(S) 2,2′ Dieth­­oxy 1,1′ binaphth­yl

organic papers

o1342

24H22O2 doi:10.1107/S1600536806007872 Acta Cryst.(2006). E62, o1342–o1343

Acta Crystallographica Section E Structure Reports

Online

ISSN 1600-5368

(

S

)-2,2

_{-Diethoxy-1,1}

_-binaphthyl

Niels Thorup,a* Heinz-Josef Deussen,b‡ Klaus Bechgaardb and Thomas Bjørnholmb

a_{Department of Chemistry, Technical University}

of Denmark, Kemitorvet, DTU-207, DK-2800 Kgs. Lyngby, Denmark, andb_{Department of}

Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark

‡ Present address: Leo Pharma A/S,

Industriparken 55, DK-2750 Ballerup, Denmark

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 295 K

Mean(C–C) = 0.004 A˚

Rfactor = 0.039

wRfactor = 0.097 Data-to-parameter ratio = 9.3

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Received 1 March 2006 Accepted 3 March 2006

#2006 International Union of Crystallography All rights reserved

The title molecule, C24H22O2, contains two planar naphthyl

ring systems. The torsion angle around the the central C—C bond is 111.3 (2) _{implying a transoid conformation with}

respect to the two ethoxy substituents. Only weak inter-molecular interactions are present in the crystal structure.

Comment

The structure of (S)-2,20_{-diethoxy-1,1}0_{-binaphthyl, (I), was}

determined as part of a study of several binaphthalene derivatives as possible candidates for second-order non-linear optics (Deussen, Hendrickset al., 1996; Deussenet al., 1998), as well as chiral dopants for nematic liquid crystals (Deussen, Shibaevet al., 1996; Shibaevet al.1997). The molecules studied for second-order non-linear optics had electron-acceptor groups at their 6,60_{-positions to increase polarizability. The}

title compound is thus not expected to exhibit second-order optical properties although the crystal structure requirement of non-centrosymmetry is fulfilled.

The molecular structure is depicted in Fig. 1. The absolute configuration is known to beS, but the chirality could not be determined based on the diffraction data (Friedel pairs were merged). As expected, each of the two naphthyl ring systems is planar. The molecule is twisted around the central C1—C13 bond with a torsion angle C2—C1—C13—C14 of 111.3 (2)_.

This conformation prevents close interactions between ring systems in neighboring molecules. There are no remarkable short intermolecular distances in the structure. Thus, the intermolecular attractions appear to be rather weak, which is in accordance with the observed low melting point (ca412 K).

Experimental

(S)-2,20_{-Diethoxy-1,1}0_{-binaphthyl was prepared as previously}

Crystal data

C24H22O2

Mr= 342.42

Orthorhombic,P212121

a= 7.5637 (5) A˚

b= 11.5604 (7) A˚

c= 21.3353 (13) A˚

V= 1865.5 (2) A˚3

Z= 4

Dx= 1.219 Mg m3

MoKradiation Cell parameters from 4698

reflections

= 1.9–26.4

= 0.08 mm1

T= 295 (2) K Prism, colorless 0.380.200.14 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer

!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 2001)

Tmin= 0.878,Tmax= 0.989 10849 measured reflections

2214 independent reflections 1719 reflections withI> 2(I)

Rint= 0.034

max= 26.4

h=9!9

k=14!13

l=26!22

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.039

wR(F2_{) = 0.097}

S= 1.04 2214 reflections 238 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0523P)2 + 0.1176P]

whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001

max= 0.13 e A˚3

min=0.11 e A˚3

Extinction correction:SHELXL97

Extinction coefficient: 0.018 (2)

H atoms were positioned geometrically (C—H = 0.93–0.97 A˚ ) and refined as riding, withUiso(H) = 1.2 or 1.5 timesUeq(C).

Data collection:SMART(Siemens, 1995); cell refinement:SAINT

(Siemens, 1995); data reduction:SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure:SHELXTL; molecular graphics:SHELXTLandPLATON

(Spek, 2003); software used to prepare material for publication:

SHELXTLandPLATON.

