Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026323/bq2022sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026323/bq2022Isup2.hkl |
CCDC reference: 654592
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- R factor = 0.041
- wR factor = 0.113
- Data-to-parameter ratio = 18.9
checkCIF/PLATON results
No syntax errors found
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 33.70 From the CIF: _reflns_number_total 2647 Count of symmetry unique reflns 2661 Completeness (_total/calc) 99.47% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 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 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 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
In accordance with previously described preparative methods (Knoevenagel et al., 1903; Wilson, 1963), a mixture of 40 ml acetylacetone (0.39 mol) and 13.5 ml of formaldehyde (37% aqueous solution; 0.18 mol) was stirred for 5 days. The product separated on standing into a gold-colored organic bottom layer (40 ml) and a pale-yellow aqueous top layer (10 ml). The organic layer was dried over MgSO4 and an equal volume of diethyl ether was added. The resulting solution was cooled in a dry ice-acetone bath to produce a white solid. After repeatedly taking up the viscous portions in a minimum of diethyl ether and cooling in the dry ice-acetone bath, a total of 11.0 g (0.052 mole, 26% yield) of crystalline solid, mp 39.5–41.0 °C, was isolated. X-ray quality crystals were obtained by cooling a solution in diethyl ether in a dry ice-acetone bath.
H atoms were placed in idealized positions with C—H distances 0.98 - 1.00 Å and thereafter treated as riding. Uiso for H was assigned as 1.2 times Ueq of the attached C atoms (1.5 for methyl). A torsional parameter was refined for each methyl group. The absolute structure could not be determined, and Friedel pairs were averaged.
The title compound, (I), was first explored by Scholtz (1897) and Knoevenagel et al. (1903). Our goal was to utilize the title compound (I) in the preparation of polynuclear metal complexes.
Solutions of (I) in CHCl3 show evidence in 1H NMR spectra for both keto and enol tautomers, but the crystal contains only the keto form. C3 and C9 (Fig. 1) are protonated and tetrahedral, all the C—C bond lengths to them are typical of single bonds, and the four C═O distances (Table 1) are typical of double bonds.
Allen et al. (1998) have shown that intermolecular carbonyl···carbonyl interactions in ketones can significantly influence the packing of such molecules, and have identified three major geometric types. The shortest such contact in (I), O3···C10 (1 - x, y - 1/2, 3/2 - z) resembles their perpendicular interaction, and its O···C distance 3.387 (2) Å is near the mean distance they report. However, the O atom in this interaction is actually nearer the methyl C [O3···C11 = 3.267 (2) Å].
The title compound was described over 100 years ago (Scholtz, 1897; Knoevenagel et al., 1903). We have recently reported the structure of 1,1',1"-[(5R,6R)-6-hydroxy-6-methyl-tetrahydro-2H-pyran-3,\ 3,5-triyl]triethanone (Burton et al., 2007), which is formed when excess formaldehyde is used in the synthesis.
For related literature, see: Allen et al. (1998); Wilson (1963).
Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. Numbering scheme and ellipsoids at the 50% level. H atoms are represented with arbitrary radius. |
C11H16O4 | Dx = 1.203 Mg m−3 |
Mr = 212.24 | Melting point = 313.5–314.0 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2556 reflections |
a = 7.810 (2) Å | θ = 2.5–33.7° |
b = 8.611 (2) Å | µ = 0.09 mm−1 |
c = 17.431 (4) Å | T = 100 K |
V = 1172.3 (5) Å3 | Fragment, colourless |
Z = 4 | 0.47 × 0.43 × 0.40 mm |
F(000) = 456 |
Nonius KappaCCD (with Oxford Cryostream) diffractometer | 2352 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.016 |
Graphite monochromator | θmax = 33.7°, θmin = 2.8° |
ω scans with κ offsets | h = −11→11 |
15692 measured reflections | k = −13→13 |
2647 independent reflections | l = −27→27 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0668P)2 + 0.1309P] where P = (Fo2 + 2Fc2)/3 |
2647 reflections | (Δ/σ)max = 0.006 |
140 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C11H16O4 | V = 1172.3 (5) Å3 |
Mr = 212.24 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.810 (2) Å | µ = 0.09 mm−1 |
b = 8.611 (2) Å | T = 100 K |
c = 17.431 (4) Å | 0.47 × 0.43 × 0.40 mm |
Nonius KappaCCD (with Oxford Cryostream) diffractometer | 2352 reflections with I > 2σ(I) |
15692 measured reflections | Rint = 0.016 |
2647 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.29 e Å−3 |
2647 reflections | Δρmin = −0.18 e Å−3 |
140 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. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.05730 (14) | 0.48942 (13) | 0.67423 (5) | 0.0284 (2) | |
O2 | −0.06423 (14) | 0.21860 (16) | 0.54715 (7) | 0.0388 (3) | |
O3 | 0.52584 (15) | 0.07629 (14) | 0.65558 (6) | 0.0346 (3) | |
O4 | 0.45874 (17) | 0.10347 (15) | 0.84527 (6) | 0.0383 (3) | |
C1 | 0.1592 (2) | 0.53906 (18) | 0.54771 (8) | 0.0296 (3) | |
H1A | 0.0884 | 0.6328 | 0.5508 | 0.044* | |
H1B | 0.1286 | 0.4802 | 0.5016 | 0.044* | |
H1C | 0.2803 | 0.5686 | 0.5452 | 0.044* | |
C2 | 0.12923 (16) | 0.44037 (15) | 0.61741 (7) | 0.0212 (2) | |
C3 | 0.19679 (15) | 0.27436 (14) | 0.61312 (6) | 0.0184 (2) | |
H3 | 0.3141 | 0.2768 | 0.5901 | 0.022* | |
C4 | 0.08071 (18) | 0.17786 (17) | 0.56105 (7) | 0.0246 (2) | |
C5 | 0.1554 (2) | 0.03050 (19) | 0.52954 (9) | 0.0366 (3) | |
H5A | 0.0644 | −0.0469 | 0.5234 | 0.055* | |
H5B | 0.2423 | −0.0092 | 0.5650 | 0.055* | |
H5C | 0.2082 | 0.0514 | 0.4796 | 0.055* | |
C6 | 0.20811 (15) | 0.19736 (15) | 0.69250 (6) | 0.0195 (2) | |
H6A | 0.1052 | 0.2245 | 0.7228 | 0.023* | |
H6B | 0.2105 | 0.0831 | 0.6863 | 0.023* | |
C7 | 0.69870 (18) | 0.2565 (2) | 0.72430 (11) | 0.0348 (3) | |
H7A | 0.7860 | 0.1755 | 0.7298 | 0.052* | |
H7B | 0.6838 | 0.3103 | 0.7734 | 0.052* | |
H7C | 0.7351 | 0.3310 | 0.6851 | 0.052* | |
C8 | 0.53220 (16) | 0.18388 (16) | 0.70076 (7) | 0.0231 (2) | |
C9 | 0.36884 (15) | 0.24996 (14) | 0.73593 (6) | 0.0182 (2) | |
H9 | 0.3751 | 0.3659 | 0.7337 | 0.022* | |
C10 | 0.36087 (17) | 0.20085 (16) | 0.82022 (7) | 0.0236 (2) | |
