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Acta Cryst. (2009). E65, o1511-o1512    [ doi:10.1107/S160053680902100X ]

2,3-Diaminopyridinium 4-nitrobenzoate

K. Balasubramani and H.-K. Fun

Abstract top

In the title salt, C5H8N3+·C7H4NO4-, the pyridine N atom of the 2,3-diaminopyridine molecule is protonated. The protonated N atom and one of the two 2-amino groups are hydrogen bonded to the 4-nitrobenzoate anion through a pair of N-H...O hydrogen bonds, forming an R22(8) ring motif. The carboxylate mean plane of the 4-nitrobenzoate anion is twisted by 3.77 (5)° from the attached ring and the nitro group is similarly twisted by 2.28 (10)°. In the crystal, the molecules are linked by N-H...O and C-H...O interactions into sheets parallel to (100).

Comment top

Pyridine and its derivatives play an important role in heterocyclic chemistry (Pozharski et al., 1997; Katritzky et al., 1996). Pyridine and its substituted derivatives are often involved in hydrogen bonding interactions (Jeffrey & Saenger, 1991; Jeffrey, 1997; Scheiner, 1997). In order to study some interesting hydrogen bonding interactions, the synthesis and structure of the title salt (I) is presented here.

The asymmetric unit of (I), Fig. 1, contains a protonated 2,3-diaminopyridinium cation and a 4-nitrobenzoate anion. In the 2,3-diaminopyridinium cation, a wide angle (123.62 (17)°) is subtended at the protonated N1 atom. The 2,3-diaminopyridinium cation is planar, with a maximum deviation of 0.005 (2)Å for atom C1. The carboxylate group is twisted slightly from the ring; the dihedral angle between C1—C6 and O3/O4/C7/C6 planes is 5.41 (10)°. The nitro group is also slightly twisted away from its attached benzene ring by 2.28 (10)°.

In the crystal packing, Fig. 2, the protonated N1 atom and the 2-amino group (N2) is hydrogen-bonded to the carboxylate oxygen atoms (O3 and O4) via a pair of N—H···O hydrogen bonds forming a ring motif, R22(8) (Bernstein et al., 1995). The 2-amino groups (N2 and N3) are involved in N—H···O3 hydrogen bonding interactions to form a R12(7) ring motif. One of the amino group hydrogen atoms, H2N3, and the ring hydrogen atom, H10A, are connected to the 4-nitro group oxygen atoms (O1 and O2) to form an R22(8) ring motif (Table 1 and Fig. 2). These molecules are linked by these interactions into sheets parallel to (100). The crystal structure is further stabilized by a π-π stacking interactions between the aminopyridine- and carboxylate-rings with centroid-to-centroid distances of 3.8343 (10) Å.

Related literature top

For substituted pyridines, see: Pozharski et al. (1997); Katritzky et al. (1996); Jeffrey & Saenger (1991); Jeffrey (1997); Scheiner (1997). For hydrogen-bond motifs, see: Bernstein et al. (1995). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

Hot methanol solutions (20 ml) of 2,3-diaminopyridine (27 mg, Aldrich) and 4-nitrobenzoic acid (42 mg, Merck) were mixed and warmed over a heating magnetic stirrer for 5 minutes. The resulting solution was allowed to cool slowly at room temperature. Crystals of (I) appeared from the mother liquor after a few days.

