supplementary materials


Acta Cryst. (2009). E65, o2408    [ doi:10.1107/S160053680903517X ]

Pyridine-4-carboximidamidate chloride

P. Fan, L. Wang and H. Zhang

Abstract top

In the title salt, C6H8N3+·Cl-, each pyridinecarboximidamidate cation is linked to two symmetry-related cations through N-H...N hydrogen bonds, and to two chloride ions by N-H...Cl hydrogen bonds. The N-H...N hydrogen bonds involve the pyridine N atom and one NH2 group. In the crystal, N-H...N and N-H...Cl hydrogen bonds extend the structure into two-dimensional layers. Weak C-H...Cl interactions further connect these layers into a three-dimensional network.

Comment top

The title compound, also known as isonicotinamidine hydrochloride, served as a key intermediate in the synthesis of pharmacologically active compounds. It had attracted a great deal of interest during recent years. A series of new piperidinyl- and 1,2,3,6-tetrahydropyridinylpyrimidine derivatives was synthesized by using isonicotinamidine as an important intermediate. Isonicotinamidine has a unique structure and exists in the form of hydrochloride or acetate (Chudinov et al., 2005; Kamei et al., 2005).

The title compound is an organic salt (Fig. 1). In the cation, dihedral angle between the pyridyl ring and the plane confined by N2, N3 and C6 is 42.1°. Each isonicotinamidine cation is connected to two other cations by N—H···N hydrogen bonds, and to two Cl- anions by N—H···Cl hydrogen bonds (Fig. 2), to form two dimensional layers including one-dimensional zigzag chains (Fig. 3). Weak C—H···Cl interactions [C···Cl = 3.556 (2) Å] link these layers to provide a three-dimensional supramolecular network.

Related literature top

For background, see: Chudinov et al. (2005); Kamei et al. (2005).

Experimental top

The title compound was prepared according to the method of Kamei et al. (2005). Block-shaped crystals suitable for X-ray diffraction were obtained from ethanol/acetone.

