In the title complex, {[La2(C5H6O4)3(H2O)4]·H2O}n, the La atoms are connected by bridging O atoms from carboxylate groups to build, through centres of inversion, two-dimensional layers parallel to the ac plane containing decanuclear 20-membered rings. The coordinated water molecules are involved in intralayer hydrogen-bond interactions. Adjacent layers are linked via hydrogen bonding to the solvent water molecules. This work represents the first example of a new substituted malonate–lanthanide complex.
Supporting information
CCDC reference: 735108
La2O3 (0.4 g, 1.2 mmol) was dissolved in dilute hydrochloric acid and the
solvent evaporated to dryness. The resulting LnCl3.nH2O was dissolved in
distilled water (20 ml) at room temperature, and then dimethylmalonic acid
(0.3 g, 2.3 mmol) and sodium dimethylmalonate (0.6 g, 3.4 mmol) were added
under continuous stirring. After filtration, slow evaporation over a period of
two weeks at room temperature provided colourless needle crystals of (I).
The H atoms of the water molecules were found in a difference Fourier map.
However, during refinement, they were fixed at O—H = 0.85 Å and their
Uiso values were set at 1.2Ueq(O). The H atoms of the C—H
groups were treated as riding, with C—H = 0.96 Å, and with
Uiso(H) = 1.5Ueq(C).
Data collection: CrystalClear (Rigaku/MSC 2005); cell refinement: CrystalClear (Rigaku/MSC 2005); data reduction: CrystalClear (Rigaku/MSC 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Poly[[tetraaquatris(µ
3-2,2-dimethylmalonato)dilanthanum(III)] monohydrate]
top
Crystal data top
[La2(C5H6O4)3(H2O)4]·H2O | F(000) = 1472 |
Mr = 758.19 | Dx = 2.109 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5452 reflections |
a = 8.3835 (17) Å | θ = 1.8–27.1° |
b = 20.229 (4) Å | µ = 3.61 mm−1 |
c = 14.101 (3) Å | T = 133 K |
β = 92.989 (3)° | Needle, colourless |
V = 2388.2 (8) Å3 | 0.12 × 0.08 × 0.06 mm |
Z = 4 | |
Data collection top
Rigaku Saturn diffractometer | 4177 independent reflections |
Radiation source: rotating anode | 3140 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.061 |
Detector resolution: 27.073 pixels mm-1 | θmax = 25.0°, θmin = 1.8° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | k = −24→24 |
Tmin = 0.715, Tmax = 0.802 | l = −16→7 |
13664 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0327P)2] where P = (Fo2 + 2Fc2)/3 |
4177 reflections | (Δ/σ)max = 0.001 |
313 parameters | Δρmax = 1.04 e Å−3 |
0 restraints | Δρmin = −0.81 e Å−3 |
Crystal data top
[La2(C5H6O4)3(H2O)4]·H2O | V = 2388.2 (8) Å3 |
Mr = 758.19 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.3835 (17) Å | µ = 3.61 mm−1 |
b = 20.229 (4) Å | T = 133 K |
c = 14.101 (3) Å | 0.12 × 0.08 × 0.06 mm |
β = 92.989 (3)° | |
Data collection top
Rigaku Saturn diffractometer | 4177 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 3140 reflections with I > 2σ(I) |
Tmin = 0.715, Tmax = 0.802 | Rint = 0.061 |
13664 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 0.94 | Δρmax = 1.04 e Å−3 |
4177 reflections | Δρmin = −0.81 e Å−3 |
313 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
La1 | 0.81569 (4) | 1.002992 (14) | 0.88348 (2) | 0.03176 (11) | |
La2 | 0.75181 (4) | 1.005917 (15) | 0.56747 (2) | 0.03202 (11) | |
O1 | 1.0018 (4) | 0.93672 (17) | 0.9889 (3) | 0.0359 (9) | |
O2 | 1.0984 (5) | 0.86669 (18) | 1.0936 (3) | 0.0396 (9) | |
O3 | 0.8677 (5) | 0.89259 (18) | 0.8264 (3) | 0.0387 (9) | |
O4 | 0.9551 (5) | 0.79494 (18) | 0.7896 (3) | 0.0414 (9) | |
O5 | 0.6403 (4) | 0.97806 (18) | 0.7306 (3) | 0.0357 (8) | |
O6 | 0.5372 (4) | 0.94219 (18) | 0.8598 (3) | 0.0372 (9) | |
O7 | 0.4754 (4) | 0.95383 (17) | 0.5639 (3) | 0.0362 (9) | |
O8 | 0.2278 (5) | 0.92818 (18) | 0.5901 (3) | 0.0385 (9) | |
O9 | 0.7094 (4) | 0.91792 (18) | 0.4367 (3) | 0.0376 (9) | |
O10 | 0.9611 (4) | 0.94825 (18) | 0.4478 (3) | 0.0366 (8) | |
O11 | 0.9108 (5) | 0.96806 (19) | 0.1881 (3) | 0.0407 (9) | |
O12 | 1.1207 (4) | 0.94045 (17) | 0.2776 (3) | 0.0344 (8) | |
C1 | 1.0255 (6) | 0.8777 (3) | 1.0154 (4) | 0.0347 (12) | |
C2 | 0.9614 (7) | 0.8207 (3) | 0.9552 (4) | 0.0385 (13) | |
C3 | 0.9278 (6) | 0.8372 (3) | 0.8485 (4) | 0.0352 (12) | |
C4 | 1.0788 (8) | 0.7636 (3) | 0.9665 (4) | 0.0464 (15) | |
