metal-organic compounds
rac-(S,S)-Bis(1-ferrocenylbut-3-enyl) ether
aCollege of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, People's Republic of China
*Correspondence e-mail: wangjianjun1030@sohu.com
The title complex, [Fe2(C5H5)2(C18H20O)], formed by dehydration of 1-ferrocenylbut-3-en-1-ol, crystallizes as a The central C—O—C fragment, in which the C atoms are the chiral centers, is characterized by an angle of 116.26 (10)° at the O atom. One ferrocene group shows a whereas the other shows an eclipsed conformation.
Related literature
For general information on ferrocenyl et al. (1996); Matković-Čalogović et al. (1993); Gasser et al. (2007). For applications of dinuclear ferrocenyl derivatives, see: Gao et al. (2011); Locke et al. (2001).
see: FergusonExperimental
Crystal data
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536812048064/bh2465sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812048064/bh2465Isup2.hkl
A solution of 1-ferrocenyl-3-buten-1-ol (5.862 g, 34.89 mmol), DCC (9.597 g, 46.52 mmol) and DMAP (2.842 g, 23.26 mmol) in CH2Cl2 (200 ml) was stirred at room temperature for 36 h. The solution was filtered off and the filtrate was washed with CH2Cl2. The organic phases were combined and dried to give a viscous yellow oil, which was chromatographed over a column of silica gel using petroleum ether as the δ 6.17–5.79 (m, 2H, H23A and H27A), 5.26–4.96 (m, 4H, H24A–H24B and H28A–H28B), 4.37 (s, 2H, H21A and H25A), 4.46–3.90 (m, 18H, H2–H10 and H12–H20), 2.84–2.46 (m, 4H, H22A–H22B and H26A–H26B). HRMS (ESI): calcd for C28H30Fe2O: 494.0990, found 494.0981.
Yellow crystals of the title compound were obtained by slow evaporation of a solution in dichloromethane/petroleum ether (60–90°C). 1H NMR (400 MHz, CDCl3)H atoms were placed in calculated positions and thereafter treated as riding atoms, with C—H = 0.98 (Cp rings and methine CH), 0.93 (vinyl CH), and 0.97 Å (methylene CH2). Isotropic displacement parameters for H atoms were calculated as Uiso(H) = 1.2Ueq(carrier C).
Due to their high iron content, bisferrocenyl derivatives have a wider range of applications in high burning rate catalysts than mononuclear ferrocenyl ones (Gao et al., 2011; Locke et al., 2001). Most of bisferrocenyl 1 A view of the is given in Fig. 1 and the in Fig. 2. Structure solution and showed that the racemic form was crystallized with both chiral centers having the same configuration.
