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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 67| Part 11| November 2011| Pages m351-m354
doi:10.1107/S0108270111042715

(η5-Cyclo­penta­dienyl)(η6-phenoxathiin 10,10-dioxide)iron(II) hexa­fluoridophosphate and phenoxathiin 10,10-di­oxide

CROSSMARK_Color_square_no_text.svg
Arthur D. Hendsbee,a Jason D. Masudaa and Adam Piórkoa*

aDepartment of Chemistry, Saint Mary's University, Halifax, Nova Scotia, Canada B3H 3C3
*Correspondence e-mail: adam.piorko@smu.ca

(Received 30 August 2011; accepted 14 October 2011; online 26 October 2011)

In the structure of the title complex salt, [Fe(C5H5)(C12H8O3S)]PF6, the coordinated cyclo­penta­dienyl (Cp) and benzene ring planes are almost parallel, with a hinge angle between the planes of 0.8 (2)°. The hinge angle between the planes of the peripheral (coordinated and uncoordinated) benzene rings in the coordinated phenoxathiin 10,10-dioxide mol­ecule is 169.9 (2)°, and the FeCp moiety is located inside the shallow fold of the heterocycle. The hinge angle between the benzene ring planes in the free heterocycle, C12H8O3S, is 171.49 (6)°.

Comment

The title complex, (I)[link] (Fig. 1[link]), was obtained in an extension of work on the synthesis of polycyclic heteroaromatic systems by the double nucleophilic aromatic substitution reaction using o-dichloro­benzene FeCp (Cp is cyclopentadienyl) and related complexes (Sutherland et al., 1982[Sutherland, R. G., Piórko, A., Gill, U. S. & Lee, C. C. (1982). J. Heterocycl. Chem. 19, 801-803.], 1988[Sutherland, R. G., Piórko, A., Lee, C. C., Simonsen, S. H. & Lynch, V. M. (1988). J. Heterocycl. Chem. 25, 1911-1916.]), followed by modification of the structure of the heterocycle by oxidation [see Lee, Chowdhury et al. (1986[Lee, C. C., Chowdhury, R. L., Piórko, A. & Sutherland, R. G. (1986). J. Organomet. Chem. 310, 391-400.]), and references therein]. This study continues our observations of changes that result in the structure of tricyclic heterocycles containing O and/or S atoms in the central ring of the system upon FeCp complexation and the introduction of substituents into a heterocycle structure. The free heterocycle, phenoxa­thiin 10,10-dioxide, (II)[link] (Fig. 2[link]), was obtained by oxidation of phenoxathiin with hydrogen peroxide in glacial acetic acid solution, as described by Gilman & Esmay (1952[Gilman, H. & Esmay, D. L. (1952). J. Am. Chem. Soc. 74, 2021-2024.]).

The asymmetric unit of (I)[link] contains one (phenoxathiin 10,10-dioxide)FeCp cation and one hexafluoridophosphate counter-anion. The FeCp moiety is located inside the shallow fold of the heterocycle. The coordinated Cp and benzene rings are nearly coplanar, with a hinge angle of 0.8 (2)°, which is in agreement with observations for both phenoxathiin and related aza­phenoxathiin FeCp complexes (Lynch et al., 1986[Lynch, V. M., Thomas, S. N., Simonsen, S. H., Piórko, A. & Sutherland, R. G. (1986). Acta Cryst. C42, 1144-1148.]; Sutherland et al., 1988[Sutherland, R. G., Piórko, A., Lee, C. C., Simonsen, S. H. & Lynch, V. M. (1988). J. Heterocycl. Chem. 25, 1911-1916.]). The centroid of the Cp ring, the Fe centre and the centroid of the benzene ring are nearly collinear, with an angle 179.35 (11)° measured between the two vectors extending from the Fe atom to the centroids in the complexed rings, and this value is typical for FeCp arene complexes [see, for example, Manzur et al. (2000[Manzur, C., Baeza, E., Millan, L., Fuentealba, M., Hamon, P., Hamon, J.-R., Boys, D. & Carrillo, D. (2000). J. Organomet. Chem. 608, 126-132.]) and Fuentealba et al. (2007[Fuentealba, M., Toupet, L., Manzur, C., Carrillo, D., Ledoux-Rak, I. & Hamon, J.-R. (2007). J. Organomet. Chem. 692, 1099-1109.])].

[Scheme 1]

The distances from the Fe1 ion to the Cp plane and to the coordinated benzene ring plane are 1.645 (2) and 1.540 (2) Å, respectively. These values are close to those reported in the literature for similar FeCp complexes [see, for example, Lynch et al. (1986[Lynch, V. M., Thomas, S. N., Simonsen, S. H., Piórko, A. & Sutherland, R. G. (1986). Acta Cryst. C42, 1144-1148.]), Abboud et al. (1990[Abboud, K. A., Lynch, V. M., Simonsen, S. H., Piórko, A. & Sutherland, R. G. (1990). Acta Cryst. C46, 1018-1022.]), Fuentealba et al. (2007[Fuentealba, M., Toupet, L., Manzur, C., Carrillo, D., Ledoux-Rak, I. & Hamon, J.-R. (2007). J. Organomet. Chem. 692, 1099-1109.]), Manzur et al. (2007[Manzur, C., Millan, L., Fuentealba, M., Hamon, J.-R., Toupet, L., Kahlal, S., Saillard, J.-Y. & Carrillo, D. (2007). Inorg. Chem. 46, 1123-1134.]) and Hendsbee et al. (2010[Hendsbee, A. D., Masuda, J. D. & Piórko, A. (2010). Acta Cryst. E66, m1154.])]. The distances from Fe1 to the C atoms of the coordinated benzene ring are within the range 2.048 (4)–2.113 (4) Å, with a mean of 2.082 (4) Å. The shortest Fe1—C distance is found for a quaternary C atom bonding to an SO2 group, while the distance to another quaternary C atom, bonding to an O atom, appears to be the longest. These distances are within the range of reported values for FeCp complexes (Abboud et al., 1990[Abboud, K. A., Lynch, V. M., Simonsen, S. H., Piórko, A. & Sutherland, R. G. (1990). Acta Cryst. C46, 1018-1022.]; Piórko et al., 1994[Piórko, A., Christie, S. & Zaworotko, M. J. (1994). Acta Cryst. C50, 1544-1545.]; Fuentealba et al., 2007[Fuentealba, M., Toupet, L., Manzur, C., Carrillo, D., Ledoux-Rak, I. & Hamon, J.-R. (2007). J. Organomet. Chem. 692, 1099-1109.]; Manzur et al., 2007[Manzur, C., Millan, L., Fuentealba, M., Hamon, J.-R., Toupet, L., Kahlal, S., Saillard, J.-Y. & Carrillo, D. (2007). Inorg. Chem. 46, 1123-1134.]; Jenkins et al., 2008[Jenkins, H. A., Masuda, J. D. & Piórko, A. (2008). Acta Cryst. E64, m1360.]). However, they differ from the data for both phenoxathiin and aza­phenoxathiin complexes, in which the two Fe—C(quaternary) distances are the longest of all six distances (Lynch et al., 1986[Lynch, V. M., Thomas, S. N., Simonsen, S. H., Piórko, A. & Sutherland, R. G. (1986). Acta Cryst. C42, 1144-1148.]; Sutherland et al., 1988[Sutherland, R. G., Piórko, A., Lee, C. C., Simonsen, S. H. & Lynch, V. M. (1988). J. Heterocycl. Chem. 25, 1911-1916.]).

