catena-Poly[[aqualanthanum(III)]-μ-(8-carboxyoctanoato)-μ-octanedioato], [La(C8H12O4)(C8H13O4)(H2O)]n, is, to our knowledge, the first reported rare-earth complex containing a flexible long-chain ligand that crystallizes without water of crystallization. The layered polymeric structure is built from infinite chains of one-edge-sharing LaO8(H2O) polyhedra, connected through the carbon backbone chains of the ligands. The two chemically different ligands act in the same coordination modes, exhibiting chelating bonds and μ-1,1-bridging monodentate linkage, and adopting the same extended conformation. In the relatively limited hydrogen-bonding network, a very strong hydrogen bond between the deprotonated and protonated ligand ends stabilizes the framework.
Supporting information
CCDC reference: 248139
Compound (I) was prepared using the procedure described by Benmerad et al. (2000a, 2000b), using a mixture of La2O3 and suberic acid in a 1:3 molar ratio and a reflux time of 10 h. Single crystals of the complex were deposited after one week when the cooled reaction mixture was allowed to stand in air at 313 K.
All H atoms bonded to C atoms were initially located from difference Fourier maps, and were then placed in calculated positions, 0.97 Å from their parent atoms, and modelled as riding. Atom H8 bonded to atom O8 was located from the Fourier syntheses and its position was refined freely, with Uiso(H) constrained to 1.2Ueq(O8).
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: enCIFer (Allen et al., 2004).
catena-Poly[[aqualanthanum(III)]-µ-(8-carboxyoctanoato)-µ-octanedioato]
top
Crystal data top
[La(C8H12O4)(C8H13O4)(H2O)] | Z = 2 |
Mr = 502.28 | F(000) = 504 |
Triclinic, P1 | Dx = 1.743 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.582 (2) Å | Cell parameters from 38534 reflections |
b = 9.079 (1) Å | θ = 2.5–30.5° |
c = 13.092 (4) Å | µ = 2.28 mm−1 |
α = 100.59 (1)° | T = 293 K |
β = 103.66 (1)° | Prism, colourless |
γ = 97.83 (1)° | 0.4 × 0.3 × 0.3 mm |
V = 957.0 (4) Å3 | |
Data collection top
Nonius KappaCCD diffractometer | 5739 independent reflections |
Radiation source: fine-focus sealed tube | 5279 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ϕ and ω scans | θmax = 30.5°, θmin = 2.5° |
Absorption correction: empirical (DENZO–SMN; Otwinowski & Minor, 1997) | h = −11→12 |
Tmin = 0.47, Tmax = 0.51 | k = −11→12 |
38534 measured reflections | l = −18→17 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.023 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.060 | w = 1/[σ2(Fo2) + (0.0417P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.008 |
5739 reflections | Δρmax = 1.03 e Å−3 |
239 parameters | Δρmin = −1.21 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0549 (15) |
Crystal data top
[La(C8H12O4)(C8H13O4)(H2O)] | γ = 97.83 (1)° |
Mr = 502.28 | V = 957.0 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.582 (2) Å | Mo Kα radiation |
b = 9.079 (1) Å | µ = 2.28 mm−1 |
c = 13.092 (4) Å | T = 293 K |
α = 100.59 (1)° | 0.4 × 0.3 × 0.3 mm |
β = 103.66 (1)° | |
Data collection top