are synthesized from with H2SO4 or Al2O3 as catalysts in the environment of high temperature and vacuum (Ferguson et al., 1996; Matković-Čalogović et al., 1993). As part of our ongoing program, the title compound was prepared from 1-ferrocenyl-3-buten-1-ol and dicyclohexylcarbodiimide (DCC), with 4-dimethylaminopyridine (DMAP) as catalyst, at room temperature, and studied by X-ray crystallography. The complex crystallizes with a triclinic in the PThe principal molecular features are the structure of the central C—O—C bridge and the conformations of the ferrocene fragments. The C—O bond lengths are 1.4399 (15) and 1.4430 (15) Å, and the C—O—C angle is 116.26 (10)°, while this angle is found between 113.7 (9) and 112.8 (9)° in the
of bis(ferrocenylmethyl)ether (Gasser et al., 2007). The cyclopentadienyl rings are twisted from the eclipsed conformation: the mean torsion angles Cn—Cg1—Cg2—Cm and Cp—Cg3—Cg4—Cq (n = 1···5, m = n + 5; p = 11···15, q = p + 5; the Cg pseudoatoms are the centroids of the four rings), for the ferrocene groups defined by Fe1 and Fe2, are 29.3 (1) and 6.1 (1)°, respectively.For general information on ferrocenyl
see: Ferguson et al. (1996); Matković-Čalogović et al. (1993); Gasser et al. (2007). For applications of dinuclear ferrocenyl derivatives, see: Gao et al. (2011); Locke et al. (2001).Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of the title complex, showing 30% probability displacement ellipsoids. All H atoms have been omitted for clarity. | |
Fig. 2. The crystal structure of the title compound. |
[Fe2(C5H5)2(C18H20O)] | Z = 2 |
Mr = 494.22 | F(000) = 516 |
Triclinic, P1 | Dx = 1.461 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.7865 (15) Å | Cell parameters from 4332 reflections |
b = 9.8274 (15) Å | θ = 3.0–28.3° |
c = 12.1816 (19) Å | µ = 1.31 mm−1 |
α = 99.405 (2)° | T = 150 K |
β = 94.976 (2)° | Block, yellow |
γ = 101.657 (2)° | 0.50 × 0.25 × 0.25 mm |
V = 1123.3 (3) Å3 |
Bruker APEXII CCD diffractometer | 5352 independent reflections |
Radiation source: fine-focus sealed tube | 4759 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
φ and ω scans | θmax = 28.2°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −9→12 |
Tmin = 0.561, Tmax = 0.736 | k = −13→8 |
7657 measured reflections | l = −16→15 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 0.81 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
5352 reflections | (Δ/σ)max = 0.001 |
280 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
0 constraints |
[Fe2(C5H5)2(C18H20O)] | γ = 101.657 (2)° |
Mr = 494.22 | V = 1123.3 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.7865 (15) Å | Mo Kα radiation |
b = 9.8274 (15) Å | µ = 1.31 mm−1 |
c = 12.1816 (19) Å | T = 150 K |
α = 99.405 (2)° | 0.50 × 0.25 × 0.25 mm |
β = 94.976 (2)° |
Bruker APEXII CCD diffractometer | 5352 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | 4759 reflections with I > 2σ(I) |
Tmin = 0.561, Tmax = 0.736 | Rint = 0.014 |
7657 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 0.81 | Δρmax = 0.36 e Å−3 |
5352 reflections | Δρmin = −0.37 e Å−3 |
280 parameters |
