The title compound, [Fe(C₅H₅)(C₁₂H₁₀NO₃S)], was synthesized from ferrocenecarboxylic acid and methyl 2-aminothiophene-3-carboxylate in modest yield. The substituted ring system is essentially planar through the amidothienylcarboxylate moiety, η⁵-(C₅H₄)CONH(C₄H₂S)CO₂Me, with the amido unit at an angle of 3.60 (7)° to the five-atom thienyl group, which is oriented at an angle of 3.17 (7)° to the ester moiety. The primary hydrogen bond is an intramolecular N-H...O=Ccarboxylate interaction [N...O 2.727 (2) Å], and the main intermolecular hydrogen bond involves a thienyl carboxylate and the carboxylate of a symmetry-related molecule [C...O 3.443 (3) Å]

Alley, Steven

Gallagher, John F.

Kenny, Peter T.M.

Lough, Alan J.

Acta Crystallographica Section E

English

Steven Alley

John F. Gallagher

Peter T. M. Kenny

Alan J. Lough

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Methyl 2-[(ferrocenylcarbonyl)amino]thiophene-3-carboxylate

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metal-organic papersActa Cryst. (2005). E61, m201±m203 doi:10.1107/S1600536804033355 Alley et al.  [Fe(C5H5)(C12H10NO3S)] m201Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368Methyl 2-[(ferrocenylcarbonyl)amino]-thiophene-3-carboxylateSteven Alley,aJohn F. Gallagher,a*Peter T. M. Kennya* andAlan J. LoughbaSchool of Chemical Sciences, National Institutefor Cellular Biotechnology, Dublin CityUniversity, Dublin 9, Ireland, and bDepartmentof Chemistry, 80 St. George Street, University ofToronto, Toronto, Ontario, Canada M5S 3H6Correspondence e-mail: john.gallagher@dcu.ie,peter.kenny@dcu.ieKey indicatorsSingle-crystal X-ray studyT = 150 KMean (C±C) = 0.003 AÊR factor = 0.033wR factor = 0.079Data-to-parameter ratio = 16.1For details of how these key indicators wereautomatically derived from the article, seehttp://journals.iucr.org/e.# 2005 International Union of CrystallographyPrinted in Great Britain ± all rights reservedThe title compound, [Fe(C5H5)(C12H10NO3S)], was synthe-sized from ferrocenecarboxylic acid and methyl 2-aminothio-phene-3-carboxylate in modest yield. The substituted ringsystem is essentially planar through the amidothienylcarboxyl-ate moiety, 5-(C5H4)CONH(C4H2S)CO2Me, with the amidounit at an angle of 3.60 (7) to the ®ve-atom thienyl group,which is oriented at an angle of 3.17 (7) to the ester moiety.The primary hydrogen bond is an intramolecular NÐH  O Ccarboxylate interaction [N  O 2.727 (2) AÊ ], and themain intermolecular hydrogen bond involves a thienylcarboxylate and the carboxylate of a symmetry-relatedmolecule [C  O 3.443 (3) AÊ ].CommentFerrocenyl derivatives have been the subject of much atten-tion in coordination chemistry, given the important roleswhich they can play, encompassing both structural and elec-tronic capabilities. The integration of ferrocene into newhybrid compounds has greatly expanded the potential andcapabilities of new materials with a range of potential appli-cations. Here, we report the synthesis and structure of the titleferrocenoylaminothienyl carboxylate derivative, (I).Two views of (I) are depicted, with the atom-numberingscheme, in Figs. 1 and 2. Bond lengths and angles are unex-ceptional and in accord with anticipated values (Allen, 2002).Received 16 November 2004Accepted 16 December 2004Online 8 January 2005Figure 1A view of (I) with the atom-numbering scheme. Displacement ellipsoidsare drawn at the 30% probability level. The intramolecular hydrogenbond is shown dashed.The FeÐC bond lengths for the substituted cyclopentadienylring of (I) are in the range 2.027 (2)±2.066 (2) AÊ and aresimilar to those observed for the unsubstituted ring [2.038 (2)±2.053 (2) AÊ ]. The Fe  Cg1 and Fe  Cg2 distances are1.6488 (10) and 1.6535 (10) AÊ , respectively, and theCg1  Fe1  Cg2 angle is 179.36 (5), where Cg1 and Cg2 arethe centroids of the substituted and unsubstituted C5 rings,respectively. The cyclopentadienyl rings deviate slightly fromeclipsed geometry, as indicated by the C1n  Cg1  Cg2  C2n torsion angles, which are in the range 8.76 (18)±9.46 (17) (n = 1±5).The substituted ring system is essentially planar through theamidothienylcarboxylate moiety. The C1/O1/N1/C2 amidomoiety is at an angle of 3.60 (7) to the C2/C3/C4/C5/S1thienyl ring, which is at an angle of 3.17 (7) to the C3/C6/C7/O2/O3 ester group. The substituted C5 ring is at an angle of12.03 (7) to the four-atom amido group and 14.10 (6) to thethienyl ring. Apart from the twisting in the interplanar angles,there is no evidence of bending in these groups due to stericeffects, in contrast to 2-(ferrocenyl)thiophene-3-carboxylicacid, where the thienyl ring bonded directly to the ferrocenylmoiety is bent signi®cantly from linearity (Gallagher et al.,2001).The primary hydrogen-bonding mode in (I) is an intra-molecular hydrogen bond involving the amido NÐH with thecarboxylate O C group, forming a ring with graph set S(6)(Bernstein et al., 1995) and directly in¯uencing the coplanarityof the atoms involved. Molecules of (I) assemble along the baxis through a CÐH  O C interaction involving thienylatom C5 and carboxylate atom O2, as indicated by C5ÐH5  (O2 C2)# in Fig. 2 [symmetry code: (#) x, 1 + y, z]. ACmethylÐH  S contact augments this about inversion centresas C7ÐH7  S1& [symmetry code: (&) 1 ÿ x, 1 ÿ y, 1 ÿ z;Figs. 2 and 3]. The closest contact involving atom Fe1 is withC12ÐH12, as C12ÐH12  Fe1$ [symmetry code: ($)ÿx, 12 + y,12 ÿ z], although this is not depicted in Fig. 2. Atom H12 ispositioned such that it also forms contacts with the two C5 ringatoms, C13 and C23. Examination of the structure withPLATON (Spek, 2003) showed that there are no solventaccessible voids in the crystal structure.A search for crystal structures incorporating the amido-thienyl fragment [as O CÐN(H)ÐC4S] in the CambridgeStructural Database (Version 5.25, July 2004; Allen, 2002)reveals a total of four derivatives (with coordinates). A relatedsearch for structures incorporating the ferrocenyl (as C5FeC5)and thiophene groups (as C4S) yields 29 systems (the secondscheme shows the structural fragments searched for in theCambridge Structural Database) (Hudson et al., 2001). Incomparison, a search with ferrocene and pyridyl (as C5N)gives 317 structures, indicating the paucity of data for S-heteroaromatic donors as ligands in ferrocene chemistry whencompared with typical heteroaromatic systems containing Ndonors such as pyridine (Allen, 2002).ExperimentalMethyl 2-N-(ferrocenoylamido)-thienyl-3-carboxylate, (I), wassynthesized in low yield from the starting materials ferrocenecarboxylic acid and methyl 2-aminothienyl-3-carboxylate usingstandard procedures. Full synthetic details, together with electro-chemical studies, will be published in a full paper to follow thisstructure report.metal-organic papersm202 Alley et al.  [Fe(C5H5)(C12H10NO3S)] Acta Cryst. (2005). E61, m201±m203Figure 2A view of the primary interactions in the crystal structure of (I). Atomslabelled with the suf®xes #, * and & are at the symmetry positions (x, 1 +y, z), (x, y ÿ 1, z) and (1 ÿ x, 1 ÿ y, 1 ÿ z), respectively.Figure 3A stereoview of the hydrogen-bonded dimer generated by the CÐH  Scontact.Crystal data[Fe(C5H5)(C12H10NO3S)]Mr = 369.21Monoclinic, P21=ca = 7.1714 (4) AÊb = 8.1184 (3) AÊc = 26.4299 (14) AÊ = 95.721 (2)V = 1531.09 (13) AÊ 3Z = 4Dx = 1.602 Mg mÿ3Mo K radiationCell parameters from 4398re¯ections = 2.6±27.5 = 1.14 mmÿ1T = 150 (1) KBlock, red0.30  0.24  0.20 mmData collectionNonius KappaCCD diffractometer’ scans, and ! scans with  offsetsAbsorption correction: multi-scan(DENZO-SMN; Otwinowski &Minor, 1997)Tmin = 0.747, Tmax = 0.7976362 measured re¯ections3420 independent re¯ections2749 re¯ections with I > 2(I)Rint = 0.030max = 27.6h = ÿ9! 