N,N-Dibenzoyl­ferrocenecarboxamide

Cetina, M.; Kovač, V.; Rapić, V.

doi:10.1107/S1600536811013754

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page m610

doi:10.1107/S1600536811013754

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N,N-Dibenzoylferrocenecarboxamide

Mario Cetina,^a ^* Veronika Kovač ^b ^* and Vladimir Rapić ^b

^aDepartment of Applied Chemistry, Faculty of Textile Technology, University of Zagreb, Prilaz baruna Filipovića 28a, HR-10000 Zagreb, Croatia, and ^bLaboratory of Organic Chemistry, Faculty of Food Technology and Biotechnology, University of Zagreb, Pierottijeva 6, HR-10000 Zagreb, Croatia
^*Correspondence e-mail: mario.cetina@ttf.hr, vkovac@pbf.hr

(Received 17 March 2011; accepted 12 April 2011; online 16 April 2011)

In the title compound, [Fe(C₅H₅)(C₂₀H₁₄NO₃)], the cyclopentadienyl rings deviate by 9.3 (2)° from an eclipsed conformation, defined by C—Cg₁—Cg₂—C pseudo-torsion angles ranging from 8.8 (1) to 9.85 (1)°. The coordination at the N atom is slightly pyramidal, as indicated by the angular sum around it of 352.6°. The amide group is inclined at 17.86 (9) and 27.27 (11)° with respect to the aromatic rings. In the crystal, molecules are linked by one C—H⋯O hydrogen bond and one C—H⋯π interaction into a two-dimensional framework parallel to the b axis.

Related literature

For background to ferrocene amides, see: Kohmoto et al. (2008 ); Masu et al. (2005 , 2006 ); Moriuchi et al. (1995 , 2000 ); Moriuchi & Hirao (2007 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

[Fe(C₅H₅)(C₂₀H₁₄NO₃)]
M_r = 437.26
Monoclinic, P 2₁ /c
a = 10.8699 (4) Å
b = 11.3387 (4) Å
c = 19.6264 (7) Å
β = 122.133 (2)°
V = 2048.42 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 295 K
0.56 × 0.53 × 0.43 mm

Data collection

Oxford Diffraction KM-4/Xcalibur diffractometer with a Sapphire3 detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.910, T_max = 1.000
14704 measured reflections
5867 independent reflections
3472 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.068
S = 0.93
5867 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C6–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O1ⁱ	0.93	2.56	3.241 (2)	131
C15—H15⋯Cg2ⁱⁱ	0.93	2.97	3.528 (2)	120
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 1999 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811013754/im2277sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811013754/im2277Isup2.hkl

checkCIF report

Comment top

Recently, aromatic foldamers with iminodicarbonyl linkers have been synthesized to investigate their structures in comparison with that of biopolymers, mostly proteins (Masu et al. 2005, 2006; Kohmoto et al. 2008). Also, considerable interest has been devoted to the synthesis of various imide based ferrocene derivatives in which the redox properties of transition metals permits their potential utilization as electrical materials and catalysts, e.g. ferrocenophanes (Moriuchi et al., 1995, 2000) or imide-bridged diferrocene for protonation-controlled regulation of electronic communication (Moriuchi & Hirao, 2007). Considering these previous studies we decided to prepare some new ferrocene containing imides notably due to investigation of their structure. During the synthesis of model substances as a part of our current research on ferrocene foldamers with iminodicarbonyl linkers we have isolated the title compound 1 and its structure is described in this paper.

A survay of Cambridge Structural Database (Allen, 2002) revealed that 1 (Fig. 1) is the first structure with a N–(C=O)₃ fragment linked to the ferrocenyl moiety. N1 is pyramidal and is displaced by 0.228 (1)Å out of the plane defined by atoms C11/C12/C19. Because of pyramidality, the angular sum around N1 is 352.6°. A somehow close C14–H14···N1 interaction of 2.55 Å seems to be indicative for a intramolecular hydrogen bond forming a five-membered ring that could be described by graph set descriptors as S(5) (Bernstein et al., 1995). On the other hand, the C14–H14···N1 angle is very small (101°) and there is no difference in chemical shifts for protons at C14 and C18 in the ¹H NMR spectrum (7.91 p.p.m., doublet, for 4 protons of the C14, C18, C21, C25), therefore indicating the absence of an intramolecular hydrogen bond at least in solution.

The C11=O1 carbonyl group and C1–C5 ring form an extended π-conjugated system, and therefore C1–C11 bond is shortened. The coplanar arrangement of a carbonyl group attached to the cyclopetadienyl (Cp) ring should allow maximum interaction of two π-systems. The C11=O1 bond is twisted out of the plane of the C1–C5 ring for 18.81 (11)°. The Cp rings deviate 9.3 (2)° from an eclipsed conformation. The value of the C–Cg₁–Cg₂–C pseudo-torsion angles, defined by joining two eclipsing Cp carbon atoms through the ring centroids range from 8.8 (1) to 9.8 (1)°. The Cp rings are almost parallel, with a dihedral angle between the mean planes of the rings of 1.84 (11)°. The amide groups do not lie in the plane of the attached aromatic rings. Thus, the plane of the C13/C12/O2/N1 atoms is inclined to the C13–C18 phenyl ring for 17.86 (9)°, and the plane of the C19/C20/O3/N1 atoms is inclined to the C20–C25 phenyl ring for even 27.27 (11)°. Two phenyl rings are perpendicular with respect to the C1–C5 ring. The corresponding dihedral angles are 85.36 (9) and 88.17 (10)° for C13–C18 and C20–C25 rings, respectively.

