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In the title compound, C4H5ClN3+·Cl, the cation is effectively planar and is protonated at the N atom adjacent to the amino group. Four different N—H...Cl hydrogen bonds serve to connect the constituent ions into supra­molecular double chains running parallel to the b axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048799/tk2198sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048799/tk2198Isup2.hkl
Contains datablock I

CCDC reference: 667336

Key indicators

  • Single-crystal X-ray study
  • T = 123 K
  • Mean [sigma](C-C)= 0.003 Å
  • R factor = 0.033
  • wR factor = 0.090
  • Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found


No errors found in this datablock

Comment top

Pyridazines have demonstrated versatile biological activities, for example, as anti-bacterial (Ishida et al., 1994), anti-depressant (Pitarch et al., 1974), and anti-hypertensive (Herter et al., 1989) agents. A search of the Cambridge Structural Database (CSD, Version 5.28, May 2007; Allen, 2002) reveals that there are 639 crystal structures containing the pyridazine moiety. Pyridazines are also useful in the design of functional synthetic oligomers and polymers, and 3,6-diaminopyridazine is used in the synthesis of related monomeric, dimeric and trimeric duplex molecular strands (Gong & Krische, 2005). Finally, 3-amino-6-chloropyridazine is an important precursor in the preparation of various pyridazine intermediates (Guery et al., 2001). Recently, the crystal structure of 3-amino-6-chloropyridazine was reported (Gao, 2007). Herein, the crystal structure of the title compound, [C4H5ClN3]Cl (I), is described.

In the cation, the chloro and amino groups are coplanar with the pyridazine ring, deviating within ±0.0220 (8) Å. Protonation occurs at the N2 atom adjacent to the the amino group. The N2—N3 distance is 1.345 (2) Å, close to the reported data for 3-amino-6-chloropyridazine, i.e. 1.355 (2) Å (Gao, 2007).

A series of intermolecular N—H···Cl hydrogen bonds (Table 1) links molecules into a double chain that runs parallel to the b axis (Fig.2).

Related literature top

For synthesis, see: Steck et al. (1954). For general background, see: Ishida et al. (1994); Pitarch et al. (1974); Herter et al. (1989); Guery et al. (2001). For related structures, see: Gong & Krische (2005); Gao (2007).

For related literature, see: Allen (2002).

Experimental top

3-Amino-6-chloropyridazine was prepared according to the literature method (Steck et al., 1954). Crystals suitable for X-ray analysis were obtained by slow evaporation of an isoproanol solution held at room temperature (m.p. 490–492 K).

Refinement top

H atoms were included in the riding model approximation with N—H = 0.88 or 0.89 Å and C—H = 0.95 Å, and with Uiso(H) = 1.2–1.5Ueq(N, C).

Structure description top

Pyridazines have demonstrated versatile biological activities, for example, as anti-bacterial (Ishida et al., 1994), anti-depressant (Pitarch et al., 1974), and anti-hypertensive (Herter et al., 1989) agents. A search of the Cambridge Structural Database (CSD, Version 5.28, May 2007; Allen, 2002) reveals that there are 639 crystal structures containing the pyridazine moiety. Pyridazines are also useful in the design of functional synthetic oligomers and polymers, and 3,6-diaminopyridazine is used in the synthesis of related monomeric, dimeric and trimeric duplex molecular strands (Gong & Krische, 2005). Finally, 3-amino-6-chloropyridazine is an important precursor in the preparation of various pyridazine intermediates (Guery et al., 2001). Recently, the crystal structure of 3-amino-6-chloropyridazine was reported (Gao, 2007). Herein, the crystal structure of the title compound, [C4H5ClN3]Cl (I), is described.

In the cation, the chloro and amino groups are coplanar with the pyridazine ring, deviating within ±0.0220 (8) Å. Protonation occurs at the N2 atom adjacent to the the amino group. The N2—N3 distance is 1.345 (2) Å, close to the reported data for 3-amino-6-chloropyridazine, i.e. 1.355 (2) Å (Gao, 2007).

A series of intermolecular N—H···Cl hydrogen bonds (Table 1) links molecules into a double chain that runs parallel to the b axis (Fig.2).

For synthesis, see: Steck et al. (1954). For general background, see: Ishida et al. (1994); Pitarch et al. (1974); Herter et al. (1989); Guery et al. (2001). For related structures, see: Gong & Krische (2005); Gao (2007).

For related literature, see: Allen (2002).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXL97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL (Bruker, 2002.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I), showing 20% probability displacement ellipsoids and the atomic numbering.
[Figure 2] Fig. 2. The crystal packing in (I), viewed approximately down the a axis. Dashed lines indicate intermolecular N—H···Cl hydrogen bonds.
3-Amino-6-chloropyridazinium chloride top
Crystal data top
C4H5ClN3+·ClZ = 2
Mr = 166.01F(000) = 168
Triclinic, P1Dx = 1.612 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.1543 (5) ÅCell parameters from 1225 reflections
b = 6.4278 (5) Åθ = 2.3–25.2°
c = 9.0298 (9) ŵ = 0.86 mm1
α = 81.763 (4)°T = 123 K
β = 75.980 (5)°Blocks, colorless
γ = 84.015 (8)°0.35 × 0.25 × 0.20 mm
V = 342.09 (5) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
1225 independent reflections
Radiation source: fine-focus sealed tube1162 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
φ and ω scansθmax = 25.2°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 77
Tmin = 0.770, Tmax = 0.841k = 77
3627 measured reflectionsl = 1010
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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-atom parameters constrained
S = 1.19 w = 1/[σ2(Fo2) + (0.0497P)2 + 0.0792P]
where P = (Fo2 + 2Fc2)/3
1225 reflections(Δ/σ)max < 0.001
82 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.48 e Å3
Crystal data top
C4H5ClN3+·Clγ = 84.015 (8)°
Mr = 166.01V = 342.09 (5) Å3
Triclinic, P1Z = 2
a = 6.1543 (5) ÅMo Kα radiation
b = 6.4278 (5) ŵ = 0.86 mm1
c = 9.0298 (9) ÅT = 123 K
α = 81.763 (4)°0.35 × 0.25 × 0.20 mm
β = 75.980 (5)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1225 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
1162 reflections with I > 2σ(I)
Tmin = 0.770, Tmax = 0.841Rint = 0.015
3627 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.090H-atom parameters constrained
S = 1.19Δρmax = 0.28 e Å3
1225 reflectionsΔρmin = 0.48 e Å3
82 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
Cl10.37244 (8)0.20568 (10)0.53712 (6)0.0609 (2)
N30.0723 (2)0.0886 (2)0.69127 (18)0.0426 (4)
N20.0734 (2)0.1271 (2)0.77190 (17)0.0410 (3)
H40.15470.01410.80430.049*
N10.2510 (3)0.3270 (3)0.89096 (18)0.0502 (4)
H1A0.32930.21260.92020.060*
H1B0.27160.44950.91620.060*
C30.1790 (3)0.4590 (3)0.6775 (2)0.0423 (4)
H30.27290.57290.64260.051*
C20.0307 (3)0.4902 (3)0.7577 (2)0.0413 (4)
H20.01560.62760.77950.050*
C10.1033 (3)0.3146 (3)0.80952 (18)0.0367 (4)
C40.1916 (3)0.2518 (3)0.64622 (19)0.0408 (4)
Cl20.62082 (8)0.21076 (7)0.10075 (5)0.0490 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0485 (3)0.0797 (4)0.0665 (4)0.0034 (3)0.0288 (2)0.0225 (3)
N30.0379 (7)0.0423 (8)0.0525 (8)0.0043 (6)0.0144 (6)0.0145 (7)
N20.0412 (7)0.0329 (7)0.0528 (8)0.0016 (6)0.0182 (6)0.0085 (6)
N10.0533 (9)0.0475 (9)0.0591 (10)0.0018 (7)0.0276 (8)0.0139 (7)
C30.0426 (9)0.0421 (10)0.0417 (9)0.0055 (7)0.0120 (7)0.0052 (7)
C20.0495 (9)0.0336 (9)0.0416 (8)0.0009 (7)0.0099 (7)0.0100 (7)
C10.0362 (8)0.0376 (9)0.0376 (8)0.0028 (7)0.0089 (6)0.0079 (7)
C40.0340 (8)0.0503 (10)0.0407 (8)0.0035 (7)0.0099 (7)0.0119 (7)
Cl20.0535 (3)0.0369 (3)0.0631 (3)0.0026 (2)0.0287 (2)0.0058 (2)
Geometric parameters (Å, º) top
Cl1—C41.7265 (17)N1—H1B0.8800
N3—C41.292 (2)C3—C21.341 (3)
N3—N21.345 (2)C3—C41.414 (3)
N2—C11.340 (2)C3—H30.9500
N2—H40.8930C2—C11.419 (2)
N1—C11.315 (2)C2—H20.9500
N1—H1A0.8801
C4—N3—N2115.16 (15)C3—C2—C1118.89 (16)
C1—N2—N3126.48 (15)C3—C2—H2120.6
C1—N2—H4118.2C1—C2—H2120.6
N3—N2—H4115.3N1—C1—N2119.45 (16)
C1—N1—H1A120.0N1—C1—C2123.89 (16)
C1—N1—H1B120.0N2—C1—C2116.66 (15)
H1A—N1—H1B120.0N3—C4—C3124.68 (16)
C2—C3—C4118.11 (16)N3—C4—Cl1115.56 (13)
C2—C3—H3120.9C3—C4—Cl1119.74 (14)
C4—C3—H3120.9
C4—N3—N2—C10.6 (3)C3—C2—C1—N20.9 (2)
C4—C3—C2—C11.0 (3)N2—N3—C4—C30.7 (2)
N3—N2—C1—N1179.13 (15)N2—N3—C4—Cl1177.91 (11)
N3—N2—C1—C20.7 (3)C2—C3—C4—N31.0 (3)
C3—C2—C1—N1178.90 (16)C2—C3—C4—Cl1177.56 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H4···Cl2i0.892.133.0099 (15)169
N1—H1A···Cl2ii0.882.703.2642 (16)123
N1—H1A···Cl2i0.882.743.4585 (17)140
N1—H1B···Cl2iii0.882.323.1681 (17)162
Symmetry codes: (i) x+1, y, z+1; (ii) x, y, z+1; (iii) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC4H5ClN3+·Cl
Mr166.01
Crystal system, space groupTriclinic, P1
Temperature (K)123
a, b, c (Å)6.1543 (5), 6.4278 (5), 9.0298 (9)
α, β, γ (°)81.763 (4), 75.980 (5), 84.015 (8)
V3)342.09 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.86
Crystal size (mm)0.35 × 0.25 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.770, 0.841
No. of measured, independent and
observed [I > 2σ(I)] reflections
3627, 1225, 1162
Rint0.015
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.090, 1.19
No. of reflections1225
No. of parameters82
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.48

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXTL (Bruker, 2002.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H4···Cl2i0.892.133.0099 (15)169
N1—H1A···Cl2ii0.882.703.2642 (16)123
N1—H1A···Cl2i0.882.743.4585 (17)140
N1—H1B···Cl2iii0.882.323.1681 (17)162
Symmetry codes: (i) x+1, y, z+1; (ii) x, y, z+1; (iii) x+1, y+1, z+1.
 

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