Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109043856/bg3111sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109043856/bg3111Isup2.hkl |
CCDC reference: 763586
The title compound was synthesized under mild hydrothermal conditions. Typically, La2O3 (0.5 mmol, 0.163 g), HIN (2.30 mmol, 0.284 g), H2BDC (0.75 mmol, 0.122 g) and H2O (10 ml) were sealed in a 25 ml Teflon-lined steel autoclave and heated under autogenous pressure at 443 K for 9 d. The yellow prism-like crystals obtained were recovered by filtration, washed with distilled water and dried in air.
All H atoms bound to C atoms were positioned geometrically, with C—H = 0.93 Å for aromatic H atoms, and constrained to ride on their parent atoms [Uiso(H) = 1.2Ueq(C)].
Data collection: APEX2 (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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: SHELXL97 (Sheldrick, 2008).
[La2(C8H4O4)2(C6H4NO2)2] | F(000) = 1632 |
Mr = 850.25 | Dx = 2.124 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 20786 reflections |
a = 9.9357 (3) Å | θ = 1.9–26.5° |
b = 12.4348 (5) Å | µ = 3.24 mm−1 |
c = 21.6047 (3) Å | T = 295 K |
β = 95.067 (4)° | Prism, yellow |
V = 2658.80 (14) Å3 | 0.25 × 0.13 × 0.12 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 5502 independent reflections |
Radiation source: fine-focus sealed tube | 4666 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
ϕ and ω scans | θmax = 26.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.498, Tmax = 0.697 | k = −15→15 |
20786 measured reflections | l = −27→26 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0352P)2 + 2.5719P] where P = (Fo2 + 2Fc2)/3 |
5502 reflections | (Δ/σ)max = 0.001 |
397 parameters | Δρmax = 1.08 e Å−3 |
0 restraints | Δρmin = −1.02 e Å−3 |
[La2(C8H4O4)2(C6H4NO2)2] | V = 2658.80 (14) Å3 |
Mr = 850.25 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.9357 (3) Å | µ = 3.24 mm−1 |
b = 12.4348 (5) Å | T = 295 K |
c = 21.6047 (3) Å | 0.25 × 0.13 × 0.12 mm |
β = 95.067 (4)° |
Bruker APEXII area-detector diffractometer | 5502 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4666 reflections with I > 2σ(I) |
Tmin = 0.498, Tmax = 0.697 | Rint = 0.049 |
20786 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.08 e Å−3 |
5502 reflections | Δρmin = −1.02 e Å−3 |
397 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 | 0.46777 (3) | 0.46595 (2) | 0.401637 (12) | 0.01631 (8) | |
La2 | 0.90824 (3) | 0.44818 (2) | 0.405811 (12) | 0.01683 (8) | |
O1 | 0.0605 (3) | 0.4668 (3) | 0.32027 (16) | 0.0253 (8) | |
O2 | 0.2654 (4) | 0.5299 (3) | 0.34815 (17) | 0.0328 (9) | |
O3 | 0.5565 (4) | 0.4610 (3) | 0.29888 (16) | 0.0270 (8) | |
O4 | 0.7745 (3) | 0.5028 (3) | 0.30861 (15) | 0.0285 (8) | |
