Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104016737/tr1093sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104016737/tr1093Isup2.hkl |
CCDC reference: 251324
Compound (I) was prepared by the reaction of 1,4-dihydrazinophthalazine with pyridine-2-carboxaldehyde, followed by an oxidative cyclization with bromine in the presence of acetic acid/sodium acetate buffer. The preparative method employed is an extension of a literature procedure (Pollak & Tisler, 1966). Single crystals for X-ray structure determination were obtained from dichloromethane/hexane by slow evaporation.
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. A view of (I), with labelling of non-H atoms. Displacement ellipsoids are shown at the 30% probability level. |
C20H12N8 | F(000) = 752 |
Mr = 364.38 | Dx = 1.453 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 8.1968 (12) Å | θ = 5.8–18.5° |
b = 12.390 (2) Å | µ = 0.10 mm−1 |
c = 16.409 (5) Å | T = 293 K |
β = 91.23 (2)° | Prism, light brown |
V = 1666.1 (6) Å3 | 0.4 × 0.3 × 0.2 mm |
Z = 4 |
Enraf–Nonius CAD-4 diffractometer | 2101 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.018 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
non–profiled ω/2θ scans | h = 0→9 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→14 |
Tmin = 0.969, Tmax = 0.981 | l = −19→19 |
3147 measured reflections | 3 standard reflections every 60 min |
2929 independent reflections | intensity decay: 1% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.04P)2 + 0.3394P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
2929 reflections | Δρmax = 0.14 e Å−3 |
254 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0127 (13) |
C20H12N8 | V = 1666.1 (6) Å3 |
Mr = 364.38 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.1968 (12) Å | µ = 0.10 mm−1 |
b = 12.390 (2) Å | T = 293 K |
c = 16.409 (5) Å | 0.4 × 0.3 × 0.2 mm |
β = 91.23 (2)° |
Enraf–Nonius CAD-4 diffractometer | 2101 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.018 |
Tmin = 0.969, Tmax = 0.981 | 3 standard reflections every 60 min |
3147 measured reflections | intensity decay: 1% |
2929 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.14 e Å−3 |
2929 reflections | Δρmin = −0.15 e Å−3 |
254 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 | ||
N1 | 0.01910 (16) | 0.84254 (11) | 0.58191 (7) | 0.0362 (3) | |
N2 | −0.01094 (16) | 0.85012 (11) | 0.66450 (7) | 0.0367 (3) | |
N11 | 0.13455 (18) | 0.89263 (13) | 0.46880 (8) | 0.0496 (4) | |
N12 | 0.03278 (19) | 0.80564 (13) | 0.45265 (8) | 0.0501 (4) | |
N14 | 0.05590 (19) | 0.89496 (13) | 0.79008 (9) | 0.0512 (4) | |
N15 | −0.09433 (19) | 0.84524 (13) | 0.78929 (8) | 0.0503 (4) | |
