research communications
κN)bis(isothiocyanato-κN)iron(II)
synthesis and thermal properties of tetrakis(4-benzoylpyridine-aInstitut für Anorganische Chemie, Universität Kiel, Max-Eyth. Str. 2, 241128 Kiel, Germany
*Correspondence e-mail: cwellm@ac.uni-kiel.de
The 2(C12H9NO)4], consists of an FeII ion that is located on a centre of inversion, as well as two 4-benzoylpyridine ligands and one thiocyanate anion in general positions. The FeII ions are coordinated by two N-terminal-bonded thiocyanate anions and four 4-benzoylpyridine ligands into discrete complexes with a slightly distorted octahedral geometry. These complexes are further linked by weak C—H⋯O hydrogen bonds into chains running along the c-axis direction. Upon heating, this complex loses half of the 4-benzoylpyridine ligands and transforms into a compound with the composition Fe(NCS)2(4-benzoylpyridine)2, that might be isotypic to the corresponding MnII compound and for which the structure is unknown.
of the title compound, [Fe(NCS)CCDC reference: 1918968
1. Chemical context
Coordination compounds based on thio- or selenocyanate anions have attracted much interest in recent years because of their luminescence behavior and their versatile magnetic properties (Mekuimemba et al., 2018; Palion-Gazda et al., 2015, 2017; Mautner et al., 2016a,b; Näther et al., 2013). For the latter, compounds are of special interest in which paramagnetic transition-metal cations are linked by the anionic ligands into 1D or 2D coordination polymers. Some of them show single-chain-magnet behavior (Wöhlert et al., 2013; 2014a; Mautner et al., 2018), others are (Suckert et al., 2016) and in a few cases the can be tuned by mixed-crystal formation (Neumann et al., 2018a, 2019; Wellm et al., 2018).
However, in most cases compounds are obtained from solution in which the anionic ligands are only terminally N-bonded, which frequently leads to the formation of discrete complexes (Mautner et al., 2015, 2017). These compounds can be transformed into coordination polymers by thermal decomposition, in which some of the co-ligands are irreversibly removed (Näther et al., 2013), leading to the formation of polymorphic or isomeric modifications (Wöhlert et al., 2014b). In several cases MnII, FeII, CoII, NiII and CdII compounds behave similarly but in others, different modifications are obtained depending on the actual metal cation.
This is the case e.g. for thiocyanate complexes with 4-benzoylpyridine as co-ligand. The discrete complexes with the composition M(NCS)2(4-benzoylpyridine)4 (M = Co and Ni) transform into isotypic chain compounds with the composition [M(NCS)2(4-benzoylpyridine)2]n, whereas both the Mn and Cd compounds each form a different crystalline phase (Neumann et al., 2018b; Wellm & Näther, 2018). Therefore, we became interested in the corresponding complex with FeII to check if this compound could also transform into a 4-benzoylpyridine-deficient phase and if this phase would be isotypic to that with MnII, CoII or CdII. The synthesis of the title compound can easily be achieved by the reaction of Fe(Cl)2·4H2O and K(SCN)2 with 4-benzoylpyridine, leading to the formation of phase pure samples (see Figure S1 in the supporting information). Upon heating, two mass losses are observed, of which the first one is in agreement with that expected for the removal of half of the 4-benzoylpyridine co-ligands (Figure S2). If the residue formed after the first thermogravimetric step is investigated by XRPD, it is obvious that a crystalline phase is formed (Figure S3) that is not isotypic to [M(NCS)2(4-benzoylpyridine)2]n (M = Co, Cd) but very similar to that of Mn(NCS)2(4-benzoylpyridine)2 (Rams et al., 2017; Neumann et al., 2018b; Wellm & Näther, 2018). Additionally, IR spectra show that the residue exhibits bridging μ-1,3-coordinating thiocyanate anions, in contrast to the terminal thiocyanate anions of the title compound (Figure S4). Unfortunately, as is the case for the MnII compound, the powder pattern cannot be indexed and no single crystals can be obtained. Therefore, the structure of this compound is still unknown.
