1′ (1 Hydro­xy­ethyl) N,N di­phenyl­ferrocene 1 carbox­amide1 1

metal-organic papers

Acta Cryst.(2005). E61, m307±m310 doi:10.1107/S1600536804033379 Mario Cetinaet al. [Fe(C₁₈H₁₄NO)(C₇H₉O)]

m307

Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

1

_{-(1-Hydroxyethyl)-}

_N,N

-diphenylferrocene-1-carboxamide

Mario Cetina,a_{* Senka „akovicÂ,}b

Antonija Hergold-BrundicÂc_and

Vladimir RapicÂb

a_{Faculty of Textile Technology, University of}

Zagreb, Pierottijeva 6, HR-10000 Zagreb, Croatia,b_{Laboratory of Organic Chemistry,}

University of Zagreb, Faculty of Food Technology and Biotechnology, Pierottijeva 6, HR-10000 Zagreb, Croatia, andc_{Laboratory of}

General and Inorganic Chemistry, Faculty of Science, University of Zagreb, Ulica kralja Zvonimira 8, HR-10000 Zagreb, Croatia

Correspondence e-mail: vrapic@pbf.hr

Key indicators Single-crystal X-ray study

T= 293 K

Mean(C±C) = 0.006 AÊ

Rfactor = 0.066

wRfactor = 0.169

Data-to-parameter ratio = 14.9

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain ± all rights reserved

In the title compound, [Fe(C18H14NO)(C7H9O)], an N,N -diphenylcarboxamide moiety and a hydroxyethyl group are attached to the ferrocene skeleton. The cyclopentadienyl rings deviate only slightly from an eclipsed conformation. Two CÐ H interactions link the molecules into sheets. According to the X-ray, IR, and 1_{H NMR data, the molecule also} possesses an intramolecular OÐH O hydrogen bond.

Comment

The increasing importance of transition metal-catalysed enantioselective reactions has paralleled the development of new ligands (Togni, 1996; Perea et al., 1998). A variety of synthetic methods have been reported in the literature for the preparation of heteroannularly substituted derivatives of ferrocenene carbinols and carboxylic acids (Little & Eisenthal, 1960, 1961). The title compound, (III), was prepared as one of the substrates for our current research on lipase-catalysed resolution of racemic ferrocene derivatives („akovic et al., 2003). Acylation of ferrocene with N,N-diphenylcarbamoyl chloride gave N,N-diphenylferrocenecarboxamide, (I), which was converted into N,N-diphenyl-10

-acetylferrocenyl-1-carboxamide, (II), by the action of acetyl chloride/AlCl3. Reduction of the ketone±amide (II) with sodium borohydride in aqueous methanol gave the alcohol±amide (III).

In (III), the cyclopentadienyl (Cp) rings bear an N,N -di-phenylcarboxamide moiety and a hydroxyethyl group (Fig. 1).

Received 15 December 2004 Accepted 16 December 2004 Online 22 January 2005

Ferrocene compounds, Part XLII. For part XLI, see BarisÏicÂ

The C1ÐCg1ÐCg2ÐC6 pseudo-torsion angle is ÿ68.3 (3)

(Cg1 and Cg2 are the centroids of the C1±C5 and C6±C10 rings, respectively). A survey of the Cambridge Structural Database (July 2004, Version 5.25; Allen, 2002) reveals that this is the ®rst structure that has the N,N -diphenylcarbox-amide moiety attached to the ferrocenyl skeleton. When we compared (III) with the structures where one phenyl ring is replaced with an H atom and the phenyl ring is not part of a polycyclic structure (Oberhoffet al., 1996; Shirinet al., 2002; Janneret al., 2003), we found that that the C11ÐN1 and N1Ð C(phenyl) bonds in (III) are slightly elongated (0.02±0.04 AÊ; Table 1).

