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

Hill, T.N.; Patel, N.

doi:10.1107/S1600536814011891

organic compounds

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Volume 70| Part 7| July 2014| Page o750

https://doi.org/10.1107/S1600536814011891

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

Tania N. Hill ^a ^* and Naadiya Patel ^a

^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.

CCDC reference: 1004533

Related literature

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

Crystal data

C₁₁H₁₁NO₅
M_r = 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 ) T_min = 0.962, T_max = 0.981
10438 measured reflections
2620 independent reflections
1476 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.129
S = 1.03
2620 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); 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 ).

Supporting information

CCDC reference: 1004533

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536814011891/bx2458sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814011891/bx2458Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536814011891/bx2458Isup3.cml

checkCIF report

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.

Structure description 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).

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

	Fig. 1. Molecular structure of (I), showing the atom labelling scheme and displacement ellipsoids at 20% probability level. (arbitrary spheres for the H atoms)
	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

C₁₁H₁₁NO₅	F(000) = 496
M_r = 237.21	D_x = 1.453 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2434 reflections
a = 13.0495 (9) Å	θ = 2.4–24.9°
b = 10.8363 (6) Å	µ = 0.12 mm⁻¹
c = 7.6723 (5) Å	T = 173 K
β = 91.268 (4)°	Cuboid, yellow
V = 1084.66 (12) Å³	0.34 × 0.21 × 0.17 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	2620 independent reflections
Radiation source: fine-focus sealed tube	1476 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
Detector resolution: 512 pixels mm^-1	θ_max = 28°, θ_min = 1.6°
ω scans	h = −17→14
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −14→12
T_min = 0.962, T_max = 0.981	l = −6→10
10438 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.047	w = 1/[σ²(F_o²) + (0.0505P)² + 0.0768P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.129	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.21 e Å⁻³
2620 reflections	Δρ_min = −0.15 e Å⁻³
156 parameters

Crystal data top

C₁₁H₁₁NO₅	V = 1084.66 (12) Å³
M_r = 237.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.0495 (9) Å	µ = 0.12 mm⁻¹
b = 10.8363 (6) Å	T = 173 K
c = 7.6723 (5) Å	0.34 × 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)
T_min = 0.962, T_max = 0.981	R_int = 0.057
10438 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.03	Δρ_max = 0.21 e Å⁻³
2620 reflections	Δρ_min = −0.15 e Å⁻³
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