x | y | z | Uiso*/Ueq | ||
Fe1 | 0.20476 (2) | 0.792940 (19) | 0.468598 (15) | 0.01300 (8) | |
Fe2 | −0.30704 (2) | 0.791879 (19) | −0.022770 (16) | 0.01411 (8) | |
O1 | −0.18694 (10) | 0.57498 (10) | 0.25064 (7) | 0.0148 (2) | |
C1 | 0.04463 (15) | 0.70792 (14) | 0.33824 (10) | 0.0142 (3) | |
C2 | 0.13856 (16) | 0.82818 (16) | 0.31344 (12) | 0.0169 (3) | |
H2A | 0.1124 | 0.9149 | 0.2978 | 0.020* | |
C3 | 0.27661 (16) | 0.80081 (17) | 0.31594 (12) | 0.0196 (3) | |
H3A | 0.3612 | 0.8648 | 0.3019 | 0.023* | |
C4 | 0.26917 (17) | 0.66318 (18) | 0.34216 (13) | 0.0202 (3) | |
H4A | 0.3479 | 0.6162 | 0.3497 | 0.024* | |
C5 | 0.12676 (15) | 0.60656 (15) | 0.35574 (11) | 0.0172 (3) | |
H5A | 0.0913 | 0.5141 | 0.3752 | 0.021* | |
C6 | 0.13881 (17) | 0.91467 (17) | 0.59802 (13) | 0.0207 (3) | |
H6A | 0.0536 | 0.9525 | 0.5942 | 0.025* | |
C7 | 0.27384 (17) | 0.98277 (15) | 0.57716 (12) | 0.0217 (3) | |
H7A | 0.2978 | 1.0758 | 0.5558 | 0.026* | |
C8 | 0.36802 (16) | 0.89279 (16) | 0.59166 (12) | 0.0204 (3) | |
H8A | 0.4681 | 0.9128 | 0.5822 | 0.024* | |
C9 | 0.29131 (17) | 0.76805 (17) | 0.62240 (12) | 0.0201 (3) | |
H9A | 0.3292 | 0.6871 | 0.6378 | 0.024* | |
C10 | 0.14978 (15) | 0.78253 (15) | 0.62714 (11) | 0.0184 (3) | |
H10A | 0.0730 | 0.7128 | 0.6460 | 0.022* | |
C11 | −0.25795 (15) | 0.71814 (15) | 0.12099 (11) | 0.0158 (3) | |
C12 | −0.40690 (15) | 0.70386 (16) | 0.09872 (11) | 0.0184 (3) | |
H12A | −0.4777 | 0.6149 | 0.0860 | 0.022* | |
C13 | −0.43463 (17) | 0.84011 (18) | 0.09606 (12) | 0.0236 (3) | |
H13A | −0.5275 | 0.8613 | 0.0819 | 0.028* | |
C14 | −0.30363 (19) | 0.94001 (17) | 0.11764 (13) | 0.0241 (3) | |
H14A | −0.2905 | 1.0422 | 0.1209 | 0.029* | |
C15 | −0.19508 (16) | 0.86556 (15) | 0.13278 (11) | 0.0194 (3) | |
H15A | −0.0941 | 0.9079 | 0.1481 | 0.023* | |
C16 | −0.22515 (19) | 0.68955 (18) | −0.15448 (13) | 0.0215 (3) | |
H16A | −0.1663 | 0.6204 | −0.1501 | 0.026* | |
C17 | −0.37461 (17) | 0.65922 (17) | −0.17461 (12) | 0.0214 (3) | |
H17A | −0.4367 | 0.5651 | −0.1864 | 0.026* | |
C18 | −0.41885 (18) | 0.78905 (18) | −0.17327 (12) | 0.0231 (3) | |
H18A | −0.5162 | 0.7998 | −0.1849 | 0.028* | |
C19 | −0.29629 (18) | 0.89995 (16) | −0.15316 (12) | 0.0231 (3) | |
H19A | −0.2945 | 1.0009 | −0.1478 | 0.028* | |
C20 | −0.17646 (17) | 0.83925 (17) | −0.14101 (12) | 0.0228 (3) | |
H20A | −0.0781 | 0.8911 | −0.1258 | 0.027* | |
C21 | −0.11241 (14) | 0.68741 (14) | 0.33961 (11) | 0.0143 (3) | |
H21A | −0.1412 | 0.7754 | 0.3311 | 0.017* | |
C22 | −0.16178 (15) | 0.64072 (15) | 0.44594 (11) | 0.0168 (3) | |
H22A | −0.1355 | 0.5520 | 0.4522 | 0.020* | |
H22B | −0.1133 | 0.7106 | 0.5104 | 0.020* | |
C23 | −0.31686 (15) | 0.62190 (15) | 0.44919 (12) | 0.0185 (3) | |
H23A | −0.3767 | 0.5692 | 0.3865 | 0.022* | |
