(S,R,Rp)-N,N-Dimethyl-1-{2-[(1-phenyl­ethyl)amino­meth­yl]ferrocen­yl}ethanamine

Zheng, X.-L.; Liu, J.-T.

doi:10.1107/S1600536809008861

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page m432

doi:10.1107/S1600536809008861

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(S,R,Rp)-N,N-Dimethyl-1-{2-[(1-phenylethyl)aminomethyl]ferrocenyl}ethanamine

Xiu-Li Zheng ^a and Jin-Ting Liu ^a ^*

^aSchool of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China
^*Correspondence e-mail: jintliu@sdu.edu.cn

(Received 7 March 2009; accepted 11 March 2009; online 25 March 2009)

The title chiral ferrocene compound, [Fe(C₅H₅)(C₁₈H₂₅N₂)], contains one planar and two central chiral centers. It is of interest with respect to asymmetric catalysis. The absolute configuration of the planar chirality is Rp at the ferrocene group and those of the two C chiral centers are R at the CH carbon of the ethanamine unit and S at the CH carbon of the phenylethylamino substituent. In the ferrocenyl unit, the cyclopentadienyl (Cp) rings are planar, with maximum deviations of 0.002 (2) Å for the substituted and 0.008 (3) Å for the unsubstituted Cp ring. The dihedral angle between the ring planes is 2.12 (15)° and the rings are twisted slightly from an eclipsed conformation by 7.06–7.60°.

Related literature

For background to the chemistry of chiral ferrocene complexes, see: Togni (1996 ); Nishibayashi et al. (1996 ). For their use in asymmetric synthesis, see: Togni et al. (1994 ); Dai et al. (2003 ). For the potential of these compounds as ligands in asymmetric catalysis, see Nikolaides et al. (2008 ). For a related structure, see: Liu et al. (2007 ).

Experimental

Crystal data

[Fe(C₅H₅)(C₁₈H₂₅N₂)]
M_r = 390.34
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.2081 (1) Å
b = 16.5546 (3) Å
c = 17.6747 (2) Å
V = 2109.07 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 293 K
0.37 × 0.24 × 0.22 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.776, T_max = 0.857
9974 measured reflections
4636 independent reflections
3817 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.085
S = 1.04
4636 reflections
240 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.32 e Å⁻³
Absolute structure: Flack (1983 ), 1859 Friedel pairs
Flack parameter: 0.010 (17)

Table 1
Selected torsion angles (°)

C1—Cg1—Cg2—C6	7.60	C4—Cg1—Cg2—C9	7.51
C2—Cg1—Cg2—C7	7.06	C5—Cg1—Cg2—C10	7.16
C3—Cg1—Cg2—C8	7.38
Cg1 is the centroid of the C1–C5 Cp ring and Cg2 is the centroid of the C6–C10 Cp ring.

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 and SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809008861/sj2592sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008861/sj2592Isup2.hkl

checkCIF report

Comment top

Ferrocenes with chirality are increasing their importance as chiral ligands in asymmetric catalysis (Togni, 1996, Nishibayashi et al., 1996). Especially ferrocene-based ligands incorporating both planar and central chirality are very important and some of them have already been applied in hydrogenation, allylic alkylation, and hydroboration (Togni et al., 1994, Dai et al., 2003). We are interested in the synthesis and the fascinating properties of chiral ferrocenes with both central and planar chirality (Liu et al., 2007).

The molecular structure of the title compound is shown in Fig. 1. The absolute configuration of the molecule is Rp at the ferrocene group, R and S at the asymmetric carbon atoms C11 and C16 respectively. Both N atoms have a pyramidal geometry with C—N—C angles between 112.0 (2) and 113.95 (18)°. The N lone-pairs are not involved in short intra- or intermolecular interactions. The two N atoms lie on the same coordination plane and may be available to coordinate to metal ions as bidentate ligands or to act as a ligand for asymmetric catalysis (Nikolaides et al., 2008).

In the molecule, the cyclopentadienyl(Cp) rings are almost parallel with a dihedral angle of 2.12 (15)° between the Cp ring planes. The Cp rings are twisted slightly from the eclipsed conformation. The values of torsion angles of the two Cp rings (C—Cg1—Cg2—C) are in the range 7.06–7.61° (Table 1). The benzene and Cp rings are obviously not parallel. The dihedral angle between the substituted Cp ring and the benzene ring is 53.59 (13)°. The Fe—C bond distances within the ferrocene group are in the range of 2.023 (3)–2.046 (2)Å for the unsubstituted cyclopentadienyl (Cp) ring (C1–C5) and 2.024 (2)–2.052 (2)Å for the substituted Cp ring (C6–C10).

Related literature top

For background to the chemistry of chiral ferrocene complexes, see: Togni (1996); Nishibayashi et al. (1996). For their use in asymmetric synthesis, see: Togni et al. (1994); Dai et al. (2003). For the potential of these compounds as ligands in asymmetric catalysis, see Nikolaides et al. (2008). For a related structure, see: Liu et al. (2007).

