Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039943/xu2309sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039943/xu2309Isup2.hkl |
CCDC reference: 660305
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.009 Å
- R factor = 0.069
- wR factor = 0.205
- Data-to-parameter ratio = 7.6
checkCIF/PLATON results
No syntax errors found
Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.124 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.12 PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) ..... 7.59 PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 300 Ang. PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 9
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.20 From the CIF: _reflns_number_total 1321 Count of symmetry unique reflns 1344 Completeness (_total/calc) 98.29% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT791_ALERT_1_G Confirm the Absolute Configuration of C7 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C8 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C12 = . S PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 7 ALERT level G = General alerts; check 6 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 5 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
To a solution of 4-nitrobenzaldehyde (0.5 mmol) and 4-methylcyclohexanone (5 mmol) in anhydrous dicloromethane (2 ml) was added L—N-phenylpyrrolidine-2-carboxamide (19 mg, 0.1 mmol). The resulting mixture was stirred at 273 K for 24 h. The reaction mixture was treated with saturated ammonium chloride solution and the aqueous layer was extracted with ethyl acetate, dried over anhydrous MgSO4. After filtration and removal of solvent under reduced pressure, the residue was purified through column chromatography on silica gel to give the title compound. Colourless single crystals of the title compound were obtained by recrystallization from an ethanol solution.
Hydroxy and methyl H atoms were placed in calculated positions with O—H = 0.82 and C—H = 0.96 Å, and torsion angles were refined, Uiso(H) = 1.5Ueq(O,C). Other H atoms were placed in calculated positions with C—H = 0.93 to 0.98 Å and refined using a riding model with Uiso(H) =1.2Ueq(C). In the absence of significant anomalous scattering effects, Friedel pairs were averaged.
Beta-hydroxy ketone can be transferred to a large variety of important product. The title compound, (I), is an very important intermediate for the construction of α,β-unsaturated carbonyl compound, which are important synthetic building blocks for the construction of many natural products (Basavaiah et al., 1996). We report here the crystal structure of the title compound, (I).
The molecular structure of (I) is shown in Fig. 1. Bond lengths and angles in (I) are normal. The benzene ring and nitro group is slightly non-planar, with a dihedral angle of 4.14 (8)°. The dihedral angle between the benzene and O4/C8/C9/C10 planes is 11.1 (3)°. The crystal packing is stabilized by O—H···O hydrogen bonding (Table 1).
For general background, see: Basavaiah et al. (1996).
