Retracted: Bis(4,4′-bipyridine-κ²N,N′)tetra­kis(nitrato-κ²O,O′)cerium(IV)

The asymmetric unit of the title compound, [Ce(NO₃)₄(C₁₀H₈N₂)₂], contains one half-mol­ecule. The Ce^IV atom, lying on a crystallographic twofold rotation axis, is ten-coordinated by two N atoms of 4,4′-bipyridine and eight O atoms of four NO₃⁻ ligands. In the crystal structure, intra- and inter­molecular C—H...O hydrogen bonds link the mol­ecules into a supra­molecular network.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.024
• wR factor = 0.074
• Data-to-parameter ratio = 13.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Ce1    -   O1      ..      16.64 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Ce1    -   O3      ..      13.36 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Ce1    -   O4      ..      12.61 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Ce1    -   O6      ..      11.49 su
PLAT430_ALERT_2_B Short Inter D...A Contact  N4     ..  N4      ..       2.64 Ang.

Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ce1    -   N3      ..       6.24 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O1
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O3
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O4
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O6
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Ce1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N2
PLAT432_ALERT_2_C Short Inter X...Y Contact  O1     ..  C8      ..       3.01 Ang.

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ce1         (3)       2.86

   0 ALERT level A = In general: serious problem
   6 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  13 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

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 herein report the crystal structure of the title compound, (I).

The asymmetric unit of the title compound, (I), contains one-half molecule (Fig. 1). The bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987). The irregular ten-coordinate environment of the Ce^IV atom, lying on a crystallographic twofold rotation axis, is completed by the two N atoms of 4,4'-bipyridine and eight O atoms of four NO₃^- ligands (Table 1). The Ce—O bonds are between 2.385 (2)–2.604 (3) Å, while the Ce—N bond length is 2.585 (3) Å.

Rings A (N3/C1—C5) and B (N4/C6—C10) are, of course, planar and the dihedral angle between them is A/B = 37.56 (2)°.

As can be seen from the packing diagram (Fig. 2), the intra- and intermolecular C—H···O hydrogen bonds (Table 2) link the molecules into a supramolecular network structure, in which they may be effective in the stabilization of the crystal structure. Dipol-dipol and van der Waals interactions are also effective in the molecular packing.

Related literature

For general backgroud, 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

For the preparation of the title compound, ammonium cerium(IV) nitrate (109.6 mg, 0.2 mmol), 4,4'-bipyridine (62.4 mg, 0.4 mmol), and distilled water (4000.0 mg) were placed into a Teflon-lined Parr bomb (23 ml) and sealed. The bomb was then heated under autogenous pressure for 7 d at 413 K and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colorless solution was decanted from small colorless crystals, which were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature (yield; 58.6 mg, 34%).

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 the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [symmetry code (A): 2 - x, y, 1 - z].
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

Bis(4,4'-bipyridine-κ²N,N')tetrakis(nitrato-κ²O,O')cerium(IV)

Crystal data

[Ce(NO3)4(C10H8N2)2]	F(000) = 1384
Mr = 700.53	Dx = 1.826 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8351 reflections
a = 19.106 (2) Å	θ = 2.5–29.5°
b = 7.8107 (8) Å	µ = 1.87 mm^−1
c = 19.000 (7) Å	T = 273 K
β = 116.004 (2)°	Plane, colorless
V = 2548.4 (10) Å^3	0.40 × 0.33 × 0.21 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer	2593 independent reflections
Radiation source: fine-focus sealed tube	2537 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
φ and ω scans	θmax = 26.7°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→24
Tmin = 0.491, Tmax = 0.675	k = −9→9
8401 measured reflections	l = −24→24

