Buy article online - an online subscription or single-article purchase is required to access this article.
The crystal structures of the title iron(III) and aluminium(III) ethyl maltolate complexes, [Fe(C7H7O3)3] and [Al(C7H7O3)3], respectively, are isomorphous. In each case, the three bidentate ligand molecules are bound to the metal atom, forming a distorted octahedral coordination geometry in a fac configuration.
Supporting information
CCDC references: 211724; 211725
For the preparation of (II), ethyl maltol and Fe(NO3)3·9H2O (8:1 molar ratio) were dissolved in ethanol–water (4:6). Red pillar-shaped crystals of (II) were obtained by slow evaporation at room temperature. For the preparation of (III), ethyl maltol and Al(NO3)3·9H2O (3:1 molar ratio) were dissolved in ethanol–water (1:1). The pH of this solution was raised to about 8 by adding ammonia solution, and the resulting solution was then heated for a few minutes and cooled to room temperature. Colorless plate-shaped crystals of (III) were obtained by slow evaporation.
Intensity decay of standard reflections for (III) was 7.3%, which was corrected. For both compounds, all H atoms were generated by calculation and refined as riding atoms.
For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 2000); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
Crystal data top
[Fe(C7H7O3)3] | F(000) = 980.0 |
Mr = 473.23 | Dx = 1.473 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 7.878 (3) Å | θ = 12.8–14.3° |
b = 8.818 (4) Å | µ = 0.76 mm−1 |
c = 30.721 (2) Å | T = 296 K |
β = 90.80 (2)° | Pillar, red |
V = 2133.9 (13) Å3 | 0.40 × 0.10 × 0.10 mm |
Z = 4 | |
Data collection top
Rigaku AFC-5R diffractometer | θmax = 27.5° |
ω scans | h = 0→10 |
5604 measured reflections | k = 0→11 |
4911 independent reflections | l = −39→39 |
2768 reflections with I > 2σ(I) | 3 standard reflections every 150 reflections |
Rint = 0.026 | intensity decay: 0.1% |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.042 | w = 1/[σ2(Fo2) + (0.0624P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.135 | (Δ/σ)max = 0.001 |
S = 0.99 | Δρmax = 0.41 e Å−3 |
4911 reflections | Δρmin = −0.32 e Å−3 |
283 parameters | |
Crystal data top
[Fe(C7H7O3)3] | V = 2133.9 (13) Å3 |
Mr = 473.23 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.878 (3) Å | µ = 0.76 mm−1 |
b = 8.818 (4) Å | T = 296 K |
c = 30.721 (2) Å | 0.40 × 0.10 × 0.10 mm |
β = 90.80 (2)° | |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.026 |
5604 measured reflections | 3 standard reflections every 150 reflections |
4911 independent reflections | intensity decay: 0.1% |
2768 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 283 parameters |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.41 e Å−3 |
4911 reflections | Δρmin = −0.32 e Å−3 |
Special details top
Refinement. Refinement using reflections with F2 > 0.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Fe | 0.91203 (5) | 0.12025 (5) | 0.35538 (1) | 0.0415 (1) | |
O1 | 1.1404 (3) | −0.3863 (3) | 0.41162 (8) | 0.0605 (6) | |
O2 | 1.0216 (3) | 0.0083 (2) | 0.40356 (7) | 0.0450 (5) | |
O3 | 0.9325 (3) | −0.0920 (2) | 0.32598 (7) | 0.0474 (5) | |
O4 | 1.2065 (4) | 0.3993 (3) | 0.23226 (8) | 0.0721 (8) | |
O5 | 1.1230 (3) | 0.2053 (2) | 0.33272 (6) | 0.0440 (5) | |
O6 | 0.8199 (3) | 0.2078 (3) | 0.29701 (7) | 0.0543 (6) | |
O7 | 0.4438 (3) | 0.3857 (3) | 0.44021 (9) | 0.0713 (7) | |
O8 | 0.8442 (3) | 0.2949 (2) | 0.39097 (7) | 0.0469 (5) | |
O9 | 0.6622 (3) | 0.0578 (3) | 0.36875 (7) | 0.0524 (6) | |
C2 | 1.1189 (4) | −0.2376 (4) | 0.4230 (1) | 0.0528 (8) | |
C3 | 1.0496 (4) | −0.1370 (4) | 0.39445 (9) | 0.0407 (7) | |
C4 | 0.9996 (4) | −0.1878 (4) | 0.3514 (1) | 0.0416 (7) | |
C5 | 1.0268 (5) | −0.3414 (4) | 0.3417 (1) | 0.0542 (9) | |
C6 | 1.0944 (5) | −0.4334 (4) | 0.3722 (1) | 0.0601 (9) | |
C7 | 1.1705 (5) | −0.2035 (5) | 0.4688 (1) | 0.071 (1) | |
C8 | 1.0324 (7) | −0.2270 (7) | 0.4992 (1) | 0.109 (2) | |
C9 | 1.2356 (5) | 0.3299 (4) | 0.2714 (1) | 0.0532 (8) | |
C10 | 1.1039 (4) | 0.2707 (3) | 0.29411 (9) | 0.0422 (7) | |
C11 | 0.9352 (4) | 0.2735 (4) | 0.2762 (1) | 0.0482 (8) | |
C12 | 0.9144 (5) | 0.3509 (4) | 0.2356 (1) | 0.064 (1) | |
C13 | 1.0481 (6) | 0.4086 (5) | 0.2164 (1) | 0.075 (1) | |
C14 | 1.4171 (5) | 0.3282 (5) | 0.2848 (1) | 0.065 (1) | |
C15 | 1.4823 (6) | 0.4715 (6) | 0.3030 (2) | 0.111 (2) | |
