Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110031318/su3049sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110031318/su3049Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110031318/su3049IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110031318/su3049IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110031318/su3049IVsup5.hkl |
CCDC references: 796058; 796059; 796060; 796061
For related literature, see: Allen (2002); Bergstrom et al. (2000); Chui et al. (2001); Dutkiewicz et al. (2007); Eddaoudi et al. (2002); Fabelo et al. (2006); Ghosh & Bharadwaj (2004); Goldberg (2005, 2008); Huang et al. (2009); Jessen et al. (1992); Lu et al. (2005); Rossi et al. (2005); Spek (2009); Wang et al. (2007); Wen et al. (2004); Wu et al. (1996, 2001).
The tetraacid ligand was obtained in a three-step procedure. First, commercially available 2,5-dihydroxy-1,4-benzenediacetic acid (0.5 g, 2.21 mmol) was dissolved in absolute EtOH (50 ml), sulfuric acid (4 ml) was added dropwise, and the mixture was refluxed overnight. The solution was then evaporated and extracted with dichloromethane. The organic extracts were collected over anhydrous sodium sulfate. Subsequent removal of the solvent gave the diethyl-2,2'-(2,5-dihydroxy-1,4-phenylene)diacetate intermediate A in 85% yield. In the second step, a mixture of A (450 mg, 4.6 mmol), methyl bromoacetate (520 mg, 3.4 mmol) and potassium carbonate (630 mg, 4.6 mmol) was dissolved in acetone (50 ml) and refluxed for 5 h at 333 K. The resulting mixture was filtered and the residue dissolved in water to remove unreacted potassium carbonate. Intermediate B, 2,2'-[2,5-bis(2-methoxy-2-oxoethoxy)-1,4-phenylene]diacetate, was isolated by filtration and dried in vacuo (yield 61%). It was then dissolved in methanol (20 ml), 5 N NaOH (3 ml) was added, and the mixture was refluxed overnight. After removal of the reaction solvent by evaporation, the crude product was treated with 0.5 N HCl, washed with water and dried in vacuo, yielding a white precipitate (in 72% yield) as the final tetraacid product, 2,2'-[2,5-bis(carboxymethoxy)-1,4-phenylene]diacetic acid (TALH4). 1H NMR (DMSO-d6, δ, p.p.m.): 12.53 (bs, 4H, –COOH), 6.81 (s, 2H, Ar—H), 4.56 (s, 4H, –OCH2), 3.53 (s, 4H, –CH2).
Compound (I) was obtained by dissolving TALH4 (5 mg, 0.015 mmol) and cadmium dinitrate tetrahydrate (9 mg, 0.03 mmol) in water (4 ml), with a few drops of ammonium hydroxide to assist in deprotonation of TALH4. The mixture was heated for 2 d in a bath reactor at 353 K, to yield colourless crystals of (I) after gradual cooling to room temperature. It turned out that under the given experimental conditions the cadmium cations did not react with TALH4, and instead the diaammonium salt of the acid was formed. FT–IR (KBr, ν, cm-1): 2963 (bs), 1716 (s), 1525 (s), 1416 (s), 1340 (b), 1301 (b), 1218 (b), 1158 (b), 1091 (s), 896 (b), 721 (s), 678 (s), 628 (s), 564 (s), 441 (s).
Compound (II) was obtained by dissolving TALH4 (3.3 mg, 0.01 mmol) and lanthanum trinitrate hexahydrate (8.2 mg, 0.02 mmol) in water (7 ml). This solution was placed in a sealed and tightly capped vessel, which was heated for 2 d at 393 K in a bath reactor. Colourless crystals of (II) precipitated in the reactor. FT–IR (KBr, ν, cm-1): 3419 (bs), 2925 (s), 1584 (s), 1512 (s), 1391 (s), 1335 (s), 1210 (s), 1053 (s), 645 (bs).
In a similar procedure, TALH4 (20 mg, 0.06 mmol) and zinc dinitrate hexahydrate (30 mg, 0.12 mmol) were dissolved in a 2:1:1 MeOH:DMF:water mixture (DMF is dimethylformamide) (4 ml) and heated for 2 d in a bath reactor at 373 K, yielding (III) as a colourless crystalline product. FT–IR (KBr, ν, cm-1): 3193 (bs), 1610 (s), 1511 (s), 1403 (s), 1306 (s), 1270 (s), 1207 (s), 1083 (s), 943 (s), 788 (s), 703 (s), 649 (s), 608 (s).
In another experiment, TALH4 (10 mg, 0.03 mmol), zinc dinitrate hexahydrate (18 mg, 0.06 mmol) and 4,4'-bipyridyl (5 mg, 0.03 mmol) were dissolved in a 6:2:1 MeOH:DMF:water mixture (4.5 ml). After heating the mixture for 2 d in a bath reactor at 373 K, followed by slow evaporation at room temperature for two weeks, X-ray quality colourless crystals of compound (IV) were obtained. FT–IR (KBr, ν, cm-1): 3392 (bs), 1602 (s), 1388 (s), 1216 (s), 1077 (s), 733 (s).
In (I), the atomic coordinates of all the H atoms, initially included in calculated positions or located in difference Fourier maps, were refined, but with Uiso = 1.2Ueq(C) for H atoms bound to C atoms, and Uiso = 1.5Ueq(O, N) for H atoms bound to O and N atoms. In compounds (II)–(IV), H atoms bound to C atoms were included in calculated positions and constrained to ride on their parent atoms, with C—H = 0.95 and 0.99 Å and with Uiso(H) = 1.2Ueq(C). Those bound to O atoms were either located in difference Fourier maps or placed in calculated positions to correspond to idealized hydrogen-bonding geometries, with O—H = 0.79–1.00 Å. Their atomic positions were not refined, and they were constrained to ride on their parent atoms with Uiso(H) = 1.5Ueq(O).
Compound (III) is a trihydrate of a 1:1 zinc:TALH22- adduct. It could be readily recognized by inspection of the difference Fourier map that the water molecules form hydration layers at the interface between the coordination networks. However, they were found to be severely disordered and could not be reliably modelled as discrete O and H atoms. Their contribution to the diffraction pattern was subtracted by the SQUEEZE procedure in PLATON (Spek, 2009). The total solvent-accessible void volume and the residual electron-density count in the unit cell were assessed by PLATON to be 270 Å3 and 86 e, respectively, which may correspond approximately to the presence of nearly three water molecules in the asymmetric unit, although independent evidence to this end could not be obtained. Moreover, the atoms of the TALH22- anion exhibit large-amplitude in-plane atomic displacement parameters, and the H atoms of the –COOH residues could not be located. The disordered water solvent and these two H atoms have been included in the chemical formula and all values derived from it. The maximum residual electron-density peaks in (III) are near the peripheral aliphatic arms: 1.33 e Å-3 at (0.036, 0.351, 0.631) and 1.01 e Å-3 at (0.045, 0.355, 0.294). Correspondingly, the structure of this product could not be determined with high precision comparable with that of structures (I), (II) and (IV). It was included in this report for the sake of completeness.
Five residual peaks above 1.0 e Å-3 were found in (II) near the aliphatic fragments and water species: 1.69 e Å-3 at (0.426, 0.456, 0.424), 1.67 e Å-3 at (0.468, 0.787, 0.028), 1.56 e Å-3 at (0.305, 0.059, 0.039), 1.49 e Å-3 at (0.460, 0.822, 0.099) and 1.47 e Å-3 at (0.251, 0.301, 0.698).
For all compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
2NH4+·C14H12O102− | F(000) = 396 |
Mr = 376.32 | Dx = 1.576 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 4.8188 (3) Å | Cell parameters from 1652 reflections |
b = 14.6889 (8) Å | θ = 2.3–26.3° |
c = 11.2087 (8) Å | µ = 0.14 mm−1 |
β = 91.855 (2)° | T = 110 K |
V = 792.97 (9) Å3 | Needle, colourless |
Z = 2 | 0.40 × 0.15 × 0.15 mm |
Nonius KappaCCD area-detector diffractometer | 1243 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.051 |
Graphite monochromator | θmax = 26.3°, θmin = 2.3° |
Detector resolution: 12.8 pixels mm-1 | h = 0→6 |
1 deg. ϕ and ω scans | k = 0→18 |
9862 measured reflections | l = −13→13 |
1598 independent reflections |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | Only H-atom coordinates refined |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0487P)2 + 0.3554P] where P = (Fo2 + 2Fc2)/3 |
1598 reflections | (Δ/σ)max = 0.003 |
148 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
2NH4+·C14H12O102− | V = 792.97 (9) Å3 |
Mr = 376.32 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.8188 (3) Å | µ = 0.14 mm−1 |
b = 14.6889 (8) Å | T = 110 K |
