Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807018831/at2273sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807018831/at2273Isup2.hkl |
CCDC reference: 1124759
Crystals of the title compound (I) were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb, which was then sealed. Ammonium cerium(IV) nitrate (109.6 mg, 0.2 mmol), 4-phenylpyridine (94.2 mg, 0.6 mmol), and distilled water (5.5 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure for 7 d at 393 K and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colourless solution was decanted from small colorless crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature. Powder X-ray diffraction was conducted on the sample.
H atoms were positioned geometrically, with C—H = 0.93 Å for aromatic H and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
Molecular magnetic compounds, such as molecular ferro- and ferrimagnets, organic magnets, single-molecule magnets and high-spin molecules, have recently attracted attention (Miller & Drillon, 2001a,b, 2002). Owing to Lanthanide metals unique physical and chemical properties, Lanthanide complexes play an important role in special materials having optical, electronic, magnetic and biological importance (Benelli et al., 1992; Deborah et al., 2000; Farrugia et al., 2000). More importantly, since the removal of lanthanides from radioactive high level liquid waste (HLLW) has been shown to improve the transmutation of long-lived transuranic elements to shortlived or even stable nuclides (Modolo & Odoj, 1998), the coordination chemistry of the 4f metals continues to attract interest. We report herein the crystal structure of the title compound, (I).
In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). The irregular ten-coordinate environment of the Ce atom is completed by The two N atoms of 4-phenylpyridine ligands and eight O atoms of four NO3- (Table 1). The Ce—O bond lengths are in the range 2.466 (2) to 2.559 (3) Å. The Ce—N bond length is 2.623 (3) Å. The C—H···O hydrogen bonds link the mononuclear complex into a supramolecular network structure (Fig. 2).
For related literature, see: Allen et al. (1987); Benelli et al. (1992); Deborah et al. (2000); Farrugia et al. (2000); Miller & Drillon (2001a,b, 2002); Modolo & Odoj (1998).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL.
[Ce(NO3)4(C11H9N)2] | F(000) = 1384 |
Mr = 698.54 | Dx = 1.840 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 8223 reflections |
a = 20.136 (5) Å | θ = 2.5–29.5° |
b = 7.8079 (14) Å | µ = 1.88 mm−1 |
c = 18.310 (3) Å | T = 273 K |
β = 118.834 (2)° | Plane, colourless |
V = 2521.8 (9) Å3 | 0.40 × 0.33 × 0.21 mm |
Z = 4 |
Bruker APEXII area-detector diffracmeter diffractometer | 2399 independent reflections |
