research communications
μ2-cyanido-iron(II)platinum(II)] acetone disolvate]
of poly[[diaquatetra-aDepartment of General and Inorganic Chemistry, National Technical University of Ukraine "Igor Sikorsky Kyiv Polytechnic Institute", Prosp. Peremogy 37, Kyiv 03056, Ukraine, bDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska St. 64, Kyiv 01601, Ukraine, cDepartment of Inorganic Polymers, "Petru Poni" Institute of Macromolecular Chemistry, Romanian Academy of Science, Aleea Grigore Ghica Voda 41-A, Iasi 700487, Romania, and dUkrOrgSyntez Ltd, Chervonotkatska St., 67, Kyiv 02094, Ukraine
*Correspondence e-mail: iryna.kuzevanova@univ.kiev.ua
In the title polymeric complex, {[FePt(CN)4(H2O)2]·2C3H6O}n, the FeII cation has an octahedral [FeN4O2] geometry being coordinated by two water molecules and four cyanide anions. The Pt cation is located on an inversion centre and has a square-planar coordination environment formed by four cyanide groups. The tetracyanoplatinate anions bridge the FeII cations to form infinite two-dimensional layers that propagate in the bc plane. Two guest molecules of acetone per FeII are located between the layers. These guest acetone molecules interact with the coordinated water molecules by O—H⋯O hydrogen bonds.
Keywords: crystal structure; Hofmann clathrate; iron(II).
1. Chemical context
Hofmann ) and was of composition [Ni(NH3)2Ni(CN)4]·2C6H6. It was a 2D coordination compound formed by infinite cyanometallic layers that propagate along the ab plane. The 2D system was supported by ammine axial ligands, and guest molecules of benzene were trapped between the layers.
and their analogues form one the most famous families of compounds that are able to incorporate guest molecules. The first clathrate was obtained by Hofmann and Küspert in 1897 (Hofmann & Küspert, 1897Later, by slight modifications of the chemical composition, several analogous compounds were obtained, leading to the creation of a new class of coordination materials. The first modification was the substitution of nickel with other transition metals, as well as the introduction of other small aromatic guest molecules that resulted in the creation of compounds with the general formula [M(NH3)2M′(CN)4]·2G (where M = Mn, Fe, Co, Ni, Cu, Zn, Cd, M′ = Ni, Pd, Pt and G = benzene, pyrrole, thiophene, aniline, biphenyl, etc.; Iwamoto, 1996). The second modification of the Hofmann clathrate was the substitution of square-planar {M′(CN)4}2− anions with tetrahedral ({M′(CN)4}2−, M′ = Cd, Hg; Arcís-Castillo et al., 2013), linear ({M′(CN)2}−, M′ = Cu, Ag, Au; Gural'skiy, Golub et al., 2016; Gural'skiy, Shylin et al., 2016), octahedral ({M′(CN)6}3−, M′ = Co, Cr; Dommann et al., 1990) and even dodecahedral ({M′(CN)8}4−, M′ = W, Nb; Ohkoshi et al., 2013) fragments. Additionally, a very important modification was made by the introduction of other organic ligands instead of ammonia. For example, by the introduction of pyridine, the first FeII-based clathrate [Fe(py)2{Pt(CN)4}] exhibiting spin-crossover (SCO) behaviour was obtained by Kitazawa et al. (1996). At the same time, the introduction of various bidentate ligands such as pyrazine (Niel et al., 2001; Gural'skiy, Shylin et al., 2016), pyrimidine (Agustí et al., 2008), bis(4-pyridyl)acetylene (Agustí et al., 2008) and others allowed the formation of 3D SCO networks.
Additionally, the characteristics of spin transition in coordination compounds are known to be extremely sensitive to any changes in the chemical environment. As Hofmann clathrate analogues are very easy to modulate, numerous SCO complexes with very different temperatures, abruptnesses and hystereses of SCO were obtained. Moreover, the ability of Hofmann clathrate analogues to incorporate guest molecules provided SCO-based chemical sensors (Ohba et al., 2009).
Herein we present a new Fe–Pt Hofmann clathrate analogue [Fe(H2O)2{Pt(CN)4}]·2(CH3)2CO.
2. Structural commentary
The title compound crystallizes in the P4/mmm The FeII cation has a [FeN4O2] coordination environment (Fig. 1) comprising four CN− anions in the equatorial positions [Fe1—N1 = 2.158 (5) Å] and two water molecules in the axial positions [Fe1—O1 = 2.130 (6) Å]. The Fe—O bonds are slightly shorter than the Fe–N bonds, thus leading to a compressed octahedral geometry. Judging by the bond length, the FeII cation is in a high-spin state at the experimental temperature (180 K). This is corroborated by the presence of H2O molecules in the coordination sphere of FeII. The cyanide anions connect the FeII and PtII cations into infinite two-dimensional layers. The PtII cation is located at a fourfold rotation axis and possesses a square-planar geometry [Pt1—C1 = 1.993 (6) Å, C1—Pt–C1 = 90°]. Thanks to the tetragonal symmetry of the crystalline compound, no deviation from an ideal octahedron is observed for FeII, Σ|90 – θ| = 0°, where θ is the N—Fe—N or O—Fe—N angles. Additionally, the compound incorporates two guest molecules of acetone per FeII centers.