The C—C distances in the coordinated ring of phenoxa­thiin 10,10-dioxide appear to be the same length as those in the uncoordinated ring, with the average distances being 1.401 (6) and 1.387 (6) Å, respectively. The C—S bonds extending from both the coordinated and uncoordinated ring C atoms to the bridging S atom are similar in length [1.757 (4) and 1.743 (4) Å, respectively]. The C—O distances, however, are quite different, as the bond extending from the bridging O atom to the C atom of the coordinated ring is significantly shorter than the C—O bond extending towards the uncoordinated ring [1.361 (5) and 1.393 (5) Å, respectively]. Both these observations agree with earlier findings for phenoxathiin and aza­phenoxathiin complexes (Lynch et al., 1986[Lynch, V. M., Thomas, S. N., Simonsen, S. H., Piórko, A. & Sutherland, R. G. (1986). Acta Cryst. C42, 1144-1148.]; Sutherland et al., 1988[Sutherland, R. G., Piórko, A., Lee, C. C., Simonsen, S. H. & Lynch, V. M. (1988). J. Heterocycl. Chem. 25, 1911-1916.]) and for dibenzodioxin complexes (Piórko et al., 1994[Piórko, A., Christie, S. & Zaworotko, M. J. (1994). Acta Cryst. C50, 1544-1545.], 1995[Piórko, A., Christie, S. & Zaworotko, M. J. (1995). Acta Cryst. C51, 26-29.]; Hendsbee et al., 2010[Hendsbee, A. D., Masuda, J. D. & Piórko, A. (2010). Acta Cryst. E66, m1154.]).

The C—C bonds in the rings of the free heterocycle, phenoxathiin 10,10-dioxide, (II)[link], have similar average lengths [1.385 (2) and 1.387 (2) Å] and are similar in length to the C—C bonds in the uncoordinated ring of complex (I). The S—C bond lengths from the bridging S atom to the benzene ring C atoms in the uncoordinated heterocycle are similar [1.7471 (16) and 1.7481 (18) Å] to those found in the complex. The C—O distances in the free heterocycle are 1.369 (2) and 1.371 (2) Å, more similar to the length of the C—O bond extending towards the coordinated ring of the FeCp complex [1.361 (5) Å] rather than that extending towards the uncoordinated ring of the FeCp complex [1.393 (5) Å].

A double nucleophilic aromatic substitution reaction yielding tricyclic heterocycle complexes may result in the formation of FeCp-in-fold, FeCp-out-of-fold or both isomeric mol­ecules of the nonplanar tricyclic heterocycle in the solid state. Examples of all three cases may be found in the literature, and all reports provide crystallographic data supporting this statement. The earlier studies of the synthesis and structure of dibenzodioxin and thianthrene FeCp complexes suggested that only FeCp-in-fold mol­ecules are formed in such a reaction. This conclusion was based on the results of several crystallographic studies (Simonsen et al., 1985[Simonsen, S. H., Lynch, V. M., Sutherland, R. G. & Piórko, A. (1985). J. Organomet. Chem. 290, 387-400.]; Abboud et al., 1990[Abboud, K. A., Lynch, V. M., Simonsen, S. H., Piórko, A. & Sutherland, R. G. (1990). Acta Cryst. C46, 1018-1022.]; Christie et al., 1994[Christie, S., Piórko, A. & Zaworotko, M. J. (1994). Acta Cryst. C50, 1868-1870.]; Piórko et al., 1994[Piórko, A., Christie, S. & Zaworotko, M. J. (1994). Acta Cryst. C50, 1544-1545.], 1995[Piórko, A., Christie, S. & Zaworotko, M. J. (1995). Acta Cryst. C51, 26-29.]). Recently, we reported that a double nucleophilic substitution reaction leading to the formation of (1,2,3,4,4a,10a-η)-1-methyl­thianthrene FeCp hexa­fluoridophosphate gave rise to a mixture of both in-fold and out-of-fold isomers, as found in a crystallographic study of the reaction products (Hendsbee et al., 2009[Hendsbee, A. D., Masuda, J. D. & Piórko, A. (2009). Acta Cryst. C65, m466-m468.]). The only previously reported out-of-fold thianthrene complex was obtained, along with its in-fold isomer, in a different reaction, a photolytic demetallation of a mixture containing cis- and trans-di(η5-Cp)(η6,η6-thianthrene)(iron)2 bis(hexa­fluoridophosphate)s, which were prepared in a ligand-exchange reaction (see Abboud et al., 1990[Abboud, K. A., Lynch, V. M., Simonsen, S. H., Piórko, A. & Sutherland, R. G. (1990). Acta Cryst. C46, 1018-1022.]).

Two phenoxathiin complexes which were obtained using a double nucleophilic substitution reaction have been reported in the literature to date. Both (phenoxathiin)FeCpPF6 (Lynch et al., 1986[Lynch, V. M., Thomas, S. N., Simonsen, S. H., Piórko, A. & Sutherland, R. G. (1986). Acta Cryst. C42, 1144-1148.]) and [(5a,6,7,8,9,9a-η)-1,4-benzoxathiino[3,2-b]pyridine]FeCpPF6 (Sutherland et al., 1988[Sutherland, R. G., Piórko, A., Lee, C. C., Simonsen, S. H. & Lynch, V. M. (1988). J. Heterocycl. Chem. 25, 1911-1916.]) contain, in the solid state, only out-of-fold FeCp moieties. In both complexes, the FeCp moiety is located outside the shallow heterocycle fold, with hinge angles of 178.7 (1) and 176.8 (1)° for the phenoxathiin and aza­phenoxathiin complexes, respectively. The hinge angle for the free phenoxathiin mol­ecule was reported as 138° (Hosoya, 1966[Hosoya, S. (1966). Acta Cryst. 20, 429-432.]) and as 147.8° (Fitzgerald et al., 1991[Fitzgerald, L. J., Gallucci, J. C. & Gerkin, R. E. (1991). Acta Cryst. C47, 381-385.]; 223 K). This angle has yet to be reported for the uncoordinated aza­phenoxathiin mol­ecule. It appears then that FeCp complexation flattens the phenoxathiin skeleton. In this study, it was found that the FeCp moiety is located inside the phenoxathiin 10,10-dioxide fold, with a hinge angle of 169.9 (2)° between the two peripheral benzene rings. Thus, oxidation of the S atom in the central ring appears to counteract the effect of FeCp complexation, causing more pronounced folding of the heterocycle mol­ecule and apparently converting the FeCp-out-of-fold isomer into the FeCp-in-fold one. For free phenoxathiin 10,10-dioxide, we found the hinge angle to be 171.49 (6)°, which means that when this mol­ecule is coordinated to FeCp it is slightly more folded. This is the first confirmed example, and only the second case in which FeCp coordination appears to increase folding of the tricyclic heterocycle mol­ecule. In the earlier case, this effect was observed in the structure of a methyl­thianthrene mol­ecule carrying a methyl group in an uncoordinated benzene ring. The structure of the free heterocycle, 2-methyl­thianthrene, has not yet been reported, so the folding angle of a parent thianthrene mol­ecule was used for comparison (Simonsen et al., 1985[Simonsen, S. H., Lynch, V. M., Sutherland, R. G. & Piórko, A. (1985). J. Organomet. Chem. 290, 387-400.]). A similar effect was reported for a structurally related thio­xanthene mol­ecule, with a methyl­ene group replacing the O atom in the central ring. Literature reports indicate that oxidation of the S atom to a dioxide results in slightly more pronounced folding of the mol­ecule. For thioxanthene, the hinge angle was reported as 135.3 (1)° (Gillean et al., 1973[Gillean, J. A., Phelps, D. W. & Cordes, A. W. (1973). Acta Cryst. B29, 2296-2298.]), while for thioxanthene 10,10-dioxide this angle was 133.9° (Chu & Chung, 1974[Chu, S. S. C. & Chung, B. (1974). Acta Cryst. B30, 1616-1618.]).

We suggest that both the increased folding and the location of the FeCp moiety inside the fold may be requirements for minimizing the inter­action of S-bonded O atoms with Fe in a complex. In this apparently favoured in-fold isomer, the distance from Fe to the proximal O atom will be longer than the analogous distance in the out-of-fold mol­ecule. With a relatively small hinge angle in the starting phenoxathiin mol­ecule, thermal flipping of this mol­ecule during oxidation, which results in inversion of the FeCp-out-of-fold isomer to the FeCp-in-fold isomer, appears to be possible and favoured at an elevated reaction temperature. However, this inversion process may be difficult to observe experimentally.

[Figure 1]
Figure 1
The cation and anion of complex (I)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.
[Figure 2]
Figure 2
The free heterocycle, (II)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.

