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Acta Cryst. (2007). E63, o3060    [ doi:10.1107/S1600536807025937 ]

(S)-(+)-2,2'-Bis(2-hydroxy-3-methoxybenzylideneamino)-1,1'-binaphthyl

W.-L. Chai, W.-Y. Bi, X.-Q. Lü, J.-R. Song and S. W. Ng

Abstract top

In the chiral title compound, C36H28N2O4, the two naphthyl systems are twisted by 81.2 (1)° about their linking C-C single bond. The OH group forms an intramolecular hydrogen bond with the imino N acceptor atom. The complete molecule has twofold symmetry and shows extensive disorder of the pendant substituted aromatic ring; the site occupancy ratio is 0.78:0.22.

Comment top

The nickel derivatives of the Schiff bases that are formed by condensing 2,2'-diamino-1,1-binaphthyl with aldehydes are catalysts for enantioselective Diels-Alder reactions (Suga et al., 2003, 2004). The present crystallographic study follows the study on racemic 2,2'-bis(2-hydroxy-3-ethoxybenzylideneamino)-1,1'-binaphthyl, which exists as a dichloromethane solvate (Che et al., 2002). The title compound is a substitutted 1,1'-binaphthyl that lies on a twofold rotation axis; the fused-rings are twisted by 81.2 (1) ° along the naphthyl–naphthyl bond. The hydroxy group forms an internal hydrogen bond with the imino nitrogen, a feature that is common to Schiff bases derived from a substituted salicyaldehyde such as o-vanillin and an amine (Cambridge Structural Database Version 5.28, November 2006).

The structure of the optically active (S)-(+)-2,2'-diamino-1,1'-binaphthyl reactant has not been reported although the R-enantiomer has already been described (in the P43212 space group) (Jones et al., 2003). The space group of the S-enantiomer should be that of the present Schiff base, i.e., P41212.

Related literature top

For the crystal structure of the racemic modification of the title compound, see Che et al., 2002; for the opposite enantiomer of the starting material, see: Jones et al. (2003).

For related literature, see: Suga et al. (2003, 2004).

Experimental top

(S)-(+)-2,2'-Diamino-1,1'-binaphthyl (0.144 g, 0.5 mmol) and o-vanillin (0.162 g, 1.05 mmol) was heated in ethanol (10 ml) for several hours. The orange compound that resulted was isolated and recrystallized from ethanol to yield orange prisms of (I) in 70% yield. CH&N elemental analysis: calc. for C36H28N2O4: C 78.24, H 5.11, N 5.07. Found: C 78.31, H 5.08, N 5.04%.

Refinement top

The 2-hydroxy-3-methoxylphenyl part of the molecule is disordered over two positions, the disorder refining to a 0.88:0.22 ratio. The aromatic ring was refined as a rigid hexagon of 1.39 Å sides. Pairs of distances for the unprimed and primed atoms were restrained to within 0.01 Å of each other, and the vibration of the disordered atoms was restrained to be nearly isotropic.

