Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105021281/ob1231sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105021281/ob1231Isup2.hkl |
CCDC reference: 282178
TlPF6 (0.40 mmol) was added to a solution of [Fe(Cp)(P(OPh)3)(PMe3)(I)] (0.40 mmol) and 4-nitrobenzonitrile (0.72 mmol) in dichloromethane (40 ml) at room temperature. The mixture was stirred at room temperature for 22 h. A change was observed from dark brown to red, with simultaneous precipitation of thallium iodide. The red solution was filtered, evaporated under vacuum to dryness, and washed several times with diethyl ether and n-hexane to remove the excess of nitrile. The dark-red residue was further purified by vapour diffusion of diethyl ether into a concentrated dichloromethane solution, affording dark-red crystals of (I) (yield 47%; m.p. 435–436 K). Analysis, calculated for C33H33F6N2O5P3Fe: C 49.49, H 4.16, N 3.50%; found: C, 49.44, H 4.12, N 3.31%. Spectroscopic analysis: IR (KBr, cm-1): ν(N≡ C) 2221, ν(NO2) 1526 and 1345; 1H NMR (300 MHz, CD3COCD3, δ, p.p.m.): 1.85 (d, 9H, J = 9.0 Hz, PMe3), 4.64 (s, 5H, η5-C5H5), 7.23 [m, 3H, P(OPh)3:H-para], 7.34–7.42 [m, 12H, P(OPh)3:H-ortho and H-meta], 8.05 (d, 2H, J = 9.0 Hz, H2, H6), 8.41 (d, 2H, J = 9.0 Hz, H3, H5); 13C{1H} NMR (75 MHz, CD3COCD3, δ, p.p.m.): 18.85 (d, JCP = -29.8 Hz, PMe3), 81.69 (η5-C5H5), 118.29 (C1), 121.70 [d, JCP = 6.8 Hz, P(OPh)3:C-ortho], 125.28 (C3, C5), 126.17 [P(OPh)3:C-para], 131.00 [P(OPh)3:C-meta], 132.81 (NC), 135.00 (C2, C6), 152.44 [P(OPh)3:C-ipso], 152.59 (C4); 31P{1H} NMR (75 MHz, CD3COCD3, δ, p.p.m.): -144.05 (h, JPF = 704.4 Hz, PF6), 27.93 (d, JPP = 100.3 Hz, PMe3), 167.93 [d, JPP = 100.3 Hz, P(OPh)3]. During the NMR experiment, no sign of nitrile-ligand dissociation was found in deutero-acetone.
Methyl H atoms were positioned geometrically, with C—H = 0.96 Å and with torsion angles taken from the electron density, and were constrained. The H atoms of the Ph and Cp rings were also positioned geometrically, with C—H = 0.93 Å. For all H atoms, Uiso(H) = 1.2Ueq(C).
The design of new monocyclopentadienyl metal derivatives for application in materials science has engrossed scientists in recent years. Our interest in these compounds stems from their use as building blocks in a three-dimensional network, which would allow us to explore new variables for the engineering and development of new solids with potential nonlinear optical (NLO) applications. It is well known that molecular polarization is responsible for high values of molecular hyperpolarizability, so tailoring the building blocks by modifying either the metal centre or the ligand environment will change and possibly enhance the molecular polarization (Whittall et al., 1998; Nalwa, 1991; Goovaerts et al., 2001). With the aim of modifying the electronic richness of the metallic centre, we have recently studied a family of iron(II) complexes [Fe(Cp)(L)(L')(p-NCR)]BF4 [Cp is η5-cyclopentadienyl; L and L' are CO, P(OPh)3 or PPh3; R is C6H4NMe2, C6H4NO2, (E)-CH═CHC6H4NMe2 or (E)-CH═CHC6H4NO2], where the organometallic fragment has been systematically enriched or depleted by changing the ligands L and L' or substituting the η5-cyclopentadienyl ligand with η5-indenyl (Garcia, Robalo, Teixeira et al., 2001). Within these studies, we have synthesized and characterized the title novel complex, [Fe(Cp)(PMe3)(P(OPh)3)(4-NCC6H4NO2)]PF6, (I), and present its structural analysis here.
Complex (I) was synthesized by treatment of the precursor [Fe(Cp)(P(OPh)3)(PMe3)(I)] with TlPF6 and a slight excess of 4-nitrobenzonitrile in dichloromethane at room temperature. After work-up and recrystallization with dichloromethane–diethyl ether, complex (I) was obtained as dark-red crystals, fairly stable towards oxidation in air and moisture in both the solid state and solution. The formulation is supported by analytical data and IR and 1H, 13C and 31P NMR spectra. In the IR spectrum, the typical band ν(CN) at 2220 cm-1 showed a negative shift of 12 cm-1 compared with the uncoordinated nitrile, as observed previously for other analogous FeII compounds (Garcia, Robalo, Dias et al., 2001). Concerning the NMR data, we observed a doublet signal at 8.05 p.p.m. for the aromatic ortho H atoms of the nitrile ligand, which is slightly shielded when compared with the corresponding signal for the uncoordinated nitrile (8.13 p.p.m., in the same solvent). These spectroscopic data are consistent with a metal–nitrile interaction, described by a nitrile σ-type coordination with a small π back-donation contribution, owing to p-bonding between the metal d orbitals and the π* orbital of the CN group. The complex shows an intense broad visible absorption band at λmax = 435 nm in chloroform. This absorption could be attributable to d–π* metal-to-ligand charge-transfer (MLCT) transition from the Fe centre to the nitrile ligand. Such low-energy MLCT bands are typically associated with large molecular quadratic NLO responses (Garcia, Robalo, Dias et al., 2001; Garcia et al., 2002).
In the solid state, complex (I) crystallizes in the monoclinic centrosymmetric space group P21/c, thus destroying our hopes of obtaining dipole supramolecular alignment. The molecular structure of the cation is presented in Fig. 1. The coordination geometry can be described as a pseudo-octahedral three-legged piano stool, on the assumption that the cyclopentadienyl group takes up three coordination sites. This geometry, similar to that of other compounds of the same family (Garcia, Robalo, Teixeira et al., 2001), is confirmed by the angles around the metal centre, which are all close to 90° (Table 1), as well as by the remaining X—Fe—Cp(centroid) angles [P1—Fe1—Cp(centroid) 124.62 (6)°, P2—Fe1—Cp(centroid) 122.67 (6)°, N1—Fe1—Cp(centroid) 123.4 (1)°]. As expected, all angles involving the Cp centroid are considerably larger than those involving the phosphite, phosphine and nitrile ligands.
In this molecule, we can observe the well known contraction of the Fe—P bond when using a phosphite ligand instead of the phosphine. Thus, the observed value of 2.1206 (14) Å, shorter than that of the trimethylphosphine ligand [2.2332 (15) Å], can be attributed to the presence of the O as the α atom of the pendent groups on the triphenylphosphite. This value agrees with the values observed for Fe(phosphine) and Fe(phosphite) derivatives in the Cambridge Structural Database (CSD, Version?; Allen, 2002), presented in Table 3, where Fe—N and N≡C distances are also included for comparison.
The Fe—N distance [1.871 (4) Å] in (I) is somewhat shorter than that found in [Fe(Cp)(CO)(P(OPh)3)(4-NCC6H4NO2)]BF4 [1.878 (10) Å Garcia, Robalo, Teixeira et al., 2001], while it is very similar to that observed in [Fe(Cp)(dppe)(4-NCC6H4NO2)]PF6 [1.874 (11) Å; dppe is diphenylphosphphinoethane; Garcia, Robalo, Dias et al., 2001]. However, the N≡C bond [1.147 (6) Å] presents the same structural features as in the free nitrile [1.155 (15) Å; Higashi & Osaki, 1977], being somewhat longer [Please check amended text] than the equivalent bonds found in the complexes listed in Table 3. These values, altogether with the bond angles Fe1—N1≡C1 and N1≡C1—C2 [175.4 (4) and 173.7 (5)°], show that, in the solid state, the nitrile group departs somewhat from the expected linear geometry, and there is no evidence of any appreciable π back-donation contribution. These results confirm the spectroscopic data found for (I), since only a small π back-donation effect was noticed. According to this behaviour, which can be correlated with the donor ability of the metal centre, we can identify the [Fe(Cp)(PMe3)(P(OPh)3)]+ fragment as a weak π-donor towards the nitrile ligand when compared with other fragments (Table 3).
