supplementary materials


wm2774 scheme

Acta Cryst. (2013). E69, m620    [ doi:10.1107/S1600536813028614 ]

Redetermination of bis­(acetyl­acetonato-[kappa]2O,O')(1,10-phenanthroline-[kappa]2N,N')manganese(II)

S. Suckert, I. Jess and C. Näther

Abstract top

In the crystal structure of the title compound, [Mn(C5H7O2)2(C12H8N2)], the Mn2+ cation is coordinated by one bidentate 1,10-phenanthroline ligand and two acetyl­acetonate anions within a slightly distorted N2O4 octa­hedron. The asymmetric unit consists of one Mn2+ cation situated on a twofold rotation axis, one half of a 1,10-phenanthroline ligand and one acetyl­acetonate anion. In comparison with the previous determination based on visually estimated intensities recorded on precession photographs, the current redetermination with image-plate data reveals bond lengths and angles with much higher precision.

Comment top

The title compound was serendipitously obtained within a project on the synthesis of manganese(III) coordination polymers containing cyanate anions and neutral N-donor co-ligands. Within this project manganese(III) acetylacetonate was reacted with 1,10-phenanthroline and potassium cyanate in acetonitrile leading to the formation of crystals of the title compound, the composition of which was determined by X-ray structure analysis. The crystal structure of this compound has already been reported by Stephens (1977) from visually estimated intensity data recorded on precession photographs. We decided to redetermine the structure on basis of image plate intensity data to achieve higher precision with respect to lattice parameters, atomic coordinates and resulting bond lengths and angles.

The manganese(II) cation is coordinated by two nitrogen atoms of the 1,10-phenanthroline ligand and four oxygen atoms of two symmetry-related acetylacetonate anions into discrete complexes that are located on twofold rotation axes (Fig. 1). The coordination polyhedron of the manganese(II) cation can be described as a slightly distorted MnN4O2 octahedron. Bond lengths and angles are comparable to those of the previous determination (Stephens, 1977), however with much higher precision, e.g. 2.2962 (18) Å for the Mn—N, and 2.1139 (16) and 2.1543 (16) Å for the two Mn—O bond lengths determined during the present redetermination versus 2.307 (5), 2.116 (5) and 2.152 (5) Å, respectively, of the previous determination.

Individual complex molecules are mainly held together by van der Waals forces. In the crystal structure, the discrete complexes are arranged in columns extending parallel to [001] (Fig. 2). Within these columns neighbouring complexes are related by centers of inversion.

Related literature top

For the previous determination of the crystal structure, see: Stephens (1977).

Experimental top

Manganese(III) 2,4-pentadionate and 1,10-phenanthroline were purchased from Alfa Aesar. Potassium cyanate was purchased from Fluka. The title compound was obtained by the reaction of 70.5 mg Mn(III) 2,4-pentadionate (0.20 mmol), 48.7 mg potassium cyanate (0.6 mmol) and 144.32 mg 1,10-phenanthroline (0.8 mmol) in 1.5 ml acetonitrile at RT in a closed 3 ml snap cap vial. After three days brown crystals of the title compound, mostly in the form of needles, were obtained by slow evaporation of the solvent.