The hydrogen atoms were placed in calculated positions (C—H = 0.93–0.96 Å, O–H 0.82 Å), and refined as riding with Uiso(H) = 1.5Ueq(carrier).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. View of (I) showing 30% displacement ellipsoids. Hydrogen atoms are drawn as spheres of arbitrary radius; the minor disorder component is not shown. Symmetry code (i): y − 1, 1 + x, 2 − z.
(S)-(+)-2,2'-Bis(2-hydroxy-3-methoxybenzylideneamino)-1,1'-binaphthyl top
Crystal data top
C36H28N2O4Z = 4
Mr = 552.60F000 = 1160
Tetragonal, P41212Dx = 1.200 Mg m−3
Hall symbol: P 4abw 2nwMo Kα radiation
λ = 0.71073 Å
a = 11.3285 (6) ÅCell parameters from 4468 reflections
b = 11.3285 Åθ = 2.5–21.0º
c = 23.837 (1) ŵ = 0.08 mm−1
α = 90ºT = 295 (2) K
β = 90ºPrism, orange
γ = 90º0.38 × 0.31 × 0.28 mm
V = 3059.1 (2) Å3
Data collection top
Bruker APEX
diffractometer		1190 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.028
Monochromator: graphiteθmax = 25.0º
T = 295(2) Kθmin = 2.0º
φ and ω scansh = −13→8
Absorption correction: nonek = −13→11
15298 measured reflectionsl = −28→28
1629 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.203  w = 1/[σ2(Fo2) + (0.1153P)2 + 0.6898P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
1629 reflectionsΔρmax = 0.19 e Å−3
240 parametersΔρmin = −0.18 e Å−3
114 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C36H28N2O4γ = 90º
Mr = 552.60V = 3059.1 (2) Å3
Tetragonal, P41212Z = 4
a = 11.3285 (6) ÅMo Kα
b = 11.3285 ŵ = 0.08 mm−1
c = 23.837 (1) ÅT = 295 (2) K
α = 90º0.38 × 0.31 × 0.28 mm
β = 90º
Data collection top
Bruker APEX
diffractometer		1629 independent reflections
Absorption correction: none1190 reflections with I > 2σ(I)
15298 measured reflectionsRint = 0.028
Refinement top
R[F2 > 2σ(F2)] = 0.058114 restraints
wR(F2) = 0.203H-atom parameters constrained
S = 1.10Δρmax = 0.19 e Å−3
1629 reflectionsΔρmin = −0.18 e Å−3
240 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O10.4176 (3)0.0978 (3)1.10647 (12)0.0838 (10)
H10.37360.10621.07950.101*
N10.3657 (3)0.1225 (3)1.00195 (13)0.0697 (10)
O2'0.578 (2)0.061 (2)1.1879 (8)0.132 (12)0.219 (14)
C1'0.5305 (9)0.1015 (11)1.0912 (10)0.068 (8)0.219 (14)
C2'0.6125 (17)0.0804 (17)1.1334 (7)0.086 (8)0.219 (14)
C3'0.7324 (14)0.080 (3)1.1210 (8)0.142 (13)0.219 (14)
H3'0.78730.06631.14930.170*0.219 (14)
C4'0.7703 (9)0.102 (3)1.0665 (9)0.125 (11)0.219 (14)
H4'0.85060.10151.05820.150*0.219 (14)
