Diaqua­bis­[bis­(pyrazin-2-yl) sulfide-κN4]bis­(thio­cyanato-κN)iron(II) monohydrate

Wöhlert, S.; Jess, I.; Näther, C.

doi:10.1107/S1600536813006314

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 4| April 2013| Page m196

doi:10.1107/S1600536813006314

Open

access

Diaquabis[bis(pyrazin-2-yl) sulfide-κN⁴]bis(thiocyanato-κN)iron(II) monohydrate

Susanne Wöhlert,^a ^* Inke Jess ^a and Christian Näther ^a

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

(Received 4 March 2013; accepted 5 March 2013; online 9 March 2013)

In the title compound [Fe(NCS)₂(C₈H₆N₄S)₂(H₂O)₂]·H₂O, the Fe^II 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 Fe^II 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.

Related literature

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

Experimental

Crystal data

[Fe(NCS)₂(C₈H₆N₄S)₂(H₂O)₂]·H₂O
M_r = 606.51
Monoclinic, C 2/c
a = 11.5110 (8) Å
b = 15.8583 (9) Å
c = 14.8025 (12) Å
β = 109.770 (8)°
V = 2542.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.96 mm⁻¹
T = 200 K
0.25 × 0.15 × 0.09 mm

Data collection

Stoe IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ) T_min = 0.690, T_max = 0.859
10774 measured reflections
2496 independent reflections
2012 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.090
S = 1.05
2496 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Selected bond lengths (Å)

Fe1—O1	2.0965 (17)
Fe1—N1	2.101 (2)
Fe1—N10	2.235 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O2⋯N11	0.84	2.00	2.834 (3)	171
O1—H1O1⋯N20ⁱ	0.84	1.94	2.765 (3)	165
O1—H2O1⋯O2ⁱⁱ	0.84	1.94	2.749 (3)	162
Symmetry codes: (i) x+1, y, z; (ii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA; data reduction: X-AREA; 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 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813006314/bt6895sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813006314/bt6895Isup2.hkl

checkCIF report

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.

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

	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.
	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]·H₂O	F(000) = 1240
M_r = 606.51	D_x = 1.584 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 10774 reflections
a = 11.5110 (8) Å	θ = 2.3–26.0°
b = 15.8583 (9) Å	µ = 0.96 mm⁻¹
c = 14.8025 (12) Å	T = 200 K
β = 109.770 (8)°	Block, red
V = 2542.9 (3) Å³	0.25 × 0.15 × 0.09 mm
Z = 4

Data collection top

Stoe IPDS-1 diffractometer	2496 independent reflections
Radiation source: fine-focus sealed tube	2012 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
phi scan	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −14→13
T_min = 0.690, T_max = 0.859	k = −19→19
10774 measured reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0412P)² + 5.1033P] where P = (F_o² + 2F_c²)/3
2496 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

[Fe(NCS)₂(C₈H₆N₄S)₂(H₂O)₂]·H₂O	V = 2542.9 (3) Å³
M_r = 606.51	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 11.5110 (8) Å	µ = 0.96 mm⁻¹
b = 15.8583 (9) Å	T = 200 K
c = 14.8025 (12) Å	0.25 × 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)
T_min = 0.690, T_max = 0.859	R_int = 0.044
10774 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.05	Δρ_max = 0.52 e Å⁻³
2496 reflections	Δρ_min = −0.49 e Å⁻³
165 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