In recent publications, the importance of intermolecular interactions involving halogens, in particular F atoms, as a possible tool in crystal engineering has been studied in great detail (Chopra et al., 2005). The three-dimensional packing of (I) shows a supramolecular organometallic zigzag chain of aligned cations (of the same conformational isomer) in an up–down configuration, obtained via a network of C—H···Fδ- interactions (Table 2) involving the F atoms of the anions and H atoms of the nitrile [H7···F6i; symmetry code (i) 1 - x, -y, 1 - z], phosphine (H33A···F6i) and phosphite [H42···F5ii; symmetry code (ii) x, 1/2 - y, z - 1/2] (Fig. 2), generating in this way a one-dimensional chain along the b axis. We have taken into account the criteria used by Reichenbacher et al. (2005), where H···F distances up to 2.9 Å can be considered as weak intermolecular interactions. These interactions organize the complex cations in pairs through the spherical anion, in such a way that their dipole moments and second-order polarizabilities cancel. A weaker interaction of the type C—H···C(π), between a C atom of the phenyl attached to the nitrile and a phenyl H atom of the phosphite ligand [C34—H34···C4iii; symmetry code (iii) x, 1/2 - y, z + 1/2], gives rise to the formation of a two-dimensional aggregation of chains of different optical isomers of the complex cation parallel to the (101) plane.
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: XCAD4 (Harms & Wocadlo, 1995); data reduction: XCAD4; program(s) used to solve structure: SIR99 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Bruno et al., 2002); software used to prepare material for publication: WinGX (Farrugia, 1999), PLATON (Spek, 2003) and enCIFer (Allen et al., 2004).
[Fe(C5H5)(C7H4N2O2)(C3H9P)(C18H15O3P)]PF6 | F(000) = 1640 |
Mr = 800.37 | Dx = 1.510 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54180 Å |
a = 10.4938 (6) Å | Cell parameters from 25 reflections |
b = 18.9715 (7) Å | θ = 16–21° |
c = 17.8707 (11) Å | µ = 5.39 mm−1 |
β = 98.221 (5)° | T = 293 K |
V = 3521.2 (3) Å3 | Plate, red |
Z = 4 | 0.3 × 0.14 × 0.1 mm |
Enraf–Nonius Turbo CAD-4 diffractometer | 3926 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 69.8°, θmin = 3.4° |
ω/2θ scans | h = −12→12 |
Absorption correction: part of the refinement model (ΔF) (Parkin et al., 1995) | k = 0→23 |
Tmin = 0.276, Tmax = 0.583 | l = 0→21 |
6598 measured reflections | 3 standard reflections every 400 reflections |
6598 independent reflections | intensity decay: none |
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)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.150 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0514P)2 + 1.6778P] where P = (Fo2 + 2Fc2)/3 |
6598 reflections | (Δ/σ)max = 0.013 |
451 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
[Fe(C5H5)(C7H4N2O2)(C3H9P)(C18H15O3P)]PF6 | V = 3521.2 (3) Å3 |
Mr = 800.37 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 10.4938 (6) Å | µ = 5.39 mm−1 |
b = 18.9715 (7) Å | T = 293 K |
c = 17.8707 (11) Å | 0.3 × 0.14 × 0.1 mm |
β = 98.221 (5)° |
Enraf–Nonius Turbo CAD-4 diffractometer | 3926 reflections with I > 2σ(I) |
Absorption correction: part of the refinement model (ΔF) (Parkin et al., 1995) | Rint = 0.000 |
Tmin = 0.276, Tmax = 0.583 | 3 standard reflections every 400 reflections |
6598 measured reflections | intensity decay: none |
6598 independent reflections |
R[F2 > 2σ(F2)] = 0.064 | 0 restraints |
wR(F2) = 0.150 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.41 e Å−3 |
6598 reflections | Δρmin = −0.27 e Å−3 |
451 parameters |
Experimental. In the absorption correction, cubic fit to sin(theta)/lambda - 24 parameters. |
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. Dark-red crystals of {Fe(η5-cyclopentadienyl)(PMe3) [P(OPh)3](4-NCC6H4 NO2)}[PF6] crystallized in the monoclinic space group P21/c. All non hydrogen atoms were refined anisotropically. 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 | 0.14412 (7) | 0.04980 (4) | 0.32461 (4) | 0.0475 (2) | |
P1 | 0.02079 (11) | 0.12905 (7) | 0.27107 (7) | 0.0488 (3) | |
P2 | 0.06863 (12) | −0.03216 (7) | 0.24005 (7) | 0.0546 (3) | |
N1 | 0.2777 (4) | 0.0668 (2) | 0.2679 (2) | 0.0561 (10) | |
C1 | 0.3578 (5) | 0.0730 (3) | 0.2310 (3) | 0.0586 (13) | |
C2 | 0.4488 (4) | 0.0763 (3) | 0.1788 (3) | 0.0534 (12) | |
C3 | 0.4541 (5) | 0.1347 (3) | 0.1338 (3) | 0.0682 (15) | |
H3 | 0.4062 | 0.1746 | 0.1416 | 0.082* | |
C4 | 0.5308 (5) | 0.1342 (3) | 0.0769 (3) | 0.0715 (15) | |
H4 | 0.5349 | 0.1733 | 0.0460 | 0.086* | |
C5 | 0.5994 (5) | 0.0756 (3) | 0.0674 (3) | 0.0661 (15) | |
C6 | 0.6018 (6) | 0.0177 (4) | 0.1134 (3) | 0.0811 (17) | |
H6 | 0.6535 | −0.0209 | 0.1067 | 0.097* | |
C7 | 0.5252 (5) | 0.0185 (3) | 0.1700 (3) | 0.0756 (16) | |
H7 | 0.5250 | −0.0200 | 0.2022 | 0.091* | |
