Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106042211/sk3066sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106042211/sk3066Isup2.hkl |
CCDC reference: 633172
The title compound was synthesized according the method described by Rafart et al. (1976). Our procedure differed from the original one by using pyridine (ABS.) instead of triethylamine in benzene. Single crystals suitable for X-ray diffractions were obtained from a concentrated dichloromethane solution of (I). 1H NMR (250.13 MHz, CDCl3, p.p.m.): δ 8.0 (m, 2H, aromatic H atoms), 7.6 (m, 2H, aromatic H atoms), 7.6 (s br, 1H, OH), 2.80 (m, 2H, CH2), 2.65 (m, 2H, CH2), 2.11 (s, 3H, CH3). 13C NMR (CDCl3, p.p.m.): δ 77.04, 208.5, 184.5, 181.0 (C═ O), 153.5, 132.7, 129.4, 122.7 (C), 134.8, 132.9, 126.6, 126.1 (CH2), 41.6, 29.5, 17.8 (CH3).
The collected frames during data collection did not show split reflections, but only 63% of the reflections used for cell determination could be indexed. For the remaining 37% no cell could be found at all. This is a warning sign for twinning. Nevertheless, the reflections were integrated the usual way. The cell parameters of (I) ostensibly indicate a monoclinic cell, since two angles are almost rectangular. Rint for the monoclinic crystal system is 0.17 (compared with 0.082 for the triclinic crystal system). However, there are no systematic extinctions and the structure cannot be solved in any of the monoclinic space groups. Thus, the structure was solved in the triclinic space group P1. After having encountered severe problems during structure solution, anisotropic refinement remained stalled at R1 = 0.14. It was therefore assumed that the crystal was twinned and a test for twinning using the program PLATON (Spek, 2003) yielded three twin matrices: (a) (100/010/ −0.132 − 0.243 1), (b) (100/010/0 0.25 1), (c) (100/010/001). The twin laws (a) and (b) define more or less arbitrarily grown together domains. The twin law (c) is a twofold rotation operation which is usually not present in the triclinic crystal system, but which is possible in the present case because two cell angles are almost 90°. On the basis of these twin laws, PLATON was used to generate a file containing the original data and the additional reflections. For refinement the data were read in via HKLF5 and three additional variables were introduced (using the BASF command) describing the fractional contributions of the twin components. Applying these twin laws provided the ultimate success (R1 dropped below 0.1). All H atoms could now be located by difference Fourier synthesis. They were refined with fixed individual displacement parameters [Uiso(H) = 1.2Ueq(C,O) or Uiso(H) = 1.5Ueq(Cmethyl)] using a riding model, with O—H distances of 0.84 Å, and C—H distances of 0.95 (aromatic), 0.98 (methyl) or 0.99 Å (methylene). The hydroxyl groups and methyl groups were allowed to rotate but not to tip. The twin ratios of the minor components refined to 0.101 (3) for (a), 0.120 (4) for (b) and 0.027 (2) for (c). Although the contribution of the domain (c) might be rather small, neglecting it leads to significantly worse figures of merit (wR2 = 0.2989, R1 = 0.0974).
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.