c = 11.2087 (8) Å | 0.40 × 0.15 × 0.15 mm |
β = 91.855 (2)° |
Nonius KappaCCD area-detector diffractometer | 1243 reflections with I > 2σ(I) |
9862 measured reflections | Rint = 0.051 |
1598 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.102 | Only H-atom coordinates refined |
S = 1.04 | Δρmax = 0.27 e Å−3 |
1598 reflections | Δρmin = −0.22 e Å−3 |
148 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 | ||
C1 | 0.8294 (4) | 0.04845 (12) | 0.07567 (17) | 0.0166 (4) | |
C2 | 0.8154 (4) | 0.06322 (13) | −0.04671 (17) | 0.0168 (4) | |
H2 | 0.696 (5) | 0.1067 (15) | −0.0789 (19) | 0.020* | |
C3 | 1.0173 (4) | −0.01523 (12) | 0.12399 (17) | 0.0168 (4) | |
O4 | 0.6641 (3) | 0.09384 (8) | 0.15602 (11) | 0.0181 (3) | |
C5 | 0.4886 (4) | 0.16176 (13) | 0.10272 (18) | 0.0183 (4) | |
H5A | 0.378 (5) | 0.1356 (14) | 0.039 (2) | 0.022* | |
H5B | 0.606 (5) | 0.2098 (15) | 0.0682 (19) | 0.022* | |
C6 | 0.2924 (4) | 0.20441 (12) | 0.19049 (17) | 0.0173 (4) | |
O7 | 0.1458 (3) | 0.26711 (9) | 0.14113 (12) | 0.0214 (3) | |
O8 | 0.2751 (3) | 0.17838 (9) | 0.29544 (12) | 0.0200 (3) | |
C9 | 1.0489 (4) | −0.03077 (13) | 0.25620 (18) | 0.0185 (4) | |
H9A | 1.074 (4) | 0.0274 (15) | 0.2995 (19) | 0.022* | |
H9B | 1.220 (5) | −0.0699 (14) | 0.2726 (19) | 0.022* | |
C10 | 0.8145 (4) | −0.08245 (12) | 0.31195 (17) | 0.0186 (4) | |
O11 | 0.7183 (3) | −0.15015 (9) | 0.24562 (12) | 0.0216 (3) | |
H11 | 0.567 (5) | −0.1823 (15) | 0.287 (2) | 0.032* | |
O12 | 0.7324 (3) | −0.06467 (9) | 0.41152 (12) | 0.0249 (4) | |
N13 | 0.7511 (4) | 0.13651 (13) | 0.42955 (17) | 0.0211 (4) | |
H13A | 0.714 (5) | 0.1672 (16) | 0.500 (2) | 0.032* | |
H13B | 0.596 (6) | 0.1456 (16) | 0.380 (2) | 0.032* | |
H13C | 0.753 (5) | 0.0723 (18) | 0.443 (2) | 0.032* | |
H13D | 0.915 (6) | 0.1590 (15) | 0.393 (2) | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0130 (9) | 0.0159 (9) | 0.0210 (10) | −0.0018 (7) | 0.0043 (8) | −0.0019 (7) |
C2 | 0.0140 (10) | 0.0149 (9) | 0.0215 (10) | −0.0004 (8) | 0.0009 (8) | 0.0027 (8) |
C3 | 0.0150 (10) | 0.0146 (9) | 0.0208 (10) | −0.0024 (7) | 0.0018 (8) | 0.0007 (7) |
O4 | 0.0180 (7) | 0.0178 (7) | 0.0185 (7) | 0.0053 (5) | 0.0014 (5) | 0.0003 (5) |
C5 | 0.0189 (11) | 0.0176 (10) | 0.0183 (10) | 0.0017 (8) | 0.0002 (8) | 0.0014 (8) |
C6 | 0.0160 (10) | 0.0165 (9) | 0.0193 (10) | −0.0019 (8) | −0.0002 (8) | 0.0003 (8) |
O7 | 0.0225 (8) | 0.0208 (7) | 0.0211 (7) | 0.0059 (6) | 0.0026 (6) | 0.0028 (5) |
O8 | 0.0188 (8) | 0.0212 (7) | 0.0199 (7) | 0.0010 (6) | 0.0021 (6) | 0.0007 (6) |
C9 | 0.0172 (10) | 0.0183 (10) | 0.0201 (10) | 0.0004 (8) | 0.0018 (8) | 0.0007 (8) |
C10 | 0.0187 (10) | 0.0193 (9) | 0.0178 (10) | 0.0027 (8) | −0.0010 (8) | 0.0022 (8) |
O11 | 0.0235 (8) | 0.0207 (7) | 0.0207 (7) | −0.0058 (6) | 0.0035 (6) | −0.0021 (6) |
O12 | 0.0276 (8) | 0.0266 (8) | 0.0209 (8) | −0.0036 (6) | 0.0058 (6) | −0.0007 (6) |
N13 | 0.0211 (10) | 0.0238 (9) | 0.0185 (9) | 0.0018 (8) | 0.0012 (8) | −0.0024 (7) |
C1—C2 | 1.388 (3) | C6—O7 | 1.276 (2) |
C1—O4 | 1.392 (2) | C9—C10 | 1.513 (3) |
C1—C3 | 1.399 (3) | C9—H9A | 0.99 (2) |
C2—C3i | 1.394 (3) | C9—H9B | 1.02 (2) |
C2—H2 | 0.92 (2) | C10—O12 | 1.224 (2) |
C3—C2i | 1.394 (3) | C10—O11 | 1.317 (2) |
C3—C9 | 1.502 (3) | O11—H11 | 0.99 (2) |
O4—C5 | 1.426 (2) | N13—H13A | 0.93 (3) |
C5—C6 | 1.522 (3) | N13—H13B | 0.93 (3) |
C5—H5A | 0.96 (2) | N13—H13C | 0.96 (3) |
C5—H5B | 0.99 (2) | N13—H13D | 0.96 (3) |
C6—O8 | 1.242 (2) | ||
C2—C1—O4 | 123.64 (17) | O7—C6—C5 | 111.33 (16) |
C2—C1—C3 | 119.82 (17) | C3—C9—C10 | 115.51 (16) |
O4—C1—C3 | 116.54 (16) | C3—C9—H9A | 111.1 (12) |
C1—C2—C3i | 121.63 (18) | C10—C9—H9A | 108.3 (12) |
C1—C2—H2 | 120.2 (13) | C3—C9—H9B | 108.7 (12) |
C3i—C2—H2 | 118.1 (13) | C10—C9—H9B | 104.6 (12) |
C2i—C3—C1 | 118.54 (18) | H9A—C9—H9B | 108.2 (18) |
C2i—C3—C9 | 119.61 (17) | O12—C10—O11 | 123.89 (18) |
C1—C3—C9 | 121.82 (17) | O12—C10—C9 | 122.49 (17) |
C1—O4—C5 | 114.08 (14) | O11—C10—C9 | 113.55 (16) |
O4—C5—C6 | 112.93 (16) | C10—O11—H11 | 110.2 (13) |
O4—C5—H5A | 109.9 (13) | H13A—N13—H13B | 106 (2) |
C6—C5—H5A | 107.7 (13) | H13A—N13—H13C | 110 (2) |
O4—C5—H5B | 108.9 (13) | H13B—N13—H13C | 104 (2) |
C6—C5—H5B | 109.5 (12) | H13A—N13—H13D | 112 (2) |
H5A—C5—H5B | 107.7 (18) | H13B—N13—H13D | 111 (2) |
O8—C6—O7 | 125.44 (17) | H13C—N13—H13D | 114 (2) |
O8—C6—C5 | 123.20 (17) |
Symmetry code: (i) −x+2, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···O7ii | 0.99 (2) | 1.52 (2) | 2.5123 (19) | 175 (2) |
N13—H13A···O7iii | 0.93 (3) | 1.89 (3) | 2.822 (2) | 178 (2) |
N13—H13B···O8 | 0.93 (3) | 1.85 (3) | 2.771 (2) | 171 (2) |
N13—H13C···O12 | 0.96 (3) | 2.05 (3) | 2.963 (2) | 160 (2) |
N13—H13D···O8iv | 0.96 (3) | 2.10 (3) | 3.043 (2) | 167 (2) |
Symmetry codes: (ii) −x+1/2, y−1/2, −z+1/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) x+1, y, z. |
[La2(C14H11O10)2(H2O)]·H2O | Z = 2 |
Mr = 992.31 | F(000) = 968 |
Triclinic, P1 | Dx = 2.118 Mg m−3 |
a = 10.2508 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.1655 (3) Å | Cell parameters from 6510 reflections |
c = 14.7606 (4) Å | θ = 2.0–27.2° |
α = 79.5944 (12)° | µ = 2.81 mm−1 |
β = 82.1510 (12)° | T = 110 K |
γ = 69.9402 (17)° | Plate, colourless |
V = 1555.74 (7) Å3 | 0.15 × 0.15 × 0.10 mm |
Nonius KappaCCD area-detector diffractometer | 6850 independent reflections |
Radiation source: fine-focus sealed tube | 5610 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
Detector resolution: 12.8 pixels mm-1 | θmax = 27.2°, θmin = 2.0° |
1 deg. ϕ and ω scans | h = 0→13 |
Absorption correction: multi-scan (Blessing, 1995) | k = −13→14 |
Tmin = 0.678, Tmax = 0.766 | l = −18→18 |
25631 measured reflections |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0491P)2 + 1.7278P] where P = (Fo2 + 2Fc2)/3 |
6850 reflections | (Δ/σ)max < 0.001 |
470 parameters | Δρmax = 1.69 e Å−3 |
0 restraints | Δρmin = −1.78 e Å−3 |
[La2(C14H11O10)2(H2O)]·H2O | γ = 69.9402 (17)° |
Mr = 992.31 | V = 1555.74 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.2508 (2) Å | Mo Kα radiation |
b = 11.1655 (3) Å | µ = 2.81 mm−1 |
c = 14.7606 (4) Å | T = 110 K |
α = 79.5944 (12)° | 0.15 × 0.15 × 0.10 mm |
β = 82.1510 (12)° |
Nonius KappaCCD area-detector diffractometer | 6850 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 5610 reflections with I > 2σ(I) |
Tmin = 0.678, Tmax = 0.766 | Rint = 0.062 |
25631 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.69 e Å−3 |
6850 reflections | Δρmin = −1.78 e Å−3 |
470 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 | ||
La1 | −0.01271 (2) | −0.18754 (2) | 0.164737 (15) | 0.00868 (8) | |
La2 | 0.27791 (2) | 0.68201 (2) | 0.368677 (15) | 0.00916 (8) | |
C1 | −0.1622 (4) | 0.1341 (4) | 0.2239 (3) | 0.0113 (8) | |
C2 | −0.1260 (4) | 0.1276 (4) | 0.3124 (3) | 0.0111 (8) | |
C3 | −0.0883 (4) | 0.2291 (4) | 0.3312 (3) | 0.0115 (9) | |
H3 | −0.0650 | 0.2281 | 0.3915 | 0.014* | |
C4 | −0.0845 (4) | 0.3304 (4) | 0.2633 (3) | 0.0113 (9) | |
C5 | −0.1203 (5) | 0.3360 (4) | 0.1741 (3) | 0.0134 (9) | |
C6 | −0.1599 (5) | 0.2366 (4) | 0.1551 (3) | 0.0145 (9) | |
H6 | −0.1854 | 0.2386 | 0.0952 | 0.017* | |
O7 | −0.1955 (3) | 0.0308 (3) | 0.2035 (2) | 0.0128 (6) | |
C8 | −0.3343 (5) | 0.0646 (4) | 0.1743 (3) | 0.0171 (10) | |
H8A | −0.3410 | 0.1178 | 0.1127 | 0.021* | |
H8B | −0.4033 | 0.1153 | 0.2185 | 0.021* | |
C9 | −0.3644 (5) | −0.0571 (4) | 0.1704 (3) | 0.0154 (9) | |
O10 | −0.4758 (4) | −0.0471 (3) | 0.1426 (2) | 0.0236 (8) | |
O11 | −0.2697 (3) | −0.1635 (3) | 0.1960 (2) | 0.0156 (7) | |
C12 | −0.1268 (4) | 0.0148 (4) | 0.3865 (3) | 0.0115 (8) | |
H12A | −0.2071 | −0.0125 | 0.3803 | 0.014* | |
H12B | −0.1398 | 0.0430 | 0.4479 | 0.014* | |
C13 | 0.0057 (4) | −0.0995 (4) | 0.3814 (3) | 0.0100 (8) | |
O14 | 0.0619 (3) | −0.1294 (3) | 0.3019 (2) | 0.0121 (6) | |
O15 | 0.0598 (3) | −0.1639 (3) | 0.45328 (19) | 0.0149 (7) | |
O16 | −0.0452 (4) | 0.4320 (3) | 0.2750 (2) | 0.0188 (7) | |
C17 | −0.0140 (5) | 0.4403 (4) | 0.3647 (3) | 0.0114 (9) | |
