catena-Poly[bis­[cis-dipyrimidine-trans-dithio­cyanato­iron(II)]-di-μ-pyrimidine-[trans-dithio­cyanato­iron(II)]-di-μ-pyrimidine]

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

doi:10.1107/S1600536809005509

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Pages m296-m297

doi:10.1107/S1600536809005509

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catena-Poly[bis[cis-dipyrimidine-trans-dithiocyanatoiron(II)]-di-μ-pyrimidine-[trans-dithiocyanatoiron(II)]-di-μ-pyrimidine]

Mario Wriedt,^a Sina Sellmer,^a Inke Jess ^a and Christian Näther ^a ^*

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

(Received 11 February 2009; accepted 16 February 2009; online 21 February 2009)

In the crystal structure of the title compound, [Fe₃(NCS)₆(C₄H₄N₂)₈]_n, each iron(II) cation is coordinated by four N-bonded pyrimidine ligands and two N-bonded thiocyanate anions in a distorted octahedral environment. The asymmetric unit consists of one iron cation located on a crystallographic center of inversion, as well as one iron cation, three thiocyanate anions and four pyrimidine ligands occupying general positions. The structure consists of square secondary building units (SBUs) with an Fe atom at each corner, which are μ-N¹:N³-bridged by the pyrimidine ligands. The SBUs are linked into infinite chains running in the c-axis direction via common opposite corners.

Related literature

For related pyrimidine structures, see: Lloret et al. (1998 ); Näther et al. (2007 ); Näther & Jess (2004 ). For general background, see: Näther & Greve (2003 ); Näther, Wriedt & Jess (2003 ); Wriedt et al. (2008 , 2009 ).

Experimental

Crystal data

[Fe₃(NCS)₆(C₄H₄N₂)₈]
M_r = 1156.77
Monoclinic, P 2₁ /c
a = 18.256 (1) Å
b = 16.2855 (9) Å
c = 8.2765 (4) Å
β = 100.042 (7)°
V = 2423.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.20 mm⁻¹
T = 170 K
0.12 × 0.10 × 0.07 mm

Data collection

Stoe IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008 ) T_min = 0.859, T_max = 0.912
20463 measured reflections
4615 independent reflections
3795 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.124
S = 1.13
4615 reflections
314 parameters
H-atom parameters constrained
Δρ_max = 0.95 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Selected bond lengths (Å)

Fe1—N41	2.075 (3)
Fe1—N51	2.089 (3)
Fe1—N1	2.252 (3)
Fe1—N31	2.254 (3)
Fe1—N21	2.262 (3)
Fe1—N11	2.304 (3)
Fe2—N61	2.075 (3)
Fe2—N61ⁱ	2.075 (3)
Fe2—N2	2.252 (3)
Fe2—N2ⁱ	2.252 (3)
Fe2—N32ⁱⁱ	2.291 (3)
Fe2—N32ⁱⁱⁱ	2.291 (3)
Symmetry codes: (i) -x, -y+1, -z+2; (ii) -x, -y+1, -z+1; (iii) x, y, z+1.

Data collection: X-AREA (Stoe, 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); software used to prepare material for publication: XCIF in SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809005509/im2102sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809005509/im2102Isup2.hkl

checkCIF report

Comment top

In our ongoing investigation on the syntheses, structures and properties of new coordination polymers based on paramagnetic metal pseudohalides and N-donor ligands, we have demonstrated that new ligand deficient coordination polymers with interesting magnetic interactions can be conveniently prepared by thermal decomposition of suitable ligand rich precursor compounds (Näther & Greve, 2003 and Wriedt et al., 2009). In further investigations we have reacted iron(II) sulfate heptahydrate and potassium thiocyanate with pyrimidine leading to the formation of single crystals of the title compound.

The 3:8 title compound [(Fe(SCN)₂)₃(µ-pyrimidine)₈(pyrimidine)₂]_n structurally (Fig. 1) represents a chain-like coordination polymer consisting of square SBU's with shared opposite corners as the characteristic motif. Each square SBU contains four iron(II) cations in its corners that are µ-1,3-(N,N') bridged by pyrimidine ligands. The commonly used corner iron cations are located on crystallographic centers of inversion and are each octahedrally coordinated by four bridging pyrimidine ligands and two symmetry related terminal N-bonded thiocyanate anions. The iron cations in general positions are each octahedrally coordinated by two bridging pyrimidine ligands as well as two terminal N-bonded pyrimidine ligands and two terminal N-bonded thiocyanate anions (Fig 2). The Fe—NCS distances amount to 2.075 (3) and 2.089 (3) Å and the Fe—N_pyrimidine distances range from 2.252 (3) to 2.304 (3) Å. The angles around the iron cations range from 86.9 (1) to 180.0°. The shortest intra- and interchain Fe···Fe distances measure to 6.2508 (6) and 8.7620 (8)Å, respectively.