2. Structural commentary
The ) is isotypic to the corresponding CoII, NiII, MnII, ZnII and CdII compounds (Drew et al., 1985; Soliman et al., 2014; Wellm & Näther, 2018; Neumann et al., 2018b). The consists of one N-bonded terminal thiocyanate anion and two crystallographically independent 4-benzoylpyridine ligands in general positions, as well as of one FeII cation located on a centre of inversion (Fig. 1). The FeII ions are sixfold coordinated by the pyridine N-atoms of the four neutral 4-benzoylpyridine ligands and the N atoms of the two terminal thiocyanate anions. The Fe—N bonds to the 4-benzoylpyridine coligands, ranging between 2.2576 (13) and 2.2597 (13) Å, are significantly longer than those to the anionic ligands of 2.0982 (14) Å (Table 1) and correspond to those observed in the isotypic compounds [M(NCS)2(C12H9NO)4] (M = Mn, Co, Ni, Zn, Cd; Wellm & Näther, 2018; Drew et al., 1985; Soliman et al., 2014; Neumann et al., 2018b). The N—M—N angles deviate from the ideal values, which shows that the octahedra are slightly distorted in agreement with the values for the angle variance (1.8) and the quadratic elongation (1.003) (Robinson et al., 1971). Furthermore, the pyridine and phenyl rings of the 4-benzoylpyridine ligands are not co-planar to the carbonyl plane. The dihedral angle between the pyrdine ring (N11/C11–15) and the carbonyl plane (C13/C16/C17/O11) amounts to 35.24 (10)°, while the one between the carbonyl plane (C13/C16/C17/O11) and the phenyl ring (C17–C22) is 24.23 (8)°. The corresponding values for the second 4-benzoylpyrdine ligand are 35.69 (9)° between the pyridine ring (N31/C31–C35) and the carbonyl plane (C33/C36/C37/O21) and 23.79 (9)° between the carbonyl plane (C33/C36/C37/O21) and the phenyl ring (C37–C42). Additionally, there are weak intramolecular C—H⋯N interactions between the thiocyanate atoms N1 and N1i and aromatic hydrogen atoms H11, H31, H15 and H35 that might contribute to the stabilization of the complexes (Table 2).
of the title compound (Fig. 13. Supramolecular features
The discrete complexes are connected by relatively weak C—H⋯O hydrogen bonds between the C—H hydrogen atoms and the atom O21(−x, 1 − y, 2 − z) of a symmetry-related 4-benzoylpyridine ligand, forming 12-membered rings that are located on centres of inversion (Fig. 2 and Table 2). Atom O21 acts as acceptor for two hydrogen bonds from C15—H15 and C35—H35; thus each complex is connected by four hydrogen bonds to two additional symmetry-equivalent complexes, leading to the formation of chains that extend along the c-axis direction (Figs. 2 and 3 and Table 2). There are no further directed interactions observed between the chains (Fig. 3).
4. Database survey
There are several crystal structures reported in the Cambridge Structure Database (Version 5.40, last update February 2018; Groom et al., 2016) that consist of transition-metal cations, thiocyanate anions and 4-benzoylpyrine. In most of these compounds, the metal cations are octahedrally coordinated. Three of them are coordination polymers in which the cations are connected by pairs of μ-1,3-coordinating thiocyanate anions, with the 4-benzoylpyridine ligands being perpendicular to the elongation axis of the chain (Neumann et al., 2018b; Rams et al., 2017; Jochim et al., 2018). The other octahedral compounds are either discrete complexes with only 4-benzoylpyridine as neutral co-ligand, isotypic to the title compound and of the general composition M(NCS)2(4-benzoylpyridine)4 (M = CoII, NiII, MnII, ZnII and CdII; Drew et al., 1985; Soliman et al., 2014; Wellm & Näther, 2018; Neumann et al., 2018b), or solvates that are built up of two terminally N-bonded thiocyanates, two 4-benzoylpyridine ligands and acetonitrile (Suckert et al., 2017b) or methanol as solvent (Suckert et al., 2017a; Wellm & Näther, 2019). Additionally, there is a quadratic planar CuII complex (Bai et al., 2011) and a tetrahedral ZnII complex (Neumann et al., 2018b) in which the metal cation is coordinated by two terminally N-bonded thiocyanates and two 4-benzoylpyridine ligands.
5. Synthesis and crystallization
Fe(Cl)2·4H2O and K(SCN)2 were purchased from Merck and 4-benzoylpyridine was purchased from Alfa Aesar.
