metal-organic compounds
Piperidinium N-(ferrocenylcarbonyl)glycinate
aDepartment of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 12840 Prague 2, Czech Republic
*Correspondence e-mail: stepnic@natur.cuni.cz
The title compound, (C5H12N)[Fe(C5H5)(C8H7NO3)], resulting from neutralization of N-(ferrocenylcarbonyl)glycine with piperidine, is built up from discrete ions that assemble into sheets via the combination of conventional and weak hydrogen bonds. The key repeating unit is constituted by two piperidium cations and two carboxylate anions that assemble into a centrosymmetric array via conventional and bifurcated N—H⋯O hydrogen bonds. The aggregates thus formed are further interlinked by N—H⋯O interactions and supportive C—H⋯O contacts into layers oriented parallel to the bc plane.
Related literature
For an overview of bioorganometallic chemistry of ferrocene, see: Štěpnička (2008). For the first synthesis of N-(ferrocenylcarbonyl)glycine, see: Schlögl (1957) and for its use in the preparation of 2-ferrocenyl-5(4H)oxazolone and its transition metal complexes, see: Bauer et al. (1999). An alternative preparative route was described by Kraatz et al. (1997). For the crystal structures of methyl N-(ferrocenylcarbonyl)glycinate and tert-butyl N-[1′-(diphenylphosphino)ferrocene-1-carbonyl]glycinate, see: Gallagher et al. (1999) and Tauchman et al. (2009), respectively. The structure of another related compound, 1,1′-bis{N-(carboxymethylene)carbamoyl}ferrocene, was reported by Appoh et al. (2004).
Experimental
Crystal data
|
Data collection
|
Refinement
|
Data collection: COLLECT (Nonius, 2000); cell HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON.
Supporting information
https://doi.org/10.1107/S1600536810041747/dn2612sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810041747/dn2612Isup2.hkl
N-(ferrocenylcarbonyl)glycine was prepared in analogy with the literature (Kraatz et al., 1997; Bauer et al., 1999; Appoh et al., 2004) as follows. Ferrocenecarboxylic acid and glycine methyl ester hydrochloride were reacted in dichloromethane in the presence peptide coupling agents (1-ethyl-3-[3-(dimethylamino)propyl]carbodiimide and 1-hydroxy-1H-1,2,3-benzotriazole) and triethylamine, which in situ converts glycine methyl ester hydrochloride to the respective free base. The resulting methyl N-(ferrocenylcarbonyl)glycinate was isolated by
(silica, dichloromethane–methanol 10:1). This ester was saponified with NaOH in refluxing water–dioxane (1:1). Subsequent acidification H3PO4 afforded free acid, which was isolated and purified by on silica using dichloromethane–methanol 5:1 as the eluent.Yellow crystals of the title compounds were obtained by mixing equimolar amounts of piperidine and N-(ferrocenylcarbonyl)glycine (50 µmol each) in dry methanol (ca 1 ml) and subsequent crystallization by a slow diffusion of diethyl ether vapours. Analysis calcd. for C18N24FeN2O3: C, 58.08; H, 6.50; N, 7.53%. Found: C, 57.73; H, 6.65; N, 7.36%.
H-atoms residing on the carbon atoms were included in their calculated positions and treated as riding atoms with Uiso(H) = 1.2 Ueq(C). Those biding to the N and O atoms were identified on the difference electron density maps and refined as described above.