N22 | −0.09507 (18) | 0.61730 (13) | 0.59863 (8) | 0.0467 (4) | |
N32 | −0.35555 (17) | 0.79389 (12) | 0.61635 (8) | 0.0448 (4) | |
C3 | 0.1035 (2) | 0.89927 (14) | 0.71459 (10) | 0.0407 (4) | |
C4 | 0.2364 (2) | 0.96101 (13) | 0.68143 (10) | 0.0393 (4) | |
C5 | 0.3548 (2) | 1.00964 (15) | 0.73134 (11) | 0.0482 (5) | |
H5 | 0.3570 | 0.9968 | 0.7872 | 0.058* | |
C6 | 0.4676 (2) | 1.07630 (17) | 0.69763 (12) | 0.0554 (5) | |
H6 | 0.5477 | 1.1080 | 0.7307 | 0.066* | |
C7 | 0.4637 (2) | 1.09698 (17) | 0.61491 (13) | 0.0597 (5) | |
H7 | 0.5396 | 1.1441 | 0.5931 | 0.072* | |
C8 | 0.3489 (2) | 1.04882 (16) | 0.56413 (12) | 0.0517 (5) | |
H8 | 0.3475 | 1.0630 | 0.5085 | 0.062* | |
C9 | 0.2353 (2) | 0.97871 (14) | 0.59715 (10) | 0.0403 (4) | |
C10 | 0.1275 (2) | 0.91271 (14) | 0.54713 (10) | 0.0399 (4) | |
C13 | −0.0324 (2) | 0.77310 (14) | 0.52089 (9) | 0.0393 (4) | |
C16 | −0.1377 (2) | 0.82081 (14) | 0.71403 (9) | 0.0394 (4) | |
C21 | −0.1209 (2) | 0.67138 (14) | 0.52889 (9) | 0.0391 (4) | |
C23 | −0.1693 (2) | 0.52197 (17) | 0.60461 (11) | 0.0545 (5) | |
H23 | −0.1544 | 0.4832 | 0.6527 | 0.065* | |
C24 | −0.2666 (2) | 0.47728 (17) | 0.54405 (12) | 0.0568 (5) | |
H24 | −0.3150 | 0.4102 | 0.5512 | 0.068* | |
C25 | −0.2906 (2) | 0.53393 (17) | 0.47285 (11) | 0.0546 (5) | |
H25 | −0.3562 | 0.5060 | 0.4310 | 0.066* | |
C26 | −0.2159 (2) | 0.63285 (16) | 0.46458 (10) | 0.0473 (5) | |
H26 | −0.2291 | 0.6728 | 0.4169 | 0.057* | |
C31 | −0.3006 (2) | 0.77931 (13) | 0.69284 (10) | 0.0392 (4) | |
C33 | −0.5062 (2) | 0.75735 (17) | 0.59940 (12) | 0.0532 (5) | |
H33 | −0.5466 | 0.7648 | 0.5463 | 0.064* | |
C34 | −0.6051 (2) | 0.70944 (16) | 0.65571 (13) | 0.0545 (5) | |
H34 | −0.7087 | 0.6848 | 0.6409 | 0.065* | |
C35 | −0.5465 (2) | 0.69901 (17) | 0.73456 (13) | 0.0575 (5) | |
H35 | −0.6114 | 0.6689 | 0.7744 | 0.069* | |
C36 | −0.3919 (2) | 0.73348 (16) | 0.75362 (11) | 0.0505 (5) | |
H36 | −0.3492 | 0.7262 | 0.8063 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0412 (7) | 0.0434 (8) | 0.0242 (7) | 0.0003 (7) | 0.0040 (5) | −0.0008 (6) |
N2 | 0.0423 (8) | 0.0433 (8) | 0.0246 (6) | −0.0014 (6) | 0.0024 (6) | −0.0012 (6) |
N11 | 0.0535 (9) | 0.0633 (10) | 0.0322 (8) | −0.0080 (8) | 0.0056 (7) | 0.0020 (7) |
N12 | 0.0551 (9) | 0.0647 (10) | 0.0308 (8) | −0.0069 (8) | 0.0054 (7) | −0.0038 (7) |
N14 | 0.0594 (10) | 0.0619 (10) | 0.0324 (8) | −0.0103 (8) | 0.0011 (7) | −0.0043 (7) |
N15 | 0.0587 (10) | 0.0603 (10) | 0.0320 (8) | −0.0103 (8) | 0.0047 (7) | −0.0037 (7) |
N22 | 0.0517 (9) | 0.0516 (9) | 0.0364 (8) | −0.0013 (7) | −0.0045 (7) | 0.0003 (7) |
N32 | 0.0443 (8) | 0.0523 (9) | 0.0378 (8) | 0.0041 (7) | 0.0038 (6) | 0.0029 (7) |
