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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): m1014–m1015.
Published online 2010 July 24. doi:  10.1107/S1600536810028941
PMCID: PMC3007293

Diaqua­bis­(seleno­cyanato-κN)bis­(pyrimidine-κN)manganese(II)

Abstract

In the crystal structure of the title compound, [Mn(NCSe)2(C4H4N2)2(H2O)2], the manganese(II) cation is coordinated by two N-bonded pyrimidine ligands, two N-bonded seleno­cyanate anions and two O-bonded water mol­ecules in a distorted octa­hedral coordination mode. The asymmetric unit consists of one manganese(II) cation, located on a centre of inversion, as well as one seleno­cyanate anion, one water mol­ecule and one pyrimidine ligand in general positions. The crystal structure consists of discrete building blocks of composition [Mn(NCSe)2(pyrimidine)2(H2O)2], which are connected into layers parallel to (101) by strong water–pyrimidine O—H(...)N hydrogen bonds.

Related literature

For a related pyrimidine structure, see: Lipkowski & Soldatov (1993 [triangle]). For general background to the use of thermal decomposition reactions for the discovery and preparation of new ligand-deficient coordination polymers with defined magnetic properties, see: Wriedt & Näther (2009a [triangle],b [triangle]); Wriedt et al. (2009a [triangle],b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1014-scheme1.jpg

Experimental

Crystal data

  • [Mn(CNSe)2(C4H4N2)2(H2O)2]
  • M r = 461.12
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1014-efi1.jpg
  • a = 9.2402 (7) Å
  • b = 9.6012 (6) Å
  • c = 10.2099 (8) Å
  • β = 111.505 (8)°
  • V = 842.74 (11) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 5.11 mm−1
  • T = 170 K
  • 0.10 × 0.07 × 0.04 mm

Data collection

  • Stoe IPDS-1 diffractometer
  • Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 [triangle]) T min = 0.653, T max = 0.818
  • 9472 measured reflections
  • 2024 independent reflections
  • 1795 reflections with I > 2σ(I)
  • R int = 0.043

Refinement

  • R[F 2 > 2σ(F 2)] = 0.026
  • wR(F 2) = 0.064
  • S = 1.03
  • 2024 reflections
  • 98 parameters
  • H-atom parameters constrained
  • Δρmax = 0.50 e Å−3
  • Δρmin = −0.51 e Å−3

Data collection: X-AREA (Stoe & Cie, 2008 [triangle]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP in SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810028941/bv2144sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028941/bv2144Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

MW thanks the Stiftung Stipendien-Fonds des Verbandes der Chemischen Industrie and the Studienstiftung des deutschen Volkes for a PhD scholarship. Moreover, we gratefully acknowledge financial support by the State of Schleswig-Holstein and the Deutsche Forschungsgemeinschaft (Project 720/3–1) and thank Professor Dr Wolfgang Bensch for the opportunity to use of his experimental facility.

supplementary crystallographic information

Comment

Recently, we have shown that thermal decomposition reactions are an elegante route for the discovering and preparation of new ligand-deficient coordination polymers with defined magnetic properties (Wriedt & Näther, 2009a, 2009b; Wriedt, Sellmer & Näther, 2009a, 2009b). In our ongoing investigation on the synthesis, structures and properties of such compounds based on paramagnetic transition metal pseudo-halides and N-donor ligands, we have reacted manganese(II) dichloride, potassium selenocyanate and pyrimidine in water. In this reaction single crystals were obtained, which were identified as the title compound by single-crystal X-ray diffraction.

The title compound of composition [Mn(NCSe)2(H2O)2(pyrimidine)2] (Fig. 1) represents a discrete coordination complex, in which the manganese(II) cation is coordinated by two selenocyanato anions, two water molecules and two pyrimidine ligands in an octahedral coordination mode. The MnN4O2 octahedron is slightly distorted with two long Mn–Npyrimidine distances of 2.3328 (18) Å, two short Mn–NCSe distances of 2.1840 (9) Å and two short Mn—OH2 distances of 2.1582 (14) Å, while the angles around the metal center range between 86.77 (7)–93.23 (7) and 180° (Tab. 1). The coordination of the metal center is similar to that in a related structure (Lipkowski & Soldatov, 1993). In the crystal structure the single complexes are connected via strong Npyrimidine···Hwater hydrogen bonds into layers (see Tab. 2), which are located in the crystallographic a/c-plane (Fig. 2 and 3). The shortest intra- and interlayer Mn···Mn distances amount to 7.2911 (5) and 9.3672 (5) Å, respectively.

