organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Ethyl (2Z)-3-hy­dr­oxy-3-(4-nitro­phen­yl)prop-2-enoate

aMolecular Sciences Institute, School of Chemistry, University of the Witwatersrand, PO WITS 2050, Johannesburg, South Africa
*Correspondence e-mail: tania.hill@gmail.com

(Received 14 April 2014; accepted 22 May 2014; online 4 June 2014)

The title compound, C11H11NO5, is essentially planar, with an r.m.s. deviation of 0.06 Å. The mol­ecular structure is stabilized by an intra­molecular O—H⋯O hydrogen bond. In the crystal, molecules are linked by two pairs of C—H⋯O hydrogen bonds, forming sheets, lying parallel to (101), which enclose R44(26) ring motifs.

Related literature

For similar crystal structures, see: Caracelli et al. (2010[Caracelli, I., Moran, P. J. S., Hinoue, L., Zukerman-Schpector, J. & Tiekink, E. R. T. (2010). Acta Cryst. E66, o396.]); Yin et al. (2004[Yin, C., Huo, F. & Yang, P. (2004). Acta Cryst. E60, o1332-o1333.]); Syu et al. (2010[Syu, S.-E., Wang, D.-W., Chen, P.-Y., Hung, Y.-T., Jhang, Y.-W., Kao, T.-T. & Lin, W. (2010). Tetrahedron Lett. 51, 5943-5946.]). For geaph-set motifs, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

[Scheme 1]

Experimental

Crystal data
  • C11H11NO5

  • Mr = 237.21

  • Monoclinic, P 21 /c

  • a = 13.0495 (9) Å

  • b = 10.8363 (6) Å

  • c = 7.6723 (5) Å

  • β = 91.268 (4)°

  • V = 1084.66 (12) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.12 mm−1

  • T = 173 K

  • 0.34 × 0.21 × 0.17 mm

Data collection
  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2004[Bruker (2004). SAINT-Plus, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.962, Tmax = 0.981

  • 10438 measured reflections

  • 2620 independent reflections

  • 1476 reflections with I > 2σ(I)

  • Rint = 0.057

Refinement
  • R[F2 > 2σ(F2)] = 0.047

  • wR(F2) = 0.129

  • S = 1.03

  • 2620 reflections

  • 156 parameters

  • H-atom parameters constrained

  • Δρmax = 0.21 e Å−3

  • Δρmin = −0.15 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1⋯O2 0.84 1.87 2.6028 (16) 146
C2—H2⋯O5i 0.95 2.5 3.362 (2) 150
C8—H8⋯O2ii 0.95 2.57 3.5050 (17) 170
Symmetry codes: (i) [-x, y+{\script{1\over 2}}, -z+{\script{5\over 2}}]; (ii) [-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2004[Bruker (2004). SAINT-Plus, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus and XPREP (Bruker, 2004[Bruker (2004). SAINT-Plus, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg & Putz, 2005)[Brandenburg, K. & Putz, H. (2005). Crystal Imapct GbR, Bonn, Germany.]; software used to prepare material for publication: WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]).

Supporting information


Comment top

The molecular structure of (I) is illustrated in Figure 1, and was obtained by recrystallization of the commercially available compound. The title compound, C11H11NO5, consists of a hydroxy (O1) and a p-nitrophenyl substituted propenoate.The molecule is essentially planar with an r.m.s. deviation of 0.065Å, the larger r.m.s. value is as a result of the slight twisting of the substituents on the propenoate backbone, the dihedral angle of the planes of the subsitutents with the propenoate plane were found to be 3.69 (4) ° for the p-nitrophenyl and 3.3 (1) ° for the ethyl ester.

The propenoate backbone was observed in the enol tautomeric form with a typical hydrogen bond interaction between the hydroxy (O1) and the carbonyl (O2) with a distance of 2.603 (2) Å. The packing of (I) is seen as parallel sheets (Figure 2) when viewed along the b-axis. The crystal and molecular structure is stabilized by two weak C—H···O hydrogen bond interactions with graph-set motif R44(26) (Bernstein, et al., 1995) and one O—H···O intramolecular hydrogen bond interaction respectively, Table 1

Related literature top

For similar crystal structures, see: Caracelli et al. (2010); Yin et al. (2004); Syu et al. (2010). For geaph-set motifs, see: Bernstein et al. (1995).