C14H12O4 | Z = 4 |
Mr = 244.24 | F(000) = 512 |
Triclinic, P1 | Dx = 1.445 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.7858 (7) Å | Cell parameters from 7890 reflections |
b = 9.2295 (15) Å | θ = 1.6–26.0° |
c = 25.447 (3) Å | µ = 0.11 mm−1 |
α = 87.469 (12)° | T = 173 K |
β = 89.288 (11)° | Needle, light brown |
γ = 89.931 (12)° | 0.33 × 0.09 × 0.09 mm |
V = 1122.8 (3) Å3 |
Stoe IPDS II two-circle diffractometer | 3038 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.082 |
Graphite monochromator | θmax = 25.7°, θmin = 1.6° |
ω scans | h = −5→5 |
9193 measured reflections | k = −11→11 |
4166 independent reflections | l = −30→30 |
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)] = 0.087 | H-atom parameters constrained |
wR(F2) = 0.282 | w = 1/[σ2(Fo2) + (0.164P)2 + 0.9504P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
4166 reflections | Δρmax = 0.37 e Å−3 |
333 parameters | Δρmin = −0.35 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.053 (13) |
C14H12O4 | γ = 89.931 (12)° |
Mr = 244.24 | V = 1122.8 (3) Å3 |
Triclinic, P1 | Z = 4 |
a = 4.7858 (7) Å | Mo Kα radiation |
b = 9.2295 (15) Å | µ = 0.11 mm−1 |
c = 25.447 (3) Å | T = 173 K |
α = 87.469 (12)° | 0.33 × 0.09 × 0.09 mm |
β = 89.288 (11)° |
Stoe IPDS II two-circle diffractometer | 3038 reflections with I > 2σ(I) |
9193 measured reflections | Rint = 0.082 |
4166 independent reflections |
R[F2 > 2σ(F2)] = 0.087 | 0 restraints |
wR(F2) = 0.282 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.37 e Å−3 |
4166 reflections | Δρmin = −0.35 e Å−3 |
333 parameters |
Experimental. |
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 | 0.6093 (8) | 0.9738 (4) | 0.08562 (13) | 0.0382 (9) | |
O2 | 0.6953 (8) | 0.8991 (4) | 0.18670 (12) | 0.0401 (9) | |
H2 | 0.7533 | 0.9703 | 0.1680 | 0.048* | |
O3 | 0.4090 (8) | 0.6518 (5) | 0.35302 (13) | 0.0437 (10) | |
O4 | −0.0042 (9) | 0.5452 (4) | 0.17603 (13) | 0.0435 (9) | |
C1 | 0.4600 (10) | 0.8771 (6) | 0.10429 (17) | 0.0324 (11) | |
C2 | 0.4985 (10) | 0.8274 (5) | 0.16030 (16) | 0.0307 (10) | |
C3 | 0.3482 (11) | 0.7197 (5) | 0.18460 (17) | 0.0340 (11) | |
C4 | 0.1339 (11) | 0.6444 (5) | 0.15533 (17) | 0.0314 (10) | |
C5 | 0.0908 (11) | 0.6894 (5) | 0.09823 (17) | 0.0310 (10) | |
C6 | 0.2458 (10) | 0.8036 (6) | 0.07427 (17) | 0.0320 (11) | |
C7 | 0.1989 (11) | 0.8459 (6) | 0.02157 (17) | 0.0356 (11) | |
H7 | 0.3013 | 0.9242 | 0.0053 | 0.043* | |
C8 | 0.0017 (11) | 0.7727 (6) | −0.00675 (18) | 0.0379 (12) | |