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).
Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms). |
C14H17NO4 | F(000) = 280 |
Mr = 263.29 | Dx = 1.283 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 28 reflections |
a = 9.917 (3) Å | θ = 4.9–9.2° |
b = 6.927 (3) Å | µ = 0.09 mm−1 |
c = 10.518 (3) Å | T = 293 K |
β = 109.35 (3)° | Block, colourless |
V = 681.7 (4) Å3 | 0.25 × 0.20 × 0.18 mm |
Z = 2 |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.124 |
Radiation source: fine-focus sealed tube | θmax = 25.2°, θmin = 2.0° |
Graphite monochromator | h = −11→0 |
ω/2θ scans | k = −8→8 |
2439 measured reflections | l = −11→12 |
1321 independent reflections | 3 standard reflections every 300 reflections |
773 reflections with I > 2σ(I) | intensity decay: 0.6% |
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)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.205 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.1226P)2] where P = (Fo2 + 2Fc2)/3 |
1321 reflections | (Δ/σ)max < 0.001 |
174 parameters | Δρmax = 0.28 e Å−3 |
1 restraint | Δρmin = −0.22 e Å−3 |
C14H17NO4 | V = 681.7 (4) Å3 |
Mr = 263.29 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.917 (3) Å | µ = 0.09 mm−1 |
b = 6.927 (3) Å | T = 293 K |
c = 10.518 (3) Å | 0.25 × 0.20 × 0.18 mm |
β = 109.35 (3)° |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.124 |
2439 measured reflections | 3 standard reflections every 300 reflections |
1321 independent reflections | intensity decay: 0.6% |
773 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.069 | 1 restraint |
wR(F2) = 0.205 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.28 e Å−3 |
1321 reflections | Δρmin = −0.22 e Å−3 |
174 parameters |
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 | 0.3277 (6) | −0.0005 (10) | 0.9818 (5) | 0.0900 (17) | |
O2 | 0.2949 (8) | 0.2523 (11) | 1.0846 (6) | 0.112 (2) | |
O3 | 0.4801 (5) | 0.7878 (7) | 0.6164 (5) | 0.0666 (12) | |
H3 | 0.5562 | 0.7380 | 0.6605 | 0.100* | |
O4 | 0.2824 (6) | 1.0356 (8) | 0.3885 (5) | 0.0797 (15) | |
N | 0.3154 (6) | 0.1751 (11) | 0.9901 (5) | 0.0728 (19) | |
C1 | 0.3416 (7) | 0.6009 (11) | 0.7890 (6) | 0.0640 (18) | |
H1 | 0.3413 | 0.7348 | 0.7957 | 0.077* | |
C2 | 0.3250 (7) | 0.4906 (10) | 0.8923 (6) | 0.0621 (17) | |
H2 | 0.3114 | 0.5478 | 0.9671 | 0.075* | |
C3 | 0.3294 (6) | 0.2947 (11) | 0.8807 (6) | 0.0546 (15) | |
C4 | 0.3480 (7) | 0.2079 (9) | 0.7711 (6) | 0.0615 (18) | |
H4 | 0.3524 | 0.0741 | 0.7664 | 0.074* | |
C5 | 0.3602 (7) | 0.3203 (10) | 0.6679 (6) | 0.0581 (16) | |
H5 | 0.3696 | 0.2616 | 0.5917 | 0.070* | |
C6 | 0.3587 (6) | 0.5168 (9) | 0.6757 (5) | 0.0493 (14) | |
C7 | 0.3760 (6) | 0.6408 (9) | 0.5629 (6) | 0.0491 (14) | |
H7 | 0.4063 | 0.5594 | 0.5011 | 0.059* | |
C8 | 0.2362 (6) | 0.7441 (9) | 0.4842 (6) | 0.0562 (16) | |
H8 | 0.2112 | 0.8309 | 0.5465 | 0.067* | |
C9 | 0.2614 (6) | 0.8666 (10) | 0.3738 (6) | 0.0573 (16) | |
C10 | 0.2588 (9) | 0.7609 (13) | 0.2488 (7) | 0.078 (2) | |
H10A | 0.3451 | 0.6842 | 0.2680 | 0.094* | |