Refinement top

All the H atoms were located from the difference Fourier map [N–H = 0.82 (3)–0.99 (3)Å and C–H = 0.91 (2)–0.99 (2) Å] and allowed to refine freely. In the absence of significant anomalous scattering effects, 2144 Friedel pairs were merged.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structures of the ions in (I), illustrating the primary mode of association between them, showing 50% probability displacement ellipsoids and the atom numbering scheme. Dashed lines indicate the hydrogen bonding.
[Figure 2] Fig. 2. The crystal packing of (I). Dashed lines indicate the hydrogen bondings.
2,3-Diaminopyridinium 4-nitrobenzoate top
Crystal data top
C5H8N3+·C7H4NO4−F(000) = 288
Mr = 276.26Dx = 1.504 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 2526 reflections
a = 8.0827 (2) Åθ = 2.8–31.7°
b = 6.7365 (1) ŵ = 0.12 mm−1
c = 11.4489 (3) ÅT = 100 K
β = 101.967 (1)°Block, brown
V = 609.83 (2) Å30.25 × 0.17 × 0.10 mm
Z = 2
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		2808 independent reflections
Radiation source: fine-focus sealed tube2155 reflections with I > 2σ(I)
graphiteRint = 0.045
φ and ω scansθmax = 34.9°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		h = −12→12
Tmin = 0.972, Tmax = 0.988k = −10→10
11659 measured reflectionsl = −17→18
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0571P)2 + 0.026P]
where P = (Fo2 + 2Fc2)/3
2808 reflections(Δ/σ)max < 0.001
229 parametersΔρmax = 0.43 e Å−3
1 restraintΔρmin = −0.30 e Å−3
Crystal data top
C5H8N3+·C7H4NO4−V = 609.83 (2) Å3
Mr = 276.26Z = 2
Monoclinic, P21Mo Kα radiation
a = 8.0827 (2) ŵ = 0.12 mm−1
b = 6.7365 (1) ÅT = 100 K
c = 11.4489 (3) Å0.25 × 0.17 × 0.10 mm
β = 101.967 (1)°
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		2808 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		2155 reflections with I > 2σ(I)
Tmin = 0.972, Tmax = 0.988Rint = 0.045
11659 measured reflectionsθmax = 34.9°
Refinement top
R[F2 > 2σ(F2)] = 0.052H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.116Δρmax = 0.43 e Å−3
S = 1.04Δρmin = −0.30 e Å−3
2808 reflectionsAbsolute structure: ?
229 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
xyzUiso*/Ueq
O1−0.0506 (2)−0.7085 (2)0.85306 (17)0.0306 (4)
O2−0.04637 (19)−0.7831 (2)0.66897 (16)0.0269 (4)
O30.35100 (19)0.1109 (2)0.60686 (14)0.0223 (3)
O40.35695 (19)0.1713 (2)0.79972 (14)0.0210 (3)
N4−0.0141 (2)−0.6717 (3)0.75606 (18)0.0213 (4)
C10.1816 (2)−0.1740 (3)0.82546 (19)0.0178 (4)
C20.1021 (2)−0.3532 (3)0.8391 (2)0.0183 (4)
C30.0723 (2)−0.4824 (3)0.7432 (2)0.0178 (4)
C40.1172 (2)−0.4421 (3)0.6355 (2)0.0196 (4)
C50.1973 (2)−0.2624 (3)0.6234 (2)0.0180 (4)
C60.2309 (2)−0.1287 (3)0.71862 (19)0.0162 (4)
C70.3201 (2)0.0666 (3)0.70675 (18)0.0169 (4)