Experimental top

(R,Sp)-2-[1-(dimethylamino)ethyl]ferrocenylaldehyde(0.285 g, 1 mmol) was dissolved in anhydrous chloroform (30 ml) and (S)-1-phenylethanamine(0.121 mg, 1 mmol) was added. The red solution was refluxed under a nitrogen atmosphere for 2 h. After removing the solvent, the residue was dissolved in 30 ml dry methanol. 0.160 g NaBH₄ were added in small portions. The mixture was stirred for 30 min, then 20 ml, 1 mol/L aqueous NaOH was added and the mixture was extracted with CHCl₃(3×30 ml). The combined organic phase was dried with anhydrous NaCO₃. The solvent was evaporated in vacuo and the residue was purified by column chromatography (silica gel; hexane-ethyl acetate, 6:2) giving the title compound as yellow crystals (0.356 mg, 91.3%). Single crystals were grown from hexane- ethylacetate (2:1) solution at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005) and SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probabiltiy level and H atoms omitted.

(S,R,Rp)-N,N-Dimethyl-1-{2-[(1- phenylethyl)aminomethyl]ferrocenyl}ethanamine top

Crystal data top

[Fe(C₅H₅)(C₁₈H₂₅N₂)]	D_x = 1.229 Mg m⁻³
M_r = 390.34	Melting point: 355 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4056 reflections
a = 7.2081 (1) Å	θ = 2.5–26.6°
b = 16.5546 (3) Å	µ = 0.72 mm⁻¹
c = 17.6747 (2) Å	T = 293 K
V = 2109.07 (5) Å³	Prism, orange
Z = 4	0.37 × 0.24 × 0.22 mm
F(000) = 832

Data collection top

Bruker APEXII CCD area-detector diffractometer	4636 independent reflections
Radiation source: fine-focus sealed tube	3817 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
T_min = 0.776, T_max = 0.857	k = −17→21
9974 measured reflections	l = −22→19

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.032	w = 1/[σ²(F_o²) + (0.0459P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.085	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 0.31 e Å⁻³
4636 reflections	Δρ_min = −0.32 e Å⁻³
240 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0097 (9)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1859 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.010 (17)

Crystal data top

[Fe(C₅H₅)(C₁₈H₂₅N₂)]	V = 2109.07 (5) Å³
M_r = 390.34	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.2081 (1) Å	µ = 0.72 mm⁻¹
b = 16.5546 (3) Å	T = 293 K
c = 17.6747 (2) Å	0.37 × 0.24 × 0.22 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	4636 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3817 reflections with I > 2σ(I)
T_min = 0.776, T_max = 0.857	R_int = 0.022
9974 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.085	Δρ_max = 0.31 e Å⁻³
S = 1.04	Δρ_min = −0.32 e Å⁻³
4636 reflections	Absolute structure: Flack (1983), 1859 Friedel pairs
240 parameters	Absolute structure parameter: 0.010 (17)
0 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