Related literature top

For related pyrimidine structures, see: Lloret et al. (1998); Näther et al. (2007); Näther & Jeß (2004). For general background, see: Näther & Greve (2003); Näther, Wriedt & Jeß (2003); Wriedt et al. (2008, 2009).

Experimental top

FeSO₄.7H₂O and pyrimidine were obtained from Alfa Aesar, KSCN was obtained from Fluka. 0.25 mmol (69.5 mg) FeSO₄ × 7 H₂O, 0.5 mmol (48.6 mg) KSCN and 9 mmol (720.8 mg) pyrimidine were transfered into a test-tube. In a solvent-free reaction at room temperature without stirring red block-shaped single crystals of the title compound were obtained after 2 weeks.

Computing details top

Data collection: X-AREA (Stoe, 2008); cell refinement: X-AREA (Stoe, 2008); data reduction: X-AREA (Stoe, 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); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the repeating unit of the title compound showing the labelling scheme. Displacement ellipsoids drawn at the 50% probability level. Symmetry codes: i = -x, -y + 1, -z + 2; ii = x, y, z + 1; iii = -x, -y + 1, -z + 1.
	Fig. 2. : Crystal structure of the title compound viewed along the b-axis.

catena-Poly[bis[cis-dipyrimidine-trans- dithiocyanatoiron(II)]-di-µ-pyrimidine-[trans-dithiocyanatoiron(II)]- di-µ-pyrimidine] top

Crystal data top

[Fe₃(NCS)₆(C₄H₄N₂)₈]	F(000) = 1176
M_r = 1156.77	D_x = 1.586 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8000 reflections
a = 18.256 (1) Å	θ = 8.3–27.2°
b = 16.2855 (9) Å	µ = 1.20 mm⁻¹
c = 8.2765 (4) Å	T = 170 K
β = 100.042 (7)°	Block, red
V = 2423.0 (2) Å³	0.12 × 0.10 × 0.07 mm
Z = 2

Data collection top

Stoe IPDS-1 diffractometer	4615 independent reflections
Radiation source: fine-focus sealed tube	3795 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
ϕ scans	θ_max = 26.0°, θ_min = 2.6°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008)	h = −22→22
T_min = 0.859, T_max = 0.912	k = −20→20
20463 measured reflections	l = −10→10

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.0419P)² + 8.0294P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max < 0.001
4615 reflections	Δρ_max = 0.95 e Å⁻³
314 parameters	Δρ_min = −0.41 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0024 (5)

Crystal data top

[Fe₃(NCS)₆(C₄H₄N₂)₈]	V = 2423.0 (2) Å³
M_r = 1156.77	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.256 (1) Å	µ = 1.20 mm⁻¹
b = 16.2855 (9) Å	T = 170 K
c = 8.2765 (4) Å	0.12 × 0.10 × 0.07 mm
β = 100.042 (7)°

