metal-organic compounds
Tris(5,6-dimethyl-1,10-phenanthroline-κ2N,N′)iron(II) bis(tricyanomethanide)
aInstitute of Chemistry, Faculty of Science, P.J. Šafárik University, Moyzesova 11, SK-041 54 Košice, Slovakia
*Correspondence e-mail: lucia.vahovska@student.upjs.sk
The title compound, [Fe(C14H12N2)3](C4N3)2, consists of one [Fe(dimephen)3]2+ complex cation (dimephen = 5,6-dimethyl-1,10-phenanthroline) and two uncoordinating tcm anions (tcm = tricyanomethanide). In the complex cation, the FeII atom is coordinated by six N atoms from three chelating dimephen ligands at an average Fe—N distance of 1.963 (4) Å giving a distorted octahedral geometry. The is stabilized by weak C—H⋯N hydrogen bonds and C≡N⋯π interactions between planar [maximum deviations of 0.024 (3) and 0.015 (3) Å] tcm anions and pyridine rings of dimephen [N2⋯centroid = 3.531 (3) and 3.726 (3) Å; C≡N⋯centroid = 96.4 (2) and 97.1 (2)°].
Related literature
[Fe(phen)2(NCS)2] (phen = 1,10-phenathroline) and [Fe(bpy)2(NCS)2] (bpy = 2,2-bipyridine) are the first known and most extensively studied compounds of iron(II) exhibiting a high spin ←→ low spin transition, see: König & Watson (1970); Müller et al. (1982). For [Fe(phen)3]2+complexes, see: Aparici Plaza et al. (2007); Odoko & Okabe (2004); Koh et al. (1994); Uçar et al. (2005); Li et al. (2008). For bond lengths and angles in dimephen, see: Toledano-Magaña et al. (2012) and in tcm ligands, see: Potočňák et al. (2002); Luo et al. (2009). For the structure, properties and bonding modes of the tcm anion, see: Golub et al. (1986); Kohout et al. (2000). For the crystal and molecular structure of phen, see: Nishigaki et al. (1978). For similar FeII complexes, see: Váhovská & Potočňák (2012).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2012); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812046880/bx2428sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812046880/bx2428Isup2.hkl
Single crystals of the title compound were obtained at the interfaces of layered systems, with the lower layer comprising an aqueous solution (5 ml) of iron(II) sulfate (0.1 mmol) and 5 ml of tcm (0.1 mmol) and the upper layer comprising a methanolic solution (3 ml) of dimephen (0.1 mmol). These layered systems were allowed to stand at room temperature. Red crystals suitable for X-ray analysis were obtained and filtered off in several days and dried on air.
Anisotropic displacement parameters were refined for all non-H atoms. The aromatic as well as methyl H atoms were placed in calculated positions and refined riding on their parent C atoms with C–H distances of 0.95 and 0.98 Å, respectively and Uiso(H) = 1.2Ueq(C) and 1.5Ueq(C) for aromatic and methyl hydrogen atoms, respectively.
The iron(II) complexes [Fe(phen)2(NCS)2] and [Fe(bpy)2(NCS)2] (bpy = 2,2-bipyridine) belong to the first known and most extensively studied compounds of iron(II) exhibiting a high spin ←→ low spin transition (Müller et al., 1982; König & Watson, 1970). By far the majority of known spin-transition compounds are octahedral FeII compounds of general formula [Fe(L)4(NCX)2] or [Fe(L)2(NCX)2] (L = monodentate or bidentate N-donor ligands, X = S, Se). In our research, which is aimed on preparation of new [Fe(L)2(Y)2] compounds (L = bpy, phen or their derivatives and Y = pseudohalide anions (dicyanamide, or tcm)) with possible spin crossover, we prepared crystals of the title compound with composition [Fe(dimephen)3](tcm)2 (I) (dimephen = 5,6-dimethyl-1,10-phenanthroline).
Structural analysis showed that
of the title compound is ionic and consists of one complex cation and two tcm counter-anions (Fig. 1).In the complex cation the FeII ion is bonded to three bidentate dimephen ligands through their nitrogen atoms resulting in a distorted octahedral arrangement with the six Fe1–N distances ranging from 1.957 (2) to 1.968 (2) Å (Table 1). These values as well as the values of N–Fe1–N bite angles (82.88 (9), 82.69 (9), 82.44 (9)°) and opposite (trans) angles (173.92 (9), 176.49 (9), 176.56 (9)°) are comparable to the corresponding distances and angles in other complexes with [Fe(phen)3]2+ cations (Aparici Plaza et al., 2007; Odoko & Okabe, 2004; Koh et al., 1994; Uçar et al., 2005; Li et al., 2008). All N–Fe1–N bond angles in (I) deviate significantly from the ideal values of 90 or 180° because of the constrained geometry of the dimephen ring systems. The values of bond distances and angles within the rings of neutral ligands are similar to those found in the similar [Cu(dimephen)3](PF6)2.CH3CN complex, too (Toledano-Magaña et al., 2012). The dimephen ligands in (I) are almost planar, the largest deviation of atom from the mean plane being 0.051 (3) Å for atom C63.
Both tcm anions are nearly planar, too (the largest deviations of atoms from the mean planes being 0.024 (3) for C1 atom and 0.015 (3) Å for C5 atom). The average C–C and C≡N bond lengths (1.404 (6) and 1.155 (3) Å, respectively), C–C–C (120.0 (3)°) and C–C≡N (179.0 (6)°) angles within the both anions are in good agreement with those found in other tricyanomethanide complexes (Potočňák et al., 2002; Luo et al., 2009).
The crystal packing in (I) is formed by weak C–H···N hydrogen bonds (Table 2) and C–N···Cg π-ring interactions. Weak hydrogen bonds occur between individual dimephen ligands and thus the structure of the cation is stabilized. Moreover, tcm anions interconnect two [Fe(dimephen)3]2+cations through hydrogen bonds and these interactions lead to infinite chain-like structure running along z axis (Fig. 2).
