Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046478/is2203sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046478/is2203Isup2.hkl |
CCDC reference: 663838
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.001 Å
- Disorder in main residue
- R factor = 0.047
- wR factor = 0.166
- Data-to-parameter ratio = 26.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.70 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C1 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C1A PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C2 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.11 PLAT301_ALERT_3_C Main Residue Disorder ......................... 11.00 Perc. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 5
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 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 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Gibson et al. (2006); Naka & Kubo (1999); Nicolaides et al. (1998); Parker & Braden (1989); Ren et al. (2006); Romero (2001). A similar acetophenone compound with a methyl group has been reported by Chakkaravarthi et al. (2007).
2,4-Dihydroxyacetophenone (4.2 g, 27.60 mmol), triethylamine (3.85 ml, 27.67 mmol) and 150 ml of dry 2-butanone were taken in a 250 ml round bottom flask and the temperature was maintained at 273 K. Then the solution of methacryloylchloride (2.7 ml, 27.74 mmol) in 20 ml of 2-butanone was added dropwise to the mixture with constant stirring for 30 min. After the addition was over, the reaction mixture was stirred for another 6 h. The salt formed during the reaction was filtered and the filtrate was washed with water and dried over anhydrous MgSO4. The filtrate was concentrated under reduced pressure and the crude product was purified by column chromatography (silica) using hexane and ethyl acetate mixture (9:1). Crystals suitable for X-ray analysis were grown by slow evaporation of an ethyl acetate solution.
The site occupancy factors of the disordered methyl and methylene groups refined to 0.50 (2). H atoms for methylene C atoms were located in a difference map and refined isotropically. The remaining H atoms were positioned geometrically and refined as riding, with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl C, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic C—H, with O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O) for OH. The distance restraints were applied to the disordered methylene C atoms.
Methacrylate derivatives have anti-inflammatory (Nicolaides et al., 1998) and antipicornaviral (Romero, 2001) properties and are efficient as agonists for different receptors (Naka & Kubo, 1999). Methacrylate activated vinyl esters are readily polymerized by free-radical polymerization to form linear, branched or network polymers (Parker & Braden, 1989).
The geometric parameters in (I) (Fig. 1) are comparable with the reported values of similar compounds (Gibson et al., 2006; Ren et al., 2006). A similar acetophenone compound with methyl group has been reported (Chakkaravarthi et al., 2007). The acetyl group is planar with the benzene ring [dihedral angle of 179.00 (7)°] and the methacryloyloxy group makes the dihedral angle of 34.67 (4)° with the benzene ring. The torsion angles O2—C4—C2—C3 and O2—C4—C2—C1 [-0.2 (6)° and 178.1 (8)°, respectively] indicate periplanar conformation of the respective moieties. The methyl and methylene groups in the terminal site are disordered over two positions with site occupancy factors of 0.50 (2). The molecular structure is stabilized by intramolecular O—H···O and C—H···O interactions and the crystal packing of (I) (Fig. 2) is stabilized by an intermolecular C—H···O hydrogen bond and a C—H···π interaction, involving the benzene C5—C10 ring (Table 1).
For related literature, see: Gibson et al. (2006); Naka & Kubo (1999); Nicolaides et al. (1998); Parker & Braden (1989); Ren et al. (2006); Romero (2001). A similar acetophenone compound with a methyl group has been reported by Chakkaravarthi et al. (2007).
Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C12H12O4 | Z = 2 |
Mr = 220.22 | F(000) = 232 |
Triclinic, P1 | Dx = 1.339 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6413 (2) Å | Cell parameters from 6586 reflections |
b = 7.2833 (3) Å | θ = 3.1–35.1° |
c = 12.4387 (4) Å | µ = 0.10 mm−1 |
α = 84.020 (1)° | T = 295 K |
β = 87.447 (2)° | Needle, colourless |
γ = 65.866 (1)° | 0.25 × 0.16 × 0.15 mm |
V = 546.09 (3) Å3 |
Bruker Kappa-APEXII diffractometer | 4847 independent reflections |
Radiation source: fine-focus sealed tube | 3225 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω and φ scans | θmax = 35.9°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.966, Tmax = 0.985 | k = −11→11 |
16320 measured reflections | l = −19→20 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.166 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0909P)2 + 0.037P] where P = (Fo2 + 2Fc2)/3 |
4847 reflections | (Δ/σ)max < 0.001 |
185 parameters | Δρmax = 0.40 e Å−3 |
2 restraints | Δρmin = −0.22 e Å−3 |
C12H12O4 | γ = 65.866 (1)° |
Mr = 220.22 | V = 546.09 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.6413 (2) Å | Mo Kα radiation |
b = 7.2833 (3) Å | µ = 0.10 mm−1 |
c = 12.4387 (4) Å | T = 295 K |
α = 84.020 (1)° | 0.25 × 0.16 × 0.15 mm |
β = 87.447 (2)° |
Bruker Kappa-APEXII diffractometer | 4847 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3225 reflections with I > 2σ(I) |
Tmin = 0.966, Tmax = 0.985 | Rint = 0.024 |
16320 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 2 restraints |
wR(F2) = 0.166 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.40 e Å−3 |
4847 reflections | Δρmin = −0.22 e Å−3 |
185 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C4 | 0.54938 (18) | 0.71905 (16) | 0.08087 (8) | 0.0457 (2) | |
C2 | 0.5104 (2) | 0.75165 (17) | −0.03777 (8) | 0.0480 (2) | |
C1 | 0.688 (2) | 0.690 (2) | −0.1025 (8) | 0.086 (3) | 0.50 (2) |
H1A | 0.681 (9) | 0.652 (8) | −0.180 (5) | 0.13 (2)* | 0.50 (2) |
H1B | 0.835 (7) | 0.591 (6) | −0.069 (3) | 0.073 (12)* | 0.50 (2) |
C3 | 0.282 (2) | 0.854 (2) | −0.0782 (10) | 0.0607 (17) | 0.50 (2) |
H3A | 0.2822 | 0.8570 | −0.1556 | 0.091* | 0.50 (2) |
H3B | 0.2173 | 0.9894 | −0.0576 | 0.091* | 0.50 (2) |
H3C | 0.1970 | 0.7813 | −0.0477 | 0.091* | 0.50 (2) |
C1A | 0.316 (3) | 0.828 (3) | −0.0779 (13) | 0.081 (4) | 0.50 (2) |
H1A1 | 0.279 (7) | 0.864 (7) | −0.154 (4) | 0.095 (12)* | 0.50 (2) |
H1A2 | 0.199 (5) | 0.882 (6) | −0.042 (3) | 0.052 (11)* | 0.50 (2) |
C3A | 0.7115 (19) | 0.6816 (18) | −0.1034 (8) | 0.075 (3) | 0.50 (2) |
H3A1 | 0.6735 | 0.7183 | −0.1785 | 0.112* | 0.50 (2) |
H3A2 | 0.7867 | 0.5373 | −0.0907 | 0.112* | 0.50 (2) |
H3A3 | 0.8061 | 0.7432 | −0.0840 | 0.112* | 0.50 (2) |
C5 | 0.34851 (15) | 0.77482 (14) | 0.24864 (7) | 0.03768 (18) | |
