Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615022512/uk3123sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615022512/uk3123Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615022512/uk3123IIsup3.hkl |
CCDC references: 1438745; 1438744
In 1970, ferrocenyl-containing acrylate polymers made their debut (Pittman, 2005) and ignited an interest in metallocene polymers that continues today (Hudson, 2001; McAdam et al., 2008; Herbert et al., 2009; Abd-El-Aziz et al., 2010; Elbert et al., 2013). Our interest is the preparation of electroactive polymers due to the possibility that they offer a muscle-like response (Hara et al., 2004; Goswami et al., 2013). For gel systems, in particular, very large volume changes are possible, associated with the influx or egress of solvent. Our choice of the ferrocenyl moiety to provide the redox-active group in these materials is based on the physical and electrochemical stability of the neutral and oxidized forms of this redox centre, and a comprehensive and versatile synthetic chemistry (Cuffe et al., 2005). However, scale-up of small-molecule chemistry to larger and `workable' gel assemblies provides special challenges. Principal among these is the need for multigram scale synthesis of starting materials. Hydroxymethylferrocene and 1,1'-bis(hydroxymethyl)ferrocene are synthesized in one simple step from commercially available ferrocenecarbaldehyde and ferrocene, respectively. Condensation of these with methacryloyl chloride generates the simple ferrocenylmethyl methacrylate monomer, (I) (Pittman et al., 1970), and the crosslinker ferrocene-1,1'-diylbis(methylene), (II) (Tsubakiyama et al., 1979).
Compound (I) was prepared in 70% yield using the methodology of Suzaki & Osakada (2007) by the condensation of hydroxymethylferrocene with methacryloyl chloride using CH2Cl2/triethylamine as the solvent/base system. Compound (II) was synthesized in a similar manner from 1,1'-bis(hydroxymethyl)ferrocene. X-ray-quality crystals were obtained from toluene layered with hexane in each case.
For (I), 1H NMR: δ 6.10 (m, 1H, CMe═CHtrans), 5.55 (m, 1H, CMe═CHcis), 4.96 (s, 2H, CH2O), 4.30 (m, 2H, Fc—H)], 4.18 (m, 2H + 5H, Fc—H), 1.94 (m, 3H, CH3).
For (II), 1H NMR: δ 6.10 (m, 2H, CMe═CHtrans), 5.56 (quin, J = 1.5 Hz, 2H, CMe═CHcis), 4.95 (s, 4H, CH2O), 4.29 and 4.18 [2 × (t, J = 1.8 Hz, 4H, Fc—H)], 1.94 (t, J = 1.2 Hz, 6H, CH3).
Crystal data, data collection and structure refinement details are summarized in Table 1. A l l H atoms were refined using a riding model, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aromatic and vinyl groups, C—H = 0.99 Å and Uiso(H) = 1.2Ueq(C) for CH2 groups, and C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for CH3 groups. The methyl H atoms in (II) were disordered equally over two sites. These H atoms were placed in calculated positions, with the two sites rotated by 60° from one another, and with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C).
The molecular structures of (I) with one methyl methacrylate unit and (II) with two methyl methacrylate unitss, one on each Cp ring, are shown in Figs. 1(a) and 1(b),respectively. The Cp rings of the central ferrocenyl group are effectively coplanar, being inclined to one another at an angle of 2.43 (9)° for (I) and 0.65 (5)° for (II). The methyl methacrylate residues are also remarkably planar, with r.m.s. deviations from the planes through all seven non-H atoms of 0.04 Å for (I), and this plane is almost orthogonal to the substituted cyclopentadienyl ring plane with a dihedral angle of 82.32 (4)°. The corresponding methyl methacrylate residues in bis-compound (II) are similarly planar, with r.m.s. deviations of 0.08 and 0.04 Å for the 1- and 1'-substituents, respectively. They also are roughly orthogonal to the rings to which they are attached, with dihedral angles 72.28 (4) and 71.48 (4)°.
While the Cp rings in (I) are almost perfectly eclipsed, with a mean C···Cg11···Cg12···C angle of 0.7 (1)° [Cg11 and Cg12 are the centroids of the C1–C5 and C11–C15 Cp rings, respectively, of (I)], those in (II) are slightly staggered and the mean angle is 11.1 (2)°. Importantly, in this latter system, the methyl methacrylate substituents are located on opposite sides of the ferrocenyl rings, with a C6···Cg21···Cg22···C16 angle of approximately 157° [Cg21 and Cg22 are the centroids of the C1–C5 and C11–C15 Cp rings, respectively, of (II)]. This geometry of the ring substituents contrasts sharply with that of its acrylate analogue [ferrocene-1,1'-diylbis(methylene) dicrylate; Cambridge Structural Database (CSD, Version 5.36, with 3 updates; Groom & Allen, 2014) refcode UDUJAF (Suzaki & Osakada, 2007)], wherein the FeII atom lies on a crystallographic twofold axis and the methyl acrylate substituents are almost eclipsed, the corresponding torsion angle being 8.1°.
A survey of the CSD revelas more than 100 methacrylate structures (see, for example: Shklover et al., 1990; Zhang & Zhang, 2011; Spirlet et al., 2000; Wendicke et al., 2003). Only one structure is reported with both ferrocenyl and methacrylate residues (Abd-El-Aziz et al., 2012). If structures with a `free' methacrylate group are considered, i.e. structures with a metal atom coordinated to the alkene group or the O atoms of the methacrylate functional group are excluded, there are 94 observations of methacrylate torsional geometry. These results show a preference for an s-trans arrangement [Vista (Groom & Allen, 2014) results: 58 for s-trans and 36 s-cis] of the vinyl and carbonyl groups (Fig. 2). Both the methacrylate group of (I) and the two unique methacrylate groups of (II) have an s-trans configuration for the C═C and C═O residues. The analogous survey of acrylate structures finds this preference is reversed (Vista results: 83 observations, with 57 for s-cis and 26 for s-trans). The structure of UDUJAF has an s-cis configuration of the acrylate residues (Suzaki & Osakada, 2007).
Only four simple ferrocenylmethyl esters have been described previously (Suzaki & Osakada, 2007; Nakatsuji et al., 2013), however, more complex biferrocene (Dong et al., 1997) and 1,2-substituted examples have been reported (Stepnicka & Cisarova, 2002; Pérez et al., 2012). Interestingly, of the reported methacrylate structures, only ten display a C—H···π(alkene) contact similar to that observed for (I) (see, for example: Hirano et al., 2002; Banwell et al., 2003; Wu et al., 2011; El Aziz et al., 2012; Kong et al., 2012), but none of these reports detailed this contact.
In the crystal lattice of (I), a double chain of molecules extending along c is generated by C12—H12···Cg12 e dge-to- face contacts (Cg12 is the centroid of the unsubstituted Cp ring) bolstered by C—H···O contacts in which the carbonyl O7 atom acts as a bifurcated acceptor forming weak C11—H11···O7 and C10—H10C···O7 hydrogen bonds (Table 2) to generate a zigzag chain motif. An equivalent but inverted double chain is linked to this by inversion dimers formed from C5—H5···O6 hydrogen bonds and C9—H9B···Cg11 e dge-to-face contacts (Table 2). The C5—H5···O6 contacts generate R22(10) rings (Bernstein et al., 1995). Repeated pairs of double chains extend along the b-axis direction, generating sheets of molecules in the bc plane (Fig. 3a). An alternative view along c (Fig. 3b) shows the double chains of molecules forming columnar stacks in a zigzag fashion along b.