	x	y	z	U_iso*/U_eq
Fe1	0.7500	0.7500	0.0000	0.01850 (14)
N1	0.6524 (2)	0.83973 (14)	0.05049 (17)	0.0283 (5)
C1	0.5978 (2)	0.88512 (16)	0.08281 (19)	0.0250 (6)
S1	0.51942 (8)	0.94785 (6)	0.12789 (7)	0.0495 (3)
N10	0.68155 (19)	0.64769 (13)	0.07296 (16)	0.0217 (4)
C10	0.5612 (2)	0.63655 (16)	0.05785 (19)	0.0231 (5)
H10	0.5030	0.6753	0.0184	0.028*
C11	0.5199 (2)	0.56900 (16)	0.09904 (19)	0.0221 (5)
C12	0.7178 (3)	0.52477 (18)	0.1702 (2)	0.0309 (6)
H12	0.7760	0.4863	0.2100	0.037*
C13	0.7596 (2)	0.59152 (17)	0.1297 (2)	0.0275 (6)
H13	0.8458	0.5978	0.1424	0.033*
N11	0.5975 (2)	0.51276 (14)	0.15487 (16)	0.0265 (5)
S2	0.36039 (6)	0.54851 (4)	0.07358 (6)	0.03024 (18)
N20	0.1422 (2)	0.71530 (17)	0.13551 (19)	0.0365 (6)
C20	0.1863 (2)	0.64829 (19)	0.1039 (2)	0.0323 (6)
H20	0.1322	0.6031	0.0752	0.039*
C21	0.3091 (2)	0.64298 (17)	0.1120 (2)	0.0264 (6)
C22	0.3399 (4)	0.7716 (3)	0.1788 (6)	0.129 (3)
H22	0.3930	0.8179	0.2049	0.155*
C23	0.2211 (3)	0.7764 (2)	0.1745 (3)	0.0604 (12)
H23	0.1938	0.8244	0.2000	0.072*
N21	0.3859 (3)	0.7044 (2)	0.1476 (4)	0.0998 (19)
O1	0.90576 (16)	0.76058 (11)	0.12427 (13)	0.0264 (4)
H1O1	0.9775	0.7416	0.1362	0.040*
H2O1	0.9184	0.8036	0.1593	0.040*
O2	0.5000	0.39109 (15)	0.2500	0.0247 (5)
H1O2	0.5302	0.4227	0.2182	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0136 (2)	0.0178 (2)	0.0259 (3)	0.00060 (19)	0.00904 (18)	−0.0007 (2)
N1	0.0268 (12)	0.0247 (11)	0.0384 (13)	0.0029 (9)	0.0175 (11)	−0.0019 (10)
C1	0.0210 (13)	0.0266 (13)	0.0261 (13)	0.0013 (11)	0.0064 (11)	−0.0026 (11)
S1	0.0410 (5)	0.0572 (5)	0.0516 (5)	0.0152 (4)	0.0173 (4)	−0.0235 (4)
N10	0.0191 (10)	0.0198 (10)	0.0292 (11)	0.0009 (8)	0.0118 (9)	0.0004 (9)
C10	0.0185 (12)	0.0223 (12)	0.0305 (14)	0.0012 (10)	0.0110 (10)	0.0006 (10)
C11	0.0210 (12)	0.0224 (12)	0.0266 (13)	−0.0022 (10)	0.0129 (10)	−0.0066 (10)
C12	0.0261 (14)	0.0291 (14)	0.0359 (15)	0.0035 (11)	0.0083 (12)	0.0092 (12)
C13	0.0193 (12)	0.0259 (13)	0.0369 (15)	0.0013 (10)	0.0091 (11)	0.0041 (11)
N11	0.0298 (12)	0.0236 (11)	0.0283 (12)	−0.0014 (9)	0.0128 (10)	0.0030 (9)
S2	0.0229 (3)	0.0244 (3)	0.0485 (4)	−0.0060 (3)	0.0187 (3)	−0.0088 (3)
N20	0.0220 (12)	0.0396 (14)	0.0479 (15)	0.0046 (11)	0.0118 (11)	−0.0067 (12)
C20	0.0200 (13)	0.0348 (15)	0.0402 (16)	−0.0011 (11)	0.0075 (12)	−0.0097 (12)
C21	0.0240 (13)	0.0259 (13)	0.0332 (14)	−0.0038 (11)	0.0149 (11)	−0.0040 (11)
C22	0.058 (3)	0.081 (3)	0.285 (9)	−0.046 (3)	0.104 (4)	−0.123 (5)
C23	0.043 (2)	0.0392 (18)	0.115 (4)	−0.0091 (15)	0.046 (2)	−0.034 (2)
N21	0.0447 (19)	0.068 (2)	0.215 (5)	−0.0369 (17)	0.080 (3)	−0.092 (3)
O1	0.0163 (8)	0.0269 (9)	0.0335 (10)	0.0015 (7)	0.0054 (7)	−0.0062 (8)
O2	0.0325 (14)	0.0181 (12)	0.0282 (14)	0.000	0.0166 (11)	0.000

