(2R,3R)-2-[(4-Chloro-phen-yl)hydroxy-meth-yl]cyclo-penta-none.

The title compound, C(12)H(13)ClO(2), was prepared by the direct asymmetric inter-molecular aldol reaction of cyclo-penta-none and 4-chloro-benzaldehyde catalysed by l-tryptophan in water. The absolute mol-ecular 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 mol-ecules are connected into a one-dimensional chain along the a axis through the formation of inter-molecular 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 ▶). For a structure with C—H⋯O hydrogen bonds, see: Nangia (2002 ▶). For a database study of C—H⋯π inter­actions in the conformation of peptides, see: Umezawa et al. (1999 ▶). For direct inter­molecular aldol reactions catalysed by acyclic amino acids, see: Córdova et al. (2006 ▶); Deng & Cai (2007 ▶). For asymmetric direct aldol reaction assisted by water and a proline-derived tetra­zole catalyst, see: Torii et al. (2004 ▶). For the development of direct catalytic asymmetric aldol, Mannich, Michael and Diels–Alder reactions, see: Notz et al. (2004 ▶).

Experimental

Crystal data

C12H13ClO2

M = 224.67

Orthorhombic,

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 ▶) 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 ▶), 572 Friedel pairs

Flack parameter: 0.09 (3)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; 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: SHELXTL and PLATON (Spek, 2003 ▶).

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

C12H13ClO2	F(000) = 472
Mr = 224.67	Dx = 1.365 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2189 reflections
a = 5.7401 (1) Å	θ = 4.9–76.7°
b = 10.4549 (2) Å	µ = 2.90 mm−1
c = 18.2135 (3) Å	T = 150 K
V = 1093.03 (3) Å3	Block, colorless
Z = 4	0.43 × 0.31 × 0.25 mm

Bruker APEXII CCD diffractometer	1936 independent reflections
Radiation source: fine-focus sealed tube	1865 reflections with I > 2σ(I)
graphite	Rint = 0.040
φ and ω scans	θmax = 76.7°, θmin = 4.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→5
Tmin = 0.336, Tmax = 0.484	k = −9→12
3762 measured reflections	l = −22→17

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.168	w = 1/[σ2(Fo2) + (0.0962P)2 + 1.0311P] where P = (Fo2 + 2Fc2)/3
S = 1.14	(Δ/σ)max < 0.001
1936 reflections	Δρmax = 0.34 e Å−3
146 parameters	Δρmin = −0.52 e Å−3
0 restraints	Absolute structure: Flack (1983), 572 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.09 (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	0.0477 (5)	0.4383 (3)	0.06246 (17)	0.0418 (7)
O2	0.5454 (4)	0.3133 (2)	−0.01098 (14)	0.0355 (6)
C3	−0.0344 (7)	0.7839 (4)	0.1635 (2)	0.0361 (8)
H3A	−0.1615	0.7951	0.1962	0.043*
C11	0.5311 (6)	0.3306 (3)	0.0549 (2)	0.0303 (7)
C2	0.0105 (6)	0.6644 (3)	0.1340 (2)	0.0324 (7)
H2A	−0.0858	0.5940	0.1469	0.039*
C6	0.2476 (6)	0.5168 (3)	0.05323 (19)	0.0291 (7)
H6A	0.283 (8)	0.528 (4)	−0.005 (2)	0.035*
C10	0.5749 (7)	0.2346 (3)	0.1141 (2)	0.0388 (8)
H10A	0.7174	0.1845	0.1036	0.047*
H10B	0.4415	0.1751	0.1188	0.047*
C12	0.2900 (8)	0.8713 (4)	0.0969 (2)	0.0423 (9)
H12A	0.3851	0.9420	0.0837	0.051*
C5	0.3327 (7)	0.7509 (3)	0.0683 (2)	0.0373 (8)
H5A	0.4601	0.7397	0.0356	0.045*
C1	0.1955 (6)	0.6465 (3)	0.08574 (18)	0.0288 (7)
C7	0.4634 (6)	0.4583 (4)	0.08953 (19)	0.0322 (7)
H7A	0.595 (8)	0.518 (5)	0.075 (2)	0.039*
C4	0.1048 (6)	0.8865 (3)	0.1455 (2)	0.0330 (7)
C9	0.6046 (7)	0.3132 (4)	0.1835 (2)	0.0443 (9)
H9A	0.7683	0.3411	0.1894	0.053*
H9B	0.5573	0.2637	0.2273	0.053*
C8	0.4435 (8)	0.4280 (4)	0.1717 (2)	0.0415 (9)
H8A	0.4946	0.5019	0.2017	0.050*
H8B	0.2810	0.4063	0.1850	0.050*
Cl1	0.05251 (19)	1.03468 (8)	0.18560 (5)	0.0445 (3)
H1	0.075 (14)	0.358 (6)	0.044 (4)	0.08 (2)*

