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ISSN: 2053-2296

[η6-1-Chloro-2-(pyrrolidin-1-yl)­benzene](η5-cyclo­penta­dien­yl)iron(II) hexa­fluoridophosphate and (η5-cyclo­penta­dien­yl){2-[η6-2-(pyrrolidin-1-yl)­phen­yl]phenol}iron(II) hexa­fluorido­phosphate

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

(Received 2 September 2011; accepted 18 November 2011; online 30 November 2011)

In the complex salt [η6-1-chloro-2-(pyrrolidin-1-yl)­ben­zene](η5-cyclo­penta­dien­yl)iron(II) hexa­fluorido­phosphate, [Fe(C5H5)(C10H12ClN)]PF6, (I), the complexed cyclo­penta­dienyl and benzene rings are almost parallel, with a dihedral angle between their planes of 2.3 (3)°. In a related complex salt, (η5-cyclo­penta­dien­yl){2-[η6-2-(pyrrolidin-1-yl)phen­yl]phenol}iron(II) hexa­fluoridophosphate, [Fe(C5H5)(C16H17NO)]PF6, (II), the analogous angle is 5.4 (1)°. In both complexes, the aromatic C atom bound to the pyrrolidine N atom is located out of the plane defined by the remaining five ring C atoms. The dihedral angles between the plane of these five ring atoms and a plane defined by the N-bound aromatic C atom and two neighboring C atoms are 9.7 (8) and 5.6 (2)° for (I) and (II), respectively.

Comment

(η6-o-Chloro-N-pyrrolidinyl­benzene)(η5-cyclo­penta­dien­yl)­iron(II) hexa­fluoridophosphate, along with similar m- and p-chloro-N-butyl­amino- and di-N-butyl­amino-, chloro-N-pyr­roli­dinyl- and di-N-pyrrolidinyl-, and some chloro­cyano­benzene complexes with a cyclo­penta­dienyliron(II) unit, were reported as part of a study of nucleophilic aromatic mono- and disubstitution reactions using o-, m- and p-dichloro­benzene–FeCp (Cp is cyclopentadienyl) complexes (Lee et al., 1989[Lee, C. C., Zhang, C. H., Abd-El-Aziz, A. S., Piórko, A. & Sutherland, R. G. (1989). J. Organomet. Chem. 364, 217-229.]) with amines and the cyanide anion. (η5-Cyclo­penta­dien­yl)(η6-o-N-pyrrolidinyl-o′-hy­droxy­biphen­yl)­iron(II) hexa­fluorido­phos­phate was obtained in another nucleophilic substitution reaction, viz. a ring-opening reaction of a furan ring in dibenzofuran facilitated by η6-complexation with an FeCp moiety (Lee et al., 1983[Lee, C. C., Piórko, A., Steele, B. R., Gill, U. S. & Sutherland, R. G. (1983). J. Organomet. Chem. 256, 303-308.]). Having previously observed a distortion of the FeCp-complexed benzene ring, which resulted from the o-dipyrrolidinyl substitution of benzene (Jenkins et al., 2009[Jenkins, H. A., Masuda, J. D. & Piórko, A. (2009). Acta Cryst. E65, m966.]), we resolved to take a closer look at FeCp complexes of related o-disubstituted benzenes in which one of the substituents is a pyrrolidinyl group, and the second may exert either steric hindrance or a significant electronic influence.

[Scheme 1]

In the title complex salts, [η6-1-chloro-2-(pyrrolidin-1-yl)­ben­zene](η5-cyclo­penta­dien­yl)iron(II) hexa­fluorido­phos­phate, (I), and (η5-cyclo­penta­dien­yl){2-[η6-2-(pyrrolidin-1-yl)phen­yl]phenol}iron(II) hexa­fluoridophosphate, (II), the Fe ion is located at distances of 1.644 (4) and 1.663 (1) Å from the Cp plane, and at distances of 1.554 (4) and 1.557 (1) Å from the benzene ring plane, respectively. These values are close to those reported in the literature for similar complexes (see, for example, Piórko et al., 1995[Piórko, A., Christie, S. & Zaworotko, M. J. (1995). Acta Cryst. C51, 26-29.]; 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.], 2009[Manzur, C., Millan, L., Fuentealba, M., Trujillo, A. & Carrillo, D. (2009). J. Organomet. Chem. 694, 2043-2046.]; Hendsbee et al., 2010[Hendsbee, A. D., Masuda, J. D. & Piórko, A. (2010). Acta Cryst. E66, m1154.], and references therein).

In complex (I)[link], the benzene and Cp rings are nearly parallel, with a dihedral angle of 2.3 (3)°, while in complex (II)[link], this angle is larger, reaching 5.4 (1)°. This second value is among the largest reported from our work, along with the value of 5.34 (13)° given previously by Jenkins et al. (2009[Jenkins, H. A., Masuda, J. D. & Piórko, A. (2009). Acta Cryst. E65, m966.]). This is also similar to the value of 5.4° reported for the hexa­ethyl­benzene–CpFe complex (Dubois et al., 1989[Dubois, R. H., Zaworotko, M. J. & White, P. S. (1989). J. Organomet. Chem. 362, 155-161.]), although lower than the value of 7° reported for the 1,1′-tri­methyl­ene­benzene–CpFe cation (Nesmeyanov et al., 1977[Nesmeyanov, A. N., Tolstaya, M. V., Rybinskaya, M. I., Shul'pin, G. B., Bokii, N. G., Batsanov, A. S. & Struchkov, Yu. T. (1977). J. Organomet. Chem. 142, 89-93.]). No standard uncertainties were provided by these authors in their reports.

For (I)[link], the average Fe—C(benzene) distance is 2.098 (10) Å, while the distances to the substituted atoms C1 and C2 are 2.085 (10) and 2.237 (8) Å, respectively. For (II)[link], the corresponding values are 2.107 (4) Å for the average, and 2.139 (3) and 2.218 (3) Å for the Fe1—C1 and Fe1—C2 distances, respectively. The distances from atom Fe1 to atom C2, which carries a pyrrolidin-1-yl substituent in both complexes, are among the largest reported for similar complexes, along with the value of 2.252 (2) Å reported previously for one of the substituted ring C atoms of a dipyrrolidinyl complex (Jenkins et al., 2009[Jenkins, H. A., Masuda, J. D. & Piórko, A. (2009). Acta Cryst. E65, m966.]). Other reports with similar Fe—Csubst distances include the structure of an Fe(Me5Cp)phenoxide–water complex [Csubst bonded to O; 2.269 (9) Å; Moulines et al., 1995[Moulines, F., Djakovitch, L., Delville-Desbois, M.-H., Robert, F., Gouzerh, P. & Astruc, D. (1995). J. Chem. Soc. Chem. Commun. pp. 463-464.]; Djakovitch et al., 1996[Djakovitch, L., Moulines, F. & Astruc, D. (1996). New J. Chem. 20, 1071-1080.]], a p-methyl­phenyl­hydrazine FeCp fragment in a tungsten complex [2.24 (1) Å; Ishii et al., 1994[Ishii, Y., Kawaguchi, Y. I., Aoki, T. & Hidai, M. (1994). Organometallics, 13, 5062-5071.]] and an N′-isopropyl­idene hydrazone of p-methyl­phenyl­hydrazine [2.201 (5) Å; 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. 694, 2043-2046.]]. Many of the Cp and penta­methyl-Cp complexes examined in a series of studies by Carrillo and coworkers (see, for example, 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., 2000[Manzur, C., Baeza, E., Millan, L., Fuentealba, M., Hamon, P., Hamon, J.-R., Boys, D. & Carrillo, D. (2000). J. Organomet. Chem. 694, 2043-2046.], 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.], 2009[Manzur, C., Millan, L., Fuentealba, M., Trujillo, A. & Carrillo, D. (2009). J. Organomet. Chem. 694, 2043-2046.]) have an Fe—Csubst (bonded to N) distance shorter than that found in our work.

