Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026372/ya2053sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026372/ya2053Isup2.hkl |
CCDC reference: 654988
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.002 Å
- R factor = 0.052
- wR factor = 0.142
- Data-to-parameter ratio = 23.4
checkCIF/PLATON results
No syntax errors found
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.807 0.990 Tmin(prime) and Tmax expected: 0.969 0.987 RR(prime) = 0.830 Please check that your absorption correction is appropriate. PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.83 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.39 PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 200 Deg.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 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 0 ALERT type 5 Informative message, check
Similar 4-keto acids based on 3-benzoylpropionic acid, which does not contain the phenolic hydroxyl group, have been characterized crystallographically. These include two polymorphs of 3-benzoylpropionic acid (Selladurai et al., 1990; Thompson et al., 1991), 4-(4-biphenyl)-4-oxobutyric acid (Kim et al., 1988), 3-[4-(methylsulfonyl)benzoyl]propionic acid (Lynch & McClenaghan, 2002) and 3-(4-methylbenzoyl)propionic acid (Ircagor 419; Frey et al., 2000), which is used as a corrosion inhibitor for mild steel. All structures contain the dimeric carboxylate hydrogen bonding seen in the title compound.
4-tert-Butylanisole (3.001 g, 18.2 mmol) and succinic anhydride (1.832 g, 18.3 mmol) were dissolved in nitrobenzene and aluminium chloride (5.1 g, 38.2 mmol) was added in portions over ice. The mixture was heated to 60 °C for 4 h and then treated with aqueous HCl (100 ml, 1 M). Extraction into chloroform (100 ml) and removal of solvent yielded a solid which was dissolved in NaOH (1 M, 100 ml). The pH was adjusted to 2 with conc HCl and the precipitate collected and recrystallized from hexane/chloroform to yield the title compound (2.350 g, 9.4 mmol, 52%). Colourless rods suitable for XRD analysis were grown by slow evaporation of a hexane/chloroform solution.
Hydroxyl H atoms were found in a Fourier difference map and their positional and isotropic displacement parameters refined [O1—H1 0.86 (2) Å; O4—H4 0.87 (2) Å]. The H atoms bound to carbon were placed in idealized positions and allowed to ride on their parent atoms with bond lengths of 0.95–0.99 Å and Uiso values set at 1.2Ueq of the corresponding carrier atom (1.5Ueq for methyl H atoms).
The title compound was synthesized as a potential corrosion inhibitor as it has a structure similar to that of successful reagent Ircagor 419TM (Frey et al., 2000) and, in addition, includes a phenolic hydroxyl group which may coordinate to a metal or form hydrogen bonds to the surface. The molecules in the crystal structure form dimers via H-bonding between two adjacent carboxylate moieties (O4—H4···O3 = 2.642 (1) Å; Figure 1) which is typical for carboxylate structures. An intramolecular hydrogen bond is also formed between the phenolic hydroxyl group and the ortho keto oxygen (O1···O29 = 2.578 (1) Å).
Each molecule is involved in π–π stacking interactions with one molecule above and one below, in the direction of the a axis. The distances between the planes of the molecules are 3.305 Å and 3.389 Å. An isotactic arrangement of these π–π stacked chains occurs, with each chain linked to the next one through the carboxylate H-bonds described above, thus forming two-dimensional sheets parallel to the ac plane (Figure 2).
Similar 4-keto acids based on 3-benzoylpropionic acid, which does not contain the phenolic hydroxyl group, have been characterized crystallographically. These include two polymorphs of 3-benzoylpropionic acid (Selladurai et al., 1990; Thompson et al., 1991), 4-(4-biphenyl)-4-oxobutyric acid (Kim et al., 1988), 3-[4-(methylsulfonyl)benzoyl]propionic acid (Lynch & McClenaghan, 2002) and 3-(4-methylbenzoyl)propionic acid (Ircagor 419; Frey et al., 2000), which is used as a corrosion inhibitor for mild steel. All structures contain the dimeric carboxylate hydrogen bonding seen in the title compound.