C5'0.6883 (15)0.123 (2)1.0243 (7)0.121 (11)0.219 (14)
H5'0.71370.13670.98780.146*0.219 (14)
C6'0.5684 (13)0.1226 (13)1.0366 (8)0.098 (10)0.219 (14)
C7'0.664 (4)0.038 (3)1.2268 (11)0.128 (12)0.219 (14)
H7A'0.62780.02071.26230.193*0.219 (14)
H7B'0.71320.10671.23060.193*0.219 (14)
H7C'0.7104−0.027251.21480.193*0.219 (14)
O20.5688 (8)0.1093 (10)1.1871 (3)0.137 (3)0.781 (14)
C10.5282 (4)0.1316 (6)1.0922 (3)0.086 (3)0.781 (14)
C20.6118 (6)0.1401 (8)1.1347 (2)0.105 (3)0.781 (14)
C30.7258 (5)0.1773 (10)1.1223 (2)0.145 (4)0.781 (14)
H30.78180.18301.15070.174*0.781 (14)
C40.7561 (4)0.2060 (10)1.0674 (3)0.145 (4)0.781 (14)
H40.83240.23081.05920.173*0.781 (14)
C50.6724 (5)0.1974 (8)1.0250 (2)0.119 (4)0.781 (14)
H50.69270.21660.98830.143*0.781 (14)
C60.5585 (4)0.1602 (6)1.0374 (3)0.089 (2)0.781 (14)
C70.6429 (16)0.1174 (15)1.2321 (4)0.236 (8)0.781 (14)
H7A0.60170.09391.26550.354*0.781 (14)
H7B0.66940.19751.23600.354*0.781 (14)
H7C0.70970.06671.22640.354*0.781 (14)
C80.4746 (4)0.1482 (5)0.99170 (18)0.0920 (17)
H80.49940.15910.95490.110*
C90.1660 (3)0.1302 (3)0.97066 (13)0.0560 (9)
C100.2827 (4)0.1112 (4)0.95811 (14)0.0630 (11)
C110.3159 (4)0.0788 (5)0.90282 (15)0.0797 (13)
H110.39500.06510.89480.096*
C120.2355 (4)0.0674 (5)0.86193 (16)0.0824 (14)
H120.25980.04600.82610.099*
C130.1139 (4)0.0876 (4)0.87250 (16)0.0743 (12)
C140.0797 (4)0.1173 (4)0.92788 (16)0.0650 (11)
C15−0.0424 (4)0.1352 (6)0.93804 (19)0.0926 (16)
H15−0.06780.15500.97390.111*
C16−0.1225 (6)0.1239 (8)0.8962 (2)0.127 (3)
H16−0.20220.13610.90350.153*
C17−0.0859 (6)0.0937 (7)0.8418 (2)0.125 (3)
H17−0.14140.08570.81330.150*
C180.0296 (5)0.0762 (6)0.83076 (19)0.1031 (19)
H180.05300.05620.79460.124*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.098 (3)0.093 (2)0.0602 (16)−0.013 (2)−0.0103 (16)0.0161 (16)
N10.063 (2)0.096 (3)0.0502 (16)0.0047 (18)0.0033 (15)−0.0002 (18)
O2'0.165 (19)0.128 (18)0.104 (16)0.008 (13)−0.074 (13)0.034 (11)
C1'0.073 (17)0.081 (13)0.051 (13)0.020 (11)−0.011 (12)0.001 (10)
C2'0.079 (14)0.093 (17)0.087 (15)0.001 (12)0.008 (12)−0.011 (12)
C3'0.13 (2)0.18 (2)0.116 (18)−0.019 (18)−0.003 (16)−0.017 (18)
C4'0.102 (17)0.18 (2)0.090 (15)0.006 (16)−0.005 (13)0.011 (16)
C5'0.074 (15)0.19 (2)0.102 (16)0.039 (15)−0.007 (13)−0.001 (16)
C6'0.072 (16)0.16 (2)0.062 (14)0.010 (14)0.015 (13)0.003 (14)
C7'0.15 (2)0.114 (18)0.126 (18)−0.002 (15)−0.071 (16)0.028 (14)
O20.156 (6)0.182 (8)0.073 (4)−0.027 (6)−0.043 (4)0.046 (4)
