Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042481/ci2455sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042481/ci2455Isup2.hkl |
CCDC reference: 663692
Key indicators
- Single-crystal X-ray study
- T = 125 K
- Mean (C-C)= 0.002 Å
- R factor = 0.033
- wR factor = 0.088
- Data-to-parameter ratio = 16.8
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). For Cambridge Structural Database (CSD), see: Allen (2002).
The title compound was prepared according to the literature method (Steck et al., 1954). Crystals suitable for X-ray analysis were obtained by slow evaporation of a isoproanol solution at room temperature (m.p. 483–485 K).
H atoms were positioned geometrically (N—H = 0.86 Å and C—H = 0.93 Å) and refined using a riding model, with Uiso(H) = 1.2–1.5Ueq(C).
Pyridazines have demonstrated versatile biological activities, for example, antibacterial (Ishida et al., 1994), antidepressant (Pitarch et al., 1974) and antihypertensive (Herter et al., 1989) activities. A search of the Cambridge Structural Database (CSD, 2007 Release, Version 5.28; Allen, 2002) reveals that there are 639 crystal structures containing the pyridazine moiety. In the design of functional synthetic oligomers and ploymers, 3,6-diaminopyridazine is applied to the design of related monomeric, dimeric and trimeric duplex molecular strands (Gong et al., 2005). And in the preparation of various pyridazines, 3-amino-6-chloropyridazine is an important intermediate (Guery et al., 2001). We report here the crystal structure of the title compound.
In the title molecule (Fig. 1), the chloro and amino groups are coplanar with the pyridazine ring. Atoms N3 and Cl1 deviate from the pyridazine plane by 0.030 (1) and 0.019 (1) Å, respectively. The N1—N2 distance of 1.3548 (17) Å is slightly shorter than the N—N distance of 1.379 (2) Å reported by Gong et al. (2005).
The intermolecular N—H···N hydrogen bonds (Table 1) link the molecules into a two-dimensional network parallel to the (100) plane (Fig.2). The pyridazine rings of the inversion-related molecules at (x, y, z) and (-x, 1 - y, -z) are stacked with their centroids separated by a distance of 3.7597 (10) Å, indicating π-π interactions. In addition, C—Cl···π [Cl···pyridazine ring centroid = 3.6065 (10) Å] interactions also contribute to the stabilization of the structure.
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). For Cambridge Structural Database (CSD), see: Allen (2002).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL.
C4H4ClN3 | F(000) = 264 |
Mr = 129.55 | Dx = 1.609 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1227 reflections |
a = 7.5235 (14) Å | θ = 2.8–27.6° |
b = 6.5887 (11) Å | µ = 0.59 mm−1 |
c = 11.1748 (19) Å | T = 125 K |
β = 105.045 (10)° | Block, colourless |
V = 534.95 (16) Å3 | 0.50 × 0.50 × 0.40 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 1227 independent reflections |
Radiation source: fine-focus sealed tube | 1153 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
φ and ω scans | θmax = 27.6°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −8→9 |
Tmin = 0.756, Tmax = 0.794 | k = −8→8 |
5258 measured reflections | l = −14→12 |
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) = 0.088 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.047P)2 + 0.167P] where P = (Fo2 + 2Fc2)/3 |
1227 reflections | (Δ/σ)max = 0.001 |
73 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
C4H4ClN3 | V = 534.95 (16) Å3 |
Mr = 129.55 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.5235 (14) Å | µ = 0.59 mm−1 |
b = 6.5887 (11) Å | T = 125 K |
c = 11.1748 (19) Å | 0.50 × 0.50 × 0.40 mm |
β = 105.045 (10)° |
Bruker SMART CCD area-detector diffractometer | 1227 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1153 reflections with I > 2σ(I) |
Tmin = 0.756, Tmax = 0.794 | Rint = 0.015 |
5258 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.25 e Å−3 |
1227 reflections | Δρmin = −0.35 e Å−3 |
73 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 | 0.34908 (6) | 0.22748 (6) | 0.47446 (3) | 0.04506 (16) | |
N1 | 0.19326 (16) | 0.58112 (18) | 0.46416 (10) | 0.0322 (3) | |
C4 | 0.17199 (19) | 0.7781 (2) | 0.63301 (12) | 0.0303 (3) | |
N3 | 0.11738 (19) | 0.9525 (2) | 0.67524 (11) | 0.0439 (3) | |
H3A | 0.0622 | 1.0436 | 0.6238 | 0.053* | |
H3B | 0.1377 | 0.9727 | 0.7537 | 0.053* | |
C2 | 0.3197 (2) | 0.4557 (2) | 0.67021 (12) | 0.0353 (3) | |
H2 | 0.3804 | 0.3520 | 0.7212 | 0.042* | |