Nonius KappaCCD diffractometer | 5739 independent reflections |
Absorption correction: empirical (DENZO–SMN; Otwinowski & Minor, 1997) | 5279 reflections with I > 2σ(I) |
Tmin = 0.47, Tmax = 0.51 | Rint = 0.039 |
38534 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.060 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 1.03 e Å−3 |
5739 reflections | Δρmin = −1.21 e Å−3 |
239 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 | 0.749250 (10) | 0.980319 (11) | 0.002455 (7) | 0.01794 (5) | |
O1 | 0.87079 (19) | 0.81489 (19) | 0.11802 (12) | 0.0366 (4) | |
O2 | 0.8784 (2) | 0.5755 (2) | 0.05009 (14) | 0.0428 (4) | |
O3 | 1.46480 (15) | 1.04292 (18) | 0.90033 (10) | 0.0259 (3) | |
O4 | 1.63649 (17) | 0.9950 (2) | 0.80454 (11) | 0.0369 (4) | |
O5 | 0.88275 (16) | 1.1578 (2) | 0.19201 (11) | 0.0335 (4) | |
O6 | 1.05355 (15) | 1.12127 (17) | 0.09302 (10) | 0.0257 (3) | |
O7 | 1.56729 (19) | 1.72928 (19) | 0.91111 (14) | 0.0442 (4) | |
O8 | 1.6359 (3) | 1.5037 (2) | 0.89694 (17) | 0.0602 (6) | |
H8 | 1.723 (3) | 1.558 (5) | 0.969 (2) | 0.072* | |
C1 | 0.9249 (2) | 0.6965 (2) | 0.12373 (15) | 0.0267 (4) | |
C2 | 1.0510 (3) | 0.6869 (3) | 0.22411 (16) | 0.0350 (5) | |
H2A | 1.1502 | 0.6695 | 0.2045 | 0.042* | |
H2B | 1.0109 | 0.5990 | 0.2494 | 0.042* | |
C3 | 1.0932 (3) | 0.8264 (3) | 0.31637 (15) | 0.0316 (4) | |
H3A | 1.1441 | 0.9128 | 0.2942 | 0.038* | |
H3B | 0.9934 | 0.8499 | 0.3325 | 0.038* | |
C4 | 1.2074 (3) | 0.8036 (3) | 0.41753 (17) | 0.0394 (5) | |
H4A | 1.1593 | 0.7130 | 0.4366 | 0.047* | |
H4B | 1.3094 | 0.7862 | 0.4023 | 0.047* | |
C5 | 1.2431 (2) | 0.9372 (3) | 0.51283 (15) | 0.0363 (5) | |
H5A | 1.1407 | 0.9563 | 0.5268 | 0.044* | |
H5B | 1.2937 | 1.0272 | 0.4943 | 0.044* | |
C6 | 1.3542 (3) | 0.9135 (3) | 0.61547 (17) | 0.0391 (5) | |
H6A | 1.3068 | 0.8205 | 0.6320 | 0.047* | |
H6B | 1.4590 | 0.9005 | 0.6029 | 0.047* | |
C7 | 1.3813 (3) | 1.0446 (3) | 0.71186 (16) | 0.0324 (5) | |
H7A | 1.4212 | 1.1390 | 0.6937 | 0.039* | |
H7B | 1.2778 | 1.0527 | 0.7281 | 0.039* | |
C8 | 1.5009 (2) | 1.0250 (2) | 0.81013 (14) | 0.0239 (4) | |
C9 | 1.0241 (2) | 1.1770 (2) | 0.18295 (14) | 0.0235 (4) | |
C10 | 1.1649 (2) | 1.2680 (3) | 0.27484 (15) | 0.0291 (4) | |
H10A | 1.2015 | 1.3638 | 0.2573 | 0.035* | |
H10B | 1.2544 | 1.2125 | 0.2809 | 0.035* | |
C11 | 1.1285 (2) | 1.3028 (3) | 0.38381 (15) | 0.0313 (4) | |
H11A | 1.0837 | 1.2083 | 0.3997 | 0.038* | |
H11B | 1.0469 | 1.3672 | 0.3808 | 0.038* | |
C12 | 1.2805 (2) | 1.3825 (3) | 0.47384 (15) | 0.0316 (4) | |
H12A | 1.3229 | 1.4781 | 0.4584 | 0.038* | |
H12B | 1.3632 | 1.3194 | 0.4743 | 0.038* | |
C13 | 1.2519 (2) | 1.4152 (3) | 0.58578 (16) | 0.0340 (5) | |
H13A | 1.1726 | 1.4817 | 0.5866 | 0.041* | |
H13B | 1.2061 | 1.3202 | 0.6006 | 0.041* | |
C14 | 1.4075 (2) | 1.4897 (3) | 0.67466 (15) | 0.0314 (4) | |
H14A | 1.4520 | 1.5856 | 0.6605 | 0.038* | |
H14B | 1.4875 | 1.4241 | 0.6728 | 0.038* | |
C15 | 1.3803 (2) | 1.5197 (3) | 0.78707 (15) | 0.0348 (5) | |
H15A | 1.3015 | 1.5864 | 0.7898 | 0.042* | |
H15B | 1.3359 | 1.4242 | 0.8018 | 0.042* | |
