data reports Ferrocenecarboxylic anhydride: a redetermination Structure description C. John McAdam and Jim Simpson*

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Ferrocenecarboxylic anhydride: a redetermination ISSN 2414-3146 C. John McAdam and Jim Simpson* Department of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand.

CCDC reference: 1515202 The title molecule, [Fe 2 (C 5 H 5 ) 2 (C 12 H 8 O 3 )], briefly reported previously [Zhang (2015). Private Communication (CCDC reference 1056736).

1 Ferrocenecarboxylic anhydride: a redetermination ISSN C. John McAdam and Jim Simpson* Department of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand. *Correspondence jsimpson@alkali.otago.ac.nz Received 3 November 2016 Accepted 5 November 2016 Edited by W. T. A. Harrison, University of Aberdeen, Scotland Keywords: crystal structure; ferrocene; acid anhydride; hydrogen bonds. CCDC reference: The title molecule, [Fe 2 (C 5 H 5 ) 2 (C 12 H 8 O 3 )], briefly reported previously [Zhang (2015). Private Communication (CCDC reference ). CCDC, Cambridge, England], comprises two ferrocenyl units connected by an acid anhydride bridge. Both ferrocene units have near coplanar [dihedral angles between the ring planes = 2.84 (4) and 1.74 (13) ] and eclipsed [pseudo torsion angles = 6.3 (2) and 5.1 (2) ] cyclopentadienyl (Cp) rings. A twist through the anhydride linkage results in a dihedral angle of (8) between the two substituted Cp rings planes. An intramolecular C HO hydrogen bond is also found. In the crystal, C HO hydrogen bonds link the molecules into a three-dimensional network. Structural data: full structural data are available from iucrdata.iucr.org Structure description The title compound is a common by-product in the synthesis of ferrocenoyl chloride from ferrocene carboxylic acid (Wang & Huang, 2000). Two ferrocene units [(C101 C105)Fe1(C106 C110)] (Fc1) and [(C201 C205)Fe2(C206 C210)] (Fc2) are bridged by an acid anhydride system, with an intramolecular C206 H206O1 hydrogen bond influencing the molecular conformation, Fig. 1. The room-temperature structure of this molecule has been deposited with the Cambridge Structural Database, CSD, (Groom et al., 2016) but no details of the molecular or crystal structure were provided (Zhang, 2015). The CSD gives four other examples of Cp carboxylic anhydrides (Elschenbroich et al., 1997; Siebler et al., 2010; Micallef et al., 2011; Liu et al., 2015). The two Cp rings of each ferrocenyl group are almost eclipsed with mean CCg1aCg1bC and CCg2aCg2bC torsion angles of 6.3 (2) and 5.1 (2) [Cg1a, Cg1b, Cg2a and Cg2b are the centroids of the C101 C105, C106 C110, C201 C205 and C206 C210 Cp rings respectively]. Within each ferrocenyl moiety the rings are close to coplanar, with angles between the Cp ring planes of 2.84 (4) for Fc1 and 1.74 (13) for Fc2. Although the two acyl carbonyls lie close to the planes of their respective Cp rings, there is a twist through 1of3

Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA C206 H206O1 0.95 2.57 3.413 (2) 149 C205 H205O2 i 0.95 2.38 3.319 (2) 169 C204 H204O1 ii 0.95 2.55 3.463 (2) 160 C207 H207O2 iii 0.95 2.64 3.

Figure 1 The structure of the title compound with ellipsoids drawn at the 50% probability level. The intramolecular C HO hydrogen bond is shown as a dashed line. Table 2 Experimental details.

