organic compounds
N,N′-Bis(2-furylmethylene)-1,1′-binaphthyl-2,2′-diamine
aDépartement de Chimie, Faculté des Sciences, 5019, Monastir, Tunisia, and bDépartement de Chimie, Faculté des Sciences, 7021, Bizerte, Tunisia
*Correspondence e-mail: najouahaj@yahoo.fr
In the title compound, C30H20N2O2, the orientation of the furyl group may induce a variety of coordination modes with this ligand. The dihedral angle between the two naphthyl rings is 79.25 (7)°. The furyl groups make dihedral angles of 62.0 (1) and 16.3 (2)° with the attached naphthyl groups. The dihedral angle between the two furyl rings is 49.3 (2)°.
Related literature
For related literature see: Chen et al. (1995); Dang et al. (1971); Grubbs et al. (1977); Horner et al. (1968); Miyashita et al. (1980); Nishinaga et al. (1988); Pertici et al. (1996); Rosini et al. (1992); Suda et al. (1983); Spassky et al. (1996); Suga et al. (2003).
Experimental
Crystal data
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Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).
Supporting information
https://doi.org/10.1107/S1600536807065750/hj2001sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807065750/hj2001Isup2.hkl
The title compound was obtained as follows: to a stirred solution of the 2-furfuraldehyde (0.067 g, 0.703 mmol) in absolute ethanol (10 ml) was added the
2,2'-diamino-1,1'-binaphthyl (0.1 g,0.35 mmol). The resulting suspension was heated at reflux for 24 h. The pure yellow ligand was obtained after crystallization in absolute ethanol.Hydrogen atoms H1, H3, H4, H5, H26, H28, H29 and H30 were located in a Fourier map and refined freely. All the other H atoms were placed in calculated positions and allowed to ride during subsequent
The range of bond lengths to hydrogen is between 0.92 and 1.09 Å. Uiso of the H atoms were set to be equal to 1.2 Uiso of the parent atoms.The importance of axially chiral ligands in catalytic asymmetric reactions is well known in the development of stereoselective hydrogenation of olefins.The low
induced by the first chiral monodentate phosphane ligands (Horner et al., 1968) was soon enhanced by chelating bisphosphanes (Dang et al., 1971). Axially chiral ligands were first reported in a hydrogenation reaction in 1977 and have gained ground ever since (Grubbs et al., 1977).In addition to the biaryl backbone bisphosphanes (2,2'-bis (diphenylphosphino)-1,1'-binaphthyl) (Miyashita et al., 1980), derivatives of the corresponding diamines (biphenyldiamine and binaphthyldiamine) have performed successfully in many asymmetric catalytic