Data collection top

Stoe IPDS-1 diffractometer	4615 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008)	3795 reflections with I > 2σ(I)
T_min = 0.859, T_max = 0.912	R_int = 0.064
20463 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.13	Δρ_max = 0.95 e Å⁻³
4615 reflections	Δρ_min = −0.41 e Å⁻³
314 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	0.26416 (3)	0.48712 (3)	0.61108 (6)	0.01115 (16)
Fe2	0.0000	0.5000	1.0000	0.01002 (18)
N41	0.26059 (19)	0.5829 (2)	0.7749 (4)	0.0202 (7)
C41	0.2859 (2)	0.6276 (2)	0.8790 (5)	0.0182 (8)
S41	0.32547 (8)	0.68848 (8)	1.02316 (17)	0.0418 (4)
N51	0.26521 (18)	0.3912 (2)	0.4439 (4)	0.0184 (7)
C51	0.26229 (19)	0.3726 (2)	0.3063 (5)	0.0127 (7)
S51	0.25824 (6)	0.35068 (7)	0.11413 (12)	0.0241 (3)
N61	0.00127 (18)	0.5933 (2)	0.8299 (4)	0.0167 (7)
C61	0.0140 (2)	0.6208 (2)	0.7072 (5)	0.0146 (8)
S61	0.03129 (7)	0.65765 (7)	0.53635 (14)	0.0292 (3)
N1	0.17147 (16)	0.42202 (19)	0.7062 (4)	0.0131 (6)
N2	0.07898 (17)	0.42630 (19)	0.8767 (4)	0.0131 (6)
C1	0.12769 (19)	0.4614 (2)	0.7952 (4)	0.0130 (7)
H1	0.1317	0.5195	0.8008	0.016*
C2	0.0754 (2)	0.3440 (2)	0.8720 (5)	0.0165 (8)
H2	0.0432	0.3166	0.9330	0.020*
C3	0.1170 (2)	0.2978 (2)	0.7813 (5)	0.0179 (8)
H3	0.1133	0.2397	0.7768	0.021*
C4	0.1643 (2)	0.3399 (2)	0.6977 (5)	0.0164 (8)
H4	0.1927	0.3099	0.6320	0.020*
N11	0.36347 (17)	0.5483 (2)	0.5208 (4)	0.0157 (7)
N12	0.4695 (2)	0.6360 (2)	0.5800 (5)	0.0264 (8)
C11	0.4082 (2)	0.6011 (3)	0.6157 (5)	0.0212 (9)
H11	0.3949	0.6149	0.7183	0.025*
C12	0.4872 (2)	0.6144 (3)	0.4348 (6)	0.0275 (10)
H12	0.5309	0.6369	0.4048	0.033*
C13	0.4452 (3)	0.5618 (3)	0.3286 (6)	0.0289 (10)
H13	0.4584	0.5482	0.2258	0.035*
C14	0.3827 (2)	0.5293 (3)	0.3769 (5)	0.0231 (9)
H14	0.3525	0.4923	0.3056	0.028*
N21	0.34829 (17)	0.4171 (2)	0.7928 (4)	0.0150 (7)
N22	0.4465 (2)	0.4159 (2)	1.0257 (5)	0.0285 (9)
C21	0.3925 (2)	0.4525 (3)	0.9200 (5)	0.0216 (9)
H21	0.3847	0.5093	0.9370	0.026*
C22	0.4557 (2)	0.3357 (3)	1.0026 (5)	0.0249 (9)
H22	0.4936	0.3074	1.0746	0.030*
C23	0.4125 (2)	0.2927 (3)	0.8790 (5)	0.0219 (9)
H23	0.4191	0.2354	0.8658	0.026*
C24	0.3587 (2)	0.3362 (2)	0.7736 (5)	0.0150 (8)
H24	0.3284	0.3080	0.6859	0.018*
N31	0.19048 (17)	0.5567 (2)	0.4101 (4)	0.0155 (7)
N32	0.09789 (17)	0.56059 (19)	0.1687 (4)	0.0143 (7)
C31	0.1369 (2)	0.5230 (2)	0.2998 (5)	0.0151 (8)
H31	0.1253	0.4670	0.3159	0.018*
C32	0.1156 (2)	0.6395 (2)	0.1491 (5)	0.0184 (8)
H32	0.0906	0.6684	0.0558	0.022*
C33	0.1689 (2)	0.6805 (3)	0.2591 (6)	0.0244 (9)
H33	0.1799	0.7368	0.2448	0.029*
C34	0.2051 (2)	0.6362 (2)	0.3899 (5)	0.0203 (9)
