Acta Cryst. (2008). E64, m1326 [ doi:10.1107/S160053680803033X ]
![[mu]](/logos/entities/mu_rmgif.gif)
3-5-aminoisophthalato)diaquadicerium(III)]In the title complex, [Ce2(C8H5NO4)3(H2O)2]n, each Ce ion is in nine-coordinated environment. Eight O atoms from six ligands participate in coordination, in addition to one O atom from a water molecule. Both carboxylate groups from the ligands chelate the Ce atoms, forming two four-membered rings. The 5-aminoisophthalate ligands also bridge the Ce centers, forming a two-dimensional network, and O-H
O and N-HO hydrogen bonds complete the structure.
5-aminoisophthalic acid (0.3 mmol, 54.6 mg) and sodium hydroxide (0.3 mmol,12.5 mg) dissolved in 20 ml water, heated to boiled and then stop heating. Cerous nitrate hexahydrate (0.3 mmol,130.3 mg) dissolved in 5 ml water was mixed with the above solution, stirring for half an hour. Then transfer them into a 50 ml teflon reactor, under autogenous pressure at 160°C for 3 days and then cooled to room temperature, after which large brown block-shaped crystals of the title complex suitable for X-ray diffraction analysis were obtained.
All H-atoms were positioned geometrically and refined using a riding model, with C—H 0.93 (aromatic) 0.93, N—H 0.86 (amino), O—H 0.85 Å (water), withUiso(H) =1.2Ueq(C).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bq2095fig1thm.gif)
| Fig. 1. The structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme. |
| [Ce2(C8H5NO4)3(H2O)2] | F(000) = 1648 |
| Mr = 853.66 | Dx = 2.240 Mg m−3 |
| Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71069 Å |
| Hall symbol: -P 2n 2ab | Cell parameters from 3043 reflections |
| a = 12.2360 (7) Å | θ = 2.3–28.4° |
| b = 8.0600 (5) Å | µ = 3.63 mm−1 |
| c = 25.6700 (15) Å | T = 298 K |
| V = 2531.6 (3) Å3 | Block, brown |
| Z = 4 | 0.21 × 0.20 × 0.19 mm |
| Siemens SMART CCD area-detector diffractometer | 2233 independent reflections |
| Radiation source: fine-focus sealed tube | 2001 reflections with I > 2σ(I) |
| graphite | Rint = 0.034 |
| φ and ω scans | θmax = 25.0°, θmin = 2.3° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −14→13 |
| Tmin = 0.516, Tmax = 0.545 | k = −9→9 |
| 11818 measured reflections | l = −30→23 |
| 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)] = 0.019 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.045 | H-atom parameters constrained |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0208P)2 + 2.5416P] where P = (Fo2 + 2Fc2)/3 |
| 2233 reflections | (Δ/σ)max = 0.001 |
| 196 parameters | Δρmax = 0.45 e Å−3 |
| 2 restraints | Δρmin = −0.64 e Å−3 |
| [Ce2(C8H5NO4)3(H2O)2] | V = 2531.6 (3) Å3 |
