Acta Cryst. (2009). E65, o239 [ doi:10.1107/S1600536808044036 ]
The title compound, C12H12N4, was synthesized by the reaction of hydrazine hydrate and 9-methyl-3,4,6,7-tetrahydro-2H-xanthene-1,8(5H,9H)-dione in ethanol. In the crystal, the molecule lies across an inversion centre. The pyridazine rings are coplanar and the C6 rings adopt envelope conformations.
The title compound was prepared by the reaction of 3,4,6,7-tetrahydro -9-methyl-2H-xanthene-1,8(5H,9H)-dione (2 mmol) and hydrazine hydrate 80% (8 mmol) in ethanol (8 ml) stirring at 353 K (yield 84%; m.p. 543–544 K). Single crystals suitable for X-ray diffraction were obtained from an ethanol solution by slow evaporation.
All H atoms were located in a difference Fourier map and refined freely [C-H = 0.95 (2)-1.04 (2) Å].
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./ci2750fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme. Atoms labelled with the suffix A are generated by the symmetry operation (1-x, -y, 1-z). |
![[Figure 2]](./ci2750fig2thm.gif)
| Fig. 2. Molecular packing in the title compound, viewed approximately along the a axis. |
| C12H12N4 | F(000) = 224 |
| Mr = 212.26 | Dx = 1.389 Mg m−3 |
| Monoclinic, P21/c | Melting point = 543–544 K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 9.698 (5) Å | Cell parameters from 734 reflections |
| b = 5.875 (3) Å | θ = 2.4–26.3° |
| c = 10.023 (5) Å | µ = 0.09 mm−1 |
| β = 117.314 (6)° | T = 298 K |
| V = 507.4 (4) Å3 | Plate, colourless |
| Z = 2 | 0.55 × 0.41 × 0.09 mm |
| Bruker SMART CCD area-detector diffractometer | 890 independent reflections |
| Radiation source: fine-focus sealed tube | 575 reflections with I > 2σ(I) |
| graphite | Rint = 0.028 |
| φ and ω scans | θmax = 25.0°, θmin = 4.1° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
| Tmin = 0.953, Tmax = 0.992 | k = −6→6 |
| 2508 measured reflections | l = −11→11 |
| 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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.123 | All H-atom parameters refined |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.0655P)2 + 0.0552P] where P = (Fo2 + 2Fc2)/3 |
| 890 reflections | (Δ/σ)max = 0.001 |
| 97 parameters | Δρmax = 0.16 e Å−3 |
| 0 restraints | Δρmin = −0.15 e Å−3 |
| C12H12N4 | V = 507.4 (4) Å3 |
| Mr = 212.26 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 9.698 (5) Å | µ = 0.09 mm−1 |
| b = 5.875 (3) Å | T = 298 K |
| c = 10.023 (5) Å | 0.55 × 0.41 × 0.09 mm |
| β = 117.314 (6)° |
| Bruker SMART CCD area-detector diffractometer | 890 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 575 reflections with I > 2σ(I) |
| Tmin = 0.953, Tmax = 0.992 | Rint = 0.028 |
| 2508 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.041 | All H-atom parameters refined |
| wR(F2) = 0.123 | Δρmax = 0.16 e Å−3 |
| S = 1.01 | Δρmin = −0.15 e Å−3 |
| 890 reflections | Absolute structure: ? |
| 97 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| N1 | 0.7159 (2) | −0.2597 (3) | 0.65617 (19) | 0.0547 (6) | |
| N2 | 0.5861 (2) | −0.3398 (3) | 0.66438 (18) | 0.0555 (6) | |
| C1 | 0.7050 (2) | −0.0820 (4) | 0.5729 (2) | 0.0466 (6) | |
| C2 | 0.56377 (19) | 0.0384 (3) | 0.49395 (18) | 0.0390 (5) | |
| C3 | 0.5474 (2) | 0.2352 (3) | 0.4062 (2) | 0.0450 (5) | |
| C4 | 0.6864 (3) | 0.3211 (5) | 0.3949 (3) | 0.0581 (7) | |
| C5 | 0.8354 (3) | 0.2567 (4) | 0.5326 (3) | 0.0647 (7) | |
| C6 | 0.8445 (3) | 0.0004 (4) | 0.5597 (3) | 0.0621 (7) | |
| H1 | 0.682 (2) | 0.250 (4) | 0.305 (3) | 0.065 (6)* | |