C3—H3···π(alkene) (Desiraju & Steiner, 1999) contacts with an H···Cg13 distance of approximately 2.78 Å (Cg13 is the centroid of the methacrylate C8═C9 double bond) link molecules in a head-to-tail fashion, forming a chain that propagates along a (Fig. 4) and links the bc sheets into a three-dimensional structure.
Inversion-dimer formation also plays a considerable role in the crystal packing for (II). However, with two methacrylate substituents, each with potential acceptor atoms, the three-dimensional structure for (II) is more complicated. The carbonyl O7 atom acts as a bifurcated acceptor forming C4—H4···O7 contacts together with C12—H12···O7 inversion dimers (Table 3). The former contact links molecules into chains along a, while the second interaction connects to a parallel chain in an obverse fashion. The overall effect is the formation of a double chain of molecules that propagates in along a (Fig. 5).
C10—H10···Cg22 and C20—H20···Cg21 e dge-to-face contacts (Table 3), involving both Cp rings and the methyl groups of the methacrylate residues from opposite rings, form chains along [110]. Bifurcated C9—H9A···O17 and C15—H15···O17 hydrogen bonds combine with C5—H5···O6 contacts to link adjacent chains again in an obverse fashion. Adjacent double chains are further joined by the C12—H12···O7 hydrogen bonds mentioned previously to generate sheets parallel to (110) (Fig. 6).
The molecular structures for both compounds are closely comparable, with (I) having a single methacrylate substituent on one Cp ring, while (II) has comparable substituents on both rings. All three methacrylate residues are reasonably planar. The variation in the substitution pattern does not effect the coplanarity of the Cp ring systems but, while the two rings in (I) are eclipsed, those for (II) are slightly staggered. This feature is the principal difference between the two closely related molecules.
The crystal packing for both structures is characterized by a propensity to form inversion dimers through C—H···O hydrogen bonds, although the additional methacrylate residue in (II) inevitably complicates the packing. Another common feature is that the O7 carbonyl atoms function as bifurcated acceptors in both molecules, as does the second O17 carbonyl atom in (II). C—H···O contacts are also supported by C—H···π(ring) edge-to-face hydrogen bonds in both systems, but a totally unique feature of the packing in (I) is the formation of chains of molecules linked by C—H···π(alkene) hydrogen bonds. These chains play an important role in forming the three-dimensional network for this structure.
For both compounds, data collection: APEX2 (Bruker, 2011); cell refinement: APEX2 and SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015) and TITAN (Hunter & Simpson, 1999); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
[Fe(C5H5)(C10H11O2)] | F(000) = 592 |
Mr = 284.13 | Dx = 1.483 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2871 (3) Å | Cell parameters from 8356 reflections |
b = 19.6330 (7) Å | θ = 2.3–32.4° |
c = 7.3663 (3) Å | µ = 1.17 mm−1 |
β = 108.604 (2)° | T = 89 K |
V = 1272.94 (8) Å3 | Plate, yellow |
Z = 4 | 0.35 × 0.34 × 0.05 mm |
Bruker APEXII CCD area-detector diffractometer | 3861 reflections with I > 2σ(I) |
Radiation source: fine focus sealed tube | Rint = 0.032 |
ω scans | θmax = 33.4°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2011) | h = −13→13 |
Tmin = 0.760, Tmax = 1.000 | k = −30→28 |
23442 measured reflections | l = −10→10 |
4534 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.071 | w = 1/[σ2(Fo2) + (0.0321P)2 + 0.4873P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
4534 reflections | Δρmax = 0.55 e Å−3 |
164 parameters | Δρmin = −0.49 e Å−3 |
[Fe(C5H5)(C10H11O2)] | V = 1272.94 (8) Å3 |
Mr = 284.13 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.2871 (3) Å | µ = 1.17 mm−1 |
b = 19.6330 (7) Å | T = 89 K |
c = 7.3663 (3) Å | 0.35 × 0.34 × 0.05 mm |
β = 108.604 (2)° |
Bruker APEXII CCD area-detector diffractometer | 4534 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2011) | 3861 reflections with I > 2σ(I) |
Tmin = 0.760, Tmax = 1.000 | Rint = 0.032 |
23442 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.55 e Å−3 |
4534 reflections | Δρmin = −0.49 e Å−3 |