H8 | −0.0281 | 0.8003 | −0.0427 | 0.045* | |
C9 | −0.1509 (12) | 0.6608 (6) | 0.01658 (19) | 0.0393 (12) | |
H9 | −0.2872 | 0.6124 | −0.0031 | 0.047* | |
C10 | −0.1056 (11) | 0.6178 (6) | 0.06952 (19) | 0.0374 (11) | |
H10 | −0.2096 | 0.5398 | 0.0855 | 0.045* | |
C31 | 0.3864 (12) | 0.6761 (6) | 0.24212 (17) | 0.0357 (11) | |
H31A | 0.5876 | 0.6779 | 0.2506 | 0.043* | |
H31B | 0.3173 | 0.5759 | 0.2490 | 0.043* | |
C32 | 0.2278 (12) | 0.7789 (6) | 0.27691 (17) | 0.0363 (11) | |
H32A | 0.2991 | 0.8784 | 0.2695 | 0.044* | |
H32B | 0.0282 | 0.7781 | 0.2672 | 0.044* | |
C33 | 0.2483 (10) | 0.7440 (6) | 0.33507 (17) | 0.0321 (11) | |
C34 | 0.0563 (12) | 0.8259 (6) | 0.36983 (18) | 0.0391 (12) | |
H34A | −0.0763 | 0.7585 | 0.3875 | 0.059* | |
H34B | −0.0463 | 0.8988 | 0.3485 | 0.059* | |
H34C | 0.1656 | 0.8742 | 0.3963 | 0.059* | |
O1A | −0.1055 (8) | 0.4935 (4) | 0.41527 (12) | 0.0373 (9) | |
O2A | −0.2110 (8) | 0.4374 (4) | 0.31561 (12) | 0.0378 (9) | |
H2A | −0.2656 | 0.5052 | 0.3342 | 0.045* | |
O3A | 0.0813 (9) | 0.1315 (5) | 0.15442 (13) | 0.0451 (10) | |
O4A | 0.4890 (8) | 0.0784 (4) | 0.32580 (12) | 0.0376 (9) | |
C1A | 0.0390 (10) | 0.3986 (5) | 0.39659 (16) | 0.0299 (10) | |
C2A | −0.0096 (10) | 0.3620 (5) | 0.34087 (16) | 0.0304 (10) | |
C3A | 0.1361 (11) | 0.2564 (6) | 0.31679 (17) | 0.0324 (11) | |
C4A | 0.3537 (10) | 0.1747 (5) | 0.34637 (17) | 0.0302 (10) | |
C5A | 0.4076 (10) | 0.2101 (6) | 0.40235 (17) | 0.0306 (10) | |
C6A | 0.2572 (10) | 0.3200 (6) | 0.42577 (16) | 0.0312 (11) | |
C7A | 0.3103 (11) | 0.3498 (6) | 0.47863 (17) | 0.0342 (11) | |
H7A | 0.2071 | 0.4233 | 0.4953 | 0.041* | |
C8A | 0.5126 (11) | 0.2721 (6) | 0.50620 (18) | 0.0373 (12) | |
H8A | 0.5498 | 0.2939 | 0.5416 | 0.045* | |
C9A | 0.6604 (12) | 0.1638 (6) | 0.48296 (19) | 0.0393 (12) | |
H9A | 0.7977 | 0.1108 | 0.5024 | 0.047* | |
C10A | 0.6099 (11) | 0.1314 (6) | 0.43085 (18) | 0.0351 (11) | |
H10A | 0.7121 | 0.0564 | 0.4149 | 0.042* | |
C31A | 0.0764 (10) | 0.2156 (6) | 0.26093 (17) | 0.0332 (11) | |
H31C | −0.0852 | 0.2728 | 0.2477 | 0.040* | |
H31D | 0.0245 | 0.1118 | 0.2611 | 0.040* | |
C32A | 0.3254 (10) | 0.2420 (6) | 0.22347 (17) | 0.0332 (11) | |
H32C | 0.3865 | 0.3441 | 0.2255 | 0.040* | |
H32D | 0.4822 | 0.1792 | 0.2354 | 0.040* | |
C33A | 0.2647 (10) | 0.2130 (6) | 0.16698 (18) | 0.0326 (11) | |
C34A | 0.4464 (12) | 0.2906 (6) | 0.12637 (18) | 0.0394 (12) | |
H34D | 0.4877 | 0.2259 | 0.0978 | 0.059* | |
H34E | 0.6213 | 0.3196 | 0.1425 | 0.059* | |