Refinement top

The aromatic hydrogen atoms were positioned with idealized geometry, methyl H atoms were allowed to rotate but not to tip, and were refined with Ueq(H) = 1.2 Ueq(C) for aromatic H atoms (1.5 for methyl H atoms) using a riding model with C—H = 0.95 Å (aromatic) and with C—H = 0.98 Å (methyl).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry code: i) -x+1,y,-z+3/2.]
[Figure 2] Fig. 2. The crystal structure of the title compound in a projection along [001].
Bis(acetylacetonato-κ2O,O')(1,10-phenanthroline-κ2N,N')manganese(II) top
Crystal data top
[Mn(C5H7O2)2(C12H8N2)]F(000) = 900
Mr = 433.36Dx = 1.405 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 17733 reflections
a = 15.8353 (7) Åθ = 1.9–26.0°
b = 10.2260 (4) ŵ = 0.68 mm1
c = 12.6532 (4) ÅT = 200 K
V = 2048.96 (14) Å3Plate, brown
Z = 40.31 × 0.19 × 0.08 mm
Data collection top
Stoe IPDS-2
diffractometer
1742 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.086
Graphite monochromatorθmax = 26.0°, θmin = 2.4°
ω scansh = 1919
14233 measured reflectionsk = 1012
2007 independent reflectionsl = 1415
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H-atom parameters constrained
S = 1.16 w = 1/[σ2(Fo2) + (0.0406P)2 + 0.9028P]
where P = (Fo2 + 2Fc2)/3
2007 reflections(Δ/σ)max < 0.001
134 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
[Mn(C5H7O2)2(C12H8N2)]V = 2048.96 (14) Å3
Mr = 433.36Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 15.8353 (7) ŵ = 0.68 mm1
b = 10.2260 (4) ÅT = 200 K
c = 12.6532 (4) Å0.31 × 0.19 × 0.08 mm
Data collection top
Stoe IPDS-2
diffractometer
1742 reflections with I > 2σ(I)
14233 measured reflectionsRint = 0.086
2007 independent reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.103Δρmax = 0.26 e Å3
S = 1.16Δρmin = 0.26 e Å3
2007 reflectionsAbsolute structure: ?
134 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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) top
xyzUiso*/Ueq
Mn10.50000.52826 (5)0.75000.03271 (17)
C10.23055 (17)0.4974 (4)0.8396 (3)0.0658 (9)
H1A0.21970.40700.81790.099*
H1B0.18190.55210.82130.099*
H1C0.23980.50040.91620.099*
C20.30819 (15)0.5480 (3)0.7834 (2)0.0425 (6)
C30.29703 (16)0.6189 (3)0.6895 (2)0.0502 (7)
H30.24060.63350.66680.060*
C40.36143 (15)0.6699 (2)0.6268 (2)0.0432 (6)
C50.3379 (2)0.7457 (3)0.5282 (3)0.0675 (9)
H5A0.36970.82790.52610.101*
H5B0.27720.76480.52910.101*
H5C0.35150.69350.46550.101*
O10.37816 (10)0.52168 (17)0.82556 (13)0.0406 (4)
O20.43944 (10)0.65765 (17)0.64402 (14)0.0435 (4)
N110.53476 (11)0.34743 (18)0.84839 (14)0.0328 (4)
C110.56836 (14)0.3481 (2)0.94437 (18)0.0362 (5)
H110.57870.43000.97750.043*
C120.58922 (14)0.2340 (2)0.99889 (19)0.0386 (5)
H120.61370.23881.06730.046*
C130.57416 (14)0.1155 (2)0.95299 (18)0.0377 (5)
H130.58840.03710.98920.045*
C140.53730 (13)0.1099 (2)0.85136 (18)0.0341 (5)
C150.51892 (13)0.2298 (2)0.80233 (17)0.0315 (5)
C160.51771 (14)0.0106 (2)0.7983 (2)0.0378 (5)
H160.53000.09150.83190.045*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0362 (3)0.0284 (3)0.0335 (3)0.0000.00258 (19)0.000
C10.0468 (15)0.088 (3)0.063 (2)0.0034 (15)0.0073 (13)0.0081 (17)
C20.0378 (12)0.0447 (14)0.0448 (14)0.0015 (10)0.0007 (10)0.0077 (11)
C30.0371 (12)0.0531 (16)0.0603 (18)0.0019 (11)0.0077 (12)0.0058 (13)
C40.0458 (13)0.0320 (12)0.0517 (15)0.0019 (10)0.0132 (11)0.0024 (11)
