supplementary materials


bt6942 scheme

Acta Cryst. (2013). E69, m657    [ doi:10.1107/S1600536813030407 ]

Bis(acetyl­acetonato-[kappa]2O,O')(pyridine-[kappa]N)(thio­cyanato-[kappa]N)manganese(III): a redetermination using data from a single crystal

S. Suckert, I. Jess and C. Näther

Abstract top

In the crystal structure of the title compound, [Mn(C5H7O2)2(NCS)(C5H5N)], the Mn3+ cation is coordin­ated by two acetyl­acetonate anions, one terminal thio­cyanate anion and one pyridine ligand within a slightly distorted octa­hedron. The asymmetric unit consists of half a complex mol­ecule with the Mn3+ cation, the thio­cyanate anion and the pyridine ligand located on a mirror plane. The acetyl­acetonate anion is in a general position. The title compound was previously described [Stults et al. (1975). Inorg. Chem. 14, 722-730] but could only be obtained as a powder. Suitable crystals have now been obtained for a high-precision single-crystal structure determination.

Comment top

Crystals of the title compound were prepared within a project on the synthesis of Manganese(III) coordination polymers containing thiocyanato anions and neutral N-donor co-ligands. Within this project manganese(III) acetylacetonate was reacted with potassium thiocyanate and pyridine in a mixture of ethanol and sulfuric acid leading to the formation of crystals of the title compound. The title compound was already described by Stults et al. (1975) but could only be obtained as a microcrystaline powder. We now have been able to get suitable crystals for a single crystal structure determination.

In the crystal structure the manganese(III) cations are coordinated by four oxygen atoms of two symmetry related acetylacetone anions and two nitrogen atoms of an N-terminal coordinated thiocyanato anion and one pyridine ligand into discrete complexes that are located on a mirror plane (Fig. 1). The coordination polyhedron of the Mn cation can be described as a slightly distorted octahedron.

Related literature top

For the microcrystaline powder structure determination, see: Stults et al. (1975).

Experimental top

Manganese(III) 2,4-pentadionate was purchased from Alfa Aesar. Potassium thiocyanate was purchased from Fluka. Pyridine was purchased from Riedel-de Haen. The title compound was prepared by the reaction of 70.5 mg Mn(III) 2,4-pentadionate (0.20 mmol) 58.3 mg potassium thiocyanate (0.6 mmol) and 32.3 µl pyridine (0.4 mmol) in a mixture of 1.0 mL ethanol and 10.68 µl sulfuric acid at RT in a closed 3 ml snap cap vial. After three days brown crystals of the title compound, mostly in the form of plates, were obtained by slow evaporation of the solvent.

