(R) (+) 2,2′ Di­amino 1,1′ bi­naphthyl

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Matthew D. Joneset al. C20H16N2 DOI: 10.1107/S1600536803011681 Acta Cryst.(2003). E59, o910±o912 Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

(

R

)-(+)-2,2

000

-Diamino-1,1

000

-binaphthyl

Matthew D. Jones,* Filipe A. Almeida Paz, John E. Davies and Brian F. G. Johnson

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, England

Correspondence e-mail: mdj22@cam.ac.uk

Key indicators Single-crystal X-ray study T= 180 K

Mean(C±C) = 0.002 AÊ Rfactor = 0.036 wRfactor = 0.100 Data-to-parameter ratio = 9.8

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

#2003 International Union of Crystallography Printed in Great Britain ± all rights reserved

The crystal structure of the title compound, C20H16N2, has

been determined at 180 (2) K in the chiral space groupP43212.

The structure is described by a herring-bone close-packing, along the a and b directions, of layers within which intermolecular NÐH and CÐH interactions can be found.

Comment

We have been focusing our research on the use of amines which can lead to the synthesis of chiral metal complexes with applications, for example, as catalysts in asymmetric hydro-genation processes (Joneset al., 2003a,b,c; Raynoret al., 2000). As part of our study, we came across (R)-2,20-diamino-1,10

-binaphthyl, (I), an interesting bidentate chiral amine capable of forming chelates with transition metal centres (Mikamiet al., 2002; Mikami & Aikawa, 2002; Jones et al., 2003a). Grid-unovaet al.(1982) have investigated the structure of racemic 2,20-diamino-1,10-binaphthyl. Here we report the crystal

structure, determined at 180 (2) K, of the pureRform.

Compound (I) crystallizes in the tetragonal chiral space groupP43212, with the origin located at 2112 and the

asym-metric unit containing only half of the molecular unit (Fig. 1). Adjacent molecules of (I) are linked by a combination of intermolecular NÐH and CÐH interactions [H1B Cgi = 2.60 (3) AÊ and N1ÐH1B Cgi = 166 (3),

H5 Cgii= 2.68 AÊ and C5ÐH5 Cgii= 159, whereCgis the

centroid of the C4±C9 aromatic ring; symmetry codes: (i)y, ÿ1 +x,ÿz; (ii)1

2+x,12ÿy,14ÿz] (see Fig. 2). Although one

could expect to ®nd a similar NÐH interaction between the N1ÐH1A bond and a neighbouring aromatic ring, the spatial arrangement of the molecules does not allow it. Indi-vidual molecules of (I) are arranged in thecdirection in a way that leads to a herring-bone packing manner (Fig. 3).

Experimental

(R)-(+)-2,20-Diamino-1,10-binaphthyl was purchased from Aldrich (99.5% purity) and used without further puri®cation. Crystals suitable for X-ray diffraction analysis were obtained by recrystal-lization from methanol.

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Crystal data

C20H16N2

Mr= 284.35 Tetragonal,P43212

a= 7.0388 (2) AÊ

c= 30.0684 (8) AÊ

V= 1489.73 (7) AÊ3

Z= 4

Dx= 1.268 Mg mÿ3

MoKradiation Cell parameters from 4522

re¯ections

= 1.0±27.5

= 0.08 mmÿ1

T= 180 (2) K Block, colourless 0.460.460.23 mm

Data collection

Nonius KappaCCD diffractometer Thin-slice!and'scans Absorption correction: multi-scan

(SORTAV; Blessing, 1995)

Tmin= 0.944,Tmax= 0.983 4236 measured re¯ections 1635 independent re¯ections

1455 re¯ections withI> 2(I)

Rint= 0.029 max= 27.5

h=ÿ9!9

k=ÿ6!9

l=ÿ39!39

Re®nement

Re®nement onF2

R[F2> 2(F2)] = 0.037

wR(F2) = 0.100

S= 1.02 1061 re¯ections 108 parameters

H atoms treated by a mixture of independent and constrained re®nement

w= 1/[2(F

o2) + (0.0563P)2 + 0.37P]

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

max= 0.17 e AÊÿ3

min=ÿ0.19 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,).