H10B | 0.2581 | 0.8539 | 0.1797 | 0.094* | |
C11 | 0.1309 (8) | 0.6310 (13) | 0.1962 (6) | 0.0726 (19) | |
H11A | 0.1376 | 0.5592 | 0.1194 | 0.087* | |
H11B | 0.0449 | 0.7090 | 0.1660 | 0.087* | |
C12 | 0.1203 (6) | 0.4908 (11) | 0.3032 (6) | 0.0654 (17) | |
H12 | 0.2088 | 0.4152 | 0.3332 | 0.078* | |
C13 | 0.1114 (6) | 0.6068 (11) | 0.4240 (6) | 0.0636 (17) | |
H13A | 0.0235 | 0.6810 | 0.3962 | 0.076* | |
H13B | 0.1067 | 0.5175 | 0.4935 | 0.076* | |
C14 | −0.0036 (9) | 0.3504 (14) | 0.2514 (9) | 0.093 (3) | |
H14A | 0.0054 | 0.2806 | 0.1757 | 0.140* | |
H14B | −0.0921 | 0.4206 | 0.2240 | 0.140* | |
H14C | −0.0025 | 0.2613 | 0.3216 | 0.140* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.120 (4) | 0.083 (4) | 0.070 (3) | −0.017 (3) | 0.035 (3) | 0.020 (3) |
O2 | 0.166 (6) | 0.118 (5) | 0.080 (4) | 0.025 (5) | 0.078 (4) | 0.025 (4) |
O3 | 0.065 (2) | 0.069 (3) | 0.067 (3) | −0.009 (2) | 0.025 (2) | 0.009 (2) |
O4 | 0.104 (4) | 0.053 (3) | 0.078 (3) | −0.001 (3) | 0.024 (3) | 0.013 (3) |
N | 0.086 (4) | 0.089 (6) | 0.050 (3) | 0.005 (3) | 0.031 (3) | 0.022 (3) |
C1 | 0.080 (4) | 0.063 (4) | 0.055 (4) | 0.017 (3) | 0.031 (3) | 0.007 (3) |
C2 | 0.084 (4) | 0.066 (5) | 0.045 (3) | 0.008 (4) | 0.032 (3) | 0.008 (3) |
C3 | 0.053 (3) | 0.068 (5) | 0.044 (3) | −0.004 (3) | 0.018 (3) | 0.012 (3) |
C4 | 0.076 (4) | 0.051 (4) | 0.057 (4) | −0.005 (3) | 0.022 (3) | 0.008 (3) |
C5 | 0.080 (4) | 0.054 (4) | 0.047 (3) | −0.007 (3) | 0.031 (3) | −0.002 (3) |
C6 | 0.054 (3) | 0.051 (4) | 0.048 (3) | 0.002 (3) | 0.023 (3) | 0.004 (3) |
C7 | 0.059 (3) | 0.045 (3) | 0.049 (3) | 0.004 (3) | 0.026 (3) | 0.005 (3) |
C8 | 0.073 (4) | 0.053 (4) | 0.051 (3) | 0.009 (3) | 0.033 (3) | 0.005 (3) |
C9 | 0.066 (4) | 0.059 (5) | 0.050 (3) | 0.009 (3) | 0.023 (3) | 0.015 (3) |
C10 | 0.106 (5) | 0.090 (6) | 0.054 (4) | −0.017 (5) | 0.047 (4) | 0.006 (4) |
C11 | 0.081 (4) | 0.085 (5) | 0.052 (4) | 0.006 (4) | 0.022 (3) | 0.005 (4) |
C12 | 0.062 (3) | 0.070 (5) | 0.062 (4) | −0.006 (4) | 0.020 (3) | 0.003 (3) |
C13 | 0.063 (4) | 0.073 (5) | 0.059 (4) | 0.006 (3) | 0.027 (3) | 0.017 (3) |
C14 | 0.083 (5) | 0.085 (6) | 0.105 (6) | −0.022 (4) | 0.022 (4) | −0.009 (5) |
O1—N | 1.229 (8) | C8—C13 | 1.523 (9) |
O2—N | 1.204 (8) | C8—C9 | 1.524 (8) |
O3—C7 | 1.426 (8) | C8—H8 | 0.9800 |
O3—H3 | 0.8200 | C9—C10 | 1.498 (9) |
O4—C9 | 1.190 (9) | C10—C11 | 1.503 (11) |
N—C3 | 1.461 (8) | C10—H10A | 0.9700 |
C1—C2 | 1.382 (9) | C10—H10B | 0.9700 |
C1—C6 | 1.387 (8) | C11—C12 | 1.516 (9) |
C1—H1 | 0.9300 | C11—H11A | 0.9700 |
C2—C3 | 1.364 (10) | C11—H11B | 0.9700 |
C2—H2 | 0.9300 | C12—C14 | 1.519 (10) |
C3—C4 | 1.366 (9) | C12—C13 | 1.531 (9) |
C4—C5 | 1.373 (9) | C12—H12 | 0.9800 |
C4—H4 | 0.9300 | C13—H13A | 0.9700 |
C5—C6 | 1.365 (9) | C13—H13B | 0.9700 |
C5—H5 | 0.9300 | C14—H14A | 0.9600 |
C6—C7 | 1.520 (7) | C14—H14B | 0.9600 |
C7—C8 | 1.535 (8) | C14—H14C | 0.9600 |
C7—H7 | 0.9800 | ||
C7—O3—H3 | 109.5 | O4—C9—C10 | 123.1 (6) |
O2—N—O1 | 123.1 (6) | O4—C9—C8 | 120.9 (6) |
O2—N—C3 | 119.0 (7) | C10—C9—C8 | 116.0 (6) |
O1—N—C3 | 117.9 (6) | C9—C10—C11 | 112.5 (5) |
