research communications
κN)bis(thiocyanato-κN)iron(II) 4-cyanopyridine disolvate
of diaquabis(4-cyanopyridine-aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth Strasse 2, D-24118 Kiel, Germany
*Correspondence e-mail: ajochim@ac.uni-kiel.de
The 2(C6H4N2)2(H2O)2]·2C6H4N2, comprises one FeII cation occupying an inversion centre as well as one thiocyanate anion, one water molecule and two 4-cyanopyridine molecules in general positions. The iron cations are coordinated by two N-bonded thiocyanate anions, two (pyridine)N-bonded 4-cyanopyridine ligands and two water molecules into discrete complexes. The resulting can be described as a slightly distorted octahedron. The discrete complexes are connected through centrosymmetric pairs of (pyridine)C—H⋯N(cyano) hydrogen bonds into chains that are further linked into a three-dimensional network through intermolecular O—H⋯N hydrogen bonds involving the 4-cyanopyridine solvent molecules.
of the title compound, [Fe(NCS)Keywords: crystal structure; hydrogen bonding; 4-cyanopyridine; iron; thiocyanate.
CCDC reference: 1534965
1. Chemical context
Thiocyanate anions are versatile ligands that can coordinate in different modes to metal cations. In most cases the anionic ligands are terminally N-bonded to the metal cation but there are also several examples for a μ-1,3 bridging mode (Werner et al., 2015; Boeckmann & Näther, 2012; Palion-Gazda et al., 2015). The latter coordination is of special interest if the compounds contain paramagnetic metal cations because then cooperative magnetic properties can be expected (Palion-Gazda et al., 2015). In this context, we have reported on several compounds with one- or two-dimensional structures based on Mn, Fe, Co or Ni as metals, thiocyanate ligands and different N-donor co-ligands that show different magnetic properties (Suckert et al., 2016; Rams et al., 2017; Boeckmann et al., 2012). Whereas compounds with a terminal coordination of the anionic ligands can usually be synthesized straightforwardly, compounds with bridging ligands are sometimes difficult to obtain from solution. Therefore, we have developed an alternative procedure which is based on thermal decomposition of precursors with a terminal NCS coordination that frequently transform into the desired polymeric compounds on heating. In the course of our investigations on the synthesis of coordination polymers with iron as metal, thiocyanate ligands and 4-cyanopyridine as co-ligands, we obtained the title compound which was identified by single crystal X-ray diffraction. Unfortunately, all samples were always contaminated with a second unknown crystalline phase, preventing any further investigations.
2. Structural commentary
The 2(C6H4N2)2(H2O)2]·2C6H4N2 contains one FeII cation that is located on an inversion centre, one thiocyanate anion, one water molecule and two 4-cyanopyridine molecules (Fig. 1). Discrete centrosymmetric [Fe(NCS)2(C6H4N2)2(H2O)2] complexes are formed, in which the FeII cations are octahedrally coordinated by two N-bonded thiocyanate anions, two (pyridine)N-bonded 4-cyanopyridine ligands and two water molecules, each of them in a trans-position (Fig. 1). The disparate bond lengths are similar to those in related thiocyanate compounds. The distortion of the octahedron is also reflected by the deviation of the bond angles from ideal values. The structure contains additional 4-cyanopyridine solvate molecules that are located in the cavities of the structure.
of [Fe(NCS)3. Supramolecular features
The discrete complexes are linked into chains parallel to [101] by centrosymmetric pairs of intermolecular C—H⋯N hydrogen bonds between the cyano group of the coordinating 4-cyanopyridine ligand and one of the pyridine H atoms (Fig. 2, Table 1). These chains are further linked by the 4-cyanopyridine solvate molecules through intermolecular O—H⋯N hydrogen bonding. One water H atom is hydrogen-bonded to the N atom of the cyano group and the other H atom to the pyridine N atom of another 4-cyanopyridine solvate molecule. Since all water H atoms are involved in hydrogen bonding, each of the complexes is surrounded by four 4-cyanopyridine ligands, of which two are hydrogen-bonded via the cyano group, whereas the other two are hydrogen-bonded via the pyridine N atom (Fig. 3, Table 1). This arrangement leads to a three-dimensional network structure. It is noted that there are additional short contacts between the thiocyanate anions and the pyridine H atoms of the coordinating 4-cyanopyridine ligand of a neighbouring complex, which is indicative of weak C—H⋯S hydrogen bonding (Table 1).
