Retracted: Tetra­kis(nitrato-κ²O,O′)bis­(4-phenyl­pyridine-κN)cerium(IV)

The Ce^IV atom in the title complex, [Ce(NO₃)₄(C₁₁H₉N)₂], is ten-coordinated by two N atoms of 4-phenyl­pyridine ligands and eight O atoms of four NO₃⁻ ligands. The Ce atom lies on a crystallographic twofold rotation axis. The Ce—O bond lengths are in the range 2.466 (2)–2.559 (3) Å. The Ce—N bond length is 2.623 (3) Å. C—H...O hydrogen bonds link the mononuclear complex into a supra­molecular network structure.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• R factor = 0.022
• wR factor = 0.072
• Data-to-parameter ratio = 12.9

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S1. Comment

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).

Related literature

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).

S2. Experimental

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.

S3. Refinement

H atoms were positioned geometrically, with C—H = 0.93 Å for aromatic H and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C).

Computing details

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.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Atoms labelled with the suffix A, B, C are generated by the symmetry operation (2 - x, y, 1 - z).
	Fig. 2. A packing diagram of (I).

Tetrakis(nitrato-κ²O,O')bis(4-phenylpyridine-κN)cerium(IV)

Crystal data

[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) Å^3	0.40 × 0.33 × 0.21 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.073	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0526P)^2 + 2.9178P] where P = (Fo^2 + 2Fc^2)/3
2399 reflections	(Δ/σ)max < 0.001
186 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.56 e Å^−3

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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—O1^i	2.466 (2)	C3—H3	0.9300
Ce1—O6^i	2.490 (3)	C4—C5	1.394 (5)
Ce1—O3^i	2.515 (3)	C4—H4	0.9300
Ce1—O4^i	2.559 (3)	C5—C6	1.488 (4)
Ce1—N3^i	2.623 (3)	C6—C7	1.389 (5)
Ce1—N1^i	2.922 (3)	C6—C11	1.393 (5)
Ce1—N2^i	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—N2^i	73.31 (8)
O1—Ce1—O4	143.29 (9)	O6—Ce1—N2^i	113.43 (9)
O1—Ce1—O6	118.74 (8)	O6^i—Ce1—N2^i	25.14 (8)
O3—Ce1—O4	102.46 (9)	O3^i—Ce1—N2^i	85.63 (8)
O3—Ce1—O6	68.11 (9)	O3—Ce1—N2^i	86.41 (9)
O4—Ce1—O6	50.15 (8)	O4^i—Ce1—N2^i	25.04 (8)
O1—Ce1—N3	74.10 (9)	O4—Ce1—N2^i	80.84 (9)
O3—Ce1—N3	68.35 (9)	N3^i—Ce1—N2^i	100.88 (9)
O4—Ce1—N3	124.25 (9)	N3—Ce1—N2^i	146.85 (8)
O6—Ce1—N3	77.66 (9)	N1^i—Ce1—N2^i	110.69 (8)
O1^i—Ce1—O1	141.76 (12)	N1—O1—Ce1	97.48 (19)
O1^i—Ce1—O6	76.88 (9)	N1—O3—Ce1	95.63 (19)
O1^i—Ce1—O6^i	118.74 (8)	N2—O4—Ce1	95.69 (18)
O1—Ce1—O6^i	76.88 (9)	N2—O6—Ce1	98.66 (18)
O6—Ce1—O6^i	134.41 (13)	O2—N1—O3	123.2 (3)
O1^i—Ce1—O3^i	51.14 (8)	O2—N1—O1	121.1 (3)
O1—Ce1—O3^i	134.17 (9)	O3—N1—O1	115.7 (3)
O6—Ce1—O3^i	106.90 (9)	O5—N2—O4	123.9 (3)
O6^i—Ce1—O3^i	68.11 (9)	O5—N2—O6	120.7 (3)
O1^i—Ce1—O3	134.17 (9)	O4—N2—O6	115.4 (3)
O6^i—Ce1—O3	106.90 (9)	C3—N3—C1	115.6 (3)
O3^i—Ce1—O3	167.84 (12)	C3—N3—Ce1	119.2 (2)
O1^i—Ce1—O4^i	143.29 (9)	C1—N3—Ce1	123.2 (2)
O1—Ce1—O4^i	74.39 (9)	N3—C1—C2	124.0 (3)
O6—Ce1—O4^i	90.63 (9)	N3—C1—H1	118.0
O6^i—Ce1—O4^i	50.15 (8)	C2—C1—H1	118.0
O3^i—Ce1—O4^i	102.46 (9)	C1—C2—C5	119.5 (3)
O3—Ce1—O4^i	67.17 (9)	C1—C2—H2	120.3
O1^i—Ce1—O4	74.38 (9)	C5—C2—H2	120.3
O6^i—Ce1—O4	90.63 (9)	N3—C3—C4	124.5 (3)
O3^i—Ce1—O4	67.17 (9)	N3—C3—H3	117.7
O4^i—Ce1—O4	71.26 (14)	C4—C3—H3	117.7
O1^i—Ce1—N3^i	74.10 (9)	C3—C4—C5	118.9 (3)
O1—Ce1—N3^i	76.18 (8)	C3—C4—H4	120.5
O6—Ce1—N3^i	145.11 (9)	C5—C4—H4	120.5
O6^i—Ce1—N3^i	77.66 (9)	C2—C5—C4	117.3 (3)
O3^i—Ce1—N3^i	68.35 (9)	C2—C5—C6	122.2 (3)
O3—Ce1—N3^i	122.33 (8)	C4—C5—C6	120.5 (3)
O4^i—Ce1—N3^i	124.26 (9)	C7—C6—C11	117.9 (3)
O4—Ce1—N3^i	135.21 (9)	C7—C6—C5	120.6 (3)
O1^i—Ce1—N3	76.18 (8)	C11—C6—C5	121.5 (3)
O6^i—Ce1—N3	145.11 (9)	C8—C7—C6	119.0 (3)
O3^i—Ce1—N3	122.33 (8)	C8—C7—H7	120.5
O4^i—Ce1—N3	135.21 (9)	C6—C7—H7	120.5
N3^i—Ce1—N3	76.97 (12)	C9—C8—C7	122.3 (3)
O1^i—Ce1—N1^i	25.73 (8)	C9—C8—H8	118.9
O1—Ce1—N1^i	144.93 (8)	C7—C8—H8	118.9
O6—Ce1—N1^i	92.35 (9)	C10—C9—C8	119.8 (3)
O6^i—Ce1—N1^i	93.24 (9)	C10—C9—H9	120.1
O3^i—Ce1—N1^i	25.42 (9)	C8—C9—H9	120.1
O3—Ce1—N1^i	158.41 (9)	C9—C10—C11	122.3 (4)
O4^i—Ce1—N1^i	124.37 (9)	C9—C10—H10	118.8
O4—Ce1—N1^i	68.90 (9)	C11—C10—H10	118.8
N3^i—Ce1—N1^i	68.82 (9)	C10—C11—C6	118.7 (3)
N3—Ce1—N1^i	99.46 (9)	C10—C11—H11	120.6
O1^i—Ce1—N2^i	135.76 (8)	C6—C11—H11	120.6

Symmetry code: (i) −x+2, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

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