Experimental top

Ethyl 4-nitrobenzoylacetate was obtained commercially. (I) It was redissolved in warm MeOH and allowed to cool to room terperature. Yellow crystals suitable for single-crystal diffraction were obtained by slow evaporation over a few days.

Refinement top

All hydrogen atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å Uiso(H)= 1.2 Ueq(C) for the aromatic H atoms, with C—H = 0.98 Å Uiso(H)= 1.5 Ueq(C) for methyl H atoms and with O—H = 0.84 Å Uiso(H)= 1.5 Ueq(O) for the hydroxyl H atoms. The methyl and hydroxyl groups were allowed to rotate with a fixed angle arround the C—C bond to best fit the experimental electron density [HFIX 137 and HFIX 147 in SHELXL97 (Sheldrick, 2008)].

Structure description top

The molecular structure of (I) is illustrated in Figure 1, and was obtained by recrystallization of the commercially available compound. The title compound, C11H11NO5, consists of a hydroxy (O1) and a p-nitrophenyl substituted propenoate.The molecule is essentially planar with an r.m.s. deviation of 0.065Å, the larger r.m.s. value is as a result of the slight twisting of the substituents on the propenoate backbone, the dihedral angle of the planes of the subsitutents with the propenoate plane were found to be 3.69 (4) ° for the p-nitrophenyl and 3.3 (1) ° for the ethyl ester.

The propenoate backbone was observed in the enol tautomeric form with a typical hydrogen bond interaction between the hydroxy (O1) and the carbonyl (O2) with a distance of 2.603 (2) Å. The packing of (I) is seen as parallel sheets (Figure 2) when viewed along the b-axis. The crystal and molecular structure is stabilized by two weak C—H···O hydrogen bond interactions with graph-set motif R44(26) (Bernstein, et al., 1995) and one O—H···O intramolecular hydrogen bond interaction respectively, Table 1

