{(R,SFc,SFc)-2′′-Bromo-2-[1-(dimethyl­amino)­ethyl-κN]-1,1′′-biferrocene}trihydridoboron

Wang, Y.; Zirakzadeh, A.; Weissensteiner, W.; Mereiter, K.

doi:10.1107/S1600536811049270

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1806-m1807

https://doi.org/10.1107/S1600536811049270

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{(R,S_Fc,S_Fc)-2′′-Bromo-2-[1-(dimethylamino)ethyl-κN]-1,1′′-biferrocene}trihydridoboron

Yaping Wang,^a Afrooz Zirakzadeh,^b Walter Weissensteiner ^b and Kurt Mereiter ^c ^*

^aCapital Medical University, Beijing, No. 10 Xitoutiao, You An Men Beijing 100069, People's Republic of China, ^bInstitute of Organic Chemistry, University of Vienna, Währingerstrasse 38, A-1090 Vienna, Austria, and ^cInstitute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/164SC, A-1060 Vienna, Austria
^*Correspondence e-mail: kurt.mereiter@tuwien.ac.at

(Received 17 November 2011; accepted 18 November 2011; online 23 November 2011)

The title structure, [Fe₂(C₅H₅)₂(C₁₄H₁₉BBrN)], contains a chiral and asymmetrically 2,2′′-disubstituted biferrocene designed as precursor for enantioselective non-C₂-symmetric biferrocenyldiphosphine catalysts. The mean bond lengths in the biferrocene unit are Fe—C = 2.048 (10) Å and C—C = 1.427 (8) Å within the cyclopentadienyl rings. The B—N bond lengths of the BH₃ protected amine is 1.631 (3) Å. The interplanar angle between the two connected cyclopentadienyl rings is 54.29 (8)° and the corresponding Fe—Cg—Cg—Fe torsion angle is −52.5°. The conformation of the molecule is stabilized by an intramolecular C—H⋯Br interaction.

Related literature

For general information on ferrocene-based diphosphines and their applications in asymmetric catalysis, see: Togni (1996 ); Blaser et al. (2007 ); Dai & Hou (2010 ). For the synthesis, coordination behavior and use in asymmetric catalysis of ligands based on biferrocenes, see: Sawamura et al. (1991 ); Nettekoven et al. (2000 ); Xiao et al. (2002 ); Espino et al. (2009 ); Kuwano (2010 ). For synthetic aspects of the title compound, see: Wang et al. (2011 ).

Experimental

Crystal data

[Fe₂(C₅H₅)₂(C₁₄H₁₉BBrN)]
M_r = 533.90
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.8791 (2) Å
b = 9.2210 (2) Å
c = 27.1292 (6) Å
V = 2221.18 (9) Å³
Z = 4
Mo Kα radiation
μ = 3.12 mm⁻¹
T = 100 K
0.33 × 0.27 × 0.21 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.54, T_max = 0.75
34891 measured reflections
6489 independent reflections
6288 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.054
S = 1.07
6489 reflections
266 parameters
H-atom parameters constrained
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.31 e Å⁻³
Absolute structure: Flack (1983 ), 2807 Friedel pairs
Flack parameter: 0.002 (5)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C21—H21⋯Br1	1.00	2.79	3.7154 (17)	154

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811049270/bq2322sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811049270/bq2322Isup2.hkl

checkCIF report

Comment top

Chiral non-racemic ferrocenyldiphosphines are widely used as ligands for highly enantioselective transition metal catalysts (Togni, 1996; Blaser et al., 2007; Dai & Hou, 2010). Most of these ferrocenyldiphosphines are based on a planar chiral 1,2-disubstituted monoferrocene backbone. On the contrary, comparatively few chiral biferrocene derivatives are in use because they tend to be restricted to C₂-symmetric entities like the BIFEP and TRAP biferrocene diphosphine ligands obtained by homocoupling of iodoferrocene derivatives, which curtails their modularity (Sawamura et al., 1991; Nettekoven et al., 2000; Xiao et al., 2002; Espino et al., 2009; Kuwano, 2010). Within a research program to open new synthetic pathways for asymmetrically substituted chiral non-racemic biferrocene diphosphines (Wang et al., 2011) the title compound, (I), was obtained as an intermediate and studied by X-ray crystallography in order to fix its absolute configuration. A view of the asymmetric unit of (I) (Fig. 1) reveals that the compound has a planar-chiral S,S-configuration for the biferrocene fragment. Fe—C and ring C—C bond lengths show usual values (Fe—C = 2.015 (2) to 2.062 (2) Å, mean value 2.048 (10) Å; C—C = 1.417 (3) to 1.444 (3) Å, mean value 1.427 (8) Å) and both ferrocene groups have approximately staggered pairs of rings. The interplanar angle between the cyclopentadienyl rings C1 trough C5 (ring 1) and C11 through C15 (ring 3) is 54.29 (8)° and the torsion angle Fe1—Cg1—Cg3—Fe2 = -52.5° (Cg1 and 3 are the corresponding ring centroids). The dimethylamino and the BH₃ group are exo-oriented displaying torsion angles of Fe1—C2—C21—N1 = 177.44 (12)° and C2—C21—N1—B1 = 176.91 (15)°. The bond lengths C12—Br1 = 1.8913 (19) Å and N1—B1 = 1.631 (1) Å adopt normal values, similar to a diastereomer of (I) (Wang et al., 2011). The conformation of the molecule is stabilized by the intramolecular C21—H21···Br1 interaction with C···Br = 3.716 (2) Å. The arrangement and cohesion of the molecules in the crystal lattice (Fig. 2) is essentially based on unremarkable van-der-Waals interactions.