Refinement top

H atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined isotropically 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); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. Symmetry code: i = -x+1, y, z.
Bis(acetylacetonato-κ2O,O')(pyridine-κN)(thiocyanato-κN)manganese(III) top
Crystal data top
[Mn(C5H7O2)2(NCS)(C5H5N)]F(000) = 808
Mr = 390.33Dx = 1.412 Mg m3
Orthorhombic, Cmc21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c -2Cell parameters from 6523 reflections
a = 13.8803 (6) Åθ = 2.9–28.0°
b = 8.3195 (5) ŵ = 0.85 mm1
c = 15.9035 (7) ÅT = 200 K
V = 1836.49 (16) Å3Plate, brown
Z = 40.17 × 0.14 × 0.09 mm
Data collection top
STOE IPDS-2
diffractometer
2267 independent reflections
Radiation source: fine-focus sealed tube2090 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ω scanθmax = 28.0°, θmin = 2.9°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
h = 1618
Tmin = 0.802, Tmax = 0.883k = 1010
6523 measured reflectionsl = 2020
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.066 w = 1/[σ2(Fo2) + (0.0294P)2 + 0.9669P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2267 reflectionsΔρmax = 0.22 e Å3
126 parametersΔρmin = 0.18 e Å3
1 restraintAbsolute structure: Flack (1983), 1086 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.015 (19)
Crystal data top
[Mn(C5H7O2)2(NCS)(C5H5N)]V = 1836.49 (16) Å3
Mr = 390.33Z = 4
Orthorhombic, Cmc21Mo Kα radiation
a = 13.8803 (6) ŵ = 0.85 mm1
b = 8.3195 (5) ÅT = 200 K
c = 15.9035 (7) Å0.17 × 0.14 × 0.09 mm
Data collection top
STOE IPDS-2
diffractometer
2267 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
2090 reflections with I > 2σ(I)
Tmin = 0.802, Tmax = 0.883Rint = 0.028
6523 measured reflectionsθmax = 28.0°
Refinement top
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.066Δρmax = 0.22 e Å3
S = 1.04Δρmin = 0.18 e Å3
2267 reflectionsAbsolute structure: Flack (1983), 1086 Friedel pairs
126 parametersAbsolute structure parameter: 0.015 (19)
1 restraint
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
Mn10.50000.70123 (5)0.26659 (3)0.03145 (11)
S10.50001.19178 (13)0.09102 (7)0.0591 (3)
C10.50001.0340 (4)0.1504 (2)0.0365 (6)
N10.50000.9206 (3)0.19339 (18)0.0442 (7)
N110.50000.4703 (3)0.35186 (15)0.0337 (5)
C110.50000.4876 (4)0.4355 (2)0.0403 (7)
H110.50000.59310.45830.048*
C120.50000.3596 (5)0.4895 (2)0.0476 (9)
H120.50000.37720.54850.057*
C130.50000.2045 (5)0.4580 (3)0.0503 (10)
H130.50000.11380.49430.060*
C140.50000.1873 (4)0.3707 (3)0.0462 (8)
H140.50000.08320.34610.055*
C150.50000.3219 (4)0.3206 (2)0.0382 (7)
H150.50000.30840.26130.046*
O10.40265 (11)0.78003 (17)0.34197 (9)0.0387 (3)
O20.40418 (10)0.60368 (17)0.19620 (9)0.0367 (3)
C20.26139 (19)0.4840 (3)0.14949 (17)0.0528 (6)
H2A0.25350.55030.09900.079*
H2B0.19790.45470.17160.079*
H2C0.29720.38620.13520.079*
C30.31578 (16)0.5768 (3)0.21467 (14)0.0366 (5)
C40.27229 (17)0.6295 (3)0.28825 (14)0.0453 (6)
H40.20810.59560.29900.054*
C50.31605 (15)0.7284 (3)0.34724 (15)0.0397 (5)
C60.2633 (2)0.7827 (4)0.42460 (18)0.0568 (7)
H6A0.30650.77690.47320.085*
H6B0.20740.71300.43410.085*
H6C0.24150.89380.41700.085*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0342 (2)0.0313 (2)0.0288 (2)0.0000.0000.0002 (2)
S10.0976 (10)0.0392 (5)0.0406 (6)0.0000.0000.0123 (4)
C10.0412 (16)0.0363 (16)0.0321 (15)0.0000.0000.0037 (12)
N10.0504 (16)0.0389 (14)0.0432 (17)0.0000.0000.0150 (13)
N110.0446 (13)0.0317 (12)0.0249 (12)0.0000.0000.0003 (10)
C110.0493 (18)0.0427 (16)0.0289 (15)0.0000.0000.0039 (13)
