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The title compounds, poly[[tetraaquadi-μ-2-hydroxypropanedioato-μ-oxalato-dilanthanum(III)] tetrahydrate], {[La2(C2O4)(C3H2O5)2(H2O)4]·4H2O}n, (I), and poly[[tetra-μ-acetato-tetraaqua-μ-oxalato-dilanthanum(III)] dihydrate], {[La2(C2O4)(C2H3O2)4(H2O)4]·2H2O}n, (II), represent crystalline hydrates of coordination polymers of diaqualanthanum(3+) ions with different combinations of bridging carboxylate ligands, viz. 2-hydroxypropanedioate and oxalate in a 2:2:1 ratio in (I), and acetate and oxalate in a 2:4:1 ratio in (II). While the acetate component was one of the reactants used, the other ligands were obtained in situ by aerial oxidation of the dihydroxyfumaric acid present in the reactions. The crystal structure of (I) consists of two-dimensional polymeric arrays with water molecules intercalated between and hydrogen bonded to the arrays. The oxalate components are located on inversion centres. The crystal structure of (II) reveals an open three-dimensional polymeric connectivity between the interacting components, with the solvent water molecules incorporated within the intralattice voids and hydrogen bonded to the polymeric framework. The LaIII ion and the noncoordinated water molecules are located on axes of twofold symmetry. The oxalate group is centred at the 222 symmetry site, the intersection of the three rotation axes. The coordination number of the LaIII ion in the two structures is 10. The significance of this study lies mainly in the characterization of two new coordination polymers, as well as in the confirmation that dihydroxyfumaric acid tends to rearrange to form smaller components in standard laboratory procedures, and should be considered a poor reagent for formulating hybrid coordination polymers with metal ions.
Supporting information
CCDC references: 730081; 730082
All reactants and solvents were obtained commercially. For both compounds, an
aqueous solution (25 ml) of La(NO3)3.6H2O (0.433 g, 1 mmol) was added
dropwise to a suspension containing dihydroxyfumaric acid (0.092 g, 0.05 mmol)
and sodium acetate trihydrate (0.136 g, 1 mmol) in H2O (25 ml). For compound
(I), the mixture was stirred overnight at room temperature. It was then
filtered and the filtrate was kept undisturbed for several days, yielding
light-yellow diffraction quality single crystals of (I). Spectroscopic
analysis: IR (KBr, ν, cm-1): 3200–3455 (broad strong band, can be assigned
as water stretching), 1632 (s, νas of COO-), 1364 (νs of
COO-), 2905 (w), 794 (m) and 690 (m) (C—H). For
compound (II), the mixture of reactants described above was refluxed to
boiling overnight, filtered and left for crystallization under ambient
conditions to yield X-ray quality crystals of (II). Spectroscopic analysis: IR
(KBr, cm-1): broad band centred at around 3448 can be assigned as due to
water stretching, 1674 and 1625 [νas(OCO-)], 1349 and 1300
[νs(OCO-)], 800 [δ(OCO, bisbidentate oxalate)], 1591 (s, acetate
stretching).
H atoms bound to C atoms were located in calculated positions and constrained to
ride on their parent atoms, with the following parameters: for (I),
Csp3—H = 1.00 Å (relates to a tertiary C atom) and
Uiso(H) = 1.2Ueq(C); for (II), Csp3—H = 0.98 Å
(relates to a terminal methyl group) and Uiso(H) =
1.5Ueq(C). H atoms bound to O atoms were either located in difference
Fourier maps or positioned to optimize intermolecular hydrogen bonding. All
O—H bond lengths were first restrained to 0.90 (2) Å, but then kept fixed
in the final least-squares cycles. In (I), these H atoms were assigned
Uiso(H) = 1.2Ueq(O), while in (II) their Uiso(H)
values were refined in an unconstrained manner. Significant residual
electron-density peaks were observed in (I) in the vicinity of the O14 water
ligand: a single peak of 2.5 e Å-3 1.3 Å from O14, and two peaks of 1.4
eÅ-3 2.8–2.9 Å from O14. They may represent an unidentified disorder of
this ligand and the possible presence of additional proximal water molecule(s)
with partial occupancy. Similarly, a single residual electron-density peak of
2.7 e Å-3 (the remaining residual peaks are below 0.55 e Å-3) located
on a twofold axis at (1/8, 1/8, -0.007) was found in (II). It could not be
accounted for, possibly resulting from a ripple of the Fourier map on a
symmetry element due to the presence of the heavy atom.
For both 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., 1999); 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).