C24 | −0.37406 (17) | 0.67602 (17) | 0.53626 (13) | 0.0242 (3) | |
H24A | −0.3169 | 0.7292 | 0.6001 | 0.029* | |
H24B | −0.4713 | 0.6608 | 0.5334 | 0.029* | |
C25 | −0.18233 (14) | 0.60277 (14) | 0.13816 (10) | 0.0139 (3) | |
H25A | −0.0842 | 0.6312 | 0.1248 | 0.017* | |
C26 | −0.25030 (14) | 0.46036 (14) | 0.06301 (11) | 0.0165 (3) | |
H26A | −0.3450 | 0.4296 | 0.0808 | 0.020* | |
H26B | −0.2571 | 0.4725 | −0.0146 | 0.020* | |
C27 | −0.17049 (16) | 0.34783 (16) | 0.07565 (12) | 0.0203 (3) | |
H27A | −0.1437 | 0.3350 | 0.1477 | 0.024* | |
C28 | −0.13596 (16) | 0.26558 (16) | −0.00995 (13) | 0.0235 (3) | |
H28A | −0.1614 | 0.2761 | −0.0829 | 0.028* | |
H28B | −0.0862 | 0.1973 | 0.0029 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01460 (12) | 0.01352 (13) | 0.00977 (12) | 0.00283 (9) | −0.00164 (8) | 0.00097 (8) |
Fe2 | 0.01641 (13) | 0.01587 (13) | 0.00999 (12) | 0.00418 (9) | −0.00097 (8) | 0.00283 (8) |
O1 | 0.0184 (5) | 0.0151 (5) | 0.0085 (4) | −0.0002 (4) | −0.0016 (3) | 0.0023 (3) |
C1 | 0.0170 (6) | 0.0169 (6) | 0.0073 (6) | 0.0030 (5) | −0.0012 (5) | 0.0007 (5) |
C2 | 0.0188 (7) | 0.0196 (7) | 0.0113 (6) | 0.0021 (5) | −0.0004 (5) | 0.0038 (5) |
C3 | 0.0178 (7) | 0.0272 (8) | 0.0125 (6) | 0.0031 (6) | 0.0005 (5) | 0.0033 (5) |
C4 | 0.0193 (7) | 0.0255 (8) | 0.0147 (7) | 0.0081 (6) | −0.0017 (5) | −0.0019 (6) |
C5 | 0.0216 (7) | 0.0160 (6) | 0.0117 (6) | 0.0036 (5) | −0.0030 (5) | −0.0010 (5) |
C6 | 0.0239 (8) | 0.0221 (7) | 0.0144 (7) | 0.0071 (6) | −0.0004 (6) | −0.0021 (5) |
C7 | 0.0311 (8) | 0.0147 (6) | 0.0159 (7) | 0.0009 (6) | 0.0007 (6) | −0.0011 (5) |
C8 | 0.0187 (7) | 0.0225 (7) | 0.0151 (7) | −0.0005 (6) | −0.0028 (5) | −0.0013 (5) |
C9 | 0.0223 (7) | 0.0216 (7) | 0.0143 (7) | 0.0037 (6) | −0.0047 (5) | 0.0027 (5) |
C10 | 0.0200 (7) | 0.0213 (7) | 0.0107 (6) | 0.0007 (6) | −0.0018 (5) | 0.0007 (5) |
C11 | 0.0185 (7) | 0.0181 (7) | 0.0100 (6) | 0.0035 (5) | −0.0012 (5) | 0.0029 (5) |
C12 | 0.0180 (7) | 0.0249 (7) | 0.0136 (6) | 0.0062 (6) | 0.0020 (5) | 0.0058 (5) |
C13 | 0.0265 (8) | 0.0340 (8) | 0.0152 (7) | 0.0168 (7) | 0.0041 (6) | 0.0052 (6) |
C14 | 0.0396 (10) | 0.0197 (7) | 0.0140 (7) | 0.0109 (7) | 0.0003 (6) | 0.0019 (5) |
C15 | 0.0260 (8) | 0.0175 (7) | 0.0126 (6) | 0.0026 (6) | −0.0034 (5) | 0.0022 (5) |
C16 | 0.0278 (8) | 0.0242 (8) | 0.0151 (7) | 0.0087 (6) | 0.0049 (6) | 0.0062 (6) |
C17 | 0.0267 (8) | 0.0247 (7) | 0.0108 (6) | 0.0031 (6) | 0.0007 (5) | 0.0018 (5) |
C18 | 0.0255 (8) | 0.0321 (8) | 0.0123 (7) | 0.0083 (7) | −0.0022 (6) | 0.0052 (6) |
C19 | 0.0346 (9) | 0.0215 (7) | 0.0155 (7) | 0.0089 (6) | 0.0020 (6) | 0.0072 (5) |
C20 | 0.0243 (8) | 0.0269 (8) | 0.0168 (7) | 0.0011 (6) | 0.0029 (6) | 0.0085 (6) |
C21 | 0.0144 (6) | 0.0159 (6) | 0.0114 (6) | 0.0024 (5) | −0.0012 (5) | 0.0019 (5) |