O5 | 0.5362 (3) | 0.6585 (3) | 0.37493 (15) | 0.0252 (8) | |
O6 | 0.7022 (3) | 0.5700 (3) | 0.42640 (16) | 0.0233 (7) | |
O7 | 0.6876 (3) | 0.6504 (3) | 0.54723 (15) | 0.0289 (8) | |
O8 | 0.9108 (3) | 0.6722 (3) | 0.55799 (16) | 0.0283 (8) | |
O9 | 0.5872 (3) | 0.4120 (3) | 0.50911 (14) | 0.0213 (7) | |
O10 | 0.6893 (3) | 0.3420 (3) | 0.43266 (15) | 0.0216 (7) | |
O11 | 0.9024 (3) | 0.4232 (3) | 0.52382 (15) | 0.0242 (7) | |
O12 | 1.0246 (3) | 0.3584 (3) | 0.60537 (16) | 0.0277 (8) | |
C1 | 0.1563 (5) | 0.5289 (4) | 0.3139 (2) | 0.0218 (10) | |
C2 | 0.1443 (5) | 0.6107 (4) | 0.2622 (2) | 0.0232 (11) | |
C3 | 0.0291 (5) | 0.6155 (4) | 0.2212 (2) | 0.0322 (12) | |
H3A | −0.0415 | 0.5671 | 0.2239 | 0.039* | |
C4 | 0.0227 (5) | 0.6943 (4) | 0.1764 (2) | 0.0333 (13) | |
H4A | −0.0547 | 0.6973 | 0.1489 | 0.040* | |
C5 | 0.2289 (5) | 0.7586 (4) | 0.2087 (3) | 0.0325 (13) | |
H5A | 0.2994 | 0.8064 | 0.2041 | 0.039* | |
C6 | 0.2449 (5) | 0.6842 (4) | 0.2558 (2) | 0.0310 (12) | |
H6A | 0.3229 | 0.6837 | 0.2830 | 0.037* | |
C7 | 0.6562 (5) | 0.5149 (4) | 0.2854 (2) | 0.0196 (10) | |
C8 | 0.6316 (5) | 0.6018 (4) | 0.2385 (2) | 0.0208 (10) | |
C9 | 0.5290 (5) | 0.5985 (4) | 0.1916 (2) | 0.0335 (13) | |
H9A | 0.4743 | 0.5379 | 0.1863 | 0.040* | |
C10 | 0.5077 (6) | 0.6852 (5) | 0.1526 (3) | 0.0391 (14) | |
H10A | 0.4381 | 0.6812 | 0.1210 | 0.047* | |
C11 | 0.6813 (6) | 0.7757 (5) | 0.2016 (3) | 0.0484 (17) | |
H11A | 0.7348 | 0.8371 | 0.2054 | 0.058* | |
C12 | 0.7117 (6) | 0.6929 (4) | 0.2420 (3) | 0.0375 (14) | |
H12A | 0.7855 | 0.6978 | 0.2716 | 0.045* | |
C13 | 0.6465 (5) | 0.6575 (4) | 0.4081 (2) | 0.0206 (10) | |
C14 | 0.7107 (5) | 0.7629 (4) | 0.4263 (2) | 0.0213 (10) | |
C15 | 0.6956 (5) | 0.8483 (4) | 0.3846 (3) | 0.0324 (12) | |
H15A | 0.6435 | 0.8396 | 0.3470 | 0.039* | |
C16 | 0.7578 (6) | 0.9465 (4) | 0.3986 (3) | 0.0395 (15) | |
H16A | 0.7510 | 1.0023 | 0.3699 | 0.047* | |
C17 | 0.8295 (6) | 0.9602 (4) | 0.4556 (3) | 0.0410 (15) | |
H17A | 0.8680 | 1.0267 | 0.4660 | 0.049* | |
C18 | 0.8448 (5) | 0.8757 (4) | 0.4973 (2) | 0.0304 (12) | |
H18A | 0.8968 | 0.8851 | 0.5348 | 0.036* | |
C19 | 0.7835 (5) | 0.7773 (4) | 0.4839 (2) | 0.0208 (10) | |
C20 | 0.7943 (5) | 0.6912 (3) | 0.5331 (2) | 0.0183 (10) | |
C21 | 0.6643 (4) | 0.3428 (4) | 0.4891 (2) | 0.0189 (10) | |
C22 | 0.7124 (5) | 0.2529 (4) | 0.5313 (2) | 0.0195 (10) | |
C23 | 0.6270 (5) | 0.1657 (4) | 0.5363 (2) | 0.0299 (12) | |
H23A | 0.5445 | 0.1632 | 0.5124 | 0.036* | |
C24 | 0.6638 (6) | 0.0839 (5) | 0.5762 (3) | 0.0434 (15) | |
H24A | 0.6053 | 0.0263 | 0.5799 | 0.052* | |
C25 | 0.7856 (6) | 0.0855 (5) | 0.6108 (3) | 0.0423 (15) | |
H25A | 0.8102 | 0.0287 | 0.6375 | 0.051* | |