HJD thanks the Gottlieb Daimler- und Karl Benz-Stiftung for a PhD stipend.

References

Deussen, H.-J., Boutton, C., Thorup, N., Geisler, T., Hendricks, E., Bechgaard, K., Persoons, A. & Bjørnholm, T. (1998).Chem. Eur. J.4, 240–250. Deussen, H.-J., Hendricks, E., Boutton, C., Krog, D., Clays, K. Bechgaard, K.,

Persoons, A. & Bjørnholm, T. (1996).J. Am. Chem. Soc.118, 6841–6852. Deussen, H.-J., Shibaev, P. V., Vinokur, R., Bjoernholm, T., Schaumburg, K.,

Bechgaard, K. & Shibaev, V. P. (1996).Liq. Cryst.21, 327–340.

Sheldrick, G. M. (2001).SADABS(Version 2.03) andSHELXTL(Version 6.12). Bruker AXS Inc., Madison, Wisconsin, USA.

Shibaev, V. P., Deussen, H.-J., Bobrovsky, A. Yu., Shibaev, P. V., Boiko, N. I., Bjornholm, T., Schaumburg, K. & Bechgaard, K. (1997).Liq. Cryst.22, 451– 457.

Siemens (1995). SMART and SAINT. Versions 4.05. Siemens AXS Inc., Madison, Wisconsin, USA.

Spek, A. L. (2003).J. Appl. Cryst.36, 7–13. Figure 1

The molecular structure of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as spheres of arbitrary radii.

Figure 2

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Acta Cryst. (2006). E62, o1342–o1343

supporting information

Acta Cryst. (2006). E62, o1342–o1343 [https://doi.org/10.1107/S1600536806007872]

(

S

)-2,2

′

-Diethoxy-1,1

′

-binaphthyl

Niels Thorup, Heinz-Josef Deussen, Klaus Bechgaard and Thomas Bj

ø

rnholm

(S)-2,2′-Diethoxy-1,1′-binaphthyl

Crystal data

C24H22O2 Mr = 342.42

Orthorhombic, P212121

Hall symbol: P 2ac 2ab

a = 7.5637 (5) Å

b = 11.5604 (7) Å

c = 21.3353 (13) Å

V = 1865.5 (2) Å3

Z = 4

F(000) = 728

Dx = 1.219 Mg m−3

Melting point: 412 K

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 4698 reflections

θ = 1.9–26.4°

µ = 0.08 mm−1 T = 295 K Prism, colorless 0.38 × 0.20 × 0.14 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 2001)

Tmin = 0.878, Tmax = 0.989

10849 measured reflections 2214 independent reflections 1719 reflections with I > 2σ(I)

Rint = 0.034

θmax = 26.4°, θmin = 1.9° h = −9→9

k = −14→13

l = −26→22

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.039} wR(F2_{) = 0.097} S = 1.04 2214 reflections 238 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.0523P)2 + 0.1176P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.13 e Å−3

Δρmin = −0.11 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

Special details

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 7.4356 (0.0012) x + 2.0995 (0.0088) y - 0.5259 (0.0101) z = 1.1865 (0.0025)

* 0.0046 (0.0018) C1 * 0.0154 (0.0019) C2 * 0.0040 (0.0019) C3 * -0.0120 (0.0022) C4 * -0.0097 (0.0024) C5 * 0.0023 (0.0023) C6 * 0.0145 (0.0022) C7 * 0.0034 (0.0024) C8 * -0.0085 (0.0021) C9 * -0.0139 (0.0018) C10 - 0.0480 (0.0026) O1 - 0.2914 (0.0040) C11 - 0.5643 (0.0052) C12 - 0.0392 (0.0033) C13

Rms deviation of fitted atoms = 0.0100

- 2.8374 (0.0031) x + 0.9911 (0.0083) y + 19.6924 (0.0043) z = 1.4447 (0.0015) Angle to previous plane (with approximate e.s.d.) = 67.92 (0.04)