H4A | 1.1785 | 0.7761 | 0.9411 | 0.070* | |
H4B | 1.0363 | 0.7257 | 0.9329 | 0.070* | |
H4C | 1.0958 | 0.7531 | 1.0326 | 0.070* | |
C5 | 0.7968 (7) | 0.8015 (3) | 0.9923 (4) | 0.0481 (15) | |
H5A | 0.8094 | 0.7898 | 1.0583 | 0.072* | |
H5B | 0.7540 | 0.7645 | 0.9567 | 0.072* | |
H5C | 0.7250 | 0.8383 | 0.9850 | 0.072* | |
C6 | 0.5384 (6) | 0.9426 (3) | 0.7711 (4) | 0.0346 (12) | |
C7 | 0.4301 (6) | 0.8972 (2) | 0.7105 (4) | 0.0341 (12) | |
C8 | 0.3736 (7) | 0.9283 (2) | 0.6169 (4) | 0.0359 (13) | |
C9 | 0.5339 (7) | 0.8375 (3) | 0.6875 (4) | 0.0394 (13) | |
H9A | 0.4692 | 0.8047 | 0.6547 | 0.059* | |
H9B | 0.5799 | 0.8191 | 0.7454 | 0.059* | |
H9C | 0.6175 | 0.8513 | 0.6479 | 0.059* | |
C10 | 0.2891 (7) | 0.8750 (3) | 0.7684 (4) | 0.0431 (14) | |
H10A | 0.2245 | 0.9127 | 0.7821 | 0.065* | |
H10B | 0.3290 | 0.8552 | 0.8267 | 0.065* | |
H10C | 0.2257 | 0.8434 | 0.7324 | 0.065* | |
C11 | 0.8475 (6) | 0.9196 (3) | 0.4040 (4) | 0.0343 (12) | |
C12 | 0.8748 (6) | 0.8863 (3) | 0.3095 (4) | 0.0340 (12) | |
C13 | 0.9736 (7) | 0.9345 (3) | 0.2548 (4) | 0.0347 (12) | |
C14 | 0.9731 (7) | 0.8240 (3) | 0.3312 (4) | 0.0435 (14) | |
H14D | 0.9927 | 0.8015 | 0.2730 | 0.065* | |
H14E | 0.9153 | 0.7953 | 0.3715 | 0.065* | |
H14C | 1.0731 | 0.8360 | 0.3629 | 0.065* | |
C15 | 0.7184 (7) | 0.8694 (3) | 0.2532 (4) | 0.0419 (13) | |
H15D | 0.6537 | 0.9085 | 0.2463 | 0.063* | |
H15E | 0.6617 | 0.8362 | 0.2866 | 0.063* | |
H15C | 0.7420 | 0.8531 | 0.1916 | 0.063* | |
O13 | 0.5899 (5) | 1.08407 (18) | 0.9111 (3) | 0.0421 (9) | |
H13A | 0.5800 | 1.1123 | 0.8666 | 0.051* | |
H13B | 0.5030 | 1.0629 | 0.9146 | 0.051* | |
O14 | 0.6889 (4) | 0.98693 (18) | 1.0483 (3) | 0.0380 (9) | |
H14A | 0.6368 | 1.0214 | 1.0619 | 0.046* | |
H14B | 0.7623 | 0.9799 | 1.0912 | 0.046* | |
O15 | 0.9136 (4) | 0.91582 (18) | 0.6406 (3) | 0.0391 (9) | |
H15A | 0.8766 | 0.9054 | 0.6937 | 0.047* | |
H15B | 1.0123 | 0.9076 | 0.6377 | 0.047* | |
O16 | 0.6087 (4) | 1.10859 (17) | 0.6128 (3) | 0.0380 (9) | |
H16A | 0.5134 | 1.1137 | 0.5908 | 0.046* | |
H16B | 0.6322 | 1.1264 | 0.6660 | 0.046* | |
O17 | 0.8488 (5) | 0.67992 (18) | 0.7160 (3) | 0.0417 (9) | |
H17A | 0.7571 | 0.6809 | 0.6872 | 0.050* | |
H17B | 0.8814 | 0.7181 | 0.7334 | 0.050* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
La1 | 0.0309 (2) | 0.03390 (17) | 0.03033 (18) | −0.00053 (12) | 0.00013 (14) | 0.00012 (13) |
La2 | 0.02979 (19) | 0.03602 (17) | 0.03013 (18) | −0.00045 (12) | 0.00034 (13) | 0.00007 (13) |
O1 | 0.035 (2) | 0.0317 (19) | 0.040 (2) | −0.0038 (15) | −0.0055 (17) | −0.0003 (16) |
O2 | 0.043 (2) | 0.0381 (19) | 0.037 (2) | 0.0010 (17) | −0.0030 (18) | −0.0002 (17) |
O3 | 0.042 (2) | 0.041 (2) | 0.032 (2) | 0.0026 (17) | −0.0033 (17) | −0.0019 (17) |
O4 | 0.047 (2) | 0.0373 (19) | 0.040 (2) | 0.0012 (17) | 0.0033 (18) | −0.0053 (18) |
O5 | 0.035 (2) | 0.0388 (19) | 0.0326 (19) | −0.0034 (16) | −0.0027 (17) | 0.0021 (16) |
O6 | 0.035 (2) | 0.0398 (19) | 0.037 (2) | −0.0033 (16) | 0.0023 (17) | −0.0008 (17) |
O7 | 0.035 (2) | 0.0385 (19) | 0.035 (2) | −0.0029 (16) | 0.0007 (17) | 0.0014 (17) |
O8 | 0.035 (2) | 0.044 (2) | 0.037 (2) | −0.0025 (16) | 0.0004 (18) | 0.0035 (17) |
O9 | 0.029 (2) | 0.045 (2) | 0.039 (2) | 0.0003 (16) | 0.0008 (17) | −0.0032 (17) |
O10 | 0.032 (2) | 0.0428 (19) | 0.034 (2) | −0.0020 (16) | −0.0023 (17) | 0.0015 (17) |
O11 | 0.037 (2) | 0.048 (2) | 0.038 (2) | 0.0012 (17) | 0.0010 (18) | 0.0029 (19) |
O12 | 0.030 (2) | 0.0372 (19) | 0.036 (2) | 0.0003 (15) | −0.0015 (16) | 0.0004 (16) |
C1 | 0.031 (3) | 0.035 (3) | 0.039 (3) | 0.001 (2) | 0.007 (3) | 0.001 (2) |
C2 | 0.044 (3) | 0.034 (3) | 0.038 (3) | 0.000 (2) | −0.002 (3) | −0.002 (2) |
C3 | 0.027 (3) | 0.036 (3) | 0.042 (3) | −0.005 (2) | 0.001 (2) | 0.000 (2) |
C4 | 0.065 (4) | 0.037 (3) | 0.036 (3) | 0.005 (3) | −0.003 (3) | −0.002 (3) |
C5 | 0.050 (4) | 0.052 (3) | 0.042 (3) | −0.017 (3) | 0.005 (3) | −0.005 (3) |
C6 | 0.033 (3) | 0.035 (3) | 0.036 (3) | 0.003 (2) | 0.004 (2) | 0.002 (2) |
C7 | 0.031 (3) | 0.035 (3) | 0.036 (3) | −0.003 (2) | −0.003 (2) | 0.000 (2) |
C8 | 0.039 (3) | 0.030 (2) | 0.038 (3) | 0.000 (2) | 0.004 (3) | −0.001 (2) |
C9 | 0.039 (3) | 0.032 (3) | 0.045 (3) | 0.001 (2) | −0.008 (3) | 0.002 (3) |