Molecules of 1 are self-assembled by C4–H4···O1 hydrogen bonds (Fig. 2; Table 1) into C(6) (Bernstein et al., 1995) spirals parallel to the b axis. Hydrogen-bonded chains are further weakly linked by one C–H···π interaction, C15–H15···Cg2, also parallel to the b axis forming a two-dimensional framework.

Related literature top

For background to ferrocene amides, see: Kohmoto et al. (2008); Masu et al. (2005, 2006); Moriuchi et al. (1995, 2000); Moriuchi & Hirao (2007). For hydrogen-bond motifs, see: Bernstein et al. (1995). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

To a suspension of hexane-washed sodium hydride (60% NaH in mineral oil, 78 mg; 2.027 mmol) in dry tetrahydrofuran (5 ml), a solution of ferrocene amide (188 mg; 0.821 mmol) in dry tetrahydrofuran (5 ml) was dropped and the mixture was heated at reflux for 2 h. After cooling benzoyl chloride (0.13 ml; 1.126 mmol) was added and the reaction mixture was stirred at room temperature overnight. After removing the solvent the remaining residue was dissolved in dichloromethane, washed with water and brine, dried over anhydrous sodium sulfate and evaporated. TLC purification gave 111 mg (41%) orange crystals of N-benzoylferrocenecarboxamide 2 and 76 mg (21%) red crystals of the title compound 1. A single-crystal of 1 was grown by slow evaporation from a saturated dichloromethane solution.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of 1, with the atom-numbering scheme. Displacement ellipsoids for non-hydrogen atoms are drawn at the 30% probability level.
	Fig. 2. Crystal packing diagram of 1, showing the C–H···O hydrogen bonds and C–H···π interactions as dashed lines. Symmetry codes are given in Table 1.

N,N-Dibenzoylferrocenecarboxamide top

Crystal data top

[Fe(C₅H₅)(C₂₀H₁₄NO₃)]	F(000) = 904
M_r = 437.26	D_x = 1.418 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 416–418 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.8699 (4) Å	Cell parameters from 5978 reflections
b = 11.3387 (4) Å	θ = 4.0–31.8°
c = 19.6264 (7) Å	µ = 0.76 mm⁻¹
β = 122.133 (2)°	T = 295 K
V = 2048.42 (13) Å³	Prism, red
Z = 4	0.56 × 0.53 × 0.43 mm

Data collection top

Oxford Diffraction KM-4/Xcalibur diffractometer with a Sapphire3 detector	5867 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3472 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
Detector resolution: 16.3426 pixels mm^-1	θ_max = 30.0°, θ_min = 4.1°
ω scans	h = −15→14
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	k = −10→15
T_min = 0.910, T_max = 1.000	l = −27→27
14704 measured 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.068	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.0306P)²] where P = (F_o² + 2F_c²)/3
5867 reflections	(Δ/σ)_max = 0.002
271 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

[Fe(C₅H₅)(C₂₀H₁₄NO₃)]	V = 2048.42 (13) Å³
M_r = 437.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.8699 (4) Å	µ = 0.76 mm⁻¹
b = 11.3387 (4) Å	T = 295 K
c = 19.6264 (7) Å	0.56 × 0.53 × 0.43 mm
β = 122.133 (2)°

Data collection top

Oxford Diffraction KM-4/Xcalibur diffractometer with a Sapphire3 detector	5867 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	3472 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.024
14704 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.068	H-atom parameters constrained
S = 0.93	Δρ_max = 0.26 e Å⁻³
5867 reflections	Δρ_min = −0.24 e Å⁻³
271 parameters

Special details top

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.32 (release 27-01-2009 CrysAlis171 .NET) (compiled Jan 27 2009,14:17:37) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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