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.074	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0526P)^2 + 3.3178P] where P = (Fo^2 + 2Fc^2)/3
2593 reflections	(Δ/σ)max < 0.001
186 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.54 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	0.33854 (2)	0.7500	0.03153 (9)
O1	1.09207 (13)	0.4419 (3)	0.88993 (15)	0.0569 (6)
O2	1.0829 (2)	0.4126 (4)	1.00244 (16)	0.0779 (8)
O3	0.99750 (16)	0.3044 (3)	0.88522 (16)	0.0573 (6)
O4	0.92877 (16)	0.0719 (3)	0.66851 (18)	0.0669 (7)
O5	0.81807 (17)	−0.0040 (4)	0.65285 (18)	0.0730 (8)
O6	0.87813 (15)	0.2149 (3)	0.72864 (16)	0.0571 (6)
N1	1.05818 (17)	0.3858 (4)	0.92901 (17)	0.0504 (6)
N2	0.87324 (16)	0.0902 (3)	0.68201 (17)	0.0485 (6)
N3	0.93573 (16)	0.6018 (4)	0.78013 (17)	0.0477 (6)
C1	0.9748 (2)	0.7369 (4)	0.8261 (2)	0.0500 (7)
H1	1.0263	0.7512	0.8348	0.060*
C2	0.9466 (2)	0.8530 (4)	0.8604 (2)	0.0475 (7)
H2	0.9768	0.9434	0.8901	0.057*
C3	0.8644 (2)	0.5861 (5)	0.7672 (2)	0.0526 (7)
H3	0.8344	0.4991	0.7344	0.063*
C4	0.8317 (2)	0.6939 (4)	0.8003 (2)	0.0496 (7)
H4	0.7800	0.6774	0.7904	0.060*
C5	0.8740 (2)	0.8308 (3)	0.8494 (2)	0.0419 (7)
C6	0.84260 (17)	0.9442 (4)	0.89068 (17)	0.0421 (6)
C7	0.7947 (2)	0.8785 (4)	0.9185 (2)	0.0478 (7)
H7	0.7817	0.7629	0.9126	0.057*
C8	0.7657 (2)	0.9864 (4)	0.9555 (2)	0.0531 (7)
H8	0.7325	0.9414	0.9749	0.064*
N4	0.7822 (2)	1.1529 (3)	0.9655 (2)	0.0545 (7)
C9	0.8276 (3)	1.2173 (5)	0.9398 (3)	0.0669 (10)
H9	0.8389	1.3337	0.9463	0.080*
C10	0.8600 (2)	1.1175 (5)	0.9028 (3)	0.0609 (10)
H10	0.8942	1.1661	0.8855	0.073*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ce1	0.03102 (14)	0.02770 (13)	0.04625 (14)	0.000	0.02651 (10)	0.000
O1	0.0442 (12)	0.0573 (14)	0.0749 (15)	−0.0090 (10)	0.0314 (11)	0.0003 (12)
O2	0.097 (2)	0.078 (2)	0.0546 (14)	−0.0085 (18)	0.0294 (14)	−0.0023 (14)
O3	0.0553 (15)	0.0614 (13)	0.0687 (15)	−0.0134 (12)	0.0397 (13)	−0.0034 (12)
O4	0.0621 (16)	0.0520 (14)	0.105 (2)	−0.0035 (12)	0.0533 (15)	−0.0174 (14)
O5	0.0616 (16)	0.0654 (16)	0.0906 (19)	−0.0287 (13)	0.0321 (14)	−0.0171 (14)
O6	0.0552 (14)	0.0488 (12)	0.0831 (16)	−0.0098 (11)	0.0449 (13)	−0.0164 (12)
N1	0.0530 (16)	0.0455 (13)	0.0567 (15)	0.0008 (13)	0.0277 (13)	0.0032 (12)
N2	0.0481 (15)	0.0409 (13)	0.0605 (15)	−0.0058 (12)	0.0277 (12)	−0.0031 (12)
N3	0.0499 (15)	0.0440 (14)	0.0641 (15)	0.0027 (12)	0.0386 (13)	−0.0034 (12)
C1	0.0507 (18)	0.0407 (16)	0.077 (2)	−0.0029 (13)	0.0447 (16)	−0.0034 (15)
C2	0.0475 (18)	0.0409 (16)	0.069 (2)	−0.0060 (12)	0.0389 (17)	−0.0078 (13)
C3	0.0469 (17)	0.0502 (18)	0.0668 (19)	−0.0022 (14)	0.0306 (15)	−0.0151 (15)
C4	0.0412 (17)	0.0516 (16)	0.0623 (18)	0.0015 (13)	0.0284 (15)	−0.0098 (15)
C5	0.0434 (17)	0.0405 (16)	0.0520 (16)	0.0037 (11)	0.0302 (14)	0.0013 (11)
C6	0.0404 (14)	0.0412 (14)	0.0527 (15)	0.0023 (12)	0.0278 (12)	−0.0028 (12)
C7	0.0444 (17)	0.0458 (15)	0.0639 (18)	−0.0028 (13)	0.0336 (15)	−0.0062 (14)
C8	0.0475 (17)	0.0573 (19)	0.0694 (19)	−0.0006 (14)	0.0393 (15)	−0.0059 (16)
N4	0.0531 (18)	0.0536 (18)	0.0732 (19)	0.0049 (11)	0.0428 (16)	−0.0106 (12)
C9	0.079 (3)	0.0452 (18)	0.105 (3)	−0.0039 (18)	0.068 (2)	−0.015 (2)
C10	0.072 (2)	0.0422 (16)	0.099 (3)	−0.0057 (16)	0.065 (2)	−0.0103 (18)