ferrocenylcarbonyl derivatives (amides) prepared from amino acids and
received considerable research attention in the recent past, mainly as precursors to redox-labelled biomolecules and as model compounds for studies focusing on stereochemistry and H-bonding interactions in (Štěpnička, 2008). N-(ferrocenylcarbonyl)glycine as the first ferrocenylated amino acid derivative was reported already in 1957 (Schlögl, 1957). It was further used in the preparation of 2-ferrocenyl-5(4H)oxazolone and its complexes with transition metals (Bauer et al., 1999) and further studied as a redox-responsive reagent for inorganic anions (Gallagher et al., 1999).Thus, piperidinium N-(ferrocenylcarbonyl)glycinate was obtained by acid-base reaction N-(ferrocenylcarbonyl)glycine with piperidine and isolated as a yellow, air-stable crystalline solid. Its molecular structure as determined by X-ray
(Figure 1) is rather unexceptional. The geometry of the ferrocene unit is regular, showing a practically negligible variation in the Fe—C bond lengths (2.029 (19)–2.051 (2) Å). Accordingly, the distance of the iron atom to cyclopentadienyl ring centroids are quite similar (1.6429 (10) and 1.6450 (10) Å for the rings C(1–5) and C(6–10), respectively), and the dihedral angle of the least-squares cyclopentadienyl planes is only 2.28 (13) °.The geometry of the glycinamide moiety is similar to those reported previously for methyl N-(ferrocenylcarbonyl)glycinate (Gallagher et al., 1999) or t-butyl N-[1'-(diphenylphosphino)ferrocene-1-carbonyl]glycinate (Tauchman et al., 2009). A difference is seen in the parameters describing the terminal carboxy group, which is deprotonated (unlike the reference compounds) and shows balanced C—O distance due to delocalization (C13—O2 = 1.255 (2) Å, C13—O3 = 1.265 (2) Å, O2—C13—O3 = 124.25 (17) °). The amide plane, {C11, O1, N1}, is rotated with respect to its bonding cyclopentadienyl ring C(1–5) by only 8.9 (2) °. As a results, the two moieties remain conjugated, which is reflected by a relative shortening of the connecting C1—C11 bond (1.486 (3) Å). Similar bond lengths (1.483 (2) and 1.491 (2) Å) were observed for two monoclinic polymorphs of carbamoylferrocene, where the amide and cyclopentadienyl planes are rotated by ca 10 ° (Štěpnička et al., 2010). The glycine moeity extends below the parent cyclopentadienyl ring at the dihedral angle C11—N1—C12—C13 of 59.3 (1) °. Finally, the piperidinium cation assumes an τ = 178.1 (2) ° and puckering amplitude Q = 0.572 (2) Å (N.B. ideal chair requires τ = 0 or 180 °). There is, however, noticeable some departure from the regular geometry since the C(21/25)—N bond lengths are slightly shorter (ca 2%) than the remaining in-ring distances (C—C = 1.513 (3)–1.525 (3) Å).
withThe crystal packing of the title compound is dominated by intermolecular hydrogen bonding interaction. The ions constituting the structure assemble pairwise around inversion centers by means of N—H···O hydrogen bonds from both NH protons at the piperidinium cation to adjacent carboxylate O atoms O2 and O3 as H-bond acceptors (Figure 2a; for parameters, see Table 1). An additional contact, N2—H3N···O2 has a rather unfavourable geometry and probably reflects an enforced proximity of the atoms involved. The four-membered centrosymmetric assemblies thus formed are interconnected by N—H···O hydrogen bonds between amide NH and carboxylate O3 and further by supportive C—H···O interactions (Figure 2a, Table 1) into layers oriented parallel to the bc plane (Figure 2b).
For an overview of bioorganometallic chemistry of ferrocene, see: Štěpnička (2008). For the first synthesis N-(ferrocenylcarbonyl)glycine, see: Schlögl (1957) and for its use in the the preparation of 2-ferrocenyl-5(4H)oxazolone and its complexes with transition metals, see: Bauer et al. (1999). An alternative preparative route was described by Kraatz et al. (1997). For the crystal structures of methyl N-(ferrocenylcarbonyl)glycinate and t-butyl N-[1'-(diphenylphosphino)ferrocene-1-carbonyl]glycinate, see: Gallagher et al. (1999) and Tauchman et al. (2009), respectively. The structure of another related compound, 1,1'-bis{N-(carboxymethylene)carbamoyl}ferrocene, was reported by Appoh et al. (2004).