Except hydrogen bonds, the π-ring interactions between nitrogen atoms from tcm anions and corresponding pyridine rings. The N2···Cg8i (i = x – 1, y, z) and N6···Cg7 distances (3.531 (3) and 3.726 (3) Å, respectively, Cg8 and Cg7 are centroids of pyridine rings with N50 and N40 atoms, respectively), the distances of N2 and N6 atoms to the planes of the corresponding dimephen rings (3.505 and 3.677 Å, respectively) as well as the C2≡N2···Cg8i and C6≡N6···Cg7 angles (96.4 (2) and 97.1 (2)°, respectively) are close to those found in similar FeII complexes (Váhovská & Potočňák, 2012). Parallel arrangement of tcm anions with dimephen molecules in (I) is shown in Fig. 3.
is stabilized byThe iron(II) complexes [Fe(phen)2(NCS)2] and [Fe(bpy)2(NCS)2] (bpy = 2,2-bipyridine) are the first known and most extensively studied compounds of iron(II) exhibiting a high spin ←→ low spin transition, see: König & Watson (1970); Müller et al. (1982). For [Fe(phen)3]2+complexes (phen = 1,10-phenathroline) see: Aparici Plaza et al. (2007); Odoko & Okabe (2004); Koh et al. (1994); Uçar et al. (2005); Li et al. (2008). For bond lengths and angles in dimephen, see: Toledano-Magaña et al. (2012) and in tcm ligands, see: Potočňák et al. (2002); Luo et al. (2009). For the structure, properties and bonding modes of the tcm anion, see: Golub et al. (1986); Kohout et al. (2000). For the crystal and molecular structure of phen, see: Nishigaki et al. (1978). For similar FeII complexes, see: Váhovská & Potočňák (2012).
Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The structure of the title compound. | |
Fig. 2. Intramolecular and intermolecular C—H···N hydrogen bonds (blue and red dashed lines, respectively) in the title compound. H-atoms not involved in hydrogen bonds are omitted because of clarity. | |
Fig. 3. π-π interactions (dashed lines) between tcm and pyridine rings in the title compound (symmetry codes: (i) = x –1, y, z). H-atoms are omitted because of clarity. |
[Fe(C14H12N2)3](C4N3)2 | Z = 2 |
Mr = 860.76 | F(000) = 892 |
Triclinic, P1 | Dx = 1.376 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.3676 (3) Å | Cell parameters from 5036 reflections |
b = 12.7079 (9) Å | θ = 3.0–29.2° |
c = 18.1998 (9) Å | µ = 0.42 mm−1 |
α = 75.458 (5)° | T = 183 K |
β = 89.623 (3)° | Needle, dark red |
γ = 82.323 (4)° | 0.66 × 0.25 × 0.03 mm |
V = 2077.52 (19) Å3 |
Agilent Xcalibur (Sapphire2) diffractometer | 8167 independent reflections |
Radiation source: fine-focus sealed tube | 6309 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 8.3438 pixels mm-1 | θmax = 26.0°, θmin = 3.0° |
ω scans | h = −11→11 |
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), based on expressions derived by Clark & Reid (1995)] | k = −15→10 |
Tmin = 0.874, Tmax = 0.986 | l = −22→21 |
15408 measured reflections |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0473P)2 + 1.1913P] where P = (Fo2 + 2Fc2)/3 |
8167 reflections | (Δ/σ)max = 0.001 |
574 parameters | Δρmax = 0.92 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
[Fe(C14H12N2)3](C4N3)2 | γ = 82.323 (4)° |
Mr = 860.76 | V = 2077.52 (19) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.3676 (3) Å | Mo Kα radiation |
b = 12.7079 (9) Å | µ = 0.42 mm−1 |
c = 18.1998 (9) Å | T = 183 K |
α = 75.458 (5)° | 0.66 × 0.25 × 0.03 mm |
β = 89.623 (3)° |
Agilent Xcalibur (Sapphire2) diffractometer | 8167 independent reflections |
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), based on expressions derived by Clark & Reid (1995)] | 6309 reflections with I > 2σ(I) |
Tmin = 0.874, Tmax = 0.986 | Rint = 0.025 |
15408 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.92 e Å−3 |
8167 reflections | Δρmin = −0.40 e Å−3 |
574 parameters |
Experimental. CrysAlis PRO (Agilent, 2012) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) |
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. |
x | y | z | Uiso*/Ueq | ||