C10.083 (6)0.101 (5)0.073 (6)0.011 (4)−0.012 (5)−0.006 (4)
C20.099 (6)0.127 (8)0.088 (5)−0.001 (5)−0.027 (4)−0.003 (5)
C30.110 (7)0.228 (13)0.097 (6)0.020 (7)−0.033 (5)−0.025 (7)
C40.066 (4)0.230 (13)0.137 (7)−0.011 (6)−0.009 (5)−0.040 (8)
C50.072 (5)0.205 (10)0.080 (4)0.005 (6)0.004 (4)−0.037 (5)
C60.061 (5)0.129 (6)0.076 (5)0.011 (4)−0.004 (4)−0.021 (4)
C70.219 (14)0.363 (19)0.126 (8)−0.064 (15)−0.083 (9)0.075 (11)
C80.069 (3)0.151 (5)0.056 (2)−0.001 (3)0.005 (2)−0.009 (3)
C90.065 (2)0.059 (2)0.0437 (18)0.0001 (17)0.0039 (17)−0.0034 (16)
C100.067 (2)0.078 (3)0.0436 (17)0.0013 (19)0.0028 (17)−0.0034 (18)
C110.071 (3)0.114 (4)0.053 (2)0.005 (3)0.014 (2)−0.011 (2)
C120.087 (3)0.115 (4)0.0447 (19)−0.001 (3)0.009 (2)−0.015 (2)
C130.082 (3)0.089 (3)0.052 (2)−0.006 (2)−0.002 (2)−0.010 (2)
C140.071 (3)0.072 (3)0.0518 (19)−0.002 (2)−0.0041 (19)−0.0090 (18)
C150.076 (3)0.137 (5)0.065 (2)0.007 (3)−0.006 (2)−0.023 (3)
C160.082 (4)0.205 (8)0.095 (4)0.002 (4)−0.020 (3)−0.043 (4)
C170.097 (4)0.196 (8)0.081 (3)0.002 (4)−0.030 (3)−0.027 (4)
C180.103 (4)0.153 (5)0.054 (2)−0.013 (4)−0.012 (3)−0.025 (3)
Geometric parameters (Å, °) top
O1—C11.353 (5)C4—H40.9300
O1—H10.8200C5—C61.3900
N1—C81.291 (6)C5—H50.9300
N1—C101.411 (5)C6—C81.451 (6)
O2'—C7'1.369 (13)C7—H7A0.9600
O2'—C2'1.378 (11)C7—H7B0.9600
C1'—C2'1.3900C7—H7C0.9600
C1'—C6'1.3900C8—H80.9300
C2'—C3'1.3900C9—C101.372 (6)
C3'—C4'1.3900C9—C141.420 (5)
C3'—H3'0.9300C9—C9i1.512 (7)
C4'—C5'1.3900C10—C111.419 (5)
C4'—H4'0.9300C11—C121.340 (6)
C5'—C6'1.3900C11—H110.9300
C5'—H5'0.9300C12—C131.419 (7)
C7'—H7A'0.9600C12—H120.9300
C7'—H7B'0.9600C13—C181.385 (6)
C7'—H7C'0.9600C13—C141.416 (6)
O2—C71.365 (9)C14—C151.419 (7)
O2—C21.386 (6)C15—C161.355 (7)
C1—C21.3900C15—H150.9300
C1—C61.3900C16—C171.403 (8)
C2—C31.3900C16—H160.9300
C3—C41.3900C17—C181.350 (8)
C3—H30.9300C17—H170.9300
C4—C51.3900C18—H180.9300
C8—N1—C10121.1 (4)C1—C6—C8121.5 (5)
C7'—O2'—C2'117.7 (14)O2—C7—H7A109.5
C2'—C1'—C6'120.0O2—C7—H7B109.5
O2'—C2'—C1'121.3 (17)H7A—C7—H7B109.5
O2'—C2'—C3'118.7 (17)O2—C7—H7C109.5
C1'—C2'—C3'120.0H7A—C7—H7C109.5
C4'—C3'—C2'120.0H7B—C7—H7C109.5
C4'—C3'—H3'120.0N1—C8—C6120.3 (4)
C2'—C3'—H3'120.0N1—C8—H8119.8
C3'—C4'—C5'120.0C6—C8—H8119.8
C3'—C4'—H4'120.0C10—C9—C14119.4 (3)
C5'—C4'—H4'120.0C10—C9—C9i120.2 (3)
C6'—C5'—C4'120.0C14—C9—C9i120.5 (4)
C6'—C5'—H5'120.0C9—C10—N1117.8 (3)
C4'—C5'—H5'120.0C9—C10—C11119.9 (4)