164 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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.65725 (13) | 0.59181 (6) | 0.62812 (16) | 0.0150 (2) | |
C2 | 0.80586 (14) | 0.60055 (6) | 0.76461 (17) | 0.0184 (2) | |
H2 | 0.8337 | 0.6332 | 0.8649 | 0.022* | |
C3 | 0.90430 (14) | 0.55162 (6) | 0.72324 (18) | 0.0200 (2) | |
H3 | 1.0093 | 0.5460 | 0.7914 | 0.024* | |
C4 | 0.81807 (13) | 0.51253 (6) | 0.56172 (18) | 0.0175 (2) | |
H4 | 0.8556 | 0.4765 | 0.5034 | 0.021* | |
C5 | 0.66577 (12) | 0.53719 (6) | 0.50349 (16) | 0.0151 (2) | |
H5 | 0.5839 | 0.5202 | 0.3997 | 0.018* | |
Fe1 | 0.81108 (2) | 0.61414 (2) | 0.49313 (2) | 0.01174 (5) | |
C6 | 0.52040 (15) | 0.63304 (6) | 0.6166 (2) | 0.0221 (2) | |
H6A | 0.5498 | 0.6808 | 0.6536 | 0.026* | |
H6B | 0.4489 | 0.6327 | 0.4841 | 0.026* | |
O6 | 0.44828 (12) | 0.60284 (5) | 0.74810 (15) | 0.0251 (2) | |
C7 | 0.38090 (12) | 0.64550 (6) | 0.83699 (17) | 0.0161 (2) | |
O7 | 0.38276 (15) | 0.70647 (5) | 0.82059 (19) | 0.0412 (3) | |
C8 | 0.30764 (12) | 0.61020 (6) | 0.96491 (17) | 0.0170 (2) | |
C9 | 0.31796 (14) | 0.54298 (7) | 0.99003 (19) | 0.0229 (2) | |
H9A | 0.3726 | 0.5165 | 0.9261 | 0.028* | |
H9B | 0.2706 | 0.5215 | 1.0718 | 0.028* | |
C10 | 0.22244 (17) | 0.65612 (8) | 1.0571 (2) | 0.0305 (3) | |
H10A | 0.1836 | 0.6295 | 1.1440 | 0.046* | |
H10B | 0.1373 | 0.6772 | 0.9580 | 0.046* | |
H10C | 0.2907 | 0.6917 | 1.1296 | 0.046* | |
C11 | 0.73444 (16) | 0.70139 (7) | 0.3442 (2) | 0.0275 (3) | |
H11 | 0.6448 | 0.7255 | 0.3403 | 0.033* | |
C12 | 0.88183 (18) | 0.71203 (6) | 0.4778 (2) | 0.0259 (3) | |
H12 | 0.9078 | 0.7445 | 0.5788 | 0.031* | |
C13 | 0.98337 (14) | 0.66563 (6) | 0.43362 (17) | 0.0197 (2) | |
H13 | 1.0891 | 0.6617 | 0.4997 | 0.024* | |
C14 | 0.89870 (14) | 0.62620 (6) | 0.27305 (17) | 0.0169 (2) | |
H14 | 0.9382 | 0.5912 | 0.2134 | 0.020* | |
C15 | 0.74508 (14) | 0.64815 (7) | 0.21720 (18) | 0.0220 (2) | |
H15 | 0.6639 | 0.6305 | 0.1137 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0186 (5) | 0.0137 (5) | 0.0160 (5) | −0.0027 (4) | 0.0101 (4) | 0.0002 (4) |
C2 | 0.0245 (6) | 0.0209 (5) | 0.0112 (5) | −0.0075 (4) | 0.0077 (4) | −0.0004 (4) |
C3 | 0.0186 (5) | 0.0229 (6) | 0.0173 (5) | −0.0025 (4) | 0.0042 (4) | 0.0074 (4) |
C4 | 0.0206 (5) | 0.0122 (5) | 0.0226 (6) | 0.0008 (4) | 0.0110 (4) | 0.0034 (4) |
C5 | 0.0170 (5) | 0.0139 (5) | 0.0158 (5) | −0.0035 (4) | 0.0073 (4) | −0.0012 (4) |
Fe1 | 0.01453 (8) | 0.01107 (8) | 0.01141 (8) | −0.00090 (5) | 0.00667 (6) | 0.00096 (5) |
C6 | 0.0277 (6) | 0.0178 (5) | 0.0294 (7) | 0.0006 (4) | 0.0213 (5) | 0.0021 (5) |
O6 | 0.0351 (5) | 0.0160 (4) | 0.0368 (5) | −0.0040 (3) | 0.0295 (5) | −0.0035 (4) |
C7 | 0.0142 (4) | 0.0193 (5) | 0.0159 (5) | 0.0023 (4) | 0.0063 (4) | 0.0006 (4) |
O7 | 0.0658 (8) | 0.0202 (5) | 0.0583 (8) | 0.0135 (5) | 0.0490 (7) | 0.0107 (5) |
C8 | 0.0137 (4) | 0.0228 (5) | 0.0163 (5) | −0.0021 (4) | 0.0070 (4) | −0.0015 (4) |
C9 | 0.0188 (5) | 0.0259 (6) | 0.0269 (6) | −0.0005 (4) | 0.0112 (5) | 0.0058 (5) |
C10 | 0.0354 (7) | 0.0295 (7) | 0.0377 (8) | −0.0043 (6) | 0.0273 (6) | −0.0088 (6) |
C11 | 0.0339 (7) | 0.0209 (6) | 0.0369 (8) | 0.0130 (5) | 0.0242 (6) | 0.0160 (5) |
C12 | 0.0462 (8) | 0.0126 (5) | 0.0282 (7) | −0.0062 (5) | 0.0250 (6) | −0.0016 (4) |
C13 | 0.0210 (5) | 0.0217 (5) | 0.0185 (5) | −0.0064 (4) | 0.0095 (4) | 0.0020 (4) |
C14 | 0.0212 (5) | 0.0186 (5) | 0.0141 (5) | 0.0002 (4) | 0.0100 (4) | 0.0020 (4) |
C15 | 0.0198 (5) | 0.0299 (6) | 0.0162 (5) | 0.0000 (5) | 0.0059 (4) | 0.0101 (5) |
C1—C5 | 1.4303 (15) | C6—H6B | 0.9900 |
C1—C2 | 1.4351 (17) | O6—C7 | 1.3354 (14) |
C1—C6 | 1.4863 (17) | C7—O7 | 1.2038 (15) |
C1—Fe1 | 2.0318 (11) | C7—C8 | 1.4968 (16) |
C2—C3 | 1.4245 (18) | C8—C9 | 1.3317 (17) |
C2—Fe1 | 2.0334 (11) | C8—C10 | 1.4977 (17) |
C2—H2 | 0.9500 | C9—H9A | 0.9500 |
C3—C4 | 1.4276 (17) | C9—H9B | 0.9500 |
C3—Fe1 | 2.0477 (12) | C10—H10A | 0.9800 |
C3—H3 | 0.9500 | C10—H10B | 0.9800 |
C4—C5 | 1.4254 (16) | C10—H10C | 0.9800 |
C4—Fe1 | 2.0539 (11) | C11—C12 | 1.423 (2) |
C4—H4 | 0.9500 | C11—C15 | 1.427 (2) |
C5—Fe1 | 2.0434 (11) | C11—H11 | 0.9500 |
C5—H5 | 0.9500 | C12—C13 | 1.4215 (18) |
Fe1—C11 | 2.0362 (12) | C12—H12 | 0.9500 |
Fe1—C15 | 2.0391 (12) | C13—C14 | 1.4224 (17) |
Fe1—C12 | 2.0457 (12) | C13—H13 | 0.9500 |