C3 | 0.26466 (19) | 0.6271 (2) | 0.71699 (11) | 0.0341 (3) | |
H3 | 0.2870 | 0.6455 | 0.8021 | 0.041* | |
C1 | 0.28026 (18) | 0.4428 (2) | 0.54031 (12) | 0.0301 (3) | |
N2 | 0.13712 (17) | 0.75340 (18) | 0.50956 (11) | 0.0330 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0612 (3) | 0.0370 (2) | 0.0391 (2) | 0.00197 (15) | 0.01685 (18) | −0.00858 (13) |
N1 | 0.0413 (6) | 0.0333 (6) | 0.0217 (5) | −0.0046 (5) | 0.0078 (4) | −0.0009 (4) |
C4 | 0.0343 (6) | 0.0328 (7) | 0.0236 (6) | −0.0024 (5) | 0.0068 (5) | 0.0002 (5) |
N3 | 0.0626 (8) | 0.0405 (7) | 0.0262 (6) | 0.0139 (6) | 0.0073 (5) | −0.0010 (5) |
C2 | 0.0442 (7) | 0.0359 (7) | 0.0244 (6) | 0.0042 (6) | 0.0064 (5) | 0.0048 (5) |
C3 | 0.0428 (7) | 0.0395 (7) | 0.0187 (5) | 0.0015 (6) | 0.0056 (5) | 0.0018 (5) |
C1 | 0.0360 (6) | 0.0301 (6) | 0.0251 (6) | −0.0046 (5) | 0.0097 (5) | −0.0026 (5) |
N2 | 0.0429 (6) | 0.0327 (6) | 0.0218 (5) | 0.0001 (4) | 0.0057 (5) | 0.0023 (4) |
Cl1—C1 | 1.7378 (14) | N3—H3A | 0.86 |
N1—C1 | 1.3015 (18) | N3—H3B | 0.86 |
N1—N2 | 1.3548 (17) | C2—C3 | 1.354 (2) |
C4—N2 | 1.3456 (17) | C2—C1 | 1.4067 (18) |
C4—N3 | 1.3460 (18) | C2—H2 | 0.93 |
C4—C3 | 1.4204 (19) | C3—H3 | 0.93 |
C1—N1—N2 | 119.64 (11) | C1—C2—H2 | 121.8 |
N2—C4—N3 | 117.82 (12) | C2—C3—C4 | 118.44 (12) |
N2—C4—C3 | 121.61 (12) | C2—C3—H3 | 120.8 |
N3—C4—C3 | 120.57 (12) | C4—C3—H3 | 120.8 |
C4—N3—H3A | 120.0 | N1—C1—C2 | 124.61 (13) |
C4—N3—H3B | 120.0 | N1—C1—Cl1 | 116.70 (10) |
H3A—N3—H3B | 120.0 | C2—C1—Cl1 | 118.69 (11) |
C3—C2—C1 | 116.44 (12) | C4—N2—N1 | 119.25 (11) |
C3—C2—H2 | 121.8 | ||
C1—C2—C3—C4 | 0.3 (2) | C3—C2—C1—N1 | −1.2 (2) |
N2—C4—C3—C2 | 0.6 (2) | C3—C2—C1—Cl1 | 179.46 (11) |
N3—C4—C3—C2 | −178.90 (14) | N3—C4—N2—N1 | 178.83 (12) |
N2—N1—C1—C2 | 1.2 (2) | C3—C4—N2—N1 | −0.6 (2) |
N2—N1—C1—Cl1 | −179.49 (9) | C1—N1—N2—C4 | −0.20 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···N2i | 0.86 | 2.26 | 3.1038 (18) | 168 |
N3—H3B···N1ii | 0.86 | 2.31 | 3.1372 (17) | 162 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C4H4ClN3 |
Mr | 129.55 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 125 |
a, b, c (Å) | 7.5235 (14), 6.5887 (11), 11.1748 (19) |
β (°) | 105.045 (10) |
V (Å3) | 534.95 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.59 |
Crystal size (mm) | 0.50 × 0.50 × 0.40 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.756, 0.794 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5258, 1227, 1153 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.652 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.088, 1.12 |
No. of reflections | 1227 |
No. of parameters | 73 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.35 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···N2i | 0.86 | 2.26 | 3.1038 (18) | 168 |
N3—H3B···N1ii | 0.86 | 2.31 | 3.1372 (17) | 162 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, −y+3/2, z+1/2. |
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Pyridazines have demonstrated versatile biological activities, for example, antibacterial (Ishida et al., 1994), antidepressant (Pitarch et al., 1974) and antihypertensive (Herter et al., 1989) activities. A search of the Cambridge Structural Database (CSD, 2007 Release, Version 5.28; Allen, 2002) reveals that there are 639 crystal structures containing the pyridazine moiety. In the design of functional synthetic oligomers and ploymers, 3,6-diaminopyridazine is applied to the design of related monomeric, dimeric and trimeric duplex molecular strands (Gong et al., 2005). And in the preparation of various pyridazines, 3-amino-6-chloropyridazine is an important intermediate (Guery et al., 2001). We report here the crystal structure of the title compound.
In the title molecule (Fig. 1), the chloro and amino groups are coplanar with the pyridazine ring. Atoms N3 and Cl1 deviate from the pyridazine plane by 0.030 (1) and 0.019 (1) Å, respectively. The N1—N2 distance of 1.3548 (17) Å is slightly shorter than the N—N distance of 1.379 (2) Å reported by Gong et al. (2005).
The intermolecular N—H···N hydrogen bonds (Table 1) link the molecules into a two-dimensional network parallel to the (100) plane (Fig.2). The pyridazine rings of the inversion-related molecules at (x, y, z) and (-x, 1 - y, -z) are stacked with their centroids separated by a distance of 3.7597 (10) Å, indicating π-π interactions. In addition, C—Cl···π [Cl···pyridazine ring centroid = 3.6065 (10) Å] interactions also contribute to the stabilization of the structure.