reactions (Rosini et al., 1992). These include stereoselective polymerizations of methacrylate (Suda et al., 1983) and lactate (Spassky et al., 1996) and numerous enantioselective modifications of such as epoxidation (Nishinaga et al., 1988), aziridination (Suga et al., 2003), cyclopropanation (Chen et al., 1995) and hydrogenation (Pertici et al., 1996). With a structurally rigid binaphthyl ligand backbone, the configuration of the ligand is fixed and its axial can efficiently be transmitted to the active site catalyst. We report here the of (I) which was synthesized via condensation of the axially chiral binaphthyldiamine with the 2-furfuraldehyde. The centrosymmetric shows that there is which may occur during the reaction of condensation. The molecule of (I) has two imine groups with bond distances N1—C1 1.264 (5) Å and N2—C26 1.268 (4) Å. Each imine group is bound to a furfuryl group such that C1—C2 1.445 (5) and C26—C27 1.431 (5) Å. Variation between N—C (N1—C1 and N2—C26) and C—C (C1—C2 and C26—C27) bonds are statistically insignificant. The naphthyl rings make a dihedral angle of 79.25 (7) ° with one another. The furyl group C2C3C4C5O1 makes a dihedral angle of 62.0 (1) ° with its attached binaphthyl group. The other furyl makes a dihedral angle of 16.3 (2) ° with its binaphthyl group. The furyl groups make a dihedral angle of 49.3 (2) ° with one another.For related literature see: Chen et al. (1995); Dang et al. (1971); Grubbs et al. (1977); Horner et al. (1968); Miyashita et al. (1980); Nishinaga et al. (1988); Pertici et al. (1996); Rosini et al. (1992); Suda et al. (1983); Spassky et al. (1996); Suga et al. (2003)
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell
CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are omitted. |
C30H20N2O2 | F(000) = 920 |
Mr = 440.48 | Dx = 1.290 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 8.2433 (2) Å | θ = 9.9–11.0° |
b = 15.5046 (3) Å | µ = 0.08 mm−1 |
c = 17.7432 (3) Å | T = 293 K |
β = 91.309 (3)° | Prism, yellow |
V = 2267.15 (8) Å3 | 0.23 × 0.15 × 0.12 mm |
Z = 4 |
Enraf–Nonius TurboCAD-4 diffractometer | Rint = 0.028 |
Radiation source: fine-focus sealed tube | θmax = 25°, θmin = 2.3° |
Graphite monochromator | h = −10→10 |
non–profiled ω scans | k = 0→18 |
4133 measured reflections | l = 0→21 |
4016 independent reflections | 2 standard reflections every 120 min |
1600 reflections with I > 2σ(I) | intensity decay: −1% |
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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.146 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0464P)2] where P = (Fo2 + 2Fc2)/3 |