Experimental

The precursor (phenoxathiin)FeCp hexa­fluoridophosphate complex was obtained in the double nucleophilic aromatic substitution reaction of the o-dichloro­benzene FeCp complex with 2-mercaptophenol, as described in the literature (Sutherland et al., 1982[Sutherland, R. G., Piórko, A., Gill, U. S. & Lee, C. C. (1982). J. Heterocycl. Chem. 19, 801-803.]). The title complex salt was obtained in an oxidation of the precursor phenoxa­thiin complex using hydrogen peroxide in trifluoro­acetic acid. This method, while used for oxidation of the amino group to a nitro group in similar complexes (see Lee et al., 1982[Lee, C. C., Gill, U. S., Iqbal, M., Azogu, C. I. & Sutherland, R. G. (1982). J. Organomet. Chem. 231, 151-159.]; Chowdhury et al., 1985[Chowdhury, R. L., Lee, C. C., Piórko, A. & Sutherland, R. G. (1985). Synth. React. Inorg. Met. Org. Chem. 15, 1237-1245.]; Lee, Abd-El-Aziz et al., 1986[Lee, C. C., Abd-El-Aziz, A. S., Chowdhury, R. L., Piórko, A. & Sutherland, R. G. (1986). Synth. React. Inorg. Met. Org. Chem. 16, 541-552.]; Abd-El-Aziz et al., 1988[Abd-El-Aziz, A. S., Lee, C. C., Piórko, A. & Sutherland, R. G. (1988). J. Organomet. Chem. 348, 95-107.]) and, more recently, for simultaneous oxidation of both amino and alkyl groups to nitro and carb­oxy groups, respectively (Abd-El-Aziz et al., 1997[Abd-El-Aziz, A. S., Boraie, W., Al-Salem, N., Sadek, S. A. & Epp, K. M. (1997). J. Chem. Soc. Perkin Trans. 1, pp. 1469-1479.]; Abd-El-Aziz & Epp, 1995[Abd-El-Aziz, A. S. & Epp, K. M. (1995). Polyhedron, pp. 957-960.]), has not been reported previously in the oxidation of sulfur-containing FeCp complexes, although it has been generally used in the oxidation of sulfur-containing heterocycles using glacial acetic acid as solvent [see, for example, oxidation of dibenzothio­phene and phenoxathiin to the corresponding dioxides by Gilman & Esmay (1952[Gilman, H. & Esmay, D. L. (1952). J. Am. Chem. Soc. 74, 2021-2024.])]. The reaction gave a 68% yield and a crystal suitable for X-ray analysis was obtained from an acetone–diethyl ether–dichloro­methane solution at 280 (2) K. The same complex was also obtained in 63% yield in an alternative oxidation of the phenoxathiin complex with m-chloro­perbenzoic acid, according to the procedure of Lee, Abd-El-Aziz et al. (1986). Phenoxathiin 10,10-dioxide, (II)[link], was obtained by oxidation of the precursor phenoxathiin using 30% hydrogen peroxide in glacial acetic acid (Gilman & Esmay, 1952[Gilman, H. & Esmay, D. L. (1952). J. Am. Chem. Soc. 74, 2021-2024.]) with a total yield of 98%. A crystal suitable for X-ray analysis was obtained upon cooling the reaction mixture to room temperature. Experimental details and analytical data for both complex (I)[link] and free heterocycle (II)[link] are provided in the Supplementary materials.

Compound (I)[link]

Crystal data

  • [Fe(C5H5)(C12H8O3S)]PF6

  • Mr = 498.16

  • Monoclinic, C c

  • a = 10.059 (2) Å

  • b = 13.618 (3) Å

  • c = 13.544 (4) Å

  • β = 104.446 (2)°

  • V = 1796.6 (8) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.12 mm−1

  • T = 100 K

  • 0.30 × 0.18 × 0.18 mm
Data collection

  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.521, Tmax = 0.746

  • 10650 measured reflections

  • 4277 independent reflections

  • 3615 reflections with I > 2σ(I)

  • Rint = 0.046
Refinement

  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.089

  • S = 1.28

  • 4277 reflections

  • 262 parameters

  • 52 restraints

  • H-atom parameters constrained

  • Δρmax = 0.87 e Å−3

  • Δρmin = −0.28 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), with 2066 Friedel pairs

  • Flack parameter: −0.037 (19)

Compound (II)[link]

Crystal data

  • C12H8O3S

  • Mr = 232.24

  • Triclinic, [P \overline 1]

  • a = 7.2067 (10) Å

  • b = 7.9568 (11) Å

  • c = 8.9360 (13) Å

  • α = 102.475 (1)°

  • β = 95.493 (2)°

  • γ = 93.399 (2)°

  • V = 496.33 (12) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.31 mm−1

  • T = 150 K

  • 0.22 × 0.20 × 0.19 mm
Data collection

  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker; 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.665, Tmax = 0.746

  • 4816 measured reflections

  • 1746 independent reflections

  • 1592 reflections with I > 2σ(I)

  • Rint = 0.019
Refinement

  • R[F2 > 2σ(F2)] = 0.030

  • wR(F2) = 0.072

  • S = 0.97

  • 1746 reflections

  • 145 parameters

  • H-atom parameters constrained

  • Δρmax = 0.33 e Å−3

  • Δρmin = −0.31 e Å−3

H atoms were placed in geometrically idealized positions, with C—H = 0.95 [for all uncoordinated and coordinated aromatic C atoms in (I)[link], and all C atoms in free heterocycle (II)] or 1.00 Å [for cyclo­penta­dienyl C atoms in (I)], and constrained to ride on their parent C atoms, with Uiso(H) = 1.2Ueq(C). For the PF6− counter-anion in (I)[link], the F atoms were restrained to have the same Uij components within a standard uncertainty of 0.05 Å2. Thermal motion of the Cp ring π-bonded to the Fe atom resulted in unsatisfactory anisotropic displacement parameters for atoms C11, C12, C13 and C15. This was resolved through the use of the restraints applied to the refinement of these atoms: the Uij components of these atoms were restrained to be equal within 0.004 Å2 and their anisotropic displacement parameters were restrained to be equal within 0.002 Å2.

For both compounds, data collection: APEX2 (Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, II, global. DOI: 10.1107/S0108270111042715/yp3006sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270111042715/yp3006Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270111042715/yp3006IIsup3.hkl

Supporting information file. DOI: 10.1107/S0108270111042715/yp3006Isup4.mol

Supporting information file. DOI: 10.1107/S0108270111042715/yp3006IIsup5.mol


Comment top

The title complex, (I), was obtained in an extension of the work on the synthesis of polycyclic heteroaromatic systems in the double nucleophilic aromatic substitution reaction using o-dichlorobenzene FeCp and related complexes (Sutherland et al., 1982, 1988), followed by modification of the heterocycle structure by oxidation (see Lee et al., 1986, and earlier work by the same authors). This study continues our observations of changes that result in the structure of tricyclic heterocycles containing O and/or S atoms in the central ring of the system upon FeCp complexation and the introduction of substituents into a heterocycle structure. The free heterocycle, phenoxathiin 10,10-dioxide, (II), was obtained in an oxidation of phenoxathiin with hydrogen peroxide in glacial acetic acid solution, as described by Gilman & Esmay (1952).

The unit cell of (I) contains four cationic molecules of the (phenoxathiin 10,10-dioxide) FeCp complex along with four hexafluoridophosphate counteranions. The FeCp moiety is located inside the shallow heterocycle fold in all molecules. The complexed Cp and benzene rings are nearly coplanar, with a dihedral angle of 0.8 (2)°, which is in agreement with observations for both phenoxathiin and related azaphenoxathiin FeCp complexes (Lynch et al., 1986; Sutherland et al., 1988). The centroid of the Cp ring, the Fe centre and the centroid of the benzene ring are nearly collinear with an angle 179.35 (11)° measured between the two vectors extending from the Fe atom to the centroids in the complexed rings, and this value is typical for FeCp arene complexes [see, for example, Manzur et al. (2000) and Fuentealba et al. (2007)].

