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organic compounds
rac-2-Hydroxy-2-(2-oxocyclopentyl)-1H-indene-1,3(2H)-dione
aDepartment of Physics, Madurai Kamaraj University, Madurai 625 021, India, bDepartment of Organic Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625 021, India, cDepartment of Physics, The Madura College, Madurai 625 011, India, and dDepartment of Food Science and Technology, University of Ruhuna, Mapalana, Kamburupitiya 81100, Sri Lanka
*Correspondence e-mail: plakshmannilantha@ymail.com
In the title compound, C14H12O4, the indene unit is essentially planar [r.m.s. deviation = 0.0309 (1) Å] and the cyclopentanone ring adopts a In the crystal, molecules are joined via pairs of O—H⋯O hydrogen bonds into centrosymmetric dimers.
Experimental
Crystal data
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Refinement
|
|
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996
); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: PLATON (Spek, 2009
); software used to prepare material for publication: SHELXL97.
Supporting information
https://doi.org/10.1107/S1600536810042856/gk2301sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810042856/gk2301Isup2.hkl
A mixture of cyclopentanone (0.5 g, 0.006 mol) and ninhydrin (1.05 g, 0.006 mol) in methanol (10 ml) was heated under reflux for 4 h in the presence of solid sodium ethoxide (0.4 g, 0.006 mol). After completion of the reaction, as was evident from TLC, the reaction mixture was poured into crushed ice, extracted with dichloromethane and subjected to column chromatographic purification using petroleum ether:ethyl acetate mixture (90:10 v/v) to obtain the product in 50% yield. The compound was further recrystallized from ethyl acetate to obtain suitable crystals for X-ray studies (m.p. 543 K)
All H atoms were placed at calculated positions and allowed to ride on their carrier atoms with C—H = 0.93–0.97 Å, Uiso = 1.2Ueq(C) and O—H = 0.82 Å, and Uiso = 1.5Ueq(O) .
Ninhydrin derivatives constitute a versatile class of compounds with profound biological activities such as antibacterial, anticonvulsant, anticancer and anti-inflammatory activities. The present work constitutes the synthesis of various ninhydrin derivatives which are being tested for anti-tubercular and other biological activities.
For a similar structure, see: Penthala et al. (2009).
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell
CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008). ![]() | Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme. |
![]() | Fig. 2. The packing diagram of the title compound. |
C14H12O4 | Z = 2 |
Mr = 244.24 | F(000) = 256 |
Triclinic, P1 | Dx = 1.384 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 8.044 (3) Å | Cell parameters from 25 reflections |
b = 8.404 (4) Å | θ = 2–25° |
c = 10.239 (3) Å | µ = 0.10 mm−1 |
α = 66.95 (3)° | T = 293 K |
β = 74.36 (2)° | Block, colourless |
γ = 68.50 (3)° | 0.26 × 0.22 × 0.19 mm |
V = 586.1 (4) Å3 |
Nonius MACH3 diffractometer | 1886 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.016 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
