supplementary materials
3-Hydroxy-3-nitromethylindolin-2-one
In the title compound, C9H8N2O4, the indolin-2-one ring system is substantially planar [maximum deviation = 0.0353 (15) Å]. In the crystal structure, intermolecular N-H
O and O-HO hydrogen bonds are responsible for the formation of a three-dimensional network.
Isatin (1 mmol) was dissolved in nitromethane (20 ml), catalyzed by DBU, until
the disappearance of the starting material, as evidenced by thin-layer
chromatography. The solvent was removed in vacuo and the residue was
separated by column chromatography (silica gel, petroleum ether/ethyl acetate
= 5:1 v/v), giving the title compound. 1H-NMR (D6—DMSO, 400 MHz): 10.56
(1H, s), 7.39 (1H, d, J = 7.2 Hz), 7.26 (1H, td, J = 7.6,
1.2 Hz), 6.98 (1H, t, J = 7.6 Hz), 6.85 (1H, d, J = 7.6 Hz),
6.75 (1H, s), 4.99 (2H, dd, J = 12.8, 8.0 Hz); 13C-NMR
(CDCl3, 100 MHz): 176.0, 142.6, 130.3, 127.9, 124.7, 121.9, 110.1, 78.5,
72.8; MS (EI) m/z: 208 (M+). 30 mg of the solid compound
was dissolved
in methanol (30 ml) and the solution was kept at room temperature for 4 d.
Slow evaporation of the solvent gave colourless single crystals suitable for
X-ray analysis.
All H atoms were positioned geometrically, with C–H = 0.93–0.97 Å,
O–H = 0.82 Å, N–H = 0.86 Å, and refined using riding model,
with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(O).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND Brandenburg (1999); software used to prepare material for publication: WinGX (Farrugia, 1999).
3-Hydroxy-3-nitromethylindolin-2-one
top
Crystal data top
| C9H8N2O4 | F(000) = 864 |
| Mr = 208.17 | Dx = 1.533 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 3122 reflections |
| a = 10.515 (2) Å | θ = 1.8–34.3° |
| b = 7.3736 (14) Å | µ = 0.12 mm−1 |
| c = 23.261 (4) Å | T = 293 K |
| V = 1803.6 (6) Å3 | Block, colourless |
| Z = 8 | 0.21 × 0.18 × 0.15 mm |
Data collection top
Bruker SMART CCD area-detector
diffractometer | 3807 independent reflections |
| Radiation source: fine-focus sealed tube | 2098 reflections with I > 2σ(I) |
| graphite | Rint = 0.026 |
| φ and ω scans | θmax = 34.3°, θmin = 1.8° |
Absorption correction: multi-scan
(SADABS; Bruker, 2002) | h = −12→12 |
| Tmin = 0.941, Tmax = 0.961 | k = −9→11 |
| 16322 measured reflections | l = −28→36 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.135 | H-atom parameters constrained |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.0699P)2 + 0.2564P]
where P = (Fo2 + 2Fc2)/3 |
| 3807 reflections | (Δ/σ)max = 0.001 |
| 136 parameters | Δρmax = 0.31 e Å−3 |
| 0 restraints | Δρmin = −0.21 e Å−3 |
Crystal data top
| C9H8N2O4 | V = 1803.6 (6) Å3 |
| Mr = 208.17 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 10.515 (2) Å | µ = 0.12 mm−1 |
| b = 7.3736 (14) Å | T = 293 K |
| c = 23.261 (4) Å | 0.21 × 0.18 × 0.15 mm |
Data collection top
Bruker SMART CCD area-detector
diffractometer | 3807 independent reflections |
Absorption correction: multi-scan
(SADABS; Bruker, 2002) | 2098 reflections with I > 2σ(I) |
| Tmin = 0.941, Tmax = 0.961 | Rint = 0.026 |
| 16322 measured reflections | θmax = 34.3° |
Refinement top
| R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
| wR(F2) = 0.135 | Δρmax = 0.31 e Å−3 |
| S = 1.03 | Δρmin = −0.21 e Å−3 |
| 3807 reflections | Absolute structure: ? |
