supplementary materials
2-(3-Oxo-1,3-dihydroisobenzofuran-1-yl)phthalazin-1(2H)-one
The reaction of 2-carboxybenzaldehyde and hydrazine hydrate unexpectedly yielded the title compound, C16H10N2O3, which comprises one phthalide ring, one phthalazine system and a chiral centre. The phthalide unit is almost perpendicular to the phthalazine system, forming a dihedral angle of 87.1 (3)°. The packing is governed by weak C-H
O hydrogen-bonding interactions, forming layers parallel to the ab plane.
2-Carboxybenzaldehyde (0.30 g, 2 mmol) and hydrazinehydrate (0.050 g, 1 mmol)
were added to methanol (20 ml), and the mixture was refluxed for 3 h at 80°C. The resulting yellow precipitate was filtered and recrystallized
from a MeOH/DMSO (5:1 v/v) solution. Colourless lamellar
crystals were obtained
on slow evaporation of the solvents at room temperature.
All H atoms were placed in calculated positions and were refined using
a riding model, with (C—H = 0.93-0.96 Å, O—H = 0.82 Å), and
with Uiso(H) = 1.2 Ueq(C) or 1.5
Ueq(C, O) for methyl and hydroxy H atoms.
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
2-(3-Oxo-1,3-dihydroisobenzofuran-1-yl)phthalazin-1(2
H)-one
top
Crystal data top
| C16H10N2O3 | Z = 2 |
| Mr = 278.26 | F(000) = 288 |
| Triclinic, P1 | Dx = 1.448 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.2356 (2) Å | Cell parameters from 2295 reflections |
| b = 8.0369 (2) Å | θ = 2.6–25.2° |
| c = 11.1686 (4) Å | µ = 0.10 mm−1 |
| α = 80.047 (2)° | T = 296 K |
| β = 86.093 (2)° | Block, colourless |
| γ = 88.655 (1)° | 0.20 × 0.18 × 0.15 mm |
| V = 638.17 (3) Å3 | |
Data collection top
Bruker APEXII area-detector
diffractometer | 1626 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.030 |
| graphite | θmax = 25.2°, θmin = 2.6° |
| ω scans | h = −8→8 |
| 6746 measured reflections | k = −9→9 |
| 2295 independent reflections | l = −13→13 |
Refinement top
| 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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.110 | H-atom parameters constrained |
| S = 1.02 | w = 1/[σ2(Fo2) + (0.0516P)2 + 0.0851P]
where P = (Fo2 + 2Fc2)/3 |
| 2295 reflections | (Δ/σ)max < 0.001 |
| 190 parameters | Δρmax = 0.14 e Å−3 |
| 0 restraints | Δρmin = −0.17 e Å−3 |
Crystal data top
| C16H10N2O3 | γ = 88.655 (1)° |
| Mr = 278.26 | V = 638.17 (3) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.2356 (2) Å | Mo Kα radiation |
| b = 8.0369 (2) Å | µ = 0.10 mm−1 |
| c = 11.1686 (4) Å | T = 296 K |
| α = 80.047 (2)° | 0.20 × 0.18 × 0.15 mm |
| β = 86.093 (2)° | |
Data collection top
Bruker APEXII area-detector
diffractometer | 1626 reflections with I > 2σ(I) |
| 6746 measured reflections | Rint = 0.030 |
| 2295 independent reflections | θmax = 25.2° |
Refinement top
| R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
| wR(F2) = 0.110 | Δρmax = 0.14 e Å−3 |
| S = 1.02 | Δρmin = −0.17 e Å−3 |
| 2295 reflections | Absolute structure: ? |
