Crystal structure of bis­[4-(di­methyl­amino)­pyridine-κN1]bis­(methanol-κO)bis­(thio­cyanato-κN)manganese(II)

Suckert, S.; Jess, I.; Näther, C.

doi:10.1107/S2056989015007318

metal-organic compounds

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Crystal structure of bis[4-(dimethylamino)pyridine-κN¹]bis(methanol-κO)bis(thiocyanato-κN)manganese(II)

Stefan Suckert,^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: ssuckert@ac.uni-kiel.de

Edited by J. Simpson, University of Otago, New Zealand (Received 11 March 2015; accepted 13 April 2015; online 30 April 2015)

The whole molecule of the title compound, [Mn(NCS)₂(CH₃OH)₂(C₅H₆N₂)₂], is generated by inversion symmetry. The Mn^II ion, which is located on an inversion center, is coordinated by two 4-(dimethylamino)pyridine ligands, two methanol ligands and two terminally N-bonded thiocyanate anions, forming a slightly distorted octahedron. In the crystal, molecules are linked by O—H⋯S hydrogen bonds, forming chains extending along the a-axis direction.

Keywords: crystal structure; discrete complex; octahedral coordination; hydrogen bonding.

CCDC reference: 1059105

1. Related literature

For the structure of another discrete complex with 4-(dimethylamino)pyridine and thiocyanate ligands, see: Chen et al. (2007 ). For general background to this work, see: Näther et al. (2013 ).

2. Experimental

2.1. Crystal data

[Mn(NCS)₂(CH₄O)₂(C₅H₆N₂)₂]
M_r = 479.52
Triclinic, $[P \overline 1]$
a = 7.0771 (7) Å
b = 8.1586 (8) Å
c = 10.6491 (10) Å
α = 76.381 (11)°
β = 81.672 (11)°
γ = 79.809 (11)°
V = 584.72 (10) Å³
Z = 1
Mo Kα radiation
μ = 0.77 mm⁻¹
T = 180 K
0.16 × 0.10 × 0.04 mm

2.2. Data collection

Stoe IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ) T_min = 0.903, T_max = 0.959
4585 measured reflections
2459 independent reflections
1885 reflections with I > 2σ(I)
R_int = 0.039

2.3. Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.100
S = 1.04
2459 reflections
133 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O31—H1O⋯S1ⁱ	0.85	2.42	3.2409 (18)	161
Symmetry code: (i) x-1, y, z.

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: 1059105

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989015007318/sj5446sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015007318/sj5446Isup2.hkl

checkCIF report

Synthesis and crystallization top

MnSO₄.H₂O was purchased from Merck and 4-(dimethylamino)pyridine and Ba(NCS)₂.3 H₂O were purchased from Alfa Aesar. Mn(NCS)₂ was synthesized by stirring 17.97 g (58.44 mmol) Ba(NCS)₂.3 H₂O and 9.88 g (58.44 mmol) MnSO₄.H₂O in 300 mL H₂O at room temperature for three hours. The white precipitate of BaSO₄ was filtered of and the solvent removed with 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 (0.18 mmol) 30.8 mg Mn(NCS)₂ and (0.3 mmol) 36.7 mg 4-(dimethylamino)pyridine in 1.0 mL methanol at room temperature. After a few days colorless plate shaped crystals of the title compound were obtained.

Refinement top

The C—H H atoms were positioned with idealized geometry and were refined isotropically with U_iso(H) = 1.2 U_eq(C) (1.5 for methyl H atoms) using a riding model with C—H = 0.95 Å for aromatic and and C—H = 0.98 Å for methyl H atoms. The O—H H atom was located in a difference map, its bond length set to ideal values of 0.85 Å and refined with U_iso(H) = 1.5 U_eq(O)using a riding model.

Related literature top

For the structure of another discrete complex with 4-(dimethylamino)pyridine and thiocyanate ligands, see: Chen et al. (2007). For general background to this work, see: Näther et al. (2013).

Structure description top

For the structure of another discrete complex with 4-(dimethylamino)pyridine and thiocyanate ligands, see: Chen et al. (2007). For general background to this work, see: Näther et al. (2013).

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. Structure of the title complex with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Symmetry code: i = -x+1,-y,-z+1.
	Fig. 2. Crystal structure of the title compound viewed perpendicular to the crystallographic a,c plane.

Bis[4-(dimethylamino)pyridine-κN¹]bis(methanol-κO)bis(thiocyanato-κN)manganese(II) top

Crystal data top

[Mn(NCS)₂(CH₄O)₂(C₅H₆N₂)₂]	Z = 1
M_r = 479.52	F(000) = 251
Triclinic, P1	D_x = 1.362 Mg m⁻³
a = 7.0771 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.1586 (8) Å	Cell parameters from 4585 reflections
c = 10.6491 (10) Å	θ = 2.6–27.0°
α = 76.381 (11)°	µ = 0.77 mm⁻¹
β = 81.672 (11)°	T = 180 K
γ = 79.809 (11)°	Plate, colorless
V = 584.72 (10) Å³	0.16 × 0.10 × 0.04 mm