C10 | 0.041 (4) | 0.046 (3) | 0.042 (3) | −0.004 (3) | 0.002 (3) | 0.004 (3) |
C11 | 0.032 (3) | 0.032 (2) | 0.038 (3) | −0.001 (2) | −0.002 (2) | 0.004 (2) |
C12 | 0.031 (3) | 0.038 (3) | 0.033 (3) | −0.001 (2) | 0.000 (2) | −0.001 (2) |
C13 | 0.035 (3) | 0.037 (3) | 0.031 (3) | 0.002 (2) | −0.001 (2) | −0.006 (2) |
C14 | 0.046 (4) | 0.036 (3) | 0.050 (4) | −0.002 (2) | 0.008 (3) | −0.002 (3) |
C15 | 0.039 (3) | 0.050 (3) | 0.036 (3) | −0.010 (3) | 0.001 (3) | −0.006 (3) |
O13 | 0.043 (2) | 0.0379 (19) | 0.046 (2) | −0.0009 (17) | 0.0052 (19) | 0.0037 (18) |
O14 | 0.036 (2) | 0.044 (2) | 0.033 (2) | 0.0044 (17) | −0.0012 (17) | −0.0005 (17) |
O15 | 0.036 (2) | 0.047 (2) | 0.034 (2) | 0.0049 (17) | 0.0049 (17) | 0.0078 (17) |
O16 | 0.031 (2) | 0.0412 (19) | 0.041 (2) | 0.0013 (16) | −0.0072 (17) | −0.0009 (17) |
O17 | 0.041 (2) | 0.0366 (19) | 0.047 (2) | −0.0023 (17) | −0.0057 (18) | −0.0014 (18) |
Geometric parameters (Å, º) top
La1—O3 | 2.421 (4) | C4—H4A | 0.9600 |
La1—O1 | 2.490 (4) | C4—H4B | 0.9600 |
La1—O13 | 2.550 (4) | C4—H4C | 0.9600 |
La1—O5 | 2.594 (4) | C5—H5A | 0.9600 |
La1—O1i | 2.604 (4) | C5—H5B | 0.9600 |
La1—O11ii | 2.620 (4) | C5—H5C | 0.9600 |
La1—O12ii | 2.623 (4) | C6—C7 | 1.523 (8) |
La1—O14 | 2.625 (4) | C7—C8 | 1.515 (8) |
La1—O6 | 2.645 (4) | C7—C9 | 1.532 (7) |
La1—O2i | 2.747 (4) | C7—C10 | 1.538 (7) |
La2—O15 | 2.466 (4) | C9—H9A | 0.9600 |
La2—O16 | 2.498 (4) | C9—H9B | 0.9600 |
La2—O7 | 2.544 (4) | C9—H9C | 0.9600 |
La2—O9 | 2.574 (4) | C10—H10A | 0.9600 |
La2—O5 | 2.590 (3) | C10—H10B | 0.9600 |
La2—O10ii | 2.599 (4) | C10—H10C | 0.9600 |
La2—O8iii | 2.604 (4) | C11—C12 | 1.522 (7) |
La2—O12ii | 2.617 (4) | C12—C13 | 1.517 (7) |
La2—O7iii | 2.712 (4) | C12—C14 | 1.528 (7) |
La2—O10 | 2.756 (4) | C12—C15 | 1.535 (8) |
O1—C1 | 1.264 (6) | C14—H14D | 0.9600 |
O2—C1 | 1.254 (7) | C14—H14E | 0.9600 |
O3—C3 | 1.260 (6) | C14—H14C | 0.9600 |
O4—C3 | 1.222 (6) | C15—H15D | 0.9600 |
O5—C6 | 1.273 (6) | C15—H15E | 0.9600 |
O6—C6 | 1.251 (7) | C15—H15C | 0.9600 |
O7—C8 | 1.273 (6) | O13—H13A | 0.8500 |
O8—C8 | 1.260 (7) | O13—H13B | 0.8497 |
O9—C11 | 1.269 (6) | O14—H14A | 0.8499 |
O10—C11 | 1.250 (7) | O14—H14B | 0.8523 |
O11—C13 | 1.253 (7) | O15—H15A | 0.8509 |
O12—C13 | 1.264 (6) | O15—H15B | 0.8472 |
C1—C2 | 1.513 (8) | O16—H16A | 0.8480 |
C2—C4 | 1.520 (8) | O16—H16B | 0.8469 |
C2—C5 | 1.551 (8) | O17—H17A | 0.8510 |
C2—C3 | 1.552 (8) | O17—H17B | 0.8516 |
| | | |
O3—La1—O1 | 65.38 (13) | O8iii—La2—C8iii | 24.04 (12) |
O3—La1—O13 | 142.38 (13) | O12ii—La2—C8iii | 129.53 (13) |
O1—La1—O13 | 134.63 (13) | O7iii—La2—C8iii | 24.57 (12) |
O3—La1—O5 | 69.44 (12) | O10—La2—C8iii | 82.27 (12) |
O1—La1—O5 | 134.55 (12) | C11—La2—C8iii | 72.40 (14) |
O13—La1—O5 | 81.88 (13) | C1—O1—La1 | 140.3 (4) |
O3—La1—O1i | 123.52 (12) | C1—O1—La1i | 99.2 (3) |
O1—La1—O1i | 60.81 (14) | La1—O1—La1i | 119.19 (14) |
O13—La1—O1i | 90.42 (12) | C1—O2—La1i | 92.6 (3) |
O5—La1—O1i | 162.25 (11) | C3—O3—La1 | 144.5 (4) |
O3—La1—O11ii | 84.36 (12) | C6—O5—La2 | 143.4 (4) |
O1—La1—O11ii | 79.43 (12) | C6—O5—La1 | 95.8 (3) |
O13—La1—O11ii | 125.92 (12) | La2—O5—La1 | 118.72 (13) |
O5—La1—O11ii | 101.11 (12) | C6—O6—La1 | 94.0 (3) |
O1i—La1—O11ii | 70.56 (12) | C8—O7—La2 | 142.6 (4) |
O3—La1—O12ii | 93.81 (11) | C8—O7—La2iii | 93.1 (3) |
O1—La1—O12ii | 127.03 (11) | La2—O7—La2iii | 119.73 (13) |
O13—La1—O12ii | 92.16 (12) | C8—O8—La2iii | 98.6 (3) |
O5—La1—O12ii | 59.83 (11) | C11—O9—La2 | 98.5 (3) |
O1i—La1—O12ii | 104.81 (11) | C11—O10—La2ii | 144.0 (3) |
O11ii—La1—O12ii | 49.23 (12) | C11—O10—La2 | 90.3 (3) |
O3—La1—O14 | 105.55 (12) | La2ii—O10—La2 | 121.45 (14) |
O1—La1—O14 | 71.04 (12) | C13—O11—La1ii | 93.9 (3) |
O13—La1—O14 | 66.83 (12) | C13—O12—La2ii | 127.1 (3) |
O5—La1—O14 | 118.24 (12) | C13—O12—La1ii | 93.5 (3) |
O1i—La1—O14 | 72.33 (11) | La2ii—O12—La1ii | 116.70 (13) |
O11ii—La1—O14 | 140.51 (13) | O2—C1—O1 | 119.3 (5) |
O12ii—La1—O14 | 158.52 (11) | O2—C1—C2 | 120.1 (5) |
O3—La1—O6 | 72.67 (12) | O1—C1—C2 | 120.6 (5) |
O1—La1—O6 | 110.28 (12) | O2—C1—La1i | 63.3 (3) |
O13—La1—O6 | 70.18 (12) | O1—C1—La1i | 56.8 (3) |
O5—La1—O6 | 49.18 (11) | C2—C1—La1i | 172.6 (3) |
O1i—La1—O6 | 142.01 (11) | C1—C2—C4 | 108.1 (5) |