2 Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA C206 H206O (2) 149 C205 H205O2 i (2) 169 C204 H204O1 ii (2) 160 C207 H207O2 iii (2) 159 Symmetry codes: (i) x þ 1; y; z þ 1; (ii) x þ 1 2 ; y þ 1 2 ; z þ 1; (iii) x þ 1 2 ; y þ 1 2 ; z. Figure 1 The structure of the title compound with ellipsoids drawn at the 50% probability level. The intramolecular C HO hydrogen bond is shown as a dashed line. Table 2 Experimental details. Crystal data Chemical formula [Fe 2 (C 5 H 5 ) 2 (C 12 H 8 O 3 )] M r Crystal system, space group Orthorhombic, Pbca Temperature (K) 100 a, b, c (Å) (2), (2), (3) V (Å 3 ) (9) Z 8 Radiation type Cu K (mm 1 ) Crystal size (mm) Data collection Diffractometer Agilent SuperNova, Dual, Cu at zero, Atlas Absorption correction Gaussian (CrysAlis PRO; Agilent, 2014) T min, T max 0.267, No. of measured, independent and 13584, 3468, 3262 observed [I > 2(I)] reflections R int (sin /) max (Å 1 ) Refinement R[F 2 >2(F 2 )], wr(f 2 ), S 0.030, 0.090, 0.84 No. of reflections 3468 No. of parameters 244 H-atom treatment H-atom parameters constrained max, min (e Å 3 ) 0.31, 0.68 Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS2013 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), TITAN2000 (Hunter & Simpson, 1999), Mercury (Macrae et al., 2008), encifer (Allen et al., 2004), PLATON (Spek, 2009), publcif (Westrip, 2010) and WinGX (Farrugia, 2012). Figure 2 Zigzag chains of molecules of the title compound along the a axis. the connecting O3 atom of the anhydride unit that results in a torsion angle of approximately for O1 C1C2 O2. Similar torsional geometry is observed in the ruthenium analogue IVOYOY (62.31 ; Micallef et al., 2011), the 1 0,2 0 -bissubstituted ferrocene system KAJBUU (57.04 ; Siebler et al., 2010) and the vanadium compound NEWFIE (66.68 ; Elschenbroich et al., 1997). In the bis-ferrocenophanone structure HOVYEY (Liu et al., 2015) where two ferrocene groups are constrained by two anhydride linkages, the two carbonyl groups are still inclined at an O CC O torsion angle of despite the fact that the bridged Cp rings are almost coplanar, suggesting the O CC O torsion is a mechanism to relieve steric strain in the molecule. Figure 3 Chains of molecules of the title compound along the b axis. Figure 4 Overall packing of the title compound viewed along the b-axis direction. 2of3 McAdam and Simpson [Fe 2 (C 5 H 5 ) 2 (C 12 H 8 O 3 )]

3 In the crystal, C204 H204O1 hydrogen bonds (Table 1) generate zigzag chains along the a axis, Fig. 2. The carbonyl oxygen atom O2 acts as a dual acceptor with C207 H207O2 hydrogen bonds forming chains along the b axis Fig. 3, and C205 H205O2-generated inversion dimers linking the two chain motifs in the third dimension with molecules stacked along the b axis in such a way that one ferrocene unit of each individual molecule lies approximately parallel to the b-axis direction while the other lies in the ac plane, Fig. 4. Synthesis and crystallization The title compound was obtained as a by-product in the synthesis of ferrocenoyl chloride from the reaction of ferrocene carboxylic acid with triphosgene and 4-dimethylaminopyridine (Wang & Huang, 2000). Orange block-shaped crystals were obtained from diffusion of a dichloromethane solution layered with petroleum ether. Refinement Crystal data, data collection and structure refinement details are summarized in Table 2. Acknowledgements We thank the NZ Ministry of Business Innovation and Employment Science Investment Fund (grant No. UOO- X1206) for support of this work and the University of Otago for the purchase of the diffractometer. References Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, England. Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, Elschenbroich, C., Schiemann, O., Burghaus, O. & Harms, K. (1997). J. Am. Chem. Soc. 119, Farrugia, L. J. (2012). J. Appl. Cryst. 45, Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, Hunter, K. A. & Simpson, J. (1999). TITAN2000. University of Otago, New Zealand. Liu, Y., Khalili Najafabadi, B., Azizpoor Fard, M. & Corrigan, J. F. (2015). Angew. Chem. Int. Ed. 54, Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, Micallef, L. S., Loughrey, B. T., Healy, P. C., Parsons, P. G. & Williams, M. L. (2011). Organometallics, 30, Sheldrick, G. M. (2008). Acta Cryst. A64, Sheldrick, G. M. (2015). Acta Cryst. C71, 3 8. Siebler, D., Förster, C. & Heinze, K. (2010). Eur. J. Inorg. Chem. pp Spek, A. L. (2009). Acta Cryst. D65, Wang, Q. & Huang, R. (2000). J. Organomet. Chem. 604, Westrip, S. P. (2010). J. Appl. Cryst. 43, Zhang, Y. (2015). Private Communication (CCDC reference ). CCDC, Cambridge, England. McAdam and Simpson [Fe 2 (C 5 H 5 ) 2 (C 12 H 8 O 3 )] 3of3

