supplementary materials


zl2549 scheme

Acta Cryst. (2013). E69, m319    [ doi:10.1107/S1600536813012609 ]

catena-Poly[[[bis(methanol-[kappa]O)bis(selenocyanato-[kappa]N)manganese(II)]-[mu]-1,2-bis(pyridin-4-yl)ethene-[kappa]2N:N'] 1,2-bis(pyridin-4-yl)ethene monosolvate]

S. Wöhlert, I. Jess and C. Näther

Abstract top

In the crystal structure of the title compound, {[Mn(NCSe)2(C12H10N2)(CH3OH)2]·C12H10N2}n, the MnII cation is coordinated by two terminal N-bonded selenocyanate anions, two methanol molecules and two 1,2-bis(pyridin-4-yl)ethene (bpe) ligands within a slightly distorted octahedral geometry. The MnII cations are linked into chains along the c-axis direction by the bpe ligands, which are further connected by intermolecular O-H...N hydrogen bonding between the methanol H atoms and additional bpe molecules that are not coordinated to the metal atoms. The MnII cation and both crystallographically independent bpe ligands are located on centers of inversion, whereas the selenocyanate and methanol ligands occupy general positions.

Comment top

Recently, we have reported on the synthesis, thermal and magnetic properties of new coordination polymers based on paramagnetic transition metal thiocyanates with different neutral co-ligands like e. g. pyridine, 1,2-bis(pyridin-4-yl)ethene (Boeckmann & Näther, 2010, 2012; Wöhlert et al., 2012). In the course of these investigations we have reacted manganese(II) chloride dihydrate with potassium selenocyanate and 1,2-bis(pyridin-4-yl)ethene in methanol, which leads to the formation of crystals of the title compound that were identified by single-crystal structure analysis.

In the crystal structure of the title compound each manganese(II) cation is coordinated by two terminally N-bonded selenocyanate anions, two methanol molecules and two 1,2-bis(pyridin-4-yl)ethene (bpe) ligands within slightly distorted octahedra (Fig. 1). The Mn—O and Mn—N distances range from 2.187 (3) Å to 2.279 (3) Å with angles arround the manganese(II) cation between 86.82 (11) ° and 93.18 (11) ° and 180 ° (Tab. 1). The Mn(II) cations are linked by the bpe ligands into chains, which elongate in the direction of the crystallographic c-axis (Fig. 2). These chains are further linked into layers by intermolecular O—H···N hydrogen bonding to the non-coordinated bpe ligands (Fig. 2, Tab. 2).

Related literature top

For background to this work see: Boeckmann & Näther (2010, 2012); Wöhlert et al. (2012).

Experimental top

MnCl2×2H2O, KNCSe and 1,2-bis(pyridin-4-yl)ethene were obtained from Alfa Aesar. All chemicals were used without further purification. 0.15 mmol (24 mg) MnCl2×2H2O and 0.2 mmol (28 mg) KNCSe were reacted with 0.3 mmol (54 mg) 1,2-bis(pyridin-4-yl)ethene in 1 ml methanol.