C3 | 0.0465 (10) | 0.0437 (10) | 0.0316 (8) | 0.0006 (8) | −0.0017 (7) | −0.0040 (7) |
C4 | 0.0412 (9) | 0.0392 (9) | 0.0375 (9) | 0.0032 (8) | −0.0003 (7) | −0.0013 (7) |
C5 | 0.0513 (11) | 0.0512 (11) | 0.0417 (10) | −0.0010 (9) | −0.0050 (8) | −0.0011 (8) |
C6 | 0.0505 (11) | 0.0564 (12) | 0.0588 (12) | −0.0088 (10) | −0.0071 (9) | −0.0032 (10) |
C7 | 0.0546 (12) | 0.0591 (13) | 0.0655 (13) | −0.0159 (10) | 0.0034 (10) | 0.0070 (10) |
C8 | 0.0549 (11) | 0.0538 (12) | 0.0463 (11) | −0.0049 (9) | 0.0029 (9) | 0.0095 (9) |
C9 | 0.0419 (9) | 0.0394 (9) | 0.0395 (9) | 0.0038 (8) | 0.0012 (7) | 0.0007 (7) |
C10 | 0.0398 (9) | 0.0468 (10) | 0.0332 (9) | 0.0024 (8) | 0.0032 (7) | 0.0047 (7) |
C13 | 0.0408 (9) | 0.0502 (10) | 0.0268 (8) | 0.0036 (8) | 0.0003 (7) | −0.0042 (7) |
C16 | 0.0474 (10) | 0.0427 (9) | 0.0282 (8) | 0.0002 (8) | 0.0067 (7) | −0.0005 (7) |
C21 | 0.0395 (9) | 0.0478 (10) | 0.0301 (8) | 0.0035 (8) | 0.0015 (7) | −0.0052 (7) |
C23 | 0.0644 (13) | 0.0529 (12) | 0.0459 (11) | −0.0041 (10) | −0.0069 (9) | 0.0055 (9) |
C24 | 0.0659 (13) | 0.0515 (11) | 0.0528 (12) | −0.0083 (10) | −0.0037 (10) | −0.0031 (9) |
C25 | 0.0594 (12) | 0.0641 (13) | 0.0401 (10) | −0.0100 (10) | −0.0049 (9) | −0.0110 (9) |
C26 | 0.0543 (11) | 0.0567 (12) | 0.0309 (9) | −0.0006 (9) | −0.0027 (8) | −0.0036 (8) |
C31 | 0.0454 (10) | 0.0381 (9) | 0.0344 (9) | 0.0022 (8) | 0.0071 (7) | −0.0018 (7) |
C33 | 0.0488 (11) | 0.0611 (12) | 0.0495 (11) | 0.0083 (10) | −0.0036 (9) | −0.0002 (9) |
C34 | 0.0424 (10) | 0.0495 (11) | 0.0718 (14) | −0.0022 (9) | 0.0048 (9) | −0.0047 (10) |
C35 | 0.0572 (12) | 0.0552 (12) | 0.0608 (13) | −0.0093 (10) | 0.0167 (10) | 0.0039 (10) |
C36 | 0.0568 (11) | 0.0553 (12) | 0.0397 (10) | −0.0058 (9) | 0.0090 (8) | 0.0036 (8) |
N1—C10 | 1.376 (2) | C7—H7 | 0.9300 |
N1—C13 | 1.380 (2) | C8—C9 | 1.392 (2) |
N1—N2 | 1.3857 (17) | C8—H8 | 0.9300 |
N2—C3 | 1.376 (2) | C9—C10 | 1.446 (2) |
N2—C16 | 1.382 (2) | C13—C21 | 1.461 (2) |
N11—C10 | 1.312 (2) | C16—C31 | 1.465 (2) |
N11—N12 | 1.385 (2) | C21—C26 | 1.383 (2) |
N12—C13 | 1.314 (2) | C23—C24 | 1.377 (3) |
N14—C3 | 1.308 (2) | C23—H23 | 0.9300 |
N14—N15 | 1.377 (2) | C24—C25 | 1.374 (3) |
N15—C16 | 1.313 (2) | C24—H24 | 0.9300 |
N22—C23 | 1.333 (2) | C25—C26 | 1.378 (3) |
N22—C21 | 1.339 (2) | C25—H25 | 0.9300 |
N32—C31 | 1.337 (2) | C26—H26 | 0.9300 |
N32—C33 | 1.339 (2) | C31—C36 | 1.382 (2) |
C3—C4 | 1.446 (2) | C33—C34 | 1.376 (3) |
C4—C5 | 1.394 (2) | C33—H33 | 0.9300 |
C4—C9 | 1.400 (2) | C34—C35 | 1.376 (3) |
C5—C6 | 1.366 (3) | C34—H34 | 0.9300 |
C5—H5 | 0.9300 | C35—C36 | 1.367 (3) |
C6—C7 | 1.381 (3) | C35—H35 | 0.9300 |
C6—H6 | 0.9300 | C36—H36 | 0.9300 |