C16 | 0.6105 (4) | 0.3990 (4) | 0.4279 (1) | 0.0561 (9) | |
C17 | 0.6854 (4) | 0.2887 (4) | 0.40421 (9) | 0.0429 (7) | |
C18 | 0.5901 (4) | 0.1569 (4) | 0.3916 (1) | 0.0471 (8) | |
C19 | 0.4187 (4) | 0.1495 (5) | 0.4053 (1) | 0.0605 (10) | |
C20 | 0.3555 (5) | 0.2632 (6) | 0.4283 (1) | 0.074 (1) | |
C21 | 0.6876 (5) | 0.5458 (5) | 0.4417 (1) | 0.073 (1) | |
C22 | 0.6230 (6) | 0.6792 (6) | 0.4161 (2) | 0.111 (2) | |
H1 | 0.9982 | −0.3792 | 0.3143 | 0.0650* | |
H2 | 1.1098 | −0.5351 | 0.3653 | 0.0721* | |
H3 | 1.2653 | −0.2681 | 0.4771 | 0.0852* | |
H4 | 1.2083 | −0.0991 | 0.4708 | 0.0852* | |
H5 | 1.0011 | −0.3322 | 0.4993 | 0.1628* | |
H6 | 0.9364 | −0.1668 | 0.4904 | 0.1628* | |
H7 | 1.0689 | −0.1975 | 0.5279 | 0.1628* | |
H8 | 0.8072 | 0.3604 | 0.2228 | 0.0772* | |
H9 | 1.0311 | 0.4591 | 0.1901 | 0.0901* | |
H10 | 1.4336 | 0.2490 | 0.3064 | 0.0777* | |
H11 | 1.4843 | 0.3018 | 0.2597 | 0.0777* | |
H12 | 1.4163 | 0.4997 | 0.3277 | 0.1669* | |
H13 | 1.4743 | 0.5496 | 0.2813 | 0.1669* | |
H14 | 1.5988 | 0.4587 | 0.3118 | 0.1669* | |
H15 | 0.3517 | 0.0660 | 0.3983 | 0.0726* | |
H16 | 0.2426 | 0.2571 | 0.4366 | 0.0891* | |
H17 | 0.8097 | 0.5395 | 0.4386 | 0.0880* | |
H18 | 0.6644 | 0.5623 | 0.4722 | 0.0880* | |
H19 | 0.6533 | 0.6677 | 0.3861 | 0.1669* | |
H20 | 0.6726 | 0.7706 | 0.4275 | 0.1669* | |
H21 | 0.5017 | 0.6846 | 0.4182 | 0.1669* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Fe | 0.0382 (2) | 0.0453 (3) | 0.0409 (2) | −0.0007 (2) | −0.0028 (2) | −0.0026 (2) |
O1 | 0.067 (2) | 0.050 (1) | 0.065 (2) | 0.008 (1) | 0.001 (1) | 0.009 (1) |
O2 | 0.051 (1) | 0.044 (1) | 0.041 (1) | −0.001 (1) | −0.0060 (9) | −0.0050 (10) |
O3 | 0.052 (1) | 0.050 (1) | 0.041 (1) | 0.001 (1) | −0.0064 (10) | −0.0079 (10) |
O4 | 0.081 (2) | 0.083 (2) | 0.053 (1) | 0.003 (2) | 0.007 (1) | 0.023 (1) |
O5 | 0.041 (1) | 0.054 (1) | 0.037 (1) | 0.0000 (10) | −0.0035 (9) | 0.0063 (10) |
O6 | 0.043 (1) | 0.066 (2) | 0.054 (1) | 0.004 (1) | −0.012 (1) | 0.005 (1) |
O7 | 0.050 (1) | 0.092 (2) | 0.072 (2) | 0.006 (1) | 0.019 (1) | −0.009 (2) |
O8 | 0.039 (1) | 0.047 (1) | 0.055 (1) | −0.0046 (10) | 0.0046 (9) | −0.007 (1) |
O9 | 0.046 (1) | 0.055 (1) | 0.056 (1) | −0.009 (1) | −0.001 (1) | −0.008 (1) |
C2 | 0.053 (2) | 0.052 (2) | 0.054 (2) | 0.001 (2) | −0.002 (2) | 0.004 (2) |
C3 | 0.036 (1) | 0.047 (2) | 0.039 (1) | −0.008 (1) | −0.001 (1) | 0.000 (1) |
C4 | 0.035 (2) | 0.047 (2) | 0.043 (2) | −0.004 (1) | 0.004 (1) | −0.005 (1) |
C5 | 0.063 (2) | 0.048 (2) | 0.052 (2) | −0.001 (2) | 0.008 (2) | −0.012 (2) |
C6 | 0.071 (2) | 0.047 (2) | 0.062 (2) | 0.001 (2) | 0.013 (2) | −0.008 (2) |
C7 | 0.080 (3) | 0.074 (3) | 0.058 (2) | 0.002 (2) | −0.020 (2) | 0.011 (2) |
C8 | 0.109 (4) | 0.163 (6) | 0.053 (2) | −0.008 (4) | −0.001 (3) | −0.010 (3) |
C9 | 0.059 (2) | 0.053 (2) | 0.047 (2) | 0.005 (2) | 0.005 (2) | 0.006 (2) |
C10 | 0.048 (2) | 0.041 (2) | 0.038 (2) | 0.007 (1) | −0.004 (1) | −0.001 (1) |
C11 | 0.050 (2) | 0.048 (2) | 0.047 (2) | 0.011 (2) | −0.008 (1) | −0.004 (1) |
C12 | 0.074 (3) | 0.066 (2) | 0.052 (2) | 0.013 (2) | −0.022 (2) | 0.006 (2) |
C13 | 0.099 (3) | 0.078 (3) | 0.049 (2) | 0.013 (3) | −0.011 (2) | 0.019 (2) |
C14 | 0.053 (2) | 0.069 (2) | 0.073 (2) | 0.003 (2) | 0.014 (2) | 0.011 (2) |
C15 | 0.086 (4) | 0.091 (4) | 0.156 (5) | −0.003 (3) | −0.037 (3) | −0.004 (4) |
C16 | 0.049 (2) | 0.067 (2) | 0.053 (2) | 0.003 (2) | 0.004 (2) | −0.005 (2) |
C17 | 0.039 (2) | 0.053 (2) | 0.037 (1) | −0.001 (1) | −0.002 (1) | 0.004 (1) |
C18 | 0.039 (2) | 0.066 (2) | 0.036 (2) | −0.004 (2) | −0.004 (1) | 0.008 (1) |
C19 | 0.041 (2) | 0.088 (3) | 0.053 (2) | −0.014 (2) | 0.004 (2) | 0.003 (2) |
C20 | 0.040 (2) | 0.114 (4) | 0.069 (3) | −0.003 (2) | 0.014 (2) | 0.004 (3) |
C21 | 0.066 (2) | 0.072 (3) | 0.082 (3) | 0.006 (2) | 0.012 (2) | −0.026 (2) |
C22 | 0.079 (3) | 0.077 (3) | 0.178 (6) | −0.002 (3) | 0.023 (4) | −0.003 (4) |
Geometric parameters (Å, º) top
Fe—O2 | 1.969 (2) | C8—H6 | 0.960 |
Fe—O3 | 2.085 (2) | C8—H7 | 0.960 |
Fe—O5 | 1.960 (2) | C9—C10 | 1.362 (5) |
Fe—O6 | 2.074 (2) | C9—C14 | 1.483 (5) |
Fe—O8 | 1.967 (2) | C10—C11 | 1.432 (4) |
Fe—O9 | 2.090 (2) | C11—C12 | 1.428 (5) |
O1—C2 | 1.368 (4) | C12—C13 | 1.316 (6) |
O1—C6 | 1.327 (4) | C12—H8 | 0.930 |
O2—C3 | 1.330 (4) | C13—H9 | 0.930 |
O3—C4 | 1.262 (4) | C14—C15 | 1.471 (7) |