The distances from the FeII ion to the Cp plane and to the complexed benzene ring plane are 1.645 (2) and 1.540 (2) Å, respectively. These values are close to those reported in the literature for similar FeCp complexes [see, for example, Lynch et al. (1986), Abboud et al. (1990), Fuentealba et al. (2007), Manzur et al. (2007) and Hendsbee et al. (2010)]. The distances from Fe to the C atoms of the complexed benzene ring are within the range 2.048 (4)–2.113 (4) Å, with a mean of 2.082 Å. The shortest Fe—C distance is found for a quaternary C atom bonding to an –SO2– group, while the distance to another quaternary C atom, bonding to an O atom, appears to be the longest. The distances are within the range of reported values for FeCp complexes (Abboud et al., 1990; Piórko et al., 1994; Fuentealba et al., 2007; Manzur et al., 2007; Jenkins et al., 2008). However, they differ from the data for both phenoxathiin and azaphenoxathiin complexes, in which both the Fe—C(quaternary) distances are the longest of all six distances (Lynch et al., 1986; Sutherland et al., 1988).

The C—C distances in the complexed ring of the phenoxathiin 10,10-dioxide appear to be slightly longer than those in the uncomplexed ring, with the average distances being 1.401 and 1.387 Å, respectively. The C—S bonds extending from both the complexed and uncomplexed ring C atoms to the bridging S atom are similar in length [1.757 (4) and 1.743 (4) Å, respectively]. The C—O distances, however, are quite different, as the bond extending from the bridging O atom to the C atom of the complexed ring is significantly shorter than the C—O bond extending towards the uncomplexed ring [1.361 (5) and 1.393 (5) Å, respectively]. Both these observations agree with earlier findings for phenoxathiin and azaphenoxathiin complexes (Lynch et al., 1986; Sutherland et al., 1988) and for dibenzodioxin complexes (Piórko et al., 1994, 1995; Hendsbee et al., 2010).

The C—C bonds in the rings of the free heterocycle, phenoxathiin 10,10-dioxide, (II), have similar average lengths (1.385 and 1.387 Å) and are similar in length to the C—C bonds in the uncomplexed ring of the heterocycle FeCp complex. The S—C bond lengths from the bridging S atom to the benzene ring C atoms in the uncomplexed heterocycle are similar [1.7471 (16) and 1.7481 (18) Å] to those found in the complex. The C—O distances in the free heterocycle are 1.369 (2) and 1.371 (2) Å, more similar to the length of the C—O bond extending towards the complexed ring of the FeCp complex [1.361 (5) Å] rather than that extending towards the uncomplexed ring of the FeCp complex [1.393 (5) Å].

A double nucleophilic aromatic substitution reaction yielding tricyclic heterocycle complexes may result in the formation of FeCp-in-fold, FeCp-out-of-fold, or both isomeric molecules of the nonplanar tricyclic heterocycle in the solid state. Examples of all three cases may be found in the literature, and all reports provide crystallographic data supporting this a statement. The earlier studies of the synthesis and structure of dibenzodioxin and thianthrene FeCp complexes suggested that only FeCp-in-fold molecules are formed in such a reaction. This conclusion was based on the results of several crystallographic studies (Simonsen et al., 1985; Abboud et al., 1990; Christie et al., 1994; Piórko et al., 1994, 1995). Recently, we reported that a double nucleophilic substitution reaction leading to the formation of (1,2,3,4,4a,10a-η)-1-methylthianthrene FeCp hexafluoridophosphate gave rise to a mixture of both in-fold and out-of-fold isomers, as found in a crystallographic study of the reaction products (Hendsbee et al., 2009). The only previously reported out-of-fold thianthrene complex was obtained, along with its in-fold isomer, in a different reaction, a photolytic demetallation of a mixture containing cis and trans di-(η5-Cp)(η6,η6-thianthrene)(iron)2 bis-hexafluoridophosphates, which were prepared in a ligand-exchange reaction (see Abboud et al., 1990).

Two phenoxathiin complexes which were obtained using a double nucleophilic substitution reaction have been reported in the literature to date. Both (phenoxathiin)FeCpPF6 (Lynch et al., 1986) and (5a,6,7,8,9,9a-η-1,4-benzoxathiino[3,2-b]pyridine)FeCpPF6 (Sutherland et al., 1988) contain, in the solid state, only out-of-fold FeCp moieties. In both complexes, the FeCp moiety is located outside the shallow heterocycle fold, with dihedral angles of 178.7 (1) and 176.8 (1)° for the phenoxathiin and azaphenoxathiin complexes, respectively. The dihedral angle for the free phenoxathiin molecule was reported as 138° (Hosoya, 1966) and as 142.3° (Fitzgerald et al., 1991; 223 K). This angle has yet to be reported for the uncomplexed azaphenoxathiin molecule. It appears then that FeCp complexation flattens the phenoxathiin skeleton. In this study it was found that the FeCp moiety is located inside the phenoxathiin 10,10-dioxide fold, with a dihedral angle of 169.9 (2)° between the two external benzene rings. Thus, oxidation of the S atom in the central ring appears to counteract the effect of FeCp complexation, causing more pronounced folding of the heterocycle molecule, and apparently converting the FeCp-out-of-fold isomer into the FeCp-in-fold one. For free phenoxathiin 10,10-dioxide we found the dihedral angle to be 171.49 (6)°, which means that when this molecule is complexed to FeCp it is slightly more folded. This is the first firmly confirmed example, and only the second case, in which FeCp complexation appears to increase folding of the tricyclic heterocycle molecule. In the earlier case this effect was observed in the structure of a methylthianthrene molecule carrying a methyl group in an uncomplexed benzene ring. The structure of the free heterocycle, 2-methylthianthrene, has not yet been reported, so the folding angle of a parent thianthrene molecule was used for comparison (Simonsen et al., 1985). A similar effect was reported for a structurally related thioxanthene molecule, with a methylene group replacing the O atom in the central ring. Literature reports indicate that oxidation of the S atom to a dioxide results in slightly more pronounced folding of the molecule. For thioxanthene, the dihedral angle was reported as 135.3 (1)° (Gillean et al., 1973), while for thioxanthene 10,10-dioxide this angle was 133.9° (Chu & Chung, 1974).

We suggest that both the increased folding and the location of the FeCp moiety inside the fold may be requirements for minimizing the interaction of S-bonded O atoms with Fe in a complex. In this apparently favoured in-fold isomer, the distance from Fe to the proximal O atom will be longer than the analogous distance in the out-of-fold molecule. With a relatively small dihedral angle in the starting phenoxathiin molecule, a thermal flipping of this molecule during oxidation, which results in inversion of the FeCp-out-of-fold isomer to the FeCp-in-fold isomer, appears to be possible and favoured at an elevated reaction temperature. However, this inversion process may be difficult to observe experimentally.

Related literature top

For related literature, see: Abboud et al. (1990); Abd-El-Aziz & Epp (1995); Abd-El-Aziz, Boraie, Al-Salem, Sadek & Epp (1997); Christie et al. (1994); Chu & Chung (1974); Fitzgerald et al. (1991); Fuentealba et al. (2007); Gillean et al. (1973); Gilman & Esmay (1952); Hendsbee et al. (2009, 2010); Hosoya (1966); Jenkins et al. (2008); Lee et al. (1982); Lee, Abd El Aziz, Chowdhury, Piórko & Sutherland (1986); Lee, Chowdhury, Piórko & Sutherland (1986); Lynch et al. (1986); Manzur et al. (2000, 2007); Piórko et al. (1994, 1995); Simonsen et al. (1985); Sutherland et al. (1982, 1988).