C7—C8 | 1.379 (3) | N22—N32 | 3.075 (2) |
C10—N1—C13 | 106.46 (13) | N12—C13—N1 | 107.66 (15) |
C10—N1—N2 | 119.52 (13) | N12—C13—C21 | 123.55 (15) |
C13—N1—N2 | 133.95 (14) | N1—C13—C21 | 128.13 (14) |
C3—N2—C16 | 106.07 (13) | N15—C16—N2 | 107.49 (15) |
C3—N2—N1 | 118.75 (13) | N15—C16—C31 | 122.08 (15) |
C16—N2—N1 | 135.17 (13) | N2—C16—C31 | 130.21 (14) |
C10—N11—N12 | 107.22 (14) | N22—C21—C26 | 123.75 (17) |
C13—N12—N11 | 109.27 (14) | N22—C21—C13 | 116.02 (14) |
C3—N14—N15 | 107.13 (14) | C26—C21—C13 | 120.10 (15) |
C16—N15—N14 | 109.65 (14) | N22—C23—C24 | 124.14 (18) |
C23—N22—C21 | 116.25 (15) | N22—C23—H23 | 117.9 |
C31—N32—C33 | 116.12 (16) | C24—C23—H23 | 117.9 |
N14—C3—N2 | 109.51 (15) | C25—C24—C23 | 118.60 (19) |
N14—C3—C4 | 128.35 (16) | C25—C24—H24 | 120.7 |
N2—C3—C4 | 121.22 (14) | C23—C24—H24 | 120.7 |
C5—C4—C9 | 120.15 (16) | C24—C25—C26 | 118.83 (17) |
C5—C4—C3 | 121.87 (16) | C24—C25—H25 | 120.6 |
C9—C4—C3 | 117.75 (15) | C26—C25—H25 | 120.6 |
C6—C5—C4 | 119.51 (17) | C25—C26—C21 | 118.42 (17) |
C6—C5—H5 | 120.2 | C25—C26—H26 | 120.8 |
C4—C5—H5 | 120.2 | C21—C26—H26 | 120.8 |
C5—C6—C7 | 120.58 (18) | N32—C31—C36 | 123.80 (16) |
C5—C6—H6 | 119.7 | N32—C31—C16 | 117.55 (15) |
C7—C6—H6 | 119.7 | C36—C31—C16 | 118.54 (15) |
C8—C7—C6 | 120.98 (19) | N32—C33—C34 | 124.05 (18) |
C8—C7—H7 | 119.5 | N32—C33—H33 | 118.0 |
C6—C7—H7 | 119.5 | C34—C33—H33 | 118.0 |
C7—C8—C9 | 119.23 (17) | C35—C34—C33 | 118.25 (18) |
C7—C8—H8 | 120.4 | C35—C34—H34 | 120.9 |
C9—C8—H8 | 120.4 | C33—C34—H34 | 120.9 |
C8—C9—C4 | 119.49 (16) | C36—C35—C34 | 119.24 (18) |
C8—C9—C10 | 122.53 (16) | C36—C35—H35 | 120.4 |
C4—C9—C10 | 117.57 (15) | C34—C35—H35 | 120.4 |
N11—C10—N1 | 109.21 (15) | C35—C36—C31 | 118.49 (18) |
N11—C10—C9 | 128.61 (16) | C35—C36—H36 | 120.8 |
N1—C10—C9 | 120.93 (14) | C31—C36—H36 | 120.8 |
C10—N1—N2—C3 | −22.1 (2) | C5—C6—C7—C8 | −1.7 (3) |
C10—N1—N2—C16 | 156.20 (17) | H6—C6—C7—H7 | −1.7 |
C13—N1—N2—C3 | 154.54 (17) | H6—C6—C7—C8 | 178.28 |
C13—N1—N2—C16 | −27.2 (3) | C6—C7—C8—H8 | −179.77 |
N2—N1—C10—N11 | −178.70 (13) | C6—C7—C8—C9 | 0.2 (3) |
N2—N1—C10—C9 | 13.0 (2) | H7—C7—C8—H8 | 0.2 |
C13—N1—C10—N11 | 3.83 (18) | H7—C7—C8—C9 | −179.77 |
C13—N1—C10—C9 | −164.48 (15) | C7—C8—C9—C4 | 2.0 (3) |
N2—N1—C13—N12 | 178.71 (15) | C7—C8—C9—C10 | −170.39 (18) |
N2—N1—C13—C21 | −10.5 (3) | H8—C8—C9—C4 | −178.02 |
C10—N1—C13—N12 | −4.35 (18) | H8—C8—C9—C10 | 9.6 |
C10—N1—C13—C21 | 166.47 (16) | C4—C9—C10—N1 | 6.1 (2) |
N1—N2—C3—N14 | −177.73 (14) | C4—C9—C10—N11 | −159.77 (17) |
N1—N2—C3—C4 | 12.3 (2) | C8—C9—C10—N1 | 178.56 (16) |
C16—N2—C3—N14 | 3.52 (18) | C8—C9—C10—N11 | 12.7 (3) |
C16—N2—C3—C4 | −166.38 (15) | N1—C13—C21—N22 | −28.8 (3) |
