4-Oxocyclo-hexa-neacetic acid: catemeric hydrogen bonding and spontaneous resolution of a single conformational enanti-omer in an achiral ∊-keto acid.

The asymmetric unit of the title compound, C(8)H(12)O(3), consists of a single conformational enanti-omer, which aggregates in the catemeric acid-to-ketone hydrogen-bonding mode [O⋯O = 2.682 (4) Å and O-H⋯O = 172 (6)°]. Four hydrogen-bonding chains of translationally related mol-ecules pass through the cell orthogonal to the 4(3) screw axis along c, alternating in the 110 and the 10 direction, with alignment with respect to this axis of + + - -. Successive chains are rotated by 90° around the c axis. One C-H⋯O=C close contact, involving the carboxyl group, exists.

Related literature

For a discussion of highly ordered carboxyl bond distances and angles, see: Borthwick (1980 ▶). For close contact information, see: Steiner (1997 ▶). For related structures, see: Abell et al. (1991 ▶); Chen et al. (2000 ▶); Desiraju (1989 ▶); Halfpenny (1990 ▶); Jacques et al. (1981 ▶); Kawai et al. (1985 ▶); McGuire et al. (1995 ▶). For background information regarding the crystallization of a single chiral conformer from a racemic solution, see: Kondepudi et al. (1990 ▶). For anti-n class="Chemical">isoketopinic acid, see: Lalancette et al. (1997 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C8H12O3

M = 156.18

Tetragonal,

a = 6.8531 (12) Å

c = 17.372 (3) Å

V = 815.9 (3) Å3

Z = 4

Cu Kα radiation

μ = 0.80 mm−1

T = 100 K

0.28 × 0.20 × 0.16 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T min = 0.806, T max = 0.882

6963 measured reflections

1310 independent reflections

1274 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.113

S = 1.18

1310 reflections

105 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.17 e Å−3

Δρmin = −0.20 e Å−3

Absolute structure: Flack (1983 ▶), 559 Friedel pairs

Flack parameter: 0.0 (4)

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810036652/sj5037sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036652/sj5037Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C8H12O3	Dx = 1.271 Mg m−3
Mr = 156.18	Melting point: 345 K
Tetragonal, P43	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 4cw	Cell parameters from 6759 reflections
a = 6.8531 (12) Å	θ = 5.1–70.5°
c = 17.372 (3) Å	µ = 0.80 mm−1
V = 815.9 (3) Å3	T = 100 K
Z = 4	Block, colourless
F(000) = 336	0.28 × 0.20 × 0.16 mm

Bruker SMART APEXII CCD area-detector diffractometer	1310 independent reflections
Radiation source: fine-focus sealed tube	1274 reflections with I > 2σ(I)
graphite	Rint = 0.029
φ and ω scans	θmax = 70.8°, θmin = 6.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −7→7
Tmin = 0.806, Tmax = 0.882	k = −8→7
6963 measured reflections	l = −20→18

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.039	w = 1/[σ2(Fo2) + (0.0369P)2 + 0.671P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.113	(Δ/σ)max < 0.001
S = 1.18	Δρmax = 0.17 e Å−3
1310 reflections	Δρmin = −0.20 e Å−3
105 parameters	Extinction correction: SHELXTL (Sheldrick, 2008b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.0023 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 559 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.0 (4)

Experimental. crystal mounted on a Cryoloop using Paratone-N

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	0.9958 (3)	1.2372 (3)	0.08526 (13)	0.0341 (5)
O2	0.2472 (4)	0.6544 (3)	0.03744 (14)	0.0460 (6)
O3	0.1245 (4)	0.5683 (4)	0.15016 (13)	0.0421 (6)
H3	0.083 (6)	0.482 (6)	0.130 (2)	0.036 (11)*
C1	0.4571 (4)	0.9768 (4)	0.10334 (18)	0.0275 (6)
H1	0.3956	1.0155	0.0534	0.033*
C2	0.6441 (4)	0.8617 (4)	0.08592 (17)	0.0289 (7)
H2A	0.7056	0.8208	0.1349	0.035*
H2B	0.6105	0.7426	0.0565	0.035*
C3	0.7890 (4)	0.9841 (4)	0.03955 (19)	0.0299 (6)
H3A	0.9128	0.9109	0.0342	0.036*
H3B	0.7358	1.0064	−0.0127	0.036*
C4	0.8297 (4)	1.1764 (4)	0.07670 (18)	0.0294 (7)
C5	0.6532 (5)	1.2912 (4)	0.10375 (19)	0.0340 (7)
H5A	0.5867	1.3494	0.0587	0.041*
H5B	0.6967	1.3990	0.1376	0.041*
C6	0.5086 (4)	1.1616 (4)	0.14778 (18)	0.0309 (7)
H6A	0.5662	1.1249	0.1980	0.037*
H6B	0.3879	1.2365	0.1580	0.037*
C7	0.3105 (4)	0.8534 (4)	0.14873 (17)	0.0284 (6)
H7A	0.3757	0.8031	0.1956	0.034*
H7B	0.2019	0.9386	0.1656	0.034*
C8	0.2272 (4)	0.6841 (4)	0.10499 (17)	0.0285 (7)