For similar crystal structures, see: Caracelli et al. (2010); Yin et al. (2004); Syu et al. (2010). For geaph-set motifs, see: Bernstein et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I), showing the atom labelling scheme and displacement ellipsoids at 20% probability level. (arbitrary spheres for the H atoms)
[Figure 2] Fig. 2. Packing of (I) viewed along the b-axis. Hydrogen atoms omitted for clarity.
Ethyl (2Z)-3-hydroxy-3-(4-nitrophenyl)prop-2-enoate top
Crystal data top
C11H11NO5F(000) = 496
Mr = 237.21Dx = 1.453 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2434 reflections
a = 13.0495 (9) Åθ = 2.4–24.9°
b = 10.8363 (6) ŵ = 0.12 mm1
c = 7.6723 (5) ÅT = 173 K
β = 91.268 (4)°Cuboid, yellow
V = 1084.66 (12) Å30.34 × 0.21 × 0.17 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2620 independent reflections
Radiation source: fine-focus sealed tube1476 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
Detector resolution: 512 pixels mm-1θmax = 28°, θmin = 1.6°
ω scansh = 1714
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
k = 1412
Tmin = 0.962, Tmax = 0.981l = 610
10438 measured reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.047 w = 1/[σ2(Fo2) + (0.0505P)2 + 0.0768P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.129(Δ/σ)max < 0.001
S = 1.03Δρmax = 0.21 e Å3
2620 reflectionsΔρmin = 0.15 e Å3
156 parameters
Crystal data top
C11H11NO5V = 1084.66 (12) Å3
Mr = 237.21Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.0495 (9) ŵ = 0.12 mm1
b = 10.8363 (6) ÅT = 173 K
c = 7.6723 (5) Å0.34 × 0.21 × 0.17 mm
β = 91.268 (4)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2620 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
1476 reflections with I > 2σ(I)
Tmin = 0.962, Tmax = 0.981Rint = 0.057
10438 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.129H-atom parameters constrained
S = 1.03Δρmax = 0.21 e Å3
2620 reflectionsΔρmin = 0.15 e Å3
156 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.10142 (14)0.26271 (15)1.0840 (2)0.0434 (4)
C20.11032 (14)0.38942 (15)1.0826 (2)0.0488 (5)
H20.05790.44021.1280.059*
C30.19712 (15)0.44047 (15)1.0135 (2)0.0466 (5)
H30.20410.52771.01010.056*
C40.27481 (13)0.36667 (13)0.9487 (2)0.0393 (4)
C50.26256 (14)0.23883 (14)0.9526 (2)0.0430 (4)
H50.31480.18720.90850.052*
C60.17583 (14)0.18653 (14)1.0193 (2)0.0446 (4)
H60.16750.09941.02070.054*
C70.36660 (14)0.42403 (13)0.87532 (19)0.0406 (4)
C80.44132 (14)0.36221 (13)0.7946 (2)0.0427 (4)
H80.43780.27480.78610.051*
C90.52669 (14)0.42678 (14)0.7207 (2)0.0419 (4)
C100.68104 (14)0.41084 (14)0.5666 (2)0.0454 (4)
H10A0.72350.45310.65690.055*
H10B0.65750.47290.47990.055*
C110.74223 (15)0.31324 (14)0.4798 (2)0.0517 (5)
H11A0.76820.25460.56750.078*
H11B0.80.35130.42060.078*
H11C0.69870.26960.39420.078*
N10.01035 (12)0.20690 (15)1.16117 (19)0.0539 (4)
O10.36768 (10)0.54740 (9)0.89365 (15)0.0503 (4)
H10.4210.57610.84950.075*
O20.53793 (9)0.54001 (9)0.72351 (14)0.0481 (4)
O30.59352 (9)0.35202 (9)0.64570 (14)0.0445 (3)
O40.05048 (11)0.27473 (14)1.2318 (2)0.0750 (5)
O50.00065 (11)0.09522 (13)1.15338 (18)0.0731 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0507 (12)0.0458 (10)0.0334 (9)0.0012 (8)0.0024 (8)0.0002 (7)
C20.0536 (13)0.0475 (10)0.0451 (10)0.0114 (9)0.0014 (9)0.0066 (8)
C30.0611 (13)0.0334 (8)0.0450 (10)0.0044 (8)0.0037 (9)0.0036 (7)
C40.0516 (11)0.0328 (8)0.0334 (9)0.0025 (7)0.0058 (8)0.0022 (6)
C50.0543 (12)0.0355 (8)0.0392 (10)0.0044 (8)0.0025 (8)0.0013 (7)
C60.0579 (12)0.0355 (9)0.0405 (10)0.0007 (8)0.0006 (8)0.0012 (7)
C70.0579 (12)0.0276 (8)0.0358 (9)0.0026 (7)0.0076 (8)0.0003 (6)
C80.0572 (12)0.0278 (8)0.0430 (10)0.0013 (8)0.0022 (8)0.0002 (7)
C90.0558 (12)0.0342 (9)0.0354 (10)0.0021 (8)0.0065 (8)0.0001 (7)
