Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051926/tk2202sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051926/tk2202Isup2.hkl |
CCDC reference: 667481
Compound (I) was prepared unintentionally during an attempt to isolate a triketone derived from terephtalic acid. In an isooctane (20 ml) solution of sodium 2,2,6,6-tetramethylheptane-3,5-dionate (0.21 g), terephtaloyl dichloride (0.20 g) was added and the mixture heated for 15 min. The NaCl precipitate was filtered off, the filtrate evaporated to approximately 5 ml, 2-propanol (10 ml) added and the mixture left for 24 h, after which crystallized large colourless plates of (I).
All H atoms were placed geometrically and included in the refinement in the riding-model approximation, with C—H = 0.93, and with Uiso = 1.2Ueq(C).
Molecules of (I) are centrosymmetric being disposed about a centre of inversion, as is the case in the crystal structures of related compounds (Brisse & Pérez, 1976; Bailey, 1949; Hašek et al., 1982 & Ciajolo et al., 1991). Similarly, all bond lengths and angles have normal values. The C1/C2/C4/O2 dihedral angle of 161.2 (2)° indicates a deviation from planarity.
The structure comprises essentially discrete molecules, with the closest intermolecular contacts being of the type C—H···O: C3—H···O1 = 3.53 Å (-1 + x, 1/2 - y, -1/2 + z), C1—H···O1 = 3.55 Å (-1 + x, 1/2 - y, -1/2 + z), and C7—H···O1 = 3.560 Å (-2 + x, 1 - y, -3/2 + z). The molecules have an elongated shape and their orientation is almost parallel with the 2a + c vector, being inclined at an angle of 7.3°. Such a tendency for parallel arrangement is also seen in the structure of the di-p-tolyl terephtalate (Ciajolo et al., 1991) derivative, but not in the structures of dimethyl (Brisse & Pérez, 1976) and diethyl (Bailey, 1949; Hašek et al., 1982) esters.
For related structures, see: dimethyl terephtalate (Brisse & Pérez, 1976), diethyl terephtelate (Bailey, 1949; Hašek et al., 1982) and di-p-tolyl terephtalate (Ciajolo et al., 1991).
Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C14H18O4 | F(000) = 268 |
Mr = 250.28 | Dx = 1.174 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1344 reflections |
a = 9.208 (3) Å | θ = 4.6–52.0° |
b = 9.718 (3) Å | µ = 0.09 mm−1 |
c = 15.844 (5) Å | T = 298 K |
β = 150.03 (2)° | Prismatic, colourless |
V = 708.2 (6) Å3 | 0.75 × 0.49 × 0.42 mm |
Z = 2 |
Oxford Diffraction Xcalibur CCD diffractometer | 1267 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.055 |
Graphite monochromator | θmax = 27.0°, θmin = 4.9° |
ω scans | h = −11→11 |
3803 measured reflections | k = −7→12 |
1521 independent reflections | l = −20→19 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.056 | w = 1/[σ2(Fo2) + (0.0956P)2 + 0.1119P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.17 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 0.28 e Å−3 |
1521 reflections | Δρmin = −0.31 e Å−3 |
84 parameters |
C14H18O4 | V = 708.2 (6) Å3 |
Mr = 250.28 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.208 (3) Å | µ = 0.09 mm−1 |
b = 9.718 (3) Å | T = 298 K |
c = 15.844 (5) Å | 0.75 × 0.49 × 0.42 mm |
β = 150.03 (2)° |
Oxford Diffraction Xcalibur CCD diffractometer | 1267 reflections with I > 2σ(I) |
3803 measured reflections | Rint = 0.055 |
1521 independent reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.17 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.28 e Å−3 |
1521 reflections | Δρmin = −0.31 e Å−3 |
84 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. |
x | y | z | Uiso*/Ueq | ||
O2 | 0.6575 (2) | 0.08936 (11) | 0.44294 (13) | 0.0556 (4) | |
C2 | 0.2478 (3) | −0.01186 (14) | 0.17469 (18) | 0.0427 (4) | |
C3 | 0.2212 (3) | 0.09717 (15) | 0.10444 (19) | 0.0475 (4) | |
H3 | 0.369 | 0.162 | 0.1743 | 0.057* | |
C1 | 0.0255 (3) | −0.10864 (15) | 0.06930 (19) | 0.0485 (4) | |
H1 | 0.0429 | −0.1813 | 0.1159 | 0.058* | |
C4 | 0.5081 (3) | −0.02752 (14) | 0.36151 (18) | 0.0458 (4) | |
O1 | 0.5706 (3) | −0.13377 (13) | 0.42786 (15) | 0.0704 (4) | |
C5 | 0.9128 (3) | 0.09072 (19) | 0.62716 (19) | 0.0574 (5) | |
H5 | 0.8796 | 0.0288 | 0.6583 | 0.069* | |
C7 | 0.9347 (4) | 0.2370 (2) | 0.6695 (3) | 0.0728 (6) | |