	U11	U22	U33	U12	U13	U23
O1	0.0210 (11)	0.0328 (14)	0.0716 (18)	−0.0039 (11)	0.0011 (12)	−0.0157 (13)
O2	0.0268 (11)	0.0352 (13)	0.0444 (13)	0.0035 (11)	0.0001 (11)	−0.0124 (10)
C3	0.0272 (15)	0.042 (2)	0.0396 (17)	0.0004 (16)	0.0043 (14)	−0.0058 (15)
C11	0.0170 (13)	0.0257 (16)	0.0481 (18)	−0.0006 (13)	−0.0004 (13)	−0.0017 (13)
C2	0.0253 (15)	0.0308 (17)	0.0410 (17)	−0.0021 (13)	0.0015 (13)	−0.0030 (14)
C6	0.0192 (13)	0.0277 (17)	0.0403 (17)	−0.0022 (13)	−0.0007 (12)	−0.0057 (14)
C10	0.0382 (19)	0.0217 (16)	0.056 (2)	0.0033 (15)	0.0023 (17)	0.0028 (15)
C12	0.042 (2)	0.035 (2)	0.050 (2)	−0.0024 (17)	0.0116 (18)	0.0000 (17)
C5	0.0322 (17)	0.0246 (17)	0.055 (2)	−0.0013 (14)	0.0142 (17)	−0.0003 (16)
C1	0.0244 (14)	0.0285 (17)	0.0334 (16)	0.0043 (13)	−0.0034 (13)	−0.0020 (13)
C7	0.0235 (14)	0.0342 (18)	0.0388 (16)	0.0018 (16)	−0.0015 (13)	−0.0035 (14)
C4	0.0350 (17)	0.0255 (16)	0.0384 (16)	0.0065 (14)	0.0005 (14)	0.0027 (13)
C9	0.0403 (19)	0.046 (2)	0.047 (2)	0.0113 (18)	−0.0042 (17)	0.0053 (18)
C8	0.0411 (19)	0.044 (2)	0.0390 (17)	0.0109 (18)	−0.0030 (16)	−0.0057 (15)
Cl1	0.0542 (6)	0.0270 (4)	0.0522 (5)	0.0076 (4)	0.0046 (4)	−0.0052 (3)

