supplementary materials


bt6895 scheme

Acta Cryst. (2013). E69, m196    [ doi:10.1107/S1600536813006314 ]

Diaquabis[bis(pyrazin-2-yl) sulfide-[kappa]N4]bis(thiocyanato-[kappa]N)iron(II) monohydrate

S. Wöhlert, I. Jess and C. Näther

Abstract top

In the title compound [Fe(NCS)2(C8H6N4S)2(H2O)2]·H2O, the FeII cation is coordinated by two N-bonded thiocyanate anions, two N4-bonded bis(pyrazin-2-yl) sulfide ligands and two water molecules in an slightly distorted octahedral geometry. The FeII cation is located on a center of inversion and the lattice water molecule on a twofold rotation axis. The thiocyanate anions, the coordinating water molecules and the sulfide ligands occupy general positions. The complex molecules and lattice water molecules are linked into a three-dimensional network by O-H-N and O-H...O hydrogen bonds.

Comment top

Recently we have reported on the synthesis and characterization of transition metal thiocyanato compounds with 2-chloropyrazine as neutral co-ligand (Wöhlert & Näther, 2013). In the course of these investigations, we have reacted iron(II)sulfate with potassium thiocyanate and 2-chloropyrazine under hydrothermal conditions, which accidently lead to the formation of single crystals of the title compound that were characterized by single-crystal X-ray diffraction. In the crystal structure, each iron(II) cation is coordinated by two N-bonded thiocyanato anions, two 2,2'-dipyrazinesulfide ligands and two water molecules within a slightly distorted octahedra (Fig.1 and Tab. 1). The Fe—N and Fe—O distances range from 2.096 5(17) Å to 2.235 (2) Å with angles arround the iron(II) cation between 87.98 (8) ° to 92.02 (8) ° and of 180 ° (Tab. 1). The asymmetric unit consists of one iron(II) cation located on a center of inversion, one water molecule on a 2-fold axis as well as of one 2,2'-dipyrazinesulfide ligand, one thiocyanato anion and one water molecule all of them located in general position. The discrete complexes are connected by the non-coordinating water molecules into a three-dimensional network through intermolecular O—H—N and O—H—O hydrogen bonding (Fig. 2). In this arrangement each non-coordinating water molecule acts as acceptor in two O—H—O hydrogen bonds and as a donor in two O—H—N hydrogen bonds (Fig. 2 and Tab.2).

Related literature top

For the background to this work, see: Wöhlert & Näther (2013)

Experimental top

FeSO4x7H2O, KNCS and 2-chloropyrazine were obtained from Alfa Aesar. All chemicals were used without further purification. 0.15 mmol (41.7 mg) FeSO4x7H2O, 0.3 mmol (29.1 mg) KNCS and 0.3 mmol (26.4 µL) 2-chloropyrazine were reacted in 1 ml water in a closed test-tube at 120 °C for 3 days. Red single crystals of the title compound were obtained after two days on cooling.

Refinement top

All C—H H atoms were located in difference map but were positioned with idealized geometry and were refined isotropic with Uiso(H) = 1.2 Ueq(C) using a riding model with C—H = 0.95 Å for aromatic H atoms. The water H atoms were located in a difference map, their bond lenghts were set to ideal values of 0.84 Å and finally they were refined using a riding model with Uiso(H) = 1.5 Ueq(O).