Data collection: SMART (Siemens, 1993); cell refinement: SAINT; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: PLATON (Spek, 2003).
C14H18O4 | Z = 2 |
Mr = 250.28 | F(000) = 268 |
Triclinic, P1 | Dx = 1.228 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0938 (2) Å | Cell parameters from 3804 reflections |
b = 8.5918 (3) Å | θ = 30.5–2.4° |
c = 11.4966 (3) Å | µ = 0.09 mm−1 |
α = 76.917 (2)° | T = 150 K |
β = 85.205 (2)° | Block, colourless |
γ = 83.318 (2)° | 0.34 × 0.26 × 0.15 mm |
V = 676.69 (4) Å3 |
Bruker SMART APEX CCD area-detector diffractometer | 3998 independent reflections |
Radiation source: fine-focus sealed tube | 2956 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ω and φ scans | θmax = 30.6°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −10→9 |
Tmin = 0.807, Tmax = 0.990 | k = −12→12 |
14490 measured reflections | l = −16→16 |
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)] = 0.052 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.142 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0764P)2 + 0.0859P] where P = (Fo2 + 2Fc2)/3 |
3998 reflections | (Δ/σ)max < 0.001 |
171 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C14H18O4 | γ = 83.318 (2)° |
Mr = 250.28 | V = 676.69 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.0938 (2) Å | Mo Kα radiation |
b = 8.5918 (3) Å | µ = 0.09 mm−1 |
c = 11.4966 (3) Å | T = 150 K |
α = 76.917 (2)° | 0.34 × 0.26 × 0.15 mm |
β = 85.205 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 3998 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 2956 reflections with I > 2σ(I) |
Tmin = 0.807, Tmax = 0.990 | Rint = 0.034 |
14490 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.142 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.43 e Å−3 |
3998 reflections | Δρmin = −0.18 e Å−3 |
171 parameters |
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. |
Refinement. Checkcif output: 912_ALERT_3_B # Missing FCF Reflections Above STH/L=0.6 ······ 159 910_ALERT_3_C # Missing FCF Reflections Below TH(Min) ······.. 1 911_ALERT_3_C # Missing FCF Refl Between THmin & STh/l= 0.600 1 The data collection strategy used aimed to achieve a complete data set to 2θ = 53 °. Some higher angle data were collected in the process and these have been included in the refinement. Please refer to the completeness statistics below ================================================================================ Resolution & Completeness Statistics (Cumulative) ================================================================================ Theta sin(th)/Lambda Complete Expected Measured Missing ——————————————————————————– 20.82 0.500 0.999 1418 1417 1 23.01 0.550 0.999 1883 1882 1 25.24 0.600 0.999 2457 2455 2 ———————————————————— ACTA Min. Res. —- 27.51 0.650 0.997 3116 3108 8 29.84 0.700 0.977 3877 3787 90 30.57 0.716 0.961 4159 3998 161 061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ············. 