| 136 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 | |
| N1 | 0.73793 (10) | 0.22536 (14) | 0.59575 (4) | 0.0345 (2) | |
| H1A | 0.8121 | 0.2684 | 0.5882 | 0.041* | |
| C7 | 0.68870 (11) | 0.20320 (15) | 0.65183 (5) | 0.0313 (3) | |
| C8 | 0.56744 (11) | 0.12898 (14) | 0.64887 (5) | 0.0294 (2) | |
| C2 | 0.53211 (11) | 0.10262 (14) | 0.58677 (5) | 0.0287 (2) | |
| O1 | 0.67140 (9) | 0.16574 (14) | 0.50346 (4) | 0.0452 (3) | |
| C3 | 0.50087 (12) | 0.08802 (17) | 0.69844 (5) | 0.0374 (3) | |
| H3A | 0.4196 | 0.0386 | 0.6966 | 0.045* | |
| C9 | 0.41221 (12) | 0.20580 (16) | 0.56828 (5) | 0.0354 (3) | |
| H9A | 0.4059 | 0.2048 | 0.5267 | 0.043* | |
| H9B | 0.3377 | 0.1453 | 0.5837 | 0.043* | |
| C6 | 0.74609 (13) | 0.24268 (17) | 0.70380 (5) | 0.0396 (3) | |
| H6A | 0.8264 | 0.2951 | 0.7055 | 0.048* | |
| N2 | 0.41524 (12) | 0.39586 (15) | 0.58894 (5) | 0.0470 (3) | |
| C5 | 0.67832 (15) | 0.20049 (18) | 0.75336 (6) | 0.0450 (3) | |
| H5A | 0.7145 | 0.2253 | 0.7890 | 0.054* | |
| C4 | 0.55872 (14) | 0.1227 (2) | 0.75123 (5) | 0.0448 (3) | |
| H4A | 0.5167 | 0.0934 | 0.7852 | 0.054* | |
| O3 | 0.50508 (14) | 0.48843 (17) | 0.57450 (9) | 0.0904 (5) | |
| O4 | 0.32881 (14) | 0.44827 (19) | 0.61941 (6) | 0.0776 (4) | |
| C1 | 0.65394 (11) | 0.17044 (15) | 0.55545 (5) | 0.0317 (3) | |
| O2 | 0.51621 (8) | −0.08414 (11) | 0.57414 (4) | 0.0391 (2) | |
| H2A | 0.4586 | −0.0966 | 0.5507 | 0.059* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| N1 | 0.0244 (5) | 0.0384 (5) | 0.0408 (5) | −0.0081 (4) | −0.0017 (4) | 0.0000 (4) |
| C7 | 0.0299 (6) | 0.0267 (5) | 0.0372 (6) | 0.0003 (4) | −0.0040 (4) | 0.0000 (4) |
| C8 | 0.0259 (6) | 0.0268 (5) | 0.0353 (5) | 0.0019 (4) | −0.0030 (4) | 0.0005 (4) |
| C2 | 0.0237 (6) | 0.0254 (5) | 0.0370 (5) | −0.0008 (4) | −0.0022 (4) | −0.0024 (4) |
| O1 | 0.0378 (5) | 0.0603 (6) | 0.0374 (5) | −0.0092 (4) | 0.0023 (4) | −0.0040 (4) |
| C3 | 0.0303 (6) | 0.0389 (6) | 0.0431 (6) | 0.0043 (5) | 0.0031 (5) | 0.0048 (5) |
| C9 | 0.0276 (6) | 0.0352 (6) | 0.0435 (6) | 0.0037 (5) | −0.0069 (5) | −0.0055 (5) |
| C6 | 0.0370 (7) | 0.0356 (6) | 0.0463 (6) | −0.0006 (5) | −0.0139 (5) | −0.0037 (5) |
| N2 | 0.0474 (7) | 0.0366 (6) | 0.0569 (7) | 0.0135 (5) | −0.0168 (5) | −0.0048 (5) |
| C5 | 0.0520 (8) | 0.0454 (7) | 0.0377 (6) | 0.0136 (6) | −0.0120 (5) | −0.0052 (5) |
| C4 | 0.0476 (8) | 0.0503 (7) | 0.0364 (6) | 0.0154 (6) | 0.0037 (5) | 0.0044 (5) |
| O3 | 0.0736 (9) | 0.0354 (6) | 0.1620 (17) | −0.0061 (6) | −0.0100 (9) | 0.0024 (7) |
| O4 | 0.0866 (10) | 0.0763 (8) | 0.0700 (8) | 0.0389 (7) | −0.0037 (7) | −0.0255 (7) |
| C1 | 0.0262 (6) | 0.0314 (5) | 0.0374 (6) | −0.0017 (4) | −0.0008 (4) | −0.0019 (4) |
| O2 | 0.0317 (5) | 0.0265 (4) | 0.0591 (5) | −0.0010 (3) | −0.0098 (4) | −0.0076 (3) |
Geometric parameters (Å, °) top
| N1—C1 | 1.3500 (16) | C3—H3A | 0.9300 |
| N1—C7 | 1.4130 (16) | C9—N2 | 1.4819 (17) |
| N1—H1A | 0.8600 | C9—H9A | 0.9700 |
| C7—C6 | 1.3822 (17) | C9—H9B | 0.9700 |
| C7—C8 | 1.3893 (17) | C6—C5 | 1.390 (2) |
| C8—C3 | 1.3823 (17) | C6—H6A | 0.9300 |
| C8—C2 | 1.5042 (15) | N2—O3 | 1.2129 (19) |
| C2—O2 | 1.4180 (13) | N2—O4 | 1.2155 (18) |
| C2—C9 | 1.5340 (16) | C5—C4 | 1.383 (2) |
| C2—C1 | 1.5563 (16) | C5—H5A | 0.9300 |
| O1—C1 | 1.2237 (14) | C4—H4A | 0.9300 |
