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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): m957.
Published online 2008 June 25. doi:  10.1107/S1600536808018552
PMCID: PMC2961770

This article has been retractedRetraction in: Acta Crystallogr Sect E Struct Rep Online. 2011 March 01; 67(Pt 3): e14    See also: PMC Retraction Policy

Bis(pentane-2,4-dionato)bis­[2-(4-pyrid­yl)-4,4,5,5-tetra­methyl­imidazoline-1-oxyl 3-oxide]nickel(II)

Abstract

In the title compound, [Ni(C5H7O2)2(C12H16N3O2)], the NiII cation is hexa­coordinated by four O and two N atoms, showing a slightly distorted octa­hedral geometry. The NiII cation lies on an inversion centre, as a consequence of which the asymmetric unit comprises one half-mol­ecule. The four O atoms belonging to two pentane-2,4-dionate ligands lie in the equatorial plane and two pyridyl N atoms occupy the axial coordination sites.

Related literature

For related literature, see: Caneschi et al. (1989 [triangle]); Tsukuda et al. (2002 [triangle]); Vostrikova et al. (2000 [triangle]); Kuchar et al. (2003 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0m957-scheme1.jpg

Experimental

Crystal data

  • [Ni(C5H7O2)2(C12H16N3O2)]
  • M r = 725.48
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m957-efi1.jpg
  • a = 6.9862 (10) Å
  • b = 10.121 (3) Å
  • c = 12.735 (3) Å
  • α = 98.20 (2)°
  • β = 103.21 (2)°
  • γ = 93.08 (2)°
  • V = 864.1 (3) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.62 mm−1
  • T = 293 (2) K
  • 0.43 × 0.28 × 0.22 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.776, T max = 0.875
  • 5805 measured reflections
  • 2968 independent reflections
  • 2356 reflections with I > 2σ(I)
  • R int = 0.032

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.101
  • S = 1.00
  • 2968 reflections
  • 229 parameters
  • H-atom parameters not refined
  • Δρmax = 0.38 e Å−3
  • Δρmin = −0.51 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808018552/kp2176sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808018552/kp2176Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the National Ministry of Science and Technology of China for support (grant No. 2001CB6105-07).

supplementary crystallographic information

Comment

Design of different kinds of metal-radical coordination architectures with appropriate organic radicals and coligands has been an important subject during the last decade because of their potential use for molecule-based magnetic materials and optical devices (Caneschi et al., 1989; Tsukuda et al., 2002; Vostrikova et al., 2000; Kuchar et al., 2003). The organic species, such as tridentate nitronyl nitroxide radical, and bidentate nitroxide radical could results in a large number of building blocks with the potential applications. In this paper, we report the structure of the title compound, (I).

The NiII cation is hexacoordinated with four O and two N atoms showing the slightly distorted octahedral geometry (Fig. 1). The NiII cation lies on an inversion centre. The four oxygen atoms belonging to two pentane-2,4-dionate lie in the equatorial plane and the two nitrogen atoms occupy the axial coordination sites. The Ni—N and Ni—O bond lengths are in the range of 2.154 (2)–2.154 (2) and 2.0239 (17)–2.0292 (16) /%A, respectively (Table 1).

Experimental

A mixture of nickel(II) acetylacetonate (1 mmoL) and 2-(4-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide (1 mmoL) in 20 mL methanol was refluxed for several h. The above cooled solution was filterated and the filtrate was kept in the ice box. One week later, green blocks of (I) were obtained with yield of ca 3%. Anal. Calc. for C34H46N6NiO8: C 56.24, H 6.34, N 11.58%; Found: C 56.19, H 6.28, N 11.47%.

Refinement

All H atoms were placed in calculated positions with C—H = 0.93Å and refined as riding with Uiso(H) = 1.2Ueq(carrier).

Figures

Fig. 1.
The molecular structure of (I) around NiII, drawn with the 30% probability displacement ellipsoids for the non-hydrogen atoms.