	x	y	z	U_iso*/U_eq
Fe1	0.22827 (2)	0.555286 (18)	0.788568 (11)	0.04543 (7)
N1	0.31428 (12)	0.20402 (10)	0.81870 (6)	0.0418 (3)
O1	0.08238 (10)	0.25999 (10)	0.72376 (6)	0.0561 (3)
O2	0.32130 (12)	0.17948 (11)	0.93657 (6)	0.0685 (3)
O3	0.35548 (15)	0.01217 (10)	0.80453 (6)	0.0727 (4)
C1	0.22015 (15)	0.39344 (13)	0.83023 (7)	0.0435 (3)
C2	0.35480 (17)	0.44935 (13)	0.88449 (8)	0.0580 (4)
H2	0.4467	0.4217	0.9000	0.070*
C3	0.3229 (2)	0.55509 (15)	0.91043 (9)	0.0733 (5)
H3	0.3911	0.6086	0.9468	0.088*
C4	0.1724 (2)	0.56619 (15)	0.87266 (9)	0.0668 (5)
H4	0.1238	0.6281	0.8795	0.080*
C5	0.10714 (17)	0.46776 (13)	0.82268 (9)	0.0524 (4)
H5	0.0079	0.4534	0.7904	0.063*
C6	0.18399 (19)	0.54441 (15)	0.67438 (9)	0.0612 (4)
H6	0.1552	0.4768	0.6427	0.073*
C7	0.3267 (2)	0.58116 (17)	0.72643 (11)	0.0699 (5)
H7	0.4100	0.5425	0.7361	0.084*
C8	0.3216 (2)	0.68789 (18)	0.76171 (12)	0.0761 (5)
H8	0.4012	0.7328	0.7986	0.091*
C9	0.1762 (2)	0.71431 (16)	0.73166 (11)	0.0713 (5)
H9	0.1419	0.7796	0.7453	0.086*
C10	0.09164 (19)	0.62606 (17)	0.67781 (10)	0.0674 (5)
H10	−0.0093	0.6222	0.6490	0.081*
C11	0.19470 (14)	0.28448 (13)	0.78516 (7)	0.0414 (3)
C12	0.38958 (17)	0.18287 (12)	0.90480 (8)	0.0483 (4)
C13	0.54864 (16)	0.17184 (13)	0.94748 (8)	0.0498 (4)
C14	0.62677 (17)	0.21187 (15)	0.91517 (9)	0.0612 (4)
H14	0.5780	0.2427	0.8633	0.073*
C15	0.77638 (18)	0.20666 (18)	0.95886 (11)	0.0778 (6)
H15	0.8286	0.2345	0.9370	0.093*
C16	0.8472 (2)	0.1599 (2)	1.03492 (13)	0.0939 (7)
H16	0.9481	0.1558	1.0647	0.113*
C17	0.7712 (3)	0.11922 (18)	1.06751 (11)	0.0896 (7)
H17	0.8208	0.0871	1.1190	0.107*
C18	0.6221 (2)	0.12535 (14)	1.02499 (8)	0.0666 (5)
H18	0.5709	0.0987	1.0477	0.080*
C19	0.31625 (16)	0.10751 (14)	0.77336 (8)	0.0475 (3)
C20	0.27699 (15)	0.13020 (14)	0.68970 (8)	0.0476 (4)
C21	0.29771 (16)	0.23823 (15)	0.66520 (8)	0.0555 (4)
H21	0.3308	0.3018	0.7006	0.067*
C22	0.2693 (2)	0.25240 (18)	0.58799 (10)	0.0744 (5)
H22	0.2849	0.3250	0.5717	0.089*
C23	0.2179 (2)	0.1583 (2)	0.53545 (11)	0.0884 (6)
H23	0.1969	0.1679	0.4832	0.106*
C24	0.1979 (2)	0.0515 (2)	0.55973 (11)	0.0918 (7)
H24	0.1638	−0.0116	0.5240	0.110*
C25	0.2275 (2)	0.03562 (17)	0.63671 (9)	0.0700 (5)
H25	0.2144	−0.0379	0.6530	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.04328 (12)	0.04295 (12)	0.04387 (11)	0.00224 (11)	0.01901 (9)	0.00300 (9)
N1	0.0486 (7)	0.0418 (7)	0.0316 (5)	0.0062 (6)	0.0190 (5)	0.0003 (5)
O1	0.0399 (5)	0.0705 (7)	0.0479 (6)	−0.0040 (5)	0.0166 (5)	−0.0101 (5)
O2	0.0894 (8)	0.0766 (8)	0.0531 (6)	0.0206 (7)	0.0471 (6)	0.0179 (6)
O3	0.1159 (10)	0.0427 (6)	0.0520 (6)	0.0101 (7)	0.0396 (7)	−0.0003 (5)
C1	0.0496 (8)	0.0431 (8)	0.0348 (6)	0.0072 (7)	0.0205 (6)	0.0042 (6)
C2	0.0570 (9)	0.0497 (9)	0.0400 (7)	0.0107 (8)	0.0073 (7)	0.0004 (7)
C3	0.0999 (14)	0.0470 (10)	0.0387 (8)	0.0114 (10)	0.0137 (9)	−0.0047 (7)
C4	0.1046 (15)	0.0523 (10)	0.0520 (9)	0.0247 (10)	0.0474 (10)	0.0090 (8)
C5	0.0644 (10)	0.0530 (10)	0.0513 (8)	0.0125 (8)	0.0385 (8)	0.0119 (7)
C6	0.0733 (11)	0.0618 (11)	0.0518 (9)	−0.0044 (10)	0.0354 (9)	0.0059 (8)
C7	0.0639 (11)	0.0749 (14)	0.0875 (12)	0.0072 (10)	0.0515 (10)	0.0173 (10)
C8	0.0698 (12)	0.0665 (13)	0.0913 (13)	−0.0222 (10)	0.0424 (11)	−0.0031 (11)
C9	0.0925 (14)	0.0491 (10)	0.0868 (13)	0.0111 (11)	0.0574 (12)	0.0188 (10)
C10	0.0572 (10)	0.0787 (13)	0.0605 (10)	0.0082 (10)	0.0275 (8)	0.0297 (10)
C11	0.0436 (8)	0.0492 (9)	0.0349 (7)	0.0033 (7)	0.0234 (6)	0.0060 (6)
C12	0.0696 (10)	0.0371 (8)	0.0360 (7)	0.0094 (8)	0.0265 (7)	0.0026 (6)
C13	0.0624 (9)	0.0385 (8)	0.0348 (7)	0.0101 (8)	0.0166 (7)	−0.0026 (6)
C14	0.0598 (10)	0.0677 (11)	0.0431 (8)	0.0110 (9)	0.0187 (8)	−0.0091 (8)
C15	0.0601 (11)	0.0908 (14)	0.0669 (11)	0.0058 (11)	0.0233 (9)	−0.0230 (10)
C16	0.0661 (12)	0.0903 (16)	0.0712 (13)	0.0221 (12)	0.0000 (11)	−0.0230 (12)
C17	0.0973 (16)	0.0644 (13)	0.0459 (10)	0.0186 (13)	−0.0031 (11)	−0.0004 (9)
C18	0.0876 (13)	0.0460 (10)	0.0382 (8)	0.0067 (9)	0.0145 (8)	0.0002 (7)
C19	0.0541 (9)	0.0447 (9)	0.0412 (7)	0.0012 (8)	0.0237 (7)	−0.0046 (7)
C20	0.0484 (8)	0.0552 (10)	0.0418 (7)	0.0021 (7)	0.0257 (7)	−0.0038 (7)
C21	0.0600 (9)	0.0643 (11)	0.0493 (8)	0.0031 (8)	0.0339 (8)	−0.0016 (8)
C22	0.0892 (13)	0.0874 (14)	0.0646 (11)	0.0029 (12)	0.0530 (10)	0.0117 (10)
C23	0.1114 (16)	0.1143 (19)	0.0530 (10)	−0.0061 (15)	0.0529 (11)	−0.0038 (12)
C24	0.1254 (18)	0.1016 (17)	0.0601 (11)	−0.0254 (14)	0.0571 (12)	−0.0279 (11)
C25	0.0933 (13)	0.0693 (12)	0.0548 (9)	−0.0129 (10)	0.0444 (10)	−0.0146 (8)