(I) poly[[tetraaquadi-µ-2-hydroxypropanedioato-µ-oxalato-dilanthanum(III)]
tetrahydrate]
top
Crystal data top
[La2(C2O4)(C3H2O5)2(H2O)4]·4H2O | F(000) = 716 |
Mr = 746.06 | Dx = 2.410 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.1139 (2) Å | Cell parameters from 2480 reflections |
b = 8.3883 (2) Å | θ = 1.4–28.2° |
c = 13.6994 (4) Å | µ = 4.21 mm−1 |
β = 100.9688 (10)° | T = 110 K |
V = 1028.19 (4) Å3 | Plate, yellow |
Z = 2 | 0.20 × 0.15 × 0.07 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2481 independent reflections |
Radiation source: fine-focus sealed tube | 1950 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 12.8 pixels mm-1 | θmax = 28.2°, θmin = 2.9° |
1 deg. ϕ and ω scans | h = 0→12 |
Absorption correction: multi-scan (Blessing, 1995) | k = 0→11 |
Tmin = 0.487, Tmax = 0.757 | l = −18→17 |
9704 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0605P)2 + 0.2879P] where P = (Fo2 + 2Fc2)/3 |
2481 reflections | (Δ/σ)max < 0.001 |
145 parameters | Δρmax = 2.55 e Å−3 |
0 restraints | Δρmin = −1.13 e Å−3 |
Crystal data top
[La2(C2O4)(C3H2O5)2(H2O)4]·4H2O | V = 1028.19 (4) Å3 |
Mr = 746.06 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.1139 (2) Å | µ = 4.21 mm−1 |
b = 8.3883 (2) Å | T = 110 K |
c = 13.6994 (4) Å | 0.20 × 0.15 × 0.07 mm |
β = 100.9688 (10)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2481 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 1950 reflections with I > 2σ(I) |
Tmin = 0.487, Tmax = 0.757 | Rint = 0.059 |
9704 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.00 | Δρmax = 2.55 e Å−3 |
2481 reflections | Δρmin = −1.13 e Å−3 |
145 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 | 0.30520 (3) | 0.33651 (3) | −0.04385 (2) | 0.01144 (12) | |
O2 | 0.4022 (4) | 0.2772 (5) | 0.1561 (3) | 0.0198 (8) | |
O3 | 0.5078 (4) | 0.4798 (4) | 0.0949 (3) | 0.0154 (8) | |
C4 | 0.5014 (6) | 0.3836 (6) | 0.1649 (4) | 0.0165 (11) | |
C5 | 0.6154 (6) | 0.4057 (6) | 0.2595 (4) | 0.0142 (10) | |
H5 | 0.6083 | 0.5182 | 0.2824 | 0.017* | |
O6 | 0.5898 (4) | 0.3024 (4) | 0.3368 (3) | 0.0165 (8) | |
H6 | 0.5193 | 0.3315 | 0.3710 | 0.020* | |
C7 | 0.7755 (6) | 0.3786 (6) | 0.2406 (4) | 0.0173 (11) | |
O8 | 0.8558 (4) | 0.2809 (4) | 0.2957 (3) | 0.0164 (8) | |
O9 | 0.8170 (4) | 0.4608 (4) | 0.1740 (3) | 0.0179 (8) | |
O10 | 0.3071 (4) | 0.0315 (4) | −0.0147 (3) | 0.0173 (8) | |
C11 | 0.4269 (6) | −0.0459 (6) | −0.0006 (4) | 0.0160 (11) | |
O12 | 0.4376 (4) | −0.1943 (4) | 0.0144 (3) | 0.0157 (8) | |
O13 | 0.2067 (4) | 0.5965 (5) | 0.0347 (3) | 0.0176 (8) | |
H13A | 0.2766 | 0.6733 | 0.0384 | 0.021* | |
H13B | 0.2089 | 0.5677 | 0.0983 | 0.021* | |
O14 | 0.0771 (4) | 0.2825 (5) | 0.0396 (3) | 0.0215 (9) | |
H14A | −0.0047 | 0.3406 | 0.0160 | 0.026* | |
H14B | 0.0944 | 0.1959 | 0.0787 | 0.026* | |
O15 | 0.3650 (5) | 0.4703 (5) | 0.3760 (3) | 0.0321 (10) | |
H15A | 0.3109 | 0.4605 | 0.4243 | 0.039* | |
H15B | 0.3033 | 0.4524 | 0.3175 | 0.039* | |
O16 | 0.3606 (5) | 0.0358 (5) | 0.2823 (3) | 0.0311 (10) | |
H16A | 0.4348 | −0.0315 | 0.2749 | 0.037* | |
H16B | 0.3873 | 0.1195 | 0.2480 | 0.037* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
La1 | 0.01149 (17) | 0.01046 (17) | 0.01195 (18) | −0.00023 (11) | 0.00113 (12) | 0.00031 (11) |
O2 | 0.0176 (19) | 0.0203 (19) | 0.021 (2) | −0.0044 (17) | 0.0019 (16) | 0.0041 (16) |