Fe1 | 0.52758 (4) | 0.38724 (3) | 0.27263 (2) | 0.01786 (11) | |
N10 | 0.6319 (2) | 0.51196 (18) | 0.23141 (12) | 0.0199 (5) | |
N20 | 0.3666 (2) | 0.50317 (18) | 0.27106 (12) | 0.0196 (5) | |
N30 | 0.5692 (2) | 0.37913 (18) | 0.37975 (12) | 0.0208 (5) | |
N40 | 0.4163 (2) | 0.26722 (18) | 0.31777 (12) | 0.0189 (5) | |
N50 | 0.6912 (2) | 0.27509 (18) | 0.26764 (12) | 0.0196 (5) | |
N60 | 0.4893 (2) | 0.37825 (18) | 0.16864 (12) | 0.0191 (5) | |
C11 | 0.5467 (3) | 0.6115 (2) | 0.22050 (14) | 0.0178 (5) | |
C12 | 0.7678 (3) | 0.5128 (2) | 0.20913 (15) | 0.0250 (6) | |
H12 | 0.8295 | 0.4451 | 0.2168 | 0.030* | |
C13 | 0.8222 (3) | 0.6097 (2) | 0.17501 (16) | 0.0279 (7) | |
H13 | 0.9186 | 0.6070 | 0.1583 | 0.034* | |
C14 | 0.7372 (3) | 0.7085 (2) | 0.16549 (16) | 0.0273 (7) | |
H14 | 0.7750 | 0.7746 | 0.1430 | 0.033* | |
C15 | 0.5938 (3) | 0.7123 (2) | 0.18903 (14) | 0.0204 (6) | |
C16 | 0.4937 (3) | 0.8123 (2) | 0.18188 (15) | 0.0235 (6) | |
C17 | 0.5497 (3) | 0.9199 (3) | 0.14961 (18) | 0.0365 (8) | |
H17A | 0.4687 | 0.9793 | 0.1376 | 0.055* | |
H17B | 0.6020 | 0.9165 | 0.1033 | 0.055* | |
H17C | 0.6148 | 0.9337 | 0.1870 | 0.055* | |
C21 | 0.4017 (3) | 0.6066 (2) | 0.24352 (14) | 0.0184 (6) | |
C22 | 0.2318 (3) | 0.4941 (2) | 0.29416 (16) | 0.0255 (6) | |
H22 | 0.2046 | 0.4230 | 0.3132 | 0.031* | |
C23 | 0.1304 (3) | 0.5858 (3) | 0.29106 (17) | 0.0297 (7) | |
H23 | 0.0362 | 0.5767 | 0.3089 | 0.036* | |
C24 | 0.1652 (3) | 0.6885 (3) | 0.26263 (16) | 0.0284 (7) | |
H24 | 0.0952 | 0.7508 | 0.2603 | 0.034* | |
C25 | 0.3061 (3) | 0.7028 (2) | 0.23650 (15) | 0.0209 (6) | |
C26 | 0.3543 (3) | 0.8075 (2) | 0.20441 (15) | 0.0245 (6) | |
C27 | 0.2448 (3) | 0.9083 (3) | 0.19628 (19) | 0.0389 (8) | |
H27A | 0.2917 | 0.9740 | 0.1775 | 0.058* | |
H27B | 0.2035 | 0.9090 | 0.2458 | 0.058* | |
H27C | 0.1680 | 0.9073 | 0.1602 | 0.058* | |
C31 | 0.5127 (3) | 0.2963 (2) | 0.42907 (14) | 0.0201 (6) | |
C32 | 0.6471 (3) | 0.4402 (2) | 0.40944 (16) | 0.0257 (6) | |
H32 | 0.6869 | 0.4988 | 0.3763 | 0.031* | |
C33 | 0.6717 (3) | 0.4202 (3) | 0.48748 (17) | 0.0326 (7) | |
H33 | 0.7272 | 0.4652 | 0.5067 | 0.039* | |
C34 | 0.6164 (3) | 0.3365 (3) | 0.53644 (17) | 0.0320 (7) | |
H34 | 0.6342 | 0.3228 | 0.5896 | 0.038* | |
C35 | 0.5328 (3) | 0.2702 (2) | 0.50797 (15) | 0.0266 (6) | |
C36 | 0.4690 (3) | 0.1787 (3) | 0.55442 (16) | 0.0300 (7) | |
C37 | 0.4985 (3) | 0.1533 (3) | 0.63885 (17) | 0.0434 (9) | |
H37A | 0.4570 | 0.0871 | 0.6641 | 0.065* | |
H37B | 0.4548 | 0.2151 | 0.6582 | 0.065* | |
H37C | 0.6027 | 0.1411 | 0.6491 | 0.065* | |
C41 | 0.4288 (2) | 0.2355 (2) | 0.39481 (14) | 0.0187 (6) | |
C42 | 0.3382 (3) | 0.2126 (2) | 0.28329 (16) | 0.0256 (6) | |
H42 | 0.3264 | 0.2345 | 0.2296 | 0.031* | |
C43 | 0.2731 (3) | 0.1237 (2) | 0.32412 (18) | 0.0301 (7) | |
H43 | 0.2195 | 0.0855 | 0.2978 | 0.036* | |
C44 | 0.2859 (3) | 0.0914 (2) | 0.40121 (17) | 0.0293 (7) | |
H44 | 0.2412 | 0.0310 | 0.4285 | 0.035* | |
C45 | 0.3654 (3) | 0.1477 (2) | 0.44031 (16) | 0.0243 (6) | |
C46 | 0.3868 (3) | 0.1207 (2) | 0.52172 (16) | 0.0286 (7) | |
C47 | 0.3141 (3) | 0.0276 (3) | 0.56809 (19) | 0.0422 (9) | |
H47A | 0.3495 | 0.0093 | 0.6210 | 0.063* | |
H47B | 0.3361 | −0.0368 | 0.5475 | 0.063* | |
H47C | 0.2097 | 0.0499 | 0.5659 | 0.063* | |
C51 | 0.6892 (3) | 0.2399 (2) | 0.20271 (15) | 0.0188 (6) | |
C52 | 0.7946 (3) | 0.2252 (2) | 0.31962 (15) | 0.0239 (6) | |
H52 | 0.7994 | 0.2494 | 0.3648 | 0.029* | |
C53 | 0.8950 (3) | 0.1397 (2) | 0.31027 (16) | 0.0278 (7) | |
H53 | 0.9671 | 0.1066 | 0.3486 | 0.033* | |
C54 | 0.8910 (3) | 0.1025 (2) | 0.24603 (17) | 0.0277 (7) | |
H54 | 0.9586 | 0.0426 | 0.2403 | 0.033* | |
C55 | 0.7863 (3) | 0.1536 (2) | 0.18851 (15) | 0.0216 (6) | |
C56 | 0.7733 (3) | 0.1236 (2) | 0.11727 (16) | 0.0258 (6) | |
C57 | 0.8814 (3) | 0.0306 (3) | 0.10493 (19) | 0.0368 (8) | |
H57A | 0.8544 | 0.0109 | 0.0587 | 0.055* | |
H57B | 0.8824 | −0.0332 | 0.1485 | 0.055* | |