C22 | 0.0168 (6) | 0.0204 (7) | 0.0121 (6) | 0.0027 (5) | −0.0001 (5) | 0.0027 (5) |
C23 | 0.0181 (7) | 0.0189 (7) | 0.0180 (7) | 0.0016 (5) | 0.0017 (5) | 0.0053 (5) |
C24 | 0.0234 (8) | 0.0285 (8) | 0.0210 (7) | 0.0043 (6) | 0.0057 (6) | 0.0060 (6) |
C25 | 0.0138 (6) | 0.0176 (6) | 0.0089 (6) | 0.0009 (5) | −0.0012 (4) | 0.0032 (5) |
C26 | 0.0171 (6) | 0.0174 (6) | 0.0131 (6) | 0.0019 (5) | −0.0009 (5) | 0.0011 (5) |
C27 | 0.0250 (7) | 0.0190 (7) | 0.0155 (7) | 0.0038 (6) | −0.0025 (5) | 0.0031 (5) |
C28 | 0.0224 (7) | 0.0225 (7) | 0.0244 (8) | 0.0066 (6) | 0.0003 (6) | 0.0003 (6) |
Fe1—C2 | 2.0504 (14) | C9—H9A | 0.9800 |
Fe1—C6 | 2.0507 (15) | C10—H10A | 0.9800 |
Fe1—C3 | 2.0519 (15) | C11—C12 | 1.433 (2) |
Fe1—C7 | 2.0531 (14) | C11—C15 | 1.433 (2) |
Fe1—C8 | 2.0574 (15) | C11—C25 | 1.5055 (19) |
Fe1—C9 | 2.0605 (15) | C12—C13 | 1.424 (2) |
Fe1—C4 | 2.0609 (15) | C12—H12A | 0.9800 |
Fe1—C10 | 2.0622 (14) | C13—C14 | 1.423 (2) |
Fe1—C5 | 2.0634 (14) | C13—H13A | 0.9800 |
Fe1—C1 | 2.0691 (13) | C14—C15 | 1.422 (2) |
Fe2—C18 | 2.0450 (15) | C14—H14A | 0.9800 |
Fe2—C15 | 2.0460 (14) | C15—H15A | 0.9800 |
Fe2—C19 | 2.0486 (14) | C16—C17 | 1.423 (2) |
Fe2—C14 | 2.0500 (15) | C16—C20 | 1.429 (2) |
Fe2—C13 | 2.0513 (15) | C16—H16A | 0.9800 |
Fe2—C17 | 2.0517 (15) | C17—C18 | 1.426 (2) |
Fe2—C12 | 2.0546 (14) | C17—H17A | 0.9800 |
Fe2—C20 | 2.0549 (15) | C18—C19 | 1.421 (2) |
Fe2—C11 | 2.0572 (14) | C18—H18A | 0.9800 |
Fe2—C16 | 2.0613 (16) | C19—C20 | 1.426 (2) |
O1—C21 | 1.4399 (15) | C19—H19A | 0.9800 |
O1—C25 | 1.4430 (15) | C20—H20A | 0.9800 |
C1—C5 | 1.4306 (19) | C21—C22 | 1.5280 (18) |
C1—C2 | 1.4349 (19) | C21—H21A | 0.9800 |
C1—C21 | 1.5111 (18) | C22—C23 | 1.4962 (19) |
C2—C3 | 1.429 (2) | C22—H22A | 0.9700 |
C2—H2A | 0.9800 | C22—H22B | 0.9700 |
C3—C4 | 1.429 (2) | C23—C24 | 1.327 (2) |
C3—H3A | 0.9800 | C23—H23A | 0.9300 |
C4—C5 | 1.427 (2) | C24—H24A | 0.9300 |
C4—H4A | 0.9800 | C24—H24B | 0.9300 |
C5—H5A | 0.9800 | C25—C26 | 1.5292 (18) |
C6—C7 | 1.420 (2) | C25—H25A | 0.9800 |
C6—C10 | 1.423 (2) | C26—C27 | 1.497 (2) |
C6—H6A | 0.9800 | C26—H26A | 0.9700 |
C7—C8 | 1.420 (2) | C26—H26B | 0.9700 |
C7—H7A | 0.9800 | C27—C28 | 1.323 (2) |
C8—C9 | 1.426 (2) | C27—H27A | 0.9300 |
C8—H8A | 0.9800 | C28—H28A | 0.9300 |
C9—C10 | 1.426 (2) | C28—H28B | 0.9300 |
C2—Fe1—C6 | 113.59 (6) | C7—C6—H6A | 126.1 |
C2—Fe1—C3 | 40.76 (6) | C10—C6—H6A | 126.1 |
C6—Fe1—C3 | 141.86 (6) | Fe1—C6—H6A | 126.1 |
C2—Fe1—C7 | 109.54 (6) | C8—C7—C6 | 108.42 (13) |
C6—Fe1—C7 | 40.48 (6) | C8—C7—Fe1 | 69.96 (8) |
C3—Fe1—C7 | 111.39 (6) | C6—C7—Fe1 | 69.67 (8) |
C2—Fe1—C8 | 134.33 (6) | C8—C7—H7A | 125.8 |
C6—Fe1—C8 | 68.19 (6) | C6—C7—H7A | 125.8 |
C3—Fe1—C8 | 108.04 (6) | Fe1—C7—H7A | 125.8 |
C7—Fe1—C8 | 40.41 (6) | C7—C8—C9 | 107.94 (14) |