3. Supramolecular features
The crystalline structure is connected by bridging tetracyanoplatinate moieties, which form a two-dimensional grid that propagates along the ab plane (Fig. 2). As imposed by symmetry, no deviation from linearity for the Fe—N—C—Pt linkages is observed [Fe—N—C = 180°, N—C—Pt = 180°, C—Pt—C = 180°]. The distance between parallel cyanometallic layers is 7.973 (6) Å. The guest acetone molecules are located between the cyanometallic layers. Each oxygen atom of the coordinated water molecules interacts with acetone by O—H⋯O hydrogen bonds (Fig. 3, Table 1), creating a three-dimensional supramolecular framewor. The size of the available voids between the cyanometallic layers allows the acetone molecules to rotate freely, thus leading to disorder of the acetone molecules over four positions.
4. Database survey
A survey of the Cambridge Structural Database (Version 5.38; Groom et al., 2016) confirmed that the title compound has never been published before. It revealed 51 cyanometallic structures of the general formula [TM(H2O)2{TM(CN)4}], where TM = any transition metal. There were also 19 hits for structures containing [Fe{Pt(CN)4}] fragments: refcodes: OVILEM, OVIRUI, OVIRUI01, OVIRUI02 and OVIRUI03 (Sciortino et al., 2017), AMIJOX (Kucheriv et al., 2016), BEDWEO and BEDWIS (Sciortino et al., 2012), CEMYUQ (Mũnoz-Lara et al., 2013), MUHMEI, MUHNAF, MUHNAF01, MUHNAF02, MUHPAH and MUHPAH01 (Martínez et al., 2009), QADDUX (Sakaida et al., 2016), QOJWIW and QOJWIW01 (Cobo et al., 2008) and TURXIP (Ohtani et al., 2013).
5. Synthesis and crystallization
Crystals of the title compound were obtained by slow diffusion (three layers) in a 3 ml tube. The first layer contained 19 mg (0.05 mmol) of K2[Pt(CN)4] in 0.5 ml of water. The middle layer contained 1.5 ml of a water:acetone (1:1) solution. The third layer contained 25 mg (0.05 mmol) of Fe(OTs)2·6H2O in 0.4 ml of acetone and 0.1 ml of water. The colourless crystals grew in the middle layer within three weeks and were kept in the mother solution prior to measurements.
6. Refinement
Crystal data, data collection and structure . All hydrogen atoms were fixed at calculated positions and refined as riding with C—H = 0.96 Å and O–H = 0.84 Å, Uiso(H) = 1.5Uiso(C,O). The OH group and the idealized methyl group were refined as rotating.
details are summarized in Table 2Supporting information
Data collection: CrysAlis PRO (Rigaku OD, 2015); cell
CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: ShelXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).[FePt(CN)4(H2O)2]·2C3H6O | Dx = 1.888 Mg m−3 |
Mr = 507.21 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P4/mmm | Cell parameters from 664 reflections |
a = 7.4802 (4) Å | θ = 2.5–28.5° |
c = 7.9725 (11) Å | µ = 8.66 mm−1 |
V = 446.09 (8) Å3 | T = 180 K |
Z = 1 | Plate, clear colourless |
F(000) = 240 | 0.05 × 0.05 × 0.02 mm |
Rigaku Oxford Diffraction Xcalibur, Eos diffractometer | 361 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 359 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 8.0797 pixels mm-1 | θmax = 29.0°, θmin = 2.6° |
ω scans | h = −5→10 |
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2015) | k = −10→5 |
Tmin = 0.699, Tmax = 1.000 | l = −10→5 |
