rac-syn-Diethyl 2-hy-droxy-4-oxo-1-phenyl-cyclo-hexane-1,2-dicarboxyl-ate.

The title compound, C(18)H(22)O(6), was obtained by the domino oxa-Michael-aldol (DOMA) reaction and has the cyclo-hexa-none ring in a chair conformation with intra-annular torsion angles in the range 49.9 (2)-58.9 (2)°. The two eth-oxy-carbonyl substituents on the cyclo-hexa-none ring adopt a syn configurations. In the crystal, the mol-ecules self-assemble through duplex inter-molecular hy-droxy-carbonyl O-H⋯O hydrogen bonds, giving centrosymmetric cyclic dimers [graph set R(2) (2)(12)] which inter-associate through weak C-H⋯O hydrogen-bonding inter-actions.

Related literature

For general background to proline-catalysed Robinson annulation, see: Eder et al. (1971 ▶); Hajos & Parrish (1974 ▶). For the catalytic asymmetric formation of chiral building blocks, see: Bui & Barbas (2000 ▶); Tanaka et al. (2003 ▶). For the the DOMA reaction, see: Nising & Bräse (2008) ▶; Sefer et al. (2010 ▶) and for asymmetric C—C bond-forming reactions, see: Sibi & Chen (2001 ▶); Tian et al. (2002 ▶); Gothelf et al. (2002 ▶); Rueping et al. (2009 ▶). For the synthesis of the title compound, see: Floyd & Miller (1963 ▶). For related structures, see: Abell et al. (1988 ▶); Hernández-Ortega et al. (2001 ▶). For graph-set analysis, see: Etter et al. (1990 ▶).

Experimental

Crystal data

C18H22O6

M = 334.36

Triclinic,

a = 8.2069 (10) Å

b = 9.9393 (16) Å

c = 11.1420 (17) Å

α = 87.408 (10)°

β = 70.610 (7)°

γ = 78.983 (9)°

V = 841.3 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 153 K

0.45 × 0.36 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID CCD diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.957, T max = 0.990

8251 measured reflections

3053 independent reflections

2695 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.103

S = 1.07

3053 reflections

221 parameters

H-atom parameters constrained

Δρmax = 0.46 e Å−3

Δρmin = −0.29 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811042048/zs2151sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811042048/zs2151Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811042048/zs2151Isup3.cml

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

C18H22O6	Z = 2
Mr = 334.36	F(000) = 356
Triclinic, P1	Dx = 1.320 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 8.2069 (10) Å	Cell parameters from 3233 reflections
b = 9.9393 (16) Å	θ = 3.1–25.3°
c = 11.1420 (17) Å	µ = 0.10 mm−1
α = 87.408 (10)°	T = 153 K
β = 70.610 (7)°	Needle-like, colorless
γ = 78.983 (9)°	0.45 × 0.36 × 0.10 mm
V = 841.3 (2) Å3

Rigaku R-AXIS RAPID CCD diffractometer	3053 independent reflections
Radiation source: fine-focus sealed tube	2695 reflections with I > 2σ(I)
graphite	Rint = 0.019
Detector resolution: 7.31 pixels mm-1	θmax = 25.4°, θmin = 3.2°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→11
Tmin = 0.957, Tmax = 0.990	l = −13→13
8251 measured reflections

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0431P)2 + 0.4508P] where P = (Fo2 + 2Fc2)/3
3053 reflections	(Δ/σ)max < 0.001
221 parameters	Δρmax = 0.46 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