O3 | 0.0190 (18) | 0.0134 (18) | 0.0131 (17) | 0.0005 (15) | 0.0013 (14) | 0.0034 (15) |
C4 | 0.022 (3) | 0.015 (2) | 0.013 (3) | 0.005 (2) | 0.004 (2) | 0.001 (2) |
C5 | 0.012 (2) | 0.017 (3) | 0.015 (3) | 0.004 (2) | 0.005 (2) | 0.002 (2) |
O6 | 0.0152 (18) | 0.0184 (18) | 0.0159 (19) | −0.0010 (15) | 0.0030 (15) | 0.0015 (15) |
C7 | 0.019 (3) | 0.015 (2) | 0.014 (3) | −0.001 (2) | −0.006 (2) | −0.001 (2) |
O8 | 0.0158 (18) | 0.0183 (18) | 0.0150 (19) | 0.0054 (16) | 0.0030 (15) | 0.0037 (15) |
O9 | 0.0187 (19) | 0.0184 (19) | 0.0168 (19) | 0.0010 (15) | 0.0039 (15) | 0.0025 (15) |
O10 | 0.0086 (16) | 0.020 (2) | 0.0238 (19) | 0.0031 (15) | 0.0041 (15) | 0.0126 (16) |
C11 | 0.015 (3) | 0.021 (3) | 0.011 (2) | −0.001 (2) | −0.002 (2) | −0.001 (2) |
O12 | 0.0140 (18) | 0.0135 (18) | 0.020 (2) | 0.0020 (15) | 0.0033 (15) | −0.0001 (15) |
O13 | 0.0165 (19) | 0.0154 (19) | 0.021 (2) | −0.0022 (15) | 0.0035 (16) | −0.0024 (15) |
O14 | 0.018 (2) | 0.0206 (19) | 0.024 (2) | 0.0018 (17) | 0.0010 (17) | 0.0038 (17) |
O15 | 0.026 (2) | 0.040 (3) | 0.032 (2) | 0.008 (2) | 0.0115 (19) | 0.000 (2) |
O16 | 0.036 (2) | 0.031 (2) | 0.026 (2) | −0.003 (2) | 0.0054 (19) | 0.0067 (18) |
Geometric parameters (Å, º) top
La1—O2 | 2.758 (4) | O6—La1iv | 2.581 (4) |
La1—O3 | 2.671 (3) | O6—H6 | 0.8984 |
La1—O3i | 2.494 (4) | C7—O8 | 1.252 (7) |
La1—O6ii | 2.581 (4) | C7—O9 | 1.257 (6) |
La1—O8ii | 2.530 (4) | O8—La1iv | 2.530 (4) |
La1—O9i | 2.560 (4) | O9—La1i | 2.560 (4) |
La1—O10 | 2.589 (4) | O10—C11 | 1.253 (6) |
La1—O12iii | 2.592 (4) | C11—O12 | 1.262 (6) |
La1—O13 | 2.662 (4) | C11—C11iii | 1.538 (10) |
La1—O14 | 2.596 (4) | O12—La1iii | 2.592 (4) |
La1—C4 | 3.097 (5) | O13—H13A | 0.9004 |
O2—C4 | 1.260 (7) | O13—H13B | 0.9008 |
O3—C4 | 1.264 (6) | O14—H14A | 0.8980 |
O3—La1i | 2.494 (4) | O14—H14B | 0.8983 |
C4—C5 | 1.510 (7) | O15—H15A | 0.9014 |
C5—O6 | 1.422 (6) | O15—H15B | 0.9005 |
C5—C7 | 1.546 (7) | O16—H16A | 0.9012 |
C5—H5 | 1.0000 | O16—H16B | 0.9037 |
| | | |
O3i—La1—O8ii | 75.50 (11) | O8ii—La1—C4 | 133.13 (13) |
O3i—La1—O9i | 67.93 (12) | O9i—La1—C4 | 131.06 (13) |
O8ii—La1—O9i | 77.30 (12) | O6ii—La1—C4 | 151.48 (13) |
O3i—La1—O6ii | 125.38 (12) | O10—La1—C4 | 89.89 (13) |
O8ii—La1—O6ii | 61.06 (12) | O14—La1—C4 | 89.17 (13) |
O9i—La1—O6ii | 71.39 (11) | O12iii—La1—C4 | 64.47 (13) |
O3i—La1—O10 | 131.97 (11) | O13—La1—C4 | 72.66 (12) |
O8ii—La1—O10 | 75.65 (12) | O3—La1—C4 | 23.88 (12) |
O9i—La1—O10 | 138.83 (12) | O2—La1—C4 | 23.96 (13) |
O6ii—La1—O10 | 68.50 (11) | C4—O2—La1 | 93.3 (3) |
O3i—La1—O14 | 151.46 (12) | C4—O3—La1i | 137.7 (3) |
O8ii—La1—O14 | 127.47 (12) | C4—O3—La1 | 97.3 (3) |
O9i—La1—O14 | 98.28 (12) | La1i—O3—La1 | 119.69 (13) |
O6ii—La1—O14 | 67.92 (12) | O3—C4—O2 | 121.0 (5) |
O10—La1—O14 | 75.06 (12) | O3—C4—C5 | 116.7 (5) |
O3i—La1—O12iii | 71.46 (11) | O2—C4—C5 | 122.3 (5) |
O8ii—La1—O12iii | 69.33 (12) | O3—C4—La1 | 58.8 (3) |
O9i—La1—O12iii | 132.41 (12) | O2—C4—La1 | 62.8 (3) |
O6ii—La1—O12iii | 116.54 (11) | C5—C4—La1 | 172.0 (4) |
O10—La1—O12iii | 62.74 (11) | O6—C5—C4 | 112.3 (4) |
O14—La1—O12iii | 128.86 (12) | O6—C5—C7 | 109.2 (4) |
O3i—La1—O13 | 84.74 (11) | C4—C5—C7 | 110.8 (4) |
O8ii—La1—O13 | 143.26 (12) | O6—C5—H5 | 108.1 |
O9i—La1—O13 | 66.56 (12) | C4—C5—H5 | 108.1 |