The cyclopentadienyl (Cp) rings deviate only slightly from the eclipsed conformation. The values of the corresponding CÐCg1ÐCg2ÐC pseudo-torsion angles, de®ned by joining two eclipsing Cp C atoms through the ring centroids range from 3.4 (3) to 4.2 (4)_{. The centroids of the Cp rings are}

almost equidistant from the Fe atom. The FeÐCg1 and FeÐ

Cg2 distances are 1.644 (2) and 1.639 (2) AÊ, respectively, and theCg1ÐFeÐCg2 angle is 178.1 (1)_.

The sum of the angles around atom N1 is nearly 360_,i.e.the

atom is sp2_{-hybridized. The carbonyl group and C1±C5 ring} form an extended -conjugated system. The coplanar arrangement of a carbonyl group attached to the ring should allow maximum interaction of the two systems (Lin et al., 1998). In (III), the C11 O1 bond is twisted out of the C1±C5 ring by 39.3 (3)_{, and the C1ÐC11 bond is longer than the}

equivalent bond in our previously reported structures where a carbonyl group is attached to the Cp ring (1.46±1.47 AÊ; Pavlovic et al., 2002; BarisÏicÂet al., 2003; Cetina et al., 2003;

Pavlovic et al., 2003). In these, the C11 O1 bond is almost coplanar with the Cp ring. The phenyl rings are rotated out of the mean plane of the C1/C11/O1/N1 atoms by 71.6 (2) (C12± C17 ring) and 44.0 (2) _{(C18±C23 ring). Furthermore, the}

C18±C23 phenyl ring is almost perpendicular with respect to the C1±C5 cyclopentadienyl ring and the C12±C17 phenyl ring; the corresponding dihedral angles are 89.4 (2) and 83.3 (2)_{, respectively.}

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Figure 1

A view of (III), with the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 20% probability level. The hydrogen bond is shown dashed.

Figure 2

Part of the crystal structure of (III), showing the C19ÐH19 Cg2i_and

C2ÐH2A Cg3ii_{interactions (Cg2 andCg3 are the C6±C10 and C18±}

C23 ring centroids) that form a chain motif and a centrosymmetric dimer. CÐH interactions are indicated by dashed lines and the unit-cell outline has been omitted for clarity. [Symmetry codes: (i)ÿ1 +x, y, z; (ii) ÿx, 1ÿy, 2ÿz.]

Figure 3

A crystal packing diagram of (III), viewed along [001], showing the formation of (010) sheets built from C19ÐH19 Cg2i _{and C2Ð}

H2A Cg3ii_{interactions. CÐH interactions are indicated by dashed}

Carbonyl atom O1 and the hydroxyl group at C24 are linked by an intramolecular hydrogen bond (Fig. 1 and Table 2). This ®nding was corroborated by spectroscopic analysis. The IR spectrum of a ca 10ÿ2_{M solution of 1-ferrocenylethanol} (Goldberget al., 1963) in CH2Cl2showed the narrow strong absorption at 3598 cmÿ1_{corresponding toOÐH (free); the} IR spectrum of (III) showed a very weak signal at this position and an additional broad band at 3388 cmÿ1 _{(OÐH N). In} the solution 1_{H NMR spectrum, the signal for the hydroxyl} proton belonging to the ®rst mentioned compound was found at3.55, and the signal of the alcohol±amide (III) had been shifted to lower ®eld (4.70 p.p.m.), which is an indication of an intramolecular hydrogen bond. It should also be noted that there are two short intramolecular contacts between the C atoms of the Cp and phenyl rings [C1 C17 = 3.114 (6) AÊ and C2 C12 = 3.031 (5) AÊ], and one between carbonyl atom O1 and phenyl-ring atom C23 [2.882 (5) AÊ].