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	0.79576 (15)	0.51980 (12)	0.38078 (11)	0.0255 (3)
O2	0.51399 (14)	0.29561 (11)	0.57801 (10)	0.0192 (3)
H2	0.4211	0.3544	0.5918	0.029*
O3	0.41781 (18)	0.26892 (13)	0.85521 (12)	0.0369 (3)
O4	0.45085 (18)	0.48608 (12)	0.82340 (12)	0.0374 (4)
O5	0.83175 (15)	0.31071 (12)	0.79925 (11)	0.0261 (3)
O6	1.03868 (14)	0.14904 (11)	0.67206 (10)	0.0207 (3)
C1	0.8099 (2)	0.43872 (16)	0.46397 (15)	0.0186 (3)
C2	0.6860 (2)	0.45938 (15)	0.59878 (15)	0.0194 (3)
H2A	0.5868	0.5351	0.6018	0.023*
H2B	0.7486	0.4865	0.6533	0.023*
C3	0.61292 (19)	0.32920 (15)	0.65220 (14)	0.0164 (3)
C4	0.76503 (19)	0.20183 (15)	0.63581 (14)	0.0158 (3)
C5	0.8748 (2)	0.18687 (15)	0.49233 (14)	0.0180 (3)
H5A	0.9718	0.1068	0.4794	0.022*
H5B	0.7992	0.1689	0.4440	0.022*
C6	0.9526 (2)	0.31423 (16)	0.43916 (15)	0.0206 (3)
H6A	1.0393	0.3268	0.4798	0.025*
H6B	1.0143	0.3016	0.3464	0.025*
C7	0.4867 (2)	0.35472 (16)	0.79048 (15)	0.0183 (3)
C8	0.3101 (3)	0.5304 (2)	0.94311 (18)	0.0439 (5)
H8A	0.3523	0.5849	0.9949	0.053*
H8B	0.2737	0.4495	0.9923	0.053*
C9	0.1584 (3)	0.6149 (3)	0.9138 (2)	0.0568 (7)
H9A	0.1967	0.6922	0.8614	0.085*
H9B	0.0659	0.6496	0.9932	0.085*
H9C	0.1124	0.5586	0.8673	0.085*
C10	0.8800 (2)	0.22881 (15)	0.71235 (14)	0.0168 (3)
C11	1.1587 (2)	0.15987 (18)	0.74163 (16)	0.0234 (4)
H11A	1.1362	0.2549	0.7744	0.028*
H11B	1.2816	0.1383	0.6834	0.028*
C12	1.1337 (3)	0.0626 (2)	0.85057 (19)	0.0361 (5)
H12A	1.0160	0.0902	0.9128	0.054*
H12B	1.2223	0.0646	0.8913	0.054*
H12C	1.1465	−0.0305	0.8188	0.054*
C13	0.69874 (19)	0.06732 (15)	0.68411 (14)	0.0169 (3)
C14	0.6427 (2)	−0.00903 (16)	0.60868 (15)	0.0198 (3)
H14	0.6423	0.0232	0.5272	0.024*
C15	0.5873 (2)	−0.13174 (16)	0.65096 (17)	0.0246 (4)
H15	0.5487	−0.1821	0.5985	0.030*
C16	0.5881 (2)	−0.18106 (17)	0.76895 (17)	0.0265 (4)
H16	0.5515	−0.2655	0.7972	0.032*
C17	0.6423 (2)	−0.10641 (18)	0.84515 (16)	0.0272 (4)
H17	0.6421	−0.1391	0.9267	0.033*
C18	0.6974 (2)	0.01642 (17)	0.80311 (15)	0.0224 (4)
H18	0.7348	0.0666	0.8564	0.027*

	U11	U22	U33	U12	U13	U23
O1	0.0242 (6)	0.0241 (6)	0.0227 (6)	0.0003 (5)	−0.0040 (5)	0.0062 (5)
O2	0.0176 (6)	0.0195 (6)	0.0212 (6)	0.0007 (4)	−0.0093 (5)	−0.0015 (4)
O3	0.0416 (8)	0.0258 (7)	0.0282 (7)	−0.0073 (6)	0.0087 (6)	0.0009 (5)
O4	0.0479 (8)	0.0205 (6)	0.0248 (7)	−0.0024 (6)	0.0120 (6)	−0.0062 (5)
O5	0.0252 (6)	0.0276 (6)	0.0254 (6)	0.0010 (5)	−0.0105 (5)	−0.0083 (5)
O6	0.0163 (6)	0.0231 (6)	0.0228 (6)	−0.0004 (4)	−0.0081 (5)	−0.0006 (5)
C1	0.0192 (8)	0.0168 (8)	0.0207 (8)	−0.0063 (6)	−0.0063 (7)	0.0025 (6)
C2	0.0197 (8)	0.0146 (7)	0.0210 (8)	−0.0006 (6)	−0.0044 (7)	0.0002 (6)
C3	0.0163 (7)	0.0161 (8)	0.0172 (8)	−0.0021 (6)	−0.0066 (6)	0.0001 (6)
C4	0.0159 (7)	0.0142 (7)	0.0162 (7)	−0.0009 (6)	−0.0047 (6)	−0.0005 (6)
C5	0.0189 (8)	0.0159 (8)	0.0164 (8)	−0.0003 (6)	−0.0035 (6)	−0.0003 (6)
C6	0.0172 (8)	0.0212 (8)	0.0195 (8)	−0.0014 (6)	−0.0024 (6)	0.0025 (6)
C7	0.0169 (8)	0.0177 (8)	0.0197 (8)	−0.0004 (6)	−0.0068 (6)	−0.0011 (6)
C8	0.0530 (13)	0.0310 (10)	0.0244 (10)	0.0039 (9)	0.0126 (9)	−0.0065 (8)
C9	0.0353 (12)	0.0859 (19)	0.0386 (12)	−0.0001 (12)	−0.0013 (10)	−0.0235 (12)
C10	0.0161 (8)	0.0159 (7)	0.0168 (8)	−0.0034 (6)	−0.0034 (6)	0.0037 (6)
C11	0.0173 (8)	0.0287 (9)	0.0272 (9)	−0.0050 (7)	−0.0113 (7)	0.0031 (7)
C12	0.0361 (11)	0.0402 (11)	0.0400 (11)	−0.0121 (9)	−0.0223 (9)	0.0165 (9)
C13	0.0135 (7)	0.0154 (7)	0.0196 (8)	−0.0007 (6)	−0.0034 (6)	−0.0007 (6)
C14	0.0187 (8)	0.0189 (8)	0.0208 (8)	−0.0013 (6)	−0.0065 (7)	−0.0004 (6)
C15	0.0237 (9)	0.0191 (8)	0.0318 (9)	−0.0042 (7)	−0.0097 (7)	−0.0033 (7)
C16	0.0236 (9)	0.0181 (8)	0.0354 (10)	−0.0071 (7)	−0.0053 (7)	0.0040 (7)
C17	0.0306 (9)	0.0263 (9)	0.0239 (9)	−0.0076 (7)	−0.0076 (7)	0.0071 (7)
C18	0.0248 (9)	0.0212 (8)	0.0224 (8)	−0.0060 (7)	−0.0086 (7)	0.0021 (7)