C11 | 0.22526 (19) | 0.27536 (18) | 0.86857 (7) | 0.0294 (3) | |
H11A | 0.2417 | 0.2456 | 0.9223 | 0.044* | |
H11B | 0.1122 | 0.2407 | 0.8512 | 0.044* | |
H11C | 0.2332 | 0.3885 | 0.8638 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0318 (5) | 0.0291 (5) | 0.0243 (4) | 0.0065 (4) | 0.0051 (4) | −0.0015 (4) |
O2 | 0.0300 (5) | 0.0493 (7) | 0.0371 (6) | 0.0006 (5) | −0.0138 (5) | −0.0062 (5) |
O3 | 0.0336 (5) | 0.0348 (6) | 0.0354 (5) | 0.0123 (5) | −0.0005 (4) | −0.0080 (5) |
O4 | 0.0445 (7) | 0.0436 (6) | 0.0269 (5) | 0.0058 (6) | −0.0062 (5) | 0.0120 (4) |
C1 | 0.0315 (6) | 0.0299 (6) | 0.0275 (6) | 0.0059 (5) | 0.0050 (5) | 0.0104 (5) |
C2 | 0.0197 (5) | 0.0237 (5) | 0.0201 (4) | 0.0015 (4) | −0.0005 (4) | 0.0018 (4) |
C3 | 0.0182 (5) | 0.0219 (5) | 0.0152 (4) | 0.0000 (4) | −0.0008 (4) | −0.0002 (4) |
C4 | 0.0287 (6) | 0.0280 (6) | 0.0169 (4) | −0.0038 (5) | −0.0027 (4) | −0.0007 (4) |
C5 | 0.0404 (8) | 0.0341 (7) | 0.0353 (7) | −0.0033 (7) | −0.0031 (6) | −0.0142 (6) |
C6 | 0.0203 (5) | 0.0220 (5) | 0.0163 (4) | −0.0024 (4) | −0.0024 (4) | 0.0018 (4) |
C7 | 0.0203 (6) | 0.0335 (7) | 0.0506 (9) | −0.0010 (6) | −0.0019 (6) | 0.0075 (7) |
C8 | 0.0211 (5) | 0.0231 (5) | 0.0250 (5) | 0.0033 (5) | −0.0009 (4) | 0.0053 (4) |
C9 | 0.0197 (4) | 0.0184 (4) | 0.0165 (4) | −0.0011 (4) | −0.0014 (4) | 0.0012 (4) |
C10 | 0.0283 (6) | 0.0249 (5) | 0.0175 (4) | −0.0066 (5) | −0.0043 (4) | 0.0018 (4) |
C11 | 0.0338 (7) | 0.0348 (7) | 0.0198 (5) | −0.0117 (6) | 0.0050 (5) | −0.0036 (5) |
O1—C2 | 1.2145 (15) | C5—H5C | 0.9800 |
O2—C4 | 1.2097 (18) | C6—C9 | 1.5343 (16) |
O3—C8 | 1.2169 (18) | C6—H6A | 0.9900 |
O4—C10 | 1.2158 (17) | C6—H6B | 0.9900 |
C1—C2 | 1.5011 (18) | C7—C8 | 1.500 (2) |
C1—H1A | 0.9800 | C7—H7A | 0.9800 |
C1—H1B | 0.9800 | C7—H7B | 0.9800 |
C1—H1C | 0.9800 | C7—H7C | 0.9800 |
C2—C3 | 1.5256 (17) | C8—C9 | 1.5256 (18) |
C3—C4 | 1.5284 (17) | C9—C10 | 1.5301 (17) |
C3—C6 | 1.5370 (16) | C9—H9 | 1.0000 |
C3—H3 | 1.0000 | C10—C11 | 1.498 (2) |
C4—C5 | 1.501 (2) | C11—H11A | 0.9800 |
C5—H5A | 0.9800 | C11—H11B | 0.9800 |
C5—H5B | 0.9800 | C11—H11C | 0.9800 |
C2—C1—H1A | 109.5 | C9—C6—H6B | 109.4 |
C2—C1—H1B | 109.5 | C3—C6—H6B | 109.4 |
H1A—C1—H1B | 109.5 | H6A—C6—H6B | 108.0 |
C2—C1—H1C | 109.5 | C8—C7—H7A | 109.5 |
H1A—C1—H1C | 109.5 | C8—C7—H7B | 109.5 |
H1B—C1—H1C | 109.5 | H7A—C7—H7B | 109.5 |
O1—C2—C1 | 122.37 (12) | C8—C7—H7C | 109.5 |
O1—C2—C3 | 121.72 (11) | H7A—C7—H7C | 109.5 |
C1—C2—C3 | 115.90 (10) | H7B—C7—H7C | 109.5 |
C2—C3—C4 | 109.48 (10) | O3—C8—C7 | 121.98 (13) |
C2—C3—C6 | 112.33 (10) | O3—C8—C9 | 120.65 (12) |
C4—C3—C6 | 109.52 (10) | C7—C8—C9 | 117.37 (12) |
C2—C3—H3 | 108.5 | C8—C9—C10 | 108.47 (10) |
C4—C3—H3 | 108.5 | C8—C9—C6 | 112.08 (10) |
C6—C3—H3 | 108.5 | C10—C9—C6 | 111.04 (10) |
O2—C4—C5 | 122.38 (14) | C8—C9—H9 | 108.4 |
O2—C4—C3 | 121.09 (13) | C10—C9—H9 | 108.4 |
C5—C4—C3 | 116.53 (12) | C6—C9—H9 | 108.4 |
C4—C5—H5A | 109.5 | O4—C10—C11 | 122.55 (12) |