| Mr = 853.66 | Z = 4 |
| Orthorhombic, Pbcn | Mo Kα radiation |
| a = 12.2360 (7) Å | µ = 3.63 mm−1 |
| b = 8.0600 (5) Å | T = 298 K |
| c = 25.6700 (15) Å | 0.21 × 0.20 × 0.19 mm |
| Siemens SMART CCD area-detector diffractometer | 2233 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2001 reflections with I > 2σ(I) |
| Tmin = 0.516, Tmax = 0.545 | Rint = 0.034 |
| 11818 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.019 | H-atom parameters constrained |
| wR(F2) = 0.045 | Δρmax = 0.45 e Å−3 |
| S = 1.04 | Δρmin = −0.64 e Å−3 |
| 2233 reflections | Absolute structure: ? |
| 196 parameters | Flack parameter: ? |
| 2 restraints | Rogers parameter: ? |
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 | ||
| Ce1 | 0.694451 (12) | 0.038178 (18) | 0.094984 (6) | 0.01318 (7) | |
| H1A | 0.4903 | −0.1228 | 0.0487 | 0.016* | |
| H1B | 0.4671 | −0.1140 | 0.0998 | 0.016* | |
| N1 | 0.1463 (2) | 0.4699 (3) | 0.15158 (11) | 0.0302 (7) | |
| H1C | 0.1531 | 0.4128 | 0.1797 | 0.036* | |
| H1D | 0.1042 | 0.5534 | 0.1571 | 0.036* | |
| N2 | 0.5000 | −0.7310 (4) | 0.2500 | 0.0418 (11) | |
| H2A | 0.5462 | −0.7843 | 0.2311 | 0.050* | |
| O1 | 0.53914 (15) | 0.2297 (2) | 0.12641 (8) | 0.0227 (5) | |
| O2 | 0.62001 (17) | 0.4491 (3) | 0.09148 (8) | 0.0250 (5) | |
| O3 | 0.38087 (15) | 0.8402 (2) | −0.01169 (8) | 0.0220 (5) | |
| O4 | 0.77549 (15) | 0.2778 (2) | 0.03332 (8) | 0.0204 (4) | |
| O5 | 0.63242 (18) | −0.0423 (2) | 0.18383 (9) | 0.0282 (5) | |
| O6 | 0.70692 (16) | −0.2648 (2) | 0.15024 (8) | 0.0232 (5) | |
| O1W | 0.51934 (16) | −0.1043 (3) | 0.07824 (9) | 0.0280 (5) | |
| C1 | 0.4286 (2) | 0.4564 (3) | 0.09890 (11) | 0.0159 (6) | |
| C2 | 0.4177 (2) | 0.5614 (3) | 0.05642 (12) | 0.0177 (6) | |
| H2 | 0.4786 | 0.5885 | 0.0365 | 0.021* | |
| C3 | 0.3163 (2) | 0.6262 (3) | 0.04351 (11) | 0.0174 (6) | |
| C4 | 0.2262 (2) | 0.5922 (4) | 0.07468 (12) | 0.0179 (6) | |
| H4 | 0.1576 | 0.6316 | 0.0652 | 0.021* | |
| C5 | 0.2384 (2) | 0.4998 (3) | 0.11991 (12) | 0.0189 (6) | |
| C6 | 0.3393 (2) | 0.4281 (3) | 0.13138 (12) | 0.0182 (6) | |
| H6 | 0.3469 | 0.3613 | 0.1607 | 0.022* | |
| C7 | 0.5365 (2) | 0.3728 (3) | 0.10682 (11) | 0.0164 (6) | |
| C8 | 0.3065 (2) | 0.7357 (3) | −0.00284 (12) | 0.0173 (6) | |
| C9 | 0.5727 (2) | −0.2982 (3) | 0.21853 (11) | 0.0171 (6) | |
| C10 | 0.5748 (2) | −0.4714 (3) | 0.21935 (12) | 0.0205 (6) | |
| H10 | 0.6261 | −0.5283 | 0.1995 | 0.025* | |
| C11 | 0.5000 | −0.5599 (5) | 0.2500 | 0.0212 (9) | |
| C12 | 0.5000 | −0.2132 (5) | 0.2500 | 0.0176 (9) | |
| H12 | 0.5000 | −0.0978 | 0.2500 | 0.021* | |