N1ÐC1 1.378 (2)

C1ÐC10 1.393 (2)

C1ÐC2 1.423 (2)

C2ÐC3 1.355 (2)

C3ÐC4 1.417 (2)

C4ÐC5 1.419 (2)

C4ÐC9 1.426 (2)

C5ÐC6 1.363 (3)

C6ÐC7 1.409 (3)

C7ÐC8 1.374 (2)

C8ÐC9 1.422 (2)

C9ÐC10 1.433 (2)

C10ÐC10iii 1.496 (3)

N1ÐC1ÐC10 121.72 (15)

N1ÐC1ÐC2 117.93 (15)

C10ÐC1ÐC2 120.30 (15)

C3ÐC2ÐC1 121.25 (16)

C2ÐC3ÐC4 120.61 (16)

C3ÐC4ÐC5 121.36 (16)

C3ÐC4ÐC9 119.09 (15)

C5ÐC4ÐC9 119.55 (16)

C6ÐC5ÐC4 121.02 (16)

C5ÐC6ÐC7 119.91 (16)

C8ÐC7ÐC6 120.63 (17)

C7ÐC8ÐC9 121.05 (17)

C8ÐC9ÐC4 117.82 (14)

C8ÐC9ÐC10 122.26 (14)

C4ÐC9ÐC10 119.91 (15)

C1ÐC10ÐC9 118.79 (14)

C1ÐC10ÐC10iii 119.46 (14) C9ÐC10ÐC10iii 121.58 (15) Symmetry code: (iii)y;x;ÿz.

All H atoms bound to C atoms were placed in calculated positions and allowed to ride during subsequent re®nement, with Uiso(H) = 1.2Ueq(C). The NH2H atoms were located in a difference Fourier map and re®ned independently. A total of 574 Friedel pairs have been merged and not used as independent data. The corresponding Flack (1983) parameter was found to be meaningless and was omitted.

Data collection:COLLECT(Nonius, 1998); cell re®nement:HKL SCALEPACK(Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to re®ne structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL; software used to prepare material for publication:SHELXTL.

We thank the EPSRC for a studentship to MDJ and for their general ®nancial support, ICI for ®nancial support, and the Newton Trust. We are also grateful to the Portuguese Foundation for Science and Technology (FCT) for ®nancial

Acta Cryst.(2003). E59, o910±o912 Matthew D. Joneset al. C20H16N2

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organic papers

Figure 2

View of the intermolecular NÐH and and CÐH interactions (dashed red lines) between adjacent molecules of (I).Cgis the centroid of

the C4±C9 aromatic ring.

Figure 3

Perspective view of (I) along the a axis. NÐH and CÐH

interactions are represented as dashed red lines. Figure 1

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organic papers

o912

Matthew D. Joneset al. C20H16N2 Acta Cryst.(2003). E59, o910±o912

support through the PhD scholarship No. SFRH/BD/3024/ 2000 given to FAAP.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994).J. Appl. Cryst.27, 435.

Blessing, R. H. (1995).Acta Cryst.A51, 33±38.

Bruker (2001). SHELXTL. Version 6.12. Bruker AXS, Inc. Madison, Wisconsin, USA.

Flack, H. D. (1983).Acta Cryst.A39, 876±881.

Gridunova, G. V., Furmanova, N. G., Shklover, V. E., Struchkov, Y. T., Ezhkova, Z. I. & Chayanov, B. A. (1982).Kristallogra®ya,27, 477±484. (In Russian.)

Jones, M. D., Paz, F. A. A., Davies, J. E. & Johnson, B. F. G. (2003a).Acta Cryst.