C26 | 0.8719 (5) | 0.1711 (4) | 0.6062 (2) | 0.0327 (12) | |
H26A | 0.9541 | 0.1725 | 0.6304 | 0.039* | |
C27 | 0.8374 (5) | 0.2550 (4) | 0.5660 (2) | 0.0205 (10) | |
C28 | 0.9286 (5) | 0.3505 (4) | 0.5645 (2) | 0.0223 (10) | |
N1 | 0.1191 (4) | 0.7665 (3) | 0.16935 (19) | 0.0284 (10) | |
N2 | 0.5802 (5) | 0.7735 (4) | 0.1574 (2) | 0.0364 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
La1 | 0.01523 (15) | 0.01797 (14) | 0.01548 (15) | −0.00097 (10) | −0.00009 (10) | 0.00008 (10) |
La2 | 0.01534 (15) | 0.01883 (15) | 0.01610 (15) | −0.00079 (10) | 0.00009 (10) | 0.00103 (10) |
O1 | 0.0210 (18) | 0.0292 (19) | 0.0262 (19) | −0.0026 (15) | 0.0052 (15) | 0.0046 (15) |
O2 | 0.026 (2) | 0.038 (2) | 0.033 (2) | −0.0015 (16) | −0.0067 (16) | 0.0108 (17) |
O3 | 0.032 (2) | 0.0280 (19) | 0.0215 (19) | −0.0030 (15) | 0.0049 (15) | 0.0014 (14) |
O4 | 0.0252 (19) | 0.036 (2) | 0.0234 (19) | 0.0030 (16) | −0.0030 (15) | 0.0031 (16) |
O5 | 0.0249 (18) | 0.0256 (18) | 0.0239 (19) | −0.0046 (14) | −0.0043 (15) | 0.0008 (15) |
O6 | 0.0235 (18) | 0.0188 (17) | 0.0277 (19) | 0.0038 (14) | 0.0023 (14) | 0.0020 (14) |
O7 | 0.0280 (19) | 0.034 (2) | 0.0251 (19) | −0.0086 (16) | 0.0042 (15) | 0.0035 (16) |
O8 | 0.0239 (19) | 0.0289 (19) | 0.031 (2) | 0.0036 (15) | −0.0047 (15) | 0.0021 (15) |
O9 | 0.0197 (17) | 0.0220 (17) | 0.0221 (18) | 0.0028 (14) | 0.0021 (14) | 0.0009 (14) |
O10 | 0.0236 (18) | 0.0224 (17) | 0.0189 (18) | −0.0007 (14) | 0.0030 (13) | −0.0017 (14) |
O11 | 0.0251 (18) | 0.0218 (17) | 0.0256 (19) | −0.0032 (15) | 0.0022 (15) | 0.0024 (15) |
O12 | 0.0219 (18) | 0.0272 (19) | 0.032 (2) | −0.0025 (15) | −0.0072 (15) | 0.0017 (15) |
C1 | 0.017 (2) | 0.029 (3) | 0.020 (3) | 0.006 (2) | 0.0044 (19) | −0.003 (2) |
C2 | 0.026 (3) | 0.022 (3) | 0.022 (3) | 0.000 (2) | 0.005 (2) | 0.001 (2) |
C3 | 0.023 (3) | 0.039 (3) | 0.033 (3) | −0.007 (2) | −0.005 (2) | 0.007 (2) |
C4 | 0.027 (3) | 0.044 (3) | 0.026 (3) | −0.010 (2) | −0.011 (2) | 0.012 (2) |
C5 | 0.030 (3) | 0.029 (3) | 0.038 (3) | −0.006 (2) | 0.001 (2) | 0.015 (2) |
C6 | 0.021 (3) | 0.034 (3) | 0.037 (3) | −0.001 (2) | −0.005 (2) | 0.008 (2) |
C7 | 0.022 (3) | 0.021 (2) | 0.016 (2) | −0.001 (2) | 0.0023 (19) | −0.0033 (19) |
C8 | 0.021 (2) | 0.023 (2) | 0.019 (3) | 0.006 (2) | 0.0037 (19) | −0.001 (2) |
C9 | 0.035 (3) | 0.031 (3) | 0.032 (3) | −0.004 (2) | −0.011 (2) | 0.009 (2) |
C10 | 0.044 (4) | 0.037 (3) | 0.033 (3) | 0.006 (3) | −0.008 (3) | 0.005 (3) |
C11 | 0.050 (4) | 0.033 (3) | 0.060 (4) | −0.013 (3) | −0.004 (3) | 0.014 (3) |
C12 | 0.034 (3) | 0.031 (3) | 0.047 (4) | 0.000 (2) | −0.003 (3) | 0.008 (3) |
C13 | 0.022 (2) | 0.027 (3) | 0.013 (2) | −0.006 (2) | 0.0035 (19) | 0.0008 (19) |
