Acta Cryst. (2008). E64, o1717-o1718 [ doi:10.1107/S1600536808024999 ]
The title compound, C10H9NO4, forms R22(8) dimers due to intermolecular O-H
O hydrogen bonding in the crystal structure. Two dimers are further linked to each other through two intermolecular C-HO hydrogen bonds, forming an R33(7) ring motif. The nitro groups form an intramolecular C-HO hydrogen bond mimicking a five-membered ring. As a result of these hydrogen bonds, polymeric sheets are formed. The aromatic ring makes a dihedral angle of 42.84 (8)° with the carboxylate group and an angle of 8.01 (14)° with the nitro group. There is a ![[pi]](/logos/entities/pi_rmgif.gif)
-interaction (N-O) between the nitro group and the aromatic ring, with a distance of 3.7572 (14) Å between the N atom and the centroid of the aromatic ring.
The title compound was prepared according to a reported procedure (Muhammad et al., 2007). A mixture of 4-nitrobenzaldehyde (1.51 g, 10 mmol), methylmalonic acid (2.36 g, 20 mmol) and piperidine (1.98 ml, 20 mmol) in a pyridine (12.5 ml) solution was heated on a steam-bath for 24 h. The reaction mixture was cooled and added to a mixture of 25 ml of concentrated HCl and 50 g of ice. The precipitate formed in the acidified mixture was filtered off and washed with ice-cold water. The product was recrystallized from ethanol. The yield was 79%.
The coordinates of H-atom attached with O1 were refined. The H-atoms attached with C-atoms were positioned geometrically, C—H = 0.93, and 0.96 Å for aromatic and methyl H, and constrained to ride on their parent atoms. The H-atoms were treated as isotropic with Uiso(H) = xUeq(C,O), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.
Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
![[Figure 1]](./cs2087fig1thm.gif)
| Fig. 1. ORTEP drawing of the title compound, C11H12O2 with the atom numbering scheme. The thermal ellipsoids are drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radii. The intramolecular H-bonds are shown by dotted lines. |
![[Figure 2]](./cs2087fig2thm.gif)
| Fig. 2. The packing figure (PLATON: Spek, 2003) which shows the dimeric nature of the compound and the interlinkages of the dimers. |
| C10H9NO4 | Z = 2 |
| Mr = 207.18 | F000 = 216 |
| Triclinic, P1 | Dx = 1.436 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71073 Å |
| a = 7.3878 (3) Å | Cell parameters from 2518 reflections |
| b = 8.1050 (5) Å | θ = 2.5–29.1º |
| c = 8.3402 (4) Å | µ = 0.11 mm−1 |
| α = 75.793 (2)º | T = 296 (2) K |
| β = 81.835 (3)º | Prismatic, colourless |
| γ = 87.686 (2)º | 0.25 × 0.20 × 0.18 mm |
| V = 479.21 (4) Å3 |
| Bruker Kappa APEXII CCD diffractometer | 2518 independent reflections |
| Radiation source: fine-focus sealed tube | 1926 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.023 |