Geometric parameters (Å, º) top

Fe1—C5	2.0260 (15)	C7—H7	0.9300
Fe1—C7	2.0269 (17)	C8—C9	1.394 (2)
Fe1—C6	2.0303 (15)	C8—H8	0.9300
Fe1—C1	2.0300 (14)	C9—C10	1.389 (2)
Fe1—C2	2.0309 (14)	C9—H9	0.9300
Fe1—C8	2.0339 (18)	C10—H10	0.9300
Fe1—C10	2.0349 (15)	C12—C13	1.472 (2)
Fe1—C9	2.0363 (16)	C13—C14	1.379 (2)
Fe1—C3	2.0399 (15)	C13—C18	1.3920 (19)
Fe1—C4	2.0430 (16)	C14—C15	1.378 (2)
N1—C19	1.4177 (17)	C14—H14	0.9300
N1—C11	1.4300 (17)	C15—C16	1.371 (3)
N1—C12	1.4531 (16)	C15—H15	0.9300
O1—C11	1.2061 (15)	C16—C17	1.367 (3)
O2—C12	1.1973 (16)	C16—H16	0.9300
O3—C19	1.2030 (17)	C17—C18	1.374 (3)
C1—C2	1.421 (2)	C17—H17	0.9300
C1—C5	1.431 (2)	C18—H18	0.9300
C1—C11	1.458 (2)	C19—C20	1.4830 (19)
C2—C3	1.416 (2)	C20—C21	1.377 (2)
C2—H2	0.9300	C20—C25	1.388 (2)
C3—C4	1.396 (3)	C21—C22	1.386 (2)
C3—H3	0.9300	C21—H21	0.9300
C4—C5	1.404 (2)	C22—C23	1.379 (3)
C4—H4	0.9300	C22—H22	0.9300
C5—H5	0.9300	C23—C24	1.361 (3)
C6—C7	1.392 (2)	C23—H23	0.9300
C6—C10	1.393 (2)	C24—C25	1.379 (2)
C6—H6	0.9300	C24—H24	0.9300
C7—C8	1.410 (2)	C25—H25	0.9300