| C13 | 0.6425 (2) | −0.1977 (3) | 0.18270 (11) | 0.0165 (6) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ce1 | 0.01069 (10) | 0.01242 (10) | 0.01642 (12) | −0.00009 (6) | −0.00036 (6) | 0.00135 (6) |
| N1 | 0.0194 (14) | 0.0396 (16) | 0.0314 (18) | 0.0059 (12) | 0.0102 (12) | 0.0138 (13) |
| N2 | 0.070 (3) | 0.0152 (19) | 0.040 (3) | 0.000 | 0.030 (2) | 0.000 |
| O1 | 0.0200 (10) | 0.0169 (10) | 0.0311 (13) | 0.0053 (8) | 0.0002 (9) | 0.0026 (9) |
| O2 | 0.0132 (11) | 0.0306 (12) | 0.0314 (14) | −0.0012 (9) | 0.0007 (9) | 0.0030 (10) |
| O3 | 0.0243 (11) | 0.0195 (11) | 0.0224 (12) | −0.0062 (9) | −0.0041 (9) | 0.0065 (9) |
| O4 | 0.0179 (10) | 0.0227 (11) | 0.0205 (11) | −0.0003 (8) | −0.0036 (9) | 0.0016 (9) |
| O5 | 0.0395 (13) | 0.0170 (11) | 0.0280 (13) | 0.0005 (9) | 0.0133 (11) | 0.0036 (9) |
| O6 | 0.0235 (11) | 0.0225 (9) | 0.0236 (12) | 0.0025 (9) | 0.0101 (9) | 0.0048 (8) |
| O1W | 0.0187 (11) | 0.0323 (12) | 0.0329 (13) | −0.0066 (10) | 0.0010 (10) | −0.0076 (11) |
| C1 | 0.0136 (14) | 0.0137 (14) | 0.0204 (16) | −0.0002 (11) | −0.0011 (11) | −0.0010 (12) |
| C2 | 0.0151 (14) | 0.0154 (14) | 0.0226 (16) | −0.0004 (11) | 0.0026 (13) | −0.0014 (12) |
| C3 | 0.0194 (15) | 0.0126 (14) | 0.0201 (16) | −0.0010 (11) | −0.0020 (12) | −0.0016 (12) |
| C4 | 0.0135 (13) | 0.0178 (14) | 0.0223 (16) | 0.0017 (12) | −0.0013 (12) | −0.0024 (13) |
| C5 | 0.0140 (14) | 0.0195 (14) | 0.0233 (17) | 0.0003 (12) | 0.0011 (13) | 0.0001 (13) |
| C6 | 0.0155 (14) | 0.0168 (14) | 0.0225 (17) | 0.0002 (11) | −0.0007 (13) | 0.0032 (12) |
| C7 | 0.0132 (14) | 0.0191 (15) | 0.0168 (15) | −0.0005 (12) | −0.0013 (12) | −0.0024 (13) |
| C8 | 0.0186 (14) | 0.0156 (14) | 0.0176 (16) | 0.0047 (12) | −0.0009 (12) | −0.0033 (12) |
| C9 | 0.0185 (14) | 0.0173 (14) | 0.0155 (15) | −0.0003 (11) | 0.0017 (12) | 0.0005 (12) |
| C10 | 0.0255 (16) | 0.0184 (14) | 0.0176 (16) | 0.0040 (12) | 0.0050 (14) | −0.0020 (13) |
| C11 | 0.032 (2) | 0.015 (2) | 0.016 (2) | 0.000 | 0.0031 (19) | 0.000 |
| C12 | 0.021 (2) | 0.016 (2) | 0.016 (2) | 0.000 | 0.0012 (17) | 0.000 |
| C13 | 0.0162 (14) | 0.0189 (14) | 0.0144 (15) | −0.0002 (12) | 0.0001 (12) | −0.0004 (12) |
| Ce1—O2i | 2.383 (2) | O6—Ce1i | 2.448 (2) |
| Ce1—O6ii | 2.448 (2) | O1W—H1A | 0.8500 |
| Ce1—O1W | 2.469 (2) | O1W—H1B | 0.8500 |
| Ce1—O5 | 2.490 (2) | C1—C2 | 1.387 (4) |
| Ce1—O3iii | 2.5263 (19) | C1—C6 | 1.393 (4) |
| Ce1—O1 | 2.5779 (19) | C1—C7 | 1.496 (4) |
| Ce1—O4i | 2.654 (2) | C2—C3 | 1.387 (4) |
| Ce1—O4 | 2.6870 (19) | C2—H2 | 0.9300 |
| Ce1—O6 | 2.828 (2) | C3—C4 | 1.389 (4) |
| Ce1—C8iii | 2.986 (3) | C3—C8 | 1.486 (4) |
| N1—C5 | 1.410 (4) | C4—C5 | 1.387 (4) |
| N1—H1C | 0.8600 | C4—H4 | 0.9300 |