4. Database survey
In the Cambridge Structure Database (Version 5.38, last update 2016; Groom et al., 2016), five structures of coordination polymers with 4-cyanopyridine and thiocyanate as ligands are reported, in which the metal cations are solely connected through μ-1,3 bridging thiocyanate anions. Two of these compounds contain copper, two cadmium and one is a bimetallic compound in which copper and mercury are present. The two copper-containing compounds are built up of chains, in which the cations are either tetrahedrally (Lin et al., 2004) or octahedrally (Machura et al., 2013a) coordinated. In the bimetallic compound the cations are linked into a three-dimensional structure (Machura et al., 2013b), whereas the two cadmium-containing compounds exhibit either one-dimensional or three-dimensional coordination networks (Chen et al., 2002).
5. Synthesis and crystallization
Iron(II) chloride tetrahydrate, potassium thiocyanate and 4-cyanopyridine were obtained from Alfa Aesar and used without further purification.
29.8 mg iron(II) chloride tetrahydrate (0.15 mmol) and 29.2 mg KSCN (0.30 mmol) were reacted with 62.5 mg 4-cyanopyridine (0.60 mmol) in 1.5 ml water at room temperature. After two days, single crystals suitable for structure analysis were obtained. The batch contained a small amount of an additional crystalline phase that could not be identified.
6. Refinement
Crystal data, data collection and structure . Hydrogen atoms of the water molecule were located from a difference map, and C-bound hydrogen atoms were refined in calculated positions [C—H = 0.95 Å and O—H = 0.84 Å] with Uiso(H) = 1.2Ueq(C) [1.5 for Ueq(O)] using a riding model (O—H hydrogen atoms were allowed to rotate but not to tip).
details are summarized in Table 2Supporting information
CCDC reference: 1534965
https://doi.org/10.1107/S205698901700322X/wm5371sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901700322X/wm5371Isup2.hkl
Data collection: X-AREA (Stoe & Cie, 2008); cell
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: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP (Sheldrick, 2008) and DIAMOND (Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).[Fe(NCS)2(C6H4N2)2(H2O)2]·2C6H4N2 | F(000) = 640 |
Mr = 624.49 | Dx = 1.324 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.5376 (4) Å | Cell parameters from 18864 reflections |
b = 15.220 (1) Å | θ = 3.8–56.3° |
c = 12.1214 (6) Å | µ = 0.66 mm−1 |