N10.5459 (2)0.4983 (2)0.80784 (16)0.0179 (3)
N20.5600 (2)0.4619 (3)0.60992 (18)0.0213 (4)
N30.7324 (2)0.8308 (3)0.62077 (18)0.0212 (4)
C80.5959 (2)0.5681 (3)0.71027 (19)0.0166 (4)
C90.6873 (2)0.7522 (3)0.72040 (19)0.0168 (4)
C100.7217 (2)0.8451 (3)0.8301 (2)0.0197 (4)
C110.6717 (2)0.7629 (3)0.9295 (2)0.0213 (4)
C120.5820 (2)0.5895 (3)0.91644 (19)0.0199 (4)
H1A0.201 (3)−0.084 (4)0.887 (2)0.020 (6)*
H2A0.068 (3)−0.384 (4)0.914 (2)0.020 (6)*
H4A0.089 (3)−0.535 (5)0.569 (2)0.033 (7)*
H5A0.232 (3)−0.233 (4)0.547 (2)0.021 (6)*
H10A0.782 (3)0.972 (5)0.834 (2)0.029 (7)*
H11A0.711 (3)0.821 (4)1.010 (2)0.027 (7)*
H12A0.540 (3)0.527 (4)0.978 (2)0.021 (6)*
H1N10.478 (3)0.375 (5)0.793 (3)0.038 (8)*
H1N20.497 (4)0.353 (5)0.608 (3)0.038 (8)*
H2N20.579 (3)0.496 (4)0.542 (2)0.017 (6)*
H1N30.735 (3)0.759 (5)0.560 (2)0.025 (7)*
H2N30.806 (4)0.917 (5)0.635 (3)0.037 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0374 (9)0.0213 (8)0.0368 (10)−0.0086 (6)0.0162 (8)0.0038 (7)
O20.0274 (7)0.0170 (7)0.0348 (10)−0.0058 (6)0.0027 (7)−0.0027 (7)
O30.0293 (7)0.0175 (6)0.0226 (8)−0.0035 (5)0.0109 (6)0.0002 (6)
O40.0281 (7)0.0164 (6)0.0199 (8)−0.0056 (5)0.0083 (6)−0.0023 (6)
N40.0165 (7)0.0146 (7)0.0320 (10)−0.0015 (6)0.0030 (7)0.0026 (8)
C10.0213 (8)0.0139 (8)0.0187 (10)−0.0012 (7)0.0053 (7)−0.0008 (8)
C20.0185 (8)0.0155 (8)0.0215 (10)−0.0007 (6)0.0054 (7)0.0030 (8)
C30.0166 (8)0.0116 (7)0.0255 (11)−0.0015 (6)0.0053 (7)0.0010 (7)
C40.0216 (8)0.0132 (8)0.0249 (11)−0.0008 (6)0.0067 (8)−0.0015 (8)
C50.0205 (8)0.0146 (8)0.0196 (10)−0.0010 (7)0.0056 (7)−0.0018 (8)
C60.0176 (8)0.0111 (8)0.0201 (10)0.0012 (6)0.0043 (7)0.0032 (7)
C70.0180 (8)0.0128 (8)0.0208 (10)0.0003 (6)0.0058 (7)0.0008 (8)
N10.0188 (7)0.0161 (7)0.0191 (9)−0.0021 (6)0.0048 (6)0.0004 (7)
N20.0300 (9)0.0176 (8)0.0182 (9)−0.0056 (6)0.0094 (7)−0.0014 (7)
N30.0273 (8)0.0178 (7)0.0201 (9)−0.0061 (7)0.0089 (7)−0.0003 (8)
C80.0158 (7)0.0136 (8)0.0208 (10)−0.0012 (6)0.0046 (7)0.0007 (8)
C90.0157 (7)0.0161 (8)0.0189 (9)0.0003 (6)0.0042 (6)0.0023 (8)
C100.0199 (8)0.0168 (8)0.0228 (11)−0.0021 (7)0.0055 (7)−0.0018 (8)
C110.0210 (8)0.0225 (9)0.0206 (11)−0.0001 (7)0.0051 (7)−0.0028 (8)
C120.0201 (8)0.0223 (9)0.0176 (10)−0.0010 (7)0.0045 (7)0.0004 (8)
Geometric parameters (Å, °) top
O1—N41.232 (2)N1—C81.349 (3)
O2—N41.232 (2)N1—C121.363 (3)
O3—C71.256 (2)N1—H1N10.99 (3)
O4—C71.260 (2)N2—C81.333 (3)
N4—C31.476 (2)N2—H1N20.89 (3)
C1—C21.391 (3)N2—H2N20.85 (3)
C1—C61.397 (3)N3—C91.373 (3)
C1—H1A0.92 (3)N3—H1N30.85 (3)
C2—C31.383 (3)N3—H2N30.82 (3)
C2—H2A0.98 (3)C8—C91.435 (3)
C3—C41.382 (3)C9—C101.379 (3)
C4—C51.394 (3)C10—C111.399 (3)
C4—H4A0.98 (3)C10—H10A0.98 (3)
C5—C61.396 (3)C11—C121.367 (3)
C5—H5A0.99 (3)C11—H11A0.99 (3)
C6—C71.520 (3)C12—H12A0.94 (3)
O2—N4—O1123.84 (17)C8—N1—C12123.62 (17)