C16 | 1.5373 (3) | 1.5923 (3) | 0.87196 (15) | 0.0302 (4) | |
OW1 | 0.7704 (2) | 1.2610 (2) | −0.01016 (15) | 0.0488 (5) | |
H2W | 0.8409 | 1.3510 | 0.0292 | 0.073* | |
H1W | 0.6694 | 1.2727 | −0.0476 | 0.073* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
La1 | 0.01515 (6) | 0.02157 (7) | 0.01572 (7) | 0.00430 (4) | 0.00269 (4) | 0.00205 (4) |
O1 | 0.0453 (9) | 0.0316 (8) | 0.0288 (8) | 0.0139 (7) | −0.0021 (7) | 0.0071 (6) |
O2 | 0.0517 (10) | 0.0323 (9) | 0.0341 (9) | 0.0159 (8) | −0.0045 (7) | −0.0034 (7) |
O3 | 0.0213 (6) | 0.0381 (8) | 0.0195 (6) | 0.0078 (6) | 0.0058 (5) | 0.0073 (6) |
O4 | 0.0288 (7) | 0.0649 (12) | 0.0220 (7) | 0.0208 (8) | 0.0085 (6) | 0.0108 (7) |
O5 | 0.0215 (6) | 0.0467 (10) | 0.0254 (7) | 0.0024 (6) | 0.0069 (6) | −0.0073 (7) |
O6 | 0.0205 (6) | 0.0332 (8) | 0.0191 (6) | 0.0061 (5) | 0.0042 (5) | −0.0042 (5) |
O7 | 0.0377 (8) | 0.0281 (8) | 0.0506 (10) | 0.0017 (7) | −0.0057 (7) | −0.0051 (7) |
O8 | 0.0702 (13) | 0.0337 (10) | 0.0524 (12) | 0.0136 (10) | −0.0214 (10) | −0.0047 (9) |
C1 | 0.0297 (9) | 0.0300 (10) | 0.0227 (9) | 0.0094 (8) | 0.0075 (7) | 0.0078 (8) |
C2 | 0.0383 (11) | 0.0380 (12) | 0.0265 (10) | 0.0147 (9) | 0.0005 (9) | 0.0071 (9) |
C3 | 0.0337 (10) | 0.0368 (12) | 0.0208 (9) | 0.0080 (9) | −0.0003 (8) | 0.0065 (8) |
C4 | 0.0419 (12) | 0.0463 (14) | 0.0247 (10) | 0.0143 (10) | −0.0028 (9) | 0.0054 (10) |
C5 | 0.0391 (12) | 0.0453 (12) | 0.0222 (10) | 0.0124 (9) | 0.0008 (9) | 0.0086 (9) |
C6 | 0.0444 (12) | 0.0431 (13) | 0.0248 (10) | 0.0164 (10) | −0.0023 (9) | 0.0042 (9) |
C7 | 0.0346 (10) | 0.0445 (13) | 0.0203 (9) | 0.0176 (9) | 0.0037 (8) | 0.0099 (9) |
C8 | 0.0232 (8) | 0.0299 (10) | 0.0186 (8) | 0.0068 (7) | 0.0044 (7) | 0.0056 (7) |
C9 | 0.0214 (8) | 0.0266 (9) | 0.0196 (8) | 0.0051 (7) | 0.0033 (7) | 0.0007 (7) |
C10 | 0.0214 (9) | 0.0373 (11) | 0.0222 (9) | 0.0022 (8) | 0.0029 (7) | −0.0028 (8) |
C11 | 0.0267 (9) | 0.0406 (12) | 0.0205 (9) | 0.0037 (8) | 0.0025 (7) | −0.0016 (8) |
C12 | 0.0294 (10) | 0.0381 (12) | 0.0210 (9) | 0.0018 (8) | 0.0026 (8) | −0.0007 (8) |
C13 | 0.0293 (10) | 0.0439 (13) | 0.0217 (9) | 0.0009 (9) | 0.0036 (8) | −0.0017 (9) |
C14 | 0.0309 (10) | 0.0364 (11) | 0.0201 (9) | −0.0014 (8) | 0.0036 (8) | −0.0009 (8) |
C15 | 0.0333 (11) | 0.0407 (12) | 0.0216 (10) | −0.0050 (9) | 0.0057 (8) | −0.0039 (9) |
C16 | 0.0370 (11) | 0.0296 (10) | 0.0172 (9) | −0.0034 (8) | 0.0045 (8) | −0.0009 (7) |
OW1 | 0.0428 (9) | 0.0262 (8) | 0.0634 (12) | 0.0032 (7) | −0.0126 (8) | 0.0123 (8) |
Geometric parameters (Å, º) top
La1—O3i | 2.4772 (12) | C5—C6 | 1.524 (3) |
La1—O1 | 2.4799 (15) | C5—H5A | 0.9700 |
La1—O7ii | 2.4920 (16) | C5—H5B | 0.9700 |
La1—O6iii | 2.5057 (12) | C6—C7 | 1.516 (3) |
La1—OW1 | 2.5688 (18) | C6—H6A | 0.9700 |
La1—O4iv | 2.5779 (14) | C6—H6B | 0.9700 |
La1—O5 | 2.5984 (14) | C7—C8 | 1.500 (3) |
La1—O6 | 2.6331 (13) | C7—H7A | 0.9700 |
La1—O3iv | 2.6807 (13) | C7—H7B | 0.9700 |
La1—C9 | 3.0010 (18) | C9—C10 | 1.505 (3) |
La1—C8iv | 3.0205 (18) | C10—C11 | 1.518 (3) |
O1—C1 | 1.235 (3) | C10—H10A | 0.9700 |
O2—C1 | 1.267 (2) | C10—H10B | 0.9700 |