Data collection: COLLECT (Nonius, 2000); cell
HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).(C5H12N)[Fe(C5H5)(C8H7NO3)] | F(000) = 784 |
Mr = 372.24 | Dx = 1.462 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3696 reflections |
a = 13.9055 (4) Å | θ = 1.0–26.4° |
b = 7.6150 (2) Å | µ = 0.91 mm−1 |
c = 16.5968 (5) Å | T = 150 K |
β = 105.780 (2)° | Plate, yellow |
V = 1691.21 (8) Å3 | 0.25 × 0.22 × 0.15 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 2960 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.044 |
Horizontally mounted graphite crystal monochromator | θmax = 26.4°, θmin = 1.5° |
Detector resolution: 9.091 pixels mm-1 | h = −17→17 |
ω and π scans to fill the Ewald sphere | k = −9→9 |
25843 measured reflections | l = −20→20 |
3456 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0234P)2 + 1.3244P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
3456 reflections | Δρmax = 0.27 e Å−3 |
217 parameters | Δρmin = −0.29 e Å−3 |
0 restraints |
(C5H12N)[Fe(C5H5)(C8H7NO3)] | V = 1691.21 (8) Å3 |
Mr = 372.24 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.9055 (4) Å | µ = 0.91 mm−1 |
b = 7.6150 (2) Å | T = 150 K |
c = 16.5968 (5) Å | 0.25 × 0.22 × 0.15 mm |
β = 105.780 (2)° |
Nonius KappaCCD diffractometer | 2960 reflections with I > 2σ(I) |
25843 measured reflections | Rint = 0.044 |
3456 independent reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.27 e Å−3 |
3456 reflections | Δρmin = −0.29 e Å−3 |
217 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two least-squares 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 least-squares planes. |
Refinement. Refinement of F2 against all diffractions. 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 > 2σ(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. |
x | y | z | Uiso*/Ueq | ||
Fe | 0.14161 (2) | 0.21877 (4) | 0.174028 (17) | 0.02423 (9) | |
O1 | 0.33180 (10) | 0.60519 (18) | 0.23818 (9) | 0.0292 (3) | |
O2 | 0.45779 (10) | 0.33934 (18) | 0.36777 (8) | 0.0276 (3) | |
O3 | 0.58097 (10) | 0.53347 (18) | 0.38131 (8) | 0.0288 (3) | |
N1 | 0.40631 (11) | 0.3748 (2) | 0.19374 (10) | 0.0231 (3) | |
H1N | 0.3988 | 0.2730 | 0.1668 | 0.028* | |
C1 | 0.22784 (14) | 0.4080 (3) | 0.14255 (12) | 0.0238 (4) | |
C2 | 0.13442 (14) | 0.4816 (3) | 0.14607 (13) | 0.0286 (4) | |
H2 | 0.1258 | 0.5733 | 0.1805 | 0.034* | |
C3 | 0.05759 (16) | 0.3900 (3) | 0.08792 (14) | 0.0339 (5) | |
H3 | −0.0106 | 0.4109 | 0.0776 | 0.041* | |
C4 | 0.10200 (16) | 0.2611 (3) | 0.04804 (13) | 0.0338 (5) | |
H4 | 0.0681 | 0.1831 | 0.0070 | 0.041* | |