| 190 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| C1 | 0.2297 (2) | 1.0612 (2) | 0.05051 (17) | 0.0452 (4) | |
| C2 | 0.2968 (2) | 1.0522 (3) | −0.06731 (17) | 0.0527 (5) | |
| H2 | 0.3332 | 1.1489 | −0.1215 | 0.063* | |
| C3 | 0.3079 (2) | 0.8959 (3) | −0.10149 (17) | 0.0546 (5) | |
| H3 | 0.3514 | 0.8863 | −0.1803 | 0.065* | |
| C4 | 0.2552 (3) | 0.7527 (3) | −0.02004 (18) | 0.0558 (5) | |
| H4 | 0.2650 | 0.6480 | −0.0448 | 0.067* | |
| C5 | 0.1881 (2) | 0.7618 (2) | 0.09758 (17) | 0.0504 (5) | |
| H5 | 0.1527 | 0.6652 | 0.1521 | 0.061* | |
| C6 | 0.1756 (2) | 0.9188 (2) | 0.13127 (15) | 0.0433 (4) | |
| C7 | 0.2067 (3) | 1.2059 (3) | 0.1138 (2) | 0.0609 (5) | |
| C8 | 0.1105 (2) | 0.9693 (2) | 0.24995 (17) | 0.0522 (5) | |
| H8 | −0.0224 | 0.9473 | 0.2655 | 0.063* | |
| C9 | 0.1102 (2) | 0.7947 (2) | 0.45282 (17) | 0.0502 (5) | |
| C10 | 0.2253 (2) | 0.7052 (2) | 0.54673 (16) | 0.0457 (4) | |
| C11 | 0.1443 (3) | 0.6004 (2) | 0.64863 (18) | 0.0569 (5) | |
| H11 | 0.0167 | 0.5861 | 0.6574 | 0.068* | |
| C12 | 0.2554 (3) | 0.5188 (3) | 0.73568 (19) | 0.0630 (5) | |
| H12 | 0.2024 | 0.4483 | 0.8036 | 0.076* | |
| C13 | 0.4459 (3) | 0.5403 (3) | 0.72353 (19) | 0.0635 (6) | |
| H13 | 0.5191 | 0.4850 | 0.7838 | 0.076* | |
| C14 | 0.5268 (3) | 0.6416 (3) | 0.62413 (19) | 0.0588 (5) | |
| H14 | 0.6546 | 0.6552 | 0.6167 | 0.071* | |
| C15 | 0.4170 (2) | 0.7251 (2) | 0.53311 (16) | 0.0463 (4) | |
| C16 | 0.4925 (2) | 0.8287 (3) | 0.42442 (17) | 0.0550 (5) | |
| H16 | 0.6202 | 0.8429 | 0.4162 | 0.066* | |
| N1 | 0.20803 (18) | 0.8852 (2) | 0.35304 (13) | 0.0496 (4) | |
| N2 | 0.39749 (19) | 0.9039 (2) | 0.33708 (14) | 0.0548 (4) | |
| O1 | 0.2366 (2) | 1.35289 (19) | 0.07887 (16) | 0.0893 (5) | |
| O2 | 0.14034 (19) | 1.14869 (17) | 0.23133 (13) | 0.0666 (4) | |
| O3 | −0.05902 (16) | 0.7908 (2) | 0.45814 (13) | 0.0764 (5) | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| C1 | 0.0396 (9) | 0.0427 (11) | 0.0528 (11) | 0.0040 (7) | −0.0141 (8) | −0.0033 (8) |
| C2 | 0.0451 (10) | 0.0558 (13) | 0.0519 (12) | −0.0009 (8) | −0.0109 (8) | 0.0087 (9) |
| C3 | 0.0503 (11) | 0.0639 (14) | 0.0491 (11) | 0.0075 (9) | −0.0068 (9) | −0.0081 (10) |
| C4 | 0.0593 (12) | 0.0505 (12) | 0.0596 (13) | 0.0046 (9) | −0.0110 (9) | −0.0128 (10) |
| C5 | 0.0481 (10) | 0.0456 (12) | 0.0549 (12) | −0.0036 (8) | −0.0090 (8) | 0.0020 (9) |
| C6 | 0.0337 (8) | 0.0470 (11) | 0.0483 (11) | 0.0026 (7) | −0.0097 (7) | −0.0034 (8) |
| C7 | 0.0630 (13) | 0.0509 (14) | 0.0694 (15) | 0.0109 (10) | −0.0240 (11) | −0.0056 (11) |
| C8 | 0.0421 (10) | 0.0608 (13) | 0.0534 (11) | 0.0081 (8) | −0.0099 (8) | −0.0074 (9) |
| C9 | 0.0356 (9) | 0.0667 (13) | 0.0490 (11) | 0.0013 (8) | −0.0035 (8) | −0.0116 (9) |
| C10 | 0.0389 (9) | 0.0547 (11) | 0.0452 (10) | 0.0042 (8) | −0.0039 (8) | −0.0131 (9) |
| C11 | 0.0470 (10) | 0.0650 (13) | 0.0577 (12) | −0.0014 (9) | −0.0024 (9) | −0.0079 (10) |