O11ii—La1—O6 | 147.15 (12) | C1—C2—C5 | 107.3 (4) |
O12ii—La1—O6 | 108.16 (12) | C4—C2—C5 | 110.9 (5) |
O14—La1—O6 | 70.04 (12) | C1—C2—C3 | 114.8 (4) |
O3—La1—O2i | 150.88 (12) | C4—C2—C3 | 110.4 (4) |
O1—La1—O2i | 107.12 (12) | C5—C2—C3 | 105.2 (5) |
O13—La1—O2i | 63.70 (12) | O4—C3—O3 | 122.8 (5) |
O5—La1—O2i | 114.69 (11) | O4—C3—C2 | 118.4 (5) |
O1i—La1—O2i | 47.82 (12) | O3—C3—C2 | 118.7 (5) |
O11ii—La1—O2i | 66.52 (11) | C2—C4—H4A | 109.5 |
O12ii—La1—O2i | 67.62 (11) | C2—C4—H4B | 109.5 |
O14—La1—O2i | 97.50 (11) | H4A—C4—H4B | 109.5 |
O6—La1—O2i | 133.26 (11) | C2—C4—H4C | 109.5 |
O3—La1—C13ii | 92.92 (13) | H4A—C4—H4C | 109.5 |
O1—La1—C13ii | 104.16 (14) | H4B—C4—H4C | 109.5 |
O13—La1—C13ii | 107.28 (13) | C2—C5—H5A | 109.5 |
O5—La1—C13ii | 82.45 (13) | C2—C5—H5B | 109.5 |
O1i—La1—C13ii | 84.64 (14) | H5A—C5—H5B | 109.5 |
O11ii—La1—C13ii | 24.80 (13) | C2—C5—H5C | 109.5 |
O12ii—La1—C13ii | 25.04 (13) | H5A—C5—H5C | 109.5 |
O14—La1—C13ii | 155.90 (13) | H5B—C5—H5C | 109.5 |
O6—La1—C13ii | 131.63 (14) | O6—C6—O5 | 119.5 (5) |
O2i—La1—C13ii | 60.60 (12) | O6—C6—C7 | 121.4 (5) |
O3—La1—C6 | 66.28 (14) | O5—C6—C7 | 118.8 (5) |
O1—La1—C6 | 122.67 (13) | O6—C6—La1 | 61.4 (3) |
O13—La1—C6 | 77.39 (14) | O5—C6—La1 | 59.2 (3) |
O5—La1—C6 | 24.93 (12) | C7—C6—La1 | 164.5 (4) |
O1i—La1—C6 | 164.95 (12) | C8—C7—C6 | 112.8 (4) |
O11ii—La1—C6 | 123.81 (13) | C8—C7—C9 | 107.3 (4) |
O12ii—La1—C6 | 84.68 (13) | C6—C7—C9 | 105.5 (4) |
O14—La1—C6 | 94.51 (13) | C8—C7—C10 | 111.6 (5) |
O6—La1—C6 | 24.56 (12) | C6—C7—C10 | 109.3 (4) |
O2i—La1—C6 | 130.00 (13) | C9—C7—C10 | 110.1 (4) |
C13ii—La1—C6 | 107.23 (15) | O8—C8—O7 | 119.6 (5) |
O15—La2—O16 | 140.22 (13) | O8—C8—C7 | 121.0 (4) |
O15—La2—O7 | 100.53 (12) | O7—C8—C7 | 119.4 (5) |
O16—La2—O7 | 84.27 (11) | O8—C8—La2iii | 57.3 (3) |
O15—La2—O9 | 80.85 (13) | O7—C8—La2iii | 62.3 (3) |
O16—La2—O9 | 135.06 (13) | C7—C8—La2iii | 177.5 (4) |
O7—La2—O9 | 66.91 (11) | C7—C9—H9A | 109.5 |
O15—La2—O5 | 71.55 (12) | C7—C9—H9B | 109.5 |
O16—La2—O5 | 75.72 (12) | H9A—C9—H9B | 109.5 |
O7—La2—O5 | 63.71 (12) | C7—C9—H9C | 109.5 |
O9—La2—O5 | 116.30 (11) | H9A—C9—H9C | 109.5 |
O15—La2—O10ii | 78.86 (12) | H9B—C9—H9C | 109.5 |
O16—La2—O10ii | 100.60 (12) | C7—C10—H10A | 109.5 |
O7—La2—O10ii | 173.15 (11) | C7—C10—H10B | 109.5 |
O9—La2—O10ii | 106.33 (11) | H10A—C10—H10B | 109.5 |
O5—La2—O10ii | 122.00 (12) | C7—C10—H10C | 109.5 |
O15—La2—O8iii | 132.56 (12) | H10A—C10—H10C | 109.5 |
O16—La2—O8iii | 81.15 (12) | H10B—C10—H10C | 109.5 |
O7—La2—O8iii | 107.17 (12) | O10—C11—O9 | 121.2 (5) |
O9—La2—O8iii | 75.86 (12) | O10—C11—C12 | 119.5 (5) |
O5—La2—O8iii | 155.76 (12) | O9—C11—C12 | 119.2 (5) |
O10ii—La2—O8iii | 69.17 (12) | O10—C11—La2 | 65.3 (3) |
O15—La2—O12ii | 76.43 (12) | O9—C11—La2 | 57.1 (3) |
O16—La2—O12ii | 67.83 (12) | C12—C11—La2 | 168.1 (4) |
O7—La2—O12ii | 121.36 (11) | C13—C12—C11 | 105.7 (4) |
O9—La2—O12ii | 156.88 (12) | C13—C12—C14 | 109.2 (4) |
O5—La2—O12ii | 59.95 (11) | C11—C12—C14 | 107.1 (5) |
O10ii—La2—O12ii | 65.26 (11) | C13—C12—C15 | 110.7 (5) |
O8iii—La2—O12ii | 117.24 (12) | C11—C12—C15 | 112.8 (4) |
O15—La2—O7iii | 149.22 (12) | C14—C12—C15 | 111.0 (5) |
O16—La2—O7iii | 66.13 (12) | O11—C13—O12 | 120.4 (5) |
O7—La2—O7iii | 60.27 (13) | O11—C13—C12 | 120.7 (5) |
O9—La2—O7iii | 69.68 (12) | O12—C13—C12 | 118.9 (5) |
O5—La2—O7iii | 113.51 (11) | O11—C13—La1ii | 61.3 (3) |
O10ii—La2—O7iii | 117.18 (11) | O12—C13—La1ii | 61.5 (3) |
O8iii—La2—O7iii | 48.59 (11) | C12—C13—La1ii | 164.5 (3) |
O12ii—La2—O7iii | 133.43 (11) | C12—C14—H14D | 109.5 |
O15—La2—O10 | 65.76 (12) | C12—C14—H14E | 109.5 |
O16—La2—O10 | 146.94 (11) | H14D—C14—H14E | 109.5 |
O7—La2—O10 | 114.89 (12) | C12—C14—H14C | 109.5 |
O9—La2—O10 | 48.49 (11) | H14D—C14—H14C | 109.5 |
O5—La2—O10 | 136.26 (11) | H14E—C14—H14C | 109.5 |
O10ii—La2—O10 | 58.55 (14) | C12—C15—H15D | 109.5 |
O8iii—La2—O10 | 67.81 (11) | C12—C15—H15E | 109.5 |
O12ii—La2—O10 | 116.18 (11) | H15D—C15—H15E | 109.5 |
O7iii—La2—O10 | 98.97 (11) | C12—C15—H15C | 109.5 |
O15—La2—C11 | 74.38 (14) | H15D—C15—H15C | 109.5 |
O16—La2—C11 | 145.36 (14) | H15E—C15—H15C | 109.5 |
O7—La2—C11 | 91.33 (13) | La1—O13—H13A | 111.4 |
O9—La2—C11 | 24.44 (12) | La1—O13—H13B | 109.3 |