O4—C9 | 1.366 (4) | C14—H10 | 0.970 |
O4—C13 | 1.336 (6) | C14—H11 | 0.970 |
O5—C10 | 1.326 (3) | C15—H12 | 0.960 |
O6—C11 | 1.259 (4) | C15—H13 | 0.960 |
O7—C16 | 1.377 (4) | C15—H14 | 0.960 |
O7—C20 | 1.333 (5) | C16—C17 | 1.356 (5) |
O8—C17 | 1.321 (4) | C16—C21 | 1.488 (6) |
O9—C18 | 1.262 (4) | C17—C18 | 1.434 (5) |
C2—C3 | 1.358 (4) | C18—C19 | 1.421 (5) |
C2—C7 | 1.490 (5) | C19—C20 | 1.327 (6) |
C3—C4 | 1.446 (4) | C19—H15 | 0.930 |
C4—C5 | 1.404 (5) | C20—H16 | 0.930 |
C5—C6 | 1.344 (5) | C21—C22 | 1.500 (7) |
C5—H1 | 0.930 | C21—H17 | 0.970 |
C6—H2 | 0.930 | C21—H18 | 0.970 |
C7—C8 | 1.458 (7) | C22—H19 | 0.960 |
C7—H3 | 0.970 | C22—H20 | 0.960 |
C7—H4 | 0.970 | C22—H21 | 0.960 |
C8—H5 | 0.960 | | |
| | | |
O1···O7i | 3.236 (4) | O5···C6vii | 3.417 (4) |
O1···C20i | 3.559 (5) | O5···C20ii | 3.477 (4) |
O2···C19ii | 3.367 (4) | O6···C14viii | 3.362 (4) |
O2···C20ii | 3.535 (5) | O6···C15viii | 3.540 (6) |
O2···C8iii | 3.585 (5) | O8···C6vii | 3.161 (4) |
O3···C12iv | 3.340 (5) | O8···C8iii | 3.548 (5) |
O3···O4v | 3.382 (4) | O9···C13iv | 3.347 (5) |
O4···C4vi | 3.567 (4) | C6···C10ix | 3.545 (5) |
O5···C19ii | 3.241 (4) | | |
| | | |
O2—Fe—O3 | 80.79 (9) | C10—C9—C14 | 126.3 (3) |
O2—Fe—O5 | 95.38 (9) | O5—C10—C9 | 123.2 (3) |
O2—Fe—O6 | 168.89 (9) | O5—C10—C11 | 116.4 (3) |
O2—Fe—O8 | 95.42 (9) | C9—C10—C11 | 120.4 (3) |
O2—Fe—O9 | 97.16 (9) | O6—C11—C10 | 117.9 (3) |
O3—Fe—O5 | 96.81 (9) | O6—C11—C12 | 126.0 (3) |
O3—Fe—O6 | 89.31 (9) | C10—C11—C12 | 116.0 (3) |
O3—Fe—O8 | 165.16 (9) | C11—C12—C13 | 119.5 (4) |
O3—Fe—O9 | 85.83 (9) | C11—C12—H8 | 120.3 |
O5—Fe—O6 | 80.71 (8) | C13—C12—H8 | 120.2 |
O5—Fe—O8 | 97.83 (9) | O4—C13—C12 | 124.2 (4) |
O5—Fe—O9 | 167.45 (9) | O4—C13—H9 | 117.9 |
O6—Fe—O8 | 95.42 (9) | C12—C13—H9 | 117.9 |
O6—Fe—O9 | 87.08 (9) | C9—C14—C15 | 115.3 (4) |
O8—Fe—O9 | 80.39 (9) | C9—C14—H10 | 108.5 |
C2—O1—C6 | 120.1 (3) | C9—C14—H11 | 108.4 |
Fe—O2—C3 | 113.4 (2) | C15—C14—H10 | 108.5 |
Fe—O3—C4 | 111.5 (2) | C15—C14—H11 | 108.5 |
C9—O4—C13 | 119.5 (3) | H10—C14—H11 | 107.5 |
Fe—O5—C10 | 113.5 (2) | C14—C15—H12 | 109.5 |
Fe—O6—C11 | 111.4 (2) | C14—C15—H13 | 109.5 |
C16—O7—C20 | 119.4 (3) | C14—C15—H14 | 109.5 |
Fe—O8—C17 | 113.9 (2) | H12—C15—H13 | 109.5 |
Fe—O9—C18 | 111.1 (2) | H12—C15—H14 | 109.5 |
O1—C2—C3 | 120.7 (3) | H13—C15—H14 | 109.5 |
O1—C2—C7 | 113.7 (3) | O7—C16—C17 | 120.7 (3) |
C3—C2—C7 | 125.5 (3) | O7—C16—C21 | 112.6 (3) |
O2—C3—C2 | 124.0 (3) | C17—C16—C21 | 126.7 (3) |
O2—C3—C4 | 116.6 (3) | O8—C17—C16 | 123.8 (3) |
C2—C3—C4 | 119.4 (3) | O8—C17—C18 | 116.4 (3) |
O3—C4—C3 | 117.7 (3) | C16—C17—C18 | 119.8 (3) |
O3—C4—C5 | 125.3 (3) | O9—C18—C17 | 118.2 (3) |
C3—C4—C5 | 117.0 (3) | O9—C18—C19 | 124.8 (3) |
C4—C5—C6 | 119.6 (3) | C17—C18—C19 | 116.9 (3) |
C4—C5—H1 | 120.2 | C18—C19—C20 | 119.2 (4) |
C6—C5—H1 | 120.2 | C18—C19—H15 | 120.4 |
O1—C6—C5 | 123.2 (3) | C20—C19—H15 | 120.4 |
O1—C6—H2 | 118.4 | O7—C20—C19 | 124.0 (3) |
C5—C6—H2 | 118.4 | O7—C20—H16 | 118.0 |
C2—C7—C8 | 112.3 (4) | C19—C20—H16 | 118.0 |
C2—C7—H3 | 109.1 | C16—C21—C22 | 113.5 (4) |
C2—C7—H4 | 109.1 | C16—C21—H17 | 108.9 |
C8—C7—H3 | 109.1 | C16—C21—H18 | 108.9 |
C8—C7—H4 | 109.1 | C22—C21—H17 | 108.9 |
H3—C7—H4 | 107.9 | C22—C21—H18 | 108.9 |
C7—C8—H5 | 109.5 | H17—C21—H18 | 107.7 |
C7—C8—H6 | 109.5 | C21—C22—H19 | 109.5 |
C7—C8—H7 | 109.5 | C21—C22—H20 | 109.5 |
H5—C8—H6 | 109.5 | C21—C22—H21 | 109.5 |
H5—C8—H7 | 109.5 | H19—C22—H20 | 109.5 |
H6—C8—H7 | 109.5 | H19—C22—H21 | 109.5 |
O4—C9—C10 | 120.2 (3) | H20—C22—H21 | 109.5 |
O4—C9—C14 | 113.5 (3) | | |
| | | |
Fe—O2—C3—C2 | −177.9 (3) | O6—Fe—O8—C17 | 85.1 (2) |
Fe—O2—C3—C4 | 1.2 (3) | O6—Fe—O9—C18 | −95.4 (2) |
Fe—O3—C4—C3 | −0.4 (3) | O6—C11—C10—C9 | 175.0 (3) |
Fe—O3—C4—C5 | 178.3 (3) | O6—C11—C12—C13 | −176.9 (4) |
Fe—O5—C10—C9 | −176.4 (3) | O7—C16—C17—O8 | 179.3 (3) |
Fe—O5—C10—C11 | 2.0 (3) | O7—C16—C17—C18 | 0.1 (5) |
Fe—O6—C11—C10 | 2.9 (4) | O7—C16—C21—C22 | −72.1 (4) |
Fe—O6—C11—C12 | −177.6 (3) | O7—C20—C19—C18 | −0.9 (6) |
Fe—O8—C17—C16 | −177.9 (3) | O8—Fe—O2—C3 | 164.5 (2) |
Fe—O8—C17—C18 | 1.2 (3) | O8—Fe—O3—C4 | −75.4 (4) |
Fe—O9—C18—C17 | −0.2 (3) | O8—Fe—O5—C10 | −94.7 (2) |
Fe—O9—C18—C19 | 178.5 (3) | O8—Fe—O6—C11 | 95.7 (2) |
O1—C2—C3—O2 | 178.6 (3) | O8—Fe—O9—C18 | 0.7 (2) |
O1—C2—C3—C4 | −0.6 (5) | O8—C17—C16—C21 | 2.6 (5) |
O1—C2—C7—C8 | −88.1 (4) | O8—C17—C18—O9 | −0.7 (4) |