H57C | 0.9774 | 0.0537 | 0.0996 | 0.055* | |
C61 | 0.5799 (3) | 0.2973 (2) | 0.14812 (14) | 0.0192 (6) | |
C62 | 0.3875 (3) | 0.4362 (2) | 0.11791 (15) | 0.0232 (6) | |
H62 | 0.3234 | 0.4930 | 0.1307 | 0.028* | |
C63 | 0.3724 (3) | 0.4158 (2) | 0.04676 (16) | 0.0289 (7) | |
H63 | 0.3001 | 0.4597 | 0.0117 | 0.035* | |
C64 | 0.4609 (3) | 0.3332 (2) | 0.02716 (16) | 0.0272 (6) | |
H64 | 0.4491 | 0.3188 | −0.0210 | 0.033* | |
C65 | 0.5700 (3) | 0.2695 (2) | 0.07885 (15) | 0.0214 (6) | |
C66 | 0.6681 (3) | 0.1789 (2) | 0.06461 (16) | 0.0252 (6) | |
C67 | 0.6472 (3) | 0.1516 (3) | −0.00986 (18) | 0.0382 (8) | |
H67A | 0.7072 | 0.0823 | −0.0100 | 0.057* | |
H67B | 0.6751 | 0.2103 | −0.0513 | 0.057* | |
H67C | 0.5457 | 0.1444 | −0.0169 | 0.057* | |
C1 | 0.0574 (3) | 0.2816 (3) | 0.04263 (18) | 0.0358 (8) | |
C2 | 0.0526 (3) | 0.3207 (3) | 0.1087 (2) | 0.0436 (9) | |
C3 | −0.0500 (3) | 0.3222 (3) | −0.0146 (2) | 0.0438 (9) | |
C4 | 0.1662 (3) | 0.1985 (3) | 0.03535 (18) | 0.0338 (7) | |
C5 | 0.9633 (3) | 0.7346 (3) | 0.44900 (18) | 0.0325 (7) | |
C6 | 0.9720 (3) | 0.6902 (3) | 0.5285 (2) | 0.0413 (8) | |
C7 | 1.0418 (3) | 0.8197 (3) | 0.41576 (19) | 0.0348 (7) | |
C8 | 0.8731 (3) | 0.6955 (3) | 0.4037 (2) | 0.0374 (8) | |
N2 | 0.0493 (3) | 0.3516 (3) | 0.1633 (2) | 0.0640 (10) | |
N3 | −0.1365 (3) | 0.3538 (3) | −0.0629 (2) | 0.0624 (10) | |
N4 | 0.2554 (3) | 0.1297 (2) | 0.02865 (17) | 0.0470 (7) | |
N6 | 0.9798 (3) | 0.6547 (3) | 0.5933 (2) | 0.0670 (10) | |
N7 | 1.1049 (3) | 0.8905 (2) | 0.38654 (18) | 0.0482 (8) | |
N8 | 0.7995 (3) | 0.6636 (3) | 0.36574 (19) | 0.0508 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01556 (18) | 0.0189 (2) | 0.0196 (2) | −0.00280 (14) | 0.00151 (14) | −0.00547 (16) |
N10 | 0.0156 (10) | 0.0235 (13) | 0.0207 (12) | −0.0017 (9) | 0.0029 (8) | −0.0062 (10) |
N20 | 0.0175 (10) | 0.0233 (13) | 0.0196 (12) | −0.0040 (9) | 0.0034 (9) | −0.0076 (10) |
N30 | 0.0171 (10) | 0.0223 (13) | 0.0242 (12) | −0.0025 (9) | 0.0005 (9) | −0.0084 (10) |
N40 | 0.0183 (10) | 0.0186 (12) | 0.0201 (12) | −0.0026 (9) | 0.0005 (9) | −0.0053 (10) |
N50 | 0.0179 (11) | 0.0215 (13) | 0.0194 (12) | −0.0052 (9) | 0.0005 (9) | −0.0037 (10) |
N60 | 0.0160 (10) | 0.0191 (12) | 0.0212 (12) | −0.0028 (9) | 0.0024 (8) | −0.0031 (10) |
C11 | 0.0196 (13) | 0.0199 (15) | 0.0146 (13) | −0.0021 (11) | −0.0009 (10) | −0.0061 (11) |
C12 | 0.0175 (13) | 0.0281 (17) | 0.0293 (16) | −0.0011 (11) | 0.0047 (11) | −0.0085 (13) |
C13 | 0.0206 (14) | 0.0351 (18) | 0.0301 (16) | −0.0108 (13) | 0.0078 (11) | −0.0084 (14) |
C14 | 0.0287 (15) | 0.0288 (17) | 0.0254 (15) | −0.0153 (13) | 0.0050 (12) | −0.0029 (13) |
C15 | 0.0255 (13) | 0.0234 (15) | 0.0139 (13) | −0.0084 (11) | −0.0018 (10) | −0.0048 (11) |
C16 | 0.0327 (15) | 0.0222 (16) | 0.0160 (14) | −0.0067 (12) | −0.0026 (11) | −0.0039 (12) |
C17 | 0.0437 (18) | 0.0239 (17) | 0.0416 (19) | −0.0100 (14) | 0.0025 (14) | −0.0050 (15) |
C21 | 0.0198 (13) | 0.0200 (15) | 0.0161 (13) | −0.0027 (11) | −0.0002 (10) | −0.0061 (11) |
C22 | 0.0199 (13) | 0.0304 (17) | 0.0282 (15) | −0.0060 (12) | 0.0048 (11) | −0.0098 (13) |
C23 | 0.0180 (13) | 0.0391 (19) | 0.0336 (17) | −0.0033 (12) | 0.0059 (12) | −0.0125 (15) |
C24 | 0.0200 (13) | 0.0308 (18) | 0.0341 (17) | 0.0050 (12) | 0.0018 (12) | −0.0119 (14) |
C25 | 0.0223 (13) | 0.0220 (15) | 0.0184 (14) | 0.0012 (11) | −0.0027 (10) | −0.0075 (12) |
C26 | 0.0306 (15) | 0.0230 (16) | 0.0192 (14) | −0.0007 (12) | −0.0018 (11) | −0.0056 (12) |
C27 | 0.0429 (18) | 0.0287 (19) | 0.0399 (19) | 0.0068 (14) | 0.0013 (14) | −0.0050 (15) |
C31 | 0.0177 (12) | 0.0223 (15) | 0.0195 (14) | 0.0006 (11) | 0.0032 (10) | −0.0055 (12) |
C32 | 0.0221 (13) | 0.0271 (16) | 0.0314 (16) | −0.0032 (12) | −0.0009 (11) | −0.0140 (13) |
C33 | 0.0304 (15) | 0.0380 (19) | 0.0353 (18) | −0.0009 (13) | −0.0075 (13) | −0.0220 (15) |
C34 | 0.0325 (16) | 0.043 (2) | 0.0219 (15) | 0.0045 (14) | −0.0036 (12) | −0.0161 (15) |