The supramolecular structure of (III) contains two very weak CÐH interactions (Figs. 2 and 3). Both interactions could be classi®ed as geometric type-III interactions, according to Malone et al.(1997), and exhibit almost similar geometry (Table 2). The C19ÐH19 Cg2i_{interaction (Cg2 is} the C6±C10 ring centroid) generated by the translation chain motif runs along [100] [symmetry code: (i)ÿ1 +x, y, z]. The H19 C10i_{distance is shorter than the distance between the} H atom and the Cp-ring centroid. The second shortest H C contact (H19 C6) is much longer than the H19 C10i contact and the C19ÐH19 bond points towards ring atom C10 rather than towards the Cp-ring centroid. On the other hand, the C2ÐH2A Cg3ii _{interaction (Cg3 is the C18±C23 ring} centroid) forms a centrosymmetric dimer [symmetry code: (ii)

ÿx, 1ÿy, 2ÿz]. The shortest contact is H2A C23ii_{and the} C2ÐH2A bond points more to ring atom C23 than to the phenyl-ring centroid. The molecules of (III) are linked by these two CÐH interactions to form (010) sheets (Fig. 3).

Experimental

N,N-Diphenylferrocenylcarboxamide, (I), was prepared in 54% yield starting from ferrocene andN,N-diphenylcarbamoyl chloride (Little & Eisenthal, 1960). By Friedel±Crafts reaction of (I) and acetyl chloride/AlCl3 in dry CH2Cl2, a 95% yield of N,N-diphenyl-10 -acetylferrocenyl-1-carboxamide, (II), was obtained (Little & Eisen-thal, 1961). To a warm solution of (II) (1.0 g, 2.365 mmol) in methanol (28 ml) containing 50% sodium hydroxide (0.03 ml), a 10% sodium borohydride solution (3.8 ml, made up in 10% aqueous sodium hydroxide) was added. The reaction mixture was stirred at room temperature for 30 min and at gentle re¯ux for an additional 5 h. On cooling, the product precipitated to give 1.0 g (99.5%) of orange crystals of (III) (m.p. 386±388 K). Single crystals of the title compound were obtained by slow evaporation of a dichlormethane solution at room temperature. IR (CH2Cl2, cmÿ1):3595 vw (OÐH, free), 3388b(OÐH asoc.), 3093w(CÐH, Fc), 3034w(CÐH, Ph), 2928m(CÐH, aliphatic), 1630s(C O), 1592 (NÐC O)1_{H NMR} (CDCl3, p.p.m.):7.30±7.35 (m, 4H, H14, H16, H20, H23; Ph), 7.10± 7.25 (m, 6H, H13, H15, H17, H19, H21, H23; Ph), 4.70 (s, 1H, OH) (disappeared after addition of D2O), 4.62 (bs, 1H, CHFc), 4.35 (s, 1H, Fc), 4.09±4.25 (m, 5H, Fc), 4.06 (m, 2H, Fc), 1.39±1.41 (d, 3H, Me).13_C NMR (CDCl3, p.p.m.):172.27 (C11), 143.5 (C12 and C18), 126.61±

129.18 (C13ÐC17), 97.32 (C1), 76.58 (C6), 73.04 (C24), 71.2, 70.27, 70.18, 68.38, 68.30, 67.49, 65.28, 65.26 (C2ÐC5 and C7ÐC10), 25.41 (C25).

Crystal data

[Fe(C18H14NO)(C7H9O)]

Mr= 425.29 Monoclinic,P21=c

a= 11.0428 (12) AÊ

b= 18.507 (2) AÊ

c= 10.1462 (11) AÊ

= 104.547 (9)

V= 2007.0 (4) AÊ3

Z= 4

Dx= 1.407 Mg mÿ3 MoKradiation Cell parameters from 3736

re¯ections

= 11.1±20.6

= 0.77 mmÿ1

T= 293 (2) K Prism, orange 0.450.240.13 mm

Data collection

Oxford Diffraction Xcalibur2 diffractometer

!scans

Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2004)

Tmin= 0.775,Tmax= 0.906

16741 measured re¯ections

3929 independent re¯ections 3473 re¯ections withI> 2(I)

Rint= 0.055 max= 26.0

h=ÿ13!13

k=ÿ22!19

l=ÿ12!12

Refinement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.066}

wR(F2_{) = 0.169}

S= 1.17 3929 re¯ections 263 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0814P)2 + 1.0597P]

whereP= (Fo2+ 2Fc2)/3 (/)max= 0.001

max= 0.54 e AÊÿ3 min=ÿ0.37 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_).

