supplementary materials


rk2101 scheme

Acta Cryst. (2008). E64, o1553    [ doi:10.1107/S1600536808022319 ]

4-Carboxypyridazin-1-ium chloride

W. Starosta and J. Leciejewicz

Abstract top

The structure of the title compound, C5H5N2O2+·Cl-, is composed of chloride anions and 4-carboxypyridazin-1-ium cations. Chloride anions bridge the cations via O-H...Cl and N-H...Cl hydrogen bonds to form ribbons. The latter, linked by van der Waals forces with lengths in the range 3.254 (2)-3.497 (2) Å, form coplanar layers. Very weak interactions operate also between adjacent layers, as indicated by their spacing of 3.339 (1) Å.

Comment top

The structure of the title compound (C5H5N2O2)+ Cl-, I, is built from chloride anions and heterocycle cations. Chloride anions bridge the cations via hydrogen bonds O2—H2···Cl1 2.05 (3)Å and N1—H1···Cl1i 2.15 (3)Å to form ribbons; symmetry code: (i) x+1/2, -y+3/2, z+1/2. The ribbons linked by van der Waals forces with lengths in the range from 3.254 (2) to 3.497 (2)Å make coplanar layers. The shortest distance between pyridazine rings belonging to adjacent layers is 3.339 (1)Å. The pyridazine ring are planar (r.m.s. 0.0060Å) and formes with the carboxylate group (C7/O1/O2) dihedral angle 27.7 (1)°. Bond lengths and bond angles within the cation agree well with those reported in the structure of pyridazine–3–carboxylic acid hydrochloride (Gryz et al., 2003).

Related literature top

For the crystal structure of pyridazine-3-carboxylic acid hydrochloride, see: Gryz et al. (2003). For a report of molecular layers in the structure of pyrazine-2-carboxylic acid, see: Takusagawa et al. (1974).

Experimental top

Single crystals of I were obtained by recrystallization of pyridazine–4–carboxylic acid (ALDRICH) from warm 1M solution of hydrochloric acid. Attempts to recrystallize from water and alcohols yielded specimens unsuitable for collecting X–ray data.

Refinement top

All H atoms bonded with C atoms were positioned geometrically and refined in riding model approximation with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C). The H atoms connected with N and O atoms were located in difference Fourier map and refined isotropically.

Computing details top

Data collection: KM-4 Software (Kuma, 1996); cell refinement: KM-4 Software (Kuma, 1996); data reduction: DATAPROC (Kuma, 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. A molecular structure of I with the atom labelling scheme. The displacement ellipsoids are drawn at 50% probability level. H atoms are presented as a small spheres of arbitrary radius.
[Figure 2] Fig. 2. The structure packing diagram of I.
4-Carboxypyridazin-1-ium chloride top
Crystal data top
C5H5N2O2+·ClF000 = 328
Mr = 160.56Dx = 1.637 Mg m3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
a = 6.8505 (14) ÅCell parameters from 6 reflections
b = 6.5905 (13) Åθ = 6–15º
c = 14.561 (3) ŵ = 0.52 mm1
β = 97.65 (3)ºT = 293 (2) K
V = 651.6 (2) Å3Block, colourless
Z = 40.39 × 0.16 × 0.12 mm
Data collection top
Kuma KM-4 four-circle
diffractometer
Rint = 0.024
Radiation source: Fine–focus sealed tubeθmax = 30.1º
Monochromator: Graphiteθmin = 2.8º
T = 293(2) Kh = 9→0
Profile data from ω/2θ scansk = 0→9
Absorption correction: Analytical
(CrysAlis RED; Oxford Diffraction, 2008)
l = 20→20
Tmin = 0.942, Tmax = 0.9523 standard reflections
2062 measured reflections every 200 reflections
1917 independent reflections intensity decay: 1.2%
1318 reflections with I > 2σ(I)
Refinement top
Refinement on F2Secondary atom site location: Difmap
Least-squares matrix: FullHydrogen site location: Geom
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.104  w = 1/[σ2(Fo2) + (0.0577P)2 + 0.1527P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
1917 reflectionsΔρmax = 0.36 e Å3
99 parametersΔρmin = 0.21 e Å3
Primary atom site location: DirectExtinction correction: None
Crystal data top
C5H5N2O2+·ClV = 651.6 (2) Å3
Mr = 160.56Z = 4
Monoclinic, P21/nMo Kα
a = 6.8505 (14) ŵ = 0.52 mm1
b = 6.5905 (13) ÅT = 293 (2) K
c = 14.561 (3) Å0.39 × 0.16 × 0.12 mm
β = 97.65 (3)º
Data collection top
Kuma KM-4 four-circle
diffractometer
1318 reflections with I > 2σ(I)
Absorption correction: Analytical
(CrysAlis RED; Oxford Diffraction, 2008)
Rint = 0.024
Tmin = 0.942, Tmax = 0.9523 standard reflections
2062 measured reflections every 200 reflections
1917 independent reflections intensity decay: 1.2%
Refinement top
R[F2 > 2σ(F2)] = 0.03099 parameters
wR(F2) = 0.104H atoms treated by a mixture of
independent and constrained refinement
S = 1.03Δρmax = 0.36 e Å3
1917 reflectionsΔρmin = 0.21 e Å3
Special details top