C2—Fe1—C9 | 174.21 (6) | C7—C8—Fe1 | 69.63 (8) |
C6—Fe1—C9 | 68.28 (6) | C9—C8—Fe1 | 69.86 (8) |
C3—Fe1—C9 | 134.47 (6) | C7—C8—H8A | 126.0 |
C7—Fe1—C9 | 68.03 (6) | C9—C8—H8A | 126.0 |
C8—Fe1—C9 | 40.52 (6) | Fe1—C8—H8A | 126.0 |
C2—Fe1—C4 | 68.33 (6) | C10—C9—C8 | 107.67 (13) |
C6—Fe1—C4 | 177.47 (6) | C10—C9—Fe1 | 69.83 (8) |
C3—Fe1—C4 | 40.66 (6) | C8—C9—Fe1 | 69.62 (8) |
C7—Fe1—C4 | 141.04 (7) | C10—C9—H9A | 126.2 |
C8—Fe1—C4 | 111.81 (6) | C8—C9—H9A | 126.2 |
C9—Fe1—C4 | 109.98 (6) | Fe1—C9—H9A | 126.2 |
C2—Fe1—C10 | 144.29 (6) | C6—C10—C9 | 108.20 (13) |
C6—Fe1—C10 | 40.47 (6) | C6—C10—Fe1 | 69.33 (8) |
C3—Fe1—C10 | 174.93 (6) | C9—C10—Fe1 | 69.70 (8) |
C7—Fe1—C10 | 67.82 (6) | C6—C10—H10A | 125.9 |
C8—Fe1—C10 | 67.96 (6) | C9—C10—H10A | 125.9 |
C9—Fe1—C10 | 40.47 (6) | Fe1—C10—H10A | 125.9 |
C4—Fe1—C10 | 137.03 (6) | C12—C11—C15 | 106.83 (13) |
C2—Fe1—C5 | 68.04 (6) | C12—C11—C25 | 126.74 (13) |
C6—Fe1—C5 | 138.15 (6) | C15—C11—C25 | 126.26 (13) |
C3—Fe1—C5 | 68.21 (6) | C12—C11—Fe2 | 69.50 (8) |
C7—Fe1—C5 | 176.90 (6) | C15—C11—Fe2 | 69.13 (8) |
C8—Fe1—C5 | 142.68 (6) | C25—C11—Fe2 | 129.98 (9) |
C9—Fe1—C5 | 114.57 (6) | C13—C12—C11 | 108.61 (14) |
C4—Fe1—C5 | 40.49 (6) | C13—C12—Fe2 | 69.58 (8) |
C10—Fe1—C5 | 112.86 (6) | C11—C12—Fe2 | 69.70 (8) |
C2—Fe1—C1 | 40.77 (5) | C13—C12—H12A | 125.7 |
C6—Fe1—C1 | 111.73 (6) | C11—C12—H12A | 125.7 |
C3—Fe1—C1 | 68.73 (6) | Fe2—C12—H12A | 125.7 |
C7—Fe1—C1 | 136.39 (6) | C14—C13—C12 | 107.90 (13) |
C8—Fe1—C1 | 174.97 (6) | C14—C13—Fe2 | 69.65 (9) |
C9—Fe1—C1 | 144.45 (6) | C12—C13—Fe2 | 69.84 (8) |
C4—Fe1—C1 | 68.51 (6) | C14—C13—H13A | 126.1 |
C10—Fe1—C1 | 115.48 (6) | C12—C13—H13A | 126.1 |
C5—Fe1—C1 | 40.51 (5) | Fe2—C13—H13A | 126.1 |
C18—Fe2—C15 | 160.62 (7) | C15—C14—C13 | 108.08 (13) |
C18—Fe2—C19 | 40.63 (7) | C15—C14—Fe2 | 69.53 (8) |
C15—Fe2—C19 | 124.65 (6) | C13—C14—Fe2 | 69.74 (9) |
C18—Fe2—C14 | 122.93 (6) | C15—C14—H14A | 126.0 |
C15—Fe2—C14 | 40.63 (6) | C13—C14—H14A | 126.0 |
C19—Fe2—C14 | 105.68 (6) | Fe2—C14—H14A | 126.0 |
C18—Fe2—C13 | 105.42 (6) | C14—C15—C11 | 108.58 (14) |
C15—Fe2—C13 | 68.39 (6) | C14—C15—Fe2 | 69.84 (8) |
C19—Fe2—C13 | 118.15 (6) | C11—C15—Fe2 | 69.97 (8) |
C14—Fe2—C13 | 40.61 (7) | C14—C15—H15A | 125.7 |
C18—Fe2—C17 | 40.74 (6) | C11—C15—H15A | 125.7 |
C15—Fe2—C17 | 157.60 (6) | Fe2—C15—H15A | 125.7 |
C19—Fe2—C17 | 68.19 (6) | C17—C16—C20 | 107.58 (14) |
C14—Fe2—C17 | 160.82 (7) | C17—C16—Fe2 | 69.39 (9) |
C13—Fe2—C17 | 124.79 (7) | C20—C16—Fe2 | 69.44 (9) |
C18—Fe2—C12 | 119.73 (6) | C17—C16—H16A | 126.2 |
C15—Fe2—C12 | 68.30 (6) | C20—C16—H16A | 126.2 |
C19—Fe2—C12 | 153.71 (6) | Fe2—C16—H16A | 126.2 |
C14—Fe2—C12 | 68.21 (6) | C16—C17—C18 | 108.52 (14) |
C13—Fe2—C12 | 40.58 (6) | C16—C17—Fe2 | 70.12 (9) |
C17—Fe2—C12 | 108.74 (6) | C18—C17—Fe2 | 69.38 (8) |