0.83 SADABS corrects for all systematic errors that lead to disparities in the intensities of symmetry-equivalent data. These may include absorption by the mount, crystal decay etc. The crystal was a rather irregular shape, having been cleaved from a larger block; this precluded integration methods for correcting for absorption. 094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ···. 2.37 Highest peak = 0.43 Deepest Hole = -0.18 These are not unreasonable. They are localized in the region of an aromatic ring |
x | y | z | Uiso*/Ueq | ||
O1 | 0.25675 (15) | 0.27572 (10) | 0.04192 (9) | 0.0344 (2) | |
C1 | 0.23777 (17) | 0.42613 (13) | −0.02693 (10) | 0.0256 (2) | |
C2 | 0.26835 (17) | 0.56259 (13) | 0.01488 (10) | 0.0235 (2) | |
O3 | 0.04561 (13) | 0.62039 (11) | 0.37232 (8) | 0.0318 (2) | |
C3 | 0.25301 (18) | 0.71372 (13) | −0.06456 (10) | 0.0249 (2) | |
H3A | 0.2753 | 0.8056 | −0.0367 | 0.030* | |
C4 | 0.20655 (18) | 0.73325 (14) | −0.18182 (10) | 0.0261 (3) | |
O4 | 0.25919 (15) | 0.47532 (13) | 0.49478 (8) | 0.0392 (3) | |
H4 | 0.157 (3) | 0.443 (2) | 0.5352 (19) | 0.059 (6)* | |
C5 | 0.16996 (19) | 0.59523 (15) | −0.21840 (10) | 0.0281 (3) | |
H5A | 0.1331 | 0.6057 | −0.2976 | 0.034* | |
C6 | 0.18548 (18) | 0.44515 (14) | −0.14380 (11) | 0.0280 (3) | |
H6A | 0.1605 | 0.3543 | −0.1720 | 0.034* | |
C21 | 0.31001 (17) | 0.54528 (14) | 0.14063 (10) | 0.0260 (2) | |
C22 | 0.33448 (19) | 0.69232 (15) | 0.18742 (10) | 0.0285 (3) | |
H22A | 0.2174 | 0.7676 | 0.1762 | 0.034* | |
H22B | 0.4408 | 0.7476 | 0.1411 | 0.034* | |
C23 | 0.3750 (2) | 0.64759 (17) | 0.31958 (11) | 0.0332 (3) | |
H23A | 0.4881 | 0.5677 | 0.3312 | 0.040* | |
H23B | 0.4046 | 0.7444 | 0.3449 | 0.040* | |
C24 | 0.21078 (19) | 0.57950 (15) | 0.39652 (10) | 0.0280 (3) | |
O29 | 0.32127 (14) | 0.41288 (11) | 0.21016 (8) | 0.0333 (2) | |
C41 | 0.1914 (2) | 0.89572 (15) | −0.27057 (11) | 0.0334 (3) | |
C42 | −0.0136 (3) | 0.93891 (19) | −0.30816 (15) | 0.0495 (4) | |
H42A | −0.0987 | 0.9467 | −0.2376 | 0.074* | |
H42B | −0.0502 | 0.8554 | −0.3450 | 0.074* | |
H42C | −0.0229 | 1.0422 | −0.3659 | 0.074* | |
C43 | 0.3241 (3) | 0.8850 (2) | −0.38152 (14) | 0.0554 (5) | |
H43A | 0.3144 | 0.9889 | −0.4386 | 0.083* | |
H43B | 0.2872 | 0.8022 | −0.4189 | 0.083* | |
H43C | 0.4555 | 0.8571 | −0.3578 | 0.083* | |
C44 | 0.2471 (3) | 1.02985 (17) | −0.21712 (15) | 0.0532 (5) | |
H44A | 0.1630 | 1.0390 | −0.1464 | 0.080* | |
H44B | 0.2350 | 1.1316 | −0.2766 | 0.080* | |
H44C | 0.3790 | 1.0051 | −0.1941 | 0.080* | |
H1 | 0.284 (3) | 0.287 (3) | 0.1107 (19) | 0.065 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0409 (6) | 0.0241 (4) | 0.0364 (5) | −0.0035 (4) | −0.0020 (4) | −0.0029 (3) |
C1 | 0.0223 (6) | 0.0244 (5) | 0.0290 (5) | −0.0017 (4) | 0.0019 (5) | −0.0054 (4) |
C2 | 0.0204 (6) | 0.0262 (5) | 0.0236 (5) | −0.0012 (4) | 0.0004 (4) | −0.0058 (4) |