O5—La2—C11 | 132.20 (13) | H13A—O13—H13B | 109.4 |
O10ii—La2—C11 | 81.93 (13) | La1—O14—H14A | 109.6 |
O8iii—La2—C11 | 67.35 (13) | La1—O14—H14B | 109.8 |
O12ii—La2—C11 | 139.49 (14) | H14A—O14—H14B | 109.7 |
O7iii—La2—C11 | 81.85 (13) | La2—O15—H15A | 109.5 |
O10—La2—C11 | 24.34 (12) | La2—O15—H15B | 130.0 |
O15—La2—C8iii | 146.59 (13) | H15A—O15—H15B | 113.3 |
O16—La2—C8iii | 72.96 (13) | La2—O16—H16A | 117.7 |
O7—La2—C8iii | 83.74 (13) | La2—O16—H16B | 119.2 |
O9—La2—C8iii | 70.35 (13) | H16A—O16—H16B | 116.3 |
O5—La2—C8iii | 136.54 (13) | H17A—O17—H17B | 112.6 |
O10ii—La2—C8iii | 93.04 (13) | | |
| | | |
O3—La1—O1—C1 | −34.1 (5) | La1—O1—C1—C2 | 22.5 (8) |
O13—La1—O1—C1 | 106.4 (5) | La1i—O1—C1—C2 | −171.8 (4) |
O5—La1—O1—C1 | −27.4 (6) | La1—O1—C1—La1i | −165.7 (5) |
O1i—La1—O1—C1 | 163.8 (6) | O2—C1—C2—C4 | −35.9 (6) |
O11ii—La1—O1—C1 | −122.7 (5) | O1—C1—C2—C4 | 146.4 (5) |
O12ii—La1—O1—C1 | −109.3 (5) | O2—C1—C2—C5 | 83.8 (6) |
O14—La1—O1—C1 | 83.9 (5) | O1—C1—C2—C5 | −93.9 (6) |
O6—La1—O1—C1 | 24.7 (5) | O2—C1—C2—C3 | −159.7 (5) |
O2i—La1—O1—C1 | 176.1 (5) | O1—C1—C2—C3 | 22.6 (7) |
C13ii—La1—O1—C1 | −120.8 (5) | La1—O3—C3—O4 | −166.3 (4) |
C6—La1—O1—C1 | 0.9 (5) | La1—O3—C3—C2 | 16.6 (9) |
O3—La1—O1—La1i | 162.13 (19) | C1—C2—C3—O4 | 143.4 (5) |
O13—La1—O1—La1i | −57.3 (2) | C4—C2—C3—O4 | 20.9 (7) |
O5—La1—O1—La1i | 168.78 (12) | C5—C2—C3—O4 | −98.9 (6) |
O1i—La1—O1—La1i | 0.0 | C1—C2—C3—O3 | −39.4 (7) |
O11ii—La1—O1—La1i | 73.53 (15) | C4—C2—C3—O3 | −161.9 (5) |
O12ii—La1—O1—La1i | 86.86 (18) | C5—C2—C3—O3 | 78.3 (6) |
O14—La1—O1—La1i | −79.88 (16) | La1—O6—C6—O5 | −12.2 (5) |
O6—La1—O1—La1i | −139.11 (13) | La1—O6—C6—C7 | 162.4 (4) |
O2i—La1—O1—La1i | 12.33 (18) | La2—O5—C6—O6 | 173.7 (3) |
C13ii—La1—O1—La1i | 75.45 (17) | La1—O5—C6—O6 | 12.4 (5) |
C6—La1—O1—La1i | −162.91 (14) | La2—O5—C6—C7 | −1.0 (8) |
O1—La1—O3—C3 | 11.7 (6) | La1—O5—C6—C7 | −162.3 (4) |
O13—La1—O3—C3 | −120.4 (6) | La2—O5—C6—La1 | 161.3 (6) |
O5—La1—O3—C3 | −163.2 (6) | O3—La1—C6—O6 | 100.3 (3) |
O1i—La1—O3—C3 | 30.5 (6) | O1—La1—C6—O6 | 65.6 (3) |
O11ii—La1—O3—C3 | 92.7 (6) | O13—La1—C6—O6 | −69.7 (3) |
O12ii—La1—O3—C3 | 141.0 (6) | O5—La1—C6—O6 | −167.7 (5) |
O14—La1—O3—C3 | −48.4 (6) | O1i—La1—C6—O6 | −33.2 (7) |
O6—La1—O3—C3 | −111.1 (6) | O11ii—La1—C6—O6 | 165.2 (3) |
O2i—La1—O3—C3 | 92.7 (6) | O12ii—La1—C6—O6 | −163.2 (3) |
C13ii—La1—O3—C3 | 116.0 (6) | O14—La1—C6—O6 | −4.7 (3) |
C6—La1—O3—C3 | −136.5 (6) | O2i—La1—C6—O6 | −108.4 (3) |
O15—La2—O5—C6 | −91.8 (6) | C13ii—La1—C6—O6 | −174.2 (3) |
O16—La2—O5—C6 | 111.1 (6) | O3—La1—C6—O5 | −92.0 (3) |
O7—La2—O5—C6 | 20.5 (5) | O1—La1—C6—O5 | −126.7 (3) |
O9—La2—O5—C6 | −22.4 (6) | O13—La1—C6—O5 | 97.9 (3) |
O10ii—La2—O5—C6 | −155.1 (5) | O1i—La1—C6—O5 | 134.5 (4) |
O8iii—La2—O5—C6 | 93.3 (6) | O11ii—La1—C6—O5 | −27.1 (3) |
O12ii—La2—O5—C6 | −176.5 (6) | O12ii—La1—C6—O5 | 4.5 (3) |
O7iii—La2—O5—C6 | 55.6 (6) | O14—La1—C6—O5 | 163.0 (3) |
O10—La2—O5—C6 | −78.8 (6) | O6—La1—C6—O5 | 167.7 (5) |
C11—La2—O5—C6 | −45.1 (6) | O2i—La1—C6—O5 | 59.2 (3) |
C8iii—La2—O5—C6 | 66.2 (6) | C13ii—La1—C6—O5 | −6.5 (3) |
O15—La2—O5—La1 | 66.83 (16) | O3—La1—C6—C7 | −4.6 (13) |
O16—La2—O5—La1 | −90.24 (16) | O1—La1—C6—C7 | −39.3 (14) |
O7—La2—O5—La1 | 179.14 (19) | O13—La1—C6—C7 | −174.7 (13) |
O9—La2—O5—La1 | 136.22 (14) | O5—La1—C6—C7 | 87.4 (13) |
O10ii—La2—O5—La1 | 3.5 (2) | O1i—La1—C6—C7 | −138.1 (12) |
O8iii—La2—O5—La1 | −108.0 (3) | O11ii—La1—C6—C7 | 60.3 (14) |
O12ii—La2—O5—La1 | −17.84 (13) | O12ii—La1—C6—C7 | 91.9 (13) |
O7iii—La2—O5—La1 | −145.76 (14) | O14—La1—C6—C7 | −109.6 (13) |
O10—La2—O5—La1 | 79.8 (2) | O6—La1—C6—C7 | −104.9 (14) |
C11—La2—O5—La1 | 113.54 (19) | O2i—La1—C6—C7 | 146.6 (13) |
C8iii—La2—O5—La1 | −135.14 (17) | C13ii—La1—C6—C7 | 80.9 (13) |
O3—La1—O5—C6 | 77.7 (3) | O6—C6—C7—C8 | 146.1 (5) |
O1—La1—O5—C6 | 71.3 (3) | O5—C6—C7—C8 | −39.3 (7) |
O13—La1—O5—C6 | −77.5 (3) | La1—C6—C7—C8 | −117.8 (12) |
O1i—La1—O5—C6 | −142.6 (4) | O6—C6—C7—C9 | −97.1 (6) |
O11ii—La1—O5—C6 | 157.3 (3) | O5—C6—C7—C9 | 77.5 (6) |
O12ii—La1—O5—C6 | −174.8 (3) | La1—C6—C7—C9 | −1.0 (15) |
O14—La1—O5—C6 | −19.4 (3) | O6—C6—C7—C10 | 21.3 (7) |
O6—La1—O5—C6 | −6.7 (3) | O5—C6—C7—C10 | −164.1 (5) |