C100.0561 (12)0.0384 (9)0.0417 (10)0.0058 (8)0.0016 (8)0.0028 (7)
C110.0601 (13)0.0435 (9)0.0519 (11)0.0023 (8)0.0072 (9)0.0013 (8)
N10.0602 (12)0.0604 (10)0.0410 (9)0.0031 (8)0.0004 (8)0.0019 (7)
O10.0658 (10)0.0291 (6)0.0562 (8)0.0011 (5)0.0053 (6)0.0010 (5)
O20.0628 (9)0.0305 (6)0.0510 (8)0.0022 (5)0.0002 (6)0.0005 (5)
O30.0546 (8)0.0319 (6)0.0471 (7)0.0002 (5)0.0036 (6)0.0002 (5)
O40.0628 (10)0.0830 (10)0.0799 (11)0.0008 (8)0.0175 (8)0.0198 (8)
O50.0831 (11)0.0572 (9)0.0796 (10)0.0103 (8)0.0190 (8)0.0101 (7)
Geometric parameters (Å, º) top
C1—C61.376 (2)C8—C91.442 (2)
C1—C21.378 (2)C8—H80.95
C1—N11.469 (2)C9—O21.2358 (17)
C2—C31.377 (2)C9—O31.3304 (19)
C2—H20.95C10—O31.4526 (19)
C3—C41.392 (2)C10—C111.491 (2)
C3—H30.95C10—H10A0.99
C4—C51.395 (2)C10—H10B0.99
C4—C71.472 (2)C11—H11A0.98
C5—C61.375 (2)C11—H11B0.98
C5—H50.95C11—H11C0.98
C6—H60.95N1—O41.2179 (18)
C7—O11.3443 (17)N1—O51.2181 (18)
C7—C81.345 (2)O1—H10.84
C6—C1—C2122.32 (16)C7—C8—H8119.6
C6—C1—N1118.82 (15)C9—C8—H8119.6
C2—C1—N1118.84 (16)O2—C9—O3122.24 (16)
C3—C2—C1118.27 (16)O2—C9—C8124.55 (16)
C3—C2—H2120.9O3—C9—C8113.20 (13)
C1—C2—H2120.9O3—C10—C11108.01 (12)
C2—C3—C4121.23 (15)O3—C10—H10A110.1
C2—C3—H3119.4C11—C10—H10A110.1
C4—C3—H3119.4O3—C10—H10B110.1
C3—C4—C5118.57 (16)C11—C10—H10B110.1
C3—C4—C7119.95 (14)H10A—C10—H10B108.4
C5—C4—C7121.47 (15)C10—C11—H11A109.5
C6—C5—C4120.87 (15)C10—C11—H11B109.5
C6—C5—H5119.6H11A—C11—H11B109.5
C4—C5—H5119.6C10—C11—H11C109.5
C5—C6—C1118.72 (15)H11A—C11—H11C109.5
C5—C6—H6120.6H11B—C11—H11C109.5
C1—C6—H6120.6O4—N1—O5123.60 (17)
O1—C7—C8122.50 (15)O4—N1—C1118.15 (15)
O1—C7—C4112.74 (14)O5—N1—C1118.24 (16)
C8—C7—C4124.74 (14)C7—O1—H1109.5
C7—C8—C9120.89 (14)C9—O3—C10116.26 (12)
C6—C1—C2—C30.0 (2)C5—C4—C7—C85.6 (2)
N1—C1—C2—C3178.54 (14)O1—C7—C8—C90.9 (2)
C1—C2—C3—C40.8 (2)C4—C7—C8—C9177.59 (14)
C2—C3—C4—C50.9 (2)C7—C8—C9—O20.6 (2)
C2—C3—C4—C7179.86 (14)C7—C8—C9—O3179.97 (14)
C3—C4—C5—C60.1 (2)C6—C1—N1—O4173.58 (15)
C7—C4—C5—C6179.12 (14)C2—C1—N1—O45.0 (2)
C4—C5—C6—C10.6 (2)C6—C1—N1—O55.3 (2)
C2—C1—C6—C50.7 (2)C2—C1—N1—O5176.14 (15)
N1—C1—C6—C5177.83 (14)O2—C9—O3—C100.1 (2)
C3—C4—C7—O15.2 (2)C8—C9—O3—C10179.31 (12)
C5—C4—C7—O1175.83 (14)C11—C10—O3—C9176.13 (13)
C3—C4—C7—C8173.38 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O20.841.872.6028 (16)146
C2—H2···O5i0.952.53.362 (2)150
C8—H8···O2ii0.952.573.5050 (17)170
Symmetry codes: (i) x, y+1/2, z+5/2; (ii) x+1, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O20.841.872.6028 (16)145.6
C2—H2···O5i0.952.53.362 (2)150.1
C8—H8···O2ii0.952.573.5050 (17)169.9
Symmetry codes: (i) x, y+1/2, z+5/2; (ii) x+1, y1/2, z+3/2.
 

Acknowledgements

The University of the Witwatersrand and the Mol­ecular Sciences Institute are thanked for providing the infrastructure and financial support. Special thanks go to Dr Andreas Lemmerer of the University of the Witwatersrand for his contributions and insights toward this project.

References

First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
First citationBrandenburg, K. & Putz, H. (2005). Crystal Imapct GbR, Bonn, Germany.  Google Scholar
First citationBruker (2004). SAINT-Plus, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCaracelli, I., Moran, P. J. S., Hinoue, L., Zukerman-Schpector, J. & Tiekink, E. R. T. (2010). Acta Cryst. E66, o396.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSyu, S.-E., Wang, D.-W., Chen, P.-Y., Hung, Y.-T., Jhang, Y.-W., Kao, T.-T. & Lin, W. (2010). Tetrahedron Lett. 51, 5943–5946.  Web of Science CSD CrossRef CAS Google Scholar
First citationYin, C., Huo, F. & Yang, P. (2004). Acta Cryst. E60, o1332–o1333.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar

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