Methyl 2-hydr­oxy-3-(2-nitro­phen­yl)-2-(2-oxocyclo­pent­yl)propanoate

In the title compound, C₁₅H₁₇NO₆, the nitro group is tilted at a dihedral angle of 44.1 (3)° with respect to the benzene ring. The five-membered cyclopentanone ring adopts an envelope conformation. Intra­molecular O—H...O hydrogen bonding is observed.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.076
• wR factor = 0.220
• Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low ....         37 Perc.

Alert level C
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C5     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C6     = ...          R

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

α-Hydroxy ester can be transferred to a large variety of important product. The title compound is a very important intermediate for the construction of α,β-unsaturated carbonyl compound, which has broad utility in organic synthesis (Basavaiah et al., 1996; Elier et al., 1956). Its crystal structure is reported here.

The molecular structure is shown in Fig. 1. Bond lengths and angles are normal. The C15-containing ester shows an extended planar conformation and makes a dihedral angle of 49.8 (2)° with the benzene plane, The nitro group is not coplanar with attached benzene ring and tilted with respect to the benzene ring with a angle of 44.1 (3)°. Intramolecular O—H···O hydrogen bonding is observed in the structure (Table 1).

Related literature

For general background, see: Basavaiah et al. (1996) check date – 2003 in list; Elier et al. (1956). For related structures, see: Langner et al. (2005); Desimoni et al. (2006).

S2. Experimental

To a mixture of anhydrous cyclopentanone (1 ml) and toluene (3 ml) was added the 3-(2-nitrophenyl)-2-oxopropanoic acid (0.5 mmol) and L-N-(pyridin-2-yl)pyrrolidine-2-carboxamide (2 mmol) and the resulting mixture was stirred at 273 K for 12 h. The reaction mixture was treated with CH₂N₂ solution in ether for 20 min. After removal of solvent, the residue was purified through flash column chromatography on a silica gel to give the title compound. Colourless single crystals suitable for X-ray diffraction were obtained by recrystallization from an ethanol solution.

S3. Refinement

H atoms were placed in calculated positions with C–H = 0.93–0.98 Å and O—H = 0.82 Å, and refined using a riding model with U_iso(H) =1.2U_eq(C,O).

Computing details

Data collection: DIFRAC (Gabe et al., 1993); cell refinement: DIFRAC (Gabe et al., 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia,1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms).