Radiation source: fine-focus sealed tube | 2357 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
φ and ω scans | θmax = 26.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −24→24 |
Tmin = 0.520, Tmax = 0.697 | k = −9→9 |
7911 measured reflections | l = −22→22 |
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)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0526P)2 + 2.9178P] where P = (Fo2 + 2Fc2)/3 |
2399 reflections | (Δ/σ)max < 0.001 |
186 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.56 e Å−3 |
[Ce(NO3)4(C11H9N)2] | V = 2521.8 (9) Å3 |
Mr = 698.54 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.136 (5) Å | µ = 1.88 mm−1 |
b = 7.8079 (14) Å | T = 273 K |
c = 18.310 (3) Å | 0.40 × 0.33 × 0.21 mm |
β = 118.834 (2)° |
Bruker APEXII area-detector diffracmeter diffractometer | 2399 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2357 reflections with I > 2σ(I) |
Tmin = 0.520, Tmax = 0.697 | Rint = 0.014 |
7911 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.47 e Å−3 |
2399 reflections | Δρmin = −0.56 e Å−3 |
186 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 | ||
Ce1 | 1.0000 | 0.33853 (2) | 0.7500 | 0.03059 (10) | |
O1 | 1.09210 (13) | 0.4420 (3) | 0.89004 (15) | 0.0554 (6) | |
O2 | 1.0830 (2) | 0.4125 (4) | 1.00259 (16) | 0.0799 (9) | |
O3 | 0.99757 (16) | 0.3044 (3) | 0.88530 (17) | 0.0565 (6) | |
O4 | 0.92865 (16) | 0.0722 (3) | 0.66855 (18) | 0.0644 (7) | |
O5 | 0.81814 (17) | −0.0034 (4) | 0.65278 (19) | 0.0721 (8) | |
O6 | 0.87792 (15) | 0.2150 (3) | 0.72861 (17) | 0.0554 (6) | |
N1 | 1.05815 (18) | 0.3856 (4) | 0.92892 (18) | 0.0502 (6) | |
N2 | 0.87318 (16) | 0.0900 (3) | 0.68174 (17) | 0.0476 (6) | |
N3 | 0.93564 (16) | 0.6015 (4) | 0.77990 (17) | 0.0469 (6) | |
C1 | 0.9748 (2) | 0.7369 (4) | 0.8260 (2) | 0.0483 (7) | |
H1 | 1.0240 | 0.7527 | 0.8352 | 0.058* | |
C2 | 0.9466 (2) | 0.8531 (4) | 0.8603 (2) | 0.0464 (8) | |
H2 | 0.9759 | 0.9459 | 0.8906 | 0.056* | |
C3 | 0.8644 (2) | 0.5862 (5) | 0.7672 (2) | 0.0519 (8) | |
H3 | 0.8352 | 0.4965 | 0.7338 | 0.062* | |
C4 | 0.8318 (2) | 0.6940 (4) | 0.8001 (2) | 0.0487 (7) | |
H4 | 0.7823 | 0.6759 | 0.7897 | 0.058* | |
C5 | 0.8740 (2) | 0.8310 (3) | 0.8495 (2) | 0.0413 (7) | |
C6 | 0.84234 (18) | 0.9443 (4) | 0.89047 (18) | 0.0417 (6) | |
C7 | 0.7944 (2) | 0.8786 (5) | 0.9183 (2) | 0.0468 (7) | |
H7 | 0.7818 | 0.7630 | 0.9119 | 0.056* | |
C8 | 0.7659 (2) | 0.9873 (5) | 0.9556 (2) | 0.0524 (8) | |
H8 | 0.7341 | 0.9430 | 0.9746 | 0.063* | |
C9 | 0.7821 (2) | 1.1523 (4) | 0.9654 (2) | 0.0432 (7) | |
H9 | 0.7614 | 1.2225 | 0.9903 | 0.052* | |
C10 | 0.8275 (3) | 1.2170 (5) | 0.9399 (3) | 0.0652 (10) | |
H10 | 0.8382 | 1.3336 | 0.9469 | 0.078* | |