H17A | 0.0684 | 0.3667 | 0.3847 | 0.014* | |
H17B | −0.0940 | 0.4394 | 0.4105 | 0.014* | |
C18 | 0.0153 (4) | 0.5667 (4) | 0.3565 (3) | 0.0107 (8) | |
O19 | −0.0590 (3) | 0.6636 (3) | 0.3064 (2) | 0.0135 (6) | |
O20 | 0.1095 (3) | 0.5653 (3) | 0.4034 (2) | 0.0139 (6) | |
C21 | −0.1016 (5) | 0.4405 (4) | 0.0977 (3) | 0.0180 (10) | |
H21A | −0.0023 | 0.4156 | 0.0740 | 0.022* | |
H21B | −0.1563 | 0.4440 | 0.0464 | 0.022* | |
C22 | −0.1437 (5) | 0.5730 (4) | 0.1238 (3) | 0.0154 (9) | |
O23 | −0.2706 (3) | 0.6174 (3) | 0.1611 (2) | 0.0216 (7) | |
H23 | −0.2766 | 0.7035 | 0.1746 | 0.032* | |
O24 | −0.0637 (3) | 0.6367 (3) | 0.1045 (2) | 0.0153 (7) | |
C25 | 0.3786 (4) | 0.3580 (4) | 0.2885 (3) | 0.0108 (8) | |
C26 | 0.3683 (4) | 0.3818 (4) | 0.1940 (3) | 0.0119 (9) | |
C27 | 0.3203 (5) | 0.3018 (4) | 0.1542 (3) | 0.0123 (9) | |
H27 | 0.3128 | 0.3163 | 0.0894 | 0.015* | |
C28 | 0.2833 (4) | 0.2004 (4) | 0.2092 (3) | 0.0109 (8) | |
C29 | 0.2958 (4) | 0.1776 (4) | 0.3048 (3) | 0.0119 (9) | |
C30 | 0.3432 (4) | 0.2578 (4) | 0.3435 (3) | 0.0128 (9) | |
H30 | 0.3514 | 0.2437 | 0.4082 | 0.015* | |
O31 | 0.4243 (3) | 0.4408 (3) | 0.3298 (2) | 0.0135 (6) | |
C32 | 0.5502 (5) | 0.3727 (4) | 0.3742 (3) | 0.0171 (10) | |
H32A | 0.6238 | 0.3288 | 0.3292 | 0.021* | |
H32B | 0.5342 | 0.3066 | 0.4248 | 0.021* | |
C33 | 0.5958 (4) | 0.4669 (4) | 0.4125 (3) | 0.0120 (9) | |
O34 | 0.6873 (3) | 0.4222 (3) | 0.46879 (19) | 0.0135 (6) | |
O35 | 0.5383 (3) | 0.5860 (3) | 0.3862 (2) | 0.0152 (7) | |
C36 | 0.3982 (5) | 0.4968 (4) | 0.1346 (3) | 0.0127 (9) | |
H36A | 0.4241 | 0.4799 | 0.0699 | 0.015* | |
H36B | 0.4770 | 0.5118 | 0.1573 | 0.015* | |
C37 | 0.2685 (4) | 0.6150 (4) | 0.1391 (3) | 0.0116 (9) | |
O38 | 0.2174 (3) | 0.6453 (3) | 0.21916 (19) | 0.0123 (6) | |
O39 | 0.2113 (3) | 0.6777 (3) | 0.0681 (2) | 0.0173 (7) | |
O40 | 0.2319 (3) | 0.1198 (3) | 0.1767 (2) | 0.0142 (6) | |
C41 | 0.2226 (5) | 0.1351 (4) | 0.0796 (3) | 0.0113 (9) | |
H41A | 0.3172 | 0.1151 | 0.0474 | 0.014* | |
H41B | 0.1689 | 0.2255 | 0.0572 | 0.014* | |
C42 | 0.1514 (5) | 0.0458 (4) | 0.0583 (3) | 0.0123 (9) | |
O43 | 0.1411 (3) | −0.0471 (3) | 0.1173 (2) | 0.0130 (6) | |
O44 | 0.1086 (3) | 0.0722 (3) | −0.0210 (2) | 0.0159 (7) | |
C45 | 0.2572 (5) | 0.0688 (4) | 0.3650 (3) | 0.0138 (9) | |
H45A | 0.1928 | 0.0456 | 0.3325 | 0.017* | |
H45B | 0.2057 | 0.1003 | 0.4225 | 0.017* | |
C46 | 0.3772 (5) | −0.0517 (4) | 0.3911 (3) | 0.0136 (9) | |
O47 | 0.3563 (3) | −0.1534 (3) | 0.4255 (2) | 0.0167 (7) | |
O48 | 0.5010 (3) | −0.0408 (3) | 0.3770 (2) | 0.0223 (8) | |
H48 | 0.5610 | −0.1134 | 0.3899 | 0.033* | |
O49 | 0.3572 (3) | 0.8184 (3) | 0.2314 (2) | 0.0205 (7) | |
H49A | 0.4088 | 0.8589 | 0.2195 | 0.031* | |
H49B | 0.3004 | 0.8634 | 0.1957 | 0.031* | |
O50 | 0.6828 (3) | −0.2582 (3) | 0.4140 (2) | 0.0181 (7) | |
H50A | 0.7559 | −0.2754 | 0.3705 | 0.027* | |
H50B | 0.6404 | −0.3157 | 0.4098 | 0.027* |
U11 | U22 | U33 | U12 | U13 | U23 | |
La1 | 0.01107 (13) | 0.00782 (13) | 0.00833 (13) | −0.00415 (10) | −0.00370 (9) | 0.00016 (9) |
La2 | 0.01044 (13) | 0.00827 (13) | 0.00985 (13) | −0.00381 (10) | −0.00407 (9) | −0.00012 (9) |
C1 | 0.012 (2) | 0.008 (2) | 0.015 (2) | −0.0033 (17) | −0.0032 (17) | −0.0031 (17) |
C2 | 0.008 (2) | 0.013 (2) | 0.012 (2) | −0.0039 (17) | −0.0002 (16) | −0.0001 (17) |
C3 | 0.016 (2) | 0.011 (2) | 0.010 (2) | −0.0053 (17) | −0.0013 (16) | −0.0030 (16) |
C4 | 0.012 (2) | 0.011 (2) | 0.014 (2) | −0.0067 (17) | −0.0041 (17) | 0.0003 (17) |
C5 | 0.018 (2) | 0.017 (2) | 0.009 (2) | −0.0089 (19) | −0.0033 (17) | −0.0025 (17) |
C6 | 0.014 (2) | 0.014 (2) | 0.016 (2) | −0.0050 (18) | −0.0059 (18) | 0.0004 (18) |
O7 | 0.0139 (16) | 0.0096 (15) | 0.0176 (15) | −0.0048 (12) | −0.0065 (12) | −0.0031 (12) |
C8 | 0.012 (2) | 0.017 (2) | 0.025 (2) | −0.0048 (19) | −0.0073 (18) | −0.0044 (19) |
C9 | 0.016 (2) | 0.014 (2) | 0.016 (2) | −0.0050 (19) | −0.0050 (18) | 0.0020 (17) |
O10 | 0.0190 (18) | 0.0192 (17) | 0.037 (2) | −0.0097 (15) | −0.0117 (15) | −0.0002 (15) |
O11 | 0.0154 (16) | 0.0096 (15) | 0.0221 (17) | −0.0040 (13) | −0.0042 (13) | −0.0012 (13) |
C12 | 0.010 (2) | 0.013 (2) | 0.010 (2) | −0.0019 (17) | −0.0009 (16) | −0.0013 (16) |
C13 | 0.013 (2) | 0.012 (2) | 0.010 (2) | −0.0097 (17) | −0.0026 (16) | −0.0015 (16) |
O14 | 0.0123 (15) | 0.0115 (15) | 0.0124 (15) | −0.0031 (12) | −0.0029 (12) | −0.0014 (12) |
O15 | 0.0187 (17) | 0.0161 (16) | 0.0079 (14) | −0.0029 (13) | −0.0038 (12) | −0.0001 (12) |
O16 | 0.036 (2) | 0.0179 (17) | 0.0111 (15) | −0.0177 (15) | −0.0085 (14) | −0.0005 (13) |
C17 | 0.016 (2) | 0.013 (2) | 0.0078 (19) | −0.0075 (18) | −0.0043 (16) | −0.0008 (16) |
C18 | 0.013 (2) | 0.009 (2) | 0.011 (2) | −0.0040 (17) | 0.0003 (16) | −0.0047 (16) |
O19 | 0.0164 (16) | 0.0108 (15) | 0.0142 (15) | −0.0062 (13) | −0.0034 (12) | 0.0010 (12) |
O20 | 0.0200 (17) | 0.0151 (16) | 0.0112 (15) | −0.0121 (13) | −0.0051 (12) | 0.0017 (12) |
C21 | 0.029 (3) | 0.014 (2) | 0.015 (2) | −0.012 (2) | −0.0037 (19) | −0.0006 (18) |
C22 | 0.026 (3) | 0.014 (2) | 0.008 (2) | −0.008 (2) | −0.0041 (18) | 0.0003 (17) |
O23 | 0.0196 (18) | 0.0150 (17) | 0.0321 (19) | −0.0065 (14) | −0.0033 (14) | −0.0058 (14) |
O24 | 0.0239 (18) | 0.0120 (15) | 0.0140 (15) | −0.0108 (14) | −0.0018 (13) | −0.0022 (12) |
C25 | 0.010 (2) | 0.008 (2) | 0.016 (2) | −0.0011 (16) | −0.0031 (16) | −0.0058 (16) |
C26 | 0.008 (2) | 0.010 (2) | 0.018 (2) | −0.0027 (17) | −0.0010 (16) | −0.0031 (17) |
C27 | 0.017 (2) | 0.010 (2) | 0.010 (2) | −0.0025 (18) | −0.0053 (17) | 0.0004 (16) |
C28 | 0.012 (2) | 0.010 (2) | 0.013 (2) | −0.0040 (17) | −0.0036 (16) | −0.0052 (16) |
C29 | 0.009 (2) | 0.013 (2) | 0.014 (2) | −0.0034 (17) | −0.0019 (16) | −0.0032 (17) |
C30 | 0.013 (2) | 0.009 (2) | 0.016 (2) | −0.0033 (17) | −0.0017 (17) | −0.0005 (17) |
O31 | 0.0134 (16) | 0.0075 (14) | 0.0197 (16) | −0.0013 (12) | −0.0087 (13) | −0.0008 (12) |
C32 | 0.013 (2) | 0.011 (2) | 0.027 (3) | −0.0008 (18) | −0.0148 (19) | 0.0011 (18) |
C33 | 0.011 (2) | 0.015 (2) | 0.010 (2) | −0.0054 (18) | 0.0013 (16) | 0.0001 (17) |
O34 | 0.0150 (16) | 0.0181 (16) | 0.0097 (14) | −0.0080 (13) | −0.0068 (12) | 0.0021 (12) |
O35 | 0.0158 (16) | 0.0086 (15) | 0.0222 (17) | −0.0048 (13) | −0.0055 (13) | −0.0006 (13) |
C36 | 0.017 (2) | 0.010 (2) | 0.012 (2) | −0.0041 (18) | −0.0035 (17) | −0.0017 (17) |
C37 | 0.013 (2) | 0.011 (2) | 0.014 (2) | −0.0076 (17) | −0.0031 (17) | −0.0002 (17) |
O38 | 0.0119 (15) | 0.0150 (15) | 0.0094 (14) | −0.0026 (13) | −0.0024 (11) | −0.0029 (12) |
O39 | 0.0226 (18) | 0.0152 (16) | 0.0121 (15) | −0.0032 (14) | −0.0050 (13) | 0.0001 (12) |
O40 | 0.0201 (17) | 0.0162 (16) | 0.0108 (15) | −0.0102 (13) | −0.0039 (12) | −0.0024 (12) |
C41 | 0.019 (2) | 0.010 (2) | 0.0077 (19) | −0.0058 (18) | −0.0027 (16) | −0.0041 (16) |
C42 | 0.013 (2) | 0.012 (2) | 0.011 (2) | −0.0025 (17) | −0.0018 (16) | −0.0033 (17) |
O43 | 0.0169 (17) | 0.0125 (15) | 0.0120 (15) | −0.0083 (13) | −0.0039 (12) | 0.0018 (12) |
O44 | 0.0229 (18) | 0.0199 (17) | 0.0108 (15) | −0.0128 (14) | −0.0112 (13) | 0.0021 (12) |
C45 | 0.013 (2) | 0.015 (2) | 0.015 (2) | −0.0081 (18) | −0.0028 (17) | 0.0005 (17) |
C46 | 0.017 (2) | 0.019 (2) | 0.008 (2) | −0.0082 (19) | −0.0043 (17) | −0.0028 (17) |
O47 | 0.0217 (18) | 0.0111 (15) | 0.0187 (16) | −0.0077 (13) | −0.0055 (13) | 0.0018 (13) |
O48 | 0.0145 (17) | 0.0157 (17) | 0.035 (2) | −0.0055 (14) | −0.0076 (15) | 0.0056 (15) |
O49 | 0.0188 (18) | 0.0239 (18) | 0.0217 (17) | −0.0128 (15) | −0.0086 (14) | 0.0063 (14) |
O50 | 0.0180 (17) | 0.0197 (17) | 0.0200 (17) | −0.0109 (14) | −0.0016 (13) | −0.0023 (13) |
La1—O44i | 2.417 (3) | O19—La1iv | 2.525 (3) |
La1—O14 | 2.519 (3) | C21—C22 | 1.499 (6) |
La1—O19ii | 2.525 (3) | C21—H21A | 0.9900 |
La1—O24ii | 2.525 (3) | C21—H21B | 0.9900 |
La1—O43 | 2.536 (3) | C22—O24 | 1.234 (5) |
La1—O11 | 2.540 (3) | C22—O23 | 1.305 (6) |
La1—O38ii | 2.579 (3) | O23—H23 | 0.9967 |
La1—O7 | 2.619 (3) | O24—La1iv | 2.525 (3) |
La1—O39ii | 2.661 (3) | C25—C30 | 1.383 (6) |