	x	y	z	U_iso*/U_eq
C1	1.0099 (3)	0.12997 (16)	0.17507 (15)	0.0575 (6)
H1	1.0734	0.1596	0.2155	0.069*
C2	0.8903 (4)	0.06312 (16)	0.18440 (17)	0.0640 (7)
H2	0.8560	0.0375	0.2324	0.077*
C3	0.8321 (4)	0.03934 (17)	0.1114 (2)	0.0773 (8)
H3	0.7485	−0.0057	0.1000	0.093*
C4	0.9105 (4)	0.0916 (2)	0.05836 (17)	0.0750 (8)
H4	0.8926	0.0890	0.0035	0.090*
C5	1.0207 (3)	0.14668 (19)	0.09645 (15)	0.0633 (7)
H5	1.0932	0.1901	0.0731	0.076*
C6	0.6597 (3)	0.25943 (12)	0.18108 (11)	0.0425 (5)
C7	0.5401 (3)	0.19310 (12)	0.20037 (11)	0.0392 (4)
C8	0.4708 (3)	0.16030 (15)	0.13168 (14)	0.0525 (5)
H8	0.3871	0.1139	0.1273	0.063*
C9	0.5447 (3)	0.20488 (18)	0.07092 (13)	0.0609 (7)
H9	0.5200	0.1952	0.0172	0.073*
C10	0.6594 (3)	0.26565 (15)	0.10043 (13)	0.0564 (6)
H10	0.7289	0.3054	0.0707	0.068*
C11	0.7553 (4)	0.31317 (12)	0.23737 (12)	0.0550 (5)
H11	0.7953	0.2780	0.2789	0.066*
C12	0.9319 (4)	0.35294 (18)	0.2063 (2)	0.0882 (10)
H12A	0.9009	0.3859	0.1634	0.132*
H12B	1.0182	0.3118	0.1911	0.132*
H12C	0.9870	0.3860	0.2448	0.132*
C13	0.5480 (6)	0.4271 (2)	0.2146 (3)	0.1220 (15)
H13A	0.4445	0.4559	0.2354	0.183*
H13B	0.5093	0.3987	0.1699	0.183*
H13C	0.6447	0.4645	0.2017	0.183*
C14	0.6865 (6)	0.4093 (2)	0.3382 (2)	0.1248 (16)
H14A	0.7824	0.4469	0.3246	0.187*
H14B	0.7360	0.3695	0.3721	0.187*
H14C	0.5868	0.4377	0.3625	0.187*
C15	0.4913 (3)	0.16768 (12)	0.27843 (12)	0.0461 (5)
H15A	0.4376	0.1140	0.2772	0.055*
H15B	0.6029	0.1655	0.3091	0.055*
C16	0.3378 (4)	0.21395 (16)	0.39411 (14)	0.0633 (7)
H16	0.4616	0.2072	0.4161	0.076*
C17	0.2528 (6)	0.28883 (17)	0.42764 (16)	0.1024 (11)
H17A	0.3336	0.3340	0.4191	0.154*
H17B	0.2356	0.2813	0.4810	0.154*
H17C	0.1349	0.2989	0.4042	0.154*
C18	0.2250 (3)	0.13936 (13)	0.41281 (11)	0.0509 (5)
C19	0.0457 (4)	0.12998 (17)	0.38743 (14)	0.0650 (7)
H19	−0.0058	0.1695	0.3565	0.078*
C20	−0.0590 (4)	0.06375 (19)	0.40671 (17)	0.0758 (8)
H20	−0.1794	0.0589	0.3883	0.091*
C21	0.0113 (5)	0.00555 (17)	0.45218 (17)	0.0759 (8)
H21	−0.0612	−0.0384	0.4663	0.091*
C22	0.1906 (5)	0.01226 (19)	0.47722 (16)	0.0807 (10)
H22	0.2409	−0.0280	0.5077	0.097*
C23	0.2971 (4)	0.07837 (17)	0.45754 (14)	0.0668 (7)
H23	0.4189	0.0819	0.4746	0.080*
Fe1	0.75311 (4)	0.155327 (15)	0.131986 (14)	0.04165 (10)
N1	0.3592 (3)	0.22386 (11)	0.31260 (10)	0.0502 (5)
H1A	0.2996	0.2595	0.2869	0.060*
N2	0.6172 (4)	0.36957 (12)	0.27003 (14)	0.0728 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0306 (11)	0.0782 (18)	0.0636 (15)	0.0089 (11)	−0.0034 (10)	−0.0003 (12)
C2	0.0506 (14)	0.0629 (15)	0.0785 (17)	0.0228 (12)	0.0044 (12)	0.0085 (13)
C3	0.0554 (15)	0.0600 (16)	0.116 (2)	0.0148 (12)	−0.0005 (16)	−0.0323 (16)
C4	0.0477 (15)	0.109 (2)	0.0685 (17)	0.0210 (15)	0.0076 (13)	−0.0260 (17)
C5	0.0323 (11)	0.0912 (19)	0.0665 (15)	0.0067 (12)	0.0094 (11)	−0.0015 (15)
C6	0.0398 (11)	0.0395 (11)	0.0483 (11)	0.0034 (9)	0.0055 (9)	0.0042 (9)
C7	0.0287 (10)	0.0402 (10)	0.0485 (11)	0.0030 (8)	0.0048 (8)	−0.0034 (9)
C8	0.0258 (9)	0.0647 (13)	0.0668 (14)	0.0042 (9)	−0.0048 (10)	−0.0160 (15)
C9	0.0439 (13)	0.0933 (19)	0.0457 (13)	0.0131 (13)	−0.0078 (11)	−0.0003 (13)
C10	0.0504 (13)	0.0651 (15)	0.0538 (13)	0.0086 (11)	0.0042 (12)	0.0160 (12)
C11	0.0559 (12)	0.0421 (10)	0.0669 (13)	−0.0068 (12)	−0.0005 (15)	−0.0005 (9)
C12	0.070 (2)	0.0742 (19)	0.120 (3)	−0.0304 (15)	0.0168 (18)	−0.0116 (19)
C13	0.143 (4)	0.065 (2)	0.157 (4)	0.043 (2)	0.039 (3)	0.013 (2)
C14	0.122 (3)	0.115 (3)	0.137 (3)	−0.041 (2)	0.029 (3)	−0.079 (2)
C15	0.0461 (12)	0.0376 (11)	0.0545 (12)	0.0032 (9)	0.0117 (10)	0.0045 (9)
C16	0.0703 (16)	0.0692 (16)	0.0503 (13)	−0.0099 (13)	0.0105 (12)	−0.0073 (12)
C17	0.148 (3)	0.0723 (18)	0.0865 (19)	−0.013 (3)	0.045 (3)	−0.0284 (15)
C18	0.0549 (15)	0.0620 (13)	0.0360 (9)	0.0027 (11)	0.0093 (10)	−0.0014 (8)
C19	0.0621 (16)	0.0756 (17)	0.0574 (15)	0.0046 (13)	0.0012 (12)	0.0194 (12)
C20	0.0616 (17)	0.092 (2)	0.0741 (18)	−0.0082 (15)	0.0021 (14)	0.0083 (16)
C21	0.090 (2)	0.0652 (17)	0.0727 (17)	−0.0054 (15)	0.0308 (17)	0.0090 (14)
C22	0.098 (3)	0.0750 (18)	0.0695 (17)	0.0160 (16)	0.0104 (15)	0.0252 (14)
C23	0.0604 (18)	0.0846 (18)	0.0555 (13)	0.0105 (13)	0.0007 (12)	0.0056 (13)
Fe1	0.02711 (14)	0.05359 (17)	0.04423 (15)	0.00363 (15)	0.00133 (16)	−0.00439 (12)
N1	0.0546 (11)	0.0482 (10)	0.0477 (10)	0.0096 (8)	0.0138 (9)	0.0055 (8)
N2	0.0835 (16)	0.0471 (12)	0.0877 (15)	−0.0094 (11)	0.0198 (14)	−0.0162 (11)