O3—C8 | 1.278 (2) | C11—C12 | 1.522 (3) |
O4—C8 | 1.246 (2) | C11—H11A | 0.9700 |
O5—C9 | 1.239 (2) | C11—H11B | 0.9700 |
O6—C9 | 1.289 (2) | C12—C13 | 1.525 (3) |
O7—C16 | 1.221 (3) | C12—H12A | 0.9700 |
O8—C16 | 1.273 (3) | C12—H12B | 0.9700 |
O8—H8 | 1.04 (3) | C13—C14 | 1.525 (3) |
C1—C2 | 1.517 (3) | C13—H13A | 0.9700 |
C2—C3 | 1.519 (3) | C13—H13B | 0.9700 |
C2—H2A | 0.9700 | C14—C15 | 1.525 (3) |
C2—H2B | 0.9700 | C14—H14A | 0.9700 |
C3—C4 | 1.516 (3) | C14—H14B | 0.9700 |
C3—H3A | 0.9700 | C15—C16 | 1.504 (3) |
C3—H3B | 0.9700 | C15—H15A | 0.9700 |
C4—C5 | 1.513 (3) | C15—H15B | 0.9700 |
C4—H4A | 0.9700 | OW1—H2W | 0.9284 |
C4—H4B | 0.9700 | OW1—H1W | 0.9212 |
| | | |
O3i—La1—O1 | 83.14 (5) | H3A—C3—H3B | 107.9 |
O3i—La1—O7ii | 74.50 (5) | C5—C4—C3 | 113.5 (2) |
O1—La1—O7ii | 79.29 (6) | C5—C4—H4A | 108.9 |
O3i—La1—O6iii | 153.83 (5) | C3—C4—H4A | 108.9 |
O1—La1—O6iii | 77.43 (5) | C5—C4—H4B | 108.9 |
O7ii—La1—O6iii | 84.72 (5) | C3—C4—H4B | 108.9 |
O3i—La1—OW1 | 100.61 (6) | H4A—C4—H4B | 107.7 |
O1—La1—OW1 | 141.61 (5) | C4—C5—C6 | 113.8 (2) |
O7ii—La1—OW1 | 138.80 (6) | C4—C5—H5A | 108.8 |
O6iii—La1—OW1 | 105.52 (6) | C6—C5—H5A | 108.8 |
O3i—La1—O4iv | 113.13 (4) | C4—C5—H5B | 108.8 |
O1—La1—O4iv | 143.12 (6) | C6—C5—H5B | 108.8 |
O7ii—La1—O4iv | 74.22 (6) | H5A—C5—H5B | 107.7 |
O6iii—La1—O4iv | 75.04 (4) | C7—C6—C5 | 113.24 (19) |
OW1—La1—O4iv | 70.44 (6) | C7—C6—H6A | 108.9 |
O3i—La1—O5 | 75.60 (4) | C5—C6—H6A | 108.9 |
O1—La1—O5 | 74.22 (5) | C7—C6—H6B | 108.9 |
O7ii—La1—O5 | 141.95 (6) | C5—C6—H6B | 108.9 |
O6iii—La1—O5 | 114.88 (4) | H6A—C6—H6B | 107.7 |
OW1—La1—O5 | 69.91 (6) | C8—C7—C6 | 112.58 (18) |
O4iv—La1—O5 | 140.34 (7) | C8—C7—H7A | 109.1 |
O3i—La1—O6 | 124.41 (4) | C6—C7—H7A | 109.1 |
O1—La1—O6 | 74.98 (5) | C8—C7—H7B | 109.1 |
O7ii—La1—O6 | 145.04 (5) | C6—C7—H7B | 109.1 |
O6iii—La1—O6 | 66.96 (5) | H7A—C7—H7B | 107.8 |
OW1—La1—O6 | 71.56 (5) | O4—C8—O3 | 120.06 (16) |
O4iv—La1—O6 | 114.90 (5) | O4—C8—C7 | 120.22 (17) |
O5—La1—O6 | 49.55 (4) | O3—C8—C7 | 119.70 (16) |
O3i—La1—O3iv | 65.98 (5) | O4—C8—La1v | 57.64 (10) |
O1—La1—O3iv | 143.27 (5) | O3—C8—La1v | 62.46 (9) |
O7ii—La1—O3iv | 73.83 (5) | C7—C8—La1v | 177.80 (13) |
O6iii—La1—O3iv | 123.47 (4) | O5—C9—O6 | 120.36 (16) |
OW1—La1—O3iv | 67.25 (5) | O5—C9—C10 | 121.34 (16) |
O4iv—La1—O3iv | 49.09 (4) | O6—C9—C10 | 118.29 (15) |
O5—La1—O3iv | 113.91 (5) | O5—C9—La1 | 59.38 (10) |
O6—La1—O3iv | 138.80 (5) | O6—C9—La1 | 61.15 (9) |
O3i—La1—C9 | 99.28 (5) | C10—C9—La1 | 176.94 (15) |
O1—La1—C9 | 71.91 (5) | C9—C10—C11 | 115.39 (16) |
O7ii—La1—C9 | 151.10 (6) | C9—C10—H10A | 108.4 |
O6iii—La1—C9 | 91.23 (4) | C11—C10—H10A | 108.4 |
OW1—La1—C9 | 69.77 (5) | C9—C10—H10B | 108.4 |
O4iv—La1—C9 | 132.21 (6) | C11—C10—H10B | 108.4 |
O5—La1—C9 | 24.21 (4) | H10A—C10—H10B | 107.5 |
O6—La1—C9 | 25.38 (4) | C10—C11—C12 | 112.05 (16) |
O3iv—La1—C9 | 130.20 (5) | C10—C11—H11A | 109.2 |
O3i—La1—C8iv | 89.85 (5) | C12—C11—H11A | 109.2 |
O1—La1—C8iv | 151.15 (5) | C10—C11—H11B | 109.2 |
O7ii—La1—C8iv | 71.88 (6) | C12—C11—H11B | 109.2 |
O6iii—La1—C8iv | 98.75 (4) | H11A—C11—H11B | 107.9 |
