Bis(acetyl­acetonato-κ²O,O′)(pyridine-κN)(thio­cyanato-κN)manganese(III): a redetermination using data from a single crystal

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.

Related literature

For the preparation of the title compound in the form of a powder, see: Stults et al. (1975).

Experimental

Crystal data

• [Mn(C₅H₇O₂)₂(NCS)(C₅H₅N)]

• M_r = 390.33

• Orthorhombic, C m c 2₁

• a = 13.8803 (6) Å

• b = 8.3195 (5) Å

• c = 15.9035 (7) Å

• V = 1836.49 (16) ų

• Z = 4

• Mo Kα radiation

• μ = 0.85 mm⁻¹

• T = 200 K

• 0.17 × 0.14 × 0.09 mm

Data collection

• STOE IPDS-2 diffractometer

• Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) T_min = 0.802, T_max = 0.883

• 6523 measured reflections

• 2267 independent reflections

• 2090 reflections with I > 2σ(I)

• R_int = 0.028

Refinement

• R[F² > 2σ(F²)] = 0.030

• wR(F²) = 0.066

• S = 1.04

• 2267 reflections

• 126 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.22 e Å⁻³

• Δρ_min = −0.18 e Å⁻³

• Absolute structure: Flack (1983), 1086 Friedel pairs

• Absolute structure parameter: 0.015 (19)

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA; data reduction: X-AREA; 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 and publCIF (Westrip, 2010).

Supporting information

S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

H atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined isotropically with U_eq(H) = 1.2 U_eq(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

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

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)

Crystal data

[Mn(C5H7O2)2(NCS)(C5H5N)]	F(000) = 808
Mr = 390.33	Dx = 1.412 Mg m^−3
Orthorhombic, Cmc21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c -2	Cell parameters from 6523 reflections
a = 13.8803 (6) Å	θ = 2.9–28.0°
b = 8.3195 (5) Å	µ = 0.85 mm^−1
c = 15.9035 (7) Å	T = 200 K
V = 1836.49 (16) Å^3	Plate, brown
Z = 4	0.17 × 0.14 × 0.09 mm

Data collection

STOE IPDS-2 diffractometer	2267 independent reflections
Radiation source: fine-focus sealed tube	2090 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω scan	θmax = 28.0°, θmin = 2.9°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −16→18
Tmin = 0.802, Tmax = 0.883	k = −10→10
6523 measured reflections	l = −20→20

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.066	w = 1/[σ^2(Fo^2) + (0.0294P)^2 + 0.9669P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2267 reflections	Δρmax = 0.22 e Å^−3
126 parameters	Δρmin = −0.18 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1086 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.015 (19)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.5000	0.70123 (5)	0.26659 (3)	0.03145 (11)
S1	0.5000	1.19178 (13)	0.09102 (7)	0.0591 (3)
C1	0.5000	1.0340 (4)	0.1504 (2)	0.0365 (6)
N1	0.5000	0.9206 (3)	0.19339 (18)	0.0442 (7)
N11	0.5000	0.4703 (3)	0.35186 (15)	0.0337 (5)
C11	0.5000	0.4876 (4)	0.4355 (2)	0.0403 (7)
H11	0.5000	0.5931	0.4583	0.048*
C12	0.5000	0.3596 (5)	0.4895 (2)	0.0476 (9)
H12	0.5000	0.3772	0.5485	0.057*
C13	0.5000	0.2045 (5)	0.4580 (3)	0.0503 (10)
H13	0.5000	0.1138	0.4943	0.060*
C14	0.5000	0.1873 (4)	0.3707 (3)	0.0462 (8)
H14	0.5000	0.0832	0.3461	0.055*
C15	0.5000	0.3219 (4)	0.3206 (2)	0.0382 (7)
H15	0.5000	0.3084	0.2613	0.046*
O1	0.40265 (11)	0.78003 (17)	0.34197 (9)	0.0387 (3)
O2	0.40418 (10)	0.60368 (17)	0.19620 (9)	0.0367 (3)
C2	0.26139 (19)	0.4840 (3)	0.14949 (17)	0.0528 (6)
H2A	0.2535	0.5503	0.0990	0.079*
H2B	0.1979	0.4547	0.1716	0.079*
H2C	0.2972	0.3862	0.1352	0.079*
C3	0.31578 (16)	0.5768 (3)	0.21467 (14)	0.0366 (5)
C4	0.27229 (17)	0.6295 (3)	0.28825 (14)	0.0453 (6)
H4	0.2081	0.5956	0.2990	0.054*
C5	0.31605 (15)	0.7284 (3)	0.34724 (15)	0.0397 (5)
C6	0.2633 (2)	0.7827 (4)	0.42460 (18)	0.0568 (7)
H6A	0.3065	0.7769	0.4732	0.085*
H6B	0.2074	0.7130	0.4341	0.085*
H6C	0.2415	0.8938	0.4170	0.085*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0342 (2)	0.0313 (2)	0.0288 (2)	0.000	0.000	0.0002 (2)
S1	0.0976 (10)	0.0392 (5)	0.0406 (6)	0.000	0.000	0.0123 (4)
C1	0.0412 (16)	0.0363 (16)	0.0321 (15)	0.000	0.000	−0.0037 (12)
N1	0.0504 (16)	0.0389 (14)	0.0432 (17)	0.000	0.000	0.0150 (13)
N11	0.0446 (13)	0.0317 (12)	0.0249 (12)	0.000	0.000	−0.0003 (10)
C11	0.0493 (18)	0.0427 (16)	0.0289 (15)	0.000	0.000	−0.0039 (13)
C12	0.052 (2)	0.059 (2)	0.0315 (18)	0.000	0.000	0.0101 (15)
C13	0.050 (2)	0.052 (2)	0.049 (2)	0.000	0.000	0.0154 (18)
C14	0.0520 (19)	0.0347 (18)	0.052 (2)	0.000	0.000	0.0025 (15)
C15	0.0486 (17)	0.0352 (15)	0.0307 (15)	0.000	0.000	−0.0058 (12)
O1	0.0418 (8)	0.0360 (8)	0.0382 (8)	0.0033 (6)	0.0038 (7)	−0.0023 (7)
O2	0.0365 (8)	0.0418 (8)	0.0320 (8)	−0.0014 (6)	−0.0003 (6)	0.0017 (6)
C2	0.0488 (14)	0.0602 (16)	0.0496 (14)	−0.0110 (12)	−0.0093 (12)	−0.0002 (12)
C3	0.0347 (11)	0.0375 (10)	0.0376 (11)	−0.0009 (8)	−0.0052 (9)	0.0077 (9)
C4	0.0350 (11)	0.0573 (14)	0.0436 (15)	−0.0014 (10)	0.0030 (9)	0.0027 (10)
C5	0.0394 (11)	0.0416 (11)	0.0380 (11)	0.0085 (9)	0.0054 (10)	0.0038 (9)
C6	0.0515 (15)	0.0711 (19)	0.0478 (13)	0.0122 (13)	0.0116 (12)	−0.0034 (14)