FeÐC6 2.029 (4)

FeÐC1 2.032 (3)

FeÐC5 2.029 (4)

FeÐC10 2.031 (4)

FeÐC7 2.033 (4)

FeÐC8 2.042 (4)

FeÐC9 2.044 (4)

FeÐC2 2.046 (4)

FeÐC4 2.040 (4)

FeÐC3 2.049 (4)

N1ÐC11 1.374 (4)

N1ÐC12 1.446 (4)

N1ÐC18 1.445 (4)

O1ÐC11 1.219 (4)

O2ÐC24 1.411 (6)

C1ÐC11 1.495 (5)

C6ÐC24 1.520 (7)

C24ÐC25 1.443 (7)

C11ÐN1ÐC12 120.1 (3) C11ÐN1ÐC18 121.9 (3) C12ÐN1ÐC18 117.3 (3) O1ÐC11ÐN1 122.4 (3)

O1ÐC11ÐC1 121.8 (3) N1ÐC11ÐC1 115.8 (3) O2ÐC24ÐC6 111.7 (4) C25ÐC24ÐC6 113.1 (5)

C12ÐN1ÐC11ÐC1 ÿ18.4 (5)

C18ÐN1ÐC11ÐC1 171.7 (3) C7ÐC6ÐC24ÐO2C7ÐC6ÐC24ÐC25 ÿ101.4 (6)20.3 (7)

Table 2

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

O2ÐH2 O1 0.82 2.08 2.876 (5) 162 C19ÐH19 Cg2i _{0.93 3.25 3.933 (5) 132}

C19ÐH19 C10i _{0.93 3.09 3.931 (6) 152}

C19ÐH19 C6i _{0.93 3.36 4.005 (6) 129}

C2ÐH2A Cg3ii _{0.93 3.20 3.912 (4) 135}

C2ÐH2A C23ii _{0.93 2.93 3.777 (5) 152}

C2ÐH2A C18ii _{0.93 3.20 4.068 (5) 156}

Symmetry codes: (i)xÿ1;y;z; (ii)ÿx;1ÿy;2ÿz. Notes:Cg2 is the C6±C10 ring centroid andCg3 is the C18±C23 ring centroid

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All H atoms were included in calculated positions as riding atoms, with OÐH = 0.82 AÊ and CÐH = 0.93 AÊ for aromatic H atoms, 0.96 AÊ for methyl H atoms or 0.98 AÊ for the methine H atom. H-atomUiso values were set at 1.5Ueq(carrier atom) for the hydroxyl and methyl H atoms, and at 1.2Ueq(carrier atom) for all other H atoms.

Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell re®nement: CrysAlis CCD; data reduction: CrysAlis RED(Oxford Diffraction, 2004); program(s) used to solve structure:SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:PLATON(Spek, 2003); soft-ware used to prepare material for publication:SHELXL97.

References

Allen, F. H. (2002).Acta Cryst.B58, 380±388.

BarisÏicÂ, L., DropucÏicÂ, M., RapicÂ, V., Pritzkow, H., Kirin, S. I. & Metzler-Nolte, N. (2004).Chem. Commun.pp. 2004±2005.

BarisÏicÂ, L., RapicÂ, V., Pritzkow, H., PavlovicÂ, G. & Nemet, I. (2003). J. Organomet. Chem.682, 131±142.

Cetina, M., JukicÂ, M., RapicÂ, V. & GolobicÂ, A. (2003).Acta Cryst.C59, m212± m214.

„akovicÂ, S., LapicÂ, J. & RapicÂ, V. (2003).Biocatal. Biotransform.21, 291±295. Goldberg, S. I., Mayo, D. W. & Alford, J. A. (1963).J. Org. Chem.28, 1708±

1710.