* -0.0109 (0.0016) C13 * -0.0183 (0.0018) C14 * 0.0085 (0.0018) C15 * 0.0181 (0.0021) C16 * -0.0044 (0.0022) C17 * -0.0059 (0.0020) C18 * -0.0097 (0.0020) C19 * 0.0036 (0.0020) C20 * 0.0155 (0.0020) C21 * 0.0035 (0.0018) C22 - 0.0003 (0.0025) O2 0.6768 (0.0036) C23 0.9882 (0.0046) C24 0.0214 (0.0030) C1

Rms deviation of fitted atoms = 0.0113

Refinement. Friedel pairs were merged before refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

O1 0.1232 (2) 0.10043 (13) −0.02160 (7) 0.0542 (4) O2 0.4422 (2) 0.04635 (15) 0.13473 (7) 0.0628 (5) C1 0.1294 (3) 0.13077 (17) 0.08651 (9) 0.0418 (5) C2 0.1133 (3) 0.20605 (18) 0.13934 (10) 0.0442 (5)

C3 0.1275 (3) 0.1659 (2) 0.20208 (10) 0.0531 (6)

H3 0.1505 0.0881 0.2094 0.064*

C4 0.1084 (4) 0.2385 (2) 0.25157 (12) 0.0657 (7)

H4 0.1177 0.2097 0.2921 0.079*

C5 0.0747 (4) 0.3566 (2) 0.24208 (13) 0.0735 (8)

H5 0.0623 0.4059 0.2762 0.088*

C6 0.0604 (4) 0.3983 (2) 0.18325 (14) 0.0697 (7)

H6 0.0379 0.4766 0.1774 0.084*

C7 0.0788 (3) 0.32569 (19) 0.13023 (12) 0.0552 (6)

C8 0.0615 (4) 0.3661 (2) 0.06835 (12) 0.0640 (7)

H8 0.0391 0.4442 0.0617 0.077*

C9 0.0763 (3) 0.29544 (18) 0.01820 (12) 0.0569 (6)

H9 0.0644 0.3251 −0.0221 0.068*

C10 0.1097 (3) 0.17673 (18) 0.02709 (10) 0.0449 (5) C11 0.0754 (4) 0.1385 (2) −0.08307 (11) 0.0699 (7)

H11A 0.1633 0.1919 −0.0991 0.084*

H11B −0.0380 0.1776 −0.0820 0.084*

C12 0.0653 (6) 0.0341 (3) −0.12354 (13) 0.1019 (11)

H12A 0.1806 0.0000 −0.1272 0.153*

H12B 0.0234 0.0556 −0.1644 0.153*

H12C −0.0146 −0.0209 −0.1052 0.153*

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Acta Cryst. (2006). E62, o1342–o1343

H15 −0.1649 0.0336 0.0489 0.062*

C16 −0.2684 (4) −0.1243 (2) 0.04188 (11) 0.0632 (7)

H16 −0.3768 −0.0999 0.0261 0.076*

C17 −0.2381 (5) −0.2416 (2) 0.05099 (13) 0.0716 (8)

H17 −0.3247 −0.2953 0.0405 0.086*

C18 −0.0831 (5) −0.2769 (2) 0.07504 (12) 0.0690 (8)

H18 −0.0648 −0.3555 0.0817 0.083*

C19 0.0539 (4) −0.19761 (19) 0.09059 (10) 0.0541 (6) C20 0.2150 (4) −0.2322 (2) 0.11621 (13) 0.0690 (8)

H20 0.2352 −0.3106 0.1231 0.083*

C21 0.3441 (4) −0.1546 (2) 0.13152 (12) 0.0669 (8)

H21 0.4499 −0.1802 0.1489 0.080*

C22 0.3164 (3) −0.0350 (2) 0.12089 (10) 0.0523 (6) C23 0.5574 (4) 0.0219 (3) 0.18695 (13) 0.0787 (9)

H23A 0.6503 −0.0310 0.1742 0.094*

H23B 0.4910 −0.0138 0.2207 0.094*

C24 0.6353 (4) 0.1329 (3) 0.20840 (17) 0.1045 (12)