| Detector resolution: 7.4 pixels mm-1 | θmax = 29.1º |
| T = 296(2) K | θmin = 2.5º |
| ω scans | h = −10→9 |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −11→9 |
| Tmin = 0.970, Tmax = 0.981 | l = −11→11 |
| 9039 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.134 | w = 1/[σ2(Fo2) + (0.0713P)2 + 0.0915P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max < 0.001 |
| 2518 reflections | Δρmax = 0.24 e Å−3 |
| 140 parameters | Δρmin = −0.21 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: ? |
| C10H9NO4 | γ = 87.686 (2)º |
| Mr = 207.18 | V = 479.21 (4) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.3878 (3) Å | Mo Kα |
| b = 8.1050 (5) Å | µ = 0.11 mm−1 |
| c = 8.3402 (4) Å | T = 296 (2) K |
| α = 75.793 (2)º | 0.25 × 0.20 × 0.18 mm |
| β = 81.835 (3)º |
| Bruker Kappa APEXII CCD diffractometer | 2518 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1926 reflections with I > 2σ(I) |
| Tmin = 0.970, Tmax = 0.981 | Rint = 0.023 |
| 9039 measured reflections |
| R[F2 > 2σ(F2)] = 0.042 | 140 parameters |
| wR(F2) = 0.134 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.02 | Δρmax = 0.24 e Å−3 |
| 2518 reflections | Δρmin = −0.21 e Å−3 |
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.04661 (16) | 0.13519 (13) | 0.29456 (12) | 0.0547 (4) | |
| O2 | 0.09796 (15) | 0.16087 (12) | 0.54300 (12) | 0.0526 (3) | |
| O3 | 0.52309 (18) | 1.11600 (15) | −0.36244 (14) | 0.0661 (4) | |
| O4 | 0.35761 (19) | 1.23296 (13) | −0.18699 (15) | 0.0648 (4) | |
| N1 | 0.41247 (18) | 1.10856 (14) | −0.23745 (14) | 0.0466 (4) | |
| C1 | 0.10453 (16) | 0.21896 (15) | 0.39150 (15) | 0.0357 (3) | |
| C2 | 0.17797 (17) | 0.39231 (15) | 0.31101 (16) | 0.0362 (3) | |
| C3 | 0.17195 (18) | 0.45348 (15) | 0.14759 (16) | 0.0378 (3) | |
| C4 | 0.22936 (17) | 0.62471 (15) | 0.04743 (15) | 0.0361 (3) | |
| C5 | 0.3308 (2) | 0.64219 (16) | −0.11015 (16) | 0.0424 (4) | |
| C6 | 0.39099 (19) | 0.80039 (17) | −0.20464 (16) | 0.0425 (4) | |
| C7 | 0.34487 (18) | 0.94026 (15) | −0.14089 (15) | 0.0375 (4) | |
| C8 | 0.2375 (2) | 0.92912 (16) | 0.01030 (17) | 0.0432 (4) | |
| C9 | 0.1804 (2) | 0.76957 (16) | 0.10462 (16) | 0.0430 (4) | |
| C10 | 0.2580 (2) | 0.47901 (17) | 0.42356 (17) | 0.0480 (4) | |
| H1 | −0.005 (3) | 0.032 (3) | 0.355 (2) | 0.0656* | |
| H3 | 0.12727 | 0.38114 | 0.09157 | 0.0454* | |
| H5 | 0.35821 | 0.54652 | −0.15208 | 0.0508* | |
| H6 | 0.46089 | 0.81202 | −0.30868 | 0.0510* | |
| H8 | 0.20402 | 1.02624 | 0.04821 | 0.0518* | |
| H9 | 0.10844 | 0.75935 | 0.20750 | 0.0516* | |
| H10A | 0.33667 | 0.40104 | 0.48836 | 0.0719* | |
| H10B | 0.16126 | 0.51574 | 0.49695 | 0.0719* | |
| H10C | 0.32723 | 0.57588 | 0.35757 | 0.0719* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0855 (8) | 0.0371 (5) | 0.0397 (5) | −0.0259 (5) | −0.0071 (5) | −0.0026 (4) |