Janner, R., Gompper, R. & Polborn, K. (2003). Personal communication. Lin, L., Berces, A., Kraatz, H.-B. (1998).J. Organomet. Chem.556, 11±20. Little, W. F. & Eisenthal, R. (1960).J. Am. Chem. Soc.82, 1577±1580. Little, W. F. & Eisenthal, R. (1961).J. Org. Chem.26, 3609±3610.

Malone, J. F., Murray, C. M., Charlton, M. H., Docherty, R. & Lavery, A. J. (1997).J. Chem. Soc. Faraday Trans.93, 3429±3436.

Oberhoff, M., Duda, L., Karl, J., Mohr, R., Erker, G., Frohlich, R. & Grehl, M. (1996).Organometallics,15, 4005±4011.

Oxford Diffraction. (2004).CrysAlis CCDandCrysAlis RED. Versions 1.4. Oxford Diffraction, Oxford, England.

PavlovicÂ, G., BarisÏicÂ, L., RapicÂ, V. & KovacÂ, V. (2003).Acta Cryst.C59, m55± m57.

PavlovicÂ, G., BarisÏicÂ, L., RapicÂ, V. & Leban, I. (2002).Acta Cryst.E58, m13± m15.

Perea, J. J. A., BoÈrner, A. & Knochel, P. (1998).Tetrahedron Lett.39, 8073± 8076.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.

Shirin, Z., Thompson, J., Liable-Sands, L., Yap, G. P. A., Rheingold, A. L. & Borovik, A. S. (2002).J. Chem. Soc. Dalton Trans.pp. 1714±1720. Spek, A. L. (2003).J. Appl. Cryst.36, 7±13.

Togni, A. (1996).Angew. Chem. Int. Ed. Engl.35, 1475±1477.

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Acta Cryst. (2005). E61, m307–m310

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Acta Cryst. (2005). E61, m307–m310 [https://doi.org/10.1107/S1600536804033379]

1

′

-(1-Hydroxyethyl)-

N,N

-diphenylferrocene-1-carboxamide

Mario Cetina, Senka

Đ

akovi

ć

, Antonija Hergold-Brundi

ć

and Vladimir Rapi

ć

1′-(1-Hydroxyethyl)-N,N-diphenylferrocene-1-carboxamide

Crystal data

[Fe(C18H14NO)(C7H9O)]

Mr = 425.29

Monoclinic, P21/c

Hall symbol: -P 2ybc a = 11.0428 (12) Å b = 18.507 (2) Å c = 10.1462 (11) Å β = 104.547 (9)° V = 2007.0 (4) Å3

Z = 4

F(000) = 888 Dx = 1.407 Mg m−3

Melting point = 386–388 K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3736 reflections θ = 11.1–20.6°

µ = 0.77 mm−1

T = 293 K Prism, orange

0.45 × 0.24 × 0.13 mm

Data collection

Oxford Diffraction Xcalibur2 diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: numerical

(CrysAlis RED; Oxford Diffraction, 2004) Tmin = 0.775, Tmax = 0.906

16741 measured reflections 3929 independent reflections

3473 reflections with I > 2σ(I) Rint = 0.055

θmax = 26.0°, θmin = 4.0°

h = −13→13 k = −22→19 l = −12→12

Standard reflections: 2 frames; every 50 frames reflections

intensity decay: none

Refinement Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.066}

wR(F2_{) = 0.169}

S = 1.17 3929 reflections 263 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(F

o2) + (0.0814P)2 + 1.0597P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 0.54 e Å−3

Δρmin = −0.37 e Å−3

Special details

Experimental. Melting points were determined with a Buechi apparatus. The IR spectra were recorded in CH2Cl2 on a

Bomem MB100 Mid FT IR spectrophotometer. The 1_{H and} 13_{C NMR spectra in CDCl}

3 were recorded on a Varian Gemini

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Acta Cryst. (2005). E61, m307–m310

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

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Acta Cryst. (2005). E61, m307–m310