Geometric parameters (Å, º)

Mn1—O2	1.9185 (15)	C14—C15	1.374 (4)
Mn1—O2^i	1.9185 (15)	C14—H14	0.9500
Mn1—O1^i	1.9216 (15)	C15—H15	0.9500
Mn1—O1	1.9216 (15)	O1—C5	1.279 (3)
Mn1—N1	2.165 (3)	O2—C3	1.281 (3)
Mn1—N11	2.352 (2)	C2—C3	1.497 (3)
S1—C1	1.617 (3)	C2—H2A	0.9800
C1—N1	1.165 (4)	C2—H2B	0.9800
N11—C15	1.331 (4)	C2—H2C	0.9800
N11—C11	1.338 (4)	C3—C4	1.388 (3)
C11—C12	1.368 (5)	C4—C5	1.388 (3)
C11—H11	0.9500	C4—H4	0.9500
C12—C13	1.384 (6)	C5—C6	1.501 (3)
C12—H12	0.9500	C6—H6A	0.9800
C13—C14	1.396 (6)	C6—H6B	0.9800
C13—H13	0.9500	C6—H6C	0.9800
O2—Mn1—O2^i	87.77 (9)	C15—C14—C13	119.5 (3)
O2—Mn1—O1^i	174.74 (7)	C15—C14—H14	120.2
O2^i—Mn1—O1^i	91.20 (6)	C13—C14—H14	120.2
O2—Mn1—O1	91.20 (6)	N11—C15—C14	122.7 (3)
O2^i—Mn1—O1	174.74 (7)	N11—C15—H15	118.7
O1^i—Mn1—O1	89.36 (9)	C14—C15—H15	118.7
O2—Mn1—N1	92.46 (8)	C5—O1—Mn1	125.95 (15)
O2^i—Mn1—N1	92.46 (8)	C3—O2—Mn1	127.15 (14)
O1^i—Mn1—N1	92.74 (7)	C3—C2—H2A	109.5
O1—Mn1—N1	92.74 (7)	C3—C2—H2B	109.5
O2—Mn1—N11	89.47 (6)	H2A—C2—H2B	109.5
O2^i—Mn1—N11	89.47 (6)	C3—C2—H2C	109.5
O1^i—Mn1—N11	85.36 (6)	H2A—C2—H2C	109.5
O1—Mn1—N11	85.36 (6)	H2B—C2—H2C	109.5
N1—Mn1—N11	177.31 (11)	O2—C3—C4	123.7 (2)
N1—C1—S1	179.8 (3)	O2—C3—C2	114.5 (2)
C1—N1—Mn1	176.6 (3)	C4—C3—C2	121.8 (2)
C15—N11—C11	118.1 (3)	C5—C4—C3	124.5 (2)
C15—N11—Mn1	122.9 (2)	C5—C4—H4	117.7
C11—N11—Mn1	119.0 (2)	C3—C4—H4	117.7
N11—C11—C12	122.7 (3)	O1—C5—C4	124.5 (2)
N11—C11—H11	118.6	O1—C5—C6	114.3 (2)
C12—C11—H11	118.6	C4—C5—C6	121.3 (2)
C11—C12—C13	119.9 (3)	C5—C6—H6A	109.5
C11—C12—H12	120.0	C5—C6—H6B	109.5
C13—C12—H12	120.0	H6A—C6—H6B	109.5
C12—C13—C14	117.1 (4)	C5—C6—H6C	109.5
C12—C13—H13	121.5	H6A—C6—H6C	109.5
C14—C13—H13	121.5	H6B—C6—H6C	109.5

Symmetry code: (i) −x+1, y, z.