C5 | 0.20758 (15) | 0.2717 (3) | 0.08169 (12) | 0.0275 (4) | |
H5 | 0.2548 | 0.2020 | 0.0666 | 0.033* | |
C6 | 0.22092 (16) | 0.1253 (3) | 0.28749 (13) | 0.0323 (5) | |
H6 | 0.2831 | 0.1657 | 0.3186 | 0.039* | |
C7 | 0.12645 (16) | 0.1899 (3) | 0.29199 (13) | 0.0331 (5) | |
H7 | 0.1160 | 0.2795 | 0.3268 | 0.040* | |
C8 | 0.05104 (17) | 0.0937 (3) | 0.23426 (14) | 0.0364 (5) | |
H8 | −0.0175 | 0.1092 | 0.2244 | 0.044* | |
C9 | 0.09846 (17) | −0.0297 (3) | 0.19440 (15) | 0.0369 (5) | |
H9 | 0.0664 | −0.1098 | 0.1536 | 0.044* | |
C10 | 0.20368 (17) | −0.0108 (3) | 0.22739 (14) | 0.0352 (5) | |
H10 | 0.2524 | −0.0763 | 0.2121 | 0.042* | |
C11 | 0.32579 (14) | 0.4699 (2) | 0.19603 (11) | 0.0225 (4) | |
C12 | 0.50438 (14) | 0.4274 (3) | 0.24432 (12) | 0.0230 (4) | |
H12A | 0.5197 | 0.5426 | 0.2262 | 0.028* | |
H12B | 0.5536 | 0.3458 | 0.2346 | 0.028* | |
C13 | 0.51381 (14) | 0.4337 (2) | 0.33808 (12) | 0.0230 (4) | |
N2 | 0.37021 (12) | 0.5724 (2) | 0.45421 (10) | 0.0283 (4) | |
H2N | 0.4048 | 0.5013 | 0.4277 | 0.034* | |
H3N | 0.3928 | 0.5410 | 0.5148 | 0.034* | |
C21 | 0.39265 (16) | 0.7595 (3) | 0.44159 (13) | 0.0329 (5) | |
H21A | 0.3741 | 0.7862 | 0.3822 | 0.039* | |
H21B | 0.4638 | 0.7805 | 0.4637 | 0.039* | |
C22 | 0.33498 (16) | 0.8779 (3) | 0.48587 (14) | 0.0343 (5) | |
H22A | 0.3467 | 0.9997 | 0.4743 | 0.041* | |
H22B | 0.3590 | 0.8599 | 0.5459 | 0.041* | |
C23 | 0.22331 (16) | 0.8399 (3) | 0.45705 (13) | 0.0326 (5) | |
H23A | 0.1974 | 0.8728 | 0.3987 | 0.039* | |
H23B | 0.1891 | 0.9095 | 0.4896 | 0.039* | |
C24 | 0.20298 (16) | 0.6455 (3) | 0.46742 (13) | 0.0325 (5) | |
H24A | 0.2212 | 0.6159 | 0.5265 | 0.039* | |
H24B | 0.1322 | 0.6221 | 0.4446 | 0.039* | |
C25 | 0.26207 (15) | 0.5325 (3) | 0.42294 (12) | 0.0297 (4) | |
H25A | 0.2507 | 0.4095 | 0.4324 | 0.036* | |
H25B | 0.2397 | 0.5544 | 0.3632 | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe | 0.02232 (15) | 0.02174 (15) | 0.02877 (16) | 0.00023 (12) | 0.00721 (11) | 0.00277 (12) |
O1 | 0.0284 (7) | 0.0236 (7) | 0.0364 (8) | 0.0000 (6) | 0.0102 (6) | −0.0050 (6) |
O2 | 0.0302 (7) | 0.0273 (7) | 0.0278 (7) | −0.0035 (6) | 0.0119 (6) | 0.0000 (6) |
O3 | 0.0303 (7) | 0.0277 (8) | 0.0252 (7) | −0.0055 (6) | 0.0021 (6) | 0.0017 (6) |
N1 | 0.0234 (8) | 0.0221 (8) | 0.0238 (8) | −0.0004 (7) | 0.0064 (7) | −0.0030 (7) |
C1 | 0.0241 (10) | 0.0215 (9) | 0.0258 (10) | 0.0010 (8) | 0.0070 (8) | 0.0055 (8) |
C2 | 0.0266 (10) | 0.0224 (10) | 0.0379 (11) | 0.0047 (8) | 0.0106 (9) | 0.0078 (9) |
C3 | 0.0241 (10) | 0.0334 (12) | 0.0417 (12) | 0.0023 (9) | 0.0046 (9) | 0.0138 (10) |