N2 | 0.6767 (6) | 0.0729 (4) | 0.0042 (4) | 0.103 (2) | |
O1 | 0.6596 (6) | 0.1191 (3) | −0.0426 (3) | 0.139 (2) | |
O2 | 0.7481 (7) | 0.0230 (4) | 0.0013 (4) | 0.177 (3) | |
O21 | −0.1314 (3) | 0.11250 (17) | 0.25229 (18) | 0.0558 (8) | |
C21 | −0.2235 (4) | 0.1292 (3) | 0.2994 (3) | 0.0560 (12) | |
C22 | −0.2608 (5) | 0.0789 (3) | 0.3462 (3) | 0.0672 (14) | |
H22 | −0.2236 | 0.0343 | 0.3487 | 0.081* | |
C23 | −0.3561 (5) | 0.0957 (4) | 0.3906 (3) | 0.0799 (18) | |
H23 | −0.3823 | 0.0621 | 0.4230 | 0.096* | |
C24 | −0.4112 (6) | 0.1615 (4) | 0.3866 (4) | 0.099 (2) | |
H24 | −0.4731 | 0.1730 | 0.4170 | 0.119* | |
C25 | −0.3737 (6) | 0.2100 (4) | 0.3370 (5) | 0.101 (2) | |
H25 | −0.4123 | 0.2543 | 0.3331 | 0.122* | |
C26 | −0.2799 (5) | 0.1943 (3) | 0.2932 (4) | 0.0803 (18) | |
H26 | −0.2552 | 0.2275 | 0.2598 | 0.096* | |
O31 | 0.0058 (3) | 0.20486 (16) | 0.3086 (2) | 0.0609 (9) | |
C31 | 0.0997 (5) | 0.2466 (2) | 0.3494 (3) | 0.0552 (12) | |
C32 | 0.2205 (5) | 0.2550 (3) | 0.3286 (4) | 0.0718 (16) | |
H32 | 0.2440 | 0.2310 | 0.2873 | 0.086* | |
C33 | 0.3058 (6) | 0.3004 (4) | 0.3711 (5) | 0.090 (2) | |
H33 | 0.3879 | 0.3070 | 0.3585 | 0.108* | |
C34 | 0.2696 (9) | 0.3349 (4) | 0.4309 (5) | 0.110 (3) | |
H34 | 0.3287 | 0.3642 | 0.4595 | 0.132* | |
C35 | 0.1506 (10) | 0.3282 (4) | 0.4504 (4) | 0.107 (3) | |
H35 | 0.1278 | 0.3534 | 0.4911 | 0.128* | |
C36 | 0.0622 (6) | 0.2831 (3) | 0.4090 (3) | 0.0755 (16) | |
H36 | −0.0203 | 0.2779 | 0.4215 | 0.091* | |
O41 | 0.0521 (3) | 0.14788 (17) | 0.18845 (18) | 0.0579 (9) | |
C41 | −0.0018 (4) | 0.2036 (3) | 0.1419 (3) | 0.0531 (12) | |
C42 | 0.0772 (5) | 0.2565 (3) | 0.1250 (3) | 0.0601 (13) | |
H42 | 0.1632 | 0.2571 | 0.1467 | 0.072* | |
C43 | 0.0298 (6) | 0.3085 (3) | 0.0761 (3) | 0.0680 (14) | |
H43 | 0.0836 | 0.3447 | 0.0646 | 0.082* | |
C44 | −0.0966 (5) | 0.3078 (3) | 0.0439 (3) | 0.0659 (14) | |
H44 | −0.1280 | 0.3431 | 0.0101 | 0.079* | |
C45 | −0.1762 (5) | 0.2557 (3) | 0.0611 (3) | 0.0776 (17) | |
H45 | −0.2625 | 0.2560 | 0.0400 | 0.093* | |
C46 | −0.1289 (5) | 0.2020 (3) | 0.1102 (3) | 0.0757 (17) | |
H46 | −0.1823 | 0.1655 | 0.1214 | 0.091* | |
C11 | 0.2058 (6) | −0.0242 (3) | 0.4098 (3) | 0.0687 (15) | |
H11 | 0.2344 | −0.0697 | 0.4019 | 0.082* | |
C12 | 0.2812 (6) | 0.0354 (3) | 0.4221 (3) | 0.0719 (16) | |
H12 | 0.3701 | 0.0366 | 0.4237 | 0.086* | |
C13 | 0.2037 (6) | 0.0939 (3) | 0.4319 (3) | 0.0739 (16) | |
H13 | 0.2310 | 0.1401 | 0.4409 | 0.089* | |
C14 | 0.0767 (6) | 0.0689 (3) | 0.4253 (3) | 0.0726 (16) | |
H14 | 0.0042 | 0.0960 | 0.4294 | 0.087* | |
C15 | 0.0776 (6) | −0.0034 (3) | 0.4115 (3) | 0.0703 (15) | |
H15 | 0.0059 | −0.0327 | 0.4046 | 0.084* | |
C311 | −0.0922 (5) | −0.0656 (3) | 0.2423 (3) | 0.0821 (18) | |
H31A | −0.1519 | −0.0270 | 0.2387 | 0.099* | |
H31B | −0.0947 | −0.0904 | 0.2889 | 0.099* | |
H31C | −0.1152 | −0.0972 | 0.2006 | 0.099* | |
C312 | 0.0599 (7) | −0.0093 (4) | 0.1406 (3) | 0.097 (2) | |
H32A | 0.0115 | 0.0334 | 0.1307 | 0.116* | |
H32B | 0.0183 | −0.0467 | 0.1101 | 0.116* | |
H32C | 0.1453 | −0.0027 | 0.1285 | 0.116* | |
C313 | 0.1621 (6) | −0.1120 (3) | 0.2461 (4) | 0.109 (3) | |
H33A | 0.2510 | −0.1007 | 0.2449 | 0.131* | |
H33B | 0.1315 | −0.1420 | 0.2041 | 0.131* | |
H33C | 0.1537 | −0.1359 | 0.2925 | 0.131* | |
P4 | 0.44533 (14) | 0.14138 (9) | 0.63252 (9) | 0.0706 (4) | |
F1 | 0.5735 (3) | 0.1836 (2) | 0.6412 (3) | 0.1420 (18) | |
F2 | 0.3157 (4) | 0.1000 (2) | 0.6222 (3) | 0.1456 (18) | |
F3 | 0.4887 (5) | 0.0968 (3) | 0.5679 (3) | 0.162 (2) | |
F4 | 0.3815 (4) | 0.1950 (2) | 0.5720 (3) | 0.1400 (17) | |
F5 | 0.3971 (5) | 0.1901 (4) | 0.6915 (3) | 0.191 (3) | |
F6 | 0.5094 (5) | 0.0868 (3) | 0.6888 (3) | 0.182 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0443 (4) | 0.0547 (4) | 0.0441 (4) | −0.0006 (4) | 0.0081 (3) | −0.0025 (4) |
P1 | 0.0414 (6) | 0.0522 (7) | 0.0539 (7) | −0.0031 (5) | 0.0103 (5) | −0.0010 (6) |
P2 | 0.0525 (7) | 0.0583 (8) | 0.0523 (7) | 0.0007 (6) | 0.0054 (6) | −0.0067 (6) |
N1 | 0.047 (2) | 0.068 (3) | 0.054 (2) | 0.001 (2) | 0.008 (2) | 0.001 (2) |
C1 | 0.048 (3) | 0.067 (3) | 0.061 (3) | −0.002 (2) | 0.006 (2) | −0.001 (3) |
C2 | 0.041 (3) | 0.067 (3) | 0.051 (3) | 0.001 (2) | 0.006 (2) | −0.001 (2) |
C3 | 0.053 (3) | 0.069 (4) | 0.084 (4) | 0.000 (3) | 0.013 (3) | −0.003 (3) |
C4 | 0.067 (3) | 0.080 (4) | 0.069 (4) | −0.007 (3) | 0.017 (3) | 0.011 (3) |
C5 | 0.051 (3) | 0.094 (4) | 0.056 (3) | −0.006 (3) | 0.018 (3) | −0.006 (3) |
C6 | 0.077 (4) | 0.091 (5) | 0.078 (4) | 0.021 (3) | 0.023 (3) | −0.003 (4) |
C7 | 0.076 (4) | 0.084 (4) | 0.071 (4) | 0.015 (3) | 0.024 (3) | 0.009 (3) |
N2 | 0.098 (5) | 0.141 (6) | 0.078 (4) | −0.018 (4) | 0.043 (4) | −0.008 (4) |
O1 | 0.174 (6) | 0.164 (6) | 0.093 (4) | −0.024 (4) | 0.066 (4) | 0.015 (4) |
O2 | 0.183 (6) | 0.220 (8) | 0.151 (5) | 0.069 (6) | 0.111 (5) | 0.018 (5) |