H24A 0.7045 0.1660 0.1752 0.157*

H24B 0.7095 0.1191 0.2441 0.157*

H24C 0.5423 0.1854 0.2197 0.157*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

C23 0.0654 (16) 0.108 (2) 0.0628 (16) 0.0114 (19) −0.0185 (15) 0.0162 (16) C24 0.080 (2) 0.137 (3) 0.097 (2) −0.024 (2) −0.0357 (19) 0.023 (2)

Geometric parameters (Å, º)

O1—C10 1.367 (3) C12—H12B 0.9600

O1—C11 1.430 (3) C12—H12C 0.9600

O2—C22 1.370 (3) C13—C22 1.378 (3)

O2—C23 1.443 (3) C13—C14 1.426 (3)

C1—C10 1.383 (3) C14—C15 1.419 (3)

C1—C2 1.429 (3) C14—C19 1.424 (3)

C1—C13 1.492 (3) C15—C16 1.365 (3)

C2—C3 1.421 (3) C15—H15 0.9300

C2—C7 1.421 (3) C16—C17 1.388 (4)

C3—C4 1.356 (3) C16—H16 0.9300

C3—H3 0.9300 C17—C18 1.344 (4)

C4—C5 1.403 (4) C17—H17 0.9300

C4—H4 0.9300 C18—C19 1.423 (4)

C5—C6 1.349 (4) C18—H18 0.9300

C5—H5 0.9300 C19—C20 1.394 (4)

C6—C7 1.415 (3) C20—C21 1.366 (4)

C6—H6 0.9300 C20—H20 0.9300

C7—C8 1.406 (3) C21—C22 1.417 (4)

C8—C9 1.351 (3) C21—H21 0.9300

C8—H8 0.9300 C23—C24 1.485 (4)

C9—C10 1.408 (3) C23—H23A 0.9700

C9—H9 0.9300 C23—H23B 0.9700

C11—C12 1.486 (4) C24—H24A 0.9600

C11—H11A 0.9700 C24—H24B 0.9600

C11—H11B 0.9700 C24—H24C 0.9600

C12—H12A 0.9600

C10—O1—C11 118.66 (18) H12B—C12—H12C 109.5

C22—O2—C23 116.9 (2) C22—C13—C14 118.9 (2)

C10—C1—C2 118.68 (18) C22—C13—C1 120.4 (2)

C10—C1—C13 120.83 (19) C14—C13—C1 120.6 (2)

C2—C1—C13 120.45 (18) C15—C14—C19 117.0 (2)

C3—C2—C7 117.4 (2) C15—C14—C13 122.72 (19)

C3—C2—C1 122.5 (2) C19—C14—C13 120.3 (2)

C7—C2—C1 120.03 (19) C16—C15—C14 121.6 (2)

C4—C3—C2 121.6 (2) C16—C15—H15 119.2

C4—C3—H3 119.2 C14—C15—H15 119.2

C2—C3—H3 119.2 C15—C16—C17 121.0 (3)

C3—C4—C5 120.6 (2) C15—C16—H16 119.5

C3—C4—H4 119.7 C17—C16—H16 119.5

C5—C4—H4 119.7 C18—C17—C16 119.6 (3)

C6—C5—C4 119.8 (2) C18—C17—H17 120.2

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Acta Cryst. (2006). E62, o1342–o1343

C4—C5—H5 120.1 C17—C18—C19 121.9 (2)

C5—C6—C7 121.6 (2) C17—C18—H18 119.1

C5—C6—H6 119.2 C19—C18—H18 119.1

C7—C6—H6 119.2 C20—C19—C18 122.9 (2)

C8—C7—C6 123.0 (2) C20—C19—C14 118.2 (2)

C8—C7—C2 118.0 (2) C18—C19—C14 118.9 (3)

C6—C7—C2 119.1 (2) C21—C20—C19 122.0 (2)

C9—C8—C7 122.3 (2) C21—C20—H20 119.0

C9—C8—H8 118.8 C19—C20—H20 119.0

C7—C8—H8 118.8 C20—C21—C22 119.8 (3)