C4 | 0.0303 (11) | 0.0381 (12) | 0.0288 (10) | −0.0063 (9) | 0.0011 (9) | 0.0030 (9) |
C5 | 0.0280 (10) | 0.0300 (11) | 0.0249 (10) | −0.0005 (9) | 0.0082 (8) | 0.0007 (8) |
C6 | 0.0330 (11) | 0.0314 (12) | 0.0312 (11) | 0.0008 (9) | 0.0064 (9) | 0.0112 (9) |
C7 | 0.0390 (12) | 0.0317 (12) | 0.0314 (11) | −0.0013 (10) | 0.0143 (9) | 0.0036 (9) |
C8 | 0.0324 (12) | 0.0377 (12) | 0.0421 (12) | −0.0059 (10) | 0.0152 (10) | 0.0077 (10) |
C9 | 0.0468 (13) | 0.0231 (11) | 0.0408 (13) | −0.0088 (10) | 0.0118 (11) | 0.0024 (10) |
C10 | 0.0417 (12) | 0.0241 (11) | 0.0412 (13) | 0.0075 (9) | 0.0135 (10) | 0.0098 (9) |
C11 | 0.0263 (10) | 0.0197 (9) | 0.0231 (9) | −0.0006 (8) | 0.0094 (8) | 0.0028 (8) |
C12 | 0.0217 (9) | 0.0210 (10) | 0.0272 (10) | −0.0006 (8) | 0.0081 (8) | −0.0001 (8) |
C13 | 0.0238 (9) | 0.0194 (9) | 0.0260 (10) | 0.0042 (8) | 0.0071 (8) | 0.0010 (8) |
N2 | 0.0316 (9) | 0.0311 (9) | 0.0234 (8) | 0.0044 (8) | 0.0096 (7) | −0.0014 (7) |
C21 | 0.0315 (11) | 0.0366 (12) | 0.0311 (11) | −0.0042 (9) | 0.0098 (9) | −0.0012 (9) |
C22 | 0.0400 (12) | 0.0276 (11) | 0.0343 (11) | 0.0012 (10) | 0.0086 (10) | −0.0025 (9) |
C23 | 0.0351 (11) | 0.0318 (11) | 0.0306 (11) | 0.0091 (9) | 0.0084 (9) | 0.0020 (9) |
C24 | 0.0307 (11) | 0.0376 (12) | 0.0302 (11) | 0.0030 (9) | 0.0102 (9) | 0.0037 (9) |
C25 | 0.0329 (11) | 0.0304 (11) | 0.0248 (10) | −0.0014 (9) | 0.0061 (9) | 0.0004 (9) |
Fe—C5 | 2.0290 (19) | C7—C8 | 1.417 (3) |
Fe—C1 | 2.0316 (19) | C7—H7 | 0.9300 |
Fe—C6 | 2.034 (2) | C8—C9 | 1.412 (3) |
Fe—C7 | 2.037 (2) | C8—H8 | 0.9300 |
Fe—C4 | 2.038 (2) | C9—C10 | 1.423 (3) |
Fe—C9 | 2.041 (2) | C9—H9 | 0.9300 |
Fe—C10 | 2.042 (2) | C10—H10 | 0.9300 |
Fe—C8 | 2.044 (2) | C12—C13 | 1.526 (3) |
Fe—C3 | 2.049 (2) | C12—H12A | 0.9700 |
Fe—C2 | 2.051 (2) | C12—H12B | 0.9700 |
O1—C11 | 1.235 (2) | N2—C25 | 1.483 (3) |
O2—C13 | 1.255 (2) | N2—C21 | 1.485 (3) |
O3—C13 | 1.265 (2) | N2—H2N | 0.9128 |
N1—C11 | 1.342 (2) | N2—H3N | 0.9980 |
N1—C12 | 1.450 (2) | C21—C22 | 1.522 (3) |
N1—H1N | 0.8865 | C21—H21A | 0.9700 |
C1—C5 | 1.422 (3) | C21—H21B | 0.9700 |
C1—C2 | 1.430 (3) | C22—C23 | 1.523 (3) |
C1—C11 | 1.486 (3) | C22—H22A | 0.9700 |
C2—C3 | 1.414 (3) | C22—H22B | 0.9700 |
C2—H2 | 0.9300 | C23—C24 | 1.525 (3) |
C3—C4 | 1.416 (3) | C23—H23A | 0.9700 |
C3—H3 | 0.9300 | C23—H23B | 0.9700 |
C4—C5 | 1.424 (3) | C24—C25 | 1.513 (3) |
C4—H4 | 0.9300 | C24—H24A | 0.9700 |
C5—H5 | 0.9300 | C24—H24B | 0.9700 |
C6—C10 | 1.413 (3) | C25—H25A | 0.9700 |
C6—C7 | 1.424 (3) | C25—H25B | 0.9700 |