ω–2θ scans | h = −1→9 |
Absorption correction: ψ scan (North et al., 1968) | k = −9→9 |
Tmin = 0.974, Tmax = 0.981 | l = −11→12 |
2534 measured reflections | 3 standard reflections every 60 min |
2054 independent reflections | intensity decay: none |
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)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0487P)2 + 0.2034P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
2054 reflections | Δρmax = 0.25 e Å−3 |
164 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.059 (7) |
C14H12O4 | γ = 68.50 (3)° |
Mr = 244.24 | V = 586.1 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.044 (3) Å | Mo Kα radiation |
b = 8.404 (4) Å | µ = 0.10 mm−1 |
c = 10.239 (3) Å | T = 293 K |
α = 66.95 (3)° | 0.26 × 0.22 × 0.19 mm |
β = 74.36 (2)° |
Nonius MACH3 diffractometer | 1886 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.016 |
Tmin = 0.974, Tmax = 0.981 | 3 standard reflections every 60 min |
2534 measured reflections | intensity decay: none |
2054 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.25 e Å−3 |
2054 reflections | Δρmin = −0.23 e Å−3 |
164 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 | ||
C1 | 0.4901 (2) | 0.0143 (2) | 0.33717 (14) | 0.0367 (4) | |
C2 | 0.6584 (2) | −0.1372 (2) | 0.32374 (19) | 0.0505 (4) | |
H2A | 0.7411 | −0.1548 | 0.3852 | 0.061* | |
H2B | 0.7191 | −0.1129 | 0.2254 | 0.061* | |
C3 | 0.5929 (3) | −0.3013 (2) | 0.3708 (2) | 0.0551 (5) | |
H3A | 0.5821 | −0.3580 | 0.4742 | 0.066* | |
H3B | 0.6745 | −0.3896 | 0.3258 | 0.066* | |
C4 | 0.4084 (2) | −0.2245 (2) | 0.3207 (2) | 0.0494 (4) | |
H4A | 0.3353 | −0.3064 | 0.3719 | 0.059* | |
H4B | 0.4206 | −0.2008 | 0.2184 | 0.059* | |
C5 | 0.3268 (2) | −0.04868 (19) | 0.35711 (15) | 0.0367 (4) | |
H5 | 0.2797 | −0.0818 | 0.4598 | 0.044* | |
C6 | 0.17097 (19) | 0.09543 (19) | 0.27852 (15) | 0.0353 (3) | |
C7 | 0.2311 (2) | 0.1817 (2) | 0.11679 (15) | 0.0387 (4) | |
C8 | 0.2136 (2) | 0.3728 (2) | 0.09029 (16) | 0.0379 (4) | |
C9 | 0.2631 (2) | 0.5004 (2) | −0.03520 (18) | 0.0502 (4) | |
H9 | 0.3169 | 0.4710 | −0.1186 | 0.060* | |
C10 | 0.2304 (3) | 0.6721 (2) | −0.0329 (2) | 0.0573 (5) | |
H10 | 0.2618 | 0.7600 | −0.1163 | 0.069* | |
C11 | 0.1513 (3) | 0.7168 (2) | 0.0916 (2) | 0.0561 (5) | |
H11 | 0.1308 | 0.8338 | 0.0902 | 0.067* | |
C12 | 0.1028 (2) | 0.5900 (2) | 0.21723 (19) | 0.0470 (4) | |
H12 | 0.0508 | 0.6193 | 0.3008 | 0.056* | |
C13 | 0.13396 (19) | 0.4179 (2) | 0.21488 (16) | 0.0366 (3) | |
C14 | 0.09696 (19) | 0.2590 (2) | 0.33215 (15) | 0.0362 (3) | |
O1 | 0.48152 (16) | 0.16243 (15) | 0.33474 (12) | 0.0484 (3) | |
O2 | 0.03172 (15) | 0.02227 (15) | 0.29221 (13) | 0.0487 (3) | |
H2 | −0.0080 | −0.0170 | 0.3773 | 0.073* | |
O3 | 0.2801 (2) | 0.10548 (17) | 0.02872 (13) | 0.0602 (4) | |
O4 | 0.01604 (16) | 0.25544 (16) | 0.45179 (12) | 0.0502 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0390 (8) | 0.0451 (9) | 0.0268 (7) | −0.0147 (7) | −0.0051 (6) | −0.0103 (6) |
C2 | 0.0385 (9) | 0.0636 (11) | 0.0529 (10) | −0.0090 (8) | −0.0067 (7) | −0.0282 (9) |
C3 | 0.0563 (11) | 0.0472 (10) | 0.0590 (11) | 0.0008 (8) | −0.0178 (8) | −0.0231 (8) |