Synthesis:
Crystals of the title compound suitable for single crystal X-ray diffraction were obtained within three days by the reaction of 59.6 mg Fe(Cl)2·4H2O (0.3 mmol) and 58.3 mg (0.6 mmol) K(SCN)2 with 27.5 mg 4-benzoylpyridine (0.15 mmol) in ethanol (1.5 mL), followed by slow evaporation of the solvent.
Experimental details:
Differential thermal analysis-thermogravimetric (DTA-TG) measurements were performed in a dynamic nitrogen atmosphere in Al2O3 crucibles using an STA PT1600 thermobalance from Linseis. The XRPD measurements were performed by using a Stoe transmission powder diffraction system (STADI P) with Cu Kα radiation that was equipped with a linear, position-sensitive MYTHEN detector from Stoe & Cie. The IR data were measured using a Bruker Alpha-P ATR-IR spectrometer.
6. Refinement
Crystal data, data collection and structure . Hydrogen atoms were positioned with idealized geometry (C—H = 0.95 Å) and were refined using a riding model with Uiso(H) = 1.2Ueq(C).
details are summarized in Table 3
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Supporting information
CCDC reference: 1918968
https://doi.org/10.1107/S2056989019007679/lh5906sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019007679/lh5906Isup2.hkl
Figure S1. Experimental (top) and calculated X-ray powder pattern of the title compound (Cu-Kalpha radiation). DOI: https://doi.org/10.1107/S2056989019007679/lh5906sup3.tif
Figure S2. DTG, TG and DTA curve of the title compound measured with 1 C/min in a nitrogen atmosphere. The mass loss calculated for the removal of one 4-benzoylpyridine ligand corresponds to 19.9%. DOI: https://doi.org/10.1107/S2056989019007679/lh5906sup4.tif
Figure S3. X-ray powder patterns of the residue obtained after the first mass loss of the title compound at 1 C (A), of the residue obtained after the first mass loss of [Mn(SCN)2(4-benzoylpyridine)4] at 1 C (B) and the calculated powder patterns for [Co(NCS)2(4-benzoylpyridine)2] (C) and [Cd(NCS)2(4-benzoylpyridine)2] (D) (Cu-Kalpha radiation). DOI: https://doi.org/10.1107/S2056989019007679/lh5906sup5.tif
Figure S4. IR spectra of the residue obtained after the first mass loss of the title compound (top) in comparism to the title compound (bottom). DOI: https://doi.org/10.1107/S2056989019007679/lh5906sup6.tif
Data collection: X-AREA (Stoe, 2008); cell
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: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).[Fe(NCS)2(C12H9NO)4] | F(000) = 936 |
Mr = 904.82 | Dx = 1.405 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0610 (6) Å | Cell parameters from 25216 reflections |
b = 20.9844 (11) Å | θ = 2.5–27.5° |