Data collection top

Stoe IPDS-1 diffractometer	1885 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.039
phi scans	θ_max = 27.0°, θ_min = 2.6°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −9→9
T_min = 0.903, T_max = 0.959	k = −10→10
4585 measured reflections	l = −13→13
2459 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.0598P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2459 reflections	Δρ_max = 0.30 e Å⁻³
133 parameters	Δρ_min = −0.59 e Å⁻³

Crystal data top

[Mn(NCS)₂(CH₄O)₂(C₅H₆N₂)₂]	γ = 79.809 (11)°
M_r = 479.52	V = 584.72 (10) Å³
Triclinic, P1	Z = 1
a = 7.0771 (7) Å	Mo Kα radiation
b = 8.1586 (8) Å	µ = 0.77 mm⁻¹
c = 10.6491 (10) Å	T = 180 K
α = 76.381 (11)°	0.16 × 0.10 × 0.04 mm
β = 81.672 (11)°

Data collection top

Stoe IPDS-1 diffractometer	2459 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	1885 reflections with I > 2σ(I)
T_min = 0.903, T_max = 0.959	R_int = 0.039
4585 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.04	Δρ_max = 0.30 e Å⁻³
2459 reflections	Δρ_min = −0.59 e Å⁻³
133 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	0.5000	0.0000	0.5000	0.02111 (15)
N1	0.6294 (3)	0.0926 (3)	0.63997 (19)	0.0312 (5)
C1	0.7395 (3)	0.1199 (3)	0.7004 (2)	0.0236 (5)
S1	0.89299 (9)	0.15954 (10)	0.78630 (6)	0.0394 (2)
O31	0.2205 (2)	0.1737 (2)	0.53900 (16)	0.0339 (4)
H1O	0.1462	0.1444	0.6079	0.051*
C31	0.0945 (4)	0.2643 (4)	0.4439 (3)	0.0486 (7)
H31A	−0.0136	0.3337	0.4847	0.073*
H31B	0.0448	0.1828	0.4074	0.073*
H31C	0.1659	0.3386	0.3743	0.073*
N11	0.5945 (3)	0.2090 (2)	0.33954 (17)	0.0222 (4)
N12	0.7263 (3)	0.6192 (2)	0.03652 (18)	0.0274 (4)
C11	0.5795 (3)	0.3682 (3)	0.3576 (2)	0.0264 (5)
H11	0.5369	0.3866	0.4427	0.032*
C12	0.6210 (3)	0.5063 (3)	0.2624 (2)	0.0252 (5)
H12	0.6057	0.6157	0.2825	0.030*
C13	0.6867 (3)	0.4861 (3)	0.1345 (2)	0.0210 (4)
C14	0.7077 (3)	0.3182 (3)	0.1162 (2)	0.0230 (4)
H14	0.7554	0.2942	0.0334	0.028*
C15	0.6594 (3)	0.1895 (3)	0.2177 (2)	0.0235 (5)
H15	0.6727	0.0783	0.2011	0.028*
C16	0.6858 (4)	0.7919 (3)	0.0569 (3)	0.0353 (6)
H16A	0.7210	0.8713	−0.0243	0.053*
H16B	0.7612	0.8015	0.1244	0.053*
H16C	0.5479	0.8196	0.0844	0.053*
C17	0.7938 (3)	0.5957 (3)	−0.0944 (2)	0.0309 (5)
H17A	0.8140	0.7059	−0.1514	0.046*
H17B	0.6972	0.5482	−0.1267	0.046*
H17C	0.9158	0.5171	−0.0934	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0216 (2)	0.0237 (3)	0.0185 (2)	−0.00575 (18)	0.00127 (17)	−0.00564 (18)
N1	0.0330 (10)	0.0364 (12)	0.0282 (10)	−0.0112 (9)	−0.0016 (8)	−0.0117 (9)
C1	0.0254 (11)	0.0242 (11)	0.0201 (10)	−0.0035 (8)	0.0040 (8)	−0.0067 (9)
S1	0.0261 (3)	0.0703 (5)	0.0288 (3)	−0.0110 (3)	0.0005 (2)	−0.0240 (3)
O31	0.0250 (8)	0.0444 (11)	0.0258 (8)	0.0030 (7)	0.0033 (6)	−0.0046 (8)
C31	0.0373 (15)	0.062 (2)	0.0343 (14)	0.0113 (13)	−0.0022 (11)	−0.0017 (13)
N11	0.0272 (9)	0.0210 (9)	0.0188 (9)	−0.0037 (7)	0.0014 (7)	−0.0070 (7)
N12	0.0300 (10)	0.0241 (10)	0.0248 (10)	−0.0039 (8)	0.0015 (8)	−0.0017 (8)
C11	0.0325 (12)	0.0263 (12)	0.0210 (11)	−0.0043 (9)	0.0028 (8)	−0.0100 (9)
C12	0.0306 (11)	0.0201 (11)	0.0267 (11)	−0.0032 (9)	−0.0011 (9)	−0.0100 (9)
C13	0.0143 (9)	0.0245 (11)	0.0238 (10)	−0.0031 (8)	−0.0019 (7)	−0.0040 (9)
C14	0.0205 (10)	0.0270 (11)	0.0210 (10)	−0.0009 (8)	0.0022 (8)	−0.0090 (9)
C15	0.0222 (10)	0.0242 (11)	0.0258 (11)	−0.0021 (8)	0.0013 (8)	−0.0119 (9)
C16	0.0405 (14)	0.0234 (12)	0.0399 (14)	−0.0064 (10)	−0.0011 (11)	−0.0034 (11)
C17	0.0274 (11)	0.0402 (14)	0.0217 (11)	−0.0070 (10)	−0.0001 (9)	0.0001 (10)

Geometric parameters (Å, º) top

Mn1—N1ⁱ	2.192 (2)	N12—C16	1.448 (3)
Mn1—N1	2.192 (2)	N12—C17	1.452 (3)
Mn1—N11	2.2302 (17)	C11—C12	1.370 (3)
Mn1—N11ⁱ	2.2302 (17)	C11—H11	0.9500
Mn1—O31	2.2676 (17)	C12—C13	1.412 (3)
Mn1—O31ⁱ	2.2676 (17)	C12—H12	0.9500
N1—C1	1.160 (3)	C13—C14	1.408 (3)
C1—S1	1.634 (2)	C14—C15	1.368 (3)
O31—C31	1.429 (3)	C14—H14	0.9500
O31—H1O	0.8500	C15—H15	0.9500
C31—H31A	0.9800	C16—H16A	0.9800
C31—H31B	0.9800	C16—H16B	0.9800
C31—H31C	0.9800	C16—H16C	0.9800
N11—C11	1.341 (3)	C17—H17A	0.9800
N11—C15	1.349 (3)	C17—H17B	0.9800
N12—C13	1.355 (3)	C17—H17C	0.9800

N1ⁱ—Mn1—N1	180.0	C13—N12—C17	121.3 (2)
N1ⁱ—Mn1—N11	89.19 (7)	C16—N12—C17	117.81 (19)
N1—Mn1—N11	90.81 (7)	N11—C11—C12	124.8 (2)
N1ⁱ—Mn1—N11ⁱ	90.81 (7)	N11—C11—H11	117.6
N1—Mn1—N11ⁱ	89.19 (7)	C12—C11—H11	117.6
N11—Mn1—N11ⁱ	180.0	C11—C12—C13	120.0 (2)
N1ⁱ—Mn1—O31	90.50 (7)	C11—C12—H12	120.0
N1—Mn1—O31	89.50 (7)	C13—C12—H12	120.0
N11—Mn1—O31	89.07 (6)	N12—C13—C14	122.6 (2)
N11ⁱ—Mn1—O31	90.93 (6)	N12—C13—C12	122.2 (2)
N1ⁱ—Mn1—O31ⁱ	89.50 (7)	C14—C13—C12	115.22 (19)
N1—Mn1—O31ⁱ	90.50 (7)	C15—C14—C13	120.1 (2)
N11—Mn1—O31ⁱ	90.93 (6)	C15—C14—H14	120.0
N11ⁱ—Mn1—O31ⁱ	89.07 (6)	C13—C14—H14	120.0
O31—Mn1—O31ⁱ	180.0	N11—C15—C14	124.7 (2)
C1—N1—Mn1	162.79 (19)	N11—C15—H15	117.6
N1—C1—S1	179.4 (2)	C14—C15—H15	117.6
C31—O31—Mn1	125.44 (16)	N12—C16—H16A	109.5
C31—O31—H1O	105.1	N12—C16—H16B	109.5
Mn1—O31—H1O	119.1	H16A—C16—H16B	109.5
O31—C31—H31A	109.5	N12—C16—H16C	109.5
O31—C31—H31B	109.5	H16A—C16—H16C	109.5
H31A—C31—H31B	109.5	H16B—C16—H16C	109.5
O31—C31—H31C	109.5	N12—C17—H17A	109.5
H31A—C31—H31C	109.5	N12—C17—H17B	109.5
H31B—C31—H31C	109.5	H17A—C17—H17B	109.5
C11—N11—C15	115.11 (18)	N12—C17—H17C	109.5
C11—N11—Mn1	120.90 (14)	H17A—C17—H17C	109.5
C15—N11—Mn1	123.89 (15)	H17B—C17—H17C	109.5
C13—N12—C16	120.6 (2)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O31—H1O···S1ⁱⁱ	0.85	2.42	3.2409 (18)	161

Symmetry code: (ii) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O31—H1O···S1ⁱ	0.85	2.42	3.2409 (18)	161.1

Symmetry code: (i) x−1, y, z.

Acknowledgements

We gratefully acknowledge financial support by the DFG (project number NA 720/5-1) and 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
Chen, F.-J., Liu, G.-Q. & Zeng, Z.-Z. (2007). Anal. Sci. X, 23, x253–x254. CSD CrossRef CAS Google Scholar
Näther, C., Wöhlert, S., Boeckmann, J., Wriedt, M. & Jess, I. (2013). Z. Anorg. Allg. Chem. 639, 2696–2714. 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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