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The title compound, C6H9N2+·C6H4NO2-, has been formed by oxidative degradation of neat bis(2-pyridyl­methyl)­amine. Hydro­gen bonds link the ions into infinite chains along the a axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101015426/os1143sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101015426/os1143Isup2.hkl
Contains datablock I

CCDC reference: 179288

Comment top

The amine bis(2-pyridylmethyl)amine is a versatile synthetic intermediate widely used in the preparation of polypyridyl ligands. The amine is usually distilled prior to use, and during the course of our studies in this field (Døssing et al., 1996, 1997), it has puzzled us that colourless needles begin to form after a couple of months' storage of the distilled amine. In order to characterize the decomposition product, a single-crystal was subjected to structure determination, which showed that the title salt, (I), consisting of a (2-pyridylmethyl)ammonium cation and a pyridine-2-carboxylate anion, had formed. A possible mechanism for the formation of (I) is shown below. \sch

In support of this mechanism, close scrutiny of a 1H NMR spectrum of a concentrated solution of aged bis(2-pyridylmethyl)amine in CD3CN indeed revealed the presence of low intensity peaks that could originate from pyridine-2-carboxaldehyde (7.61, 7.91, 8.77 and 10.00 p.p.m. in CD3CN). It is important to emphasize that these peaks are absent in a spectrum of freshly distilled bis(2-pyridylmethyl)amine. The presence of traces of impurities might catalyse the oxidative degradation. A similar (FeIII-promoted) oxidative degradation of a polypyridyl compound has been reported by Renz et al. (1999).

The Cambridge Structural Database (Allen et al., 1993) contains numerous structural reports of the pyridine-2-carboxylate anion, whereas the structure of the (2-pyridylmethyl)ammonium cation has no precedent. The bond lengths and angles in the cation and anion are normal. The pyridyl rings of the two ions are almost orthogonal [87.4 (5)°].

The structure of (I) shows four hydrogen bonds (Table 1) linking the ions into infinite chains along the a axis. The anion carboxylic O atoms and the pyridyl N atom act as hydrogen-bond acceptors, with the donor being the aliphatic N atom in the cation.

Related literature top

For related literature, see: Allen & Kennard (1993); Døssing et al. (1996, 1997); Larsen et al. (1986); Renz et al. (1999).