Fe1—C14 | 2.0465 (11) | C14—C15 | 1.4198 (17) |
Fe1—C13 | 2.0546 (11) | C14—H14 | 0.9500 |
C6—O6 | 1.4670 (14) | C15—H15 | 0.9500 |
C6—H6A | 0.9900 | ||
C5—C1—C2 | 107.55 (10) | C14—Fe1—C4 | 108.53 (5) |
C5—C1—C6 | 126.38 (11) | C3—Fe1—C4 | 40.74 (5) |
C2—C1—C6 | 126.06 (11) | C1—Fe1—C13 | 158.06 (5) |
C5—C1—Fe1 | 69.89 (6) | C2—Fe1—C13 | 122.61 (5) |
C2—C1—Fe1 | 69.39 (6) | C11—Fe1—C13 | 68.49 (5) |
C6—C1—Fe1 | 125.21 (8) | C15—Fe1—C13 | 68.48 (5) |
C3—C2—C1 | 108.00 (10) | C5—Fe1—C13 | 160.09 (5) |
C3—C2—Fe1 | 70.11 (7) | C12—Fe1—C13 | 40.57 (5) |
C1—C2—Fe1 | 69.27 (6) | C14—Fe1—C13 | 40.59 (5) |
C3—C2—H2 | 126.0 | C3—Fe1—C13 | 108.61 (5) |
C1—C2—H2 | 126.0 | C4—Fe1—C13 | 124.38 (5) |
Fe1—C2—H2 | 126.2 | O6—C6—C1 | 107.72 (10) |
C2—C3—C4 | 108.25 (10) | O6—C6—H6A | 110.2 |
C2—C3—Fe1 | 69.03 (7) | C1—C6—H6A | 110.2 |
C4—C3—Fe1 | 69.86 (7) | O6—C6—H6B | 110.2 |
C2—C3—H3 | 125.9 | C1—C6—H6B | 110.2 |
C4—C3—H3 | 125.9 | H6A—C6—H6B | 108.5 |
Fe1—C3—H3 | 126.8 | C7—O6—C6 | 117.02 (9) |
C5—C4—C3 | 107.89 (10) | O7—C7—O6 | 123.40 (11) |
C5—C4—Fe1 | 69.25 (6) | O7—C7—C8 | 123.20 (11) |
C3—C4—Fe1 | 69.40 (7) | O6—C7—C8 | 113.36 (10) |
C5—C4—H4 | 126.1 | C9—C8—C7 | 121.29 (11) |
C3—C4—H4 | 126.1 | C9—C8—C10 | 123.95 (12) |
Fe1—C4—H4 | 126.9 | C7—C8—C10 | 114.76 (11) |
C4—C5—C1 | 108.31 (10) | C8—C9—H9A | 120.0 |
C4—C5—Fe1 | 70.04 (6) | C8—C9—H9B | 120.0 |
C1—C5—Fe1 | 69.02 (6) | H9A—C9—H9B | 120.0 |
C4—C5—H5 | 125.8 | C8—C10—H10A | 109.5 |
C1—C5—H5 | 125.8 | C8—C10—H10B | 109.5 |
Fe1—C5—H5 | 126.7 | H10A—C10—H10B | 109.5 |
C1—Fe1—C2 | 41.34 (5) | C8—C10—H10C | 109.5 |
C1—Fe1—C11 | 105.41 (5) | H10A—C10—H10C | 109.5 |
C2—Fe1—C11 | 121.77 (5) | H10B—C10—H10C | 109.5 |
C1—Fe1—C15 | 121.59 (5) | C12—C11—C15 | 107.95 (11) |
C2—Fe1—C15 | 158.35 (5) | C12—C11—Fe1 | 69.95 (7) |
C11—Fe1—C15 | 40.99 (6) | C15—C11—Fe1 | 69.61 (7) |
C1—Fe1—C5 | 41.09 (4) | C12—C11—H11 | 126.0 |
C2—Fe1—C5 | 69.08 (5) | C15—C11—H11 | 126.0 |
C11—Fe1—C5 | 121.38 (5) | Fe1—C11—H11 | 126.0 |
C15—Fe1—C5 | 106.69 (5) | C13—C12—C11 | 108.03 (11) |
C1—Fe1—C12 | 121.21 (5) | C13—C12—Fe1 | 70.05 (7) |
C2—Fe1—C12 | 106.65 (5) | C11—C12—Fe1 | 69.23 (7) |
C11—Fe1—C12 | 40.82 (6) | C13—C12—H12 | 126.0 |
C15—Fe1—C12 | 68.72 (6) | C11—C12—H12 | 126.0 |
C5—Fe1—C12 | 157.56 (5) | Fe1—C12—H12 | 126.3 |
C1—Fe1—C14 | 158.75 (5) | C12—C13—C14 | 107.94 (11) |
C2—Fe1—C14 | 159.15 (5) | C12—C13—Fe1 | 69.38 (7) |
C11—Fe1—C14 | 68.58 (5) | C14—C13—Fe1 | 69.40 (6) |
C15—Fe1—C14 | 40.67 (5) | C12—C13—H13 | 126.0 |
C5—Fe1—C14 | 123.32 (5) | C14—C13—H13 | 126.0 |
C12—Fe1—C14 | 68.39 (5) | Fe1—C13—H13 | 126.8 |
C1—Fe1—C3 | 69.09 (5) | C15—C14—C13 | 108.27 (11) |
C2—Fe1—C3 | 40.86 (5) | C15—C14—Fe1 | 69.38 (7) |
C11—Fe1—C3 | 158.92 (6) | C13—C14—Fe1 | 70.01 (7) |
C15—Fe1—C3 | 159.17 (6) | C15—C14—H14 | 125.9 |
C5—Fe1—C3 | 68.64 (5) | C13—C14—H14 | 125.9 |
C12—Fe1—C3 | 123.39 (6) | Fe1—C14—H14 | 126.3 |
C14—Fe1—C3 | 123.72 (5) | C14—C15—C11 | 107.80 (12) |
C1—Fe1—C4 | 69.02 (5) | C14—C15—Fe1 | 69.94 (7) |
C2—Fe1—C4 | 68.86 (5) | C11—C15—Fe1 | 69.40 (7) |
C11—Fe1—C4 | 158.10 (6) | C14—C15—H15 | 126.1 |
C15—Fe1—C4 | 122.62 (5) | C11—C15—H15 | 126.1 |
C5—Fe1—C4 | 40.72 (4) | Fe1—C15—H15 | 126.1 |
C12—Fe1—C4 | 160.14 (6) |
Cg11 and Cg12 are the centroids of the C1–C5 and C11–C15 rings, respectively, for (I). Cg13 is the centroid of the C8═C9 double bond. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O6i | 0.95 | 2.63 | 3.2958 (14) | 128 |
C10—H10C···O7ii | 0.98 | 2.44 | 3.3789 (18) | 161 |
C11—H11···O7iii | 0.95 | 2.74 | 3.6889 (18) | 179 |
C9—H9B···Cg11iv | 0.95 | 2.79 | 3.6983 (15) | 161 |
C12—H12···Cg12v | 0.95 | 2.78 | 3.6631 (15) | 155 |
C3—H3···Cg13vi | 0.95 | 2.78 | 3.689 (2) | 161 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z+1/2; (iii) x, −y+3/2, z−1/2; (iv) −x+1, −y+1, −z+2; (v) x, −y+1/2, z−1/2; (vi) x−1, y, z. |
[Fe(C10H11O2)2] | Z = 2 |
Mr = 382.22 | F(000) = 400 |
Triclinic, P1 | Dx = 1.465 Mg m−3 |
a = 8.7326 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.3037 (3) Å | Cell parameters from 6188 reflections |
c = 11.0775 (4) Å | θ = 4.4–66.4° |
α = 64.245 (2)° | µ = 0.89 mm−1 |
β = 77.333 (2)° | T = 89 K |
γ = 77.167 (2)° | Block, yellow |
V = 866.70 (5) Å3 | 0.33 × 0.17 × 0.14 mm |
Bruker APEXII CCD area-detector diffractometer | 6012 independent reflections |
