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

Werner, J.; Jess, I.; Näther, C.

doi:10.1107/S2056989015004533

metal-organic compounds

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Volume 71| Part 4| April 2015| Pages m81-m82

doi:10.1107/S2056989015004533

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

Julia Werner,^a ^* Inke Jess ^a and Christian Näther ^a

^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 Mn^II 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].

Keywords: crystal structure; manganese(II); octahedral coordination; hydrogen bonding.

CCDC reference: 1052202

1. Related literature

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

2. Experimental

2.1. Crystal data

[Mn(NCS)₂(C₇H₇NO)₂(C₂H₆O)₂]
M_r = 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 ) T_min = 0.966, T_max = 0.977
6535 measured reflections
2583 independent reflections
2163 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: X-AREA; data reduction: X-AREA; 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 ).

Supporting information

CCDC reference: 1052202

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2056989015004533/wm5131sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015004533/wm5131Isup2.hkl

checkCIF report

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 U_iso(H) = 1.2U_eq(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 U_iso(H) = 1.5U_eq(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

Refinement details top

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

	Fig. 1. The coordination environment of the Mn^II atom in the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) -x + 2, -y + 1, -z + 1.]
	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
M_r = 505.51	F(000) = 263
Triclinic, P1	D_x = 1.380 Mg m⁻³
a = 6.9547 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7733 (9) Å	Cell parameters from 6535 reflections
c = 10.1859 (9) Å	θ = 2.4–27.0°
α = 117.449 (10)°	µ = 0.75 mm⁻¹
β = 94.978 (11)°	T = 200 K
γ = 93.379 (11)°	Block, colorless
V = 608.23 (11) Å³	0.04 × 0.03 × 0.02 mm

Data collection top

Stoe IPDS-1 diffractometer	2163 reflections with I > 2σ(I)
phi scans	R_int = 0.039
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	θ_max = 27.0°, θ_min = 2.4°
T_min = 0.966, T_max = 0.977	h = −8→8
6535 measured reflections	k = −12→12
2583 independent reflections	l = −13→13

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.033	w = 1/[σ²(F_o²) + (0.0565P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.088	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.26 e Å⁻³
2583 reflections	Δρ_min = −0.35 e Å⁻³
144 parameters	Extinction correction: SHELXL2013 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.069 (8)

Crystal data top

[Mn(NCS)₂(C₇H₇NO)₂(C₂H₆O)₂]	γ = 93.379 (11)°
M_r = 505.51	V = 608.23 (11) Å³
Triclinic, P1	Z = 1
a = 6.9547 (7) Å	Mo Kα radiation
b = 9.7733 (9) Å	µ = 0.75 mm⁻¹
c = 10.1859 (9) Å	T = 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)
T_min = 0.966, T_max = 0.977	R_int = 0.039
6535 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.04	Δρ_max = 0.26 e Å⁻³
2583 reflections	Δρ_min = −0.35 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Mn1	1.0000	0.5000	0.5000	0.02081 (14)
N1	0.9402 (2)	0.42929 (18)	0.66517 (15)	0.0300 (3)
C1	0.8976 (2)	0.35987 (19)	0.72660 (17)	0.0245 (3)
S1	0.83508 (10)	0.25963 (7)	0.80913 (7)	0.05345 (19)
N11	0.8542 (2)	0.25989 (15)	0.30663 (15)	0.0250 (3)
C11	0.8030 (3)	0.1414 (2)	0.33223 (19)	0.0339 (4)
H11	0.8081	0.1609	0.4329	0.041*
C12	0.7431 (3)	−0.0080 (2)	0.22080 (19)	0.0338 (4)
H12	0.7099	−0.0886	0.2451	0.041*
C13	0.7325 (2)	−0.03842 (18)	0.07316 (17)	0.0241 (3)
C14	0.7813 (3)	0.0837 (2)	0.04487 (18)	0.0276 (4)
H14	0.7738	0.0676	−0.0549	0.033*
C15	0.8413 (3)	0.2296 (2)	0.16300 (18)	0.0278 (4)
H15	0.8749	0.3123	0.1417	0.033*
C16	0.6741 (3)	−0.19848 (19)	−0.05499 (18)	0.0285 (4)
C17	0.6365 (3)	−0.3314 (2)	−0.0243 (2)	0.0417 (5)
H17A	0.6077	−0.4275	−0.1188	0.063*
H17B	0.5254	−0.3158	0.0322	0.063*
H17C	0.7515	−0.3384	0.0341	0.063*
O11	0.6621 (2)	−0.21465 (16)	−0.18155 (14)	0.0409 (3)
C21	0.6624 (4)	0.8271 (3)	0.4935 (3)	0.0549 (6)
H21A	0.5856	0.8597	0.4296	0.082*
H21B	0.6313	0.8831	0.5958	0.082*
H21C	0.8010	0.8504	0.4921	0.082*
C22	0.6154 (3)	0.6558 (2)	0.4366 (2)	0.0367 (4)
H22A	0.4748	0.6326	0.4363	0.044*
H22B	0.6445	0.5999	0.3325	0.044*
O21	0.72349 (18)	0.60072 (14)	0.52571 (12)	0.0291 (3)
H1O1	0.6854	0.6446	0.6101	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0266 (2)	0.01896 (19)	0.01844 (18)	0.00180 (12)	0.00503 (13)	0.00984 (14)
N1	0.0409 (9)	0.0290 (7)	0.0236 (7)	0.0005 (6)	0.0079 (6)	0.0150 (6)
C1	0.0280 (8)	0.0232 (7)	0.0217 (7)	0.0021 (6)	0.0039 (6)	0.0099 (6)
S1	0.0678 (4)	0.0535 (4)	0.0652 (4)	0.0037 (3)	0.0157 (3)	0.0489 (3)
N11	0.0295 (7)	0.0219 (7)	0.0220 (6)	0.0014 (5)	0.0027 (5)	0.0091 (6)
C11	0.0525 (12)	0.0266 (8)	0.0206 (7)	−0.0014 (8)	0.0051 (7)	0.0099 (7)
C12	0.0539 (12)	0.0225 (8)	0.0245 (8)	−0.0016 (8)	0.0056 (8)	0.0111 (7)
C13	0.0237 (8)	0.0241 (7)	0.0219 (7)	0.0041 (6)	0.0051 (6)	0.0080 (6)
C14	0.0323 (9)	0.0305 (8)	0.0194 (7)	0.0012 (7)	0.0039 (6)	0.0114 (7)
C15	0.0338 (9)	0.0267 (8)	0.0240 (7)	−0.0015 (7)	0.0026 (7)	0.0136 (7)
C16	0.0273 (8)	0.0258 (8)	0.0254 (8)	0.0060 (7)	0.0056 (7)	0.0053 (7)
C17	0.0550 (13)	0.0229 (9)	0.0374 (10)	−0.0008 (8)	0.0026 (9)	0.0069 (8)
O11	0.0527 (8)	0.0372 (7)	0.0221 (6)	0.0057 (6)	0.0073 (6)	0.0043 (5)
C21	0.0604 (15)	0.0522 (13)	0.0762 (16)	0.0160 (11)	0.0178 (13)	0.0477 (13)
C22	0.0325 (9)	0.0459 (11)	0.0341 (9)	0.0083 (8)	0.0003 (7)	0.0210 (9)
O21	0.0336 (6)	0.0315 (6)	0.0238 (5)	0.0115 (5)	0.0080 (5)	0.0128 (5)