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 code: i = -x + 3/2, -y + 3/2, -z.
[Figure 2] Fig. 2. Crystal structure of the title compound with view along the a-axis (orange = iron, blue = nitrogen, yellow = sulfur, red = oxygen, grey = carbon, white = hydrogen). Intermolecular hydrogen bonding is shown as dashed lines.
Diaquabis[bis(pyrazin-2-yl) sulfide-κN4]bis(thiocyanato-κN)iron(II) monohydrate top
Crystal data top
[Fe(NCS)2(C8H6N4S)2(H2O)2]·H2OF(000) = 1240
Mr = 606.51Dx = 1.584 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 10774 reflections
a = 11.5110 (8) Åθ = 2.3–26.0°
b = 15.8583 (9) ŵ = 0.96 mm1
c = 14.8025 (12) ÅT = 200 K
β = 109.770 (8)°Block, red
V = 2542.9 (3) Å30.25 × 0.15 × 0.09 mm
Z = 4
Data collection top
Stoe IPDS-1
diffractometer
2496 independent reflections
Radiation source: fine-focus sealed tube2012 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
phi scanθmax = 26.0°, θmin = 2.3°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
h = 1413
Tmin = 0.690, Tmax = 0.859k = 1919
10774 measured reflectionsl = 1818
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0412P)2 + 5.1033P]
where P = (Fo2 + 2Fc2)/3
2496 reflections(Δ/σ)max < 0.001
165 parametersΔρmax = 0.52 e Å3
0 restraintsΔρmin = 0.49 e Å3
Crystal data top
[Fe(NCS)2(C8H6N4S)2(H2O)2]·H2OV = 2542.9 (3) Å3
Mr = 606.51Z = 4
Monoclinic, C2/cMo Kα radiation
a = 11.5110 (8) ŵ = 0.96 mm1
b = 15.8583 (9) ÅT = 200 K
c = 14.8025 (12) Å0.25 × 0.15 × 0.09 mm
β = 109.770 (8)°
Data collection top
Stoe IPDS-1
diffractometer
2496 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
2012 reflections with I > 2σ(I)
Tmin = 0.690, Tmax = 0.859Rint = 0.044
10774 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.090Δρmax = 0.52 e Å3
S = 1.05Δρmin = 0.49 e Å3
2496 reflectionsAbsolute structure: ?
165 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
Fe10.75000.75000.00000.01850 (14)
N10.6524 (2)0.83973 (14)0.05049 (17)0.0283 (5)
C10.5978 (2)0.88512 (16)0.08281 (19)0.0250 (6)
S10.51942 (8)0.94785 (6)0.12789 (7)0.0495 (3)
N100.68155 (19)0.64769 (13)0.07296 (16)0.0217 (4)
C100.5612 (2)0.63655 (16)0.05785 (19)0.0231 (5)
H100.50300.67530.01840.028*
C110.5199 (2)0.56900 (16)0.09904 (19)0.0221 (5)
C120.7178 (3)0.52477 (18)0.1702 (2)0.0309 (6)
H120.77600.48630.21000.037*
C130.7596 (2)0.59152 (17)0.1297 (2)0.0275 (6)
H130.84580.59780.14240.033*
N110.5975 (2)0.51276 (14)0.15487 (16)0.0265 (5)
S20.36039 (6)0.54851 (4)0.07358 (6)0.03024 (18)
N200.1422 (2)0.71530 (17)0.13551 (19)0.0365 (6)
C200.1863 (2)0.64829 (19)0.1039 (2)0.0323 (6)
H200.13220.60310.07520.039*
C210.3091 (2)0.64298 (17)0.1120 (2)0.0264 (6)
C220.3399 (4)0.7716 (3)0.1788 (6)0.129 (3)
H220.39300.81790.20490.155*
C230.2211 (3)0.7764 (2)0.1745 (3)0.0604 (12)
H230.19380.82440.20000.072*
N210.3859 (3)0.7044 (2)0.1476 (4)0.0998 (19)
O10.90576 (16)0.76058 (11)0.12427 (13)0.0264 (4)
H1O10.97750.74160.13620.040*
H2O10.91840.80360.15930.040*
O20.50000.39109 (15)0.25000.0247 (5)
H1O20.53020.42270.21820.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0136 (2)0.0178 (2)0.0259 (3)0.00060 (19)0.00904 (18)0.0007 (2)
N10.0268 (12)0.0247 (11)0.0384 (13)0.0029 (9)0.0175 (11)0.0019 (10)
C10.0210 (13)0.0266 (13)0.0261 (13)0.0013 (11)0.0064 (11)0.0026 (11)