Refinement top

H atoms were located from difference maps and freely refined.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. View of (I), showing atomic labels and displacement ellipsoids drawn at 30% probability level.
[Figure 2] Fig. 2. N—H···N and N—H···Cl hydrogen bonds in the crystal.
[Figure 3] Fig. 3. View of the hydrogen bonded one-dimensional chain along b axis.
Pyridine-4-carboximidamidate chloride top
Crystal data top
C6H8N3+·ClF(000) = 656
Mr = 157.60Dx = 1.432 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 542 reflections
a = 7.3928 (13) Åθ = 2.3–22.8°
b = 10.4467 (16) ŵ = 0.44 mm1
c = 18.925 (3) ÅT = 293 K
V = 1461.6 (4) Å3Block, colourless
Z = 80.37 × 0.32 × 0.21 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
1435 independent reflections
Radiation source: fine-focus sealed tube1215 reflections with I > 2σ(I)
graphiteRint = 0.018
φ and ω scansθmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 91
Tmin = 0.853, Tmax = 0.911k = 112
1949 measured reflectionsl = 231
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) = 0.092 w = 1/[σ2(Fo2) + (0.0416P)2 + 0.5489P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
1435 reflectionsΔρmax = 0.23 e Å3
124 parametersΔρmin = 0.17 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0056 (15)
Crystal data top
C6H8N3+·ClV = 1461.6 (4) Å3
Mr = 157.60Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 7.3928 (13) ŵ = 0.44 mm1
b = 10.4467 (16) ÅT = 293 K
c = 18.925 (3) Å0.37 × 0.32 × 0.21 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
1435 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
1215 reflections with I > 2σ(I)
Tmin = 0.853, Tmax = 0.911Rint = 0.018
1949 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.033All H-atom parameters refined
wR(F2) = 0.092Δρmax = 0.23 e Å3
S = 1.03Δρmin = 0.17 e Å3
1435 reflectionsAbsolute structure: ?
124 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.0852 (2)0.38353 (14)0.75509 (8)0.0367 (4)
C10.0499 (3)0.36114 (17)0.82329 (10)0.0367 (4)
Cl10.15740 (8)0.91636 (4)1.05546 (2)0.0432 (2)
N20.0353 (2)0.79417 (15)0.89141 (9)0.0369 (4)
C20.0593 (3)0.45387 (17)0.87518 (9)0.0341 (4)
N30.1766 (3)0.66264 (17)0.97084 (9)0.0428 (4)
C30.1026 (2)0.57807 (15)0.85578 (9)0.0285 (4)
C40.1401 (3)0.60305 (17)0.78520 (9)0.0337 (4)
C50.1315 (3)0.50297 (18)0.73774 (9)0.0376 (4)
C60.1052 (2)0.68338 (16)0.90895 (9)0.0310 (4)
H40.171 (3)0.6863 (18)0.7679 (10)0.033 (5)*
H10.015 (3)0.275 (2)0.8348 (11)0.044 (6)*
H20.032 (3)0.4327 (18)0.9204 (11)0.041 (5)*
H50.159 (3)0.519 (2)0.6925 (12)0.048 (6)*
H2B0.037 (3)0.854 (2)0.9202 (13)0.060 (7)*
H2A0.016 (3)0.803 (2)0.8500 (12)0.050 (6)*
H3B0.229 (4)0.590 (2)0.9833 (12)0.056 (7)*
H3A0.184 (3)0.732 (2)1.0012 (14)0.061 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0452 (9)0.0312 (8)0.0338 (8)0.0019 (7)0.0001 (7)0.0051 (7)
C10.0439 (11)0.0261 (9)0.0400 (10)0.0002 (8)0.0007 (9)0.0007 (7)
Cl10.0580 (3)0.0357 (3)0.0359 (3)0.0007 (2)0.0055 (2)0.00566 (18)
N20.0484 (10)0.0262 (8)0.0360 (9)0.0009 (7)0.0006 (8)0.0043 (7)
C20.0436 (11)0.0306 (9)0.0280 (9)0.0035 (8)0.0027 (8)0.0019 (7)
N30.0613 (12)0.0348 (9)0.0323 (8)0.0070 (8)0.0090 (8)0.0067 (7)
C30.0313 (9)0.0266 (8)0.0277 (8)0.0021 (7)0.0020 (7)0.0021 (7)
C40.0421 (10)0.0280 (9)0.0310 (9)0.0020 (8)0.0003 (8)0.0024 (7)
C50.0488 (12)0.0377 (10)0.0264 (9)0.0002 (8)0.0022 (8)0.0012 (8)
C60.0348 (9)0.0280 (9)0.0300 (9)0.0018 (7)0.0031 (7)0.0020 (7)
Geometric parameters (Å, °) top
N1—C51.335 (2)N3—C61.303 (2)
N1—C11.337 (2)N3—H3B0.89 (2)
C1—C21.381 (3)N3—H3A0.93 (3)
C1—H10.96 (2)C3—C41.389 (2)
N2—C61.310 (2)C3—C61.491 (2)
N2—H2B0.83 (3)C4—C51.380 (3)
N2—H2A0.88 (2)C4—H40.958 (19)
C2—C31.386 (2)C5—H50.90 (2)
C2—H20.91 (2)
C5—N1—C1116.80 (15)C2—C3—C4118.47 (16)
N1—C1—C2123.63 (17)C2—C3—C6120.99 (15)
N1—C1—H1115.7 (12)C4—C3—C6120.52 (15)
C2—C1—H1120.6 (12)C5—C4—C3118.33 (17)
C6—N2—H2B119.8 (17)C5—C4—H4118.5 (11)
C6—N2—H2A119.2 (15)C3—C4—H4123.2 (11)
H2B—N2—H2A121 (2)N1—C5—C4124.05 (17)
C1—C2—C3118.68 (16)N1—C5—H5118.2 (15)
C1—C2—H2119.3 (13)C4—C5—H5117.7 (15)
C3—C2—H2122.0 (13)N3—C6—N2122.31 (17)
C6—N3—H3B123.9 (15)N3—C6—C3119.28 (16)
C6—N3—H3A116.9 (16)N2—C6—C3118.41 (16)
H3B—N3—H3A119 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N1i0.88 (2)2.22 (2)3.058 (2)160 (2)
N3—H3A···Cl10.93 (2)2.19 (2)3.100 (2)167 (2)
N2—H2B···Cl10.83 (2)2.79 (2)3.476 (2)142 (2)
N3—H3B···Cl1ii0.89 (2)2.41 (2)3.270 (2)161 (2)
C5—H5···Cl1iii0.90 (2)2.68 (2)3.556 (2)166 (2)
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x+1/2, y−1/2, z; (iii) x, −y+3/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °)
top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N1i0.88 (2)2.22 (2)3.058 (2)160 (2)
N3—H3A···Cl10.93 (2)2.19 (2)3.100 (2)167 (2)
N2—H2B···Cl10.83 (2)2.79 (2)3.476 (2)142 (2)
N3—H3B···Cl1ii0.89 (2)2.41 (2)3.270 (2)161 (2)
C5—H5···Cl1iii0.90 (2)2.68 (2)3.556 (2)166 (2)
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x+1/2, y−1/2, z; (iii) x, −y+3/2, z−1/2.
references
References top

Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Chudinov, M. V., Konstantinova, I. D., Ryzhova, O. I., Esipov, R. S., Yurkevich, A. M., Shvets, V. I. & Miroshnikov, A. I. (2005). Pharm. Chem. J. 39, 212–215.

Kamei, K., Maeda, N., Katsuragi-Ogino, R., Koyama, M., Nakajima, M., Tatsuoka, T., Ohno, T. & Inoue, T. (2005). Bioorg. Med. Chem. Lett. 15, 2990–2993.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.