C14 | 0.020 (2) | 0.021 (2) | 0.023 (3) | −0.0032 (19) | 0.0036 (19) | 0.004 (2) |
C15 | 0.033 (3) | 0.027 (3) | 0.036 (3) | −0.001 (2) | −0.007 (2) | 0.008 (2) |
C16 | 0.045 (4) | 0.028 (3) | 0.043 (4) | −0.011 (3) | −0.004 (3) | 0.017 (3) |
C17 | 0.042 (4) | 0.022 (3) | 0.056 (4) | −0.011 (2) | −0.012 (3) | 0.004 (3) |
C18 | 0.029 (3) | 0.027 (3) | 0.034 (3) | −0.008 (2) | −0.005 (2) | 0.002 (2) |
C19 | 0.019 (2) | 0.024 (2) | 0.020 (3) | 0.000 (2) | 0.0029 (19) | 0.002 (2) |
C20 | 0.025 (3) | 0.016 (2) | 0.013 (2) | −0.0015 (19) | −0.0017 (19) | −0.0036 (18) |
C21 | 0.016 (2) | 0.016 (2) | 0.024 (3) | −0.0025 (18) | −0.0015 (19) | 0.0005 (19) |
C22 | 0.022 (2) | 0.020 (2) | 0.017 (2) | −0.0001 (19) | 0.0053 (19) | −0.0014 (19) |
C23 | 0.026 (3) | 0.028 (3) | 0.036 (3) | −0.004 (2) | 0.001 (2) | 0.005 (2) |
C24 | 0.041 (3) | 0.032 (3) | 0.058 (4) | −0.009 (3) | 0.010 (3) | 0.017 (3) |
C25 | 0.049 (4) | 0.027 (3) | 0.050 (4) | −0.003 (3) | −0.008 (3) | 0.019 (3) |
C26 | 0.028 (3) | 0.033 (3) | 0.036 (3) | 0.003 (2) | −0.006 (2) | 0.008 (2) |
C27 | 0.021 (2) | 0.018 (2) | 0.022 (3) | 0.0019 (19) | 0.004 (2) | 0.0027 (19) |
C28 | 0.021 (3) | 0.023 (3) | 0.024 (3) | 0.002 (2) | 0.006 (2) | −0.003 (2) |
N1 | 0.030 (2) | 0.030 (2) | 0.027 (2) | 0.0041 (19) | 0.0065 (19) | 0.0079 (19) |
N2 | 0.041 (3) | 0.036 (3) | 0.034 (3) | 0.011 (2) | 0.012 (2) | 0.012 (2) |
La1—O2 | 2.366 (3) | C5—H5A | 0.9300 |
La1—O3 | 2.461 (3) | C6—H6A | 0.9300 |
La1—O5 | 2.569 (3) | C7—C8 | 1.487 (6) |
La1—O6 | 2.677 (3) | C8—C9 | 1.373 (6) |
La1—O7i | 2.449 (3) | C8—C12 | 1.383 (7) |
La1—O9i | 2.551 (3) | C9—C10 | 1.374 (7) |
La1—O9 | 2.601 (3) | C9—H9A | 0.9300 |
La1—O10 | 2.723 (3) | C10—N2 | 1.312 (7) |
La1—N2ii | 2.734 (4) | C10—H10A | 0.9300 |
La2—O1iii | 2.500 (3) | C11—N2 | 1.324 (7) |
La2—O4 | 2.479 (3) | C11—C12 | 1.366 (8) |
La2—O6 | 2.616 (3) | C11—H11A | 0.9300 |
La2—O8iv | 2.416 (3) | C12—H12A | 0.9300 |
La2—O10 | 2.652 (3) | C13—C14 | 1.495 (6) |
La2—O11 | 2.574 (3) | C14—C15 | 1.393 (7) |
La2—O11iv | 2.811 (3) | C14—C19 | 1.394 (6) |
La2—O12iv | 2.513 (3) | C15—C16 | 1.389 (7) |
La2—N1ii | 2.782 (4) | C15—H15A | 0.9300 |
O1—C1 | 1.243 (6) | C16—C17 | 1.377 (8) |
O2—C1 | 1.258 (6) | C16—H16A | 0.9300 |
O3—C7 | 1.251 (6) | C17—C18 | 1.384 (7) |
O4—C7 | 1.246 (6) | C17—H17A | 0.9300 |
O5—C13 | 1.255 (5) | C18—C19 | 1.385 (6) |
O6—C13 | 1.268 (5) | C18—H18A | 0.9300 |
O7—C20 | 1.238 (5) | C19—C20 | 1.506 (6) |
O8—C20 | 1.255 (5) | C21—C22 | 1.494 (6) |
O10—C21 | 1.266 (5) | C22—C23 | 1.387 (7) |
O11—C28 | 1.272 (6) | C22—C27 | 1.392 (6) |
O12—C28 | 1.245 (5) | C23—C24 | 1.362 (7) |
C1—C2 | 1.508 (7) | C23—H23A | 0.9300 |
C2—C6 | 1.370 (7) | C24—C25 | 1.365 (8) |
C2—C3 | 1.385 (6) | C24—H24A | 0.9300 |