Experimental top

The precursor (phenoxathiin)FeCp hexafluoridophosphate complex was obtained in the double nucleophilic aromatic substitution reaction of the o-dichlorobenzene FeCp complex with 2-mercaptophenol, as described in the literature (Sutherland et al., 1982). The title complex salt was obtained in an oxidation of the precursor phenoxathiin complex using hydrogen peroxide in trifluoroacetic acid. This method, while used for oxidation of the amino group to a nitro group in similar complexes (see Lee et al., 1982, and later work by the same authors) and, more recently, for simultaneous oxidation of both amino and alkyl groups to nitro and carboxy groups, respectively (Abd-El-Aziz et al., 1997; Abd-El-Aziz & Epp, 1995), has not been previously reported in the oxidation of sulfur-containing FeCp complexes, although it has been generally used in the oxidation of sulfur-containing heterocycles using glacial acetic acid as a solvent [see, for example, oxidation of dibenzothiophene and phenoxathiin to the corresponding dioxides by Gilman & Esmay (1952)]. The reaction gave 68% yield and the crystal suitable for X-ray examination was obtained from the acetone–diethyl ether–dichloromethane solution at 280 (2) K. The same complex was also obtained in 63% yield in an alternative oxidation of the phenoxathiin complex with m-chloroperbenzoic acid, according to the procedure of Lee, Abd El Aziz et al. (1986). Phenoxathiin 10,10-dioxide, (II), was obtained by oxidation of the precursor phenoxathiin using 30% hydrogen peroxide in glacial acetic acid (Gilman & Esmay, 1952) with a total yield of 98%. The crystal suitable for X-ray examination was obtained upon cooling the reaction mixture to room temperature. Experimental details and analytical data for both the complex (I) and free heterocycle (II) are provided in the Supplementary materials.

Refinement top

H atoms were placed in geometrically idealized positions, with C—H = 0.95 [all uncoordinated and coordinated aromatic C atoms in (I), and all C atoms in free heterocycle (II)] or 1.00 Å [cyclopentadienyl C atoms in (I)], and constrained to ride on their parent C atoms, with Uiso(H) = 1.2Ueq(C). For the counter-anion PF6- group in (I), the F atoms were restrained to have the same Uij components within a standard uncertainty of 0.05 Å2. The complexed heterocycle structure contains a cyclopentadienyl (Cp) ring which is π-bonded to an Fe atom, and the thermal motion of this Cp ring resulted in unsatisfactory anisotropic displacement parameters for atoms C11, C12, C13 and C15. This was resolved through the use of the restraints applied to the refinement of these atoms: the Uij components of these atoms were restrained to be equal within 0.004 Å2, and their anisotropic displacement parameters were restrained to be equal within 0.002 Å2.

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The cation and anion of complex (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. The free heterocycle, (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.
(I) (η5-Cyclopentadienyl)(η6-phenoxathiin 10,10-dioxide)iron(II) hexafluoridophosphate top
Crystal data top
[Fe(C5H5)(C12H8O3S)]PF6F(000) = 1000
Mr = 498.16Dx = 1.842 Mg m−3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 5464 reflections
a = 10.059 (2) Åθ = 2.6–27.8°
b = 13.618 (3) ŵ = 1.12 mm−1
c = 13.544 (4) ÅT = 100 K
β = 104.446 (2)°Block, yellow
V = 1796.6 (8) Å30.30 × 0.18 × 0.18 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer		4277 independent reflections
Radiation source: fine-focus sealed tube3615 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
ϕ and ω scansθmax = 28.4°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		h = −13→13
Tmin = 0.521, Tmax = 0.746k = −17→17
10650 measured reflectionsl = −17→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.089 w = 1/[σ2(Fo2) + (0.P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.28(Δ/σ)max = 0.010
4277 reflectionsΔρmax = 0.87 e Å−3
262 parametersΔρmin = −0.28 e Å−3
52 restraintsAbsolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: −0.037 (19)
Crystal data top
[Fe(C5H5)(C12H8O3S)]PF6V = 1796.6 (8) Å3
Mr = 498.16Z = 4
Monoclinic, CcMo Kα radiation
a = 10.059 (2) ŵ = 1.12 mm−1
b = 13.618 (3) ÅT = 100 K
c = 13.544 (4) Å0.30 × 0.18 × 0.18 mm
β = 104.446 (2)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		4277 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		3615 reflections with I > 2σ(I)
Tmin = 0.521, Tmax = 0.746Rint = 0.046
10650 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.089Δρmax = 0.87 e Å−3
S = 1.28Δρmin = −0.28 e Å−3
4277 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs?
262 parametersAbsolute structure parameter: −0.037 (19)
52 restraints
Special details top

Experimental. Solid (phenoxathiin)FeCp hexafluoridophosphate (0.932 g, 2.0 mmol) was added to a mixture of trifluoroacetic acid (20 ml) and 30% hydrogen peroxide (20 ml). The resulting mixture was stirred for 3 h at 333 K, cooled to room temperature and poured into water (120 ml). The solution was extracted with dichloromethane (3 × 20 ml) and then with a 4:1 (v/v) mixture of dichloromethane and nitromethane. The combined extracts were evaporated at reduced pressure, and then acetone (30 ml) was added to the flask and the solvent removed again by evaporation. The addition of acetone and evaporation were repeated twice more to remove water. Finally, the crude product was dissolved in a minimum volume of acetone, diethyl ether was added to start precipitation, and dichloromethane was added to clear the solution. The final solution was kept in a refrigerator at 280 (2) K with the occasional addition of a small volume of diethyl ether until crystals of (I) suitable for data collection appeared in the flask. After collecting these crystals, the complex remaining in solution was precipitated upon addition of an excess of diethyl ether. The product was collected on a sintered glass filter, washed with diethyl ether and dried to give a yellow–orange powder. The total mass of recovered product was 0.678 g (68% yield).

Analytical data for the complex. Elemental analysis, calculated: C 40.97%, H 2.63%; found: C 41.06%, H 2.33%. 1H NMR (300.133 MHz, acetone-d6, δ, p.p.m.): Cp 5.25 (5H, s); complexed benzene ring 6.82 (1 H, t, J = 6.0 Hz), 6.90 (1 H, t, J = 6.4 Hz, d, J = 1.1 Hz), 7.19 (1H, d, J = 6.4 Hz), 7.28 (1 H, d, J = 6.0 Hz, d, J = 1.1 Hz); uncomplexed benzene ring 7.74 (1 H, d, J = 8.6 Hz), 7.6 (1 H, degenerate t, J = 7.8 Hz, d, J = 0.9 Hz), 8.02 (1 H, d, J = 8.6 Hz, d, J = 7.6 Hz, d, J = 1.8 Hz), 8.23 (1H, d, J = 7.8 Hz, d, J = 1.8 Hz). 13C NMR (75.469 MHz, acetone-d6, δ, p.p.m.): 79.4 (Cp), 80.5, 81.1, 87.3, 90.5, 94.1 (C of complexed benzene ring), 94.1, 125.0 (quaternary C of complexed benzene ring), 121.0, 124.4, 128.6, 137.6 (C of uncomplexed benzene ring), 127.5, 152.1 (quaternary C of uncomplexed benzene ring).

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.

The H atoms were placed in geometrically idealized positions, with C—H = 0.95 (all uncoordinated and coordinated aromatic C atoms) or 1.00 Å (cyclopentadienyl C atoms), and constrained to ride on their parent C atoms, with Uiso(H) = 1.2Ueq(C). For the counter-anion PF6 group in (I), the F atoms were restrained to have the same Uij components within a standard uncertainty of 0.05 Å2. The complexed heterocycle structure contains a cyclopentadienyl (Cp) ring which is π-bonded to an Fe atom, and the thermal motion of this Cp ring resulted in unsatisfactory anisotropic displacement parameters for atoms C11, C12, C13 and C15. This was resolved through use of the restrains applied to the refinement of these atoms: the Uij components of these atoms were restrained to be equal to within 0.004 Å2, and their anisotropic