| C12 | 0.0674 (13) | 0.0620 (14) | 0.0570 (13) | 0.0014 (10) | −0.0053 (10) | −0.0029 (10) |
| C13 | 0.0685 (13) | 0.0649 (14) | 0.0577 (13) | 0.0123 (10) | −0.0199 (10) | −0.0078 (11) |
| C14 | 0.0436 (10) | 0.0724 (14) | 0.0624 (13) | 0.0080 (9) | −0.0150 (9) | −0.0134 (11) |
| C15 | 0.0385 (9) | 0.0541 (11) | 0.0490 (11) | 0.0045 (8) | −0.0075 (8) | −0.0157 (9) |
| C16 | 0.0314 (9) | 0.0761 (14) | 0.0574 (12) | −0.0005 (8) | −0.0052 (8) | −0.0105 (10) |
| N1 | 0.0320 (7) | 0.0707 (11) | 0.0447 (9) | 0.0051 (7) | −0.0048 (6) | −0.0061 (7) |
| N2 | 0.0331 (8) | 0.0770 (12) | 0.0527 (10) | 0.0007 (7) | −0.0038 (7) | −0.0068 (8) |
| O1 | 0.1198 (14) | 0.0428 (10) | 0.1065 (13) | 0.0052 (8) | −0.0350 (10) | −0.0064 (9) |
| O2 | 0.0757 (9) | 0.0616 (10) | 0.0661 (10) | 0.0228 (7) | −0.0169 (7) | −0.0194 (7) |
| O3 | 0.0307 (7) | 0.1177 (13) | 0.0730 (10) | −0.0009 (7) | −0.0059 (6) | 0.0066 (9) |
Geometric parameters (Å, °) top
| C1—C6 | 1.376 (2) | C9—O3 | 1.223 (2) |
| C1—C2 | 1.384 (3) | C9—N1 | 1.382 (2) |
| C1—C7 | 1.463 (3) | C9—C10 | 1.464 (2) |
| C2—C3 | 1.374 (3) | C10—C15 | 1.395 (2) |
| C2—H2 | 0.9300 | C10—C11 | 1.396 (3) |
| C3—C4 | 1.381 (3) | C11—C12 | 1.372 (3) |
| C3—H3 | 0.9300 | C11—H11 | 0.9300 |
| C4—C5 | 1.382 (3) | C12—C13 | 1.388 (3) |
| C4—H4 | 0.9300 | C12—H12 | 0.9300 |
| C5—C6 | 1.377 (3) | C13—C14 | 1.364 (3) |
| C5—H5 | 0.9300 | C13—H13 | 0.9300 |
| C6—C8 | 1.495 (2) | C14—C15 | 1.401 (2) |
| C7—O1 | 1.198 (2) | C14—H14 | 0.9300 |
| C7—O2 | 1.371 (3) | C15—C16 | 1.431 (3) |
| C8—O2 | 1.440 (2) | C16—N2 | 1.287 (2) |
| C8—N1 | 1.449 (2) | C16—H16 | 0.9300 |
| C8—H8 | 0.9800 | N1—N2 | 1.3786 (18) |
| | | |
| C6—C1—C2 | 121.43 (18) | O3—C9—C10 | 124.45 (17) |
| C6—C1—C7 | 108.00 (17) | N1—C9—C10 | 114.62 (15) |
| C2—C1—C7 | 130.55 (18) | C15—C10—C11 | 120.32 (16) |
| C3—C2—C1 | 117.82 (18) | C15—C10—C9 | 119.31 (16) |
| C3—C2—H2 | 121.1 | C11—C10—C9 | 120.37 (16) |
| C1—C2—H2 | 121.1 | C12—C11—C10 | 119.18 (18) |
| C2—C3—C4 | 120.73 (19) | C12—C11—H11 | 120.4 |
| C2—C3—H3 | 119.6 | C10—C11—H11 | 120.4 |
| C4—C3—H3 | 119.6 | C11—C12—C13 | 120.7 (2) |
| C3—C4—C5 | 121.39 (19) | C11—C12—H12 | 119.6 |
| C3—C4—H4 | 119.3 | C13—C12—H12 | 119.6 |
| C5—C4—H4 | 119.3 | C14—C13—C12 | 120.66 (19) |
| C6—C5—C4 | 117.77 (17) | C14—C13—H13 | 119.7 |
| C6—C5—H5 | 121.1 | C12—C13—H13 | 119.7 |
| C4—C5—H5 | 121.1 | C13—C14—C15 | 119.88 (18) |
| C1—C6—C5 | 120.86 (17) | C13—C14—H14 | 120.1 |
| C1—C6—C8 | 108.75 (16) | C15—C14—H14 | 120.1 |
| C5—C6—C8 | 130.38 (17) | C10—C15—C14 | 119.22 (18) |
| O1—C7—O2 | 120.9 (2) | C10—C15—C16 | 117.71 (16) |
| O1—C7—C1 | 130.7 (2) | C14—C15—C16 | 123.06 (17) |
| O2—C7—C1 | 108.36 (18) | N2—C16—C15 | 125.13 (16) |
| O2—C8—N1 | 110.25 (14) | N2—C16—H16 | 117.4 |
| O2—C8—C6 | 104.41 (14) | C15—C16—H16 | 117.4 |
| N1—C8—C6 | 114.15 (14) | N2—N1—C9 | 126.76 (14) |
| O2—C8—H8 | 109.3 | N2—N1—C8 | 113.34 (14) |