Related literature top

For general information on ferrocene-based diphosphines and their applications in asymmetric catalysis, see: Togni (1996); Blaser et al. (2007); Dai & Hou (2010). For the synthesis, coordination behavior and use in asymmetric catalysis of ligands based on biferrocenes, see: Sawamura et al. (1991); Nettekoven et al. (2000); Xiao et al. (2002); Espino et al. (2009); Kuwano (2010). For synthetic aspects of the title compound, see: Wang et al. (2011).

Experimental top

To a stirred solution of (R,S_Fc,S_Fc)-2''-bromo-2-[1-N,N-(dimethylamino)ethyl]-1,1''-biferrocene (100 mg, 0.19 mmol; Wang et al., 2011) in THF (3 ml) was added BH₃.THF (1 M, 0.7 ml, 0.7 mmol) at 0 °C. Stirring was continued for 1 h at r.t. before the reaction mixture was quenched at 0 °C by dropwise addition of water. The organics were extracted with dichloromethane, the combined solutions were washed with water and dried with MgSO₄. The solvents were removed and the residue was purified by chromatography (aluminium oxide, eluent CH₂Cl₂). Crystals suitable for X-ray diffraction were obtained from ethyl acetate by slow evaporation at r.t..

¹HNMR (400 MHz, CDCl₃) δ 1.09–2.00 (br s, 3H, H1), 1.81 (s, 3H, H23), 1.84 (d, J = 6.9 Hz, 3H, H22), 2.13 (s, 3H, H24), 3.94 (dd, J₁= 2.6 Hz, J₂ = 1.6 Hz, 1H, H15), 4.05 (q, J = 6.9 Hz,1H, H21), 4.09 (dd, J₁ = J₂ = 2.6 Hz, 1H,H14), 4.36 (s, 5H, H16–H20), 4.36–4.38 (m, 1H, H3), 4.39 (s, 5H, H6–H10), 4.43(dd, J₁ = J₂ = 2.5 Hz, 1H, H4), 4.50 (dd, J₁= 2.5 Hz, J₂ = 1.5 Hz, 1H, H5), 4.64 (dd, J₁= 2.6 Hz, J₂ = 1.6 Hz, 1H, H13).

¹³C{¹H} NMR (100.6 MHz, CDCl₃):δ 17.8 (C22), 44.6 (C24), 52.5 (C23), 63.2 (C21), 66.5 (C14), 67.6(C4), 67.8 (C3), 69.3 (C5), 70.9 (5 C, C6–C10), 71.6 (5 C, C16–C20), 72.2 (C13),72.3 (C15).

Structure description top

For general information on ferrocene-based diphosphines and their applications in asymmetric catalysis, see: Togni (1996); Blaser et al. (2007); Dai & Hou (2010). For the synthesis, coordination behavior and use in asymmetric catalysis of ligands based on biferrocenes, see: Sawamura et al. (1991); Nettekoven et al. (2000); Xiao et al. (2002); Espino et al. (2009); Kuwano (2010). For synthetic aspects of the title compound, see: Wang et al. (2011).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level.
	Fig. 2. Crystal structure of the title compound with view along the crystallographic b-axis.

{(R,S_Fc,S_Fc)-2''-Bromo-2-[1-(dimethylamino)ethyl- κN]-1,1''-biferrocene}trihydridoboron top

Crystal data top

[Fe₂(C₅H₅)₂(C₁₄H₁₉BBrN)]	F(000) = 1088
M_r = 533.90	D_x = 1.597 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9916 reflections
a = 8.8791 (2) Å	θ = 2.3–30.1°
b = 9.2210 (2) Å	µ = 3.12 mm⁻¹
c = 27.1292 (6) Å	T = 100 K
V = 2221.18 (9) Å³	Prism, yellow
Z = 4	0.33 × 0.27 × 0.21 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	6489 independent reflections
Radiation source: fine-focus sealed tube	6288 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
φ and ω scans	θ_max = 30.1°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −12→11
T_min = 0.54, T_max = 0.75	k = −12→12
34891 measured reflections	l = −38→38

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.054	w = 1/[σ²(F_o²) + (0.0234P)² + 1.1731P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
6489 reflections	Δρ_max = 0.69 e Å⁻³
266 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 2807 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.002 (5)