4016 reflections | (Δ/σ)max < 0.001 |
331 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C30H20N2O2 | V = 2267.15 (8) Å3 |
Mr = 440.48 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.2433 (2) Å | µ = 0.08 mm−1 |
b = 15.5046 (3) Å | T = 293 K |
c = 17.7432 (3) Å | 0.23 × 0.15 × 0.12 mm |
β = 91.309 (3)° |
Enraf–Nonius TurboCAD-4 diffractometer | Rint = 0.028 |
4133 measured reflections | 2 standard reflections every 120 min |
4016 independent reflections | intensity decay: −1% |
1600 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.146 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | Δρmax = 0.17 e Å−3 |
4016 reflections | Δρmin = −0.18 e Å−3 |
331 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.9295 (4) | 0.7193 (2) | −0.20480 (18) | 0.0883 (10) | |
O2 | 0.4942 (3) | 0.94701 (19) | −0.06519 (15) | 0.0583 (7) | |
N1 | 1.0080 (4) | 0.7947 (2) | −0.0674 (2) | 0.0614 (10) | |
N2 | 0.6396 (3) | 0.7971 (2) | −0.00840 (18) | 0.0503 (9) | |
C1 | 1.0368 (5) | 0.8348 (3) | −0.1278 (3) | 0.0640 (13) | |
H1 | 1.086 (4) | 0.900 (2) | −0.128 (2) | 0.077* | |
C2 | 1.0049 (5) | 0.7968 (3) | −0.2010 (3) | 0.0572 (11) | |
C3 | 1.0277 (6) | 0.8265 (3) | −0.2713 (3) | 0.0731 (15) | |
H3 | 1.068 (5) | 0.882 (3) | −0.281 (2) | 0.088* | |
C4 | 0.9647 (6) | 0.7628 (4) | −0.3211 (3) | 0.0820 (16) | |
H4 | 0.959 (5) | 0.767 (3) | −0.373 (2) | 0.098* | |
C5 | 0.9084 (6) | 0.7002 (4) | −0.2798 (3) | 0.0917 (17) | |
H5 | 0.863 (5) | 0.635 (3) | −0.284 (2) | 0.110* | |
C6 | 1.0290 (4) | 0.8361 (2) | 0.0035 (2) | 0.0510 (11) | |
C7 | 1.1278 (5) | 0.9100 (3) | 0.0148 (3) | 0.0685 (13) | |
H7 | 1.1838 | 0.9331 | −0.0254 | 0.082* | |
C8 | 1.1413 (5) | 0.9477 (3) | 0.0842 (3) | 0.0670 (12) | |
H8 | 1.2056 | 0.9965 | 0.0908 | 0.080* | |
C9 | 1.0583 (5) | 0.9130 (3) | 0.1462 (3) | 0.0530 (11) | |
C10 | 1.0706 (5) | 0.9520 (3) | 0.2183 (3) | 0.0677 (13) | |
H10 | 1.1338 | 1.0012 | 0.2252 | 0.081* | |
C11 | 0.9906 (6) | 0.9180 (3) | 0.2772 (3) | 0.0758 (14) | |
H11 | 1.0008 | 0.9432 | 0.3247 | 0.091* | |
C12 | 0.8931 (5) | 0.8453 (3) | 0.2669 (2) | 0.0688 (13) | |
H12 | 0.8363 | 0.8233 | 0.3073 | 0.083* | |
C13 | 0.8799 (5) | 0.8062 (3) | 0.1986 (2) | 0.0568 (11) | |
H13 | 0.8159 | 0.7571 | 0.1930 | 0.068* | |
C14 | 0.9628 (4) | 0.8395 (2) | 0.1355 (2) | 0.0461 (10) | |
C15 | 0.9504 (4) | 0.7992 (2) | 0.0629 (2) | 0.0440 (10) | |
C16 | 0.8575 (4) | 0.7176 (2) | 0.05238 (19) | 0.0417 (9) | |
C17 | 0.7078 (4) | 0.7177 (3) | 0.0167 (2) | 0.0475 (10) | |