Experimental

MnCl2, KNCSe and pyrimidine were obtained from Alfa Aesar. 1 mmol (126 mg) MnCl2, 2 mmol (288 mg) KNCSe, 0.25 mmol (20 mg) pyrimidine and 3 ml water were reacted in a closed snap-vail without stirring. After the mixture was standing for several days at room temperature colorless block shaped single crystals of the title compound were obtained in a mixture with unknown phases.

Refinement

All non-hydrogen atoms were refined anisotropic. The OH-hydrogen atoms were located in difference map, where the bond lengths set to ideal values and were refined using a riding model. All other H atoms were located in difference map but were positioned with idealized geometry and were refined isotropic with Ueq(H) = 1.2 Ueq(C) of the parent atom using a riding model with C—H = 0.95 Å.

Figures

Fig. 1.
: Crystal structure of the discrete title compound with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) -x+1, -y+2, -z+1.]
Fig. 2.
: Crystal structure of the title compound with view along the crystallographic b axis. The dashed lines indicate N···H—O hydrogen bonding.
Fig. 3.
: Packing of two single layers with view approximately along the crystallographic b axis. The dashed lines indicate N···H—O hydrogen bonding.

Crystal data

[Mn(CNSe)2(C4H4N2)2(H2O)2]F(000) = 446
Mr = 461.12Dx = 1.817 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 9472 reflections
a = 9.2402 (7) Åθ = 2.6–28.0°
b = 9.6012 (6) ŵ = 5.11 mm1
c = 10.2099 (8) ÅT = 170 K
β = 111.505 (8)°Block, colourless
V = 842.74 (11) Å30.10 × 0.07 × 0.04 mm
Z = 2

Data collection

Stoe IPDS-1 diffractometer2024 independent reflections
Radiation source: fine-focus sealed tube1795 reflections with I > 2σ(I)
graphiteRint = 0.043
Phi scansθmax = 28.0°, θmin = 2.6°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)h = −12→12
Tmin = 0.653, Tmax = 0.818k = −12→12
9472 measured reflectionsl = −13→13

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026H-atom parameters constrained
wR(F2) = 0.064w = 1/[σ2(Fo2) + (0.0376P)2 + 0.3681P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.002
2024 reflectionsΔρmax = 0.50 e Å3
98 parametersΔρmin = −0.51 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0110 (14)

Special details

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)

xyzUiso*/Ueq
Mn10.50001.00000.50000.01759 (12)
N10.4202 (2)0.77991 (19)0.54320 (18)0.0208 (4)
N20.3036 (2)0.5623 (2)0.45030 (19)0.0289 (4)
C10.3525 (3)0.6901 (3)0.4381 (2)0.0265 (5)
H10.33800.72080.34560.032*
C20.3267 (3)0.5183 (3)0.5807 (2)0.0298 (5)
H20.29470.42710.59380.036*
C30.3961 (3)0.6023 (3)0.6969 (2)0.0299 (5)
H30.41280.57050.78940.036*
C40.4398 (3)0.7336 (2)0.6731 (2)0.0261 (5)
H40.48560.79400.75110.031*
N110.7272 (2)0.9064 (2)0.5380 (2)0.0300 (4)
C110.8449 (2)0.8544 (2)0.5539 (2)0.0214 (4)
Se111.02886 (3)0.77302 (3)0.58075 (3)0.02776 (10)
O10.42680 (19)0.94905 (18)0.27927 (15)0.0283 (3)
H1O10.47820.90610.23920.042*
H2O10.34480.97300.21340.042*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Mn10.0178 (2)0.0179 (2)0.0143 (2)0.00340 (15)0.00258 (15)−0.00073 (14)
N10.0200 (8)0.0227 (9)0.0175 (8)−0.0008 (7)0.0044 (7)−0.0010 (6)
N20.0341 (10)0.0270 (11)0.0222 (9)−0.0077 (8)0.0061 (7)−0.0039 (7)
C10.0300 (11)0.0291 (12)0.0185 (10)−0.0042 (9)0.0068 (8)−0.0022 (8)
C20.0345 (12)0.0246 (12)0.0279 (11)−0.0045 (9)0.0086 (9)0.0002 (9)
C30.0381 (12)0.0285 (12)0.0200 (10)−0.0020 (10)0.0070 (9)0.0028 (9)
C40.0289 (11)0.0253 (11)0.0191 (9)−0.0015 (9)0.0030 (8)−0.0021 (8)
N110.0230 (9)0.0297 (11)0.0367 (10)0.0060 (8)0.0101 (8)0.0036 (8)
C110.0218 (9)0.0218 (10)0.0205 (9)−0.0012 (8)0.0078 (7)0.0022 (7)
Se110.02287 (14)0.02978 (16)0.03597 (15)0.00821 (9)0.01709 (10)0.00904 (9)
O10.0356 (8)0.0300 (9)0.0136 (6)0.0116 (7)0.0024 (6)−0.0026 (6)