C18—Fe2—C20 | 68.52 (6) | C16—C17—H17A | 125.7 |
C15—Fe2—C20 | 108.43 (6) | C18—C17—H17A | 125.7 |
C19—Fe2—C20 | 40.68 (6) | Fe2—C17—H17A | 125.7 |
C14—Fe2—C20 | 119.83 (7) | C19—C18—C17 | 107.66 (14) |
C13—Fe2—C20 | 153.74 (7) | C19—C18—Fe2 | 69.82 (9) |
C17—Fe2—C20 | 68.18 (6) | C17—C18—Fe2 | 69.88 (8) |
C12—Fe2—C20 | 164.60 (6) | C19—C18—H18A | 126.2 |
C18—Fe2—C11 | 155.89 (7) | C17—C18—H18A | 126.2 |
C15—Fe2—C11 | 40.89 (6) | Fe2—C18—H18A | 126.2 |
C19—Fe2—C11 | 162.99 (7) | C18—C19—C20 | 108.30 (14) |
C14—Fe2—C11 | 68.73 (6) | C18—C19—Fe2 | 69.55 (9) |
C13—Fe2—C11 | 68.77 (6) | C20—C19—Fe2 | 69.90 (8) |
C17—Fe2—C11 | 122.23 (6) | C18—C19—H19A | 125.9 |
C12—Fe2—C11 | 40.80 (5) | C20—C19—H19A | 125.9 |
C20—Fe2—C11 | 126.96 (6) | Fe2—C19—H19A | 125.9 |
C18—Fe2—C16 | 68.56 (7) | C19—C20—C16 | 107.94 (15) |
C15—Fe2—C16 | 122.45 (7) | C19—C20—Fe2 | 69.42 (9) |
C19—Fe2—C16 | 68.37 (6) | C16—C20—Fe2 | 69.93 (9) |
C14—Fe2—C16 | 156.05 (8) | C19—C20—H20A | 126.0 |
C13—Fe2—C16 | 162.95 (8) | C16—C20—H20A | 126.0 |
C17—Fe2—C16 | 40.49 (6) | Fe2—C20—H20A | 126.0 |
C12—Fe2—C16 | 127.34 (6) | O1—C21—C1 | 110.91 (10) |
C20—Fe2—C16 | 40.63 (6) | O1—C21—C22 | 103.96 (10) |
C11—Fe2—C16 | 109.82 (6) | C1—C21—C22 | 113.26 (11) |
C21—O1—C25 | 116.26 (10) | O1—C21—H21A | 109.5 |
C5—C1—C2 | 106.88 (12) | C1—C21—H21A | 109.5 |
C5—C1—C21 | 126.00 (13) | C22—C21—H21A | 109.5 |
C2—C1—C21 | 127.05 (12) | C23—C22—C21 | 113.86 (11) |
C5—C1—Fe1 | 69.53 (8) | C23—C22—H22A | 108.8 |
C2—C1—Fe1 | 68.92 (8) | C21—C22—H22A | 108.8 |
C21—C1—Fe1 | 129.00 (9) | C23—C22—H22B | 108.8 |
C3—C2—C1 | 108.67 (13) | C21—C22—H22B | 108.8 |
C3—C2—Fe1 | 69.68 (8) | H22A—C22—H22B | 107.7 |
C1—C2—Fe1 | 70.32 (8) | C24—C23—C22 | 123.85 (14) |
C3—C2—H2A | 125.7 | C24—C23—H23A | 118.1 |
C1—C2—H2A | 125.7 | C22—C23—H23A | 118.1 |
Fe1—C2—H2A | 125.7 | C23—C24—H24A | 120.0 |
C2—C3—C4 | 107.79 (13) | C23—C24—H24B | 120.0 |
C2—C3—Fe1 | 69.56 (8) | H24A—C24—H24B | 120.0 |
C4—C3—Fe1 | 70.00 (8) | O1—C25—C11 | 110.74 (10) |
C2—C3—H3A | 126.1 | O1—C25—C26 | 104.26 (10) |
C4—C3—H3A | 126.1 | C11—C25—C26 | 113.26 (11) |
Fe1—C3—H3A | 126.1 | O1—C25—H25A | 109.5 |
C5—C4—C3 | 107.79 (13) | C11—C25—H25A | 109.5 |
C5—C4—Fe1 | 69.85 (8) | C26—C25—H25A | 109.5 |
C3—C4—Fe1 | 69.33 (8) | C27—C26—C25 | 113.16 (11) |
C5—C4—H4A | 126.1 | C27—C26—H26A | 108.9 |
C3—C4—H4A | 126.1 | C25—C26—H26A | 108.9 |
Fe1—C4—H4A | 126.1 | C27—C26—H26B | 108.9 |
C4—C5—C1 | 108.87 (13) | C25—C26—H26B | 108.9 |
C4—C5—Fe1 | 69.66 (8) | H26A—C26—H26B | 107.8 |
C1—C5—Fe1 | 69.96 (8) | C28—C27—C26 | 123.68 (14) |
C4—C5—H5A | 125.6 | C28—C27—H27A | 118.2 |
C1—C5—H5A | 125.6 | C26—C27—H27A | 118.2 |
Fe1—C5—H5A | 125.6 | C27—C28—H28A | 120.0 |
C7—C6—C10 | 107.77 (13) | C27—C28—H28B | 120.0 |