C5'—C6'—C1'120.0N1—C10—C11122.3 (4)
O2'—C7'—H7A'109.5C12—C11—C10121.4 (4)
O2'—C7'—H7B'109.5C12—C11—H11119.3
H7A'—C7'—H7B'109.5C10—C11—H11119.3
O2'—C7'—H7C'109.5C11—C12—C13121.0 (4)
H7A'—C7'—H7C'109.5C11—C12—H12119.5
H7B'—C7'—H7C'109.5C13—C12—H12119.5
C7—O2—C2118.4 (8)C18—C13—C14120.2 (5)
O1—C1—C2117.9 (5)C18—C13—C12121.8 (4)
O1—C1—C6122.1 (5)C14—C13—C12118.0 (4)
C2—C1—C6120.0C13—C14—C15117.4 (4)
O2—C2—C3126.5 (6)C13—C14—C9120.4 (4)
O2—C2—C1113.5 (6)C15—C14—C9122.3 (4)
C3—C2—C1120.0C16—C15—C14120.9 (5)
C4—C3—C2120.0C16—C15—H15119.5
C4—C3—H3120.0C14—C15—H15119.5
C2—C3—H3120.0C15—C16—C17120.3 (6)
C3—C4—C5120.0C15—C16—H16119.8
C3—C4—H4120.0C17—C16—H16119.8
C5—C4—H4120.0C18—C17—C16120.2 (5)
C6—C5—C4120.0C18—C17—H17119.9
C6—C5—H5120.0C16—C17—H17119.9
C4—C5—H5120.0C17—C18—C13120.9 (5)
C5—C6—C1120.0C17—C18—H18119.5
C5—C6—C8118.5 (5)C13—C18—H18119.5
C7'—O2'—C2'—C1'178.9 (8)C1—C6—C8—N17.5 (7)
C7'—O2'—C2'—C3'−1.8 (14)C14—C9—C10—N1−178.7 (4)
C6'—C1'—C2'—O2'179.3 (7)C9i—C9—C10—N12.0 (6)
C6'—C1'—C2'—C3'0.0C14—C9—C10—C11−0.1 (6)
O2'—C2'—C3'—C4'−179.3 (6)C9i—C9—C10—C11−179.3 (4)
C1'—C2'—C3'—C4'0.0C8—N1—C10—C9−154.8 (4)
C2'—C3'—C4'—C5'0.0C8—N1—C10—C1126.6 (7)
C3'—C4'—C5'—C6'0.0C9—C10—C11—C120.8 (7)
C4'—C5'—C6'—C1'0.0N1—C10—C11—C12179.4 (5)
C2'—C1'—C6'—C5'0.0C10—C11—C12—C130.1 (8)
C7—O2—C2—C31.4 (11)C11—C12—C13—C18−180.0 (5)
C7—O2—C2—C1−178.3 (7)C11—C12—C13—C14−1.5 (8)
O1—C1—C2—O21.3 (6)C18—C13—C14—C15−0.4 (7)
C6—C1—C2—O2179.7 (5)C12—C13—C14—C15−178.9 (5)
O1—C1—C2—C3−178.4 (4)C18—C13—C14—C9−179.4 (5)
C6—C1—C2—C30.0C12—C13—C14—C92.1 (7)
O2—C2—C3—C4−179.7 (5)C10—C9—C14—C13−1.4 (6)
C1—C2—C3—C40.0C9i—C9—C14—C13177.9 (4)
C2—C3—C4—C50.0C10—C9—C14—C15179.8 (5)
C3—C4—C5—C60.0C9i—C9—C14—C15−1.0 (6)
C4—C5—C6—C10.0C13—C14—C15—C160.1 (9)
C4—C5—C6—C8−177.8 (4)C9—C14—C15—C16179.0 (6)
O1—C1—C6—C5178.4 (5)C14—C15—C16—C170.2 (11)
C2—C1—C6—C50.0C15—C16—C17—C18−0.3 (13)
O1—C1—C6—C8−3.9 (5)C16—C17—C18—C130.0 (12)
C2—C1—C6—C8177.7 (4)C14—C13—C18—C170.4 (10)
C10—N1—C8—C6179.6 (4)C12—C13—C18—C17178.8 (6)
C5—C6—C8—N1−174.8 (4)
Symmetry codes: (i) y, x, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.862.575 (4)145
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.862.575 (4)145
Acknowledgements top

The authors thank Northwest University and the University of Malaya for generously supporting this study.

references
References top

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