c = 11.2527 (9) Å | µ = 0.51 mm−1 |
β = 90.526 (9)° | T = 200 K |
V = 2139.5 (2) Å3 | Needle, light yellow |
Z = 2 | 0.16 × 0.04 × 0.03 mm |
STOE IPDS-1 diffractometer | 4090 reflections with I > 2σ(I) |
φ scans | Rint = 0.060 |
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008) | θmax = 27.5°, θmin = 2.5° |
Tmin = 0.817, Tmax = 0.965 | h = −11→11 |
25216 measured reflections | k = −27→27 |
4907 independent reflections | l = −14→14 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.044 | w = 1/[σ2(Fo2) + (0.0769P)2 + 0.3118P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.113 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.50 e Å−3 |
4907 reflections | Δρmin = −0.51 e Å−3 |
287 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.026 (2) |
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 | 0.0000 | 0.5000 | 0.5000 | 0.01655 (12) | |
N1 | 0.21274 (16) | 0.51129 (6) | 0.43099 (13) | 0.0221 (3) | |
C1 | 0.32862 (18) | 0.52598 (7) | 0.39685 (14) | 0.0204 (3) | |
S1 | 0.48986 (5) | 0.54766 (3) | 0.34977 (5) | 0.03812 (15) | |
N11 | 0.05996 (15) | 0.40356 (6) | 0.57514 (12) | 0.0204 (3) | |
C11 | 0.18068 (19) | 0.37360 (7) | 0.53597 (16) | 0.0248 (3) | |
H11 | 0.2429 | 0.3953 | 0.4819 | 0.030* | |
C12 | 0.2190 (2) | 0.31228 (8) | 0.57078 (17) | 0.0270 (4) | |
H12 | 0.3043 | 0.2924 | 0.5393 | 0.032* | |
C13 | 0.13182 (19) | 0.28026 (7) | 0.65168 (15) | 0.0224 (3) | |
C14 | 0.0108 (2) | 0.31223 (8) | 0.69739 (15) | 0.0255 (3) | |
H14 | −0.0487 | 0.2927 | 0.7562 | 0.031* | |
C15 | −0.02230 (19) | 0.37287 (8) | 0.65646 (15) | 0.0246 (3) | |
H15 | −0.1068 | 0.3938 | 0.6871 | 0.030* | |
C16 | 0.1689 (2) | 0.21450 (8) | 0.69528 (16) | 0.0288 (4) | |
C17 | 0.2345 (2) | 0.16681 (7) | 0.61300 (16) | 0.0252 (4) | |
C18 | 0.3114 (2) | 0.11520 (9) | 0.66334 (19) | 0.0319 (4) | |
H18 | 0.3276 | 0.1133 | 0.7468 | 0.038* | |
C19 | 0.3635 (2) | 0.06699 (9) | 0.5907 (2) | 0.0393 (5) | |
H19 | 0.4160 | 0.0322 | 0.6246 | 0.047* | |
C20 | 0.3395 (2) | 0.06935 (9) | 0.4693 (2) | 0.0400 (5) | |
H20 | 0.3751 | 0.0360 | 0.4202 | 0.048* | |
C21 | 0.2638 (2) | 0.11996 (9) | 0.41879 (19) | 0.0367 (4) | |
H21 | 0.2475 | 0.1212 | 0.3353 | 0.044* | |
C22 | 0.2112 (2) | 0.16913 (8) | 0.49028 (16) | 0.0286 (4) | |
H22 | 0.1599 | 0.2041 | 0.4556 | 0.034* | |
O11 | 0.1429 (2) | 0.20092 (7) | 0.79860 (13) | 0.0537 (5) | |
N31 | 0.07705 (15) | 0.54355 (6) | 0.67343 (12) | 0.0206 (3) | |
C31 | 0.2025 (2) | 0.57704 (8) | 0.68418 (15) | 0.0274 (4) | |
H31 | 0.2607 | 0.5831 | 0.6153 | 0.033* | |
C32 | 0.2519 (2) | 0.60332 (9) | 0.79080 (16) | 0.0277 (4) | |
H32 | 0.3403 | 0.6276 | 0.7937 | 0.033* | |
C33 | 0.17005 (18) | 0.59348 (7) | 0.89320 (14) | 0.0217 (3) | |