C18 | 0.6187 (5) | 0.6405 (3) | 0.0082 (2) | 0.0637 (12) | |
H18 | 0.5171 | 0.6412 | −0.0156 | 0.076* | |
C19 | 0.6821 (5) | 0.5652 (3) | 0.0349 (2) | 0.0703 (13) | |
H19 | 0.6199 | 0.5152 | 0.0309 | 0.085* | |
C20 | 0.8384 (5) | 0.5600 (3) | 0.0684 (2) | 0.0585 (11) | |
C21 | 0.9119 (7) | 0.4816 (3) | 0.0909 (2) | 0.0769 (14) | |
H21 | 0.8541 | 0.4303 | 0.0859 | 0.092* | |
C22 | 1.0659 (7) | 0.4800 (3) | 0.1198 (3) | 0.0835 (16) | |
H22 | 1.1131 | 0.4280 | 0.1346 | 0.100* | |
C23 | 1.1524 (6) | 0.5562 (3) | 0.1273 (2) | 0.0754 (14) | |
H23 | 1.2581 | 0.5548 | 0.1467 | 0.090* | |
C24 | 1.0856 (5) | 0.6329 (3) | 0.1068 (2) | 0.0610 (12) | |
H24 | 1.1461 | 0.6831 | 0.1129 | 0.073* | |
C25 | 0.9267 (5) | 0.6381 (2) | 0.0765 (2) | 0.0472 (10) | |
C26 | 0.5987 (5) | 0.8037 (3) | −0.0775 (2) | 0.0540 (11) | |
H26 | 0.619 (4) | 0.759 (2) | −0.1130 (19) | 0.065* | |
C27 | 0.5253 (5) | 0.8786 (3) | −0.1108 (2) | 0.0525 (11) | |
C28 | 0.4798 (7) | 0.8988 (3) | −0.1816 (3) | 0.0823 (16) | |
H28 | 0.500 (5) | 0.863 (3) | −0.223 (2) | 0.099* | |
C29 | 0.4167 (6) | 0.9820 (4) | −0.1811 (3) | 0.0842 (17) | |
H29 | 0.370 (5) | 1.015 (3) | −0.221 (2) | 0.102* | |
C30 | 0.4264 (6) | 1.0095 (3) | −0.1108 (3) | 0.0713 (14) | |
H30 | 0.399 (5) | 1.066 (2) | −0.082 (2) | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C15 | 0.039 (2) | 0.042 (2) | 0.050 (3) | −0.0070 (19) | −0.009 (2) | 0.006 (2) |
O2 | 0.0567 (17) | 0.0603 (19) | 0.0581 (17) | 0.0050 (16) | 0.0043 (14) | 0.0058 (17) |
C14 | 0.037 (2) | 0.044 (3) | 0.056 (3) | −0.004 (2) | −0.013 (2) | 0.004 (2) |
N2 | 0.0426 (19) | 0.057 (2) | 0.051 (2) | −0.0002 (17) | −0.0076 (17) | −0.0008 (18) |
C16 | 0.043 (2) | 0.041 (2) | 0.041 (2) | −0.005 (2) | −0.0010 (18) | 0.0004 (19) |
C6 | 0.048 (3) | 0.047 (3) | 0.058 (3) | −0.004 (2) | −0.002 (2) | 0.003 (2) |
C17 | 0.046 (2) | 0.047 (3) | 0.049 (3) | −0.004 (2) | −0.006 (2) | 0.000 (2) |
N1 | 0.065 (2) | 0.065 (2) | 0.055 (2) | −0.013 (2) | 0.0055 (19) | 0.011 (2) |
O1 | 0.104 (3) | 0.089 (3) | 0.073 (2) | −0.031 (2) | 0.0025 (19) | 0.001 (2) |
C9 | 0.045 (3) | 0.045 (3) | 0.068 (3) | −0.004 (2) | −0.014 (2) | −0.002 (2) |
C18 | 0.058 (3) | 0.053 (3) | 0.079 (3) | −0.011 (3) | −0.014 (2) | −0.009 (2) |
C27 | 0.055 (3) | 0.055 (3) | 0.047 (3) | −0.008 (2) | −0.009 (2) | 0.007 (2) |
C12 | 0.080 (3) | 0.073 (3) | 0.053 (3) | −0.006 (3) | −0.005 (2) | −0.010 (3) |
C25 | 0.055 (3) | 0.043 (3) | 0.044 (2) | −0.006 (2) | −0.001 (2) | 0.000 (2) |
C2 | 0.056 (3) | 0.050 (3) | 0.066 (3) | −0.002 (2) | 0.009 (2) | 0.007 (3) |