C7—C6—Fe1 | 69.85 (8) | H28A—C28—H28B | 120.0 |
C10—C6—Fe1 | 70.20 (8) |
Experimental details
Crystal data | |
Chemical formula | [Fe2(C5H5)2(C18H20O)] |
Mr | 494.22 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 9.7865 (15), 9.8274 (15), 12.1816 (19) |
α, β, γ (°) | 99.405 (2), 94.976 (2), 101.657 (2) |
V (Å3) | 1123.3 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.31 |
Crystal size (mm) | 0.50 × 0.25 × 0.25 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2007) |
Tmin, Tmax | 0.561, 0.736 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7657, 5352, 4759 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.664 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.100, 0.81 |
No. of reflections | 5352 |
No. of parameters | 280 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.37 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work was supported by the National Natural Science Foundation of China (No. 20874068), the Natural Science Foundation of Jiangsu Province (No. BK2009584) and the Undergraduate Innovating Experimentation Project of Soochow University (No. 5731510110).
References
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Due to their high iron content, bisferrocenyl derivatives have a wider range of applications in high burning rate catalysts than mononuclear ferrocenyl ones (Gao et al., 2011; Locke et al., 2001). Most of bisferrocenyl ethers are synthesized from alcohols with H2SO4 or Al2O3 as catalysts in the environment of high temperature and vacuum (Ferguson et al., 1996; Matković-Čalogović et al., 1993). As part of our ongoing program, the title compound was prepared from 1-ferrocenyl-3-buten-1-ol and dicyclohexylcarbodiimide (DCC), with 4-dimethylaminopyridine (DMAP) as catalyst, at room temperature, and studied by X-ray crystallography. The complex crystallizes with a triclinic unit cell in the P1 space group. A view of the asymmetric unit is given in Fig. 1 and the crystal structure in Fig. 2. Structure solution and refinement showed that the racemic form was crystallized with both chiral centers having the same configuration.
The principal molecular features are the structure of the central C—O—C bridge and the conformations of the ferrocene fragments. The C—O bond lengths are 1.4399 (15) and 1.4430 (15) Å, and the C—O—C angle is 116.26 (10)°, while this angle is found between 113.7 (9) and 112.8 (9)° in the crystal structure of bis(ferrocenylmethyl)ether (Gasser et al., 2007). The cyclopentadienyl rings are twisted from the eclipsed conformation: the mean torsion angles Cn—Cg1—Cg2—Cm and Cp—Cg3—Cg4—Cq (n = 1···5, m = n + 5; p = 11···15, q = p + 5; the Cg pseudoatoms are the centroids of the four rings), for the ferrocene groups defined by Fe1 and Fe2, are 29.3 (1) and 6.1 (1)°, respectively.