La1—C37ii | 2.993 (4) | C25—C26 | 1.384 (6) |
La1—La2ii | 4.2365 (3) | C25—O31 | 1.422 (5) |
La2—O20 | 2.450 (3) | C26—C27 | 1.399 (6) |
La2—O34iii | 2.486 (3) | C26—C36 | 1.516 (6) |
La2—O38 | 2.509 (3) | C27—C28 | 1.401 (6) |
La2—O49 | 2.524 (3) | C27—H27 | 0.9500 |
La2—O35 | 2.543 (3) | C28—O40 | 1.366 (5) |
La2—O47iv | 2.546 (3) | C28—C29 | 1.403 (6) |
La2—O15iv | 2.625 (3) | C29—C30 | 1.388 (6) |
La2—O14iv | 2.638 (3) | C29—C45 | 1.506 (6) |
La2—O31 | 2.718 (3) | C30—H30 | 0.9500 |
La2—C13iv | 3.021 (4) | O31—C32 | 1.432 (5) |
La2—La1iv | 4.2365 (3) | C32—C33 | 1.507 (6) |
C1—C6 | 1.390 (6) | C32—H32A | 0.9900 |
C1—C2 | 1.390 (6) | C32—H32B | 0.9900 |
C1—O7 | 1.401 (5) | C33—O34 | 1.249 (5) |
C2—C3 | 1.397 (6) | C33—O35 | 1.267 (5) |
C2—C12 | 1.513 (6) | O34—La2iii | 2.486 (3) |
C3—C4 | 1.377 (6) | C36—C37 | 1.522 (6) |
C3—H3 | 0.9500 | C36—H36A | 0.9900 |
C4—O16 | 1.372 (5) | C36—H36B | 0.9900 |
C4—C5 | 1.399 (6) | C37—O39 | 1.246 (5) |
C5—C6 | 1.389 (6) | C37—O38 | 1.281 (5) |
C5—C21 | 1.513 (6) | C37—La1iv | 2.993 (4) |
C6—H6 | 0.9500 | O38—La1iv | 2.579 (3) |
O7—C8 | 1.446 (5) | O39—La1iv | 2.661 (3) |
C8—C9 | 1.506 (6) | O40—C41 | 1.424 (5) |
C8—H8A | 0.9900 | C41—C42 | 1.517 (6) |
C8—H8B | 0.9900 | C41—H41A | 0.9900 |
C9—O10 | 1.228 (5) | C41—H41B | 0.9900 |
C9—O11 | 1.282 (5) | C42—O43 | 1.253 (5) |
C12—C13 | 1.516 (6) | C42—O44 | 1.256 (5) |
C12—H12A | 0.9900 | O44—La1i | 2.417 (3) |
C12—H12B | 0.9900 | C45—C46 | 1.510 (6) |
C13—O15 | 1.249 (5) | C45—H45A | 0.9900 |
C13—O14 | 1.283 (5) | C45—H45B | 0.9900 |
C13—La2ii | 3.021 (4) | C46—O47 | 1.233 (5) |
O14—La2ii | 2.638 (3) | C46—O48 | 1.302 (5) |
O15—La2ii | 2.625 (3) | O47—La2ii | 2.546 (3) |
O16—C17 | 1.429 (5) | O48—H48 | 0.8400 |
C17—C18 | 1.522 (6) | O49—H49A | 0.7901 |
C17—H17A | 0.9900 | O49—H49B | 0.8098 |
C17—H17B | 0.9900 | O50—H50A | 0.9083 |
C18—O20 | 1.257 (5) | O50—H50B | 0.9045 |
C18—O19 | 1.264 (5) | ||
O44i—La1—O14 | 135.79 (10) | C1—O7—C8 | 114.7 (3) |
O44i—La1—O19ii | 141.58 (10) | C1—O7—La1 | 124.7 (2) |
O14—La1—O19ii | 71.92 (9) | C8—O7—La1 | 117.6 (2) |
O44i—La1—O24ii | 79.43 (10) | O7—C8—C9 | 108.9 (4) |
O14—La1—O24ii | 144.30 (9) | O7—C8—H8A | 109.9 |
O19ii—La1—O24ii | 74.51 (9) | C9—C8—H8A | 109.9 |
O44i—La1—O43 | 80.64 (9) | O7—C8—H8B | 109.9 |
O14—La1—O43 | 67.71 (9) | C9—C8—H8B | 109.9 |
O19ii—La1—O43 | 136.88 (9) | H8A—C8—H8B | 108.3 |
O24ii—La1—O43 | 138.09 (10) | O10—C9—O11 | 125.4 (4) |
O44i—La1—O11 | 76.77 (10) | O10—C9—C8 | 118.1 (4) |
O14—La1—O11 | 107.74 (10) | O11—C9—C8 | 116.5 (4) |
O19ii—La1—O11 | 67.95 (10) | C9—O11—La1 | 121.3 (3) |
O24ii—La1—O11 | 69.52 (10) | C2—C12—C13 | 113.1 (3) |
O43—La1—O11 | 139.24 (10) | C2—C12—H12A | 109.0 |
O44i—La1—O38ii | 138.18 (10) | C13—C12—H12A | 109.0 |
O14—La1—O38ii | 68.29 (9) | C2—C12—H12B | 109.0 |
O19ii—La1—O38ii | 69.33 (9) | C13—C12—H12B | 109.0 |
O24ii—La1—O38ii | 88.83 (10) | H12A—C12—H12B | 107.8 |
O43—La1—O38ii | 82.07 (9) | O15—C13—O14 | 120.3 (4) |
O11—La1—O38ii | 135.82 (9) | O15—C13—C12 | 120.9 (4) |
O44i—La1—O7 | 73.64 (10) | O14—C13—C12 | 118.9 (4) |
O14—La1—O7 | 72.08 (9) | O15—C13—La2ii | 59.8 (2) |
O19ii—La1—O7 | 99.75 (9) | O14—C13—La2ii | 60.5 (2) |
O24ii—La1—O7 | 126.11 (10) | C12—C13—La2ii | 177.1 (3) |
O43—La1—O7 | 81.92 (9) | C13—O14—La1 | 136.3 (3) |
O11—La1—O7 | 59.40 (9) | C13—O14—La2ii | 94.4 (2) |
O38ii—La1—O7 | 140.34 (9) | La1—O14—La2ii | 110.46 (11) |
O44i—La1—O39ii | 88.88 (10) | C13—O15—La2ii | 95.9 (3) |
O14—La1—O39ii | 109.37 (10) | C4—O16—C17 | 119.1 (3) |
O19ii—La1—O39ii | 107.55 (9) | O16—C17—C18 | 106.4 (3) |
O24ii—La1—O39ii | 69.84 (10) | O16—C17—H17A | 110.4 |
O43—La1—O39ii | 73.28 (10) | C18—C17—H17A | 110.4 |
O11—La1—O39ii | 138.69 (10) | O16—C17—H17B | 110.4 |
O38ii—La1—O39ii | 49.61 (9) | C18—C17—H17B | 110.4 |
O7—La1—O39ii | 151.74 (9) | H17A—C17—H17B | 108.6 |
O44i—La1—C37ii | 113.46 (11) | O20—C18—O19 | 126.0 (4) |
O14—La1—C37ii | 90.17 (10) | O20—C18—C17 | 116.0 (4) |
O19ii—La1—C37ii | 87.34 (10) | O19—C18—C17 | 117.9 (4) |
O24ii—La1—C37ii | 76.40 (11) | C18—O19—La1iv | 135.2 (3) |
O43—La1—C37ii | 78.40 (10) | C18—O20—La2 | 129.8 (3) |
O11—La1—C37ii | 141.95 (10) | C22—C21—C5 | 115.9 (4) |
O38ii—La1—C37ii | 25.19 (10) | C22—C21—H21A | 108.3 |
O7—La1—C37ii | 157.43 (10) | C5—C21—H21A | 108.3 |
O39ii—La1—C37ii | 24.58 (10) | C22—C21—H21B | 108.3 |
O44i—La1—La2ii | 156.54 (7) | C5—C21—H21B | 108.3 |
O14—La1—La2ii | 35.68 (7) | H21A—C21—H21B | 107.4 |
O19ii—La1—La2ii | 61.87 (7) | O24—C22—O23 | 123.6 (4) |
O24ii—La1—La2ii | 115.04 (7) | O24—C22—C21 | 120.3 (4) |
O43—La1—La2ii | 76.43 (6) | O23—C22—C21 | 115.9 (4) |
O11—La1—La2ii | 124.71 (7) | C22—O23—H23 | 103.4 |
O38ii—La1—La2ii | 33.11 (6) | C22—O24—La1iv | 138.8 (3) |
O7—La1—La2ii | 107.56 (6) | C30—C25—C26 | 121.7 (4) |
O39ii—La1—La2ii | 79.91 (7) | C30—C25—O31 | 119.5 (4) |
C37ii—La1—La2ii | 57.04 (8) | C26—C25—O31 | 118.7 (4) |
O20—La2—O34iii | 76.24 (9) | C25—C26—C27 | 118.4 (4) |
O20—La2—O38 | 71.50 (10) | C25—C26—C36 | 121.7 (4) |
O34iii—La2—O38 | 141.27 (10) | C27—C26—C36 | 119.8 (4) |
O20—La2—O49 | 137.22 (10) | C26—C27—C28 | 120.5 (4) |
O34iii—La2—O49 | 146.47 (10) | C26—C27—H27 | 119.8 |
O38—La2—O49 | 67.96 (10) | C28—C27—H27 | 119.8 |
O20—La2—O35 | 126.11 (10) | O40—C28—C27 | 124.5 (4) |
O34iii—La2—O35 | 71.63 (10) | O40—C28—C29 | 115.5 (4) |
O38—La2—O35 | 111.63 (10) | C27—C28—C29 | 120.0 (4) |
O49—La2—O35 | 82.29 (10) | C30—C29—C28 | 119.0 (4) |
O20—La2—O47iv | 142.81 (10) | C30—C29—C45 | 120.1 (4) |
O34iii—La2—O47iv | 81.02 (10) | C28—C29—C45 | 120.8 (4) |
O38—La2—O47iv | 137.55 (10) | C25—C30—C29 | 120.4 (4) |
O49—La2—O47iv | 70.81 (10) | C25—C30—H30 | 119.8 |
O35—La2—O47iv | 71.66 (10) | C29—C30—H30 | 119.8 |
O20—La2—O15iv | 75.10 (10) | C25—O31—C32 | 112.0 (3) |
O34iii—La2—O15iv | 80.20 (10) | C25—O31—La2 | 128.3 (2) |
O38—La2—O15iv | 110.77 (9) | C32—O31—La2 | 117.8 (2) |
O49—La2—O15iv | 107.08 (10) | O31—C32—C33 | 109.1 (3) |
O35—La2—O15iv | 136.93 (10) | O31—C32—H32A | 109.9 |
O47iv—La2—O15iv | 72.29 (10) | C33—C32—H32A | 109.9 |
O20—La2—O14iv | 82.71 (10) | O31—C32—H32B | 109.9 |
O34iii—La2—O14iv | 128.90 (9) | C33—C32—H32B | 109.9 |
O38—La2—O14iv | 67.51 (9) | H32A—C32—H32B | 108.3 |
O49—La2—O14iv | 69.82 (10) | O34—C33—O35 | 124.3 (4) |
O35—La2—O14iv | 150.35 (9) | O34—C33—C32 | 117.7 (4) |
O47iv—La2—O14iv | 89.32 (9) | O35—C33—C32 | 118.0 (4) |
O15iv—La2—O14iv | 49.32 (9) | C33—O34—La2iii | 141.5 (3) |
O20—La2—O31 | 75.42 (10) | C33—O35—La2 | 121.7 (3) |
O34iii—La2—O31 | 83.34 (9) | C26—C36—C37 | 109.0 (3) |
O38—La2—O31 | 68.37 (9) | C26—C36—H36A | 109.9 |
O49—La2—O31 | 101.25 (10) | C37—C36—H36A | 109.9 |
O35—La2—O31 | 59.05 (9) | C26—C36—H36B | 109.9 |
O47iv—La2—O31 | 130.70 (10) | C37—C36—H36B | 109.9 |
O15iv—La2—O31 | 148.87 (9) | H36A—C36—H36B | 108.3 |
O14iv—La2—O31 | 134.99 (9) | O39—C37—O38 | 121.0 (4) |
O20—La2—C13iv | 78.47 (11) | O39—C37—C36 | 121.6 (4) |
O34iii—La2—C13iv | 104.32 (10) | O38—C37—C36 | 117.4 (4) |
O38—La2—C13iv | 89.80 (10) | O39—C37—La1iv | 62.6 (2) |
O49—La2—C13iv | 88.20 (11) | O38—C37—La1iv | 59.0 (2) |
O35—La2—C13iv | 150.82 (10) | C36—C37—La1iv | 169.4 (3) |
O47iv—La2—C13iv | 79.17 (10) | C37—O38—La2 | 143.6 (3) |
O15iv—La2—C13iv | 24.29 (10) | C37—O38—La1iv | 95.8 (2) |
O14iv—La2—C13iv | 25.05 (10) | La2—O38—La1iv | 112.73 (11) |
O31—La2—C13iv | 150.13 (10) | C37—O39—La1iv | 92.8 (3) |
O20—La2—La1iv | 70.20 (7) | C28—O40—C41 | 117.9 (3) |
O34iii—La2—La1iv | 143.56 (7) | O40—C41—C42 | 109.9 (3) |
O38—La2—La1iv | 34.15 (7) | O40—C41—H41A | 109.7 |
O49—La2—La1iv | 68.74 (7) | C42—C41—H41A | 109.7 |
O35—La2—La1iv | 141.37 (7) | O40—C41—H41B | 109.7 |
O47iv—La2—La1iv | 118.64 (7) | C42—C41—H41B | 109.7 |
O15iv—La2—La1iv | 77.87 (6) | H41A—C41—H41B | 108.2 |
O14iv—La2—La1iv | 33.86 (6) | O43—C42—O44 | 125.0 (4) |
O31—La2—La1iv | 101.19 (6) | O43—C42—C41 | 120.1 (4) |
C13iv—La2—La1iv | 55.73 (8) | O44—C42—C41 | 114.8 (4) |
C6—C1—C2 | 121.9 (4) | C42—O43—La1 | 140.3 (3) |
C6—C1—O7 | 119.9 (4) | C42—O44—La1i | 162.9 (3) |