	x	y	z	U_iso*/U_eq
C1	0.10142 (14)	0.26271 (15)	1.0840 (2)	0.0434 (4)
C2	0.11032 (14)	0.38942 (15)	1.0826 (2)	0.0488 (5)
H2	0.0579	0.4402	1.128	0.059*
C3	0.19712 (15)	0.44047 (15)	1.0135 (2)	0.0466 (5)
H3	0.2041	0.5277	1.0101	0.056*
C4	0.27481 (13)	0.36667 (13)	0.9487 (2)	0.0393 (4)
C5	0.26256 (14)	0.23883 (14)	0.9526 (2)	0.0430 (4)
H5	0.3148	0.1872	0.9085	0.052*
C6	0.17583 (14)	0.18653 (14)	1.0193 (2)	0.0446 (4)
H6	0.1675	0.0994	1.0207	0.054*
C7	0.36660 (14)	0.42403 (13)	0.87532 (19)	0.0406 (4)
C8	0.44132 (14)	0.36221 (13)	0.7946 (2)	0.0427 (4)
H8	0.4378	0.2748	0.7861	0.051*
C9	0.52669 (14)	0.42678 (14)	0.7207 (2)	0.0419 (4)
C10	0.68104 (14)	0.41084 (14)	0.5666 (2)	0.0454 (4)
H10A	0.7235	0.4531	0.6569	0.055*
H10B	0.6575	0.4729	0.4799	0.055*
C11	0.74223 (15)	0.31324 (14)	0.4798 (2)	0.0517 (5)
H11A	0.7682	0.2546	0.5675	0.078*
H11B	0.8	0.3513	0.4206	0.078*
H11C	0.6987	0.2696	0.3942	0.078*
N1	0.01035 (12)	0.20690 (15)	1.16117 (19)	0.0539 (4)
O1	0.36768 (10)	0.54740 (9)	0.89365 (15)	0.0503 (4)
H1	0.421	0.5761	0.8495	0.075*
O2	0.53793 (9)	0.54001 (9)	0.72351 (14)	0.0481 (4)
O3	0.59352 (9)	0.35202 (9)	0.64570 (14)	0.0445 (3)
O4	−0.05048 (11)	0.27473 (14)	1.2318 (2)	0.0750 (5)
O5	0.00065 (11)	0.09522 (13)	1.15338 (18)	0.0731 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0507 (12)	0.0458 (10)	0.0334 (9)	−0.0012 (8)	−0.0024 (8)	−0.0002 (7)
C2	0.0536 (13)	0.0475 (10)	0.0451 (10)	0.0114 (9)	−0.0014 (9)	−0.0066 (8)
C3	0.0611 (13)	0.0334 (8)	0.0450 (10)	0.0044 (8)	−0.0037 (9)	−0.0036 (7)
C4	0.0516 (11)	0.0328 (8)	0.0334 (9)	0.0025 (7)	−0.0058 (8)	−0.0022 (6)
C5	0.0543 (12)	0.0355 (8)	0.0392 (10)	0.0044 (8)	0.0025 (8)	−0.0013 (7)
C6	0.0579 (12)	0.0355 (9)	0.0405 (10)	−0.0007 (8)	0.0006 (8)	−0.0012 (7)
C7	0.0579 (12)	0.0276 (8)	0.0358 (9)	0.0026 (7)	−0.0076 (8)	0.0003 (6)
C8	0.0572 (12)	0.0278 (8)	0.0430 (10)	−0.0013 (8)	−0.0022 (8)	0.0002 (7)
C9	0.0558 (12)	0.0342 (9)	0.0354 (10)	0.0021 (8)	−0.0065 (8)	0.0001 (7)
C10	0.0561 (12)	0.0384 (9)	0.0417 (10)	−0.0058 (8)	−0.0016 (8)	0.0028 (7)
C11	0.0601 (13)	0.0435 (9)	0.0519 (11)	−0.0023 (8)	0.0072 (9)	−0.0013 (8)
N1	0.0602 (12)	0.0604 (10)	0.0410 (9)	−0.0031 (8)	−0.0004 (8)	−0.0019 (7)
O1	0.0658 (10)	0.0291 (6)	0.0562 (8)	−0.0011 (5)	0.0053 (6)	−0.0010 (5)
O2	0.0628 (9)	0.0305 (6)	0.0510 (8)	−0.0022 (5)	0.0002 (6)	0.0005 (5)
O3	0.0546 (8)	0.0319 (6)	0.0471 (7)	−0.0002 (5)	0.0036 (6)	0.0002 (5)
O4	0.0628 (10)	0.0830 (10)	0.0799 (11)	0.0008 (8)	0.0175 (8)	−0.0198 (8)
O5	0.0831 (11)	0.0572 (9)	0.0796 (10)	−0.0103 (8)	0.0190 (8)	0.0101 (7)

Geometric parameters (Å, º) top

C1—C6	1.376 (2)	C8—C9	1.442 (2)
C1—C2	1.378 (2)	C8—H8	0.95
C1—N1	1.469 (2)	C9—O2	1.2358 (17)
C2—C3	1.377 (2)	C9—O3	1.3304 (19)
C2—H2	0.95	C10—O3	1.4526 (19)
C3—C4	1.392 (2)	C10—C11	1.491 (2)
C3—H3	0.95	C10—H10A	0.99
C4—C5	1.395 (2)	C10—H10B	0.99
C4—C7	1.472 (2)	C11—H11A	0.98
C5—C6	1.375 (2)	C11—H11B	0.98
C5—H5	0.95	C11—H11C	0.98
C6—H6	0.95	N1—O4	1.2179 (18)
C7—O1	1.3443 (17)	N1—O5	1.2181 (18)
C7—C8	1.345 (2)	O1—H1	0.84