O1—C6—C5—C4 | −1.1 (6) | O8—C17—C18—C19 | −179.5 (3) |
O2—Fe—O3—C4 | 0.8 (2) | O9—Fe—O2—C3 | 83.5 (2) |
O2—Fe—O5—C10 | 169.1 (2) | O9—Fe—O3—C4 | −97.2 (2) |
O2—Fe—O6—C11 | −71.5 (5) | O9—Fe—O5—C10 | −13.8 (5) |
O2—Fe—O8—C17 | −97.4 (2) | O9—Fe—O6—C11 | 175.7 (2) |
O2—Fe—O9—C18 | 95.0 (2) | O9—Fe—O8—C17 | −1.0 (2) |
O2—C3—C2—C7 | 1.5 (5) | O9—C18—C17—C16 | 178.5 (3) |
O2—C3—C4—O3 | −0.6 (4) | O9—C18—C19—C20 | −178.0 (3) |
O2—C3—C4—C5 | −179.3 (3) | C2—O1—C6—C5 | 0.4 (5) |
O3—Fe—O2—C3 | −1.1 (2) | C2—C3—C4—C5 | −0.1 (4) |
O3—Fe—O5—C10 | 87.8 (2) | C3—C2—O1—C6 | 0.5 (5) |
O3—Fe—O6—C11 | −98.4 (2) | C3—C2—C7—C8 | 89.1 (5) |
O3—Fe—O8—C17 | −23.0 (4) | C3—C4—C5—C6 | 0.9 (5) |
O3—Fe—O9—C18 | 175.1 (2) | C4—C3—C2—C7 | −177.6 (3) |
O3—C4—C3—C2 | 178.6 (3) | C6—O1—C2—C7 | 177.8 (3) |
O3—C4—C5—C6 | −177.7 (3) | C9—O4—C13—C12 | −1.9 (6) |
O4—C9—C10—O5 | −178.3 (3) | C9—C10—C11—C12 | −4.6 (5) |
O4—C9—C10—C11 | 3.4 (5) | C10—C9—O4—C13 | −0.1 (5) |
O4—C9—C14—C15 | 78.3 (5) | C10—C9—C14—C15 | −101.6 (5) |
O4—C13—C12—C11 | 0.5 (6) | C10—C11—C12—C13 | 2.7 (5) |
O5—Fe—O2—C3 | −97.1 (2) | C11—C10—C9—C14 | −176.8 (3) |
O5—Fe—O3—C4 | 95.1 (2) | C13—O4—C9—C14 | −180.0 (3) |
O5—Fe—O6—C11 | −1.4 (2) | C16—O7—C20—C19 | 0.8 (6) |
O5—Fe—O8—C17 | 166.4 (2) | C16—C17—C18—C19 | −0.3 (4) |
O5—Fe—O9—C18 | −82.2 (5) | C17—C16—O7—C20 | −0.4 (5) |
O5—C10—C9—C14 | 1.6 (5) | C17—C16—C21—C22 | 104.9 (5) |
O5—C10—C11—O6 | −3.4 (4) | C17—C18—C19—C20 | 0.7 (5) |
O5—C10—C11—C12 | 177.0 (3) | C18—C17—C16—C21 | −176.6 (3) |
O6—Fe—O2—C3 | −28.4 (6) | C20—O7—C16—C21 | 176.8 (3) |
O6—Fe—O3—C4 | 175.7 (2) | C20—O7—C16—C21 | 176.8 (3) |
O6—Fe—O5—C10 | −0.4 (2) | | |
Symmetry codes: (i) x+1, y−1, z; (ii) x+1, y, z; (iii) −x+2, −y, −z+1; (iv) −x+3/2, y−1/2, −z+1/2; (v) −x+5/2, y−1/2, −z+1/2; (vi) −x+5/2, y+1/2, −z+1/2; (vii) x, y+1, z; (viii) x−1, y, z; (ix) x, y−1, z. |
Crystal data top
[Al(C7H7O3)3] | F(000) = 928.0 |
Mr = 444.36 | Dx = 1.395 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2yn | Cell parameters from 10 reflections |
a = 7.897 (4) Å | θ = 10.4–11.8° |
b = 8.696 (9) Å | µ = 0.15 mm−1 |
c = 30.801 (4) Å | T = 296 K |
β = 91.40 (3)° | Plate, colorless |
V = 2115 (2) Å3 | 0.20 × 0.20 × 0.10 mm |
Z = 4 | |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.127 |
ω scans | θmax = 27.5° |
Absorption correction: ψ scan (North et al., 1968) | h = 0→10 |
Tmin = 0.952, Tmax = 0.999 | k = 0→11 |
5552 measured reflections | l = −39→40 |
4868 independent reflections | 3 standard reflections every 150 reflections |
1804 reflections with I > 2σ(I) | intensity decay: 7.3% |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.064 | w = 1/[σ2(Fo2) + (0.1054P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.228 | (Δ/σ)max < 0.001 |
S = 0.94 | Δρmax = 0.37 e Å−3 |
4868 reflections | Δρmin = −0.42 e Å−3 |
280 parameters | |
Crystal data top
[Al(C7H7O3)3] | V = 2115 (2) Å3 |
Mr = 444.36 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.897 (4) Å | µ = 0.15 mm−1 |
b = 8.696 (9) Å | T = 296 K |
c = 30.801 (4) Å | 0.20 × 0.20 × 0.10 mm |
β = 91.40 (3)° | |
Data collection top
Rigaku AFC-5R diffractometer | 1804 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.127 |
Tmin = 0.952, Tmax = 0.999 | 3 standard reflections every 150 reflections |
5552 measured reflections | intensity decay: 7.3% |
4868 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.064 | 280 parameters |
wR(F2) = 0.228 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.37 e Å−3 |
4868 reflections | Δρmin = −0.42 e Å−3 |
Special details top
Refinement. Refinement using reflections with F2 > −10.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Al | 0.4051 (2) | 0.1075 (2) | 0.35649 (4) | 0.0452 (4) | |
O1 | 0.6317 (4) | −0.3904 (4) | 0.4135 (1) | 0.0644 (9) | |
O2 | 0.5087 (4) | 0.0069 (4) | 0.40387 (9) | 0.0482 (8) | |
O3 | 0.4337 (4) | −0.0891 (4) | 0.32664 (9) | 0.0498 (8) | |
O4 | 0.6793 (5) | 0.3827 (5) | 0.2350 (1) | 0.075 (1) | |
O5 | 0.6057 (3) | 0.1899 (4) | 0.33642 (8) | 0.0456 (7) | |
O6 | 0.3054 (4) | 0.1895 (4) | 0.3028 (1) | 0.0552 (8) | |
O7 | −0.0579 (4) | 0.3645 (5) | 0.4369 (1) | 0.076 (1) | |
O8 | 0.3448 (4) | 0.2795 (4) | 0.38932 (9) | 0.0507 (8) | |
O9 | 0.1779 (4) | 0.0351 (4) | 0.3695 (1) | 0.0568 (9) | |
C2 | 0.6080 (6) | −0.2412 (6) | 0.4249 (1) | 0.053 (1) | |