Crystal data top

[Fe₂(C₅H₅)₂(C₁₄H₁₉BBrN)]	V = 2221.18 (9) Å³
M_r = 533.90	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.8791 (2) Å	µ = 3.12 mm⁻¹
b = 9.2210 (2) Å	T = 100 K
c = 27.1292 (6) Å	0.33 × 0.27 × 0.21 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	6489 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	6288 reflections with I > 2σ(I)
T_min = 0.54, T_max = 0.75	R_int = 0.034
34891 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.054	Δρ_max = 0.69 e Å⁻³
S = 1.07	Δρ_min = −0.31 e Å⁻³
6489 reflections	Absolute structure: Flack (1983), 2807 Friedel pairs
266 parameters	Absolute structure parameter: 0.002 (5)
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
Br1	0.47251 (2)	0.185812 (19)	0.380922 (6)	0.01470 (4)
Fe1	0.30161 (3)	0.53063 (3)	0.298698 (9)	0.01275 (6)
Fe2	0.08967 (3)	0.22678 (3)	0.408373 (10)	0.01436 (6)
N1	0.57286 (19)	0.66124 (17)	0.43320 (6)	0.0148 (3)
B1	0.7399 (3)	0.6249 (3)	0.45489 (8)	0.0203 (4)
H1A	0.7446	0.6526	0.4897	0.030*
H1B	0.8157	0.6795	0.4363	0.030*
H1C	0.7598	0.5208	0.4517	0.030*
C1	0.2564 (2)	0.5202 (2)	0.37276 (6)	0.0123 (3)
C2	0.3899 (2)	0.60595 (19)	0.36404 (6)	0.0120 (3)
C3	0.3469 (2)	0.7240 (2)	0.33252 (7)	0.0162 (4)
H3	0.4123	0.7975	0.3205	0.019*
C4	0.1907 (3)	0.7127 (2)	0.32241 (7)	0.0199 (4)
H4	0.1337	0.7774	0.3026	0.024*
C5	0.1340 (2)	0.5881 (2)	0.34696 (7)	0.0176 (4)
H5	0.0326	0.5554	0.3464	0.021*
C6	0.2974 (2)	0.3255 (2)	0.27028 (7)	0.0178 (3)
H6	0.2661	0.2406	0.2873	0.021*
C7	0.4464 (2)	0.3820 (2)	0.26885 (6)	0.0159 (4)
H7	0.5320	0.3414	0.2847	0.019*
C8	0.4446 (2)	0.5103 (2)	0.23954 (7)	0.0180 (4)
H8	0.5288	0.5704	0.2325	0.022*
C9	0.2947 (3)	0.5326 (2)	0.22272 (7)	0.0227 (4)
H9	0.2612	0.6100	0.2024	0.027*
C10	0.2035 (3)	0.4183 (2)	0.24179 (7)	0.0224 (4)
H10	0.0985	0.4063	0.2364	0.027*
C11	0.2337 (2)	0.4012 (2)	0.40848 (7)	0.0125 (3)
C12	0.3112 (2)	0.2670 (2)	0.41713 (6)	0.0134 (3)
C13	0.2534 (2)	0.1987 (2)	0.46023 (7)	0.0180 (4)
H13	0.2861	0.1093	0.4739	0.022*
C14	0.1379 (2)	0.2896 (2)	0.47874 (7)	0.0198 (4)
H14	0.0789	0.2713	0.5073	0.024*
C15	0.1248 (2)	0.4126 (2)	0.44759 (7)	0.0180 (4)
H15	0.0554	0.4900	0.4519	0.022*
C16	−0.0151 (2)	0.2224 (2)	0.34155 (7)	0.0210 (4)
H16	0.0022	0.2875	0.3150	0.025*
C17	0.0622 (2)	0.0887 (2)	0.35010 (7)	0.0202 (4)
H17	0.1403	0.0495	0.3302	0.024*
C18	0.0020 (3)	0.0248 (2)	0.39343 (7)	0.0233 (4)
H18	0.0326	−0.0647	0.4076	0.028*
C19	−0.1121 (3)	0.1181 (2)	0.41198 (9)	0.0255 (4)
H19	−0.1709	0.1015	0.4407	0.031*
C20	−0.1235 (2)	0.2405 (2)	0.38022 (8)	0.0229 (4)
H20	−0.1907	0.3198	0.3840	0.028*
C21	0.5465 (2)	0.58227 (18)	0.38436 (6)	0.0122 (3)
H21	0.5562	0.4762	0.3913	0.015*
C22	0.6685 (2)	0.6203 (2)	0.34687 (7)	0.0192 (4)
H22A	0.6581	0.5578	0.3178	0.029*
H22B	0.7679	0.6055	0.3617	0.029*
H22C	0.6578	0.7220	0.3370	0.029*
C23	0.4604 (3)	0.6085 (2)	0.46983 (7)	0.0190 (4)
H23A	0.4772	0.6570	0.5015	0.029*
H23B	0.4714	0.5035	0.4741	0.029*
H23C	0.3586	0.6303	0.4580	0.029*
C24	0.5543 (3)	0.8216 (2)	0.42826 (8)	0.0235 (4)
H24A	0.4509	0.8435	0.4181	0.035*
H24B	0.6248	0.8583	0.4034	0.035*
H24C	0.5750	0.8681	0.4600	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01301 (8)	0.01403 (7)	0.01707 (8)	0.00257 (7)	0.00186 (7)	0.00236 (6)
Fe1	0.01316 (13)	0.01367 (12)	0.01141 (11)	0.00278 (10)	−0.00227 (10)	0.00025 (9)
Fe2	0.01111 (13)	0.01697 (12)	0.01499 (12)	−0.00394 (10)	0.00234 (10)	−0.00310 (9)
N1	0.0172 (8)	0.0131 (7)	0.0141 (7)	−0.0022 (6)	−0.0019 (6)	−0.0017 (5)
B1	0.0170 (11)	0.0248 (11)	0.0191 (10)	−0.0028 (9)	−0.0051 (8)	−0.0003 (8)
C1	0.0099 (8)	0.0141 (8)	0.0129 (7)	0.0009 (6)	0.0002 (6)	−0.0022 (6)
C2	0.0117 (9)	0.0119 (7)	0.0124 (7)	0.0018 (6)	0.0002 (6)	−0.0024 (6)
C3	0.0192 (10)	0.0123 (8)	0.0171 (8)	0.0023 (7)	−0.0013 (7)	0.0010 (7)
C4	0.0207 (10)	0.0171 (9)	0.0219 (9)	0.0077 (8)	−0.0032 (8)	−0.0009 (7)
C5	0.0114 (9)	0.0200 (9)	0.0215 (9)	0.0053 (7)	−0.0011 (7)	−0.0026 (7)
C6	0.0195 (9)	0.0180 (8)	0.0159 (8)	−0.0017 (8)	0.0012 (7)	−0.0030 (7)
C7	0.0195 (11)	0.0152 (8)	0.0130 (7)	0.0032 (7)	0.0008 (6)	−0.0008 (6)
C8	0.0216 (11)	0.0180 (9)	0.0143 (8)	0.0009 (7)	0.0022 (7)	0.0013 (6)
C9	0.0277 (11)	0.0277 (10)	0.0129 (8)	0.0057 (9)	−0.0038 (8)	0.0020 (7)
C10	0.0208 (10)	0.0297 (11)	0.0167 (8)	0.0007 (9)	−0.0060 (8)	−0.0058 (8)
C11	0.0096 (8)	0.0156 (8)	0.0124 (7)	−0.0027 (6)	0.0005 (6)	−0.0028 (6)
C12	0.0120 (9)	0.0168 (8)	0.0115 (7)	−0.0035 (7)	0.0001 (6)	−0.0012 (6)
C13	0.0187 (10)	0.0215 (9)	0.0137 (7)	−0.0048 (8)	−0.0007 (6)	0.0024 (7)
C14	0.0167 (9)	0.0278 (11)	0.0149 (8)	−0.0087 (8)	0.0040 (7)	−0.0027 (7)
C15	0.0155 (10)	0.0231 (9)	0.0153 (8)	−0.0042 (7)	0.0035 (7)	−0.0060 (7)
C16	0.0174 (10)	0.0248 (9)	0.0207 (8)	−0.0060 (8)	−0.0014 (7)	−0.0052 (7)
C17	0.0190 (11)	0.0208 (9)	0.0209 (9)	−0.0056 (7)	0.0016 (7)	−0.0084 (7)
C18	0.0265 (12)	0.0200 (9)	0.0235 (9)	−0.0089 (8)	0.0011 (8)	−0.0031 (7)
C19	0.0180 (11)	0.0299 (11)	0.0285 (10)	−0.0116 (9)	0.0031 (8)	−0.0057 (9)
C20	0.0124 (9)	0.0283 (10)	0.0281 (10)	−0.0036 (7)	−0.0025 (8)	−0.0095 (9)
C21	0.0111 (8)	0.0127 (7)	0.0128 (7)	−0.0003 (6)	−0.0011 (6)	−0.0022 (6)
C22	0.0147 (10)	0.0272 (10)	0.0158 (8)	−0.0035 (8)	0.0026 (7)	0.0005 (7)
C23	0.0201 (10)	0.0230 (9)	0.0140 (8)	−0.0023 (8)	0.0036 (7)	−0.0044 (7)
C24	0.0306 (12)	0.0117 (8)	0.0283 (10)	0.0005 (8)	−0.0067 (8)	−0.0028 (7)

