2-Acetonyl-2-hydroxy­indan-1,3-dione

Fun, H.-K.; Quah, C.K.; Parveen, M.; Ghalib, R.M.; Mehdi, S.H.

doi:10.1107/S1600536809016067

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1209

doi:10.1107/S1600536809016067

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2-Acetonyl-2-hydroxyindan-1,3-dione

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § Mehtab Parveen,^b ¶ Raza Murad Ghalib ^b and Sayed Hasan Mehdi ^b

^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

(Received 23 April 2009; accepted 29 April 2009; online 7 May 2009)

In the title compound, C₁₂H₁₀O₄, the five-membered ring adopts an envelope conformation, with the Csp³ atom at the flap [deviation = 0.145 (2) Å]. In the crystal structure, 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

C₁₂H₁₀O₄
M_r = 218.20
Orthorhombic, P n a 2₁
a = 18.1190 (2) Å
b = 8.8135 (1) Å
c = 6.2585 (1) Å
V = 999.43 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.29 × 0.19 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.969, T_max = 0.992
14417 measured reflections
1818 independent reflections
1720 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.106
S = 1.18
1818 reflections
150 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x, y, z-1; (iii) $[-x, -y, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016067/ci2791sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016067/ci2791Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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 chromatography 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).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: 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).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The crystal packing of the title compound, viewed along the c axis. Intermolecular hydrogen bonds are shown as dashed lines.

2-Acetonyl-2-hydroxyindan-1,3-dione top

Crystal data top

C₁₂H₁₀O₄	F(000) = 456
M_r = 218.20	D_x = 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

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1818 independent reflections
Radiation source: fine-focus sealed tube	1720 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 31.7°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −26→26
T_min = 0.969, T_max = 0.992	k = −12→13
14417 measured reflections	l = −9→9

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)] = 0.033	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(F_o²) + (0.0696P)² + 0.0468P] where P = (F_o² + 2F_c²)/3
1818 reflections	(Δ/σ)_max = 0.001
150 parameters	Δρ_max = 0.42 e Å⁻³
1 restraint	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₂H₁₀O₄	V = 999.43 (2) Å³
M_r = 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

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1818 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1720 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.992	R_int = 0.034
14417 measured reflections

Refinement top

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	Δρ_max = 0.42 e Å⁻³
1818 reflections	Δρ_min = −0.24 e Å⁻³
150 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.969, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	14417, 1818, 1720
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.24

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009.

¶Additional correspondence author, e-mail: mehtab_organic@rediffmail.com.

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

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