C6—H6 | 0.9300 | ||
C5—Fe—C1 | 41.00 (8) | C10—C6—C7 | 108.0 (2) |
C5—Fe—C6 | 121.73 (8) | C10—C6—Fe | 70.00 (12) |
C1—Fe—C6 | 106.07 (8) | C7—C6—Fe | 69.64 (12) |
C5—Fe—C7 | 158.99 (9) | C10—C6—H6 | 126.0 |
C1—Fe—C7 | 123.11 (8) | C7—C6—H6 | 126.0 |
C6—Fe—C7 | 40.93 (9) | Fe—C6—H6 | 125.9 |
C5—Fe—C4 | 40.99 (8) | C8—C7—C6 | 108.0 (2) |
C1—Fe—C4 | 68.76 (8) | C8—C7—Fe | 69.93 (12) |
C6—Fe—C4 | 158.79 (9) | C6—C7—Fe | 69.43 (12) |
C7—Fe—C4 | 158.97 (9) | C8—C7—H7 | 126.0 |
C5—Fe—C9 | 121.53 (9) | C6—C7—H7 | 126.0 |
C1—Fe—C9 | 157.05 (9) | Fe—C7—H7 | 126.2 |
C6—Fe—C9 | 68.42 (9) | C9—C8—C7 | 107.9 (2) |
C7—Fe—C9 | 68.21 (9) | C9—C8—Fe | 69.68 (12) |
C4—Fe—C9 | 107.89 (9) | C7—C8—Fe | 69.44 (12) |
C5—Fe—C10 | 105.85 (9) | C9—C8—H8 | 126.1 |
C1—Fe—C10 | 120.62 (8) | C7—C8—H8 | 126.1 |
C6—Fe—C10 | 40.57 (9) | Fe—C8—H8 | 126.4 |
C7—Fe—C10 | 68.45 (9) | C8—C9—C10 | 108.3 (2) |
C4—Fe—C10 | 123.02 (9) | C8—C9—Fe | 69.88 (12) |
C9—Fe—C10 | 40.80 (9) | C10—C9—Fe | 69.63 (12) |
C5—Fe—C8 | 158.01 (9) | C8—C9—H9 | 125.8 |
C1—Fe—C8 | 160.30 (9) | C10—C9—H9 | 125.8 |
C6—Fe—C8 | 68.62 (9) | Fe—C9—H9 | 126.2 |
C7—Fe—C8 | 40.63 (9) | C6—C10—C9 | 107.8 (2) |
C4—Fe—C8 | 123.03 (9) | C6—C10—Fe | 69.43 (12) |
C9—Fe—C8 | 40.44 (9) | C9—C10—Fe | 69.57 (12) |
C10—Fe—C8 | 68.46 (9) | C6—C10—H10 | 126.1 |
C5—Fe—C3 | 68.66 (8) | C9—C10—H10 | 126.1 |
C1—Fe—C3 | 68.52 (8) | Fe—C10—H10 | 126.5 |
C6—Fe—C3 | 158.55 (9) | O1—C11—N1 | 122.50 (18) |
C7—Fe—C3 | 123.40 (9) | O1—C11—C1 | 120.83 (17) |
C4—Fe—C3 | 40.54 (9) | N1—C11—C1 | 116.63 (17) |
C9—Fe—C3 | 124.61 (9) | N1—C12—C13 | 113.93 (15) |
C10—Fe—C3 | 160.19 (9) | N1—C12—H12A | 108.8 |
C8—Fe—C3 | 109.10 (9) | C13—C12—H12A | 108.8 |
C5—Fe—C2 | 68.87 (8) | N1—C12—H12B | 108.8 |
C1—Fe—C2 | 41.02 (7) | C13—C12—H12B | 108.8 |
C6—Fe—C2 | 122.11 (9) | H12A—C12—H12B | 107.7 |
C7—Fe—C2 | 108.14 (9) | O2—C13—O3 | 124.25 (17) |
C4—Fe—C2 | 68.31 (9) | O2—C13—C12 | 119.45 (17) |
C9—Fe—C2 | 160.71 (9) | O3—C13—C12 | 116.28 (16) |
C10—Fe—C2 | 157.30 (9) | C25—N2—C21 | 112.28 (16) |
C8—Fe—C2 | 124.52 (9) | C25—N2—H2N | 109.1 |
C3—Fe—C2 | 40.34 (8) | C21—N2—H2N | 110.0 |
C11—N1—C12 | 119.69 (16) | C25—N2—H3N | 108.4 |
C11—N1—H1N | 120.1 | C21—N2—H3N | 110.5 |
C12—N1—H1N | 119.7 | H2N—N2—H3N | 106.3 |
C5—C1—C2 | 107.95 (18) | N2—C21—C22 | 109.99 (17) |
C5—C1—C11 | 128.91 (18) | N2—C21—H21A | 109.7 |
C2—C1—C11 | 123.13 (18) | C22—C21—H21A | 109.7 |
C5—C1—Fe | 69.40 (11) | N2—C21—H21B | 109.7 |
C2—C1—Fe | 70.21 (11) | C22—C21—H21B | 109.7 |
C11—C1—Fe | 125.49 (13) | H21A—C21—H21B | 108.2 |