Geometric parameters (Å, °)

Mn1—O12.1582 (14)C1—H10.9500
Mn1—O1i2.1582 (14)C2—C31.383 (3)
Mn1—N112.1840 (19)C2—H20.9500
Mn1—N11i2.1840 (19)C3—C41.372 (3)
Mn1—N1i2.3328 (18)C3—H30.9500
Mn1—N12.3328 (18)C4—H40.9500
N1—C11.340 (3)N11—C111.153 (3)
N1—C41.347 (3)C11—Se111.798 (2)
N2—C11.329 (3)O1—H1O10.8400
N2—C21.337 (3)O1—H2O10.8400
O1—Mn1—O1i180.0C1—N2—C2116.70 (19)
O1—Mn1—N1190.29 (7)N2—C1—N1126.4 (2)
O1i—Mn1—N1189.71 (7)N2—C1—H1116.8
O1—Mn1—N11i89.71 (7)N1—C1—H1116.8
O1i—Mn1—N11i90.29 (7)N2—C2—C3121.7 (2)
N11—Mn1—N11i180.0N2—C2—H2119.2
O1—Mn1—N1i90.44 (6)C3—C2—H2119.2
O1i—Mn1—N1i89.56 (6)C4—C3—C2117.2 (2)
N11—Mn1—N1i93.23 (7)C4—C3—H3121.4
N11i—Mn1—N1i86.77 (7)C2—C3—H3121.4
O1—Mn1—N189.56 (6)N1—C4—C3122.4 (2)
O1i—Mn1—N190.44 (6)N1—C4—H4118.8
N11—Mn1—N186.77 (7)C3—C4—H4118.8
N11i—Mn1—N193.23 (7)C11—N11—Mn1177.7 (2)
N1i—Mn1—N1180.00 (9)N11—C11—Se11179.4 (2)
C1—N1—C4115.56 (19)Mn1—O1—H1O1127.1
C1—N1—Mn1121.24 (15)Mn1—O1—H2O1128.3
C4—N1—Mn1123.19 (14)H1O1—O1—H2O1104.5

Symmetry codes: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H2O1···N2ii0.841.932.748 (2)164

Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BV2144).

References

  • Lipkowski, J. & Soldatov, D. (1993). Supramol. Chem.3, 43–46.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE Stoe & Cie, Darmstadt, Germany.
  • Wriedt, M. & Näther, C. (2009a). Dalton Trans. pp. 10192–10198. [PubMed]
  • Wriedt, M. & Näther, C. (2009b). Z. Anorg. Allg. Chem.636, 569–575.
  • Wriedt, M., Sellmer, S. & Näther, C. (2009a). Dalton Trans. pp. 7975–7984. [PubMed]
  • Wriedt, M., Sellmer, S. & Näther, C. (2009b). Inorg. Chem.48, 6896–6903. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography