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

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catena-Poly[[bis­­(thio­cyanato-κN)iron(II)]-bis­­(μ-dipyrazin-2-yl di­sulfide-κ2N4:N4′)]

aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany
*Correspondence e-mail: swoehlert@ac.uni-kiel.de

(Received 26 July 2013; accepted 6 August 2013; online 10 August 2013)

In the title compound, [Fe(NCS)2(C8H6N4S2)2]n, the FeII cation is coordinated by two terminal N-bonded thio­cyanate anions and four bridging N:N′-bridging dipyrazin-2-yl di­sulfide ligands in an octa­hedral geometry. The FeII cations are connected via bridging 4,4′-di­pyrazine ligands into chains along the b-axis direction. The asymmetric unit consists of one FeII cation located on position with site symmetry 2/m, one thio­cyanate anion located on a mirror plane and one di­sulfide ligand located on a twofold rotation axis.

Related literature

For general background to this work, see: Wriedt & Näther (2011[Wriedt, M. & Näther, C. (2011). Z. Anorg. Allg. Chem. 637, 666-671.]). For a description of the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]).

[Scheme 1]

Experimental

Crystal data
  • [Fe(NCS)2(C8H6N4S2)2]

  • Mr = 616.59

  • Orthorhombic, C m c a

  • a = 19.053 (1) Å

  • b = 8.0559 (5) Å

  • c = 16.1952 (9) Å

  • V = 2485.8 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.14 mm−1

  • T = 293 K

  • 0.11 × 0.08 × 0.05 mm

Data collection
  • Stoe IPDS-2 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 = 0.782, Tmax = 0.902

  • 7765 measured reflections

  • 1242 independent reflections

  • 1077 reflections with I > 2σ(I)

  • Rint = 0.035

Refinement
  • R[F2 > 2σ(F2)] = 0.051

  • wR(F2) = 0.113

  • S = 1.15

  • 1242 reflections

  • 86 parameters

  • H-atom parameters constrained

  • Δρmax = 0.69 e Å−3

  • Δρmin = −0.34 e Å−3

Table 1
Selected geometric parameters (Å, °)

Fe1—N1 2.061 (4)
Fe1—N10 2.273 (3)
N1i—Fe1—N1 180.00 (18)
N1i—Fe1—N10 89.81 (11)
N1—Fe1—N10 90.19 (11)
N10—Fe1—N10ii 90.62 (13)
N10—Fe1—N10iii 89.38 (13)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, y, z; (iii) x, -y, -z+1.

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.]) and DIAMOND (Brandenburg, 2012[Brandenburg, K. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: XCIF in SHELXTL.

Supporting information


Comment top

This work is part of a project on the synthesis and characterization of new coordination compounds based on transition metal thiocyanates and different N-donor ligand (Wriedt & Näther, 2011). Crystals of the title compound were obtained by accident in the reaction of iron(II) sulfate heptahydrate with potassium thiocyanate and 2-chloropyrazine. To identify the product of this reaction a structure determination was performed.

In the crystal structure of the title compound each iron(II) cation is octahedrally coordinated by two terminal N-bonded thiocyanato anions and four bridging dipyrazine-disulfide ligands that has accidently formed in the reaction (Fig. 1 and Tab. 1). The Fe—NCS distances of 2.061 (4) Å and the Fe—N(dipyrazine-disulfide) distances of 2.273 (3) Å are in the normal range (Tab. 1). The FeII cations are located on position 2/m, the thiocyanato anions on a mirror plane and the dipyrazine-disulfide ligands on a 2-fold axis (Fig. 1). The iron(II) cations are linked into chains by the dipyrazine-disulfide ligands that elongate in the direction of the crystallographic b-axis (Fig. 2). It must be noted that according to a search in the CCDC database such compounds with dipyrazine-disulfide are unknown (ConQuest Ver. 1.14 2012, Allen, 2002).

Related literature top

For general background to this work, see: Wriedt & Näther (2011). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

FeSO4.7H2O and 2-chloropyrazine were obtained from Sigma Aldrich. KNCS was obtained from Alfa Aesar. 0.6 mmol (168.8 mg) FeSO4.7H2O, 1.2 mmol (118.5 mg) KNCS and 0.15 mmol (13.2 µL) 2-chloropyrazine were reacted with 1 mL H2O in a closed test-tube at 120°C for three days. On cooling red block-shaped single crystals of the title compound has formed.

Refinement top

All H atoms were located in difference map but were positioned with idealized geometry and were refined isotropic with Uiso(H) = 1.2 Ueq(C) of the parent atom using a riding model with C—H = 0.93 Å.

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, 2012); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry code: i = -x + 1, -y, -z + 1; ii = x, -y, -z + 1; iii = -x + 1, y, z; iv = x, -y + 1, -z + 1.
[Figure 2] Fig. 2. View of the chains that elongate in the direction of the crystallographic b axis.
catena-Poly[[bis(thiocyanato-κN)iron(II)]-bis(µ-dipyrazin-2-yl disulfide-κ2N4:N4')] top
Crystal data top
[Fe(NCS)2(C8H6N4S2)2]F(000) = 1248
Mr = 616.59Dx = 1.648 Mg m3
Orthorhombic, CmcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2Cell parameters from 7765 reflections
a = 19.053 (1) Åθ = 3.0–26.0°
b = 8.0559 (5) ŵ = 1.14 mm1
c = 16.1952 (9) ÅT = 293 K
V = 2485.8 (2) Å3Block, red
Z = 40.11 × 0.08 × 0.05 mm
Data collection top
Stoe IPDS-2
diffractometer
1242 independent reflections
Radiation source: fine-focus sealed tube1077 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
ω scanθmax = 26.0°, θmin = 3.0°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
h = 2321
Tmin = 0.782, Tmax = 0.902k = 99
7765 measured reflectionsl = 1917
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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.15 w = 1/[σ2(Fo2) + (0.0413P)2 + 5.3642P]
where P = (Fo2 + 2Fc2)/3
1242 reflections(Δ/σ)max < 0.001
86 parametersΔρmax = 0.69 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
[Fe(NCS)2(C8H6N4S2)2]V = 2485.8 (2) Å3
Mr = 616.59Z = 4
Orthorhombic, CmcaMo Kα radiation
a = 19.053 (1) ŵ = 1.14 mm1
b = 8.0559 (5) ÅT = 293 K
c = 16.1952 (9) Å0.11 × 0.08 × 0.05 mm
Data collection top
Stoe IPDS-2
diffractometer
1242 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
1077 reflections with I > 2σ(I)
Tmin = 0.782, Tmax = 0.902Rint = 0.035
7765 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.15Δρmax = 0.69 e Å3
1242 reflectionsΔρmin = 0.34 e Å3
86 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.

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 > 2sigma(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
Fe10.50000.00000.50000.0384 (3)
N10.50000.1936 (5)0.5832 (3)0.0507 (10)
C10.50000.3240 (5)0.6134 (3)0.0397 (10)
S10.50000.50646 (16)0.65366 (9)0.0640 (4)
N100.41517 (13)0.1291 (3)0.42501 (17)0.0428 (6)
C100.37695 (15)0.2524 (4)0.4557 (2)0.0445 (7)
H100.38190.28180.51090.053*
C110.32962 (17)0.3380 (4)0.4062 (2)0.0490 (8)
C120.3600 (2)0.1830 (6)0.2972 (2)0.0713 (11)
H120.35610.15630.24150.086*
C130.4057 (2)0.0943 (5)0.3454 (2)0.0579 (9)
H130.43090.00730.32190.070*
N110.32128 (18)0.3053 (4)0.3271 (2)0.0649 (9)
S110.27348 (5)0.50102 (12)0.43778 (8)0.0687 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0371 (5)0.0304 (4)0.0478 (5)0.0000.0000.0021 (4)
N10.053 (2)0.039 (2)0.060 (2)0.0000.0000.0075 (19)
C10.037 (2)0.041 (2)0.041 (2)0.0000.0000.0057 (19)
S10.0814 (10)0.0398 (7)0.0709 (9)0.0000.0000.0098 (6)
N100.0386 (14)0.0393 (13)0.0505 (15)0.0010 (11)0.0018 (12)0.0033 (11)
C100.0367 (15)0.0400 (16)0.0567 (18)0.0007 (13)0.0023 (15)0.0000 (14)
C110.0394 (17)0.0375 (16)0.070 (2)0.0023 (13)0.0072 (16)0.0005 (15)
C120.080 (3)0.079 (3)0.055 (2)0.011 (2)0.010 (2)0.005 (2)
C130.060 (2)0.057 (2)0.056 (2)0.0099 (18)0.0037 (18)0.0035 (17)
N110.065 (2)0.0616 (19)0.068 (2)0.0059 (16)0.0192 (17)0.0015 (16)
S110.0492 (5)0.0527 (5)0.1041 (8)0.0138 (4)0.0205 (5)0.0146 (6)
Geometric parameters (Å, º) top
Fe1—N1i2.061 (4)C10—C111.390 (4)
Fe1—N12.061 (4)C10—H100.9300
Fe1—N102.273 (3)C11—N111.318 (5)
Fe1—N10ii2.273 (3)C11—S111.769 (3)
Fe1—N10iii2.273 (3)C12—N111.323 (5)
Fe1—N10i2.273 (3)C12—C131.371 (5)
N1—C11.158 (6)C12—H120.9300
C1—S11.608 (5)C13—H130.9300
N10—C101.328 (4)S11—S11iv2.015 (2)
N10—C131.332 (5)
N1i—Fe1—N1180.00 (18)C10—N10—C13116.5 (3)
N1i—Fe1—N1089.81 (11)C10—N10—Fe1122.1 (2)
N1—Fe1—N1090.19 (11)C13—N10—Fe1121.1 (2)
N1i—Fe1—N10ii89.81 (11)N10—C10—C11120.7 (3)
N1—Fe1—N10ii90.19 (11)N10—C10—H10119.6
N10—Fe1—N10ii90.62 (13)C11—C10—H10119.6
N1i—Fe1—N10iii90.19 (11)N11—C11—C10122.7 (3)
N1—Fe1—N10iii89.81 (11)N11—C11—S11110.9 (3)
N10—Fe1—N10iii89.38 (13)C10—C11—S11126.4 (3)
N10ii—Fe1—N10iii180.0N11—C12—C13122.3 (4)
N1i—Fe1—N10i90.19 (11)N11—C12—H12118.9
N1—Fe1—N10i89.81 (11)C13—C12—H12118.9
N10—Fe1—N10i180.00 (11)N10—C13—C12121.8 (4)
N10ii—Fe1—N10i89.38 (13)N10—C13—H13119.1
N10iii—Fe1—N10i90.62 (13)C12—C13—H13119.1
C1—N1—Fe1164.1 (4)C11—N11—C12116.0 (3)
N1—C1—S1179.0 (4)C11—S11—S11iv106.45 (13)
Symmetry codes: (i) x+1, y, z+1; (ii) x+1, y, z; (iii) x, y, z+1; (iv) x, y+1, z+1.
Selected geometric parameters (Å, º) top
Fe1—N12.061 (4)Fe1—N102.273 (3)
N1i—Fe1—N1180.00 (18)N10—Fe1—N10ii90.62 (13)
N1i—Fe1—N1089.81 (11)N10—Fe1—N10iii89.38 (13)
N1—Fe1—N1090.19 (11)
Symmetry codes: (i) x+1, y, z+1; (ii) x+1, y, z; (iii) x, y, z+1.
 

Acknowledgements

We gratefully acknowledge financial support by the State of Schleswig–Holstein and the Deutsche Forschungsgemein­schaft (project 720/3-1). We thank Professor Dr Wolfgang Bensch for the opportunity to use his experimental facility.

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CrossRef CAS IUCr Journals
First citationBrandenburg, K. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationStoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.
First citationWriedt, M. & Näther, C. (2011). Z. Anorg. Allg. Chem. 637, 666–671.  Web of Science CSD CrossRef CAS

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