4 full crystallographic data [ Ferrocenecarboxylic anhydride: a redetermination C. John McAdam and Jim Simpson Ferrocenecarboxylic anhydride Crystal data [Fe 2 (C 5 H 5 ) 2 (C 12 H 8 O 3 )] M r = Orthorhombic, Pbca a = (2) Å b = (2) Å c = (3) Å V = (9) Å 3 Z = 8 F(000) = 1808 Data collection Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer Radiation source: SuperNova (Cu) X-ray Source Detector resolution: pixels mm -1 ω scans Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014) T min = 0.267, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 244 parameters 0 restraints D x = Mg m 3 Cu Kα radiation, λ = Å Cell parameters from 7707 reflections θ = µ = mm 1 T = 100 K Block, orange mm measured reflections 3468 independent reflections 3262 reflections with I > 2σ(I) R int = θ max = 73.3, θ min = 4.6 h = k = 14 8 l = Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.089P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.31 e Å 3 Δρ min = 0.68 e Å 3 Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. data-1

5 Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq Fe (2) (2) (2) (11) Fe (2) (2) (2) (11) O (9) (11) (7) (3) O (8) (10) (6) (3) C (11) (16) (9) (4) C (13) (16) (9) (4) H * O (8) (10) (6) (3) C (12) (15) (10) (4) H * C (13) (14) (9) (4) H * C (13) (14) (9) (4) H * C (12) (14) (9) (3) C (12) (15) (9) (4) C (13) (14) (8) (4) H * C (13) (16) (10) (4) H * C (13) (15) (10) (4) H * C (13) (16) (10) (4) H * C (12) (16) (10) (4) H * C (14) (15) (10) (4) H * C (11) (14) (8) (3) C (12) (2) (10) (4) H * C (15) (14) (9) (4) H * C (15) (18) (11) (4) H * C (13) (17) (10) (4) H * C (16) (17) (11) (5) H * C (16) (15) (11) (4) H * C (12) (17) (9) (4) H * C (12) (15) (9) (4) H * data-2

6 Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Fe (18) (19) (17) (9) (10) (9) Fe (17) (18) (17) (9) (10) (9) O (7) (7) (7) (5) (5) (5) O (6) (6) (6) (5) (5) (5) C (8) (9) (8) (6) (6) (7) C (8) (9) (9) (7) (7) (7) O (6) (6) (6) (5) (5) (5) C (9) (8) (9) (7) (7) (7) C (8) (8) (8) (7) (7) (7) C (8) (9) (8) (7) (7) (6) C (8) (8) (8) (6) (6) (6) C (8) (9) (8) (7) (7) (6) C (9) (8) (9) (7) (7) (6) C (10) (10) (8) (7) (7) (7) C (10) (8) (9) (7) (7) (7) C (8) (10) (9) (7) (7) (7) C (9) (10) (9) (7) (7) (8) C (10) (9) (9) (7) (8) (7) C (8) (7) (8) (6) (6) (6) C (9) (11) (9) (8) (7) (8) C (10) (8) (8) (8) (7) (7) C (11) (9) (9) (9) (8) (8) C (8) (10) (8) (8) (7) (8) C (13) (10) (9) (9) (9) (8) C (11) (9) (10) (8) (9) (8) C (8) (10) (8) (8) (7) (8) C (8) (9) (8) (7) (7) (7) Geometric parameters (Å, º) Fe1 C (17) C102 C (2) Fe1 C (18) C102 H Fe1 C (19) C202 C (3) Fe1 C (2) C202 C (2) Fe1 C (2) C202 H Fe1 C (18) C101 C (2) Fe1 C (18) C101 C (2) Fe1 C (18) C105 C (3) Fe1 C (18) C105 H Fe1 C (19) C210 C (3) Fe2 C (18) C210 C (3) Fe2 C (18) C210 H Fe2 C (18) C106 C (3) Fe2 C (19) C106 H Fe2 C (17) C204 C (3) data-3