Geometric parameters (Å, º) top

C1—C2	1.413 (4)	C12—H12A	0.9600
C1—C5	1.419 (4)	C12—H12B	0.9600
C1—Fe1	2.045 (2)	C12—H12C	0.9600
C1—H1	0.9800	C13—N2	1.454 (4)
C2—C3	1.412 (4)	C13—H13A	0.9600
C2—Fe1	2.041 (2)	C13—H13B	0.9600
C2—H2	0.9800	C13—H13C	0.9600
C3—C4	1.395 (4)	C14—N2	1.460 (4)
C3—Fe1	2.036 (3)	C14—H14A	0.9600
C3—H3	0.9800	C14—H14B	0.9600
C4—C5	1.384 (4)	C14—H14C	0.9600
C4—Fe1	2.024 (3)	C15—N1	1.462 (2)
C4—H4	0.9800	C15—H15A	0.9700
C5—Fe1	2.033 (2)	C15—H15B	0.9700
C5—H5	0.9800	C16—N1	1.458 (3)
C6—C10	1.429 (3)	C16—C17	1.504 (4)
C6—C7	1.437 (3)	C16—C18	1.515 (3)
C6—C11	1.502 (3)	C16—H16	0.9800
C6—Fe1	2.043 (2)	C17—H17A	0.9600
C7—C8	1.421 (3)	C17—H17B	0.9600
C7—C15	1.485 (3)	C17—H17C	0.9600
C7—Fe1	2.0514 (18)	C18—C19	1.377 (3)
C8—C9	1.408 (4)	C18—C23	1.384 (3)
C8—Fe1	2.0368 (19)	C19—C20	1.374 (4)
C8—H8	0.9800	C19—H19	0.9300
C9—C10	1.403 (4)	C20—C21	1.353 (4)
C9—Fe1	2.024 (2)	C20—H20	0.9300
C9—H9	0.9800	C21—C22	1.371 (4)
C10—Fe1	2.025 (2)	C21—H21	0.9300
C10—H10	0.9800	C22—C23	1.381 (4)
C11—N2	1.482 (3)	C22—H22	0.9300
C11—C12	1.535 (3)	C23—H23	0.9300
C11—H11	0.9800	N1—H1A	0.8600

C2—C1—C5	107.5 (2)	C7—C15—H15A	109.4
C2—C1—Fe1	69.61 (14)	N1—C15—H15B	109.4
C5—C1—Fe1	69.18 (14)	C7—C15—H15B	109.4
C2—C1—H1	126.3	H15A—C15—H15B	108.0
C5—C1—H1	126.3	N1—C16—C17	109.9 (2)
Fe1—C1—H1	126.3	N1—C16—C18	111.36 (19)
C3—C2—C1	107.0 (3)	C17—C16—C18	111.5 (2)
C3—C2—Fe1	69.52 (16)	N1—C16—H16	108.0
C1—C2—Fe1	69.94 (14)	C17—C16—H16	108.0
C3—C2—H2	126.5	C18—C16—H16	108.0
C1—C2—H2	126.5	C16—C17—H17A	109.5
Fe1—C2—H2	126.5	C16—C17—H17B	109.5
C4—C3—C2	108.7 (3)	H17A—C17—H17B	109.5
C4—C3—Fe1	69.44 (17)	C16—C17—H17C	109.5
C2—C3—Fe1	69.94 (14)	H17A—C17—H17C	109.5
C4—C3—H3	125.6	H17B—C17—H17C	109.5
C2—C3—H3	125.6	C19—C18—C23	117.2 (2)
Fe1—C3—H3	125.6	C19—C18—C16	121.6 (2)
C5—C4—C3	108.3 (3)	C23—C18—C16	121.2 (2)
C5—C4—Fe1	70.42 (15)	C20—C19—C18	121.7 (3)
C3—C4—Fe1	70.36 (15)	C20—C19—H19	119.2
C5—C4—H4	125.8	C18—C19—H19	119.2
C3—C4—H4	125.8	C21—C20—C19	120.6 (3)
Fe1—C4—H4	125.8	C21—C20—H20	119.7
C4—C5—C1	108.5 (3)	C19—C20—H20	119.7
C4—C5—Fe1	69.67 (14)	C20—C21—C22	119.2 (3)
C1—C5—Fe1	70.10 (13)	C20—C21—H21	120.4
C4—C5—H5	125.8	C22—C21—H21	120.4
C1—C5—H5	125.8	C21—C22—C23	120.5 (3)
Fe1—C5—H5	125.8	C21—C22—H22	119.8
C10—C6—C7	106.91 (19)	C23—C22—H22	119.8
C10—C6—C11	128.2 (2)	C22—C23—C18	120.9 (3)
C7—C6—C11	124.79 (18)	C22—C23—H23	119.6
C10—C6—Fe1	68.76 (13)	C18—C23—H23	119.6
C7—C6—Fe1	69.75 (11)	C4—Fe1—C9	106.55 (12)
C11—C6—Fe1	129.02 (16)	C4—Fe1—C10	118.70 (12)
C8—C7—C6	107.48 (18)	C9—Fe1—C10	40.54 (10)
C8—C7—C15	127.04 (19)	C4—Fe1—C5	39.90 (11)
C6—C7—C15	125.40 (18)	C9—Fe1—C5	124.61 (11)
C8—C7—Fe1	69.11 (11)	C10—Fe1—C5	107.13 (11)
C6—C7—Fe1	69.16 (11)	C4—Fe1—C3	40.20 (12)
C15—C7—Fe1	129.67 (14)	C9—Fe1—C3	119.66 (12)
C9—C8—C7	108.6 (2)	C10—Fe1—C3	153.46 (13)
C9—C8—Fe1	69.22 (13)	C5—Fe1—C3	67.24 (13)
C7—C8—Fe1	70.22 (11)	C4—Fe1—C8	125.42 (11)
C9—C8—H8	125.7	C9—Fe1—C8	40.57 (10)
C7—C8—H8	125.7	C10—Fe1—C8	68.27 (10)
Fe1—C8—H8	125.7	C5—Fe1—C8	161.76 (11)
C10—C9—C8	108.4 (2)	C3—Fe1—C8	108.50 (11)
C10—C9—Fe1	69.80 (13)	C4—Fe1—C2	68.29 (12)
C8—C9—Fe1	70.22 (13)	C9—Fe1—C2	154.81 (11)
C10—C9—H9	125.8	C10—Fe1—C2	163.91 (11)
C8—C9—H9	125.8	C5—Fe1—C2	68.16 (12)
Fe1—C9—H9	125.8	C3—Fe1—C2	40.54 (12)
C9—C10—C6	108.7 (2)	C8—Fe1—C2	121.03 (11)
C9—C10—Fe1	69.66 (14)	C4—Fe1—C6	153.86 (12)
C6—C10—Fe1	70.11 (13)	C9—Fe1—C6	68.90 (9)
C9—C10—H10	125.7	C10—Fe1—C6	41.12 (9)
C6—C10—H10	125.7	C5—Fe1—C6	120.20 (11)
Fe1—C10—H10	125.7	C3—Fe1—C6	164.47 (11)
N2—C11—C6	108.8 (2)	C8—Fe1—C6	68.77 (9)
N2—C11—C12	115.25 (19)	C2—Fe1—C6	126.70 (10)
C6—C11—C12	113.4 (2)	C4—Fe1—C1	67.97 (11)
N2—C11—H11	106.2	C9—Fe1—C1	162.51 (11)
C6—C11—H11	106.2	C10—Fe1—C1	126.11 (11)
C12—C11—H11	106.2	C5—Fe1—C1	40.72 (10)
C11—C12—H12A	109.5	C3—Fe1—C1	67.64 (11)
C11—C12—H12B	109.5	C8—Fe1—C1	156.02 (11)
H12A—C12—H12B	109.5	C2—Fe1—C1	40.45 (11)
C11—C12—H12C	109.5	C6—Fe1—C1	108.25 (10)
H12A—C12—H12C	109.5	C4—Fe1—C7	163.22 (11)
H12B—C12—H12C	109.5	C9—Fe1—C7	68.60 (9)
N2—C13—H13A	109.5	C10—Fe1—C7	68.78 (9)
N2—C13—H13B	109.5	C5—Fe1—C7	155.95 (10)
H13A—C13—H13B	109.5	C3—Fe1—C7	127.02 (11)
N2—C13—H13C	109.5	C8—Fe1—C7	40.67 (9)
H13A—C13—H13C	109.5	C2—Fe1—C7	108.85 (10)
H13B—C13—H13C	109.5	C6—Fe1—C7	41.09 (8)
N2—C14—H14A	109.5	C1—Fe1—C7	121.37 (9)
N2—C14—H14B	109.5	C16—N1—C15	113.94 (19)
H14A—C14—H14B	109.5	C16—N1—H1A	123.0
N2—C14—H14C	109.5	C15—N1—H1A	123.0
H14A—C14—H14C	109.5	C13—N2—C14	112.2 (3)
H14B—C14—H14C	109.5	C13—N2—C11	112.3 (2)
N1—C15—C7	110.97 (16)	C14—N2—C11	112.0 (3)
N1—C15—H15A	109.4

C5—C1—C2—C3	0.9 (3)	C1—C5—Fe1—C7	49.8 (3)
Fe1—C1—C2—C3	59.90 (17)	C2—C3—Fe1—C4	120.1 (2)
C5—C1—C2—Fe1	−59.04 (17)	C4—C3—Fe1—C9	80.4 (2)
C1—C2—C3—C4	−1.4 (3)	C2—C3—Fe1—C9	−159.44 (15)
Fe1—C2—C3—C4	58.77 (19)	C4—C3—Fe1—C10	45.2 (3)
C1—C2—C3—Fe1	−60.17 (17)	C2—C3—Fe1—C10	165.3 (2)
C2—C3—C4—C5	1.4 (3)	C4—C3—Fe1—C5	−37.59 (16)
Fe1—C3—C4—C5	60.48 (19)	C2—C3—Fe1—C5	82.53 (18)
C2—C3—C4—Fe1	−59.08 (18)	C4—C3—Fe1—C8	123.44 (17)
C3—C4—C5—C1	−0.9 (3)	C2—C3—Fe1—C8	−116.43 (17)
Fe1—C4—C5—C1	59.58 (18)	C4—C3—Fe1—C2	−120.1 (2)
C3—C4—C5—Fe1	−60.44 (19)	C4—C3—Fe1—C6	−159.4 (3)
C2—C1—C5—C4	0.0 (3)	C2—C3—Fe1—C6	−39.3 (5)
Fe1—C1—C5—C4	−59.32 (18)	C4—C3—Fe1—C1	−81.85 (18)
C2—C1—C5—Fe1	59.31 (17)	C2—C3—Fe1—C1	38.27 (16)
C10—C6—C7—C8	0.3 (2)	C4—C3—Fe1—C7	164.90 (15)
C11—C6—C7—C8	177.2 (2)	C2—C3—Fe1—C7	−74.98 (19)
Fe1—C6—C7—C8	−58.68 (13)	C9—C8—Fe1—C4	−72.9 (2)
C10—C6—C7—C15	−176.47 (19)	C7—C8—Fe1—C4	167.16 (16)
C11—C6—C7—C15	0.5 (3)	C7—C8—Fe1—C9	−119.9 (2)
Fe1—C6—C7—C15	124.58 (19)	C9—C8—Fe1—C10	37.60 (15)
C10—C6—C7—Fe1	58.96 (15)	C7—C8—Fe1—C10	−82.29 (14)
C11—C6—C7—Fe1	−124.1 (2)	C9—C8—Fe1—C5	−41.1 (4)
C6—C7—C8—C9	−0.1 (2)	C7—C8—Fe1—C5	−161.0 (3)
C15—C7—C8—C9	176.6 (2)	C9—C8—Fe1—C3	−114.31 (18)
Fe1—C7—C8—C9	−58.76 (15)	C7—C8—Fe1—C3	125.79 (15)
C6—C7—C8—Fe1	58.71 (14)	C9—C8—Fe1—C2	−157.09 (16)
C15—C7—C8—Fe1	−124.6 (2)	C7—C8—Fe1—C2	83.01 (16)
C7—C8—C9—C10	−0.2 (3)	C9—C8—Fe1—C6	81.95 (16)
Fe1—C8—C9—C10	−59.58 (17)	C7—C8—Fe1—C6	−37.95 (12)
C7—C8—C9—Fe1	59.38 (15)	C9—C8—Fe1—C1	169.3 (2)
C8—C9—C10—C6	0.4 (3)	C7—C8—Fe1—C1	49.4 (3)
Fe1—C9—C10—C6	−59.47 (16)	C9—C8—Fe1—C7	119.9 (2)
C8—C9—C10—Fe1	59.84 (17)	C3—C2—Fe1—C4	−36.93 (17)
C7—C6—C10—C9	−0.4 (3)	C1—C2—Fe1—C4	81.06 (18)
C11—C6—C10—C9	−177.2 (2)	C3—C2—Fe1—C9	45.8 (3)
Fe1—C6—C10—C9	59.19 (17)	C1—C2—Fe1—C9	163.8 (2)
C7—C6—C10—Fe1	−59.59 (14)	C3—C2—Fe1—C10	−155.9 (3)
C11—C6—C10—Fe1	123.6 (2)	C1—C2—Fe1—C10	−37.9 (4)
C10—C6—C11—N2	101.0 (3)	C3—C2—Fe1—C5	−80.05 (19)
C7—C6—C11—N2	−75.2 (3)	C1—C2—Fe1—C5	37.95 (16)
Fe1—C6—C11—N2	−166.40 (16)	C1—C2—Fe1—C3	118.0 (2)
C10—C6—C11—C12	−28.7 (3)	C3—C2—Fe1—C8	82.3 (2)
C7—C6—C11—C12	155.1 (2)	C1—C2—Fe1—C8	−159.69 (15)
Fe1—C6—C11—C12	63.9 (3)	C3—C2—Fe1—C6	167.79 (17)
C8—C7—C15—N1	−101.7 (2)	C1—C2—Fe1—C6	−74.21 (19)
C6—C7—C15—N1	74.4 (3)	C3—C2—Fe1—C1	−118.0 (2)
Fe1—C7—C15—N1	165.68 (15)	C3—C2—Fe1—C7	125.43 (17)
N1—C16—C18—C19	−59.7 (3)	C1—C2—Fe1—C7	−116.57 (16)
C17—C16—C18—C19	63.5 (3)	C10—C6—Fe1—C4	47.4 (3)
N1—C16—C18—C23	121.7 (2)	C7—C6—Fe1—C4	165.9 (2)
C17—C16—C18—C23	−115.2 (3)	C11—C6—Fe1—C4	−75.2 (3)
C23—C18—C19—C20	1.2 (4)	C10—C6—Fe1—C9	−37.20 (15)
C16—C18—C19—C20	−177.5 (2)	C7—C6—Fe1—C9	81.22 (13)
C18—C19—C20—C21	0.6 (4)	C11—C6—Fe1—C9	−159.8 (2)
C19—C20—C21—C22	−1.8 (5)	C7—C6—Fe1—C10	118.42 (19)
C20—C21—C22—C23	1.3 (4)	C11—C6—Fe1—C10	−122.6 (2)
C21—C22—C23—C18	0.5 (4)	C10—C6—Fe1—C5	81.47 (17)
C19—C18—C23—C22	−1.7 (4)	C7—C6—Fe1—C5	−160.10 (13)
C16—C18—C23—C22	177.0 (2)	C11—C6—Fe1—C5	−41.2 (2)
C5—C4—Fe1—C9	124.64 (19)	C10—C6—Fe1—C3	−163.6 (3)
C3—C4—Fe1—C9	−116.63 (18)	C7—C6—Fe1—C3	−45.1 (4)
C5—C4—Fe1—C10	82.5 (2)	C11—C6—Fe1—C3	73.8 (4)
C3—C4—Fe1—C10	−158.81 (17)	C10—C6—Fe1—C8	−80.85 (16)
C3—C4—Fe1—C5	118.7 (3)	C7—C6—Fe1—C8	37.57 (13)
C5—C4—Fe1—C3	−118.7 (3)	C11—C6—Fe1—C8	156.5 (2)
C5—C4—Fe1—C8	165.07 (16)	C10—C6—Fe1—C2	165.56 (16)
C3—C4—Fe1—C8	−76.2 (2)	C7—C6—Fe1—C2	−76.01 (15)
C5—C4—Fe1—C2	−81.49 (19)	C11—C6—Fe1—C2	42.9 (2)
C3—C4—Fe1—C2	37.24 (17)	C10—C6—Fe1—C1	124.46 (15)
C5—C4—Fe1—C6	48.9 (3)	C7—C6—Fe1—C1	−117.11 (13)
C3—C4—Fe1—C6	167.7 (2)	C11—C6—Fe1—C1	1.8 (2)
C5—C4—Fe1—C1	−37.75 (17)	C10—C6—Fe1—C7	−118.42 (19)
C3—C4—Fe1—C1	80.98 (18)	C11—C6—Fe1—C7	118.9 (2)
C5—C4—Fe1—C7	−164.8 (3)	C2—C1—Fe1—C4	−81.93 (19)
C3—C4—Fe1—C7	−46.1 (4)	C5—C1—Fe1—C4	37.02 (19)
C10—C9—Fe1—C4	−115.05 (17)	C2—C1—Fe1—C9	−156.7 (3)
C8—C9—Fe1—C4	125.64 (17)	C5—C1—Fe1—C9	−37.8 (4)
C8—C9—Fe1—C10	−119.3 (2)	C2—C1—Fe1—C10	167.83 (15)
C10—C9—Fe1—C5	−75.16 (18)	C5—C1—Fe1—C10	−73.2 (2)
C8—C9—Fe1—C5	165.53 (15)	C2—C1—Fe1—C5	−118.9 (2)
C10—C9—Fe1—C3	−156.65 (17)	C2—C1—Fe1—C3	−38.36 (18)
C8—C9—Fe1—C3	84.04 (18)	C5—C1—Fe1—C3	80.6 (2)
C10—C9—Fe1—C8	119.3 (2)	C2—C1—Fe1—C8	47.0 (3)
C10—C9—Fe1—C2	170.9 (2)	C5—C1—Fe1—C8	166.0 (2)
C8—C9—Fe1—C2	51.6 (3)	C5—C1—Fe1—C2	118.9 (2)
C10—C9—Fe1—C6	37.72 (14)	C2—C1—Fe1—C6	125.67 (16)
C8—C9—Fe1—C6	−81.60 (15)	C5—C1—Fe1—C6	−115.39 (17)
C10—C9—Fe1—C1	−46.1 (4)	C2—C1—Fe1—C7	82.42 (17)
C8—C9—Fe1—C1	−165.4 (3)	C5—C1—Fe1—C7	−158.63 (16)
C10—C9—Fe1—C7	81.95 (15)	C8—C7—Fe1—C4	−38.8 (4)
C8—C9—Fe1—C7	−37.36 (13)	C6—C7—Fe1—C4	−158.1 (4)
C9—C10—Fe1—C4	81.92 (18)	C15—C7—Fe1—C4	82.6 (4)
C6—C10—Fe1—C4	−158.28 (14)	C8—C7—Fe1—C9	37.27 (15)
C6—C10—Fe1—C9	119.8 (2)	C6—C7—Fe1—C9	−82.02 (14)
C9—C10—Fe1—C5	123.64 (15)	C15—C7—Fe1—C9	158.7 (2)
C6—C10—Fe1—C5	−116.56 (15)	C8—C7—Fe1—C10	80.94 (15)
C9—C10—Fe1—C3	50.4 (3)	C6—C7—Fe1—C10	−38.35 (13)
C6—C10—Fe1—C3	170.2 (2)	C15—C7—Fe1—C10	−157.7 (2)
