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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): m1604.
Published online 2008 November 22. doi:  10.1107/S1600536808038440
PMCID: PMC2959951

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[2,4-penta­nedionato(1−)]bis­[4,4,5,5-tetra­methyl­-2-(4-pyrid­yl)-imidazoline-1-oxyl 3-oxide]manganese(II)

Abstract

In the title compound, [Mn(C5H7O2)2(C12H16N3O2)], the manganese(II) cation (site symmetry An external file that holds a picture, illustration, etc.
Object name is e-64-m1604-efi1.jpg) is hexa­coordinated by four O and two N atoms in a distorted trans-MnN2O4 octa­hedral geometry. The four O atoms belonging to two 2,4-penta­nedionate anions lie in the equatorial plane and the two N atoms occupy the axial coordination sites.

Related literature

For related structures, see: Caruso et al. (2005 [triangle]); Iskander et al. (2001 [triangle]); Rajak et al. (2000 [triangle]); Sangeetha et al. (2000 [triangle]); Sutradhar et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1604-scheme1.jpg

Experimental

Crystal data

  • [Mn(C5H7O2)2(C12H16N3O2)]
  • M r = 721.71
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1604-efi2.jpg
  • a = 7.277 (3) Å
  • b = 9.7167 (15) Å
  • c = 13.2643 (15) Å
  • α = 97.978 (10)°
  • β = 103.342 (10)°
  • γ = 92.869 (10)°
  • V = 900.4 (4) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.42 mm−1
  • T = 293 (2) K
  • 0.12 × 0.10 × 0.08 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.951, T max = 0.970
  • 6210 measured reflections
  • 3264 independent reflections
  • 2511 reflections with I > 2σ(I)
  • R int = 0.033

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.118
  • S = 1.00
  • 3264 reflections
  • 229 parameters
  • H-atom parameters constrained
  • Δρmax = 0.58 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 bond lengths (Å)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038440/hb2842sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808038440/hb2842Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

To design different kinds of metal-based coordination architectures with appropriate organic radicals and co-ligands has been an important subject during the last decade because of its potential usages for molecule-based magnetic materials and optical devices. Varying the organic units, such as tridentate nitronyl nitroxide radical, and bidentate nitroxide radical could results in a large number of building blocks with the potentional applications. In this paper, we report the structure of the title compound, (I).

As shown in Fig. 1, the manganese(II) cation is hexacoordinated with four O and two N atoms showing a slightly distorted octahedral geometry. The Mn(II) cation lies on an inversion centre. The four oxygen atoms belonging to two 2,4-pentanedionate lie in the equatorial plane and the two nitrogen atoms lie in the axial coordination sites (Table 1).

Experimental

A mixture of manganese(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 hours. The above cooled solution was filtered and the filtrate was kept in an ice box. One week later, brown blocks of (I) were obtained with a yield of ca 3%. Anal. Calc. for C34H46N6MnO8: C 56.48, H 6.31, N 11.55%; Found: C 56.53, H 6.37, N 11.64%.

Refinement

All H atoms were placed in calculated positions with C—H = 0.93–0.96 Å and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of (I) around Mn(II), drawn with 30% probability displacement ellipsoids for the non-hydrogen atoms. The unlabelled atoms are generated by the symmetry operation (-x, -y, -z).

Crystal data

[Mn(C5H7O2)2(C12H16N3O2)]Z = 1
Mr = 721.71F000 = 381
Triclinic, P1Dx = 1.331 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 7.277 (3) ÅCell parameters from 3264 reflections
b = 9.7167 (15) Åθ = 2.9–25.5º
c = 13.2643 (15) ŵ = 0.42 mm1
α = 97.978 (10)ºT = 293 (2) K
β = 103.342 (10)ºBlock, brown
γ = 92.869 (10)º0.12 × 0.10 × 0.08 mm
V = 900.4 (4) Å3

Data collection

Bruker APEXII CCD area-detector diffractometer3264 independent reflections
Radiation source: fine-focus sealed tube2511 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.033
T = 293(2) Kθmax = 25.5º
[var phi] and ω scansθmin = 2.9º
Absorption correction: multi-scan(SADABS; Bruker, 2001)h = −6→8
Tmin = 0.951, Tmax = 0.970k = −11→11
6210 measured reflectionsl = −11→16

