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

Wöhlert, S.; Wriedt, M.; Jess, I.; Näther, C.

doi:10.1107/S160053681003624X

metal-organic compounds

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Volume 66| Part 10| October 2010| Page m1256

doi:10.1107/S160053681003624X

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

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

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

(Received 3 September 2010; accepted 9 September 2010; online 15 September 2010)

In the title compound, {(C₁₂H₁₂N₂)[Fe(NCS)₄]}_n, each Fe^II cation is coordinated by four N-bonded and two S-bonded thiocyanate anions in an octahedral coordination mode. The asymmetric unit consists of one Fe^II cation, located on a center of inversion, as well as one protonated (E)-4,4′-(ethene-1,2-diyl)dipyridinium dication and two thiocyanate anions in general positions. The crystal structure consists of Fe—(NCS)₂—Fe chains extending along the a axis, in which two further thiocyanate anions are only terminally bonded via nitrogen. Non-coordinating (E)-4,4′-(ethene-1,2-diyl)dipyridinium cations are found between the chains.

Related literature

For general background, see: Wriedt & Näther (2009a ,b ); Wriedt et al. (2009a ,b ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

(C₁₂H₁₂N₂)[Fe(NCS)₄]
M_r = 472.41
Monoclinic, P 2₁ /c
a = 5.7360 (2) Å
b = 11.5093 (4) Å
c = 15.0971 (6) Å
β = 96.562 (3)°
V = 990.14 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.20 mm⁻¹
T = 293 K
0.16 × 0.13 × 0.09 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ) T_min = 0.826, T_max = 0.895
16607 measured reflections
2379 independent reflections
2173 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.068
S = 1.09
2379 reflections
124 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Fe1—N11	2.1090 (16)
Fe1—N1	2.1165 (15)
Fe1—S1ⁱ	2.6375 (5)

N11ⁱⁱ—Fe1—N1	89.61 (7)
N11ⁱⁱ—Fe1—N1ⁱⁱ	90.39 (7)
N11ⁱⁱ—Fe1—S1ⁱ	90.74 (5)
N1ⁱⁱ—Fe1—S1ⁱ	87.23 (4)
N11ⁱⁱ—Fe1—S1ⁱⁱⁱ	89.26 (5)
N1ⁱⁱ—Fe1—S1ⁱⁱⁱ	92.77 (4)
Symmetry codes: (i) -x+1, -y, -z+1; (ii)-x+2, -y, -z+1; (iii) 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/S160053681003624X/im2228sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681003624X/im2228Isup2.hkl

checkCIF report

Comment top

Recently, we have shown that thermal decomposition reactions are an elegant route for the discovering and preparation of new ligand-deficient coordination polymers with defined magnetic properties (Wriedt & Näther, 2009a, 2009b; Wriedt et al., 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 iron(II) sulfate heptahydrate, potassium thiocyanate and E-1,2-di(4'-pyridyl)-ethene in water. In this reaction single crystals of the title compound were obtained, which were characterized by single crystal X-ray diffraction.

The title compound of composition [Fe(NCS)₄]_n-[E-1,2-di(4'-pyridinium)-ethene]_n (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. 3). The octahedral coordination of each Fe cation is completed by two N-bonded thiocyanato anions. It must be noted that according to a search in the CCDC database (ConQuest Ver. 1.12 2010) such chains with transition metals are unknown (Allen, 2002).

Between the chains noncoordinating protonated (E)-4,4'-(ethene-1,2-diyl)dipyridinium cations are found, which are stacked in the direction of the crystallographic a-axis involving weak π-π-stacking interactions (Fig. 2). The FeN₄S₂ octahedron is slightly distorted with two long Fe—SCN distances of 2.6375 (5) Å and short Fe—NCS distances of 2.109 (2) and 2.116 (2) Å. The angles arround the metal atoms range between 87.23 (5) to 92.77 (5) and 180° (Tab. 1). The shortest intramolecular Fe···Fe distance amounts to 5.7360 (2) Å and the shortest intermolecular Fe···Fe distance amounts to 9.4919 (3) Å.

Related literature top

For general background, see: Wriedt & Näther (2009a,b); Wriedt et al. (2009a,b). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

FeSO₄ × 7 H₂O and 1,2-di(4'-pyridyl)-ethene were obtained from Sigma Aldrich. KNCS was obtained from Alfa Aesar. 0.6 mmol (168.8 mg) FeSO₄ × 7 H₂O, 1.2 mmol (118.5 mg) KNCS and 0.15 mmol (28.2 mg) 1,2-di(4'-pyridyl)-ethene were reacted with 1 mL H₂O in a closed test-tube at 120°C for three days. On cooling green block-shaped single crystals of the title compound were obtained in a mixture with unknown phases.

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 codes: i = -x + 1, -y + 1, -z + 1; ii = -x+1, -y, -z+1; iii = +x+1, +y, +z; iv = -x+2, -y+1, -z+1.
	Fig. 2. : Packing arrangement of the title compound with view approximately along the crystallographic a-axis.
	Fig. 3. : Packing arrangement of the title compound with view on the inorganic part Fe(NCS)₂–(NCS)₂–Fe(NCS)₂ approximately along the crystallographic b-axis. The non-coordinated organic cations were omitted for clearity.

