metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890
Volume 71| Part 4| April 2015| Pages m81-m82

Crystal structure of bis­­(4-acetyl­pyridine-κN)bis­­(ethanol-κO)bis­­(thio­cyanato-κN)manganese(II)

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aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany
*Correspondence e-mail: jwerner@ac.uni-kiel.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 24 February 2015; accepted 4 March 2015; online 11 March 2015)

In the crystal structure of the title compound, [Mn(NCS)2(C7H7NO)2(C2H5OH)2], the MnII atom is coordin­ated by two N-bonded thio­cyanate anions, two 4-acetyl­pyridine ligands, and two ethanol mol­ecules within a slightly distorted octa­hedron. The asymmetric unit consits of one manganese cation, located on a centre of inversion, one thio­cyanate anion, one 4-acetyl­pyridine ligand and one ethanol mol­ecule in general positions. The discrete complexes are connected by inter­molecular O—H⋯O hydrogen bonds between the alcohol OH group and the carbonyl O atom into chains parallel to [011].

1. Related literature

For a similar structure with thio­cyanato ligands in terminal coordination to a manganese(II) atom, see: Li et al. (2007[Li, H., Li, C.-J. & Hu, Z.-Q. (2007). Acta Cryst. E63, m407-m408.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • [Mn(NCS)2(C7H7NO)2(C2H6O)2]

  • Mr = 505.51

  • Triclinic, [P \overline 1]

  • a = 6.9547 (7) Å

  • b = 9.7733 (9) Å

  • c = 10.1859 (9) Å

  • α = 117.449 (10)°

  • β = 94.978 (11)°

  • γ = 93.379 (11)°

  • V = 608.23 (11) Å3

  • Z = 1

  • Mo Kα radiation

  • μ = 0.75 mm−1

  • T = 200 K

  • 0.04 × 0.03 × 0.02 mm

2.2. Data collection

  • Stoe IPDS-1 diffractometer

  • Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008[Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]) Tmin = 0.966, Tmax = 0.977

  • 6535 measured reflections

  • 2583 independent reflections

  • 2163 reflections with I > 2σ(I)

  • Rint = 0.039

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.033

  • wR(F2) = 0.088

  • S = 1.04

  • 2583 reflections

  • 144 parameters

  • H-atom parameters constrained

  • Δρmax = 0.26 e Å−3

  • Δρmin = −0.35 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O21—H1O1⋯O11i 0.84 1.95 2.7714 (17) 164
Symmetry code: (i) x, y+1, z+1.

Data collection: X-AREA (Stoe & Cie, 2008[Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]); molecular graphics: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Synthesis and crystallization top

MnSO4·H2O was purchased from Merck; 4-acetyl­pyridine and Ba(NCS)2·3H2O were purchased from Alfa Aesar. Mn(NCS)2 was synthesized by stirring 17.97 g (58.44 mmol) Ba(NCS)2·3H2O and 9.88 g (58.44 mmol) MnSO4·H2O in 400 ml water at room temperature for three hours. The white residue of BaSO4 was filtered off and the solvent evaporated using a rotary evaporator. The homogeneity of the product was investigated by X-ray powder diffraction and elemental analysis. The title compound was prepared by the reaction of 42.8 mg (0.25 mmol) Mn(NCS)2 and 55.1 µl (0.50 mmol) 4-acetyl­pyridine in 1.5 ml ethanol at room temperature. After several days, suitable crystals of the title compound were obtained.

Refinement top

The C-bound H atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined with Uiso(H) = 1.2Ueq(C) (1.5 for methyl H atoms) using a riding model with C—H = 0.95 Å for aromatic, C—H = 0.99 Å for methyl­ene and C—H = 0.98 Å for methyl H atoms. The O-bound H atom was located in a difference map. Its bond length was set to a value of 0.84 Å and it was refined with Uiso(H) = 1.5Ueq(O) using a riding model.