Geometric parameters (Å, º) top

Br1—C12	1.8913 (19)	C6—C10	1.423 (3)
Fe1—C6	2.043 (2)	C6—H6	0.9500
Fe1—C3	2.046 (2)	C7—C8	1.426 (3)
Fe1—C7	2.046 (2)	C7—H7	0.9500
Fe1—C4	2.050 (2)	C8—C9	1.421 (3)
Fe1—C1	2.051 (2)	C8—H8	0.9500
Fe1—C5	2.052 (2)	C9—C10	1.426 (3)
Fe1—C10	2.053 (2)	C9—H9	0.9500
Fe1—C8	2.055 (2)	C10—H10	0.9500
Fe1—C2	2.059 (2)	C11—C12	1.435 (3)
Fe1—C9	2.062 (2)	C11—C15	1.440 (3)
Fe2—C12	2.015 (2)	C12—C13	1.424 (2)
Fe2—C16	2.038 (2)	C13—C14	1.417 (3)
Fe2—C13	2.040 (2)	C13—H13	0.9500
Fe2—C14	2.041 (2)	C14—C15	1.419 (3)
Fe2—C15	2.041 (2)	C14—H14	0.9500
Fe2—C17	2.044 (2)	C15—H15	0.9500
Fe2—C20	2.045 (2)	C16—C17	1.430 (3)
Fe2—C11	2.055 (2)	C16—C20	1.433 (3)
Fe2—C19	2.056 (2)	C16—H16	0.9500
Fe2—C18	2.059 (2)	C17—C18	1.419 (3)
N1—C23	1.490 (3)	C17—H17	0.9500
N1—C24	1.494 (3)	C18—C19	1.421 (3)
N1—C21	1.530 (2)	C18—H18	0.9500
N1—B1	1.631 (3)	C19—C20	1.424 (3)
B1—H1A	0.9800	C19—H19	0.9500
B1—H1B	0.9800	C20—H20	0.9500
B1—H1C	0.9800	C21—C22	1.527 (3)
C1—C5	1.437 (3)	C21—H21	1.0000
C1—C2	1.444 (3)	C22—H22A	0.9800
C1—C11	1.477 (3)	C22—H22B	0.9800
C2—C3	1.436 (2)	C22—H22C	0.9800
C2—C21	1.512 (3)	C23—H23A	0.9800
C3—C4	1.418 (3)	C23—H23B	0.9800
C3—H3	0.9500	C23—H23C	0.9800
C4—C5	1.420 (3)	C24—H24A	0.9800
C4—H4	0.9500	C24—H24B	0.9800
C5—H5	0.9500	C24—H24C	0.9800
C6—C7	1.422 (3)