C4 | 0.0534 (10) | 0.0382 (9) | 0.0599 (10) | −0.0117 (7) | −0.0158 (8) | −0.0162 (7) |
C5 | 0.0392 (8) | 0.0369 (8) | 0.0330 (7) | −0.0144 (6) | −0.0043 (6) | −0.0082 (6) |
C6 | 0.0368 (8) | 0.0355 (8) | 0.0349 (7) | −0.0164 (6) | −0.0048 (6) | −0.0077 (6) |
C7 | 0.0419 (8) | 0.0409 (8) | 0.0338 (8) | −0.0138 (6) | −0.0051 (6) | −0.0117 (6) |
C8 | 0.0378 (8) | 0.0392 (8) | 0.0345 (7) | −0.0138 (6) | −0.0071 (6) | −0.0064 (6) |
C9 | 0.0581 (10) | 0.0529 (10) | 0.0353 (8) | −0.0246 (8) | −0.0039 (7) | −0.0043 (7) |
C10 | 0.0668 (12) | 0.0465 (10) | 0.0520 (10) | −0.0299 (9) | −0.0110 (9) | 0.0044 (8) |
C11 | 0.0639 (11) | 0.0356 (9) | 0.0691 (12) | −0.0193 (8) | −0.0185 (9) | −0.0073 (8) |
C12 | 0.0483 (9) | 0.0397 (9) | 0.0527 (10) | −0.0113 (7) | −0.0083 (7) | −0.0158 (7) |
C13 | 0.0335 (7) | 0.0367 (8) | 0.0372 (8) | −0.0108 (6) | −0.0057 (6) | −0.0087 (6) |
C14 | 0.0312 (7) | 0.0400 (8) | 0.0343 (8) | −0.0118 (6) | −0.0028 (6) | −0.0091 (6) |
O1 | 0.0516 (7) | 0.0463 (7) | 0.0537 (7) | −0.0207 (5) | −0.0116 (5) | −0.0145 (5) |
O2 | 0.0464 (7) | 0.0514 (7) | 0.0525 (7) | −0.0268 (5) | −0.0123 (5) | −0.0066 (5) |
O3 | 0.0894 (10) | 0.0528 (7) | 0.0402 (6) | −0.0226 (7) | −0.0035 (6) | −0.0195 (6) |
O4 | 0.0528 (7) | 0.0511 (7) | 0.0383 (6) | −0.0173 (5) | 0.0087 (5) | −0.0143 (5) |
C1—O1 | 1.2116 (19) | C6—C7 | 1.545 (2) |
C1—C2 | 1.499 (2) | C7—O3 | 1.2059 (19) |
C1—C5 | 1.526 (2) | C7—C8 | 1.479 (2) |
C2—C3 | 1.512 (3) | C8—C9 | 1.384 (2) |
C2—H2A | 0.9700 | C8—C13 | 1.393 (2) |
C2—H2B | 0.9700 | C9—C10 | 1.378 (3) |
C3—C4 | 1.528 (3) | C9—H9 | 0.9300 |
C3—H3A | 0.9700 | C10—C11 | 1.391 (3) |
C3—H3B | 0.9700 | C10—H10 | 0.9300 |
C4—C5 | 1.531 (2) | C11—C12 | 1.379 (3) |
C4—H4A | 0.9700 | C11—H11 | 0.9300 |
C4—H4B | 0.9700 | C12—C13 | 1.383 (2) |
C5—C6 | 1.534 (2) | C12—H12 | 0.9300 |
C5—H5 | 0.9800 | C13—C14 | 1.469 (2) |
C6—O2 | 1.4160 (18) | C14—O4 | 1.2169 (18) |
C6—C14 | 1.536 (2) | O2—H2 | 0.8200 |
O1—C1—C2 | 126.74 (15) | C5—C6—C14 | 110.99 (12) |
O1—C1—C5 | 124.60 (14) | O2—C6—C7 | 107.82 (12) |
C2—C1—C5 | 108.66 (13) | C5—C6—C7 | 113.02 (12) |
C1—C2—C3 | 104.51 (14) | C14—C6—C7 | 102.49 (12) |
C1—C2—H2A | 110.9 | O3—C7—C8 | 126.80 (14) |
C3—C2—H2A | 110.9 | O3—C7—C6 | 125.30 (14) |
C1—C2—H2B | 110.9 | C8—C7—C6 | 107.89 (13) |
C3—C2—H2B | 110.9 | C9—C8—C13 | 120.56 (15) |
H2A—C2—H2B | 108.9 | C9—C8—C7 | 129.09 (15) |
C2—C3—C4 | 103.75 (14) | C13—C8—C7 | 110.35 (13) |
C2—C3—H3A | 111.0 | C10—C9—C8 | 118.04 (17) |
C4—C3—H3A | 111.0 | C10—C9—H9 | 121.0 |
C2—C3—H3B | 111.0 | C8—C9—H9 | 121.0 |
C4—C3—H3B | 111.0 | C9—C10—C11 | 121.33 (16) |
H3A—C3—H3B | 109.0 | C9—C10—H10 | 119.3 |
C3—C4—C5 | 102.74 (13) | C11—C10—H10 | 119.3 |
C3—C4—H4A | 111.2 | C12—C11—C10 | 120.90 (17) |
C5—C4—H4A | 111.2 | C12—C11—H11 | 119.6 |
C3—C4—H4B | 111.2 | C10—C11—H11 | 119.6 |
C5—C4—H4B | 111.2 | C11—C12—C13 | 117.90 (17) |
H4A—C4—H4B | 109.1 | C11—C12—H12 | 121.1 |
C1—C5—C4 | 103.78 (13) | C13—C12—H12 | 121.1 |
C1—C5—C6 | 114.77 (12) | C12—C13—C8 | 121.28 (14) |
C4—C5—C6 | 117.09 (13) | C12—C13—C14 | 129.02 (15) |
C1—C5—H5 | 106.9 | C8—C13—C14 | 109.69 (14) |