| N1—H1D | 0.8599 | C5—C6 | 1.395 (4) |
| N2—C11 | 1.379 (5) | C6—H6 | 0.9300 |
| N2—H2A | 0.8600 | C8—O4iii | 1.276 (3) |
| O1—C7 | 1.258 (3) | C8—Ce1iii | 2.986 (3) |
| O2—C7 | 1.256 (3) | C9—C12 | 1.384 (3) |
| O2—Ce1ii | 2.383 (2) | C9—C10 | 1.396 (4) |
| O3—C8 | 1.261 (3) | C9—C13 | 1.494 (4) |
| O3—Ce1iii | 2.5263 (19) | C10—C11 | 1.402 (3) |
| O4—C8iii | 1.276 (3) | C10—H10 | 0.9300 |
| O4—Ce1ii | 2.654 (2) | C11—C10iv | 1.402 (3) |
| O5—C13 | 1.259 (3) | C12—C9iv | 1.384 (3) |
| O6—C13 | 1.268 (3) | C12—H12 | 0.9300 |
| O2i—Ce1—O6ii | 75.39 (7) | C8iii—O4—Ce1ii | 122.81 (17) |
| O2i—Ce1—O1W | 132.85 (7) | C8iii—O4—Ce1 | 90.56 (16) |
| O6ii—Ce1—O1W | 146.17 (7) | Ce1ii—O4—Ce1 | 105.55 (7) |
| O2i—Ce1—O5 | 104.28 (7) | C13—O5—Ce1 | 102.02 (18) |
| O6ii—Ce1—O5 | 77.79 (7) | C13—O6—Ce1i | 164.58 (18) |
| O1W—Ce1—O5 | 76.92 (7) | C13—O6—Ce1 | 85.86 (16) |
| O2i—Ce1—O3iii | 115.63 (7) | Ce1i—O6—Ce1 | 107.23 (7) |
| O6ii—Ce1—O3iii | 114.74 (6) | Ce1—O1W—H1A | 126.9 |
| O1W—Ce1—O3iii | 73.53 (7) | Ce1—O1W—H1B | 125.6 |
| O5—Ce1—O3iii | 139.93 (7) | H1A—O1W—H1B | 104.5 |
| O2i—Ce1—O1 | 153.47 (7) | C2—C1—C6 | 119.7 (3) |
| O6ii—Ce1—O1 | 78.08 (6) | C2—C1—C7 | 117.8 (3) |
| O1W—Ce1—O1 | 72.14 (7) | C6—C1—C7 | 122.5 (2) |
| O5—Ce1—O1 | 69.18 (7) | C3—C2—C1 | 120.2 (3) |
| O3iii—Ce1—O1 | 76.33 (7) | C3—C2—H2 | 119.9 |
| O2i—Ce1—O4i | 66.87 (7) | C1—C2—H2 | 119.9 |
| O6ii—Ce1—O4i | 142.22 (6) | C2—C3—C4 | 119.9 (3) |
| O1W—Ce1—O4i | 69.43 (6) | C2—C3—C8 | 119.1 (2) |
| O5—Ce1—O4i | 112.50 (6) | C4—C3—C8 | 121.0 (2) |
| O3iii—Ce1—O4i | 81.52 (6) | C5—C4—C3 | 120.2 (3) |
| O1—Ce1—O4i | 139.66 (6) | C5—C4—H4 | 119.9 |
| O2i—Ce1—O4 | 80.95 (6) | C3—C4—H4 | 119.9 |
| O6ii—Ce1—O4 | 72.12 (7) | C4—C5—C6 | 119.6 (3) |
| O1W—Ce1—O4 | 123.51 (7) | C4—C5—N1 | 119.3 (3) |
| O5—Ce1—O4 | 147.09 (6) | C6—C5—N1 | 121.0 (3) |
| O3iii—Ce1—O4 | 49.99 (6) | C1—C6—C5 | 120.0 (3) |
| O1—Ce1—O4 | 91.49 (6) | C1—C6—H6 | 120.0 |
| O4i—Ce1—O4 | 99.54 (6) | C5—C6—H6 | 120.0 |
| O2i—Ce1—O6 | 72.98 (6) | O2—C7—O1 | 123.6 (3) |
| O6ii—Ce1—O6 | 104.06 (7) | O2—C7—C1 | 117.1 (2) |
| O1W—Ce1—O6 | 74.48 (7) | O1—C7—C1 | 119.3 (2) |
| O5—Ce1—O6 | 48.09 (6) | O3—C8—O4iii | 120.9 (3) |
| O3iii—Ce1—O6 | 141.19 (6) | O3—C8—C3 | 118.9 (2) |
| O1—Ce1—O6 | 113.57 (6) | O4iii—C8—C3 | 120.2 (2) |
| O4i—Ce1—O6 | 66.99 (6) | O3—C8—Ce1iii | 56.79 (15) |
| O4—Ce1—O6 | 153.67 (5) | O4iii—C8—Ce1iii | 64.13 (15) |
| O2i—Ce1—C8iii | 99.07 (7) | C3—C8—Ce1iii | 175.47 (19) |
| O6ii—Ce1—C8iii | 93.72 (7) | C12—C9—C10 | 119.9 (3) |
| O1W—Ce1—C8iii | 98.21 (7) | C12—C9—C13 | 117.3 (3) |
| O5—Ce1—C8iii | 152.07 (7) | C10—C9—C13 | 122.8 (3) |