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 F^2^ against ALL reflections. The weighted R–factor wR and goodness of fit S are based on F^2^, conventional R–factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R–factors(gt) etc. and is not relevant to the choice of reflections for refinement. R–factors based on F^2^ 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
Cl10.61082 (6)0.18289 (6)0.39362 (3)0.03696 (13)
O10.8041 (2)0.6663 (2)0.46266 (8)0.0485 (3)
C30.8870 (3)0.9337 (3)0.61752 (11)0.0382 (4)
H30.83950.99430.56130.046*
C40.8811 (2)0.7225 (2)0.62339 (10)0.0296 (3)
O20.7273 (2)0.4276 (2)0.56133 (8)0.0414 (3)
C70.7988 (2)0.6028 (3)0.53974 (10)0.0330 (3)
C50.9550 (2)0.6321 (2)0.70515 (11)0.0337 (3)
H50.95480.49180.71200.040*
N20.9559 (2)1.0516 (2)0.68707 (10)0.0414 (3)
C61.0306 (3)0.7589 (3)0.77771 (11)0.0376 (4)
H61.08410.70450.83450.045*
N11.0257 (2)0.9555 (2)0.76522 (10)0.0368 (3)
H11.063 (3)1.042 (4)0.8143 (17)0.063 (7)*
H20.675 (4)0.358 (4)0.5097 (19)0.069 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0472 (2)0.02641 (19)0.0353 (2)0.00189 (16)0.00212 (15)0.00355 (14)
O10.0698 (9)0.0472 (8)0.0264 (6)0.0011 (7)0.0010 (5)0.0038 (5)
C30.0507 (10)0.0319 (8)0.0309 (7)0.0058 (7)0.0017 (7)0.0058 (6)
C40.0313 (7)0.0310 (7)0.0259 (6)0.0027 (6)0.0021 (5)0.0015 (5)
O20.0567 (8)0.0354 (6)0.0303 (6)0.0046 (6)0.0010 (5)0.0028 (5)
C70.0371 (8)0.0336 (8)0.0267 (7)0.0064 (6)0.0017 (6)0.0005 (6)
C50.0406 (8)0.0291 (7)0.0295 (7)0.0003 (6)0.0025 (6)0.0030 (5)
N20.0554 (9)0.0296 (7)0.0386 (7)0.0022 (7)0.0041 (6)0.0022 (5)
C60.0463 (9)0.0349 (8)0.0288 (7)0.0010 (7)0.0045 (6)0.0028 (6)
N10.0443 (8)0.0340 (7)0.0315 (6)0.0034 (6)0.0023 (5)0.0034 (5)
Geometric parameters (Å, °) top
O1—C71.203 (2)O2—H20.91 (3)
C3—N21.313 (2)C5—C61.392 (2)
C3—C41.395 (2)C5—H50.9300
C3—H30.9300N2—N11.334 (2)
C4—C51.367 (2)C6—N11.308 (2)
C4—C71.497 (2)C6—H60.9300
O2—C71.309 (2)N1—H10.92 (3)
N2—C3—C4123.60 (15)C4—C5—C6117.17 (16)
N2—C3—H3118.2C4—C5—H5121.4
C4—C3—H3118.2C6—C5—H5121.4
C5—C4—C3118.55 (15)C3—N2—N1115.32 (14)
C5—C4—C7122.31 (15)N1—C6—C5119.27 (15)
C3—C4—C7119.12 (14)N1—C6—H6120.4
C7—O2—H2111.4 (17)C5—C6—H6120.4
O1—C7—O2126.14 (16)C6—N1—N2126.06 (15)
O1—C7—C4121.39 (16)C6—N1—H1120.2 (16)
O2—C7—C4112.47 (13)N2—N1—H1113.5 (16)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···Cl10.91 (3)2.05 (3)2.9464 (14)169 (2)
N1—H1···Cl1i0.92 (3)2.15 (3)3.0373 (15)160 (2)
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °)
top
D—H···AD—HH···AD···AD—H···A
O2—H2···Cl10.91 (3)2.05 (3)2.9464 (14)169 (2)
N1—H1···Cl1i0.92 (3)2.15 (3)3.0373 (15)160 (2)
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2.
references
References top

Gryz, M., Starosta, W., Ptasiewicz-Bąk, H. & Leciejewicz, J. (2003). J. Coord. Chem. 56, 1505–1511.

Kuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland.

Kuma (2001). DATAPROC. Kuma Diffraction Ltd, Wrocław, Poland.

Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England

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

Takusagawa, F., Higuchi, T. & Shimada, A. (1974). Bull. Chem. Soc. Jpn, 47, 1409–1414.