C6—Fe1—C3	168.54 (8)	C3—C4—H4	125.8
C6—Fe1—C7	40.70 (8)	C5—C4—H4	125.8
C3—Fe1—C7	129.63 (8)	Fe1—C4—H4	126.4
C6—Fe1—C4	150.24 (9)	C4—C5—C1	108.25 (18)
C3—Fe1—C4	40.51 (8)	C4—C5—Fe1	69.66 (12)
C7—Fe1—C4	167.05 (8)	C1—C5—Fe1	69.48 (11)
C6—Fe1—C1	108.81 (7)	C4—C5—H5	125.9
C3—Fe1—C1	68.91 (7)	C1—C5—H5	125.9
C7—Fe1—C1	118.62 (7)	Fe1—C5—H5	126.6
C4—Fe1—C1	68.73 (8)	C7—C6—C10	108.03 (18)
C6—Fe1—C5	117.84 (8)	C7—C6—Fe1	69.75 (11)
C3—Fe1—C5	68.35 (8)	C10—C6—Fe1	70.03 (12)
C7—Fe1—C5	151.80 (8)	C7—C6—H6	126.0
C4—Fe1—C5	40.51 (8)	C10—C6—H6	126.0
C1—Fe1—C5	40.99 (8)	Fe1—C6—H6	125.8
C6—Fe1—C10	40.67 (8)	C6—C7—C8	107.99 (17)
C3—Fe1—C10	149.38 (8)	C6—C7—Fe1	69.55 (11)
C7—Fe1—C10	68.35 (9)	C8—C7—Fe1	69.99 (11)
C4—Fe1—C10	116.45 (9)	C6—C7—H7	126.0
C1—Fe1—C10	129.05 (8)	C8—C7—H7	126.0
C5—Fe1—C10	107.62 (9)	Fe1—C7—H7	126.0
C6—Fe1—C8	68.41 (8)	C9—C8—C7	108.04 (18)
C3—Fe1—C8	107.95 (8)	C9—C8—Fe1	70.08 (11)
C7—Fe1—C8	40.69 (7)	C7—C8—Fe1	69.32 (11)
C4—Fe1—C8	128.05 (8)	C9—C8—H8	126.0
C1—Fe1—C8	151.85 (8)	C7—C8—H8	126.0
C5—Fe1—C8	165.93 (8)	Fe1—C8—H8	126.2
C10—Fe1—C8	68.20 (9)	C8—C9—C10	107.95 (18)
C6—Fe1—C2	130.10 (7)	C8—C9—Fe1	69.53 (11)
C3—Fe1—C2	40.96 (7)	C10—C9—Fe1	69.37 (11)
C7—Fe1—C2	109.12 (7)	C8—C9—H9	126.0
C4—Fe1—C2	68.67 (8)	C10—C9—H9	126.0
C1—Fe1—C2	41.14 (7)	Fe1—C9—H9	126.6
C5—Fe1—C2	68.86 (8)	C6—C10—C9	108.0 (2)
C10—Fe1—C2	168.28 (8)	C6—C10—Fe1	69.30 (11)
C8—Fe1—C2	117.91 (8)	C9—C10—Fe1	70.07 (12)
C6—Fe1—C9	68.32 (8)	C6—C10—H10	126.0
C3—Fe1—C9	116.51 (8)	C9—C10—H10	126.0
C7—Fe1—C9	68.23 (8)	Fe1—C10—H10	126.2
C4—Fe1—C9	106.98 (8)	C12—C11—C15	105.34 (16)
C1—Fe1—C9	166.83 (9)	C12—C11—C1	133.01 (16)
C5—Fe1—C9	127.89 (9)	C15—C11—C1	121.38 (17)
C10—Fe1—C9	40.56 (9)	C12—C11—Fe2	67.89 (10)
C8—Fe1—C9	40.39 (9)	C15—C11—Fe2	68.91 (11)
C2—Fe1—C9	150.32 (9)	C1—C11—Fe2	131.69 (13)
C12—Fe2—C16	123.64 (8)	C13—C12—C11	110.07 (17)
C12—Fe2—C13	41.10 (7)	C13—C12—Br1	121.62 (15)
C16—Fe2—C13	159.46 (8)	C11—C12—Br1	128.27 (13)
C12—Fe2—C14	68.45 (8)	C13—C12—Fe2	70.36 (11)
C16—Fe2—C14	159.00 (9)	C11—C12—Fe2	70.83 (11)
C13—Fe2—C14	40.64 (8)	Br1—C12—Fe2	127.24 (9)
C12—Fe2—C15	68.59 (8)	C14—C13—C12	106.86 (18)
C16—Fe2—C15	123.37 (9)	C14—C13—Fe2	69.71 (11)
C13—Fe2—C15	68.79 (9)	C12—C13—Fe2	68.54 (11)
C14—Fe2—C15	40.69 (8)	C14—C13—H13	126.6
C12—Fe2—C17	108.80 (8)	C12—C13—H13	126.6
C16—Fe2—C17	41.00 (9)	Fe2—C13—H13	126.7
C13—Fe2—C17	122.65 (9)	C13—C14—C15	108.74 (17)
C14—Fe2—C17	157.73 (9)	C13—C14—Fe2	69.64 (11)
C15—Fe2—C17	160.77 (8)	C15—C14—Fe2	69.68 (11)
C12—Fe2—C20	159.37 (8)	C13—C14—H14	125.6
C16—Fe2—C20	41.10 (9)	C15—C14—H14	125.6