Experimental top

Freshly distilled bis(2-pyridylmethyl)amine (Larsen et al., 1986) was left in a closed flask for about three months, during which colourless needles of (I) formed. The mother liquor was decanted off and the crystals were washed with diethyl ether and air dried.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: DREADD (Blessing, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular view of (I), with displacement ellipsoids drawn at the 50% probability level and H atoms shown as spheres of arbitrary radii.
(2-Pyridylmethyl)ammonium pyridine-2-carboxylate top
Crystal data top
C6H9N2+·C6H4NO2F(000) = 488
Mr = 231.25Dx = 1.307 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54180 Å
a = 6.4233 (9) ÅCell parameters from 20 reflections
b = 9.0728 (18) Åθ = 39.3–43.8°
c = 20.265 (3) ŵ = 0.75 mm1
β = 95.700 (11)°T = 122 K
V = 1175.1 (3) Å3Needle, colourless
Z = 40.19 × 0.06 × 0.02 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.025
Radiation source: fine-focus sealed tubeθmax = 75.0°, θmin = 4.4°
Graphite monochromatorh = 88
ω/2θ scansk = 011
4776 measured reflectionsl = 025
2412 independent reflections5 standard reflections every 167 min
2140 reflections with I > 2σ(I) intensity decay: 4.5%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033All H-atom parameters refined
wR(F2) = 0.119 w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2412 reflectionsΔρmax = 0.29 e Å3
207 parametersΔρmin = 0.18 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0120 (14)
Crystal data top
C6H9N2+·C6H4NO2V = 1175.1 (3) Å3
Mr = 231.25Z = 4
Monoclinic, P21/cCu Kα radiation
a = 6.4233 (9) ŵ = 0.75 mm1
b = 9.0728 (18) ÅT = 122 K
c = 20.265 (3) Å0.19 × 0.06 × 0.02 mm
β = 95.700 (11)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.025
4776 measured reflections5 standard reflections every 167 min
2412 independent reflections intensity decay: 4.5%
2140 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.119All H-atom parameters refined
S = 1.00Δρmax = 0.29 e Å3
2412 reflectionsΔρmin = 0.18 e Å3
207 parameters
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
xyzUiso*/Ueq
C10.18390 (16)0.33894 (11)0.38952 (5)0.0202 (2)
C20.02792 (15)0.28040 (11)0.33368 (5)0.0196 (2)
C30.09091 (19)0.18135 (12)0.28715 (6)0.0270 (3)
C40.30398 (18)0.29114 (14)0.28076 (5)0.0292 (3)
C50.25469 (19)0.19433 (14)0.23157 (6)0.0309 (3)
C60.0539 (2)0.13815 (13)0.23503 (6)0.0324 (3)
C70.75862 (17)0.24344 (12)0.50895 (6)0.0261 (3)
C80.58952 (17)0.20647 (11)0.55274 (5)0.0229 (3)
C90.5797 (2)0.06513 (13)0.57965 (6)0.0309 (3)
C100.4236 (2)0.03386 (13)0.61969 (6)0.0348 (3)
C110.2816 (2)0.14310 (15)0.63175 (6)0.0332 (3)
C120.30333 (18)0.28077 (13)0.60322 (6)0.0287 (3)
O10.11368 (12)0.42770 (9)0.42944 (4)0.0274 (2)
O20.36799 (12)0.29485 (9)0.39017 (4)0.0283 (2)
N10.16701 (14)0.33402 (11)0.33111 (4)0.0246 (2)
N20.45458 (14)0.31311 (10)0.56429 (4)0.0236 (2)
N30.71603 (14)0.38256 (10)0.47272 (4)0.0203 (2)
H30.239 (3)0.1468 (18)0.2917 (8)0.041 (4)*
H40.449 (3)0.3261 (19)0.2794 (8)0.046 (4)*
H50.360 (3)0.1641 (18)0.1959 (8)0.041 (4)*
H60.017 (2)0.0712 (19)0.2007 (8)0.045 (4)*
H1N30.725 (2)0.4624 (18)0.5029 (8)0.036 (4)*
H2N30.585 (3)0.3764 (17)0.4482 (8)0.037 (4)*
H3N30.821 (3)0.3990 (17)0.4453 (8)0.038 (4)*
H7A0.898 (3)0.2511 (19)0.5348 (8)0.038 (4)*
H7B0.770 (3)0.163 (2)0.4775 (9)0.045 (4)*
H90.679 (2)0.0096 (18)0.5697 (7)0.036 (4)*
H100.407 (2)0.0658 (18)0.6390 (8)0.046 (4)*
H110.173 (3)0.1250 (19)0.6597 (9)0.051 (5)*
H120.207 (2)0.3641 (16)0.6127 (7)0.028 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0193 (5)0.0209 (5)0.0208 (5)0.0019 (4)0.0035 (4)0.0009 (4)
C20.0202 (5)0.0203 (5)0.0188 (5)0.0030 (4)0.0037 (4)0.0010 (4)