C2—C1—O7 | 118.2 (4) | C29—C45—C46 | 115.8 (4) |
C1—C2—C3 | 117.8 (4) | C29—C45—H45A | 108.3 |
C1—C2—C12 | 121.5 (4) | C46—C45—H45A | 108.3 |
C3—C2—C12 | 120.7 (4) | C29—C45—H45B | 108.3 |
C4—C3—C2 | 120.8 (4) | C46—C45—H45B | 108.3 |
C4—C3—H3 | 119.6 | H45A—C45—H45B | 107.4 |
C2—C3—H3 | 119.6 | O47—C46—O48 | 122.9 (4) |
O16—C4—C3 | 124.6 (4) | O47—C46—C45 | 120.7 (4) |
O16—C4—C5 | 114.3 (4) | O48—C46—C45 | 116.4 (4) |
C3—C4—C5 | 121.1 (4) | C46—O47—La2ii | 135.8 (3) |
C6—C5—C4 | 118.5 (4) | C46—O48—H48 | 109.5 |
C6—C5—C21 | 120.6 (4) | La2—O49—H49A | 138.5 |
C4—C5—C21 | 120.6 (4) | La2—O49—H49B | 118.2 |
C5—C6—C1 | 119.9 (4) | H49A—O49—H49B | 96.4 |
C5—C6—H6 | 120.0 | H50A—O50—H50B | 103.4 |
C1—C6—H6 | 120.0 |
Symmetry codes: (i) −x, −y, −z; (ii) x, y−1, z; (iii) −x+1, −y+1, −z+1; (iv) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O23—H23···O11iv | 1.00 | 1.60 | 2.593 (4) | 174 |
O48—H48···O50 | 0.84 | 1.68 | 2.522 (5) | 179 |
O49—H49A···O10v | 0.79 | 1.96 | 2.710 (5) | 158 |
O49—H49B···O43iv | 0.81 | 2.00 | 2.797 (4) | 170 |
O50—H50A···O19vi | 0.91 | 1.95 | 2.839 (4) | 164 |
O50—H50B···O35ii | 0.90 | 1.86 | 2.753 (4) | 171 |
Symmetry codes: (ii) x, y−1, z; (iv) x, y+1, z; (v) x+1, y+1, z; (vi) x+1, y−1, z. |
[Zn(C14H12O10)]·3H2O | F(000) = 944 |
Mr = 459.65 | Dx = 1.711 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9186 (4) Å | Cell parameters from 4095 reflections |
b = 12.2656 (7) Å | θ = 2.5–26.3° |
c = 16.3199 (8) Å | µ = 1.45 mm−1 |
β = 91.384 (4)° | T = 110 K |
V = 1784.75 (16) Å3 | Needle, colourless |
Z = 4 | 0.30 × 0.10 × 0.10 mm |
Nonius KappaCCD area-detector diffractometer | 3624 independent reflections |
Radiation source: fine-focus sealed tube | 2367 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.078 |
Detector resolution: 12.8 pixels mm-1 | θmax = 26.3°, θmin = 2.5° |
0.5 deg. ϕ and ω scans | h = 0→11 |
Absorption correction: multi-scan (Blessing, 1995) | k = 0→15 |
Tmin = 0.675, Tmax = 0.871 | l = −20→20 |
15967 measured reflections |
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)] = 0.073 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.220 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.1335P)2] where P = (Fo2 + 2Fc2)/3 |
3624 reflections | (Δ/σ)max = 0.005 |
226 parameters | Δρmax = 1.33 e Å−3 |
0 restraints | Δρmin = −0.57 e Å−3 |
[Zn(C14H12O10)]·3H2O | V = 1784.75 (16) Å3 |
Mr = 459.65 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.9186 (4) Å | µ = 1.45 mm−1 |
b = 12.2656 (7) Å | T = 110 K |
c = 16.3199 (8) Å | 0.30 × 0.10 × 0.10 mm |
β = 91.384 (4)° |
Nonius KappaCCD area-detector diffractometer | 3624 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 2367 reflections with I > 2σ(I) |
Tmin = 0.675, Tmax = 0.871 | Rint = 0.078 |
15967 measured reflections |
R[F2 > 2σ(F2)] = 0.073 | 0 restraints |
wR(F2) = 0.220 | H-atom parameters constrained |
S = 1.08 | Δρmax = 1.33 e Å−3 |
3624 reflections | Δρmin = −0.57 e Å−3 |
226 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. The asymmetric unit contains also 3 disordered molecules of water as crystallization solvent, which could not be resolved reliably by discrete atoms. Their contribution to the diffraction pattern was thus subtracted by the SQUEEZE procedure in PLATON (Spek, 2009). The H atoms of the two COOH groups could not be located as well. |
x | y | z | Uiso*/Ueq | ||
Zn1 | −0.43579 (7) | 0.23131 (6) | 0.70375 (4) | 0.0372 (3) | |
C1 | −0.1194 (6) | 0.3255 (5) | 0.4548 (4) | 0.0451 (15) | |
C2 | −0.0477 (7) | 0.3433 (5) | 0.3837 (3) | 0.0424 (14) | |
C3 | 0.0954 (7) | 0.3774 (5) | 0.3867 (3) | 0.0403 (14) | |
H3 | 0.1454 | 0.3903 | 0.3369 | 0.048* | |
C4 | 0.1723 (6) | 0.3942 (5) | 0.4604 (4) | 0.0480 (16) | |
C5 | 0.0953 (7) | 0.3729 (5) | 0.5346 (3) | 0.0436 (15) | |
C6 | −0.0499 (7) | 0.3386 (5) | 0.5279 (3) | 0.0396 (14) | |
H6 | −0.1032 | 0.3236 | 0.5764 | 0.047* | |
O7 | −0.2719 (4) | 0.2925 (4) | 0.4452 (2) | 0.0477 (11) | |
C8 | −0.3490 (7) | 0.2658 (5) | 0.5170 (4) | 0.0463 (15) | |
H8A | −0.4582 | 0.2706 | 0.5052 | 0.056* | |
H8B | −0.3237 | 0.3204 | 0.5598 | 0.056* | |
C9 | −0.3136 (8) | 0.1542 (6) | 0.5501 (4) | 0.0552 (17) | |
O10 | −0.3531 (5) | 0.1321 (3) | 0.6221 (2) | 0.0450 (10) | |
O11 | −0.2576 (7) | 0.0843 (4) | 0.5031 (3) | 0.086 (2) | |
C12 | −0.1290 (7) | 0.3210 (6) | 0.3009 (3) | 0.0476 (15) | |
H12A | −0.2272 | 0.3587 | 0.3002 | 0.057* | |
H12B | −0.0691 | 0.3522 | 0.2564 | 0.057* | |
C13 | −0.1547 (7) | 0.2007 (6) | 0.2839 (4) | 0.0450 (15) | |
O14 | −0.2702 (4) | 0.1757 (3) | 0.2403 (2) | 0.0412 (9) | |
O15 | −0.0643 (5) | 0.1327 (4) | 0.3119 (3) | 0.0643 (14) | |
O16 | 0.3215 (5) | 0.4255 (4) | 0.4703 (2) | 0.0485 (11) | |
C17 | 0.3945 (7) | 0.4502 (5) | 0.3985 (3) | 0.0465 (15) | |
H17A | 0.4880 | 0.4901 | 0.4129 | 0.056* | |
H17B | 0.3299 | 0.4996 | 0.3652 | 0.056* | |
C18 | 0.4340 (7) | 0.3520 (6) | 0.3466 (3) | 0.0471 (15) | |
O19 | 0.4951 (5) | 0.3787 (4) | 0.2786 (2) | 0.0493 (11) | |
O20 | 0.4103 (6) | 0.2567 (4) | 0.3682 (3) | 0.0527 (12) | |
C21 | 0.1813 (7) | 0.3894 (6) | 0.6153 (4) | 0.0486 (15) | |
H21A | 0.1095 | 0.3857 | 0.6605 | 0.058* | |
H21B | 0.2249 | 0.4637 | 0.6156 | 0.058* | |
C22 | 0.3063 (7) | 0.3081 (6) | 0.6325 (4) | 0.0472 (15) | |
O23 | 0.4192 (4) | 0.3426 (3) | 0.6753 (2) | 0.0423 (10) | |
O24 | 0.2967 (6) | 0.2143 (4) | 0.6058 (3) | 0.0640 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0368 (4) | 0.0432 (5) | 0.0316 (4) | 0.0019 (3) | 0.0022 (3) | 0.0052 (3) |
C1 | 0.036 (3) | 0.039 (4) | 0.061 (4) | 0.000 (3) | −0.001 (3) | −0.002 (3) |
C2 | 0.055 (4) | 0.036 (4) | 0.036 (3) | 0.006 (3) | −0.011 (3) | −0.002 (2) |
C3 | 0.057 (4) | 0.039 (4) | 0.026 (3) | 0.009 (3) | 0.014 (2) | 0.003 (2) |
C4 | 0.030 (3) | 0.030 (3) | 0.084 (5) | 0.002 (2) | −0.002 (3) | −0.003 (3) |
C5 | 0.067 (4) | 0.036 (4) | 0.027 (3) | 0.015 (3) | −0.008 (3) | −0.002 (2) |
C6 | 0.048 (3) | 0.036 (3) | 0.035 (3) | 0.011 (3) | 0.019 (2) | 0.007 (2) |
O7 | 0.042 (2) | 0.064 (3) | 0.037 (2) | −0.006 (2) | 0.0001 (17) | 0.0039 (19) |
C8 | 0.046 (4) | 0.056 (4) | 0.037 (3) | −0.003 (3) | 0.015 (3) | 0.001 (3) |
C9 | 0.070 (4) | 0.051 (4) | 0.046 (4) | 0.016 (3) | 0.011 (3) | 0.004 (3) |
O10 | 0.055 (3) | 0.042 (3) | 0.039 (2) | 0.0097 (19) | 0.0099 (18) | 0.0027 (17) |
O11 | 0.144 (6) | 0.066 (4) | 0.049 (3) | 0.041 (4) | 0.028 (3) | −0.002 (3) |
C12 | 0.049 (4) | 0.058 (4) | 0.036 (3) | −0.006 (3) | 0.008 (3) | −0.003 (3) |
C13 | 0.043 (4) | 0.050 (4) | 0.042 (3) | 0.000 (3) | 0.003 (3) | −0.008 (3) |
O14 | 0.039 (2) | 0.042 (3) | 0.043 (2) | 0.0005 (18) | 0.0005 (17) | −0.0094 (18) |
O15 | 0.055 (3) | 0.047 (3) | 0.089 (4) | 0.017 (2) | −0.026 (3) | −0.019 (2) |
O16 | 0.043 (2) | 0.063 (3) | 0.040 (2) | −0.008 (2) | 0.0015 (18) | −0.0051 (19) |
C17 | 0.052 (4) | 0.049 (4) | 0.039 (3) | −0.002 (3) | 0.010 (3) | −0.001 (3) |
C18 | 0.062 (4) | 0.047 (4) | 0.033 (3) | 0.006 (3) | 0.017 (3) | −0.002 (3) |
O19 | 0.055 (3) | 0.049 (3) | 0.044 (2) | 0.004 (2) | 0.0091 (19) | −0.0072 (19) |
O20 | 0.064 (3) | 0.052 (3) | 0.043 (2) | 0.014 (2) | 0.005 (2) | −0.0023 (19) |
C21 | 0.046 (4) | 0.057 (4) | 0.044 (3) | 0.004 (3) | 0.004 (3) | −0.008 (3) |
C22 | 0.039 (3) | 0.044 (4) | 0.059 (4) | 0.005 (3) | 0.006 (3) | 0.008 (3) |
O23 | 0.037 (2) | 0.052 (3) | 0.038 (2) | 0.0023 (19) | 0.0019 (17) | 0.0066 (18) |
O24 | 0.061 (3) | 0.045 (3) | 0.085 (4) | 0.007 (2) | −0.012 (3) | −0.003 (3) |
Zn1—O23i | 1.929 (4) | C9—O10 | 1.264 (7) |
Zn1—O19ii | 1.931 (4) | C12—C13 | 1.517 (10) |
Zn1—O14iii | 1.948 (4) | C12—H12A | 0.9900 |
Zn1—O10 | 1.962 (4) | C12—H12B | 0.9900 |
C1—C6 | 1.341 (8) | C13—O15 | 1.241 (8) |
C1—C2 | 1.357 (8) | C13—O14 | 1.276 (7) |
C1—O7 | 1.424 (7) | O14—Zn1iv | 1.948 (4) |
C2—C3 | 1.343 (9) | O16—C17 | 1.387 (6) |
C2—C12 | 1.543 (8) | C17—C18 | 1.519 (8) |
C3—C4 | 1.385 (9) | C17—H17A | 0.9900 |
C3—H3 | 0.9500 | C17—H17B | 0.9900 |
C4—O16 | 1.391 (7) | C18—O20 | 1.241 (7) |
C4—C5 | 1.431 (8) | C18—O19 | 1.290 (7) |
