparallel 4-aminopyridinium cations, with a centroid-to-centroid distance of 3.473 Å, whilst the isonicotinate anions are separated by 3.520 Å.

Figure 1
Asymmetric unit of (I)

, shown with 50% probability displacement ellipsoids.

Figure 2
Packing diagram of (I)

, viewed down the b axis. Dashed lines indicate hydrogen bonds.

Experimental

Compound (I) was formed during an attempt to prepare N-(pyridine-4-methylene)pyridin-4-amine. 4-Aminopyridine (1.24 g, 13.2 mmol) was dissolved in anhydrous xylene (80 ml), and pyridine-4-carbaldehyde (1.3 ml, 13.6 mmol) and acetic acid (0.38 ml, 6.6 mmol) were added dropwise with stirring. The mixture was heated to reflux in a Dean–Stark apparatus for 20 h. After removing the solvent in vacuo, a yellow oil was obtained. Crystalline (I) was obtained from a chloroform solution of this oil after layering with diethyl ether (1.64 g, 53% yield). IR (KBr, cm⁻¹): 677, 769, 1204, 1373, 1542, 1603, 1650, 3415.

Crystal data

C₅H₇N $[{}_{2}^{\,+}]$ ·C₆H₄NO $[{}_{2}^{\,- }]$ ·H₂O
M_r = 235.24
Triclinic, P $[\overline{1}]$
a = 6.7128 (3) Å
b = 6.7911 (2) Å
c = 13.6379 (8) Å
α = 75.830 (3)°
β = 75.999 (2)°
γ = 78.326 (3)°
V = 578.08 (5) Å³
Z = 2
D_x = 1.351 Mg m⁻³
Mo Kα radiation
Cell parameters from 2294 reflections
θ = 1.0–26.4°
μ = 0.10 mm⁻¹
T = 123 (2) K
Cut plate, colourless
0.45 × 0.37 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
ω and φ scans
Absorption correction: none
9253 measured reflections
2348 independent reflections
1848 reflections with I > 2σ(I)
R_int = 0.030
θ_max = 26.4°
h = −8 → 8
k = −8 → 8
l = −17 → 17

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.090
S = 1.04
2348 reflections
207 parameters
All H-atom parameters refined
w = 1/[σ²(F_o²) + (0.0417P)² + 0.1136P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.15 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.046 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯N1ⁱ	0.957 (19)	1.854 (19)	2.7978 (16)	167.9 (16)
N2—H2N⋯O3ⁱⁱ	0.921 (18)	1.911 (18)	2.8313 (18)	175.8 (14)
N2—H1N⋯O1ⁱⁱⁱ	0.890 (18)	1.938 (19)	2.8283 (16)	177.5 (15)
O3—H1W⋯O2	0.89 (2)	1.86 (2)	2.7369 (15)	172.1 (18)
O3—H2W⋯O1ⁱⁱⁱ	0.85 (2)	1.92 (2)	2.7635 (15)	173 (2)
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z; (iii) x, y+1, z.

All H-atom parameters were refined freely; C—H distances are in the range 0.953 (16)–0.993 (16) Å.

Data collection: DENZO (Otwinowski & Minor, 1997 ) and COLLECT (Hooft, 1988 ); cell refinement: DENZO and COLLECT; data reduction: DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805000887/fl6142sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805000887/fl6142Isup2.hkl

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1988); cell refinement: DENZO and COLLECT; data reduction: DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

4-Aminopyridinium isonicotinate monohydrate top

Crystal data top

C₅H₇N₂⁺·C₆H₄NO₂⁻·H₂O	Z = 2
M_r = 235.24	F(000) = 248
Triclinic, P1	D_x = 1.351 Mg m⁻³
a = 6.7128 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.7911 (2) Å	Cell parameters from 2294 reflections
c = 13.6379 (8) Å	θ = 1.0–26.4°
α = 75.830 (3)°	µ = 0.10 mm⁻¹
β = 75.999 (2)°	T = 123 K
γ = 78.326 (3)°	Cut plate, colourless
V = 578.08 (5) Å³	0.45 × 0.37 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	1848 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 26.4°, θ_min = 1.6°
ω and φ scans	h = −8→8
9253 measured reflections	k = −8→8
2348 independent reflections	l = −17→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)] = 0.036	All H-atom parameters refined
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0417P)² + 0.1136P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2348 reflections	Δρ_max = 0.17 e Å⁻³
207 parameters	Δρ_min = −0.15 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.046 (11)

