catena-Poly[(E)-4,4′-(ethane-1,2-di­yl)dipyridinium [[bis­(thio­cyanato-κN)ferrate(II)]-di-μ-thio­cyanato-κ2N:S;κ2S:N]]

Wöhlert, S.; Jess, I.; Näther, C.

doi:10.1107/S1600536811039924

metal-organic compounds

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Volume 67| Part 11| November 2011| Page m1503

doi:10.1107/S1600536811039924

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catena-Poly[(E)-4,4′-(ethane-1,2-diyl)dipyridinium [[bis(thiocyanato-κN)ferrate(II)]-di-μ-thiocyanato-κ²N:S;κ²S:N]]

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 27 September 2011; accepted 28 September 2011; online 8 October 2011)

In the crystal structure of the title compound, {(C₁₂H₁₄N₂)[Fe(NCS)₄]}_n, the iron(II) cation is coordinated by four N-bonded and two S-bonded thiocyanate anions in a distorted octahedral coordination mode. The asymmetric unit consists of half an iron(II) cation and half a protonated (E)-4,4′-(ethane-1,2-diyl)dipyridinium dication, each located on a centre of inversion. In addition, there are two thiocyanate anions in general positions. The crystal structure consists of Fe—(NCS)₂—Fe chains in which each iron(II) cation is additionally coordinated by two terminal N-bonded thiocyanate anions. Non-coordinating dipyridinium dications are present between the thiocyanatoferrate(II) chains and are connected to the anions via N—H⋯N and N—H⋯S hydrogen-bond interactions.

Related literature

For coordination polymers based on transition metal thio- and selenocyanates, see: Wöhlert et al. (2011 ); Boeckmann et al. (2010 ). For a similar structure, see: Wöhlert et al. (2010 ).

Experimental

Crystal data

(C₁₂H₁₄N₂)[Fe(NCS)₄]
M_r = 474.42
Triclinic, $[P \overline 1]$
a = 5.6818 (3) Å
b = 9.0957 (6) Å
c = 10.9259 (7) Å
α = 105.586 (5)°
β = 103.633 (5)°
γ = 101.383 (5)°
V = 507.65 (5) Å³
Z = 1
Mo Kα radiation
μ = 1.17 mm⁻¹
T = 293 K
0.19 × 0.15 × 0.09 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) T_min = 0.806, T_max = 0.899
7638 measured reflections
2101 independent reflections
1838 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.063
S = 1.03
2101 reflections
124 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Fe1—N1	2.1011 (15)
Fe1—N2	2.1376 (14)
Fe1—S2ⁱ	2.6729 (5)

N1ⁱⁱ—Fe1—N1	180
N1ⁱⁱ—Fe1—N2	88.06 (6)
N1—Fe1—N2	91.94 (6)
N2ⁱⁱ—Fe1—S2ⁱⁱⁱ	86.73 (4)
N1—Fe1—S2ⁱ	86.79 (4)
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+1, -z+1; (iii) -x, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N10—H10A⋯N1	0.86	2.34	3.029 (2)	137
N10—H10A⋯S2ⁱ	0.86	2.73	3.4369 (15)	141
Symmetry code: (i) x+1, y, 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, 1999 ); software used to prepare material for publication: XCIF in SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811039924/bt5657sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811039924/bt5657Isup2.hkl

checkCIF report

Comment top

In our current work, we are interested in the structure and properties of new coordination polymers based on transition metal thio- and selenocyanates (Wöhlert et al., 2011; Boeckmann, Wriedt & Näther, 2010). In our ongoing investigation in this field we have reacted iron(II) sulfate heptahydrate, potassium thiocyanate and E-1,2-bis(4-pyridyl)-ethane in water. In this reaction red single crystals of the title compound were obtained, which were identified by single crystal X-ray diffraction.

