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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2445.
Published online 2010 August 28. doi:  10.1107/S1600536810034240
PMCID: PMC3008112

Ethyl 5-amino-1-(6-chloro­pyridazin-3-yl)-1H-pyrazole-4-carboxyl­ate

Abstract

In the title compound, C10H10ClN5O2, the dihedral angle between the aromatic rings is 0.16 (9)°. Two S(6) ring motifs are formed due to intra­molecular N—H(...)N and N—H(...)O hydrogen bonds. In the crystal, inversion dimers linked by pairs of N—H(...)N hydrogen bonds generate R 2 2(14) [or R 4 4(10) via the intra­molecular hydrogen bonds] ring motifs. Polymeric chains propagating in [210] are formed as a result of inter­linking the dimers by pairs of C—H(...)N inter­actions, completing R 2 2(6) ring motifs.

Related literature

For biochemical background and related structures, see: Ather et al. (2010a [triangle],b [triangle],c [triangle]). For graph-set notation, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2445-scheme1.jpg

Experimental

Crystal data

  • C10H10ClN5O2
  • M r = 267.68
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2445-efi1.jpg
  • a = 5.3618 (3) Å
  • b = 8.6168 (4) Å
  • c = 13.1585 (7) Å
  • α = 77.734 (2)°
  • β = 82.928 (1)°
  • γ = 86.722 (2)°
  • V = 589.24 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.33 mm−1
  • T = 296 K
  • 0.25 × 0.20 × 0.08 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.982, T max = 0.988
  • 8832 measured reflections
  • 2125 independent reflections
  • 1721 reflections with I > 2σ(I)
  • R int = 0.032

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.101
  • S = 1.06
  • 2125 reflections
  • 164 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810034240/hb5619sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810034240/hb5619Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. They also acknowledge the technical support provided by Bana Inter­national, Karachi, Pakistan.

supplementary crystallographic information

Comment

In continuation of our studies of pyrazolylpyridazine derivatives (Ather et al., 2010a, b, c), the title compound (I, Fig. 1) is being reported here.

In (I), the 1-(6-chloropyridazin-3-yl)-1H-pyrazol-5-amine moiety A (C1—C7/N1—N5/CL1) and ethyl formate group B (C8—C10/O1/O2) are planar with r. m. s. deviations of 0.0026 and 0.0293 Å, respectively. The dihedral angle between A/B is 3.09 (12)°. There exist two S(6) ring motifs (Bernstein et al., 1995) due to N–H···N and N—H···O types of intramolecular H-bondings (Table 1, Fig. 1). The molecules are dimerized due to N–H···N type of H-bonding (Table 2, Fig. 2) with R44(10) ring motifs. The dimers are interliked in the from of polymeric chains due to H-bondings of C—H···N type with R22(6) ring motifs (Table 2, Fig. 2).

Experimental

3-Chloro-6-hydrazinylpyridazine (2 g, 13.84 mmol) and ethylethoxymethylene cyanoacetate (2.35 g, 13.84 mmol) were dissolved in acetic acid (10 ml). The obtained reaction mixture was refluxed for 4 h and cooled to room temperature. The resulting product was poured in 100 ml of distiled water and the precipitates were formed. The precipitates obtained by filteration were washed three times by water. The crude material obtained was dried and purified by column chromatography. The final product was re-crystallized in benzene to obtain light brown plates of (I).

Refinement

The H-atoms were positioned geometrically (N–H = 0.86, C–H = 0.93–0.97 Å) and were included in the refinement in the riding model approximation, with Uiso(H) = xUeq(C, N), where x = 1.5 for methyl and x = 1.2 for all other H-atoms.

Figures

Fig. 1.
View of (I) with displacement ellipsoids drawn at the 50% probability level. H-atoms are shown as small spheres of arbitrary radius. The dotted lines indicate the intramolecular H-bonds.
Fig. 2.
Packing diagram of (I) showing that the molecules form dimers, which are interlinked in the form of polymeric chains.

Crystal data

C10H10ClN5O2Z = 2
Mr = 267.68F(000) = 276
Triclinic, P1Dx = 1.509 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.3618 (3) ÅCell parameters from 1721 reflections
b = 8.6168 (4) Åθ = 2.4–25.2°
c = 13.1585 (7) ŵ = 0.33 mm1
α = 77.734 (2)°T = 296 K
β = 82.928 (1)°Plate, light brown
γ = 86.722 (2)°0.25 × 0.20 × 0.08 mm
V = 589.24 (5) Å3