H7A | 0.9438 | 0.2986 | 0.6268 | 0.109* | |
H7B | 1.1071 | 0.247 | 0.7899 | 0.109* | |
H7C | 0.7671 | 0.2584 | 0.6188 | 0.109* | |
C6 | 1.1736 (4) | 0.0427 (3) | 0.7094 (3) | 0.0848 (7) | |
H6A | 1.1394 | −0.0487 | 0.6715 | 0.127* | |
H6B | 1.3413 | 0.0425 | 0.8299 | 0.127* | |
H6C | 1.2065 | 0.1037 | 0.6792 | 0.127* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0551 (7) | 0.0525 (7) | 0.0425 (6) | −0.0100 (5) | 0.0399 (6) | −0.0063 (4) |
C2 | 0.0446 (7) | 0.0404 (7) | 0.0419 (8) | 0.0014 (5) | 0.0373 (7) | 0.0001 (5) |
C3 | 0.0472 (8) | 0.0431 (8) | 0.0458 (8) | −0.0068 (6) | 0.0393 (7) | −0.0040 (6) |
C1 | 0.0539 (8) | 0.0425 (7) | 0.0474 (8) | −0.0043 (6) | 0.0437 (8) | −0.0004 (6) |
C4 | 0.0456 (7) | 0.0447 (8) | 0.0427 (8) | −0.0007 (6) | 0.0377 (7) | −0.0006 (6) |
O1 | 0.0657 (8) | 0.0545 (7) | 0.0485 (7) | −0.0020 (5) | 0.0434 (7) | 0.0057 (5) |
C5 | 0.0510 (9) | 0.0657 (11) | 0.0421 (9) | −0.0100 (7) | 0.0384 (8) | −0.0054 (7) |
C7 | 0.0743 (12) | 0.0767 (13) | 0.0617 (11) | −0.0183 (10) | 0.0581 (11) | −0.0197 (9) |
C6 | 0.0573 (11) | 0.0934 (16) | 0.0656 (12) | 0.0003 (10) | 0.0478 (11) | −0.0053 (11) |
O2—C4 | 1.3311 (18) | C5—C7 | 1.509 (3) |
O2—C5 | 1.469 (2) | C5—H5 | 0.98 |
C2—C1 | 1.393 (2) | C7—H7A | 0.96 |
C2—C3 | 1.396 (2) | C7—H7B | 0.96 |
C2—C4 | 1.496 (2) | C7—H7C | 0.96 |
C3—H3 | 0.93 | C6—H6A | 0.96 |
C1—H1 | 0.93 | C6—H6B | 0.96 |
C4—O1 | 1.2058 (19) | C6—H6C | 0.96 |
C5—C6 | 1.504 (3) | ||
C4—O2—C5 | 117.70 (12) | O2—C5—H5 | 109.5 |
C1—C2—C3 | 119.73 (14) | C6—C5—H5 | 109.5 |
C1—C2—C4 | 118.34 (13) | C7—C5—H5 | 109.5 |
C3—C2—C4 | 121.92 (13) | C5—C7—H7A | 109.5 |
C1i—C3—C2 | 119.93 (13) | C5—C7—H7B | 109.5 |
C1i—C3—H3 | 120 | H7A—C7—H7B | 109.5 |
C2—C3—H3 | 120 | C5—C7—H7C | 109.5 |
C3i—C1—C2 | 120.34 (14) | H7A—C7—H7C | 109.5 |
C3i—C1—H1 | 119.8 | H7B—C7—H7C | 109.5 |
C2—C1—H1 | 119.8 | C5—C6—H6A | 109.5 |
O1—C4—O2 | 125.00 (15) | C5—C6—H6B | 109.5 |
O1—C4—C2 | 123.28 (13) | H6A—C6—H6B | 109.5 |
O2—C4—C2 | 111.72 (12) | C5—C6—H6C | 109.5 |
O2—C5—C6 | 108.93 (16) | H6A—C6—H6C | 109.5 |
O2—C5—C7 | 105.04 (14) | H6B—C6—H6C | 109.5 |
C6—C5—C7 | 114.16 (17) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1ii | 0.93 | 2.90 | 3.532 (4) | 126 |
C1—H1···O1iii | 0.93 | 2.93 | 3.546 (3) | 125 |
C7—H7B···O1iv | 0.96 | 2.67 | 3.560 (4) | 153 |
Symmetry codes: (ii) −x+1, y+1/2, −z+1/2; (iii) x−1, −y−1/2, z−1/2; (iv) −x+2, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C14H18O4 |
Mr | 250.28 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 9.208 (3), 9.718 (3), 15.844 (5) |
β (°) | 150.03 (2) |
V (Å3) | 708.2 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.75 × 0.49 × 0.42 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3803, 1521, 1267 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.17, 1.07 |
No. of reflections | 1521 |
No. of parameters | 84 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.31 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1i | 0.93 | 2.90 | 3.532 (4) | 126 |
C1—H1···O1ii | 0.93 | 2.93 | 3.546 (3) | 125 |
C7—H7B···O1iii | 0.96 | 2.67 | 3.560 (4) | 153 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x−1, −y−1/2, z−1/2; (iii) −x+2, y+1/2, −z+3/2. |
Molecules of (I) are centrosymmetric being disposed about a centre of inversion, as is the case in the crystal structures of related compounds (Brisse & Pérez, 1976; Bailey, 1949; Hašek et al., 1982 & Ciajolo et al., 1991). Similarly, all bond lengths and angles have normal values. The C1/C2/C4/O2 dihedral angle of 161.2 (2)° indicates a deviation from planarity.
The structure comprises essentially discrete molecules, with the closest intermolecular contacts being of the type C—H···O: C3—H···O1 = 3.53 Å (-1 + x, 1/2 - y, -1/2 + z), C1—H···O1 = 3.55 Å (-1 + x, 1/2 - y, -1/2 + z), and C7—H···O1 = 3.560 Å (-2 + x, 1 - y, -3/2 + z). The molecules have an elongated shape and their orientation is almost parallel with the 2a + c vector, being inclined at an angle of 7.3°. Such a tendency for parallel arrangement is also seen in the structure of the di-p-tolyl terephtalate (Ciajolo et al., 1991) derivative, but not in the structures of dimethyl (Brisse & Pérez, 1976) and diethyl (Bailey, 1949; Hašek et al., 1982) esters.