| O3iii—Ce1—C8iii | 24.68 (7) | C9—C10—C11 | 120.4 (3) |
| O1—Ce1—C8iii | 83.09 (7) | C9—C10—H10 | 119.8 |
| O4i—Ce1—C8iii | 90.61 (7) | C11—C10—H10 | 119.8 |
| O4—Ce1—C8iii | 25.31 (6) | N2—C11—C10iv | 120.60 (18) |
| O6—Ce1—C8iii | 157.60 (7) | N2—C11—C10 | 120.60 (18) |
| C5—N1—H1C | 119.9 | C10iv—C11—C10 | 118.8 (4) |
| C5—N1—H1D | 116.1 | C9iv—C12—C9 | 120.6 (4) |
| H1C—N1—H1D | 109.7 | C9iv—C12—H12 | 119.7 |
| C11—N2—H2A | 120.0 | C9—C12—H12 | 119.7 |
| C7—O1—Ce1 | 116.27 (17) | O5—C13—O6 | 120.0 (3) |
| C7—O2—Ce1ii | 155.62 (19) | O5—C13—C9 | 118.0 (2) |
| C8—O3—Ce1iii | 98.53 (17) | O6—C13—C9 | 121.9 (2) |
| Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) −x+3/2, y+1/2, z; (iii) −x+1, −y+1, −z; (iv) −x+1, y, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O5v | 0.86 | 2.63 | 3.436 (3) | 157. |
| N1—H1D···O1vi | 0.86 | 2.39 | 3.154 (3) | 148. |
| O1W—H1A···O3v | 0.85 | 2.07 | 2.898 (3) | 165. |
| Symmetry codes: (v) x, y−1, z; (vi) −x+1/2, y+1/2, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O5i | 0.86 | 2.63 | 3.436 (3) | 157. |
| N1—H1D···O1ii | 0.86 | 2.39 | 3.154 (3) | 148. |
| O1W—H1A···O3i | 0.85 | 2.07 | 2.898 (3) | 165. |
| Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y+1/2, z. |
The authors acknowledge the financial support of the Shandong Province Science Foundation and the State Key Laboratory of Crystalline Materials, Shandong University, People's Republic of China.
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5-aminoisophthalic acid forms covalent bonds with metal ions, especially with transition metals through nitrogen atom of amino group as well as oxygen atoms of carboxylic groups (Wu et al., 2002a; Wu et al., 2002b; Liao et al., 2004) and with lanthanide ions as strong Pearsons acids through oxygen atoms of carboxylic groups (Rzaczynska et al., 1994). Carboxylic groups of acid have a great ability to form infinite connection with metal ions and remarkable versatility in adopting different modes of bonding-from unidendate, chelating and bridging, sometimes in more than one way in the same compound (Daiguebonne et al., 2000). In this paper, we present a title complex, (C24H19Ce2N3O14)n, (I), synthesized by a condensation reaction of 5-aminoisophthalic acid with cerous nitrate under the condition of high pressure.
The molecular structure of the title complex, (I), is shown in Fig.1. The ligands construct a floor-like layer by chelating and bridging metal ions. The carboxy groups link layers in η1,3 mode, thus resulting in one-dimension metal-channels along b-axis, and the water molecules coordinating with metal ions are pending in these channels.