C9—C10—Fe1—C8	−37.62 (14)	C8—C7—Fe1—C5	165.5 (2)
C6—C10—Fe1—C8	82.17 (15)	C6—C7—Fe1—C5	46.2 (3)
C9—C10—Fe1—C2	−166.0 (3)	C15—C7—Fe1—C5	−73.1 (3)
C6—C10—Fe1—C2	−46.2 (4)	C8—C7—Fe1—C3	−74.46 (18)
C9—C10—Fe1—C6	−119.8 (2)	C6—C7—Fe1—C3	166.25 (14)
C9—C10—Fe1—C1	164.45 (15)	C15—C7—Fe1—C3	46.9 (2)
C6—C10—Fe1—C1	−75.75 (18)	C6—C7—Fe1—C8	−119.29 (18)
C9—C10—Fe1—C7	−81.48 (14)	C15—C7—Fe1—C8	121.4 (2)
C6—C10—Fe1—C7	38.32 (13)	C8—C7—Fe1—C2	−116.01 (15)
C1—C5—Fe1—C4	−119.5 (3)	C6—C7—Fe1—C2	124.70 (14)
C4—C5—Fe1—C9	−73.4 (2)	C15—C7—Fe1—C2	5.4 (2)
C1—C5—Fe1—C9	167.07 (16)	C8—C7—Fe1—C6	119.29 (18)
C4—C5—Fe1—C10	−114.5 (2)	C15—C7—Fe1—C6	−119.3 (2)
C1—C5—Fe1—C10	125.96 (17)	C8—C7—Fe1—C1	−158.82 (15)
C4—C5—Fe1—C3	37.86 (19)	C6—C7—Fe1—C1	81.89 (15)
C1—C5—Fe1—C3	−81.7 (2)	C15—C7—Fe1—C1	−37.4 (2)
C4—C5—Fe1—C8	−42.1 (4)	C17—C16—N1—C15	161.4 (3)
C1—C5—Fe1—C8	−161.6 (3)	C18—C16—N1—C15	−74.6 (3)
C4—C5—Fe1—C2	81.8 (2)	C7—C15—N1—C16	−166.5 (2)
C1—C5—Fe1—C2	−37.71 (17)	C6—C11—N2—C13	−67.2 (3)
C4—C5—Fe1—C6	−157.39 (18)	C12—C11—N2—C13	61.4 (3)
C1—C5—Fe1—C6	83.07 (19)	C6—C11—N2—C14	165.4 (2)
C4—C5—Fe1—C1	119.5 (3)	C12—C11—N2—C14	−65.9 (3)
C4—C5—Fe1—C7	169.3 (2)

Experimental details

Crystal data
Chemical formula	[Fe(C₅H₅)(C₁₈H₂₅N₂)]
M_r	390.34
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	7.2081 (1), 16.5546 (3), 17.6747 (2)
V (Å³)	2109.07 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.72
Crystal size (mm)	0.37 × 0.24 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.776, 0.857
No. of measured, independent and observed [I > 2σ(I)] reflections	9974, 4636, 3817
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.085, 1.04
No. of reflections	4636
No. of parameters	240
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.32
Absolute structure	Flack (1983), 1859 Friedel pairs
Absolute structure parameter	0.010 (17)

Computer programs: , APEX2 (Bruker, 2005) and SAINT (Bruker, 2005), SAINT (Bruker, 2005), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999).

Table 1 top

Selected torsion angles (°)

C1—Cg1—Cg2—C6	7.60	C4—Cg1—Cg2—C9	7.51
C2—Cg1—Cg2—C7	7.06	C5—Cg1—Cg2—C10	7.16
C3—Cg1—Cg2—C8	7.38

Cg1 is the centroid of the C1–C5 Cp ring and Cg2 is the centroid of the C6–C10 Cp ring.

Acknowledgements

The authors thank the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry, for support of this work.

References

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