In the title compound, methyl 4-(3-formyl-2,4-dihydroxy-6-methyl-benzoyloxy)-2-hydroxy-3,6-dimethylbenzoate, C
19H
18O
8, there are three intramolecular O—H
O hydrogen bonds, with lengths 2.5515 (14), 2.5711 (15), and 2.5437 (13) Å. The two aromatic rings form a dihedral angle of 60.38 (3)°, differing from that in the previously reported
Pbca polymorph,
viz. 84 (1)°.
Supporting information
CCDC reference: 193756
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.002 Å
- R factor = 0.050
- wR factor = 0.137
- Data-to-parameter ratio = 22.3
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Data collection: COLLECT (Nonius, 1999); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL 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.
Methyl 4-(3-formyl-2,4-dihydroxy-6-methyl-benzoyloxy)-2-hydroxy-
3,6-dimethyl-benzoate
top
Crystal data top
C19H18O8 | F(000) = 784 |
Mr = 374.33 | Dx = 1.484 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5466 reflections |
a = 10.929 (3) Å | θ = 2.5–32.0° |
b = 10.976 (3) Å | µ = 0.12 mm−1 |
c = 14.843 (3) Å | T = 120 K |
β = 109.745 (12)° | Prism, colorless |
V = 1675.7 (7) Å3 | 0.40 × 0.30 × 0.15 mm |
Z = 4 | |
Data collection top
KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer | 4257 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.025 |
Graphite monochromator | θmax = 32.0°, θmin = 2.7° |
ω scans with κ offsets | h = −16→16 |
21781 measured reflections | k = −16→15 |
5796 independent reflections | l = −22→22 |
Refinement top
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.137 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0551P)2 + 0.7055P] where P = (Fo2 + 2Fc2)/3 |
5796 reflections | (Δ/σ)max < 0.001 |
260 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.00936 (9) | 0.22817 (10) | 0.12734 (7) | 0.0280 (2) | |
O2 | 0.28830 (10) | 0.07016 (9) | 0.03346 (7) | 0.0248 (2) | |
H2O | 0.2043 (19) | 0.0886 (17) | 0.0052 (14) | 0.037* | |
O3 | 0.05911 (10) | 0.15003 (10) | 0.00532 (7) | 0.0294 (2) | |
O4 | 0.61784 (8) | 0.15025 (9) | 0.32857 (6) | 0.0216 (2) | |
O5 | 0.56142 (9) | 0.04303 (10) | 0.43694 (7) | 0.0277 (2) | |
O6 | 1.16021 (9) | 0.12662 (10) | 0.66952 (7) | 0.0274 (2) | |
H6O | 1.1607 (19) | 0.0925 (18) | 0.7251 (15) | 0.041* | |
O7 | 0.72501 (9) | 0.00250 (9) | 0.60260 (7) | 0.0240 (2) | |