C11 | 0.8601 (2) | 1.1179 (5) | 0.9030 (3) | 0.0584 (9) | |
H11 | 0.8932 | 1.1663 | 0.8869 | 0.070* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ce1 | 0.03366 (14) | 0.02779 (14) | 0.03943 (14) | 0.000 | 0.02487 (11) | 0.000 |
O1 | 0.0484 (13) | 0.0571 (14) | 0.0632 (14) | −0.0087 (11) | 0.0289 (11) | 0.0003 (11) |
O2 | 0.106 (2) | 0.077 (2) | 0.0445 (14) | −0.0077 (18) | 0.0270 (14) | −0.0024 (13) |
O3 | 0.0604 (16) | 0.0609 (13) | 0.0585 (14) | −0.0146 (12) | 0.0369 (13) | −0.0036 (12) |
O4 | 0.0678 (16) | 0.0518 (14) | 0.0884 (18) | −0.0028 (12) | 0.0495 (15) | −0.0157 (13) |
O5 | 0.0679 (17) | 0.0646 (17) | 0.0759 (17) | −0.0294 (14) | 0.0283 (14) | −0.0158 (13) |
O6 | 0.0596 (15) | 0.0489 (13) | 0.0705 (15) | −0.0100 (11) | 0.0416 (13) | −0.0151 (12) |
N1 | 0.0571 (17) | 0.0455 (14) | 0.0483 (15) | 0.0011 (13) | 0.0258 (13) | 0.0023 (12) |
N2 | 0.0519 (15) | 0.0403 (14) | 0.0519 (14) | −0.0053 (12) | 0.0259 (12) | −0.0023 (12) |
N3 | 0.0549 (16) | 0.0443 (14) | 0.0548 (15) | 0.0022 (12) | 0.0370 (13) | −0.0024 (12) |
C1 | 0.0545 (19) | 0.0411 (16) | 0.0655 (19) | −0.0035 (14) | 0.0418 (16) | −0.0038 (14) |
C2 | 0.053 (2) | 0.0409 (16) | 0.0591 (19) | −0.0054 (12) | 0.0376 (17) | −0.0061 (12) |
C3 | 0.0501 (18) | 0.0512 (19) | 0.0571 (18) | −0.0017 (14) | 0.0279 (15) | −0.0135 (15) |
C4 | 0.0438 (17) | 0.0520 (17) | 0.0537 (18) | 0.0007 (14) | 0.0262 (15) | −0.0096 (15) |
C5 | 0.0460 (18) | 0.0403 (17) | 0.0459 (16) | 0.0036 (11) | 0.0288 (14) | 0.0013 (11) |
C6 | 0.0442 (15) | 0.0415 (15) | 0.0450 (14) | 0.0024 (12) | 0.0259 (12) | −0.0011 (12) |
C7 | 0.0472 (17) | 0.0460 (15) | 0.0560 (18) | −0.0019 (14) | 0.0318 (15) | −0.0066 (14) |
C8 | 0.0498 (17) | 0.061 (2) | 0.0587 (18) | 0.0003 (15) | 0.0363 (15) | −0.0027 (15) |
C9 | 0.0468 (18) | 0.0441 (18) | 0.0518 (17) | 0.0054 (11) | 0.0342 (15) | −0.0109 (12) |
C10 | 0.085 (3) | 0.0458 (18) | 0.091 (3) | −0.0031 (19) | 0.063 (2) | −0.0130 (19) |
C11 | 0.076 (3) | 0.0427 (16) | 0.085 (3) | −0.0056 (17) | 0.062 (2) | −0.0095 (17) |
Ce1—O1 | 2.466 (2) | C1—C2 | 1.373 (4) |
Ce1—O3 | 2.515 (3) | C1—H1 | 0.9300 |
Ce1—O4 | 2.559 (3) | C2—C5 | 1.387 (5) |
Ce1—O6 | 2.490 (3) | C2—H2 | 0.9300 |
Ce1—N3 | 2.623 (3) | C3—C4 | 1.373 (5) |
Ce1—O1i | 2.466 (2) | C3—H3 | 0.9300 |
Ce1—O6i | 2.490 (3) | C4—C5 | 1.394 (5) |
Ce1—O3i | 2.515 (3) | C4—H4 | 0.9300 |
Ce1—O4i | 2.559 (3) | C5—C6 | 1.488 (4) |
Ce1—N3i | 2.623 (3) | C6—C7 | 1.389 (5) |
Ce1—N1i | 2.922 (3) | C6—C11 | 1.393 (5) |
Ce1—N2i | 2.962 (3) | C7—C8 | 1.376 (5) |
O1—N1 | 1.279 (4) | C7—H7 | 0.9300 |
O2—N1 | 1.210 (4) | C8—C9 | 1.319 (5) |
O3—N1 | 1.260 (4) | C8—H8 | 0.9300 |
O4—N2 | 1.259 (4) | C9—C10 | 1.312 (5) |
O5—N2 | 1.214 (4) | C9—H9 | 0.9300 |
O6—N2 | 1.273 (4) | C10—C11 | 1.383 (5) |
N3—C3 | 1.343 (4) | C10—H10 | 0.9300 |