C3 | 0.5415 (5) | −0.1382 (5) | 0.3955 (1) | 0.044 (1) | |
C4 | 0.4977 (5) | −0.1901 (6) | 0.3521 (1) | 0.046 (1) | |
C5 | 0.5270 (6) | −0.3455 (6) | 0.3425 (2) | 0.055 (1) | |
C6 | 0.5904 (6) | −0.4395 (6) | 0.3733 (2) | 0.061 (1) | |
C7 | 0.6544 (7) | −0.2070 (7) | 0.4709 (2) | 0.070 (2) | |
C8 | 0.5171 (10) | −0.236 (1) | 0.5003 (2) | 0.114 (3) | |
C9 | 0.7128 (6) | 0.3145 (6) | 0.2741 (2) | 0.058 (1) | |
C10 | 0.5861 (5) | 0.2540 (5) | 0.2974 (1) | 0.046 (1) | |
C11 | 0.4154 (6) | 0.2569 (6) | 0.2806 (1) | 0.050 (1) | |
C12 | 0.3861 (7) | 0.3321 (6) | 0.2403 (2) | 0.065 (1) | |
C13 | 0.5177 (9) | 0.3916 (7) | 0.2198 (2) | 0.078 (2) | |
C14 | 0.8971 (6) | 0.3122 (7) | 0.2859 (2) | 0.074 (2) | |
C15 | 0.9666 (8) | 0.4613 (8) | 0.3011 (3) | 0.110 (2) | |
C16 | 0.1084 (6) | 0.3853 (7) | 0.4254 (2) | 0.061 (1) | |
C17 | 0.1867 (5) | 0.2729 (6) | 0.4022 (1) | 0.048 (1) | |
C18 | 0.0989 (6) | 0.1352 (6) | 0.3910 (1) | 0.053 (1) | |
C19 | −0.0742 (6) | 0.1208 (7) | 0.4034 (2) | 0.064 (1) | |
C20 | −0.1423 (7) | 0.2379 (9) | 0.4254 (2) | 0.079 (2) | |
C21 | 0.1799 (7) | 0.5315 (7) | 0.4391 (2) | 0.079 (2) | |
C22 | 0.1116 (9) | 0.6696 (9) | 0.4145 (3) | 0.124 (3) | |
H1 | 0.5024 | −0.3831 | 0.3148 | 0.0659* | |
H2 | 0.6063 | −0.5426 | 0.3665 | 0.0730* | |
H3 | 0.7511 | −0.2695 | 0.4796 | 0.0844* | |
H4 | 0.6879 | −0.1000 | 0.4733 | 0.0844* | |
H5 | 0.5475 | −0.1973 | 0.5286 | 0.1712* | |
H6 | 0.4968 | −0.3446 | 0.5020 | 0.1712* | |
H7 | 0.4164 | −0.1851 | 0.4897 | 0.1712* | |
H8 | 0.2771 | 0.3399 | 0.2284 | 0.0783* | |
H9 | 0.4970 | 0.4420 | 0.1936 | 0.0939* | |
H10 | 0.9165 | 0.2363 | 0.3085 | 0.0890* | |
H11 | 0.9592 | 0.2796 | 0.2607 | 0.0890* | |
H12 | 1.0870 | 0.4527 | 0.3053 | 0.1645* | |
H13 | 0.9159 | 0.4889 | 0.3280 | 0.1645* | |
H14 | 0.9419 | 0.5391 | 0.2797 | 0.1645* | |
H15 | −0.1372 | 0.0334 | 0.3964 | 0.0762* | |
H16 | −0.2551 | 0.2300 | 0.4330 | 0.0949* | |
H17 | 0.3016 | 0.5275 | 0.4358 | 0.0949* | |
H18 | 0.1586 | 0.5456 | 0.4697 | 0.0949* | |
H19 | 0.1639 | 0.7614 | 0.4258 | 0.1854* | |
H20 | −0.0088 | 0.6758 | 0.4178 | 0.1854* | |
H21 | 0.1364 | 0.6594 | 0.3843 | 0.1854* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Al | 0.0424 (7) | 0.0506 (8) | 0.0424 (7) | −0.0022 (6) | −0.0065 (5) | −0.0003 (6) |
O1 | 0.070 (2) | 0.062 (2) | 0.062 (2) | 0.008 (2) | −0.001 (2) | 0.004 (2) |
O2 | 0.052 (2) | 0.050 (2) | 0.042 (2) | 0.001 (1) | −0.009 (1) | −0.005 (1) |
O3 | 0.052 (2) | 0.057 (2) | 0.041 (2) | 0.001 (2) | −0.009 (1) | −0.003 (2) |
O4 | 0.079 (3) | 0.091 (3) | 0.057 (2) | 0.001 (2) | 0.005 (2) | 0.025 (2) |
O5 | 0.038 (2) | 0.059 (2) | 0.040 (2) | −0.002 (1) | −0.007 (1) | 0.007 (1) |
O6 | 0.045 (2) | 0.070 (2) | 0.049 (2) | 0.003 (2) | −0.011 (1) | 0.008 (2) |
O7 | 0.052 (2) | 0.101 (3) | 0.076 (3) | 0.000 (2) | 0.016 (2) | −0.004 (2) |
O8 | 0.042 (2) | 0.053 (2) | 0.056 (2) | −0.003 (1) | 0.000 (1) | −0.006 (2) |
O9 | 0.046 (2) | 0.066 (2) | 0.058 (2) | −0.008 (2) | 0.004 (1) | −0.007 (2) |
C2 | 0.059 (3) | 0.052 (3) | 0.047 (3) | 0.000 (2) | −0.008 (2) | 0.002 (2) |
C3 | 0.043 (2) | 0.048 (3) | 0.040 (2) | −0.005 (2) | 0.000 (2) | 0.000 (2) |
C4 | 0.035 (2) | 0.059 (3) | 0.043 (2) | −0.005 (2) | 0.004 (2) | −0.008 (2) |
C5 | 0.062 (3) | 0.052 (3) | 0.050 (3) | 0.005 (3) | 0.004 (2) | −0.007 (2) |
C6 | 0.066 (3) | 0.046 (3) | 0.071 (4) | 0.005 (3) | 0.011 (3) | −0.010 (3) |
C7 | 0.085 (4) | 0.069 (4) | 0.057 (3) | −0.004 (3) | −0.013 (3) | 0.016 (3) |
C8 | 0.115 (5) | 0.164 (8) | 0.063 (4) | −0.007 (5) | −0.008 (3) | −0.011 (4) |
C9 | 0.060 (3) | 0.064 (3) | 0.050 (3) | −0.004 (3) | −0.002 (2) | 0.006 (3) |
C10 | 0.047 (3) | 0.049 (3) | 0.041 (2) | 0.006 (2) | −0.001 (2) | 0.000 (2) |
C11 | 0.052 (3) | 0.053 (3) | 0.045 (3) | 0.013 (2) | −0.011 (2) | 0.001 (2) |
C12 | 0.073 (3) | 0.068 (4) | 0.054 (3) | 0.013 (3) | −0.021 (3) | 0.009 (3) |
C13 | 0.102 (5) | 0.083 (4) | 0.049 (3) | 0.015 (4) | −0.010 (3) | 0.017 (3) |
C14 | 0.056 (3) | 0.091 (4) | 0.076 (4) | −0.001 (3) | 0.012 (3) | 0.006 (3) |
C15 | 0.079 (4) | 0.088 (5) | 0.161 (7) | 0.001 (4) | −0.032 (4) | −0.016 (5) |
C16 | 0.049 (3) | 0.080 (4) | 0.054 (3) | 0.008 (3) | −0.001 (2) | −0.003 (3) |
C17 | 0.042 (2) | 0.056 (3) | 0.044 (3) | 0.006 (2) | −0.005 (2) | 0.004 (2) |
C18 | 0.045 (3) | 0.076 (4) | 0.037 (2) | −0.004 (3) | −0.004 (2) | 0.007 (2) |
C19 | 0.049 (3) | 0.078 (4) | 0.064 (3) | −0.009 (3) | 0.001 (2) | 0.000 (3) |
