organic compounds
2-Acetonyl-2-hydroxyindan-1,3-dione
aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and bDepartment of Chemistry, Aligarh Muslim University, Aligarh 202 002, Uttar Pradesh, India
*Correspondence e-mail: hkfun@usm.my
In the title compound, C12H10O4, the five-membered ring adopts an with the Csp3 atom at the flap [deviation = 0.145 (2) Å]. In the molecules are linked by intermolecular O—H⋯O and C—H⋯O hydrogen bonds, forming a three-dimensional network.
Related literature
For the activities and applications of ninhydrin derivatives, see: Ruhemann (1910); Kaiser et al. (1970). For bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).
Supporting information
10.1107/S1600536809016067/ci2791sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809016067/ci2791Isup2.hkl
The title compound was synthesized by the reaction of ninhydrin (1.78 g), trichloroacetic acid (1.64 g) and catalytic amount of magnesium in presence of acetone. Ninhydrin and tricholoro acetic acid in molar ratio 1:1 were allowed to reflux with acetone in presence of Mg turnings for 1 h. The reaction mixture was dried under reduced pressure and was purified by
over silica gel column. Elution of the column with petroleum ether-diethyl ether (4:1) followed by crystallization with petroleum ether-chloroform (1:1) afforded fine crystals of the title compound (120 mg, m.p. 399 K).Atom H1O3 was located in a difference Fourier map and refined freely. The remaining H atoms were positioned geometrically and refined using a riding model, with C-H = 0.93–0.97 Å and Uiso(H) = 1.2 and 1.5 Ueq(C). A rotating-group model was applied for the methyl group. In the absence of significant
1513 Friedel pairs were merged for the final refinement.Data collection: APEX2 (Bruker, 2005); cell
SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).C12H10O4 | F(000) = 456 |
Mr = 218.20 | Dx = 1.450 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 5199 reflections |
a = 18.1190 (2) Å | θ = 3.2–31.5° |
b = 8.8135 (1) Å | µ = 0.11 mm−1 |
c = 6.2585 (1) Å | T = 100 K |
V = 999.43 (2) Å3 | Plate, yellow |
Z = 4 | 0.29 × 0.19 × 0.08 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 1818 independent reflections |
Radiation source: fine-focus sealed tube | 1720 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ϕ and ω scans | θmax = 31.7°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −26→26 |
Tmin = 0.969, Tmax = 0.992 | k = −12→13 |
14417 measured reflections | l = −9→9 |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.18 | w = 1/[σ2(Fo2) + (0.0696P)2 + 0.0468P] where P = (Fo2 + 2Fc2)/3 |
1818 reflections | (Δ/σ)max = 0.001 |
150 parameters | Δρmax = 0.42 e Å−3 |
1 restraint | Δρmin = −0.24 e Å−3 |
C12H10O4 | V = 999.43 (2) Å3 |
Mr = 218.20 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 18.1190 (2) Å | µ = 0.11 mm−1 |
b = 8.8135 (1) Å | T = 100 K |
c = 6.2585 (1) Å | 0.29 × 0.19 × 0.08 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 1818 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1720 reflections with I > 2σ(I) |