E59, m6±m7.

Jones, M. D., Paz, F. A. A., Davies, J. E. & Johnson, B. F. G. (2003b).Acta Cryst.

E59, m105±m107.

Jones, M. D., Paz, F. A. A., Davies, J. E. & Johnson, B. F. G. (2003c).Acta Cryst.

E59, m111±m113.

Mikami, K. & Aikawa, K. (2002).Org. Lett.4, 99±101. Mikami, K., Aikawa, K. & Yusa, Y. (2002).Org. Lett.4, 95±97. Nonius (1998).COLLECT. Nonius BV, Delft, The Netherlands.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,

Macromolecular Crystallography, Part A, edited by C. W. Carter Jr and R. M. Sweet, pp. 307±326. New York: Academic Press.

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Acta Cryst. (2003). E59, o910–o912

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Acta Cryst. (2003). E59, o910–o912 [doi:10.1107/S1600536803011681]

(R)-(+)-2,2

-Diamino-1,1

-binaphthyl

Matthew D. Jones, Filipe A. Almeida Paz, John E. Davies and Brian F. G. Johnson

S1. Comment

We have been focusing our research on the use of amines which can lead to the synthesis of chiral metal complexes with

applications, for example, as catalysts in asymmetric hydrogenation processes (Jones et al., 2003a,b,c; Raynor et al.,

2000). As part of our study, we came across (R)-2,2′-diamino-1,1′-binaphthyl, (I), an interesting bidentate chiral amine

capable of forming chelates with transition metal centres (Mikami, Aikawa & Yusa, 2002; Mikami & Aikawa, 2002;

Jones et al., 2003a). Gridunova et al. (1982) have investigated the structure of racemic 2,2′-diamino-1,1′-binaphthyl.

Here we report the crystal structure, determined at 180 (2) K, of the pure R form.

Compound (I) crystallizes in the tetragonal chiral space group P43212, with the origin located at 2112 and the

asymmetric unit containing only half of the molecular unit (Fig. 1). Adjacent molecules of (I) are linked by a combination

of intermolecular N—H···π and C—H···π interactions [H1B···Cgi = 2.60 (3) Å and N1—H1B···Cgi = 166 (3)°, H5···Cgii =

2.68 Å and C5—H5···Cgii = 159°, where Cg is the centroid of the C4–C9 aromatic ring; symmetry codes: (i) y, −1 + x,

z; (ii) 1/2 + x, 1/2 − y, 1/4 − z] (see Fig. 2). Although one could expect to find a similar N—H···π interaction between the

N1—H1A bond and a neighbouring aromatic ring, the spatial arrangement of the molecules does not allow it. Individual

molecules of (I) are arranged in the c direction in a way that leads to a herring-bone packing manner (Fig. 3).

S2. Experimental

(R)-(+)-2,2′-Diamino-1,1′-binaphthyl was purchased from Aldrich (99.5% purity) and used without further purification.

Crystals suitable for X-Ray diffraction analysis were obtained by recrystallization from methanol.

S3. Refinement

All H atoms bound to C atoms were placed in calculated positions and allowed to ride during subsequent refinement,

with Uiso(H) = 1.2Ueq(C). The NH2 H atoms were located in difference Fourier maps and refined independently. A total of

574 Friedel pairs have been merged and not used as independent data. The corresponding Flack (1983) parameter was

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Acta Cryst. (2003). E59, o910–o912

Figure 1

The molecular structure of (I), showing the labelling scheme for all non-H atoms in the asymmetric unit. Displacement

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Acta Cryst. (2003). E59, o910–o912

Figure 2

View of the intermolecular N—H···π and and C—H···π interactions (dashed red lines) between adjacent molecules of (I).

Cg is the centroid of the C4–C9 aromatic ring.

