4-Carboxy­pyridazin-1-ium chloride

Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536808022319

organic compounds

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Volume 64| Part 8| August 2008| Page o1553

doi:10.1107/S1600536808022319

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4-Carboxypyridazin-1-ium chloride

Wojciech Starosta ^a and Janusz Leciejewicz ^a ^*

^aInstitute of Nuclear Chemistry and Technology, ulica Dorodna 16, 03-195 Warszawa, Poland
^*Correspondence e-mail: jlec@ichtj.waw.pl

(Received 4 July 2008; accepted 16 July 2008; online 19 July 2008)

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.

Related literature

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

Crystal data

C₅H₅N₂O₂⁺·Cl⁻
M_r = 160.56
Monoclinic, P 2₁ /n
a = 6.8505 (14) Å
b = 6.5905 (13) Å
c = 14.561 (3) Å
β = 97.65 (3)°
V = 651.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.52 mm⁻¹
T = 293 (2) K
0.39 × 0.16 × 0.12 mm

Data collection

Kuma KM-4 four-circle diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ) T_min = 0.942, T_max = 0.952
2062 measured reflections
1917 independent reflections
1318 reflections with I > 2σ(I)
R_int = 0.024
3 standard reflections every 200 reflections intensity decay: 1.1%

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.104
S = 1.03
1917 reflections
99 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯Cl1	0.91 (3)	2.05 (3)	2.9464 (14)	169 (2)
N1—H1⋯Cl1ⁱ	0.92 (3)	2.15 (3)	3.0373 (15)	160 (2)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: KM-4 Software (Kuma, 1996 $[Kuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland.]$ ); cell refinement: KM-4 Software; data reduction: DATAPROC (Kuma, 2001 $[Kuma (2001). DATAPROC. Kuma Diffraction Ltd, Wrocław, Poland.]$ ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808022319/rk2101sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808022319/rk2101Isup2.hkl

checkCIF report

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.

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

	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.
	Fig. 2. The structure packing diagram of I.

4-Carboxypyridazin-1-ium chloride top

Crystal data top

C₅H₅N₂O₂⁺·Cl⁻	F(000) = 328
M_r = 160.56	D_x = 1.637 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.8505 (14) Å	Cell parameters from 6 reflections
b = 6.5905 (13) Å	θ = 6–15°
c = 14.561 (3) Å	µ = 0.52 mm⁻¹
β = 97.65 (3)°	T = 293 K
V = 651.6 (2) Å³	Block, colourless
Z = 4	0.39 × 0.16 × 0.12 mm

Data collection top

Kuma KM-4 four-circle diffractometer	1318 reflections with I > 2σ(I)
Radiation source: Fine–focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 30.1°, θ_min = 2.8°
Profile data from ω/2θ scans	h = −9→0
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = 0→9
T_min = 0.942, T_max = 0.952	l = −20→20
2062 measured reflections	3 standard reflections every 200 reflections
1917 independent reflections	intensity decay: 1.2%

Refinement top

Refinement on F²	Primary atom site location: Direct
Least-squares matrix: Full	Secondary atom site location: Difmap
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: Geom
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0577P)² + 0.1527P] where P = (F_o² + 2F_c²)/3
1917 reflections	(Δ/σ)_max = 0.001
99 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₅H₅N₂O₂⁺·Cl⁻	V = 651.6 (2) Å³
M_r = 160.56	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.8505 (14) Å	µ = 0.52 mm⁻¹
b = 6.5905 (13) Å	T = 293 K
c = 14.561 (3) Å	0.39 × 0.16 × 0.12 mm
β = 97.65 (3)°