N3—C1 | 1.346 (5) | C11—H11 | 0.9300 |
O1—Ce1—O3 | 51.14 (8) | O1—Ce1—N2i | 73.31 (8) |
O1—Ce1—O4 | 143.29 (9) | O6—Ce1—N2i | 113.43 (9) |
O1—Ce1—O6 | 118.74 (8) | O6i—Ce1—N2i | 25.14 (8) |
O3—Ce1—O4 | 102.46 (9) | O3i—Ce1—N2i | 85.63 (8) |
O3—Ce1—O6 | 68.11 (9) | O3—Ce1—N2i | 86.41 (9) |
O4—Ce1—O6 | 50.15 (8) | O4i—Ce1—N2i | 25.04 (8) |
O1—Ce1—N3 | 74.10 (9) | O4—Ce1—N2i | 80.84 (9) |
O3—Ce1—N3 | 68.35 (9) | N3i—Ce1—N2i | 100.88 (9) |
O4—Ce1—N3 | 124.25 (9) | N3—Ce1—N2i | 146.85 (8) |
O6—Ce1—N3 | 77.66 (9) | N1i—Ce1—N2i | 110.69 (8) |
O1i—Ce1—O1 | 141.76 (12) | N1—O1—Ce1 | 97.48 (19) |
O1i—Ce1—O6 | 76.88 (9) | N1—O3—Ce1 | 95.63 (19) |
O1i—Ce1—O6i | 118.74 (8) | N2—O4—Ce1 | 95.69 (18) |
O1—Ce1—O6i | 76.88 (9) | N2—O6—Ce1 | 98.66 (18) |
O6—Ce1—O6i | 134.41 (13) | O2—N1—O3 | 123.2 (3) |
O1i—Ce1—O3i | 51.14 (8) | O2—N1—O1 | 121.1 (3) |
O1—Ce1—O3i | 134.17 (9) | O3—N1—O1 | 115.7 (3) |
O6—Ce1—O3i | 106.90 (9) | O5—N2—O4 | 123.9 (3) |
O6i—Ce1—O3i | 68.11 (9) | O5—N2—O6 | 120.7 (3) |
O1i—Ce1—O3 | 134.17 (9) | O4—N2—O6 | 115.4 (3) |
O6i—Ce1—O3 | 106.90 (9) | C3—N3—C1 | 115.6 (3) |
O3i—Ce1—O3 | 167.84 (12) | C3—N3—Ce1 | 119.2 (2) |
O1i—Ce1—O4i | 143.29 (9) | C1—N3—Ce1 | 123.2 (2) |
O1—Ce1—O4i | 74.39 (9) | N3—C1—C2 | 124.0 (3) |
O6—Ce1—O4i | 90.63 (9) | N3—C1—H1 | 118.0 |
O6i—Ce1—O4i | 50.15 (8) | C2—C1—H1 | 118.0 |
O3i—Ce1—O4i | 102.46 (9) | C1—C2—C5 | 119.5 (3) |
O3—Ce1—O4i | 67.17 (9) | C1—C2—H2 | 120.3 |
O1i—Ce1—O4 | 74.38 (9) | C5—C2—H2 | 120.3 |
O6i—Ce1—O4 | 90.63 (9) | N3—C3—C4 | 124.5 (3) |
O3i—Ce1—O4 | 67.17 (9) | N3—C3—H3 | 117.7 |
O4i—Ce1—O4 | 71.26 (14) | C4—C3—H3 | 117.7 |
O1i—Ce1—N3i | 74.10 (9) | C3—C4—C5 | 118.9 (3) |
O1—Ce1—N3i | 76.18 (8) | C3—C4—H4 | 120.5 |
O6—Ce1—N3i | 145.11 (9) | C5—C4—H4 | 120.5 |
O6i—Ce1—N3i | 77.66 (9) | C2—C5—C4 | 117.3 (3) |
O3i—Ce1—N3i | 68.35 (9) | C2—C5—C6 | 122.2 (3) |
O3—Ce1—N3i | 122.33 (8) | C4—C5—C6 | 120.5 (3) |
O4i—Ce1—N3i | 124.26 (9) | C7—C6—C11 | 117.9 (3) |
O4—Ce1—N3i | 135.21 (9) | C7—C6—C5 | 120.6 (3) |
O1i—Ce1—N3 | 76.18 (8) | C11—C6—C5 | 121.5 (3) |
O6i—Ce1—N3 | 145.11 (9) | C8—C7—C6 | 119.0 (3) |
O3i—Ce1—N3 | 122.33 (8) | C8—C7—H7 | 120.5 |
O4i—Ce1—N3 | 135.21 (9) | C6—C7—H7 | 120.5 |
N3i—Ce1—N3 | 76.97 (12) | C9—C8—C7 | 122.3 (3) |
O1i—Ce1—N1i | 25.73 (8) | C9—C8—H8 | 118.9 |
O1—Ce1—N1i | 144.93 (8) | C7—C8—H8 | 118.9 |
O6—Ce1—N1i | 92.35 (9) | C10—C9—C8 | 119.8 (3) |
O6i—Ce1—N1i | 93.24 (9) | C10—C9—H9 | 120.1 |
O3i—Ce1—N1i | 25.42 (9) | C8—C9—H9 | 120.1 |
O3—Ce1—N1i | 158.41 (9) | C9—C10—C11 | 122.3 (4) |
O4i—Ce1—N1i | 124.37 (9) | C9—C10—H10 | 118.8 |
O4—Ce1—N1i | 68.90 (9) | C11—C10—H10 | 118.8 |
N3i—Ce1—N1i | 68.82 (9) | C10—C11—C6 | 118.7 (3) |
N3—Ce1—N1i | 99.46 (9) | C10—C11—H11 | 120.6 |