β = 96.195 (6)° | T = 200 K |
V = 1565.88 (15) Å3 | Block, yellow |
Z = 2 | 0.13 × 0.10 × 0.06 mm |
Stoe IPDS-1 diffractometer | 2960 reflections with I > 2σ(I) |
Phi scans | Rint = 0.047 |
Absorption correction: numerical (X-RED and X-SHAPE; Stoe & Cie, 2008) | θmax = 28.1°, θmin = 2.7° |
Tmin = 0.884, Tmax = 0.953 | h = −11→10 |
18486 measured reflections | k = −20→20 |
3743 independent reflections | l = −16→16 |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.037 | w = 1/[σ2(Fo2) + (0.0581P)2 + 0.1102P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.094 | (Δ/σ)max = 0.001 |
S = 1.03 | Δρmax = 0.26 e Å−3 |
3743 reflections | Δρmin = −0.46 e Å−3 |
188 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.019 (3) |
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. |
x | y | z | Uiso*/Ueq | ||
Fe1 | 0.5000 | 0.5000 | 1.0000 | 0.02513 (11) | |
N1 | 0.58788 (18) | 0.62971 (9) | 0.99472 (12) | 0.0358 (3) | |
C1 | 0.62673 (19) | 0.69914 (10) | 0.96961 (13) | 0.0305 (3) | |
S1 | 0.68128 (7) | 0.79604 (3) | 0.93149 (5) | 0.05165 (16) | |
N11 | 0.42359 (17) | 0.50738 (9) | 0.81712 (11) | 0.0317 (3) | |
C11 | 0.2830 (2) | 0.47429 (11) | 0.77885 (14) | 0.0351 (4) | |
H11 | 0.2267 | 0.4414 | 0.8283 | 0.042* | |
C12 | 0.2158 (2) | 0.48550 (11) | 0.67119 (15) | 0.0390 (4) | |
H12 | 0.1150 | 0.4617 | 0.6472 | 0.047* | |
C13 | 0.2990 (2) | 0.53234 (13) | 0.59914 (14) | 0.0399 (4) | |
C14 | 0.4458 (2) | 0.56588 (13) | 0.63609 (15) | 0.0425 (4) | |
H14 | 0.5055 | 0.5976 | 0.5877 | 0.051* | |
C15 | 0.5029 (2) | 0.55172 (12) | 0.74578 (14) | 0.0381 (4) | |
H15 | 0.6036 | 0.5747 | 0.7718 | 0.046* | |
C16 | 0.2332 (3) | 0.54478 (18) | 0.48511 (18) | 0.0570 (6) | |
N12 | 0.1795 (3) | 0.5537 (2) | 0.39540 (17) | 0.0837 (8) | |
O1 | 0.28045 (13) | 0.55033 (7) | 1.02877 (9) | 0.0320 (2) | |
H1 | 0.2201 | 0.5134 | 1.0535 | 0.048* | |
H2 | 0.2728 | 0.5951 | 1.0684 | 0.048* | |
N21 | 1.2086 (2) | 0.80713 (12) | 0.64837 (15) | 0.0523 (4) | |
C21 | 1.0626 (3) | 0.7796 (2) | 0.6202 (2) | 0.0774 (9) | |
H21 | 1.0072 | 0.8031 | 0.5546 | 0.093* | |
C22 | 0.9863 (3) | 0.71950 (19) | 0.67912 (19) | 0.0685 (8) | |
H22 | 0.8813 | 0.7018 | 0.6554 | 0.082* | |
C23 | 1.0672 (2) | 0.68573 (11) | 0.77413 (14) | 0.0347 (4) | |
C24 | 1.2197 (2) | 0.71283 (11) | 0.80597 (15) | 0.0378 (4) | |
H24 | 1.2775 | 0.6904 | 0.8713 | 0.045* | |
C25 | 1.2856 (2) | 0.77362 (13) | 0.73992 (17) | 0.0445 (4) | |
H25 | 1.3907 | 0.7923 | 0.7609 | 0.053* | |