C20 | 0.048 (3) | 0.105 (5) | 0.085 (4) | −0.004 (3) | 0.006 (3) | 0.000 (4) |
C21 | 0.073 (4) | 0.064 (4) | 0.101 (5) | 0.000 (3) | 0.010 (3) | −0.019 (4) |
C22 | 0.094 (5) | 0.095 (6) | 0.182 (8) | 0.002 (5) | −0.001 (5) | 0.008 (6) |
Geometric parameters (Å, º) top
Al—O2 | 1.872 (3) | C8—H6 | 0.960 |
Al—O3 | 1.956 (3) | C8—H7 | 0.960 |
Al—O5 | 1.858 (3) | C9—C10 | 1.353 (6) |
Al—O6 | 1.949 (3) | C9—C14 | 1.491 (7) |
Al—O8 | 1.874 (3) | C10—C11 | 1.432 (6) |
Al—O9 | 1.952 (3) | C11—C12 | 1.417 (7) |
O1—C2 | 1.359 (6) | C12—C13 | 1.333 (9) |
O1—C6 | 1.343 (6) | C12—H8 | 0.930 |
O2—C3 | 1.315 (5) | C13—H9 | 0.930 |
O3—C4 | 1.274 (5) | C14—C15 | 1.479 (10) |
O4—C9 | 1.362 (6) | C14—H10 | 0.970 |
O4—C13 | 1.350 (8) | C14—H11 | 0.970 |
O5—C10 | 1.329 (5) | C15—H12 | 0.960 |
O6—C11 | 1.263 (6) | C15—H13 | 0.960 |
O7—C16 | 1.380 (6) | C15—H14 | 0.960 |
O7—C20 | 1.330 (8) | C16—C17 | 1.368 (7) |
O8—C17 | 1.321 (5) | C16—C21 | 1.449 (8) |
O9—C18 | 1.268 (6) | C17—C18 | 1.422 (7) |
C2—C3 | 1.369 (6) | C18—C19 | 1.434 (7) |
C2—C7 | 1.485 (7) | C19—C20 | 1.343 (9) |
C3—C4 | 1.445 (6) | C19—H15 | 0.930 |
C4—C5 | 1.403 (7) | C20—H16 | 0.930 |
C5—C6 | 1.338 (7) | C21—C22 | 1.51 (1) |
C5—H1 | 0.930 | C21—H17 | 0.970 |
C6—H2 | 0.930 | C21—H18 | 0.970 |
C7—C8 | 1.451 (9) | C22—H19 | 0.960 |
C7—H3 | 0.970 | C22—H20 | 0.960 |
C7—H4 | 0.970 | C22—H21 | 0.960 |
C8—H5 | 0.960 | | |
| | | |
O1···O7i | 3.314 (5) | O6···C14vi | 3.424 (6) |
O2···C19ii | 3.439 (6) | O6···C15vi | 3.569 (8) |
O2···C20ii | 3.461 (7) | O8···C6v | 3.166 (6) |
O2···C8iii | 3.571 (8) | O8···C8iii | 3.565 (7) |
O3···C12iv | 3.293 (6) | O9···C13iv | 3.362 (7) |
O5···C19ii | 3.279 (6) | O9···C22vii | 3.512 (9) |
O5···C20ii | 3.373 (6) | C6···C10vii | 3.544 (7) |
O5···C6v | 3.420 (6) | | |
| | | |
O2—Al—O3 | 84.6 (1) | C10—C9—C14 | 126.6 (4) |
O2—Al—O5 | 94.6 (1) | O5—C10—C9 | 124.9 (4) |
O2—Al—O6 | 172.7 (2) | O5—C10—C11 | 114.9 (4) |
O2—Al—O8 | 93.7 (1) | C9—C10—C11 | 120.2 (4) |
O2—Al—O9 | 94.4 (1) | O6—C11—C10 | 116.8 (4) |
O3—Al—O5 | 94.1 (1) | O6—C11—C12 | 126.0 (4) |
O3—Al—O6 | 88.3 (1) | C10—C11—C12 | 117.2 (4) |
O3—Al—O8 | 170.0 (1) | C11—C12—C13 | 118.8 (5) |
O3—Al—O9 | 86.1 (1) | C11—C12—H8 | 120.6 |
O5—Al—O6 | 84.6 (1) | C13—C12—H8 | 120.6 |
O5—Al—O8 | 95.8 (1) | O4—C13—C12 | 123.7 (5) |
O5—Al—O9 | 171.0 (1) | O4—C13—H9 | 118.2 |
O6—Al—O8 | 93.6 (1) | C12—C13—H9 | 118.2 |
O6—Al—O9 | 86.4 (1) | C9—C14—C15 | 114.7 (5) |
O8—Al—O9 | 84.3 (1) | C9—C14—H10 | 108.6 |
C2—O1—C6 | 120.7 (4) | C9—C14—H11 | 108.6 |
Al—O2—C3 | 112.3 (2) | C15—C14—H10 | 108.6 |
Al—O3—C4 | 111.2 (3) | C15—C14—H11 | 108.6 |
C9—O4—C13 | 119.5 (4) | H10—C14—H11 | 107.6 |
Al—O5—C10 | 112.4 (2) | C14—C15—H12 | 109.5 |
Al—O6—C11 | 111.1 (3) | C14—C15—H13 | 109.5 |
C16—O7—C20 | 120.9 (5) | C14—C15—H14 | 109.5 |
Al—O8—C17 | 112.4 (3) | H12—C15—H13 | 109.5 |
Al—O9—C18 | 110.6 (3) | H12—C15—H14 | 109.5 |
O1—C2—C3 | 120.5 (4) | H13—C15—H14 | 109.5 |
O1—C2—C7 | 113.9 (4) | O7—C16—C17 | 119.0 (5) |
C3—C2—C7 | 125.5 (5) | O7—C16—C21 | 114.0 (5) |
O2—C3—C2 | 125.0 (4) | C17—C16—C21 | 127.0 (5) |
O2—C3—C4 | 115.9 (4) | O8—C17—C16 | 124.6 (4) |
C2—C3—C4 | 119.1 (4) | O8—C17—C18 | 115.0 (4) |
O3—C4—C3 | 115.9 (4) | C16—C17—C18 | 120.3 (4) |
O3—C4—C5 | 126.9 (4) | O9—C18—C17 | 117.5 (4) |
C3—C4—C5 | 117.3 (4) | O9—C18—C19 | 124.3 (5) |
C4—C5—C6 | 120.0 (5) | C17—C18—C19 | 118.1 (5) |
C4—C5—H1 | 120.0 | C18—C19—C20 | 117.6 (5) |
C6—C5—H1 | 120.0 | C18—C19—H15 | 121.2 |
O1—C6—C5 | 122.4 (5) | C20—C19—H15 | 121.2 |
O1—C6—H2 | 118.8 | O7—C20—C19 | 123.9 (5) |
C5—C6—H2 | 118.8 | O7—C20—H16 | 118.0 |
C2—C7—C8 | 113.0 (5) | C19—C20—H16 | 118.0 |
C2—C7—H3 | 109.0 | C16—C21—C22 | 114.8 (5) |
C2—C7—H4 | 109.0 | C16—C21—H17 | 108.6 |
C8—C7—H3 | 109.0 | C16—C21—H18 | 108.6 |
C8—C7—H4 | 109.0 | C22—C21—H17 | 108.6 |
H3—C7—H4 | 107.8 | C22—C21—H18 | 108.6 |
C7—C8—H5 | 109.5 | H17—C21—H18 | 107.5 |
C7—C8—H6 | 109.5 | C21—C22—H19 | 109.5 |
C7—C8—H7 | 109.5 | C21—C22—H20 | 109.5 |
H5—C8—H6 | 109.5 | C21—C22—H21 | 109.5 |
H5—C8—H7 | 109.5 | H19—C22—H20 | 109.5 |
H6—C8—H7 | 109.5 | H19—C22—H21 | 109.5 |
O4—C9—C10 | 120.5 (4) | H20—C22—H21 | 109.5 |
O4—C9—C14 | 112.8 (4) | | |
| | | |
Al—O2—C3—C2 | −176.1 (4) | O6—Al—O9—C18 | −91.3 (3) |
Al—O2—C3—C4 | 1.9 (4) | O6—C11—C10—C9 | 175.5 (4) |
Al—O3—C4—C3 | −2.7 (4) | O6—C11—C12—C13 | −176.7 (5) |