H34	0.2417	0.6627	0.4684	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0097 (3)	0.0137 (3)	0.0102 (3)	−0.00061 (19)	0.0022 (2)	−0.0013 (2)
Fe2	0.0084 (3)	0.0124 (4)	0.0098 (4)	0.0004 (3)	0.0029 (3)	0.0014 (3)
N41	0.0200 (17)	0.0208 (18)	0.0212 (18)	−0.0004 (14)	0.0073 (15)	−0.0038 (14)
C41	0.0174 (18)	0.0167 (19)	0.020 (2)	0.0057 (15)	0.0032 (16)	−0.0026 (16)
S41	0.0447 (7)	0.0309 (7)	0.0414 (7)	0.0109 (5)	−0.0158 (6)	−0.0206 (6)
N51	0.0190 (17)	0.0198 (17)	0.0169 (17)	0.0001 (13)	0.0047 (14)	−0.0014 (14)
C51	0.0103 (16)	0.0106 (17)	0.0170 (19)	0.0005 (13)	0.0015 (14)	−0.0018 (14)
S51	0.0343 (6)	0.0272 (5)	0.0112 (5)	−0.0026 (4)	0.0052 (4)	−0.0027 (4)
N61	0.0162 (16)	0.0181 (17)	0.0161 (17)	0.0015 (12)	0.0035 (13)	0.0033 (13)
C61	0.0127 (17)	0.0131 (17)	0.0178 (19)	0.0037 (14)	0.0022 (15)	−0.0002 (15)
S61	0.0441 (7)	0.0281 (6)	0.0189 (5)	0.0067 (5)	0.0147 (5)	0.0085 (4)
N1	0.0085 (14)	0.0158 (16)	0.0155 (15)	−0.0002 (11)	0.0034 (12)	−0.0004 (12)
N2	0.0114 (14)	0.0153 (15)	0.0132 (15)	0.0004 (12)	0.0039 (12)	−0.0001 (12)
C1	0.0110 (16)	0.0159 (18)	0.0126 (17)	0.0012 (14)	0.0035 (14)	0.0007 (14)
C2	0.0151 (18)	0.0142 (18)	0.022 (2)	−0.0018 (14)	0.0075 (16)	0.0016 (15)
C3	0.0166 (18)	0.0114 (17)	0.026 (2)	−0.0026 (14)	0.0042 (16)	−0.0024 (15)
C4	0.0124 (17)	0.0175 (19)	0.020 (2)	0.0009 (14)	0.0039 (15)	−0.0038 (15)
N11	0.0107 (14)	0.0210 (17)	0.0153 (16)	−0.0021 (12)	0.0015 (13)	0.0017 (13)
N12	0.0231 (18)	0.032 (2)	0.027 (2)	−0.0136 (15)	0.0106 (16)	−0.0069 (16)
C11	0.0184 (19)	0.026 (2)	0.021 (2)	−0.0072 (16)	0.0072 (17)	−0.0056 (16)
C12	0.024 (2)	0.038 (3)	0.024 (2)	−0.0139 (19)	0.0140 (18)	−0.0027 (19)
C13	0.028 (2)	0.040 (3)	0.021 (2)	−0.012 (2)	0.0124 (19)	−0.0024 (19)
C14	0.024 (2)	0.031 (2)	0.015 (2)	−0.0097 (17)	0.0052 (17)	−0.0062 (17)
N21	0.0131 (15)	0.0181 (16)	0.0139 (15)	−0.0007 (12)	0.0026 (13)	0.0022 (13)
N22	0.0267 (19)	0.026 (2)	0.0274 (19)	−0.0014 (15)	−0.0108 (16)	0.0036 (16)
C21	0.025 (2)	0.021 (2)	0.0167 (19)	0.0001 (16)	−0.0026 (17)	0.0009 (16)
C22	0.021 (2)	0.027 (2)	0.026 (2)	0.0033 (17)	−0.0006 (18)	0.0084 (18)
C23	0.022 (2)	0.022 (2)	0.021 (2)	0.0063 (16)	0.0013 (17)	0.0055 (16)
C24	0.0157 (18)	0.0183 (19)	0.0114 (18)	0.0018 (14)	0.0036 (15)	0.0022 (14)
N31	0.0115 (15)	0.0181 (16)	0.0163 (16)	−0.0014 (12)	0.0011 (13)	0.0007 (13)
N32	0.0116 (15)	0.0154 (16)	0.0156 (16)	−0.0005 (12)	0.0012 (13)	−0.0015 (12)
C31	0.0112 (17)	0.0169 (18)	0.0165 (18)	0.0004 (14)	0.0010 (15)	−0.0004 (15)
C32	0.0155 (18)	0.0185 (19)	0.020 (2)	0.0003 (15)	−0.0008 (16)	0.0061 (15)
C33	0.023 (2)	0.017 (2)	0.031 (2)	−0.0046 (16)	−0.0027 (18)	0.0032 (17)
C34	0.0185 (19)	0.020 (2)	0.020 (2)	−0.0045 (15)	−0.0032 (16)	−0.0030 (16)