O2i—La1—O5—C6 | −133.6 (3) | La1—C6—C7—C10 | 117.3 (12) |
C13ii—La1—O5—C6 | 173.7 (3) | La2iii—O8—C8—O7 | −3.4 (5) |
O3—La1—O5—La2 | −89.64 (16) | La2iii—O8—C8—C7 | 177.8 (4) |
O1—La1—O5—La2 | −96.09 (18) | La2—O7—C8—O8 | 156.0 (4) |
O13—La1—O5—La2 | 115.12 (17) | La2iii—O7—C8—O8 | 3.2 (5) |
O1i—La1—O5—La2 | 50.1 (4) | La2—O7—C8—C7 | −25.2 (8) |
O11ii—La1—O5—La2 | −10.04 (17) | La2iii—O7—C8—C7 | −178.0 (4) |
O12ii—La1—O5—La2 | 17.83 (13) | La2—O7—C8—La2iii | 152.8 (5) |
O14—La1—O5—La2 | 173.27 (12) | C6—C7—C8—O8 | −130.1 (5) |
O6—La1—O5—La2 | −174.1 (2) | C9—C7—C8—O8 | 114.1 (5) |
O2i—La1—O5—La2 | 59.06 (18) | C10—C7—C8—O8 | −6.6 (7) |
C13ii—La1—O5—La2 | 6.36 (16) | C6—C7—C8—O7 | 51.1 (6) |
C6—La1—O5—La2 | −167.4 (4) | C9—C7—C8—O7 | −64.7 (6) |
O3—La1—O6—C6 | −70.7 (3) | C10—C7—C8—O7 | 174.6 (4) |
O1—La1—O6—C6 | −125.2 (3) | La2ii—O10—C11—O9 | −165.6 (4) |
O13—La1—O6—C6 | 103.3 (3) | La2—O10—C11—O9 | −11.9 (5) |
O5—La1—O6—C6 | 6.8 (3) | La2ii—O10—C11—C12 | 14.1 (9) |
O1i—La1—O6—C6 | 166.6 (3) | La2—O10—C11—C12 | 167.8 (4) |
O11ii—La1—O6—C6 | −23.0 (4) | La2ii—O10—C11—La2 | −153.7 (6) |
O12ii—La1—O6—C6 | 17.7 (3) | La2—O9—C11—O10 | 12.9 (5) |
O14—La1—O6—C6 | 175.0 (3) | La2—O9—C11—C12 | −166.8 (4) |
O2i—La1—O6—C6 | 93.7 (3) | O15—La2—C11—O10 | −65.4 (3) |
C13ii—La1—O6—C6 | 7.5 (4) | O16—La2—C11—O10 | 112.2 (3) |
O15—La2—O7—C8 | 57.6 (5) | O7—La2—C11—O10 | −166.0 (3) |
O16—La2—O7—C8 | −82.5 (5) | O9—La2—C11—O10 | −167.9 (5) |
O9—La2—O7—C8 | 132.8 (5) | O5—La2—C11—O10 | −111.2 (3) |
O5—La2—O7—C8 | −5.6 (5) | O10ii—La2—C11—O10 | 15.2 (3) |
O8iii—La2—O7—C8 | −161.4 (5) | O8iii—La2—C11—O10 | 86.0 (3) |
O12ii—La2—O7—C8 | −22.9 (6) | O12ii—La2—C11—O10 | −20.0 (4) |
O7iii—La2—O7—C8 | −148.2 (6) | O7iii—La2—C11—O10 | 134.3 (3) |
O10—La2—O7—C8 | 125.6 (5) | C8iii—La2—C11—O10 | 111.0 (3) |
C11—La2—O7—C8 | 131.9 (5) | O15—La2—C11—O9 | 102.5 (3) |
C8iii—La2—O7—C8 | −155.9 (5) | O16—La2—C11—O9 | −79.9 (4) |
O15—La2—O7—La2iii | −154.19 (15) | O7—La2—C11—O9 | 1.9 (3) |
O16—La2—O7—La2iii | 65.73 (16) | O5—La2—C11—O9 | 56.7 (4) |
O9—La2—O7—La2iii | −78.97 (16) | O10ii—La2—C11—O9 | −176.9 (3) |
O5—La2—O7—La2iii | 142.61 (19) | O8iii—La2—C11—O9 | −106.2 (3) |
O8iii—La2—O7—La2iii | −13.16 (18) | O12ii—La2—C11—O9 | 147.9 (3) |
O12ii—La2—O7—La2iii | 125.39 (15) | O7iii—La2—C11—O9 | −57.8 (3) |
O7iii—La2—O7—La2iii | 0.0 | O10—La2—C11—O9 | 167.9 (5) |
O10—La2—O7—La2iii | −86.15 (17) | C8iii—La2—C11—O9 | −81.1 (3) |
C11—La2—O7—La2iii | −79.83 (17) | O15—La2—C11—C12 | 177.8 (17) |
C8iii—La2—O7—La2iii | −7.70 (15) | O16—La2—C11—C12 | −4.6 (18) |
O15—La2—O9—C11 | −72.3 (3) | O7—La2—C11—C12 | 77.3 (17) |
O16—La2—O9—C11 | 127.6 (3) | O9—La2—C11—C12 | 75.3 (17) |
O7—La2—O9—C11 | −177.9 (4) | O5—La2—C11—C12 | 132.0 (17) |
O5—La2—O9—C11 | −136.3 (3) | O10ii—La2—C11—C12 | −101.6 (17) |
O10ii—La2—O9—C11 | 3.2 (3) | O8iii—La2—C11—C12 | −30.8 (17) |
O8iii—La2—O9—C11 | 66.1 (3) | O12ii—La2—C11—C12 | −136.8 (17) |
O12ii—La2—O9—C11 | −61.7 (4) | O7iii—La2—C11—C12 | 17.5 (17) |
O7iii—La2—O9—C11 | 116.7 (3) | O10—La2—C11—C12 | −116.8 (18) |
O10—La2—O9—C11 | −6.6 (3) | C8iii—La2—C11—C12 | −5.8 (17) |
C8iii—La2—O9—C11 | 90.6 (3) | O10—C11—C12—C13 | −43.9 (6) |
O15—La2—O10—C11 | 106.2 (3) | O9—C11—C12—C13 | 135.8 (5) |
O16—La2—O10—C11 | −105.2 (3) | La2—C11—C12—C13 | 67.3 (18) |
O7—La2—O10—C11 | 15.5 (3) | O10—C11—C12—C14 | 72.5 (6) |
O9—La2—O10—C11 | 6.7 (3) | O9—C11—C12—C14 | −107.8 (5) |
O5—La2—O10—C11 | 92.7 (3) | La2—C11—C12—C14 | −176.3 (15) |
O10ii—La2—O10—C11 | −162.3 (4) | O10—C11—C12—C15 | −165.1 (5) |
O8iii—La2—O10—C11 | −83.8 (3) | O9—C11—C12—C15 | 14.6 (7) |
O12ii—La2—O10—C11 | 165.6 (3) | La2—C11—C12—C15 | −53.9 (19) |
O7iii—La2—O10—C11 | −45.8 (3) | La1ii—O11—C13—O12 | 17.7 (5) |
C8iii—La2—O10—C11 | −63.9 (3) | La1ii—O11—C13—C12 | −162.3 (4) |
O15—La2—O10—La2ii | −91.55 (18) | La2ii—O12—C13—O11 | 109.9 (5) |
O16—La2—O10—La2ii | 57.0 (3) | La1ii—O12—C13—O11 | −17.7 (5) |
O7—La2—O10—La2ii | 177.76 (14) | La2ii—O12—C13—C12 | −70.0 (5) |
O9—La2—O10—La2ii | 168.9 (2) | La1ii—O12—C13—C12 | 162.4 (4) |
O5—La2—O10—La2ii | −105.03 (18) | La2ii—O12—C13—La1ii | 127.6 (3) |
O10ii—La2—O10—La2ii | 0.0 | C11—C12—C13—O11 | −104.2 (6) |
O8iii—La2—O10—La2ii | 78.43 (17) | C14—C12—C13—O11 | 140.9 (5) |