Methyl 2-hydroxy-3-(2-nitrophenyl)-2-(2-oxocyclopentyl)propanoate

Crystal data

C15H17NO6	F(000) = 648
Mr = 307.30	Dx = 1.397 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 19 reflections
a = 14.556 (4) Å	θ = 5.0–9.3°
b = 5.540 (2) Å	µ = 0.11 mm^−1
c = 18.194 (6) Å	T = 292 K
β = 95.12 (3)°	Block, colourless
V = 1461.3 (8) Å^3	0.25 × 0.22 × 0.05 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.010
Radiation source: fine-focus sealed tube	θmax = 25.1°, θmin = 1.4°
Graphite monochromator	h = −17→17
ω/2θ scan	k = 0→6
2595 measured reflections	l = −4→21
2591 independent reflections	3 standard reflections every 300 reflections
949 reflections with I > 2σ(I)	intensity decay: 4.8%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.220	H-atom parameters constrained
S = 0.91	w = 1/[σ^2(Fo^2) + (0.107P)^2] where P = (Fo^2 + 2Fc^2)/3
2591 reflections	(Δ/σ)max = 0.001
201 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.0421 (3)	0.2211 (8)	0.2122 (3)	0.0735 (15)
O2	0.1788 (3)	0.1796 (7)	0.0950 (2)	0.0445 (10)
H2	0.2285	0.2059	0.0785	0.053*
O3	0.2303 (2)	−0.0964 (6)	0.27028 (19)	0.0421 (10)
O4	0.2620 (3)	0.2696 (7)	0.2269 (2)	0.0583 (12)
O5	0.3485 (4)	0.3703 (9)	0.0026 (3)	0.0834 (16)
O6	0.2893 (3)	0.0276 (9)	−0.0299 (2)	0.0691 (14)
N1	0.3379 (4)	0.1526 (11)	0.0124 (3)	0.0549 (14)
C1	0.0238 (4)	0.0522 (11)	0.1718 (3)	0.0456 (15)
C2	−0.0695 (4)	−0.0067 (12)	0.1355 (3)	0.0541 (17)
H2A	−0.0909	0.1195	0.1012	0.065*
H2B	−0.1137	−0.0252	0.1720	0.065*
C3	−0.0574 (4)	−0.2430 (12)	0.0950 (3)	0.0548 (17)
H3A	−0.0713	−0.3797	0.1254	0.066*
H3B	−0.0973	−0.2487	0.0494	0.066*
C4	0.0428 (4)	−0.2444 (11)	0.0796 (3)	0.0471 (15)
H4A	0.0523	−0.1489	0.0363	0.056*
H4B	0.0643	−0.4077	0.0723	0.056*
C5	0.0921 (3)	−0.1321 (10)	0.1492 (3)	0.0392 (14)
H5	0.0981	−0.2572	0.1874	0.047*
C6	0.1875 (4)	−0.0227 (9)	0.1435 (3)	0.0365 (13)
C7	0.2303 (4)	0.0695 (10)	0.2176 (3)	0.0379 (13)
C8	0.2536 (4)	−0.2062 (10)	0.1124 (3)	0.0400 (14)
H8A	0.2485	−0.3581	0.1382	0.048*
H8B	0.2334	−0.2342	0.0608	0.048*
C9	0.3530 (4)	−0.1341 (10)	0.1178 (3)	0.0362 (13)
C10	0.4123 (4)	−0.2346 (10)	0.1729 (3)	0.0412 (14)
H10	0.3888	−0.3479	0.2039	0.049*
C11	0.5037 (4)	−0.1768 (12)	0.1844 (3)	0.0558 (17)
H11	0.5413	−0.2555	0.2208	0.067*
C12	0.5397 (4)	−0.0019 (12)	0.1417 (3)	0.0517 (17)
H12	0.6016	0.0408	0.1497	0.062*
C13	0.4844 (4)	0.1078 (11)	0.0880 (3)	0.0509 (17)
H13	0.5083	0.2277	0.0595	0.061*
C14	0.3933 (4)	0.0434 (10)	0.0753 (3)	0.0414 (14)
C15	0.2697 (4)	−0.0246 (11)	0.3430 (3)	0.0530 (17)
H15A	0.3355	−0.0110	0.3429	0.064*
H15B	0.2553	−0.1437	0.3785	0.064*
H15C	0.2445	0.1284	0.3557	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.078 (3)	0.058 (3)	0.087 (4)	−0.003 (3)	0.021 (3)	−0.036 (3)
O2	0.052 (2)	0.035 (2)	0.048 (2)	0.002 (2)	0.0130 (19)	0.0112 (19)
O3	0.061 (3)	0.026 (2)	0.039 (2)	−0.0021 (19)	−0.0014 (17)	0.0054 (18)
O4	0.081 (3)	0.035 (3)	0.056 (3)	−0.010 (2)	−0.008 (2)	−0.003 (2)
O5	0.132 (5)	0.052 (3)	0.066 (3)	−0.001 (3)	0.008 (3)	0.020 (3)
O6	0.075 (3)	0.087 (4)	0.044 (3)	−0.005 (3)	−0.003 (2)	−0.004 (3)
N1	0.073 (4)	0.051 (4)	0.043 (3)	0.009 (3)	0.017 (3)	0.007 (3)
C1	0.051 (4)	0.038 (4)	0.049 (4)	0.005 (3)	0.011 (3)	−0.001 (3)
C2	0.047 (4)	0.064 (5)	0.050 (4)	0.011 (3)	0.004 (3)	0.002 (3)
C3	0.041 (4)	0.066 (4)	0.056 (4)	−0.004 (3)	−0.003 (3)	−0.001 (3)
C4	0.050 (4)	0.041 (4)	0.049 (3)	−0.003 (3)	−0.001 (3)	−0.005 (3)
C5	0.037 (3)	0.047 (4)	0.033 (3)	−0.003 (3)	0.000 (2)	0.004 (3)
C6	0.049 (3)	0.031 (3)	0.030 (3)	0.007 (3)	0.006 (2)	0.005 (3)
C7	0.039 (3)	0.023 (3)	0.052 (4)	−0.001 (3)	0.007 (3)	−0.005 (3)
C8	0.053 (4)	0.028 (3)	0.040 (3)	0.003 (3)	0.008 (3)	−0.004 (3)
C9	0.040 (3)	0.033 (3)	0.036 (3)	0.003 (3)	0.004 (2)	−0.007 (3)
C10	0.041 (3)	0.032 (3)	0.050 (3)	0.004 (3)	0.001 (3)	0.001 (3)
C11	0.058 (4)	0.052 (4)	0.056 (4)	0.004 (4)	−0.001 (3)	0.003 (3)
C12	0.038 (3)	0.062 (4)	0.053 (4)	−0.005 (3)	−0.003 (3)	−0.017 (4)
C13	0.058 (4)	0.049 (4)	0.048 (4)	−0.020 (3)	0.019 (3)	−0.012 (3)
C14	0.051 (4)	0.039 (4)	0.035 (3)	0.007 (3)	0.010 (3)	−0.008 (3)
C15	0.057 (4)	0.063 (4)	0.037 (3)	−0.001 (3)	−0.002 (3)	0.009 (3)

