Piperidinium N-(ferrocenylcarbon­yl)glycinate

Štěpnička, P.; Zábranský, M.; Císařová, I.

doi:10.1107/S1600536810041747

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 12| December 2010| Pages m1506-m1507

https://doi.org/10.1107/S1600536810041747

Open

access

Piperidinium N-(ferrocenylcarbonyl)glycinate

Petr Štěpnička,^a ^* Martin Zábranský ^a and Ivana Císařová ^a

^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

(Received 11 October 2010; accepted 15 October 2010; online 6 November 2010)

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

(C₅H₁₂N)[Fe(C₅H₅)(C₈H₇NO₃)]
M_r = 372.24
Monoclinic, P 2₁ /c
a = 13.9055 (4) Å
b = 7.6150 (2) Å
c = 16.5968 (5) Å
β = 105.780 (2)°
V = 1691.21 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.91 mm⁻¹
T = 150 K
0.25 × 0.22 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer
25843 measured reflections
3456 independent reflections
2960 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.076
S = 1.11
3456 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 2000 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810041747/dn2612sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810041747/dn2612Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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).

Experimental top

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 column chromatography (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 column chromatography 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%.

Structure description top

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: 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).

Figures top

	Fig. 1. View of the ions constituting the structure of the title compound showing the atom numbering scheme and displacement ellipsoids for the non-H atoms at the 30% probability level (N.B. Mutual orientation of the ions corresponds with that encountered in the crystal).
	Fig. 2. (a) View of the hydrogen-bonded aggregate in the crystal structure of the title compound, showing the H-bonds as dashed lines. For clarity, only NH protons are shown and the bulky ferrocenyl groups are replaced with filled black squares. (c) View of the unit cell along the crystallographic b axis.

Piperidinium N-(ferrocenylcarbonyl)glycinate top

Crystal data top

(C₅H₁₂N)[Fe(C₅H₅)(C₈H₇NO₃)]	F(000) = 784
M_r = 372.24	D_x = 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

Data collection top

Nonius KappaCCD diffractometer	2960 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.044
Horizontally mounted graphite crystal monochromator	θ_max = 26.4°, θ_min = 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 top

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(F_o²) + (0.0234P)² + 1.3244P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
3456 reflections	Δρ_max = 0.27 e Å⁻³
217 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints

Crystal data top

(C₅H₁₂N)[Fe(C₅H₅)(C₈H₇NO₃)]	V = 1691.21 (8) Å³
M_r = 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)°

Data collection top

Nonius KappaCCD diffractometer	2960 reflections with I > 2σ(I)
25843 measured reflections	R_int = 0.044
3456 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.076	H-atom parameters constrained
S = 1.11	Δρ_max = 0.27 e Å⁻³
3456 reflections	Δρ_min = −0.29 e Å⁻³
217 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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)]
M_r	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
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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