C34 | 0.04162 (19) | 0.55810 (8) | 0.88302 (15) | 0.0239 (3) | |
H34 | −0.0168 | 0.5500 | 0.9511 | 0.029* | |
C35 | −0.00132 (19) | 0.53446 (8) | 0.77268 (15) | 0.0232 (3) | |
H35 | −0.0904 | 0.5107 | 0.7672 | 0.028* | |
C36 | 0.21784 (19) | 0.61552 (8) | 1.01527 (15) | 0.0252 (3) | |
C37 | 0.29466 (19) | 0.67775 (8) | 1.03193 (15) | 0.0242 (3) | |
C38 | 0.2782 (2) | 0.72793 (9) | 0.95250 (17) | 0.0335 (4) | |
H38 | 0.2207 | 0.7224 | 0.8822 | 0.040* | |
C39 | 0.3458 (3) | 0.78642 (9) | 0.9755 (2) | 0.0383 (5) | |
H39 | 0.3335 | 0.8208 | 0.9214 | 0.046* | |
C40 | 0.4306 (2) | 0.79423 (9) | 1.07696 (19) | 0.0363 (4) | |
H40 | 0.4772 | 0.8340 | 1.0923 | 0.044* | |
C41 | 0.4480 (2) | 0.74438 (10) | 1.15663 (18) | 0.0372 (4) | |
H41 | 0.5067 | 0.7500 | 1.2262 | 0.045* | |
C42 | 0.3800 (2) | 0.68632 (9) | 1.13492 (16) | 0.0309 (4) | |
H42 | 0.3913 | 0.6523 | 1.1900 | 0.037* | |
O21 | 0.19095 (18) | 0.58129 (7) | 1.10006 (12) | 0.0400 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01555 (17) | 0.01668 (16) | 0.01743 (17) | −0.00085 (10) | 0.00129 (12) | −0.00031 (11) |
N1 | 0.0182 (7) | 0.0252 (6) | 0.0229 (7) | 0.0000 (5) | 0.0008 (5) | 0.0007 (5) |
C1 | 0.0222 (8) | 0.0205 (7) | 0.0183 (7) | 0.0020 (6) | −0.0022 (6) | 0.0004 (6) |
S1 | 0.0200 (2) | 0.0558 (3) | 0.0387 (3) | −0.00491 (19) | 0.00399 (19) | 0.0148 (2) |
N11 | 0.0235 (7) | 0.0174 (6) | 0.0201 (6) | 0.0003 (5) | −0.0002 (5) | −0.0009 (5) |
C11 | 0.0256 (8) | 0.0194 (7) | 0.0294 (9) | 0.0008 (6) | 0.0058 (7) | 0.0008 (6) |
C12 | 0.0267 (9) | 0.0205 (7) | 0.0340 (9) | 0.0041 (6) | 0.0060 (7) | 0.0000 (7) |
C13 | 0.0282 (8) | 0.0174 (7) | 0.0217 (8) | −0.0004 (6) | −0.0032 (6) | −0.0011 (6) |
C14 | 0.0306 (9) | 0.0236 (8) | 0.0225 (8) | −0.0013 (6) | 0.0032 (7) | 0.0027 (6) |
C15 | 0.0243 (8) | 0.0245 (8) | 0.0250 (8) | 0.0024 (6) | 0.0042 (6) | 0.0013 (6) |
C16 | 0.0381 (10) | 0.0224 (8) | 0.0257 (8) | 0.0001 (7) | −0.0038 (7) | 0.0026 (6) |
C17 | 0.0260 (8) | 0.0177 (7) | 0.0318 (9) | −0.0011 (6) | −0.0020 (7) | 0.0024 (6) |
C18 | 0.0300 (9) | 0.0259 (8) | 0.0398 (11) | 0.0019 (7) | −0.0070 (8) | 0.0071 (7) |
C19 | 0.0299 (10) | 0.0269 (9) | 0.0610 (14) | 0.0106 (7) | 0.0012 (9) | 0.0075 (9) |
C20 | 0.0395 (11) | 0.0279 (9) | 0.0527 (13) | 0.0067 (8) | 0.0126 (10) | −0.0018 (8) |
C21 | 0.0459 (12) | 0.0281 (9) | 0.0362 (10) | 0.0045 (8) | 0.0086 (9) | −0.0008 (8) |
C22 | 0.0358 (10) | 0.0212 (7) | 0.0290 (9) | 0.0031 (6) | 0.0008 (7) | 0.0033 (6) |
O11 | 0.1029 (15) | 0.0328 (7) | 0.0256 (7) | 0.0158 (8) | 0.0054 (8) | 0.0069 (6) |
N31 | 0.0232 (7) | 0.0191 (6) | 0.0194 (7) | −0.0018 (5) | 0.0016 (5) | −0.0012 (5) |
C31 | 0.0299 (9) | 0.0330 (9) | 0.0193 (8) | −0.0106 (7) | 0.0052 (7) | −0.0038 (6) |
C32 | 0.0270 (9) | 0.0338 (9) | 0.0224 (8) | −0.0118 (7) | 0.0020 (7) | −0.0033 (7) |
C33 | 0.0252 (8) | 0.0209 (7) | 0.0189 (7) | 0.0012 (6) | −0.0006 (6) | −0.0003 (6) |
C34 | 0.0261 (8) | 0.0266 (7) | 0.0189 (7) | −0.0017 (6) | 0.0043 (6) | 0.0006 (6) |
C35 | 0.0221 (8) | 0.0260 (8) | 0.0215 (8) | −0.0044 (6) | 0.0019 (6) | −0.0011 (6) |
C36 | 0.0263 (9) | 0.0303 (8) | 0.0189 (8) | 0.0010 (6) | 0.0001 (6) | 0.0003 (6) |
C37 | 0.0240 (8) | 0.0290 (8) | 0.0194 (8) | 0.0012 (6) | 0.0010 (6) | −0.0042 (6) |
C38 | 0.0422 (11) | 0.0304 (9) | 0.0278 (9) | −0.0002 (8) | −0.0076 (8) | −0.0024 (7) |
C39 | 0.0482 (12) | 0.0274 (9) | 0.0394 (11) | −0.0012 (8) | 0.0007 (9) | −0.0014 (8) |
C40 | 0.0321 (10) | 0.0359 (10) | 0.0409 (11) | −0.0051 (8) | 0.0077 (8) | −0.0161 (8) |
C41 | 0.0305 (10) | 0.0503 (11) | 0.0309 (10) | −0.0052 (8) | −0.0041 (8) | −0.0124 (8) |
C42 | 0.0315 (10) | 0.0387 (10) | 0.0224 (8) | 0.0001 (7) | −0.0033 (7) | −0.0033 (7) |
O21 | 0.0545 (9) | 0.0444 (8) | 0.0210 (6) | −0.0136 (7) | −0.0015 (6) | 0.0055 (6) |
Fe1—N1i | 2.0982 (14) | C20—H20 | 0.9500 |
Fe1—N1 | 2.0982 (14) | C21—C22 | 1.395 (3) |
Fe1—N11 | 2.2576 (13) | C21—H21 | 0.9500 |
Fe1—N11i | 2.2576 (13) | C22—H22 | 0.9500 |
Fe1—N31 | 2.2597 (13) | N31—C31 | 1.341 (2) |
Fe1—N31i | 2.2597 (13) | N31—C35 | 1.343 (2) |
N1—C1 | 1.163 (2) | C31—C32 | 1.391 (2) |
C1—S1 | 1.6237 (17) | C31—H31 | 0.9500 |
N11—C11 | 1.340 (2) | C32—C33 | 1.392 (2) |
N11—C15 | 1.349 (2) | C32—H32 | 0.9500 |
C11—C12 | 1.388 (2) | C33—C34 | 1.384 (2) |
C11—H11 | 0.9500 | C33—C36 | 1.509 (2) |
C12—C13 | 1.384 (2) | C34—C35 | 1.389 (2) |
C12—H12 | 0.9500 | C34—H34 | 0.9500 |
C13—C14 | 1.388 (2) | C35—H35 | 0.9500 |
C13—C16 | 1.502 (2) | C36—O21 | 1.221 (2) |
C14—C15 | 1.385 (2) | C36—C37 | 1.491 (2) |
C14—H14 | 0.9500 | C37—C38 | 1.388 (3) |
C15—H15 | 0.9500 | C37—C42 | 1.399 (2) |
C16—O11 | 1.222 (2) | C38—C39 | 1.395 (3) |
C16—C17 | 1.491 (2) | C38—H38 | 0.9500 |
C17—C22 | 1.396 (3) | C39—C40 | 1.380 (3) |
C17—C18 | 1.404 (2) | C39—H39 | 0.9500 |
C18—C19 | 1.386 (3) | C40—C41 | 1.386 (3) |
C18—H18 | 0.9500 | C40—H40 | 0.9500 |
C19—C20 | 1.383 (3) | C41—C42 | 1.386 (3) |
C19—H19 | 0.9500 | C41—H41 | 0.9500 |
C20—C21 | 1.383 (3) | C42—H42 | 0.9500 |
N1i—Fe1—N1 | 180.0 | C19—C20—H20 | 119.8 |
N1i—Fe1—N11 | 88.79 (5) | C21—C20—H20 | 119.8 |
N1—Fe1—N11 | 91.21 (5) | C20—C21—C22 | 120.1 (2) |
N1i—Fe1—N11i | 91.21 (5) | C20—C21—H21 | 119.9 |
N1—Fe1—N11i | 88.79 (5) | C22—C21—H21 | 119.9 |
N11—Fe1—N11i | 180.0 | C21—C22—C17 | 119.71 (17) |
N1i—Fe1—N31 | 90.21 (5) | C21—C22—H22 | 120.1 |
N1—Fe1—N31 | 89.79 (5) | C17—C22—H22 | 120.1 |