Al—O3—C4—C5 | 176.2 (4) | O7—C16—C17—O8 | 179.9 (4) |
Al—O5—C10—C9 | −175.9 (4) | O7—C16—C17—C18 | −1.5 (7) |
Al—O5—C10—C11 | 4.5 (5) | O7—C16—C21—C22 | −71.1 (7) |
Al—O6—C11—C10 | 2.7 (5) | O7—C20—C19—C18 | −1.1 (8) |
Al—O6—C11—C12 | −178.7 (4) | O8—Al—O2—C3 | 167.6 (3) |
Al—O8—C17—C16 | −177.8 (4) | O8—Al—O5—C10 | −95.6 (3) |
Al—O8—C17—C18 | 3.5 (5) | O8—Al—O6—C11 | 95.3 (3) |
Al—O9—C18—C17 | −1.5 (5) | O8—Al—O9—C18 | 2.7 (3) |
Al—O9—C18—C19 | 176.1 (4) | O8—C17—C16—C21 | 1.7 (8) |
O1—C2—C3—O2 | 177.6 (4) | O8—C17—C18—O9 | −1.3 (6) |
O1—C2—C3—C4 | −0.3 (6) | O8—C17—C18—C19 | −179.1 (4) |
O1—C2—C7—C8 | −86.4 (6) | O9—Al—O2—C3 | 83.0 (3) |
O1—C6—C5—C4 | −1.6 (7) | O9—Al—O3—C4 | −91.8 (3) |
O2—Al—O3—C4 | 3.0 (3) | O9—Al—O6—C11 | 179.3 (3) |
O2—Al—O5—C10 | 170.3 (3) | O9—Al—O8—C17 | −3.4 (3) |
O2—Al—O8—C17 | −97.5 (3) | O9—C18—C17—C16 | −180.0 (4) |
O2—Al—O9—C18 | 96.0 (3) | O9—C18—C19—C20 | −178.6 (5) |
O2—C3—C2—C7 | −0.1 (7) | C2—O1—C6—C5 | 1.0 (7) |
O2—C3—C4—O3 | 0.7 (5) | C2—C3—C4—C5 | −0.2 (6) |
O2—C3—C4—C5 | −178.4 (4) | C3—C2—O1—C6 | 0.0 (7) |
O3—Al—O2—C3 | −2.6 (3) | C3—C2—C7—C8 | 91.5 (7) |
O3—Al—O5—C10 | 85.4 (3) | C3—C4—C5—C6 | 1.1 (6) |
O3—Al—O6—C11 | −94.5 (3) | C4—C3—C2—C7 | −178.0 (4) |
O3—Al—O9—C18 | −179.8 (3) | C6—O1—C2—C7 | 177.9 (4) |
O3—C4—C3—C2 | 178.8 (4) | C9—O4—C13—C12 | −2.4 (8) |
O3—C4—C5—C6 | −177.8 (4) | C9—C10—C11—C12 | −3.3 (7) |
O4—C9—C10—O5 | −177.6 (4) | C10—C9—O4—C13 | 0.9 (7) |
O4—C9—C10—C11 | 1.9 (7) | C10—C9—C14—C15 | −105.7 (7) |
O4—C9—C14—C15 | 76.1 (6) | C10—C11—C12—C13 | 1.9 (7) |
O4—C13—C12—C11 | 0.9 (9) | C11—C10—C9—C14 | −176.2 (5) |
O5—Al—O2—C3 | −96.3 (3) | C13—O4—C9—C14 | 179.3 (5) |
O5—Al—O3—C4 | 97.2 (3) | C16—O7—C20—C19 | 1.9 (8) |
O5—Al—O6—C11 | −0.2 (3) | C16—C17—C18—C19 | 2.2 (7) |
O5—Al—O8—C17 | 167.6 (3) | C17—C16—O7—C20 | −0.5 (7) |
O5—C10—C9—C14 | 4.2 (8) | C17—C16—C21—C22 | 107.1 (7) |
O5—C10—C11—O6 | −4.9 (6) | C17—C18—C19—C20 | −0.9 (7) |
O5—C10—C11—C12 | 176.3 (4) | C18—C17—C16—C21 | −179.7 (5) |
O6—Al—O3—C4 | −178.3 (3) | C20—O7—C16—C21 | 177.9 (5) |
O6—Al—O5—C10 | −2.5 (3) | C20—O7—C16—C21 | 177.9 (5) |
O6—Al—O8—C17 | 82.6 (3) | | |
Symmetry codes: (i) x+1, y−1, z; (ii) x+1, y, z; (iii) −x+1, −y, −z+1; (iv) −x+1/2, y−1/2, −z+1/2; (v) x, y+1, z; (vi) x−1, y, z; (vii) x, y−1, z. |
Experimental details
| (II) | (III) |
Crystal data |
Chemical formula | [Fe(C7H7O3)3] | [Al(C7H7O3)3] |
Mr | 473.23 | 444.36 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 7.878 (3), 8.818 (4), 30.721 (2) | 7.897 (4), 8.696 (9), 30.801 (4) |
β (°) | 90.80 (2) | 91.40 (3) |
V (Å3) | 2133.9 (13) | 2115 (2) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.76 | 0.15 |
Crystal size (mm) | 0.40 × 0.10 × 0.10 | 0.20 × 0.20 × 0.10 |
|
Data collection |
Diffractometer | Rigaku AFC-5R diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | – | ψ scan (North et al., 1968) |
Tmin, Tmax | – | 0.952, 0.999 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5604, 4911, 2768 | 5552, 4868, 1804 |
Rint | 0.026 | 0.127 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.135, 0.99 | 0.064, 0.228, 0.94 |
No. of reflections | 4911 | 4868 |
No. of parameters | 283 | 280 |
No. of restraints | ? | ? |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.32 | 0.37, −0.42 |
Selected geometric parameters (Å, º) for (II) topFe—O2 | 1.969 (2) | O2—C3 | 1.330 (4) |
Fe—O3 | 2.085 (2) | O3—C4 | 1.262 (4) |
Fe—O5 | 1.960 (2) | O5—C10 | 1.326 (3) |
Fe—O6 | 2.074 (2) | O6—C11 | 1.259 (4) |
Fe—O8 | 1.967 (2) | O8—C17 | 1.321 (4) |
Fe—O9 | 2.090 (2) | O9—C18 | 1.262 (4) |
| | | |
O2—Fe—O3 | 80.79 (9) | O8—Fe—O9 | 80.39 (9) |
O5—Fe—O6 | 80.71 (8) | | |
Selected geometric parameters (Å, º) for (III) topAl—O2 | 1.872 (3) | O2—C3 | 1.315 (5) |
Al—O3 | 1.956 (3) | O3—C4 | 1.274 (5) |
Al—O5 | 1.858 (3) | O5—C10 | 1.329 (5) |
Al—O6 | 1.949 (3) | O6—C11 | 1.263 (6) |
Al—O8 | 1.874 (3) | O8—C17 | 1.321 (5) |
Al—O9 | 1.952 (3) | O9—C18 | 1.268 (6) |
| | | |
O2—Al—O3 | 84.6 (1) | O8—Al—O9 | 84.3 (1) |
O5—Al—O6 | 84.6 (1) | | |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