The distance of the pyrrolidine N atom from the C1–C6 ring plane is 0.099 (13) and 0.034 (4) Å, respectively, in (I)[link] and (II)[link]. The N atom in each complex is located on the opposite side of the plane defined by the complexed benzene ring with respect to the Fe atom attached to this ring. These values and the long Fe1—C2 distances prompted examination of additional selected angles and planes to discern possible deformations of a complexed aromatic ring. Examination of the Fe—CsubstX angles (where X is the atom of a substituent bonded to the complexed benzene ring and Csubst is the atom in the complex ring to which substituent X is attached) revealed that for the two different substituents present in the studied complexes, the angles have quite different values. It was expected that a longer Fe—N (bonded to aromatic C) distance may be reflected in a smaller Fe1—C2—N1 angle. For (II)[link], the values are 135.4 (2)° for Fe1—C1—C7 and 133.8 (2)° for Fe1—C2—N1, which is in agreement with the expected order. For (I)[link], however, these values are 133.1 (5)° for Fe1—C1—Cl1 and 135.2 (6)° for Fe1—C2—N1, thus the expecta­tions were not substanti­ated in the case of this complex. As the N atoms are found above the complexed benzene-ring plane, on the side opposite to Fe, in both complexes, the dihedral angles between the planes formed by each substituted C atom and its direct neighbors in a ring versus planes of other ring C atoms were also examined. For (I)[link], a plane centered at C1 and defined by atoms C2/C1/C6 inter­sects the C2/C3/C4/C5/C6 plane at a dihedral angle of 6.4 (5)° and inter­sects the plane formed by the unsubstituted ring C atoms C3/C4/C5/C6 at a dihedral angle of 5.1 (6)°, the angles being essentially the same. The C1/C2/C3 plane, centered upon C2, which is an N-bound C atom, inter­sects the C3/C4/C5/C6/C1 plane at an angle of 9.7 (8)° and inter­sects the plane defined by unsubstituted ring C atoms C3/C4/C5/C6 at an angle of 10.2 (9)°. For (II)[link], the values between planes are as follows: 2.8 (2)° between C2/C1/C6 and C2/C3/C4/C5/C6, 2.5 (2)° between C2/C1/C6 and C3/C4/C5/C6, 5.6 (2)° between C1/C2/C3 and C3/C4/C5/C6/C1, and 6.2 (2)° between C1/C2/C3 and C3/C4/C5/C6. These angles seem to suggest that a longer Fe1—C2 distance and a larger dihedral angle between the C1/C2/C3 planes and a plane defined by the ring C atoms excluding atom C2 observed for (I)[link] may be a result of the electronic influence of the chlorine neighbor and, for (II)[link], steric crowding exerted by the second, directly linked, benzene ring. Similar values, viz. 6.0 (5) and 7.1 (6)°, have been reported for phenyl­hydrazine complexes studied by 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. 694, 2043-2046.]). The pyrrolidine ring of (I)[link] in the solid state adopts a twisted conformation with C12 and C13 located out of the plane defined by the remaining three atoms. In comparison with C12, atom C13 is further away from the o-chloro substituent and from the Fe atom. A similar situation is observed for (II)[link], with C22 and C23 located out of the C21/N1/C24 plane. In comparison with C22, atom C23 is further away from the uncomplexed ring of the biphenyl skeleton and from the Fe atom. Bond lengths in the pyrrolidine rings of both complexes are similar and in line with literature values (Allen et al., 1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]). The N atoms in both complexes show similar bond lengths to ring atom C2 [1.344 (11) Å for (I)[link] and 1.356 (4) Å for (II)] and to the methyl­ene C atoms of the pyrrolidine rings [range 1.476 (4)–1.484 (12) Å]. The C2—N1 bond length in each complex, which is in agreement with the Car—Nsp2 bond length (Allen et al., 1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]), implies that depyramidalization of the N atom takes effect in both complexes. This suggestion is corroborated by the geometry around the N atom; the sum of angles is close to 360° in each complex [358.4 (9) and 357.1 (4)°, respectively, in (I)[link] and (II)[link], and this may, as discussed by 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. 694, 2043-2046.]), result from a partial delocalization of the N1 lone pair of electrons toward the complexed benzene ring.

The average C—C bond length for the complexed benzene ring of (I)[link] is 1.410 (14) Å. For (II)[link], the average is 1.419 (4) Å and the bond between substituted atoms C1 and C2 [1.441 (4) Å] is slightly longer than the average. In (I)[link], the C1—Cl1 bond length and the Fe1—C1 distance [1.728 (10) and 2.085 (10) Å, respectively] are similar to values reported for the same bonds in an o-dichloro­benzene–FeCp complex (Crane, 2003[Crane, J. D. (2003). Acta Cryst. E59, m1004-m1005.]). The second benzene ring in (II)[link] shows no unusual features, and the C1—C7 bond between the rings has a length of 1.491 (4) Å, which is in agreement with literature data (Allen et al., 1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]). The plane of this second ring is tilted at 74.9 (3)° with respect to the plane of the complexed ring.

[Figure 1]
Figure 1
View of complex (I), showing the labeling of the non-H atoms and displacement ellipsoids at the 50% probability level. H atoms have been omitted for clarity.
[Figure 2]
Figure 2
View of complex (II), showing the labeling of the non-H atoms and displacement ellipsoids at the 50% probability level. H atoms have been omitted for clarity.

Experimental

Complex (I) was prepared from (o-dichloro­benzene)FeCp·PF6 and pyrrolidine according to the method of Lee et al. (1989[Lee, C. C., Zhang, C. H., Abd-El-Aziz, A. S., Piórko, A. & Sutherland, R. G. (1989). J. Organomet. Chem. 364, 217-229.]). Complex (II) was prepared by ring opening of dibenzofuran in a reaction of (dibenzofuran)FeCp·PF6 with pyrrolidine as described by Lee et al. (1983[Lee, C. C., Piórko, A., Steele, B. R., Gill, U. S. & Sutherland, R. G. (1983). J. Organomet. Chem. 256, 303-308.]). In each case, the crystals used for data collection were grown by cooling of a solution in a mixture of acetone, diethyl ether and dichloro­methane at 280 K for an extended period of time. It should be noted that, despite our numerous crystallization attempts under different conditions, the quality of the crystals of complex (I) was not as good as the quality of those of complex (II), and this affected both our results and their analysis.

Compound (I)[link]

Crystal data
  • [Fe(C5H5)(C10H12ClN)]PF6

  • Mr = 447.57

  • Monoclinic, P 21

  • a = 7.000 (2) Å

  • b = 13.401 (4) Å

  • c = 8.805 (3) Å

  • β = 95.183 (4)°

  • V = 822.6 (4) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 1.23 mm−1

  • T = 100 K

  • 0.24 × 0.20 × 0.15 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2008[Bruker (2008). SADABS and CELL_NOW. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.522, Tmax = 0.746

  • 7536 measured reflections

  • 2880 independent reflections

  • 2553 reflections with I > 2σ(I)

  • Rint = 0.058

Refinement
  • R[F2 > 2σ(F2)] = 0.081

  • wR(F2) = 0.206

  • S = 1.09

  • 2880 reflections

  • 227 parameters

  • 507 restraints

  • H-atom parameters constrained

  • Δρmax = 1.89 e Å−3

  • Δρmin = −1.12 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 1374 Friedel pairs

  • Flack parameter: 0.36 (5)

Compound (II)[link]

Crystal data
  • [Fe(C5H5)(C16H17NO)]PF6

  • Mr = 505.22

  • Monoclinic, P 21 /n

  • a = 10.9764 (11) Å

  • b = 9.4221 (10) Å

  • c = 19.393 (2) Å

  • β = 91.608 (1)°

  • V = 2004.8 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.90 mm−1

  • T = 100 K

  • 0.33 × 0.30 × 0.28 mm

.
Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2008[Bruker (2008). SADABS and CELL_NOW. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.691, Tmax = 0.745

  • 9910 measured reflections

  • 3451 independent reflections

  • 2720 reflections with I > 2σ(I)