C35 | 0.0224 (14) | 0.0332 (18) | 0.0221 (15) | 0.0061 (12) | −0.0005 (11) | −0.0084 (13) |
C36 | 0.0256 (14) | 0.0362 (19) | 0.0209 (15) | 0.0083 (13) | 0.0044 (11) | −0.0006 (13) |
C37 | 0.0424 (18) | 0.057 (2) | 0.0242 (17) | 0.0025 (16) | 0.0032 (14) | −0.0024 (16) |
C41 | 0.0139 (12) | 0.0195 (15) | 0.0215 (14) | 0.0005 (10) | 0.0032 (10) | −0.0042 (11) |
C42 | 0.0232 (14) | 0.0291 (17) | 0.0254 (15) | −0.0065 (12) | −0.0005 (11) | −0.0071 (13) |
C43 | 0.0246 (14) | 0.0270 (17) | 0.0424 (19) | −0.0093 (12) | −0.0004 (12) | −0.0123 (14) |
C44 | 0.0245 (14) | 0.0219 (16) | 0.0405 (18) | −0.0087 (12) | 0.0082 (12) | −0.0033 (14) |
C45 | 0.0180 (13) | 0.0234 (16) | 0.0286 (15) | 0.0001 (11) | 0.0050 (11) | −0.0029 (13) |
C46 | 0.0231 (14) | 0.0311 (17) | 0.0254 (16) | 0.0039 (12) | 0.0060 (11) | 0.0002 (13) |
C47 | 0.0385 (17) | 0.041 (2) | 0.0369 (19) | −0.0039 (15) | 0.0125 (14) | 0.0073 (16) |
C51 | 0.0170 (12) | 0.0196 (14) | 0.0216 (14) | −0.0074 (10) | 0.0051 (10) | −0.0062 (11) |
C52 | 0.0221 (13) | 0.0296 (17) | 0.0197 (14) | −0.0034 (12) | −0.0018 (11) | −0.0054 (12) |
C53 | 0.0190 (13) | 0.0322 (18) | 0.0287 (16) | 0.0007 (12) | −0.0032 (11) | −0.0029 (14) |
C54 | 0.0201 (13) | 0.0227 (16) | 0.0393 (18) | 0.0016 (11) | 0.0034 (12) | −0.0082 (14) |
C55 | 0.0177 (12) | 0.0201 (15) | 0.0276 (15) | −0.0054 (11) | 0.0044 (11) | −0.0053 (12) |
C56 | 0.0227 (14) | 0.0236 (16) | 0.0350 (17) | −0.0060 (11) | 0.0085 (12) | −0.0132 (13) |
C57 | 0.0303 (16) | 0.038 (2) | 0.049 (2) | −0.0019 (14) | 0.0074 (14) | −0.0248 (17) |
C61 | 0.0202 (13) | 0.0167 (14) | 0.0211 (14) | −0.0073 (10) | 0.0056 (10) | −0.0033 (11) |
C62 | 0.0221 (13) | 0.0220 (15) | 0.0246 (15) | −0.0028 (11) | −0.0002 (11) | −0.0040 (12) |
C63 | 0.0287 (15) | 0.0292 (17) | 0.0256 (16) | −0.0056 (13) | −0.0060 (12) | −0.0001 (13) |
C64 | 0.0330 (15) | 0.0312 (17) | 0.0190 (14) | −0.0096 (13) | −0.0005 (11) | −0.0064 (13) |
C65 | 0.0235 (13) | 0.0227 (15) | 0.0200 (14) | −0.0095 (11) | 0.0028 (10) | −0.0059 (12) |
C66 | 0.0263 (14) | 0.0258 (16) | 0.0279 (16) | −0.0109 (12) | 0.0076 (12) | −0.0113 (13) |
C67 | 0.0456 (18) | 0.041 (2) | 0.0348 (18) | −0.0060 (15) | 0.0022 (14) | −0.0212 (16) |
C1 | 0.0270 (15) | 0.0319 (19) | 0.044 (2) | −0.0007 (13) | 0.0069 (14) | −0.0022 (16) |
C2 | 0.0298 (17) | 0.040 (2) | 0.056 (2) | 0.0020 (15) | 0.0137 (16) | −0.0059 (18) |
C3 | 0.0318 (17) | 0.032 (2) | 0.056 (2) | −0.0013 (14) | 0.0117 (16) | 0.0075 (17) |
C4 | 0.0314 (16) | 0.0288 (18) | 0.0372 (18) | −0.0050 (14) | 0.0032 (13) | −0.0004 (15) |
C5 | 0.0263 (15) | 0.0321 (18) | 0.0421 (19) | −0.0075 (13) | 0.0061 (13) | −0.0132 (15) |
C6 | 0.0290 (16) | 0.043 (2) | 0.054 (2) | −0.0148 (15) | 0.0125 (15) | −0.0121 (18) |
C7 | 0.0269 (15) | 0.0275 (18) | 0.051 (2) | −0.0034 (13) | 0.0056 (14) | −0.0123 (16) |
C8 | 0.0278 (16) | 0.0316 (19) | 0.055 (2) | −0.0055 (14) | 0.0107 (15) | −0.0153 (17) |
N2 | 0.055 (2) | 0.069 (3) | 0.074 (3) | −0.0022 (17) | 0.0231 (18) | −0.032 (2) |
N3 | 0.0396 (17) | 0.061 (2) | 0.068 (2) | 0.0018 (15) | 0.0005 (16) | 0.0144 (19) |
N4 | 0.0468 (17) | 0.0364 (18) | 0.0525 (19) | 0.0050 (14) | 0.0044 (14) | −0.0071 (15) |
N6 | 0.059 (2) | 0.088 (3) | 0.055 (2) | −0.033 (2) | 0.0127 (17) | −0.009 (2) |
N7 | 0.0428 (16) | 0.0360 (18) | 0.066 (2) | −0.0129 (14) | 0.0066 (14) | −0.0097 (16) |
N8 | 0.0401 (16) | 0.052 (2) | 0.070 (2) | −0.0119 (14) | 0.0044 (15) | −0.0304 (18) |
Fe1—N20 | 1.957 (2) | C36—C37 | 1.508 (4) |
Fe1—N10 | 1.959 (2) | C37—H37A | 0.9800 |
Fe1—N60 | 1.963 (2) | C37—H37B | 0.9800 |
Fe1—N30 | 1.965 (2) | C37—H37C | 0.9800 |
Fe1—N50 | 1.967 (2) | C41—C45 | 1.411 (4) |
Fe1—N40 | 1.968 (2) | C42—C43 | 1.399 (4) |
N10—C12 | 1.334 (3) | C42—H42 | 0.9500 |
N10—C11 | 1.372 (3) | C43—C44 | 1.361 (4) |
N20—C22 | 1.339 (3) | C43—H43 | 0.9500 |
N20—C21 | 1.368 (3) | C44—C45 | 1.406 (4) |
N30—C32 | 1.339 (3) | C44—H44 | 0.9500 |
N30—C31 | 1.365 (3) | C45—C46 | 1.443 (4) |