O3 | 0.0267 (5) | 0.0390 (5) | 0.0274 (4) | −0.0007 (4) | −0.0024 (4) | −0.0035 (3) |
C3 | 0.0260 (6) | 0.0248 (5) | 0.0245 (5) | −0.0020 (4) | 0.0000 (4) | −0.0074 (4) |
C4 | 0.0282 (7) | 0.0260 (5) | 0.0234 (5) | −0.0016 (4) | −0.0005 (5) | −0.0049 (4) |
O4 | 0.0284 (6) | 0.0598 (6) | 0.0245 (4) | −0.0027 (5) | −0.0047 (4) | 0.0009 (4) |
C5 | 0.0285 (7) | 0.0329 (6) | 0.0247 (5) | −0.0023 (5) | −0.0024 (5) | −0.0099 (4) |
C6 | 0.0279 (7) | 0.0273 (5) | 0.0314 (6) | −0.0033 (5) | −0.0002 (5) | −0.0125 (4) |
C21 | 0.0205 (6) | 0.0331 (6) | 0.0233 (5) | −0.0007 (4) | 0.0009 (4) | −0.0055 (4) |
C22 | 0.0293 (7) | 0.0352 (6) | 0.0215 (5) | −0.0039 (5) | −0.0009 (5) | −0.0073 (4) |
C23 | 0.0289 (7) | 0.0478 (7) | 0.0243 (5) | −0.0071 (5) | −0.0030 (5) | −0.0086 (5) |
C24 | 0.0297 (7) | 0.0353 (6) | 0.0213 (5) | −0.0030 (5) | −0.0029 (5) | −0.0108 (4) |
O29 | 0.0366 (6) | 0.0332 (4) | 0.0267 (4) | −0.0013 (4) | −0.0023 (4) | −0.0007 (3) |
C41 | 0.0438 (8) | 0.0282 (6) | 0.0266 (5) | −0.0041 (5) | −0.0044 (5) | −0.0017 (4) |
C42 | 0.0538 (11) | 0.0377 (7) | 0.0515 (9) | 0.0022 (7) | −0.0158 (8) | 0.0028 (6) |
C43 | 0.0701 (13) | 0.0504 (9) | 0.0362 (7) | −0.0051 (8) | 0.0119 (8) | 0.0044 (6) |
C44 | 0.0850 (14) | 0.0297 (6) | 0.0452 (8) | −0.0146 (7) | −0.0201 (9) | 0.0016 (6) |
O1—C1 | 1.3524 (14) | C22—C23 | 1.5238 (16) |
O1—H1 | 0.86 (2) | C22—H22A | 0.99 |
C1—C6 | 1.3925 (17) | C22—H22B | 0.99 |
C1—C2 | 1.4087 (16) | C23—C24 | 1.4945 (19) |
C2—C3 | 1.4067 (15) | C23—H23A | 0.99 |
C2—C21 | 1.4709 (16) | C23—H23B | 0.99 |
O3—C24 | 1.2199 (15) | C41—C44 | 1.526 (2) |
C3—C4 | 1.3832 (16) | C41—C42 | 1.532 (2) |
C3—H3A | 0.95 | C41—C43 | 1.534 (2) |
C4—C5 | 1.4022 (17) | C42—H42A | 0.98 |
C4—C41 | 1.5296 (16) | C42—H42B | 0.98 |
O4—C24 | 1.3156 (14) | C42—H42C | 0.98 |
O4—H4 | 0.87 (2) | C43—H43A | 0.98 |
C5—C6 | 1.3757 (17) | C43—H43B | 0.98 |
C5—H5A | 0.95 | C43—H43C | 0.98 |
C6—H6A | 0.95 | C44—H44A | 0.98 |
C21—O29 | 1.2318 (14) | C44—H44B | 0.98 |
C21—C22 | 1.5131 (17) | C44—H44C | 0.98 |
C1—O1—H1 | 105.5 (14) | C22—C23—H23A | 109.2 |
O1—C1—C6 | 117.98 (10) | C24—C23—H23B | 109.2 |
O1—C1—C2 | 122.74 (11) | C22—C23—H23B | 109.2 |
C6—C1—C2 | 119.28 (10) | H23A—C23—H23B | 107.9 |
C3—C2—C1 | 118.83 (10) | O3—C24—O4 | 122.72 (12) |
C3—C2—C21 | 121.44 (10) | O3—C24—C23 | 123.00 (11) |
C1—C2—C21 | 119.71 (10) | O4—C24—C23 | 114.24 (11) |
C4—C3—C2 | 122.29 (10) | C44—C41—C4 | 112.10 (11) |
C4—C3—H3A | 118.9 | C44—C41—C42 | 108.46 (13) |
C2—C3—H3A | 118.9 | C4—C41—C42 | 109.44 (12) |
C3—C4—C5 | 117.00 (10) | C44—C41—C43 | 108.31 (14) |
C3—C4—C41 | 123.41 (10) | C4—C41—C43 | 109.30 (11) |
C5—C4—C41 | 119.59 (10) | C42—C41—C43 | 109.19 (13) |
C24—O4—H4 | 108.8 (13) | C41—C42—H42A | 109.5 |
C6—C5—C4 | 122.40 (11) | C41—C42—H42B | 109.5 |
C6—C5—H5A | 118.8 | H42A—C42—H42B | 109.5 |
C4—C5—H5A | 118.8 | C41—C42—H42C | 109.5 |