C3—C4 | 1.375 (7) | C25—C26 | 1.376 (7) |
C3—H3A | 0.9300 | C25—H25A | 0.9300 |
C4—N1 | 1.331 (6) | C26—C27 | 1.382 (7) |
C4—H4A | 0.9300 | C26—H26A | 0.9300 |
C5—N1 | 1.326 (6) | C27—C28 | 1.495 (6) |
C5—C6 | 1.375 (7) | ||
O2—La1—O7i | 82.91 (12) | C6—C2—C1 | 120.9 (4) |
O2—La1—O3 | 85.67 (12) | C3—C2—C1 | 120.6 (4) |
O7i—La1—O3 | 133.05 (11) | C4—C3—C2 | 117.7 (5) |
O2—La1—O9i | 86.54 (12) | C4—C3—H3A | 121.1 |
O7i—La1—O9i | 79.90 (11) | C2—C3—H3A | 121.1 |
O3—La1—O9i | 144.55 (10) | N1—C4—C3 | 124.9 (5) |
O2—La1—O5 | 78.89 (11) | N1—C4—H4A | 117.6 |
O7i—La1—O5 | 147.33 (11) | C3—C4—H4A | 117.6 |
O3—La1—O5 | 72.40 (11) | N1—C5—C6 | 124.0 (5) |
O9i—La1—O5 | 72.17 (10) | N1—C5—H5A | 118.0 |
O2—La1—O9 | 145.46 (11) | C6—C5—H5A | 118.0 |
O7i—La1—O9 | 72.61 (10) | C2—C6—C5 | 119.1 (5) |
O3—La1—O9 | 128.86 (11) | C2—C6—H6A | 120.5 |
O9i—La1—O9 | 65.79 (11) | C5—C6—H6A | 120.5 |
O5—La1—O9 | 109.40 (10) | O4—C7—O3 | 125.4 (5) |
O2—La1—O6 | 128.46 (11) | O4—C7—C8 | 117.0 (4) |
O7i—La1—O6 | 140.12 (11) | O3—C7—C8 | 117.5 (4) |
O3—La1—O6 | 79.49 (11) | C9—C8—C12 | 116.9 (5) |
O9i—La1—O6 | 78.58 (10) | C9—C8—C7 | 123.2 (4) |
O5—La1—O6 | 49.57 (10) | C12—C8—C7 | 119.9 (4) |
O9—La1—O6 | 68.02 (10) | C8—C9—C10 | 119.5 (5) |
O2—La1—O10 | 160.78 (11) | C8—C9—H9A | 120.3 |
O7i—La1—O10 | 94.75 (11) | C10—C9—H9A | 120.3 |
O3—La1—O10 | 82.05 (10) | N2—C10—C9 | 123.7 (5) |
O9i—La1—O10 | 111.92 (10) | N2—C10—H10A | 118.1 |
O5—La1—O10 | 111.03 (10) | C9—C10—H10A | 118.1 |
O9—La1—O10 | 48.61 (9) | N2—C11—C12 | 123.8 (6) |
O6—La1—O10 | 63.51 (10) | N2—C11—H11A | 118.1 |
O2—La1—N2ii | 87.75 (14) | C12—C11—H11A | 118.1 |
O7i—La1—N2ii | 66.60 (12) | C11—C12—C8 | 119.2 (5) |
O3—La1—N2ii | 67.57 (12) | C11—C12—H12A | 120.4 |
O9i—La1—N2ii | 146.47 (12) | C8—C12—H12A | 120.4 |
O5—La1—N2ii | 138.56 (12) | O5—C13—O6 | 121.5 (4) |
O9—La1—N2ii | 103.77 (13) | O5—C13—C14 | 118.2 (4) |
O6—La1—N2ii | 128.97 (12) | O6—C13—C14 | 120.3 (4) |
O10—La1—N2ii | 73.92 (12) | O5—C13—La1 | 59.5 (2) |
O8iv—La2—O4 | 140.53 (12) | O6—C13—La1 | 64.5 (2) |
O8iv—La2—O1iii | 79.36 (11) | C14—C13—La1 | 162.9 (3) |
O4—La2—O1iii | 70.26 (11) | C15—C14—C19 | 119.8 (4) |
O8iv—La2—O12iv | 115.34 (11) | C15—C14—C13 | 118.6 (4) |
O4—La2—O12iv | 77.47 (11) | C19—C14—C13 | 121.6 (4) |
O1iii—La2—O12iv | 69.95 (11) | C16—C15—C14 | 120.5 (5) |
O8iv—La2—O11 | 71.68 (11) | C16—C15—H15A | 119.8 |
O4—La2—O11 | 144.59 (11) | C14—C15—H15A | 119.8 |
O1iii—La2—O11 | 144.22 (11) | C17—C16—C15 | 119.3 (5) |
O12iv—La2—O11 | 103.89 (11) | C17—C16—H16A | 120.3 |
O8iv—La2—O6 | 151.03 (11) | C15—C16—H16A | 120.3 |
O4—La2—O6 | 67.45 (11) | C16—C17—C18 | 120.4 (5) |
O1iii—La2—O6 | 127.26 (10) | C16—C17—H17A | 119.8 |
O12iv—La2—O6 | 71.36 (10) | C18—C17—H17A | 119.8 |