  • Rint = 0.040

Refinement
  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 0.122

  • S = 0.85

  • 3451 reflections

  • 281 parameters

  • H-atom parameters constrained

  • Δρmax = 0.60 e Å−3

  • Δρmin = −0.36 e Å−3

For (I) and (II), the H atoms were placed in geometrically idealized positions, with C—H distances of 1.0 Å for all complexed, uncomplexed aromatic and Cp H atoms, 0.99 Å for aliphatic H atoms, and 0.84 Å for the hydroxy H atoms. H atoms were constrained to ride on the parent C atom, with Uiso(H) = 1.2Ueq(C) for the aromatic, Cp and aliphatic H atoms, and Uiso(H) = 1.5Ueq(O) for the hydroxy H atoms. The structure of (I) contains two mol­ecules of a single enanti­omer in the unit cell, and the structure itself was refined as an enanti­omeric mixture. The major twin domain refined to 0.64 (5). A warning was generated by PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); ADDSYM indicated P21/m pseudosymmetry. The pseudo-inversion symmetry indicated is not present as crystallographic symmetry, as a complete overlap of the two mol­ecules is not formed upon application of the proposed inversion symmetry element (only 88% of the atoms are related by the additional symmetry element). Additionally, an extensive search for the cell of apparently higher symmetry was attempted using CELL_NOW (Bruker, 2008[Bruker (2008). SADABS and CELL_NOW. Bruker AXS Inc., Madison, Wisconsin, USA.]), with a total of 4399 reflections indexed and a minimum I/σ(I) value of 1.75 for the spots harvested. The search for a larger cell was unsuccessful and therefore the pseudosymmetry warning was ignored and the refinement was completed in the space group P21. Three outlying reflections with h, k, l values (4,0,0), (4,[\bar 1],[\bar 1]) and (4,0,2) were omitted from the refinement. This complex contains a 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 C1–C6 (coordinated aromatic ring) and atoms C21–C25 (complexed Cp ring). This was resolved through the use of restraints applied to the refinement of these atoms: the Uij components of these atoms were restrained to be equal to within 0.001 Å2 and their anisotropic displacement parameters were restrained to be equal to within 0.02 Å2.

For both compounds, data collection: APEX2 (Bruker, 2010[Bruker (2010). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2010[Bruker (2010). APEX2 and SAINT. 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


Comment top

[(η5-Cyclopentadienyl)(η6-o-chloro-N-pyrrolidinylbenzene)iron(II)] hexafluoridophosphate, along with similar m- and p-chloro-N-butylamino- and di-N-butylamino-, chloro-N-pyrrolidino- and di-N-pyrrolidino-, and some chlorocyanobenzene complexes with a cyclopentadienyliron(II) moiety, were reported in the study of nucleophilic aromatic mono- and di-substitution reactions using o-, m- and p-dichlorobenzene FeCp complexes (Lee et al., 1989) with amines and the cyanide anion. [(η5-Cyclopentadienyl)(η6-o-N-pyrrolidinyl-o'-hydroxybiphenyl)iron(II)] hexafluoridophosphate was obtained in another nucleophilic substitution reaction, a ring-opening reaction of a furan ring in dibenzofuran facilitated by η6-complexation with an FeCp moiety (Lee et al., 1983). Having previously observed a distortion of the FeCp-complexed benzene ring, which resulted from the o-dipyrrolidinyl substitution of benzene (Jenkins et al., 2009), we resolved to take a closer look at FeCp complexes of related o-disubstituted benzenes in which one of the substituents is a pyrrolidinyl group, and the second one may exert either steric hindrance or a significant electronic influence.

The ORTEP view of the chloropyrrolidinyl, (I), and pyrrolidinylbiphenyl, (II), complexes is shown in Figs. 1 and 2, respectively. The Fe ion is located at distances of 1.644 (4) and 1.663 (1) Å from the Cp plane, and 1.554 (4) and 1.557 (1) Å from the phenyl ring plane, respectively, for both complexes. These values are close to those reported in the literature for similar complexes (see, for example, Piórko et al., 1995; Fuentealba et al., 2007; Manzur et al., 2007, 2009; Hendsbee et al., 2010, and literature cited therein).

In the chloropyrrolidinyl complex, (I), the benzene and Cp rings are nearly parallel with a dihedral angle of 2.3 (3)°, while in the pyrrolidinylbiphenyl complex, (II), this angle is larger, reaching 5.4 (1)°. This second value is among the largest reported from our work, along with the value 5.34 (13)° given previously by Jenkins et al. (2009). This value is also similar to 5.4° reported for the hexaethylbenzene–CpFe complex (Dubois et al., 1989), although lower than the value 7° reported for the 1,1'-trimethylenebenzene–CpFe cation (Nesmeyanov et al., 1977). No standard uncertainties were provided by these authors in their reports.

For (I) the Fe–phenyl-ring C-atom distance averages at 2.098 Å, while the distances towards the quaternary carbon atoms are 2.085 (10) and 2.237 (8) Å for Fe—C1 (bonding Cl) and Fe—C2 (bonding N), respectively. For (II) the similar values are 2.107 Å for an average, and 2.139 (3) and 2.218 (3) Å for Fe—C1 (bonding C of the second ring) and Fe—C2 (bonding N), respectively. The values for the Fe—C2 distance, which carries an N-pyrrolidinyl substituent in both complexes, are among the largest reported for similar complexes, along with the value 2.252 (2) Å reported earlier for one of the quaternary ring carbon atoms of a dipyrrolidinyl complex (Jenkins et al., 2009). The other reports on the Fe—Cquat of similar value came from examination of the structure of an Fe(Me5Cp) phenoxide–water complex, with an Fe–quaternary C bonding oxygen distance of 2.269 (9) Å (Moulines et al., 1995; Djakovitch et al., 1996), a p-methylphenylhydrazine FeCp fragment in a tungsten complex at 2.24 (1) Å (Ishii et al., 1994), and for N'-isopropylidene hydrazone of p-methylphenylhydrazine at 2.201 (5) Å (Manzur et al., 2000). Most of the hydrazones for many of both Cp and pentamethylCp complexes examined in a series of studies by Carrillo and coworkers (see, for example, Fuentealba et al., 2007; Manzur et al., 2000, 2007, 2009) have an Fe–quaternary C bonding N distance shorter than that found in our work.

The distance of the pyrrolidinyl nitrogen atom from the C1–C6 phenyl-ring plane is 0.099 (13) and 0.034 (4) Å, respectively, for complexes (I) and (II) [ok as edited?]. Both nitrogen atoms appear to be elevated above the respective plane of the complexed ring. These values and long Fe—C2 distances prompted examination of additional selected angles and planes to discern possible deformations of a complexed aromatic ring. Examination of the angles (Fe–quaternary C–bonded atom of substituent X) [Fe—Cquat—X where X is the bonded substituent] for two different substituents revealed that this angle has quite different values in the studied complexes. It was expected that a longer Fe–N-bonded quaternary carbon distance may be reflected in a smaller Fe—C2—N1 angle. For (II) the respective values were 135.4 (2)° for Fe—C1—C7, and 133.8 (2)° for Fe—C2—N1, which is in agreement with the expected order. For (I), however, these values were 133.1 (5)° for Fe—C1—Cl and 135.2 (6)° for Fe—C2—N1, thus the expectations were not substantiated in the case of this complex. As the nitrogen atoms are found above the complexed phenyl-ring plane in both complexes, dihedral angles between the planes formed by each quaternary carbon atom and its direct neighbors in a ring versus planes of other ring carbon atoms were also examined. For (I) a plane centered at the C1 carbon and defined by C2—C1—C6 atoms intersects a plane C2—C3—C4—C5—C6 at a dihedral angle 6.4 (5)°, and a plane made of non-quaternary carbon atoms C3—C4—C5—C6 at 5.1 (6)°, thus essentially this angle is the same. A plane based upon carbon atoms C1—C2— C3, centered upon C2 which is an N-bonding carbon atom, intersects a plane of atoms C3—C4—C5—C6—C1 at 9.7 (8)°, and the plane defined by non-quaternary ring carbon atoms C3—C4—C5—C6 at 10.2 (9)°. For (II) the respective values for similar angles between planes are as follows: C2—C1—C6 and C2—C3—C4—C5—C6 angle 2.8 (2)°; C2—C1—C6 and C3—C4—C5—C6 angle 2.5 (2)°; C1—C2—C3 and C3—C4—C5—C6—C1 at 5.6 (2)°; and, finally, C1—C2—C3 and C3—C4—C5—C6 at 6.2 (2)°. These numbers seem to suggest that a longer Fe—C2 distance and larger dihedral angle between the planes C1—C2—C3 and a plane defined by the ring carbons excluding C2 observed for (I) may be the result of the electronic influence of the chlorine neighbor and, for (II), steric crowding exerted by the second, directly linked phenyl ring. Similar values, 6.0 (5)° and 7.1 (6)°, have been reported for phenylhydrazine complexes studied by Manzur et al. (2000). The pyrrolidinyl ring of (I) in the solid state adopted a twisted conformation with carbon atoms C12 and C13 (C13 is further away from the o-chloro substituent) located below and above, respectively, the plane defined by the remaining three atoms. A similar picture is observed for (II), with carbon atoms C22 and C23 (C23 is further away from the second ring of biphenyl skeleton) located below and above, respectively, the plane of the atoms C21—N1—C24. Bond lengths in the pyrrolidinyl rings of both complexes are similar and in line with literature values (Allen et al., 1987). Nitrogen atoms in both complexes show similar bond lengths toward aromatic ring carbon atoms C2 [1.343 (11) Å for (I) and 1.356 (4) Å for (II)], and toward methylene carbon atoms of pyrrolidinyl rings [range 1.476 (4)–1.484 (12) Å]. The C2—N1 bond length in each complex, which is in agreement with the Car—planar Nsp2 bond length (Allen et al., 1987), implies that depyramidalization of the N atom takes effect in both complexes. This suggestion is corroborated by the geometry around the N atom – the sum of angles is close to 360° in each complex [358.4 (9) and 357.1 (4)°, respectively, in (I) and (II) [ok as edited?]], and this may, as discussed by Manzur et al. (2000), result from a partial delocalization of the N1 lone pair of electrons toward the complexed phenyl ring.