N11—Fe1—N31 | 88.15 (5) | C31—N31—C35 | 116.99 (14) |
N11i—Fe1—N31 | 91.85 (5) | C31—N31—Fe1 | 123.01 (11) |
N1i—Fe1—N31i | 89.79 (5) | C35—N31—Fe1 | 119.96 (11) |
N1—Fe1—N31i | 90.21 (5) | N31—C31—C32 | 123.48 (16) |
N11—Fe1—N31i | 91.85 (5) | N31—C31—H31 | 118.3 |
N11i—Fe1—N31i | 88.15 (5) | C32—C31—H31 | 118.3 |
N31—Fe1—N31i | 180.00 (7) | C31—C32—C33 | 119.05 (16) |
C1—N1—Fe1 | 170.93 (13) | C31—C32—H32 | 120.5 |
N1—C1—S1 | 179.08 (15) | C33—C32—H32 | 120.5 |
C11—N11—C15 | 117.19 (14) | C34—C33—C32 | 117.73 (15) |
C11—N11—Fe1 | 119.46 (11) | C34—C33—C36 | 118.27 (15) |
C15—N11—Fe1 | 123.32 (11) | C32—C33—C36 | 123.88 (15) |
N11—C11—C12 | 123.01 (16) | C33—C34—C35 | 119.59 (15) |
N11—C11—H11 | 118.5 | C33—C34—H34 | 120.2 |
C12—C11—H11 | 118.5 | C35—C34—H34 | 120.2 |
C13—C12—C11 | 119.53 (16) | N31—C35—C34 | 123.15 (15) |
C13—C12—H12 | 120.2 | N31—C35—H35 | 118.4 |
C11—C12—H12 | 120.2 | C34—C35—H35 | 118.4 |
C12—C13—C14 | 117.79 (15) | O21—C36—C37 | 120.89 (16) |
C12—C13—C16 | 122.26 (16) | O21—C36—C33 | 118.27 (16) |
C14—C13—C16 | 119.87 (16) | C37—C36—C33 | 120.84 (14) |
C15—C14—C13 | 119.35 (16) | C38—C37—C42 | 119.42 (17) |
C15—C14—H14 | 120.3 | C38—C37—C36 | 122.42 (16) |
C13—C14—H14 | 120.3 | C42—C37—C36 | 118.07 (16) |
N11—C15—C14 | 123.00 (16) | C37—C38—C39 | 120.24 (18) |
N11—C15—H15 | 118.5 | C37—C38—H38 | 119.9 |
C14—C15—H15 | 118.5 | C39—C38—H38 | 119.9 |
O11—C16—C17 | 121.05 (16) | C40—C39—C38 | 119.87 (19) |
O11—C16—C13 | 118.74 (17) | C40—C39—H39 | 120.1 |
C17—C16—C13 | 120.21 (15) | C38—C39—H39 | 120.1 |
C22—C17—C18 | 119.72 (17) | C39—C40—C41 | 120.32 (18) |
C22—C17—C16 | 122.25 (15) | C39—C40—H40 | 119.8 |
C18—C17—C16 | 117.80 (17) | C41—C40—H40 | 119.8 |
C19—C18—C17 | 119.70 (19) | C40—C41—C42 | 120.11 (18) |
C19—C18—H18 | 120.1 | C40—C41—H41 | 119.9 |
C17—C18—H18 | 120.1 | C42—C41—H41 | 119.9 |
C20—C19—C18 | 120.35 (18) | C41—C42—C37 | 120.03 (18) |
C20—C19—H19 | 119.8 | C41—C42—H42 | 120.0 |
C18—C19—H19 | 119.8 | C37—C42—H42 | 120.0 |
C19—C20—C21 | 120.41 (19) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···N1 | 0.95 | 2.51 | 3.136 (2) | 123 |
C15—H15···N1i | 0.95 | 2.57 | 3.134 (2) | 118 |
C15—H15···O21ii | 0.95 | 2.57 | 3.293 (2) | 133 |
C31—H31···N1 | 0.95 | 2.60 | 3.168 (2) | 119 |
C35—H35···N1i | 0.95 | 2.52 | 3.125 (2) | 121 |
C35—H35···O21ii | 0.95 | 2.61 | 3.309 (2) | 131 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+1, −z+2. |
Acknowledgements
We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.
Funding information
This project was supported by the Deutsche Forschungsgemeinschaft (Project No. NA 720/6–1) and the State of Schleswig-Holstein.
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