Related literature top

For a similar structure with thiocyanato anions in terminal coordination to a manganese(II) atom, see: Li et al. (2007).

Structure description top

For a similar structure with thiocyanato anions in terminal coordination to a manganese(II) atom, see: Li et al. (2007).

Synthesis and crystallization top

MnSO4·H2O was purchased from Merck; 4-acetyl­pyridine and Ba(NCS)2·3H2O were purchased from Alfa Aesar. Mn(NCS)2 was synthesized by stirring 17.97 g (58.44 mmol) Ba(NCS)2·3H2O and 9.88 g (58.44 mmol) MnSO4·H2O in 400 ml water at room temperature for three hours. The white residue of BaSO4 was filtered off and the solvent evaporated using a rotary evaporator. The homogeneity of the product was investigated by X-ray powder diffraction and elemental analysis. The title compound was prepared by the reaction of 42.8 mg (0.25 mmol) Mn(NCS)2 and 55.1 µl (0.50 mmol) 4-acetyl­pyridine in 1.5 ml ethanol at room temperature. After several days, suitable crystals of the title compound were obtained.

Refinement details top

The C-bound H atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined with Uiso(H) = 1.2Ueq(C) (1.5 for methyl H atoms) using a riding model with C—H = 0.95 Å for aromatic, C—H = 0.99 Å for methyl­ene and C—H = 0.98 Å for methyl H atoms. The O-bound H atom was located in a difference map. Its bond length was set to a value of 0.84 Å and it was refined with Uiso(H) = 1.5Ueq(O) using a riding model.