Geometric parameters (Å, º) top

Fe1—N41	2.075 (3)	N12—C11	1.334 (5)
Fe1—N51	2.089 (3)	N12—C12	1.344 (6)
Fe1—N1	2.252 (3)	C11—H11	0.9500
Fe1—N31	2.254 (3)	C12—C13	1.364 (6)
Fe1—N21	2.262 (3)	C12—H12	0.9500
Fe1—N11	2.304 (3)	C13—C14	1.378 (6)
Fe2—N61	2.075 (3)	C13—H13	0.9500
Fe2—N61ⁱ	2.075 (3)	C14—H14	0.9500
Fe2—N2	2.252 (3)	N21—C21	1.340 (5)
Fe2—N2ⁱ	2.252 (3)	N21—C24	1.345 (5)
Fe2—N32ⁱⁱ	2.291 (3)	N22—C22	1.334 (6)
Fe2—N32ⁱⁱⁱ	2.291 (3)	N22—C21	1.339 (5)
N41—C41	1.161 (5)	C21—H21	0.9500
C41—S41	1.621 (4)	C22—C23	1.371 (6)
N51—C51	1.171 (5)	C22—H22	0.9500
C51—S51	1.619 (4)	C23—C24	1.388 (5)
N61—C61	1.169 (5)	C23—H23	0.9500
C61—S61	1.618 (4)	C24—H24	0.9500
N1—C1	1.341 (5)	N31—C31	1.335 (5)
N1—C4	1.344 (5)	N31—C34	1.338 (5)
N2—C1	1.335 (5)	N32—C31	1.338 (5)
N2—C2	1.343 (5)	N32—C32	1.343 (5)
C1—H1	0.9500	N32—Fe2^iv	2.291 (3)
C2—C3	1.380 (6)	C31—H31	0.9500
C2—H2	0.9500	C32—C33	1.382 (6)
C3—C4	1.379 (6)	C32—H32	0.9500
C3—H3	0.9500	C33—C34	1.372 (6)
C4—H4	0.9500	C33—H33	0.9500
N11—C14	1.336 (5)	C34—H34	0.9500
N11—C11	1.342 (5)