O21 | 0.0412 (17) | 0.064 (2) | 0.063 (2) | −0.0083 (15) | 0.0112 (15) | −0.0087 (17) |
C21 | 0.032 (2) | 0.069 (3) | 0.067 (3) | −0.002 (2) | 0.007 (2) | −0.002 (3) |
C22 | 0.054 (3) | 0.076 (4) | 0.073 (4) | −0.003 (3) | 0.011 (3) | 0.010 (3) |
C23 | 0.056 (3) | 0.117 (5) | 0.070 (4) | −0.020 (4) | 0.017 (3) | 0.002 (4) |
C24 | 0.063 (4) | 0.125 (6) | 0.118 (6) | −0.004 (4) | 0.041 (4) | −0.039 (5) |
C25 | 0.064 (4) | 0.090 (5) | 0.158 (7) | 0.017 (4) | 0.045 (4) | −0.006 (5) |
C26 | 0.059 (3) | 0.071 (4) | 0.116 (5) | 0.012 (3) | 0.031 (3) | 0.019 (4) |
O31 | 0.0465 (18) | 0.050 (2) | 0.087 (2) | −0.0023 (15) | 0.0090 (17) | −0.0117 (18) |
C31 | 0.061 (3) | 0.044 (3) | 0.058 (3) | −0.002 (2) | 0.001 (2) | 0.000 (2) |
C32 | 0.054 (3) | 0.058 (3) | 0.100 (4) | −0.003 (3) | 0.001 (3) | 0.002 (3) |
C33 | 0.059 (4) | 0.088 (5) | 0.116 (6) | −0.006 (3) | −0.011 (4) | 0.020 (4) |
C34 | 0.128 (7) | 0.090 (5) | 0.093 (6) | −0.025 (5) | −0.044 (5) | 0.015 (5) |
C35 | 0.189 (9) | 0.073 (5) | 0.055 (4) | −0.013 (6) | 0.003 (5) | −0.007 (3) |
C36 | 0.109 (5) | 0.060 (3) | 0.061 (3) | −0.002 (3) | 0.025 (3) | 0.003 (3) |
O41 | 0.0516 (19) | 0.065 (2) | 0.061 (2) | 0.0074 (16) | 0.0186 (16) | 0.0125 (17) |
C41 | 0.052 (3) | 0.061 (3) | 0.048 (3) | 0.003 (2) | 0.014 (2) | 0.004 (2) |
C42 | 0.051 (3) | 0.071 (3) | 0.059 (3) | −0.007 (3) | 0.013 (2) | 0.010 (3) |
C43 | 0.078 (4) | 0.067 (4) | 0.062 (3) | −0.005 (3) | 0.021 (3) | 0.008 (3) |
C44 | 0.076 (4) | 0.067 (4) | 0.057 (3) | 0.016 (3) | 0.017 (3) | 0.012 (3) |
C45 | 0.057 (3) | 0.103 (5) | 0.072 (4) | 0.004 (3) | 0.007 (3) | 0.020 (4) |
C46 | 0.055 (3) | 0.095 (5) | 0.075 (4) | −0.013 (3) | 0.002 (3) | 0.026 (3) |
C11 | 0.088 (4) | 0.059 (3) | 0.060 (3) | 0.014 (3) | 0.012 (3) | 0.013 (3) |
C12 | 0.064 (3) | 0.092 (5) | 0.054 (3) | −0.003 (3) | −0.009 (3) | 0.007 (3) |
C13 | 0.106 (5) | 0.057 (3) | 0.052 (3) | 0.002 (3) | −0.011 (3) | −0.007 (3) |
C14 | 0.070 (4) | 0.103 (5) | 0.046 (3) | 0.021 (3) | 0.013 (3) | −0.008 (3) |
C15 | 0.077 (4) | 0.087 (4) | 0.048 (3) | −0.019 (3) | 0.010 (3) | −0.001 (3) |
C311 | 0.074 (4) | 0.080 (4) | 0.093 (4) | −0.021 (3) | 0.015 (3) | −0.027 (3) |
C312 | 0.141 (6) | 0.096 (5) | 0.057 (4) | −0.034 (4) | 0.026 (4) | −0.020 (3) |
C313 | 0.099 (5) | 0.076 (4) | 0.140 (6) | 0.030 (4) | −0.024 (5) | −0.045 (4) |
P4 | 0.0552 (8) | 0.0793 (11) | 0.0773 (10) | 0.0055 (8) | 0.0089 (7) | 0.0028 (8) |
F1 | 0.072 (2) | 0.148 (4) | 0.198 (5) | −0.031 (3) | −0.008 (3) | 0.022 (4) |
F2 | 0.080 (3) | 0.131 (4) | 0.224 (5) | −0.031 (3) | 0.012 (3) | 0.024 (4) |
F3 | 0.156 (4) | 0.186 (5) | 0.152 (4) | 0.048 (4) | 0.049 (3) | −0.053 (4) |
F4 | 0.137 (4) | 0.121 (3) | 0.148 (4) | 0.016 (3) | −0.031 (3) | 0.039 (3) |
F5 | 0.158 (4) | 0.277 (7) | 0.147 (4) | 0.015 (5) | 0.048 (4) | −0.103 (5) |
F6 | 0.135 (4) | 0.212 (5) | 0.181 (5) | −0.001 (4) | −0.033 (4) | 0.129 (4) |
Fe1—N1 | 1.871 (4) | C32—H32 | 0.9300 |
Fe1—C15 | 2.055 (5) | C33—C34 | 1.354 (10) |
Fe1—C14 | 2.057 (5) | C33—H33 | 0.9300 |
Fe1—C13 | 2.102 (5) | C34—C35 | 1.350 (10) |
Fe1—C11 | 2.104 (5) | C34—H34 | 0.9300 |
Fe1—C12 | 2.112 (5) | C35—C36 | 1.393 (9) |
Fe1—P1 | 2.1206 (14) | C35—H35 | 0.9300 |
Fe1—P2 | 2.2332 (15) | C36—H36 | 0.9300 |
P1—O41 | 1.598 (3) | O41—C41 | 1.412 (5) |
P1—O31 | 1.604 (3) | C41—C42 | 1.362 (6) |
P1—O21 | 1.615 (3) | C41—C46 | 1.373 (6) |
P2—C313 | 1.800 (6) | C42—C43 | 1.365 (7) |
P2—C311 | 1.809 (5) | C42—H42 | 0.9300 |
P2—C312 | 1.819 (6) | C43—C44 | 1.368 (7) |
N1—C1 | 1.147 (6) | C43—H43 | 0.9300 |
C1—C2 | 1.429 (7) | C44—C45 | 1.357 (7) |
C2—C3 | 1.375 (7) | C44—H44 | 0.9300 |
C2—C7 | 1.381 (7) | C45—C46 | 1.390 (7) |
C3—C4 | 1.383 (7) | C45—H45 | 0.9300 |
C3—H3 | 0.9300 | C46—H46 | 0.9300 |
C4—C5 | 1.348 (7) | C11—C12 | 1.380 (7) |
C4—H4 | 0.9300 | C11—C15 | 1.407 (7) |
C5—C6 | 1.371 (8) | C11—H11 | 0.9300 |
C5—N2 | 1.483 (7) | C12—C13 | 1.401 (7) |
C6—C7 | 1.378 (7) | C12—H12 | 0.9300 |
C6—H6 | 0.9300 | C13—C14 | 1.403 (7) |
C7—H7 | 0.9300 | C13—H13 | 0.9300 |
N2—O1 | 1.208 (8) | C14—C15 | 1.393 (8) |
N2—O2 | 1.213 (8) | C14—H14 | 0.9300 |
O21—C21 | 1.407 (5) | C15—H15 | 0.9300 |
C21—C22 | 1.362 (7) | C311—H31A | 0.9600 |
C21—C26 | 1.367 (7) | C311—H31B | 0.9600 |
C22—C23 | 1.399 (7) | C311—H31C | 0.9600 |
C22—H22 | 0.9300 | C312—H32A | 0.9600 |
C23—C24 | 1.374 (9) | C312—H32B | 0.9600 |
C23—H23 | 0.9300 | C312—H32C | 0.9600 |
C24—C25 | 1.373 (9) | C313—H33A | 0.9600 |
C24—H24 | 0.9300 | C313—H33B | 0.9600 |
C25—C26 | 1.375 (8) | C313—H33C | 0.9600 |
C25—H25 | 0.9300 | P4—F6 | 1.531 (4) |
C26—H26 | 0.9300 | P4—F5 | 1.542 (5) |
O31—C31 | 1.387 (5) | P4—F3 | 1.551 (4) |
C31—C36 | 1.374 (7) | P4—F1 | 1.554 (4) |
C31—C32 | 1.381 (7) | P4—F2 | 1.559 (4) |
C32—C33 | 1.387 (8) | P4—F4 | 1.564 (4) |
N1—Fe1—C15 | 148.8 (2) | C35—C34—C33 | 122.1 (7) |
N1—Fe1—C14 | 145.2 (2) | C35—C34—H34 | 118.9 |