Tmin = 0.969, Tmax = 0.992 | Rint = 0.034 |
14417 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 1 restraint |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.18 | Δρmax = 0.42 e Å−3 |
1818 reflections | Δρmin = −0.24 e Å−3 |
150 parameters |
Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K. |
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 | ||
O1 | 0.13189 (7) | 0.07160 (14) | 0.5143 (2) | 0.0217 (3) | |
O2 | 0.21514 (6) | 0.36656 (13) | 1.0967 (2) | 0.0158 (2) | |
O3 | 0.27231 (6) | 0.16183 (13) | 0.7536 (2) | 0.0153 (2) | |
O4 | 0.06202 (6) | 0.15803 (14) | 1.0224 (2) | 0.0165 (3) | |
C1 | 0.14680 (8) | 0.17868 (17) | 0.6278 (3) | 0.0130 (3) | |
C2 | 0.12208 (8) | 0.33840 (16) | 0.6024 (3) | 0.0121 (3) | |
C3 | 0.07836 (8) | 0.40053 (18) | 0.4425 (3) | 0.0145 (3) | |
H3A | 0.0609 | 0.3415 | 0.3301 | 0.017* | |
C4 | 0.06148 (8) | 0.55486 (19) | 0.4566 (3) | 0.0161 (3) | |
H4A | 0.0314 | 0.5991 | 0.3535 | 0.019* | |
C5 | 0.08914 (9) | 0.64417 (18) | 0.6239 (3) | 0.0163 (3) | |
H5A | 0.0784 | 0.7473 | 0.6273 | 0.020* | |
C6 | 0.13236 (8) | 0.58104 (17) | 0.7850 (3) | 0.0144 (3) | |
H6A | 0.1502 | 0.6401 | 0.8967 | 0.017* | |
C7 | 0.14801 (8) | 0.42619 (16) | 0.7731 (3) | 0.0115 (3) | |
C8 | 0.18969 (8) | 0.32969 (16) | 0.9244 (3) | 0.0115 (3) | |
C9 | 0.19764 (8) | 0.17061 (16) | 0.8252 (3) | 0.0107 (3) | |
C10 | 0.17882 (8) | 0.04091 (17) | 0.9758 (3) | 0.0125 (3) | |
H10A | 0.1889 | −0.0547 | 0.9049 | 0.015* | |
H10B | 0.2103 | 0.0470 | 1.1008 | 0.015* | |
C11 | 0.09891 (8) | 0.04343 (17) | 1.0464 (3) | 0.0121 (3) | |
C12 | 0.06798 (9) | −0.10028 (18) | 1.1373 (3) | 0.0173 (3) | |
H12A | 0.0295 | −0.0763 | 1.2371 | 0.026* | |
H12B | 0.1064 | −0.1552 | 1.2092 | 0.026* | |
H12C | 0.0482 | −0.1614 | 1.0240 | 0.026* | |
H1O3 | 0.2777 (12) | 0.069 (3) | 0.713 (5) | 0.029 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0303 (6) | 0.0148 (5) | 0.0200 (6) | 0.0013 (4) | −0.0085 (5) | −0.0058 (5) |
O2 | 0.0176 (5) | 0.0137 (5) | 0.0161 (6) | 0.0002 (4) | −0.0044 (5) | −0.0035 (4) |
O3 | 0.0116 (5) | 0.0132 (5) | 0.0211 (6) | 0.0002 (4) | 0.0044 (5) | −0.0038 (4) |
O4 | 0.0150 (5) | 0.0170 (5) | 0.0174 (6) | 0.0032 (4) | 0.0002 (5) | −0.0008 (5) |
C1 | 0.0142 (6) | 0.0114 (6) | 0.0133 (7) | −0.0005 (5) | −0.0010 (6) | −0.0014 (5) |
C2 | 0.0127 (6) | 0.0113 (6) | 0.0124 (7) | 0.0001 (4) | 0.0006 (5) | −0.0010 (5) |
C3 | 0.0153 (6) | 0.0160 (7) | 0.0123 (7) | −0.0008 (5) | −0.0012 (6) | 0.0003 (6) |
C4 | 0.0159 (6) | 0.0167 (7) | 0.0156 (7) | 0.0019 (5) | −0.0010 (6) | 0.0044 (6) |
C5 | 0.0182 (6) | 0.0127 (6) | 0.0181 (8) | 0.0030 (5) | 0.0002 (6) | 0.0011 (6) |
C6 | 0.0156 (6) | 0.0111 (6) | 0.0165 (7) | 0.0012 (5) | −0.0008 (6) | −0.0022 (6) |
C7 | 0.0119 (6) | 0.0105 (6) | 0.0122 (7) | 0.0004 (4) | 0.0004 (5) | 0.0000 (5) |
C8 | 0.0095 (5) | 0.0114 (6) | 0.0135 (7) | −0.0011 (5) | 0.0002 (5) | −0.0017 (5) |
C9 | 0.0097 (5) | 0.0099 (6) | 0.0125 (6) | 0.0008 (4) | 0.0002 (5) | −0.0016 (5) |