Figure 3

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Acta Cryst. (2003). E59, o910–o912

(R)-(+)-2,2′-Diamino-1,1′-binaphthalene

Crystal data

C20H16N2

Mr = 284.35 Tetragonal, P43212 Hall symbol: P 4nw 2abw

a = 7.0388 (2) Å

c = 30.0684 (8) Å

V = 1489.73 (7) Å3

Z = 4

F(000) = 600

Dx = 1.268 Mg m−3

Mo radiation, λ = 0.71073 Å Cell parameters from 4522 reflections

θ = 1.0–27.5°

µ = 0.08 mm−1

T = 180 K Block, colourless 0.46 × 0.46 × 0.23 mm

Data collection

Nonius KappaCCD diffractometer

Radiation source: fine-focus sealed tube Thin–slice ω and φ scans

Absorption correction: multi-scan (SORTAV; Blessing, 1995)

Tmin = 0.944, Tmax = 0.983 4236 measured reflections

1635 independent reflections 1455 reflections with I > 2σ(I)

Rint = 0.029

θmax = 27.5°, θmin = 3.5°

h = −9→9

k = −6→9

l = −39→39

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 > 2σ(F2)] = 0.037

wR(F2) = 0.100

S = 1.02 1061 reflections 108 parameters 2 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2(F

o2) + (0.0563P)2 + 0.37P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001 Δρmax = 0.17 e Å−3 Δρmin = −0.19 e Å−3

Special details

Experimental. Friedel equivalents merged for refinement. H-atom from –NH2 group have been located in difference Fourier maps. The N–H distance has been restrained to be 0.88 (1) A.

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)

x y z Uiso*/Ueq

N1 0.4707 (3) 0.1703 (2) −0.05183 (5) 0.0366 (4)

H1A 0.368 (2) 0.239 (3) −0.0574 (8) 0.053 (7)*

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C1 0.5529 (2) 0.2117 (2) −0.01137 (5) 0.0257 (4)

C2 0.6753 (3) 0.0735 (2) 0.00785 (6) 0.0319 (4)

H2 0.6970 −0.0427 −0.0074 0.038*

C3 0.7617 (2) 0.1046 (3) 0.04747 (6) 0.0303 (4)

H3 0.8408 0.0090 0.0599 0.036*

C4 0.7352 (2) 0.2782 (2) 0.07047 (5) 0.0239 (4)

C5 0.8226 (2) 0.3122 (3) 0.11225 (6) 0.0291 (4)

H5 0.8995 0.2163 0.1253 0.035*

C6 0.7980 (3) 0.4804 (3) 0.13397 (6) 0.0335 (4)

H6 0.8563 0.5006 0.1621 0.040*

C7 0.6859 (3) 0.6244 (3) 0.11468 (6) 0.0328 (4)

H7 0.6703 0.7421 0.1297 0.039*

C8 0.5989 (2) 0.5963 (2) 0.07429 (5) 0.0260 (4)

H8 0.5244 0.6952 0.0617 0.031*

C9 0.6186 (2) 0.4215 (2) 0.05104 (5) 0.0210 (3)

C10 0.5244 (2) 0.3859 (2) 0.00963 (5) 0.0212 (3)

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

N1 0.0516 (11) 0.0268 (8) 0.0314 (8) 0.0000 (8) −0.0124 (8) −0.0075 (7)

C1 0.0293 (9) 0.0236 (8) 0.0243 (8) −0.0021 (7) −0.0017 (7) 0.0004 (6)

C2 0.0396 (10) 0.0226 (8) 0.0335 (8) 0.0059 (8) 0.0008 (8) −0.0021 (7)

C3 0.0290 (9) 0.0280 (9) 0.0339 (9) 0.0064 (7) −0.0016 (8) 0.0076 (8)

C4 0.0194 (7) 0.0292 (8) 0.0231 (8) −0.0022 (6) 0.0005 (6) 0.0066 (7)

C5 0.0221 (8) 0.0402 (9) 0.0248 (8) −0.0036 (8) −0.0024 (7) 0.0101 (7)