OW1—La1—C8iv | 67.18 (5) | C11—C12—C13 | 114.20 (17) |
O4iv—La1—C8iv | 24.09 (4) | C11—C12—H12A | 108.7 |
O5—La1—C8iv | 130.92 (5) | C13—C12—H12A | 108.7 |
O6—La1—C8iv | 130.36 (5) | C11—C12—H12B | 108.7 |
O3iv—La1—C8iv | 25.01 (4) | C13—C12—H12B | 108.7 |
C9—La1—C8iv | 136.93 (5) | H12A—C12—H12B | 107.6 |
C1—O1—La1 | 147.96 (14) | C14—C13—C12 | 112.96 (17) |
C8—O3—La1i | 147.97 (12) | C14—C13—H13A | 109.0 |
C8—O3—La1v | 92.54 (10) | C12—C13—H13A | 109.0 |
La1i—O3—La1v | 114.02 (5) | C14—C13—H13B | 109.0 |
C8—O4—La1v | 98.26 (11) | C12—C13—H13B | 109.0 |
C9—O5—La1 | 96.41 (11) | H13A—C13—H13B | 107.8 |
C9—O6—La1iii | 148.14 (11) | C13—C14—C15 | 113.20 (16) |
C9—O6—La1 | 93.47 (10) | C13—C14—H14A | 108.9 |
La1iii—O6—La1 | 113.03 (5) | C15—C14—H14A | 108.9 |
C16—O7—La1vi | 154.95 (16) | C13—C14—H14B | 108.9 |
C16—O8—H8 | 109 (2) | C15—C14—H14B | 108.9 |
O1—C1—O2 | 123.85 (19) | H14A—C14—H14B | 107.8 |
O1—C1—C2 | 120.73 (19) | C16—C15—C14 | 111.20 (16) |
O2—C1—C2 | 115.40 (19) | C16—C15—H15A | 109.4 |
C1—C2—C3 | 115.15 (18) | C14—C15—H15A | 109.4 |
C1—C2—H2A | 108.5 | C16—C15—H15B | 109.4 |
C3—C2—H2A | 108.5 | C14—C15—H15B | 109.4 |
C1—C2—H2B | 108.5 | H15A—C15—H15B | 108.0 |
C3—C2—H2B | 108.5 | O7—C16—O8 | 123.2 (2) |
H2A—C2—H2B | 107.5 | O7—C16—C15 | 120.7 (2) |
C4—C3—C2 | 112.39 (19) | O8—C16—C15 | 116.0 (2) |
C4—C3—H3A | 109.1 | La1—OW1—H2W | 134.3 |
C2—C3—H3A | 109.1 | La1—OW1—H1W | 107.5 |
C4—C3—H3B | 109.1 | H2W—OW1—H1W | 115.1 |
C2—C3—H3B | 109.1 | | |
| | | |
O3i—La1—O1—C1 | 126.0 (3) | C5—C6—C7—C8 | −175.64 (19) |
O7ii—La1—O1—C1 | 50.5 (3) | La1v—O4—C8—O3 | 2.3 (2) |
O6iii—La1—O1—C1 | −36.4 (3) | La1v—O4—C8—C7 | −179.38 (17) |
OW1—La1—O1—C1 | −135.6 (3) | La1i—O3—C8—O4 | −149.24 (19) |
O4iv—La1—O1—C1 | 6.1 (3) | La1v—O3—C8—O4 | −2.2 (2) |
O5—La1—O1—C1 | −157.1 (3) | La1i—O3—C8—C7 | 32.4 (4) |
O6—La1—O1—C1 | −105.6 (3) | La1v—O3—C8—C7 | 179.48 (18) |
O3iv—La1—O1—C1 | 93.9 (3) | La1i—O3—C8—La1v | −147.0 (3) |
C9—La1—O1—C1 | −131.9 (3) | C6—C7—C8—O4 | 50.7 (3) |
C8iv—La1—O1—C1 | 48.9 (3) | C6—C7—C8—O3 | −131.0 (2) |
O3i—La1—O5—C9 | 167.62 (15) | La1—O5—C9—O6 | 4.8 (2) |
O1—La1—O5—C9 | 80.82 (14) | La1—O5—C9—C10 | −176.53 (18) |
O7ii—La1—O5—C9 | 128.49 (13) | La1iii—O6—C9—O5 | −151.85 (19) |
O6iii—La1—O5—C9 | 13.15 (15) | La1—O6—C9—O5 | −4.7 (2) |
OW1—La1—O5—C9 | −85.15 (14) | La1iii—O6—C9—C10 | 29.4 (4) |
O4iv—La1—O5—C9 | −83.37 (15) | La1—O6—C9—C10 | 176.57 (17) |
O6—La1—O5—C9 | −2.67 (12) | La1iii—O6—C9—La1 | −147.1 (3) |
O3iv—La1—O5—C9 | −137.38 (13) | O3i—La1—C9—O5 | −12.15 (14) |
C8iv—La1—O5—C9 | −115.44 (13) | O1—La1—C9—O5 | −91.74 (14) |
O3i—La1—O6—C9 | −8.88 (14) | O7ii—La1—C9—O5 | −86.80 (17) |
O1—La1—O6—C9 | −79.38 (12) | O6iii—La1—C9—O5 | −168.08 (14) |
O7ii—La1—O6—C9 | −123.35 (13) | OW1—La1—C9—O5 | 85.82 (14) |
O6iii—La1—O6—C9 | −161.86 (15) | O4iv—La1—C9—O5 | 121.13 (14) |
OW1—La1—O6—C9 | 81.51 (12) | O6—La1—C9—O5 | 175.3 (2) |
O4iv—La1—O6—C9 | 138.57 (12) | O3iv—La1—C9—O5 | 54.15 (16) |
O5—La1—O6—C9 | 2.55 (12) | C8iv—La1—C9—O5 | 87.69 (15) |
O3iv—La1—O6—C9 | 83.03 (13) | O3i—La1—C9—O6 | 172.59 (11) |