C3—C2—C1 | 107.76 (19) | C21—C22—C23 | 111.20 (18) |
C3—C2—Fe | 69.78 (12) | C21—C22—H22A | 109.4 |
C1—C2—Fe | 68.77 (11) | C23—C22—H22A | 109.4 |
C3—C2—H2 | 126.1 | C21—C22—H22B | 109.4 |
C1—C2—H2 | 126.1 | C23—C22—H22B | 109.4 |
Fe—C2—H2 | 126.9 | H22A—C22—H22B | 108.0 |
C2—C3—C4 | 108.44 (18) | C22—C23—C24 | 110.71 (18) |
C2—C3—Fe | 69.89 (11) | C22—C23—H23A | 109.5 |
C4—C3—Fe | 69.30 (12) | C24—C23—H23A | 109.5 |
C2—C3—H3 | 125.8 | C22—C23—H23B | 109.5 |
C4—C3—H3 | 125.8 | C24—C23—H23B | 109.5 |
Fe—C3—H3 | 126.6 | H23A—C23—H23B | 108.1 |
C3—C4—C5 | 108.16 (19) | C25—C24—C23 | 110.77 (17) |
C3—C4—Fe | 70.16 (12) | C25—C24—H24A | 109.5 |
C5—C4—Fe | 69.17 (11) | C23—C24—H24A | 109.5 |
C3—C4—H4 | 125.9 | C25—C24—H24B | 109.5 |
C5—C4—H4 | 125.9 | C23—C24—H24B | 109.5 |
Fe—C4—H4 | 126.3 | H24A—C24—H24B | 108.1 |
C1—C5—C4 | 107.69 (18) | N2—C25—C24 | 110.26 (17) |
C1—C5—Fe | 69.60 (11) | N2—C25—H25A | 109.6 |
C4—C5—Fe | 69.85 (12) | C24—C25—H25A | 109.6 |
C1—C5—H5 | 126.2 | N2—C25—H25B | 109.6 |
C4—C5—H5 | 126.2 | C24—C25—H25B | 109.6 |
Fe—C5—H5 | 126.0 | H25A—C25—H25B | 108.1 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O2 | 0.91 | 1.86 | 2.764 (2) | 172 |
N2—H3N···O3i | 1.00 | 1.76 | 2.749 (2) | 172 |
N2—H3N···O2i | 1.00 | 2.60 | 3.325 (2) | 130 |
N1—H1N···O3ii | 0.89 | 2.04 | 2.908 (2) | 166 |
C5—H5···O3ii | 0.93 | 2.56 | 3.366 (3) | 146 |
C12—H12B···O1ii | 0.97 | 2.39 | 3.307 (3) | 158 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | (C5H12N)[Fe(C5H5)(C8H7NO3)] |
Mr | 372.24 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 13.9055 (4), 7.6150 (2), 16.5968 (5) |
β (°) | 105.780 (2) |
V (Å3) | 1691.21 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.91 |
Crystal size (mm) | 0.25 × 0.22 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25843, 3456, 2960 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.076, 1.11 |
No. of reflections | 3456 |
No. of parameters | 217 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.29 |
Computer programs: COLLECT (Nonius, 2000), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O2 | 0.91 | 1.86 | 2.764 (2) | 172 |
N2—H3N···O3i | 1.00 | 1.76 | 2.749 (2) | 172 |
N2—H3N···O2i | 1.00 | 2.60 | 3.325 (2) | 130 |
N1—H1N···O3ii | 0.89 | 2.04 | 2.908 (2) | 166 |
C5—H5···O3ii | 0.93 | 2.56 | 3.366 (3) | 146 |
C12—H12B···O1ii | 0.97 | 2.39 | 3.307 (3) | 158 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+1/2. |
Acknowledgements
This work was supported financially by the Ministry of Education, Youth and Sports of the Czech Republic (project No. MSM0021620857).