Geometric parameters (Å, º)

Ce1—O1	2.591 (3)	C1—C2	1.359 (4)
Ce1—O3	2.604 (3)	C1—H1	0.9300
Ce1—O4	2.596 (3)	C2—C5	1.319 (5)
Ce1—O6	2.385 (2)	C2—H2	0.9300
Ce1—N3	2.585 (3)	C3—C4	1.356 (4)
Ce1—O6^i	2.386 (2)	C3—H3	0.9300
Ce1—N3^i	2.585 (3)	C4—C5	1.417 (5)
Ce1—O1^i	2.591 (3)	C4—H4	0.9300
Ce1—O4^i	2.596 (3)	C5—C6	1.474 (4)
Ce1—O3^i	2.604 (3)	C6—C7	1.344 (4)
Ce1—N2^i	2.925 (3)	C6—C10	1.388 (5)
O1—N1	1.258 (4)	C7—C8	1.362 (4)
O2—N1	1.279 (4)	C7—H7	0.9300
O3—N1	1.263 (4)	C8—N4	1.332 (4)
O4—N2	1.204 (4)	C8—H8	0.9300
O5—N2	1.203 (4)	N4—C9	1.272 (5)
O6—N2	1.292 (4)	C9—C10	1.368 (5)
N3—C3	1.280 (4)	C9—H9	0.9300
N3—C1	1.365 (5)	C10—H10	0.9300
O1—Ce1—O3	46.95 (8)	O1—Ce1—N2^i	72.25 (8)
O1—Ce1—O4	143.55 (9)	O4—Ce1—N2^i	81.22 (8)
O1—Ce1—O6	118.27 (8)	O4^i—Ce1—N2^i	24.28 (8)
O3—Ce1—O4	105.94 (9)	O3—Ce1—N2^i	82.31 (9)
O3—Ce1—O6	71.80 (9)	O3^i—Ce1—N2^i	89.89 (8)
O4—Ce1—O6	49.94 (8)	N1—O1—Ce1	101.74 (19)
O1—Ce1—N3	72.52 (9)	N1—O3—Ce1	100.94 (18)
O3—Ce1—N3	69.32 (9)	N2—O4—Ce1	93.31 (19)
O4—Ce1—N3	126.48 (9)	N2—O6—Ce1	101.16 (18)
O6—Ce1—N3	80.59 (9)	O1—N1—O3	110.4 (3)
O6—Ce1—O6^i	132.25 (13)	O1—N1—O2	123.1 (3)
O6—Ce1—N3^i	143.85 (9)	O3—N1—O2	126.5 (3)
O6^i—Ce1—N3^i	80.59 (9)	O5—N2—O4	120.3 (3)
O6^i—Ce1—N3	143.85 (10)	O5—N2—O6	124.2 (3)
N3^i—Ce1—N3	74.59 (12)	O4—N2—O6	115.5 (3)
O6—Ce1—O1^i	77.21 (9)	C3—N3—C1	115.8 (3)
O6^i—Ce1—O1^i	118.27 (8)	C3—N3—Ce1	116.8 (2)