C8—C9—C10 119.8 (2) C20—C21—H21 120.1

C8—C9—H9 120.1 C22—C21—H21 120.1

C10—C9—H9 120.1 O2—C22—C13 117.1 (2)

O1—C10—C1 116.16 (18) O2—C22—C21 122.2 (2)

O1—C10—C9 122.69 (19) C13—C22—C21 120.8 (2)

C1—C10—C9 121.1 (2) O2—C23—C24 108.0 (2)

O1—C11—C12 107.2 (2) O2—C23—H23A 110.1

O1—C11—H11A 110.3 C24—C23—H23A 110.1

C12—C11—H11A 110.3 O2—C23—H23B 110.1

O1—C11—H11B 110.3 C24—C23—H23B 110.1

C12—C11—H11B 110.3 H23A—C23—H23B 108.4

H11A—C11—H11B 108.5 C23—C24—H24A 109.5

C11—C12—H12A 109.5 C23—C24—H24B 109.5

C11—C12—H12B 109.5 H24A—C24—H24B 109.5

H12A—C12—H12B 109.5 C23—C24—H24C 109.5

C11—C12—H12C 109.5 H24A—C24—H24C 109.5

H12A—C12—H12C 109.5 H24B—C24—H24C 109.5

C10—C1—C2—C3 178.5 (2) C10—C1—C13—C14 −66.4 (3)

C13—C1—C2—C3 0.9 (3) C2—C1—C13—C14 111.3 (2)

C10—C1—C2—C7 −0.3 (3) C22—C13—C14—C15 178.00 (19)

C13—C1—C2—C7 −178.0 (2) C1—C13—C14—C15 −0.2 (3)

C7—C2—C3—C4 0.2 (3) C22—C13—C14—C19 0.1 (3)

C1—C2—C3—C4 −178.7 (2) C1—C13—C14—C19 −178.16 (19)

C2—C3—C4—C5 −0.4 (4) C19—C14—C15—C16 −1.1 (3)

C3—C4—C5—C6 0.3 (5) C13—C14—C15—C16 −179.1 (2)

C4—C5—C6—C7 −0.1 (5) C14—C15—C16—C17 −0.3 (4)

C5—C6—C7—C8 178.8 (3) C15—C16—C17—C18 1.5 (4)

C5—C6—C7—C2 −0.1 (4) C16—C17—C18—C19 −1.2 (4)

C3—C2—C7—C8 −179.0 (2) C17—C18—C19—C20 179.3 (2)

C1—C2—C7—C8 0.0 (3) C17—C18—C19—C14 −0.3 (4)

C3—C2—C7—C6 0.0 (3) C15—C14—C19—C20 −178.2 (2)

C1—C2—C7—C6 178.9 (2) C13—C14—C19—C20 −0.1 (3)

C6—C7—C8—C9 −178.8 (3) C15—C14—C19—C18 1.4 (3)

C2—C7—C8—C9 0.1 (4) C13—C14—C19—C18 179.47 (19)

C7—C8—C9—C10 0.2 (4) C18—C19—C20—C21 −179.2 (2)

C11—O1—C10—C1 169.8 (2) C14—C19—C20—C21 0.3 (4)

C2—C1—C10—O1 −178.86 (18) C23—O2—C22—C13 148.9 (2)

C13—C1—C10—O1 −1.2 (3) C23—O2—C22—C21 −31.4 (3)

C2—C1—C10—C9 0.6 (3) C14—C13—C22—O2 179.51 (18)

C13—C1—C10—C9 178.3 (2) C1—C13—C22—O2 −2.3 (3)

C8—C9—C10—O1 178.9 (2) C14—C13—C22—C21 −0.2 (3)

C8—C9—C10—C1 −0.6 (4) C1—C13—C22—C21 178.0 (2)

C10—O1—C11—C12 −168.1 (2) C20—C21—C22—O2 −179.3 (2)

C10—C1—C13—C22 115.5 (2) C20—C21—C22—C13 0.4 (4)