References
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Appoh, F. E., Sutherland, T. C. & Kraatz, H.-B. (2004). J. Organomet. Chem. 689, 4669–4677. Web of Science CrossRef CAS Google Scholar
Bauer, W., Polborn, K. & Beck, W. (1999). J. Organomet. Chem. 579, 269–279. Web of Science CSD CrossRef CAS Google Scholar
Gallagher, J. F., Kenny, P. T. M. & Sheehy, M. J. (1999). Inorg. Chem. Commun. 2, 200–202. Web of Science CSD CrossRef CAS Google Scholar
Kraatz, H.-B., Lusztyk, J. & Enright, G. D. (1997). Inorg. Chem. 36, 2400–2405. CSD CrossRef PubMed CAS Web of Science Google Scholar
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Schlögl, K. (1957). Monatsh. Chem. 88, 601–621. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Štěpnička, P. (2008). Ferrocenes: Ligands, Materials and Biomolecules. Wiley: Chichester. Google Scholar
Tauchman, J., Císařová, I. & Štěpnička, P. (2009). Organometallics, 28, 3288–3302. Web of Science CSD CrossRef CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
ferrocenylcarbonyl derivatives (amides) prepared from amino acids and peptides received considerable research attention in the recent past, mainly as precursors to redox-labelled biomolecules and as model compounds for studies focusing on stereochemistry and H-bonding interactions in peptides (Štěpnička, 2008). N-(ferrocenylcarbonyl)glycine as the first ferrocenylated amino acid derivative was reported already in 1957 (Schlögl, 1957). It was further used in the preparation of 2-ferrocenyl-5(4H)oxazolone and its complexes with transition metals (Bauer et al., 1999) and further studied as a redox-responsive reagent for inorganic anions (Gallagher et al., 1999).
Thus, piperidinium N-(ferrocenylcarbonyl)glycinate was obtained by acid-base reaction N-(ferrocenylcarbonyl)glycine with piperidine and isolated as a yellow, air-stable crystalline solid. Its molecular structure as determined by X-ray diffraction analysis (Figure 1) is rather unexceptional. The geometry of the ferrocene unit is regular, showing a practically negligible variation in the Fe—C bond lengths (2.029 (19)–2.051 (2) Å). Accordingly, the distance of the iron atom to cyclopentadienyl ring centroids are quite similar (1.6429 (10) and 1.6450 (10) Å for the rings C(1–5) and C(6–10), respectively), and the dihedral angle of the least-squares cyclopentadienyl planes is only 2.28 (13) °.
The geometry of the glycinamide moiety is similar to those reported previously for methyl N-(ferrocenylcarbonyl)glycinate (Gallagher et al., 1999) or t-butyl N-[1'-(diphenylphosphino)ferrocene-1-carbonyl]glycinate (Tauchman et al., 2009). A difference is seen in the parameters describing the terminal carboxy group, which is deprotonated (unlike the reference compounds) and shows balanced C—O distance due to delocalization (C13—O2 = 1.255 (2) Å, C13—O3 = 1.265 (2) Å, O2—C13—O3 = 124.25 (17) °). The amide plane, {C11, O1, N1}, is rotated with respect to its bonding cyclopentadienyl ring C(1–5) by only 8.9 (2) °. As a results, the two moieties remain conjugated, which is reflected by a relative shortening of the connecting C1—C11 bond (1.486 (3) Å). Similar bond lengths (1.483 (2) and 1.491 (2) Å) were observed for two monoclinic polymorphs of carbamoylferrocene, where the amide and cyclopentadienyl planes are rotated by ca 10 ° (Štěpnička et al., 2010). The glycine moeity extends below the parent cyclopentadienyl ring at the dihedral angle C11—N1—C12—C13 of 59.3 (1) °. Finally, the piperidinium cation assumes an envelope conformation with τ = 178.1 (2) ° and puckering amplitude Q = 0.572 (2) Å (N.B. ideal chair requires τ = 0 or 180 °). There is, however, noticeable some departure from the regular geometry since the C(21/25)—N bond lengths are slightly shorter (ca 2%) than the remaining in-ring distances (C—C = 1.513 (3)–1.525 (3) Å).
The crystal packing of the title compound is dominated by intermolecular hydrogen bonding interaction. The ions constituting the structure assemble pairwise around inversion centers by means of N—H···O hydrogen bonds from both NH protons at the piperidinium cation to adjacent carboxylate O atoms O2 and O3 as H-bond acceptors (Figure 2a; for parameters, see Table 1). An additional contact, N2—H3N···O2 has a rather unfavourable geometry and probably reflects an enforced proximity of the atoms involved. The four-membered centrosymmetric assemblies thus formed are interconnected by N—H···O hydrogen bonds between amide NH and carboxylate O3 and further by supportive C—H···O interactions (Figure 2a, Table 1) into layers oriented parallel to the bc plane (Figure 2b).