C15—Fe1—C14 | 39.6 (2) | C33—C34—H34 | 118.9 |
N1—Fe1—C13 | 106.1 (2) | C34—C35—C36 | 119.5 (7) |
C15—Fe1—C13 | 66.1 (2) | C34—C35—H35 | 120.3 |
C14—Fe1—C13 | 39.4 (2) | C36—C35—H35 | 120.3 |
N1—Fe1—C11 | 109.3 (2) | C31—C36—C35 | 118.6 (6) |
C15—Fe1—C11 | 39.5 (2) | C31—C36—H36 | 120.7 |
C14—Fe1—C11 | 66.0 (2) | C35—C36—H36 | 120.7 |
C13—Fe1—C11 | 65.5 (2) | C41—O41—P1 | 126.4 (3) |
N1—Fe1—C12 | 89.7 (2) | C42—C41—C46 | 120.7 (5) |
C15—Fe1—C12 | 65.1 (2) | C42—C41—O41 | 118.5 (4) |
C14—Fe1—C12 | 65.2 (2) | C46—C41—O41 | 120.6 (4) |
C13—Fe1—C12 | 38.8 (2) | C41—C42—C43 | 119.8 (5) |
C11—Fe1—C12 | 38.2 (2) | C41—C42—H42 | 120.1 |
N1—Fe1—P1 | 95.12 (13) | C43—C42—H42 | 120.1 |
C15—Fe1—P1 | 115.94 (18) | C42—C43—C44 | 120.3 (5) |
C14—Fe1—P1 | 90.34 (17) | C42—C43—H43 | 119.8 |
C13—Fe1—P1 | 102.25 (16) | C44—C43—H43 | 119.8 |
C11—Fe1—P1 | 154.76 (17) | C45—C44—C43 | 120.2 (5) |
C12—Fe1—P1 | 139.77 (18) | C45—C44—H44 | 119.9 |
N1—Fe1—P2 | 88.55 (13) | C43—C44—H44 | 119.9 |
C15—Fe1—P2 | 92.48 (17) | C44—C45—C46 | 120.0 (5) |
C14—Fe1—P2 | 125.53 (19) | C44—C45—H45 | 120.0 |
C13—Fe1—P2 | 157.55 (17) | C46—C45—H45 | 120.0 |
C11—Fe1—P2 | 93.86 (17) | C41—C46—C45 | 118.8 (5) |
C12—Fe1—P2 | 127.01 (18) | C41—C46—H46 | 120.6 |
P1—Fe1—P2 | 93.08 (5) | C45—C46—H46 | 120.6 |
O41—P1—O31 | 103.40 (19) | C12—C11—C15 | 107.1 (5) |
O41—P1—O21 | 100.32 (17) | C12—C11—Fe1 | 71.2 (3) |
O31—P1—O21 | 96.22 (17) | C15—C11—Fe1 | 68.4 (3) |
O41—P1—Fe1 | 112.49 (13) | C12—C11—H11 | 126.4 |
O31—P1—Fe1 | 122.45 (14) | C15—C11—H11 | 126.4 |
O21—P1—Fe1 | 118.52 (13) | Fe1—C11—H11 | 125.5 |
C313—P2—C311 | 101.9 (3) | C11—C12—C13 | 109.8 (5) |
C313—P2—C312 | 102.1 (3) | C11—C12—Fe1 | 70.6 (3) |
C311—P2—C312 | 100.9 (3) | C13—C12—Fe1 | 70.2 (3) |
C313—P2—Fe1 | 114.1 (2) | C11—C12—H12 | 125.1 |
C311—P2—Fe1 | 118.09 (19) | C13—C12—H12 | 125.1 |
C312—P2—Fe1 | 117.3 (2) | Fe1—C12—H12 | 125.7 |
C1—N1—Fe1 | 175.4 (4) | C12—C13—C14 | 106.5 (5) |
N1—C1—C2 | 173.7 (5) | C12—C13—Fe1 | 71.0 (3) |
C3—C2—C7 | 120.1 (5) | C14—C13—Fe1 | 68.5 (3) |
C3—C2—C1 | 120.3 (5) | C12—C13—H13 | 126.8 |
C7—C2—C1 | 119.5 (5) | C14—C13—H13 | 126.8 |
C2—C3—C4 | 120.0 (5) | Fe1—C13—H13 | 125.3 |
C2—C3—H3 | 120.0 | C15—C14—C13 | 108.5 (5) |
C4—C3—H3 | 120.0 | C15—C14—Fe1 | 70.2 (3) |
C5—C4—C3 | 118.4 (5) | C13—C14—Fe1 | 72.0 (3) |
C5—C4—H4 | 120.8 | C15—C14—H14 | 125.7 |
C3—C4—H4 | 120.8 | C13—C14—H14 | 125.7 |
C4—C5—C6 | 123.3 (5) | Fe1—C14—H14 | 123.7 |
C4—C5—N2 | 119.1 (6) | C14—C15—C11 | 108.1 (5) |
C6—C5—N2 | 117.6 (6) | C14—C15—Fe1 | 70.3 (3) |
C5—C6—C7 | 118.0 (6) | C11—C15—Fe1 | 72.1 (3) |
C5—C6—H6 | 121.0 | C14—C15—H15 | 125.9 |
C7—C6—H6 | 121.0 | C11—C15—H15 | 125.9 |
C6—C7—C2 | 120.0 (6) | Fe1—C15—H15 | 123.3 |
C6—C7—H7 | 120.0 | P2—C311—H31A | 109.5 |
C2—C7—H7 | 120.0 | P2—C311—H31B | 109.5 |
O1—N2—O2 | 124.7 (7) | H31A—C311—H31B | 109.5 |
O1—N2—C5 | 117.2 (7) | P2—C311—H31C | 109.5 |
O2—N2—C5 | 118.0 (7) | H31A—C311—H31C | 109.5 |
C21—O21—P1 | 125.2 (3) | H31B—C311—H31C | 109.5 |
C22—C21—C26 | 121.6 (5) | P2—C312—H32A | 109.5 |
C22—C21—O21 | 119.5 (5) | P2—C312—H32B | 109.5 |
C26—C21—O21 | 118.8 (5) | H32A—C312—H32B | 109.5 |
C21—C22—C23 | 118.6 (6) | P2—C312—H32C | 109.5 |
C21—C22—H22 | 120.7 | H32A—C312—H32C | 109.5 |
C23—C22—H22 | 120.7 | H32B—C312—H32C | 109.5 |
C24—C23—C22 | 120.5 (6) | P2—C313—H33A | 109.5 |
C24—C23—H23 | 119.7 | P2—C313—H33B | 109.5 |
C22—C23—H23 | 119.7 | H33A—C313—H33B | 109.5 |
C25—C24—C23 | 119.0 (6) | P2—C313—H33C | 109.5 |
C25—C24—H24 | 120.5 | H33A—C313—H33C | 109.5 |
C23—C24—H24 | 120.5 | H33B—C313—H33C | 109.5 |
C24—C25—C26 | 121.0 (6) | F6—P4—F5 | 96.5 (4) |
C24—C25—H25 | 119.5 | F6—P4—F3 | 88.4 (3) |
C26—C25—H25 | 119.5 | F5—P4—F3 | 175.1 (3) |
C21—C26—C25 | 119.1 (6) | F6—P4—F1 | 89.5 (3) |
C21—C26—H26 | 120.4 | F5—P4—F1 | 89.3 (3) |
C25—C26—H26 | 120.4 | F3—P4—F1 | 90.8 (3) |
C31—O31—P1 | 128.9 (3) | F6—P4—F2 | 91.7 (3) |
C36—C31—C32 | 121.8 (5) | F5—P4—F2 | 90.9 (3) |
C36—C31—O31 | 115.8 (5) | F3—P4—F2 | 88.9 (3) |
C32—C31—O31 | 122.3 (5) | F1—P4—F2 | 178.7 (3) |
C31—C32—C33 | 118.0 (6) | F6—P4—F4 | 177.4 (3) |
C31—C32—H32 | 121.0 | F5—P4—F4 | 86.1 (3) |
C33—C32—H32 | 121.0 | F3—P4—F4 | 89.0 (3) |
C34—C33—C32 | 120.1 (7) | F1—P4—F4 | 90.7 (3) |
C34—C33—H33 | 120.0 | F2—P4—F4 | 88.1 (2) |
C32—C33—H33 | 120.0 | ||
N1—Fe1—P1—O41 | 23.85 (19) | O31—C31—C36—C35 | −177.5 (5) |
C15—Fe1—P1—O41 | −159.2 (2) | C34—C35—C36—C31 | 0.2 (10) |
C14—Fe1—P1—O41 | 169.4 (2) | O31—P1—O41—C41 | −38.0 (4) |
C13—Fe1—P1—O41 | 131.5 (2) | O21—P1—O41—C41 | 61.0 (4) |
C11—Fe1—P1—O41 | −170.8 (4) | Fe1—P1—O41—C41 | −172.1 (3) |
C12—Fe1—P1—O41 | 119.4 (3) | P1—O41—C41—C42 | 115.0 (4) |
P2—Fe1—P1—O41 | −64.97 (15) | P1—O41—C41—C46 | −69.6 (6) |
N1—Fe1—P1—O31 | −100.2 (2) | C46—C41—C42—C43 | 0.2 (8) |
C15—Fe1—P1—O31 | 76.7 (2) | O41—C41—C42—C43 | 175.6 (4) |
C14—Fe1—P1—O31 | 45.3 (2) | C41—C42—C43—C44 | −0.2 (8) |