Data collection

Bruker Kappa APEXII CCD diffractometer2125 independent reflections
Radiation source: fine-focus sealed tube1721 reflections with I > 2σ(I)
graphiteRint = 0.032
Detector resolution: 8.10 pixels mm-1θmax = 25.2°, θmin = 2.4°
ω scansh = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −10→10
Tmin = 0.982, Tmax = 0.988l = −15→15
8832 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.049P)2 + 0.1261P] where P = (Fo2 + 2Fc2)/3
2125 reflections(Δ/σ)max = 0.001
164 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = −0.16 e Å3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
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)

xyzUiso*/Ueq
Cl11.21255 (10)0.81971 (7)−0.39777 (4)0.0677 (2)
O10.0151 (3)0.69934 (15)0.27701 (10)0.0604 (4)
O20.3413 (3)0.52161 (16)0.27988 (10)0.0640 (5)
N10.8615 (3)0.69752 (18)−0.12132 (12)0.0510 (5)
N21.0286 (3)0.70752 (18)−0.20741 (12)0.0542 (5)
N30.4983 (2)0.78156 (16)−0.03130 (10)0.0431 (5)
N40.2872 (3)0.88448 (17)−0.03037 (12)0.0502 (5)
N50.6846 (3)0.56546 (17)0.08430 (12)0.0555 (5)
C10.6639 (3)0.79680 (19)−0.12305 (13)0.0415 (5)
C20.6174 (3)0.9141 (2)−0.21063 (15)0.0533 (6)
C30.7854 (3)0.9223 (2)−0.29680 (15)0.0561 (6)
C40.9885 (3)0.8155 (2)−0.29040 (14)0.0481 (6)
C50.1714 (3)0.8415 (2)0.06357 (14)0.0500 (6)
C60.2931 (3)0.7149 (2)0.12671 (13)0.0445 (5)
C70.5052 (3)0.67718 (19)0.06360 (13)0.0422 (5)
C80.2250 (3)0.6341 (2)0.23350 (14)0.0486 (6)
C9−0.0707 (5)0.6236 (3)0.38284 (17)0.0732 (8)
C10−0.2913 (4)0.7155 (3)0.42191 (19)0.0806 (9)
H20.477680.98310−0.209530.0639*
H30.765390.99675−0.357970.0673*
H50.022100.890120.086730.0600*
H5A0.806220.555120.036860.0665*
H5B0.678870.503660.145120.0665*
H9A0.063060.619350.426850.0879*
H9B−0.117310.515680.385140.0879*
H10A−0.422480.719870.377780.1208*
H10B−0.242950.821390.420990.1208*
H10C−0.351080.664600.492220.1208*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0694 (3)0.0765 (4)0.0499 (3)0.0052 (3)0.0126 (2)−0.0098 (3)
O10.0675 (8)0.0591 (8)0.0434 (7)0.0132 (6)0.0109 (6)0.0005 (6)
O20.0691 (9)0.0651 (9)0.0483 (8)0.0172 (7)−0.0037 (7)0.0029 (6)
N10.0510 (8)0.0536 (9)0.0424 (8)0.0121 (7)0.0004 (7)−0.0037 (7)
N20.0530 (9)0.0583 (10)0.0457 (9)0.0122 (7)0.0024 (7)−0.0064 (8)
N30.0442 (8)0.0407 (8)0.0398 (8)0.0096 (6)−0.0023 (6)−0.0027 (6)
N40.0469 (8)0.0485 (8)0.0486 (9)0.0168 (7)−0.0014 (7)−0.0022 (7)
N50.0544 (9)0.0579 (10)0.0445 (9)0.0196 (7)−0.0021 (7)0.0032 (7)
C10.0422 (9)0.0420 (9)0.0395 (9)0.0041 (7)−0.0040 (7)−0.0085 (7)
C20.0535 (10)0.0515 (10)0.0480 (11)0.0137 (8)−0.0039 (8)−0.0003 (8)
C30.0608 (11)0.0570 (11)0.0428 (10)0.0081 (9)−0.0026 (9)0.0026 (9)
C40.0512 (10)0.0512 (10)0.0403 (10)0.0011 (8)−0.0008 (8)−0.0093 (8)
C50.0472 (9)0.0500 (10)0.0479 (10)0.0106 (8)0.0013 (8)−0.0064 (8)
C60.0462 (9)0.0451 (9)0.0390 (9)0.0058 (7)−0.0027 (7)−0.0050 (8)
C70.0441 (9)0.0404 (9)0.0400 (9)0.0047 (7)−0.0058 (7)−0.0050 (7)
C80.0526 (10)0.0482 (10)0.0429 (10)0.0042 (8)−0.0034 (8)−0.0073 (8)
C90.0894 (15)0.0670 (13)0.0492 (12)0.0089 (11)0.0189 (11)0.0010 (10)
C100.0777 (15)0.0906 (17)0.0658 (15)0.0008 (13)0.0197 (12)−0.0161 (13)

Geometric parameters (Å, °)