C5—Fe1—C7	156.04 (7)	Fe1—C5—H5	125.6
C5—Fe1—C6	121.39 (7)	C7—C6—C10	108.43 (16)
C7—Fe1—C6	40.14 (7)	C7—C6—Fe1	69.80 (9)
C5—Fe1—C1	41.32 (6)	C10—C6—Fe1	70.14 (9)
C7—Fe1—C1	121.55 (7)	C7—C6—H6	125.8
C6—Fe1—C1	110.74 (6)	C10—C6—H6	125.8
C5—Fe1—C2	69.06 (7)	Fe1—C6—H6	125.9
C7—Fe1—C2	109.23 (7)	C6—C7—C8	107.29 (16)
C6—Fe1—C2	129.30 (7)	C6—C7—Fe1	70.06 (9)
C1—Fe1—C2	40.98 (6)	C8—C7—Fe1	69.95 (10)
C5—Fe1—C8	161.66 (7)	C6—C7—H7	126.4
C7—Fe1—C8	40.64 (7)	C8—C7—H7	126.4
C6—Fe1—C8	67.47 (7)	Fe1—C7—H7	125.2
C1—Fe1—C8	155.13 (7)	C9—C8—C7	107.99 (17)
C2—Fe1—C8	119.49 (8)	C9—C8—Fe1	70.07 (10)
C5—Fe1—C10	108.23 (6)	C7—C8—Fe1	69.42 (10)
C7—Fe1—C10	67.61 (7)	C9—C8—H8	126.0
C6—Fe1—C10	40.09 (7)	C7—C8—H8	126.0
C1—Fe1—C10	128.56 (7)	Fe1—C8—H8	126.1
C2—Fe1—C10	166.69 (7)	C10—C9—C8	108.05 (17)
C8—Fe1—C10	67.22 (7)	C10—C9—Fe1	69.99 (10)
C5—Fe1—C9	125.12 (7)	C8—C9—Fe1	69.88 (10)
C7—Fe1—C9	67.87 (7)	C10—C9—H9	126.0
C6—Fe1—C9	67.34 (7)	C8—C9—H9	126.0
C1—Fe1—C9	164.26 (7)	Fe1—C9—H9	125.7
C2—Fe1—C9	152.35 (8)	C9—C10—C6	108.24 (16)
C8—Fe1—C9	40.05 (7)	C9—C10—Fe1	70.10 (9)
C10—Fe1—C9	39.91 (7)	C6—C10—Fe1	69.78 (9)
C5—Fe1—C3	67.84 (7)	C9—C10—H10	125.9
C7—Fe1—C3	127.41 (8)	C6—C10—H10	125.9
C6—Fe1—C3	165.89 (8)	Fe1—C10—H10	125.8
C1—Fe1—C3	68.26 (6)	O1—C11—N1	120.15 (13)
C2—Fe1—C3	40.71 (6)	O1—C11—C1	124.46 (13)
C8—Fe1—C3	107.15 (8)	N1—C11—C1	115.38 (12)
C10—Fe1—C3	151.55 (8)	O2—C12—N1	119.28 (14)
C9—Fe1—C3	117.63 (8)	O2—C12—C13	124.53 (13)
C5—Fe1—C4	40.37 (6)	N1—C12—C13	116.14 (13)
C7—Fe1—C4	163.00 (8)	C14—C13—C18	119.43 (16)
C6—Fe1—C4	153.85 (8)	C14—C13—C12	122.32 (13)
C1—Fe1—C4	68.54 (6)	C18—C13—C12	118.14 (16)
C2—Fe1—C4	68.45 (7)	C15—C14—C13	120.74 (16)
C8—Fe1—C4	124.62 (8)	C15—C14—H14	119.6
C10—Fe1—C4	118.52 (7)	C13—C14—H14	119.6
C9—Fe1—C4	105.92 (7)	C16—C15—C14	119.2 (2)
C3—Fe1—C4	40.00 (7)	C16—C15—H15	120.4
C19—N1—C11	121.13 (11)	C14—C15—H15	120.4
C19—N1—C12	114.53 (11)	C17—C16—C15	120.73 (19)
C11—N1—C12	116.91 (11)	C17—C16—H16	119.6
C2—C1—C5	107.47 (13)	C15—C16—H16	119.6
C2—C1—C11	128.32 (13)	C16—C17—C18	120.67 (17)
C5—C1—C11	124.12 (13)	C16—C17—H17	119.7
C2—C1—Fe1	69.54 (8)	C18—C17—H17	119.7
C5—C1—Fe1	69.19 (8)	C17—C18—C13	119.24 (19)
C11—C1—Fe1	123.82 (9)	C17—C18—H18	120.4
C3—C2—C1	107.17 (15)	C13—C18—H18	120.4
C3—C2—Fe1	69.99 (8)	O3—C19—N1	119.61 (12)
C1—C2—Fe1	69.48 (8)	O3—C19—C20	122.30 (13)
C3—C2—H2	126.4	N1—C19—C20	118.01 (13)
C1—C2—H2	126.4	C21—C20—C25	119.73 (14)
Fe1—C2—H2	125.7	C21—C20—C19	122.44 (13)
C4—C3—C2	109.11 (15)	C25—C20—C19	117.66 (14)
C4—C3—Fe1	70.12 (8)	C20—C21—C22	120.14 (16)
C2—C3—Fe1	69.30 (8)	C20—C21—H21	119.9
C4—C3—H3	125.4	C22—C21—H21	119.9
C2—C3—H3	125.4	C23—C22—C21	119.62 (18)
Fe1—C3—H3	126.7	C23—C22—H22	120.2
C3—C4—C5	108.25 (15)	C21—C22—H22	120.2
C3—C4—Fe1	69.88 (10)	C24—C23—C22	120.22 (17)
C5—C4—Fe1	69.17 (9)	C24—C23—H23	119.9
C3—C4—H4	125.9	C22—C23—H23	119.9
C5—C4—H4	125.9	C23—C24—C25	120.80 (18)
Fe1—C4—H4	126.6	C23—C24—H24	119.6
C4—C5—C1	107.99 (15)	C25—C24—H24	119.6
C4—C5—Fe1	70.47 (10)	C24—C25—C20	119.47 (18)
C1—C5—Fe1	69.49 (8)	C24—C25—H25	120.3
C4—C5—H5	126.0	C20—C25—H25	120.3
C1—C5—H5	126.0