C5—C6—C1 | 120.12 (10) | H42A—C42—H42C | 109.5 |
C5—C6—H6A | 119.9 | H42B—C42—H42C | 109.5 |
C1—C6—H6A | 119.9 | C41—C43—H43A | 109.5 |
O29—C21—C2 | 121.18 (11) | C41—C43—H43B | 109.5 |
O29—C21—C22 | 118.85 (10) | H43A—C43—H43B | 109.5 |
C2—C21—C22 | 119.95 (10) | C41—C43—H43C | 109.5 |
C21—C22—C23 | 111.33 (10) | H43A—C43—H43C | 109.5 |
C21—C22—H22A | 109.4 | H43B—C43—H43C | 109.5 |
C23—C22—H22A | 109.4 | C41—C44—H44A | 109.5 |
C21—C22—H22B | 109.4 | C41—C44—H44B | 109.5 |
C23—C22—H22B | 109.4 | H44A—C44—H44B | 109.5 |
H22A—C22—H22B | 108.0 | C41—C44—H44C | 109.5 |
C24—C23—C22 | 112.24 (11) | H44A—C44—H44C | 109.5 |
C24—C23—H23A | 109.2 | H44B—C44—H44C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O29 | 0.86 (2) | 1.80 (2) | 2.5777 (14) | 150 (2) |
O4—H4···O3i | 0.87 (2) | 1.78 (2) | 2.6417 (15) | 175.8 (19) |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C14H18O4 |
Mr | 250.28 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 7.0938 (2), 8.5918 (3), 11.4966 (3) |
α, β, γ (°) | 76.917 (2), 85.205 (2), 83.318 (2) |
V (Å3) | 676.69 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.34 × 0.26 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.807, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14490, 3998, 2956 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.716 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.142, 1.03 |
No. of reflections | 3998 |
No. of parameters | 171 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.43, −0.18 |
Computer programs: SMART (Siemens, 1993), SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2004), PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O29 | 0.86 (2) | 1.80 (2) | 2.5777 (14) | 150 (2) |
O4—H4···O3i | 0.87 (2) | 1.78 (2) | 2.6417 (15) | 175.8 (19) |
Symmetry code: (i) −x, −y+1, −z+1. |
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The title compound was synthesized as a potential corrosion inhibitor as it has a structure similar to that of successful reagent Ircagor 419TM (Frey et al., 2000) and, in addition, includes a phenolic hydroxyl group which may coordinate to a metal or form hydrogen bonds to the surface. The molecules in the crystal structure form dimers via H-bonding between two adjacent carboxylate moieties (O4—H4···O3 = 2.642 (1) Å; Figure 1) which is typical for carboxylate structures. An intramolecular hydrogen bond is also formed between the phenolic hydroxyl group and the ortho keto oxygen (O1···O29 = 2.578 (1) Å).
Each molecule is involved in π–π stacking interactions with one molecule above and one below, in the direction of the a axis. The distances between the planes of the molecules are 3.305 Å and 3.389 Å. An isotactic arrangement of these π–π stacked chains occurs, with each chain linked to the next one through the carboxylate H-bonds described above, thus forming two-dimensional sheets parallel to the ac plane (Figure 2).