The title compound of composition [Fe(NCS)₄]_n-E-1,2-bis(4-pyridinium)-ethane (Fig. 1) represents an 1-D coordination polymer, in which each iron(II) cation is connected by four µ-1,3 bridging thiocyanato anions into chains that elongate in the direction of the crystallographic a axis (Fig. 2). Between these chains noncoordinating protonated E-1,2-bis(4-pyridinium)-ethane ligands are found, that are linked to the anions by weak hydrogen bonding interactions (Table 1). The FeN₄S₂ octahedron is slightly distorted with two long Fe—SCN distances of 2.6729 (5) Å and short Fe—NCS distances of 2.1011 (15) and 2.1376 (14)Å. The angles arround the metal cations range from 86.73 (5) to 93.27 (4) and 180° (Tab. 1). The shortest intramolecular Fe···Fe distance amounts to 5.6818 (3) Å and the shortest intermolecular Fe···Fe distance amounts to 9.0957 (6) Å. It must be noted that the structure is very similar but not isotypic to that of iron(II) thiocyanate and E-1,2-bis(4-pyridinium)-ethylene reported recently (Wöhlert et al., 2010).

Related literature top

For coordination polymers based on transition metal thio- and selenocyanates, see: Wöhlert et al. (2011); Boeckmann et al. (2010). For a similar compound, see: Wöhlert et al. (2010).

Experimental top

FeSO₄^.7H₂O and 1,2-bis(4-pyridyl)-ethane were obtained from Sigma Aldrich. KNCS are obtained from Alfa Aesar. 0.6 mmol (168.0 mg) FeSO₄^.7H₂O, 1.2 mmol (117.7 mg) KNCS and 0.15 mmol (27.2 mg) 1,2-bis(4-pyridyl)-ethane were reacted with 1 mL H₂O in closed test-tube at 120°C for three days. On cooling red block-shaped single crystals of the title compound were obtained in a mixture with a second crystalline phase that was not yet identified.

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, 1999); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 30% probability level. Symmetry code: i = -x + 1, -y + 1, -z + 1; ii = -x, -y +1, -z +1; iii = x+1, y, z; iv = -x, -y +2, -z.
	Fig. 2. : Crystal structure of the title compound viewed along the crystallographic b axis.

catena-Poly[(E)-4,4'-(ethane-1,2-diyl)dipyridinium [[bis(thiocyanato-κN)ferrate(II)]-di-µ-thiocyanato- κ²N:S;κ²S:N]] top

Crystal data top

(C₁₂H₁₄N₂)[Fe(NCS)₄]	Z = 1
M_r = 474.42	F(000) = 242
Triclinic, P1	D_x = 1.552 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.6818 (3) Å	Cell parameters from 7638 reflections
b = 9.0957 (6) Å	θ = 2.0–26.5°
c = 10.9259 (7) Å	µ = 1.17 mm⁻¹
α = 105.586 (5)°	T = 293 K
β = 103.633 (5)°	Block, red
γ = 101.383 (5)°	0.19 × 0.15 × 0.09 mm
V = 507.65 (5) Å³

Data collection top

Stoe IPDS-2 diffractometer	2101 independent reflections
Radiation source: fine-focus sealed tube	1838 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 26.5°, θ_min = 2.0°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −7→6
T_min = 0.806, T_max = 0.899	k = −11→11
7638 measured reflections	l = −13→13

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.063	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0393P)² + 0.0464P] where P = (F_o² + 2F_c²)/3
2101 reflections	(Δ/σ)_max < 0.001
124 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

(C₁₂H₁₄N₂)[Fe(NCS)₄]	γ = 101.383 (5)°
M_r = 474.42	V = 507.65 (5) Å³
Triclinic, P1	Z = 1
a = 5.6818 (3) Å	Mo Kα radiation
b = 9.0957 (6) Å	µ = 1.17 mm⁻¹
c = 10.9259 (7) Å	T = 293 K
α = 105.586 (5)°	0.19 × 0.15 × 0.09 mm
β = 103.633 (5)°

Data collection top

Stoe IPDS-2 diffractometer	2101 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	1838 reflections with I > 2σ(I)
T_min = 0.806, T_max = 0.899	R_int = 0.030
7638 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.063	H-atom parameters constrained
S = 1.03	Δρ_max = 0.26 e Å⁻³
2101 reflections	Δρ_min = −0.40 e Å⁻³
124 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