C5—C6 | 1.364 (8) | O19—Zn1v | 1.931 (4) |
C5—C21 | 1.521 (8) | C21—C22 | 1.517 (9) |
C6—H6 | 0.9500 | C21—H21A | 0.9900 |
O7—C8 | 1.412 (6) | C21—H21B | 0.9900 |
C8—C9 | 1.502 (10) | C22—O24 | 1.233 (8) |
C8—H8A | 0.9900 | C22—O23 | 1.283 (8) |
C8—H8B | 0.9900 | O23—Zn1vi | 1.929 (4) |
C9—O11 | 1.261 (8) | ||
O23i—Zn1—O19ii | 115.09 (17) | O10—C9—C8 | 117.9 (5) |
O23i—Zn1—O14iii | 99.11 (18) | C9—O10—Zn1 | 128.0 (4) |
O19ii—Zn1—O14iii | 117.83 (17) | C13—C12—C2 | 113.5 (5) |
O23i—Zn1—O10 | 122.41 (16) | C13—C12—H12A | 108.9 |
O19ii—Zn1—O10 | 97.32 (19) | C2—C12—H12A | 108.9 |
O14iii—Zn1—O10 | 106.05 (17) | C13—C12—H12B | 108.9 |
C6—C1—C2 | 121.6 (6) | C2—C12—H12B | 108.9 |
C6—C1—O7 | 123.5 (5) | H12A—C12—H12B | 107.7 |
C2—C1—O7 | 114.8 (5) | O15—C13—O14 | 123.6 (6) |
C3—C2—C1 | 119.1 (5) | O15—C13—C12 | 119.5 (6) |
C3—C2—C12 | 120.9 (5) | O14—C13—C12 | 116.9 (6) |
C1—C2—C12 | 119.9 (6) | C13—O14—Zn1iv | 128.7 (4) |
C2—C3—C4 | 121.9 (5) | C17—O16—C4 | 115.5 (5) |
C2—C3—H3 | 119.1 | O16—C17—C18 | 114.7 (5) |
C4—C3—H3 | 119.1 | O16—C17—H17A | 108.6 |
C3—C4—O16 | 126.4 (6) | C18—C17—H17A | 108.6 |
C3—C4—C5 | 118.1 (5) | O16—C17—H17B | 108.6 |
O16—C4—C5 | 115.4 (6) | C18—C17—H17B | 108.6 |
C6—C5—C4 | 117.6 (5) | H17A—C17—H17B | 107.6 |
C6—C5—C21 | 124.6 (5) | O20—C18—O19 | 124.2 (6) |
C4—C5—C21 | 117.8 (6) | O20—C18—C17 | 123.0 (5) |
C1—C6—C5 | 121.7 (5) | O19—C18—C17 | 112.8 (6) |
C1—C6—H6 | 119.1 | C18—O19—Zn1v | 121.0 (4) |
C5—C6—H6 | 119.1 | C5—C21—C22 | 115.2 (5) |
C8—O7—C1 | 117.2 (5) | C5—C21—H21A | 108.5 |
O7—C8—C9 | 114.0 (5) | C22—C21—H21A | 108.5 |
O7—C8—H8A | 108.7 | C5—C21—H21B | 108.5 |
C9—C8—H8A | 108.7 | C22—C21—H21B | 108.5 |
O7—C8—H8B | 108.7 | H21A—C21—H21B | 107.5 |
C9—C8—H8B | 108.7 | O24—C22—O23 | 123.1 (6) |
H8A—C8—H8B | 107.6 | O24—C22—C21 | 120.3 (6) |
O11—C9—O10 | 122.8 (6) | O23—C22—C21 | 116.6 (6) |
O11—C9—C8 | 119.0 (6) | C22—O23—Zn1vi | 114.3 (4) |
Symmetry codes: (i) x−1, y, z; (ii) x−1, −y+1/2, z+1/2; (iii) x, −y+1/2, z+1/2; (iv) x, −y+1/2, z−1/2; (v) x+1, −y+1/2, z−1/2; (vi) x+1, y, z. |
[Zn2(C14H10O10)(C10H8N2)(H2O)2]·2H2O | Z = 1 |
Mr = 697.24 | F(000) = 356 |
Triclinic, P1 | Dx = 1.778 Mg m−3 |
a = 7.7218 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.3520 (5) Å | Cell parameters from 2455 reflections |
c = 10.7204 (6) Å | θ = 2.0–26.7° |
α = 108.621 (3)° | µ = 1.92 mm−1 |
β = 94.915 (3)° | T = 110 K |
γ = 92.412 (3)° | Prism, colourless |
V = 651.01 (6) Å3 | 0.20 × 0.10 × 0.10 mm |
Nonius KappaCCD area-detector diffractometer | 2794 independent reflections |
Radiation source: fine-focus sealed tube | 2330 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 12.8 pixels mm-1 | θmax = 27.0°, θmin = 2.0° |
1 deg. ϕ and ω scans | h = 0→9 |
Absorption correction: multi-scan (Blessing, 1995) | k = −10→10 |
Tmin = 0.700, Tmax = 0.831 | l = −13→13 |
7281 measured reflections |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0254P)2 + 0.9668P] where P = (Fo2 + 2Fc2)/3 |
2794 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.71 e Å−3 |
[Zn2(C14H10O10)(C10H8N2)(H2O)2]·2H2O | γ = 92.412 (3)° |
Mr = 697.24 | V = 651.01 (6) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.7218 (4) Å | Mo Kα radiation |
b = 8.3520 (5) Å | µ = 1.92 mm−1 |
c = 10.7204 (6) Å | T = 110 K |
α = 108.621 (3)° | 0.20 × 0.10 × 0.10 mm |
β = 94.915 (3)° |
Nonius KappaCCD area-detector diffractometer | 2794 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 2330 reflections with I > 2σ(I) |
Tmin = 0.700, Tmax = 0.831 | Rint = 0.059 |
7281 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.48 e Å−3 |
2794 reflections | Δρmin = −0.71 e Å−3 |
190 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 | ||
Zn1 | 0.64853 (5) | 0.35334 (5) | 0.67884 (4) | 0.01753 (13) | |
C1 | 1.0378 (4) | 0.1350 (4) | −0.0481 (3) | 0.0155 (7) | |
C2 | 0.9607 (4) | 0.1625 (4) | 0.0693 (3) | 0.0161 (7) | |
H2 | 0.9340 | 0.2739 | 0.1176 | 0.019* | |
C3 | 0.9220 (4) | 0.0295 (4) | 0.1168 (3) | 0.0152 (7) | |
O4 | 0.8396 (3) | 0.0465 (3) | 0.2291 (2) | 0.0197 (5) | |
C5 | 0.8222 (4) | 0.2147 (4) | 0.3107 (3) | 0.0168 (7) | |
H5A | 0.7530 | 0.2747 | 0.2599 | 0.020* | |
H5B | 0.9387 | 0.2759 | 0.3397 | 0.020* | |
C6 | 0.7325 (4) | 0.2128 (4) | 0.4305 (3) | 0.0191 (7) | |
O7 | 0.7171 (3) | 0.3634 (3) | 0.5098 (2) | 0.0204 (5) | |
O8 | 0.6809 (4) | 0.0844 (3) | 0.4519 (2) | 0.0292 (6) | |
C9 | 1.0814 (4) | 0.2794 (4) | −0.0984 (3) | 0.0169 (7) | |
H9A | 1.1850 | 0.2524 | −0.1476 | 0.020* | |
H9B | 1.1151 | 0.3818 | −0.0209 | 0.020* | |
C10 | 0.9401 (5) | 0.3233 (4) | −0.1874 (3) | 0.0180 (7) | |
O11 | 0.7855 (3) | 0.2555 (3) | −0.2018 (2) | 0.0197 (5) | |
O12 | 0.9777 (3) | 0.4316 (3) | −0.2403 (2) | 0.0247 (6) | |
O13 | 0.4125 (3) | 0.2444 (3) | 0.6720 (2) | 0.0217 (5) | |
H13A | 0.3919 | 0.1362 | 0.6293 | 0.033* | |
H13B | 0.3323 | 0.2822 | 0.6100 | 0.033* | |
N14 | 0.5879 (3) | 0.5959 (3) | 0.7833 (3) | 0.0158 (6) | |
C15 | 0.4943 (4) | 0.6114 (4) | 0.8861 (3) | 0.0201 (7) | |
H15 | 0.4500 | 0.5111 | 0.8996 | 0.024* | |
C16 | 0.4594 (4) | 0.7656 (4) | 0.9733 (3) | 0.0184 (7) | |
H16 | 0.3957 | 0.7698 | 1.0461 | 0.022* | |
C17 | 0.5181 (4) | 0.9151 (4) | 0.9538 (3) | 0.0149 (7) | |
C18 | 0.6101 (4) | 0.8997 (4) | 0.8445 (3) | 0.0186 (7) | |
H18 | 0.6494 | 0.9979 | 0.8255 | 0.022* | |
C19 | 0.6437 (4) | 0.7397 (4) | 0.7635 (3) | 0.0195 (7) | |
H19 | 0.7091 | 0.7316 | 0.6909 | 0.023* | |
O20 | 0.8341 (3) | 0.6429 (3) | 0.4561 (2) | 0.0262 (6) | |
H20A | 0.7952 | 0.5501 | 0.4734 | 0.039* | |
H20B | 0.8955 | 0.6185 | 0.3855 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0220 (2) | 0.0162 (2) | 0.0159 (2) | 0.00335 (15) | 0.00553 (15) | 0.00610 (15) |
C1 | 0.0128 (15) | 0.0163 (16) | 0.0182 (16) | 0.0021 (13) | 0.0032 (13) | 0.0061 (13) |
C2 | 0.0130 (16) | 0.0184 (16) | 0.0166 (16) | 0.0026 (13) | 0.0037 (13) | 0.0046 (13) |
C3 | 0.0141 (15) | 0.0193 (16) | 0.0122 (15) | 0.0029 (13) | 0.0056 (13) | 0.0039 (13) |
O4 | 0.0268 (13) | 0.0168 (12) | 0.0167 (12) | 0.0041 (10) | 0.0118 (10) | 0.0045 (9) |
C5 | 0.0212 (17) | 0.0162 (16) | 0.0122 (16) | 0.0020 (14) | 0.0039 (13) | 0.0027 (13) |
C6 | 0.0177 (17) | 0.0210 (18) | 0.0174 (17) | 0.0028 (14) | 0.0034 (14) | 0.0040 (14) |
O7 | 0.0284 (13) | 0.0157 (12) | 0.0167 (12) | 0.0029 (10) | 0.0084 (10) | 0.0026 (9) |
O8 | 0.0433 (16) | 0.0180 (13) | 0.0286 (14) | 0.0018 (11) | 0.0185 (13) | 0.0073 (11) |
C9 | 0.0172 (16) | 0.0154 (16) | 0.0167 (16) | 0.0025 (13) | 0.0074 (14) | 0.0015 (13) |
C10 | 0.0286 (19) | 0.0126 (16) | 0.0133 (16) | 0.0060 (14) | 0.0074 (14) | 0.0031 (13) |
O11 | 0.0196 (12) | 0.0208 (12) | 0.0212 (12) | −0.0002 (10) | 0.0041 (10) | 0.0102 (10) |
O12 | 0.0291 (14) | 0.0229 (13) | 0.0280 (14) | 0.0012 (11) | 0.0056 (11) | 0.0159 (11) |
O13 | 0.0236 (13) | 0.0166 (12) | 0.0242 (13) | 0.0021 (10) | 0.0040 (10) | 0.0049 (10) |
N14 | 0.0169 (14) | 0.0159 (14) | 0.0144 (13) | 0.0028 (11) | 0.0051 (11) | 0.0036 (11) |
C15 | 0.0229 (18) | 0.0186 (17) | 0.0197 (18) | 0.0011 (14) | 0.0021 (15) | 0.0078 (14) |
C16 | 0.0212 (17) | 0.0190 (17) | 0.0171 (17) | 0.0029 (14) | 0.0070 (14) | 0.0075 (13) |
C17 | 0.0119 (15) | 0.0174 (17) | 0.0162 (16) | 0.0016 (13) | 0.0010 (13) | 0.0067 (14) |
C18 | 0.0171 (17) | 0.0175 (16) | 0.0208 (17) | 0.0004 (13) | 0.0040 (14) | 0.0051 (13) |
C19 | 0.0183 (17) | 0.0219 (18) | 0.0191 (17) | 0.0047 (14) | 0.0068 (14) | 0.0060 (14) |
O20 | 0.0270 (14) | 0.0257 (13) | 0.0289 (14) | 0.0003 (11) | 0.0075 (11) | 0.0121 (11) |
Zn1—O7 | 1.957 (2) | C9—H9B | 0.9900 |
Zn1—O11i | 1.983 (2) | C10—O12 | 1.248 (4) |
Zn1—O13 | 1.988 (2) | C10—O11 | 1.275 (4) |
Zn1—N14 | 2.073 (3) | O11—Zn1iii | 1.983 (2) |
C1—C2 | 1.395 (4) | O13—H13A | 0.8730 |
C1—C3ii | 1.398 (4) | O13—H13B | 1.0025 |
C1—C9 | 1.507 (5) | N14—C15 | 1.345 (4) |
C2—C3 | 1.394 (5) | N14—C19 | 1.344 (4) |
C2—H2 | 0.9500 | C15—C16 | 1.381 (4) |
C3—O4 | 1.380 (4) | C15—H15 | 0.9500 |
C3—C1ii | 1.398 (4) | C16—C17 | 1.394 (5) |
O4—C5 | 1.417 (4) | C16—H16 | 0.9500 |