H34F | 0.3488 | 0.3770 | 0.1123 | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.041 (2) | 0.043 (2) | 0.0305 (16) | −0.0045 (17) | 0.0009 (15) | 0.0001 (15) |
O2 | 0.043 (2) | 0.050 (2) | 0.0271 (16) | −0.0040 (18) | −0.0052 (15) | 0.0005 (15) |
O3 | 0.044 (2) | 0.058 (2) | 0.0285 (16) | 0.0139 (19) | −0.0008 (15) | 0.0000 (16) |
O4 | 0.051 (2) | 0.045 (2) | 0.0340 (17) | −0.0048 (19) | −0.0010 (16) | 0.0053 (16) |
C1 | 0.032 (3) | 0.039 (3) | 0.027 (2) | 0.004 (2) | 0.0018 (18) | −0.0015 (19) |
C2 | 0.032 (3) | 0.036 (3) | 0.024 (2) | 0.004 (2) | 0.0002 (18) | −0.0019 (18) |
C3 | 0.045 (3) | 0.032 (3) | 0.025 (2) | 0.008 (2) | 0.0030 (19) | 0.0001 (18) |
C4 | 0.037 (3) | 0.031 (2) | 0.026 (2) | 0.003 (2) | 0.0036 (19) | 0.0012 (18) |
C5 | 0.034 (3) | 0.033 (2) | 0.027 (2) | 0.005 (2) | −0.0011 (18) | −0.0017 (18) |
C6 | 0.033 (3) | 0.037 (3) | 0.026 (2) | 0.005 (2) | −0.0022 (18) | 0.0021 (19) |
C7 | 0.040 (3) | 0.044 (3) | 0.022 (2) | 0.002 (2) | 0.0005 (19) | 0.0029 (19) |
C8 | 0.038 (3) | 0.049 (3) | 0.026 (2) | 0.001 (2) | −0.0040 (19) | −0.004 (2) |
C9 | 0.041 (3) | 0.046 (3) | 0.031 (2) | −0.002 (2) | −0.005 (2) | −0.009 (2) |
C10 | 0.038 (3) | 0.039 (3) | 0.035 (2) | −0.003 (2) | 0.003 (2) | −0.002 (2) |
C31 | 0.041 (3) | 0.041 (3) | 0.024 (2) | 0.004 (2) | −0.0037 (19) | 0.0012 (19) |
C32 | 0.045 (3) | 0.039 (3) | 0.025 (2) | 0.006 (2) | −0.0030 (19) | −0.0016 (19) |
C33 | 0.034 (3) | 0.036 (3) | 0.026 (2) | 0.001 (2) | −0.0037 (18) | −0.0004 (18) |
C34 | 0.046 (3) | 0.044 (3) | 0.027 (2) | 0.008 (2) | 0.002 (2) | −0.001 (2) |
O1A | 0.040 (2) | 0.044 (2) | 0.0287 (16) | 0.0078 (17) | 0.0017 (14) | −0.0033 (15) |
O2A | 0.037 (2) | 0.049 (2) | 0.0280 (16) | 0.0125 (17) | −0.0028 (14) | −0.0042 (15) |
O3A | 0.044 (2) | 0.059 (3) | 0.0329 (17) | −0.011 (2) | −0.0038 (16) | −0.0103 (17) |
O4A | 0.044 (2) | 0.039 (2) | 0.0297 (16) | 0.0082 (17) | −0.0009 (14) | −0.0048 (14) |
C1A | 0.030 (2) | 0.037 (3) | 0.024 (2) | −0.001 (2) | 0.0009 (17) | −0.0036 (18) |
C2A | 0.031 (3) | 0.038 (3) | 0.022 (2) | −0.002 (2) | −0.0016 (18) | −0.0016 (18) |
C3A | 0.032 (3) | 0.040 (3) | 0.026 (2) | −0.002 (2) | 0.0016 (18) | −0.0047 (19) |
C4A | 0.030 (2) | 0.033 (2) | 0.027 (2) | −0.003 (2) | 0.0011 (18) | −0.0054 (18) |
C5A | 0.030 (3) | 0.038 (3) | 0.023 (2) | −0.003 (2) | 0.0007 (18) | −0.0027 (18) |
C6A | 0.034 (3) | 0.038 (3) | 0.022 (2) | −0.001 (2) | 0.0004 (18) | −0.0009 (18) |
