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

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

aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24098 Kiel, Germany
*Correspondence e-mail: mwriedt@ac.uni-kiel.de

(Received 18 May 2010; accepted 20 July 2010; online 24 July 2010)

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[Lipkowski, J. & Soldatov, D. (1993). Supramol. Chem. 3, 43-46.]). 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[Wriedt, M. & Näther, C. (2009a). Dalton Trans. pp. 10192-10198.],b[Wriedt, M. & Näther, C. (2009b). Z. Anorg. Allg. Chem. 636, 569-575.]); Wriedt et al. (2009a[Wriedt, M., Sellmer, S. & Näther, C. (2009a). Dalton Trans. pp. 7975-7984.],b[Wriedt, M., Sellmer, S. & Näther, C. (2009b). Inorg. Chem. 48, 6896-6903.]).

[Scheme 1]

Experimental

Crystal data
  • [Mn(CNSe)2(C4H4N2)2(H2O)2]

  • Mr = 461.12

  • Monoclinic, P 21 /n

  • 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[Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]) Tmin = 0.653, Tmax = 0.818

  • 9472 measured reflections

  • 2024 independent reflections

  • 1795 reflections with I > 2σ(I)

  • Rint = 0.043

Refinement
  • R[F2 > 2σ(F2)] = 0.026

  • wR(F2) = 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

Table 1
Selected geometric parameters (Å, °)

Mn1—O1 2.1582 (14)
Mn1—N11 2.1840 (19)
Mn1—N1 2.3328 (18)
O1—Mn1—O1i 180.0
O1—Mn1—N11 90.29 (7)
O1i—Mn1—N11 89.71 (7)
O1—Mn1—N1i 90.44 (6)
N11—Mn1—N1i 93.23 (7)
N11i—Mn1—N1i 86.77 (7)
O1—Mn1—N1 89.56 (6)
Symmetry code: (i) -x+1, -y+2, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H2O1⋯N2ii 0.84 1.93 2.748 (2) 164
Symmetry code: (ii) [-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

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: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

Supporting information


Comment top

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.

Related literature top

For a related pyrimidine structure, see: Lipkowski & Soldatov (1993). 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,b); Wriedt, Sellmer & Näther (2009a,b).

Experimental top

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 top

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.

Structure description top

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.

For a related pyrimidine structure, see: Lipkowski & Soldatov (1993). 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,b); Wriedt, Sellmer & Näther (2009a,b).

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); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] 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.]
[Figure 2] Fig. 2. : Crystal structure of the title compound with view along the crystallographic b axis. The dashed lines indicate N···H—O hydrogen bonding.
[Figure 3] Fig. 3. : Packing of two single layers with view approximately along the crystallographic b axis. The dashed lines indicate N···H—O hydrogen bonding.
Diaquabis(selenocyanato-κN)bis(pyrimidine-κN)manganese(II) top
Crystal data top
[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 top
Stoe IPDS-1
diffractometer
2024 independent reflections
Radiation source: fine-focus sealed tube1795 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
Phi scansθmax = 28.0°, θmin = 2.6°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
h = 1212
Tmin = 0.653, Tmax = 0.818k = 1212
9472 measured reflectionsl = 1313
Refinement top
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) = 0.064 w = 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)
Crystal data top
[Mn(CNSe)2(C4H4N2)2(H2O)2]V = 842.74 (11) Å3
Mr = 461.12Z = 2
Monoclinic, P21/nMo Kα radiation
a = 9.2402 (7) ŵ = 5.11 mm1
b = 9.6012 (6) ÅT = 170 K
c = 10.2099 (8) Å0.10 × 0.07 × 0.04 mm
β = 111.505 (8)°
Data collection top
Stoe IPDS-1
diffractometer
2024 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
1795 reflections with I > 2σ(I)
Tmin = 0.653, Tmax = 0.818Rint = 0.043
9472 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.064H-atom parameters constrained
S = 1.03Δρmax = 0.50 e Å3
2024 reflectionsΔρmin = 0.51 e Å3
98 parameters
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
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) top
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, º) top
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 code: (i) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H2O1···N2ii0.841.932.748 (2)164
Symmetry code: (ii) x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Mn(CNSe)2(C4H4N2)2(H2O)2]
Mr461.12
Crystal system, space groupMonoclinic, P21/n
Temperature (K)170
a, b, c (Å)9.2402 (7), 9.6012 (6), 10.2099 (8)
β (°) 111.505 (8)
V3)842.74 (11)
Z2
Radiation typeMo Kα
µ (mm1)5.11
Crystal size (mm)0.10 × 0.07 × 0.04
Data collection
DiffractometerStoe IPDS1
Absorption correctionNumerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
Tmin, Tmax0.653, 0.818
No. of measured, independent and
observed [I > 2σ(I)] reflections
9472, 2024, 1795
Rint0.043
(sin θ/λ)max1)0.660
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.064, 1.03
No. of reflections2024
No. of parameters98
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.50, 0.51

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), XCIF in SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Mn1—O12.1582 (14)Mn1—N12.3328 (18)
Mn1—N112.1840 (19)
O1—Mn1—O1i180.0N11—Mn1—N1i93.23 (7)
O1—Mn1—N1190.29 (7)N11i—Mn1—N1i86.77 (7)
O1i—Mn1—N1189.71 (7)O1—Mn1—N189.56 (6)
O1—Mn1—N1i90.44 (6)
Symmetry code: (i) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H2O1···N2ii0.841.932.748 (2)163.8
Symmetry code: (ii) x+1/2, y+1/2, z+1/2.
 

Acknowledgements

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.

References

First citationLipkowski, J. & Soldatov, D. (1993). Supramol. Chem. 3, 43–46.  CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationStoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.  Google Scholar
First citationWriedt, M. & Näther, C. (2009a). Dalton Trans. pp. 10192–10198.  Web of Science CSD CrossRef Google Scholar
First citationWriedt, M. & Näther, C. (2009b). Z. Anorg. Allg. Chem. 636, 569–575.  Web of Science CSD CrossRef Google Scholar
First citationWriedt, M., Sellmer, S. & Näther, C. (2009a). Dalton Trans. pp. 7975–7984.  Web of Science CSD CrossRef Google Scholar
First citationWriedt, M., Sellmer, S. & Näther, C. (2009b). Inorg. Chem. 48, 6896–6903.  Web of Science CSD CrossRef CAS PubMed Google Scholar

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