Radiation source: fine-focus sealed tube | 5239 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω scans | θmax = 33.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2011) | h = −12→13 |
Tmin = 0.826, Tmax = 1.000 | k = −15→15 |
16574 measured reflections | l = −15→16 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0428P)2 + 0.2726P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
6012 reflections | Δρmax = 0.55 e Å−3 |
226 parameters | Δρmin = −0.36 e Å−3 |
[Fe(C10H11O2)2] | γ = 77.167 (2)° |
Mr = 382.22 | V = 866.70 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.7326 (3) Å | Mo Kα radiation |
b = 10.3037 (3) Å | µ = 0.89 mm−1 |
c = 11.0775 (4) Å | T = 89 K |
α = 64.245 (2)° | 0.33 × 0.17 × 0.14 mm |
β = 77.333 (2)° |
Bruker APEXII CCD area-detector diffractometer | 6012 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2011) | 5239 reflections with I > 2σ(I) |
Tmin = 0.826, Tmax = 1.000 | Rint = 0.028 |
16574 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.55 e Å−3 |
6012 reflections | Δρmin = −0.36 e Å−3 |
226 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. The hydrogen atoms on both methyl groups in (II) were equally disordered over two sites. These hydrogen atoms were placed in calculated positions, with the two sites rotated by 60° from one another and with d(C—H) = 0.98 and Uiso = 1.5Ueq (C). |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | −0.02772 (14) | 0.46803 (13) | 0.79640 (13) | 0.0146 (2) | |
C2 | −0.00934 (15) | 0.52560 (13) | 0.65176 (13) | 0.0158 (2) | |
H2 | −0.0865 | 0.5340 | 0.5992 | 0.019* | |
C3 | 0.14439 (16) | 0.56809 (14) | 0.60009 (15) | 0.0205 (3) | |
H3 | 0.1875 | 0.6097 | 0.5072 | 0.025* | |
C4 | 0.22230 (16) | 0.53727 (15) | 0.71202 (17) | 0.0225 (3) | |
H4 | 0.3266 | 0.5542 | 0.7068 | 0.027* | |
C5 | 0.11628 (16) | 0.47662 (15) | 0.83315 (15) | 0.0192 (3) | |
H5 | 0.1373 | 0.4470 | 0.9227 | 0.023* | |
C6 | −0.17190 (15) | 0.41250 (14) | 0.89001 (13) | 0.0161 (2) | |
H6A | −0.2221 | 0.3637 | 0.8523 | 0.019* | |
H6B | −0.1416 | 0.3401 | 0.9786 | 0.019* | |
C7 | −0.38673 (14) | 0.60403 (14) | 0.81739 (13) | 0.0154 (2) | |
C8 | −0.49034 (15) | 0.73143 (14) | 0.83828 (15) | 0.0187 (2) | |
C9 | −0.49011 (17) | 0.75462 (16) | 0.95003 (16) | 0.0228 (3) | |
H9A | −0.5565 | 0.8356 | 0.9625 | 0.027* | |
H9B | −0.4236 | 0.6898 | 1.0156 | 0.027* | |
C10 | −0.5891 (2) | 0.82563 (18) | 0.73125 (19) | 0.0308 (3) | |
H10A | −0.5694 | 0.7877 | 0.6612 | 0.046* | 0.5 |
H10B | −0.7013 | 0.8272 | 0.7702 | 0.046* | 0.5 |
H10C | −0.5623 | 0.9247 | 0.6911 | 0.046* | 0.5 |
H10D | −0.6526 | 0.9054 | 0.7538 | 0.046* | 0.5 |
H10E | −0.5207 | 0.8658 | 0.6447 | 0.046* | 0.5 |
H10F | −0.6597 | 0.7684 | 0.7239 | 0.046* | 0.5 |
C11 | 0.36581 (15) | 0.22038 (13) | 0.69983 (13) | 0.0153 (2) | |
C12 | 0.26370 (16) | 0.23798 (14) | 0.60767 (13) | 0.0165 (2) | |
H12 | 0.2879 | 0.2771 | 0.5118 | 0.020* | |
C13 | 0.11925 (16) | 0.18672 (14) | 0.68441 (14) | 0.0181 (2) | |
H13 | 0.0297 | 0.1867 | 0.6488 | 0.022* | |
C14 | 0.13307 (16) | 0.13546 (14) | 0.82419 (14) | 0.0188 (3) | |
H14 | 0.0540 | 0.0951 | 0.8980 | 0.023* | |
C15 | 0.28520 (16) | 0.15493 (14) | 0.83428 (13) | 0.0172 (2) | |
H15 | 0.3260 | 0.1291 | 0.9157 | 0.021* | |
C16 | 0.52631 (16) | 0.26619 (15) | 0.65811 (16) | 0.0227 (3) | |
H16A | 0.5265 | 0.3562 | 0.5738 | 0.027* | |
H16B | 0.5532 | 0.2872 | 0.7295 | 0.027* | |
C17 | 0.72726 (15) | 0.06167 (14) | 0.73767 (14) | 0.0177 (2) | |
C18 | 0.83536 (15) | −0.05837 (14) | 0.70811 (14) | 0.0161 (2) | |
C19 | 0.83380 (19) | −0.07587 (18) | 0.59305 (17) | 0.0286 (3) | |
H19A | 0.9014 | −0.1541 | 0.5763 | 0.034* | |
H19B | 0.7651 | −0.0098 | 0.5298 | 0.034* | |
C20 | 0.93687 (18) | −0.15452 (16) | 0.81048 (17) | 0.0260 (3) | |
H20A | 0.9181 | −0.1214 | 0.8838 | 0.039* | 0.5 |
H20B | 0.9124 | −0.2541 | 0.8470 | 0.039* | 0.5 |
H20C | 1.0483 | −0.1527 | 0.7694 | 0.039* | 0.5 |
H20D | 1.0011 | −0.2307 | 0.7830 | 0.039* | 0.5 |
H20E | 1.0068 | −0.0980 | 0.8198 | 0.039* | 0.5 |
H20F | 0.8709 | −0.1994 | 0.8974 | 0.039* | 0.5 |
O6 | −0.28472 (11) | 0.53304 (10) | 0.90844 (10) | 0.01733 (18) | |
O7 | −0.39331 (11) | 0.56930 (11) | 0.72745 (10) | 0.01967 (19) | |
O16 | 0.64456 (11) | 0.15078 (11) | 0.63586 (11) | 0.0219 (2) | |