Refinement top

All C—H atoms were positions with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined isotropic with Uiso(H) = 1.2 Ueq(C) using a riding model with C—H = 0.94 and 0.97 Å. The O—H H atom was located in a difference map, its bond length was set to 0.83 Å, and finally it was refined isotropically with Uiso(H) = 1.5 Ueq(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: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. : Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: i = -x+2, -y+1, -z+1; ii = -x+1, -y+1, -z; iii = -x+2, -y, -z+1.
[Figure 2] Fig. 2. : Crystal structure of the title compound with view along the a-axis (black = manganese, blue = nitrogen, orange = selenium, red = oxygen, grey = carbon, white = hydrogen). Intermolecular hydrogen bonding is shown as dashed lines.
catena-Poly[[[bis(methanol-κO)bis(selenocyanato-κN)manganese(II)]-µ-1,2-bis(pyridin-4-yl)ethene-κ2N:N'] 1,2-bis(pyridin-4-yl)ethene monosolvate] top
Crystal data top
[Mn(NCSe)2(C12H10N2)(CH4O)2]·C12H10N2F(000) = 694
Mr = 693.42Dx = 1.499 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 14170 reflections
a = 7.3580 (6) Åθ = 2.8–25.0°
b = 17.2445 (11) ŵ = 2.83 mm1
c = 12.1219 (9) ÅT = 220 K
β = 92.630 (9)°Block, yellow
V = 1536.5 (2) Å30.13 × 0.08 × 0.05 mm
Z = 2
Data collection top
Stoe IPDS-1
diffractometer
2633 independent reflections
Radiation source: fine-focus sealed tube2072 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.091
phi scanθmax = 25.0°, θmin = 2.8°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
h = 88
Tmin = 0.754, Tmax = 0.862k = 2020
14170 measured reflectionsl = 1314
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.077P)2]
where P = (Fo2 + 2Fc2)/3
2633 reflections(Δ/σ)max < 0.001
179 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.78 e Å3
Crystal data top
[Mn(NCSe)2(C12H10N2)(CH4O)2]·C12H10N2V = 1536.5 (2) Å3
Mr = 693.42Z = 2
Monoclinic, P21/cMo Kα radiation
a = 7.3580 (6) ŵ = 2.83 mm1
b = 17.2445 (11) ÅT = 220 K
c = 12.1219 (9) Å0.13 × 0.08 × 0.05 mm
β = 92.630 (9)°
Data collection top
Stoe IPDS-1
diffractometer
2633 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
2072 reflections with I > 2σ(I)
Tmin = 0.754, Tmax = 0.862Rint = 0.091
14170 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.112Δρmax = 0.38 e Å3
S = 0.99Δρmin = 0.78 e Å3
2633 reflectionsAbsolute structure: ?
179 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
Mn11.00000.50000.50000.02859 (18)
N10.8412 (3)0.59745 (16)0.5588 (2)0.0411 (6)
C10.7531 (4)0.65174 (18)0.5703 (3)0.0383 (7)
Se10.61619 (5)0.73559 (2)0.58880 (5)0.0748 (2)
N100.8026 (3)0.49379 (14)0.3495 (2)0.0317 (5)
C100.7810 (4)0.55472 (17)0.2815 (3)0.0337 (7)
H100.83520.60200.30320.040*
C110.6839 (4)0.55203 (17)0.1814 (3)0.0329 (6)
H110.67370.59640.13660.039*
C120.6011 (3)0.48261 (16)0.1474 (2)0.0281 (6)
C130.6159 (4)0.42049 (17)0.2201 (3)0.0342 (7)
H130.55740.37330.20250.041*
C140.7172 (4)0.42818 (17)0.3185 (3)0.0358 (7)
H140.72640.38520.36610.043*
C150.5041 (4)0.47366 (18)0.0402 (3)0.0312 (6)
H150.44230.42670.02680.037*
N300.9261 (4)0.26379 (17)0.5841 (4)0.0604 (9)
C301.0231 (6)0.2228 (2)0.6583 (4)0.0605 (10)
H301.06910.24830.72220.073*
C311.0604 (5)0.1445 (2)0.6469 (4)0.0528 (9)
H311.12970.11820.70210.063*
C320.9951 (4)0.10541 (19)0.5537 (3)0.0413 (8)
C330.8968 (5)0.1487 (2)0.4737 (4)0.0576 (10)
H330.85180.12520.40810.069*
C340.8666 (5)0.2261 (2)0.4925 (5)0.0663 (12)
H340.80040.25440.43790.080*
C351.0281 (4)0.02177 (19)0.5422 (3)0.0403 (7)
H351.09500.00290.60010.048*
O10.8375 (3)0.41425 (12)0.58486 (19)0.0386 (5)
H1O10.87410.36870.58400.058*
C20.6647 (5)0.4215 (2)0.6300 (4)0.0636 (11)
H2A0.65650.47120.66710.095*
H2B0.64800.38000.68270.095*
H2C0.57090.41830.57130.095*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0300 (3)0.0289 (3)0.0260 (3)0.0065 (2)0.0084 (2)0.0038 (2)
N10.0433 (14)0.0367 (14)0.0427 (17)0.0107 (12)0.0045 (12)0.0074 (12)