| O2 | 0.0801 (7) | 0.0381 (5) | 0.0357 (5) | −0.0229 (5) | −0.0058 (5) | 0.0008 (4) |
| O3 | 0.0862 (8) | 0.0524 (7) | 0.0487 (6) | −0.0249 (6) | 0.0068 (6) | 0.0033 (5) |
| O4 | 0.1010 (9) | 0.0290 (5) | 0.0614 (7) | −0.0085 (5) | −0.0120 (6) | −0.0036 (5) |
| N1 | 0.0638 (7) | 0.0340 (6) | 0.0385 (6) | −0.0119 (5) | −0.0133 (5) | 0.0030 (5) |
| C1 | 0.0399 (6) | 0.0288 (6) | 0.0353 (6) | −0.0057 (5) | −0.0021 (5) | −0.0028 (4) |
| C2 | 0.0379 (6) | 0.0278 (5) | 0.0392 (6) | −0.0052 (5) | −0.0024 (5) | −0.0019 (5) |
| C3 | 0.0443 (6) | 0.0284 (6) | 0.0380 (6) | −0.0068 (5) | −0.0037 (5) | −0.0029 (5) |
| C4 | 0.0416 (6) | 0.0294 (6) | 0.0342 (6) | −0.0041 (5) | −0.0064 (5) | −0.0004 (4) |
| C5 | 0.0569 (8) | 0.0300 (6) | 0.0375 (6) | −0.0005 (5) | −0.0009 (5) | −0.0062 (5) |
| C6 | 0.0521 (7) | 0.0360 (6) | 0.0338 (6) | −0.0020 (5) | 0.0023 (5) | −0.0023 (5) |
| C7 | 0.0468 (7) | 0.0281 (6) | 0.0343 (6) | −0.0062 (5) | −0.0093 (5) | 0.0017 (5) |
| C8 | 0.0607 (8) | 0.0292 (6) | 0.0380 (6) | 0.0016 (5) | −0.0052 (6) | −0.0062 (5) |
| C9 | 0.0554 (8) | 0.0348 (6) | 0.0334 (6) | −0.0009 (5) | 0.0030 (5) | −0.0029 (5) |
| C10 | 0.0626 (8) | 0.0353 (7) | 0.0437 (7) | −0.0160 (6) | −0.0124 (6) | 0.0001 (5) |
| O1—C1 | 1.2996 (16) | C5—C6 | 1.3832 (19) |
| O2—C1 | 1.2300 (15) | C6—C7 | 1.3774 (19) |
| O3—N1 | 1.2204 (17) | C7—C8 | 1.3759 (19) |
| O4—N1 | 1.2185 (16) | C8—C9 | 1.3855 (19) |
| O1—H1 | 0.93 (2) | C3—H3 | 0.9300 |
| N1—C7 | 1.4698 (17) | C5—H5 | 0.9300 |
| C1—C2 | 1.4880 (18) | C6—H6 | 0.9300 |
| C2—C3 | 1.3376 (18) | C8—H8 | 0.9300 |
| C2—C10 | 1.4965 (19) | C9—H9 | 0.9300 |
| C3—C4 | 1.4770 (18) | C10—H10A | 0.9600 |
| C4—C9 | 1.3887 (18) | C10—H10B | 0.9600 |
| C4—C5 | 1.3951 (18) | C10—H10C | 0.9600 |
| O1···C8i | 3.3471 (17) | C4···H10C | 2.7200 |
| O1···C6ii | 3.4128 (19) | C4···H3ii | 3.0300 |
| O1···O2iii | 2.6333 (15) | C9···H10C | 2.6400 |
| O2···O1iii | 2.6333 (15) | C10···H9 | 2.8300 |
| O2···C1iii | 3.3657 (16) | C10···H10Bv | 3.0700 |
| O2···N1iv | 3.1112 (17) | H1···O1iii | 2.882 (17) |
| O1···H1iii | 2.882 (17) | H1···O2iii | 1.71 (2) |
| O1···H3 | 2.3100 | H1···C1iii | 2.59 (2) |
| O1···H8i | 2.5500 | H1···H1iii | 2.36 (2) |
| O2···H10B | 2.8600 | H3···O1 | 2.3100 |
| O2···H10A | 2.5900 | H3···H5 | 2.5900 |
| O2···H1iii | 1.71 (2) | H3···C4ii | 3.0300 |
| O2···H9v | 2.6000 | H5···O4i | 2.6300 |
| O3···H6 | 2.4400 | H5···H3 | 2.5900 |
| O3···H10Avi | 2.7600 | H6···O3 | 2.4400 |
| O3···H6vii | 2.6500 | H6···O3vii | 2.6500 |
| O3···H10Cviii | 2.7800 | H6···C2x | 3.0800 |
| O4···H5ix | 2.6300 | H8···O1ix | 2.5500 |
| O4···H8 | 2.4200 | H8···O4 | 2.4200 |
| O4···H10Avi | 2.7400 | H9···C2 | 2.9300 |
| O4···H10Cviii | 2.8500 | H9···C10 | 2.8300 |
| N1···O2vi | 3.1112 (17) | H9···H10C | 2.4200 |