O1—C1	1.2206 (19)	C8—C9	1.486 (3)
O2—C3	1.4241 (18)	C8—H8A	0.9900
O2—H2	0.8400	C8—H8B	0.9900
O3—C7	1.194 (2)	C9—H9A	0.9800
O4—C7	1.3230 (19)	C9—H9B	0.9800
O4—C8	1.464 (2)	C9—H9C	0.9800
O5—C10	1.2043 (19)	C11—C12	1.501 (2)
O6—C10	1.3326 (19)	C11—H11A	0.9900
O6—C11	1.4617 (19)	C11—H11B	0.9900
C1—C6	1.497 (2)	C12—H12A	0.9800
C1—C2	1.505 (2)	C12—H12B	0.9800
C2—C3	1.542 (2)	C12—H12C	0.9800
C2—H2A	0.9900	C13—C14	1.393 (2)
C2—H2B	0.9900	C13—C18	1.395 (2)
C3—C7	1.545 (2)	C14—C15	1.391 (2)
C3—C4	1.568 (2)	C14—H14	0.9500
C4—C10	1.530 (2)	C15—C16	1.384 (2)
C4—C13	1.546 (2)	C15—H15	0.9500
C4—C5	1.550 (2)	C16—C17	1.380 (3)
C5—C6	1.533 (2)	C16—H16	0.9500
C5—H5A	0.9900	C17—C18	1.390 (2)
C5—H5B	0.9900	C17—H17	0.9500
C6—H6A	0.9900	C18—H18	0.9500
C6—H6B	0.9900
C3—O2—H2	109.5	O4—C8—H8B	109.9
C7—O4—C8	117.92 (14)	C9—C8—H8B	109.9
C10—O6—C11	117.03 (12)	H8A—C8—H8B	108.3
O1—C1—C6	122.31 (14)	C8—C9—H9A	109.5
O1—C1—C2	121.82 (14)	C8—C9—H9B	109.5
C6—C1—C2	115.86 (13)	H9A—C9—H9B	109.5
C1—C2—C3	112.37 (13)	C8—C9—H9C	109.5
C1—C2—H2A	109.1	H9A—C9—H9C	109.5
C3—C2—H2A	109.1	H9B—C9—H9C	109.5
C1—C2—H2B	109.1	O5—C10—O6	124.40 (14)
C3—C2—H2B	109.1	O5—C10—C4	124.04 (14)
H2A—C2—H2B	107.9	O6—C10—C4	111.56 (13)
O2—C3—C2	108.84 (12)	O6—C11—C12	110.41 (14)
O2—C3—C7	107.31 (12)	O6—C11—H11A	109.6
C2—C3—C7	110.70 (12)	C12—C11—H11A	109.6
O2—C3—C4	104.69 (11)	O6—C11—H11B	109.6
C2—C3—C4	111.26 (12)	C12—C11—H11B	109.6
C7—C3—C4	113.68 (12)	H11A—C11—H11B	108.1
C10—C4—C13	107.52 (12)	C11—C12—H12A	109.5
C10—C4—C5	109.82 (12)	C11—C12—H12B	109.5
C13—C4—C5	110.10 (12)	H12A—C12—H12B	109.5
C10—C4—C3	108.55 (12)	C11—C12—H12C	109.5
C13—C4—C3	113.42 (12)	H12A—C12—H12C	109.5
C5—C4—C3	107.40 (12)	H12B—C12—H12C	109.5
C6—C5—C4	113.04 (12)	C14—C13—C18	117.75 (14)
C6—C5—H5A	109.0	C14—C13—C4	121.03 (14)
C4—C5—H5A	109.0	C18—C13—C4	121.20 (14)
C6—C5—H5B	109.0	C15—C14—C13	120.96 (15)
C4—C5—H5B	109.0	C15—C14—H14	119.5
H5A—C5—H5B	107.8	C13—C14—H14	119.5
C1—C6—C5	110.24 (12)	C16—C15—C14	120.46 (16)
C1—C6—H6A	109.6	C16—C15—H15	119.8