N1—N2—C16—N15 | 177.71 (15) | N1—C13—C21—C26 | 155.25 (17) |
N1—N2—C16—C31 | −7.7 (3) | N12—C13—C21—N22 | 140.68 (17) |
C3—N2—C16—N15 | −3.85 (18) | N12—C13—C21—C26 | −35.3 (3) |
C3—N2—C16—C31 | 170.74 (17) | N2—C16—C31—N32 | −18.1 (3) |
C10—N11—N12—C13 | −0.94 (19) | N2—C16—C31—C36 | 165.71 (17) |
N12—N11—C10—N1 | −1.85 (18) | N15—C16—C31—N32 | 155.82 (16) |
N12—N11—C10—C9 | 165.29 (17) | N15—C16—C31—C36 | −20.4 (3) |
N11—N12—C13—N1 | 3.32 (18) | N22—C21—C26—C25 | 1.0 (3) |
N11—N12—C13—C21 | −168.02 (15) | N22—C21—C26—H26 | −178.98 |
C3—N14—N15—C16 | −0.66 (19) | C13—C21—C26—C25 | 176.64 (16) |
N15—N14—C3—N2 | −1.84 (19) | C13—C21—C26—H26 | −3.4 |
N15—N14—C3—C4 | 167.14 (17) | N22—C23—C24—H24 | 179.56 |
N14—N15—C16—N2 | 2.84 (19) | N22—C23—C24—C25 | −0.4 (3) |
N14—N15—C16—C31 | −172.28 (15) | H23—C23—C24—H24 | −0.5 |
C23—N22—C21—C13 | −176.85 (16) | H23—C23—C24—C25 | 179.55 |
C23—N22—C21—C26 | −1.1 (3) | C23—C24—C25—H25 | −179.66 |
C21—N22—C23—H23 | −179.22 | C23—C24—C25—C26 | 0.3 (3) |
C21—N22—C23—C24 | 0.8 (3) | H24—C24—C25—H25 | 0.3 |
C33—N32—C31—C16 | −178.47 (16) | H24—C24—C25—C26 | −179.66 |
C33—N32—C31—C36 | −2.5 (3) | C24—C25—C26—C21 | −0.6 (3) |
C31—N32—C33—H33 | −178.45 | C24—C25—C26—H26 | 179.39 |
C31—N32—C33—C34 | 1.6 (3) | H25—C25—C26—C21 | 179.39 |
N2—C3—C4—C5 | −178.85 (16) | H25—C25—C26—H26 | −0.6 |
N2—C3—C4—C9 | 6.5 (2) | N32—C31—C36—C35 | 1.3 (3) |
N14—C3—C4—C5 | 13.3 (3) | N32—C31—C36—H36 | −178.73 |
N14—C3—C4—C9 | −161.29 (18) | C16—C31—C36—C35 | 177.22 (17) |
C3—C4—C5—H5 | 6.8 | C16—C31—C36—H36 | −2.8 |
C3—C4—C5—C6 | −173.16 (17) | N32—C33—C34—H34 | −179.45 |
C9—C4—C5—H5 | −178.69 | N32—C33—C34—C35 | 0.5 (3) |
C9—C4—C5—C6 | 1.3 (3) | H33—C33—C34—H34 | 0.5 |
C3—C4—C9—C8 | 171.93 (16) | H33—C33—C34—C35 | −179.45 |
C3—C4—C9—C10 | −15.3 (2) | C33—C34—C35—H35 | 178.18 |
C5—C4—C9—C8 | −2.8 (3) | C33—C34—C35—C36 | −1.8 (3) |
C5—C4—C9—C10 | 169.99 (16) | H34—C34—C35—H35 | −1.8 |
C4—C5—C6—H6 | −179.07 | H34—C34—C35—C36 | 178.17 |
C4—C5—C6—C7 | 0.9 (3) | C34—C35—C36—C31 | 1.0 (3) |
H5—C5—C6—H6 | 0.9 | C34—C35—C36—H36 | −179.02 |
H5—C5—C6—C7 | −179.08 | H35—C35—C36—C31 | −179.02 |
C5—C6—C7—H7 | 178.29 | H35—C35—C36—H36 | 1.0 |
Experimental details
Crystal data | |
Chemical formula | C20H12N8 |
Mr | 364.38 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.1968 (12), 12.390 (2), 16.409 (5) |
β (°) | 91.23 (2) |
V (Å3) | 1666.1 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.4 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.969, 0.981 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3147, 2929, 2101 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.095, 1.02 |