| H2 | 0.678 (2) | 0.487 (4) | 0.382 (2) | 0.076 (7)* | |
| H3 | 0.930 (3) | 0.308 (4) | 0.522 (3) | 0.086 (8)* | |
| H4 | 0.839 (3) | 0.340 (4) | 0.623 (3) | 0.079 (7)* | |
| H5 | 0.846 (2) | −0.086 (4) | 0.470 (2) | 0.072 (7)* | |
| H6 | 0.936 (3) | −0.039 (4) | 0.649 (3) | 0.081 (7)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0567 (12) | 0.0508 (12) | 0.0500 (10) | 0.0164 (9) | 0.0187 (9) | 0.0061 (8) |
| N2 | 0.0652 (12) | 0.0458 (11) | 0.0474 (11) | 0.0115 (9) | 0.0189 (9) | 0.0086 (8) |
| C1 | 0.0501 (12) | 0.0467 (12) | 0.0395 (10) | 0.0102 (10) | 0.0175 (9) | −0.0019 (10) |
| C2 | 0.0445 (11) | 0.0386 (11) | 0.0306 (9) | 0.0072 (8) | 0.0146 (8) | −0.0029 (8) |
| C3 | 0.0574 (13) | 0.0386 (12) | 0.0351 (10) | 0.0051 (10) | 0.0178 (9) | −0.0010 (9) |
| C4 | 0.0737 (17) | 0.0505 (15) | 0.0555 (14) | −0.0061 (12) | 0.0344 (13) | −0.0027 (12) |
| C5 | 0.0595 (15) | 0.0680 (17) | 0.0681 (16) | −0.0087 (13) | 0.0306 (13) | −0.0101 (13) |
| C6 | 0.0484 (14) | 0.0707 (18) | 0.0650 (16) | 0.0111 (11) | 0.0242 (13) | −0.0033 (12) |
| N1—C1 | 1.310 (3) | C4—C5 | 1.518 (3) |
| N1—N2 | 1.381 (2) | C4—H1 | 0.98 (2) |
| N2—C3i | 1.309 (3) | C4—H2 | 0.98 (2) |
| C1—C2 | 1.417 (3) | C5—C6 | 1.526 (3) |
| C1—C6 | 1.499 (3) | C5—H3 | 1.01 (2) |
| C2—C2i | 1.373 (3) | C5—H4 | 1.01 (2) |
| C2—C3 | 1.417 (3) | C6—H5 | 1.04 (2) |
| C3—N2i | 1.309 (3) | C6—H6 | 0.95 (2) |
| C3—C4 | 1.492 (3) | ||
| C1—N1—N2 | 120.01 (17) | C5—C4—H2 | 111.0 (13) |
| C3i—N2—N1 | 120.67 (18) | H1—C4—H2 | 109.4 (18) |
| N1—C1—C2 | 121.89 (19) | C4—C5—C6 | 111.2 (2) |
| N1—C1—C6 | 120.07 (18) | C4—C5—H3 | 111.1 (13) |
| C2—C1—C6 | 118.0 (2) | C6—C5—H3 | 109.2 (14) |
| C2i—C2—C3 | 118.3 (2) | C4—C5—H4 | 108.6 (14) |
| C2i—C2—C1 | 117.8 (2) | C6—C5—H4 | 110.1 (13) |
| C3—C2—C1 | 123.94 (17) | H3—C5—H4 | 106.5 (19) |
| N2i—C3—C2 | 121.33 (19) | C1—C6—C5 | 110.70 (19) |
| N2i—C3—C4 | 120.3 (2) | C1—C6—H5 | 107.1 (12) |
| C2—C3—C4 | 118.39 (18) | C5—C6—H5 | 110.5 (12) |
| C3—C4—C5 | 111.3 (2) | C1—C6—H6 | 109.2 (14) |
| C3—C4—H1 | 105.8 (12) | C5—C6—H6 | 111.1 (15) |
| C5—C4—H1 | 110.6 (12) | H5—C6—H6 | 108.2 (19) |
| C3—C4—H2 | 108.6 (13) |
| Symmetry codes: (i) −x+1, −y, −z+1. |
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It is well known that six-membered nitrogen-containing heterocycles are abundant in numerous natural products that exhibit important biological properties. For example, cinnolines and their derivatives exhibit a diverse range of biological properties (Lewgowd & Stanczak, 2007) such as molluscicidal activity (Abdelrazek et al., 2006), cytotoxic activity (Lewgowd et al., 2005), transient receptor potential vanilloid 1 (TRPV1) receptor antagonists (Gomtsyan et al., 2005), and topoisomerase I (TOP1)-targeting activity and cytotoxicity (Singh et al., 2003). They also acted as anticancer agents active on a multidrug resistant cell line (Stefanska et al., 2003). They can also be used as bactericides in pharmaceutical industry (Inoue et al., 1993; Tutsumi et al.,1992). The chemistry of cinnolines has received much attention based on the above facts.
The title molecule lies across an inversion centre (Fig. 1). The two pyridazine rings (C1/C2/C2A/C3A/N2/N1 and C1A/C2A/C2/C3/N2A/N1A) are conjugated and are coplanar. The two cyclohexene rings (C1—C6 and C1A—C6A) adopt envelope conformations, with atoms C5 and C5A deviate from the C1/C2/C3/C4/C6 and C1A/C2A/C3A/C4A/C6A planes by 0.656 (3) and 0.656 (3) Å, respectively.
A view of the crystal packing is shown in Fig.2.