| C3—C4 | 1.3940 (19) | O2—H2A | 0.8200 |
| | | |
| C1—N1—C7 | 111.51 (10) | C2—C9—H9A | 109.4 |
| C1—N1—H1A | 124.2 | N2—C9—H9B | 109.4 |
| C7—N1—H1A | 124.2 | C2—C9—H9B | 109.4 |
| C6—C7—C8 | 121.81 (11) | H9A—C9—H9B | 108.0 |
| C6—C7—N1 | 128.55 (11) | C7—C6—C5 | 117.02 (12) |
| C8—C7—N1 | 109.63 (10) | C7—C6—H6A | 121.5 |
| C3—C8—C7 | 120.63 (11) | C5—C6—H6A | 121.5 |
| C3—C8—C2 | 130.37 (11) | O3—N2—O4 | 124.39 (14) |
| C7—C8—C2 | 108.98 (10) | O3—N2—C9 | 117.33 (13) |
| O2—C2—C8 | 110.71 (9) | O4—N2—C9 | 118.28 (14) |
| O2—C2—C9 | 109.07 (9) | C4—C5—C6 | 121.94 (12) |
| C8—C2—C9 | 114.09 (9) | C4—C5—H5A | 119.0 |
| O2—C2—C1 | 108.19 (9) | C6—C5—H5A | 119.0 |
| C8—C2—C1 | 101.81 (9) | C5—C4—C3 | 120.29 (12) |
| C9—C2—C1 | 112.70 (9) | C5—C4—H4A | 119.9 |
| C8—C3—C4 | 118.28 (12) | C3—C4—H4A | 119.9 |
| C8—C3—H3A | 120.9 | O1—C1—N1 | 126.62 (11) |
| C4—C3—H3A | 120.9 | O1—C1—C2 | 125.24 (10) |
| N2—C9—C2 | 111.13 (9) | N1—C1—C2 | 108.05 (10) |
| N2—C9—H9A | 109.4 | C2—O2—H2A | 109.5 |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O2i | 0.86 | 2.13 | 2.9849 (14) | 171 |
| O2—H2A···O1ii | 0.82 | 1.93 | 2.7408 (13) | 171 |
| Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) −x+1, −y, −z+1. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O2i | 0.86 | 2.13 | 2.9849 (14) | 171 |
| O2—H2A···O1ii | 0.82 | 1.93 | 2.7408 (13) | 171 |
| Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) −x+1, −y, −z+1. |
This work was supported financially by two grants from the Natural Science
Research Plan Projects of Shaanxi Science and Technology Department (SJ08B20)
and the Scientific Research Plan Projects of Shaanxi Education Department (08 J K 413).
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Bruker (2002). SMART, SAINT and SADABS. 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.
Imre, F., Miklós, N., Áron, S., Gábor, B. & László, T. (2001). Tetrahedron, 57, 1129–1137.
Long, D. R., Richards, C. G. & Ross, M. S. F. (1978). J. Heterocycl. Chem. 15, 633–637.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
![[Figure 1]](./rz2364fig1thm.gif)
![[Figure 2]](./rz2364fig2thm.gif)
3-Hydroxy-3-nitromethyl-1,3-dihydro-indolin-2-one, an important intermediate for the synthesis of natural products, has been synthesized by Henry reaction (Imre et al.,2001; Long et al., 1978). Dehydration of this compound as well as its derivatives provides 3-nitromethylene-1,3-dihydro-indolin-2-one, which is used as a dipolarophile in 1,3-dipolar cycloadditon reactions to synthesize spiro-oxindole compounds. In this paper we report the X-ray crystal structure of the title compound.
The X-ray structural analysis confirmed the assignment of the structure of the title compound from spectroscopic data. The molecular structure is depicted in Fig. 1, and a packing diagram of is depicted in Fig. 2. Geometric parameters of the title compound are in the usual ranges. The indolin-2-one ring system is substantially planar, with a maximum deviation of 0.0353 (15) Å for atom C4. In the crystal structure, intermolecular N–H···O and O–H···O hydrogen bonds (Table 1) are effective in the stabilization of the structure and are responsible for the formation of a three-dimensional network. The O atoms of nitro group are not involved in any hydrogen bond.