No. of reflections | 2929 |
No. of parameters | 254 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.14, −0.15 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
N1—C10 | 1.376 (2) | N22—C23 | 1.333 (2) |
N1—C13 | 1.380 (2) | N22—C21 | 1.339 (2) |
N1—N2 | 1.3857 (17) | N32—C31 | 1.337 (2) |
N2—C3 | 1.376 (2) | N32—C33 | 1.339 (2) |
N2—C16 | 1.382 (2) | C3—C4 | 1.446 (2) |
N11—C10 | 1.312 (2) | C4—C9 | 1.400 (2) |
N11—N12 | 1.385 (2) | C9—C10 | 1.446 (2) |
N12—C13 | 1.314 (2) | C13—C21 | 1.461 (2) |
N14—C3 | 1.308 (2) | C16—C31 | 1.465 (2) |
N14—N15 | 1.377 (2) | N22—N32 | 3.075 (2) |
N15—C16 | 1.313 (2) | ||
C10—N1—C13 | 106.46 (13) | N2—C3—C4 | 121.22 (14) |
C10—N1—N2 | 119.52 (13) | C9—C4—C3 | 117.75 (15) |
C13—N1—N2 | 133.95 (14) | C4—C9—C10 | 117.57 (15) |
C3—N2—C16 | 106.07 (13) | N11—C10—N1 | 109.21 (15) |
C3—N2—N1 | 118.75 (13) | N11—C10—C9 | 128.61 (16) |
C16—N2—N1 | 135.17 (13) | N1—C10—C9 | 120.93 (14) |
C10—N11—N12 | 107.22 (14) | N12—C13—N1 | 107.66 (15) |
C13—N12—N11 | 109.27 (14) | N12—C13—C21 | 123.55 (15) |
C3—N14—N15 | 107.13 (14) | N1—C13—C21 | 128.13 (14) |
C16—N15—N14 | 109.65 (14) | N15—C16—N2 | 107.49 (15) |
N14—C3—N2 | 109.51 (15) | N15—C16—C31 | 122.08 (15) |
N14—C3—C4 | 128.35 (16) | N2—C16—C31 | 130.21 (14) |
C10—N1—N2—C3 | −22.1 (2) | N1—C13—C21—N22 | −28.8 (3) |
C10—N1—N2—C16 | 156.20 (17) | N1—C13—C21—C26 | 155.25 (17) |
C13—N1—N2—C3 | 154.54 (17) | N12—C13—C21—N22 | 140.68 (17) |
C13—N1—N2—C16 | −27.2 (3) | N12—C13—C21—C26 | −35.3 (3) |
N2—N1—C13—N12 | 178.71 (15) | N2—C16—C31—N32 | −18.1 (3) |
N2—N1—C13—C21 | −10.5 (3) | N2—C16—C31—C36 | 165.71 (17) |
N1—N2—C16—N15 | 177.71 (15) | N15—C16—C31—N32 | 155.82 (16) |
N1—N2—C16—C31 | −7.7 (3) | N15—C16—C31—C36 | −20.4 (3) |
Table 2. Torsion angle C3-N4-N4'-C3' in (I), (II) & (III). |
Compound | Torsion angle (°) | Substituents on R1, R2 |
Ia | 27.2 (3) | py, py |
IIb | 91.9 (5) | H, H |
IIac | 84.1 (2) | Me, Me |
IIbd | 74.3 (5) | Me, Ph |
IIcc | 64.1 (2) | Ph, Ph |
IIIae | 7.8 (5) | Me, Me |
IIIbf | 20.7 (5) | Me, Ph |
IIIcg | 27.5 (5) | Ph, Ph |
Notes: (a) this work; (b) Domiano (1977); (c) Carlsen et al. (1992); (d) Sadibakasov et al. (1977); (e) Sadibakasov et al. (1977a); (f) Sadibakasov et al. (1977b); (g) Sadibakasov et al. (1977c). |
As a building block towards construction of polyheterocyclic ring systems of pharmaceutical interest, 1,4-dihydrazinophthalazine has attracted attention because it exhibits antihypertensive properties (Newkome & Paudler, 1982; Amer & Zimmer, 1983; Amer et al., 1987). Many of its metabolites or derivatives are important because of their antibacterial and antitumor activities (Reece, 1981; Schneider et al., 1988).
