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Acta Crystallogr Sect E Struct Rep Online. 2009 January 1; 65(Pt 1): o164–o165.
Published online 2008 December 20. doi:  10.1107/S160053680804261X
PMCID: PMC2968076

(2R,3R)-2-[(4-Chloro­phen­yl)hydroxy­meth­yl]cyclo­penta­none

Abstract

The title compound, C12H13ClO2, was prepared by the direct asymmetric inter­molecular aldol reaction of cyclo­penta­none and 4-chloro­benzaldehyde catalysed by l-tryptophan in water. The absolute mol­ecular structure was determined to be a racemic twin with 91% (2R,3R) isomer and 9% of the (2S,3S) form. In the crystal structure, the mol­ecules are connected into a one-dimensional chain along the a axis through the formation of inter­molecular O—H(...)O hydrogen bonds. Further, non-conventional C—H(...)O and C—H(...)π contacts are observed in the structure, which consolidate the crystal packing.

Related literature

For the structure of 2-[hydr­oxy(4-nitro­phen­yl)meth­yl]-4-methyl­cyclo­hexa­none, see: Li (2007 [triangle]). For a structure with C—H(...)O hydrogen bonds, see: Nangia (2002 [triangle]). For a database study of C—H(...)π inter­actions in the conformation of peptides, see: Umezawa et al. (1999 [triangle]). For direct inter­molecular aldol reactions catalysed by acyclic amino acids, see: Córdova et al. (2006 [triangle]); Deng & Cai (2007 [triangle]). For asymmetric direct aldol reaction assisted by water and a proline-derived tetra­zole catalyst, see: Torii et al. (2004 [triangle]). For the development of direct catalytic asymmetric aldol, Mannich, Michael and Diels–Alder reactions, see: Notz et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o164-scheme1.jpg

Experimental

Crystal data

  • C12H13ClO2
  • M r = 224.67
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o164-efi1.jpg
  • a = 5.7401 (1) Å
  • b = 10.4549 (2) Å
  • c = 18.2135 (3) Å
  • V = 1093.03 (3) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 2.90 mm−1
  • T = 150 (2) K
  • 0.43 × 0.31 × 0.25 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.336, T max = 0.484
  • 3762 measured reflections
  • 1936 independent reflections
  • 1865 reflections with I > 2σ(I)
  • R int = 0.040

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.168
  • S = 1.14
  • 1936 reflections
  • 146 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.52 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 572 Friedel pairs
  • Flack parameter: 0.09 (3)

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680804261X/si2143sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680804261X/si2143Isup2.hkl

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

Acknowledgments

This work was supported by the Doctoral Foundation and Cultivatable Foundation (2008-PYJJ-011) of Luoyang Normal University.

supplementary crystallographic information

Comment

The direct asymmetric aldol reaction is one of the most important C—C bond-forming reactions (Notz et al., 2004.). It is not surprising that a large number of catalysts and methods have been developed to achieve efficient adducts with high diastereo- and enantioselectivities (Córdova et al. 2006; Torii et al. 2004.). Our primary results demonstrating that acyclic amino acids could catalyze the direct stereoseletive aldol reaction in water micelles (Deng & Cai, 2007). In this contribution, as an extension to our previous studies, we report the synthesis and crystal structure of the title compound.

In the title compound (Fig. 1.), the bond lengths and angles are within ranges as reported by Li (2007). The structural analysis reveals that the absolute molecular structure was a (2R, 3R)- isomer. The most striking feature of the title compound is the interesting arrangement of the title molecules, which connect each other to form a one-dimension chain along the a axis by intermolecular O—H···O hydrogen bonds (Fig. 2). Furthermore, the weak non-conventional intermolecular C—H···π contact is observed, in which C5—H5A is donor and the chlorophenyl ring Cg2 (C1, C2, C3, C4, C12, C5) is π acceptor (Umezawa et al., 1999). This contact, with additional intermolecular C—H···O interactions (Nangia et al. 2002), further consolidate the crystal packing. Details of hydrogen bonds are given in Table 1.

Experimental

4-chlorobenzaldehyde (71 mm g, 0.5 mmol) and cyclopentanone (0.5 ml) was added to a solution of L-tryptophan (30.6 mg, 0.15 mmol) and pure water (0.5 ml) at room temperature. The mixture was stirred, monitored by TLC. The mixture was quenched with a saturated aqueous NaHCO3 solution and extracted by ethyl acetate (3× ml). The resulting solvent was removed in vacuo to yield the crude product. Purification by silica gel chromatography using 100 ~200 mesh ZCX II eluted by hexane-ethyl acetate (3:1, v/v) gave the yellow solid (70 mg, yield 63%). The crystalline compound was obtained through the slow volatilization of ethyl acetate containing the title compound.