O11—La2—O6 | 79.35 (11) | C17—C18—C19 | 120.9 (5) |
O8iv—La2—O10 | 102.81 (11) | C17—C18—H18A | 119.5 |
O4—La2—O10 | 86.18 (11) | C19—C18—H18A | 119.5 |
O1iii—La2—O10 | 140.28 (10) | C18—C19—C14 | 118.9 (4) |
O12iv—La2—O10 | 136.66 (10) | C18—C19—C20 | 118.6 (4) |
O11—La2—O10 | 68.45 (10) | C14—C19—C20 | 122.5 (4) |
O6—La2—O10 | 65.30 (10) | O7—C20—O8 | 126.5 (4) |
O8iv—La2—N1ii | 73.56 (12) | O7—C20—C19 | 117.2 (4) |
O4—La2—N1ii | 73.19 (12) | O8—C20—C19 | 116.2 (4) |
O1iii—La2—N1ii | 71.22 (11) | O9—C21—O10 | 121.0 (4) |
O12iv—La2—N1ii | 137.25 (12) | O9—C21—C22 | 118.4 (4) |
O11—La2—N1ii | 118.07 (11) | O10—C21—C22 | 120.2 (4) |
O6—La2—N1ii | 122.15 (11) | O9—C21—La1 | 59.0 (2) |
O10—La2—N1ii | 71.55 (11) | O10—C21—La1 | 64.6 (2) |
O8iv—La2—O11iv | 74.59 (11) | C22—C21—La1 | 156.6 (3) |
O4—La2—O11iv | 125.81 (11) | C23—C22—C27 | 119.7 (4) |
O1iii—La2—O11iv | 85.83 (10) | C23—C22—C21 | 117.8 (4) |
O12iv—La2—O11iv | 48.46 (10) | C27—C22—C21 | 122.4 (4) |
O11—La2—O11iv | 66.77 (11) | C24—C23—C22 | 120.1 (5) |
O6—La2—O11iv | 94.29 (10) | C24—C23—H23A | 120.0 |
O10—La2—O11iv | 133.44 (10) | C22—C23—H23A | 120.0 |
N1ii—La2—O11iv | 143.52 (11) | C23—C24—C25 | 120.7 (5) |
C1—O1—La2v | 131.2 (3) | C23—C24—H24A | 119.6 |
C1—O2—La1 | 159.3 (3) | C25—C24—H24A | 119.6 |
C7—O3—La1 | 123.4 (3) | C24—C25—C26 | 120.0 (5) |
C7—O4—La2 | 142.2 (3) | C24—C25—H25A | 120.0 |
C13—O5—La1 | 95.6 (3) | C26—C25—H25A | 120.0 |
C13—O6—La2 | 140.4 (3) | C25—C26—C27 | 120.5 (5) |
C13—O6—La1 | 90.2 (3) | C25—C26—H26A | 119.7 |
La2—O6—La1 | 111.49 (11) | C27—C26—H26A | 119.7 |
C20—O7—La1i | 160.3 (3) | C26—C27—C22 | 118.9 (4) |
C20—O8—La2iv | 152.5 (3) | C26—C27—C28 | 119.7 (4) |
C21—O9—La1i | 147.9 (3) | C22—C27—C28 | 121.1 (4) |
C21—O9—La1 | 96.6 (3) | O12—C28—O11 | 122.1 (4) |
La1i—O9—La1 | 114.21 (11) | O12—C28—C27 | 118.4 (4) |
C21—O10—La2 | 116.2 (3) | O11—C28—C27 | 119.5 (4) |
C21—O10—La1 | 90.5 (3) | O12—C28—La2iv | 54.6 (2) |
La2—O10—La1 | 108.97 (11) | O11—C28—La2iv | 68.3 (3) |
C28—O11—La2 | 138.5 (3) | C27—C28—La2iv | 165.5 (3) |
C28—O11—La2iv | 86.8 (3) | C5—N1—C4 | 115.9 (4) |
La2—O11—La2iv | 113.23 (11) | C5—N1—La2vi | 117.8 (3) |
C28—O12—La2iv | 101.6 (3) | C4—N1—La2vi | 125.5 (3) |
O1—C1—O2 | 124.7 (5) | C10—N2—C11 | 116.8 (5) |
O1—C1—C2 | 119.3 (4) | C10—N2—La1vi | 128.6 (4) |
O2—C1—C2 | 115.9 (4) | C11—N2—La1vi | 114.1 (4) |
C6—C2—C3 | 118.4 (5) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+1/2; (iii) x+1, y, z; (iv) −x+2, −y+1, −z+1; (v) x−1, y, z; (vi) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [La2(C8H4O4)2(C6H4NO2)2] |
Mr | 850.25 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 9.9357 (3), 12.4348 (5), 21.6047 (3) |