C6 0.0311 (9) 0.0475 (11) 0.0218 (8) −0.0093 (9) −0.0052 (7) 0.0026 (8)

C7 0.0377 (10) 0.0344 (9) 0.0264 (8) −0.0074 (8) −0.0003 (8) −0.0066 (8)

C8 0.0278 (8) 0.0257 (8) 0.0245 (8) −0.0020 (7) −0.0001 (7) 0.0002 (7)

C9 0.0193 (7) 0.0238 (8) 0.0198 (7) −0.0035 (6) 0.0015 (6) 0.0033 (6)

C10 0.0218 (7) 0.0219 (8) 0.0200 (7) −0.0011 (6) 0.0003 (6) 0.0028 (6)

Geometric parameters (Å, º)

N1—C1 1.378 (2) C5—C6 1.363 (3)

N1—H1A 0.884 (10) C5—H5 0.950

N1—H1B 0.884 (10) C6—C7 1.409 (3)

C1—C10 1.393 (2) C6—H6 0.950

C1—C2 1.423 (2) C7—C8 1.374 (2)

C2—C3 1.355 (2) C7—H7 0.950

C2—H2 0.950 C8—C9 1.422 (2)

C3—C4 1.417 (2) C8—H8 0.950

C3—H3 0.950 C9—C10 1.433 (2)

C4—C5 1.419 (2) C10—C10i 1.496 (3)

C4—C9 1.426 (2)

C1—N1—H1A 113.1 (15) C4—C5—H5 119.5

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H1A—N1—H1B 114 (2) C5—C6—H6 120.0

N1—C1—C10 121.72 (15) C7—C6—H6 120.0

N1—C1—C2 117.93 (15) C8—C7—C6 120.63 (17)

C10—C1—C2 120.30 (15) C8—C7—H7 119.7

C3—C2—C1 121.25 (16) C6—C7—H7 119.7

C3—C2—H2 119.4 C7—C8—C9 121.05 (17)

C1—C2—H2 119.4 C7—C8—H8 119.5

C2—C3—C4 120.61 (16) C9—C8—H8 119.5

C2—C3—H3 119.7 C8—C9—C4 117.82 (14)

C4—C3—H3 119.7 C8—C9—C10 122.26 (14)

C3—C4—C5 121.36 (16) C4—C9—C10 119.91 (15)

C3—C4—C9 119.09 (15) C1—C10—C9 118.79 (14)

C5—C4—C9 119.55 (16) C1—C10—C10i 119.46 (14)

C6—C5—C4 121.02 (16) C9—C10—C10i 121.58 (15)

C6—C5—H5 119.5

N1—C1—C2—C3 179.76 (17) C3—C4—C9—C8 −178.28 (14)

C10—C1—C2—C3 2.3 (3) C5—C4—C9—C8 1.6 (2)

C1—C2—C3—C4 −1.3 (3) C3—C4—C9—C10 2.4 (2)

C2—C3—C4—C5 179.19 (17) C5—C4—C9—C10 −177.80 (14)

C2—C3—C4—C9 −1.0 (2) N1—C1—C10—C9 −178.22 (15)

C3—C4—C5—C6 179.34 (16) C2—C1—C10—C9 −0.8 (2)

C9—C4—C5—C6 −0.5 (2) N1—C1—C10—C10i 6.4 (2)

C4—C5—C6—C7 −0.7 (3) C2—C1—C10—C10i −176.20 (14)

C5—C6—C7—C8 0.8 (3) C8—C9—C10—C1 179.22 (14)

C6—C7—C8—C9 0.3 (3) C4—C9—C10—C1 −1.5 (2)

C7—C8—C9—C4 −1.5 (2) C8—C9—C10—C10i −5.5 (2)

C7—C8—C9—C10 177.85 (15) C4—C9—C10—C10i 173.83 (12)

Figure

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Figure 2

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References

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