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: SHELXL2013 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The coordination environment of the MnII atom in the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) -x + 2, -y + 1, -z + 1.]
[Figure 2] Fig. 2. Crystal structure of the title compound in a view along [010]. Hydrogen bonds are indicated by dashed lines.
Bis(ethanol-κO)bis[1-(pyridin-4-yl)ethan-1-one-κN]bis(thiocyanato-κN)manganese(II) top
Crystal data top
[Mn(NCS)2(C7H7NO)2(C2H6O)2]Z = 1
Mr = 505.51F(000) = 263
Triclinic, P1Dx = 1.380 Mg m3
a = 6.9547 (7) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.7733 (9) ÅCell parameters from 6535 reflections
c = 10.1859 (9) Åθ = 2.4–27.0°
α = 117.449 (10)°µ = 0.75 mm1
β = 94.978 (11)°T = 200 K
γ = 93.379 (11)°Block, colorless
V = 608.23 (11) Å30.04 × 0.03 × 0.02 mm
Data collection top
Stoe IPDS-1
diffractometer
2163 reflections with I > 2σ(I)
phi scansRint = 0.039
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
θmax = 27.0°, θmin = 2.4°
Tmin = 0.966, Tmax = 0.977h = 88
6535 measured reflectionsk = 1212
2583 independent reflectionsl = 1313
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.033 w = 1/[σ2(Fo2) + (0.0565P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.088(Δ/σ)max < 0.001
S = 1.04Δρmax = 0.26 e Å3
2583 reflectionsΔρmin = 0.35 e Å3
144 parametersExtinction correction: SHELXL2013 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.069 (8)
Crystal data top
[Mn(NCS)2(C7H7NO)2(C2H6O)2]γ = 93.379 (11)°
Mr = 505.51V = 608.23 (11) Å3
Triclinic, P1Z = 1
a = 6.9547 (7) ÅMo Kα radiation
b = 9.7733 (9) ŵ = 0.75 mm1
c = 10.1859 (9) ÅT = 200 K
α = 117.449 (10)°0.04 × 0.03 × 0.02 mm
β = 94.978 (11)°
Data collection top
Stoe IPDS-1
diffractometer
2583 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
2163 reflections with I > 2σ(I)
Tmin = 0.966, Tmax = 0.977Rint = 0.039
6535 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.088H-atom parameters constrained
S = 1.04Δρmax = 0.26 e Å3
2583 reflectionsΔρmin = 0.35 e Å3
144 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mn11.00000.50000.50000.02081 (14)
N10.9402 (2)0.42929 (18)0.66517 (15)0.0300 (3)
C10.8976 (2)0.35987 (19)0.72660 (17)0.0245 (3)
S10.83508 (10)0.25963 (7)0.80913 (7)0.05345 (19)
N110.8542 (2)0.25989 (15)0.30663 (15)0.0250 (3)
C110.8030 (3)0.1414 (2)0.33223 (19)0.0339 (4)
H110.80810.16090.43290.041*
C120.7431 (3)0.0080 (2)0.22080 (19)0.0338 (4)
H120.70990.08860.24510.041*
C130.7325 (2)0.03842 (18)0.07316 (17)0.0241 (3)
C140.7813 (3)0.0837 (2)0.04487 (18)0.0276 (4)
H140.77380.06760.05490.033*
C150.8413 (3)0.2296 (2)0.16300 (18)0.0278 (4)
H150.87490.31230.14170.033*
C160.6741 (3)0.19848 (19)0.05499 (18)0.0285 (4)
C170.6365 (3)0.3314 (2)0.0243 (2)0.0417 (5)
H17A0.60770.42750.11880.063*
H17B0.52540.31580.03220.063*
H17C0.75150.33840.03410.063*
O110.6621 (2)0.21465 (16)0.18155 (14)0.0409 (3)
C210.6624 (4)0.8271 (3)0.4935 (3)0.0549 (6)
H21A0.58560.85970.42960.082*
H21B0.63130.88310.59580.082*
H21C0.80100.85040.49210.082*
C220.6154 (3)0.6558 (2)0.4366 (2)0.0367 (4)
H22A0.47480.63260.43630.044*
H22B0.64450.59990.33250.044*
O210.72349 (18)0.60072 (14)0.52571 (12)0.0291 (3)
H1O10.68540.64460.61010.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0266 (2)0.01896 (19)0.01844 (18)0.00180 (12)0.00503 (13)0.00984 (14)
N10.0409 (9)0.0290 (7)0.0236 (7)0.0005 (6)0.0079 (6)0.0150 (6)
