Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807017849/bt2339sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807017849/bt2339Isup2.hkl |
CCDC reference: 647584
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C)= 0.002 Å
- R factor = 0.034
- wR factor = 0.101
- Data-to-parameter ratio = 16.1
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
Compound (I) was obtained by the method of Hu et al. (2006). Crystals suitable for structure analysis were obtained by slow evaporation of a solution in a mixture of tetrafuaran and acetone (2:1 v/v) as light-brown crystalline prisms.
The hydroxyl H atoms were located in difference Fourier maps and refined isotropically, with the O—H bond restrained to 0.82 (2) Å. Carbon-bound H atoms were added in calculated positions and refined using a riding model, with
C—H = 0.93–0.98 Å, and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl). The methyl group was allowed to rotate but not to tip.
Caffeic acid and its derivatives are widely distributed in the plant kingdom (Chen et al., 1999). The compounds are known to have antiatherosclerotic, antibacterial, anti-inflammatory, antiproliferative, immunostimulatory, antioxidative, antiviral and neuroprotective properties (Son & Lewis, 2002). In a continuation of our work on the structure–activity relationship of caffeic acid derivatives, we have obtained the title light-brown crystalline compound, (I), synthesized by a one-pot method (Hu et al., 2006).
The molecular structure of (I) is illustrated in Fig. 1. The acyclic double bond is E configured. The crystal packing (Fig. 2) is stabilized by intermolecular O—H···O and C—H···O hydrogen bonds (Table 1). The molecules of the caffeic acid ester form stacks along the a axis in a head-to-head manner
to form a dimeric structure.
For related literature, see: Chen et al. (1999); Hu et al. (2006); Son & Lewis (2002).
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The structure of (I), shown with 30% probability displacement ellipsoids. | |
Fig. 2. A packing diagram for (I), showing the hydrogen-bond pattern (dashed lines). |
C12H14O4 | F(000) = 944 |
Mr = 222.23 | Dx = 1.282 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2969 reflections |
a = 18.883 (3) Å | θ = 2.2–27.9° |
b = 10.9652 (16) Å | µ = 0.10 mm−1 |
c = 12.4783 (18) Å | T = 296 K |
β = 116.948 (2)° | Block, light brown |
V = 2303.2 (6) Å3 | 0.30 × 0.20 × 0.15 mm |
Z = 8 |
Bruker SMART APEXII CCD area-detector diffractometer | 2495 independent reflections |
Radiation source: fine-focus sealed tube | 1949 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
φ and ω scans | θmax = 27.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −24→23 |
Tmin = 0.972, Tmax = 0.983 | k = −13→14 |
7001 measured reflections | l = −15→15 |