C8iv—La1—O6—C9 | 116.44 (12) | O1—La1—C9—O6 | 93.00 (12) |
O3i—La1—O6—La1iii | 152.99 (6) | O7ii—La1—C9—O6 | 97.93 (15) |
O1—La1—O6—La1iii | 82.48 (7) | O6iii—La1—C9—O6 | 16.65 (14) |
O7ii—La1—O6—La1iii | 38.51 (12) | OW1—La1—C9—O6 | −89.44 (12) |
O6iii—La1—O6—La1iii | 0.0 | O4iv—La1—C9—O6 | −54.13 (14) |
OW1—La1—O6—La1iii | −116.63 (7) | O5—La1—C9—O6 | −175.3 (2) |
O4iv—La1—O6—La1iii | −59.57 (8) | O3iv—La1—C9—O6 | −121.12 (11) |
O5—La1—O6—La1iii | 164.41 (10) | C8iv—La1—C9—O6 | −87.58 (13) |
O3iv—La1—O6—La1iii | −115.11 (6) | O5—C9—C10—C11 | 13.1 (3) |
C9—La1—O6—La1iii | 161.86 (15) | O6—C9—C10—C11 | −168.2 (2) |
C8iv—La1—O6—La1iii | −81.70 (8) | C9—C10—C11—C12 | 174.9 (2) |
La1—O1—C1—O2 | −28.9 (4) | C10—C11—C12—C13 | −178.0 (2) |
La1—O1—C1—C2 | 153.0 (2) | C11—C12—C13—C14 | 177.9 (2) |
O1—C1—C2—C3 | 4.3 (3) | C12—C13—C14—C15 | −178.8 (2) |
O2—C1—C2—C3 | −174.0 (2) | C13—C14—C15—C16 | 179.6 (2) |
C1—C2—C3—C4 | 174.54 (19) | La1vi—O7—C16—O8 | 22.8 (5) |
C2—C3—C4—C5 | −176.4 (2) | La1vi—O7—C16—C15 | −155.0 (3) |
C3—C4—C5—C6 | 178.5 (2) | C14—C15—C16—O7 | 101.4 (3) |
C4—C5—C6—C7 | −176.8 (2) | C14—C15—C16—O8 | −76.5 (3) |
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) x−1, y−1, z−1; (iii) −x+2, −y+2, −z; (iv) x−1, y, z−1; (v) x+1, y, z+1; (vi) x+1, y+1, z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O8—H8···O2vi | 1.04 (3) | 1.46 (3) | 2.441 (3) | 153 |
OW1—H2W···O2vii | 0.929 | 1.976 | 2.782 (3) | 144 |
OW1—H1W···O8iv | 0.921 | 2.374 | 2.947 (3) | 120 |
OW1—H1W···O3iv | 0.921 | 2.411 | 2.908 (3) | 114 |
Symmetry codes: (iv) x−1, y, z−1; (vi) x+1, y+1, z+1; (vii) x, y+1, z. |
Experimental details
Crystal data |
Chemical formula | [La(C8H12O4)(C8H13O4)(H2O)] |
Mr | 502.28 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.582 (2), 9.079 (1), 13.092 (4) |
α, β, γ (°) | 100.59 (1), 103.66 (1), 97.83 (1) |
V (Å3) | 957.0 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.28 |
Crystal size (mm) | 0.4 × 0.3 × 0.3 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Empirical (DENZO–SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.47, 0.51 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 38534, 5739, 5279 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.714 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.060, 1.09 |
No. of reflections | 5739 |
No. of parameters | 239 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.03, −1.21 |
Selected geometric parameters (Å, º) topLa1—O3i | 2.4772 (12) | O1—C1 | 1.235 (3) |
La1—O1 | 2.4799 (15) | O2—C1 | 1.267 (2) |
La1—O7ii | 2.4920 (16) | O3—C8 | 1.278 (2) |
La1—O6iii | 2.5057 (12) | O4—C8 | 1.246 (2) |
La1—OW1 | 2.5688 (18) | O5—C9 | 1.239 (2) |
La1—O4iv | 2.5779 (14) | O6—C9 | 1.289 (2) |
La1—O5 | 2.5984 (14) | O7—C16 | 1.221 (3) |
La1—O6 | 2.6331 (13) | O8—C16 | 1.273 (3) |
La1—O3iv | 2.6807 (13) | O8—H8 | 1.04 (3) |
| | | |
O1—La1—O7ii | 79.29 (6) | La1i—O3—La1v | 114.02 (5) |
O1—La1—O5 | 74.22 (5) | La1iii—O6—La1 | 113.03 (5) |
O6iii—La1—O6 | 66.96 (5) | O1—C1—O2 | 123.85 (19) |
O5—La1—O6 | 49.55 (4) | O4—C8—O3 | 120.06 (16) |