C2—C1—C6 | 121.6 (7) | C9—C10—H10A | 109.1 |
C2—C1—H1 | 119.2 | C11—C10—H10A | 109.1 |
C6—C1—H1 | 119.2 | C9—C10—H10B | 109.1 |
C3—C2—C1 | 117.7 (6) | C11—C10—H10B | 109.1 |
C3—C2—H2 | 121.2 | H10A—C10—H10B | 107.8 |
C1—C2—H2 | 121.2 | C10—C11—C12 | 111.6 (5) |
C2—C3—C4 | 122.0 (6) | C10—C11—H11A | 109.3 |
C2—C3—N | 118.6 (6) | C12—C11—H11A | 109.3 |
C4—C3—N | 119.4 (6) | C10—C11—H11B | 109.3 |
C3—C4—C5 | 119.4 (6) | C12—C11—H11B | 109.3 |
C3—C4—H4 | 120.3 | H11A—C11—H11B | 108.0 |
C5—C4—H4 | 120.3 | C11—C12—C14 | 113.0 (6) |
C6—C5—C4 | 120.8 (6) | C11—C12—C13 | 108.5 (6) |
C6—C5—H5 | 119.6 | C14—C12—C13 | 111.9 (5) |
C4—C5—H5 | 119.6 | C11—C12—H12 | 107.8 |
C5—C6—C1 | 118.6 (6) | C14—C12—H12 | 107.8 |
C5—C6—C7 | 120.7 (5) | C13—C12—H12 | 107.8 |
C1—C6—C7 | 120.8 (6) | C8—C13—C12 | 114.3 (4) |
O3—C7—C6 | 110.5 (5) | C8—C13—H13A | 108.7 |
O3—C7—C8 | 106.6 (5) | C12—C13—H13A | 108.7 |
C6—C7—C8 | 111.6 (4) | C8—C13—H13B | 108.7 |
O3—C7—H7 | 109.4 | C12—C13—H13B | 108.7 |
C6—C7—H7 | 109.4 | H13A—C13—H13B | 107.6 |
C8—C7—H7 | 109.4 | C12—C14—H14A | 109.5 |
C13—C8—C9 | 110.3 (5) | C12—C14—H14B | 109.5 |
C13—C8—C7 | 113.4 (5) | H14A—C14—H14B | 109.5 |
C9—C8—C7 | 108.9 (4) | C12—C14—H14C | 109.5 |
C13—C8—H8 | 108.0 | H14A—C14—H14C | 109.5 |
C9—C8—H8 | 108.0 | H14B—C14—H14C | 109.5 |
C7—C8—H8 | 108.0 |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4i | 0.82 | 2.31 | 2.947 (7) | 135 |
O3—H3···O2ii | 0.82 | 2.60 | 3.206 (8) | 132 |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+1, y+1/2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C14H17NO4 |
Mr | 263.29 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 9.917 (3), 6.927 (3), 10.518 (3) |
β (°) | 109.35 (3) |
V (Å3) | 681.7 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.25 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2439, 1321, 773 |
Rint | 0.124 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.205, 0.97 |
No. of reflections | 1321 |
No. of parameters | 174 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.22 |
Computer programs: DIFRAC (Gabe et al., 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4i | 0.82 | 2.31 | 2.947 (7) | 135 |
O3—H3···O2ii | 0.82 | 2.60 | 3.206 (8) | 132 |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+1, y+1/2, −z+2. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
Beta-hydroxy ketone can be transferred to a large variety of important product. The title compound, (I), is an very important intermediate for the construction of α,β-unsaturated carbonyl compound, which are important synthetic building blocks for the construction of many natural products (Basavaiah et al., 1996). We report here the crystal structure of the title compound, (I).
The molecular structure of (I) is shown in Fig. 1. Bond lengths and angles in (I) are normal. The benzene ring and nitro group is slightly non-planar, with a dihedral angle of 4.14 (8)°. The dihedral angle between the benzene and O4/C8/C9/C10 planes is 11.1 (3)°. The crystal packing is stabilized by O—H···O hydrogen bonding (Table 1).