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)] = 0.035 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.101 | w = 1/[σ2(Fo2) + (0.0484P)2 + 0.7676P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
2495 reflections | Δρmax = 0.18 e Å−3 |
155 parameters | Δρmin = −0.15 e Å−3 |
2 restraints | Extinction correction: SHELXTL (Bruker, 2003), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0041 (6) |
C12H14O4 | V = 2303.2 (6) Å3 |
Mr = 222.23 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.883 (3) Å | µ = 0.10 mm−1 |
b = 10.9652 (16) Å | T = 296 K |
c = 12.4783 (18) Å | 0.30 × 0.20 × 0.15 mm |
β = 116.948 (2)° |
Bruker SMART APEXII CCD area-detector diffractometer | 2495 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1949 reflections with I > 2σ(I) |
Tmin = 0.972, Tmax = 0.983 | Rint = 0.018 |
7001 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 2 restraints |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.18 e Å−3 |
2495 reflections | Δρmin = −0.15 e Å−3 |
155 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 | 0.20300 (7) | 1.15279 (9) | −0.16760 (9) | 0.0566 (3) | |
H1X | 0.2248 (10) | 1.2043 (16) | −0.1107 (15) | 0.084 (6)* | |
O2 | 0.25503 (6) | 1.11303 (8) | 0.07069 (8) | 0.0499 (3) | |
H2X | 0.2829 (9) | 1.0814 (15) | 0.1383 (13) | 0.067 (5)* | |
O3 | 0.15173 (6) | 0.50624 (8) | 0.21782 (8) | 0.0529 (3) | |
O4 | 0.10009 (6) | 0.47109 (8) | 0.02084 (8) | 0.0505 (3) | |
C1 | 0.13035 (8) | 0.84559 (12) | −0.17544 (11) | 0.0480 (3) | |
H1 | 0.1023 | 0.7866 | −0.2326 | 0.058* | |
C2 | 0.14602 (8) | 0.95669 (12) | −0.21239 (11) | 0.0491 (3) | |
H2 | 0.1285 | 0.9720 | −0.2938 | 0.059* | |
C3 | 0.18741 (7) | 1.04461 (11) | −0.12904 (11) | 0.0410 (3) | |
C4 | 0.21382 (7) | 1.02111 (10) | −0.00688 (10) | 0.0366 (3) | |
C5 | 0.19794 (7) | 0.91036 (10) | 0.02980 (10) | 0.0368 (3) | |
H5 | 0.2154 | 0.8954 | 0.1113 | 0.044* | |
C6 | 0.15580 (7) | 0.82035 (10) | −0.05418 (11) | 0.0381 (3) | |
C7 | 0.13882 (7) | 0.70091 (11) | −0.01975 (11) | 0.0398 (3) | |
H7 | 0.1140 | 0.6448 | −0.0816 | 0.048* | |
C8 | 0.15487 (7) | 0.66342 (11) | 0.08999 (11) | 0.0415 (3) | |
H8 | 0.1793 | 0.7180 | 0.1533 | 0.050* | |
C9 | 0.13650 (7) | 0.54176 (11) | 0.11710 (11) | 0.0407 (3) | |
C10 | 0.08026 (8) | 0.34821 (12) | 0.04033 (12) | 0.0487 (3) | |
H10A | 0.0427 | 0.3503 | 0.0735 | 0.058* | |
H10B | 0.1276 | 0.3057 | 0.0965 | 0.058* | |
C11 | 0.04452 (9) | 0.28422 (13) | −0.07845 (13) | 0.0552 (4) | |
H11A | 0.0826 | 0.2829 | −0.1107 | 0.066* | |
H11B | −0.0020 | 0.3287 | −0.1344 | 0.066* | |
C12 | 0.02101 (10) | 0.15461 (14) | −0.06656 (18) | 0.0691 (5) | |
H12A | 0.0674 | 0.1095 | −0.0139 | 0.104* | |
H12B | −0.0029 | 0.1166 | −0.1443 | 0.104* | |
H12C | −0.0163 | 0.1557 | −0.0340 | 0.104* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0909 (8) | 0.0354 (5) | 0.0421 (5) | −0.0036 (5) | 0.0288 (5) | 0.0071 (4) |
O2 | 0.0726 (6) | 0.0288 (4) | 0.0381 (5) | −0.0043 (4) | 0.0161 (5) | 0.0008 (4) |