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.118  w = 1/[σ2(Fo2) + (0.07P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.007
3264 reflectionsΔρmax = 0.58 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
Mn10.00000.00000.00000.0236 (6)
C1−0.0486 (4)0.2828 (3)0.0582 (2)0.0237 (6)
C20.2048 (4)0.2371 (3)−0.0432 (2)0.0249 (6)
C30.3726 (4)0.2936 (3)−0.0812 (2)0.0343 (7)
H3A0.48380.2496−0.05220.052*
H3B0.39460.3926−0.05890.052*
H3C0.34490.2741−0.15640.052*
C40.1139 (4)0.3210 (3)0.0232 (2)0.0264 (6)
H40.16720.41220.04670.032*
C5−0.1320 (4)0.3856 (3)0.1294 (2)0.0319 (7)
H5A−0.26650.38300.10190.048*
H5B−0.07540.47810.13270.048*
H5C−0.10660.36070.19850.048*
C60.1703 (4)0.1166 (3)0.2387 (2)0.0220 (6)
H60.04170.12380.23380.026*
C70.4138 (4)0.0539 (3)0.1578 (2)0.0232 (6)
H70.45390.01870.09840.028*
C80.5526 (4)0.0956 (3)0.2535 (2)0.0246 (6)
H80.68020.08710.25600.030*
C90.2971 (4)0.1612 (3)0.3371 (2)0.0222 (6)
H90.25260.19670.39500.027*
C100.4944 (4)0.1510 (3)0.3461 (2)0.0222 (6)
C110.6315 (4)0.1986 (3)0.4507 (2)0.0222 (6)
C120.9181 (3)0.2690 (3)0.58642 (19)0.0210 (6)
C130.7430 (4)0.2984 (3)0.6343 (2)0.0232 (6)
C140.7504 (4)0.2549 (3)0.7443 (2)0.0307 (7)
H14A0.63610.27700.76520.046*
H14B0.85760.30460.79480.046*
H14C0.76200.15640.74040.046*
C150.6888 (4)0.4434 (3)0.6352 (2)0.0328 (7)
H15A0.68780.47150.56850.049*
H15B0.77860.50450.68940.049*
H15C0.56480.44830.64830.049*
C161.0020 (4)0.1369 (3)0.6128 (2)0.0254 (6)
H16A0.90330.06230.59690.038*
H16B1.06340.14920.68610.038*
H16C1.09300.11470.57220.038*
C171.0770 (4)0.3830 (3)0.6102 (2)0.0260 (6)
H17A1.16890.35650.57110.039*
H17B1.13630.39750.68380.039*
H17C1.02710.46770.59080.039*
N10.2243 (3)0.0629 (2)0.14911 (16)0.0214 (5)
N20.5856 (3)0.2134 (2)0.54863 (17)0.0250 (5)
N30.8188 (3)0.2417 (2)0.46660 (17)0.0221 (5)
O1−0.1368 (2)0.16513 (17)0.03794 (14)0.0254 (4)
O20.9120 (3)0.25072 (19)0.39302 (14)0.0277 (4)