C6 | 0.16421 (15) | 0.74879 (16) | 0.29206 (7) | 0.0410 (2) | |
H6 | 0.0614 | 0.7390 | 0.2472 | 0.049* | |
C7 | 0.13639 (14) | 0.73772 (14) | 0.40255 (7) | 0.03719 (18) | |
H7 | 0.0123 | 0.7224 | 0.4319 | 0.045* | |
C8 | 0.29124 (13) | 0.74898 (12) | 0.47183 (6) | 0.03183 (16) | |
C9 | 0.47621 (13) | 0.77413 (13) | 0.42489 (7) | 0.03407 (17) | |
C10 | 0.50213 (14) | 0.79139 (15) | 0.31304 (7) | 0.03920 (19) | |
H10 | 0.6214 | 0.8138 | 0.2824 | 0.047* | |
C11 | 0.26509 (14) | 0.73650 (14) | 0.58983 (7) | 0.03631 (18) | |
C12 | 0.07174 (17) | 0.70661 (17) | 0.64152 (7) | 0.0448 (2) | |
H12A | 0.0908 | 0.6845 | 0.7185 | 0.067* | |
H12B | 0.0611 | 0.5915 | 0.6154 | 0.067* | |
H12C | −0.0608 | 0.8247 | 0.6239 | 0.067* | |
O1 | 0.72558 (15) | 0.63635 (18) | 0.12312 (7) | 0.0732 (3) | |
O2 | 0.35578 (12) | 0.79405 (13) | 0.13645 (5) | 0.04900 (19) | |
O3 | 0.63603 (12) | 0.77904 (13) | 0.48540 (6) | 0.04826 (19) | |
H3 | 0.6021 | 0.7732 | 0.5495 | 0.072* | |
O4 | 0.40266 (14) | 0.75142 (14) | 0.64788 (6) | 0.0531 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C4 | 0.0455 (5) | 0.0536 (5) | 0.0339 (4) | −0.0166 (4) | 0.0071 (3) | −0.0048 (3) |
C2 | 0.0570 (6) | 0.0562 (6) | 0.0314 (4) | −0.0238 (5) | 0.0075 (4) | −0.0064 (4) |
C1 | 0.099 (5) | 0.120 (8) | 0.040 (4) | −0.046 (5) | 0.000 (3) | −0.008 (3) |
C3 | 0.067 (4) | 0.076 (3) | 0.034 (3) | −0.024 (3) | −0.010 (3) | −0.0037 (18) |
C1A | 0.080 (6) | 0.118 (8) | 0.039 (4) | −0.033 (5) | 0.007 (3) | −0.011 (4) |
C3A | 0.087 (4) | 0.081 (4) | 0.043 (4) | −0.021 (3) | 0.035 (3) | −0.018 (3) |
C5 | 0.0352 (4) | 0.0469 (5) | 0.0287 (3) | −0.0147 (3) | 0.0028 (3) | −0.0036 (3) |
C6 | 0.0343 (4) | 0.0595 (5) | 0.0323 (4) | −0.0215 (4) | −0.0005 (3) | −0.0067 (3) |
C7 | 0.0298 (3) | 0.0523 (5) | 0.0337 (4) | −0.0209 (3) | 0.0026 (3) | −0.0052 (3) |
C8 | 0.0283 (3) | 0.0383 (4) | 0.0293 (3) | −0.0139 (3) | 0.0014 (2) | −0.0044 (3) |
C9 | 0.0279 (3) | 0.0418 (4) | 0.0342 (4) | −0.0154 (3) | 0.0010 (3) | −0.0059 (3) |
C10 | 0.0337 (4) | 0.0527 (5) | 0.0347 (4) | −0.0215 (4) | 0.0057 (3) | −0.0051 (3) |
C11 | 0.0348 (4) | 0.0427 (4) | 0.0305 (3) | −0.0148 (3) | 0.0011 (3) | −0.0037 (3) |
C12 | 0.0419 (5) | 0.0586 (6) | 0.0341 (4) | −0.0221 (4) | 0.0059 (3) | −0.0015 (4) |
O1 | 0.0458 (4) | 0.1051 (8) | 0.0423 (4) | −0.0040 (5) | 0.0040 (3) | −0.0084 (4) |
O2 | 0.0422 (4) | 0.0737 (5) | 0.0279 (3) | −0.0209 (3) | 0.0037 (2) | −0.0038 (3) |
O3 | 0.0353 (3) | 0.0785 (5) | 0.0406 (3) | −0.0318 (3) | 0.0002 (3) | −0.0103 (3) |
O4 | 0.0502 (4) | 0.0843 (6) | 0.0335 (3) | −0.0355 (4) | −0.0030 (3) | −0.0075 (3) |
C4—O1 | 1.1920 (14) | C5—C10 | 1.3751 (12) |
C4—O2 | 1.3618 (12) | C5—O2 | 1.3886 (10) |
C4—C2 | 1.4872 (14) | C5—C6 | 1.3912 (12) |