C7A | 0.041 (3) | 0.039 (3) | 0.023 (2) | 0.003 (2) | 0.0007 (19) | −0.0060 (19) |
C8A | 0.038 (3) | 0.048 (3) | 0.026 (2) | 0.000 (2) | −0.0022 (19) | −0.003 (2) |
C9A | 0.043 (3) | 0.047 (3) | 0.028 (2) | 0.002 (2) | −0.005 (2) | 0.001 (2) |
C10A | 0.038 (3) | 0.039 (3) | 0.028 (2) | 0.005 (2) | 0.0014 (19) | −0.0039 (19) |
C31A | 0.029 (3) | 0.045 (3) | 0.026 (2) | −0.003 (2) | −0.0041 (18) | −0.0078 (19) |
C32A | 0.031 (3) | 0.043 (3) | 0.026 (2) | −0.001 (2) | −0.0033 (18) | −0.0036 (19) |
C33A | 0.032 (3) | 0.038 (3) | 0.028 (2) | 0.000 (2) | −0.0024 (18) | −0.0035 (19) |
C34A | 0.042 (3) | 0.048 (3) | 0.028 (2) | 0.001 (2) | 0.000 (2) | 0.000 (2) |
O1—C1 | 1.220 (6) | O1A—C1A | 1.224 (6) |
O2—C2 | 1.354 (6) | O2A—C2A | 1.342 (6) |
O2—H2 | 0.8400 | O2A—H2A | 0.8400 |
O3—C33 | 1.223 (6) | O3A—C33A | 1.212 (6) |
O4—C4 | 1.225 (6) | O4A—C4A | 1.231 (6) |
C1—C6 | 1.471 (7) | C1A—C6A | 1.462 (7) |
C1—C2 | 1.491 (6) | C1A—C2A | 1.493 (6) |
C2—C3 | 1.351 (7) | C2A—C3A | 1.360 (7) |
C3—C4 | 1.469 (7) | C3A—C4A | 1.479 (7) |
C3—C31 | 1.514 (6) | C3A—C31A | 1.517 (6) |
C4—C5 | 1.510 (6) | C4A—C5A | 1.501 (6) |
C5—C10 | 1.384 (7) | C5A—C6A | 1.393 (7) |
C5—C6 | 1.402 (7) | C5A—C10A | 1.400 (7) |
C6—C7 | 1.401 (6) | C6A—C7A | 1.411 (6) |
C7—C8 | 1.389 (8) | C7A—C8A | 1.384 (7) |
C7—H7 | 0.9500 | C7A—H7A | 0.9500 |
C8—C9 | 1.375 (8) | C8A—C9A | 1.374 (8) |
C8—H8 | 0.9500 | C8A—H8A | 0.9500 |
C9—C10 | 1.407 (7) | C9A—C10A | 1.396 (7) |
C9—H9 | 0.9500 | C9A—H9A | 0.9500 |
C10—H10 | 0.9500 | C10A—H10A | 0.9500 |
C31—C32 | 1.522 (7) | C31A—C32A | 1.530 (7) |
C31—H31A | 0.9900 | C31A—H31C | 0.9900 |
C31—H31B | 0.9900 | C31A—H31D | 0.9900 |
C32—C33 | 1.505 (6) | C32A—C33A | 1.506 (6) |
C32—H32A | 0.9900 | C32A—H32C | 0.9900 |
C32—H32B | 0.9900 | C32A—H32D | 0.9900 |
C33—C34 | 1.495 (7) | C33A—C34A | 1.500 (7) |
C34—H34A | 0.9800 | C34A—H34D | 0.9800 |
C34—H34B | 0.9800 | C34A—H34E | 0.9800 |
C34—H34C | 0.9800 | C34A—H34F | 0.9800 |
C2—O2—H2 | 109.5 | C2A—O2A—H2A | 109.5 |
O1—C1—C6 | 123.6 (4) | O1A—C1A—C6A | 123.6 (4) |
O1—C1—C2 | 118.8 (4) | O1A—C1A—C2A | 118.1 (4) |
C6—C1—C2 | 117.5 (4) | C6A—C1A—C2A | 118.3 (4) |
C3—C2—O2 | 120.6 (4) | O2A—C2A—C3A | 121.1 (4) |
C3—C2—C1 | 123.7 (4) | O2A—C2A—C1A | 116.2 (4) |
O2—C2—C1 | 115.6 (4) | C3A—C2A—C1A | 122.6 (4) |
C2—C3—C4 | 119.7 (4) | C2A—C3A—C4A | 119.3 (4) |
C2—C3—C31 | 122.1 (5) | C2A—C3A—C31A | 122.2 (5) |
C4—C3—C31 | 118.2 (4) | C4A—C3A—C31A | 118.5 (4) |
O4—C4—C3 | 121.4 (4) | O4A—C4A—C3A | 121.0 (4) |