O17 | 0.71661 (16) | 0.07759 (13) | 0.84086 (12) | 0.0344 (3) | |
Fe1 | 0.16056 (2) | 0.35072 (2) | 0.72526 (2) | 0.01210 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0131 (5) | 0.0133 (5) | 0.0187 (6) | 0.0028 (4) | −0.0044 (4) | −0.0089 (4) |
C2 | 0.0135 (5) | 0.0129 (5) | 0.0187 (6) | 0.0031 (4) | −0.0044 (4) | −0.0056 (4) |
C3 | 0.0157 (6) | 0.0114 (5) | 0.0277 (7) | 0.0005 (4) | −0.0008 (5) | −0.0041 (5) |
C4 | 0.0144 (6) | 0.0167 (6) | 0.0411 (8) | 0.0007 (5) | −0.0062 (5) | −0.0163 (6) |
C5 | 0.0162 (6) | 0.0188 (6) | 0.0295 (7) | 0.0054 (5) | −0.0091 (5) | −0.0171 (5) |
C6 | 0.0147 (5) | 0.0144 (5) | 0.0173 (6) | 0.0042 (4) | −0.0033 (4) | −0.0071 (5) |
C7 | 0.0110 (5) | 0.0153 (5) | 0.0181 (6) | −0.0009 (4) | −0.0007 (4) | −0.0063 (4) |
C8 | 0.0127 (5) | 0.0154 (6) | 0.0270 (7) | −0.0005 (4) | 0.0007 (5) | −0.0099 (5) |
C9 | 0.0193 (6) | 0.0226 (7) | 0.0298 (7) | 0.0016 (5) | −0.0006 (5) | −0.0170 (6) |
C10 | 0.0267 (7) | 0.0258 (7) | 0.0445 (10) | 0.0109 (6) | −0.0178 (7) | −0.0194 (7) |
C11 | 0.0143 (5) | 0.0123 (5) | 0.0172 (6) | 0.0035 (4) | −0.0031 (4) | −0.0063 (4) |
C12 | 0.0196 (6) | 0.0153 (5) | 0.0137 (5) | 0.0038 (4) | −0.0038 (4) | −0.0072 (4) |
C13 | 0.0183 (6) | 0.0165 (6) | 0.0237 (6) | 0.0004 (4) | −0.0047 (5) | −0.0126 (5) |
C14 | 0.0223 (6) | 0.0123 (5) | 0.0195 (6) | −0.0020 (4) | 0.0013 (5) | −0.0065 (5) |
C15 | 0.0232 (6) | 0.0124 (5) | 0.0146 (6) | 0.0044 (4) | −0.0062 (5) | −0.0058 (4) |
C16 | 0.0139 (6) | 0.0163 (6) | 0.0346 (8) | 0.0052 (5) | −0.0047 (5) | −0.0102 (6) |
C17 | 0.0158 (6) | 0.0145 (5) | 0.0187 (6) | 0.0014 (4) | 0.0003 (4) | −0.0060 (5) |
C18 | 0.0126 (5) | 0.0139 (5) | 0.0205 (6) | 0.0009 (4) | −0.0010 (4) | −0.0076 (5) |
C19 | 0.0290 (8) | 0.0290 (8) | 0.0305 (8) | 0.0061 (6) | −0.0054 (6) | −0.0190 (7) |
C20 | 0.0244 (7) | 0.0202 (6) | 0.0349 (8) | 0.0072 (5) | −0.0112 (6) | −0.0142 (6) |
O6 | 0.0148 (4) | 0.0195 (4) | 0.0185 (4) | 0.0054 (3) | −0.0043 (3) | −0.0113 (4) |
O7 | 0.0170 (4) | 0.0217 (5) | 0.0207 (5) | 0.0028 (4) | −0.0056 (4) | −0.0102 (4) |
O16 | 0.0155 (4) | 0.0215 (5) | 0.0265 (5) | 0.0080 (4) | −0.0056 (4) | −0.0114 (4) |
O17 | 0.0486 (7) | 0.0283 (6) | 0.0231 (6) | 0.0153 (5) | −0.0093 (5) | −0.0153 (5) |
Fe1 | 0.01121 (9) | 0.01061 (9) | 0.01471 (9) | 0.00188 (6) | −0.00334 (6) | −0.00628 (7) |
C1—C2 | 1.4312 (18) | C11—C12 | 1.4272 (19) |
C1—C5 | 1.4354 (18) | C11—C15 | 1.4306 (18) |
C1—C6 | 1.4899 (18) | C11—C16 | 1.4903 (18) |
C1—Fe1 | 2.0401 (12) | C11—Fe1 | 2.0331 (12) |
C2—C3 | 1.4240 (18) | C12—C13 | 1.4242 (19) |
C2—Fe1 | 2.0441 (12) | C12—Fe1 | 2.0478 (12) |
C2—H2 | 0.9500 | C12—H12 | 0.9500 |
C3—C4 | 1.426 (2) | C13—C14 | 1.426 (2) |
C3—Fe1 | 2.0506 (13) | C13—Fe1 | 2.0487 (13) |
C3—H3 | 0.9500 | C13—H13 | 0.9500 |
C4—C5 | 1.425 (2) | C14—C15 | 1.422 (2) |
C4—Fe1 | 2.0463 (13) | C14—Fe1 | 2.0463 (13) |
C4—H4 | 0.9500 | C14—H14 | 0.9500 |
C5—Fe1 | 2.0451 (13) | C15—Fe1 | 2.0486 (13) |
C5—H5 | 0.9500 | C15—H15 | 0.9500 |
C6—O6 | 1.4640 (15) | C16—O16 | 1.4624 (16) |
C6—H6A | 0.9900 | C16—H16A | 0.9900 |
C6—H6B | 0.9900 | C16—H16B | 0.9900 |
C7—O7 | 1.2117 (16) | C17—O17 | 1.2049 (17) |
C7—O6 | 1.3451 (16) | C17—O16 | 1.3413 (17) |
C7—C8 | 1.4966 (18) | C17—C18 | 1.4919 (17) |
C8—C9 | 1.359 (2) | C18—C19 | 1.366 (2) |
C8—C10 | 1.472 (2) | C18—C20 | 1.459 (2) |
C9—H9A | 0.9500 | C19—H19A | 0.9500 |
C9—H9B | 0.9500 | C19—H19B | 0.9500 |
C10—H10A | 0.9800 | C20—H20A | 0.9800 |
C10—H10B | 0.9800 | C20—H20B | 0.9800 |
C10—H10C | 0.9800 | C20—H20C | 0.9800 |
C10—H10D | 0.9800 | C20—H20D | 0.9800 |
C10—H10E | 0.9800 | C20—H20E | 0.9800 |
C10—H10F | 0.9800 | C20—H20F | 0.9800 |
C2—C1—C5 | 107.37 (11) | C14—C15—C11 | 107.77 (12) |
C2—C1—C6 | 125.72 (12) | C14—C15—Fe1 | 69.60 (7) |
C5—C1—C6 | 126.90 (12) | C11—C15—Fe1 | 68.90 (7) |
C2—C1—Fe1 | 69.64 (7) | C14—C15—H15 | 126.1 |
C5—C1—Fe1 | 69.62 (7) | C11—C15—H15 | 126.1 |
C6—C1—Fe1 | 126.87 (9) | Fe1—C15—H15 | 126.9 |
C3—C2—C1 | 108.32 (12) | O16—C16—C11 | 110.02 (11) |
C3—C2—Fe1 | 69.90 (7) | O16—C16—H16A | 109.7 |
C1—C2—Fe1 | 69.34 (7) | C11—C16—H16A | 109.7 |
C3—C2—H2 | 125.8 | O16—C16—H16B | 109.7 |
C1—C2—H2 | 125.8 | C11—C16—H16B | 109.7 |
Fe1—C2—H2 | 126.5 | H16A—C16—H16B | 108.2 |
C2—C3—C4 | 108.10 (12) | O17—C17—O16 | 123.79 (12) |
C2—C3—Fe1 | 69.40 (7) | O17—C17—C18 | 123.78 (13) |