C10 | 0.0117 (6) | 0.0106 (6) | 0.0152 (7) | 0.0008 (4) | 0.0009 (5) | 0.0006 (5) |
C11 | 0.0125 (6) | 0.0142 (6) | 0.0097 (6) | −0.0006 (5) | −0.0007 (5) | −0.0019 (5) |
C12 | 0.0177 (7) | 0.0147 (7) | 0.0195 (8) | −0.0027 (5) | 0.0039 (6) | −0.0004 (6) |
O1—C1 | 1.212 (2) | C5—H5A | 0.93 |
O2—C8 | 1.217 (2) | C6—C7 | 1.396 (2) |
O3—C9 | 1.4273 (17) | C6—H6A | 0.93 |
O3—H1O3 | 0.86 (3) | C7—C8 | 1.480 (2) |
O4—C11 | 1.2205 (19) | C8—C9 | 1.540 (2) |
C1—C2 | 1.486 (2) | C9—C10 | 1.521 (2) |
C1—C9 | 1.542 (2) | C10—C11 | 1.514 (2) |
C2—C3 | 1.389 (2) | C10—H10A | 0.97 |
C2—C7 | 1.400 (2) | C10—H10B | 0.97 |
C3—C4 | 1.397 (2) | C11—C12 | 1.498 (2) |
C3—H3A | 0.93 | C12—H12A | 0.96 |
C4—C5 | 1.402 (2) | C12—H12B | 0.96 |
C4—H4A | 0.93 | C12—H12C | 0.96 |
C5—C6 | 1.393 (2) | ||
C9—O3—H1O3 | 104.5 (16) | O2—C8—C9 | 124.39 (14) |
O1—C1—C2 | 127.44 (16) | C7—C8—C9 | 108.24 (14) |
O1—C1—C9 | 124.53 (14) | O3—C9—C10 | 111.50 (12) |
C2—C1—C9 | 108.02 (12) | O3—C9—C8 | 105.33 (11) |
C3—C2—C7 | 121.55 (13) | C10—C9—C8 | 114.42 (14) |
C3—C2—C1 | 128.51 (15) | O3—C9—C1 | 108.50 (13) |
C7—C2—C1 | 109.92 (14) | C10—C9—C1 | 113.41 (12) |
C2—C3—C4 | 117.60 (15) | C8—C9—C1 | 103.00 (12) |
C2—C3—H3A | 121.2 | C11—C10—C9 | 112.60 (12) |
C4—C3—H3A | 121.2 | C11—C10—H10A | 109.1 |
C3—C4—C5 | 121.03 (15) | C9—C10—H10A | 109.1 |
C3—C4—H4A | 119.5 | C11—C10—H10B | 109.1 |
C5—C4—H4A | 119.5 | C9—C10—H10B | 109.1 |
C6—C5—C4 | 121.14 (14) | H10A—C10—H10B | 107.8 |
C6—C5—H5A | 119.4 | O4—C11—C12 | 122.79 (14) |
C4—C5—H5A | 119.4 | O4—C11—C10 | 120.01 (14) |
C5—C6—C7 | 117.80 (15) | C12—C11—C10 | 117.16 (13) |
C5—C6—H6A | 121.1 | C11—C12—H12A | 109.5 |
C7—C6—H6A | 121.1 | C11—C12—H12B | 109.5 |
C6—C7—C2 | 120.84 (15) | H12A—C12—H12B | 109.5 |
C6—C7—C8 | 129.16 (15) | C11—C12—H12C | 109.5 |
C2—C7—C8 | 109.98 (13) | H12A—C12—H12C | 109.5 |
O2—C8—C7 | 127.35 (14) | H12B—C12—H12C | 109.5 |
O1—C1—C2—C3 | −1.6 (3) | C2—C7—C8—C9 | 6.84 (16) |
C9—C1—C2—C3 | 177.10 (15) | O2—C8—C9—O3 | −74.26 (18) |
O1—C1—C2—C7 | 176.83 (17) | C7—C8—C9—O3 | 104.64 (14) |
C9—C1—C2—C7 | −4.49 (17) | O2—C8—C9—C10 | 48.55 (19) |
C7—C2—C3—C4 | 0.5 (2) | C7—C8—C9—C10 | −132.56 (13) |
C1—C2—C3—C4 | 178.78 (15) | O2—C8—C9—C1 | 172.10 (14) |
C2—C3—C4—C5 | 1.4 (2) | C7—C8—C9—C1 | −9.00 (15) |
C3—C4—C5—C6 | −2.1 (3) | O1—C1—C9—O3 | 75.56 (19) |
C4—C5—C6—C7 | 0.8 (2) | C2—C1—C9—O3 | −103.16 (14) |
C5—C6—C7—C2 | 1.1 (2) | O1—C1—C9—C10 | −48.9 (2) |
C5—C6—C7—C8 | −177.55 (15) | C2—C1—C9—C10 | 132.37 (13) |
C3—C2—C7—C6 | −1.8 (2) | O1—C1—C9—C8 | −173.13 (16) |
C1—C2—C7—C6 | 179.63 (14) | C2—C1—C9—C8 | 8.15 (16) |
C3—C2—C7—C8 | 177.09 (14) | O3—C9—C10—C11 | −177.41 (13) |
C1—C2—C7—C8 | −1.45 (17) | C8—C9—C10—C11 | 63.19 (17) |
C6—C7—C8—O2 | 4.5 (3) | C1—C9—C10—C11 | −54.58 (17) |
C2—C7—C8—O2 | −174.31 (15) | C9—C10—C11—O4 | −16.2 (2) |
C6—C7—C8—C9 | −174.36 (15) | C9—C10—C11—C12 | 161.75 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1O3···O2i | 0.86 (3) | 1.93 (3) | 2.7907 (16) | 174 (3) |
C3—H3A···O4ii | 0.93 | 2.51 | 3.401 (2) | 159 |