Refinement

All H atoms were positioned geometrically and treated as riding, with C—H bond lengths constrained to 0.95 Å (aromatic CH), 0.99 Å (methylene CH2), or 0.92 Å (hydroxy), and with Uĩso~(H) = 1.2Ueq(C) or 1.5Ueq(methylene C). Moreover, the Flack parameter was refined as 0.09 (3) and indicates a possible racemic twin of about 10%. This may be because the number of measured Friedel pairs is relatively low. 572 Friedel pairs were measured, which is a fraction of measured Friedel pairs of 0.419, as indicated in the check.cif of PLATON (Spek, 2003).

Figures

Fig. 1.
View of the title molecular structure with atom numbering scheme and 30% probability displacement ellipsoids for non-hydrogen atoms.
Fig. 2.
View of the one-dimension chain along the a axis by intermolecular O—H···O hydrogen bonds.

Crystal data

C12H13ClO2F(000) = 472
Mr = 224.67Dx = 1.365 Mg m3
Orthorhombic, P212121Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2abCell parameters from 2189 reflections
a = 5.7401 (1) Åθ = 4.9–76.7°
b = 10.4549 (2) ŵ = 2.90 mm1
c = 18.2135 (3) ÅT = 150 K
V = 1093.03 (3) Å3Block, colorless
Z = 40.43 × 0.31 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer1936 independent reflections
Radiation source: fine-focus sealed tube1865 reflections with I > 2σ(I)
graphiteRint = 0.040
[var phi] and ω scansθmax = 76.7°, θmin = 4.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −7→5
Tmin = 0.336, Tmax = 0.484k = −9→12
3762 measured reflectionsl = −22→17

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.168w = 1/[σ2(Fo2) + (0.0962P)2 + 1.0311P] where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max < 0.001
1936 reflectionsΔρmax = 0.34 e Å3
146 parametersΔρmin = −0.52 e Å3
0 restraintsAbsolute structure: Flack (1983), 572 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.09 (3)

Special details

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)

xyzUiso*/Ueq
O10.0477 (5)0.4383 (3)0.06246 (17)0.0418 (7)
O20.5454 (4)0.3133 (2)−0.01098 (14)0.0355 (6)
C3−0.0344 (7)0.7839 (4)0.1635 (2)0.0361 (8)
H3A−0.16150.79510.19620.043*
C110.5311 (6)0.3306 (3)0.0549 (2)0.0303 (7)
C20.0105 (6)0.6644 (3)0.1340 (2)0.0324 (7)
H2A−0.08580.59400.14690.039*
C60.2476 (6)0.5168 (3)0.05323 (19)0.0291 (7)
H6A0.283 (8)0.528 (4)−0.005 (2)0.035*
C100.5749 (7)0.2346 (3)0.1141 (2)0.0388 (8)
H10A0.71740.18450.10360.047*
H10B0.44150.17510.11880.047*
C120.2900 (8)0.8713 (4)0.0969 (2)0.0423 (9)
H12A0.38510.94200.08370.051*
C50.3327 (7)0.7509 (3)0.0683 (2)0.0373 (8)
H5A0.46010.73970.03560.045*
C10.1955 (6)0.6465 (3)0.08574 (18)0.0288 (7)
C70.4634 (6)0.4583 (4)0.08953 (19)0.0322 (7)
H7A0.595 (8)0.518 (5)0.075 (2)0.039*
C40.1048 (6)0.8865 (3)0.1455 (2)0.0330 (7)
C90.6046 (7)0.3132 (4)0.1835 (2)0.0443 (9)
H9A0.76830.34110.18940.053*
H9B0.55730.26370.22730.053*
C80.4435 (8)0.4280 (4)0.1717 (2)0.0415 (9)
H8A0.49460.50190.20170.050*
H8B0.28100.40630.18500.050*
Cl10.05251 (19)1.03468 (8)0.18560 (5)0.0445 (3)
H10.075 (14)0.358 (6)0.044 (4)0.08 (2)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0210 (11)0.0328 (14)0.0716 (18)−0.0039 (11)0.0011 (12)−0.0157 (13)
O20.0268 (11)0.0352 (13)0.0444 (13)0.0035 (11)0.0001 (11)−0.0124 (10)
C30.0272 (15)0.042 (2)0.0396 (17)0.0004 (16)0.0043 (14)−0.0058 (15)
C110.0170 (13)0.0257 (16)0.0481 (18)−0.0006 (13)−0.0004 (13)−0.0017 (13)
C20.0253 (15)0.0308 (17)0.0410 (17)−0.0021 (13)0.0015 (13)−0.0030 (14)
C60.0192 (13)0.0277 (17)0.0403 (17)−0.0022 (13)−0.0007 (12)−0.0057 (14)
C100.0382 (19)0.0217 (16)0.056 (2)0.0033 (15)0.0023 (17)0.0028 (15)
C120.042 (2)0.035 (2)0.050 (2)−0.0024 (17)0.0116 (18)0.0000 (17)
C50.0322 (17)0.0246 (17)0.055 (2)−0.0013 (14)0.0142 (17)−0.0003 (16)
C10.0244 (14)0.0285 (17)0.0334 (16)0.0043 (13)−0.0034 (13)−0.0020 (13)
C70.0235 (14)0.0342 (18)0.0388 (16)0.0018 (16)−0.0015 (13)−0.0035 (14)
C40.0350 (17)0.0255 (16)0.0384 (16)0.0065 (14)0.0005 (14)0.0027 (13)
C90.0403 (19)0.046 (2)0.047 (2)0.0113 (18)−0.0042 (17)0.0053 (18)
C80.0411 (19)0.044 (2)0.0390 (17)0.0109 (18)−0.0030 (16)−0.0057 (15)
Cl10.0542 (6)0.0270 (4)0.0522 (5)0.0076 (4)0.0046 (4)−0.0052 (3)