O3i—La1—O3iv | 65.98 (5) | O5—C9—O6 | 120.36 (16) |
O4iv—La1—O3iv | 49.09 (4) | O7—C16—O8 | 123.2 (2) |
| | | |
C1—C2—C3—C4 | 174.54 (19) | C9—C10—C11—C12 | 174.9 (2) |
C2—C3—C4—C5 | −176.4 (2) | C10—C11—C12—C13 | −178.0 (2) |
C3—C4—C5—C6 | 178.5 (2) | C11—C12—C13—C14 | 177.9 (2) |
C4—C5—C6—C7 | −176.8 (2) | C12—C13—C14—C15 | −178.8 (2) |
C5—C6—C7—C8 | −175.64 (19) | C13—C14—C15—C16 | 179.6 (2) |
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) x−1, y−1, z−1; (iii) −x+2, −y+2, −z; (iv) x−1, y, z−1; (v) x+1, y, z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O8—H8···O2vi | 1.04 (3) | 1.46 (3) | 2.441 (3) | 153 |
OW1—H2W···O2vii | 0.929 | 1.976 | 2.782 (3) | 144 |
OW1—H1W···O8iv | 0.921 | 2.374 | 2.947 (3) | 120 |
OW1—H1W···O3iv | 0.921 | 2.411 | 2.908 (3) | 114 |
Symmetry codes: (iv) x−1, y, z−1; (vi) x+1, y+1, z+1; (vii) x, y+1, z. |
In the past decade, a particular emphasis on design, crystal packing and properties of organic–inorganic compounds has appeared, as a result of the wide variety of structural types leading, when the framework is open, to microporous materials. ?These polynuclear complexes are constructed of flexible dicarboxylate ligands, completely or partially deprotonated, linked to metal centers that assume high coordination numbers, such as lanthanides; such complexes can be used successfully as drying agents in catalysis or in ?the environmental? domain. Other applications have also been reported (Piguet & Bünzli, 1999; Parker et al., 2002). Most of the resulting neutral lanthanide polymers are hydrated, owing to the fact that their layered structures can accommodate interlayer guest molecules. These uncoordinated molecules are thought to play a crucial role in the crystalline stability, in that one characteristic common to most of these solid compounds is the inclusion, in channels, of water molecules (Antivec-Fidancev et al., 2002), which are difficult to remove without destroying the crystallinity.
We report here the crystal structure of the title compound, (I), [aqua(suberato)(hydrogensuberato)lanthanum(III)] (Benmerad et al., 2002), which has high stability and good crystallinity, despite the presence of long alkyl chains and the lack of any uncoordinated water molecules.
The complex [La(C8H12O4)(C8H13O4)(H2O)] has a chemical formula similar to those of the isostructural lanthanum(III) glutarate (Benmerad et al., 2000a) and pimelate complexes (Dimos et al., 2002). Like these two compounds, (I) contains both protonated (HL) and deprotonated (L) ligands. Nevertheless, the crystal structure of the complex is completely different from the glutarate and pimelate analogues, from the point of view of connectivity, interlayer interactions, framework characteristics and packing arrangement. Despite its long-alkyl-chain ligand (eight C atoms) and its open framework, complex (I) remains stable up to 550 K, which is a very high temperature compared with the thermal stability of suberic acid (293–421 K) or of the only known suberato complex Co(C8H12O4)·1.5(H2O), which decomposes at 333 K (Allan & Dalrymple, 1993).