C13—Fe2—C20	157.70 (8)	Fe2—C14—H14	126.6
C14—Fe2—C20	121.74 (9)	C14—C15—C11	108.99 (18)
C15—Fe2—C20	106.51 (8)	C14—C15—Fe2	69.63 (11)
C17—Fe2—C20	68.84 (9)	C11—C15—Fe2	69.93 (10)
C12—Fe2—C11	41.28 (7)	C14—C15—H15	125.5
C16—Fe2—C11	107.51 (8)	C11—C15—H15	125.5
C13—Fe2—C11	69.80 (8)	Fe2—C15—H15	126.5
C14—Fe2—C11	69.25 (8)	C17—C16—C20	107.67 (18)
C15—Fe2—C11	41.15 (7)	C17—C16—Fe2	69.74 (11)
C17—Fe2—C11	124.25 (8)	C20—C16—Fe2	69.69 (11)
C20—Fe2—C11	121.89 (8)	C17—C16—H16	126.2
C12—Fe2—C19	159.19 (9)	C20—C16—H16	126.2
C16—Fe2—C19	68.58 (9)	Fe2—C16—H16	126.0
C13—Fe2—C19	121.78 (9)	C18—C17—C16	108.16 (19)
C14—Fe2—C19	106.07 (9)	C18—C17—Fe2	70.32 (11)
C15—Fe2—C19	121.18 (9)	C16—C17—Fe2	69.27 (11)
C17—Fe2—C19	68.22 (9)	C18—C17—H17	125.9
C20—Fe2—C19	40.63 (9)	C16—C17—H17	125.9
C11—Fe2—C19	157.55 (9)	Fe2—C17—H17	126.1
C12—Fe2—C18	123.97 (9)	C17—C18—C19	108.1 (2)
C16—Fe2—C18	68.54 (9)	C17—C18—Fe2	69.21 (11)
C13—Fe2—C18	106.89 (9)	C19—C18—Fe2	69.67 (12)
C14—Fe2—C18	121.37 (8)	C17—C18—H18	126.0
C15—Fe2—C18	156.91 (8)	C19—C18—H18	126.0
C17—Fe2—C18	40.47 (8)	Fe2—C18—H18	126.7
C20—Fe2—C18	68.42 (9)	C18—C19—C20	108.41 (19)
C11—Fe2—C18	160.67 (8)	C18—C19—Fe2	69.92 (12)
C19—Fe2—C18	40.41 (9)	C20—C19—Fe2	69.27 (12)
C23—N1—C24	107.98 (16)	C18—C19—H19	125.8
C23—N1—C21	108.64 (14)	C20—C19—H19	125.8
C24—N1—C21	112.12 (14)	Fe2—C19—H19	126.6
C23—N1—B1	107.57 (15)	C19—C20—C16	107.67 (19)
C24—N1—B1	109.64 (16)	C19—C20—Fe2	70.10 (13)
C21—N1—B1	110.73 (15)	C16—C20—Fe2	69.21 (11)
N1—B1—H1A	109.5	C19—C20—H20	126.2
N1—B1—H1B	109.5	C16—C20—H20	126.2
H1A—B1—H1B	109.5	Fe2—C20—H20	126.1
N1—B1—H1C	109.5	C2—C21—C22	112.12 (15)
H1A—B1—H1C	109.5	C2—C21—N1	112.82 (14)
H1B—B1—H1C	109.5	C22—C21—N1	111.04 (15)
C5—C1—C2	107.56 (16)	C2—C21—H21	106.8
C5—C1—C11	122.70 (17)	C22—C21—H21	106.8
C2—C1—C11	128.77 (16)	N1—C21—H21	106.8
C5—C1—Fe1	69.53 (11)	C21—C22—H22A	109.5
C2—C1—Fe1	69.71 (10)	C21—C22—H22B	109.5
C11—C1—Fe1	134.76 (13)	H22A—C22—H22B	109.5
C3—C2—C1	107.17 (16)	C21—C22—H22C	109.5
C3—C2—C21	124.81 (17)	H22A—C22—H22C	109.5
C1—C2—C21	128.00 (15)	H22B—C22—H22C	109.5
C3—C2—Fe1	69.03 (10)	N1—C23—H23A	109.5
C1—C2—Fe1	69.15 (10)	N1—C23—H23B	109.5
C21—C2—Fe1	127.99 (12)	H23A—C23—H23B	109.5
C4—C3—C2	108.60 (18)	N1—C23—H23C	109.5
C4—C3—Fe1	69.90 (11)	H23A—C23—H23C	109.5
C2—C3—Fe1	70.01 (10)	H23B—C23—H23C	109.5
C4—C3—H3	125.7	N1—C24—H24A	109.5
C2—C3—H3	125.7	N1—C24—H24B	109.5
Fe1—C3—H3	126.0	H24A—C24—H24B	109.5
C3—C4—C5	108.41 (17)	N1—C24—H24C	109.5
C3—C4—Fe1	69.59 (11)	H24A—C24—H24C	109.5
C5—C4—Fe1	69.82 (11)	H24B—C24—H24C	109.5