β (°) | 95.067 (4) |
V (Å3) | 2658.80 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.24 |
Crystal size (mm) | 0.25 × 0.13 × 0.12 |
Data collection | |
Diffractometer | Bruker APEXII area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.498, 0.697 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20786, 5502, 4666 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.082, 1.03 |
No. of reflections | 5502 |
No. of parameters | 397 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.08, −1.02 |
Computer programs: APEX2 (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).
La1—O2 | 2.366 (3) | La2—O1iii | 2.500 (3) |
La1—O3 | 2.461 (3) | La2—O4 | 2.479 (3) |
La1—O5 | 2.569 (3) | La2—O6 | 2.616 (3) |
La1—O6 | 2.677 (3) | La2—O8iv | 2.416 (3) |
La1—O7i | 2.449 (3) | La2—O10 | 2.652 (3) |
La1—O9i | 2.551 (3) | La2—O11 | 2.574 (3) |
La1—O9 | 2.601 (3) | La2—O11iv | 2.811 (3) |
La1—O10 | 2.723 (3) | La2—O12iv | 2.513 (3) |
La1—N2ii | 2.734 (4) | La2—N1ii | 2.782 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+1/2; (iii) x+1, y, z; (iv) −x+2, −y+1, −z+1. |
The rational design and construction of metal–organic coordination networks have aroused great interest owing to their intriguing topological architectures and their potential application as functional materials (Meares & Wensel, 1984; Scott & Horrocks, 1992; Reineke et al., 1999; Eddaoudi et al., 2001). Carboxylate lanthanide networks in particular have attracted increasing attention due to their ability to both chelate to a metal and simultaneously bridge to adjacent metals, especially with the larger and less rigid coordination spheres of rare earth elements. To design such coordination polymers, an effective synthetic approach is based on the deliberate combination of appropriate metal ions and multifunctional ligands. Up to now, a variety of multicarboxylate ligands such as pyridinecarboxylate, imidazoledicarboxylic acid and pyrazinecarboxylic acid etc. have been successfully employed as bridging groups to construct one-, two- and three-dimensional networks (Choi et al., 1998; MacGillivray et al., 1998; Evans et al., 1999; Chen et al., 2001; Suresh et al., 2001; Kumagai et al., 2002; Lu & Babb, 2003; Song et al., 2003). Our interest is to explore the cooperativity of mixed organic ligands in coordinating metal centres, and to construct novel coordination polymers with interesting and complicated architectures and topologies. As a continuation of our previous work (Wang, Li et al., 2007; Wang, Huang et al., 2007), here we report a new lanthanide coordination polymer, [La2(C6H4NO2)2(C8H4O4)2]n, (I), which displays an interesting three-dimensional coordination framework with nanometre-sized channels.