O1i—Ce1—N2i | 135.76 (8) | C6—C11—H11 | 120.6 |
Symmetry code: (i) −x+2, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1 | 0.93 | 2.73 | 3.096 (4) | 105 |
C3—H3···O6 | 0.93 | 2.38 | 3.027 (4) | 127 |
Experimental details
Crystal data | |
Chemical formula | [Ce(NO3)4(C11H9N)2] |
Mr | 698.54 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 273 |
a, b, c (Å) | 20.136 (5), 7.8079 (14), 18.310 (3) |
β (°) | 118.834 (2) |
V (Å3) | 2521.8 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.88 |
Crystal size (mm) | 0.40 × 0.33 × 0.21 |
Data collection | |
Diffractometer | Bruker APEXII area-detector diffracmeter |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.520, 0.697 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7911, 2399, 2357 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.073, 1.09 |
No. of reflections | 2399 |
No. of parameters | 186 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.56 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996), SHELXTL.
Ce1—O1 | 2.466 (2) | Ce1—O6 | 2.490 (3) |
Ce1—O3 | 2.515 (3) | Ce1—N3 | 2.623 (3) |
Ce1—O4 | 2.559 (3) | ||
O1—Ce1—O3 | 51.14 (8) | O4—Ce1—O6 | 50.15 (8) |
O1—Ce1—O4 | 143.29 (9) | O1—Ce1—N3 | 74.10 (9) |
O1—Ce1—O6 | 118.74 (8) | O3—Ce1—N3 | 68.35 (9) |
O3—Ce1—O4 | 102.46 (9) | O4—Ce1—N3 | 124.25 (9) |
O3—Ce1—O6 | 68.11 (9) | O6—Ce1—N3 | 77.66 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1 | 0.93 | 2.73 | 3.096 (4) | 105 |
C3—H3···O6 | 0.93 | 2.38 | 3.027 (4) | 127 |
Molecular magnetic compounds, such as molecular ferro- and ferrimagnets, organic magnets, single-molecule magnets and high-spin molecules, have recently attracted attention (Miller & Drillon, 2001a,b, 2002). Owing to Lanthanide metals unique physical and chemical properties, Lanthanide complexes play an important role in special materials having optical, electronic, magnetic and biological importance (Benelli et al., 1992; Deborah et al., 2000; Farrugia et al., 2000). More importantly, since the removal of lanthanides from radioactive high level liquid waste (HLLW) has been shown to improve the transmutation of long-lived transuranic elements to shortlived or even stable nuclides (Modolo & Odoj, 1998), the coordination chemistry of the 4f metals continues to attract interest. We report herein the crystal structure of the title compound, (I).
In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). The irregular ten-coordinate environment of the Ce atom is completed by The two N atoms of 4-phenylpyridine ligands and eight O atoms of four NO3- (Table 1). The Ce—O bond lengths are in the range 2.466 (2) to 2.559 (3) Å. The Ce—N bond length is 2.623 (3) Å. The C—H···O hydrogen bonds link the mononuclear complex into a supramolecular network structure (Fig. 2).