organic papers
Acta Cryst.(2007). E63, o271–o272 doi:10.1107/S1600536806053074 Kanget al. C
11H13NO5
o271
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
1,5-Dihydroxy-1-(3-nitrophenyl)pentan-3-one
Tai-Ran Kang, Long He* and Cheng Gao
College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002, People’s Republic of China
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study T= 153 K
Mean(C–C) = 0.002 A˚ Rfactor = 0.027 wRfactor = 0.073 Data-to-parameter ratio = 9.3
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
Received 27 November 2006 Accepted 7 December 2006
#2007 International Union of Crystallography All rights reserved
Intermolecular O—H O and weak C—H O hydrogen bonding helps to stabilize the crystal structure of the title compound, C11H13NO5.
Comment
Optically active polyhydroxy compounds are very useful intermediates in asymmetric organic syntheses. We have recently reported the crystal structures of some reagents for the synthesis of polyhydroxy compounds (Heet al., 2006). The title compound, (I), is an important synthetic building block for optically active 1,3,5-triols (Chen et al., 1987). We report here the crystal structure of (I).
The molecular structure of (I) is shown in Fig. 1. Bond lengths and angles in (I) are normal. The O1-hydroxy group forms bifurcated hydrogen bonds (Table 1). Intermolecular O—H O and weak C—H O hydrogen bonding helps to stabilize the crystal structure.
Experimental
To a solution of 3-nitrobenzaldehyde (75.5 mg, 0.5 mmol) and (S)-N -phenylpyrrolidine-2-carboxamide (19 mg, 20 mmol) in a mixture of water (1 ml) and THF (1 ml) was added 4-hydroxybutan-2-one (0.5 ml). The mixture was stirred at 273 K for 5 d. It was then treated with saturated ammonium chloride solution. The aqueous layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The solvent was removed and the residue was purified by column chromatography on silica gel (eluant: hexane–ethyl acetate 1:1). Colourless single crystals of (I) were obtained by recrystalliza-tion from an ethanol solurecrystalliza-tion.
Crystal data
C11H13NO5
Mr= 239.22
Orthorhombic,P212121
a= 5.0521 (1) A˚
b= 6.9787 (2) A˚
c= 31.1510 (6) A˚
V= 1098.29 (4) A˚3
Z= 4
Dx= 1.447 Mg m3
MoKradiation = 0.12 mm1
T= 153 (2) K Block, colourless 0.240.230.15 mm
Data collection
Rigaku R-AXIS RAPID diffractometer !scans
Absorption correction: none 10797 measured reflections
1513 independent reflections 1467 reflections withI> 2(I)
Rint= 0.016
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.027
wR(F2) = 0.073
S= 1.00 1513 reflections 163 parameters
H atoms treated by a mixture of independent and constrained refinement
w= 1/[2
(Fo2) + (0.0486P)2
+ 0.259P]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.001
max= 0.22 e A˚3
min=0.16 e A˚ 3
Extinction correction:SHELXL97
[image:2.610.313.566.71.196.2] [image:2.610.46.297.229.293.2]Extinction coefficient: 0.025 (4)
Table 1
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
O1—H1O O2 0.88 (2) 2.12 (2) 2.7977 (15) 133.6 (19) O1—H1O O3i
0.88 (2) 2.33 (2) 2.9577 (15) 128.5 (18) O3—H3O O3ii 0.86 (3) 1.95 (3) 2.8036 (9) 169 (3) C8—H8B O2iii
0.99 2.33 3.2664 (18) 158
C10—H10A O1iv
0.99 2.36 3.1949 (17) 142
Symmetry codes: (i) x;y1;z; (ii) x1 2;yþ
5
2;zþ1; (iii) xþ1;y;z; (iv)
x;yþ1;z.
Carbon-bound H atom were positioned geometrically (C—H = 0.95–1.00 A˚ ) and allowed to ride on the parent C atoms, withUiso(H)
= 1.2Ueq(C). Hydroxy H atoms were located in a difference Fourier
map and refined isotropically. In the absence of significant anomalous scattering effects, Friedel pairs were merged; the absolute config-uration of (I) was not determined, and is assigned here arbitrarily.