C12—H12A···O4iii | 0.96 | 2.54 | 3.408 (2) | 150 |
Symmetry codes: (i) −x+1/2, y−1/2, z−1/2; (ii) x, y, z−1; (iii) −x, −y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H10O4 |
Mr | 218.20 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 100 |
a, b, c (Å) | 18.1190 (2), 8.8135 (1), 6.2585 (1) |
V (Å3) | 999.43 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.29 × 0.19 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.969, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14417, 1818, 1720 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.738 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.106, 1.18 |
No. of reflections | 1818 |
No. of parameters | 150 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.42, −0.24 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1O3···O2i | 0.86 (3) | 1.93 (3) | 2.7907 (16) | 174 (3) |
C3—H3A···O4ii | 0.93 | 2.51 | 3.401 (2) | 159 |
C12—H12A···O4iii | 0.96 | 2.54 | 3.408 (2) | 150 |
Symmetry codes: (i) −x+1/2, y−1/2, z−1/2; (ii) x, y, z−1; (iii) −x, −y, z+1/2. |
Acknowledgements
HKF and CKQ acknowledge funding from the Malaysian Government and Universiti Sains Malaysia (USM) under the Research University Golden Goose Grant (No. 1001/PFIZIK/811012). CKQ thanks USM for a Research Fellowship.
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Kaiser, E., Colescott, R. L., Bossinger, C. D. & Cook, P. I. (1970). Anal. Biochem. 34, 595–598. CrossRef CAS PubMed Web of Science Google Scholar
Ruhemann, S. (1910). J. Chem. Soc. 97, 1440, 2025–2031. 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
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Ninhydrin is used to detect α-amino acids, proteins and dipeptides. When it reacts with free amines, a deep blue or purple colour known as Ruhemann's purple (RP) is evolved (Ruhemann, 1910). Ninhydrin is also used to monitor deprotection in solid phase peptide synthesis (Kaiser Test) (Kaiser et al., 1970). It is one of the most widely used reagents for chemical development of fingerprints on porous surfaces. We herein present the crystal structure of the title compound, a derivative of ninhydrin.
Bond lengths (Allen et al., 1987) and angles in the title molecule (Fig. 1) are within normal ranges. The indan ring system (C1-C9) is almost planar, with a maximum deviation of 0.072 (1) Å for atom C9 while the dihedral angle formed by the benzene ring and the five-membered ring is 1.87 (8)°. The keto atom O1 lies 0.075 (2) Å from the indan plane whereas the keto atom O2 is displaced from the C1-C9 plane by 0.184 (2) Å. The five-membered ring adopts an envelope conformation, with atom C9 at the flap [deviation 0.145 (2) Å]. The C2—C1—C9—O3 torsion angle is 103.16 (14) Å.
In the crystal structure (Fig. 2), the molecules are linked by intermolecular O3—H1O3···O2 and C3—H3A···O4 hydrogen bonds (Table 1) into a two-dimensional network parallel to the (100). The adjacent networks are linked via C12—H12A···O4 hydrogen bonds to form a three-dimensional network.