O6ii—La1—O13 | 110.58 (11) | C7—C5—H5 | 108.1 |
O10—La1—O13 | 137.74 (12) | C5—O6—La1iv | 122.3 (3) |
O14—La1—O13 | 66.73 (12) | C5—O6—H6 | 117.3 |
O12iii—La1—O13 | 132.74 (11) | La1iv—O6—H6 | 109.0 |
O3i—La1—O3 | 60.31 (13) | O8—C7—O9 | 125.0 (5) |
O8ii—La1—O3 | 125.32 (11) | O8—C7—C5 | 117.2 (5) |
O9i—La1—O3 | 110.30 (11) | O9—C7—C5 | 117.7 (5) |
O6ii—La1—O3 | 173.48 (11) | C7—O8—La1iv | 126.6 (4) |
O10—La1—O3 | 110.60 (11) | C7—O9—La1i | 135.9 (4) |
O14—La1—O3 | 105.56 (11) | C11—O10—La1 | 121.1 (3) |
O12iii—La1—O3 | 67.32 (11) | O10—C11—O12 | 125.1 (5) |
O13—La1—O3 | 65.43 (11) | O10—C11—C11iii | 118.0 (6) |
O3i—La1—O2 | 106.42 (11) | O12—C11—C11iii | 116.9 (6) |
O8ii—La1—O2 | 135.69 (12) | C11—O12—La1iii | 121.3 (3) |
O9i—La1—O2 | 145.70 (12) | La1—O13—H13A | 108.6 |
O6ii—La1—O2 | 127.53 (11) | La1—O13—H13B | 103.0 |
O10—La1—O2 | 71.18 (12) | H13A—O13—H13B | 104.7 |
O14—La1—O2 | 70.34 (11) | La1—O14—H14A | 115.2 |
O12iii—La1—O2 | 69.70 (12) | La1—O14—H14B | 109.8 |
O13—La1—O2 | 79.36 (11) | H14A—O14—H14B | 133.9 |
O3—La1—O2 | 47.69 (11) | H15A—O15—H15B | 107.6 |
O3i—La1—C4 | 82.81 (13) | H16A—O16—H16B | 98.4 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1, −y, −z; (iv) x+1/2, −y+1/2, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···O15 | 0.90 | 1.84 | 2.625 (6) | 145 |
O13—H13A···O12v | 0.90 | 1.92 | 2.795 (5) | 164 |
O13—H13B···O16vi | 0.90 | 1.88 | 2.739 (6) | 158 |
O14—H14A···O13vii | 0.90 | 1.91 | 2.785 (5) | 163 |
O14—H14B···O15viii | 0.90 | 2.00 | 2.871 (6) | 162 |
O15—H15A···O10vi | 0.90 | 1.88 | 2.733 (6) | 156 |
O15—H15B···O16vi | 0.90 | 1.95 | 2.746 (6) | 146 |
O16—H16A···O9ix | 0.90 | 2.24 | 2.952 (6) | 136 |
O16—H16B···O2 | 0.90 | 1.85 | 2.736 (6) | 166 |
Symmetry codes: (v) x, y+1, z; (vi) −x+1/2, y+1/2, −z+1/2; (vii) −x, −y+1, −z; (viii) −x+1/2, y−1/2, −z+1/2; (ix) −x+3/2, y−1/2, −z+1/2. |
(II) poly[[tetra-µ-2-acetato-tetraaqua-µ-oxalato-dilanthanum(III)] dihydrate]
top
Crystal data top
[La2(C2O4)(C2H3O2)4(H2O)4]·2H2O | Dx = 2.132 Mg m−3 |
Mr = 710.12 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Fddd | Cell parameters from 1446 reflections |
a = 12.1763 (2) Å | θ = 2.4–27.9° |
b = 13.3596 (2) Å | µ = 3.89 mm−1 |
c = 27.2064 (6) Å | T = 110 K |
V = 4425.68 (14) Å3 | Plate, colourless |
Z = 8 | 0.35 × 0.30 × 0.15 mm |
F(000) = 2736 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1320 independent reflections |
Radiation source: fine-focus sealed tube | 1112 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 12.8 pixels mm-1 | θmax = 27.9°, θmin = 2.4° |
1 deg. ϕ scan | h = 0→16 |
Absorption correction: multi-scan (Blessing, 1995) | k = 0→17 |
Tmin = 0.343, Tmax = 0.593 | l = 0→35 |
7496 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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.38 | w = 1/[σ2(Fo2) + (0.0258P)2 + 4.6692P] where P = (Fo2 + 2Fc2)/3 |
1320 reflections | (Δ/σ)max = 0.001 |
74 parameters | Δρmax = 2.66 e Å−3 |
0 restraints | Δρmin = −1.07 e Å−3 |
Crystal data top
[La2(C2O4)(C2H3O2)4(H2O)4]·2H2O | V = 4425.68 (14) Å3 |
Mr = 710.12 | Z = 8 |
Orthorhombic, Fddd | Mo Kα radiation |
a = 12.1763 (2) Å | µ = 3.89 mm−1 |
b = 13.3596 (2) Å | T = 110 K |
c = 27.2064 (6) Å | 0.35 × 0.30 × 0.15 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1320 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 1112 reflections with I > 2σ(I) |