9k = ÿ10! 10l = ÿ34! 34RefinementRe®nement on F 2R[F 2 > 2(F 2)] = 0.033wR(F 2) = 0.079S = 1.043420 re¯ections213 parametersH atoms treated by a mixture ofindependent and constrainedre®nementw = 1/[2(Fo2) + (0.022P)2+ 1.1497P]where P = (Fo2 + 2Fc2)/3(/)max = 0.001max = 0.29 e AÊÿ3min = ÿ0.35 e AÊ ÿ3Extinction correction: noneTable 1Selected geometric parameters (AÊ , ).S1ÐC2 1.725 (2)S1ÐC5 1.730 (2)O1ÐC1 1.232 (2)C1ÐN1 1.370 (3)C1ÐC11 1.471 (3)N1ÐC2 1.376 (3)N1ÐH1 0.80 (2)C2ÐC3 1.381 (3)C3ÐC4 1.430 (3)C3ÐC6 1.463 (3)C4ÐC5 1.348 (3)C6ÐO2 1.218 (2)C6ÐO3 1.345 (3)O3ÐC7 1.446 (3)C2ÐS1ÐC5 90.93 (11)C1ÐN1ÐC2 125.81 (19)C1ÐN1ÐH1 120.9 (17)C2ÐN1ÐH1 113.3 (17)O1ÐC1ÐN1 121.1 (2)O1ÐC1ÐC11 123.0 (2)N1ÐC1ÐC11 115.88 (18)N1ÐC2ÐC3 124.49 (19)S1ÐC2ÐN1 123.54 (16)S1ÐC2ÐC3 111.94 (15)C2ÐC3ÐC4 111.75 (19)C2ÐC3ÐC6 121.37 (18)C4ÐC3ÐC6 126.9 (2)C3ÐC4ÐC5 112.7 (2)S1ÐC5ÐC4 112.68 (17)O2ÐC6ÐO3 123.12 (19)O2ÐC6ÐC3 124.9 (2)O3ÐC6ÐC3 112.01 (18)C6ÐO3ÐC7 115.83 (18)C1ÐC11ÐC12 123.62 (18)C1ÐC11ÐC15 128.61 (19)C1ÐC11ÐFe1 121.52 (15)O1ÐC1ÐN1ÐC2 2.1 (4)C1ÐN1ÐC2ÐS1 2.7 (3)N1ÐC2ÐC3ÐC6 1.0 (3)C2ÐC3ÐC6ÐO2 3.6 (3)O2ÐC6ÐO3ÐC7 0.6 (3)O1ÐC1ÐC11ÐC12 14.8 (3)N1ÐC1ÐC11ÐC15 8.5 (3)O1ÐC1ÐC11ÐFe1 100.9 (2)Table 2Hydrogen-bond geometry (AÊ , ).DÐH  A DÐH H  A D  A DÐH  AN1ÐH1  O2 0.80 (2) 2.08 (2) 2.727 (2) 137 (2)C5ÐH5  O2i 0.95 2.53 3.442 (3) 161C7ÐH7C  S1ii 0.98 2.89 3.682 (3) 139Symmetry codes: (i) x; y  1; z; (ii) ÿx 1;ÿy 1;ÿz 1.The H atom bound to N re®ned to an NÐH distance of 0.80 (2) AÊ .All H atoms bound to C atoms were treated as riding, with methylCÐH = 0.98 AÊ and aromatic CÐH = 0.95 AÊ , and with Uiso(H) =1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for the remainder.Data collection: KappaCCD Server Software (Nonius, 1997); cellre®nement: DENZO-SMN (Otwinowski & Minor, 1997); datareduction: DENZO-SMN; program(s) used to solve structure:SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek,2003) and ORTEX (McArdle, 1995); software used to preparematerial for publication: PREP8 (Ferguson, 1998).SA, JFG and PTMK thank Dublin City University and theDepartment of Education, Ireland, for funding the NationalInstitute for Cellular Biotechnology (PRTLI programme,round 3, 2001±2008).ReferencesAllen, F. H. (2002). Acta Cryst. B58, 380±388.Bernstein, J., Davies, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.Int. Ed. Engl. 34, 1555±1573.Ferguson, G. (1998). PREP8. University of Guelph, Canada.Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl.Cryst. 22, 384±387.Gallagher, J. F., Hudson, R. D. A. & Manning, A. R. (2001). Acta Cryst. C57,28±30.Hudson, R. D. A., Asselsbergh, I., Clays, K., Cuffe, L. P., Gallagher, J. F.,Manning, A. R., Persoons, A. & Wostyn, K. (2001). J. Organomet. Chem.637, 435±444.McArdle, P. (1995). J. Appl. Cryst. 28, 65±65.Nonius (1997). KappaCCD Server Software. Windows 3.11 Version. NoniusBV, Delft, The Netherlands.Otwinowski, Z. & Minor W. (1997). Methods in Enzymology, Vol. 276,Macromolecular Crystallography, Part A, edited by C. W. Carter Jr. & R. M.Sweet, pp. 307±326. New York: Academic Press.Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University ofGoÈ ttingen, Germany.Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.metal-organic papersActa Cryst. (2005). E61, m201±m203 Alley et al.  [Fe(C5H5)(C12H10NO3S)] m203

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Methyl 2-[(ferrocenylcarbonyl)amino]thiophene-3-carboxylate

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