Cl1—C41.7337 (18)C2—C31.351 (3)
O1—C81.348 (2)C3—C41.384 (2)
O1—C91.438 (3)C5—C61.405 (2)
O2—C81.214 (2)C6—C71.389 (2)
N1—N21.346 (2)C6—C81.442 (2)
N1—C11.323 (2)C9—C101.486 (4)
N2—C41.307 (2)C2—H20.9300
N3—N41.398 (2)C3—H30.9300
N3—C11.395 (2)C5—H50.9300
N3—C71.378 (2)C9—H9A0.9700
N4—C51.301 (2)C9—H9B0.9700
N5—C71.332 (2)C10—H10A0.9600
N5—H5A0.8600C10—H10B0.9600
N5—H5B0.8600C10—H10C0.9600
C1—C21.400 (2)
C8—O1—C9115.59 (16)N3—C7—N5124.20 (15)
N2—N1—C1119.35 (15)N3—C7—C6105.71 (14)
N1—N2—C4118.42 (16)O1—C8—O2123.39 (16)
N4—N3—C1118.30 (13)O1—C8—C6111.74 (15)
N4—N3—C7111.47 (12)O2—C8—C6124.87 (16)
C1—N3—C7130.23 (13)O1—C9—C10109.1 (2)
N3—N4—C5104.02 (14)C1—C2—H2122.00
H5A—N5—H5B120.00C3—C2—H2122.00
C7—N5—H5A120.00C2—C3—H3121.00
C7—N5—H5B120.00C4—C3—H3121.00
N1—C1—N3116.76 (15)N4—C5—H5123.00
N1—C1—C2123.38 (16)C6—C5—H5123.00
N3—C1—C2119.86 (15)O1—C9—H9A110.00
C1—C2—C3116.75 (16)O1—C9—H9B110.00
C2—C3—C4117.32 (17)C10—C9—H9A110.00
N2—C4—C3124.78 (17)C10—C9—H9B110.00
Cl1—C4—C3119.87 (14)H9A—C9—H9B108.00
Cl1—C4—N2115.35 (13)C9—C10—H10A109.00
N4—C5—C6113.70 (15)C9—C10—H10B109.00
C5—C6—C7105.11 (15)C9—C10—H10C109.00
C5—C6—C8130.39 (16)H10A—C10—H10B109.00
C7—C6—C8124.51 (15)H10A—C10—H10C109.00
N5—C7—C6130.09 (16)H10B—C10—H10C109.00
C9—O1—C8—O2−2.0 (3)C1—N3—C7—C6−179.82 (16)
C9—O1—C8—C6178.45 (17)N3—N4—C5—C60.2 (2)
C8—O1—C9—C10176.03 (17)N1—C1—C2—C30.6 (3)
C1—N1—N2—C4−0.3 (2)N3—C1—C2—C3179.95 (16)
N2—N1—C1—N3−179.52 (15)C1—C2—C3—C4−0.6 (2)
N2—N1—C1—C2−0.1 (3)C2—C3—C4—Cl1−179.69 (14)
N1—N2—C4—Cl1−179.85 (13)C2—C3—C4—N20.2 (3)
N1—N2—C4—C30.2 (3)N4—C5—C6—C7−0.2 (2)
C1—N3—N4—C5179.72 (14)N4—C5—C6—C8−179.72 (17)
C7—N3—N4—C50.00 (18)C5—C6—C7—N30.21 (18)
N4—N3—C1—N1−179.93 (15)C5—C6—C7—N5−179.42 (18)
N4—N3—C1—C20.6 (2)C8—C6—C7—N3179.73 (16)
C7—N3—C1—N1−0.3 (3)C8—C6—C7—N50.1 (3)
C7—N3—C1—C2−179.69 (16)C5—C6—C8—O1−2.9 (3)
N4—N3—C7—N5179.53 (15)C5—C6—C8—O2177.57 (18)
N4—N3—C7—C6−0.13 (18)C7—C6—C8—O1177.73 (16)
C1—N3—C7—N5−0.2 (3)C7—C6—C8—O2−1.8 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N5—H5A···N10.862.172.775 (2)127
N5—H5B···O20.862.402.942 (2)122
N5—H5B···N2i0.862.413.017 (2)128
C5—H5···N4ii0.932.533.313 (2)142

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x, −y+2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5619).

References

  • Ather, A. Q., Tahir, M. N., Khan, M. A. & Athar, M. M. (2010a). Acta Cryst. E66, o1327. [PMC free article] [PubMed]
  • Ather, A. Q., Tahir, M. N., Khan, M. A., Athar, M. M. & Bueno, E. A. S. (2010b). Acta Cryst. E66, o1900. [PMC free article] [PubMed]
  • Ather, A. Q., Tahir, M. N., Khan, M. A., Athar, M. M. & Bueno, E. A. S. (2010c). Acta Cryst. E66, o2016. [PMC free article] [PubMed]
  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Bruker (2005). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2009). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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