	x	y	z	U_iso*/U_eq
Fe1	0.5000	0.5000	0.5000	0.02833 (10)
N1	0.4723 (3)	0.45516 (18)	0.29744 (15)	0.0398 (3)
C1	0.5464 (3)	0.40682 (18)	0.20845 (16)	0.0311 (3)
S1	0.64953 (10)	0.33771 (7)	0.08533 (5)	0.04980 (14)
N2	0.2339 (3)	0.63622 (17)	0.48892 (15)	0.0356 (3)
C2	0.0753 (3)	0.69028 (18)	0.51257 (15)	0.0283 (3)
S2	−0.14718 (8)	0.76903 (5)	0.54918 (5)	0.03592 (12)
N10	0.4056 (3)	0.77059 (17)	0.27628 (15)	0.0384 (3)
H10A	0.4891	0.7200	0.3178	0.046*
C10	0.5213 (3)	0.9178 (2)	0.28629 (19)	0.0413 (4)
H10	0.6894	0.9642	0.3374	0.050*
C11	0.3919 (4)	1.0005 (2)	0.22104 (18)	0.0399 (4)
H11	0.4724	1.1029	0.2273	0.048*
C12	0.1399 (3)	0.9314 (2)	0.14537 (16)	0.0333 (4)
C13	0.0289 (3)	0.7782 (2)	0.13838 (18)	0.0390 (4)
H13	−0.1393	0.7289	0.0886	0.047*
C14	0.1652 (4)	0.6990 (2)	0.20418 (19)	0.0410 (4)
H14	0.0905	0.5958	0.1986	0.049*
C15	−0.0056 (4)	1.0190 (2)	0.07142 (17)	0.0416 (4)
H15A	0.0637	1.1324	0.1177	0.050*
H15B	−0.1800	0.9896	0.0701	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.02747 (17)	0.03565 (18)	0.03103 (17)	0.01680 (13)	0.01363 (13)	0.01564 (13)
N1	0.0459 (9)	0.0434 (8)	0.0355 (8)	0.0179 (7)	0.0150 (7)	0.0153 (6)
C1	0.0323 (8)	0.0272 (7)	0.0324 (8)	0.0078 (6)	0.0059 (7)	0.0116 (6)
S1	0.0492 (3)	0.0540 (3)	0.0424 (3)	0.0118 (2)	0.0221 (2)	0.0048 (2)
N2	0.0292 (7)	0.0391 (7)	0.0465 (8)	0.0149 (6)	0.0158 (6)	0.0192 (6)
C2	0.0246 (7)	0.0288 (7)	0.0327 (8)	0.0073 (6)	0.0078 (6)	0.0130 (6)
S2	0.0281 (2)	0.0341 (2)	0.0472 (2)	0.01455 (16)	0.01351 (18)	0.01003 (18)
N10	0.0410 (8)	0.0391 (8)	0.0416 (8)	0.0172 (6)	0.0088 (7)	0.0226 (6)
C10	0.0339 (9)	0.0418 (9)	0.0442 (10)	0.0083 (7)	0.0028 (8)	0.0173 (8)
C11	0.0460 (10)	0.0306 (8)	0.0422 (9)	0.0093 (7)	0.0082 (8)	0.0161 (7)
C12	0.0414 (9)	0.0376 (8)	0.0270 (7)	0.0192 (7)	0.0115 (7)	0.0135 (7)
C13	0.0336 (9)	0.0424 (9)	0.0391 (9)	0.0082 (7)	0.0061 (7)	0.0165 (8)
C14	0.0449 (10)	0.0343 (9)	0.0450 (10)	0.0072 (7)	0.0115 (8)	0.0198 (8)
C15	0.0517 (11)	0.0469 (10)	0.0369 (9)	0.0292 (9)	0.0128 (8)	0.0204 (8)

Geometric parameters (Å, º) top

Fe1—N1ⁱ	2.1011 (15)	N10—H10A	0.8600
Fe1—N1	2.1011 (15)	C10—C11	1.369 (2)
Fe1—N2ⁱ	2.1376 (14)	C10—H10	0.9300
Fe1—N2	2.1376 (14)	C11—C12	1.391 (3)
Fe1—S2ⁱⁱ	2.6729 (5)	C11—H11	0.9300
Fe1—S2ⁱⁱⁱ	2.6729 (5)	C12—C13	1.385 (2)
N1—C1	1.163 (2)	C12—C15	1.504 (2)
C1—S1	1.6157 (18)	C13—C14	1.368 (3)
N2—C2	1.156 (2)	C13—H13	0.9300
C2—S2	1.6472 (16)	C14—H14	0.9300
S2—Fe1^iv	2.6729 (5)	C15—C15^v	1.525 (4)
N10—C14	1.333 (2)	C15—H15A	0.9700
N10—C10	1.333 (2)	C15—H15B	0.9700

N1ⁱ—Fe1—N1	180.000 (1)	C10—N10—H10A	118.8
N1ⁱ—Fe1—N2ⁱ	91.94 (6)	N10—C10—C11	119.77 (16)
N1—Fe1—N2ⁱ	88.06 (6)	N10—C10—H10	120.1
N1ⁱ—Fe1—N2	88.06 (6)	C11—C10—H10	120.1
N1—Fe1—N2	91.94 (6)	C10—C11—C12	120.07 (16)
N2ⁱ—Fe1—N2	180.000 (1)	C10—C11—H11	120.0
N1ⁱ—Fe1—S2ⁱⁱ	86.79 (4)	C12—C11—H11	120.0
N1—Fe1—S2ⁱⁱ	93.21 (4)	C13—C12—C11	117.78 (15)
N2ⁱ—Fe1—S2ⁱⁱ	86.73 (4)	C13—C12—C15	121.12 (16)
N2—Fe1—S2ⁱⁱ	93.27 (4)	C11—C12—C15	121.09 (16)
N1ⁱ—Fe1—S2ⁱⁱⁱ	93.21 (4)	C14—C13—C12	120.42 (16)
N1—Fe1—S2ⁱⁱⁱ	86.79 (4)	C14—C13—H13	119.8
N2ⁱ—Fe1—S2ⁱⁱⁱ	93.27 (4)	C12—C13—H13	119.8
N2—Fe1—S2ⁱⁱⁱ	86.73 (4)	N10—C14—C13	119.63 (16)
S2ⁱⁱ—Fe1—S2ⁱⁱⁱ	180.000 (13)	N10—C14—H14	120.2
C1—N1—Fe1	149.29 (13)	C13—C14—H14	120.2
N1—C1—S1	179.28 (15)	C12—C15—C15^v	111.35 (18)
C2—N2—Fe1	158.76 (13)	C12—C15—H15A	109.4
N2—C2—S2	178.92 (16)	C15^v—C15—H15A	109.4
C2—S2—Fe1^iv	98.29 (6)	C12—C15—H15B	109.4
C14—N10—C10	122.34 (15)	C15^v—C15—H15B	109.4
C14—N10—H10A	118.8	H15A—C15—H15B	108.0

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) x+1, y, z; (iv) x−1, y, z; (v) −x, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10A···N1	0.86	2.34	3.029 (2)	137
N10—H10A···S2ⁱⁱⁱ	0.86	2.73	3.4369 (15)	141

Symmetry code: (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	(C₁₂H₁₄N₂)[Fe(NCS)₄]
M_r	474.42
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.6818 (3), 9.0957 (6), 10.9259 (7)
α, β, γ (°)	105.586 (5), 103.633 (5), 101.383 (5)
V (Å³)	507.65 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.17
Crystal size (mm)	0.19 × 0.15 × 0.09

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)
T_min, T_max	0.806, 0.899
No. of measured, independent and observed [I > 2σ(I)] reflections	7638, 2101, 1838
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.063, 1.03
No. of reflections	2101
No. of parameters	124
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.40

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), XCIF in SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Fe1—N1	2.1011 (15)	Fe1—S2ⁱ	2.6729 (5)
Fe1—N2	2.1376 (14)

N1ⁱⁱ—Fe1—N1	180.000 (1)	N2ⁱⁱ—Fe1—S2ⁱⁱⁱ	86.73 (4)
N1ⁱⁱ—Fe1—N2	88.06 (6)	N1—Fe1—S2ⁱ	86.79 (4)
N1—Fe1—N2	91.94 (6)

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10A···N1	0.86	2.34	3.029 (2)	137.4
N10—H10A···S2ⁱ	0.86	2.73	3.4369 (15)	141.0

Symmetry code: (i) x+1, y, z.

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

Boeckmann, J., Wriedt, M. & Näther, C. (2010). Eur. J. Inorg. Chem. 12, 1820–1828. Web of Science CSD CrossRef Google Scholar
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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
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Wöhlert, S., Wriedt, M., Jess, I. & Näther, C. (2010). Acta Cryst. E66, m1256. Web of Science CSD CrossRef IUCr Journals Google Scholar

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