Data collection:RAPID-AUTO(Rigaku/MSC, 2004); cell refine-ment: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular
graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication:SHELXTL.
The diffraction data were collected at the Centre for Testing and Analysis, Chengdu Branch, Chinese Academy of Sciences. We acknowledge financial support from China West Normal University (No. 05B022).
References
Bruker (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.
Chen, K. M., Hardtman, G. E., Prasad, K. & Repic, O. (1987).Tetrahedron Lett.28, 155–158.
He, L., Yang, H.-L. & Kang, T.-R. (2006).Acta Cryst.E62, o5656–o5657. Rigaku/MSC (2004). RAPID-AUTO. Rigaku/MSC Inc., The Woodlands,
Texas, USA.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.
Figure 1
supporting information
sup-1 Acta Cryst. (2007). E63, o271–o272
supporting information
Acta Cryst. (2007). E63, o271–o272 [https://doi.org/10.1107/S1600536806053074]
1,5-Dihydroxy-1-(3-nitrophenyl)pentan-3-one
Tai-Ran Kang, Long He and Cheng Gao
1,5-Dihydroxy-1-(3-nitrophenyl)pentan-3-one
Crystal data
C11H13NO5
Mr = 239.22
Orthorhombic, P212121
Hall symbol: P 2ac 2ab a = 5.0521 (1) Å b = 6.9787 (2) Å c = 31.1510 (6) Å V = 1098.29 (4) Å3
Z = 4
F(000) = 504 Dx = 1.447 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 10500 reflections θ = 3.2–27.5°
µ = 0.12 mm−1
T = 153 K Block, colourless 0.24 × 0.23 × 0.15 mm
Data collection
Rigaku R-AXIS RAPID diffractometer
Radiation source: Rotating Anode Graphite monochromator
ω scans
10797 measured reflections 1513 independent reflections
1467 reflections with I > 2σ(I) Rint = 0.016
θmax = 27.5°, θmin = 3.2°
h = −6→6 k = −9→9 l = −40→40
Refinement
Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.027
wR(F2) = 0.073
S = 1.00 1513 reflections 163 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(F
o2) + (0.0486P)2 + 0.259P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.22 e Å−3
Δρmin = −0.16 e Å−3
Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.025 (4)
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
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)
x y z Uiso*/Ueq
O1 0.0749 (2) 0.32593 (15) 0.59773 (3) 0.0264 (3)
O2 −0.1839 (2) 0.63151 (14) 0.55750 (3) 0.0207 (2)
O3 −0.1643 (2) 1.19917 (16) 0.51586 (4) 0.0257 (3)
O4 0.7515 (2) −0.07638 (16) 0.64335 (4) 0.0299 (3)
O5 1.0051 (3) −0.00873 (18) 0.69712 (4) 0.0377 (3)
N 0.8210 (3) 0.02925 (17) 0.67275 (4) 0.0217 (3)
C1 0.6788 (3) 0.21105 (19) 0.67907 (4) 0.0175 (3)
C2 0.7480 (3) 0.3272 (2) 0.71330 (4) 0.0209 (3)
H2 0.8851 0.2916 0.7326 0.025*
C3 0.6100 (3) 0.4974 (2) 0.71842 (4) 0.0236 (3)
H3 0.6523 0.5802 0.7416 0.028*
C4 0.4095 (3) 0.5479 (2) 0.68980 (4) 0.0215 (3)
H4 0.3155 0.6644 0.6939 0.026*
C5 0.3453 (3) 0.4293 (2) 0.65525 (4) 0.0171 (3)
C6 0.4812 (3) 0.25773 (19) 0.65000 (4) 0.0177 (3)
H6 0.4395 0.1740 0.6269 0.021*
C7 0.1310 (3) 0.48748 (19) 0.62371 (4) 0.0168 (3)
H7 −0.0321 0.5226 0.6401 0.020*
C8 0.2188 (3) 0.6603 (2) 0.59712 (4) 0.0185 (3)
H8A 0.2688 0.7658 0.6168 0.022*
H8B 0.3776 0.6250 0.5803 0.022*
C9 0.0063 (3) 0.73043 (19) 0.56688 (4) 0.0153 (3)
C10 0.0429 (3) 0.9272 (2) 0.54760 (4) 0.0179 (3)
H10A 0.1187 1.0138 0.5696 0.021*
H10B 0.1704 0.9189 0.5235 0.021*
C11 −0.2135 (3) 1.0106 (2) 0.53139 (5) 0.0227 (3)
H11A −0.2853 0.9297 0.5080 0.027*
H11B −0.3452 1.0148 0.5549 0.027*
H1O −0.039 (5) 0.362 (3) 0.5779 (6) 0.035 (6)*
H3O −0.318 (5) 1.243 (4) 0.5085 (8) 0.057 (7)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
O1 0.0336 (6) 0.0156 (5) 0.0299 (5) 0.0023 (5) −0.0159 (5) −0.0030 (4)
O2 0.0177 (5) 0.0186 (4) 0.0258 (5) −0.0026 (4) −0.0038 (4) 0.0014 (4)
O3 0.0203 (5) 0.0200 (5) 0.0367 (5) −0.0005 (5) −0.0047 (5) 0.0122 (4)
O4 0.0342 (6) 0.0223 (5) 0.0332 (6) 0.0075 (5) −0.0067 (5) −0.0061 (4)
O5 0.0375 (6) 0.0338 (6) 0.0417 (6) 0.0152 (6) −0.0186 (6) −0.0009 (6)
supporting information
sup-3 Acta Cryst. (2007). E63, o271–o272
C1 0.0173 (6) 0.0171 (6) 0.0183 (5) 0.0010 (6) 0.0014 (5) 0.0037 (5)
C2 0.0217 (6) 0.0251 (7) 0.0159 (5) 0.0003 (6) −0.0015 (5) 0.0036 (5)
C3 0.0281 (7) 0.0258 (7) 0.0170 (6) 0.0007 (7) −0.0027 (6) −0.0036 (6)
C4 0.0244 (7) 0.0196 (6) 0.0205 (6) 0.0035 (6) 0.0000 (5) −0.0016 (5)
C5 0.0176 (6) 0.0171 (6) 0.0166 (5) 0.0006 (6) −0.0003 (5) 0.0025 (5)
C6 0.0194 (6) 0.0168 (6) 0.0169 (5) −0.0005 (6) −0.0012 (5) 0.0011 (5)
C7 0.0162 (6) 0.0143 (6) 0.0198 (5) 0.0003 (5) −0.0016 (5) 0.0002 (5)
C8 0.0148 (6) 0.0191 (6) 0.0217 (6) −0.0007 (5) −0.0032 (5) 0.0043 (5)
C9 0.0135 (6) 0.0161 (6) 0.0162 (5) 0.0015 (5) 0.0015 (5) −0.0006 (5)
C10 0.0155 (6) 0.0153 (6) 0.0228 (6) 0.0002 (6) −0.0013 (5) 0.0025 (5)
C11 0.0200 (7) 0.0180 (6) 0.0300 (6) −0.0028 (6) −0.0068 (6) 0.0080 (6)
Geometric parameters (Å, º)
O1—C7 1.4164 (16) C4—H4 0.9500
O1—H1O 0.88 (2) C5—C6 1.3900 (19)
O2—C9 1.2185 (17) C5—C7 1.5172 (18)
O3—C11 1.4242 (17) C6—H6 0.9500
O3—H3O 0.86 (3) C7—C8 1.5289 (18)
O4—N 1.2268 (16) C7—H7 1.0000
O5—N 1.2296 (16) C8—C9 1.5097 (18)
N—C1 1.4711 (18) C8—H8A 0.9900
C1—C2 1.3843 (19) C8—H8B 0.9900
C1—C6 1.3869 (18) C9—C10 1.5100 (18)
C2—C3 1.386 (2) C10—C11 1.5073 (19)
C2—H2 0.9500 C10—H10A 0.9900
C3—C4 1.395 (2) C10—H10B 0.9900
C3—H3 0.9500 C11—H11A 0.9900
C4—C5 1.3958 (19) C11—H11B 0.9900
C7—O1—H1O 107.8 (14) C5—C7—C8 110.78 (11)
C11—O3—H3O 105 (2) O1—C7—H7 108.8
O4—N—O5 123.21 (13) C5—C7—H7 108.8
O4—N—C1 118.59 (12) C8—C7—H7 108.8
O5—N—C1 118.20 (12) C9—C8—C7 112.79 (11)
C2—C1—C6 123.17 (13) C9—C8—H8A 109.0
C2—C1—N 119.01 (12) C7—C8—H8A 109.0
C6—C1—N 117.82 (12) C9—C8—H8B 109.0
C1—C2—C3 117.60 (13) C7—C8—H8B 109.0
C1—C2—H2 121.2 H8A—C8—H8B 107.8
C3—C2—H2 121.2 O2—C9—C8 121.78 (12)
C2—C3—C4 120.56 (13) O2—C9—C10 121.08 (12)
C2—C3—H3 119.7 C8—C9—C10 117.11 (11)
C4—C3—H3 119.7 C11—C10—C9 112.27 (11)
C3—C4—C5 120.78 (14) C11—C10—H10A 109.2
C3—C4—H4 119.6 C9—C10—H10A 109.1
C5—C4—H4 119.6 C11—C10—H10B 109.1
C6—C5—C7 120.45 (12) H10A—C10—H10B 107.9
C4—C5—C7 120.43 (12) O3—C11—C10 108.71 (12)
C1—C6—C5 118.77 (12) O3—C11—H11A 109.9
C1—C6—H6 120.6 C10—C11—H11A 109.9
C5—C6—H6 120.6 O3—C11—H11B 109.9
O1—C7—C5 107.45 (11) C10—C11—H11B 109.9
O1—C7—C8 112.11 (11) H11A—C11—H11B 108.3
O4—N—C1—C2 177.17 (13) C7—C5—C6—C1 178.91 (12)
O5—N—C1—C2 −3.27 (19) C6—C5—C7—O1 11.47 (17)
O4—N—C1—C6 −3.07 (19) C4—C5—C7—O1 −168.85 (13)
O5—N—C1—C6 176.49 (13) C6—C5—C7—C8 −111.30 (14)
C6—C1—C2—C3 0.4 (2) C4—C5—C7—C8 68.38 (16)
N—C1—C2—C3 −179.88 (12) O1—C7—C8—C9 63.08 (15)
C1—C2—C3—C4 −0.1 (2) C5—C7—C8—C9 −176.89 (11)
C2—C3—C4—C5 −0.6 (2) C7—C8—C9—O2 −16.94 (18)
C3—C4—C5—C6 1.0 (2) C7—C8—C9—C10 164.78 (11)
C3—C4—C5—C7 −178.65 (13) O2—C9—C10—C11 21.99 (17)
C2—C1—C6—C5 0.1 (2) C8—C9—C10—C11 −159.71 (12)
N—C1—C6—C5 −179.68 (12) C9—C10—C11—O3 176.99 (11)
C4—C5—C6—C1 −0.8 (2)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O1—H1O···O2 0.88 (2) 2.12 (2) 2.7977 (15) 133.6 (19)
O1—H1O···O3i 0.88 (2) 2.33 (2) 2.9577 (15) 128.5 (18)
O3—H3O···O3ii 0.86 (3) 1.95 (3) 2.8036 (9) 169 (3)
C8—H8B···O2iii 0.99 2.33 3.2664 (18) 158
C10—H10A···O1iv 0.99 2.36 3.1949 (17) 142