Fig. 1 shows the general features of the structure, without the hydrogen bonding. This layer-type polymeric structure is built up from infinite chains of one-edge-sharing LaO8(H2O) polyhedra, running along the [100] direction, connected through the carbon backbone of the ligands. The resulting cross-linked single chains form stable layers, despite the lack of additional hydrogen bonds involving water guest molecules. Adjacent metal centers are doubly bridged by pairs of ligands to form repeated four-membered La/O/La/O rings, within which the distances between two neighbour La3+ ions are almost equal [4.287 (1) Å (connection across O6 atoms) and 4.328 (1) Å (connection across O3 atoms)]. Fig. 2 shows the coordination around the La atom and reveals eight O atoms belonging to carboxylate ligands, equally distributed between three non-independent HL and L ligands on one hand, and one aqua ligand on the other hand. Unlike other known lanthanum dicarboxylates (Marrot & Trombe 1993, 1994; Kiritsis et al., 1998; Benmerad et al., 2000a, 2000b; Dimos et al., 2002) and despite the fact that this long-alkyl-chain ligand is more sterically demanding, the dispersion of the La—O bond lengths of is smaller [2.477 (4)–2.679 (7) Å; Table 1].
The two ligands are involved in the same coordination modes. They are bridging–chelating by one function, exhibiting µ-1,1-bridging via atom O6 for HL and atom O3 for L. They are monodentate by the second function, involving atom O7 for HL and atom O1 for L. As a consequence, all O atoms of the ligands are bonded to the metal cation, except O8, which is bonded to an H atom (the ligand being protonated), and atom O2 of the deprotonated ligand, which shares the same H atom (H8) with O8 in a hydrogen bond. The HL and L ligands clearly have different chemical characteristics, despite their identical coordination modes. The L ligand exhibits two functions typical of carboxylate groups, whereas in the HL ligand, the two different end functional groups seem to have the same character, related to carboxylate geometry. A similar bonding situation is found in related? complexes containing protonated ligands (Benmerad et al., 2000a; Dimos et al., 2002). As indicated by the torsion angles (Table 1), the conformations of the L and HL ligands are almost identical; they adopt an extended conformation. However, the two end functional groups involved in the bridging–chelating mode deviate significantly from the ideal anti–anti value (180°) for the HL ligand [O6—C9—C10—C11 = −168.2 (2)° and O5—C9—C10—C11 = 13.0 (3)°] and from the syn–anti values (60 and 180°) for the L ligand [O4—C8—C7—C6 = 50.7 (3)° and O3—C8—C7—C6 = −131.0 (3)°].
The La atom is nine-coordinate (Fig. 3), forming a monocapped dodecahedron, the cap being atom O7ii. This configuration is confirmed by the dihedral angle between the OW1/O3iv/O6iii/O1 and O5/O3i/O4iv/O6 planes [65 (s.u.?)°], which is close to the value for an idealized D2 geometry (ca 60°; Drew, 1977). As shown in Table 2, the hydrogen-bonding network is relatively limited. However, as mentioned above, there is a very strong hydrogen bond between the HL and L ligands; the protonated acid group donates atom H8 via a very short hydrogen bond [1.54 (1) Å] to atom O2.
In the absence of any uncoordinated water molecules lying between the layers and playing a templating role during crystallization, it can reasonably be assumed that this strong bond stabilizes the open framework. This new lanthanum dicarboxylate is noteworthy for several characteristics. The lack of any uncoordinated water molecule is very rare in this kind of material.
While 20 hydrated rare-earth complexes obtained with aliphatic HOOC-(CH2)n-COOH acids have been structurally characterized, only two have been reported that contain no water of crystallization, and these contain ligands having either a short alkyl spacer unit (n = 1; Hansson, 1973; Hernandez-Molina et al., 2002) or no alkyl spacer (n = 0; Trollet et al., 1997). In the higher series (n > 1),, only one family has been reported (Thomas & Trombe, 2001).
The structure of a suberato nickel(II) complex has been published recently (Zhang, 2003). This complex, like (I), is distinguished by its good crystallinity, which is unexpected when the acid has a long aliphatic chain (Bussien-Gaillard et al., 1998). These results highlight the need for caution about the specific character of the rare-earth dicarboxylates, the templating role of water molecules during crystallization and the effect of the hydrogen-bond network on enhancing the crystalline stability. One important structural crystallographic feature influencing the kind of framework seems to be the subfeature including four-membered rings and creating, in some cases, packing with a grid arrangement of the metal ions. In view of the limited number of complexes studied (Kiritsis et al., 1998; Wang et al., 2000; Sun et al., 2002), we cannot yet assess whether this feature? depends on the parity of n, but we note that an even number of C atoms in the alkyl spacer can introduce higher local symmetry, which in turn may influence the interlayer interactions.