7 Fe2 C (19) C204 H Fe2 C (18) C208 C (3) Fe2 C (18) C208 C (3) Fe2 C (19) C208 H Fe2 C (2) C103 C (3) O2 C (2) C103 H O1 C (2) C209 H C2 O (2) C104 H C2 C (3) C108 C (3) C205 C (3) C108 H C205 C (2) C206 C (3) C205 H C206 H O3 C (2) C109 C (3) C107 C (3) C109 H C107 C (3) C110 H C107 H C207 H C102 C (3) C203 H C101 Fe1 C (7) C103 C102 H C101 Fe1 C (8) C101 C102 H C105 Fe1 C (8) Fe1 C102 H C101 Fe1 C (8) C203 C202 C (16) C105 Fe1 C (8) C203 C202 Fe (10) C110 Fe1 C (9) C201 C202 Fe (10) C101 Fe1 C (8) C203 C202 H C105 Fe1 C (8) C201 C202 H C110 Fe1 C (9) Fe2 C202 H C109 Fe1 C (9) C105 C101 C (15) C101 Fe1 C (7) C105 C101 C (16) C105 Fe1 C (8) C102 C101 C (15) C110 Fe1 C (8) C105 C101 Fe (10) C109 Fe1 C (9) C102 C101 Fe (10) C108 Fe1 C (9) C1 C101 Fe (12) C101 Fe1 C (7) C205 C201 C (16) C105 Fe1 C (7) C205 C201 C (16) C110 Fe1 C (8) C202 C201 C (16) C109 Fe1 C (8) C205 C201 Fe (10) C108 Fe1 C (8) C202 C201 Fe (10) C102 Fe1 C (8) C2 C201 Fe (12) C101 Fe1 C (8) C104 C105 C (16) C105 Fe1 C (7) C104 C105 Fe (10) C110 Fe1 C (7) C101 C105 Fe (10) C109 Fe1 C (9) C104 C105 H C108 Fe1 C (8) C101 C105 H C102 Fe1 C (8) Fe1 C105 H C104 Fe1 C (8) C209 C210 C (17) C101 Fe1 C (7) C209 C210 Fe (11) C105 Fe1 C (7) C206 C210 Fe (10) data-4

8 C110 Fe1 C (8) C209 C210 H C109 Fe1 C (8) C206 C210 H C108 Fe1 C (8) Fe2 C210 H C102 Fe1 C (7) C107 C106 C (17) C104 Fe1 C (8) C107 C106 Fe (10) C106 Fe1 C (7) C110 C106 Fe (10) C101 Fe1 C (7) C107 C106 H C105 Fe1 C (7) C110 C106 H C110 Fe1 C (8) Fe1 C106 H C109 Fe1 C (8) C205 C204 C (17) C108 Fe1 C (9) C205 C204 Fe (11) C102 Fe1 C (7) C203 C204 Fe (11) C104 Fe1 C (8) C205 C204 H C106 Fe1 C (8) C203 C204 H C107 Fe1 C (8) Fe2 C204 H C201 Fe2 C (7) C209 C208 C (18) C201 Fe2 C (8) C209 C208 Fe (11) C202 Fe2 C (8) C207 C208 Fe (10) C201 Fe2 C (8) C209 C208 H C202 Fe2 C (9) C207 C208 H C208 Fe2 C (8) Fe2 C208 H C201 Fe2 C (7) C104 C103 C (17) C202 Fe2 C (7) C104 C103 Fe (10) C208 Fe2 C (8) C102 C103 Fe (10) C209 Fe2 C (8) C104 C103 H C201 Fe2 C (7) C102 C103 H C202 Fe2 C (7) Fe1 C103 H C208 Fe2 C (8) O1 C1 O (15) C209 Fe2 C (8) O1 C1 C (16) C203 Fe2 C (8) O3 C1 C (14) C201 Fe2 C (8) C208 C209 C (17) C202 Fe2 C (8) C208 C209 Fe (11) C208 Fe2 C (8) C210 C209 Fe (11) C209 Fe2 C (8) C208 C209 H C203 Fe2 C (8) C210 C209 H C205 Fe2 C (8) Fe2 C209 H C201 Fe2 C (8) C105 C104 C (16) C202 Fe2 C (8) C105 C104 Fe (10) C208 Fe2 C (8) C103 C104 Fe (11) C209 Fe2 C (7) C105 C104 H C203 Fe2 C (8) C103 C104 H C205 Fe2 C (8) Fe1 C104 H C210 Fe2 C (8) C107 C108 C (18) C201 Fe2 C (8) C107 C108 Fe (11) C202 Fe2 C (8) C109 C108 Fe (11) C208 Fe2 C (8) C107 C108 H C209 Fe2 C (8) C109 C108 H C203 Fe2 C (8) Fe1 C108 H data-5