C4—C3—Fe1 | 69.47 (8) | O16—C17—C18 | 112.42 (11) |
C2—C3—H3 | 126.0 | C19—C18—C20 | 123.60 (12) |
C4—C3—H3 | 126.0 | C19—C18—C17 | 120.73 (13) |
Fe1—C3—H3 | 126.7 | C20—C18—C17 | 115.65 (12) |
C5—C4—C3 | 108.05 (12) | C18—C19—H19A | 120.0 |
C5—C4—Fe1 | 69.57 (7) | C18—C19—H19B | 120.0 |
C3—C4—Fe1 | 69.80 (8) | H19A—C19—H19B | 120.0 |
C5—C4—H4 | 126.0 | C18—C20—H20A | 109.5 |
C3—C4—H4 | 126.0 | C18—C20—H20B | 109.5 |
Fe1—C4—H4 | 126.2 | H20A—C20—H20B | 109.5 |
C4—C5—C1 | 108.16 (12) | C18—C20—H20C | 109.5 |
C4—C5—Fe1 | 69.66 (8) | H20A—C20—H20C | 109.5 |
C1—C5—Fe1 | 69.24 (7) | H20B—C20—H20C | 109.5 |
C4—C5—H5 | 125.9 | C18—C20—H20D | 109.5 |
C1—C5—H5 | 125.9 | H20A—C20—H20D | 141.1 |
Fe1—C5—H5 | 126.7 | H20B—C20—H20D | 56.3 |
O6—C6—C1 | 110.05 (10) | H20C—C20—H20D | 56.3 |
O6—C6—H6A | 109.7 | C18—C20—H20E | 109.5 |
C1—C6—H6A | 109.7 | H20A—C20—H20E | 56.3 |
O6—C6—H6B | 109.7 | H20B—C20—H20E | 141.1 |
C1—C6—H6B | 109.7 | H20C—C20—H20E | 56.3 |
H6A—C6—H6B | 108.2 | H20D—C20—H20E | 109.5 |
O7—C7—O6 | 123.65 (11) | C18—C20—H20F | 109.5 |
O7—C7—C8 | 123.57 (12) | H20A—C20—H20F | 56.3 |
O6—C7—C8 | 112.77 (11) | H20B—C20—H20F | 56.3 |
C9—C8—C10 | 123.98 (13) | H20C—C20—H20F | 141.1 |
C9—C8—C7 | 120.60 (13) | H20D—C20—H20F | 109.5 |
C10—C8—C7 | 115.43 (13) | H20E—C20—H20F | 109.5 |
C8—C9—H9A | 120.0 | C7—O6—C6 | 116.32 (10) |
C8—C9—H9B | 120.0 | C17—O16—C16 | 116.99 (11) |
H9A—C9—H9B | 120.0 | C11—Fe1—C1 | 165.58 (5) |
C8—C10—H10A | 109.5 | C11—Fe1—C2 | 151.83 (5) |
C8—C10—H10B | 109.5 | C1—Fe1—C2 | 41.03 (5) |
H10A—C10—H10B | 109.5 | C11—Fe1—C5 | 127.01 (5) |
C8—C10—H10C | 109.5 | C1—Fe1—C5 | 41.14 (5) |
H10A—C10—H10C | 109.5 | C2—Fe1—C5 | 68.79 (5) |
H10B—C10—H10C | 109.5 | C11—Fe1—C14 | 68.78 (5) |
C8—C10—H10D | 109.5 | C1—Fe1—C14 | 108.11 (5) |
H10A—C10—H10D | 141.1 | C2—Fe1—C14 | 127.89 (5) |
H10B—C10—H10D | 56.3 | C5—Fe1—C14 | 119.23 (6) |
H10C—C10—H10D | 56.3 | C11—Fe1—C4 | 106.91 (5) |
C8—C10—H10E | 109.5 | C1—Fe1—C4 | 69.07 (5) |
H10A—C10—H10E | 56.3 | C2—Fe1—C4 | 68.66 (5) |
H10B—C10—H10E | 141.1 | C5—Fe1—C4 | 40.78 (6) |
H10C—C10—H10E | 56.3 | C14—Fe1—C4 | 152.91 (6) |
H10D—C10—H10E | 109.5 | C11—Fe1—C12 | 40.94 (5) |
C8—C10—H10F | 109.5 | C1—Fe1—C12 | 152.40 (5) |
H10A—C10—H10F | 56.3 | C2—Fe1—C12 | 118.10 (5) |
H10B—C10—H10F | 56.3 | C5—Fe1—C12 | 164.93 (6) |
H10C—C10—H10F | 141.1 | C14—Fe1—C12 | 68.46 (5) |
H10D—C10—H10F | 109.5 | C4—Fe1—C12 | 126.76 (6) |
H10E—C10—H10F | 109.5 | C11—Fe1—C15 | 41.03 (5) |
C12—C11—C15 | 107.88 (11) | C1—Fe1—C15 | 127.62 (5) |
C12—C11—C16 | 124.30 (12) | C2—Fe1—C15 | 165.87 (5) |
C15—C11—C16 | 127.81 (13) | C5—Fe1—C15 | 107.96 (5) |
C12—C11—Fe1 | 70.08 (7) | C14—Fe1—C15 | 40.63 (6) |
C15—C11—Fe1 | 70.06 (7) | C4—Fe1—C15 | 118.50 (6) |
C16—C11—Fe1 | 124.63 (9) | C12—Fe1—C15 | 68.66 (5) |
C13—C12—C11 | 108.13 (11) | C11—Fe1—C13 | 68.88 (5) |
C13—C12—Fe1 | 69.69 (7) | C1—Fe1—C13 | 118.61 (5) |
C11—C12—Fe1 | 68.98 (7) | C2—Fe1—C13 | 107.70 (5) |
C13—C12—H12 | 125.9 | C5—Fe1—C13 | 153.24 (6) |
C11—C12—H12 | 125.9 | C14—Fe1—C13 | 40.76 (6) |
Fe1—C12—H12 | 127.0 | C4—Fe1—C13 | 164.74 (6) |
C12—C13—C14 | 107.79 (12) | C12—Fe1—C13 | 40.69 (5) |
C12—C13—Fe1 | 69.62 (7) | C15—Fe1—C13 | 68.63 (5) |
C14—C13—Fe1 | 69.53 (7) | C11—Fe1—C3 | 117.70 (5) |
C12—C13—H13 | 126.1 | C1—Fe1—C3 | 68.92 (5) |
C14—C13—H13 | 126.1 | C2—Fe1—C3 | 40.70 (5) |
Fe1—C13—H13 | 126.3 | C5—Fe1—C3 | 68.58 (6) |
C15—C14—C13 | 108.41 (11) | C14—Fe1—C3 | 165.43 (6) |
C15—C14—Fe1 | 69.77 (7) | C4—Fe1—C3 | 40.73 (6) |
C13—C14—Fe1 | 69.71 (7) | C12—Fe1—C3 | 107.17 (6) |
C15—C14—H14 | 125.8 | C15—Fe1—C3 | 152.30 (6) |
C13—C14—H14 | 125.8 | C13—Fe1—C3 | 127.05 (6) |
Fe1—C14—H14 | 126.3 | ||
C5—C1—C2—C3 | 0.43 (14) | C15—C11—C12—Fe1 | 60.13 (8) |
C6—C1—C2—C3 | 179.35 (11) | C16—C11—C12—Fe1 | −118.98 (12) |
Fe1—C1—C2—C3 | −59.22 (9) | C11—C12—C13—C14 | −0.83 (14) |
C5—C1—C2—Fe1 | 59.64 (8) | Fe1—C12—C13—C14 | −59.26 (9) |
C6—C1—C2—Fe1 | −121.43 (12) | C11—C12—C13—Fe1 | 58.43 (9) |
C1—C2—C3—C4 | 0.00 (14) | C12—C13—C14—C15 | 0.08 (14) |
Fe1—C2—C3—C4 | −58.87 (9) | Fe1—C13—C14—C15 | −59.24 (9) |
C1—C2—C3—Fe1 | 58.87 (9) | C12—C13—C14—Fe1 | 59.32 (9) |
C2—C3—C4—C5 | −0.43 (15) | C13—C14—C15—C11 | 0.70 (14) |
Fe1—C3—C4—C5 | −59.26 (9) | Fe1—C14—C15—C11 | −58.50 (8) |
C2—C3—C4—Fe1 | 58.83 (9) | C13—C14—C15—Fe1 | 59.20 (9) |