C120.052 (2)0.059 (2)0.0315 (18)0.0000.0000.0101 (15)
C130.050 (2)0.052 (2)0.049 (2)0.0000.0000.0154 (18)
C140.0520 (19)0.0347 (18)0.052 (2)0.0000.0000.0025 (15)
C150.0486 (17)0.0352 (15)0.0307 (15)0.0000.0000.0058 (12)
O10.0418 (8)0.0360 (8)0.0382 (8)0.0033 (6)0.0038 (7)0.0023 (7)
O20.0365 (8)0.0418 (8)0.0320 (8)0.0014 (6)0.0003 (6)0.0017 (6)
C20.0488 (14)0.0602 (16)0.0496 (14)0.0110 (12)0.0093 (12)0.0002 (12)
C30.0347 (11)0.0375 (10)0.0376 (11)0.0009 (8)0.0052 (9)0.0077 (9)
C40.0350 (11)0.0573 (14)0.0436 (15)0.0014 (10)0.0030 (9)0.0027 (10)
C50.0394 (11)0.0416 (11)0.0380 (11)0.0085 (9)0.0054 (10)0.0038 (9)
C60.0515 (15)0.0711 (19)0.0478 (13)0.0122 (13)0.0116 (12)0.0034 (14)
Geometric parameters (Å, º) top
Mn1—O21.9185 (15)C14—C151.374 (4)
Mn1—O2i1.9185 (15)C14—H140.9500
Mn1—O1i1.9216 (15)C15—H150.9500
Mn1—O11.9216 (15)O1—C51.279 (3)
Mn1—N12.165 (3)O2—C31.281 (3)
Mn1—N112.352 (2)C2—C31.497 (3)
S1—C11.617 (3)C2—H2A0.9800
C1—N11.165 (4)C2—H2B0.9800
N11—C151.331 (4)C2—H2C0.9800
N11—C111.338 (4)C3—C41.388 (3)
C11—C121.368 (5)C4—C51.388 (3)
C11—H110.9500C4—H40.9500
C12—C131.384 (6)C5—C61.501 (3)
C12—H120.9500C6—H6A0.9800
C13—C141.396 (6)C6—H6B0.9800
C13—H130.9500C6—H6C0.9800
O2—Mn1—O2i87.77 (9)C15—C14—C13119.5 (3)
O2—Mn1—O1i174.74 (7)C15—C14—H14120.2
O2i—Mn1—O1i91.20 (6)C13—C14—H14120.2
O2—Mn1—O191.20 (6)N11—C15—C14122.7 (3)
O2i—Mn1—O1174.74 (7)N11—C15—H15118.7
O1i—Mn1—O189.36 (9)C14—C15—H15118.7
O2—Mn1—N192.46 (8)C5—O1—Mn1125.95 (15)
O2i—Mn1—N192.46 (8)C3—O2—Mn1127.15 (14)
O1i—Mn1—N192.74 (7)C3—C2—H2A109.5
O1—Mn1—N192.74 (7)C3—C2—H2B109.5
O2—Mn1—N1189.47 (6)H2A—C2—H2B109.5
O2i—Mn1—N1189.47 (6)C3—C2—H2C109.5
O1i—Mn1—N1185.36 (6)H2A—C2—H2C109.5
O1—Mn1—N1185.36 (6)H2B—C2—H2C109.5
N1—Mn1—N11177.31 (11)O2—C3—C4123.7 (2)
N1—C1—S1179.8 (3)O2—C3—C2114.5 (2)
C1—N1—Mn1176.6 (3)C4—C3—C2121.8 (2)
C15—N11—C11118.1 (3)C5—C4—C3124.5 (2)
C15—N11—Mn1122.9 (2)C5—C4—H4117.7
C11—N11—Mn1119.0 (2)C3—C4—H4117.7
N11—C11—C12122.7 (3)O1—C5—C4124.5 (2)
N11—C11—H11118.6O1—C5—C6114.3 (2)
C12—C11—H11118.6C4—C5—C6121.3 (2)
C11—C12—C13119.9 (3)C5—C6—H6A109.5
C11—C12—H12120.0C5—C6—H6B109.5
C13—C12—H12120.0H6A—C6—H6B109.5
C12—C13—C14117.1 (4)C5—C6—H6C109.5
C12—C13—H13121.5H6A—C6—H6C109.5
C14—C13—H13121.5H6B—C6—H6C109.5
Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula[Mn(C5H7O2)2(NCS)(C5H5N)]
Mr390.33
Crystal system, space groupOrthorhombic, Cmc21
Temperature (K)200
a, b, c (Å)13.8803 (6), 8.3195 (5), 15.9035 (7)
V3)1836.49 (16)
Z4
Radiation typeMo Kα
µ (mm1)0.85
Crystal size (mm)0.17 × 0.14 × 0.09
Data collection
DiffractometerSTOE IPDS2
diffractometer
Absorption correctionNumerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
Tmin, Tmax0.802, 0.883
No. of measured, independent and
observed [I > 2σ(I)] reflections
6523, 2267, 2090
Rint0.028
(sin θ/λ)max1)0.660
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.066, 1.04
No. of reflections2267
No. of parameters126
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.22, 0.18
Absolute structureFlack (1983), 1086 Friedel pairs
Absolute structure parameter0.015 (19)

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXL97 (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

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

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

Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.

Stults, B. R., Marianelli, R. S. & Day, V. W. (1975). Inorg. Chem. 14, 722–730.

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