Tmin = 0.343, Tmax = 0.593 | Rint = 0.042 |
7496 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.38 | Δρmax = 2.66 e Å−3 |
1320 reflections | Δρmin = −1.07 e Å−3 |
74 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 | 0.6250 | 0.1250 | 0.003858 (10) | 0.01266 (11) | |
O2 | 0.4412 (2) | 0.21462 (19) | 0.03257 (10) | 0.0203 (6) | |
C3 | 0.3788 (3) | 0.1391 (3) | 0.03239 (12) | 0.0133 (6) | |
O4 | 0.4149 (2) | 0.05523 (19) | 0.01742 (10) | 0.0182 (5) | |
C5 | 0.2621 (3) | 0.1477 (3) | 0.04934 (18) | 0.0288 (10) | |
H5A | 0.2570 | 0.1988 | 0.0751 | 0.043* | |
H5B | 0.2377 | 0.0831 | 0.0625 | 0.043* | |
H5C | 0.2154 | 0.1667 | 0.0216 | 0.043* | |
O6 | 0.6405 (2) | 0.2242 (2) | 0.08432 (9) | 0.0205 (6) | |
C7 | 0.6250 | 0.1826 (4) | 0.1250 | 0.0158 (10) | |
O8 | 0.5057 (2) | 0.14738 (19) | −0.07403 (10) | 0.0211 (6) | |
H8A | 0.4624 | 0.0955 | −0.0789 | 0.047 (16)* | |
H8B | 0.5347 | 0.1567 | −0.1044 | 0.056 (18)* | |
O9 | 0.3750 | 0.3750 | 0.08952 (14) | 0.0220 (8) | |
H9 | 0.4001 | 0.3238 | 0.0712 | 0.07 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
La1 | 0.01229 (16) | 0.01193 (16) | 0.01377 (16) | −0.00078 (11) | 0.000 | 0.000 |
O2 | 0.0145 (12) | 0.0164 (12) | 0.0302 (15) | −0.0016 (10) | 0.0030 (11) | −0.0041 (11) |
C3 | 0.0157 (16) | 0.0128 (15) | 0.0116 (15) | −0.0018 (14) | 0.0002 (13) | −0.0021 (13) |
O4 | 0.0157 (12) | 0.0149 (12) | 0.0239 (14) | 0.0015 (10) | 0.0023 (11) | −0.0032 (11) |
C5 | 0.0148 (18) | 0.023 (2) | 0.049 (3) | 0.0019 (16) | 0.0062 (18) | −0.0060 (18) |
O6 | 0.0277 (15) | 0.0200 (13) | 0.0139 (13) | −0.0051 (11) | 0.0009 (11) | 0.0012 (10) |
C7 | 0.010 (2) | 0.025 (3) | 0.012 (2) | 0.000 | −0.004 (2) | 0.000 |
O8 | 0.0237 (14) | 0.0211 (13) | 0.0186 (14) | −0.0055 (12) | −0.0023 (11) | 0.0002 (10) |
O9 | 0.031 (2) | 0.0184 (19) | 0.0167 (19) | 0.0059 (17) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
La1—O2 | 2.655 (2) | C3—O4 | 1.271 (4) |
La1—O2i | 2.655 (2) | C3—C5 | 1.498 (5) |
La1—O4 | 2.748 (2) | O4—La1ii | 2.524 (2) |
La1—O4i | 2.748 (2) | C5—H5A | 0.9800 |
La1—O4ii | 2.524 (2) | C5—H5B | 0.9800 |
La1—O4iii | 2.524 (2) | C5—H5C | 0.9800 |
La1—O6 | 2.566 (3) | O6—C7 | 1.253 (4) |
La1—O6i | 2.566 (3) | C7—O6iv | 1.252 (4) |
La1—O8 | 2.587 (3) | C7—C7i | 1.540 (10) |
La1—O8i | 2.587 (3) | O8—H8A | 0.8801 |
La1—C3i | 3.102 (4) | O8—H8B | 0.9062 |
La1—C3 | 3.102 (4) | O9—H9 | 0.9001 |
O2—C3 | 1.263 (4) | | |
| | | |
O4iii—La1—O4ii | 153.47 (13) | O4iii—La1—C3i | 85.97 (8) |
O4iii—La1—O6i | 134.63 (9) | O4ii—La1—C3i | 100.67 (8) |
O4ii—La1—O6i | 71.88 (9) | O6i—La1—C3i | 79.98 (9) |
O4iii—La1—O6 | 71.88 (8) | O6—La1—C3i | 75.35 (9) |
O4ii—La1—O6 | 134.63 (9) | O8i—La1—C3i | 69.83 (9) |
O6i—La1—O6 | 62.87 (12) | O8—La1—C3i | 139.01 (9) |
O4iii—La1—O8i | 79.29 (8) | O2i—La1—C3i | 23.75 (8) |
O4ii—La1—O8i | 79.04 (8) | O2—La1—C3i | 140.18 (9) |
O6i—La1—O8i | 132.88 (9) | O4i—La1—C3i | 24.13 (8) |
O6—La1—O8i | 135.84 (8) | O4—La1—C3i | 147.72 (8) |
O4iii—La1—O8 | 79.04 (8) | O4iii—La1—C3 | 100.67 (8) |
O4ii—La1—O8 | 79.29 (8) | O4ii—La1—C3 | 85.97 (8) |
O6i—La1—O8 | 135.84 (8) | O6i—La1—C3 | 75.35 (9) |
O6—La1—O8 | 132.88 (9) | O6—La1—C3 | 79.98 (9) |
O8i—La1—O8 | 69.99 (12) | O8i—La1—C3 | 139.01 (9) |
O4iii—La1—O2i | 109.61 (8) | O8—La1—C3 | 69.82 (9) |
O4ii—La1—O2i | 78.42 (8) | O2i—La1—C3 | 140.18 (9) |
O6i—La1—O2i | 65.04 (8) | O2—La1—C3 | 23.75 (8) |
O6—La1—O2i | 85.41 (9) | O4i—La1—C3 | 147.72 (8) |
O8i—La1—O2i | 73.47 (9) | O4—La1—C3 | 24.13 (8) |
O8—La1—O2i | 140.04 (9) | C3i—La1—C3 | 151.02 (13) |
O4iii—La1—O2 | 78.43 (8) | C3—O2—La1 | 98.4 (2) |
O4ii—La1—O2 | 109.61 (8) | O2—C3—O4 | 119.8 (3) |
O6i—La1—O2 | 85.41 (9) | O2—C3—C5 | 120.6 (3) |
O6—La1—O2 | 65.04 (8) | O4—C3—C5 | 119.6 (3) |
O8i—La1—O2 | 140.04 (9) | O2—C3—La1 | 57.85 (18) |
O8—La1—O2 | 73.47 (9) | O4—C3—La1 | 62.11 (18) |
O2i—La1—O2 | 145.78 (12) | C5—C3—La1 | 176.4 (3) |
O4iii—La1—O4i | 61.84 (9) | C3—O4—La1ii | 148.1 (2) |
O4ii—La1—O4i | 122.24 (9) | C3—O4—La1 | 93.8 (2) |
O6i—La1—O4i | 97.40 (8) | La1ii—O4—La1 | 118.16 (9) |
O6—La1—O4i | 69.02 (8) | C3—C5—H5A | 109.5 |
O8i—La1—O4i | 68.05 (8) | C3—C5—H5B | 109.5 |
O8—La1—O4i | 126.43 (8) | H5A—C5—H5B | 109.5 |
O2i—La1—O4i | 47.84 (7) | C3—C5—H5C | 109.5 |
O2—La1—O4i | 126.31 (8) | H5A—C5—H5C | 109.5 |
O4iii—La1—O4 | 122.24 (9) | H5B—C5—H5C | 109.5 |
O4ii—La1—O4 | 61.84 (9) | C7—O6—La1 | 121.0 (3) |
O6i—La1—O4 | 69.02 (8) | O6iv—C7—O6 | 127.4 (5) |
O6—La1—O4 | 97.40 (8) | O6iv—C7—C7i | 116.3 (3) |
O8i—La1—O4 | 126.43 (8) | O6—C7—C7i | 116.3 (3) |
O8—La1—O4 | 68.05 (8) | La1—O8—H8A | 111.6 |
O2i—La1—O4 | 126.31 (8) | La1—O8—H8B | 122.9 |
O2—La1—O4 | 47.84 (7) | H8A—O8—H8B | 101.9 |
O4i—La1—O4 | 164.56 (12) | | |
Symmetry codes: (i) −x+5/4, −y+1/4, z; (ii) −x+1, −y, −z; (iii) x+1/4, y+1/4, −z; (iv) −x+5/4, y, −z+1/4. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O8—H8A···O6v | 0.88 | 1.85 | 2.720 (4) | 170 |
O8—H8B···O9vi | 0.91 | 1.93 | 2.781 (4) | 156 |
O9—H9···O2 | 0.90 | 1.87 | 2.764 (3) | 176 |
Symmetry codes: (v) x−1/4, y−1/4, −z; (vi) −x+1, y−1/4, z−1/4. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [La2(C2O4)(C3H2O5)2(H2O)4]·4H2O | [La2(C2O4)(C2H3O2)4(H2O)4]·2H2O |
Mr | 746.06 | 710.12 |
Crystal system, space group | Monoclinic, P21/n | Orthorhombic, Fddd |
Temperature (K) | 110 | 110 |
a, b, c (Å) | 9.1139 (2), 8.3883 (2), 13.6994 (4) | 12.1763 (2), 13.3596 (2), 27.2064 (6) |
α, β, γ (°) | 90, 100.9688 (10), 90 | 90, 90, 90 |
V (Å3) | 1028.19 (4) | 4425.68 (14) |
Z | 2 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 4.21 | 3.89 |
Crystal size (mm) | 0.20 × 0.15 × 0.07 | 0.35 × 0.30 × 0.15 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.487, 0.757 | 0.343, 0.593 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9704, 2481, 1950 | 7496, 1320, 1112 |
Rint | 0.059 | 0.042 |
(sin θ/λ)max (Å−1) | 0.664 | 0.658 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.098, 1.00 | 0.028, 0.066, 1.38 |
No. of reflections | 2481 | 1320 |
No. of parameters | 145 | 74 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.55, −1.13 | 2.66, −1.07 |
Selected bond lengths (Å) for (I) topLa1—O2 | 2.758 (4) | La1—O9i | 2.560 (4) |
La1—O3 | 2.671 (3) | La1—O10 | 2.589 (4) |
La1—O3i | 2.494 (4) | La1—O12iii | 2.592 (4) |
La1—O6ii | 2.581 (4) | La1—O13 | 2.662 (4) |
La1—O8ii | 2.530 (4) | La1—O14 | 2.596 (4) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···O15 | 0.90 | 1.84 | 2.625 (6) | 145 |
O13—H13A···O12iv | 0.90 | 1.92 | 2.795 (5) | 164 |
O13—H13B···O16v | 0.90 | 1.88 | 2.739 (6) | 158 |
O14—H14A···O13vi | 0.90 | 1.91 | 2.785 (5) | 163 |
O14—H14B···O15vii | 0.90 | 2.00 | 2.871 (6) | 162 |
O15—H15A···O10v | 0.90 | 1.88 | 2.733 (6) | 156 |
O15—H15B···O16v | 0.90 | 1.95 | 2.746 (6) | 146 |
O16—H16A···O9viii | 0.90 | 2.24 | 2.952 (6) | 136 |
O16—H16B···O2 | 0.90 | 1.85 | 2.736 (6) | 166 |
Symmetry codes: (iv) x, y+1, z; (v) −x+1/2, y+1/2, −z+1/2; (vi) −x, −y+1, −z; (vii) −x+1/2, y−1/2, −z+1/2; (viii) −x+3/2, y−1/2, −z+1/2. |
Selected bond lengths (Å) for (II) topLa1—O2 | 2.655 (2) | La1—O6 | 2.566 (3) |
La1—O4 | 2.748 (2) | La1—O8 | 2.587 (3) |
La1—O4i | 2.524 (2) | | |
Symmetry code: (i) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O8—H8A···O6ii | 0.88 | 1.85 | 2.720 (4) | 170 |
O8—H8B···O9iii | 0.91 | 1.93 | 2.781 (4) | 156 |
O9—H9···O2 | 0.90 | 1.87 | 2.764 (3) | 176 |
Symmetry codes: (ii) x−1/4, y−1/4, −z; (iii) −x+1, y−1/4, z−1/4. |
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This report is part of a broad study related to the formulation of extended coordination polymers by reacting lanthanide metal ions with organic polycarboxylic acids as chelating ligands (George et al., 2006; Lipstman et al., 2007; Muniappan et al., 2007; Koner & Goldberg, 2008). The latter may link simultaneously to metal centres in a variety of coordination modes and generate extended coordination networks and frameworks. The lanthanide ions provide a very attractive interface to promote the formation of such polymeric arrays due to their large size, spatial divergence of the valent orbitals, high coordination numbers and (due to their `hard' nature) high affinity for oxo ligands. Moreover, deprotonated carboxylate ligands act also as counterions to balance the charge. The high propensity of the lanthanides to form multicomponent structures with acetate, oxalate and other small carboxylate anions is well documented in the Cambridge Structural Database (CSD; November 2008 Version?) (Allen, 2002). Their reaction with more bulky tetra(carboxyphenyl)porphyrin ligands has led to the formulation of robust microporous solids (George, et al., 2006; Lipstman et al., 2007; Muniappan et al., 2007). Examples of coordination networks formed by the reaction of first-row transition metals with polycarboxylic acid ligands are also known (e.g. Abrahams et al., 2006; Goldberg, 2005).
In the above context, we reacted lanthanum nitrate salt with the dicarboxylic acid dihydroxyfumaric acid in the presence of sodium acetate, aiming to explore the capacity of the multidentate fumaric acid moiety to induce the formation of extended coordination polymers under different conditions. However, in the experiments we performed and in the presence of the lanthanum metal ions, the dihydroxyfumaric acid decomposed to 2-hydroxypropanedioate and oxalate anions via a metal-promoted benzilic acid-type rearrangement (Selman & Eastman, 1960). Similar aerial oxidation reactions of dihydroxyfumaric acid to smaller components have been reported in earlier studies with first-row transition metals (Abrahams et al., 2006, 2004). Thus, with the ligands generated in situ, coordination polymers of the following stoichiometric composition have been obtained and structurally characterized: [La(H2O)2(OOCCHOHCOO)(OOCCOO)1/2].2H2O, (I), and [La(H2O)2(CH3COO)2(OOCCOO)1/2].H2O, (II). Representations of the two structures are shown in Figs. 1 and 2, respectively.
Structure (I) can be best described as composed of two-dimensional coordination networks between the component species. As shown in Fig. 3, the LaIII ion exhibits multiple binding modes to the surrounding species. It coordinates to three hydroxymalonate units, involving both their carboxylate and hydroxyl sites. Two additional ligating sites are associated with the carboxylate groups of the oxalate anion. The coordination environment of the LaIII ion is supplemented by two molecules of water, O13 and O14, which are oriented outward, above and below and roughly perpendicular to the surface of the coordination network. The coordination number of the LaIII ions is essentially 10, the La—O bond distances varying from 2.494 (4) to 2.758 (4) Å (Table 1). Each of the multidentate 2-hydroxypropanedioate ligands coordinates simultaneously to three metal centres, while the bisbidentate oxalate moiety (with four carboxylate O sites) bridges two neighbouring metal ions. This extensive crosslinking yields a robust coordination network, aligned in the crystal approximately normal to the [201] direction. The polymeric layers are stacked in a parallel manner along the normal direction, intercalating molecules of noncoordinated solvent water (O15 and O16) between them (Fig. 4). These water species provide an extensive O—H···O hydrogen-bonding connection scheme between neighbouring polymeric arrays (Table 2), yielding a fully interlinked intermolecular organization.
The structure of (II) represents a three-dimensional coordination polymer. This compound was prepared under harsher conditions than compound (I): an overnight reflux at elevated temperature, compared with simple stirring of the reaction mixture at room temperature. This resulted in incorporation of the acetate anions into the coordination environment of the metal and elimination of possible coordination of the hydroxymalonic species, as in (I). A modular description of the observed coordination networking follows.
The LaIII ions of (II) are assembled into polymeric chains by the bridging acetate ligands, with two acetate moieties connecting between each pair of neighbouring diaqua-metal ions (Fig. 5, Table 3). Such coordination has been observed previously with the acetate ligand (Dan et al., 2006), as well as with a number of other monocarboxylate entities (CSD; How many hits? If less than 10, please give references and refcodes). These chains are oriented perpendicular to the c axis, being centred at the z-coordinated levels of 0, 1/4, 1/2 and 3/4. Chains located at z = 0 and z = 1/2 propagate along [110], while those located at z = 1/4 and z = 3/4 are aligned along [110]. The periphery of these chains is decorated by the lipophilic methyl groups. At each z-coordinate level, neighbouring chains are related to one another by translation along either [110] (at z = 0 and 1/2) or [110] (at z = 1/4 and 3/4), respectively. They are interlinked by O—H···O hydrogen bonding through the non-coordinated water solvent molecule (Table 4), thus forming layers parallel to the ab plane. These chains, and thus the layers, at different z levels are intercoordinated further by oxalate ligands in the c direction. A given chain at one z level (e.g. at z = 1/2) is linked simultaneously to different (perpendicularly oriented) chains at the neighbouring z levels (at z = 1/4 and z = 3/4), thus yielding a unique three-dimensional coordination framework. Hence, coordination between the LaIII ions through the acetate ligands, along with hydrogen bonding between the polymeric chains thus formed, forms layers parallel to (001), while additional multiple coordination between the metal ions through the oxalate ligands connects these layers along [001].
A view of the crystal structure of (II) is shown in Fig. 6. It illustrates the layered arrangement of the acetate-bridged polymeric chains, which extend parallel to the ab plane at equal intervals along the c axis, and the effective bridging between these layers along c by the oxalate `pillars'. Similar polymeric coordination modes of lanthanide oxalates have been reported earlier (e.g. Song & Mao, 2005). However, to the best of our knowledge, structures of polymeric arrays involving a combination of acetate and oxalate ligands in the same compound have not been reported to date.
The La—O coordination bonds in (II) are within the range 2.524 (2)–2.748 (2) Å (Table 3). The observed coordination number of the metal ion is 10 in (I) and (II), although the 3+ lanthanides most commonly exhibit coordination numbers up to 9 (Muniappan et al., 2007; Lipstman et al., 2007). This observation can be associated with the bifurcated nature of the carboxylate binding, and the occurrence of somewhat elongated (>2.6 Å) La—O bonds. A survey of the CSD involving 3436 hits from crystal structures with R < 0.05 reveals that previously reported La—O bond lengths range from 2.136 to 3.224 Å, with a mean distance of 2.57 (12) Å. The La—O distance ranges observed in (I) and (II) are thus in agreement with the previously reported data.
In summary, this study reports two new metal–ligand coordination polymers involving LaIII ions and small carboxylate ligands. They were found to reveal unique coordination connectivities, expanding on the known structural variety involving lanthanide metal ions. The diverse coordination capacity of these ions may justify further research in this area.