C2—C1A | 1.281 (14) | C6—C7 | 1.3770 (12) |
C2—C1 | 1.339 (10) | C6—H6 | 0.9300 |
C2—C3A | 1.464 (9) | C7—C8 | 1.4034 (11) |
C2—C3 | 1.476 (14) | C7—H7 | 0.9300 |
C1—H1A | 1.04 (6) | C8—C9 | 1.4076 (11) |
C1—H1B | 1.03 (4) | C8—C11 | 1.4680 (11) |
C3—H3A | 0.9600 | C9—O3 | 1.3425 (10) |
C3—H3B | 0.9600 | C9—C10 | 1.3932 (12) |
C3—H3C | 0.9600 | C10—H10 | 0.9300 |
C1A—H1A1 | 0.97 (5) | C11—O4 | 1.2346 (11) |
C1A—H1A2 | 0.85 (4) | C11—C12 | 1.4952 (13) |
C3A—H1A | 1.04 (6) | C12—H12A | 0.9600 |
C3A—H1B | 0.91 (4) | C12—H12B | 0.9600 |
C3A—H3A1 | 0.9600 | C12—H12C | 0.9600 |
C3A—H3A2 | 0.9600 | O3—H3 | 0.8200 |
C3A—H3A3 | 0.9600 | ||
O1—C4—O2 | 123.66 (9) | C2—C3A—H3A3 | 109.5 |
O1—C4—C2 | 125.19 (10) | H3A1—C3A—H3A3 | 109.5 |
O2—C4—C2 | 111.14 (9) | H3A2—C3A—H3A3 | 109.5 |
C1A—C2—C1 | 120.4 (9) | C10—C5—O2 | 123.66 (8) |
C1A—C2—C3A | 123.4 (9) | C10—C5—C6 | 121.75 (8) |
C1—C2—C3 | 123.5 (8) | O2—C5—C6 | 114.48 (8) |
C3A—C2—C3 | 126.5 (7) | C7—C6—C5 | 118.95 (8) |
C1A—C2—C4 | 122.1 (8) | C7—C6—H6 | 120.5 |
C1—C2—C4 | 117.5 (5) | C5—C6—H6 | 120.5 |
C3A—C2—C4 | 114.4 (5) | C6—C7—C8 | 121.44 (7) |
C3—C2—C4 | 119.0 (6) | C6—C7—H7 | 119.3 |
C2—C1—H1A | 122 (3) | C8—C7—H7 | 119.3 |
C2—C1—H1B | 118 (2) | C7—C8—C9 | 117.93 (7) |
H1A—C1—H1B | 108 (4) | C7—C8—C11 | 122.26 (7) |
C2—C3—H3A | 109.5 | C9—C8—C11 | 119.81 (7) |
C2—C3—H3B | 109.5 | O3—C9—C10 | 117.31 (7) |
H3A—C3—H3B | 109.5 | O3—C9—C8 | 121.74 (7) |
C2—C3—H3C | 109.5 | C10—C9—C8 | 120.93 (7) |
H3A—C3—H3C | 109.5 | C5—C10—C9 | 118.93 (7) |
H3B—C3—H3C | 109.5 | C5—C10—H10 | 120.5 |
C2—C3—H1A2 | 118 (3) | C9—C10—H10 | 120.5 |
H3A—C3—H1A2 | 132.3 | O4—C11—C8 | 120.27 (8) |
H1A1—C3—H1A2 | 131 (5) | O4—C11—C12 | 119.01 (8) |
C2—C1A—H1A1 | 126 (3) | C8—C11—C12 | 120.72 (7) |
C2—C1A—H1A2 | 124 (3) | C11—C12—H12A | 109.5 |
H1A1—C1A—H1A2 | 108 (4) | C11—C12—H12B | 109.5 |
C2—C3A—H1A | 111 (4) | H12A—C12—H12B | 109.5 |
C2—C3A—H1B | 116 (3) | C11—C12—H12C | 109.5 |
H1A—C3A—H1B | 117 (4) | H12A—C12—H12C | 109.5 |
C2—C3A—H3A1 | 109.5 | H12B—C12—H12C | 109.5 |
C2—C3A—H3A2 | 109.5 | C4—O2—C5 | 121.97 (8) |
H3A1—C3A—H3A2 | 109.5 | C9—O3—H3 | 109.5 |
O1—C4—C2—C1A | 174.4 (10) | C7—C8—C9—C10 | 1.28 (13) |
O2—C4—C2—C1A | −4.8 (10) | C11—C8—C9—C10 | −178.40 (8) |
O1—C4—C2—C1 | −2.7 (8) | O2—C5—C10—C9 | 178.52 (9) |
O2—C4—C2—C1 | 178.1 (8) | C6—C5—C10—C9 | 2.40 (15) |
O1—C4—C2—C3A | −2.9 (6) | O3—C9—C10—C5 | 176.14 (8) |
O2—C4—C2—C3A | 177.9 (6) | C8—C9—C10—C5 | −2.76 (14) |
O1—C4—C2—C3 | 178.9 (6) | C7—C8—C11—O4 | −178.43 (9) |
O2—C4—C2—C3 | −0.2 (6) | C9—C8—C11—O4 | 1.23 (14) |
C10—C5—C6—C7 | −0.55 (15) | C7—C8—C11—C12 | 1.28 (14) |
O2—C5—C6—C7 | −177.00 (8) | C9—C8—C11—C12 | −179.05 (8) |
C5—C6—C7—C8 | −1.00 (15) | O1—C4—O2—C5 | −1.74 (18) |
C6—C7—C8—C9 | 0.62 (14) | C2—C4—O2—C5 | 177.45 (9) |