O30.1567 (2)0.11183 (18)−0.07693 (14)0.0259 (4)
O40.4265 (3)0.1723 (2)0.56899 (15)0.0351 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Mn10.0270 (15)0.0192 (14)0.0214 (15)0.0067 (11)0.0002 (11)0.0001 (11)
C10.0267 (14)0.0198 (13)0.0197 (14)0.0041 (10)−0.0057 (11)0.0045 (10)
C20.0244 (14)0.0214 (13)0.0246 (15)0.0003 (10)−0.0055 (11)0.0087 (11)
C30.0301 (16)0.0276 (15)0.0445 (19)−0.0007 (12)0.0041 (14)0.0122 (13)
C40.0316 (15)0.0180 (13)0.0256 (15)0.0005 (11)−0.0013 (12)0.0040 (11)
C50.0373 (17)0.0220 (14)0.0327 (17)0.0074 (12)0.0012 (13)0.0017 (12)
C60.0193 (13)0.0234 (13)0.0245 (15)0.0035 (10)0.0056 (11)0.0061 (11)
C70.0246 (14)0.0242 (13)0.0212 (15)0.0045 (10)0.0052 (11)0.0045 (11)
C80.0208 (14)0.0270 (14)0.0258 (16)0.0026 (10)0.0051 (11)0.0044 (11)
C90.0238 (14)0.0234 (13)0.0199 (14)0.0033 (10)0.0055 (11)0.0038 (10)
C100.0233 (14)0.0217 (13)0.0209 (15)0.0006 (10)0.0035 (11)0.0045 (10)
C110.0230 (14)0.0260 (13)0.0178 (14)0.0022 (10)0.0051 (11)0.0030 (11)
C120.0201 (13)0.0256 (14)0.0151 (14)0.0009 (10)0.0007 (10)0.0026 (10)
C130.0224 (14)0.0268 (14)0.0185 (14)0.0038 (11)0.0009 (11)0.0029 (11)
C140.0270 (15)0.0405 (17)0.0236 (16)0.0033 (12)0.0035 (12)0.0060 (12)
C150.0292 (16)0.0346 (16)0.0330 (18)0.0106 (12)0.0046 (13)0.0017 (13)
C160.0225 (14)0.0250 (14)0.0284 (16)0.0034 (10)0.0040 (12)0.0058 (11)
C170.0254 (14)0.0254 (14)0.0254 (16)0.0013 (11)0.0031 (12)0.0034 (11)
N10.0236 (12)0.0185 (11)0.0221 (13)0.0025 (8)0.0051 (10)0.0039 (9)
N20.0175 (12)0.0340 (13)0.0225 (13)0.0003 (9)0.0038 (9)0.0040 (10)
N30.0192 (11)0.0260 (11)0.0206 (12)0.0014 (9)0.0038 (10)0.0041 (9)
O10.0261 (10)0.0207 (9)0.0268 (11)0.0038 (7)0.0006 (8)0.0039 (8)
O20.0235 (10)0.0367 (11)0.0239 (11)0.0013 (8)0.0087 (8)0.0033 (8)
O30.0280 (10)0.0210 (9)0.0258 (11)−0.0002 (7)0.0011 (8)0.0031 (8)
O40.0205 (10)0.0555 (14)0.0309 (12)−0.0011 (9)0.0076 (9)0.0113 (10)