H23 0.0396 0.6482 1.1550 0.057* C24 0.3638 (5) 0.7508 (3) 0.8218 (6) 0.0769 (14) H24 0.3266 0.7608 0.7253 0.092* C25 0.4815 (5) 0.7888 (3) 0.8617 (9) 0.116 (3) H25A 0.4673 0.8397 0.8474 0.174* H25B 0.5361 0.7720 0.8080 0.174* H25C 0.5195 0.7799 0.9563 0.174*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Fe 0.0359 (3) 0.0444 (3) 0.0413 (3) 0.0026 (2) 0.0115 (2) 0.0011 (2) N1 0.0384 (15) 0.0486 (16) 0.0428 (16) −0.0036 (13) 0.0132 (13) −0.0086 (13) O1 0.0542 (16) 0.0504 (15) 0.0695 (18) −0.0124 (13) 0.0249 (14) −0.0158 (14) O2 0.099 (3) 0.066 (2) 0.152 (4) −0.0164 (19) 0.072 (3) −0.023 (2) C1 0.0345 (17) 0.0453 (19) 0.0402 (18) 0.0025 (14) 0.0092 (15) −0.0049 (15) C2 0.0427 (19) 0.046 (2) 0.059 (2) −0.0025 (16) 0.0181 (17) −0.0076 (18) C3 0.045 (2) 0.063 (3) 0.056 (2) 0.0017 (18) 0.0105 (18) −0.014 (2) C4 0.052 (2) 0.088 (3) 0.0363 (19) 0.017 (2) 0.0147 (17) 0.001 (2) C5 0.049 (2) 0.053 (2) 0.052 (2) 0.0122 (17) 0.0155 (18) 0.0117 (18) C6 0.046 (2) 0.063 (3) 0.067 (3) −0.0117 (19) 0.020 (2) −0.014 (2) C7 0.040 (2) 0.080 (3) 0.046 (2) −0.0042 (19) 0.0059 (17) −0.011 (2) C8 0.050 (2) 0.073 (3) 0.064 (3) 0.011 (2) 0.002 (2) 0.011 (2) C9 0.039 (2) 0.080 (3) 0.081 (3) 0.018 (2) 0.010 (2) −0.015 (3) C10 0.047 (2) 0.080 (3) 0.072 (3) −0.006 (2) 0.028 (2) −0.009 (2) C11 0.0389 (18) 0.0386 (18) 0.0436 (18) 0.0023 (14) 0.0113 (15) −0.0005 (15) C12 0.0319 (16) 0.053 (2) 0.0424 (19) −0.0021 (15) 0.0100 (14) −0.0094 (16) C13 0.048 (2) 0.056 (2) 0.052 (2) −0.0071 (17) 0.0127 (18) −0.0035 (18) C14 0.059 (3) 0.061 (3) 0.072 (3) −0.016 (2) 0.020 (2) −0.017 (2) C15 0.047 (2) 0.090 (3) 0.058 (3) −0.011 (2) 0.011 (2) −0.031 (2) C16 0.050 (2) 0.090 (3) 0.042 (2) 0.008 (2) 0.0035 (18) −0.004 (2) C17 0.046 (2) 0.061 (2) 0.053 (2) 0.0060 (18) 0.0103 (18) −0.0026 (19) C18 0.0412 (18) 0.0386 (18) 0.0400 (18) 0.0009 (14) 0.0131 (15) −0.0018 (14) C19 0.041 (2) 0.083 (3) 0.049 (2) 0.0038 (19) 0.0127 (17) −0.013 (2) C20 0.050 (2) 0.107 (4) 0.063 (3) 0.007 (2) 0.022 (2) −0.016 (3) C21 0.074 (3) 0.073 (3) 0.055 (3) 0.007 (2) 0.032 (2) −0.007 (2) C22 0.070 (3) 0.056 (2) 0.039 (2) −0.003 (2) 0.0071 (19) −0.0006 (18) C23 0.044 (2) 0.049 (2) 0.046 (2) −0.0017 (16) 0.0061 (16) 0.0006 (17) C24 0.070 (3) 0.059 (3) 0.108 (4) −0.014 (2) 0.035 (3) −0.012 (3) C25 0.073 (4) 0.077 (4) 0.206 (8) −0.010 (3) 0.046 (4) 0.019 (4)