N3^i—Ce1—O1^i	72.52 (9)	C1—N3—Ce1	125.2 (2)
N3—Ce1—O1^i	78.74 (9)	C2—C1—N3	127.0 (3)
O6^i—Ce1—O1	77.21 (9)	C2—C1—H1	116.5
N3^i—Ce1—O1	78.74 (9)	N3—C1—H1	116.5
O1^i—Ce1—O1	143.71 (12)	C5—C2—C1	116.6 (3)
O6^i—Ce1—O4	89.66 (9)	C5—C2—H2	121.7
N3^i—Ce1—O4	133.00 (9)	C1—C2—H2	121.7
O1^i—Ce1—O4	72.27 (9)	N3—C3—C4	121.3 (3)
O6—Ce1—O4^i	89.66 (9)	N3—C3—H3	119.3
O6^i—Ce1—O4^i	49.94 (8)	C4—C3—H3	119.3
N3^i—Ce1—O4^i	126.48 (9)	C3—C4—C5	121.9 (3)
N3—Ce1—O4^i	133.00 (9)	C3—C4—H4	119.1
O1^i—Ce1—O4^i	143.55 (9)	C5—C4—H4	119.1
O1—Ce1—O4^i	72.27 (9)	C2—C5—C4	117.4 (3)
O4—Ce1—O4^i	73.30 (14)	C2—C5—C6	118.8 (3)
O6^i—Ce1—O3	103.27 (9)	C4—C5—C6	123.8 (3)
N3^i—Ce1—O3	121.06 (8)	C7—C6—C10	117.6 (3)
O1^i—Ce1—O3	138.28 (8)	C7—C6—C5	119.1 (3)
O4^i—Ce1—O3	63.97 (9)	C10—C6—C5	123.3 (3)
O6—Ce1—O3^i	103.27 (9)	C6—C7—C8	117.9 (3)
O6^i—Ce1—O3^i	71.80 (9)	C6—C7—H7	121.1
N3^i—Ce1—O3^i	69.32 (9)	C8—C7—H7	121.1
N3—Ce1—O3^i	121.06 (8)	N4—C8—C7	123.7 (3)
O1^i—Ce1—O3^i	46.95 (8)	N4—C8—H8	118.2
O1—Ce1—O3^i	138.27 (8)	C7—C8—H8	118.2
O4—Ce1—O3^i	63.97 (9)	C9—N4—C8	119.3 (3)
O4^i—Ce1—O3^i	105.94 (9)	N4—C9—C10	120.8 (4)
O3—Ce1—O3^i	168.25 (12)	N4—C9—H9	119.6
O6—Ce1—N2^i	111.37 (9)	C10—C9—H9	119.6
O6^i—Ce1—N2^i	25.69 (8)	C9—C10—C6	120.7 (3)
N3^i—Ce1—N2^i	104.09 (8)	C9—C10—H10	119.6
N3—Ce1—N2^i	144.26 (9)	C6—C10—H10	119.6
O1^i—Ce1—N2^i	135.89 (7)

Symmetry code: (i) −x+2, y, −z+3/2.