C13—Fe1—P1—O31 | 7.4 (2) | C42—C43—C44—C45 | 0.8 (8) |
C11—Fe1—P1—O31 | 65.1 (4) | C43—C44—C45—C46 | −1.5 (9) |
C12—Fe1—P1—O31 | −4.7 (3) | C42—C41—C46—C45 | −0.8 (8) |
P2—Fe1—P1—O31 | 170.94 (16) | O41—C41—C46—C45 | −176.1 (5) |
N1—Fe1—P1—O21 | 140.31 (19) | C44—C45—C46—C41 | 1.4 (9) |
C15—Fe1—P1—O21 | −42.8 (2) | N1—Fe1—C11—C12 | 63.0 (4) |
C14—Fe1—P1—O21 | −74.1 (2) | C15—Fe1—C11—C12 | −118.0 (5) |
C13—Fe1—P1—O21 | −112.0 (2) | C14—Fe1—C11—C12 | −79.8 (4) |
C11—Fe1—P1—O21 | −54.3 (4) | C13—Fe1—C11—C12 | −36.4 (4) |
C12—Fe1—P1—O21 | −124.1 (3) | P1—Fe1—C11—C12 | −101.6 (5) |
P2—Fe1—P1—O21 | 51.49 (15) | P2—Fe1—C11—C12 | 152.8 (3) |
N1—Fe1—P2—C313 | 73.7 (3) | N1—Fe1—C11—C15 | −179.0 (3) |
C15—Fe1—P2—C313 | −75.1 (3) | C14—Fe1—C11—C15 | 38.2 (3) |
C14—Fe1—P2—C313 | −98.6 (3) | C13—Fe1—C11—C15 | 81.6 (4) |
C13—Fe1—P2—C313 | −57.8 (6) | C12—Fe1—C11—C15 | 118.0 (5) |
C11—Fe1—P2—C313 | −35.5 (3) | P1—Fe1—C11—C15 | 16.4 (6) |
C12—Fe1—P2—C313 | −14.8 (4) | P2—Fe1—C11—C15 | −89.2 (3) |
P1—Fe1—P2—C313 | 168.8 (3) | C15—C11—C12—C13 | 0.2 (6) |
N1—Fe1—P2—C311 | −166.7 (3) | Fe1—C11—C12—C13 | 59.4 (4) |
C15—Fe1—P2—C311 | 44.5 (3) | C15—C11—C12—Fe1 | −59.2 (4) |
C14—Fe1—P2—C311 | 21.0 (3) | N1—Fe1—C12—C11 | −122.8 (4) |
C13—Fe1—P2—C311 | 61.7 (5) | C15—Fe1—C12—C11 | 38.3 (3) |
C11—Fe1—P2—C311 | 84.1 (3) | C14—Fe1—C12—C11 | 82.1 (4) |
C12—Fe1—P2—C311 | 104.8 (3) | C13—Fe1—C12—C11 | 120.6 (5) |
P1—Fe1—P2—C311 | −71.6 (2) | P1—Fe1—C12—C11 | 139.7 (3) |
N1—Fe1—P2—C312 | −45.6 (3) | P2—Fe1—C12—C11 | −34.8 (4) |
C15—Fe1—P2—C312 | 165.6 (3) | N1—Fe1—C12—C13 | 116.6 (4) |
C14—Fe1—P2—C312 | 142.1 (3) | C15—Fe1—C12—C13 | −82.3 (4) |
C13—Fe1—P2—C312 | −177.2 (5) | C14—Fe1—C12—C13 | −38.5 (4) |
C11—Fe1—P2—C312 | −154.8 (3) | C11—Fe1—C12—C13 | −120.6 (5) |
C12—Fe1—P2—C312 | −134.1 (3) | P1—Fe1—C12—C13 | 19.1 (5) |
P1—Fe1—P2—C312 | 49.5 (3) | P2—Fe1—C12—C13 | −155.4 (3) |
C15—Fe1—N1—C1 | 73 (5) | C11—C12—C13—C14 | 0.0 (6) |
C14—Fe1—N1—C1 | 149 (5) | Fe1—C12—C13—C14 | 59.6 (4) |
C13—Fe1—N1—C1 | 143 (5) | C11—C12—C13—Fe1 | −59.6 (4) |
C11—Fe1—N1—C1 | 74 (5) | N1—Fe1—C13—C12 | −68.5 (4) |
C12—Fe1—N1—C1 | 107 (5) | C15—Fe1—C13—C12 | 79.3 (4) |
P1—Fe1—N1—C1 | −113 (5) | C14—Fe1—C13—C12 | 117.2 (5) |
P2—Fe1—N1—C1 | −20 (5) | C11—Fe1—C13—C12 | 35.8 (3) |
Fe1—N1—C1—C2 | 34 (10) | P1—Fe1—C13—C12 | −167.5 (3) |
N1—C1—C2—C3 | 97 (5) | P2—Fe1—C13—C12 | 60.5 (7) |
N1—C1—C2—C7 | −79 (5) | N1—Fe1—C13—C14 | 174.3 (3) |
C7—C2—C3—C4 | 3.5 (8) | C15—Fe1—C13—C14 | −37.9 (3) |
C1—C2—C3—C4 | −172.0 (5) | C11—Fe1—C13—C14 | −81.4 (4) |
C2—C3—C4—C5 | −0.3 (8) | C12—Fe1—C13—C14 | −117.2 (5) |
C3—C4—C5—C6 | −3.1 (9) | P1—Fe1—C13—C14 | 75.3 (3) |
C3—C4—C5—N2 | 176.8 (5) | P2—Fe1—C13—C14 | −56.8 (6) |
C4—C5—C6—C7 | 3.2 (9) | C12—C13—C14—C15 | −0.2 (6) |
N2—C5—C6—C7 | −176.8 (5) | Fe1—C13—C14—C15 | 61.0 (4) |
C5—C6—C7—C2 | 0.2 (9) | C12—C13—C14—Fe1 | −61.2 (4) |
C3—C2—C7—C6 | −3.5 (8) | N1—Fe1—C14—C15 | −127.7 (4) |
C1—C2—C7—C6 | 172.0 (5) | C13—Fe1—C14—C15 | −118.1 (5) |
C4—C5—N2—O1 | −10.7 (9) | C11—Fe1—C14—C15 | −38.1 (3) |
C6—C5—N2—O1 | 169.2 (6) | C12—Fe1—C14—C15 | −80.2 (4) |
C4—C5—N2—O2 | 172.4 (7) | P1—Fe1—C14—C15 | 132.8 (3) |
C6—C5—N2—O2 | −7.6 (10) | P2—Fe1—C14—C15 | 38.7 (4) |
O41—P1—O21—C21 | −143.9 (4) | N1—Fe1—C14—C13 | −9.6 (6) |
O31—P1—O21—C21 | −39.0 (4) | C15—Fe1—C14—C13 | 118.1 (5) |
Fe1—P1—O21—C21 | 93.3 (4) | C11—Fe1—C14—C13 | 80.0 (4) |
P1—O21—C21—C22 | −97.0 (5) | C12—Fe1—C14—C13 | 37.9 (3) |
P1—O21—C21—C26 | 87.4 (5) | P1—Fe1—C14—C13 | −109.1 (3) |
C26—C21—C22—C23 | −2.2 (8) | P2—Fe1—C14—C13 | 156.9 (3) |
O21—C21—C22—C23 | −177.6 (4) | C13—C14—C15—C11 | 0.3 (6) |
C21—C22—C23—C24 | 0.3 (9) | Fe1—C14—C15—C11 | 62.5 (4) |
C22—C23—C24—C25 | 1.6 (10) | C13—C14—C15—Fe1 | −62.2 (4) |
C23—C24—C25—C26 | −1.7 (11) | C12—C11—C15—C14 | −0.3 (6) |
C22—C21—C26—C25 | 2.1 (9) | Fe1—C11—C15—C14 | −61.4 (4) |
O21—C21—C26—C25 | 177.5 (5) | C12—C11—C15—Fe1 | 61.0 (4) |
C24—C25—C26—C21 | −0.1 (10) | N1—Fe1—C15—C14 | 119.4 (5) |
O41—P1—O31—C31 | −89.1 (4) | C13—Fe1—C15—C14 | 37.7 (3) |
O21—P1—O31—C31 | 168.7 (4) | C11—Fe1—C15—C14 | 117.6 (5) |
Fe1—P1—O31—C31 | 39.0 (5) | C12—Fe1—C15—C14 | 80.5 (4) |
P1—O31—C31—C36 | −142.9 (4) | P1—Fe1—C15—C14 | −54.7 (4) |
P1—O31—C31—C32 | 41.4 (7) | P2—Fe1—C15—C14 | −149.4 (3) |
C36—C31—C32—C33 | 1.8 (8) | N1—Fe1—C15—C11 | 1.8 (6) |
O31—C31—C32—C33 | 177.2 (5) | C14—Fe1—C15—C11 | −117.6 (5) |
C31—C32—C33—C34 | −0.1 (9) | C13—Fe1—C15—C11 | −79.8 (4) |
C32—C33—C34—C35 | −1.5 (11) | C12—Fe1—C15—C11 | −37.0 (3) |
C33—C34—C35—C36 | 1.5 (12) | P1—Fe1—C15—C11 | −172.3 (3) |
C32—C31—C36—C35 | −1.8 (8) | P2—Fe1—C15—C11 | 93.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···F6i | 0.93 | 2.39 | 3.278 (8) | 159 |
C313—H33A···F6i | 0.96 | 2.64 | 3.510 (8) | 152 |
C42—H42···F5ii | 0.93 | 2.67 | 3.546 (7) | 157 |