The average C—C bond length for the complexed phenyl ring of (I) is 1.410 Å. For (II) this average is 1.419 Å and a bond between quaternary carbon atoms C1—C2 [1.441 (4) Å] is slightly longer than the average. In (I) the C1—Cl bond length and the Fe—C1 distance, 1.728 (10) and 2.085 (10) Å, respectively, are similar to values reported for the same bonds in an o-dichlorobenzene FeCp complex (Crane, 2003). The second phenyl ring in the structure of (II) shows no unusual features, and a bond between the rings at C1—C7 has a length of 1.491 (4) Å, which is in agreement with literature data (Allen et al., 1987). The plane of this second ring is tilted at 74.9 (3)° against the plane of the complexed ring.

Related literature top

For related literature, see: Allen et al. (1987); Crane (2003); Djakovitch et al. (1996); Dubois et al. (1989); Fuentealba et al. (2007); Hendsbee et al. (2010); Ishii et al. (1994); Jenkins et al. (2009); Lee et al. (1983, 1989); Manzur et al. (2000, 2007, 2009); Moulines et al. (1995); Nesmeyanov et al. (1977); Piórko et al. (1995); Spek (2009).

Experimental top

The title compounds were prepared following methods described in the literature. [(η5-Cyclopentadienyl)(η6-o-chloro-N-pyrrolidinylbenzene) iron(II)] hexafluoridophosphate was prepared from (o-dichlorobenzene)FeCp PF6 in reaction with pyrrolidine according to the method of Lee et al. (1989). The [(η5-C5H5)(η6-o-N-pyrrolidinyl-o'- hydroxybiphenyl)iron] hexafluoridophosphate was prepared in a ring opening of dibenzofuran in a reaction of (dibenzofuran) FeCp PF6 with pyrrolidine as described by Lee et al. (1983). In both cases the best crystals used for data collection were grown by cooling a solution of each complex in a mixture of acetone, diethyl ether and dichloromethane at 280 K for an extended period of time. It should be noted that, despite our countless crystallization attempts under different conditions, the quality of the chloropyrrolidinyl complex crystals was not as good as for the pyrridinylbiphenyl complex, and this affected both our results and their analysis.

Refinement top

For [(η5-cyclopentadienyl)(η6-o-chloro-N-pyrrolidinylbenzene)iron(II)] hexafluoridophosphate the H atoms were placed in geometrically idealized positions with C—H distances of 1.00 Å for all complexed, uncomplexed aromatic and Cp protons, and 0.99 Å for aliphatic protons, and constrained to ride on their parent C atoms with Uiso(H) = 1.2Ueq(C). The structure contains two molecules of a single enantiomer in the unit cell, and the structure itself was refined as an enantiomeric mixture using TWIN and BASF commands (BASF = 0.358). A warning was generated by PLATON (Spek, 2009); ADDSYM indicated P21/m pseudo-symmetry. The pseudo-inversion symmetry indicated is not present as crystallographic symmetry, as a complete overlap of the two molecules is not formed upon application of the proposed inversion symmetry element. Additionally, an extensive search for the cell of apparently higher symmetry was attempted using CELL_NOW with a total of 4399 reflections indexed and a minimum [I/σ(I)] value of 1.75 for the spots harvested. The search for a larger cell was unsuccessful and therefore the pseudo-symmetry warning was ignored and refinement was completed in space group P21. Three outlying reflections with h, k, l values (4,0,0), (4,-1,-1), and (4,0,2) were omitted from the refinement using the OMIT command. This complex contains a cyclopentadienyl (Cp) ring which is π-bonded to a Fe atom, and the thermal motion of this Cp ring resulted in unsatisfactory anisotropic displacement parameters for atoms C1–C6 (coordinated aromatic ring) and atoms C21–C25 (complexed Cp). This was resolved through use of the restraints applied to the refinement of these atoms: the Uij components of these atoms were restrained to be equal to within 0.001 Å2 and their anisotropic displacement parameters were restrained to be equal to within 0.02 Å2. For the [(η5-C5H5)(η6-o-N-pyrrolidinyl-o'-hydroxybiphenyl)iron] hexafluoridophosphate the H atoms were placed in geometrically idealized positions with C—H distances of 1.0 Å for all complexed, uncomplexed aromatic and Cp protons, 0.99 Å for aliphatic protons, and 0.84 Å for R—O—H protons. Protons were constrained to ride on the parent C atom with Uiso(H) = 1.2Ueq(C) for the aromatic, Cp and aliphatic protons, and Uiso(H) = 1.5Ueq (O) for R—O—H protons.