Crystal data

[Ni(C5H7O2)2(C12H16N3O2)]Z = 1
Mr = 725.48F000 = 384
Triclinic, P1Dx = 1.394 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 6.9862 (10) ÅCell parameters from 2968 reflections
b = 10.121 (3) Åθ = 3.1–25.0º
c = 12.735 (3) ŵ = 0.62 mm1
α = 98.20 (2)ºT = 293 (2) K
β = 103.21 (2)ºBlock, green
γ = 93.08 (2)º0.43 × 0.28 × 0.22 mm
V = 864.1 (3) Å3

Data collection

Bruker APEXII CCD area-detector diffractometer2968 independent reflections
Radiation source: fine-focus sealed tube2356 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.032
T = 293(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 3.1º
Absorption correction: multi-scan(SADABS; Bruker, 2001)h = −6→8
Tmin = 0.776, Tmax = 0.876k = −12→12
5805 measured reflectionsl = −11→15

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H-atom parameters not refined
wR(F2) = 0.101  w = 1/[σ2(Fo2) + (0.0577P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
2968 reflectionsΔρmax = 0.38 e Å3
229 parametersΔρmin = −0.51 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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 (Å2)

xyzUiso*/Ueq
Ni10.00000.00000.00000.01842 (16)
C10.6315 (4)0.1982 (3)0.4503 (2)0.0171 (5)
C20.4941 (4)0.1511 (2)0.3460 (2)0.0157 (5)
C30.5524 (4)0.0953 (3)0.2533 (2)0.0182 (5)
H30.68520.08630.25620.022*
C40.4134 (4)0.0538 (2)0.1578 (2)0.0169 (5)
H40.45510.01750.09650.020*
C50.1699 (4)0.1168 (2)0.2385 (2)0.0163 (5)
H50.03600.12430.23340.020*
C60.2972 (3)0.1614 (2)0.33692 (19)0.0159 (5)
H60.25110.19800.39670.019*
C70.9190 (3)0.2686 (2)0.58605 (18)0.0148 (5)
C80.7425 (4)0.2983 (3)0.6346 (2)0.0181 (5)
C90.6895 (4)0.4438 (3)0.6355 (2)0.0260 (6)
H9A0.69550.47110.56710.039*
H9B0.78160.50130.69380.039*
H9C0.55850.45000.64620.039*
C100.7513 (4)0.2543 (3)0.7443 (2)0.0232 (6)
H10A0.63330.27470.76740.035*
H10B0.86400.30080.79710.035*
H10C0.76230.15950.73780.035*
C111.0773 (3)0.3828 (3)0.6102 (2)0.0186 (6)
H11A1.17580.35990.57080.028*
H11B1.13720.39980.68720.028*
H11C1.02010.46160.58820.028*
C121.0024 (4)0.1370 (3)0.6126 (2)0.0186 (5)
H12A0.89650.06720.59670.028*
H12B1.06840.14800.68860.028*
H12C1.09450.11330.56900.028*
C13−0.1318 (4)0.3856 (3)0.1296 (2)0.0236 (6)
H13A−0.27200.38320.10170.035*
H13B−0.07160.47310.12950.035*
H13C−0.10420.36610.20280.035*
C14−0.0496 (4)0.2828 (2)0.05844 (19)0.0169 (5)