C26 | 0.049 (3) | 0.059 (3) | 0.053 (3) | −0.005 (2) | −0.003 (2) | −0.009 (2) |
C20 | 0.068 (3) | 0.053 (3) | 0.055 (3) | −0.009 (3) | 0.001 (2) | 0.002 (2) |
C8 | 0.051 (3) | 0.056 (3) | 0.094 (4) | −0.015 (2) | −0.007 (3) | −0.008 (3) |
C13 | 0.062 (3) | 0.051 (3) | 0.057 (3) | −0.008 (2) | −0.007 (2) | 0.000 (2) |
C24 | 0.068 (3) | 0.055 (3) | 0.059 (3) | 0.006 (2) | −0.016 (2) | 0.005 (2) |
C1 | 0.071 (3) | 0.055 (3) | 0.066 (3) | 0.001 (3) | 0.010 (3) | −0.005 (3) |
C7 | 0.059 (3) | 0.063 (3) | 0.084 (4) | −0.021 (2) | 0.007 (3) | 0.005 (3) |
C30 | 0.066 (3) | 0.067 (3) | 0.081 (4) | 0.005 (3) | 0.009 (3) | 0.024 (3) |
C11 | 0.089 (4) | 0.072 (4) | 0.065 (3) | −0.002 (3) | −0.019 (3) | −0.015 (3) |
C10 | 0.067 (3) | 0.051 (3) | 0.084 (3) | −0.009 (2) | −0.024 (3) | −0.011 (3) |
C21 | 0.117 (4) | 0.049 (3) | 0.065 (3) | −0.003 (3) | 0.004 (3) | 0.009 (2) |
C23 | 0.085 (3) | 0.064 (3) | 0.076 (3) | 0.010 (3) | −0.017 (3) | 0.008 (3) |
C19 | 0.079 (3) | 0.048 (3) | 0.084 (3) | −0.022 (3) | −0.002 (3) | −0.003 (3) |
C29 | 0.089 (4) | 0.081 (4) | 0.082 (4) | −0.009 (3) | −0.025 (3) | 0.026 (3) |
C5 | 0.095 (4) | 0.110 (5) | 0.071 (4) | −0.016 (4) | −0.001 (3) | −0.014 (4) |
C4 | 0.073 (3) | 0.115 (5) | 0.058 (3) | 0.016 (3) | 0.010 (3) | 0.003 (4) |
C3 | 0.092 (4) | 0.062 (3) | 0.067 (3) | 0.005 (3) | 0.023 (3) | 0.010 (3) |
C28 | 0.112 (4) | 0.071 (4) | 0.062 (4) | 0.000 (3) | −0.013 (3) | 0.001 (3) |
C22 | 0.115 (5) | 0.067 (4) | 0.068 (3) | 0.028 (4) | −0.003 (3) | 0.017 (3) |
C15—C6 | 1.374 (5) | C26—H26 | 0.95 (3) |
C15—C14 | 1.434 (5) | C20—C19 | 1.409 (5) |
C15—C16 | 1.488 (5) | C20—C21 | 1.413 (6) |
O2—C27 | 1.363 (4) | C8—C7 | 1.366 (5) |
O2—C30 | 1.373 (5) | C8—H8 | 0.9300 |
C14—C9 | 1.395 (5) | C13—H13 | 0.9300 |
C14—C13 | 1.421 (5) | C24—C23 | 1.357 (5) |
N2—C26 | 1.268 (4) | C24—H24 | 0.9300 |
N2—C17 | 1.421 (4) | C1—H1 | 1.09 (4) |
C16—C17 | 1.374 (4) | C7—H7 | 0.9300 |
C16—C25 | 1.420 (5) | C30—C29 | 1.320 (6) |
C6—C7 | 1.418 (5) | C30—H30 | 1.04 (4) |
C6—N1 | 1.420 (4) | C11—C10 | 1.356 (6) |
C17—C18 | 1.410 (5) | C11—H11 | 0.9300 |
N1—C1 | 1.264 (5) | C10—H10 | 0.9300 |
O1—C2 | 1.354 (5) | C21—C22 | 1.359 (6) |
O1—C5 | 1.370 (5) | C21—H21 | 0.9300 |
C9—C8 | 1.415 (5) | C23—C22 | 1.385 (6) |
C9—C10 | 1.416 (5) | C23—H23 | 0.9300 |
C18—C19 | 1.361 (5) | C19—H19 | 0.9300 |
C18—H18 | 0.9300 | C29—C28 | 1.392 (6) |
C27—C28 | 1.339 (5) | C29—H29 | 0.95 (4) |
C27—C26 | 1.431 (5) | C5—C4 | 1.308 (7) |
C12—C13 | 1.357 (5) | C5—H5 | 1.08 (4) |
C12—C11 | 1.394 (5) | C4—C3 | 1.416 (7) |
C12—H12 | 0.9300 | C4—H4 | 0.92 (4) |