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); 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. View of the cation showing the labeling of non-H atoms of (o-chloro-N-pyrrolidinylbenzene) FeCp PF6 complex with displacement ellipsoids shown at 50% probability levels. Hydrogen atoms are omitted for clarity.
[Figure 2] Fig. 2. View of the cation showing the labeling of non-H atoms of (o-N-pyrrolidinyl-o'-hydroxybiphenyl) FeCp PF6 complex with displacement ellipsoids shown at 50% probability levels. Hydrogen atoms are omitted for clarity.
(I) [η6-1-Chloro-2-(pyrrolidin-1-yl)benzene](η5-cyclopentadienyl)iron(II) hexafluoridophosphate top
Crystal data top
[Fe(C5H5)(C10H12ClN)]PF6F(000) = 452
Mr = 447.57Dx = 1.800 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 4368 reflections
a = 7.000 (2) Åθ = 0.5–0.8°
b = 13.401 (4) ŵ = 1.23 mm1
c = 8.805 (3) ÅT = 100 K
β = 95.183 (4)°Plate, orange
V = 822.6 (4) Å30.24 × 0.20 × 0.15 mm
Z = 2
Data collection top
Bruker APEXII CCD
diffractometer
2880 independent reflections
Radiation source: fine-focus sealed tube2553 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.058
ϕ and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 88
Tmin = 0.522, Tmax = 0.746k = 1515
7536 measured reflectionsl = 1010
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)] = 0.081H-atom parameters constrained
wR(F2) = 0.206 w = 1/[σ2(Fo2) + (0.0848P)2 + 8.2992P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
2880 reflectionsΔρmax = 1.89 e Å3
227 parametersΔρmin = 1.12 e Å3
507 restraintsAbsolute structure: Flack (1983), 1374 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.36 (5)
Crystal data top
[Fe(C5H5)(C10H12ClN)]PF6V = 822.6 (4) Å3
Mr = 447.57Z = 2
Monoclinic, P21Mo Kα radiation
a = 7.000 (2) ŵ = 1.23 mm1
b = 13.401 (4) ÅT = 100 K
c = 8.805 (3) Å0.24 × 0.20 × 0.15 mm
β = 95.183 (4)°
Data collection top
Bruker APEXII CCD
diffractometer
2880 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
2553 reflections with I > 2σ(I)
Tmin = 0.522, Tmax = 0.746Rint = 0.058
7536 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.081H-atom parameters constrained
wR(F2) = 0.206Δρmax = 1.89 e Å3
S = 1.09Δρmin = 1.12 e Å3
2880 reflectionsAbsolute structure: Flack (1983), 1374 Friedel pairs
227 parametersAbsolute structure parameter: 0.36 (5)
507 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.91533 (18)0.75779 (9)0.53024 (15)0.0205 (3)
C10.6598 (14)0.6771 (7)0.5177 (11)0.0211 (4)
C20.6209 (11)0.7545 (8)0.4082 (10)0.0211 (4)
C30.6892 (14)0.8507 (7)0.4600 (11)0.0211 (4)
C40.7497 (13)0.8719 (7)0.6117 (11)0.0211 (4)
C50.7738 (13)0.7949 (7)0.7184 (11)0.0212 (4)
C60.7265 (14)0.6970 (7)0.6696 (11)0.0212 (4)
H30.71010.90250.38150.025*
H40.81160.93780.63690.025*
H50.84760.80660.81950.025*
H60.77030.63990.73710.025*
Cl10.6057 (4)0.55268 (16)0.4851 (3)0.0308 (6)
N10.5490 (10)0.7411 (6)0.2630 (9)0.0229 (17)
C110.5404 (17)0.6456 (7)0.1773 (11)0.029 (2)
H11A0.42570.60640.19770.035*
H11B0.65670.60490.20360.035*
C120.529 (2)0.6809 (10)0.0081 (13)0.042 (3)
H12A0.65800.69150.02630.051*
H12B0.45740.63260.06060.051*
C130.4210 (17)0.7779 (11)0.0169 (12)0.042 (3)
H13A0.28290.76560.02560.050*
H13B0.43500.81950.07440.050*
C140.5143 (17)0.8280 (8)0.1602 (12)0.032 (3)
H14A0.63560.86160.14070.039*
H14B0.42690.87700.20200.039*
C211.1141 (13)0.6545 (7)0.4948 (11)0.0213 (4)
H211.09340.58060.49160.026*
C221.0850 (13)0.7245 (7)0.3609 (12)0.0212 (4)
H221.04230.70670.25280.025*
C231.1333 (14)0.8199 (7)0.4191 (11)0.0212 (4)
H231.12630.88370.36000.025*
C241.1891 (14)0.8101 (7)0.5708 (11)0.0212 (4)
H241.22530.86770.63970.025*
C251.1787 (14)0.7096 (7)0.6224 (12)0.0212 (4)
H251.21260.68410.72810.025*
P10.9812 (4)0.99521 (19)0.0244 (3)0.0242 (6)
F10.8990 (11)1.0087 (5)0.1850 (7)0.0436 (17)
F21.1952 (10)1.0018 (5)0.1046 (8)0.0449 (18)
F31.0658 (10)0.9805 (5)0.1339 (8)0.0411 (17)
F40.7737 (10)0.9866 (5)0.0536 (9)0.050 (2)
F50.9791 (11)1.1130 (5)0.0040 (9)0.0446 (19)
F60.9838 (9)0.8770 (4)0.0486 (7)0.0341 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0192 (5)0.0146 (6)0.0278 (6)0.0012 (5)0.0023 (4)0.0012 (5)
C10.0197 (6)0.0153 (6)0.0284 (7)0.0011 (6)0.0024 (5)0.0011 (6)
C20.0197 (6)0.0153 (6)0.0283 (7)0.0011 (6)0.0024 (5)0.0011 (6)
C30.0197 (6)0.0153 (6)0.0284 (7)0.0011 (6)0.0024 (5)0.0011 (6)
C40.0198 (6)0.0153 (6)0.0283 (7)0.0011 (6)0.0024 (5)0.0011 (6)
C50.0198 (6)0.0154 (6)0.0284 (7)0.0011 (6)0.0024 (5)0.0011 (6)
C60.0198 (6)0.0154 (6)0.0284 (7)0.0011 (6)0.0024 (5)0.0011 (6)
Cl10.0391 (15)0.0108 (12)0.0418 (16)0.0043 (10)0.0007 (12)0.0005 (11)
N10.019 (4)0.021 (4)0.028 (4)0.003 (3)0.005 (3)0.000 (4)
C110.049 (7)0.018 (5)0.021 (5)0.008 (5)0.008 (5)0.010 (4)
C120.063 (9)0.041 (8)0.021 (6)0.021 (6)0.001 (5)0.005 (5)
C130.034 (6)0.065 (10)0.026 (5)0.000 (6)0.001 (4)0.006 (6)
C140.036 (6)0.031 (6)0.030 (6)0.014 (5)0.001 (5)0.005 (5)
C210.0199 (6)0.0154 (6)0.0285 (7)0.0010 (6)0.0024 (5)0.0011 (6)
C220.0198 (6)0.0155 (6)0.0284 (7)0.0010 (6)0.0024 (5)0.0011 (6)
C230.0198 (6)0.0154 (6)0.0284 (7)0.0011 (6)0.0024 (5)0.0012 (6)
C240.0198 (6)0.0155 (6)0.0284 (7)0.0010 (6)0.0024 (5)0.0012 (6)
C250.0198 (6)0.0154 (6)0.0285 (7)0.0011 (6)0.0023 (5)0.0011 (6)
P10.0314 (14)0.0117 (13)0.0283 (14)0.0015 (10)0.0041 (11)0.0030 (10)
F10.072 (5)0.026 (3)0.032 (3)0.007 (3)0.003 (3)0.003 (3)
F20.039 (4)0.018 (3)0.072 (5)0.009 (3)0.024 (3)0.006 (3)
F30.052 (4)0.028 (4)0.045 (4)0.004 (3)0.014 (3)0.008 (3)
F40.049 (4)0.017 (3)0.075 (5)0.006 (3)0.037 (4)0.003 (3)
F50.063 (5)0.015 (3)0.053 (4)0.002 (3)0.005 (4)0.001 (3)
F60.043 (4)0.008 (3)0.048 (4)0.007 (2)0.012 (3)0.004 (3)
Geometric parameters (Å, º) top
Fe1—C12.085 (10)C11—H11A0.9900
Fe1—C22.237 (8)C11—H11B0.9900
Fe1—C32.064 (10)C12—H12A0.9900
Fe1—C42.085 (10)C12—H12B0.9900
Fe1—C52.067 (10)C13—C121.508 (17)
Fe1—C62.052 (10)C13—H13A0.9900
Fe1—C212.008 (9)C13—H13B0.9900
Fe1—C222.038 (10)C14—C131.524 (17)
Fe1—C232.061 (10)C14—H14A0.9900
Fe1—C242.041 (10)C14—H14B0.9900
Fe1—C252.051 (10)C21—H211.0000
C1—C21.425 (14)C22—C211.506 (13)
C3—C21.435 (14)C22—H221.0000
C3—H31.0000C23—C221.407 (13)
C3—C41.394 (14)C23—H231.0000
C4—H41.0000C23—C241.364 (14)
C5—C41.395 (13)C24—H241.0000
C5—H51.0000C25—C241.425 (12)
C6—C51.411 (12)C25—H251.0000
C6—H61.0000C25—C211.386 (14)
C1—C61.402 (14)P1—F11.585 (7)
Cl1—C11.728 (10)P1—F21.600 (7)
N1—C21.344 (11)P1—F31.575 (7)
N1—C111.484 (12)P1—F41.554 (7)
N1—C141.482 (13)P1—F51.588 (7)
C11—C121.558 (15)P1—F61.599 (6)
Fe1—C3—H3118.0C21—Fe1—C4167.0 (4)
Fe1—C4—H4118.7C21—Fe1—C5132.9 (4)
Fe1—C5—H5120.3C21—Fe1—C6108.2 (4)