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.06320 (5)0.09010 (4)0.70531 (4)0.02552 (14)
C10.2221 (4)0.0277 (3)0.8146 (3)0.0263 (9)
H10.2245−0.02400.86210.032*
C20.2422 (4)0.0078 (3)0.7182 (3)0.0267 (9)
H20.2583−0.05740.69900.032*
C30.2381 (4)0.0857 (3)0.6507 (3)0.0290 (9)
H30.25170.07230.58510.035*
C40.2149 (4)0.1826 (3)0.6758 (3)0.0300 (9)
H40.21020.23360.62720.036*
C4A0.1987 (4)0.2036 (3)0.7731 (3)0.0264 (9)
C10A0.1981 (4)0.1254 (3)0.8407 (3)0.0225 (8)
O50.1739 (3)0.2994 (2)0.7910 (2)0.0331 (7)
C5A0.1270 (4)0.3280 (3)0.8751 (3)0.0257 (9)
C60.0945 (4)0.4269 (3)0.8774 (3)0.0304 (9)
H60.10330.46890.82340.037*
C70.0500 (4)0.4635 (3)0.9572 (4)0.0373 (11)
H70.02970.53150.95920.045*
C80.0337 (4)0.4018 (3)1.0364 (3)0.0351 (10)
H80.00100.42771.09110.042*
C90.0655 (4)0.3034 (3)1.0342 (3)0.0298 (9)
H90.05620.26131.08800.036*
C9A0.1116 (4)0.2659 (3)0.9522 (3)0.0223 (8)
S100.16192 (11)0.14315 (7)0.95985 (8)0.0269 (2)
O20.0495 (3)0.0825 (2)0.9681 (2)0.0399 (8)
O30.2878 (3)0.1301 (2)1.0364 (2)0.0337 (7)
C11−0.1138 (5)0.1583 (4)0.6355 (4)0.0490 (12)
H11−0.12330.22850.61350.059*
C12−0.1239 (5)0.1223 (4)0.7294 (4)0.0488 (12)
H12−0.13990.16310.78680.059*
C13−0.1011 (5)0.0201 (3)0.7330 (4)0.0414 (11)
H13−0.1022−0.02540.79070.050*
C14−0.0871 (4)−0.0056 (3)0.6336 (3)0.0338 (10)
H14−0.0713−0.07340.61060.041*
C15−0.0910 (5)0.0790 (4)0.5764 (4)0.0406 (11)
H15−0.08090.08260.50490.049*
P10.09922 (12)0.75056 (8)0.85832 (9)0.0312 (3)
F10.0852 (4)0.65239 (19)0.7938 (2)0.0636 (9)
F2−0.0128 (3)0.7119 (2)0.9118 (2)0.0519 (7)
F30.1117 (3)0.84921 (19)0.9229 (2)0.0563 (8)
F40.2081 (3)0.79130 (19)0.8012 (2)0.0554 (8)
F5−0.0164 (3)0.7989 (2)0.7700 (2)0.0651 (9)
F60.2163 (3)0.7011 (2)0.9436 (3)0.0675 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0271 (3)0.0232 (3)0.0247 (3)0.0025 (3)0.0034 (2)−0.0011 (3)
P10.0380 (6)0.0224 (5)0.0351 (6)−0.0033 (5)0.0128 (5)−0.0055 (5)
F10.120 (3)0.0206 (14)0.0559 (19)−0.0082 (16)0.032 (2)−0.0068 (12)
C90.028 (2)0.030 (2)0.031 (2)−0.0048 (18)0.0051 (18)−0.0025 (19)
F20.0525 (17)0.0442 (17)0.067 (2)−0.0053 (14)0.0303 (15)0.0102 (15)
O20.056 (2)0.0287 (17)0.0425 (18)−0.0058 (15)0.0268 (16)0.0005 (14)
C80.029 (2)0.037 (3)0.040 (3)0.000 (2)0.010 (2)−0.018 (2)
F30.093 (2)0.0319 (15)0.0565 (19)−0.0163 (16)0.0426 (17)−0.0179 (13)
O30.0502 (19)0.0287 (16)0.0211 (15)0.0073 (14)0.0064 (14)0.0055 (12)
C70.035 (3)0.019 (2)0.051 (3)0.0090 (19)−0.001 (2)−0.006 (2)
F40.078 (2)0.0311 (15)0.076 (2)−0.0032 (14)0.0537 (18)−0.0041 (14)
C60.034 (2)0.021 (2)0.032 (2)0.0004 (19)−0.0001 (18)0.0043 (18)
C5A0.031 (2)0.0204 (19)0.022 (2)−0.0034 (17)−0.0002 (17)−0.0013 (16)
F50.065 (2)0.053 (2)0.069 (2)0.0000 (16)0.0021 (17)0.0246 (17)
O50.0511 (19)0.0234 (15)0.0254 (15)−0.0016 (14)0.0109 (13)0.0018 (12)
C4A0.031 (2)0.025 (2)0.024 (2)−0.0032 (17)0.0083 (17)−0.0038 (17)
C40.030 (2)0.033 (2)0.027 (2)−0.0030 (19)0.0064 (18)−0.0027 (18)
F60.055 (2)0.058 (2)0.078 (2)0.0035 (16)−0.0051 (17)0.0206 (18)
C30.025 (2)0.041 (3)0.0207 (19)−0.0009 (19)0.0066 (16)−0.0068 (18)
C20.021 (2)0.023 (2)0.032 (2)0.0046 (16)−0.0006 (17)−0.0038 (17)
C10A0.022 (2)0.026 (2)0.0188 (19)−0.0007 (16)0.0027 (16)−0.0059 (16)
C10.024 (2)0.027 (2)0.024 (2)−0.0013 (18)−0.0015 (17)0.0041 (17)
S100.0403 (6)0.0174 (5)0.0247 (5)−0.0005 (4)0.0112 (4)0.0002 (4)
C9A0.027 (2)0.0206 (19)0.0201 (19)−0.0008 (16)0.0067 (17)−0.0028 (16)
C110.036 (2)0.035 (2)0.063 (3)0.007 (2)−0.012 (2)0.0089 (19)
C120.032 (2)0.050 (2)0.065 (3)0.003 (2)0.015 (2)−0.023 (2)
C130.039 (2)0.042 (2)0.054 (3)−0.011 (2)0.032 (2)−0.012 (2)
C140.031 (2)0.031 (2)0.038 (3)0.0011 (19)0.006 (2)−0.0076 (19)
C150.028 (2)0.044 (2)0.043 (3)0.0003 (19)−0.0042 (18)0.0102 (18)
Geometric parameters (Å, º) top
Fe1—C112.021 (5)C6—H60.9500
Fe1—C132.022 (4)C5A—C9A1.382 (5)
Fe1—C152.032 (5)C5A—O51.393 (5)
Fe1—C122.037 (5)O5—C4A1.361 (5)
Fe1—C10A2.048 (4)C4A—C10A1.406 (6)
Fe1—C142.048 (4)C4A—C41.398 (5)
Fe1—C12.071 (4)C4—C31.397 (6)
Fe1—C32.073 (4)C4—H40.9500
Fe1—C22.091 (4)C3—C21.394 (6)
Fe1—C42.093 (4)C3—H30.9500
Fe1—C4A2.113 (4)C2—C11.397 (5)
P1—F21.575 (3)C2—H20.9500
P1—F61.580 (3)C10A—C11.413 (5)
P1—F11.584 (3)C10A—S101.757 (4)
P1—F51.588 (3)C1—H10.9500
P1—F41.590 (3)S10—C9A1.743 (4)
P1—F31.591 (3)C11—C121.390 (8)
C9—C81.380 (6)C11—C151.396 (7)
C9—C9A1.402 (5)C11—H111.0000
C9—H90.9500C12—C131.409 (7)
O2—S101.427 (3)C12—H121.0000
C8—C71.403 (7)C13—C141.432 (6)
C8—H80.9500C13—H131.0000
O3—S101.434 (3)C14—C151.382 (6)
C7—C61.364 (6)C14—H141.0000
C7—H70.9500C15—H151.0000
C6—C5A1.388 (5)
C11—Fe1—C1368.8 (2)C5A—C6—H6120.1
C11—Fe1—C1540.3 (2)C9A—C5A—C6120.4 (4)