C25—C24 | 1.407 (5) | C3—H3 | 0.94 (4) |
C25—C20 | 1.418 (5) | C28—H28 | 0.93 (4) |
C2—C3 | 1.348 (5) | C22—H22 | 0.9300 |
C2—C1 | 1.445 (5) | ||
C6—C15—C14 | 118.8 (4) | C12—C13—H13 | 119.6 |
C6—C15—C16 | 120.6 (3) | C14—C13—H13 | 119.6 |
C14—C15—C16 | 120.6 (4) | C23—C24—C25 | 121.4 (4) |
C27—O2—C30 | 106.2 (3) | C23—C24—H24 | 119.3 |
C9—C14—C13 | 118.0 (4) | C25—C24—H24 | 119.3 |
C9—C14—C15 | 120.4 (4) | N1—C1—C2 | 121.8 (4) |
C13—C14—C15 | 121.6 (4) | N1—C1—H1 | 122 (2) |
C26—N2—C17 | 117.9 (3) | C2—C1—H1 | 115.8 (19) |
C17—C16—C25 | 119.3 (3) | C8—C7—C6 | 120.5 (4) |
C17—C16—C15 | 120.8 (3) | C8—C7—H7 | 119.8 |
C25—C16—C15 | 119.9 (3) | C6—C7—H7 | 119.8 |
C15—C6—C7 | 120.6 (4) | C29—C30—O2 | 110.1 (5) |
C15—C6—N1 | 116.2 (4) | C29—C30—H30 | 136 (2) |
C7—C6—N1 | 123.2 (4) | O2—C30—H30 | 114 (2) |
C16—C17—C18 | 120.6 (4) | C10—C11—C12 | 120.2 (4) |
C16—C17—N2 | 119.3 (3) | C10—C11—H11 | 119.9 |
C18—C17—N2 | 120.0 (3) | C12—C11—H11 | 119.9 |
C1—N1—C6 | 120.5 (4) | C11—C10—C9 | 120.2 (4) |
C2—O1—C5 | 106.8 (4) | C11—C10—H10 | 119.9 |
C14—C9—C8 | 119.1 (4) | C9—C10—H10 | 119.9 |
C14—C9—C10 | 120.1 (4) | C22—C21—C20 | 120.9 (5) |
C8—C9—C10 | 120.9 (4) | C22—C21—H21 | 119.6 |
C19—C18—C17 | 119.8 (4) | C20—C21—H21 | 119.6 |
C19—C18—H18 | 120.1 | C24—C23—C22 | 121.2 (4) |
C17—C18—H18 | 120.1 | C24—C23—H23 | 119.4 |
C28—C27—O2 | 108.8 (4) | C22—C23—H23 | 119.4 |
C28—C27—C26 | 133.2 (5) | C18—C19—C20 | 122.4 (4) |
O2—C27—C26 | 118.0 (4) | C18—C19—H19 | 118.8 |
C13—C12—C11 | 120.9 (4) | C20—C19—H19 | 118.8 |
C13—C12—H12 | 119.6 | C30—C29—C28 | 106.9 (5) |
C11—C12—H12 | 119.6 | C30—C29—H29 | 123 (3) |
C24—C25—C20 | 117.4 (4) | C28—C29—H29 | 130 (3) |
C24—C25—C16 | 121.9 (4) | C4—C5—O1 | 110.2 (5) |
C20—C25—C16 | 120.6 (4) | C4—C5—H5 | 142 (2) |
C3—C2—O1 | 109.3 (4) | O1—C5—H5 | 107 (2) |
C3—C2—C1 | 131.9 (5) | C5—C4—C3 | 107.3 (5) |
O1—C2—C1 | 118.7 (4) | C5—C4—H4 | 127 (3) |
N2—C26—C27 | 124.5 (4) | C3—C4—H4 | 126 (3) |
N2—C26—H26 | 122 (2) | C2—C3—C4 | 106.4 (4) |
C27—C26—H26 | 113 (2) | C2—C3—H3 | 123 (3) |
C19—C20—C21 | 123.4 (4) | C4—C3—H3 | 130 (3) |
C19—C20—C25 | 117.2 (4) | C27—C28—C29 | 107.9 (5) |
C21—C20—C25 | 119.4 (4) | C27—C28—H28 | 123 (3) |
C7—C8—C9 | 120.5 (4) | C29—C28—H28 | 129 (3) |
C7—C8—H8 | 119.7 | C21—C22—C23 | 119.7 (5) |
C9—C8—H8 | 119.7 | C21—C22—H22 | 120.2 |
C12—C13—C14 | 120.7 (4) | C23—C22—H22 | 120.2 |
C6—C15—C14—C9 | −2.4 (5) | C16—C25—C20—C19 | 0.8 (5) |
C16—C15—C14—C9 | 176.0 (3) | C24—C25—C20—C21 | 0.2 (5) |
C6—C15—C14—C13 | 177.8 (3) | C16—C25—C20—C21 | 178.3 (4) |
C16—C15—C14—C13 | −3.8 (5) | C14—C9—C8—C7 | 0.3 (6) |