C26 | 0.9913 (2) | 0.62137 (12) | 0.83758 (14) | 0.0361 (4) | |
N22 | 0.9307 (2) | 0.56987 (11) | 0.88643 (14) | 0.0460 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.02351 (17) | 0.02120 (16) | 0.03167 (17) | −0.00047 (11) | 0.00745 (11) | 0.00057 (11) |
N1 | 0.0402 (9) | 0.0231 (6) | 0.0448 (8) | −0.0057 (5) | 0.0075 (6) | 0.0016 (5) |
C1 | 0.0277 (8) | 0.0303 (8) | 0.0329 (8) | −0.0006 (6) | 0.0004 (6) | −0.0007 (6) |
S1 | 0.0599 (3) | 0.0304 (2) | 0.0628 (3) | −0.0137 (2) | −0.0017 (2) | 0.0132 (2) |
N11 | 0.0305 (7) | 0.0324 (7) | 0.0328 (7) | 0.0002 (5) | 0.0053 (5) | −0.0015 (5) |
C11 | 0.0343 (9) | 0.0308 (8) | 0.0408 (9) | −0.0028 (6) | 0.0061 (7) | −0.0035 (6) |
C12 | 0.0341 (9) | 0.0375 (9) | 0.0446 (9) | 0.0010 (7) | 0.0001 (7) | −0.0080 (7) |
C13 | 0.0397 (10) | 0.0458 (10) | 0.0338 (8) | 0.0094 (8) | 0.0022 (7) | −0.0055 (7) |
C14 | 0.0393 (10) | 0.0550 (11) | 0.0342 (8) | 0.0011 (8) | 0.0086 (7) | 0.0046 (8) |
C15 | 0.0325 (9) | 0.0472 (10) | 0.0353 (8) | −0.0032 (7) | 0.0071 (7) | 0.0014 (7) |
C16 | 0.0451 (12) | 0.0819 (16) | 0.0433 (11) | 0.0035 (11) | 0.0015 (9) | −0.0003 (10) |
N12 | 0.0618 (14) | 0.140 (2) | 0.0460 (11) | −0.0095 (14) | −0.0079 (9) | 0.0126 (13) |
O1 | 0.0272 (6) | 0.0284 (5) | 0.0422 (6) | −0.0004 (4) | 0.0117 (5) | −0.0031 (4) |
N21 | 0.0464 (10) | 0.0518 (10) | 0.0607 (10) | −0.0051 (8) | 0.0144 (8) | 0.0215 (8) |
C21 | 0.0541 (15) | 0.111 (2) | 0.0643 (15) | −0.0162 (14) | −0.0084 (11) | 0.0537 (15) |
C22 | 0.0417 (12) | 0.105 (2) | 0.0554 (13) | −0.0231 (12) | −0.0112 (10) | 0.0401 (13) |
C23 | 0.0313 (9) | 0.0379 (9) | 0.0351 (8) | −0.0039 (7) | 0.0048 (6) | 0.0051 (6) |
C24 | 0.0338 (10) | 0.0367 (9) | 0.0421 (9) | −0.0014 (7) | 0.0005 (7) | 0.0066 (7) |
C25 | 0.0341 (10) | 0.0406 (10) | 0.0593 (11) | −0.0058 (7) | 0.0068 (8) | 0.0074 (8) |
C26 | 0.0315 (9) | 0.0419 (9) | 0.0351 (8) | −0.0026 (7) | 0.0039 (6) | 0.0020 (7) |
N22 | 0.0397 (9) | 0.0490 (9) | 0.0508 (9) | −0.0068 (7) | 0.0122 (7) | 0.0104 (7) |
Fe1—O1i | 2.0888 (11) | C14—H14 | 0.9500 |
Fe1—O1 | 2.0888 (11) | C15—H15 | 0.9500 |
Fe1—N1 | 2.1153 (13) | C16—N12 | 1.141 (3) |
Fe1—N1i | 2.1153 (13) | O1—H1 | 0.8400 |
Fe1—N11i | 2.2451 (14) | O1—H2 | 0.8400 |
Fe1—N11 | 2.2451 (14) | N21—C21 | 1.325 (3) |
N1—C1 | 1.158 (2) | N21—C25 | 1.329 (3) |
C1—S1 | 1.6286 (16) | C21—C22 | 1.368 (3) |
N11—C15 | 1.337 (2) | C21—H21 | 0.9500 |
N11—C11 | 1.338 (2) | C22—C23 | 1.377 (3) |