O4—C4—C5 | 120.2 (4) | O4A—C4A—C5A | 120.0 (4) |
C3—C4—C5 | 118.4 (4) | C3A—C4A—C5A | 119.1 (4) |
C10—C5—C6 | 119.9 (4) | C6A—C5A—C10A | 120.3 (4) |
C10—C5—C4 | 119.5 (4) | C6A—C5A—C4A | 120.3 (4) |
C6—C5—C4 | 120.7 (4) | C10A—C5A—C4A | 119.3 (4) |
C7—C6—C5 | 119.9 (5) | C5A—C6A—C7A | 119.1 (5) |
C7—C6—C1 | 120.2 (5) | C5A—C6A—C1A | 120.3 (4) |
C5—C6—C1 | 119.9 (4) | C7A—C6A—C1A | 120.6 (4) |
C8—C7—C6 | 119.5 (5) | C8A—C7A—C6A | 120.0 (5) |
C8—C7—H7 | 120.2 | C8A—C7A—H7A | 120.0 |
C6—C7—H7 | 120.2 | C6A—C7A—H7A | 120.0 |
C9—C8—C7 | 120.7 (4) | C9A—C8A—C7A | 120.7 (4) |
C9—C8—H8 | 119.6 | C9A—C8A—H8A | 119.6 |
C7—C8—H8 | 119.6 | C7A—C8A—H8A | 119.6 |
C8—C9—C10 | 120.1 (5) | C8A—C9A—C10A | 120.3 (5) |
C8—C9—H9 | 120.0 | C8A—C9A—H9A | 119.8 |
C10—C9—H9 | 120.0 | C10A—C9A—H9A | 119.8 |
C5—C10—C9 | 119.9 (5) | C9A—C10A—C5A | 119.5 (5) |
C5—C10—H10 | 120.1 | C9A—C10A—H10A | 120.2 |
C9—C10—H10 | 120.1 | C5A—C10A—H10A | 120.2 |
C3—C31—C32 | 110.6 (4) | C3A—C31A—C32A | 113.0 (4) |
C3—C31—H31A | 109.5 | C3A—C31A—H31C | 109.0 |
C32—C31—H31A | 109.5 | C32A—C31A—H31C | 109.0 |
C3—C31—H31B | 109.5 | C3A—C31A—H31D | 109.0 |
C32—C31—H31B | 109.5 | C32A—C31A—H31D | 109.0 |
H31A—C31—H31B | 108.1 | H31C—C31A—H31D | 107.8 |
C33—C32—C31 | 115.0 (4) | C33A—C32A—C31A | 114.0 (4) |
C33—C32—H32A | 108.5 | C33A—C32A—H32C | 108.8 |
C31—C32—H32A | 108.5 | C31A—C32A—H32C | 108.8 |
C33—C32—H32B | 108.5 | C33A—C32A—H32D | 108.8 |
C31—C32—H32B | 108.5 | C31A—C32A—H32D | 108.8 |
H32A—C32—H32B | 107.5 | H32C—C32A—H32D | 107.7 |
O3—C33—C34 | 121.6 (4) | O3A—C33A—C34A | 121.2 (4) |
O3—C33—C32 | 122.1 (4) | O3A—C33A—C32A | 122.7 (4) |
C34—C33—C32 | 116.3 (4) | C34A—C33A—C32A | 116.1 (4) |
C33—C34—H34A | 109.5 | C33A—C34A—H34D | 109.5 |
C33—C34—H34B | 109.5 | C33A—C34A—H34E | 109.5 |
H34A—C34—H34B | 109.5 | H34D—C34A—H34E | 109.5 |
C33—C34—H34C | 109.5 | C33A—C34A—H34F | 109.5 |
H34A—C34—H34C | 109.5 | H34D—C34A—H34F | 109.5 |
H34B—C34—H34C | 109.5 | H34E—C34A—H34F | 109.5 |
O1—C1—C2—C3 | −178.8 (5) | O1A—C1A—C2A—O2A | 0.0 (7) |
C6—C1—C2—C3 | 0.0 (7) | C6A—C1A—C2A—O2A | −179.7 (4) |
O1—C1—C2—O2 | 2.0 (7) | O1A—C1A—C2A—C3A | −178.7 (5) |
C6—C1—C2—O2 | −179.2 (4) | C6A—C1A—C2A—C3A | 1.6 (7) |
O2—C2—C3—C4 | 179.4 (4) | O2A—C2A—C3A—C4A | −179.2 (4) |
C1—C2—C3—C4 | 0.3 (7) | C1A—C2A—C3A—C4A | −0.6 (7) |
O2—C2—C3—C31 | 1.4 (7) | O2A—C2A—C3A—C31A | −1.3 (8) |
C1—C2—C3—C31 | −177.7 (5) | C1A—C2A—C3A—C31A | 177.3 (5) |
C2—C3—C4—O4 | 179.3 (5) | C2A—C3A—C4A—O4A | 179.9 (5) |