	U11	U22	U33	U12	U13	U23
O1	0.0344 (12)	0.0356 (12)	0.0322 (12)	−0.0107 (9)	−0.0004 (9)	0.0009 (9)
O2	0.0644 (16)	0.0488 (14)	0.0248 (12)	−0.0289 (12)	0.0023 (12)	−0.0052 (10)
O3	0.0544 (15)	0.0413 (14)	0.0305 (12)	−0.0195 (12)	0.0077 (11)	−0.0039 (11)
C1	0.0327 (15)	0.0281 (15)	0.0217 (14)	−0.0034 (12)	−0.0037 (12)	0.0028 (12)
C2	0.0366 (16)	0.0244 (15)	0.0258 (16)	−0.0003 (12)	−0.0009 (13)	−0.0002 (12)
C3	0.0321 (16)	0.0318 (15)	0.0257 (15)	0.0002 (12)	−0.0033 (13)	0.0002 (13)
C4	0.0353 (16)	0.0308 (15)	0.0222 (14)	−0.0054 (13)	−0.0014 (13)	0.0070 (12)
C5	0.0407 (18)	0.0254 (16)	0.0358 (18)	−0.0041 (13)	−0.0004 (14)	−0.0018 (13)
C6	0.0282 (15)	0.0294 (16)	0.0352 (17)	0.0007 (11)	−0.0004 (13)	−0.0025 (14)
C7	0.0311 (15)	0.0299 (15)	0.0244 (15)	−0.0004 (11)	−0.0004 (12)	0.0015 (12)
C8	0.0270 (15)	0.0351 (16)	0.0234 (16)	0.0001 (12)	−0.0016 (12)	0.0002 (12)

O1—C4	1.222 (4)	C3—H3A	0.9900
O2—C8	1.199 (4)	C3—H3B	0.9900
O3—C8	1.319 (4)	C4—C5	1.518 (4)
O3—H3	0.74 (4)	C5—C6	1.535 (4)
C1—C6	1.524 (4)	C5—H5A	0.9900
C1—C7	1.532 (4)	C5—H5B	0.9900
C1—C2	1.535 (4)	C6—H6A	0.9900
C1—H1	1.0000	C6—H6B	0.9900
C2—C3	1.529 (4)	C7—C8	1.500 (4)
C2—H2A	0.9900	C7—H7A	0.9900
C2—H2B	0.9900	C7—H7B	0.9900
C3—C4	1.494 (4)
C8—O3—H3	114 (3)	C4—C5—C6	111.6 (2)
C6—C1—C7	110.5 (2)	C4—C5—H5A	109.3
C6—C1—C2	109.5 (2)	C6—C5—H5A	109.3
C7—C1—C2	111.4 (2)	C4—C5—H5B	109.3
C6—C1—H1	108.5	C6—C5—H5B	109.3
C7—C1—H1	108.5	H5A—C5—H5B	108.0
C2—C1—H1	108.5	C1—C6—C5	112.2 (2)
C3—C2—C1	111.4 (2)	C1—C6—H6A	109.2
C3—C2—H2A	109.4	C5—C6—H6A	109.2
C1—C2—H2A	109.4	C1—C6—H6B	109.2
C3—C2—H2B	109.4	C5—C6—H6B	109.2
C1—C2—H2B	109.4	H6A—C6—H6B	107.9
H2A—C2—H2B	108.0	C8—C7—C1	114.6 (2)
C4—C3—C2	112.2 (3)	C8—C7—H7A	108.6
C4—C3—H3A	109.2	C1—C7—H7A	108.6
C2—C3—H3A	109.2	C8—C7—H7B	108.6
C4—C3—H3B	109.2	C1—C7—H7B	108.6
C2—C3—H3B	109.2	H7A—C7—H7B	107.6
H3A—C3—H3B	107.9	O2—C8—O3	122.8 (3)
O1—C4—C3	121.8 (3)	O2—C8—C7	125.7 (3)
O1—C4—C5	121.9 (3)	O3—C8—C7	111.5 (3)
C3—C4—C5	116.3 (3)
C6—C1—C2—C3	−58.4 (3)	C7—C1—C6—C5	−179.2 (2)
C7—C1—C2—C3	179.1 (2)	C2—C1—C6—C5	57.8 (3)
C1—C2—C3—C4	52.9 (3)	C4—C5—C6—C1	−51.0 (3)
C2—C3—C4—O1	132.3 (3)	C6—C1—C7—C8	171.1 (2)
C2—C3—C4—C5	−47.3 (4)	C2—C1—C7—C8	−67.0 (3)
O1—C4—C5—C6	−133.5 (3)	C1—C7—C8—O2	−9.6 (4)
C3—C4—C5—C6	46.0 (4)	C1—C7—C8—O3	171.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1i	0.75 (6)	1.94 (6)	2.682 (4)	172 (6)
C7—H7A···O2ii	0.99	2.51	3.439 (5)	156

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1i	0.75 (6)	1.94 (6)	2.682 (4)	172 (6)
C7—H7A⋯O2ii	0.99	2.51	3.439 (5)	156

Symmetry codes: (i) ; (ii) .