O3 | 0.0723 (6) | 0.0436 (5) | 0.0362 (5) | −0.0049 (4) | 0.0188 (5) | 0.0033 (4) |
O4 | 0.0716 (6) | 0.0367 (5) | 0.0377 (5) | −0.0134 (4) | 0.0200 (4) | −0.0017 (4) |
C1 | 0.0613 (8) | 0.0415 (7) | 0.0352 (6) | −0.0052 (6) | 0.0166 (6) | −0.0055 (5) |
C2 | 0.0674 (9) | 0.0438 (7) | 0.0314 (6) | 0.0013 (6) | 0.0183 (6) | 0.0040 (5) |
C3 | 0.0537 (7) | 0.0319 (6) | 0.0388 (6) | 0.0062 (5) | 0.0220 (6) | 0.0060 (5) |
C4 | 0.0456 (6) | 0.0281 (5) | 0.0352 (6) | 0.0041 (5) | 0.0174 (5) | −0.0005 (4) |
C5 | 0.0469 (6) | 0.0323 (6) | 0.0311 (6) | 0.0040 (5) | 0.0175 (5) | 0.0018 (4) |
C6 | 0.0445 (6) | 0.0331 (6) | 0.0368 (6) | 0.0017 (5) | 0.0186 (5) | 0.0001 (5) |
C7 | 0.0462 (7) | 0.0332 (6) | 0.0387 (6) | −0.0029 (5) | 0.0179 (5) | −0.0039 (5) |
C8 | 0.0505 (7) | 0.0334 (6) | 0.0391 (6) | −0.0027 (5) | 0.0191 (5) | −0.0044 (5) |
C9 | 0.0461 (7) | 0.0368 (6) | 0.0361 (6) | 0.0006 (5) | 0.0159 (5) | 0.0000 (5) |
C10 | 0.0579 (8) | 0.0363 (7) | 0.0473 (7) | −0.0085 (6) | 0.0198 (6) | 0.0019 (5) |
C11 | 0.0589 (8) | 0.0487 (8) | 0.0561 (8) | −0.0080 (6) | 0.0244 (7) | −0.0092 (6) |
C12 | 0.0677 (10) | 0.0474 (8) | 0.0927 (12) | −0.0124 (7) | 0.0367 (9) | −0.0176 (8) |
O1—C3 | 1.3615 (15) | C5—H5 | 0.9300 |
O1—H1X | 0.853 (14) | C6—C7 | 1.4586 (16) |
O2—C4 | 1.3696 (14) | C7—C8 | 1.3265 (17) |
O2—H2X | 0.840 (13) | C7—H7 | 0.9300 |
O3—C9 | 1.2192 (14) | C8—C9 | 1.4563 (17) |
O4—C9 | 1.3295 (15) | C8—H8 | 0.9300 |
O4—C10 | 1.4482 (15) | C10—C11 | 1.4960 (19) |
C1—C2 | 1.3813 (19) | C10—H10A | 0.9700 |
C1—C6 | 1.3921 (17) | C10—H10B | 0.9700 |
C1—H1 | 0.9300 | C11—C12 | 1.516 (2) |
C2—C3 | 1.3731 (18) | C11—H11A | 0.9700 |
C2—H2 | 0.9300 | C11—H11B | 0.9700 |
C3—C4 | 1.3963 (17) | C12—H12A | 0.9599 |
C4—C5 | 1.3779 (16) | C12—H12B | 0.9599 |
C5—C6 | 1.3963 (16) | C12—H12C | 0.9599 |
C3—O1—H1X | 112.5 (13) | C7—C8—C9 | 123.82 (11) |
C4—O2—H2X | 107.6 (12) | C7—C8—H8 | 118.1 |
C9—O4—C10 | 117.25 (10) | C9—C8—H8 | 118.1 |
C2—C1—C6 | 121.17 (12) | O3—C9—O4 | 121.93 (11) |
C2—C1—H1 | 119.4 | O3—C9—C8 | 124.22 (11) |
C6—C1—H1 | 119.4 | O4—C9—C8 | 113.84 (10) |
C3—C2—C1 | 120.06 (11) | O4—C10—C11 | 107.75 (11) |
C3—C2—H2 | 120.0 | O4—C10—H10A | 110.2 |
C1—C2—H2 | 120.0 | C11—C10—H10A | 110.2 |
O1—C3—C2 | 118.95 (11) | O4—C10—H10B | 110.2 |
O1—C3—C4 | 121.27 (11) | C11—C10—H10B | 110.2 |
C2—C3—C4 | 119.77 (11) | H10A—C10—H10B | 108.5 |
O2—C4—C5 | 123.59 (10) | C10—C11—C12 | 111.31 (13) |
O2—C4—C3 | 116.31 (10) | C10—C11—H11A | 109.4 |
C5—C4—C3 | 120.10 (11) | C12—C11—H11A | 109.4 |
C4—C5—C6 | 120.62 (11) | C10—C11—H11B | 109.4 |
C4—C5—H5 | 119.7 | C12—C11—H11B | 109.4 |
C6—C5—H5 | 119.7 | H11A—C11—H11B | 108.0 |
C1—C6—C5 | 118.29 (11) | C11—C12—H12A | 109.5 |
C1—C6—C7 | 119.01 (11) | C11—C12—H12B | 109.5 |
C5—C6—C7 | 122.69 (11) | H12A—C12—H12B | 109.5 |
C8—C7—C6 | 127.19 (11) | C11—C12—H12C | 109.5 |
C8—C7—H7 | 116.4 | H12A—C12—H12C | 109.5 |
C6—C7—H7 | 116.4 | H12B—C12—H12C | 109.5 |