C6—C7—C8—C11 | −179.70 (8) | C10—C5—O2—C4 | 38.32 (15) |
C7—C8—C9—O3 | −177.57 (8) | C6—C5—O2—C4 | −145.30 (10) |
C11—C8—C9—O3 | 2.75 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4 | 0.82 | 1.81 | 2.5334 (10) | 147 |
C10—H10···O1 | 0.93 | 2.40 | 2.8163 (12) | 107 |
C7—H7···O3i | 0.93 | 2.43 | 3.3372 (11) | 164 |
C12—H12C···Cgii | 0.96 | 2.81 | 3.6718 (12) | 149 |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H12O4 |
Mr | 220.22 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 6.6413 (2), 7.2833 (3), 12.4387 (4) |
α, β, γ (°) | 84.020 (1), 87.447 (2), 65.866 (1) |
V (Å3) | 546.09 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.25 × 0.16 × 0.15 |
Data collection | |
Diffractometer | Bruker Kappa-APEXII |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.966, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16320, 4847, 3225 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.825 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.166, 1.04 |
No. of reflections | 4847 |
No. of parameters | 185 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.22 |
Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4 | 0.82 | 1.81 | 2.5334 (10) | 147 |
C10—H10···O1 | 0.93 | 2.40 | 2.8163 (12) | 107 |
C7—H7···O3i | 0.93 | 2.43 | 3.3372 (11) | 164 |
C12—H12C···Cgii | 0.96 | 2.81 | 3.6718 (12) | 149 |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y+2, −z+1. |
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Methacrylate derivatives have anti-inflammatory (Nicolaides et al., 1998) and antipicornaviral (Romero, 2001) properties and are efficient as agonists for different receptors (Naka & Kubo, 1999). Methacrylate activated vinyl esters are readily polymerized by free-radical polymerization to form linear, branched or network polymers (Parker & Braden, 1989).
The geometric parameters in (I) (Fig. 1) are comparable with the reported values of similar compounds (Gibson et al., 2006; Ren et al., 2006). A similar acetophenone compound with methyl group has been reported (Chakkaravarthi et al., 2007). The acetyl group is planar with the benzene ring [dihedral angle of 179.00 (7)°] and the methacryloyloxy group makes the dihedral angle of 34.67 (4)° with the benzene ring. The torsion angles O2—C4—C2—C3 and O2—C4—C2—C1 [-0.2 (6)° and 178.1 (8)°, respectively] indicate periplanar conformation of the respective moieties. The methyl and methylene groups in the terminal site are disordered over two positions with site occupancy factors of 0.50 (2). The molecular structure is stabilized by intramolecular O—H···O and C—H···O interactions and the crystal packing of (I) (Fig. 2) is stabilized by an intermolecular C—H···O hydrogen bond and a C—H···π interaction, involving the benzene C5—C10 ring (Table 1).