Geometric parameters (Å, º) top

Fe1—O1ⁱ	2.0965 (17)	C12—H12	0.9500
Fe1—O1	2.0965 (17)	C13—H13	0.9500
Fe1—N1	2.101 (2)	S2—C21	1.773 (3)
Fe1—N1ⁱ	2.101 (2)	N20—C23	1.319 (4)
Fe1—N10	2.235 (2)	N20—C20	1.329 (4)
Fe1—N10ⁱ	2.235 (2)	C20—C21	1.381 (4)
N1—C1	1.160 (3)	C20—H20	0.9500
C1—S1	1.630 (3)	C21—N21	1.302 (4)
N10—C10	1.339 (3)	C22—N21	1.340 (5)
N10—C13	1.340 (3)	C22—C23	1.349 (5)
C10—C11	1.393 (4)	C22—H22	0.9500
C10—H10	0.9500	C23—H23	0.9500
C11—N11	1.333 (3)	O1—H1O1	0.8400
C11—S2	1.775 (3)	O1—H2O1	0.8400
C12—N11	1.339 (4)	O2—H1O2	0.8400
C12—C13	1.381 (4)

O1ⁱ—Fe1—O1	180.0	N11—C12—C13	121.9 (2)
O1ⁱ—Fe1—N1	87.98 (8)	N11—C12—H12	119.1
O1—Fe1—N1	92.02 (8)	C13—C12—H12	119.1
O1ⁱ—Fe1—N1ⁱ	92.02 (8)	N10—C13—C12	121.5 (2)
O1—Fe1—N1ⁱ	87.98 (8)	N10—C13—H13	119.2
N1—Fe1—N1ⁱ	180.00 (12)	C12—C13—H13	119.2
O1ⁱ—Fe1—N10	91.68 (8)	C11—N11—C12	116.6 (2)
O1—Fe1—N10	88.32 (8)	C21—S2—C11	102.11 (12)
N1—Fe1—N10	90.08 (8)	C23—N20—C20	116.9 (3)
N1ⁱ—Fe1—N10	89.92 (8)	N20—C20—C21	121.3 (3)
O1ⁱ—Fe1—N10ⁱ	88.32 (8)	N20—C20—H20	119.3
O1—Fe1—N10ⁱ	91.68 (8)	C21—C20—H20	119.3
N1—Fe1—N10ⁱ	89.92 (8)	N21—C21—C20	121.6 (3)
N1ⁱ—Fe1—N10ⁱ	90.08 (8)	N21—C21—S2	120.6 (2)
N10—Fe1—N10ⁱ	180.00 (9)	C20—C21—S2	117.8 (2)
C1—N1—Fe1	175.3 (2)	N21—C22—C23	122.7 (3)
N1—C1—S1	179.1 (2)	N21—C22—H22	118.6
C10—N10—C13	117.0 (2)	C23—C22—H22	118.6
C10—N10—Fe1	121.96 (17)	N20—C23—C22	121.1 (3)
C13—N10—Fe1	120.93 (17)	N20—C23—H23	119.5
N10—C10—C11	121.0 (2)	C22—C23—H23	119.5
N10—C10—H10	119.5	C21—N21—C22	116.2 (3)
C11—C10—H10	119.5	Fe1—O1—H1O1	130.1
N11—C11—C10	122.0 (2)	Fe1—O1—H2O1	121.7
N11—C11—S2	115.92 (19)	H1O1—O1—H2O1	102.0
C10—C11—S2	121.9 (2)

Symmetry code: (i) −x+3/2, −y+3/2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···N11	0.84	2.00	2.834 (3)	171
O1—H1O1···N20ⁱⁱ	0.84	1.94	2.765 (3)	165
O1—H2O1···O2ⁱⁱⁱ	0.84	1.94	2.749 (3)	162

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

Experimental details

Crystal data
Chemical formula	[Fe(NCS)₂(C₈H₆N₄S)₂(H₂O)₂]·H₂O
M_r	606.51
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	11.5110 (8), 15.8583 (9), 14.8025 (12)
β (°)	109.770 (8)
V (Å³)	2542.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.96
Crystal size (mm)	0.25 × 0.15 × 0.09

Data collection
Diffractometer	Stoe IPDS1 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)
T_min, T_max	0.690, 0.859
No. of measured, independent and observed [I > 2σ(I)] reflections	10774, 2496, 2012
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.090, 1.05
No. of reflections	2496
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.49

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011), XCIF in SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Fe1—O1	2.0965 (17)	Fe1—N10	2.235 (2)
Fe1—N1	2.101 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···N11	0.84	2.00	2.834 (3)	171.0
O1—H1O1···N20ⁱ	0.84	1.94	2.765 (3)	165.3
O1—H2O1···O2ⁱⁱ	0.84	1.94	2.749 (3)	162.1

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

Acknowledgements

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

Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wöhlert, S. & Näther, C. (2013). Eur. J. Inorg. Chem. doi:10.1002/ejic.201201486. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.