H7O | 0.6519 (19) | 0.0059 (17) | 0.5546 (14) | 0.036* | |
O8 | 1.08114 (10) | 0.02204 (10) | 0.79484 (7) | 0.0299 (2) | |
C1 | 0.48601 (11) | 0.15799 (12) | 0.26991 (8) | 0.0182 (2) | |
C2 | 0.40202 (12) | 0.22551 (12) | 0.30214 (8) | 0.0199 (2) | |
H2 | 0.4331 | 0.2625 | 0.3636 | 0.024* | |
C3 | 0.27324 (12) | 0.23953 (12) | 0.24560 (8) | 0.0186 (2) | |
C4 | 0.23023 (11) | 0.18357 (11) | 0.15373 (8) | 0.0177 (2) | |
C5 | 0.32103 (12) | 0.12114 (11) | 0.12148 (8) | 0.0185 (2) | |
C6 | 0.45190 (12) | 0.10629 (11) | 0.18017 (9) | 0.0189 (2) | |
C7 | 0.54606 (14) | 0.03773 (14) | 0.14543 (11) | 0.0289 (3) | |
H7A | 0.5891 | 0.0945 | 0.1148 | 0.043* | |
H7B | 0.4992 | −0.0242 | 0.0990 | 0.043* | |
H7C | 0.6114 | −0.0019 | 0.1998 | 0.043* | |
C8 | 0.18933 (13) | 0.31664 (14) | 0.28570 (10) | 0.0275 (3) | |
H8A | 0.1257 | 0.2647 | 0.3005 | 0.041* | |
H8B | 0.1437 | 0.3781 | 0.2384 | 0.041* | |
H8C | 0.2441 | 0.3572 | 0.3443 | 0.041* | |
C9 | 0.09397 (12) | 0.18620 (12) | 0.08857 (9) | 0.0203 (2) | |
C10 | −0.12623 (13) | 0.22889 (16) | 0.06652 (11) | 0.0325 (3) | |
H10A | −0.1369 | 0.2810 | 0.0107 | 0.049* | |
H10B | −0.1797 | 0.2605 | 0.1027 | 0.049* | |
H10C | −0.1537 | 0.1457 | 0.0451 | 0.049* | |
C11 | 0.64570 (12) | 0.09578 (11) | 0.41488 (9) | 0.0186 (2) | |
C12 | 0.78207 (11) | 0.10492 (11) | 0.47735 (8) | 0.0163 (2) | |
C13 | 0.81263 (12) | 0.05667 (11) | 0.57094 (8) | 0.0172 (2) | |
C14 | 0.94016 (12) | 0.06362 (11) | 0.63768 (9) | 0.0185 (2) | |
C15 | 1.03717 (12) | 0.11816 (12) | 0.60878 (9) | 0.0197 (2) | |
C16 | 1.00832 (12) | 0.16495 (12) | 0.51672 (9) | 0.0199 (2) | |
H16 | 1.0755 | 0.2010 | 0.4986 | 0.024* | |
C17 | 0.88335 (12) | 0.15983 (11) | 0.45121 (9) | 0.0181 (2) | |
C18 | 0.86281 (13) | 0.21517 (14) | 0.35434 (9) | 0.0256 (3) | |
H18A | 0.9466 | 0.2417 | 0.3506 | 0.038* | |
H18B | 0.8045 | 0.2855 | 0.3449 | 0.038* | |
H18C | 0.8240 | 0.1544 | 0.3045 | 0.038* | |
C19 | 0.97066 (13) | 0.01870 (13) | 0.73465 (9) | 0.0237 (3) | |
H19 | 0.9011 (17) | −0.0163 (16) | 0.7525 (12) | 0.028* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0149 (4) | 0.0405 (6) | 0.0255 (5) | 0.0023 (4) | 0.0026 (4) | −0.0024 (4) |
O2 | 0.0237 (5) | 0.0279 (5) | 0.0187 (4) | 0.0030 (4) | 0.0018 (4) | −0.0059 (4) |
O3 | 0.0236 (5) | 0.0391 (6) | 0.0192 (4) | 0.0040 (4) | −0.0012 (4) | −0.0018 (4) |
O4 | 0.0131 (4) | 0.0316 (5) | 0.0180 (4) | −0.0019 (3) | 0.0024 (3) | 0.0060 (4) |
O5 | 0.0158 (4) | 0.0371 (6) | 0.0268 (5) | −0.0050 (4) | 0.0028 (4) | 0.0116 (4) |
O6 | 0.0158 (4) | 0.0377 (6) | 0.0233 (5) | −0.0030 (4) | −0.0003 (4) | −0.0010 (4) |
O7 | 0.0181 (4) | 0.0317 (5) | 0.0207 (4) | −0.0035 (4) | 0.0045 (4) | 0.0069 (4) |
O8 | 0.0259 (5) | 0.0355 (6) | 0.0219 (4) | 0.0043 (4) | −0.0003 (4) | 0.0014 (4) |
C1 | 0.0134 (5) | 0.0219 (6) | 0.0174 (5) | −0.0014 (4) | 0.0025 (4) | 0.0046 (4) |
C2 | 0.0189 (6) | 0.0245 (6) | 0.0152 (5) | −0.0025 (5) | 0.0045 (4) | 0.0008 (4) |
C3 | 0.0176 (5) | 0.0214 (6) | 0.0171 (5) | −0.0005 (4) | 0.0061 (4) | 0.0011 (4) |
C4 | 0.0159 (5) | 0.0185 (5) | 0.0166 (5) | 0.0003 (4) | 0.0028 (4) | 0.0026 (4) |
C5 | 0.0207 (6) | 0.0176 (5) | 0.0161 (5) | −0.0006 (4) | 0.0047 (4) | 0.0008 (4) |
C6 | 0.0187 (6) | 0.0174 (5) | 0.0198 (5) | 0.0008 (4) | 0.0052 (4) | 0.0023 (4) |
C7 | 0.0257 (7) | 0.0302 (7) | 0.0312 (7) | 0.0082 (6) | 0.0104 (6) | −0.0001 (6) |
C8 | 0.0230 (6) | 0.0368 (8) | 0.0227 (6) | 0.0035 (6) | 0.0078 (5) | −0.0048 (6) |
C9 | 0.0182 (6) | 0.0201 (6) | 0.0203 (5) | 0.0009 (5) | 0.0035 (4) | 0.0048 (5) |
C10 | 0.0160 (6) | 0.0433 (9) | 0.0336 (7) | 0.0030 (6) | 0.0023 (5) | 0.0008 (6) |
C11 | 0.0164 (5) | 0.0200 (6) | 0.0186 (5) | −0.0002 (4) | 0.0048 (4) | 0.0024 (4) |
C12 | 0.0137 (5) | 0.0171 (5) | 0.0170 (5) | 0.0000 (4) | 0.0037 (4) | 0.0008 (4) |
C13 | 0.0162 (5) | 0.0166 (5) | 0.0189 (5) | −0.0004 (4) | 0.0058 (4) | −0.0002 (4) |
C14 | 0.0178 (5) | 0.0185 (6) | 0.0176 (5) | 0.0013 (4) | 0.0041 (4) | −0.0001 (4) |
C15 | 0.0144 (5) | 0.0205 (6) | 0.0213 (5) | −0.0002 (4) | 0.0023 (4) | −0.0045 (5) |
C16 | 0.0154 (5) | 0.0214 (6) | 0.0233 (6) | −0.0025 (4) | 0.0068 (5) | −0.0014 (5) |
C17 | 0.0172 (5) | 0.0173 (5) | 0.0202 (5) | 0.0007 (4) | 0.0068 (4) | 0.0004 (4) |
C18 | 0.0173 (6) | 0.0346 (7) | 0.0246 (6) | −0.0032 (5) | 0.0069 (5) | 0.0076 (5) |
C19 | 0.0230 (6) | 0.0250 (6) | 0.0205 (6) | 0.0028 (5) | 0.0040 (5) | 0.0021 (5) |
Geometric parameters (Å, º) top
O1—C9 | 1.3260 (16) | C7—H7A | 0.9800 |
O1—C10 | 1.4515 (16) | C7—H7B | 0.9800 |
O2—C5 | 1.3536 (15) | C7—H7C | 0.9800 |
O2—H2O | 0.89 (2) | C8—H8A | 0.9800 |
O3—C9 | 1.2294 (16) | C8—H8B | 0.9800 |
O4—C11 | 1.3520 (15) | C8—H8C | 0.9800 |
O4—C1 | 1.4119 (14) | C10—H10A | 0.9800 |
O5—C11 | 1.2225 (15) | C10—H10B | 0.9800 |
O6—C15 | 1.3456 (15) | C10—H10C | 0.9800 |
O6—H6O | 0.90 (2) | C11—C12 | 1.4688 (16) |
O7—C13 | 1.3398 (15) | C12—C13 | 1.4172 (16) |
O7—H7O | 0.87 (2) | C12—C17 | 1.4244 (17) |
O8—C19 | 1.2363 (16) | C13—C14 | 1.4131 (17) |
C1—C6 | 1.3783 (17) | C14—C15 | 1.4050 (18) |
C1—C2 | 1.3847 (18) | C14—C19 | 1.4497 (17) |
C2—C3 | 1.3823 (17) | C15—C16 | 1.3926 (18) |
C2—H2 | 0.9500 | C16—C17 | 1.3844 (17) |
C3—C4 | 1.4230 (17) | C16—H16 | 0.9500 |
C3—C8 | 1.5099 (18) | C17—C18 | 1.5063 (17) |
C4—C5 | 1.4158 (17) | C18—H18A | 0.9800 |
C4—C9 | 1.4767 (16) | C18—H18B | 0.9800 |
C5—C6 | 1.4104 (17) | C18—H18C | 0.9800 |
C6—C7 | 1.4998 (18) | C19—H19 | 0.966 (18) |
| | | |
C9—O1—C10 | 116.55 (11) | O1—C9—C4 | 114.79 (11) |
C5—O2—H2O | 104.7 (12) | O1—C10—H10A | 109.5 |
C11—O4—C1 | 117.86 (9) | O1—C10—H10B | 109.5 |
C15—O6—H6O | 106.2 (13) | H10A—C10—H10B | 109.5 |
C13—O7—H7O | 105.0 (13) | O1—C10—H10C | 109.5 |
C6—C1—C2 | 124.04 (11) | H10A—C10—H10C | 109.5 |
C6—C1—O4 | 117.24 (11) | H10B—C10—H10C | 109.5 |
C2—C1—O4 | 118.46 (11) | O5—C11—O4 | 120.96 (11) |
C3—C2—C1 | 120.51 (11) | O5—C11—C12 | 123.98 (11) |
C3—C2—H2 | 119.7 | O4—C11—C12 | 115.06 (10) |
C1—C2—H2 | 119.7 | C13—C12—C17 | 118.53 (11) |
C2—C3—C4 | 118.21 (11) | C13—C12—C11 | 116.49 (10) |
C2—C3—C8 | 116.90 (11) | C17—C12—C11 | 124.97 (11) |
C4—C3—C8 | 124.87 (11) | O7—C13—C14 | 115.50 (10) |
C5—C4—C3 | 119.39 (11) | O7—C13—C12 | 123.37 (11) |
C5—C4—C9 | 117.05 (11) | C14—C13—C12 | 121.13 (11) |
C3—C4—C9 | 123.56 (11) | C15—C14—C13 | 118.44 (11) |
O2—C5—C6 | 115.51 (11) | C15—C14—C19 | 120.26 (11) |
O2—C5—C4 | 122.66 (11) | C13—C14—C19 | 121.28 (11) |
C6—C5—C4 | 121.83 (11) | O6—C15—C16 | 118.41 (11) |
C1—C6—C5 | 115.86 (11) | O6—C15—C14 | 120.74 (11) |
C1—C6—C7 | 123.08 (11) | C16—C15—C14 | 120.85 (11) |
C5—C6—C7 | 121.06 (11) | C17—C16—C15 | 121.12 (11) |
C6—C7—H7A | 109.5 | C17—C16—H16 | 119.4 |
C6—C7—H7B | 109.5 | C15—C16—H16 | 119.4 |
H7A—C7—H7B | 109.5 | C16—C17—C12 | 119.93 (11) |
C6—C7—H7C | 109.5 | C16—C17—C18 | 116.59 (11) |
H7A—C7—H7C | 109.5 | C12—C17—C18 | 123.48 (11) |
H7B—C7—H7C | 109.5 | C17—C18—H18A | 109.5 |
C3—C8—H8A | 109.5 | C17—C18—H18B | 109.5 |