C150.1142 (4)0.3210 (2)0.0228 (2)0.0193 (6)
H150.16810.40940.04470.023*
C160.2042 (4)0.2369 (2)−0.0434 (2)0.0183 (6)
C170.3724 (4)0.2937 (3)−0.0815 (2)0.0257 (6)
H17A0.48770.2489−0.05600.039*
H17B0.39810.3877−0.05310.039*
H17C0.34000.2812−0.15990.039*
N10.2240 (3)0.06298 (19)0.14880 (16)0.0147 (4)
N20.5853 (3)0.2130 (2)0.54884 (17)0.0188 (5)
N30.8188 (3)0.2419 (2)0.46714 (16)0.0154 (5)
O10.4272 (2)0.1725 (2)0.56916 (14)0.0276 (5)
O20.9117 (2)0.25109 (18)0.39294 (14)0.0212 (4)
O3−0.1365 (2)0.16536 (16)0.03800 (13)0.0173 (4)
O40.1568 (2)0.11205 (17)−0.07687 (13)0.0183 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ni10.0180 (3)0.0196 (3)0.0157 (3)0.00152 (18)0.00049 (19)0.00216 (19)
C10.0170 (13)0.0237 (14)0.0112 (13)0.0031 (10)0.0052 (10)0.0011 (10)
C20.0157 (13)0.0186 (13)0.0127 (13)0.0000 (10)0.0026 (10)0.0040 (10)
C30.0149 (13)0.0234 (14)0.0164 (14)0.0020 (10)0.0039 (11)0.0028 (11)
C40.0173 (13)0.0198 (13)0.0143 (13)0.0030 (10)0.0041 (10)0.0039 (10)
C50.0133 (12)0.0192 (13)0.0180 (14)0.0022 (10)0.0045 (10)0.0069 (10)
C60.0166 (13)0.0217 (13)0.0100 (13)0.0024 (10)0.0039 (10)0.0026 (10)
C70.0139 (12)0.0242 (14)0.0047 (12)0.0012 (10)0.0009 (10)0.0000 (10)
C80.0134 (13)0.0279 (15)0.0114 (13)0.0040 (10)0.0003 (10)0.0018 (11)
C90.0217 (14)0.0332 (16)0.0218 (15)0.0111 (12)0.0025 (11)0.0012 (12)
C100.0186 (14)0.0393 (17)0.0112 (14)0.0027 (11)0.0023 (11)0.0046 (12)
C110.0155 (13)0.0246 (14)0.0144 (14)0.0020 (10)0.0016 (10)0.0017 (11)
C120.0148 (13)0.0241 (14)0.0170 (14)0.0024 (10)0.0039 (10)0.0034 (11)
C130.0270 (15)0.0192 (14)0.0214 (15)0.0067 (11)0.0002 (11)0.0001 (11)
C140.0179 (13)0.0193 (14)0.0094 (13)0.0045 (10)−0.0062 (10)0.0029 (10)
C150.0221 (14)0.0155 (13)0.0168 (14)0.0003 (10)−0.0029 (11)0.0035 (10)
C160.0165 (13)0.0207 (14)0.0144 (13)−0.0002 (10)−0.0061 (10)0.0087 (10)
C170.0190 (14)0.0257 (15)0.0308 (16)−0.0023 (11)0.0009 (12)0.0093 (12)
N10.0183 (11)0.0148 (11)0.0113 (11)0.0021 (8)0.0037 (9)0.0019 (8)
N20.0099 (11)0.0332 (13)0.0128 (12)0.0012 (9)0.0023 (9)0.0030 (9)
N30.0096 (10)0.0243 (12)0.0112 (11)−0.0003 (8)0.0012 (9)0.0014 (8)
O10.0109 (9)0.0545 (13)0.0181 (10)−0.0025 (8)0.0046 (8)0.0083 (9)
O20.0145 (9)0.0369 (11)0.0126 (9)0.0002 (8)0.0058 (7)0.0010 (8)
O30.0157 (9)0.0184 (9)0.0159 (9)0.0034 (7)−0.0005 (7)0.0022 (7)
O40.0172 (9)0.0214 (10)0.0140 (9)−0.0006 (7)−0.0002 (7)0.0027 (7)