C5—C1—C2—C3	−0.7 (2)	Fe2—C11—C12—C13	−59.61 (13)
C11—C1—C2—C3	−169.48 (17)	C15—C11—C12—Br1	−178.14 (14)
C5—C1—C2—C21	177.98 (17)	C1—C11—C12—Br1	−4.3 (3)
C11—C1—C2—C21	9.2 (3)	Fe2—C11—C12—Br1	122.80 (15)
Fe1—C1—C2—C21	−122.56 (18)	C15—C11—C12—Fe2	59.06 (12)
C5—C1—C2—Fe1	−59.46 (12)	C1—C11—C12—Fe2	−127.1 (2)
C11—C1—C2—Fe1	131.75 (19)	C11—C12—C13—C14	0.5 (2)
C1—C2—C3—C4	0.6 (2)	Br1—C12—C13—C14	178.23 (13)
C21—C2—C3—C4	−178.11 (16)	Fe2—C12—C13—C14	−59.44 (13)
Fe1—C2—C3—C4	59.45 (13)	C11—C12—C13—Fe2	59.90 (13)
C1—C2—C3—Fe1	−58.84 (12)	Br1—C12—C13—Fe2	−122.33 (13)
C21—C2—C3—Fe1	122.43 (17)	C12—C13—C14—C15	−0.2 (2)
C2—C3—C4—C5	−0.3 (2)	Fe2—C13—C14—C15	−58.87 (14)
Fe1—C3—C4—C5	59.22 (14)	C12—C13—C14—Fe2	58.69 (13)
C2—C3—C4—Fe1	−59.52 (13)	C13—C14—C15—C11	−0.2 (2)
C3—C4—C5—C1	−0.1 (2)	Fe2—C14—C15—C11	−59.02 (13)
Fe1—C4—C5—C1	58.94 (13)	C13—C14—C15—Fe2	58.84 (14)
C3—C4—C5—Fe1	−59.08 (14)	C12—C11—C15—C14	0.4 (2)
C2—C1—C5—C4	0.5 (2)	C1—C11—C15—C14	−174.31 (16)
C11—C1—C5—C4	170.14 (16)	Fe2—C11—C15—C14	58.83 (14)
Fe1—C1—C5—C4	−59.06 (13)	C12—C11—C15—Fe2	−58.39 (12)
C2—C1—C5—Fe1	59.57 (12)	C1—C11—C15—Fe2	126.86 (17)
C11—C1—C5—Fe1	−130.80 (17)	C20—C16—C17—C18	0.2 (2)
C10—C6—C7—C8	0.2 (2)	Fe2—C16—C17—C18	59.79 (14)
Fe1—C6—C7—C8	−59.66 (13)	C20—C16—C17—Fe2	−59.61 (13)
C10—C6—C7—Fe1	59.81 (14)	C16—C17—C18—C19	−0.1 (2)
C6—C7—C8—C9	−0.2 (2)	Fe2—C17—C18—C19	59.00 (15)
Fe1—C7—C8—C9	−59.61 (14)	C16—C17—C18—Fe2	−59.13 (14)
C6—C7—C8—Fe1	59.38 (13)	C17—C18—C19—C20	0.0 (2)
C7—C8—C9—C10	0.2 (2)	Fe2—C18—C19—C20	58.75 (14)
Fe1—C8—C9—C10	−58.92 (14)	C17—C18—C19—Fe2	−58.72 (14)
C7—C8—C9—Fe1	59.13 (13)	C18—C19—C20—C16	0.1 (2)
C7—C6—C10—C9	0.0 (2)	Fe2—C19—C20—C16	59.23 (14)
Fe1—C6—C10—C9	59.62 (14)	C18—C19—C20—Fe2	−59.15 (15)
C7—C6—C10—Fe1	−59.64 (13)	C17—C16—C20—C19	−0.2 (2)
C8—C9—C10—C6	−0.1 (2)	Fe2—C16—C20—C19	−59.80 (14)
Fe1—C9—C10—C6	−59.14 (13)	C17—C16—C20—Fe2	59.63 (14)
C8—C9—C10—Fe1	59.02 (14)	C3—C2—C21—C22	−38.2 (2)
C5—C1—C11—C12	137.0 (2)	C1—C2—C21—C22	143.31 (18)
C2—C1—C11—C12	−55.7 (3)	Fe1—C2—C21—C22	51.2 (2)
Fe1—C1—C11—C12	44.1 (3)	C3—C2—C21—N1	88.0 (2)
C5—C1—C11—C15	−49.9 (3)	C1—C2—C21—N1	−90.4 (2)
C2—C1—C11—C15	117.3 (2)	Fe1—C2—C21—N1	177.44 (12)
Fe1—C1—C11—C15	−142.88 (17)	C23—N1—C21—C2	58.98 (19)
C5—C1—C11—Fe2	38.9 (3)	C24—N1—C21—C2	−60.3 (2)
C2—C1—C11—Fe2	−153.86 (15)	B1—N1—C21—C2	176.91 (15)
Fe1—C1—C11—Fe2	−54.1 (3)	C23—N1—C21—C22	−174.18 (16)
C15—C11—C12—C13	−0.6 (2)	C24—N1—C21—C22	66.6 (2)
C1—C11—C12—C13	173.31 (19)	B1—N1—C21—C22	−56.26 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21···Br1	1.00	2.79	3.7154 (17)	154