Geometric parameters (Å, º)

O1—C1	1.205 (7)	C5—C6	1.527 (7)
O2—C6	1.426 (6)	C5—H5	0.9800
O2—H2	0.8200	C6—C7	1.521 (7)
O3—C7	1.329 (6)	C6—C8	1.542 (7)
O3—C15	1.449 (6)	C8—C9	1.496 (7)
O4—C7	1.206 (6)	C8—H8A	0.9700
O5—N1	1.230 (6)	C8—H8B	0.9700
O6—N1	1.214 (6)	C9—C10	1.380 (7)
N1—C14	1.470 (7)	C9—C14	1.410 (7)
C1—C2	1.492 (8)	C10—C11	1.365 (8)
C1—C5	1.508 (8)	C10—H10	0.9300
C2—C3	1.520 (8)	C11—C12	1.374 (8)
C2—H2A	0.9700	C11—H11	0.9300
C2—H2B	0.9700	C12—C13	1.353 (8)
C3—C4	1.509 (7)	C12—H12	0.9300
C3—H3A	0.9700	C13—C14	1.373 (7)
C3—H3B	0.9700	C13—H13	0.9300
C4—C5	1.530 (7)	C15—H15A	0.9600
C4—H4A	0.9700	C15—H15B	0.9600
C4—H4B	0.9700	C15—H15C	0.9600
C6—O2—H2	109.5	C7—C6—C8	109.1 (4)
C7—O3—C15	116.3 (4)	C5—C6—C8	111.3 (4)
O6—N1—O5	122.7 (6)	O4—C7—O3	124.0 (5)
O6—N1—C14	120.4 (6)	O4—C7—C6	123.7 (5)
O5—N1—C14	116.7 (6)	O3—C7—C6	112.4 (4)
O1—C1—C2	125.7 (5)	C9—C8—C6	115.5 (4)
O1—C1—C5	125.2 (5)	C9—C8—H8A	108.4
C2—C1—C5	109.1 (5)	C6—C8—H8A	108.4
C1—C2—C3	105.2 (5)	C9—C8—H8B	108.4
C1—C2—H2A	110.7	C6—C8—H8B	108.4
C3—C2—H2A	110.7	H8A—C8—H8B	107.5
C1—C2—H2B	110.7	C10—C9—C14	114.6 (5)
C3—C2—H2B	110.7	C10—C9—C8	118.6 (5)
H2A—C2—H2B	108.8	C14—C9—C8	126.6 (5)
C4—C3—C2	104.5 (5)	C11—C10—C9	123.6 (6)
C4—C3—H3A	110.9	C11—C10—H10	118.2
C2—C3—H3A	110.9	C9—C10—H10	118.2
C4—C3—H3B	110.9	C10—C11—C12	119.6 (6)
C2—C3—H3B	110.9	C10—C11—H11	120.2
H3A—C3—H3B	108.9	C12—C11—H11	120.2
C3—C4—C5	103.6 (4)	C13—C12—C11	119.5 (5)
C3—C4—H4A	111.0	C13—C12—H12	120.3
C5—C4—H4A	111.0	C11—C12—H12	120.3
C3—C4—H4B	111.0	C12—C13—C14	120.6 (6)
C5—C4—H4B	111.0	C12—C13—H13	119.7
H4A—C4—H4B	109.0	C14—C13—H13	119.7
C1—C5—C6	112.1 (5)	C13—C14—C9	122.1 (5)
C1—C5—C4	103.2 (4)	C13—C14—N1	118.6 (5)
C6—C5—C4	117.9 (4)	C9—C14—N1	119.2 (5)
C1—C5—H5	107.7	O3—C15—H15A	109.5
C6—C5—H5	107.7	O3—C15—H15B	109.5
C4—C5—H5	107.7	H15A—C15—H15B	109.5
O2—C6—C7	107.0 (4)	O3—C15—H15C	109.5
O2—C6—C5	108.8 (4)	H15A—C15—H15C	109.5
C7—C6—C5	112.1 (4)	H15B—C15—H15C	109.5
O2—C6—C8	108.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O5	0.82	2.49	3.283 (7)	162
O2—H2···O6	0.82	2.45	3.018 (5)	127