Fe1—C6—H6118.7C21—Fe1—C2243.7 (4)
Fe1—C21—H21125.9C21—Fe1—C2369.6 (4)
Fe1—C22—H22127.2C21—Fe1—C2467.1 (4)
Fe1—C23—H23126.1C21—Fe1—C2539.9 (4)
Fe1—C24—H24123.6C21—C25—Fe168.4 (6)
Fe1—C25—H25127.2C21—C25—C24105.5 (9)
C1—C2—C3113.7 (8)C21—C22—Fe167.1 (5)
C1—Fe1—C238.3 (4)C21—C22—H22127.2
C1—C2—Fe165.1 (5)C21—C25—H25127.2
C1—C6—C5121.1 (9)C22—Fe1—C1113.7 (4)
C1—C6—Fe171.5 (6)C22—Fe1—C2102.5 (4)
C1—C6—H6118.7C22—Fe1—C3113.2 (4)
C2—C1—Cl1124.3 (7)C22—Fe1—C4142.3 (4)
C2—C1—Fe176.6 (5)C22—Fe1—C5173.0 (4)
C2—C3—Fe177.2 (5)C22—Fe1—C6143.1 (4)
C2—C3—H3118.0C22—Fe1—C2340.2 (4)
C2—N1—C11126.4 (9)C22—Fe1—C2466.6 (4)
C2—N1—C14120.2 (9)C22—Fe1—C2570.0 (4)
C3—Fe1—C170.5 (4)C22—C21—Fe169.2 (5)
C3—Fe1—C238.7 (4)C22—C23—Fe169.0 (6)
C3—Fe1—C439.3 (4)C22—C23—H23126.1
C3—C2—Fe164.1 (5)C22—C21—H21125.9
C3—C4—Fe169.6 (5)C23—Fe1—C1148.5 (4)
C3—C4—H4118.7C23—Fe1—C2118.0 (4)
C3—Fe1—C23101.2 (4)C23—Fe1—C4109.0 (4)
C4—Fe1—C184.1 (4)C23—C22—Fe170.8 (6)
C4—Fe1—C270.3 (4)C23—C22—C21105.7 (8)
C4—C3—C2123.5 (9)C23—C22—H22127.2
C4—C3—Fe171.2 (6)C23—C24—Fe171.4 (6)
C4—C5—C6118.2 (9)C23—C24—C25112.7 (9)
C4—C5—Fe171.1 (6)C23—C24—H24123.6
C4—C3—H3118.0C24—Fe1—C1167.1 (4)
C4—C5—H5120.3C24—Fe1—C2154.2 (4)
C5—Fe1—C172.3 (4)C24—Fe1—C3121.9 (4)
C5—Fe1—C284.4 (4)C24—Fe1—C4103.3 (4)
C5—Fe1—C371.6 (4)C24—Fe1—C5106.7 (4)
C5—Fe1—C439.3 (4)C24—Fe1—C6132.6 (4)
C5—Fe1—C23135.4 (4)C24—Fe1—C2338.8 (4)
C5—Fe1—C25103.7 (4)C24—Fe1—C2540.8 (3)
C5—C4—Fe169.6 (5)C24—C25—Fe169.3 (6)
C5—C6—Fe170.5 (6)C24—C25—H25127.2
C5—C4—C3120.2 (9)C24—C23—C22107.9 (9)
C5—C4—H4118.7C24—C23—Fe169.8 (6)
C5—C6—H6118.7C24—C23—H23126.1
C6—Fe1—C139.6 (4)C25—Fe1—C1126.4 (4)
C6—Fe1—C270.4 (4)C25—Fe1—C2160.1 (4)
C6—Fe1—C384.3 (4)C25—Fe1—C3161.1 (4)
C6—Fe1—C471.2 (4)C25—Fe1—C4127.1 (4)
C6—Fe1—C540.1 (3)C25—Fe1—C2368.7 (4)
C6—Fe1—C23171.4 (4)C25—C24—Fe170.0 (6)
C6—Fe1—C25104.1 (4)C25—C21—Fe171.7 (6)
C6—C1—Fe168.9 (5)C25—C21—C22108.3 (8)
C6—C1—C2122.3 (9)C25—C21—H21125.9
C6—C1—Cl1113.0 (7)C25—C24—H24123.6
C6—C5—Fe169.4 (6)N1—C2—Fe1135.2 (6)
C6—C5—H5120.3N1—C2—C1125.3 (9)
Cl1—C1—Fe1133.1 (5)N1—C2—C3120.5 (9)
H11A—C11—H11B109.1N1—C11—C12102.8 (8)
C11—C12—H12A111.5N1—C11—H11A111.2
C11—C12—H12B111.5N1—C11—H11B111.2
H12A—C12—H12B109.3N1—C14—C13101.1 (9)
C12—C11—H11A111.2N1—C14—H14A111.5
C12—C11—H11B111.2N1—C14—H14B111.5
C12—C13—C14104.1 (9)F1—P1—F589.2 (4)
C12—C13—H13A110.9F1—P1—F689.7 (4)
C12—C13—H13B110.9F1—P1—F290.0 (4)
C13—C12—C11101.3 (9)F2—P1—F689.8 (3)
C13—C12—H12A111.5F3—P1—F591.4 (4)
C13—C12—H12B111.5F3—P1—F689.6 (4)
C13—C14—H14A111.5F3—P1—F289.2 (4)
C13—C14—H14B111.5F3—P1—F1179.0 (4)
H13A—C13—H13B109.0F4—P1—F390.6 (4)
C14—C13—H13A110.9F4—P1—F190.1 (5)
C14—C13—H13B110.9F4—P1—F591.4 (4)
C14—N1—C11111.8 (8)F4—P1—F2178.9 (4)
H14A—C14—H14B109.4F4—P1—F689.1 (3)
C21—Fe1—C1103.7 (4)F5—P1—F6178.8 (4)
C21—Fe1—C2122.2 (4)F5—P1—F289.6 (4)
C21—Fe1—C3153.2 (4)
(II) (η5-cyclopentadienyl){2-[η6-2-(pyrrolidin-1-yl)phenyl]phenol}iron(II) hexafluoridophosphate top
Crystal data top
[Fe(C5H5)(C16H17NO)]PF6F(000) = 1032
Mr = 505.22Dx = 1.674 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4370 reflections
a = 10.9764 (11) Åθ = 2.9–24.9°
b = 9.4221 (10) ŵ = 0.90 mm1
c = 19.393 (2) ÅT = 100 K
β = 91.608 (1)°Block, brown
V = 2004.8 (4) Å30.33 × 0.30 × 0.28 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer
3451 independent reflections
Radiation source: fine-focus sealed tube2720 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.040
ϕ and ω scansθmax = 24.9°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 1212
Tmin = 0.691, Tmax = 0.745k = 1111
9910 measured reflectionsl = 1922
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H-atom parameters constrained
S = 0.85 w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
3451 reflections(Δ/σ)max < 0.001
281 parametersΔρmax = 0.60 e Å3
0 restraintsΔρmin = 0.36 e Å3
Crystal data top
[Fe(C5H5)(C16H17NO)]PF6V = 2004.8 (4) Å3
Mr = 505.22Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.9764 (11) ŵ = 0.90 mm1
b = 9.4221 (10) ÅT = 100 K
c = 19.393 (2) Å0.33 × 0.30 × 0.28 mm
β = 91.608 (1)°
Data collection top
Bruker APEXII CCD
diffractometer
3451 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
2720 reflections with I > 2σ(I)
Tmin = 0.691, Tmax = 0.745Rint = 0.040
9910 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.122H-atom parameters constrained
S = 0.85Δρmax = 0.60 e Å3
3451 reflectionsΔρmin = 0.36 e Å3
281 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.49533 (4)0.19729 (4)0.19044 (2)0.01588 (16)
C10.3646 (3)0.1834 (3)0.26993 (15)0.0161 (6)
C20.4026 (3)0.0401 (3)0.25601 (15)0.0180 (6)
C30.4084 (3)0.0005 (3)0.18487 (15)0.0206 (7)
H30.45790.08450.17280.025*
C40.3660 (3)0.0897 (3)0.13090 (16)0.0215 (7)
H40.38470.06450.08220.026*
C50.3239 (3)0.2273 (3)0.14553 (16)0.0213 (7)
H50.31210.29780.10740.026*
C60.3253 (3)0.2725 (3)0.21433 (15)0.0184 (6)
H60.31640.37630.22360.022*
C70.3529 (3)0.2451 (3)0.34022 (15)0.0173 (6)
C80.2562 (3)0.2022 (3)0.38040 (15)0.0184 (6)
O10.18164 (19)0.0968 (2)0.35416 (11)0.0253 (5)
H10.11380.10070.37300.038*
C90.2380 (3)0.2636 (3)0.44431 (15)0.0220 (7)
H90.17240.23300.47160.026*
C100.3152 (3)0.3693 (3)0.46806 (15)0.0228 (7)
H100.30280.41110.51190.027*
C110.4105 (3)0.4150 (3)0.42868 (15)0.0240 (7)
H110.46360.48790.44510.029*
C120.4278 (3)0.3529 (3)0.36454 (15)0.0210 (7)
H120.49240.38530.33700.025*
N10.4419 (2)0.0535 (2)0.30488 (12)0.0198 (6)
C210.4754 (3)0.0197 (3)0.37728 (15)0.0243 (7)
H21A0.40220.01440.40580.029*
H21B0.51990.07160.38060.029*
C220.5577 (3)0.1437 (3)0.39999 (18)0.0298 (8)
H22A0.64430.12260.39150.036*
H22B0.54850.16530.44950.036*
C230.5120 (3)0.2656 (3)0.35507 (19)0.0315 (8)
H23A0.43630.30690.37320.038*
H23B0.57430.34100.35180.038*
C240.4881 (3)0.1948 (3)0.28565 (18)0.0259 (7)
H24A0.56400.18690.25950.031*
H24B0.42660.24800.25770.031*
C310.6567 (3)0.2581 (4)0.23864 (17)0.0255 (7)
H310.67350.26100.28960.031*
C320.6095 (3)0.3712 (3)0.19759 (16)0.0232 (7)
H320.58700.46770.21450.028*
C330.5993 (3)0.3232 (3)0.12884 (17)0.0241 (7)
H330.56860.38010.08840.029*
C340.6392 (3)0.1800 (3)0.12681 (17)0.0255 (7)
H340.64290.11880.08480.031*
C350.6758 (3)0.1403 (3)0.19478 (17)0.0268 (7)
H350.70890.04570.20930.032*
P20.65847 (8)0.73081 (9)0.06508 (4)0.0237 (2)
F10.6155 (3)0.6100 (3)0.01285 (12)0.0644 (7)
F20.74912 (16)0.62375 (19)0.10345 (10)0.0313 (5)
F30.5652 (2)0.8390 (3)0.02847 (12)0.0546 (7)
F40.7001 (2)0.8531 (2)0.11736 (11)0.0578 (7)
F50.5540 (2)0.6833 (3)0.11673 (13)0.0626 (8)
F60.76073 (19)0.7797 (2)0.01392 (11)0.0426 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0136 (3)0.0174 (2)0.0166 (3)0.00013 (16)0.00057 (18)0.00130 (16)
C10.0113 (15)0.0182 (14)0.0188 (15)0.0019 (11)0.0014 (12)0.0011 (11)
C20.0111 (15)0.0194 (14)0.0236 (16)0.0029 (12)0.0009 (12)0.0009 (12)
C30.0191 (16)0.0191 (14)0.0239 (16)0.0021 (12)0.0042 (13)0.0026 (12)
C40.0162 (16)0.0273 (16)0.0210 (16)0.0063 (13)0.0004 (12)0.0018 (13)
C50.0143 (16)0.0303 (17)0.0194 (16)0.0025 (13)0.0011 (13)0.0031 (13)
C60.0124 (15)0.0213 (15)0.0215 (16)0.0001 (12)0.0028 (12)0.0015 (12)
C70.0191 (16)0.0162 (13)0.0167 (15)0.0042 (12)0.0003 (12)0.0036 (11)
C80.0168 (16)0.0161 (14)0.0221 (16)0.0011 (12)0.0002 (13)0.0020 (12)
O10.0200 (12)0.0283 (11)0.0280 (12)0.0084 (10)0.0067 (9)0.0053 (9)
C90.0217 (18)0.0253 (16)0.0192 (17)0.0023 (14)0.0043 (13)0.0024 (13)
C100.0292 (18)0.0218 (15)0.0172 (15)0.0032 (14)0.0009 (13)0.0009 (12)
C110.0302 (18)0.0201 (15)0.0213 (16)0.0033 (14)0.0052 (14)0.0012 (12)
C120.0235 (17)0.0204 (15)0.0192 (16)0.0038 (13)0.0005 (13)0.0041 (12)
N10.0185 (14)0.0162 (12)0.0246 (14)0.0010 (10)0.0009 (11)0.0022 (10)
C210.0249 (17)0.0215 (15)0.0264 (17)0.0029 (13)0.0025 (14)0.0059 (13)
C220.0229 (18)0.0301 (17)0.0361 (19)0.0050 (15)0.0034 (15)0.0103 (15)
C230.0230 (19)0.0207 (16)0.051 (2)0.0038 (14)0.0041 (16)0.0097 (15)
C240.0234 (18)0.0180 (15)0.0366 (19)0.0019 (13)0.0052 (15)0.0031 (13)
C310.0180 (17)0.0322 (17)0.0261 (17)0.0069 (14)0.0017 (14)0.0039 (14)
C320.0196 (16)0.0234 (16)0.0269 (17)0.0070 (13)0.0040 (13)0.0004 (13)
C330.0178 (17)0.0266 (16)0.0284 (18)0.0044 (13)0.0061 (14)0.0047 (13)
C340.0181 (17)0.0303 (17)0.0287 (18)0.0010 (14)0.0106 (14)0.0007 (14)
C350.0135 (16)0.0305 (17)0.0366 (19)0.0025 (14)0.0021 (14)0.0082 (15)
P20.0211 (5)0.0293 (5)0.0207 (5)0.0021 (4)0.0002 (4)0.0053 (3)
F10.095 (2)0.0546 (15)0.0423 (14)0.0369 (14)0.0245 (13)0.0029 (11)
F20.0291 (11)0.0252 (10)0.0395 (11)0.0080 (8)0.0026 (9)0.0048 (8)
F30.0384 (13)0.0706 (16)0.0548 (15)0.0169 (12)0.0003 (11)0.0388 (12)
F40.107 (2)0.0299 (11)0.0353 (13)0.0136 (13)0.0129 (13)0.0045 (9)
F50.0326 (13)0.095 (2)0.0611 (16)0.0190 (13)0.0215 (12)0.0473 (14)
F60.0356 (13)0.0529 (13)0.0398 (13)0.0070 (10)0.0071 (10)0.0121 (10)
Geometric parameters (Å, º) top
Fe1—C12.139 (3)C12—H120.9500
Fe1—C22.218 (3)C7—C121.382 (4)
Fe1—C32.086 (3)C2—N11.356 (4)
Fe1—C42.070 (3)N1—C241.476 (4)
Fe1—C52.070 (3)N1—C211.476 (4)
Fe1—C62.061 (3)C21—C221.533 (4)
Fe1—C312.061 (3)C21—H21A0.9900
Fe1—C322.066 (3)C21—H21B0.9900
Fe1—C332.053 (3)C23—C221.518 (5)
Fe1—C342.038 (3)C22—H22A0.9900
Fe1—C352.051 (3)C22—H22B0.9900
C2—C11.441 (4)C23—H23A0.9900
C3—C21.432 (4)C23—H23B0.9900
C3—H31.0000C24—C231.519 (5)
C3—C41.411 (4)C24—H24A0.9900
C4—H41.0000C24—H24B0.9900
C4—C51.407 (4)C32—C311.419 (5)
C5—H51.0000C31—H311.0000
C6—C51.400 (4)C32—H321.0000
C6—H61.0000C33—C321.409 (4)
C6—C11.424 (4)C33—H331.0000
C1—C71.491 (4)C34—C331.420 (4)
C7—C81.394 (4)C34—H341.0000
C8—O11.375 (3)C34—C351.417 (5)
O1—H10.8400C35—H351.0000
C8—C91.388 (4)C35—C311.418 (5)
C9—H90.9500P2—F11.587 (2)
C9—C101.379 (4)P2—F21.5873 (19)
C10—H100.9500P2—F31.597 (2)
C11—C101.381 (4)P2—F41.593 (2)
C11—H110.9500P2—F51.607 (2)
C12—C111.392 (4)P2—F61.587 (2)
Fe1—C3—H3118.3C22—C21—H21A111.0
Fe1—C4—H4119.1C22—C21—H21B111.0
Fe1—C5—H5120.0H22A—C22—H22B109.1
Fe1—C6—H6118.0C23—C22—C21103.2 (3)
Fe1—C31—H31126.0C23—C22—H22A111.1
Fe1—C32—H32126.0C23—C22—H22B111.1
Fe1—C33—H33125.8H23A—C23—H23B109.1
Fe1—C34—H34126.1C23—C24—H24A111.2
Fe1—C35—H35126.0C23—C24—H24B111.2
C1—Fe1—C238.56 (10)C24—C23—H23A111.2
C1—C2—Fe167.75 (16)C24—C23—H23B111.2
C1—C6—Fe173.16 (17)H24A—C24—H24B109.1
C1—C6—H6118.0C24—N1—C21110.9 (2)
C2—C1—Fe173.70 (16)C31—Fe1—C1105.99 (12)
C2—C1—C7124.7 (3)C31—Fe1—C2109.17 (12)
C2—C3—Fe175.62 (17)C31—Fe1—C3131.05 (12)
C2—N1—C21126.2 (2)C31—Fe1—C4163.06 (13)
C2—N1—C24121.0 (3)C31—Fe1—C5155.82 (13)
C3—C2—C1116.4 (3)C31—Fe1—C3240.23 (13)
C2—C3—H3118.3C31—C32—Fe169.69 (17)
C3—Fe1—C170.60 (11)C31—C32—H32126.0
C3—Fe1—C238.72 (11)C31—C35—C34108.0 (3)
C3—C2—Fe165.66 (16)C31—C35—Fe170.18 (18)
C3—C4—Fe170.78 (16)C31—C35—H35126.0
C3—C4—H4119.1C32—Fe1—C1114.73 (11)
C4—C3—C2122.5 (3)C32—Fe1—C2141.15 (12)
C4—C3—H3118.3C32—Fe1—C3169.82 (12)
C4—Fe1—C184.75 (11)C32—Fe1—C4146.25 (12)
C4—Fe1—C270.98 (11)C32—Fe1—C5117.56 (12)
C4—Fe1—C339.68 (11)C32—C31—Fe170.08 (18)
C4—Fe1—C539.74 (12)C32—C31—H31126.0
C4—C3—Fe169.54 (16)C32—C33—C34108.4 (3)
C4—C5—Fe170.13 (17)C32—C33—Fe170.49 (17)
C4—C5—H5120.0C32—C33—H33125.8
C5—Fe1—C172.04 (11)C33—Fe1—C1148.20 (11)
C5—Fe1—C284.60 (11)C33—Fe1—C2172.40 (12)
C5—Fe1—C371.97 (12)C33—Fe1—C3138.10 (12)
C5—C4—Fe170.13 (17)C33—Fe1—C4110.02 (12)
C5—C4—C3120.1 (3)C33—Fe1—C5100.94 (12)
C5—C4—H4119.1C33—Fe1—C6116.98 (12)
C5—C6—Fe170.54 (17)C33—Fe1—C3167.56 (13)
C5—C6—C1122.5 (3)C33—Fe1—C3240.02 (12)
C5—C6—H6118.0C33—C32—C31107.9 (3)
C6—Fe1—C139.59 (11)C33—C32—Fe169.50 (17)
C6—Fe1—C270.59 (11)C33—C32—H32126.0
C6—Fe1—C384.34 (12)C33—C34—H34126.1
C6—Fe1—C471.48 (12)C34—Fe1—C1168.03 (12)
C6—Fe1—C539.62 (12)C34—Fe1—C2132.04 (11)
C6—Fe1—C31125.08 (13)C34—Fe1—C3104.98 (12)
C6—Fe1—C32105.30 (12)C34—Fe1—C498.86 (13)
C6—C1—Fe167.25 (16)C34—Fe1—C5117.82 (13)
C6—C1—C2119.6 (3)C34—Fe1—C6152.32 (13)
C6—C1—C7115.5 (2)C34—Fe1—C3168.05 (13)
C6—C5—Fe169.83 (18)C34—Fe1—C3267.98 (13)
C6—C5—C4118.5 (3)C34—Fe1—C3340.63 (12)
C6—C5—H5120.0C34—Fe1—C3540.56 (13)
C7—C1—Fe1135.4 (2)C34—C33—Fe169.11 (17)
C7—C12—C11121.3 (3)C34—C33—H33125.8
C7—C12—H12119.4C34—C35—Fe169.20 (18)
C8—C7—C1119.0 (3)C34—C35—H35126.0
C8—C9—H9120.1C35—Fe1—C1128.36 (12)
C8—O1—H1109.5C35—Fe1—C2105.05 (12)
C9—C8—C7120.6 (3)C35—Fe1—C3102.07 (12)
C9—C10—H10119.7C35—Fe1—C4122.75 (13)
C10—C9—C8119.8 (3)C35—Fe1—C5156.61 (13)
C10—C9—H9120.1C35—Fe1—C6163.74 (13)
C10—C11—C12119.2 (3)C35—Fe1—C3140.34 (13)
C10—C11—H11120.4C35—Fe1—C3267.77 (13)
C11—C10—C9120.6 (3)C35—Fe1—C3367.88 (13)
C11—C10—H10119.7C35—C31—C32108.0 (3)
C12—C7—C1122.2 (3)C35—C31—Fe169.48 (18)
C12—C7—C8118.5 (3)C35—C31—H31126.0
C12—C11—H11120.4C35—C34—C33107.7 (3)
C11—C12—H12119.4C35—C34—Fe170.25 (18)
N1—C2—Fe1133.8 (2)C33—C34—Fe170.26 (17)
N1—C2—C3118.8 (3)C35—C34—H34126.1
N1—C2—C1124.5 (3)F1—P2—F290.85 (12)
N1—C21—C22103.8 (2)F1—P2—F389.90 (15)
N1—C21—H21A111.0F1—P2—F4179.30 (15)
N1—C21—H21B111.0F1—P2—F589.63 (15)
N1—C24—C23102.9 (3)F1—P2—F690.68 (13)
N1—C24—H24A111.2F2—P2—F3178.37 (12)
N1—C24—H24B111.2F2—P2—F489.79 (11)
O1—C8—C9122.2 (3)F2—P2—F588.83 (11)
O1—C8—C7117.2 (3)F3—P2—F589.73 (12)
C21—C22—H22A111.1F4—P2—F389.45 (13)
C21—C22—H22B111.1F4—P2—F590.11 (15)
H21A—C21—H21B109.0F6—P2—F291.85 (11)
C22—C23—C24102.9 (3)F6—P2—F389.59 (12)
C22—C23—H23A111.2F6—P2—F489.58 (13)
C22—C23—H23B111.2F6—P2—F5179.25 (13)