Geometric parameters (Å, °)

Ni1—O3i2.0239 (17)C9—H9B0.9600
Ni1—O32.0239 (17)C9—H9C0.9600
Ni1—O4i2.0292 (16)C10—H10A0.9600
Ni1—O42.0292 (16)C10—H10B0.9600
Ni1—N12.154 (2)C10—H10C0.9600
Ni1—N1i2.154 (2)C11—H11A0.9600
C1—N31.318 (3)C11—H11B0.9600
C1—N21.355 (3)C11—H11C0.9600
C1—C21.450 (3)C12—H12A0.9600
C2—C61.364 (3)C12—H12B0.9600
C2—C31.390 (4)C12—H12C0.9600
C3—C41.366 (4)C13—C141.506 (3)
C3—H30.9300C13—H13A0.9600
C4—N11.312 (3)C13—H13B0.9600
C4—H40.9300C13—H13C0.9600
C5—N11.337 (3)C14—O31.269 (3)
C5—C61.361 (3)C14—C151.380 (4)
C5—H50.9300C15—C161.388 (4)
C6—H60.9300C15—H150.9300
C7—N31.495 (3)C16—O41.275 (3)
C7—C111.503 (3)C16—C171.488 (3)
C7—C81.526 (3)C17—H17A0.9600
C7—C121.533 (3)C17—H17B0.9600
C8—N21.491 (3)C17—H17C0.9600
C8—C101.515 (3)N2—O11.252 (3)
C8—C91.537 (4)N3—O21.273 (3)
C9—H9A0.9600
O3i—Ni1—O3180.00 (12)C8—C10—H10A109.5
O3i—Ni1—O4i87.77 (7)C8—C10—H10B109.5
O3—Ni1—O4i92.23 (7)H10A—C10—H10B109.5
O3i—Ni1—O492.23 (7)C8—C10—H10C109.5
O3—Ni1—O487.77 (7)H10A—C10—H10C109.5
O4i—Ni1—O4180.00 (9)H10B—C10—H10C109.5
O3i—Ni1—N191.68 (7)C7—C11—H11A109.5
O3—Ni1—N188.33 (7)C7—C11—H11B109.5
O4i—Ni1—N191.41 (7)H11A—C11—H11B109.5
O4—Ni1—N188.59 (7)C7—C11—H11C109.5
O3i—Ni1—N1i88.32 (7)H11A—C11—H11C109.5
O3—Ni1—N1i91.67 (7)H11B—C11—H11C109.5
O4i—Ni1—N1i88.59 (7)C7—C12—H12A109.5
O4—Ni1—N1i91.41 (7)C7—C12—H12B109.5
N1—Ni1—N1i180.00 (8)H12A—C12—H12B109.5
N3—C1—N2107.4 (2)C7—C12—H12C109.5
N3—C1—C2127.1 (2)H12A—C12—H12C109.5
N2—C1—C2125.4 (2)H12B—C12—H12C109.5
C6—C2—C3117.6 (2)C14—C13—H13A109.5
C6—C2—C1119.1 (2)C14—C13—H13B109.5
C3—C2—C1123.3 (2)H13A—C13—H13B109.5
C4—C3—C2119.6 (2)C14—C13—H13C109.5
C4—C3—H3120.2H13A—C13—H13C109.5
C2—C3—H3120.2H13B—C13—H13C109.5
N1—C4—C3123.0 (2)O3—C14—C15125.1 (2)
N1—C4—H4118.5O3—C14—C13116.2 (2)
C3—C4—H4118.5C15—C14—C13118.7 (2)
N1—C5—C6124.5 (2)C14—C15—C16124.7 (2)
N1—C5—H5117.8C14—C15—H15117.7
C6—C5—H5117.8C16—C15—H15117.7
C5—C6—C2118.5 (2)O4—C16—C15126.3 (2)
C5—C6—H6120.7O4—C16—C17114.7 (2)
C2—C6—H6120.7C15—C16—C17118.9 (2)
N3—C7—C11110.84 (19)C16—C17—H17A109.5
N3—C7—C8100.11 (18)C16—C17—H17B109.5
C11—C7—C8114.5 (2)H17A—C17—H17B109.5
N3—C7—C12105.69 (19)C16—C17—H17C109.5
C11—C7—C12112.2 (2)H17A—C17—H17C109.5
C8—C7—C12112.4 (2)H17B—C17—H17C109.5
N2—C8—C798.88 (19)C4—N1—C5116.8 (2)
N2—C8—C10109.8 (2)C4—N1—Ni1124.33 (16)
C7—C8—C10115.3 (2)C5—N1—Ni1118.92 (16)
N2—C8—C9106.9 (2)O1—N2—C1127.2 (2)
C7—C8—C9113.5 (2)O1—N2—C8121.2 (2)
C10—C8—C9111.4 (2)C1—N2—C8111.4 (2)
C8—C9—H9A109.5O2—N3—C1125.5 (2)
C8—C9—H9B109.5O2—N3—C7122.47 (18)
H9A—C9—H9B109.5C1—N3—C7111.82 (19)
C8—C9—H9C109.5C14—O3—Ni1122.70 (15)
H9A—C9—H9C109.5C16—O4—Ni1121.69 (15)
H9B—C9—H9C109.5

Symmetry codes: (i) −x, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KP2176).

References

  • Bruker (2001). SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2004). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Caneschi, A., Gatteschi, D., Renard, J. P., Rey, P. & Sessoli, R. (1989). J. Am. Chem. Soc.111, 785–786.
  • Kuchar, J., Cernak, J., Zak, Z. & Massa, W. (2003). Monogr. Ser. Int. Conf. Coord. Chem., 6, 127-132.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tsukuda, T., Suzuki, T. & Kaizaki, S. (2002). J. Chem. Soc. Dalton Trans. pp. 1721–1726.
  • Vostrikova, K. E., Luneau, D., Wernsdorfer, W., Rey, P. & Verdaguer, M. (2000). J. Am. Chem. Soc.122, 718–719.

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