C34—H34···C4iii | 0.93 | 2.76 | 3.55 (1) | 143 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z−1/2; (iii) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C5H5)(C7H4N2O2)(C3H9P)(C18H15O3P)]PF6 |
Mr | 800.37 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.4938 (6), 18.9715 (7), 17.8707 (11) |
β (°) | 98.221 (5) |
V (Å3) | 3521.2 (3) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 5.39 |
Crystal size (mm) | 0.3 × 0.14 × 0.1 |
Data collection | |
Diffractometer | Enraf–Nonius Turbo CAD-4 |
Absorption correction | Part of the refinement model (ΔF) (Parkin et al., 1995) |
Tmin, Tmax | 0.276, 0.583 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6598, 6598, 3926 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.064, 0.150, 1.08 |
No. of reflections | 6598 |
No. of parameters | 451 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.27 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), XCAD4, SIR99 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and Mercury (Bruno et al., 2002), WinGX (Farrugia, 1999), PLATON (Spek, 2003) and enCIFer (Allen et al., 2004).
Fe1—N1 | 1.871 (4) | P1—O21 | 1.615 (3) |
Fe1—C15 | 2.055 (5) | P2—C313 | 1.800 (6) |
Fe1—C14 | 2.057 (5) | P2—C311 | 1.809 (5) |
Fe1—C13 | 2.102 (5) | P2—C312 | 1.819 (6) |
Fe1—C11 | 2.104 (5) | N1—C1 | 1.147 (6) |
Fe1—C12 | 2.112 (5) | C1—C2 | 1.429 (7) |
Fe1—P1 | 2.1206 (14) | C5—N2 | 1.483 (7) |
Fe1—P2 | 2.2332 (15) | N2—O1 | 1.208 (8) |
P1—O41 | 1.598 (3) | N2—O2 | 1.213 (8) |
P1—O31 | 1.604 (3) | ||
N1—Fe1—P1 | 95.12 (13) | C1—N1—Fe1 | 175.4 (4) |
N1—Fe1—P2 | 88.55 (13) | N1—C1—C2 | 173.7 (5) |
P1—Fe1—P2 | 93.08 (5) | ||
C4—C5—N2—O1 | −10.7 (9) | C4—C5—N2—O2 | 172.4 (7) |
C6—C5—N2—O1 | 169.2 (6) | C6—C5—N2—O2 | −7.6 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···F6i | 0.93 | 2.39 | 3.278 (8) | 159 |
C313—H33A···F6i | 0.96 | 2.64 | 3.510 (8) | 152 |
C42—H42···F5ii | 0.93 | 2.67 | 3.546 (7) | 157 |
C34—H34···C4iii | 0.93 | 2.76 | 3.55 (1) | 143 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z−1/2; (iii) x, −y+1/2, z+1/2. |
Compound | Fe—PPPh | Fe—PPOPh | Fe—N | N≡C |
[Fe(Cp)(dppe)(NCCH3)]BPh4a | 2.205 | 1.881 | 1.137 | |
2.194 | ||||
[Fe(Cp)(dppm)(NCCH3)]PF6b | 2.196 | 1.892 | 1.135 | |
2.207 | ||||
[Fe(acetyl-Cp)(dppe)(NCCH3)]PF6c | 2.207 | 1.895 | 1.126 | |
2.232 | ||||
[Fe(Cp*)(dppe)(NCCH3)]PF6d | 2.218 | 1.905 | 1.133 | |
2.237 | ||||
[Fe(Cp)(P(OPh)3)2(NCCH3)]PF6e | 2.143 | 1.918 | 1.132 | |
2.165 | ||||
[Fe(Cp)(P(OMe)3)2(NCCH3)]PF6f | 2.175 | 1.924 | 1.094 | |
2.182 | ||||
[Fe(Cp)(dppe)(NCPhNO2)]PF6, (II) | 2.209 (3) | 1.874 (11) | 1.129 (14) | |
2.210 (4) | ||||
[Fe(Cp)(CO)(P(OPh)3)(NCPhNO2)]BF4, (III) | 2.159 (3) | 1.878 (10) | 1.139 (14) | |
[Fe(Ind)(CO)(P(OPh)3)(NCPhNO2)]BF4 g | 2.139 (3) | 1.900 (8) | 1.155 (12) | |
[Fe(Cp)(dppp)(NCPhNO2)]PF6, (IV) | 2.211 (3) | 1.902 (9) | 1.141 (15) | |
2.219 (3) | ||||
[Fe(Cp)(PMe3)(P(OPh)3)(NCPhNO2)]PF6, (I) | 2.233 (2) | 2.121 (1) | 1.871 (4) | 1.147 (6) |
p-NCPhNO2, (V) | 1.155 (15) |
References: (I) this work; (II) Garcia, Robalo, Dias et al. (2001); (III)
Garcia, Robalo, Teixeira et al. (2001); (IV) Wenseleers et al.,
2003); (V) Higashi & Osaki (1977). Notes: geometrical parameters taken from the Cambridge Structural Database are indicated without their s.u. values. Refcodes: (a) PEACFE, (b) VEBSIE, (c) KEJPOE, (d) KICNIT, (e) XATDUR, (f) JIPYAI, (g) QUSPOJ. Please provide references for CSD refcodes. |
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The design of new monocyclopentadienyl metal derivatives for application in materials science has engrossed scientists in recent years. Our interest in these compounds stems from their use as building blocks in a three-dimensional network, which would allow us to explore new variables for the engineering and development of new solids with potential nonlinear optical (NLO) applications. It is well known that molecular polarization is responsible for high values of molecular hyperpolarizability, so tailoring the building blocks by modifying either the metal centre or the ligand environment will change and possibly enhance the molecular polarization (Whittall et al., 1998; Nalwa, 1991; Goovaerts et al., 2001). With the aim of modifying the electronic richness of the metallic centre, we have recently studied a family of iron(II) complexes [Fe(Cp)(L)(L')(p-NCR)]BF4 [Cp is η5-cyclopentadienyl; L and L' are CO, P(OPh)3 or PPh3; R is C6H4NMe2, C6H4NO2, (E)-CH═CHC6H4NMe2 or (E)-CH═CHC6H4NO2], where the organometallic fragment has been systematically enriched or depleted by changing the ligands L and L' or substituting the η5-cyclopentadienyl ligand with η5-indenyl (Garcia, Robalo, Teixeira et al., 2001). Within these studies, we have synthesized and characterized the title novel complex, [Fe(Cp)(PMe3)(P(OPh)3)(4-NCC6H4NO2)]PF6, (I), and present its structural analysis here.