C31—C3—C4—O4 | −2.6 (7) | C31A—C3A—C4A—O4A | 2.0 (7) |
C2—C3—C4—C5 | 0.7 (7) | C2A—C3A—C4A—C5A | 0.2 (7) |
C31—C3—C4—C5 | 178.8 (4) | C31A—C3A—C4A—C5A | −177.8 (4) |
O4—C4—C5—C10 | 0.0 (7) | O4A—C4A—C5A—C6A | 179.4 (5) |
C3—C4—C5—C10 | 178.6 (5) | C3A—C4A—C5A—C6A | −0.9 (7) |
O4—C4—C5—C6 | 179.4 (5) | O4A—C4A—C5A—C10A | −0.8 (7) |
C3—C4—C5—C6 | −2.0 (7) | C3A—C4A—C5A—C10A | 178.9 (4) |
C10—C5—C6—C7 | 0.8 (7) | C10A—C5A—C6A—C7A | −0.5 (7) |
C4—C5—C6—C7 | −178.6 (5) | C4A—C5A—C6A—C7A | 179.3 (5) |
C10—C5—C6—C1 | −178.3 (5) | C10A—C5A—C6A—C1A | −177.8 (5) |
C4—C5—C6—C1 | 2.3 (7) | C4A—C5A—C6A—C1A | 2.0 (7) |
O1—C1—C6—C7 | −1.6 (8) | O1A—C1A—C6A—C5A | 178.0 (5) |
C2—C1—C6—C7 | 179.7 (4) | C2A—C1A—C6A—C5A | −2.3 (7) |
O1—C1—C6—C5 | 177.5 (5) | O1A—C1A—C6A—C7A | 0.8 (8) |
C2—C1—C6—C5 | −1.3 (7) | C2A—C1A—C6A—C7A | −179.6 (5) |
C5—C6—C7—C8 | −1.0 (8) | C5A—C6A—C7A—C8A | 1.1 (8) |
C1—C6—C7—C8 | 178.1 (5) | C1A—C6A—C7A—C8A | 178.4 (5) |
C6—C7—C8—C9 | 1.0 (8) | C6A—C7A—C8A—C9A | −1.1 (8) |
C7—C8—C9—C10 | −0.9 (8) | C7A—C8A—C9A—C10A | 0.5 (8) |
C6—C5—C10—C9 | −0.6 (8) | C8A—C9A—C10A—C5A | 0.1 (8) |
C4—C5—C10—C9 | 178.8 (5) | C6A—C5A—C10A—C9A | −0.1 (8) |
C8—C9—C10—C5 | 0.7 (8) | C4A—C5A—C10A—C9A | −179.9 (5) |
C2—C3—C31—C32 | 80.8 (6) | C2A—C3A—C31A—C32A | 118.0 (5) |
C4—C3—C31—C32 | −97.2 (5) | C4A—C3A—C31A—C32A | −64.2 (6) |
C3—C31—C32—C33 | 179.2 (5) | C3A—C31A—C32A—C33A | −175.6 (5) |
C31—C32—C33—O3 | 9.0 (7) | C31A—C32A—C33A—O3A | −24.4 (7) |
C31—C32—C33—C34 | −169.6 (5) | C31A—C32A—C33A—C34A | 156.0 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3Ai | 0.84 | 2.18 | 2.916 (6) | 147 |
O2A—H2A···O3ii | 0.84 | 2.13 | 2.871 (5) | 148 |
O2—H2···O1 | 0.84 | 2.21 | 2.670 (5) | 114 |
O2A—H2A···O1A | 0.84 | 2.21 | 2.665 (4) | 114 |
Symmetry codes: (i) x+1, y+1, z; (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C14H12O4 |
Mr | 244.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 4.7858 (7), 9.2295 (15), 25.447 (3) |
α, β, γ (°) | 87.469 (12), 89.288 (11), 89.931 (12) |
V (Å3) | 1122.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.33 × 0.09 × 0.09 |
Data collection | |
Diffractometer | Stoe IPDS II two-circle diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9193, 4166, 3038 |
Rint | 0.082 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.087, 0.282, 1.11 |
No. of reflections | 4166 |
No. of parameters | 333 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.35 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991), SHELXL97.