Data collection top

Kuma KM-4 four-circle diffractometer	1318 reflections with I > 2σ(I)
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	R_int = 0.024
T_min = 0.942, T_max = 0.952	3 standard reflections every 200 reflections
2062 measured reflections	intensity decay: 1.2%
1917 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.36 e Å⁻³
1917 reflections	Δρ_min = −0.21 e Å⁻³
99 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.61082 (6)	0.18289 (6)	0.39362 (3)	0.03696 (13)
O1	0.8041 (2)	0.6663 (2)	0.46266 (8)	0.0485 (3)
C3	0.8870 (3)	0.9337 (3)	0.61752 (11)	0.0382 (4)
H3	0.8395	0.9943	0.5613	0.046*
C4	0.8811 (2)	0.7225 (2)	0.62339 (10)	0.0296 (3)
O2	0.7273 (2)	0.4276 (2)	0.56133 (8)	0.0414 (3)
C7	0.7988 (2)	0.6028 (3)	0.53974 (10)	0.0330 (3)
C5	0.9550 (2)	0.6321 (2)	0.70515 (11)	0.0337 (3)
H5	0.9548	0.4918	0.7120	0.040*
N2	0.9559 (2)	1.0516 (2)	0.68707 (10)	0.0414 (3)
C6	1.0306 (3)	0.7589 (3)	0.77771 (11)	0.0376 (4)
H6	1.0841	0.7045	0.8345	0.045*
N1	1.0257 (2)	0.9555 (2)	0.76522 (10)	0.0368 (3)
H1	1.063 (3)	1.042 (4)	0.8143 (17)	0.063 (7)*
H2	0.675 (4)	0.358 (4)	0.5097 (19)	0.069 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0472 (2)	0.02641 (19)	0.0353 (2)	0.00189 (16)	−0.00212 (15)	−0.00355 (14)
O1	0.0698 (9)	0.0472 (8)	0.0264 (6)	0.0011 (7)	−0.0010 (5)	0.0038 (5)
C3	0.0507 (10)	0.0319 (8)	0.0309 (7)	0.0058 (7)	0.0017 (7)	0.0058 (6)
C4	0.0313 (7)	0.0310 (7)	0.0259 (6)	0.0027 (6)	0.0021 (5)	0.0015 (5)
O2	0.0567 (8)	0.0354 (6)	0.0303 (6)	−0.0046 (6)	−0.0010 (5)	−0.0028 (5)
C7	0.0371 (8)	0.0336 (8)	0.0267 (7)	0.0064 (6)	−0.0017 (6)	0.0005 (6)
C5	0.0406 (8)	0.0291 (7)	0.0295 (7)	0.0003 (6)	−0.0025 (6)	0.0030 (5)
N2	0.0554 (9)	0.0296 (7)	0.0386 (7)	0.0022 (7)	0.0041 (6)	0.0022 (5)
C6	0.0463 (9)	0.0349 (8)	0.0288 (7)	−0.0010 (7)	−0.0045 (6)	0.0028 (6)
N1	0.0443 (8)	0.0340 (7)	0.0315 (6)	−0.0034 (6)	0.0023 (5)	−0.0034 (5)

Geometric parameters (Å, º) top

O1—C7	1.203 (2)	O2—H2	0.91 (3)
C3—N2	1.313 (2)	C5—C6	1.392 (2)
C3—C4	1.395 (2)	C5—H5	0.9300
C3—H3	0.9300	N2—N1	1.334 (2)
C4—C5	1.367 (2)	C6—N1	1.308 (2)
C4—C7	1.497 (2)	C6—H6	0.9300
O2—C7	1.309 (2)	N1—H1	0.92 (3)

N2—C3—C4	123.60 (15)	C4—C5—C6	117.17 (16)
N2—C3—H3	118.2	C4—C5—H5	121.4
C4—C3—H3	118.2	C6—C5—H5	121.4
C5—C4—C3	118.55 (15)	C3—N2—N1	115.32 (14)
C5—C4—C7	122.31 (15)	N1—C6—C5	119.27 (15)
C3—C4—C7	119.12 (14)	N1—C6—H6	120.4
C7—O2—H2	111.4 (17)	C5—C6—H6	120.4
O1—C7—O2	126.14 (16)	C6—N1—N2	126.06 (15)
O1—C7—C4	121.39 (16)	C6—N1—H1	120.2 (16)
O2—C7—C4	112.47 (13)	N2—N1—H1	113.5 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···Cl1	0.91 (3)	2.05 (3)	2.9464 (14)	169 (2)
N1—H1···Cl1ⁱ	0.92 (3)	2.15 (3)	3.0373 (15)	160 (2)

Symmetry code: (i) x+1/2, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₅H₅N₂O₂⁺·Cl⁻
M_r	160.56
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.8505 (14), 6.5905 (13), 14.561 (3)
β (°)	97.65 (3)
V (Å³)	651.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.52
Crystal size (mm)	0.39 × 0.16 × 0.12

Data collection
Diffractometer	Kuma KM-4 four-circle diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.942, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	2062, 1917, 1318
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.104, 1.03
No. of reflections	1917
No. of parameters	99
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.21

Computer programs: KM-4 Software (Kuma, 1996), DATAPROC (Kuma, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···Cl1	0.91 (3)	2.05 (3)	2.9464 (14)	169 (2)
N1—H1···Cl1ⁱ	0.92 (3)	2.15 (3)	3.0373 (15)	160 (2)

Symmetry code: (i) x+1/2, −y+3/2, z+1/2.

References

Gryz, M., Starosta, W., Ptasiewicz-Bąk, H. & Leciejewicz, J. (2003). J. Coord. Chem. 56, 1505–1511. Web of Science CSD CrossRef CAS Google Scholar
Kuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland. Google Scholar
Kuma (2001). DATAPROC. Kuma Diffraction Ltd, Wrocław, Poland. Google Scholar
Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Takusagawa, F., Higuchi, T. & Shimada, A. (1974). Bull. Chem. Soc. Jpn, 47, 1409–1414. CrossRef CAS Web of Science Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1553

doi:10.1107/S1600536808022319

Open

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