O12ii—La2—O10—La2ii | −32.1 (2) | C15—C12—C13—O11 | 18.4 (7) |
O7iii—La2—O10—La2ii | 116.46 (16) | C11—C12—C13—O12 | 75.8 (6) |
C11—La2—O10—La2ii | 162.3 (4) | C14—C12—C13—O12 | −39.2 (6) |
C8iii—La2—O10—La2ii | 98.38 (18) | C15—C12—C13—O12 | −161.7 (5) |
La1i—O2—C1—O1 | −9.7 (5) | C11—C12—C13—La1ii | 162.9 (13) |
La1i—O2—C1—C2 | 172.5 (4) | C14—C12—C13—La1ii | 47.9 (16) |
La1—O1—C1—O2 | −155.3 (4) | C15—C12—C13—La1ii | −74.6 (15) |
La1i—O1—C1—O2 | 10.4 (5) | | |
Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+2, −y+2, −z+1; (iii) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O17—H17B···O4 | 0.85 | 1.84 | 2.681 (5) | 171 |
O17—H17A···O2iv | 0.85 | 2.06 | 2.810 (6) | 146 |
O16—H16B···O17v | 0.85 | 1.98 | 2.819 (5) | 169 |
O16—H16A···O9iii | 0.85 | 1.99 | 2.773 (5) | 153 |
O15—H15B···O8vi | 0.85 | 2.00 | 2.777 (5) | 151 |
O15—H15A···O3 | 0.85 | 1.90 | 2.709 (5) | 160 |
O14—H14B···O11vii | 0.85 | 1.82 | 2.667 (6) | 176 |
O14—H14A···O6viii | 0.85 | 2.01 | 2.754 (5) | 145 |
O13—H13B···O14viii | 0.85 | 1.99 | 2.828 (5) | 168 |
O13—H13A···O17v | 0.85 | 1.91 | 2.707 (5) | 155 |
Symmetry codes: (iii) −x+1, −y+2, −z+1; (iv) x−1/2, −y+3/2, z−1/2; (v) −x+3/2, y+1/2, −z+3/2; (vi) x+1, y, z; (vii) x, y, z+1; (viii) −x+1, −y+2, −z+2. |
Experimental details
Crystal data |
Chemical formula | [La2(C5H6O4)3(H2O)4]·H2O |
Mr | 758.19 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 133 |
a, b, c (Å) | 8.3835 (17), 20.229 (4), 14.101 (3) |
β (°) | 92.989 (3) |
V (Å3) | 2388.2 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.61 |
Crystal size (mm) | 0.12 × 0.08 × 0.06 |
|
Data collection |
Diffractometer | Rigaku Saturn diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2005) |
Tmin, Tmax | 0.715, 0.802 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13664, 4177, 3140 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.088, 0.94 |
No. of reflections | 4177 |
No. of parameters | 313 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.04, −0.81 |
Selected geometric parameters (Å, º) topLa1—O3 | 2.421 (4) | La2—O7 | 2.544 (4) |
La1—O1 | 2.490 (4) | La2—O9 | 2.574 (4) |
La1—O13 | 2.550 (4) | La2—O5 | 2.590 (3) |
La1—O5 | 2.594 (4) | La2—O10ii | 2.599 (4) |
La1—O1i | 2.604 (4) | La2—O8iii | 2.604 (4) |
La1—O11ii | 2.620 (4) | La2—O12ii | 2.617 (4) |
La1—O12ii | 2.623 (4) | La2—O7iii | 2.712 (4) |
La1—O14 | 2.625 (4) | La2—O10 | 2.756 (4) |
La1—O6 | 2.645 (4) | O3—C3 | 1.260 (6) |
La1—O2i | 2.747 (4) | O4—C3 | 1.222 (6) |
La2—O15 | 2.466 (4) | O6—C6 | 1.251 (7) |
La2—O16 | 2.498 (4) | O7—C8 | 1.273 (6) |
| | | |
O11ii—La1—O12ii | 49.23 (12) | O9—La2—O10 | 48.49 (11) |
O13—La1—O14 | 66.83 (12) | C1—C2—C3 | 114.8 (4) |
O5—La1—O6 | 49.18 (11) | C8—C7—C6 | 112.8 (4) |
O15—La2—O16 | 140.22 (13) | C13—C12—C11 | 105.7 (4) |
O8iii—La2—O7iii | 48.59 (11) | | |
Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+2, −y+2, −z+1; (iii) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O17—H17B···O4 | 0.85 | 1.84 | 2.681 (5) | 171 |
O17—H17A···O2iv | 0.85 | 2.06 | 2.810 (6) | 146 |
O16—H16B···O17v | 0.85 | 1.98 | 2.819 (5) | 169 |
O16—H16A···O9iii | 0.85 | 1.99 | 2.773 (5) | 153 |
O15—H15B···O8vi | 0.85 | 2.00 | 2.777 (5) | 151 |
O15—H15A···O3 | 0.85 | 1.90 | 2.709 (5) | 160 |
O14—H14B···O11vii | 0.85 | 1.82 | 2.667 (6) | 176 |
O14—H14A···O6viii | 0.85 | 2.01 | 2.754 (5) | 145 |
O13—H13B···O14viii | 0.85 | 1.99 | 2.828 (5) | 168 |
O13—H13A···O17v | 0.85 | 1.91 | 2.707 (5) | 155 |
Symmetry codes: (iii) −x+1, −y+2, −z+1; (iv) x−1/2, −y+3/2, z−1/2; (v) −x+3/2, y+1/2, −z+3/2; (vi) x+1, y, z; (vii) x, y, z+1; (viii) −x+1, −y+2, −z+2. |
Recently, the design and preparation of novel lanthanide dicarboxylate metal–organic frameworks have received considerable attention because of the interesting properties that they exhibit, such as porosity, luminescence, magnetism and catalytic activity (Shi et al., 2008; Luo et al., 2008; Ghosh & Bharadwaj, 2005; Mahata & Natarajan, 2007; Wang et al., 2007). Of these, malonate has been used as the ligand of choice for the design of such metal–organic frameworks/molecular assemblies because of its manifold coordination modes and the variety of the resulting architectures (Hansson, 1973a,b; Canadillas-Delgado et al., 2006). Two complexes with lanthanum have been reported to date, one containing the malonate dianion (Marrot & Trombe, 1993; Benmerad et al., 2000) and the other both the malonate dianion and the hydrogen malonate anion as ligands (Marrot & Trombe, 1994). However, in spite of this wealth of possibilities, no complexes of a lanthanide with dimethylmalonate have been reported to date. Using the 2,2-dimethylmalonate dianion as a ligand, we have obtained the title novel ten-coordinate dimethylmalonate–La complex, (I), which is described here.