Geometric parameters (Å, º)

Fe—C6 2.029 (4) C8—H8 0.9300

Fe—C1 2.032 (3) C9—C10 1.413 (7)

Fe—C5 2.029 (4) C9—H9 0.9300

Fe—C10 2.031 (4) C10—H10 0.9300

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Acta Cryst. (2005). E61, m307–m310

Fe—C8 2.042 (4) C12—C17 1.382 (5) Fe—C9 2.044 (4) C13—C14 1.385 (6)

Fe—C2 2.046 (4) C13—H13 0.9300

Fe—C4 2.040 (4) C14—C15 1.378 (6)

Fe—C3 2.049 (4) C14—H14 0.9300

N1—C11 1.374 (4) C15—C16 1.369 (7)

N1—C12 1.446 (4) C15—H15 0.9300

N1—C18 1.445 (4) C16—C17 1.387 (6)

O1—C11 1.219 (4) C16—H16 0.9300

O2—C24 1.411 (6) C17—H17 0.9300

O2—H2 0.8200 C18—C23 1.376 (5)

C1—C2 1.424 (5) C18—C19 1.383 (5) C1—C5 1.428 (5) C19—C20 1.383 (6)

C1—C11 1.495 (5) C19—H19 0.9300

C2—C3 1.424 (5) C20—C21 1.376 (6)

C2—H2A 0.9300 C20—H20 0.9300

C3—C4 1.397 (6) C21—C22 1.367 (6)

C3—H3 0.9300 C21—H21 0.9300

C4—C5 1.418 (6) C22—C23 1.385 (5)

C4—H4 0.9300 C22—H22 0.9300

C5—H5 0.9300 C23—H23 0.9300

C6—C10 1.421 (6) C24—C25 1.443 (7)

C6—C7 1.430 (6) C24—H24 0.9800

C6—C24 1.520 (7) C25—H25A 0.9600

C7—C8 1.412 (6) C25—H25B 0.9600

C7—H7 0.9300 C25—H25C 0.9600

C8—C9 1.425 (7)

supporting information

sup-5

Acta Cryst. (2005). E61, m307–m310

supporting information

sup-6

Acta Cryst. (2005). E61, m307–m310

C3—C4—Fe 70.4 (2) O2—C24—C25 107.7 (5) C5—C4—Fe 69.2 (2) O2—C24—C6 111.7 (4) C3—C4—H4 125.4 C25—C24—C6 113.1 (5)

C5—C4—H4 125.3 O2—C24—H24 108.1

Fe—C4—H4 126.7 C25—C24—H24 108.1 C4—C5—C1 107.1 (3) C6—C24—H24 108.1 C4—C5—Fe 70.0 (2) C24—C25—H25A 109.5 C1—C5—Fe 69.5 (2) C24—C25—H25B 109.5 C4—C5—H5 126.4 H25A—C25—H25B 109.5 C1—C5—H5 126.4 C24—C25—H25C 109.5 Fe—C5—H5 125.6 H25A—C25—H25C 109.5 C10—C6—C7 105.9 (4) H25B—C25—H25C 109.5

supporting information

sup-7

Acta Cryst. (2005). E61, m307–m310

supporting information

sup-8

Acta Cryst. (2005). E61, m307–m310

supporting information

sup-9

Acta Cryst. (2005). E61, m307–m310

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A O2—H2···O1 0.82 2.08 2.876 (5) 162 C19—H19···Cg2i _{0.93 3.25 3.933 (5) 132}

C19—H19···C10i _{0.93 3.09 3.931 (6) 152}

C19—H19···C6i _{0.93 3.36 4.005 (6) 129}

C2—H2A···Cg3ii _{0.93 3.20 3.912 (4) 135}

C2—H2A···C23ii _{0.93 2.93 3.777 (5) 152}

C2—H2A···C18ii _{0.93 3.20 4.068 (5) 156}