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

Crystal data top

(C₁₂H₁₂N₂)[Fe(NCS)₄]	F(000) = 480
M_r = 472.41	D_x = 1.585 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 16607 reflections
a = 5.7360 (2) Å	θ = 2–28°
b = 11.5093 (4) Å	µ = 1.20 mm⁻¹
c = 15.0971 (6) Å	T = 293 K
β = 96.562 (3)°	Block, green
V = 990.14 (6) Å³	0.16 × 0.13 × 0.09 mm
Z = 2

Data collection top

Stoe IPDS-2 diffractometer	2379 independent reflections
Radiation source: fine-focus sealed tube	2173 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 28.0°, θ_min = 2.2°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −7→7
T_min = 0.826, T_max = 0.895	k = −15→15
16607 measured reflections	l = −19→19

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.068	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0291P)² + 0.4228P] where P = (F_o² + 2F_c²)/3
2379 reflections	(Δ/σ)_max = 0.001
124 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

(C₁₂H₁₂N₂)[Fe(NCS)₄]	V = 990.14 (6) Å³
M_r = 472.41	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.7360 (2) Å	µ = 1.20 mm⁻¹
b = 11.5093 (4) Å	T = 293 K
c = 15.0971 (6) Å	0.16 × 0.13 × 0.09 mm
β = 96.562 (3)°

Data collection top

Stoe IPDS-2 diffractometer	2379 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	2173 reflections with I > 2σ(I)
T_min = 0.826, T_max = 0.895	R_int = 0.029
16607 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.068	H-atom parameters constrained
S = 1.09	Δρ_max = 0.57 e Å⁻³
2379 reflections	Δρ_min = −0.21 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	1.0000	0.0000	0.5000	0.03128 (10)
N2	0.3720 (3)	0.38242 (17)	0.30355 (13)	0.0541 (4)
H2	0.2544	0.3548	0.2697	0.065*
S1	0.26743 (7)	0.16763 (4)	0.57486 (3)	0.03779 (11)
C1	0.5284 (3)	0.12116 (14)	0.55629 (11)	0.0334 (3)
N1	0.7106 (3)	0.08926 (14)	0.54301 (11)	0.0430 (4)
S11	1.12064 (9)	−0.23939 (5)	0.76873 (3)	0.04587 (13)
C11	1.0730 (3)	−0.15568 (16)	0.68107 (12)	0.0371 (4)
N11	1.0414 (3)	−0.09600 (16)	0.61976 (11)	0.0490 (4)
C21	0.6655 (4)	0.52070 (17)	0.32949 (15)	0.0522 (5)
H21	0.7402	0.5868	0.3113	0.063*
C22	0.7421 (3)	0.46922 (17)	0.41067 (13)	0.0425 (4)
C23	0.6230 (4)	0.3727 (2)	0.43548 (15)	0.0571 (6)
H23	0.6699	0.3361	0.4895	0.069*
C24	0.4368 (4)	0.3310 (2)	0.38090 (17)	0.0620 (6)
H24	0.3550	0.2664	0.3979	0.074*
C25	0.4812 (4)	0.47453 (19)	0.27648 (15)	0.0555 (6)
H25	0.4323	0.5077	0.2213	0.067*
C26	0.9479 (4)	0.52118 (18)	0.46271 (14)	0.0494 (5)
H26	1.0085	0.5891	0.4410	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.02351 (16)	0.04009 (18)	0.03042 (17)	0.00428 (13)	0.00389 (12)	0.00449 (13)
N2	0.0395 (9)	0.0612 (11)	0.0580 (11)	−0.0001 (8)	−0.0097 (8)	−0.0187 (9)
S1	0.0277 (2)	0.0431 (2)	0.0430 (2)	0.00552 (16)	0.00590 (16)	−0.00552 (18)
C1	0.0305 (8)	0.0355 (8)	0.0338 (8)	−0.0023 (6)	0.0025 (6)	−0.0036 (6)
N1	0.0276 (7)	0.0470 (8)	0.0549 (9)	0.0011 (6)	0.0061 (6)	−0.0103 (7)
S11	0.0449 (3)	0.0521 (3)	0.0399 (2)	0.0004 (2)	0.00183 (19)	0.0133 (2)
C11	0.0297 (8)	0.0441 (9)	0.0372 (9)	−0.0029 (7)	0.0025 (6)	0.0003 (7)
N11	0.0494 (9)	0.0565 (10)	0.0395 (8)	−0.0047 (8)	−0.0020 (7)	0.0121 (7)
C21	0.0602 (13)	0.0386 (10)	0.0549 (12)	−0.0038 (9)	−0.0060 (10)	0.0019 (8)
C22	0.0389 (9)	0.0434 (10)	0.0435 (10)	−0.0004 (7)	−0.0029 (8)	−0.0071 (8)
C23	0.0644 (14)	0.0628 (13)	0.0417 (10)	−0.0140 (11)	−0.0043 (10)	0.0063 (9)
C24	0.0612 (14)	0.0671 (14)	0.0573 (13)	−0.0247 (12)	0.0048 (11)	−0.0017 (11)
C25	0.0639 (14)	0.0466 (11)	0.0510 (12)	0.0118 (10)	−0.0146 (10)	−0.0034 (9)
C26	0.0510 (11)	0.0445 (10)	0.0504 (11)	−0.0050 (8)	−0.0048 (9)	0.0022 (8)