C6—C1—C2	122.32 (16)	C7—C8—H8	119.6
C6—C1—N1	118.82 (15)	C9—C8—H8	119.6
C2—C1—N1	118.84 (16)	O2—C9—O3	122.24 (16)
C3—C2—C1	118.27 (16)	O2—C9—C8	124.55 (16)
C3—C2—H2	120.9	O3—C9—C8	113.20 (13)
C1—C2—H2	120.9	O3—C10—C11	108.01 (12)
C2—C3—C4	121.23 (15)	O3—C10—H10A	110.1
C2—C3—H3	119.4	C11—C10—H10A	110.1
C4—C3—H3	119.4	O3—C10—H10B	110.1
C3—C4—C5	118.57 (16)	C11—C10—H10B	110.1
C3—C4—C7	119.95 (14)	H10A—C10—H10B	108.4
C5—C4—C7	121.47 (15)	C10—C11—H11A	109.5
C6—C5—C4	120.87 (15)	C10—C11—H11B	109.5
C6—C5—H5	119.6	H11A—C11—H11B	109.5
C4—C5—H5	119.6	C10—C11—H11C	109.5
C5—C6—C1	118.72 (15)	H11A—C11—H11C	109.5
C5—C6—H6	120.6	H11B—C11—H11C	109.5
C1—C6—H6	120.6	O4—N1—O5	123.60 (17)
O1—C7—C8	122.50 (15)	O4—N1—C1	118.15 (15)
O1—C7—C4	112.74 (14)	O5—N1—C1	118.24 (16)
C8—C7—C4	124.74 (14)	C7—O1—H1	109.5
C7—C8—C9	120.89 (14)	C9—O3—C10	116.26 (12)

C6—C1—C2—C3	0.0 (2)	C5—C4—C7—C8	5.6 (2)
N1—C1—C2—C3	178.54 (14)	O1—C7—C8—C9	−0.9 (2)
C1—C2—C3—C4	−0.8 (2)	C4—C7—C8—C9	177.59 (14)
C2—C3—C4—C5	0.9 (2)	C7—C8—C9—O2	−0.6 (2)
C2—C3—C4—C7	179.86 (14)	C7—C8—C9—O3	−179.97 (14)
C3—C4—C5—C6	−0.1 (2)	C6—C1—N1—O4	173.58 (15)
C7—C4—C5—C6	−179.12 (14)	C2—C1—N1—O4	−5.0 (2)
C4—C5—C6—C1	−0.6 (2)	C6—C1—N1—O5	−5.3 (2)
C2—C1—C6—C5	0.7 (2)	C2—C1—N1—O5	176.14 (15)
N1—C1—C6—C5	−177.83 (14)	O2—C9—O3—C10	−0.1 (2)
C3—C4—C7—O1	5.2 (2)	C8—C9—O3—C10	179.31 (12)
C5—C4—C7—O1	−175.83 (14)	C11—C10—O3—C9	−176.13 (13)
C3—C4—C7—C8	−173.38 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+1/2, −z+5/2; (ii) −x+1, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.84	1.87	2.6028 (16)	145.6
C2—H2···O5ⁱ	0.95	2.5	3.362 (2)	150.1
C8—H8···O2ⁱⁱ	0.95	2.57	3.5050 (17)	169.9

Symmetry codes: (i) −x, y+1/2, −z+5/2; (ii) −x+1, y−1/2, −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

Bernstein, 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
Brandenburg, K. & Putz, H. (2005). Crystal Imapct GbR, Bonn, Germany. Google Scholar
Bruker (2004). SAINT-Plus, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Caracelli, 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
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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. Web of Science CSD CrossRef CAS Google Scholar
Yin, C., Huo, F. & Yang, P. (2004). Acta Cryst. E60, o1332–o1333. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar