Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010300341X/ta1398sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010300341X/ta1398Isup2.hkl |
CCDC reference: 217128
Mellitic acid was supplied by Aldrich Chemical Company Inc. and oxide of erbium was supplied by Rhodia Inc. Both were used without further purification. By reaction with NaOH, the mellitic acid provided the hexasodium mellitate salt. By reaction with HCl, the erbium oxide led to the pentahydrated erbium chloride. Dilute aqueous solutions of ErIII chloride and hexasodium mellitate were allowed to diffuse slowly through an agar gel medium in a U-shaped tube. After one and a half months, pale pink single crystals of (I) were collected. Analysis calculated (found) for Er2[C(CO2)6](H2O)10·4H2O: Er 36.3 (36.3); C 15.5 (15.6); H 3.2 (3.0); O 45.3% (45.1%).
The s.u.s of the cell constants indicate the internal consistency of the measurements themselves, i.e. the precision of the measurement, not their accuracy. The maximum in the final difference map is 2.08 Å from O3W and the minimum is 0.77 Å from Er.
Data collection: COLLECT (Nonius, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandeburg, 2000); software used to prepare material for publication: SHELXL97.
[Er2(C12O12)(H2O)10]·4H2O | Dx = 2.444 Mg m−3 |
Mr = 922.86 | Melting point: not measured K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.4499 (1) Å | Cell parameters from 8641 reflections |
b = 9.2595 (2) Å | θ = 1.0–30.0° |
c = 16.2911 (4) Å | µ = 6.76 mm−1 |
β = 100.3390 (8)° | T = 298 K |
V = 1253.95 (4) Å3 | Plate, pale pink |
Z = 2 | 0.31 × 0.09 × 0.06 mm |
F(000) = 832 |
Nonius KappaCCD area-detector diffractometer | 3648 independent reflections |
Radiation source: Enraf-Nonius FR-590 | 2884 reflections with I > 2σ(I) |
Horizonally mounted graphite crystal monochromator | Rint = 0.049 |
Detector resolution: 9 pixels mm-1 | θmax = 30.0°, θmin = 2.5° |
CCD rotation images, thick slices scans | h = −11→9 |
Absorption correction: analytical (Alcock, 1970) | k = −13→11 |
Tmin = 0.256, Tmax = 0.646 | l = −21→22 |
17561 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters not defined |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.0438P)2 + 4.4981P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3648 reflections | Δρmax = 2.48 e Å−3 |
199 parameters | Δρmin = −2.05 e Å−3 |
0 restraints |
[Er2(C12O12)(H2O)10]·4H2O | V = 1253.95 (4) Å3 |
Mr = 922.86 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.4499 (1) Å | µ = 6.76 mm−1 |
b = 9.2595 (2) Å | T = 298 K |
c = 16.2911 (4) Å | 0.31 × 0.09 × 0.06 mm |
β = 100.3390 (8)° |
Nonius KappaCCD area-detector diffractometer | 3648 independent reflections |
Absorption correction: analytical (Alcock, 1970) | 2884 reflections with I > 2σ(I) |
Tmin = 0.256, Tmax = 0.646 | Rint = 0.049 |
17561 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters not defined |
S = 1.03 | Δρmax = 2.48 e Å−3 |
3648 reflections | Δρmin = −2.05 e Å−3 |
199 parameters |
Experimental. Data collection was performed at the Centre de Diffractométrie, Université de Rennes, France. A crystal-to-detector distance of 25 mm was used and a total of 163 frames were recorded, using Δω 2° rotation scans, with exposure time = 40 sec/°.). |
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 | Occ. (<1) | |
Er | 0.44714 (2) | 0.09373 (2) | 0.166967 (13) | 0.01942 (9) | |
O1 | 0.3852 (5) | −0.1071 (4) | 0.0788 (3) | 0.0305 (9) | |
O2 | 0.2436 (4) | −0.0332 (5) | 0.2225 (3) | 0.0327 (9) | |
O3 | 0.5629 (5) | 0.3262 (5) | 0.1793 (3) | 0.0432 (11) | |
O4 | 0.5821 (6) | −0.1022 (6) | 0.2418 (4) | 0.0666 (19) | |
O5 | 0.4831 (6) | 0.1657 (8) | 0.3068 (3) | 0.0645 (17) | |
O11 | 0.2213 (4) | 0.2442 (4) | 0.1606 (2) | 0.0251 (8) | |
O12 | −0.0095 (5) | 0.3468 (5) | 0.1020 (3) | 0.0378 (10) | |
C12 | 0.0892 (5) | 0.2457 (5) | 0.1092 (3) | 0.0190 (10) | |
C11 | 0.0474 (5) | 0.1155 (5) | 0.0537 (3) | 0.0162 (9) | |
O21 | 0.3902 (4) | 0.1855 (4) | 0.0308 (2) | 0.0224 (8) | |
O22 | 0.2539 (4) | 0.2518 (4) | −0.0932 (2) | 0.0297 (9) | |
C22 | 0.2662 (5) | 0.1823 (5) | −0.0270 (3) | 0.0184 (9) | |
C21 | 0.1282 (5) | 0.0886 (5) | −0.0130 (3) | 0.0154 (9) | |
O31 | 0.3177 (4) | −0.0687 (4) | −0.1181 (2) | 0.0274 (8) | |
O32 | 0.0834 (5) | −0.0705 (5) | −0.2082 (2) | 0.0356 (10) | |
C32 | 0.1670 (5) | −0.0595 (5) | −0.1375 (3) | 0.0191 (9) | |
C31 | 0.0804 (5) | −0.0276 (5) | −0.0658 (3) | 0.0156 (9) | |
O1W | 0.1943 (11) | −0.3524 (13) | 0.0654 (7) | 0.037 (2) | 0.50 |
O2W | 0.291 (4) | −0.3798 (18) | 0.110 (2) | 0.193 (16) | 0.50 |
O3W | 0.671 (6) | −0.531 (4) | 0.0462 (10) | 0.433 (7) | 0.50 |
O4W | 0.5025 (13) | −0.4638 (13) | 0.0816 (10) | 0.073 (4) | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Er | 0.01265 (11) | 0.02931 (15) | 0.01631 (13) | −0.00125 (8) | 0.00263 (8) | 0.00118 (9) |
O1 | 0.030 (2) | 0.032 (2) | 0.032 (2) | −0.0035 (15) | 0.0102 (16) | −0.0039 (17) |
O2 | 0.0203 (17) | 0.043 (2) | 0.035 (2) | −0.0008 (16) | 0.0049 (15) | 0.0167 (19) |
O3 | 0.036 (2) | 0.040 (3) | 0.054 (3) | −0.0133 (19) | 0.011 (2) | −0.021 (2) |
O4 | 0.032 (3) | 0.086 (4) | 0.080 (4) | 0.008 (2) | 0.005 (3) | 0.055 (3) |
O5 | 0.045 (3) | 0.123 (5) | 0.025 (2) | −0.031 (3) | 0.004 (2) | −0.014 (3) |
O11 | 0.0181 (15) | 0.028 (2) | 0.0270 (19) | −0.0027 (13) | −0.0005 (13) | −0.0068 (15) |
O12 | 0.032 (2) | 0.031 (2) | 0.046 (3) | 0.0123 (18) | −0.0048 (17) | −0.014 (2) |
C12 | 0.0144 (19) | 0.025 (3) | 0.018 (2) | 0.0003 (17) | 0.0040 (16) | −0.0038 (19) |
C11 | 0.0125 (19) | 0.018 (2) | 0.017 (2) | 0.0003 (15) | 0.0015 (16) | −0.0038 (17) |
O21 | 0.0170 (15) | 0.030 (2) | 0.0179 (17) | −0.0084 (13) | −0.0020 (12) | 0.0014 (14) |
O22 | 0.0258 (17) | 0.038 (2) | 0.0238 (19) | −0.0056 (15) | −0.0008 (14) | 0.0102 (16) |
C22 | 0.016 (2) | 0.020 (2) | 0.020 (2) | −0.0028 (16) | 0.0034 (16) | 0.0003 (18) |
C21 | 0.0108 (18) | 0.017 (2) | 0.018 (2) | −0.0004 (15) | 0.0017 (15) | 0.0009 (17) |
O31 | 0.0155 (16) | 0.037 (2) | 0.031 (2) | 0.0004 (14) | 0.0077 (14) | −0.0023 (17) |
O32 | 0.028 (2) | 0.062 (3) | 0.0154 (19) | −0.0058 (18) | 0.0028 (15) | −0.0068 (18) |
C32 | 0.0147 (19) | 0.024 (3) | 0.020 (2) | −0.0027 (17) | 0.0075 (17) | −0.0023 (19) |
C31 | 0.0116 (18) | 0.022 (2) | 0.013 (2) | 0.0012 (16) | 0.0010 (15) | −0.0006 (18) |
O1W | 0.028 (4) | 0.046 (6) | 0.033 (5) | 0.003 (4) | −0.004 (3) | 0.005 (4) |
O2W | 0.31 (4) | 0.041 (9) | 0.31 (4) | 0.013 (16) | 0.27 (3) | 0.027 (16) |
O3W | 0.80 (3) | 0.422 (17) | 0.036 (9) | −0.566 | −0.05 (2) | 0.041 (17) |
O4W | 0.055 (7) | 0.050 (7) | 0.118 (12) | −0.006 (5) | 0.028 (7) | 0.029 (7) |
Er—O31i | 2.281 (3) | C11—C21 | 1.405 (6) |
Er—O5 | 2.341 (5) | O21—C22 | 1.277 (5) |
Er—O21 | 2.343 (3) | O22—C22 | 1.244 (6) |
Er—O11 | 2.350 (3) | C22—C21 | 1.504 (6) |
Er—O1 | 2.351 (4) | C21—C31 | 1.392 (6) |
Er—O3 | 2.358 (4) | O31—C32 | 1.259 (6) |
Er—O4 | 2.362 (5) | O31—Eri | 2.281 (3) |
Er—O2 | 2.391 (4) | O32—C32 | 1.243 (6) |
O11—C12 | 1.269 (5) | C32—C31 | 1.514 (6) |
O12—C12 | 1.246 (6) | C31—C11ii | 1.394 (6) |
C12—C11 | 1.510 (6) | O1W—O2W | 1.03 (4) |
C11—C31ii | 1.394 (6) | O3W—O4W | 1.74 (6) |
O31i—Er—O5 | 113.56 (16) | O1—Er—O2 | 75.27 (15) |
O31i—Er—O21 | 75.54 (13) | O3—Er—O2 | 137.06 (16) |
O5—Er—O21 | 141.9 (2) | O4—Er—O2 | 74.97 (16) |
O31i—Er—O11 | 142.76 (14) | C12—O11—Er | 130.3 (3) |
O5—Er—O11 | 80.61 (18) | O12—C12—O11 | 124.4 (5) |
O21—Er—O11 | 73.49 (13) | O12—C12—C11 | 117.6 (4) |
O31i—Er—O1 | 79.55 (14) | O11—C12—C11 | 118.0 (4) |
O5—Er—O1 | 142.7 (2) | C31ii—C11—C21 | 120.1 (4) |
O21—Er—O1 | 73.94 (14) | C31ii—C11—C12 | 119.0 (4) |
O11—Er—O1 | 110.62 (13) | C21—C11—C12 | 120.7 (4) |
O31i—Er—O3 | 75.44 (14) | C22—O21—Er | 133.8 (3) |
O5—Er—O3 | 71.2 (2) | O22—C22—O21 | 123.9 (4) |
O21—Er—O3 | 76.19 (15) | O22—C22—C21 | 118.9 (4) |
O11—Er—O3 | 77.50 (14) | O21—C22—C21 | 117.2 (4) |
O1—Er—O3 | 144.88 (15) | C31—C21—C11 | 119.2 (4) |
O31i—Er—O4 | 74.43 (17) | C31—C21—C22 | 119.9 (4) |
O5—Er—O4 | 75.5 (3) | C11—C21—C22 | 120.9 (4) |
O21—Er—O4 | 139.9 (2) | C32—O31—Eri | 145.6 (3) |
O11—Er—O4 | 142.33 (17) | O32—C32—O31 | 127.4 (5) |
O1—Er—O4 | 75.0 (2) | O32—C32—C31 | 117.3 (4) |
O3—Er—O4 | 120.19 (19) | O31—C32—C31 | 115.3 (4) |
O31i—Er—O2 | 144.37 (14) | C21—C31—C11ii | 120.6 (4) |
O5—Er—O2 | 75.40 (17) | C21—C31—C32 | 120.1 (4) |
O21—Er—O2 | 119.80 (12) | C11ii—C31—C32 | 119.3 (4) |
O11—Er—O2 | 71.02 (13) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Er2(C12O12)(H2O)10]·4H2O |
Mr | 922.86 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 8.4499 (1), 9.2595 (2), 16.2911 (4) |
β (°) | 100.3390 (8) |
V (Å3) | 1253.95 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 6.76 |
Crystal size (mm) | 0.31 × 0.09 × 0.06 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Analytical (Alcock, 1970) |
Tmin, Tmax | 0.256, 0.646 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17561, 3648, 2884 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.093, 1.03 |
No. of reflections | 3648 |
No. of parameters | 199 |
H-atom treatment | H-atom parameters not defined |
Δρmax, Δρmin (e Å−3) | 2.48, −2.05 |
Computer programs: COLLECT (Nonius, 1997-2000), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandeburg, 2000), SHELXL97.
Er—O31i | 2.281 (3) | Er—O1 | 2.351 (4) |
Er—O5 | 2.341 (5) | Er—O3 | 2.358 (4) |
Er—O21 | 2.343 (3) | Er—O4 | 2.362 (5) |
Er—O11 | 2.350 (3) | Er—O2 | 2.391 (4) |
Symmetry code: (i) −x+1, −y, −z. |
Aromatic acids usually form rare earth salts which exhibit optical properties (strong fluorescent emission) and possess very important physical and biological properties. Mellitic acid (benzenehexacarboxylic acid) can lose from two to six H atoms, depending on the reaction conditions used, and this gives rise to a great diversity of salts. The mellitate anion is known to be a multidentate agent via its carboxylate O atoms to metal cations, such as main group metal ions (for example Ca or Al; Uchtman & Jandacek, 1980; Giacovazzo et al., 1973), transition metal ions (CuII, NiII, CoIII or YIII; Endres & Knieszner, 1984; Robl & Hentschel 1991, 1992) or rare earth ions (LaIII; Wu et al., 1996). In these materials, the dimensionality of the networks varies from three-dimensional in Al2[C6(CO2)6].16(H2O) to two-dimensional in the Cu compound, where layers are linked to each other by hydrogen bonds, and one-dimensional in Co or Ni compounds, where infinite chains are formed. We present here the crystal structure of the title compound, (I), an Er compound with mellitate. \sch
The title compound, (I), forms a one-dimensional polymer. As shown in Fig. 1, the chains are formed by the succession of one organic ligand and a pair of Er atoms along a. Each chain is separated from neighbouring chains by free water molecules (Fig. 2).
The Er atom in (I) is eight-coordinated, by three O atoms from two mellitate ions and by five water O atoms. The Er—O distances are quite homogeneous (Table 1) and the environment of the Er atom is a slightly distorted square antiprism (Fig. 3). The mellitate ion is located about an inversion centre and each ligand is bonded to four different Er atoms. The six carboxylate groups are each linked to an Er atom via one O atom, while the other O atom remains free. The carboxylate groups are highly twisted out of the plane of the benzene ring Is this added text OK? (twist angles lie in the range 50–70°). This twisting ability of a carboxylato group involved in a rare-earth-containing coordination polymer has already been reported in a terephthalate compound (Reineke et al., 1999) and in a benzenetetracarboxylate compound (Cao et al., 2002).
In addition to the five water molecules in the first coordination sphere of the Er atoms, two water molecules per Er atom were refined (Fig. 2). This is in accordance with the results of the thermogravimetric analysis. For the two sets of sites O1W—O4W and O2W—O3W, a disorder model (0.5:0.5) was introduced. These water molecules build a complex network of hydrogen bonding between themselves, the carboxylate O atoms and the water molecules of the first coordination sphere. These O atoms from the water molecules of crystallization exhibit high thermal displacement parameters. We attribute these high parameters to the existence of numerous hydrogen bonds of comparable importance.
It is interesting to note that the crystal structure of (I) differs from the La-containing structure already reported by Wu et al. (1993). The La-containing material was synthesized by hydrothermal methods, whereas both Y– and Er-containing compounds have been obtained by slow diffusion in gel media.