| N1···C8viii | 3.378 (2) | H9···O2v | 2.6000 |
| C1···O2iii | 3.3657 (16) | H10A···O2 | 2.5900 |
| C2···C6x | 3.5837 (19) | H10A···O3iv | 2.7600 |
| C6···O1ii | 3.4128 (19) | H10A···O4iv | 2.7400 |
| C6···C2x | 3.5837 (19) | H10B···O2 | 2.8600 |
| C8···N1viii | 3.378 (2) | H10B···C1v | 3.0800 |
| C8···O1ix | 3.3471 (17) | H10B···C2v | 2.9500 |
| C9···C10 | 3.1937 (19) | H10B···C10v | 3.0700 |
| C10···C9 | 3.1937 (19) | H10B···H10Bv | 2.4000 |
| C1···H10Bv | 3.0800 | H10C···C4 | 2.7200 |
| C1···H1iii | 2.59 (2) | H10C···C9 | 2.6400 |
| C2···H9 | 2.9300 | H10C···H9 | 2.4200 |
| C2···H10Bv | 2.9500 | H10C···O3viii | 2.7800 |
| C2···H6x | 3.0800 | H10C···O4viii | 2.8500 |
| C1—O1—H1 | 111.6 (12) | C7—C8—C9 | 118.33 (12) |
| O3—N1—O4 | 123.45 (13) | C4—C9—C8 | 120.81 (12) |
| O3—N1—C7 | 118.21 (12) | C2—C3—H3 | 117.00 |
| O4—N1—C7 | 118.33 (12) | C4—C3—H3 | 117.00 |
| O1—C1—O2 | 122.55 (12) | C4—C5—H5 | 120.00 |
| O1—C1—C2 | 116.77 (11) | C6—C5—H5 | 120.00 |
| O2—C1—C2 | 120.68 (11) | C5—C6—H6 | 121.00 |
| C1—C2—C10 | 115.28 (11) | C7—C6—H6 | 121.00 |
| C3—C2—C10 | 126.40 (12) | C7—C8—H8 | 121.00 |
| C1—C2—C3 | 118.29 (11) | C9—C8—H8 | 121.00 |
| C2—C3—C4 | 126.35 (12) | C4—C9—H9 | 120.00 |
| C3—C4—C9 | 121.47 (11) | C8—C9—H9 | 120.00 |
| C5—C4—C9 | 119.09 (12) | C2—C10—H10A | 109.00 |
| C3—C4—C5 | 119.41 (11) | C2—C10—H10B | 109.00 |
| C4—C5—C6 | 120.66 (12) | C2—C10—H10C | 109.00 |
| C5—C6—C7 | 118.38 (12) | H10A—C10—H10B | 109.00 |
| N1—C7—C6 | 119.04 (11) | H10A—C10—H10C | 110.00 |
| N1—C7—C8 | 118.35 (11) | H10B—C10—H10C | 109.00 |
| C6—C7—C8 | 122.61 (12) | ||
| O3—N1—C7—C6 | −7.7 (2) | C2—C3—C4—C9 | −44.9 (2) |
| O3—N1—C7—C8 | 172.34 (13) | C3—C4—C5—C6 | −178.09 (13) |
| O4—N1—C7—C6 | 173.58 (14) | C9—C4—C5—C6 | 3.7 (2) |
| O4—N1—C7—C8 | −6.4 (2) | C3—C4—C9—C8 | 179.06 (13) |
| O1—C1—C2—C3 | 3.07 (18) | C5—C4—C9—C8 | −2.7 (2) |
| O1—C1—C2—C10 | −174.99 (12) | C4—C5—C6—C7 | −1.4 (2) |
| O2—C1—C2—C3 | −176.04 (13) | C5—C6—C7—N1 | 178.15 (13) |
| O2—C1—C2—C10 | 5.90 (18) | C5—C6—C7—C8 | −1.9 (2) |
| C1—C2—C3—C4 | 176.84 (12) | N1—C7—C8—C9 | −177.24 (13) |
| C10—C2—C3—C4 | −5.3 (2) | C6—C7—C8—C9 | 2.8 (2) |
| C2—C3—C4—C5 | 136.88 (15) | C7—C8—C9—C4 | −0.4 (2) |
| Symmetry codes: (i) x, y−1, z; (ii) −x, −y+1, −z; (iii) −x, −y, −z+1; (iv) x, y−1, z+1; (v) −x, −y+1, −z+1; (vi) x, y+1, z−1; (vii) −x+1, −y+2, −z−1; (viii) −x+1, −y+2, −z; (ix) x, y+1, z; (x) −x+1, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O2iii | 0.93 (2) | 1.71 (2) | 2.6333 (15) | 177 (2) |
| C3—H3···O1 | 0.93 | 2.31 | 2.7080 (17) | 105 |
| C8—H8···O1ix | 0.93 | 2.55 | 3.3471 (17) | 144 |
| C9—H9···O2v | 0.93 | 2.60 | 3.4912 (17) | 161 |
| Symmetry codes: (iii) −x, −y, −z+1; (ix) x, y+1, z; (v) −x, −y+1, −z+1. |
| O1—C1 | 1.2996 (16) | O4—N1 | 1.2185 (16) |
| O2—C1 | 1.2300 (15) | N1—C7 | 1.4698 (17) |