Pyranone ligands have remarkable properties for clinical purposes. These ligands are relevant to the control of metal levels in the body and so far have been tested for administration for the amelioration of anaemia (Hider et al., 1984a,b), and the removal of iron (Kontoghiorghes et al., 1990) and aluminium (Kontoghiorghes, 1995) overload. One of these ligands, viz. ethyl maltol (2-ethyl-3-hydroxyl-4-pyranone), (I), is suitable for oral administration since it has no toxic effect. It has been tested for the characteristics of iron uptake (Levey et al., 1988; Maxton et al., 1994). In this study, to determine the chelating mode of ethyl maltol to Fe3+ and Al3+ atoms, we have analyzed the crystal structures of the title complexes fac-tris(2-ethyl-3-oxo-4H-pyran-4-onato)iron(III), (II), and fac-tris(2-ethyl-3-oxo-4H-pyran-4-onato)aluminium(III), (III), which are isomorphous.
In (II), the Fe atom is bound by the deprotonated hydroxyl and keto O atoms of three bidentate ligands to form a distorted octahedral structure (Fig. 1). These O atoms of each ligand form a five-membered chelate ring with the Fe atom. In the ligand molecule, the C—Oketo bond lengths [O3—C4 = 1.262 (4) Å, O6—C11 = 1.259 (4) Å and O9—C18 = 1.262 (4) Å] are longer than those of free ethyl maltol in the crystal [1.235 (2)–1.256 (6) Å; Brown et al., 1995], and the C—OOH bonds [O2—C3 = 1.330 (4) Å, O5—C10 = 1.326 (3) Å and O8—C17 = 1.321 (4) Å] are shorter than those of the free molecule [1.347 (3)–1.356 (6) Å]. This indicates the distinction between the two types of Lewis acid–base interactions. The Fe atom lies in a trigonally distorted octahedral environment, coordinated to the six O atoms of three bidentate ligands in a fac configuration, that is, the three longer Fe—Oketo bonds (Fe—O3, Fe—O6 and Fe—O9) are cis to each other, and the three shorter Fe—OOH bonds (Fe—O2, Fe—O5 and Fe—O8) are also cis. The distortion of the octahedral environment is due to the differences found in the Fe—O bond lengths [Fe—Oketo = 2.074 (2)–2.090 (2) Å and Fe—OOH = 1.960 (2)–1.969 (2) Å]. This situation is similar to those in the crystal structure of the maltolate–Fe3+ complex (Ahmet et al., 1988). The differences between the Fe—Oketo and Fe—OOH bond lengths are due to the negative charge at the deprotonated O atoms.
In (III), coordination about the Al atom is similar to that in (II). The Al atom is surrounded by six O atoms of three bidentate ligands in a fac configuration in a distorted octahedral environment (Fig. 2). In the ligand molecule, the C—Oketo bond lengths [O3—C4 = 1.274 (6) Å, O6—C11 = 1.263 (6) Å and O9—C18 = 1.268 (6) Å] are longer than those of free ethyl maltol and the C—OOH bonds [O2—C3 = 1.315 (5) Å, O5—C10 = 1.329 (5) Å and O8—C17 = 1.321 (5) Å] are shorter than those of the free molecule. The overall conformational tendency of (III) is similar to that in the crystal structures of maltolate–Al3+ complexes (Finnegan et al., 1986; Yu et al., 2002).
Despite the conformational similarity of the crystal structures of (II) and (III), the bite angles, O—M—O, of the ethyl maltolate ligands are different. Those for the Fe3+ complex [range 80.39 (9)–80.79 (9)°] are smaller than those for the Al3+ complex [range 84.3 (1)–84.6 (1)°]. This correlates to the M—O bond lengths [Fe—O = 1.960 (2)–2.090 (2) Å and Al—O = 1.860 (3)–1.956 (4) Å], namely the steric constraint imposed by the ionic radii (0.79 Å for Fe3+ and 0.68 Å for Al3+; Shannon, 1976).
Until now, the crystal structures of the Sn4+ (Lu et al., 1999; Alshehri et al., 2000), Ti4+ (Alshehri et al., 2000) and Bi3+ (Burgess et al., 1994) complexes of ethyl maltol have been reported. In these complexes, similar to (II) and (III), the metal atoms are bound by bidentate ligand molecules to form five membered chelate rings. These structures, except for the Ti4+ complex, show the same trends consistent with the increasing radius of the metal ion. The M—O bond lengths increase and the O—M—O bond angles decrease with increasing ionic radius.
Comparing the present two complexes with the corresponding maltolate complexes shows that all four crystal structures are similar in the fact that the metal atoms are bound by six O atoms of bidentate ligand molecules to form distorted octahedral structures, but are different with regard to their geometrical isomerism properties. In the ethyl maltolate complexes, the ligand molecules are coordinated in a fac configuration, in contrast in the maltolate complexes, which exhibit a mer configuration. This may be due to the bulky hydrophobic ethyl groups of the ethyl maltolate ligand molecules.