1126 measured reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.046 | w = 1/[σ2(Fo2) + (0.0197P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
361 reflections | Δρmax = 1.25 e Å−3 |
34 parameters | Δρmin = −1.06 e Å−3 |
0 restraints |
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 | Occ. (<1) | |
Pt1 | 0.500000 | 0.500000 | 0.500000 | 0.01400 (17) | |
Fe1 | 0.000000 | 0.000000 | 0.500000 | 0.0104 (4) | |
O1 | 0.000000 | 0.000000 | 0.2329 (8) | 0.0276 (16) | |
H1A | 0.105309 | 0.000432 | 0.196819 | 0.041* | 0.25 |
H1B | −0.043425 | 0.098216 | 0.196839 | 0.041* | 0.125 |
C1 | 0.3116 (6) | 0.3116 (6) | 0.500000 | 0.0186 (15) | |
N1 | 0.2040 (5) | 0.2040 (5) | 0.500000 | 0.0210 (13) | |
C3 | 0.475 (9) | 0.036 (8) | 0.1546 (18) | 0.08 (2) | 0.25 |
H3A | 0.473348 | 0.162844 | 0.175407 | 0.114* | 0.25 |
H3B | 0.531096 | −0.023709 | 0.246770 | 0.114* | 0.25 |
H3C | 0.354004 | −0.005924 | 0.142949 | 0.114* | 0.25 |
O2 | 0.7276 (18) | 0.043 (3) | 0.000000 | 0.055 (5) | 0.25 |
C2 | 0.574 (2) | 0.000000 | 0.000000 | 0.055 (5) | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.00585 (17) | 0.00585 (17) | 0.0303 (3) | 0.000 | 0.000 | 0.000 |
Fe1 | 0.0068 (5) | 0.0068 (5) | 0.0177 (10) | 0.000 | 0.000 | 0.000 |
O1 | 0.030 (2) | 0.030 (2) | 0.023 (4) | 0.000 | 0.000 | 0.000 |
C1 | 0.0092 (18) | 0.0092 (18) | 0.037 (4) | 0.003 (2) | 0.000 | 0.000 |
N1 | 0.0121 (16) | 0.0121 (16) | 0.039 (4) | −0.005 (2) | 0.000 | 0.000 |
C3 | 0.04 (4) | 0.13 (5) | 0.056 (9) | −0.03 (2) | 0.013 (14) | −0.05 (2) |
O2 | 0.019 (4) | 0.109 (15) | 0.036 (6) | −0.005 (10) | 0.000 | 0.000 |
C2 | 0.019 (4) | 0.109 (15) | 0.036 (6) | −0.005 (10) | 0.000 | 0.000 |
Pt1—C1i | 1.993 (6) | Fe1—N1v | 2.158 (5) |
Pt1—C1 | 1.993 (6) | Fe1—N1vi | 2.158 (5) |
Pt1—C1ii | 1.993 (6) | Fe1—N1 | 2.158 (5) |
Pt1—C1iii | 1.993 (6) | C1—N1 | 1.138 (8) |
Fe1—O1iv | 2.130 (6) | C3—C2 | 1.46 (4) |
Fe1—O1 | 2.130 (6) | O2—O2vii | 0.64 (5) |
Fe1—N1iv | 2.158 (5) | O2—C2 | 1.19 (2) |
C1i—Pt1—C1ii | 90.0 | O1iv—Fe1—N1vi | 90.0 |
C1ii—Pt1—C1 | 90.0 | N1iv—Fe1—N1vi | 90.0 |
C1i—Pt1—C1 | 180.0 | N1—Fe1—N1vi | 90.0 |
C1i—Pt1—C1iii | 90.0 | N1iv—Fe1—N1v | 90.0 |
C1iii—Pt1—C1 | 90.0 | N1—Fe1—N1iv | 180.0 |
C1ii—Pt1—C1iii | 180.0 | N1—Fe1—N1v | 90.0 |
O1—Fe1—O1iv | 180.0 | N1vi—Fe1—N1v | 180.0 |
O1—Fe1—N1 | 90.0 | N1—C1—Pt1 | 180.0 |
O1—Fe1—N1vi | 90.0 | C1—N1—Fe1 | 180.0 |
O1iv—Fe1—N1v | 90.0 | O2vii—O2—C2 | 74.4 (12) |
O1iv—Fe1—N1 | 90.0 | O2vii—C2—C3 | 123 (2) |
O1—Fe1—N1v | 90.0 | O2—C2—C3 | 116 (2) |
O1—Fe1—N1iv | 90.0 | O2—C2—O2vii | 31 (2) |
O1iv—Fe1—N1iv | 90.0 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) y, −x+1, −z+1; (iii) −y+1, x, z; (iv) −x, −y, −z+1; (v) −y, x, z; (vi) y, −x, −z+1; (vii) x, −y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2viii | 0.84 | 2.03 | 2.775 (11) | 147 |
O1—H1A···O2ix | 0.84 | 2.03 | 2.775 (11) | 148 |
O1—H1B···O2x | 0.85 | 2.04 | 2.775 (11) | 144 |
O1—H1B···O2xi | 0.85 | 2.14 | 2.775 (11) | 131 |
Symmetry codes: (viii) −x+1, −y, z; (ix) −x+1, y, −z; (x) −y, −x+1, −z; (xi) y, −x+1, z. |
Funding information
Funding for this research was provided by: Ministry of Education and Science of Ukraine (grant No. 19BF037-01M; grant No. 19BF037-01).
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