C5—C6 | 1.514 (4) | C17—C18 | 1.396 (4) |
C5—H5A | 0.9900 | C17—C17iv | 1.501 (6) |
C5—H5B | 0.9900 | C18—C19 | 1.391 (4) |
C6—O8 | 1.225 (4) | C18—H18 | 0.9500 |
C6—O7 | 1.290 (4) | C19—H19 | 0.9500 |
C9—C10 | 1.522 (5) | O20—H20A | 0.8980 |
C9—H9A | 0.9900 | O20—H20B | 0.8998 |
O7—Zn1—O11i | 124.79 (10) | C1—C9—H9B | 108.0 |
O7—Zn1—O13 | 115.69 (10) | C10—C9—H9B | 108.0 |
O11i—Zn1—O13 | 100.83 (10) | H9A—C9—H9B | 107.2 |
O7—Zn1—N14 | 106.20 (10) | O12—C10—O11 | 121.5 (3) |
O11i—Zn1—N14 | 110.06 (10) | O12—C10—C9 | 118.5 (3) |
O13—Zn1—N14 | 95.44 (10) | O11—C10—C9 | 119.9 (3) |
C2—C1—C3ii | 118.5 (3) | C10—O11—Zn1iii | 105.5 (2) |
C2—C1—C9 | 121.0 (3) | Zn1—O13—H13A | 119.1 |
C3ii—C1—C9 | 120.5 (3) | Zn1—O13—H13B | 107.4 |
C3—C2—C1 | 121.1 (3) | H13A—O13—H13B | 95.5 |
C3—C2—H2 | 119.4 | C15—N14—C19 | 117.1 (3) |
C1—C2—H2 | 119.4 | C15—N14—Zn1 | 116.7 (2) |
O4—C3—C2 | 124.2 (3) | C19—N14—Zn1 | 126.0 (2) |
O4—C3—C1ii | 115.5 (3) | N14—C15—C16 | 123.5 (3) |
C2—C3—C1ii | 120.3 (3) | N14—C15—H15 | 118.3 |
C3—O4—C5 | 116.0 (2) | C16—C15—H15 | 118.3 |
O4—C5—C6 | 109.9 (3) | C15—C16—C17 | 119.7 (3) |
O4—C5—H5A | 109.7 | C15—C16—H16 | 120.2 |
C6—C5—H5A | 109.7 | C17—C16—H16 | 120.2 |
O4—C5—H5B | 109.7 | C16—C17—C18 | 117.2 (3) |
C6—C5—H5B | 109.7 | C16—C17—C17iv | 121.1 (3) |
H5A—C5—H5B | 108.2 | C18—C17—C17iv | 121.8 (4) |
O8—C6—O7 | 122.9 (3) | C19—C18—C17 | 119.5 (3) |
O8—C6—C5 | 124.7 (3) | C19—C18—H18 | 120.2 |
O7—C6—C5 | 112.4 (3) | C17—C18—H18 | 120.2 |
C6—O7—Zn1 | 110.4 (2) | N14—C19—C18 | 123.1 (3) |
C1—C9—C10 | 117.2 (3) | N14—C19—H19 | 118.5 |
C1—C9—H9A | 108.0 | C18—C19—H19 | 118.5 |
C10—C9—H9A | 108.0 | H20A—O20—H20B | 112.9 |
Symmetry codes: (i) x, y, z+1; (ii) −x+2, −y, −z; (iii) x, y, z−1; (iv) −x+1, −y+2, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13A···O8v | 0.87 | 1.81 | 2.676 (3) | 172 |
O13—H13B···O20vi | 1.00 | 1.65 | 2.632 (3) | 164 |
O20—H20A···O7 | 0.90 | 1.82 | 2.714 (3) | 179 |
O20—H20B···O12vii | 0.90 | 1.85 | 2.753 (3) | 180 |
Symmetry codes: (v) −x+1, −y, −z+1; (vi) −x+1, −y+1, −z+1; (vii) −x+2, −y+1, −z. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | 2NH4+·C14H12O102− | [La2(C14H11O10)2(H2O)]·H2O | [Zn(C14H12O10)]·3H2O | [Zn2(C14H10O10)(C10H8N2)(H2O)2]·2H2O |
Mr | 376.32 | 992.31 | 459.65 | 697.24 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 110 | 110 | 110 | 110 |
a, b, c (Å) | 4.8188 (3), 14.6889 (8), 11.2087 (8) | 10.2508 (2), 11.1655 (3), 14.7606 (4) | 8.9186 (4), 12.2656 (7), 16.3199 (8) | 7.7218 (4), 8.3520 (5), 10.7204 (6) |
α, β, γ (°) | 90, 91.855 (2), 90 | 79.5944 (12), 82.1510 (12), 69.9402 (17) | 90, 91.384 (4), 90 | 108.621 (3), 94.915 (3), 92.412 (3) |
V (Å3) | 792.97 (9) | 1555.74 (7) | 1784.75 (16) | 651.01 (6) |
Z | 2 | 2 | 4 | 1 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.14 | 2.81 | 1.45 | 1.92 |
Crystal size (mm) | 0.40 × 0.15 × 0.15 | 0.15 × 0.15 × 0.10 | 0.30 × 0.10 × 0.10 | 0.20 × 0.10 × 0.10 |
Data collection | ||||
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – | Multi-scan (Blessing, 1995) | Multi-scan (Blessing, 1995) | Multi-scan (Blessing, 1995) |
Tmin, Tmax | – | 0.678, 0.766 | 0.675, 0.871 | 0.700, 0.831 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9862, 1598, 1243 | 25631, 6850, 5610 | 15967, 3624, 2367 | 7281, 2794, 2330 |
Rint | 0.051 | 0.062 | 0.078 | 0.059 |
(sin θ/λ)max (Å−1) | 0.624 | 0.643 | 0.624 | 0.639 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.102, 1.04 | 0.037, 0.089, 1.03 | 0.073, 0.220, 1.08 | 0.048, 0.092, 1.07 |
No. of reflections | 1598 | 6850 | 3624 | 2794 |
No. of parameters | 148 | 470 | 226 | 190 |
H-atom treatment | Only H-atom coordinates refined | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.22 | 1.69, −1.78 | 1.33, −0.57 | 0.48, −0.71 |
Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···O7i | 0.99 (2) | 1.52 (2) | 2.5123 (19) | 175 (2) |
N13—H13A···O7ii | 0.93 (3) | 1.89 (3) | 2.822 (2) | 178 (2) |
N13—H13B···O8 | 0.93 (3) | 1.85 (3) | 2.771 (2) | 171 (2) |
N13—H13C···O12 | 0.96 (3) | 2.05 (3) | 2.963 (2) | 160 (2) |
N13—H13D···O8iii | 0.96 (3) | 2.10 (3) | 3.043 (2) | 167 (2) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x+1, y, z. |
La1—O44i | 2.417 (3) | La2—O20 | 2.450 (3) |
La1—O14 | 2.519 (3) | La2—O34iii | 2.486 (3) |
La1—O19ii | 2.525 (3) | La2—O38 | 2.509 (3) |
La1—O24ii | 2.525 (3) | La2—O49 | 2.524 (3) |
La1—O43 | 2.536 (3) | La2—O35 | 2.543 (3) |
La1—O11 | 2.540 (3) | La2—O47iv | 2.546 (3) |
La1—O38ii | 2.579 (3) | La2—O15iv | 2.625 (3) |
La1—O7 | 2.619 (3) | La2—O14iv | 2.638 (3) |
La1—O39ii | 2.661 (3) | La2—O31 | 2.718 (3) |
La1—La2ii | 4.2365 (3) |
Symmetry codes: (i) −x, −y, −z; (ii) x, y−1, z; (iii) −x+1, −y+1, −z+1; (iv) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O23—H23···O11iv | 1.00 | 1.60 | 2.593 (4) | 174 |
O48—H48···O50 | 0.84 | 1.68 | 2.522 (5) | 179 |
O49—H49A···O10v | 0.79 | 1.96 | 2.710 (5) | 158 |
O49—H49B···O43iv | 0.81 | 2.00 | 2.797 (4) | 170 |
O50—H50A···O19vi | 0.91 | 1.95 | 2.839 (4) | 164 |
O50—H50B···O35ii | 0.90 | 1.86 | 2.753 (4) | 171 |
Symmetry codes: (ii) x, y−1, z; (iv) x, y+1, z; (v) x+1, y+1, z; (vi) x+1, y−1, z. |
Zn1—O23i | 1.929 (4) | Zn1—O14iii | 1.948 (4) |
Zn1—O19ii | 1.931 (4) | Zn1—O10 | 1.962 (4) |
Symmetry codes: (i) x−1, y, z; (ii) x−1, −y+1/2, z+1/2; (iii) x, −y+1/2, z+1/2. |
Zn1—O7 | 1.957 (2) | Zn1—O13 | 1.988 (2) |
Zn1—O11i | 1.983 (2) | Zn1—N14 | 2.073 (3) |
Symmetry code: (i) x, y, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13A···O8ii | 0.87 | 1.81 | 2.676 (3) | 172 |
O13—H13B···O20iii | 1.00 | 1.65 | 2.632 (3) | 164 |
O20—H20A···O7 | 0.90 | 1.82 | 2.714 (3) | 179 |
O20—H20B···O12iv | 0.90 | 1.85 | 2.753 (3) | 180 |
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+2, −y+1, −z. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
This study is part of our exploratory search for multidentate polycarboxylic acid ligands that can be utilized, in combination with metal cations, in the construction of coordination networks (Goldberg, 2005, 2008). These ligands can be readily deprotonated to balance the charge of the metal cations they interact with (and thus enjoy electrostatic attraction to the metal centres) without the need to incorporate foreign anions into the product. Much current research activity has been directed towards the programmed synthesis of open metal–organic frameworks (MOFs) in view of their potential utility in gas storage (e.g. Eddaoudi et al., 2002). Divergent disposition of the carboxylic acid sensor groups substituted on rigid aromatic backbones was found to be a crucial element in the design of microporous solids (Rossi et al., 2005; Eddaoudi et al., 2002). In this context, the present work expands in particular on earlier studies with the tetrafunctional ligand benzene-1,2,4,5-tetracarboxylic acid (e.g. Fabelo et al., 2006; Ghosh & Bharadwaj, 2004). We use the same aromatic backbone (the benzene ring) but with longer carboxylic acid substituents, by introducing in TALH4 –CH2– and –OCH2– spacers between the acid groups and the benzene ring. By doing so, our design also imparts some additional conformational flexibility to the organic component, due to the aliphatic nature of the added spacer groups. It was anticipated that the –COOH functions in this ligand may orient in different directions, in and out of the plane of the aromatic core, and thus direct possible coordination to potential metal cation connectors in two- and three-dimensions to yield TALH4-based robust metal–organic networks and frameworks.