C6—C15—C16—C17 | −76.0 (5) | C10—C9—C8—C7 | −179.5 (4) |
C14—C15—C16—C17 | 105.6 (4) | C11—C12—C13—C14 | −1.2 (6) |
C6—C15—C16—C25 | 101.2 (4) | C9—C14—C13—C12 | 0.3 (5) |
C14—C15—C16—C25 | −77.2 (4) | C15—C14—C13—C12 | −179.9 (4) |
C14—C15—C6—C7 | 3.3 (5) | C20—C25—C24—C23 | 0.3 (6) |
C16—C15—C6—C7 | −175.1 (4) | C16—C25—C24—C23 | −177.8 (4) |
C14—C15—C6—N1 | −178.1 (3) | C6—N1—C1—C2 | −175.2 (4) |
C16—C15—C6—N1 | 3.5 (5) | C3—C2—C1—N1 | −179.0 (5) |
C25—C16—C17—C18 | 4.0 (5) | O1—C2—C1—N1 | 5.7 (7) |
C15—C16—C17—C18 | −178.7 (4) | C9—C8—C7—C6 | 0.6 (6) |
C25—C16—C17—N2 | −179.1 (3) | C15—C6—C7—C8 | −2.5 (6) |
C15—C16—C17—N2 | −1.8 (5) | N1—C6—C7—C8 | 179.1 (4) |
C26—N2—C17—C16 | 124.2 (4) | C27—O2—C30—C29 | −0.4 (5) |
C26—N2—C17—C18 | −58.9 (5) | C13—C12—C11—C10 | 1.7 (7) |
C15—C6—N1—C1 | 160.8 (4) | C12—C11—C10—C9 | −1.3 (6) |
C7—C6—N1—C1 | −20.7 (6) | C14—C9—C10—C11 | 0.4 (6) |
C13—C14—C9—C8 | −179.6 (3) | C8—C9—C10—C11 | −179.9 (4) |
C15—C14—C9—C8 | 0.6 (5) | C19—C20—C21—C22 | 177.0 (4) |
C13—C14—C9—C10 | 0.1 (5) | C25—C20—C21—C22 | −0.3 (6) |
C15—C14—C9—C10 | −179.6 (3) | C25—C24—C23—C22 | −0.7 (7) |
C16—C17—C18—C19 | −0.6 (6) | C17—C18—C19—C20 | −2.8 (6) |
N2—C17—C18—C19 | −177.5 (4) | C21—C20—C19—C18 | −174.6 (4) |
C30—O2—C27—C28 | 0.6 (5) | C25—C20—C19—C18 | 2.7 (6) |
C30—O2—C27—C26 | 179.4 (3) | O2—C30—C29—C28 | 0.1 (6) |
C17—C16—C25—C24 | 173.9 (3) | C2—O1—C5—C4 | −1.1 (6) |
C15—C16—C25—C24 | −3.4 (5) | O1—C5—C4—C3 | 0.5 (7) |
C17—C16—C25—C20 | −4.1 (5) | O1—C2—C3—C4 | −0.9 (5) |
C15—C16—C25—C20 | 178.6 (3) | C1—C2—C3—C4 | −176.6 (5) |
C5—O1—C2—C3 | 1.2 (5) | C5—C4—C3—C2 | 0.2 (6) |
C5—O1—C2—C1 | 177.5 (4) | O2—C27—C28—C29 | −0.5 (6) |
C17—N2—C26—C27 | 178.6 (3) | C26—C27—C28—C29 | −179.1 (4) |
C28—C27—C26—N2 | 177.2 (5) | C30—C29—C28—C27 | 0.2 (6) |
O2—C27—C26—N2 | −1.4 (6) | C20—C21—C22—C23 | −0.1 (7) |
C24—C25—C20—C19 | −177.3 (4) | C24—C23—C22—C21 | 0.6 (7) |
Experimental details
Crystal data | |
Chemical formula | C30H20N2O2 |
Mr | 440.48 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.2433 (2), 15.5046 (3), 17.7432 (3) |
β (°) | 91.309 (3) |
V (Å3) | 2267.15 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.23 × 0.15 × 0.12 |
Data collection | |
Diffractometer | Enraf–Nonius TurboCAD-4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4133, 4016, 1600 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.146, 0.97 |
No. of reflections | 4016 |
No. of parameters | 331 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.18 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).