O1—C6	1.420 (4)	C10—H10B	0.9900
O1—H1	0.92 (7)	C12—C5	1.384 (6)
O2—C11	1.216 (4)	C12—C4	1.392 (5)
C3—C4	1.378 (5)	C12—H12A	0.9500
C3—C2	1.384 (5)	C5—C1	1.383 (5)
C3—H3A	0.9500	C5—H5A	0.9500
C11—C10	1.494 (5)	C7—C8	1.534 (5)
C11—C7	1.528 (5)	C7—H7A	1.01 (5)
C2—C1	1.392 (5)	C4—Cl1	1.739 (4)
C2—H2A	0.9500	C9—C8	1.530 (5)
C6—C1	1.510 (5)	C9—H9A	0.9900
C6—C7	1.531 (5)	C9—H9B	0.9900
C6—H6A	1.08 (4)	C8—H8A	0.9900
C10—C9	1.517 (6)	C8—H8B	0.9900
C10—H10A	0.9900
C6—O1—H1	111 (5)	C1—C5—H5A	119.0
C4—C3—C2	120.2 (3)	C12—C5—H5A	119.0
C4—C3—H3A	119.9	C5—C1—C2	118.3 (3)
C2—C3—H3A	119.9	C5—C1—C6	120.4 (3)
O2—C11—C10	126.9 (3)	C2—C1—C6	121.3 (3)
O2—C11—C7	123.7 (3)	C11—C7—C6	112.1 (3)
C10—C11—C7	109.3 (3)	C11—C7—C8	104.0 (3)
C3—C2—C1	120.5 (3)	C6—C7—C8	116.3 (3)
C3—C2—H2A	119.7	C11—C7—H7A	104 (3)
C1—C2—H2A	119.7	C6—C7—H7A	104 (3)
O1—C6—C1	108.2 (3)	C8—C7—H7A	115 (2)
O1—C6—C7	111.8 (3)	C3—C4—C12	120.3 (3)
C1—C6—C7	110.4 (3)	C3—C4—Cl1	119.6 (3)
O1—C6—H6A	109 (2)	C12—C4—Cl1	120.1 (3)
C1—C6—H6A	109 (2)	C10—C9—C8	103.9 (3)
C7—C6—H6A	108 (2)	C10—C9—H9A	111.0
C11—C10—C9	104.9 (3)	C8—C9—H9A	111.0
C11—C10—H10A	110.8	C10—C9—H9B	111.0
C9—C10—H10A	110.8	C8—C9—H9B	111.0
C11—C10—H10B	110.8	H9A—C9—H9B	109.0
C9—C10—H10B	110.8	C9—C8—C7	104.7 (3)
H10A—C10—H10B	108.8	C9—C8—H8A	110.8
C5—C12—C4	118.6 (4)	C7—C8—H8A	110.8
C5—C12—H12A	120.7	C9—C8—H8B	110.8
C4—C12—H12A	120.7	C7—C8—H8B	110.8
C1—C5—C12	122.0 (3)	H8A—C8—H8B	108.9
C4—C3—C2—C1	−0.3 (5)	O2—C11—C7—C8	173.9 (4)
O2—C11—C10—C9	163.5 (4)	C10—C11—C7—C8	−6.1 (4)
C7—C11—C10—C9	−16.5 (4)	O1—C6—C7—C11	63.0 (4)
C4—C12—C5—C1	0.8 (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—C6	179.9 (4)	C1—C6—C7—C8	64.1 (4)
C3—C2—C1—C5	0.1 (5)	C2—C3—C4—C12	0.7 (6)
C3—C2—C1—C6	179.8 (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—C5	74.0 (4)	C5—C12—C4—Cl1	177.4 (3)
O1—C6—C1—C2	17.0 (4)	C11—C10—C9—C8	32.5 (4)
C7—C6—C1—C2	−105.7 (4)	C10—C9—C8—C7	−36.6 (4)
O2—C11—C7—C6	47.5 (4)	C11—C7—C8—C9	26.1 (4)
C10—C11—C7—C6	−132.5 (3)	C6—C7—C8—C9	149.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2i	0.92 (7)	1.89 (7)	2.793 (4)	165 (7)
C10—H10A···O2ii	0.99	2.53	3.328 (5)	138
C5—H5A···Cg2iii	0.95	2.96	3.818 (4)	150

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2i	0.92 (7)	1.89 (7)	2.793 (4)	165 (7)
C10—H10A⋯O2ii	0.99	2.53	3.328 (5)	138
C5—H5A⋯Cg2iii	0.95	2.96	3.818 (4)	150

Symmetry codes: (i) ; (ii) ; (iii) . Cg2 is the centroid of the C1–C5,C12 ring.