O2—N4—C3118.06 (18)C8—N1—H1N1113.8 (17)
O1—N4—C3118.10 (18)C12—N1—H1N1122.6 (17)
C2—C1—C6120.69 (19)C8—N2—H1N2119.0 (19)
C2—C1—H1A119.4 (17)C8—N2—H2N2126.1 (17)
C6—C1—H1A119.9 (17)H1N2—N2—H2N2114 (2)
C3—C2—C1117.7 (2)C9—N3—H1N3121 (2)
C3—C2—H2A122.2 (16)C9—N3—H2N3114 (2)
C1—C2—H2A120.1 (16)H1N3—N3—H2N3115 (3)
C4—C3—C2123.38 (18)N2—C8—N1118.49 (17)
C4—C3—N4118.44 (18)N2—C8—C9123.34 (19)
C2—C3—N4118.18 (18)N1—C8—C9118.16 (18)
C3—C4—C5118.21 (19)N3—C9—C10122.90 (18)
C3—C4—H4A120.7 (17)N3—C9—C8119.10 (19)
C5—C4—H4A121.1 (17)C10—C9—C8117.97 (18)
C4—C5—C6120.13 (19)C9—C10—C11121.58 (18)
C4—C5—H5A118.6 (16)C9—C10—H10A116.5 (16)
C6—C5—H5A121.2 (16)C11—C10—H10A121.9 (16)
C5—C6—C1119.87 (17)C12—C11—C10119.1 (2)
C5—C6—C7120.51 (17)C12—C11—H11A120.1 (16)
C1—C6—C7119.62 (17)C10—C11—H11A120.5 (16)
O3—C7—O4125.37 (18)N1—C12—C11119.6 (2)
O3—C7—C6118.35 (18)N1—C12—H12A115.8 (16)
O4—C7—C6116.28 (17)C11—C12—H12A124.6 (16)
C6—C1—C2—C3−0.8 (3)C1—C6—C7—O3−174.40 (17)
C1—C2—C3—C4−0.1 (3)C5—C6—C7—O4−174.72 (17)
C1—C2—C3—N4−179.16 (16)C1—C6—C7—O45.6 (2)
O2—N4—C3—C4−1.9 (3)C12—N1—C8—N2177.00 (18)
O1—N4—C3—C4178.55 (18)C12—N1—C8—C9−2.2 (3)
O2—N4—C3—C2177.21 (18)N2—C8—C9—N33.9 (3)
O1—N4—C3—C2−2.3 (3)N1—C8—C9—N3−176.90 (17)
C2—C3—C4—C50.4 (3)N2—C8—C9—C10−177.88 (18)
N4—C3—C4—C5179.44 (17)N1—C8—C9—C101.3 (2)
C3—C4—C5—C60.2 (3)N3—C9—C10—C11178.94 (19)
C4—C5—C6—C1−1.0 (3)C8—C9—C10—C110.8 (3)
C4—C5—C6—C7179.32 (16)C9—C10—C11—C12−2.1 (3)
C2—C1—C6—C51.3 (3)C8—N1—C12—C110.9 (3)
C2—C1—C6—C7−179.02 (17)C10—C11—C12—N11.3 (3)
C5—C6—C7—O35.3 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···O40.99 (3)1.70 (3)2.671 (2)167 (3)
N2—H1N2···O30.89 (3)2.01 (3)2.901 (2)178 (5)
N2—H2N2···O3i0.86 (2)2.06 (2)2.903 (2)171 (2)
N3—H1N3···O3i0.85 (3)2.14 (3)2.951 (3)159 (2)
N3—H2N3···O2ii0.82 (3)2.34 (3)3.140 (2)165 (3)
C10—H10A···O1ii0.98 (3)2.53 (3)3.507 (2)176.9 (16)
C11—H11A···O4iii0.99 (2)2.56 (2)3.216 (3)123.5 (19)
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x+1, y+2, z; (iii) −x+1, y+1/2, −z+2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···O40.99 (3)1.70 (3)2.671 (2)167 (3)
N2—H1N2···O30.89 (3)2.01 (3)2.901 (2)178 (5)
N2—H2N2···O3i0.86 (2)2.06 (2)2.903 (2)171 (2)
N3—H1N3···O3i0.85 (3)2.14 (3)2.951 (3)159 (2)
N3—H2N3···O2ii0.82 (3)2.34 (3)3.140 (2)165 (3)
C10—H10A···O1ii0.98 (3)2.53 (3)3.507 (2)176.9 (16)
C11—H11A···O4iii0.99 (2)2.56 (2)3.216 (3)123.5 (19)
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x+1, y+2, z; (iii) −x+1, y+1/2, −z+2.
Acknowledgements top

HKF and KBS thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. KBS thanks Universiti Sains Malaysia for a post–doctoral research fellowship. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

references
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