C13—Fe1—C1568.9 (2)C9A—C5A—O5124.9 (3)
C11—Fe1—C1240.1 (2)C6—C5A—O5114.8 (3)
C13—Fe1—C1240.63 (19)C4A—O5—C5A121.9 (3)
C15—Fe1—C1267.4 (2)O5—C4A—C10A125.4 (3)
C11—Fe1—C10A128.37 (19)O5—C4A—C4115.8 (3)
C13—Fe1—C10A109.52 (18)C10A—C4A—C4118.7 (4)
C15—Fe1—C10A168.67 (19)O5—C4A—Fe1130.7 (3)
C12—Fe1—C10A103.79 (19)C10A—C4A—Fe167.8 (2)
C11—Fe1—C1467.06 (19)C4—C4A—Fe169.8 (2)
C13—Fe1—C1441.19 (18)C3—C4—C4A119.3 (4)
C15—Fe1—C1439.61 (18)C3—C4—Fe169.6 (2)
C12—Fe1—C1467.09 (19)C4A—C4—Fe171.4 (2)
C10A—Fe1—C14145.08 (18)C3—C4—H4120.4
C11—Fe1—C1162.9 (2)C4A—C4—H4120.4
C13—Fe1—C1101.23 (18)Fe1—C4—H4131.3
C15—Fe1—C1150.64 (19)C4—C3—C2122.6 (4)
C12—Fe1—C1123.6 (2)C4—C3—Fe171.2 (2)
C10A—Fe1—C140.13 (15)C2—C3—Fe171.1 (2)
C14—Fe1—C1115.14 (17)C4—C3—H3118.7
C11—Fe1—C3125.0 (2)C2—C3—H3118.7
C13—Fe1—C3149.12 (18)Fe1—C3—H3132.3
C15—Fe1—C3103.03 (18)C1—C2—C3118.6 (4)
C12—Fe1—C3164.6 (2)C1—C2—Fe169.6 (2)
C10A—Fe1—C383.95 (16)C3—C2—Fe169.7 (2)
C14—Fe1—C3113.83 (17)C1—C2—H2120.7
C1—Fe1—C370.77 (16)C3—C2—H2120.7
C11—Fe1—C2157.6 (2)Fe1—C2—H2132.8
C13—Fe1—C2117.29 (17)C4A—C10A—C1121.4 (4)
C15—Fe1—C2119.26 (18)C4A—C10A—S10122.0 (3)
C12—Fe1—C2155.9 (2)C1—C10A—S10116.6 (3)
C10A—Fe1—C271.75 (16)C4A—C10A—Fe172.8 (2)
C14—Fe1—C2102.53 (16)C1—C10A—Fe170.8 (2)
C1—Fe1—C239.22 (15)S10—C10A—Fe1127.7 (2)
C3—Fe1—C239.12 (16)C2—C1—C10A119.4 (4)
C11—Fe1—C4103.50 (19)C2—C1—Fe171.2 (2)
C13—Fe1—C4171.01 (19)C10A—C1—Fe169.1 (2)
C15—Fe1—C4108.51 (18)C2—C1—H1120.3
C12—Fe1—C4130.4 (2)C10A—C1—H1120.3
C10A—Fe1—C471.23 (16)Fe1—C1—H1132.3
C14—Fe1—C4141.19 (18)O2—S10—O3116.44 (19)
C1—Fe1—C485.08 (16)O2—S10—C9A109.62 (19)
C3—Fe1—C439.17 (16)O3—S10—C9A110.67 (19)
C2—Fe1—C471.62 (16)O2—S10—C10A110.01 (19)
C11—Fe1—C4A105.3 (2)O3—S10—C10A107.43 (18)
C13—Fe1—C4A137.11 (17)C9A—S10—C10A101.62 (19)
C15—Fe1—C4A134.38 (18)C5A—C9A—C9119.9 (4)
C12—Fe1—C4A107.13 (18)C5A—C9A—S10123.1 (3)
C10A—Fe1—C4A39.46 (16)C9—C9A—S10116.8 (3)
C14—Fe1—C4A172.40 (17)C12—C11—C15108.2 (4)
C1—Fe1—C4A71.99 (16)C12—C11—Fe170.6 (3)
C3—Fe1—C4A70.33 (16)C15—C11—Fe170.2 (3)
C2—Fe1—C4A84.69 (16)C12—C11—H11125.9
C4—Fe1—C4A38.82 (14)C15—C11—H11125.9
F2—P1—F690.56 (17)Fe1—C11—H11125.9
F2—P1—F189.76 (17)C11—C12—C13109.3 (4)
F6—P1—F189.48 (18)C11—C12—Fe169.4 (3)
F2—P1—F590.66 (17)C13—C12—Fe169.1 (3)
F6—P1—F5178.2 (2)C11—C12—H12125.3
F1—P1—F589.23 (18)C13—C12—H12125.3
F2—P1—F4178.0 (2)Fe1—C12—H12125.3
F6—P1—F491.48 (19)C12—C13—C14105.2 (4)
F1—P1—F490.22 (17)C12—C13—Fe170.3 (3)
F5—P1—F487.30 (18)C14—C13—Fe170.4 (3)
F2—P1—F389.83 (16)C12—C13—H13127.3
F6—P1—F390.90 (18)C14—C13—H13127.3
F1—P1—F3179.4 (2)Fe1—C13—H13127.3
F5—P1—F390.40 (18)C15—C14—C13109.1 (4)
F4—P1—F390.17 (15)C15—C14—Fe169.6 (3)
C8—C9—C9A119.6 (4)C13—C14—Fe168.4 (2)
C8—C9—H9120.2C15—C14—H14125.4
C9A—C9—H9120.2C13—C14—H14125.4
C9—C8—C7119.6 (4)Fe1—C14—H14125.4
C9—C8—H8120.2C14—C15—C11108.0 (5)
C7—C8—H8120.2C14—C15—Fe170.8 (3)
C6—C7—C8120.7 (4)C11—C15—Fe169.5 (3)
C6—C7—H7119.6C14—C15—H15126.0
C8—C7—H7119.6C11—C15—H15126.0
C7—C6—C5A119.9 (4)Fe1—C15—H15126.0
C7—C6—H6120.1
(II) Phenoxathiin 10,10-dioxide top
Crystal data top
C12H8O3SZ = 2
Mr = 232.24F(000) = 240
Triclinic, P1Dx = 1.554 Mg m−3
Hall symbol: -P 1Melting point: 419 K
a = 7.2067 (10) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.9568 (11) ÅCell parameters from 4033 reflections
c = 8.9360 (13) Åθ = 2.4–28.2°
α = 102.475 (1)°µ = 0.31 mm−1
β = 95.493 (2)°T = 150 K
γ = 93.399 (2)°Needle, colourless
V = 496.33 (12) Å30.22 × 0.20 × 0.19 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		1746 independent reflections
Radiation source: fine-focus sealed tube1592 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ϕ and ω scansθmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker; 2008)		h = −8→8
Tmin = 0.665, Tmax = 0.746k = −9→9
4816 measured reflectionsl = −10→10
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.0265P)2 + 0.3858P]
where P = (Fo2 + 2Fc2)/3
1746 reflections(Δ/σ)max = 0.001
145 parametersΔρmax = 0.33 e Å−3
0 restraintsΔρmin = −0.31 e Å−3
Crystal data top
C12H8O3Sγ = 93.399 (2)°
Mr = 232.24V = 496.33 (12) Å3
Triclinic, P1Z = 2
a = 7.2067 (10) ÅMo Kα radiation
b = 7.9568 (11) ŵ = 0.31 mm−1
c = 8.9360 (13) ÅT = 150 K
α = 102.475 (1)°0.22 × 0.20 × 0.19 mm
β = 95.493 (2)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		1746 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker; 2008)		1592 reflections with I > 2σ(I)
Tmin = 0.665, Tmax = 0.746Rint = 0.019
4816 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.072H-atom parameters constrained
S = 0.97Δρmax = 0.33 e Å−3
1746 reflectionsΔρmin = −0.31 e Å−3
145 parameters
Special details top