Geometric parameters (Å, º) top

Mn1—N1ⁱ	2.1543 (15)	C14—C15	1.385 (2)
Mn1—N1	2.1543 (15)	C14—H14	0.9500
Mn1—O21ⁱ	2.1928 (12)	C15—H15	0.9500
Mn1—O21	2.1929 (12)	C16—O11	1.219 (2)
Mn1—N11ⁱ	2.3508 (14)	C16—C17	1.484 (3)
Mn1—N11	2.3508 (14)	C17—H17A	0.9800
N1—C1	1.157 (2)	C17—H17B	0.9800
C1—S1	1.6211 (18)	C17—H17C	0.9800
N11—C11	1.334 (2)	C21—C22	1.502 (3)
N11—C15	1.346 (2)	C21—H21A	0.9800
C11—C12	1.383 (2)	C21—H21B	0.9800
C11—H11	0.9500	C21—H21C	0.9800
C12—C13	1.386 (2)	C22—O21	1.435 (2)
C12—H12	0.9500	C22—H22A	0.9900
C13—C14	1.381 (3)	C22—H22B	0.9900
C13—C16	1.505 (2)	O21—H1O1	0.8400

N1ⁱ—Mn1—N1	180.0	C13—C14—H14	120.2
N1ⁱ—Mn1—O21ⁱ	88.59 (5)	C15—C14—H14	120.2
N1—Mn1—O21ⁱ	91.41 (5)	N11—C15—C14	123.05 (16)
N1ⁱ—Mn1—O21	91.41 (5)	N11—C15—H15	118.5
N1—Mn1—O21	88.59 (5)	C14—C15—H15	118.5
O21ⁱ—Mn1—O21	180.0	O11—C16—C17	122.10 (16)
N1ⁱ—Mn1—N11ⁱ	91.13 (5)	O11—C16—C13	118.40 (17)
N1—Mn1—N11ⁱ	88.87 (5)	C17—C16—C13	119.49 (16)
O21ⁱ—Mn1—N11ⁱ	92.35 (5)	C16—C17—H17A	109.5
O21—Mn1—N11ⁱ	87.65 (5)	C16—C17—H17B	109.5
N1ⁱ—Mn1—N11	88.87 (5)	H17A—C17—H17B	109.5
N1—Mn1—N11	91.13 (5)	C16—C17—H17C	109.5
O21ⁱ—Mn1—N11	87.65 (5)	H17A—C17—H17C	109.5
O21—Mn1—N11	92.35 (5)	H17B—C17—H17C	109.5
N11ⁱ—Mn1—N11	180.0	C22—C21—H21A	109.5
C1—N1—Mn1	164.93 (13)	C22—C21—H21B	109.5
N1—C1—S1	178.67 (16)	H21A—C21—H21B	109.5
C11—N11—C15	116.73 (14)	C22—C21—H21C	109.5
C11—N11—Mn1	121.49 (11)	H21A—C21—H21C	109.5
C15—N11—Mn1	121.25 (11)	H21B—C21—H21C	109.5
N11—C11—C12	123.87 (16)	O21—C22—C21	112.19 (18)
N11—C11—H11	118.1	O21—C22—H22A	109.2
C12—C11—H11	118.1	C21—C22—H22A	109.2
C11—C12—C13	118.96 (17)	O21—C22—H22B	109.2
C11—C12—H12	120.5	C21—C22—H22B	109.2
C13—C12—H12	120.5	H22A—C22—H22B	107.9
C14—C13—C12	117.87 (15)	C22—O21—Mn1	130.79 (11)
C14—C13—C16	119.69 (15)	C22—O21—H1O1	105.5
C12—C13—C16	122.44 (16)	Mn1—O21—H1O1	120.2
C13—C14—C15	119.50 (15)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O21—H1O1···O11ⁱⁱ	0.84	1.95	2.7714 (17)	164

Symmetry code: (ii) x, y+1, z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O21—H1O1···O11ⁱ	0.84	1.95	2.7714 (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

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

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

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doi:10.1107/S2056989015004533

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

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

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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