9 C205 Fe2 C (8) C207 C206 C (17) C210 Fe2 C (8) C207 C206 Fe (10) C207 Fe2 C (8) C210 C206 Fe (11) C201 Fe2 C (7) C207 C206 H C202 Fe2 C (7) C210 C206 H C208 Fe2 C (8) Fe2 C206 H C209 Fe2 C (7) C110 C109 C (18) C203 Fe2 C (7) C110 C109 Fe (11) C205 Fe2 C (7) C108 C109 Fe (11) C210 Fe2 C (8) C110 C109 H C207 Fe2 C (8) C108 C109 H C206 Fe2 C (8) Fe1 C109 H O2 C2 O (17) C109 C110 C (18) O2 C2 C (16) C109 C110 Fe (12) O3 C2 C (15) C106 C110 Fe (11) C204 C205 C (16) C109 C110 H C204 C205 Fe (11) C106 C110 H C201 C205 Fe (10) Fe1 C110 H C204 C205 H C208 C207 C (16) C201 C205 H C208 C207 Fe (10) Fe2 C205 H C206 C207 Fe (10) C1 O3 C (13) C208 C207 H C108 C107 C (17) C206 C207 H C108 C107 Fe (11) Fe2 C207 H C106 C107 Fe (10) C202 C203 C (17) C108 C107 H C202 C203 Fe (10) C106 C107 H C204 C203 Fe (10) Fe1 C107 H C202 C203 H C103 C102 C (16) C204 C203 H C103 C102 Fe (10) Fe2 C203 H C101 C102 Fe (9) O2 C2 O3 C (2) C105 C101 C1 O3 8.2 (2) C201 C2 O3 C (15) C102 C101 C1 O (15) C103 C102 C101 C (2) Fe1 C101 C1 O (17) Fe1 C102 C101 C (12) C207 C208 C209 C (2) C103 C102 C101 C (16) Fe2 C208 C209 C (13) Fe1 C102 C101 C (16) C207 C208 C209 Fe (12) C103 C102 C101 Fe (12) C206 C210 C209 C (2) C204 C205 C201 C (2) Fe2 C210 C209 C (13) Fe2 C205 C201 C (12) C206 C210 C209 Fe (13) C204 C205 C201 C (17) C101 C105 C104 C (19) Fe2 C205 C201 C (17) Fe1 C105 C104 C (13) C204 C205 C201 Fe (13) C101 C105 C104 Fe (11) C203 C202 C201 C (2) C102 C103 C104 C (2) Fe2 C202 C201 C (12) Fe1 C103 C104 C (12) C203 C202 C201 C (17) C102 C103 C104 Fe (13) Fe2 C202 C201 C (18) C106 C107 C108 C (2) data-6

10 C203 C202 C201 Fe (12) Fe1 C107 C108 C (14) O2 C2 C201 C (3) C106 C107 C108 Fe (12) O3 C2 C201 C (15) C209 C210 C206 C (2) O2 C2 C201 C (18) Fe2 C210 C206 C (12) O3 C2 C201 C (2) C209 C210 C206 Fe (13) O2 C2 C201 Fe (2) C107 C108 C109 C (2) O3 C2 C201 Fe (15) Fe1 C108 C109 C (14) C102 C101 C105 C (19) C107 C108 C109 Fe (14) C1 C101 C105 C (17) C108 C109 C110 C (2) Fe1 C101 C105 C (12) Fe1 C109 C110 C (14) C102 C101 C105 Fe (12) C108 C109 C110 Fe (14) C1 C101 C105 Fe (18) C107 C106 C110 C (2) C108 C107 C106 C (2) Fe1 C106 C110 C (14) Fe1 C107 C106 C (13) C107 C106 C110 Fe (13) C108 C107 C106 Fe (13) C209 C208 C207 C (2) C201 C205 C204 C (2) Fe2 C208 C207 C (12) Fe2 C205 C204 C (13) C209 C208 C207 Fe (12) C201 C205 C204 Fe (13) C210 C206 C207 C (2) C101 C102 C103 C (2) Fe2 C206 C207 C (12) Fe1 C102 C103 C (13) C210 C206 C207 Fe (13) C101 C102 C103 Fe (12) C201 C202 C203 C (2) C2 O3 C1 O (2) Fe2 C202 C203 C (13) C2 O3 C1 C (15) C201 C202 C203 Fe (12) C105 C101 C1 O (17) C205 C204 C203 C (2) C102 C101 C1 O (3) Fe2 C204 C203 C (13) Fe1 C101 C1 O (19) C205 C204 C203 Fe (14) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A C206 H206 O (2) 149 C205 H205 O2 i (2) 169 C204 H204 O1 ii (2) 160 C207 H207 O2 iii (2) 159 Symmetry codes: (i) x+1, y, z+1; (ii) x+1/2, y+1/2, z+1; (iii) x+1/2, y+1/2, z. data-7

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