C6—C1—C2—C3 | 0.1 (2) | C4—C5—C6—C1 | −0.06 (18) |
C1—C2—C3—O1 | 179.16 (12) | C4—C5—C6—C7 | 178.80 (11) |
C1—C2—C3—C4 | 0.2 (2) | C1—C6—C7—C8 | −176.34 (13) |
O1—C3—C4—O2 | 0.75 (17) | C5—C6—C7—C8 | 4.8 (2) |
C2—C3—C4—O2 | 179.66 (11) | C6—C7—C8—C9 | −179.45 (12) |
O1—C3—C4—C5 | −179.33 (11) | C10—O4—C9—O3 | −1.15 (18) |
C2—C3—C4—C5 | −0.42 (18) | C10—O4—C9—C8 | 179.58 (11) |
O2—C4—C5—C6 | −179.75 (11) | C7—C8—C9—O3 | 179.28 (13) |
C3—C4—C5—C6 | 0.34 (18) | C7—C8—C9—O4 | −1.47 (19) |
C2—C1—C6—C5 | −0.1 (2) | C9—O4—C10—C11 | −176.71 (11) |
C2—C1—C6—C7 | −179.04 (12) | O4—C10—C11—C12 | −179.36 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1X···O2 | 0.85 (1) | 2.30 (2) | 2.7109 (14) | 110 (2) |
O1—H1X···O2i | 0.85 (1) | 2.06 (2) | 2.7956 (14) | 144 (2) |
O2—H2X···O3ii | 0.84 (1) | 1.85 (1) | 2.6878 (13) | 176 (2) |
C8—H8···O1iii | 0.93 | 2.51 | 3.3979 (16) | 160 |
Symmetry codes: (i) −x+1/2, −y+5/2, −z; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x, −y+2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H14O4 |
Mr | 222.23 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 18.883 (3), 10.9652 (16), 12.4783 (18) |
β (°) | 116.948 (2) |
V (Å3) | 2303.2 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.30 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.972, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7001, 2495, 1949 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.101, 1.03 |
No. of reflections | 2495 |
No. of parameters | 155 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.15 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SHELXTL (Bruker, 2003), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1X···O2 | 0.853 (14) | 2.298 (19) | 2.7109 (14) | 110.0 (15) |
O1—H1X···O2i | 0.853 (14) | 2.057 (17) | 2.7956 (14) | 144.4 (18) |
O2—H2X···O3ii | 0.840 (13) | 1.849 (14) | 2.6878 (13) | 175.9 (17) |
C8—H8···O1iii | 0.93 | 2.51 | 3.3979 (16) | 160.0 |
Symmetry codes: (i) −x+1/2, −y+5/2, −z; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x, −y+2, z+1/2. |
Caffeic acid and its derivatives are widely distributed in the plant kingdom (Chen et al., 1999). The compounds are known to have antiatherosclerotic, antibacterial, anti-inflammatory, antiproliferative, immunostimulatory, antioxidative, antiviral and neuroprotective properties (Son & Lewis, 2002). In a continuation of our work on the structure–activity relationship of caffeic acid derivatives, we have obtained the title light-brown crystalline compound, (I), synthesized by a one-pot method (Hu et al., 2006).
The molecular structure of (I) is illustrated in Fig. 1. The acyclic double bond is E configured. The crystal packing (Fig. 2) is stabilized by intermolecular O—H···O and C—H···O hydrogen bonds (Table 1). The molecules of the caffeic acid ester form stacks along the a axis in a head-to-head manner
to form a dimeric structure.