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

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.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.047
• wR factor = 0.129
• Data-to-parameter ratio = 16.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N1     --  C1      ..        5.4 su
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -0.696 Why ?

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Why ?
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT960_ALERT_3_G Number of Intensities with I  <   - 2*sig(I) ...          2 Check

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   2 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

All hydrogen atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å U_iso(H)= 1.2 U_eq(C) for the aromatic H atoms, with C—H = 0.98 Å U_iso(H)= 1.5 U_eq(C) for methyl H atoms and with O—H = 0.84 Å U_iso(H)= 1.5 U_eq(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)].

Computing details

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

	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

Crystal data

C11H11NO5	F(000) = 496
Mr = 237.21	Dx = 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) Å^3	0.34 × 0.21 × 0.17 mm
Z = 4

Data collection

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

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.047	w = 1/[σ^2(Fo^2) + (0.0505P)^2 + 0.0768P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.129	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.21 e Å^−3
2620 reflections	Δρmin = −0.15 e Å^−3
156 parameters

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O5^i	0.95	2.5	3.362 (2)	150
C8—H8···O2^ii	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.