C11—C12 | 1.378 (3) | C22—H22 | 0.9500 |
C11—H11 | 0.9500 | C23—C24 | 1.380 (3) |
C12—C13 | 1.382 (3) | C23—C26 | 1.442 (2) |
C12—H12 | 0.9500 | C24—C25 | 1.382 (3) |
C13—C14 | 1.382 (3) | C24—H24 | 0.9500 |
C13—C16 | 1.447 (3) | C25—H25 | 0.9500 |
C14—C15 | 1.383 (3) | C26—N22 | 1.140 (2) |
O1i—Fe1—O1 | 180.0 | C14—C13—C16 | 120.42 (19) |
O1i—Fe1—N1 | 90.55 (5) | C13—C14—C15 | 117.86 (17) |
O1—Fe1—N1 | 89.45 (5) | C13—C14—H14 | 121.1 |
O1i—Fe1—N1i | 89.45 (5) | C15—C14—H14 | 121.1 |
O1—Fe1—N1i | 90.55 (5) | N11—C15—C14 | 123.35 (17) |
N1—Fe1—N1i | 180.0 | N11—C15—H15 | 118.3 |
O1i—Fe1—N11i | 88.63 (5) | C14—C15—H15 | 118.3 |
O1—Fe1—N11i | 91.37 (5) | N12—C16—C13 | 179.0 (3) |
N1—Fe1—N11i | 90.59 (5) | Fe1—O1—H1 | 114.2 |
N1i—Fe1—N11i | 89.41 (5) | Fe1—O1—H2 | 121.3 |
O1i—Fe1—N11 | 91.37 (5) | H1—O1—H2 | 104.5 |
O1—Fe1—N11 | 88.63 (5) | C21—N21—C25 | 117.42 (17) |
N1—Fe1—N11 | 89.41 (5) | N21—C21—C22 | 124.4 (2) |
N1i—Fe1—N11 | 90.59 (5) | N21—C21—H21 | 117.8 |
N11i—Fe1—N11 | 180.0 | C22—C21—H21 | 117.8 |
C1—N1—Fe1 | 166.44 (14) | C21—C22—C23 | 117.5 (2) |
N1—C1—S1 | 178.74 (15) | C21—C22—H22 | 121.2 |
C15—N11—C11 | 117.64 (15) | C23—C22—H22 | 121.2 |
C15—N11—Fe1 | 123.39 (12) | C22—C23—C24 | 119.69 (17) |
C11—N11—Fe1 | 118.54 (11) | C22—C23—C26 | 119.08 (17) |
N11—C11—C12 | 123.23 (17) | C24—C23—C26 | 121.22 (15) |
N11—C11—H11 | 118.4 | C23—C24—C25 | 117.94 (17) |
C12—C11—H11 | 118.4 | C23—C24—H24 | 121.0 |
C11—C12—C13 | 118.18 (17) | C25—C24—H24 | 121.0 |
C11—C12—H12 | 120.9 | N21—C25—C24 | 123.03 (18) |
C13—C12—H12 | 120.9 | N21—C25—H25 | 118.5 |
C12—C13—C14 | 119.72 (17) | C24—C25—H25 | 118.5 |
C12—C13—C16 | 119.85 (19) | N22—C26—C23 | 179.1 (2) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···N12ii | 0.95 | 2.52 | 3.437 (3) | 162 |
C14—H14···S1iii | 0.95 | 3.01 | 3.960 (2) | 177 |
O1—H1···N22i | 0.84 | 2.00 | 2.8380 (19) | 177 |
O1—H2···N21iv | 0.84 | 1.89 | 2.7159 (19) | 168 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x, −y+1, −z+1; (iii) x, −y+3/2, z−1/2; (iv) x−1, −y+3/2, z+1/2. |
Acknowledgements
This project was supported by the Deutsche Forschungsgemeinschaft (Project No. NA 720/5–1) and the State of Schleswig-Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.
Funding information
Funding for this research was provided by: Deutsche Forschungsgemeinschaft (award No. NA 720/5–1); State of Schleswig-Holstein.
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