C4—C5—H5B | 109.5 | O4—C10—C9 | 120.66 (12) |
H5A—C5—H5B | 109.5 | C11—C10—C9 | 116.78 (11) |
C4—C5—H5C | 109.5 | C10—C11—H11A | 109.5 |
H5A—C5—H5C | 109.5 | C10—C11—H11B | 109.5 |
H5B—C5—H5C | 109.5 | H11A—C11—H11B | 109.5 |
C9—C6—C3 | 111.34 (9) | C10—C11—H11C | 109.5 |
C9—C6—H6A | 109.4 | H11A—C11—H11C | 109.5 |
C3—C6—H6A | 109.4 | H11B—C11—H11C | 109.5 |
O1—C2—C3—C4 | 106.19 (14) | O3—C8—C9—C10 | 107.67 (13) |
C1—C2—C3—C4 | −74.56 (13) | C7—C8—C9—C10 | −72.17 (14) |
O1—C2—C3—C6 | −15.71 (16) | O3—C8—C9—C6 | −15.27 (16) |
C1—C2—C3—C6 | 163.54 (11) | C7—C8—C9—C6 | 164.88 (12) |
C2—C3—C4—O2 | −20.20 (17) | C3—C6—C9—C8 | −70.39 (13) |
C6—C3—C4—O2 | 103.37 (14) | C3—C6—C9—C10 | 168.12 (10) |
C2—C3—C4—C5 | 160.62 (12) | C8—C9—C10—O4 | −11.25 (17) |
C6—C3—C4—C5 | −75.80 (14) | C6—C9—C10—O4 | 112.32 (14) |
C2—C3—C6—C9 | −79.56 (12) | C8—C9—C10—C11 | 170.22 (11) |
C4—C3—C6—C9 | 158.56 (10) | C6—C9—C10—C11 | −66.21 (14) |
Experimental details
Crystal data | |
Chemical formula | C11H16O4 |
Mr | 212.24 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 7.810 (2), 8.611 (2), 17.431 (4) |
V (Å3) | 1172.3 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.47 × 0.43 × 0.40 |
Data collection | |
Diffractometer | Nonius KappaCCD (with Oxford Cryostream) |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15692, 2647, 2352 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.781 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.113, 1.04 |
No. of reflections | 2647 |
No. of parameters | 140 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.18 |
Computer programs: COLLECT (Nonius, 2000), SCALEPACK (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
O1—C2 | 1.2145 (15) | C2—C3 | 1.5256 (17) |
O2—C4 | 1.2097 (18) | C3—C4 | 1.5284 (17) |
O3—C8 | 1.2169 (18) | C8—C9 | 1.5256 (18) |
O4—C10 | 1.2158 (17) | C9—C10 | 1.5301 (17) |
O1—C2—C3—C6 | −15.71 (16) | O3—C8—C9—C6 | −15.27 (16) |
C6—C3—C4—O2 | 103.37 (14) | C6—C9—C10—O4 | 112.32 (14) |
The title compound, (I), was first explored by Scholtz (1897) and Knoevenagel et al. (1903). Our goal was to utilize the title compound (I) in the preparation of polynuclear metal complexes.
Solutions of (I) in CHCl3 show evidence in 1H NMR spectra for both keto and enol tautomers, but the crystal contains only the keto form. C3 and C9 (Fig. 1) are protonated and tetrahedral, all the C—C bond lengths to them are typical of single bonds, and the four C═O distances (Table 1) are typical of double bonds.
Allen et al. (1998) have shown that intermolecular carbonyl···carbonyl interactions in ketones can significantly influence the packing of such molecules, and have identified three major geometric types. The shortest such contact in (I), O3···C10 (1 - x, y - 1/2, 3/2 - z) resembles their perpendicular interaction, and its O···C distance 3.387 (2) Å is near the mean distance they report. However, the O atom in this interaction is actually nearer the methyl C [O3···C11 = 3.267 (2) Å].