The asymmetric unit in the structure of (I) contains two independent ten-coordinate La atoms, three independent dimethylmalonate dianions, L1, L2 and L3 (containing O atoms O1–O4, O5–O8 and O9–O12, respectively), four coordinated water molecules and one solvent water molecule. Selected geometric parameters are given in Table 1. Fig. 1 shows a symmetry-expanded view, which displays the full coordination of the two La atoms and the details of the symmetry codes used below.
All the symmetry-related La atoms of (I) are related by inversion centres. Thus, the L1 dianion is coordinated to centrosymmetrically related atoms La1 and La1i via bis-bidentate 1,2-chelating and six-membered ring modes. The L2 dianion binds to atoms La1, La2 and La2iii, with the two carboxylate groups using two bis-bidentate 1,2-chelating modes and one six-membered ring mode. The L3 ligand also adopts two bis-bidentate 1,2-chelating and one six-membered chelating mode to connect to atoms La2, La1ii and La2ii, but it differs from the L2 ligand with the bond angle at C12 being smaller than the normal value (Table 1), indicating that there is greater distortion in this six-membered ring. This smaller angle had been observed in polymeric tetraaquatris(malonato)dilanthanum(III) monohydrate complexes (Benmerad et al., 2000).
The La—O distances in (I) (Table 1) are comparable with the values reported for polymeric tetraaquatris(malonato)dilanthanum(III) monohydrate (Benmerad et al., 2000), but with three La—O bonds being considerably longer. These longer distances seem to be rather typical of the chelating carboxylate group (Hansson, 1973a,b). The La geometries do not approximate to an idealized polyhedron, a bicapped square antiprism or a bicapped dodecahedron. This is not surprising in view of the steric requirements of the dimethylmalonate ligands in the structure and the large distortions imposed by the bite angles, which are considerably smaller (Table 1) (see Benmerad et al., 2000). Through the centres of inversion, each group of six La2 atoms and four La1 atoms builds up a decanuclear 20-membered ring. These decanuclear rings are further joined into a two-dimensional layer structure parallel to the ac plane (Fig. 2).
Within these layers, strong intra- and intermolecular hydrogen-bond interactions (entries 6 and 7 in Table 2; Brown, 1976) are responsible for the formation of two six-membered hydrogen-bonded S(6) and R11(6) ring graph sets (Bernstein et al., 1995). The two coordinated water molecules O13 and O14 are involved in a hydrogen bond (entry 9 in Table 2) which crosslinks two La1 atoms together within the decanuclear 20-membered ring via an R22(8) motif (Fig. 2), thus enhancing the stability of the decanuclear 20-membered ring. These two-dimensional dianionic (dimethylmalonate)lanthanum metal–organic layers occur near y = 0 and y = 1/2 by way of the crystallographic twofold screw axis. The solvent water molecule (O17), acting as both proton donor and acceptor, provides strong interlayer binding along the b axis through further hydrogen bonds (entries 1–3 and 10 in Table 2; Fig. 3).
A comparison with the two previously reported lanthanum malonate compounds (Marrot & Trombe, 1993; Benmerad et al., 2000) reveals that all these structures contain the same number of water molecules. However, the two crystallographically independent La atoms of the former are nine- and eight-coordinate, respectively, while in the latter there is only one crystallographically independent La atom and two independent malonate dianions. The present work therefore represents a new example of the substituted malonate series of lanthanide complexes.