Geometric parameters (Å, º) top

Fe1—N11	2.1090 (16)	C11—N11	1.150 (2)
Fe1—N11ⁱ	2.1090 (16)	C21—C25	1.359 (3)
Fe1—N1	2.1165 (15)	C21—C22	1.387 (3)
Fe1—N1ⁱ	2.1165 (15)	C21—H21	0.9300
Fe1—S1ⁱⁱ	2.6375 (5)	C22—C23	1.378 (3)
Fe1—S1ⁱⁱⁱ	2.6375 (5)	C22—C26	1.469 (3)
N2—C25	1.320 (3)	C23—C24	1.360 (3)
N2—C24	1.324 (3)	C23—H23	0.9300
N2—H2	0.8600	C24—H24	0.9300
S1—C1	1.6437 (17)	C25—H25	0.9300
S1—Fe1^iv	2.6375 (5)	C26—C26^v	1.307 (4)
C1—N1	1.147 (2)	C26—H26	0.9300
S11—C11	1.6345 (19)

N11—Fe1—N11ⁱ	180.0	N11—C11—S11	179.25 (19)
N11—Fe1—N1	90.39 (7)	C11—N11—Fe1	174.08 (17)
N11ⁱ—Fe1—N1	89.61 (7)	C25—C21—C22	120.0 (2)
N11—Fe1—N1ⁱ	89.61 (7)	C25—C21—H21	120.0
N11ⁱ—Fe1—N1ⁱ	90.39 (7)	C22—C21—H21	120.0
N1—Fe1—N1ⁱ	180.0 (9)	C23—C22—C21	117.88 (18)
N11—Fe1—S1ⁱⁱ	89.26 (5)	C23—C22—C26	125.17 (19)
N11ⁱ—Fe1—S1ⁱⁱ	90.74 (5)	C21—C22—C26	116.93 (19)
N1—Fe1—S1ⁱⁱ	92.77 (4)	C24—C23—C22	120.0 (2)
N1ⁱ—Fe1—S1ⁱⁱ	87.23 (4)	C24—C23—H23	120.0
N11—Fe1—S1ⁱⁱⁱ	90.74 (5)	C22—C23—H23	120.0
N11ⁱ—Fe1—S1ⁱⁱⁱ	89.26 (5)	N2—C24—C23	119.9 (2)
N1—Fe1—S1ⁱⁱⁱ	87.23 (4)	N2—C24—H24	120.1
N1ⁱ—Fe1—S1ⁱⁱⁱ	92.77 (4)	C23—C24—H24	120.1
S1ⁱⁱ—Fe1—S1ⁱⁱⁱ	180.0	N2—C25—C21	119.8 (2)
C25—N2—C24	122.48 (18)	N2—C25—H25	120.1
C25—N2—H2	118.8	C21—C25—H25	120.1
C24—N2—H2	118.8	C26^v—C26—C22	124.7 (3)
C1—S1—Fe1^iv	100.68 (6)	C26^v—C26—H26	117.6
N1—C1—S1	179.60 (19)	C22—C26—H26	117.6
C1—N1—Fe1	166.29 (15)

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

Experimental details

Crystal data
Chemical formula	(C₁₂H₁₂N₂)[Fe(NCS)₄]
M_r	472.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.7360 (2), 11.5093 (4), 15.0971 (6)
β (°)	96.562 (3)
V (Å³)	990.14 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.20
Crystal size (mm)	0.16 × 0.13 × 0.09

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)
T_min, T_max	0.826, 0.895
No. of measured, independent and observed [I > 2σ(I)] reflections	16607, 2379, 2173
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.068, 1.09
No. of reflections	2379
No. of parameters	124
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.21

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—N11	2.1090 (16)	Fe1—S1ⁱ	2.6375 (5)
Fe1—N1	2.1165 (15)	S1—Fe1ⁱⁱ	2.6375 (5)

N11ⁱⁱⁱ—Fe1—N1	89.61 (7)	N1ⁱⁱⁱ—Fe1—S1ⁱ	87.23 (4)
N11ⁱⁱⁱ—Fe1—N1ⁱⁱⁱ	90.39 (7)	N11ⁱⁱⁱ—Fe1—S1^iv	89.26 (5)
N11ⁱⁱⁱ—Fe1—S1ⁱ	90.74 (5)	N1ⁱⁱⁱ—Fe1—S1^iv	92.77 (4)

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

References

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