C5—Fe1—C1—C2	−118.97 (12)	C4—Fe1—C6—C10	42.5 (2)
C7—Fe1—C1—C2	83.25 (11)	C10—C6—C7—C8	−0.62 (19)
C6—Fe1—C1—C2	126.64 (10)	Fe1—C6—C7—C8	−60.33 (12)
C8—Fe1—C1—C2	45.68 (19)	C10—C6—C7—Fe1	59.71 (11)
C10—Fe1—C1—C2	168.54 (10)	C5—Fe1—C7—C6	47.3 (2)
C9—Fe1—C1—C2	−153.4 (2)	C1—Fe1—C7—C6	85.21 (12)
C3—Fe1—C1—C2	−38.25 (10)	C2—Fe1—C7—C6	128.82 (10)
C4—Fe1—C1—C2	−81.42 (10)	C8—Fe1—C7—C6	−117.97 (16)
C7—Fe1—C1—C5	−157.78 (10)	C10—Fe1—C7—C6	−37.35 (10)
C6—Fe1—C1—C5	−114.38 (9)	C9—Fe1—C7—C6	−80.62 (12)
C2—Fe1—C1—C5	118.97 (12)	C3—Fe1—C7—C6	170.76 (10)
C8—Fe1—C1—C5	164.66 (15)	C4—Fe1—C7—C6	−152.1 (2)
C10—Fe1—C1—C5	−72.49 (11)	C5—Fe1—C7—C8	165.24 (15)
C9—Fe1—C1—C5	−34.5 (3)	C6—Fe1—C7—C8	117.97 (16)
C3—Fe1—C1—C5	80.72 (10)	C1—Fe1—C7—C8	−156.81 (10)
C4—Fe1—C1—C5	37.56 (9)	C2—Fe1—C7—C8	−113.21 (11)
C5—Fe1—C1—C11	117.88 (15)	C10—Fe1—C7—C8	80.63 (12)
C7—Fe1—C1—C11	−39.89 (15)	C9—Fe1—C7—C8	37.35 (11)
C6—Fe1—C1—C11	3.50 (14)	C3—Fe1—C7—C8	−71.27 (13)
C2—Fe1—C1—C11	−123.14 (16)	C4—Fe1—C7—C8	−34.1 (3)
C8—Fe1—C1—C11	−77.5 (2)	C6—C7—C8—C9	0.7 (2)
C10—Fe1—C1—C11	45.39 (15)	Fe1—C7—C8—C9	−59.68 (12)
C9—Fe1—C1—C11	83.4 (3)	C6—C7—C8—Fe1	60.40 (11)
C3—Fe1—C1—C11	−161.40 (14)	C5—Fe1—C8—C9	−41.7 (3)
C4—Fe1—C1—C11	155.44 (14)	C7—Fe1—C8—C9	119.15 (17)
C5—C1—C2—C3	1.11 (16)	C6—Fe1—C8—C9	81.09 (12)
C11—C1—C2—C3	177.67 (14)	C1—Fe1—C8—C9	172.06 (13)
Fe1—C1—C2—C3	60.12 (11)	C2—Fe1—C8—C9	−155.32 (11)
C5—C1—C2—Fe1	−59.02 (9)	C10—Fe1—C8—C9	37.49 (11)
C11—C1—C2—Fe1	117.55 (14)	C3—Fe1—C8—C9	−112.78 (12)
C5—Fe1—C2—C3	−79.95 (12)	C4—Fe1—C8—C9	−72.35 (14)
C7—Fe1—C2—C3	125.52 (12)	C5—Fe1—C8—C7	−160.81 (19)
C6—Fe1—C2—C3	165.99 (11)	C6—Fe1—C8—C7	−38.06 (11)
C1—Fe1—C2—C3	−118.15 (15)	C1—Fe1—C8—C7	52.9 (2)
C8—Fe1—C2—C3	82.07 (14)	C2—Fe1—C8—C7	85.53 (12)
C10—Fe1—C2—C3	−160.6 (3)	C10—Fe1—C8—C7	−81.65 (12)
C9—Fe1—C2—C3	46.7 (2)	C9—Fe1—C8—C7	−119.15 (17)
C4—Fe1—C2—C3	−36.51 (12)	C3—Fe1—C8—C7	128.07 (11)
C5—Fe1—C2—C1	38.20 (9)	C4—Fe1—C8—C7	168.50 (11)
C7—Fe1—C2—C1	−116.33 (10)	C7—C8—C9—C10	−0.6 (2)
C6—Fe1—C2—C1	−75.85 (12)	Fe1—C8—C9—C10	−59.83 (12)
C8—Fe1—C2—C1	−159.77 (9)	C7—C8—C9—Fe1	59.27 (12)
C10—Fe1—C2—C1	−42.5 (3)	C5—Fe1—C9—C10	−75.83 (13)
C9—Fe1—C2—C1	164.85 (14)	C7—Fe1—C9—C10	81.10 (12)
C3—Fe1—C2—C1	118.15 (15)	C6—Fe1—C9—C10	37.52 (10)
C4—Fe1—C2—C1	81.65 (10)	C1—Fe1—C9—C10	−48.7 (3)
C1—C2—C3—C4	−0.84 (18)	C2—Fe1—C9—C10	170.52 (14)
Fe1—C2—C3—C4	58.96 (11)	C8—Fe1—C9—C10	118.98 (17)
C1—C2—C3—Fe1	−59.80 (10)	C3—Fe1—C9—C10	−157.08 (12)
C5—Fe1—C3—C4	−37.38 (10)	C4—Fe1—C9—C10	−115.66 (12)
C7—Fe1—C3—C4	164.07 (11)	C5—Fe1—C9—C8	165.18 (11)
C6—Fe1—C3—C4	−170.8 (3)	C7—Fe1—C9—C8	−37.88 (11)