Compound (I) was formed by serendipity, while attempting to coordinate TALH4 to cadmium(II) cations in a mildly basic environment of ammonium hydroxide. It represents a 2:1 NH4+–TALH22- hydrogen-bonded trimer, with the organic ligand entities located on centres of inversion (Fig. 1). The nearly linear N—H···O hydrogen-bonding interactions are associated with double deprotonation of TALH4, which occurs preferentially on the two more acidic carboxylic acid functions in the carboxymethoxy residues. As a result, the TALH22- anion, which bears two carboxylate H-atom acceptors and two carboxylic acid H-atom donor groups is self-complimentary for hydrogen bonding (Table 1). Correspondingly, every TALH22- unit associates via O—H···-OOC charge-assisted hydrogen bonds to four neighbouring TALH22- ligands. In addition, the two carboxylate functions interact via NH4+···-OOC hydrogen bonds with six adjacent ammonium cations (Fig. 2). The tetrahedral tetradentate functionality of the latter allows it to form hydrogen bonds to two carboxylate functionalities of a given ligand (Fig. 1), as well as to the carboxylate functions of two other ligands (Table 1). The supramolecular charge-assisted hydrogen bonding between the component species extends throughout the crystal structure in three dimensions (Fig. 2). Electrostatic interactions between the charged components further stabilize the three-dimensionally interlinked supramolecular assembly in (I). The structures of ammonium salts of the closely related benzene-1,2,4,5-tetracarboxylic acid reveal similar N—H···O and O—H···O hydrogen-bonding interactions between the component species (Dutkiewicz et al., 2007; Bergstrom et al., 2000; Jessen et al., 1992).
Reaction of the lanthanum salt with TALH4 led to the formation of a two-dimensional coordination polymer of 1:1 La3+:TALH3- stoichiometry, (II) (Fig. 3). The two crystallographically independent metal cations that form a dinuclear cluster are nine-coordinate (Table 2). Atom La1 coordinates to six carboxylate groups of different TALH3- anions in a monodentate fashion, to another carboxylate group in a bidentate fashion, and also to the ether-O site of one of the ligands. Atom La2 coordinates to five carboxylate groups of adjacent TALH3- anions in a monodentate fashion, to another carboxylate group in a bidentate fashion, to an ether-O site of one of the ligands, and finally to a water molecule (Table 2). In the resulting coordination network, adjacent LaIII cations (whether within the dinuclear cluster or between clusters) are bridged by several organic ligands. This leads to the formation of robust polymeric arrays which extend parallel to the (101) plane of the crystal structure, in which the TALH3- components are arranged in two layers, due to the multiple coordination capacity of the inorganic connectors and the spatial disposition of their coordination valencies (Fig. 4). The layered assemblies have corrugated surfaces lined with the metal-coordinated water molecules and the –COOH residues. In the crystal structure, the double-layer polymeric networks are held together by an extensive array of O—H···O hydrogen bonds, which involves the H atoms of the metal-coordinated water ligand O49, the carboxylic acid functions OH23 and OH48, and the non-coordinated water molecules O50 trapped in the structure (Table 3). The observed multiple coordination pattern of the oxophilic LaIII cations to carboxylic acid/carboxylate/water ligands, within the range La—O = 2.4–2.7 Å, is similar to earlier documented findings in polymeric networks incorporating La3+ cations and deprotonated pyrromellitic acid anions (Wen et al., 2004; Chui et al., 2001; Wu et al., 1996).
A similar reaction between the tetraacid ligand and a zinc salt also resulted in the formation of a coordination polymer with two-dimensional connectivity, (III) (Fig. 5). In the layered arrays, rows of the TALH22- ligand alternate with rows of the ZnII cation connectors in both directions (Fig. 6). The latter are characterized by a tetrahedral coordination environment, linking in a monodentate manner to the carboxylate/carboxylic acid groups of four neighbouring ligands (Table 4). Each pair of neighbouring ZnII cations in the layer is bridged by two ligand anions. The layered arrays are oriented perpendicular to the b axis of the crystal, being centred at y = 1/4 and 3/4. Although the ZnII cation connectors are characterized by a tetrahedral coordination geometry, the observed coordination pattern is limited to two dimensions, the coordination directionality of the ZnII cations not being matched by a complimentary spatial disposition of the COO/COOH ligating sites in the organic ligand. Rather, the adapted conformation of the aliphatic arms in TALH22- minimizes the empty space within the coordinated layer (Fig. 6). Noncoordinated water molecules are intercalated between the coordination layers in zones centred at y = 0 and 1/2, and form hydrogen bonds between them. However, due to the poor quality of the crystals, associated with severe disorder of the crystallization solvent, these interactions could not be characterized reliably. The low quality of the diffraction data in this case is also affected by possible orientational in-layer disorder of the TALH22- anions, which have a nearly square shape and a similar coordination environment in the four lateral directions. Considering also the loose packing of the layers along the normal axis, a random interchange between the positions of the –CH2COO/-CH2COOH and –OCH2COO/-OCH2COOH groups (the H atoms of these fragments could not be located) in selected/fault sites of the crystal structure cannot be excluded.
Zinc cations are known to be well coordinated by ligands with both O- and N- ligating sites. Correspondingly, on addition of the 4,4'-bipyridyl reagent (bpy) to the reaction mixture of zinc dinitrate and TALH4, the two ligands may compete for coordination sites on the metal core. Indeed, compound (IV) represents a ternary product of 2:1:1 Zn2+:TAL4-:bpy stoichiometry (Fig. 7), where the two multidentate organic linkers (which reside on two different inversion centres) are coordinated to the metal. The ZnII cation connectors reveal a tetrahedral coordination geometry, each associated with the carboxylate groups of two neighbouring TAL4- ligands (in a monodentate mode), the N-site of the bpy component and a molecule of water (Table 5). The TAL4- tetraanion is linked simultaneously in the lateral directions to four different ZnII cations, while the bidentate bpy ligand bridges two ZnII cation nodes. As illustrated in Fig. 8, this results in the formation of two-dimensional coordination networks aligned parallel to the (210) plane of the crystal structure. The metal-bound water ligands are oriented perpendicular to the network mean plane in alternating directions. The thin shape of the bpy linkers in the grid networks creates open voids between them, which are penetrated from above and below by the O13 metal-bound water ligands of adjacent layers. In addition, non-coordinated water species O20 are accommodated between the layers. The two water molecules form bridges by hydrogen bonding between the interpentrating coordination networks (Table 6).
Coordination polymers sustained by zinc–carboxylate coordination synthons are abundant in the literature. The observed Zn—O and Zn—N coordination distances (Tables 4 and 5) are in the normally expected ranges for such polymeric compounds, as confirmed by a survey of Cambridge Structural Database (CSD, Version 5.31, May 2010 update; Allen, 2002). Among these related polymeric compounds, recent references to zinc–pyromellitate coordination compounds (Lu et al., 2005; Wang et al., 2007) and to those also incorporating the bpy ligand (Wu et al., 2001; Huang et al., 2009) are of particular relevance.
In summary, we have reported here the synthesis of a new tetracarboxylic acid ligand, TALH4, and demonstrated its capacity to form coordination networks with metal cations. In spite of the conformational flexibility imparted to this ligand by inserting aliphatic spacers between the aromatic core and the four diverging –COOH groups, the formation of only two-dimensional coordination polymers has been observed so far. However, the coordination polymerization in (II)–(IV) is supplemented by hydrogen-bonding interactions along the third dimension.