As a derivative of 1,4-dihydrazinophthalazine, the structure of the title compound, (I), is interesting because two triazole rings are annealed to a parent phthalazine skeleton and two pendant pyridyl moieties are further connected to the triazole rings. If (I) is without a C6 ring, the remaining 4,4'-bis-1,2,4-triazole skeleton, (II), is that of a group of well known spin-crossover coordination complexes (Garcia et al., 2001; Boillot et al., 2002; Enachescu et al., 2003).
A view of (I), with the numbering scheme, is shown in Fig. 1, and selected geometric parameters are given in Table 1. Compound (I) is helical in that the two triazole rings are twisted in different directions, one up and one down, in relation to the similarly twisted plane of the fused four-ring system. The molecular symmetry of (I) in the crystalline states conforms to the chemical point group C2. The bond lengths are in accordance with anticipated values (Orpen et al., 1994).
The skeleton of (II) has two perpendicular triazole rings connected through a N—N bond (Domiano, 1977). Table 2 gives the C3—N4—N4'—C3' torsion angles for some 3,3'-disubstituted-4,4'-bis-1,2,4-triazoles (Sadybakasov et al., 1977; Carlsen et al., 1992). This torsion angle does not stay at 90° with 3,3'-Me or Ph substituents. Clearly, the torsion angle decreases with increasing size of the substituents. The nature of the driving force is believed to be electronically attractive rather than sterically repulsive, as illustrated by, for example, π–π interactions (Sinnokrot, et al., 2002) in the case of 3-Ph,3'-Ph (IIc).
When annealing with pyridazine or phthalazine, the constrained bis-1,2,4-triazole skeleton is expected to be planar. With substituents on the 3,3'-positions of the bis-1,2,4-triazole moiety, the C3—N4—N4'—C3' torsion angle deviates from 0° and increases with increasing steric bulkiness of the substituents (e.g. IIIa < IIIb < IIIc), as shown in Table 2 (Sadybakasov et al., 1977a-c). The C3—N4—N4'—C3' torsion angle is a convenient parameter for the measurement of planarity. This torsion angle in (I), having two pyridyl groups, corresponds well to that of (IIIc), having two phenyl groups. The deviation from planarity is attributed to the bulkiness of the substituents.
However, the shortest distance between the two pyridyl groups in (I) has been found to be between atoms N22 and N32, only 3.075 (2) Å apart. As a pyridyl group is generally regarded as a dipole and the two pyridyl rings in (I) are positioned with the two negative N atoms in close proximity, the short N···N contact is considered part of the more important, attractive, π–π interactions rather than the negative dipole interactions. As a reference point, the shortest distance between the two phenyl rings in (IIIc) is 3.246 (2) Å, between the two ipso C atoms. The distance between the two ortho C atoms is 3.718 (2) Å.
The C—N bonds in bis-1,2,4-triazole are classified into localized single bonds (e.g. N1—C10 and N1—C13) and double bonds (e.g. N11=C10 and N12=C13). The N1—C13 single bond is associated with a larger endo angle, N1—C13—C21, whereas the N12=C13 double bond has a smaller exo angle, N12=C13—C21.
The intermolecular short contacts are mostly due to C—H···π or C—H···N interactions. Also noticable are the π—π interactions between two inversion-symmetry-related molecules [e.g. C10a···C10b = 3.362 (2) Å, C10a···N11b = 3.327 (2) Å and N11a···C10b = 3.327 (2) Å].