C3—C4—C5—C1 | 0.69 (14) | C12—C11—C15—C14 | −1.21 (14) |
Fe1—C4—C5—C1 | −58.71 (9) | C16—C11—C15—C14 | 177.87 (12) |
C3—C4—C5—Fe1 | 59.40 (9) | Fe1—C11—C15—C14 | 58.93 (9) |
C2—C1—C5—C4 | −0.69 (14) | C12—C11—C15—Fe1 | −60.14 (8) |
C6—C1—C5—C4 | −179.60 (12) | C16—C11—C15—Fe1 | 118.93 (13) |
Fe1—C1—C5—C4 | 58.97 (9) | C12—C11—C16—O16 | −85.75 (15) |
C2—C1—C5—Fe1 | −59.66 (8) | C15—C11—C16—O16 | 95.31 (16) |
C6—C1—C5—Fe1 | 121.43 (12) | Fe1—C11—C16—O16 | −174.03 (9) |
C2—C1—C6—O6 | −85.46 (15) | O17—C17—C18—C19 | 175.54 (15) |
C5—C1—C6—O6 | 93.26 (14) | O16—C17—C18—C19 | −5.14 (19) |
Fe1—C1—C6—O6 | −175.66 (8) | O17—C17—C18—C20 | −3.1 (2) |
O7—C7—C8—C9 | 172.28 (13) | O16—C17—C18—C20 | 176.23 (12) |
O6—C7—C8—C9 | −8.25 (18) | O7—C7—O6—C6 | 3.27 (18) |
O7—C7—C8—C10 | −7.6 (2) | C8—C7—O6—C6 | −176.20 (10) |
O6—C7—C8—C10 | 171.90 (12) | C1—C6—O6—C7 | 87.20 (13) |
C15—C11—C12—C13 | 1.27 (14) | O17—C17—O16—C16 | −5.0 (2) |
C16—C11—C12—C13 | −177.85 (11) | C18—C17—O16—C16 | 175.65 (11) |
Fe1—C11—C12—C13 | −58.87 (9) | C11—C16—O16—C17 | −97.76 (14) |
Cg21 and Cg22 are the centroids of the C1–C5 and C11–C15 rings, respectively, for (II). |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O7i | 0.95 | 2.55 | 3.4926 (17) | 172 |
C5—H5···O6ii | 0.95 | 2.59 | 3.4499 (17) | 151 |
C9—H9A···O17ii | 0.95 | 2.70 | 3.4956 (17) | 142 |
C15—H15···O17iii | 0.95 | 2.62 | 3.3451 (17) | 133 |
C12—H12···O7iv | 0.95 | 2.51 | 3.4285 (17) | 162 |
C10—H10D···Cg22v | 0.98 | 2.77 | 3.698 (2) | 159 |
C20—H20D···Cg21vi | 0.98 | 2.91 | 3.8463 (19) | 161 |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+2; (iii) −x+1, −y, −z+2; (iv) −x, −y+1, −z+1; (v) x−1, y+1, z; (vi) x+1, y−1, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Fe(C5H5)(C10H11O2)] | [Fe(C10H11O2)2] |
Mr | 284.13 | 382.22 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 89 | 89 |
a, b, c (Å) | 9.2871 (3), 19.6330 (7), 7.3663 (3) | 8.7326 (3), 10.3037 (3), 11.0775 (4) |
α, β, γ (°) | 90, 108.604 (2), 90 | 64.245 (2), 77.333 (2), 77.167 (2) |
V (Å3) | 1272.94 (8) | 866.70 (5) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.17 | 0.89 |
Crystal size (mm) | 0.35 × 0.34 × 0.05 | 0.33 × 0.17 × 0.14 |
Data collection | ||
Diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2011) | Multi-scan (SADABS; Bruker, 2011) |
Tmin, Tmax | 0.760, 1.000 | 0.826, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23442, 4534, 3861 | 16574, 6012, 5239 |
Rint | 0.032 | 0.028 |
(sin θ/λ)max (Å−1) | 0.775 | 0.775 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.071, 1.05 | 0.034, 0.088, 1.05 |
No. of reflections | 4534 | 6012 |
No. of parameters | 164 | 226 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.55, −0.49 | 0.55, −0.36 |
Computer programs: APEX2 (Bruker, 2011), APEX2 and SAINT (Bruker, 2011), SAINT (Bruker, 2011), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015) and TITAN (Hunter & Simpson, 1999), Mercury (Macrae et al., 2008), SHELXL2014 (Sheldrick, 2015), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Cg11 and Cg12 are the centroids of the C1–C5 and C11–C15 rings, respectively, for (I). Cg13 is the centroid of the C8═C9 double bond. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O6i | 0.95 | 2.63 | 3.2958 (14) | 128 |
C10—H10C···O7ii | 0.98 | 2.44 | 3.3789 (18) | 161 |
C11—H11···O7iii | 0.95 | 2.74 | 3.6889 (18) | 179 |
C9—H9B···Cg11iv | 0.95 | 2.79 | 3.6983 (15) | 161 |
C12—H12···Cg12v | 0.95 | 2.78 | 3.6631 (15) | 155 |
C3—H3···Cg13vi | 0.95 | 2.78 | 3.689 (2) | 161 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z+1/2; (iii) x, −y+3/2, z−1/2; (iv) −x+1, −y+1, −z+2; (v) x, −y+1/2, z−1/2; (vi) x−1, y, z. |
Cg21 and Cg22 are the centroids of the C1–C5 and C11–C15 rings, respectively, for (II). |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O7i | 0.95 | 2.55 | 3.4926 (17) | 171.5 |
C5—H5···O6ii | 0.95 | 2.59 | 3.4499 (17) | 150.7 |
C9—H9A···O17ii | 0.95 | 2.70 | 3.4956 (17) | 141.5 |
C15—H15···O17iii | 0.95 | 2.62 | 3.3451 (17) | 133.4 |
C12—H12···O7iv | 0.95 | 2.51 | 3.4285 (17) | 162.2 |
C10—H10D···Cg22v | 0.98 | 2.77 | 3.698 (2) | 159 |
C20—H20D···Cg21vi | 0.98 | 2.91 | 3.8463 (19) | 161 |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+2; (iii) −x+1, −y, −z+2; (iv) −x, −y+1, −z+1; (v) x−1, y+1, z; (vi) x+1, y−1, z. |