C2—C3—C31—C32 | 80.8 (6) | C2A—C3A—C31A—C32A | 118.0 (5) |
C3—C31—C32—C33 | 179.2 (5) | C3A—C31A—C32A—C33A | −175.6 (5) |
C31—C32—C33—C34 | −169.6 (5) | C31A—C32A—C33A—C34A | 156.0 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3Ai | 0.84 | 2.18 | 2.916 (6) | 147 |
O2A—H2A···O3ii | 0.84 | 2.13 | 2.871 (5) | 148 |
O2—H2···O1 | 0.84 | 2.21 | 2.670 (5) | 114 |
O2A—H2A···O1A | 0.84 | 2.21 | 2.665 (4) | 114 |
Symmetry codes: (i) x+1, y+1, z; (ii) x−1, y, z. |
2-Hydroxy-3-alkyl-1,4-naphthoquinones are well known as antimalarial agents (Fieser & Heymann, 1948; Fieser & Nazer, 1967; Fieser & Schirmer, 1967). In rats they were found to cause haemolysis and renal damage (Munday et al., 1995). Recently, we have shown that this class of 1,4-naphthoquinones are also able to act as competitive inhibitors with IC50 values in the µM range in dihaem-containing membrane protein complexes (Madej, Nasiri, Hilgendorff, Schwalbe & Lancaster, 2006; Madej, Nasiri, Hilgendorff, Schwalbe, Unden & Lancaster, 2006). To possibly improve the binding affinity of the inhibitors, the alkyl side chain at the 3-position of 1,4-naphthoquinone was changed. Here, a Michael-type reaction was used for the introduction of the 3-oxobutyl residue.
The title compound, (I), was originally synthesized by the reaction of 2-hydroxy-1,4-naphthoquinone with methylvinylketone as an α,β-unsaturated ketone in the ratio 1:2 (Rafart et al., 1976). For substituted 2-hydroxy-1,4-naphthoquinone, a higher concentration of the ketone was used (Cassis et al., 1982). In the case of (I), we observed that a slight increase of methylvinylketone results in the formation of the carbon and oxygen bialkylated by-product.
A perspective view of the title compound is shown in Fig. 1. Bond lengths and angles can be regarded as normal (Cambridge Strcutural Database; Version 5.27 of November 2005, updated August 2006; Mogul Version 1.1; Allen, 2002). There are two very similar molecules in the asymmetric unit. In both independent molecules the naphthoquinone ring system is almost planar (the r.m.s. deviation for the non-H atoms is 0.120 and 0.036 Å). The oxobutyl side chain has an all-trans conformation and the mean plane through the five non-H atoms is twisted by 86.7 (3) and 71.8 (4)° with respect to the naphthoquinone ring system. This is the only difference between the two molecules in the asymmetric unit (Table 1). A least-squares fit of the ten cyclic C atoms of the two molecules gives an r.m.s. deviation of 0.013 Å (Fig. 2). The crystal packing (Fig. 3) shows that the molecules form hydrogen-bonded zigzag chains running along the b axis (Table 2). In addition to the intermolecular hydrogen bonds, an intramolecular O—H···O contact can be observed between the hydroxyl group and the adjacent carbonyl O atom (Table 2).
The crystal structure of the related hydroxynaphthoquinone, the natural product lapachone (Larsen et al., 1992), differs from (I) by a methyl group instead of a keto O atom at C33 and by a double bond between C32 and C33 instead of a single bond. Nevertheless, both molecules show similar geometrical features.