C5—C6—H6A	109.6	C14—C15—H15	119.8
C1—C6—H6B	109.6	C17—C16—C15	119.34 (16)
C5—C6—H6B	109.6	C17—C16—H16	120.3
H6A—C6—H6B	108.1	C15—C16—H16	120.3
O3—C7—O4	124.13 (15)	C16—C17—C18	120.26 (16)
O3—C7—C3	124.09 (14)	C16—C17—H17	119.9
O4—C7—C3	111.44 (13)	C18—C17—H17	119.9
O4—C8—C9	108.77 (17)	C17—C18—C13	121.22 (15)
O4—C8—H8A	109.9	C17—C18—H18	119.4
C9—C8—H8A	109.9	C13—C18—H18	119.4
O1—C1—C2—C3	131.17 (15)	C2—C3—C7—O4	9.43 (18)
C6—C1—C2—C3	−49.84 (18)	C4—C3—C7—O4	135.52 (14)
C1—C2—C3—O2	−62.33 (16)	C7—O4—C8—C9	−110.0 (2)
C1—C2—C3—C7	179.96 (13)	C11—O6—C10—O5	2.0 (2)
C1—C2—C3—C4	52.53 (17)	C11—O6—C10—C4	−177.03 (12)
O2—C3—C4—C10	179.76 (11)	C13—C4—C10—O5	−101.99 (17)
C2—C3—C4—C10	62.36 (16)	C5—C4—C10—O5	138.22 (15)
C7—C3—C4—C10	−63.44 (16)	C3—C4—C10—O5	21.1 (2)
O2—C3—C4—C13	−60.81 (15)	C13—C4—C10—O6	77.06 (15)
C2—C3—C4—C13	−178.21 (12)	C5—C4—C10—O6	−42.73 (16)
C7—C3—C4—C13	55.99 (17)	C3—C4—C10—O6	−159.87 (12)
O2—C3—C4—C5	61.07 (14)	C10—O6—C11—C12	88.62 (17)
C2—C3—C4—C5	−56.33 (16)	C10—C4—C13—C14	−158.13 (14)
C7—C3—C4—C5	177.88 (12)	C5—C4—C13—C14	−38.52 (19)
C10—C4—C5—C6	−59.02 (16)	C3—C4—C13—C14	81.85 (17)
C13—C4—C5—C6	−177.22 (12)	C10—C4—C13—C18	20.14 (19)
C3—C4—C5—C6	58.84 (16)	C5—C4—C13—C18	139.75 (15)
O1—C1—C6—C5	−130.89 (16)	C3—C4—C13—C18	−99.88 (17)
C2—C1—C6—C5	50.13 (18)	C18—C13—C14—C15	0.0 (2)
C4—C5—C6—C1	−55.46 (17)	C4—C13—C14—C15	178.36 (14)
C8—O4—C7—O3	−4.0 (3)	C13—C14—C15—C16	−0.5 (2)
C8—O4—C7—C3	169.59 (16)	C14—C15—C16—C17	0.8 (3)
O2—C3—C7—O3	64.36 (19)	C15—C16—C17—C18	−0.7 (3)
C2—C3—C7—O3	−176.99 (15)	C16—C17—C18—C13	0.2 (3)
C4—C3—C7—O3	−50.9 (2)	C14—C13—C18—C17	0.1 (2)
O2—C3—C7—O4	−109.22 (14)	C4—C13—C18—C17	−178.23 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1i	0.84	1.91	2.7491 (18)	177
C15—H15···O2ii	0.95	2.55	3.486 (2)	169
C8—H8A···O5iii	0.99	2.44	3.095 (2)	124

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1i	0.84	1.91	2.7491 (18)	177
C15—H15⋯O2ii	0.95	2.55	3.486 (2)	169
C8—H8A⋯O5iii	0.99	2.44	3.095 (2)	124

Symmetry codes: (i) ; (ii) ; (iii) .