Geometric parameters (Å, °)

O1—C61.420 (4)C10—H10B0.9900
O1—H10.92 (7)C12—C51.384 (6)
O2—C111.216 (4)C12—C41.392 (5)
C3—C41.378 (5)C12—H12A0.9500
C3—C21.384 (5)C5—C11.383 (5)
C3—H3A0.9500C5—H5A0.9500
C11—C101.494 (5)C7—C81.534 (5)
C11—C71.528 (5)C7—H7A1.01 (5)
C2—C11.392 (5)C4—Cl11.739 (4)
C2—H2A0.9500C9—C81.530 (5)
C6—C11.510 (5)C9—H9A0.9900
C6—C71.531 (5)C9—H9B0.9900
C6—H6A1.08 (4)C8—H8A0.9900
C10—C91.517 (6)C8—H8B0.9900
C10—H10A0.9900
C6—O1—H1111 (5)C1—C5—H5A119.0
C4—C3—C2120.2 (3)C12—C5—H5A119.0
C4—C3—H3A119.9C5—C1—C2118.3 (3)
C2—C3—H3A119.9C5—C1—C6120.4 (3)
O2—C11—C10126.9 (3)C2—C1—C6121.3 (3)
O2—C11—C7123.7 (3)C11—C7—C6112.1 (3)
C10—C11—C7109.3 (3)C11—C7—C8104.0 (3)
C3—C2—C1120.5 (3)C6—C7—C8116.3 (3)
C3—C2—H2A119.7C11—C7—H7A104 (3)
C1—C2—H2A119.7C6—C7—H7A104 (3)
O1—C6—C1108.2 (3)C8—C7—H7A115 (2)
O1—C6—C7111.8 (3)C3—C4—C12120.3 (3)
C1—C6—C7110.4 (3)C3—C4—Cl1119.6 (3)
O1—C6—H6A109 (2)C12—C4—Cl1120.1 (3)
C1—C6—H6A109 (2)C10—C9—C8103.9 (3)
C7—C6—H6A108 (2)C10—C9—H9A111.0
C11—C10—C9104.9 (3)C8—C9—H9A111.0
C11—C10—H10A110.8C10—C9—H9B111.0
C9—C10—H10A110.8C8—C9—H9B111.0
C11—C10—H10B110.8H9A—C9—H9B109.0
C9—C10—H10B110.8C9—C8—C7104.7 (3)
H10A—C10—H10B108.8C9—C8—H8A110.8
C5—C12—C4118.6 (4)C7—C8—H8A110.8
C5—C12—H12A120.7C9—C8—H8B110.8
C4—C12—H12A120.7C7—C8—H8B110.8
C1—C5—C12122.0 (3)H8A—C8—H8B108.9
C4—C3—C2—C1−0.3 (5)O2—C11—C7—C8173.9 (4)
O2—C11—C10—C9163.5 (4)C10—C11—C7—C8−6.1 (4)
C7—C11—C10—C9−16.5 (4)O1—C6—C7—C1163.0 (4)
C4—C12—C5—C10.8 (7)C1—C6—C7—C11−176.4 (3)
C12—C5—C1—C2−0.4 (6)O1—C6—C7—C8−56.5 (4)
C12—C5—C1—C6179.9 (4)C1—C6—C7—C864.1 (4)
C3—C2—C1—C50.1 (5)C2—C3—C4—C120.7 (6)
C3—C2—C1—C6179.8 (3)C2—C3—C4—Cl1−177.7 (3)
O1—C6—C1—C5−163.3 (3)C5—C12—C4—C3−1.0 (6)
C7—C6—C1—C574.0 (4)C5—C12—C4—Cl1177.4 (3)
O1—C6—C1—C217.0 (4)C11—C10—C9—C832.5 (4)
C7—C6—C1—C2−105.7 (4)C10—C9—C8—C7−36.6 (4)
O2—C11—C7—C647.5 (4)C11—C7—C8—C926.1 (4)
C10—C11—C7—C6−132.5 (3)C6—C7—C8—C9149.8 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.92 (7)1.89 (7)2.793 (4)165 (7)
C10—H10A···O2ii0.992.533.328 (5)138
C5—H5A···Cg2iii0.952.963.818 (4)150

Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) x+1/2, −y+1/2, −z; (iii) −x, y+3/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2143).

References

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