C3—C8—H8B | 109.5 | H18A—C18—H18B | 109.5 |
H8A—C8—H8B | 109.5 | C17—C18—H18C | 109.5 |
C3—C8—H8C | 109.5 | H18A—C18—H18C | 109.5 |
H8A—C8—H8C | 109.5 | H18B—C18—H18C | 109.5 |
H8B—C8—H8C | 109.5 | O8—C19—C14 | 123.25 (13) |
O3—C9—O1 | 121.58 (12) | O8—C19—H19 | 118.7 (10) |
O3—C9—C4 | 123.61 (12) | C14—C19—H19 | 118.0 (10) |
| | | |
C11—O4—C1—C6 | −122.35 (13) | C1—O4—C11—O5 | 8.02 (18) |
C11—O4—C1—C2 | 63.23 (15) | C1—O4—C11—C12 | −172.30 (11) |
C6—C1—C2—C3 | 3.5 (2) | O5—C11—C12—C13 | −4.84 (19) |
O4—C1—C2—C3 | 177.52 (11) | O4—C11—C12—C13 | 175.49 (11) |
C1—C2—C3—C4 | −0.42 (18) | O5—C11—C12—C17 | 176.26 (13) |
C1—C2—C3—C8 | −178.85 (12) | O4—C11—C12—C17 | −3.41 (18) |
C2—C3—C4—C5 | −3.11 (18) | C17—C12—C13—O7 | −179.56 (11) |
C8—C3—C4—C5 | 175.18 (12) | C11—C12—C13—O7 | 1.46 (18) |
C2—C3—C4—C9 | 176.71 (12) | C17—C12—C13—C14 | 0.67 (18) |
C8—C3—C4—C9 | −5.0 (2) | C11—C12—C13—C14 | −178.30 (11) |
C3—C4—C5—O2 | −177.17 (11) | O7—C13—C14—C15 | 179.32 (11) |
C9—C4—C5—O2 | 3.00 (18) | C12—C13—C14—C15 | −0.90 (18) |
C3—C4—C5—C6 | 3.92 (18) | O7—C13—C14—C19 | −2.26 (18) |
C9—C4—C5—C6 | −175.91 (11) | C12—C13—C14—C19 | 177.52 (12) |
C2—C1—C6—C5 | −2.70 (18) | C13—C14—C15—O6 | −179.76 (11) |
O4—C1—C6—C5 | −176.78 (11) | C19—C14—C15—O6 | 1.80 (19) |
C2—C1—C6—C7 | 177.47 (13) | C13—C14—C15—C16 | 0.37 (18) |
O4—C1—C6—C7 | 3.39 (18) | C19—C14—C15—C16 | −178.07 (12) |
O2—C5—C6—C1 | 179.97 (11) | O6—C15—C16—C17 | −179.49 (12) |
C4—C5—C6—C1 | −1.05 (18) | C14—C15—C16—C17 | 0.38 (19) |
O2—C5—C6—C7 | −0.19 (18) | C15—C16—C17—C12 | −0.61 (19) |
C4—C5—C6—C7 | 178.79 (12) | C15—C16—C17—C18 | 178.97 (12) |
C10—O1—C9—O3 | 0.13 (19) | C13—C12—C17—C16 | 0.09 (18) |
C10—O1—C9—C4 | −178.22 (12) | C11—C12—C17—C16 | 178.97 (12) |
C5—C4—C9—O3 | −8.62 (19) | C13—C12—C17—C18 | −179.46 (12) |
C3—C4—C9—O3 | 171.55 (13) | C11—C12—C17—C18 | −0.6 (2) |
C5—C4—C9—O1 | 169.70 (11) | C15—C14—C19—O8 | −2.3 (2) |
C3—C4—C9—O1 | −10.13 (18) | C13—C14—C19—O8 | 179.28 (13) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O3 | 0.89 (2) | 1.72 (2) | 2.5515 (14) | 152.5 (18) |
O6—H6O···O8 | 0.90 (2) | 1.74 (2) | 2.5711 (15) | 151.1 (18) |
O7—H7O···O5 | 0.87 (2) | 1.74 (2) | 2.5437 (13) | 151.9 (18) |
O7—H7O···O5i | 0.87 (2) | 2.437 (19) | 3.0251 (14) | 125.1 (16) |
Symmetry code: (i) −x+1, −y, −z+1. |