Complex (I) was synthesized by treatment of the precursor [Fe(Cp)(P(OPh)3)(PMe3)(I)] with TlPF6 and a slight excess of 4-nitrobenzonitrile in dichloromethane at room temperature. After work-up and recrystallization with dichloromethane–diethyl ether, complex (I) was obtained as dark-red crystals, fairly stable towards oxidation in air and moisture in both the solid state and solution. The formulation is supported by analytical data and IR and 1H, 13C and 31P NMR spectra. In the IR spectrum, the typical band ν(CN) at 2220 cm-1 showed a negative shift of 12 cm-1 compared with the uncoordinated nitrile, as observed previously for other analogous FeII compounds (Garcia, Robalo, Dias et al., 2001). Concerning the NMR data, we observed a doublet signal at 8.05 p.p.m. for the aromatic ortho H atoms of the nitrile ligand, which is slightly shielded when compared with the corresponding signal for the uncoordinated nitrile (8.13 p.p.m., in the same solvent). These spectroscopic data are consistent with a metal–nitrile interaction, described by a nitrile σ-type coordination with a small π back-donation contribution, owing to p-bonding between the metal d orbitals and the π* orbital of the CN group. The complex shows an intense broad visible absorption band at λmax = 435 nm in chloroform. This absorption could be attributable to d–π* metal-to-ligand charge-transfer (MLCT) transition from the Fe centre to the nitrile ligand. Such low-energy MLCT bands are typically associated with large molecular quadratic NLO responses (Garcia, Robalo, Dias et al., 2001; Garcia et al., 2002).
In the solid state, complex (I) crystallizes in the monoclinic centrosymmetric space group P21/c, thus destroying our hopes of obtaining dipole supramolecular alignment. The molecular structure of the cation is presented in Fig. 1. The coordination geometry can be described as a pseudo-octahedral three-legged piano stool, on the assumption that the cyclopentadienyl group takes up three coordination sites. This geometry, similar to that of other compounds of the same family (Garcia, Robalo, Teixeira et al., 2001), is confirmed by the angles around the metal centre, which are all close to 90° (Table 1), as well as by the remaining X—Fe—Cp(centroid) angles [P1—Fe1—Cp(centroid) 124.62 (6)°, P2—Fe1—Cp(centroid) 122.67 (6)°, N1—Fe1—Cp(centroid) 123.4 (1)°]. As expected, all angles involving the Cp centroid are considerably larger than those involving the phosphite, phosphine and nitrile ligands.
In this molecule, we can observe the well known contraction of the Fe—P bond when using a phosphite ligand instead of the phosphine. Thus, the observed value of 2.1206 (14) Å, shorter than that of the trimethylphosphine ligand [2.2332 (15) Å], can be attributed to the presence of the O as the α atom of the pendent groups on the triphenylphosphite. This value agrees with the values observed for Fe(phosphine) and Fe(phosphite) derivatives in the Cambridge Structural Database (CSD, Version?; Allen, 2002), presented in Table 3, where Fe—N and N≡C distances are also included for comparison.
The Fe—N distance [1.871 (4) Å] in (I) is somewhat shorter than that found in [Fe(Cp)(CO)(P(OPh)3)(4-NCC6H4NO2)]BF4 [1.878 (10) Å Garcia, Robalo, Teixeira et al., 2001], while it is very similar to that observed in [Fe(Cp)(dppe)(4-NCC6H4NO2)]PF6 [1.874 (11) Å; dppe is diphenylphosphphinoethane; Garcia, Robalo, Dias et al., 2001]. However, the N≡C bond [1.147 (6) Å] presents the same structural features as in the free nitrile [1.155 (15) Å; Higashi & Osaki, 1977], being somewhat longer [Please check amended text] than the equivalent bonds found in the complexes listed in Table 3. These values, altogether with the bond angles Fe1—N1≡C1 and N1≡C1—C2 [175.4 (4) and 173.7 (5)°], show that, in the solid state, the nitrile group departs somewhat from the expected linear geometry, and there is no evidence of any appreciable π back-donation contribution. These results confirm the spectroscopic data found for (I), since only a small π back-donation effect was noticed. According to this behaviour, which can be correlated with the donor ability of the metal centre, we can identify the [Fe(Cp)(PMe3)(P(OPh)3)]+ fragment as a weak π-donor towards the nitrile ligand when compared with other fragments (Table 3).
In recent publications, the importance of intermolecular interactions involving halogens, in particular F atoms, as a possible tool in crystal engineering has been studied in great detail (Chopra et al., 2005). The three-dimensional packing of (I) shows a supramolecular organometallic zigzag chain of aligned cations (of the same conformational isomer) in an up–down configuration, obtained via a network of C—H···Fδ- interactions (Table 2) involving the F atoms of the anions and H atoms of the nitrile [H7···F6i; symmetry code (i) 1 - x, -y, 1 - z], phosphine (H33A···F6i) and phosphite [H42···F5ii; symmetry code (ii) x, 1/2 - y, z - 1/2] (Fig. 2), generating in this way a one-dimensional chain along the b axis. We have taken into account the criteria used by Reichenbacher et al. (2005), where H···F distances up to 2.9 Å can be considered as weak intermolecular interactions. These interactions organize the complex cations in pairs through the spherical anion, in such a way that their dipole moments and second-order polarizabilities cancel. A weaker interaction of the type C—H···C(π), between a C atom of the phenyl attached to the nitrile and a phenyl H atom of the phosphite ligand [C34—H34···C4iii; symmetry code (iii) x, 1/2 - y, z + 1/2], gives rise to the formation of a two-dimensional aggregation of chains of different optical isomers of the complex cation parallel to the (101) plane.