S10.0410 (5)0.0572 (5)0.0516 (5)0.0152 (4)0.0173 (4)0.0235 (4)
N100.0191 (10)0.0198 (10)0.0292 (11)0.0009 (8)0.0118 (9)0.0004 (9)
C100.0185 (12)0.0223 (12)0.0305 (14)0.0012 (10)0.0110 (10)0.0006 (10)
C110.0210 (12)0.0224 (12)0.0266 (13)0.0022 (10)0.0129 (10)0.0066 (10)
C120.0261 (14)0.0291 (14)0.0359 (15)0.0035 (11)0.0083 (12)0.0092 (12)
C130.0193 (12)0.0259 (13)0.0369 (15)0.0013 (10)0.0091 (11)0.0041 (11)
N110.0298 (12)0.0236 (11)0.0283 (12)0.0014 (9)0.0128 (10)0.0030 (9)
S20.0229 (3)0.0244 (3)0.0485 (4)0.0060 (3)0.0187 (3)0.0088 (3)
N200.0220 (12)0.0396 (14)0.0479 (15)0.0046 (11)0.0118 (11)0.0067 (12)
C200.0200 (13)0.0348 (15)0.0402 (16)0.0011 (11)0.0075 (12)0.0097 (12)
C210.0240 (13)0.0259 (13)0.0332 (14)0.0038 (11)0.0149 (11)0.0040 (11)
C220.058 (3)0.081 (3)0.285 (9)0.046 (3)0.104 (4)0.123 (5)
C230.043 (2)0.0392 (18)0.115 (4)0.0091 (15)0.046 (2)0.034 (2)
N210.0447 (19)0.068 (2)0.215 (5)0.0369 (17)0.080 (3)0.092 (3)
O10.0163 (8)0.0269 (9)0.0335 (10)0.0015 (7)0.0054 (7)0.0062 (8)
O20.0325 (14)0.0181 (12)0.0282 (14)0.0000.0166 (11)0.000
Geometric parameters (Å, º) top
Fe1—O1i2.0965 (17)C12—H120.9500
Fe1—O12.0965 (17)C13—H130.9500
Fe1—N12.101 (2)S2—C211.773 (3)
Fe1—N1i2.101 (2)N20—C231.319 (4)
Fe1—N102.235 (2)N20—C201.329 (4)
Fe1—N10i2.235 (2)C20—C211.381 (4)
N1—C11.160 (3)C20—H200.9500
C1—S11.630 (3)C21—N211.302 (4)
N10—C101.339 (3)C22—N211.340 (5)
N10—C131.340 (3)C22—C231.349 (5)
C10—C111.393 (4)C22—H220.9500
C10—H100.9500C23—H230.9500
C11—N111.333 (3)O1—H1O10.8400
C11—S21.775 (3)O1—H2O10.8400
C12—N111.339 (4)O2—H1O20.8400
C12—C131.381 (4)
O1i—Fe1—O1180.0N11—C12—C13121.9 (2)
O1i—Fe1—N187.98 (8)N11—C12—H12119.1
O1—Fe1—N192.02 (8)C13—C12—H12119.1
O1i—Fe1—N1i92.02 (8)N10—C13—C12121.5 (2)
O1—Fe1—N1i87.98 (8)N10—C13—H13119.2
N1—Fe1—N1i180.00 (12)C12—C13—H13119.2
O1i—Fe1—N1091.68 (8)C11—N11—C12116.6 (2)
O1—Fe1—N1088.32 (8)C21—S2—C11102.11 (12)
N1—Fe1—N1090.08 (8)C23—N20—C20116.9 (3)
N1i—Fe1—N1089.92 (8)N20—C20—C21121.3 (3)
O1i—Fe1—N10i88.32 (8)N20—C20—H20119.3
O1—Fe1—N10i91.68 (8)C21—C20—H20119.3
N1—Fe1—N10i89.92 (8)N21—C21—C20121.6 (3)
N1i—Fe1—N10i90.08 (8)N21—C21—S2120.6 (2)
N10—Fe1—N10i180.00 (9)C20—C21—S2117.8 (2)
C1—N1—Fe1175.3 (2)N21—C22—C23122.7 (3)
N1—C1—S1179.1 (2)N21—C22—H22118.6
C10—N10—C13117.0 (2)C23—C22—H22118.6
C10—N10—Fe1121.96 (17)N20—C23—C22121.1 (3)
C13—N10—Fe1120.93 (17)N20—C23—H23119.5
N10—C10—C11121.0 (2)C22—C23—H23119.5
N10—C10—H10119.5C21—N21—C22116.2 (3)
C11—C10—H10119.5Fe1—O1—H1O1130.1
N11—C11—C10122.0 (2)Fe1—O1—H2O1121.7
N11—C11—S2115.92 (19)H1O1—O1—H2O1102.0
C10—C11—S2121.9 (2)
Symmetry code: (i) x+3/2, y+3/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1O2···N110.842.002.834 (3)171
O1—H1O1···N20ii0.841.942.765 (3)165
O1—H2O1···O2iii0.841.942.749 (3)162
Symmetry codes: (ii) x+1, y, z; (iii) x+1/2, y+1/2, z.
Selected bond lengths (Å) top
Fe1—O12.0965 (17)Fe1—N102.235 (2)
Fe1—N12.101 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1O2···N110.842.002.834 (3)171.0
O1—H1O1···N20i0.841.942.765 (3)165.3
O1—H2O1···O2ii0.841.942.749 (3)162.1
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, y+1/2, z.
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

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. & Näther, C. (2013). Eur. J. Inorg. Chem. doi:10.1002/ejic.201201486.