N40—C42 | 1.331 (3) | C46—C47 | 1.510 (4) |
N40—C41 | 1.359 (3) | C47—H47A | 0.9800 |
N50—C52 | 1.335 (3) | C47—H47B | 0.9800 |
N50—C51 | 1.365 (3) | C47—H47C | 0.9800 |
N60—C62 | 1.337 (3) | C51—C55 | 1.404 (4) |
N60—C61 | 1.369 (3) | C51—C61 | 1.420 (4) |
C11—C15 | 1.394 (4) | C52—C53 | 1.383 (4) |
C11—C21 | 1.423 (3) | C52—H52 | 0.9500 |
C12—C13 | 1.393 (4) | C53—C54 | 1.369 (4) |
C12—H12 | 0.9500 | C53—H53 | 0.9500 |
C13—C14 | 1.366 (4) | C54—C55 | 1.408 (4) |
C13—H13 | 0.9500 | C54—H54 | 0.9500 |
C14—C15 | 1.406 (4) | C55—C56 | 1.450 (4) |
C14—H14 | 0.9500 | C56—C66 | 1.369 (4) |
C15—C16 | 1.454 (4) | C56—C57 | 1.511 (4) |
C16—C26 | 1.371 (4) | C57—H57A | 0.9800 |
C16—C17 | 1.507 (4) | C57—H57B | 0.9800 |
C17—H17A | 0.9800 | C57—H57C | 0.9800 |
C17—H17B | 0.9800 | C61—C65 | 1.399 (4) |
C17—H17C | 0.9800 | C62—C63 | 1.394 (4) |
C21—C25 | 1.394 (4) | C62—H62 | 0.9500 |
C22—C23 | 1.392 (4) | C63—C64 | 1.367 (4) |
C22—H22 | 0.9500 | C63—H63 | 0.9500 |
C23—C24 | 1.360 (4) | C64—C65 | 1.413 (4) |
C23—H23 | 0.9500 | C64—H64 | 0.9500 |
C24—C25 | 1.419 (4) | C65—C66 | 1.449 (4) |
C24—H24 | 0.9500 | C66—C67 | 1.501 (4) |
C25—C26 | 1.443 (4) | C67—H67A | 0.9800 |
C26—C27 | 1.506 (4) | C67—H67B | 0.9800 |
C27—H27A | 0.9800 | C67—H67C | 0.9800 |
C27—H27B | 0.9800 | C1—C4 | 1.397 (4) |
C27—H27C | 0.9800 | C1—C3 | 1.402 (5) |
C31—C35 | 1.398 (4) | C1—C2 | 1.411 (5) |
C31—C41 | 1.419 (4) | C2—N2 | 1.155 (5) |
C32—C33 | 1.394 (4) | C3—N3 | 1.156 (4) |
C32—H32 | 0.9500 | C4—N4 | 1.155 (4) |
C33—C34 | 1.363 (4) | C5—C7 | 1.398 (4) |
C33—H33 | 0.9500 | C5—C8 | 1.403 (5) |
C34—C35 | 1.411 (4) | C5—C6 | 1.413 (5) |
C34—H34 | 0.9500 | C6—N6 | 1.151 (4) |
C35—C36 | 1.453 (4) | C7—N7 | 1.157 (4) |
C36—C46 | 1.367 (4) | C8—N8 | 1.157 (4) |
N20—Fe1—N10 | 82.89 (9) | C34—C35—C36 | 124.8 (3) |
N20—Fe1—N60 | 94.50 (9) | C46—C36—C35 | 120.5 (3) |
N10—Fe1—N60 | 89.17 (9) | C46—C36—C37 | 123.2 (3) |
N20—Fe1—N30 | 89.92 (9) | C35—C36—C37 | 116.3 (3) |
N10—Fe1—N30 | 95.52 (9) | C36—C37—H37A | 109.5 |
N60—Fe1—N30 | 173.92 (9) | C36—C37—H37B | 109.5 |
N20—Fe1—N50 | 176.49 (9) | H37A—C37—H37B | 109.5 |
N10—Fe1—N50 | 94.93 (9) | C36—C37—H37C | 109.5 |
N60—Fe1—N50 | 82.70 (9) | H37A—C37—H37C | 109.5 |
N30—Fe1—N50 | 93.03 (9) | H37B—C37—H37C | 109.5 |
N20—Fe1—N40 | 94.31 (9) | N40—C41—C45 | 124.1 (2) |
N10—Fe1—N40 | 176.56 (9) | N40—C41—C31 | 115.8 (2) |
N60—Fe1—N40 | 93.05 (9) | C45—C41—C31 | 120.1 (2) |
N30—Fe1—N40 | 82.45 (9) | N40—C42—C43 | 121.7 (3) |
N50—Fe1—N40 | 87.97 (9) | N40—C42—H42 | 119.1 |
C12—N10—C11 | 117.2 (2) | C43—C42—H42 | 119.1 |
C12—N10—Fe1 | 129.55 (19) | C44—C43—C42 | 120.6 (3) |
C11—N10—Fe1 | 113.15 (15) | C44—C43—H43 | 119.7 |
C22—N20—C21 | 117.6 (2) | C42—C43—H43 | 119.7 |
C22—N20—Fe1 | 129.00 (19) | C43—C44—C45 | 119.8 (3) |
C21—N20—Fe1 | 113.43 (16) | C43—C44—H44 | 120.1 |
C32—N30—C31 | 117.4 (2) | C45—C44—H44 | 120.1 |
C32—N30—Fe1 | 129.23 (19) | C44—C45—C41 | 115.9 (2) |
C31—N30—Fe1 | 113.32 (17) | C44—C45—C46 | 124.7 (3) |
C42—N40—C41 | 117.8 (2) | C41—C45—C46 | 119.3 (3) |
C42—N40—Fe1 | 129.02 (18) | C36—C46—C45 | 120.4 (3) |
C41—N40—Fe1 | 113.08 (17) | C36—C46—C47 | 122.3 (3) |
C52—N50—C51 | 117.3 (2) | C45—C46—C47 | 117.4 (3) |
C52—N50—Fe1 | 129.58 (19) | C46—C47—H47A | 109.5 |
C51—N50—Fe1 | 112.98 (17) | C46—C47—H47B | 109.5 |
C62—N60—C61 | 117.4 (2) | H47A—C47—H47B | 109.5 |
C62—N60—Fe1 | 129.68 (19) | C46—C47—H47C | 109.5 |
C61—N60—Fe1 | 112.91 (17) | H47A—C47—H47C | 109.5 |
N10—C11—C15 | 124.3 (2) | H47B—C47—H47C | 109.5 |
N10—C11—C21 | 115.3 (2) | N50—C51—C55 | 124.1 (2) |
C15—C11—C21 | 120.5 (2) | N50—C51—C61 | 115.4 (2) |
N10—C12—C13 | 122.2 (3) | C55—C51—C61 | 120.5 (2) |
N10—C12—H12 | 118.9 | N50—C52—C53 | 122.5 (3) |
C13—C12—H12 | 118.9 | N50—C52—H52 | 118.7 |
C14—C13—C12 | 120.2 (2) | C53—C52—H52 | 118.7 |
C14—C13—H13 | 119.9 | C54—C53—C52 | 120.3 (3) |
C12—C13—H13 | 119.9 | C54—C53—H53 | 119.8 |
C13—C14—C15 | 119.9 (2) | C52—C53—H53 | 119.8 |