C10.0337 (14)0.0325 (16)0.048 (2)0.0011 (13)0.0026 (13)0.0061 (13)
Se10.0493 (3)0.0317 (3)0.1452 (5)0.01097 (15)0.0249 (3)0.0019 (2)
N100.0335 (12)0.0324 (13)0.0282 (13)0.0039 (10)0.0084 (10)0.0004 (10)
C100.0348 (14)0.0307 (15)0.0344 (17)0.0000 (11)0.0100 (12)0.0011 (12)
C110.0376 (14)0.0320 (15)0.0282 (17)0.0010 (11)0.0072 (12)0.0040 (11)
C120.0232 (12)0.0339 (15)0.0268 (15)0.0029 (10)0.0045 (10)0.0019 (11)
C130.0350 (14)0.0332 (16)0.0337 (17)0.0035 (11)0.0062 (12)0.0011 (12)
C140.0410 (16)0.0329 (16)0.0324 (17)0.0011 (12)0.0091 (13)0.0031 (12)
C150.0263 (13)0.0369 (15)0.0297 (16)0.0013 (11)0.0065 (11)0.0009 (12)
N300.0468 (17)0.0362 (17)0.099 (3)0.0034 (13)0.0122 (17)0.0041 (17)
C300.059 (2)0.046 (2)0.078 (3)0.0011 (17)0.010 (2)0.001 (2)
C310.0517 (19)0.045 (2)0.062 (3)0.0026 (15)0.0041 (17)0.0050 (17)
C320.0278 (14)0.0377 (17)0.059 (2)0.0014 (12)0.0099 (13)0.0125 (15)
C330.0503 (19)0.0381 (19)0.083 (3)0.0021 (15)0.0075 (19)0.0109 (19)
C340.050 (2)0.042 (2)0.106 (4)0.0091 (16)0.007 (2)0.020 (2)
C350.0299 (14)0.0361 (17)0.055 (2)0.0042 (12)0.0062 (13)0.0136 (14)
O10.0332 (10)0.0350 (12)0.0476 (14)0.0057 (8)0.0001 (9)0.0008 (9)
C20.052 (2)0.055 (2)0.085 (3)0.0040 (17)0.023 (2)0.007 (2)
Geometric parameters (Å, º) top
Mn1—N12.185 (3)C15—H150.9400
Mn1—N1i2.185 (3)N30—C301.327 (6)
Mn1—O12.188 (2)N30—C341.343 (6)
Mn1—O1i2.188 (2)C30—C311.386 (6)
Mn1—N10i2.281 (2)C30—H300.9400
Mn1—N102.281 (2)C31—C321.383 (6)
N1—C11.151 (4)C31—H310.9400
C1—Se11.782 (3)C32—C331.399 (5)
N10—C141.340 (4)C32—C351.470 (5)
N10—C101.341 (4)C33—C341.374 (6)
C10—C111.381 (4)C33—H330.9400
C10—H100.9400C34—H340.9400
C11—C121.397 (4)C35—C35iii1.321 (7)
C11—H110.9400C35—H350.9400
C12—C131.388 (4)O1—C21.413 (4)
C12—C151.462 (4)O1—H1O10.8300
C13—C141.384 (4)C2—H2A0.9700
C13—H130.9400C2—H2B0.9700
C14—H140.9400C2—H2C0.9700
C15—C15ii1.331 (6)
N1—Mn1—N1i180.00 (14)N10—C14—H14118.3
N1—Mn1—O193.12 (10)C13—C14—H14118.3
N1i—Mn1—O186.88 (10)C15ii—C15—C12125.6 (4)
N1—Mn1—O1i86.88 (10)C15ii—C15—H15117.2
N1i—Mn1—O1i93.12 (10)C12—C15—H15117.2
O1—Mn1—O1i180.00 (8)C30—N30—C34116.6 (3)
N1—Mn1—N10i91.91 (9)N30—C30—C31123.6 (4)
N1i—Mn1—N10i88.09 (9)N30—C30—H30118.2
O1—Mn1—N10i89.85 (9)C31—C30—H30118.2
O1i—Mn1—N10i90.15 (9)C32—C31—C30119.6 (4)
N1—Mn1—N1088.09 (9)C32—C31—H31120.2
N1i—Mn1—N1091.91 (9)C30—C31—H31120.2
O1—Mn1—N1090.15 (9)C31—C32—C33117.0 (3)
O1i—Mn1—N1089.85 (8)C31—C32—C35120.2 (3)
N10i—Mn1—N10180.000 (1)C33—C32—C35122.8 (4)
C1—N1—Mn1167.9 (3)C34—C33—C32119.1 (4)
N1—C1—Se1179.6 (3)C34—C33—H33120.4
C14—N10—C10116.6 (2)C32—C33—H33120.4
C14—N10—Mn1122.50 (19)N30—C34—C33123.9 (4)
C10—N10—Mn1120.54 (19)N30—C34—H34118.0
N10—C10—C11123.8 (3)C33—C34—H34118.0
N10—C10—H10118.1C35iii—C35—C32125.7 (4)
C11—C10—H10118.1C35iii—C35—H35117.2
C10—C11—C12119.3 (3)C32—C35—H35117.2
C10—C11—H11120.3C2—O1—Mn1130.0 (2)
C12—C11—H11120.3C2—O1—H1O1112.7
C13—C12—C11117.0 (3)Mn1—O1—H1O1116.7
C13—C12—C15120.3 (3)O1—C2—H2A109.5
C11—C12—C15122.8 (3)O1—C2—H2B109.5
C14—C13—C12119.8 (3)H2A—C2—H2B109.5
C14—C13—H13120.1O1—C2—H2C109.5
C12—C13—H13120.1H2A—C2—H2C109.5
N10—C14—C13123.4 (3)H2B—C2—H2C109.5
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+1, y+1, z; (iii) x+2, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···N300.831.852.675 (4)173
Selected bond lengths (Å) top
Mn1—N12.185 (3)Mn1—N102.281 (2)
Mn1—O12.188 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···N300.831.852.675 (4)172.9
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 facility.

references
References top

Boeckmann, J. & Näther, C. (2010). Dalton Trans. 39, 11019–11026.

Boeckmann, J. & Näther, C. (2012). Polyhedron, 31, 587–595.

Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany.

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

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

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

Wöhlert, S., Jess, I. & Näther, C. (2012). Z. Naturforsch. Teil B, 67, 41–50.