C1—Fe1—C3—C4	−82.09 (11)	C6—Fe1—C9—C8	−81.46 (12)
C2—Fe1—C3—C4	−120.59 (16)	C1—Fe1—C9—C8	−167.6 (2)
C8—Fe1—C3—C4	123.87 (11)	C2—Fe1—C9—C8	51.5 (2)
C10—Fe1—C3—C4	50.2 (2)	C10—Fe1—C9—C8	−118.98 (17)
C9—Fe1—C3—C4	81.82 (12)	C3—Fe1—C9—C8	83.94 (14)
C5—Fe1—C3—C2	83.21 (11)	C4—Fe1—C9—C8	125.36 (12)
C7—Fe1—C3—C2	−75.34 (14)	C8—C9—C10—C6	0.17 (19)
C6—Fe1—C3—C2	−50.2 (3)	Fe1—C9—C10—C6	−59.58 (11)
C1—Fe1—C3—C2	38.50 (10)	C8—C9—C10—Fe1	59.76 (12)
C8—Fe1—C3—C2	−115.55 (12)	C7—C6—C10—C9	0.28 (18)
C10—Fe1—C3—C2	170.78 (14)	Fe1—C6—C10—C9	59.78 (11)
C9—Fe1—C3—C2	−157.59 (11)	C7—C6—C10—Fe1	−59.50 (11)
C4—Fe1—C3—C2	120.59 (16)	C5—Fe1—C10—C9	123.38 (11)
C2—C3—C4—C5	0.24 (18)	C7—Fe1—C10—C9	−81.81 (12)
Fe1—C3—C4—C5	58.70 (10)	C6—Fe1—C10—C9	−119.21 (15)
C2—C3—C4—Fe1	−58.46 (11)	C1—Fe1—C10—C9	164.91 (10)
C5—Fe1—C4—C3	119.75 (14)	C2—Fe1—C10—C9	−160.6 (3)
C7—Fe1—C4—C3	−48.2 (3)	C8—Fe1—C10—C9	−37.63 (11)
C6—Fe1—C4—C3	174.93 (14)	C3—Fe1—C10—C9	46.4 (2)
C1—Fe1—C4—C3	81.33 (10)	C4—Fe1—C10—C9	80.61 (13)
C2—Fe1—C4—C3	37.14 (10)	C5—Fe1—C10—C6	−117.41 (10)
C8—Fe1—C4—C3	−74.61 (12)	C7—Fe1—C10—C6	37.40 (10)
C10—Fe1—C4—C3	−155.39 (10)	C1—Fe1—C10—C6	−75.88 (12)
C9—Fe1—C4—C3	−114.23 (11)	C2—Fe1—C10—C6	−41.4 (3)
C7—Fe1—C4—C5	−168.0 (2)	C8—Fe1—C10—C6	81.58 (11)
C6—Fe1—C4—C5	55.18 (19)	C9—Fe1—C10—C6	119.21 (15)
C1—Fe1—C4—C5	−38.42 (9)	C3—Fe1—C10—C6	165.63 (15)
C2—Fe1—C4—C5	−82.61 (10)	C4—Fe1—C10—C6	−160.18 (10)
C8—Fe1—C4—C5	165.64 (10)	C19—N1—C11—O1	13.67 (19)
C10—Fe1—C4—C5	84.86 (11)	C12—N1—C11—O1	−134.58 (14)
C9—Fe1—C4—C5	126.02 (10)	C19—N1—C11—C1	−166.52 (12)
C3—Fe1—C4—C5	−119.75 (14)	C12—N1—C11—C1	45.23 (16)
C3—C4—C5—C1	0.46 (17)	C2—C1—C11—O1	−156.27 (14)
Fe1—C4—C5—C1	59.60 (10)	C5—C1—C11—O1	19.8 (2)
C3—C4—C5—Fe1	−59.14 (12)	Fe1—C1—C11—O1	−66.65 (18)
C2—C1—C5—C4	−0.98 (16)	C2—C1—C11—N1	23.9 (2)
C11—C1—C5—C4	−177.72 (13)	C5—C1—C11—N1	−160.03 (12)
Fe1—C1—C5—C4	−60.21 (10)	Fe1—C1—C11—N1	113.55 (11)
C2—C1—C5—Fe1	59.24 (10)	C19—N1—C12—O2	−113.74 (16)
C11—C1—C5—Fe1	−117.51 (12)	C11—N1—C12—O2	36.58 (19)
C7—Fe1—C5—C4	171.38 (16)	C19—N1—C12—C13	68.71 (16)
C6—Fe1—C5—C4	−154.92 (10)	C11—N1—C12—C13	−140.97 (13)
C1—Fe1—C5—C4	118.85 (13)	O2—C12—C13—C14	−159.20 (16)
C2—Fe1—C5—C4	80.96 (10)	N1—C12—C13—C14	18.2 (2)
C8—Fe1—C5—C4	−40.4 (3)	O2—C12—C13—C18	17.1 (2)
C10—Fe1—C5—C4	−112.88 (11)	N1—C12—C13—C18	−165.53 (12)
C9—Fe1—C5—C4	−71.97 (12)	C18—C13—C14—C15	−0.2 (2)
C3—Fe1—C5—C4	37.05 (9)	C12—C13—C14—C15	175.99 (15)
C7—Fe1—C5—C1	52.53 (19)	C13—C14—C15—C16	0.7 (3)
C6—Fe1—C5—C1	86.23 (10)	C14—C15—C16—C17	−0.2 (3)
C2—Fe1—C5—C1	−37.90 (8)	C15—C16—C17—C18	−0.6 (3)