C13—C14—H14 | 120.1 | C53—C54—C55 | 119.7 (3) |
C15—C14—H14 | 120.1 | C53—C54—H54 | 120.2 |
C11—C15—C14 | 116.3 (3) | C55—C54—H54 | 120.2 |
C11—C15—C16 | 119.0 (2) | C51—C55—C54 | 116.1 (3) |
C14—C15—C16 | 124.8 (2) | C51—C55—C56 | 119.0 (2) |
C26—C16—C15 | 120.5 (2) | C54—C55—C56 | 124.9 (3) |
C26—C16—C17 | 122.1 (3) | C66—C56—C55 | 120.5 (3) |
C15—C16—C17 | 117.4 (2) | C66—C56—C57 | 122.9 (3) |
C16—C17—H17A | 109.5 | C55—C56—C57 | 116.7 (3) |
C16—C17—H17B | 109.5 | C56—C57—H57A | 109.5 |
H17A—C17—H17B | 109.5 | C56—C57—H57B | 109.5 |
C16—C17—H17C | 109.5 | H57A—C57—H57B | 109.5 |
H17A—C17—H17C | 109.5 | C56—C57—H57C | 109.5 |
H17B—C17—H17C | 109.5 | H57A—C57—H57C | 109.5 |
N20—C21—C25 | 124.5 (2) | H57B—C57—H57C | 109.5 |
N20—C21—C11 | 115.2 (2) | N60—C61—C65 | 124.4 (2) |
C25—C21—C11 | 120.3 (2) | N60—C61—C51 | 115.6 (2) |
N20—C22—C23 | 121.8 (3) | C65—C61—C51 | 120.1 (2) |
N20—C22—H22 | 119.1 | N60—C62—C63 | 122.0 (3) |
C23—C22—H22 | 119.1 | N60—C62—H62 | 119.0 |
C24—C23—C22 | 120.5 (2) | C63—C62—H62 | 119.0 |
C24—C23—H23 | 119.8 | C64—C63—C62 | 120.4 (3) |
C22—C23—H23 | 119.8 | C64—C63—H63 | 119.8 |
C23—C24—C25 | 120.0 (3) | C62—C63—H63 | 119.8 |
C23—C24—H24 | 120.0 | C63—C64—C65 | 119.7 (3) |
C25—C24—H24 | 120.0 | C63—C64—H64 | 120.1 |
C21—C25—C24 | 115.7 (2) | C65—C64—H64 | 120.1 |
C21—C25—C26 | 119.6 (2) | C61—C65—C64 | 116.1 (3) |
C24—C25—C26 | 124.7 (3) | C61—C65—C66 | 119.5 (2) |
C16—C26—C25 | 120.2 (3) | C64—C65—C66 | 124.4 (3) |
C16—C26—C27 | 122.8 (3) | C56—C66—C65 | 120.3 (3) |
C25—C26—C27 | 117.1 (2) | C56—C66—C67 | 123.4 (3) |
C26—C27—H27A | 109.5 | C65—C66—C67 | 116.3 (3) |
C26—C27—H27B | 109.5 | C66—C67—H67A | 109.5 |
H27A—C27—H27B | 109.5 | C66—C67—H67B | 109.5 |
C26—C27—H27C | 109.5 | H67A—C67—H67B | 109.5 |
H27A—C27—H27C | 109.5 | C66—C67—H67C | 109.5 |
H27B—C27—H27C | 109.5 | H67A—C67—H67C | 109.5 |
N30—C31—C35 | 124.3 (3) | H67B—C67—H67C | 109.5 |
N30—C31—C41 | 115.2 (2) | C4—C1—C3 | 119.6 (3) |
C35—C31—C41 | 120.5 (2) | C4—C1—C2 | 119.9 (3) |
N30—C32—C33 | 121.9 (3) | C3—C1—C2 | 120.4 (3) |
N30—C32—H32 | 119.0 | N2—C2—C1 | 179.3 (4) |
C33—C32—H32 | 119.0 | N3—C3—C1 | 178.1 (4) |
C34—C33—C32 | 120.4 (3) | N4—C4—C1 | 179.2 (4) |
C34—C33—H33 | 119.8 | C7—C5—C8 | 120.0 (3) |
C32—C33—H33 | 119.8 | C7—C5—C6 | 119.8 (3) |
C33—C34—C35 | 119.8 (3) | C8—C5—C6 | 120.2 (3) |
C33—C34—H34 | 120.1 | N6—C6—C5 | 179.5 (4) |
C35—C34—H34 | 120.1 | N7—C7—C5 | 178.3 (4) |
C31—C35—C34 | 116.1 (3) | N8—C8—C5 | 179.3 (4) |
C31—C35—C36 | 119.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C52—H52···N30 | 0.95 | 2.59 | 3.070 (3) | 112 |
C22—H22···N40 | 0.95 | 2.59 | 3.089 (4) | 113 |
C32—H32···N8 | 0.95 | 2.43 | 3.266 (4) | 146 |
C42—H42···N60 | 0.95 | 2.57 | 3.056 (3) | 112 |
C22—H22···N6i | 0.95 | 2.54 | 3.271 (4) | 134 |
C12—H12···N2ii | 0.95 | 2.55 | 3.352 (4) | 142 |
C62—H62···N3iii | 0.95 | 2.51 | 3.266 (4) | 137 |
C44—H44···N7iv | 0.95 | 2.59 | 3.312 (4) | 133 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) −x, −y+1, −z; (iv) x−1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C14H12N2)3](C4N3)2 |
Mr | 860.76 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 183 |
a, b, c (Å) | 9.3676 (3), 12.7079 (9), 18.1998 (9) |
α, β, γ (°) | 75.458 (5), 89.623 (3), 82.323 (4) |
V (Å3) | 2077.52 (19) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.42 |
Crystal size (mm) | 0.66 × 0.25 × 0.03 |
Data collection | |
Diffractometer | Agilent Xcalibur (Sapphire2) |
Absorption correction | Analytical [CrysAlis PRO (Agilent, 2012), based on expressions derived by Clark & Reid (1995)] |
Tmin, Tmax | 0.874, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15408, 8167, 6309 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.125, 1.07 |
No. of reflections | 8167 |
No. of parameters | 574 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.92, −0.40 |
Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2001).