C50.0617 (17)0.0625 (19)0.078 (2)0.0140 (15)0.0290 (16)0.0291 (17)
O10.0387 (8)0.0461 (10)0.0370 (9)0.0003 (7)0.0000 (7)0.0026 (7)
O20.0406 (8)0.0395 (9)0.0504 (10)0.0021 (7)0.0056 (8)0.0119 (8)
N110.0391 (9)0.0296 (9)0.0297 (10)0.0001 (7)0.0014 (7)0.0005 (8)
C110.0407 (11)0.0359 (12)0.0320 (12)0.0009 (9)0.0012 (9)0.0016 (10)
C120.0422 (12)0.0417 (13)0.0320 (12)0.0024 (10)0.0046 (9)0.0014 (10)
C130.0411 (12)0.0373 (13)0.0348 (12)0.0049 (10)0.0005 (9)0.0075 (10)
C140.0374 (11)0.0330 (11)0.0320 (12)0.0028 (9)0.0026 (9)0.0021 (10)
C150.0346 (10)0.0301 (11)0.0297 (12)0.0000 (8)0.0016 (8)0.0005 (9)
C160.0419 (12)0.0289 (11)0.0426 (14)0.0024 (9)0.0049 (10)0.0051 (10)
Geometric parameters (Å, º) top
Mn1—O2i2.1139 (16)C5—H5A0.9800
Mn1—O22.1139 (16)C5—H5B0.9800
Mn1—O1i2.1543 (16)C5—H5C0.9800
Mn1—O12.1543 (16)N11—C111.326 (3)
Mn1—N11i2.2962 (18)N11—C151.360 (3)
Mn1—N112.2962 (18)C11—C121.395 (3)
C1—C21.512 (4)C11—H110.9500
C1—H1A0.9800C12—C131.366 (3)
C1—H1B0.9800C12—H120.9500
C1—H1C0.9800C13—C141.413 (3)
C2—O11.259 (3)C13—H130.9500
C2—C31.403 (4)C14—C151.405 (3)
C3—C41.394 (4)C14—C161.437 (3)
C3—H30.9500C15—C15i1.453 (4)
C4—O21.261 (3)C16—C16i1.344 (5)
C4—C51.515 (4)C16—H160.9500
O2i—Mn1—O2102.50 (10)C4—C5—H5A109.5
O2i—Mn1—O1i83.96 (6)C4—C5—H5B109.5
O2—Mn1—O1i98.30 (6)H5A—C5—H5B109.5
O2i—Mn1—O198.30 (6)C4—C5—H5C109.5
O2—Mn1—O183.96 (6)H5A—C5—H5C109.5
O1i—Mn1—O1176.42 (10)H5B—C5—H5C109.5
O2i—Mn1—N11i163.09 (7)C2—O1—Mn1126.41 (16)
O2—Mn1—N11i92.95 (7)C4—O2—Mn1128.08 (16)
O1i—Mn1—N11i87.07 (6)C11—N11—C15118.14 (19)
O1—Mn1—N11i90.04 (7)C11—N11—Mn1126.04 (15)
O2i—Mn1—N1192.95 (7)C15—N11—Mn1115.82 (14)
O2—Mn1—N11163.09 (7)N11—C11—C12122.9 (2)
O1i—Mn1—N1190.04 (6)N11—C11—H11118.5
O1—Mn1—N1187.07 (6)C12—C11—H11118.5
N11i—Mn1—N1172.71 (9)C13—C12—C11119.4 (2)
C2—C1—H1A109.5C13—C12—H12120.3
C2—C1—H1B109.5C11—C12—H12120.3
H1A—C1—H1B109.5C12—C13—C14119.7 (2)
C2—C1—H1C109.5C12—C13—H13120.2
H1A—C1—H1C109.5C14—C13—H13120.2
H1B—C1—H1C109.5C15—C14—C13116.9 (2)
O1—C2—C3125.5 (2)C15—C14—C16119.8 (2)
O1—C2—C1116.3 (2)C13—C14—C16123.3 (2)
C3—C2—C1118.2 (2)N11—C15—C14123.0 (2)
C4—C3—C2125.7 (2)N11—C15—C15i117.82 (12)
C4—C3—H3117.1C14—C15—C15i119.19 (13)
C2—C3—H3117.1C16i—C16—C14120.99 (13)
O2—C4—C3125.5 (2)C16i—C16—H16119.5
O2—C4—C5115.8 (2)C14—C16—H16119.5
C3—C4—C5118.7 (2)
Symmetry code: (i) x+1, y, z+3/2.

Experimental details

Crystal data
Chemical formula[Mn(C5H7O2)2(C12H8N2)]
Mr433.36
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)200
a, b, c (Å)15.8353 (7), 10.2260 (4), 12.6532 (4)
V3)2048.96 (14)
Z4
Radiation typeMo Kα
µ (mm1)0.68
Crystal size (mm)0.31 × 0.19 × 0.08
Data collection
DiffractometerStoe IPDS2
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
14233, 2007, 1742
Rint0.086
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.103, 1.16
No. of reflections2007
No. of parameters134
No. of restraints0
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.26, 0.26

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Acknowledgements top

We gratefully acknowledge financial support by the DFG (project No. NA 720/3–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

references
References top

Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Stephens, F. S. (1977). Acta Cryst. B33, 3492–3495.

Stoe & Cie (2008). X-AREA. Stoe & Cie, Darmstadt, Germany.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.