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	0.22409 (15)	0.15150 (13)	0.22438 (7)	0.0316 (3)
O2	0.14675 (14)	0.48046 (14)	0.23744 (7)	0.0290 (3)
O3	−0.04150 (18)	0.87519 (19)	0.24467 (10)	0.0483 (3)
N1	0.30325 (18)	0.5187 (2)	−0.14614 (9)	0.0343 (3)
N2	0.5281 (2)	0.90081 (17)	0.33110 (9)	0.0261 (3)
N3	0.35573 (19)	0.65430 (17)	0.63958 (9)	0.0301 (3)
C1	0.20050 (19)	0.34213 (19)	0.18639 (10)	0.0233 (3)
C2	0.3330 (2)	0.3211 (2)	−0.09781 (11)	0.0345 (4)
C3	0.3025 (2)	0.2581 (2)	0.00823 (11)	0.0281 (3)
C4	0.23968 (18)	0.40528 (19)	0.06936 (10)	0.0221 (3)
C5	0.2115 (2)	0.6099 (2)	0.01998 (10)	0.0251 (3)
C6	0.2442 (2)	0.6593 (2)	−0.08700 (11)	0.0303 (3)
C7	0.5595 (2)	0.64381 (19)	0.59471 (11)	0.0280 (3)
C8	0.6208 (2)	0.72207 (18)	0.49221 (10)	0.0242 (3)
C9	0.4716 (2)	0.81926 (17)	0.43125 (10)	0.0220 (3)
C10	0.2598 (2)	0.82558 (19)	0.48123 (10)	0.0254 (3)
C11	0.2077 (2)	0.7433 (2)	0.58388 (11)	0.0295 (3)
H3N	0.320 (3)	0.604 (3)	0.7125 (15)	0.051 (5)*
H2	0.378 (2)	0.219 (2)	−0.1425 (12)	0.040 (4)*
H1W	0.030 (3)	0.752 (3)	0.2392 (15)	0.060 (6)*
H2N	0.668 (3)	0.898 (2)	0.3041 (12)	0.037 (4)*
H3	0.325 (2)	0.109 (2)	0.0397 (12)	0.037 (4)*
H2W	0.048 (3)	0.953 (3)	0.2359 (16)	0.067 (6)*
H1N	0.433 (3)	0.977 (3)	0.2965 (13)	0.042 (5)*
H5	0.167 (2)	0.718 (2)	0.0595 (11)	0.024 (3)*
H6	0.225 (2)	0.800 (2)	−0.1230 (12)	0.037 (4)*
H7	0.659 (2)	0.578 (2)	0.6396 (12)	0.032 (4)*
H8	0.765 (2)	0.712 (2)	0.4621 (11)	0.027 (4)*
H10	0.153 (2)	0.889 (2)	0.4410 (12)	0.032 (4)*
H11	0.067 (2)	0.744 (2)	0.6204 (12)	0.034 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0368 (6)	0.0263 (5)	0.0301 (6)	−0.0058 (4)	−0.0126 (4)	0.0035 (4)
O2	0.0330 (5)	0.0318 (5)	0.0212 (5)	−0.0023 (4)	−0.0058 (4)	−0.0055 (4)
O3	0.0302 (6)	0.0324 (6)	0.0791 (9)	−0.0057 (5)	0.0027 (6)	−0.0182 (6)
N1	0.0254 (6)	0.0570 (8)	0.0208 (6)	−0.0095 (5)	−0.0047 (5)	−0.0060 (5)
N2	0.0269 (7)	0.0265 (6)	0.0216 (6)	−0.0016 (5)	−0.0040 (5)	−0.0014 (5)
N3	0.0437 (7)	0.0282 (6)	0.0175 (6)	−0.0076 (5)	−0.0033 (5)	−0.0040 (5)
C1	0.0192 (6)	0.0276 (7)	0.0227 (7)	−0.0048 (5)	−0.0067 (5)	−0.0010 (5)
C2	0.0286 (8)	0.0504 (9)	0.0271 (8)	−0.0049 (7)	−0.0039 (6)	−0.0155 (7)
C3	0.0237 (7)	0.0334 (8)	0.0281 (8)	−0.0029 (6)	−0.0059 (6)	−0.0087 (6)
C4	0.0152 (6)	0.0295 (7)	0.0220 (7)	−0.0045 (5)	−0.0051 (5)	−0.0036 (5)
C5	0.0208 (7)	0.0296 (7)	0.0244 (7)	−0.0055 (5)	−0.0053 (5)	−0.0027 (6)
C6	0.0249 (7)	0.0397 (8)	0.0238 (7)	−0.0092 (6)	−0.0067 (6)	0.0035 (6)
C7	0.0391 (8)	0.0228 (7)	0.0254 (7)	−0.0045 (6)	−0.0132 (6)	−0.0048 (5)
C8	0.0273 (7)	0.0211 (6)	0.0253 (7)	−0.0036 (5)	−0.0060 (6)	−0.0064 (5)
C9	0.0294 (7)	0.0157 (6)	0.0215 (7)	−0.0034 (5)	−0.0040 (5)	−0.0058 (5)
C10	0.0280 (7)	0.0220 (6)	0.0244 (7)	−0.0013 (5)	−0.0045 (6)	−0.0044 (5)
C11	0.0336 (8)	0.0264 (7)	0.0261 (8)	−0.0049 (6)	0.0014 (6)	−0.0081 (5)