N41—Fe1—N51	178.69 (13)	N1—C4—H4	118.9
N41—Fe1—N1	90.82 (13)	C3—C4—H4	118.9
N51—Fe1—N1	88.50 (12)	C14—N11—C11	116.2 (3)
N41—Fe1—N31	91.24 (13)	C14—N11—Fe1	122.3 (3)
N51—Fe1—N31	87.72 (12)	C11—N11—Fe1	121.4 (3)
N1—Fe1—N31	96.10 (11)	C11—N12—C12	115.4 (4)
N41—Fe1—N21	92.26 (13)	N12—C11—N11	126.3 (4)
N51—Fe1—N21	88.85 (12)	N12—C11—H11	116.8
N1—Fe1—N21	89.70 (11)	N11—C11—H11	116.8
N31—Fe1—N21	173.18 (12)	N12—C12—C13	123.0 (4)
N41—Fe1—N11	90.18 (13)	N12—C12—H12	118.5
N51—Fe1—N11	90.56 (13)	C13—C12—H12	118.5
N1—Fe1—N11	176.83 (11)	C12—C13—C14	117.1 (4)
N31—Fe1—N11	86.88 (11)	C12—C13—H13	121.5
N21—Fe1—N11	87.25 (11)	C14—C13—H13	121.5
N61—Fe2—N61ⁱ	180.000 (1)	N11—C14—C13	122.0 (4)
N61—Fe2—N2	89.96 (12)	N11—C14—H14	119.0
N61ⁱ—Fe2—N2	90.04 (12)	C13—C14—H14	119.0
N61—Fe2—N2ⁱ	90.04 (12)	C21—N21—C24	115.9 (3)
N61ⁱ—Fe2—N2ⁱ	89.96 (12)	C21—N21—Fe1	123.5 (3)
N2—Fe2—N2ⁱ	180.000 (1)	C24—N21—Fe1	120.6 (2)
N61—Fe2—N32ⁱⁱ	90.10 (12)	C22—N22—C21	116.0 (4)
N61ⁱ—Fe2—N32ⁱⁱ	89.90 (12)	N22—C21—N21	126.6 (4)
N2—Fe2—N32ⁱⁱ	89.27 (11)	N22—C21—H21	116.7
N2ⁱ—Fe2—N32ⁱⁱ	90.73 (11)	N21—C21—H21	116.7
N61—Fe2—N32ⁱⁱⁱ	89.90 (12)	N22—C22—C23	122.4 (4)
N61ⁱ—Fe2—N32ⁱⁱⁱ	90.10 (12)	N22—C22—H22	118.8
N2—Fe2—N32ⁱⁱⁱ	90.73 (11)	C23—C22—H22	118.8
N2ⁱ—Fe2—N32ⁱⁱⁱ	89.27 (11)	C22—C23—C24	117.4 (4)
N32ⁱⁱ—Fe2—N32ⁱⁱⁱ	180.000 (1)	C22—C23—H23	121.3
C41—N41—Fe1	154.5 (3)	C24—C23—H23	121.3
N41—C41—S41	177.0 (4)	N21—C24—C23	121.6 (4)
C51—N51—Fe1	146.5 (3)	N21—C24—H24	119.2
N51—C51—S51	177.7 (3)	C23—C24—H24	119.2
C61—N61—Fe2	153.7 (3)	C31—N31—C34	116.8 (3)
N61—C61—S61	179.3 (4)	C31—N31—Fe1	124.8 (3)
C1—N1—C4	116.2 (3)	C34—N31—Fe1	118.2 (2)
C1—N1—Fe1	121.5 (2)	C31—N32—C32	115.6 (3)
C4—N1—Fe1	121.5 (3)	C31—N32—Fe2^iv	123.0 (3)
C1—N2—C2	116.5 (3)	C32—N32—Fe2^iv	121.2 (2)
C1—N2—Fe2	122.4 (2)	N31—C31—N32	126.1 (4)
C2—N2—Fe2	120.9 (3)	N31—C31—H31	117.0
N2—C1—N1	125.9 (3)	N32—C31—H31	117.0
N2—C1—H1	117.1	N32—C32—C33	122.7 (4)
N1—C1—H1	117.1	N32—C32—H32	118.7
N2—C2—C3	122.1 (4)	C33—C32—H32	118.7
N2—C2—H2	119.0	C34—C33—C32	116.9 (4)
C3—C2—H2	119.0	C34—C33—H33	121.6
C4—C3—C2	117.0 (4)	C32—C33—H33	121.6
C4—C3—H3	121.5	N31—C34—C33	121.9 (4)
C2—C3—H3	121.5	N31—C34—H34	119.0
N1—C4—C3	122.2 (4)	C33—C34—H34	119.0

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

Experimental details

Crystal data
Chemical formula	[Fe₃(NCS)₆(C₄H₄N₂)₈]
M_r	1156.77
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	170
a, b, c (Å)	18.256 (1), 16.2855 (9), 8.2765 (4)
β (°)	100.042 (7)
V (Å³)	2423.0 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.20
Crystal size (mm)	0.12 × 0.10 × 0.07

Data collection
Diffractometer	Stoe IPDS1 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe, 2008)
T_min, T_max	0.859, 0.912
No. of measured, independent and observed [I > 2σ(I)] reflections	20463, 4615, 3795
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.124, 1.13
No. of reflections	4615
No. of parameters	314
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.95, −0.41

Computer programs: X-AREA (Stoe, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), XCIF in SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Fe1—N41	2.075 (3)	Fe2—N61	2.075 (3)
Fe1—N51	2.089 (3)	Fe2—N61ⁱ	2.075 (3)
Fe1—N1	2.252 (3)	Fe2—N2	2.252 (3)
Fe1—N31	2.254 (3)	Fe2—N2ⁱ	2.252 (3)
Fe1—N21	2.262 (3)	Fe2—N32ⁱⁱ	2.291 (3)
Fe1—N11	2.304 (3)	Fe2—N32ⁱⁱⁱ	2.291 (3)

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

Acknowledgements

MW thanks the Stiftung Stipendien-Fonds des Verbandes der Chemischen Industrie and the Studienstiftung des deutschen Volkes" for a PhD scholarship. Moreover, we gratefully acknowledge financial support by the State of Schleswig-Holstein and we thank Professor Dr. Wolfgang Bensch for the opportunity to use his experimental facility.

References

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