Geometric parameters (Å, °)

Mn1—O1i1.9964 (17)C9—C101.422 (4)
Mn1—O11.9964 (17)C9—H90.9300
Mn1—O32.0597 (17)C10—C111.508 (4)
Mn1—O3i2.0597 (17)C11—N31.365 (3)
Mn1—N12.242 (2)C11—N21.405 (3)
Mn1—N1i2.242 (2)C12—C161.498 (3)
C1—O11.246 (3)C12—C171.507 (3)
C1—C41.417 (4)C12—N31.566 (3)
C1—C51.524 (4)C12—C131.571 (4)
C2—O31.241 (3)C13—C151.482 (4)
C2—C41.415 (4)C13—N21.527 (3)
C2—C31.530 (4)C13—C141.564 (4)
C3—H3A0.9600C14—H14A0.9600
C3—H3B0.9600C14—H14B0.9600
C3—H3C0.9600C14—H14C0.9600
C4—H40.9300C15—H15A0.9600
C5—H5A0.9600C15—H15B0.9600
C5—H5B0.9600C15—H15C0.9600
C5—H5C0.9600C16—H16A0.9600
C6—N11.379 (3)C16—H16B0.9600
C6—C91.412 (4)C16—H16C0.9600
C6—H60.9300C17—H17A0.9600
C7—N11.364 (3)C17—H17B0.9600
C7—C81.421 (4)C17—H17C0.9600
C7—H70.9300N2—O41.304 (3)
C8—C101.434 (4)N3—O21.320 (3)
C8—H80.9300
O1i—Mn1—O1180.0N3—C11—N2108.1 (2)
O1i—Mn1—O387.80 (7)N3—C11—C10126.2 (2)
O1—Mn1—O392.20 (7)N2—C11—C10125.6 (2)
O1i—Mn1—O3i92.20 (7)C16—C12—C17108.1 (2)
O1—Mn1—O3i87.80 (7)C16—C12—N3106.9 (2)
O3—Mn1—O3i180.0C17—C12—N3110.9 (2)
O1i—Mn1—N190.40 (7)C16—C12—C13112.5 (2)
O1—Mn1—N189.60 (7)C17—C12—C13117.4 (2)
O3—Mn1—N189.56 (7)N3—C12—C13100.45 (18)
O3i—Mn1—N190.44 (7)C15—C13—N2103.7 (2)
O1i—Mn1—N1i89.60 (7)C15—C13—C14109.2 (2)
O1—Mn1—N1i90.40 (7)N2—C13—C14112.0 (2)
O3—Mn1—N1i90.44 (7)C15—C13—C12114.0 (2)
O3i—Mn1—N1i89.56 (7)N2—C13—C12100.01 (19)
N1—Mn1—N1i180.0C14—C13—C12116.9 (2)
O1—C1—C4125.9 (2)C13—C14—H14A109.5
O1—C1—C5112.3 (2)C13—C14—H14B109.5
C4—C1—C5121.8 (2)H14A—C14—H14B109.5
O3—C2—C4123.9 (2)C13—C14—H14C109.5
O3—C2—C3113.3 (2)H14A—C14—H14C109.5
C4—C2—C3122.8 (2)H14B—C14—H14C109.5
C2—C3—H3A109.5C13—C15—H15A109.5
C2—C3—H3B109.5C13—C15—H15B109.5
H3A—C3—H3B109.5H15A—C15—H15B109.5
C2—C3—H3C109.5C13—C15—H15C109.5
H3A—C3—H3C109.5H15A—C15—H15C109.5
H3B—C3—H3C109.5H15B—C15—H15C109.5
C2—C4—C1127.8 (2)C12—C16—H16A109.5
C2—C4—H4116.1C12—C16—H16B109.5
C1—C4—H4116.1H16A—C16—H16B109.5
C1—C5—H5A109.5C12—C16—H16C109.5
C1—C5—H5B109.5H16A—C16—H16C109.5
H5A—C5—H5B109.5H16B—C16—H16C109.5
C1—C5—H5C109.5C12—C17—H17A109.5
H5A—C5—H5C109.5C12—C17—H17B109.5
H5B—C5—H5C109.5H17A—C17—H17B109.5
N1—C6—C9124.4 (2)C12—C17—H17C109.5
N1—C6—H6117.8H17A—C17—H17C109.5
C9—C6—H6117.8H17B—C17—H17C109.5
N1—C7—C8123.1 (2)C7—N1—C6116.8 (2)
N1—C7—H7118.5C7—N1—Mn1124.50 (17)
C8—C7—H7118.5C6—N1—Mn1118.67 (16)
C7—C8—C10119.5 (2)O4—N2—C11127.6 (2)
C7—C8—H8120.2O4—N2—C13120.6 (2)
C10—C8—H8120.2C11—N2—C13111.6 (2)
C6—C9—C10118.6 (2)O2—N3—C11126.1 (2)
C6—C9—H9120.7O2—N3—C12122.78 (18)
C10—C9—H9120.7C11—N3—C12110.91 (19)
C9—C10—C8117.6 (2)C1—O1—Mn1118.40 (17)
C9—C10—C11119.2 (2)C2—O3—Mn1119.22 (17)
C8—C10—C11123.2 (2)

Symmetry codes: (i) −x, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2842).

References

  • Bruker (2001). SAINT-Plus and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2004). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Caruso, U., Centore, R., Panunzi, B., Roviello, A. & Tuzi, A. (2005). Eur. J. Inorg. Chem. pp. 2747–2758.
  • Iskander, M. F., Khalil, T. E., Haase, W., Werner, R., Svoboda, I. & Fuess, H. (2001). Polyhedron, 20, 2787–2792.
  • Rajak, K. K., Baruah, B., Rath, S. P. & Chakravorty, A. (2000). Inorg. Chem.39, 1598–1605. [PubMed]
  • Sangeetha, N. R. & Pal, S. (2000). Bull. Chem. Soc. Jpn, 73, 357–361.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sutradhar, M., Mukherjee, G., Drew, M. G. B. & Ghosh, S. (2006). Inorg. Chem.45, 5150–5158. [PubMed]

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