N2—C26 | 1.268 (4) | C27—C26 | 1.431 (5) |
N2—C17 | 1.421 (4) | C2—C1 | 1.445 (5) |
C6—N1 | 1.420 (4) | C26—H26 | 0.95 (3) |
N1—C1 | 1.264 (5) | C1—H1 | 1.09 (4) |
C26—N2—C17 | 117.9 (3) | C18—C17—N2 | 120.0 (3) |
C15—C6—N1 | 116.2 (4) | C1—N1—C6 | 120.5 (4) |
C7—C6—N1 | 123.2 (4) | N2—C26—C27 | 124.5 (4) |
C16—C17—N2 | 119.3 (3) | N1—C1—C2 | 121.8 (4) |
C6—C15—C16—C17 | −76.0 (5) | C6—C15—C16—C25 | 101.2 (4) |
References
Chen, G. M., Chen, F. & Zhou, C. (1995). Gaodeng Xuexiao Huaxue Xuebao, 16, 216–218. CAS Google Scholar
Dang, T. P. & Kagan, H. B. (1971). J. Chem. Soc. Chem. Commun. pp. 481–482. CrossRef Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Grubbs, R. H. & De Vries, R. A. (1977). Tetrahedron Lett. 22, 1879–1880. CrossRef Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Horner, L., Siegel, H. & Buthe, H. (1968). Angew. Chem. Int. Ed. Engl. 7, 942–943. CrossRef CAS Web of Science Google Scholar
Miyashita, A., Yasuda, A., Takaya, H., Toriumi, K., Ito, T., Souchi, T. & Noyori, R. (1980). J. Am. Chem. Soc. 102, 7932–7934. CSD CrossRef CAS Web of Science Google Scholar
Nishinaga, A., Yamato, H., Abe, T., Maruyama, K. & Matsuura, T. (1988). Tetrahedron Lett. 29, 6309–6312. CrossRef CAS Web of Science Google Scholar
Pertici, P., DArata, F. & Rosini, C. (1996). J. Organomet. Chem. 515, 163–171. CrossRef CAS Web of Science Google Scholar
Rosini, C., Franzini, L., Raffaelli, A. & Salvadori, P. (1992). Synthesis, pp. 503–517. CrossRef Google Scholar
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany. Google Scholar
Spassky, N., Wisniewski, M., Pluta, C. & Le Borgne, A. (1996). Macromol. Chem. Phys. 197, 2627–2637. CrossRef CAS Web of Science Google Scholar
Suda, H., Kanoh, S., Murose, N., Goka, S. & Motoi, M. (1983). Polym. Bull. 10, 162–167. CrossRef CAS Google Scholar
Suga, H., Kakehi, A., Ito, S., Ibata, T., Fudo, T., Watanabe, Y. & Kinoshita, Y. (2003). Bull. Chem. Soc. Jpn, 76, 189–199. Web of Science CrossRef CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The importance of axially chiral ligands in catalytic asymmetric reactions is well known in the development of stereoselective hydrogenation of olefins.The low enantiomeric excess induced by the first chiral monodentate phosphane ligands (Horner et al., 1968) was soon enhanced by chelating bisphosphanes (Dang et al., 1971). Axially chiral ligands were first reported in a hydrogenation reaction in 1977 and have gained ground ever since (Grubbs et al., 1977).In addition to the biaryl backbone bisphosphanes (2,2'-bis (diphenylphosphino)-1,1'-binaphthyl) (Miyashita et al., 1980), derivatives of the corresponding diamines (biphenyldiamine and binaphthyldiamine) have performed successfully in many asymmetric catalytic reactions (Rosini et al., 1992). These include stereoselective polymerizations of methacrylate (Suda et al., 1983) and lactate (Spassky et al., 1996) and numerous enantioselective modifications of olefins such as epoxidation (Nishinaga et al., 1988), aziridination (Suga et al., 2003), cyclopropanation (Chen et al., 1995) and hydrogenation (Pertici et al., 1996). With a structurally rigid binaphthyl ligand backbone, the configuration of the ligand is fixed and its axial chirality can efficiently be transmitted to the active site catalyst. We report here the crystal structure of (I) which was synthesized via condensation of the axially chiral binaphthyldiamine with the 2-furfuraldehyde. The centrosymmetric crystal structure shows that there is racemization which may occur during the reaction of condensation. The molecule of (I) has two imine groups with bond distances N1—C1 1.264 (5) Å and N2—C26 1.268 (4) Å. Each imine group is bound to a furfuryl group such that C1—C2 1.445 (5) and C26—C27 1.431 (5) Å. Variation between N—C (N1—C1 and N2—C26) and C—C (C1—C2 and C26—C27) bonds are statistically insignificant. The naphthyl rings make a dihedral angle of 79.25 (7) ° with one another. The furyl group C2C3C4C5O1 makes a dihedral angle of 62.0 (1) ° with its attached binaphthyl group. The other furyl makes a dihedral angle of 16.3 (2) ° with its binaphthyl group. The furyl groups make a dihedral angle of 49.3 (2) ° with one another.