Geometric parameters (Å, º) top

O1—C1	1.2640 (15)	C3—C4	1.3924 (18)
O2—C1	1.2486 (15)	C3—H3	0.993 (16)
O3—H1W	0.89 (2)	C4—C5	1.3844 (18)
O3—H2W	0.85 (2)	C5—C6	1.3873 (19)
N1—C6	1.3370 (19)	C5—H5	0.971 (14)
N1—C2	1.341 (2)	C6—H6	0.961 (16)
N2—C9	1.3342 (16)	C7—C8	1.3610 (19)
N2—H2N	0.921 (18)	C7—H7	0.981 (16)
N2—H1N	0.890 (18)	C8—C9	1.4129 (19)
N3—C11	1.3516 (19)	C8—H8	0.954 (15)
N3—C7	1.3520 (19)	C9—C10	1.4171 (19)
N3—H3N	0.957 (19)	C10—C11	1.3614 (19)
C1—C4	1.5192 (18)	C10—H10	0.975 (16)
C2—C3	1.380 (2)	C11—H11	0.953 (16)
C2—H2	0.987 (16)

H1W—O3—H2W	106.0 (19)	C4—C5—H5	120.6 (8)
C6—N1—C2	117.13 (12)	C6—C5—H5	120.2 (8)
C9—N2—H2N	117.4 (10)	N1—C6—C5	123.35 (13)
C9—N2—H1N	119.6 (11)	N1—C6—H6	116.0 (9)
H2N—N2—H1N	121.7 (15)	C5—C6—H6	120.7 (9)
C11—N3—C7	120.86 (12)	N3—C7—C8	120.80 (13)
C11—N3—H3N	121.0 (11)	N3—C7—H7	116.8 (9)
C7—N3—H3N	118.1 (11)	C8—C7—H7	122.4 (9)
O2—C1—O1	125.12 (12)	C7—C8—C9	120.31 (13)
O2—C1—C4	118.15 (11)	C7—C8—H8	119.3 (9)
O1—C1—C4	116.73 (11)	C9—C8—H8	120.4 (9)
N1—C2—C3	123.37 (13)	N2—C9—C8	121.35 (12)
N1—C2—H2	116.2 (9)	N2—C9—C10	121.65 (12)
C3—C2—H2	120.4 (9)	C8—C9—C10	117.00 (12)
C2—C3—C4	119.18 (13)	C11—C10—C9	120.09 (13)
C2—C3—H3	119.7 (9)	C11—C10—H10	120.8 (9)
C4—C3—H3	121.1 (9)	C9—C10—H10	119.1 (9)
C5—C4—C3	117.80 (12)	N3—C11—C10	120.93 (13)
C5—C4—C1	121.38 (12)	N3—C11—H11	116.3 (9)
C3—C4—C1	120.81 (11)	C10—C11—H11	122.8 (9)
C4—C5—C6	119.16 (13)

C6—N1—C2—C3	1.1 (2)	C2—N1—C6—C5	−0.5 (2)
N1—C2—C3—C4	−0.7 (2)	C4—C5—C6—N1	−0.3 (2)
C2—C3—C4—C5	−0.27 (19)	C11—N3—C7—C8	−0.23 (18)
C2—C3—C4—C1	178.83 (12)	N3—C7—C8—C9	1.17 (18)
O2—C1—C4—C5	−1.76 (18)	C7—C8—C9—N2	178.61 (12)
O1—C1—C4—C5	177.80 (11)	C7—C8—C9—C10	−1.56 (17)
O2—C1—C4—C3	179.18 (11)	N2—C9—C10—C11	−179.09 (12)
O1—C1—C4—C3	−1.26 (17)	C8—C9—C10—C11	1.08 (18)
C3—C4—C5—C6	0.74 (18)	C7—N3—C11—C10	−0.26 (19)
C1—C4—C5—C6	−178.35 (11)	C9—C10—C11—N3	−0.19 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N1ⁱ	0.957 (19)	1.854 (19)	2.7978 (16)	167.9 (16)
N2—H2N···O3ⁱⁱ	0.921 (18)	1.911 (18)	2.8313 (18)	175.8 (14)
N2—H1N···O1ⁱⁱⁱ	0.890 (18)	1.938 (19)	2.8283 (16)	177.5 (15)
O3—H1W···O2	0.89 (2)	1.86 (2)	2.7369 (15)	172.1 (18)
O3—H2W···O1ⁱⁱⁱ	0.85 (2)	1.92 (2)	2.7635 (15)	173 (2)

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

Acknowledgements

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Cowan, J. A., Howard, J. A. K., Leech, M. A. & Williams, I. D. (2001). Acta Cryst. E57, o563–o565. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hooft, R. (1988). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany. Google Scholar
Teulon, P., Delaplane, R. G., Olovsson, I. & Roziere, J. (1985). Acta Cryst. C41, 479–483. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.