C10.0280 (8)0.0232 (7)0.0217 (7)0.0021 (6)0.0039 (6)0.0099 (6)
S10.0678 (4)0.0535 (4)0.0652 (4)0.0037 (3)0.0157 (3)0.0489 (3)
N110.0295 (7)0.0219 (7)0.0220 (6)0.0014 (5)0.0027 (5)0.0091 (6)
C110.0525 (12)0.0266 (8)0.0206 (7)0.0014 (8)0.0051 (7)0.0099 (7)
C120.0539 (12)0.0225 (8)0.0245 (8)0.0016 (8)0.0056 (8)0.0111 (7)
C130.0237 (8)0.0241 (7)0.0219 (7)0.0041 (6)0.0051 (6)0.0080 (6)
C140.0323 (9)0.0305 (8)0.0194 (7)0.0012 (7)0.0039 (6)0.0114 (7)
C150.0338 (9)0.0267 (8)0.0240 (7)0.0015 (7)0.0026 (7)0.0136 (7)
C160.0273 (8)0.0258 (8)0.0254 (8)0.0060 (7)0.0056 (7)0.0053 (7)
C170.0550 (13)0.0229 (9)0.0374 (10)0.0008 (8)0.0026 (9)0.0069 (8)
O110.0527 (8)0.0372 (7)0.0221 (6)0.0057 (6)0.0073 (6)0.0043 (5)
C210.0604 (15)0.0522 (13)0.0762 (16)0.0160 (11)0.0178 (13)0.0477 (13)
C220.0325 (9)0.0459 (11)0.0341 (9)0.0083 (8)0.0003 (7)0.0210 (9)
O210.0336 (6)0.0315 (6)0.0238 (5)0.0115 (5)0.0080 (5)0.0128 (5)
Geometric parameters (Å, º) top
Mn1—N1i2.1543 (15)C14—C151.385 (2)
Mn1—N12.1543 (15)C14—H140.9500
Mn1—O21i2.1928 (12)C15—H150.9500
Mn1—O212.1929 (12)C16—O111.219 (2)
Mn1—N11i2.3508 (14)C16—C171.484 (3)
Mn1—N112.3508 (14)C17—H17A0.9800
N1—C11.157 (2)C17—H17B0.9800
C1—S11.6211 (18)C17—H17C0.9800
N11—C111.334 (2)C21—C221.502 (3)
N11—C151.346 (2)C21—H21A0.9800
C11—C121.383 (2)C21—H21B0.9800
C11—H110.9500C21—H21C0.9800
C12—C131.386 (2)C22—O211.435 (2)
C12—H120.9500C22—H22A0.9900
C13—C141.381 (3)C22—H22B0.9900
C13—C161.505 (2)O21—H1O10.8400
N1i—Mn1—N1180.0C13—C14—H14120.2
N1i—Mn1—O21i88.59 (5)C15—C14—H14120.2
N1—Mn1—O21i91.41 (5)N11—C15—C14123.05 (16)
N1i—Mn1—O2191.41 (5)N11—C15—H15118.5
N1—Mn1—O2188.59 (5)C14—C15—H15118.5
O21i—Mn1—O21180.0O11—C16—C17122.10 (16)
N1i—Mn1—N11i91.13 (5)O11—C16—C13118.40 (17)
N1—Mn1—N11i88.87 (5)C17—C16—C13119.49 (16)
O21i—Mn1—N11i92.35 (5)C16—C17—H17A109.5
O21—Mn1—N11i87.65 (5)C16—C17—H17B109.5
N1i—Mn1—N1188.87 (5)H17A—C17—H17B109.5
N1—Mn1—N1191.13 (5)C16—C17—H17C109.5
O21i—Mn1—N1187.65 (5)H17A—C17—H17C109.5
O21—Mn1—N1192.35 (5)H17B—C17—H17C109.5
N11i—Mn1—N11180.0C22—C21—H21A109.5
C1—N1—Mn1164.93 (13)C22—C21—H21B109.5
N1—C1—S1178.67 (16)H21A—C21—H21B109.5
C11—N11—C15116.73 (14)C22—C21—H21C109.5
C11—N11—Mn1121.49 (11)H21A—C21—H21C109.5
C15—N11—Mn1121.25 (11)H21B—C21—H21C109.5
N11—C11—C12123.87 (16)O21—C22—C21112.19 (18)
N11—C11—H11118.1O21—C22—H22A109.2
C12—C11—H11118.1C21—C22—H22A109.2
C11—C12—C13118.96 (17)O21—C22—H22B109.2
C11—C12—H12120.5C21—C22—H22B109.2
C13—C12—H12120.5H22A—C22—H22B107.9
C14—C13—C12117.87 (15)C22—O21—Mn1130.79 (11)
C14—C13—C16119.69 (15)C22—O21—H1O1105.5
C12—C13—C16122.44 (16)Mn1—O21—H1O1120.2
C13—C14—C15119.50 (15)
Symmetry code: (i) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O21—H1O1···O11ii0.841.952.7714 (17)164
Symmetry code: (ii) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O21—H1O1···O11i0.841.952.7714 (17)164.1
Symmetry code: (i) x, y+1, z+1.
 

Acknowledgements

We gratefully acknowledge financial support by the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

References

First citationBrandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationLi, H., Li, C.-J. & Hu, Z.-Q. (2007). Acta Cryst. E63, m407–m408.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationStoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.  Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 4| April 2015| Pages m81-m82
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