C8—Fe1—C5—C1	−159.3 (2)	C16—C17—C18—C13	1.1 (3)
C10—Fe1—C5—C1	128.27 (9)	C14—C13—C18—C17	−0.6 (2)
C9—Fe1—C5—C1	169.18 (9)	C12—C13—C18—C17	−177.01 (15)
C3—Fe1—C5—C1	−81.80 (9)	C11—N1—C19—O3	−136.69 (15)
C4—Fe1—C5—C1	−118.85 (13)	C12—N1—C19—O3	12.3 (2)
C5—Fe1—C6—C7	−159.55 (10)	C11—N1—C19—C20	46.64 (18)
C1—Fe1—C6—C7	−114.76 (11)	C12—N1—C19—C20	−164.41 (13)
C2—Fe1—C6—C7	−71.92 (13)	O3—C19—C20—C21	−148.83 (16)
C8—Fe1—C6—C7	38.52 (11)	N1—C19—C20—C21	27.7 (2)
C10—Fe1—C6—C7	119.42 (15)	O3—C19—C20—C25	26.5 (2)
C9—Fe1—C6—C7	82.06 (12)	N1—C19—C20—C25	−156.95 (14)
C3—Fe1—C6—C7	−31.6 (3)	C25—C20—C21—C22	0.0 (2)
C4—Fe1—C6—C7	161.93 (15)	C19—C20—C21—C22	175.18 (15)
C5—Fe1—C6—C10	81.04 (12)	C20—C21—C22—C23	1.1 (3)
C7—Fe1—C6—C10	−119.42 (15)	C21—C22—C23—C24	−1.3 (3)
C1—Fe1—C6—C10	125.82 (10)	C22—C23—C24—C25	0.4 (3)
C2—Fe1—C6—C10	168.66 (10)	C23—C24—C25—C20	0.6 (3)
C8—Fe1—C6—C10	−80.90 (11)	C21—C20—C25—C24	−0.8 (3)
C9—Fe1—C6—C10	−37.36 (10)	C19—C20—C25—C24	−176.26 (17)
C3—Fe1—C6—C10	−151.0 (3)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C6–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1ⁱ	0.93	2.56	3.241 (2)	131
C15—H15···Cg2ⁱⁱ	0.93	2.97	3.528 (2)	120

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Fe(C₅H₅)(C₂₀H₁₄NO₃)]
M_r	437.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	10.8699 (4), 11.3387 (4), 19.6264 (7)
β (°)	122.133 (2)
V (Å³)	2048.42 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.76
Crystal size (mm)	0.56 × 0.53 × 0.43

Data collection
Diffractometer	Oxford Diffraction KM-4/Xcalibur diffractometer with a Sapphire3 detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.910, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	14704, 5867, 3472
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.068, 0.93
No. of reflections	5867
No. of parameters	271
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.24

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 1999), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C6–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1ⁱ	0.93	2.56	3.241 (2)	131
C15—H15···Cg2ⁱⁱ	0.93	2.97	3.528 (2)	120

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2.

Acknowledgements

This research was supported by the Ministry of Science, Education and Sports of the Republic of Croatia (grant Nos. 058–1191344-3122 and 119–1193079-3069).

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
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Volume 67| Part 5| May 2011| Page m610

doi:10.1107/S1600536811013754

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