Experimental. Phenoxathiin 10,10-dioxide, (II), was obtained by oxidation of the precursor phenoxathiin using 30% hydrogen peroxide in glacial acetic acid (Gilman & Esmay, 1952). The mixture was refluxed for 1 h and crystals grew from the solution upon cooling overnight. An additional quantity of the product was recovered from the mother liquor diluted with water upon extraction with chloroform. The total yield of the product was 98%.

Analytical data for the free heterocycle: m.p. 419 (1) K (419–420 K; Gilman & Esmay, 1952). 1H NMR (300.133 MHz, chloroform-d, δ, p.p.m.): 7.40 (2 H, overlapping t and d, J ca 7.9 Hz), 7.64 (1 H, quasi-t, J ca 7.9 Hz, d, J = 1.4 Hz, d, 1.1 Hz), 8.06 (1 H, d, J = 7.9 Hz, d, J = 1.1 Hz).

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.

The H atoms were placed in geometrically idealized positions with C–H distances of 0.95 Å (all C atoms) and protons were constrained to ride on the parent C atom with Uiso(H) = 1.2Ueq(C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.1730 (2)0.8723 (2)0.5920 (2)0.0319 (4)
H10.16670.97080.54810.038*
C20.1331 (2)0.8833 (2)0.7410 (2)0.0352 (4)
H20.09940.98900.80000.042*
C30.1422 (2)0.7390 (2)0.8051 (2)0.0341 (4)
H30.11440.74660.90800.041*
C40.1912 (2)0.5853 (2)0.7204 (2)0.0314 (4)
H40.19670.48720.76480.038*
C4A0.2327 (2)0.5738 (2)0.56992 (19)0.0263 (4)
C10A0.2227 (2)0.7172 (2)0.5048 (2)0.0263 (4)
O50.28352 (18)0.41578 (14)0.49805 (13)0.0318 (3)
C5A0.3064 (2)0.3761 (2)0.34446 (19)0.0250 (4)
C9A0.2983 (2)0.4920 (2)0.24852 (19)0.0254 (4)
C60.3378 (2)0.2051 (2)0.2853 (2)0.0291 (4)
H60.34660.12620.35120.035*
C70.3561 (2)0.1507 (2)0.1311 (2)0.0334 (4)
H70.37670.03350.09090.040*
C80.3448 (3)0.2646 (2)0.0331 (2)0.0362 (4)
H80.35630.2254−0.07350.043*
C90.3168 (3)0.4345 (2)0.0921 (2)0.0326 (4)
H90.31010.51320.02590.039*
S100.27213 (6)0.71137 (5)0.31608 (5)0.02954 (14)
O20.1129 (2)0.75920 (17)0.22942 (15)0.0440 (4)
O30.44674 (19)0.80965 (15)0.31868 (16)0.0407 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0291 (9)0.0244 (9)0.0412 (10)0.0039 (7)−0.0009 (8)0.0065 (7)
C20.0277 (9)0.0314 (10)0.0417 (11)0.0053 (7)0.0013 (8)−0.0016 (8)
C30.0264 (9)0.0409 (10)0.0318 (9)0.0000 (8)0.0027 (7)0.0023 (8)
C40.0295 (9)0.0318 (9)0.0332 (9)−0.0005 (7)0.0009 (7)0.0102 (8)
C4A0.0248 (9)0.0224 (8)0.0313 (9)0.0019 (6)−0.0002 (7)0.0063 (7)
C10A0.0240 (8)0.0232 (8)0.0318 (9)0.0022 (6)0.0001 (7)0.0076 (7)
O50.0475 (8)0.0207 (6)0.0302 (6)0.0087 (5)0.0065 (5)0.0096 (5)
C5A0.0238 (8)0.0216 (8)0.0296 (9)0.0009 (6)0.0014 (7)0.0068 (7)
C9A0.0251 (8)0.0197 (8)0.0320 (9)0.0015 (6)0.0012 (7)0.0078 (7)
C60.0264 (9)0.0213 (8)0.0413 (10)0.0020 (7)0.0042 (7)0.0106 (7)
C70.0315 (9)0.0216 (9)0.0447 (11)0.0008 (7)0.0086 (8)0.0009 (8)
C80.0401 (10)0.0333 (10)0.0328 (10)−0.0019 (8)0.0074 (8)0.0021 (8)
C90.0370 (10)0.0300 (9)0.0322 (9)−0.0004 (8)0.0032 (8)0.0108 (7)
S100.0394 (3)0.0192 (2)0.0325 (2)0.00554 (17)0.00337 (18)0.01074 (17)
O20.0588 (9)0.0371 (7)0.0399 (8)0.0206 (7)−0.0021 (6)0.0157 (6)
O30.0529 (8)0.0235 (6)0.0481 (8)−0.0036 (6)0.0155 (6)0.0111 (6)
Geometric parameters (Å, º) top
C1—C21.374 (3)C5A—C61.389 (2)
C1—H10.9500C6—C71.374 (3)
C2—H20.9500C6—H60.9500
C3—C21.392 (3)C7—C81.390 (3)
C3—H30.9500C7—H70.9500
C4—C31.376 (3)C8—H80.9500
C4—H40.9500C9—C81.375 (3)
C4A—C41.391 (2)C9—H90.9500
C10A—C4A1.390 (2)C9A—C91.396 (2)
C10A—C11.397 (2)S10—C9A1.7471 (16)
O5—C4A1.371 (2)S10—C10A1.7481 (18)
O5—C5A1.369 (2)S10—O21.4388 (13)
C5A—C9A1.388 (2)S10—O31.4371 (14)
C1—C2—C3119.80 (17)C5A—C6—H6120.1
C1—C2—H2120.1C5A—C9A—S10122.70 (13)
C1—C10A—S10118.18 (13)C6—C5A—C9A119.95 (16)
C2—C1—C10A120.30 (16)C6—C7—C8120.94 (16)
C2—C1—H1119.8C6—C7—H7119.5
C2—C3—H3119.8C7—C6—C5A119.71 (16)
C3—C4—C4A119.93 (17)C7—C6—H6120.1
C3—C4—H4120.0C7—C8—H8120.3
C3—C2—H2120.1C8—C9—C9A120.41 (16)
C4—C4A—C10A119.91 (16)C8—C9—H9119.8
C4—C3—C2120.49 (17)C8—C7—H7119.5
C4—C3—H3119.8C9—C9A—S10117.69 (13)
C4A—C10A—C1119.57 (16)C9—C8—C7119.37 (17)
C4A—C10A—S10122.25 (13)C9—C8—H8120.3
C4A—C4—H4120.0C9A—S10—C10A101.57 (8)
C10A—C1—H1119.8C9A—C9—H9119.8
O5—C4A—C4114.81 (14)O2—S10—C10A109.52 (8)
O5—C4A—C10A125.28 (15)O2—S10—C9A109.30 (8)
O5—C5A—C6115.17 (14)O3—S10—O2116.26 (8)
O5—C5A—C9A124.88 (15)O3—S10—C9A109.47 (8)
C5A—O5—C4A122.20 (13)O3—S10—C10A109.71 (8)
C5A—C9A—C9119.58 (15)

Experimental details

(I)(II)
Crystal data
Chemical formula[Fe(C5H5)(C12H8O3S)]PF6C12H8O3S
Mr498.16232.24
Crystal system, space groupMonoclinic, CcTriclinic, P1
Temperature (K)100150
a, b, c (Å)10.059 (2), 13.618 (3), 13.544 (4)7.2067 (10), 7.9568 (11), 8.9360 (13)
α, β, γ (°)90, 104.446 (2), 90102.475 (1), 95.493 (2), 93.399 (2)
V (Å3)1796.6 (8)496.33 (12)
Z42
Radiation typeMo KαMo Kα
µ (mm−1)1.120.31
Crystal size (mm)0.30 × 0.18 × 0.180.22 × 0.20 × 0.19
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer		Bruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)		Multi-scan
(SADABS; Bruker; 2008)
Tmin, Tmax0.521, 0.7460.665, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections		10650, 4277, 3615 4816, 1746, 1592
Rint0.0460.019
(sin θ/λ)max (Å−1)0.6690.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.089, 1.28 0.030, 0.072, 0.97
No. of reflections42771746
No. of parameters262145
No. of restraints520
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.87, −0.280.33, −0.31
Absolute structureFlack (1983), with how many Friedel pairs??
Absolute structure parameter−0.037 (19)?

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

 

Acknowledgements

The authors thank Saint Mary's University for financial support.

References

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CHEMISTRY
ISSN: 2053-2296
Volume 67| Part 11| November 2011| Pages m351-m354
doi:10.1107/S0108270111042715
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