Experimental details

Crystal data
Chemical formula	[Fe₂(C₅H₅)₂(C₁₄H₁₉BBrN)]
M_r	533.90
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	8.8791 (2), 9.2210 (2), 27.1292 (6)
V (Å³)	2221.18 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.12
Crystal size (mm)	0.33 × 0.27 × 0.21

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.54, 0.75
No. of measured, independent and observed [I > 2σ(I)] reflections	34891, 6489, 6288
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.054, 1.07
No. of reflections	6489
No. of parameters	266
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.31
Absolute structure	Flack (1983), 2807 Friedel pairs
Absolute structure parameter	0.002 (5)

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SAINT and XPREP (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21···Br1	1.00	2.79	3.7154 (17)	153.6

Acknowledgements

Generous support by the Beijing Nova Program (2009 B37) and the Educational Council Foundation of Beijing (KM201010025012, PHR201008395 and PHR201007114) is gratefully acknowledged. This work was also kindly supported by SOLVIAS AG (Basel).

References

Blaser, H.-U., Pugin, B., Spindler, F. & Thommen, M. (2007). Acc. Chem. Res. 40, 1240–1250. Web of Science CrossRef PubMed CAS Google Scholar
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Dai, L.-X. & Hou, X.-L. (2010). Chiral Ferrocenes in Asymmetric Catalysis. Weinheim: Wiley-VCH. Google Scholar
Espino, G., Xiao, L., Puchberger, M., Mereiter, K., Spindler, F., Manzano, B. R., Jalon, F. A. & Weissensteiner, W. (2009). Dalton Trans. pp. 2751–2763. Web of Science CrossRef Google Scholar
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Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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Volume 67| Part 12| December 2011| Pages m1806-m1807

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

{(R,SFc,SFc)-2′′-Bromo-2-[1-(di­methyl­amino)­ethyl-κN]-1,1′′-biferrocene}trihydridoboron

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

{(R,S_Fc,S_Fc)-2′′-Bromo-2-[1-(dimethylamino)ethyl-κN]-1,1′′-biferrocene}trihydridoboron