C30.0294 (6)0.0246 (5)0.0270 (6)0.0016 (4)0.0026 (4)0.0049 (4)
C40.0216 (5)0.0421 (6)0.0233 (6)0.0034 (5)0.0001 (4)0.0005 (5)
C50.0323 (6)0.0379 (6)0.0214 (5)0.0095 (5)0.0025 (4)0.0001 (4)
C60.0424 (7)0.0287 (6)0.0258 (6)0.0036 (5)0.0025 (5)0.0085 (4)
C70.0228 (5)0.0225 (5)0.0330 (6)0.0056 (4)0.0023 (4)0.0002 (4)
C80.0244 (5)0.0219 (5)0.0214 (5)0.0001 (4)0.0032 (4)0.0013 (4)
C90.0420 (7)0.0220 (5)0.0279 (5)0.0028 (5)0.0010 (5)0.0005 (4)
C100.0512 (8)0.0245 (5)0.0280 (6)0.0076 (5)0.0002 (5)0.0052 (4)
C110.0364 (7)0.0367 (6)0.0265 (6)0.0097 (5)0.0030 (5)0.0043 (5)
C120.0259 (5)0.0326 (6)0.0280 (6)0.0002 (4)0.0038 (4)0.0046 (4)
O10.0206 (4)0.0339 (4)0.0279 (4)0.0012 (3)0.0036 (3)0.0131 (3)
O20.0199 (4)0.0341 (4)0.0307 (4)0.0027 (3)0.0008 (3)0.0085 (3)
N10.0197 (4)0.0326 (5)0.0219 (5)0.0014 (3)0.0036 (3)0.0015 (4)
N20.0229 (5)0.0237 (5)0.0240 (5)0.0006 (3)0.0012 (3)0.0024 (3)
N30.0178 (4)0.0221 (4)0.0213 (4)0.0006 (3)0.0035 (3)0.0026 (3)
Geometric parameters (Å, º) top
C1—O21.2472 (13)C7—H7A0.995 (17)
C1—O11.2564 (13)C7—H7B0.976 (18)
C1—C21.5299 (14)C8—N21.3351 (14)
C2—N11.3395 (14)C8—C91.3974 (15)
C2—C31.3914 (15)C9—C101.3807 (18)
C3—C61.3924 (16)C9—H90.967 (16)
C3—H30.995 (16)C10—C111.3853 (19)
C4—N11.3370 (14)C10—H100.995 (17)
C4—C51.3884 (17)C11—C121.3894 (17)
C4—H40.985 (17)C11—H110.954 (19)
C5—C61.3821 (18)C12—N21.3435 (14)
C5—H50.979 (17)C12—H121.006 (15)
C6—H60.970 (17)N3—H1N30.946 (16)
C7—N31.4724 (14)N3—H2N30.933 (16)
C7—C81.5071 (15)N3—H3N30.927 (17)
O2—C1—O1126.84 (10)N2—C8—C9122.80 (11)
O2—C1—C2116.55 (9)N2—C8—C7117.40 (9)
O1—C1—C2116.61 (9)C9—C8—C7119.80 (10)
N1—C2—C3122.81 (10)C10—C9—C8118.78 (11)
N1—C2—C1116.34 (9)C10—C9—H9120.8 (9)
C3—C2—C1120.80 (9)C8—C9—H9120.4 (9)
C2—C3—C6118.57 (11)C9—C10—C11119.09 (11)
C2—C3—H3118.7 (9)C9—C10—H10121.9 (10)
C6—C3—H3122.7 (9)C11—C10—H10118.9 (10)
N1—C4—C5123.50 (11)C10—C11—C12118.34 (11)
N1—C4—H4118.6 (10)C10—C11—H11120.9 (11)
C5—C4—H4117.8 (10)C12—C11—H11120.8 (11)
C6—C5—C4118.37 (10)N2—C12—C11123.32 (11)
C6—C5—H5120.6 (10)N2—C12—H12116.1 (8)
C4—C5—H5121.1 (10)C11—C12—H12120.5 (8)
C5—C6—C3118.98 (11)C4—N1—C2117.76 (9)
C5—C6—H6119.1 (10)C8—N2—C12117.68 (10)
C3—C6—H6121.9 (10)C7—N3—H1N3109.7 (9)
N3—C7—C8112.05 (9)C7—N3—H2N3109.1 (10)
N3—C7—H7A108.4 (10)H1N3—N3—H2N3112.7 (13)
C8—C7—H7A111.7 (9)C7—N3—H3N3109.1 (10)
N3—C7—H7B109.6 (10)H1N3—N3—H3N3105.1 (13)
C8—C7—H7B109.0 (10)H2N3—N3—H3N3111.1 (13)
H7A—C7—H7B105.8 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H1N3···O1i0.946 (16)1.913 (16)2.7672 (13)149.0 (13)
N3—H2N3···O20.933 (16)1.885 (17)2.7722 (13)157.9 (14)
N3—H3N3···N1ii0.927 (17)2.396 (16)3.0694 (13)129.4 (13)
N3—H3N3···O1ii0.927 (17)1.956 (17)2.8117 (12)152.5 (14)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC6H9N2+·C6H4NO2
Mr231.25
Crystal system, space groupMonoclinic, P21/c
Temperature (K)122
a, b, c (Å)6.4233 (9), 9.0728 (18), 20.265 (3)
β (°) 95.700 (11)
V3)1175.1 (3)
Z4
Radiation typeCu Kα
µ (mm1)0.75
Crystal size (mm)0.19 × 0.06 × 0.02
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4776, 2412, 2140
Rint0.025
(sin θ/λ)max1)0.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.119, 1.00
No. of reflections2412
No. of parameters207
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.29, 0.18

Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, DREADD (Blessing, 1987), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H1N3···O1i0.946 (16)1.913 (16)2.7672 (13)149.0 (13)
N3—H2N3···O20.933 (16)1.885 (17)2.7722 (13)157.9 (14)
N3—H3N3···N1ii0.927 (17)2.396 (16)3.0694 (13)129.4 (13)
N3—H3N3···O1ii0.927 (17)1.956 (17)2.8117 (12)152.5 (14)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z.
 

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