As shown in Fig. 1, the asymmetric unit contains two unique lanthanum(III) atoms, two BDC2- ligands and two IN- ligands. The La1 and La2 atoms are both nine-coordinate with distorted tricapped trigonal prismatic geometries. Each La atom is surrounded by two carboxylate O atoms from two IN ligands, six carboxylate O atoms from four BDC ligands and one pyridyl N atom. Interestingly, there are no hydroxo or aqua ligands within the structure, despite the synthesis being carried out in aqueous condition. The La—O bond distances are rather disperse and range from 2.366 (3) to 2.811 (3) Å; the La—N bond distances, however, are more even, with a range of 2.734 (4)-2.782 (4) Å.
The BDC ligands in the asymmetric unit exhibit two types of coordination modes as depicted in Fig. 2: one coordinates four LaIII ions in a pentadentate chelating–bridging mode (Fig. 2a), while the other binds to four LaIII ions in a heptadentate chelating–bridging mode (Fig. 2b). The IN ligands, however, adopt the same tridentate bridging mode with both carboxylate groups adopting a bimonodenate coordination mode, connecting two LaIII ions, while the N atom simultaneously coordinates a third LaIII centre (Fig. 2c). On the basis of these connection schemes of the BDC ligands, the lanthanum centres are bridged by oxo groups to form an infinite ladder-like chain along the a axis, with separations between adjacent LaIII ions of 4.326 (3), 4.375 (1), 4.499 (7) and 5.572 (1) Å, respectively (Fig. 3a). The remaining coordination sites of LaIII ions, however, are filled by the IN ligands. Thus, an interesting one-dimensional La–carboxylate chain with mixed ligands is formed (Fig. 3b), which is somewhat similar to that of {[Ln2(C6H4NO2)2(C8H4O4)(OH)2(H2O)].H2O} n (Ln = Er and Tm) (Wang, Huang et al., 2007). However, what makes the difference is that the pyridyl N atom in that case is free and noncoordinated, thus making no contribution to the expansion of such chains into high-dimensional architecture, whereas the IN ligands in the present structure, acting as tri-connectors, not only afford the carboxylate groups as donor atoms, but also provide their pyridyl N atoms to covalently coordinate the LaIII ions. It is worth noting that carboxylate O atoms usually prefer to bind hard lanthanide ions while the softer N atom is ideally suited to bind soft transition metal ions such as Ag and Cu, according to the hard–soft acid–base theory. A search of the literature and the Cambridge Structural Database (CSD, Februry 2009; Allen, 2002) reveals that, despite the existence of several 3d–4f and 4d–4f heterometallic Ln–TM [TM = transition metal?] coordination polymers incorporating the IN ligand (Zhang et al., 2005; Luo et al., 2006; Gu & Xue, 2006; Liu et al., 2006; Gu & Xue, 2007a,b; Cheng et al., 2008; Wang et al., 2008; Lian et al., 2009), the lanthanide frameworks directly assembled from the covalent N—Ln linkage mode are relatively rare (Gu & Xue, 2007a,b). In the title compound, however, adjacent La–carboxylate chains are directly interconnected with each other by the covalent N—Ln linkages, forming a three-dimensional framework and leaving in between rectangular one-dimensional channels parallel to the chains, in part occupied by BDC ligands and with approximate dimensions 12 x 17 Å, as defined by the limiting La centres (Fig. 4).