| O3—N1 | 1.2204 (17) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O2i | 0.93 (2) | 1.71 (2) | 2.6333 (15) | 177 (2) |
| C3—H3···O1 | 0.93 | 2.31 | 2.7080 (17) | 105 |
| C8—H8···O1ii | 0.93 | 2.55 | 3.3471 (17) | 144 |
| C9—H9···O2iii | 0.93 | 2.60 | 3.4912 (17) | 161 |
| Symmetry codes: (i) −x, −y, −z+1; (ii) x, y+1, z; (iii) −x, −y+1, −z+1. |
The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore and for financial support to Niaz Muhammad for PhD studies under the Indigenous Scholarship Scheme.
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Cinnamic acid derivatives are widely used chemicals in a variety of fields (Ma et al., 2004). They have been applied as antibacterial agents for suppression of bacterial growth (Fujii et al., 2002). In wine, cinnamic acid and its derivatives join benzoic acid derivatives and flavonoids in creating pigments and tannin agents that give each vintage its characteristic bouquet and color. The title compound has been prepared in continuation of synthesizing various derivatives of cinamic acids (Niaz et al., 2008; Muhammad, Ali, Tahir & Zia-ur-Rehman, 2008; Muhammad, Tahir, Ali, Zia-ur-Rehman & Kashmiri, 2008) and their tin complexes (Muhammad et al., 2008a,b).
The crystal structures of 3-(4-isopropylphenyl)-2-methylacrylic acid (Muhammad, Tahir, Ali, Zia-ur-Rehman & Kashmiri, 2008), of 3-(4-clorophenyl)-2-methylacrylic acid (Muhammad, Tahir, Zia-ur-Rehman, Ali & Shaheen, 2008) and of 3-(4-bromophenyl)-2-methylacrylic acid (Muhammad et al., 2007) have been reported. The title compound differs from these compounds due to the nitro group at para position. In the crystal structure of the title compound, the exocyclic Csp2—Csp2 bonds are of 1.4770 (18) and 1.4880 (18) Å, the C==C is of 1.3376 (18) Å. The C—O bond length 1.2996 (16) Å is normal, much like the C=O bond length of 1.2300 (15) Å. The resonant N—O bond lengths are equal (1.2185 (16) and 1.2204 (17) Å). There is an interamolecular H-bond of C—H···O type (Table 1, Fig 1). Centrosymmetric R22(8) dimers (Bernstein et al. 1995) are formed due to the intermolecular O1—H1···O2i [symmetry code: i = -x, -y, -z + 1] hydrogen bonding. Two adjacent dimers are linked to each other through two intermolecular H-bonds of C—H···O type forming an R33(7) motif (Bernstein et al. 1995). The group of two dimers are linked to each other by intermolcular H-bonding (Table 1, Fig 2). There exist an N1—O4···Cgii [symmetry code: ii = -x + 1, -y + 2, -z] interaction with a distance of 3.7572 (14) Å between the N-atom and the centroid of the (C4—C9) aromatic ring. The aromatic ring makes a dihedral angle of 42.84 (8)° with with the carboxylate (O1/C1/O2) moiety and 8.01 (14)° with the (N1/O3/O4) nitro group. Due to the intermolecular H-bonding polymeric sheets are formed.