Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048799/tk2198sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048799/tk2198Isup2.hkl |
CCDC reference: 667336
Key indicators
- Single-crystal X-ray study
- T = 123 K
- Mean (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
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).
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).
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).
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).
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.
C4H5ClN3+·Cl− | Z = 2 |
Mr = 166.01 | F(000) = 168 |
Triclinic, P1 | Dx = 1.612 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.1543 (5) Å | Cell parameters from 1225 reflections |
b = 6.4278 (5) Å | θ = 2.3–25.2° |
c = 9.0298 (9) Å | µ = 0.86 mm−1 |
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 |
Bruker SMART CCD area-detector diffractometer | 1225 independent reflections |
Radiation source: fine-focus sealed tube | 1162 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
φ and ω scans | θmax = 25.2°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −7→7 |
Tmin = 0.770, Tmax = 0.841 | k = −7→7 |
3627 measured reflections | l = −10→10 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H-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 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
C4H5ClN3+·Cl− | γ = 84.015 (8)° |
Mr = 166.01 | V = 342.09 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.1543 (5) Å | Mo Kα radiation |
b = 6.4278 (5) Å | µ = 0.86 mm−1 |
c = 9.0298 (9) Å | T = 123 K |
α = 81.763 (4)° | 0.35 × 0.25 × 0.20 mm |
β = 75.980 (5)° |
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 = 0.841 | Rint = 0.015 |
3627 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.19 | Δρmax = 0.28 e Å−3 |
1225 reflections | Δρmin = −0.48 e Å−3 |
82 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | −0.37244 (8) | 0.20568 (10) | 0.53712 (6) | 0.0609 (2) | |
N3 | −0.0723 (2) | 0.0886 (2) | 0.69127 (18) | 0.0426 (4) | |
N2 | 0.0734 (2) | 0.1271 (2) | 0.77190 (17) | 0.0410 (3) | |
H4 | 0.1547 | 0.0141 | 0.8043 | 0.049* | |
N1 | 0.2510 (3) | 0.3270 (3) | 0.89096 (18) | 0.0502 (4) | |
H1A | 0.3293 | 0.2126 | 0.9202 | 0.060* | |
H1B | 0.2716 | 0.4495 | 0.9162 | 0.060* | |
C3 | −0.1790 (3) | 0.4590 (3) | 0.6775 (2) | 0.0423 (4) | |
H3 | −0.2729 | 0.5729 | 0.6426 | 0.051* | |
C2 | −0.0307 (3) | 0.4902 (3) | 0.7577 (2) | 0.0413 (4) | |
H2 | −0.0156 | 0.6276 | 0.7795 | 0.050* | |
C1 | 0.1033 (3) | 0.3146 (3) | 0.80952 (18) | 0.0367 (4) | |
C4 | −0.1916 (3) | 0.2518 (3) | 0.64622 (19) | 0.0408 (4) | |
Cl2 | 0.62082 (8) | 0.21076 (7) | 0.10075 (5) | 0.0490 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0485 (3) | 0.0797 (4) | 0.0665 (4) | −0.0034 (3) | −0.0288 (2) | −0.0225 (3) |
N3 | 0.0379 (7) | 0.0423 (8) | 0.0525 (8) | −0.0043 (6) | −0.0144 (6) | −0.0145 (7) |
N2 | 0.0412 (7) | 0.0329 (7) | 0.0528 (8) | 0.0016 (6) | −0.0182 (6) | −0.0085 (6) |
N1 | 0.0533 (9) | 0.0475 (9) | 0.0591 (10) | −0.0018 (7) | −0.0276 (8) | −0.0139 (7) |
C3 | 0.0426 (9) | 0.0421 (10) | 0.0417 (9) | 0.0055 (7) | −0.0120 (7) | −0.0052 (7) |
C2 | 0.0495 (9) | 0.0336 (9) | 0.0416 (8) | −0.0009 (7) | −0.0099 (7) | −0.0100 (7) |
C1 | 0.0362 (8) | 0.0376 (9) | 0.0376 (8) | −0.0028 (7) | −0.0089 (6) | −0.0079 (7) |
C4 | 0.0340 (8) | 0.0503 (10) | 0.0407 (8) | −0.0035 (7) | −0.0099 (7) | −0.0119 (7) |
Cl2 | 0.0535 (3) | 0.0369 (3) | 0.0631 (3) | 0.0026 (2) | −0.0287 (2) | −0.0058 (2) |
Cl1—C4 | 1.7265 (17) | N1—H1B | 0.8800 |
N3—C4 | 1.292 (2) | C3—C2 | 1.341 (3) |
N3—N2 | 1.345 (2) | C3—C4 | 1.414 (3) |
N2—C1 | 1.340 (2) | C3—H3 | 0.9500 |
N2—H4 | 0.8930 | C2—C1 | 1.419 (2) |
N1—C1 | 1.315 (2) | C2—H2 | 0.9500 |
N1—H1A | 0.8801 | ||
C4—N3—N2 | 115.16 (15) | C3—C2—C1 | 118.89 (16) |
C1—N2—N3 | 126.48 (15) | C3—C2—H2 | 120.6 |
C1—N2—H4 | 118.2 | C1—C2—H2 | 120.6 |
N3—N2—H4 | 115.3 | N1—C1—N2 | 119.45 (16) |
C1—N1—H1A | 120.0 | N1—C1—C2 | 123.89 (16) |
C1—N1—H1B | 120.0 | N2—C1—C2 | 116.66 (15) |
H1A—N1—H1B | 120.0 | N3—C4—C3 | 124.68 (16) |
C2—C3—C4 | 118.11 (16) | N3—C4—Cl1 | 115.56 (13) |
C2—C3—H3 | 120.9 | C3—C4—Cl1 | 119.74 (14) |
C4—C3—H3 | 120.9 | ||
C4—N3—N2—C1 | 0.6 (3) | C3—C2—C1—N2 | 0.9 (2) |
C4—C3—C2—C1 | −1.0 (3) | N2—N3—C4—C3 | −0.7 (2) |
N3—N2—C1—N1 | 179.13 (15) | N2—N3—C4—Cl1 | 177.91 (11) |
N3—N2—C1—C2 | −0.7 (3) | C2—C3—C4—N3 | 1.0 (3) |
C3—C2—C1—N1 | −178.90 (16) | C2—C3—C4—Cl1 | −177.56 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H4···Cl2i | 0.89 | 2.13 | 3.0099 (15) | 169 |
N1—H1A···Cl2ii | 0.88 | 2.70 | 3.2642 (16) | 123 |
N1—H1A···Cl2i | 0.88 | 2.74 | 3.4585 (17) | 140 |
N1—H1B···Cl2iii | 0.88 | 2.32 | 3.1681 (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 formula | C4H5ClN3+·Cl− |
Mr | 166.01 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 342.09 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.86 |
Crystal size (mm) | 0.35 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.770, 0.841 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3627, 1225, 1162 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.090, 1.19 |
No. of reflections | 1225 |
No. of parameters | 82 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.48 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXTL (Bruker, 2002.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H4···Cl2i | 0.89 | 2.13 | 3.0099 (15) | 169 |
N1—H1A···Cl2ii | 0.88 | 2.70 | 3.2642 (16) | 123 |
N1—H1A···Cl2i | 0.88 | 2.74 | 3.4585 (17) | 140 |
N1—H1B···Cl2iii | 0.88 | 2.32 | 3.1681 (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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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).