Experimental details

(I)(II)
Crystal data
Chemical formula[Fe(C5H5)(C10H12ClN)]PF6[Fe(C5H5)(C16H17NO)]PF6
Mr447.57505.22
Crystal system, space groupMonoclinic, P21Monoclinic, P21/n
Temperature (K)100100
a, b, c (Å)7.000 (2), 13.401 (4), 8.805 (3)10.9764 (11), 9.4221 (10), 19.393 (2)
β (°) 95.183 (4) 91.608 (1)
V3)822.6 (4)2004.8 (4)
Z24
Radiation typeMo KαMo Kα
µ (mm1)1.230.90
Crystal size (mm)0.24 × 0.20 × 0.150.33 × 0.30 × 0.28
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Bruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Multi-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.522, 0.7460.691, 0.745
No. of measured, independent and
observed [I > 2σ(I)] reflections
7536, 2880, 2553 9910, 3451, 2720
Rint0.0580.040
(sin θ/λ)max1)0.5940.593
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.081, 0.206, 1.09 0.037, 0.122, 0.85
No. of reflections28803451
No. of parameters227281
No. of restraints5070
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.89, 1.120.60, 0.36
Absolute structureFlack (1983), 1374 Friedel pairs?
Absolute structure parameter0.36 (5)?

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), 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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