| N1—C8—H8 | 109.3 | C9—N1—C8 | 119.88 (14) |
| C6—C8—H8 | 109.3 | C16—N2—N1 | 116.35 (15) |
| O3—C9—N1 | 120.92 (17) | C7—O2—C8 | 110.40 (15) |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C16—H16···O3i | 0.93 | 2.41 | 3.2935 (19) | 158 |
| C4—H4···O1ii | 0.93 | 2.54 | 3.215 (2) | 130 |
| Symmetry codes: (i) x+1, y, z; (ii) x, y−1, z. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C16—H16···O3i | 0.93 | 2.41 | 3.2935 (19) | 158 |
| C4—H4···O1ii | 0.93 | 2.54 | 3.215 (2) | 130 |
| Symmetry codes: (i) x+1, y, z; (ii) x, y−1, z. |
The authors acknowledge South China Normal University for supporting this work.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Li, J., Zhang, F. X. & Shi, Q. Z. (2002). Chin. J. Inorg. Chem. 6, 643–645.
Nelson, S. M., Esho, F. S. & Drew, M. G. B. (1982). J. Chem. Soc. Dalton Trans. pp. 407–415.
Özbey, S., Ide, S. & Kendi, E. (1998). J. Mol. Struct. 442, 23–30.
Roesky, H. W. & Andruh, M. (2003). Coord. Chem. Rev. 236, 91–119.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
![[Figure 1]](./rz2283fig1thm.gif)
![[Figure 2]](./rz2283fig2thm.gif)
Hydrogen bonding as an important type of non-covalent interaction plays a great role in supramolecular chemistry and material sciences (Bernstein et al., 1995). Hydrogen bonding between solvent molecules and heterocycle compounds containing O or N donors has been confirmed to be a useful and powerful organizing force to form supramolecules (Roesky & Andruh, 2003). It has been reported (Nelson et al., 1982) that the reaction of 2,6-diacetylpyridine and 1,2-phenylenediamine can form benzimidazole groups via oxidative dehydrogenation. Recently, in the reaction of 5-bromo-2-hydroxybenzaldehyde and 1,2-phenylenediamine in the presence of anhydrous ethanol solution a benzimidazole derivate have also been isolated (Li et al., 2002). In this paper, we chose 2-carboxybenzaldehyde and hydrazinehydrate as reagents and unexpectedly isolated the heterocyclic title compound.
The molecular structure of the title compound is shown in Fig. 1. The phthalazine system is almost planar with the N1—C9—C10—C11 and C14—C15—C16—N2 torsion angles of -175.9 (2) and 178.0 (2)°, respectively. The phthalide ring system is also almost planar, the O2—C8—C6—C5 torsion angle being -176.7 (2)°. The C8—N1 bond length (1.449 (2) Å) indicates single bond character, and the corresponding bond angles demonstrate the sp3 character of the C8 atom (chiral centre). The C16—N2 bond length (1.287 (2) Å) in the phthalazine ring has double bond character and is shorter than that found in the azomethine group of a related compound (Özbey et al., 1998). The phthalide ring system is almost perpendicular to the phthalazine ring system, the dihedral angle they form being 87.1 (3)°. In the crystal structure, the molecules are linked via weak C—H···O hydrogen bonding interactions forming layers parallel to the ab plane (Table 1, Fig. 2).