C4—C5—H5 | 106.9 | O4—C14—C13 | 126.49 (15) |
C6—C5—H5 | 106.9 | O4—C14—C6 | 124.45 (13) |
O2—C6—C5 | 111.26 (12) | C13—C14—C6 | 109.03 (12) |
O2—C6—C14 | 110.92 (12) | C6—O2—H2 | 109.5 |
O1—C1—C2—C3 | 166.12 (15) | O3—C7—C8—C13 | 173.24 (16) |
C5—C1—C2—C3 | −13.03 (17) | C6—C7—C8—C13 | −5.46 (17) |
C1—C2—C3—C4 | 33.50 (18) | C13—C8—C9—C10 | −0.3 (2) |
C2—C3—C4—C5 | −41.27 (18) | C7—C8—C9—C10 | 179.19 (16) |
O1—C1—C5—C4 | 168.45 (14) | C8—C9—C10—C11 | 0.5 (3) |
C2—C1—C5—C4 | −12.37 (16) | C9—C10—C11—C12 | −0.1 (3) |
O1—C1—C5—C6 | 39.4 (2) | C10—C11—C12—C13 | −0.5 (3) |
C2—C1—C5—C6 | −141.39 (14) | C11—C12—C13—C8 | 0.7 (2) |
C3—C4—C5—C1 | 32.54 (16) | C11—C12—C13—C14 | 179.53 (15) |
C3—C4—C5—C6 | 160.13 (14) | C9—C8—C13—C12 | −0.3 (2) |
C1—C5—C6—O2 | 174.96 (11) | C7—C8—C13—C12 | −179.90 (14) |
C4—C5—C6—O2 | 52.92 (18) | C9—C8—C13—C14 | −179.32 (14) |
C1—C5—C6—C14 | −61.01 (16) | C7—C8—C13—C14 | 1.09 (17) |
C4—C5—C6—C14 | 176.94 (12) | C12—C13—C14—O4 | 7.0 (3) |
C1—C5—C6—C7 | 53.49 (17) | C8—C13—C14—O4 | −174.07 (15) |
C4—C5—C6—C7 | −68.56 (17) | C12—C13—C14—C6 | −175.15 (15) |
O2—C6—C7—O3 | −54.4 (2) | C8—C13—C14—C6 | 3.77 (16) |
C5—C6—C7—O3 | 69.0 (2) | O2—C6—C14—O4 | 56.38 (19) |
C14—C6—C7—O3 | −171.52 (16) | C5—C6—C14—O4 | −67.85 (19) |
O2—C6—C7—C8 | 124.29 (13) | C7—C6—C14—O4 | 171.22 (14) |
C5—C6—C7—C8 | −112.31 (14) | O2—C6—C14—C13 | −121.51 (13) |
C14—C6—C7—C8 | 7.21 (15) | C5—C6—C14—C13 | 114.26 (13) |
O3—C7—C8—C9 | −6.3 (3) | C7—C6—C14—C13 | −6.67 (15) |
C6—C7—C8—C9 | 174.99 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O4i | 0.82 | 2.09 | 2.791 (2) | 143 |
C2—H2A···O4ii | 0.97 | 2.60 | 3.560 (2) | 171 |
C2—H2B···O3iii | 0.97 | 2.58 | 3.423 (2) | 146 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C14H12O4 |
Mr | 244.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.044 (3), 8.404 (4), 10.239 (3) |
α, β, γ (°) | 66.95 (3), 74.36 (2), 68.50 (3) |
V (Å3) | 586.1 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.26 × 0.22 × 0.19 |
Data collection | |
Diffractometer | Nonius MACH3 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.974, 0.981 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2534, 2054, 1886 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.104, 1.07 |
No. of reflections | 2054 |
No. of parameters | 164 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.23 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O4i | 0.82 | 2.09 | 2.791 (2) | 143 |
Symmetry code: (i) −x, −y, −z+1. |
Acknowledgements
JKS thanks the UGC for an RFSMS fellowship.
References
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1996). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Penthala, N. R., Reddy, T. R. Y., Parkin, S. & Crooks, P. A. (2009). Acta Cryst. E65, o1877. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Ninhydrin derivatives constitute a versatile class of compounds with profound biological activities such as antibacterial, anticonvulsant, anticancer and anti-inflammatory activities. The present work constitutes the synthesis of various ninhydrin derivatives which are being tested for anti-tubercular and other biological activities.