Fe1—N20 | 1.957 (2) | Fe1—N30 | 1.965 (2) |
Fe1—N10 | 1.959 (2) | Fe1—N50 | 1.967 (2) |
Fe1—N60 | 1.963 (2) | Fe1—N40 | 1.968 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C52—H52···N30 | 0.95 | 2.59 | 3.070 (3) | 111.6 |
C22—H22···N40 | 0.95 | 2.59 | 3.089 (4) | 112.7 |
C32—H32···N8 | 0.95 | 2.43 | 3.266 (4) | 146.2 |
C42—H42···N60 | 0.95 | 2.57 | 3.056 (3) | 112.1 |
C22—H22···N6i | 0.95 | 2.54 | 3.271 (4) | 134.3 |
C12—H12···N2ii | 0.95 | 2.55 | 3.352 (4) | 142.3 |
C62—H62···N3iii | 0.95 | 2.51 | 3.266 (4) | 136.7 |
C44—H44···N7iv | 0.95 | 2.59 | 3.312 (4) | 133.0 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) −x, −y+1, −z; (iv) x−1, y−1, z. |
Acknowledgements
This work was supported by the Slovak Research and Development Agency under contract No. APVV-0014–11 and by the internal P. J. Šafárik University grant system (VVGS-PF-2012–24 and VVGS 1/12–13).
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The iron(II) complexes [Fe(phen)2(NCS)2] and [Fe(bpy)2(NCS)2] (bpy = 2,2-bipyridine) belong to the first known and most extensively studied compounds of iron(II) exhibiting a high spin ←→ low spin transition (Müller et al., 1982; König & Watson, 1970). By far the majority of known spin-transition compounds are octahedral FeII compounds of general formula [Fe(L)4(NCX)2] or [Fe(L)2(NCX)2] (L = monodentate or bidentate N-donor ligands, X = S, Se). In our research, which is aimed on preparation of new [Fe(L)2(Y)2] compounds (L = bpy, phen or their derivatives and Y = pseudohalide anions (dicyanamide, or tcm)) with possible spin crossover, we prepared crystals of the title compound with composition [Fe(dimephen)3](tcm)2 (I) (dimephen = 5,6-dimethyl-1,10-phenanthroline).
Structural analysis showed that crystal structure of the title compound is ionic and consists of one complex cation and two tcm counter-anions (Fig. 1).
In the complex cation the FeII ion is bonded to three bidentate dimephen ligands through their nitrogen atoms resulting in a distorted octahedral arrangement with the six Fe1–N distances ranging from 1.957 (2) to 1.968 (2) Å (Table 1). These values as well as the values of N–Fe1–N bite angles (82.88 (9), 82.69 (9), 82.44 (9)°) and opposite (trans) angles (173.92 (9), 176.49 (9), 176.56 (9)°) are comparable to the corresponding distances and angles in other complexes with [Fe(phen)3]2+ cations (Aparici Plaza et al., 2007; Odoko & Okabe, 2004; Koh et al., 1994; Uçar et al., 2005; Li et al., 2008). All N–Fe1–N bond angles in (I) deviate significantly from the ideal values of 90 or 180° because of the constrained geometry of the dimephen ring systems. The values of bond distances and angles within the rings of neutral ligands are similar to those found in the similar [Cu(dimephen)3](PF6)2.CH3CN complex, too (Toledano-Magaña et al., 2012). The dimephen ligands in (I) are almost planar, the largest deviation of atom from the mean plane being 0.051 (3) Å for atom C63.
Both tcm anions are nearly planar, too (the largest deviations of atoms from the mean planes being 0.024 (3) for C1 atom and 0.015 (3) Å for C5 atom). The average C–C and C≡N bond lengths (1.404 (6) and 1.155 (3) Å, respectively), C–C–C (120.0 (3)°) and C–C≡N (179.0 (6)°) angles within the both anions are in good agreement with those found in other tricyanomethanide complexes (Potočňák et al., 2002; Luo et al., 2009).
The crystal packing in (I) is formed by weak C–H···N hydrogen bonds (Table 2) and C–N···Cg π-ring interactions. Weak hydrogen bonds occur between individual dimephen ligands and thus the structure of the cation is stabilized. Moreover, tcm anions interconnect two [Fe(dimephen)3]2+cations through hydrogen bonds and these interactions lead to infinite chain-like structure running along z axis (Fig. 2).
Except hydrogen bonds, the crystal structure is stabilized by π-ring interactions between nitrogen atoms from tcm anions and corresponding pyridine rings. The N2···Cg8i (i = x – 1, y, z) and N6···Cg7 distances (3.531 (3) and 3.726 (3) Å, respectively, Cg8 and Cg7 are centroids of pyridine rings with N50 and N40 atoms, respectively), the distances of N2 and N6 atoms to the planes of the corresponding dimephen rings (3.505 and 3.677 Å, respectively) as well as the C2≡N2···Cg8i and C6≡N6···Cg7 angles (96.4 (2) and 97.1 (2)°, respectively) are close to those found in similar FeII complexes (Váhovská & Potočňák, 2012). Parallel arrangement of tcm anions with dimephen molecules in (I) is shown in Fig. 3.