(R,R) N,N′ Bis(5 chloro­salicyl­­idene) 1,2 cyclo­hexane­di­amine

organic papers

Acta Cryst.(2004). E60, o2397±o2398 doi:10.1107/S1600536804029319 Ming-Hua Yanget al. C₂₀H₂₀Cl₂N₂O₂

o2397

Structure Reports Online

ISSN 1600-5368

(

R

,

R

)-

N

,

N

-Bis(5-chlorosalicylidene)-1,2-cyclohexanediamine

Ming-Hua Yang, Yi-Zhi Li, Cheng-Jian Zhu,* Yi Pan and Shan-Hui Liu

Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, People's Republic of China

Correspondence e-mail: llyyjz@nju.edu.cn

Key indicators Single-crystal X-ray study T= 293 K

Mean(C±C) = 0.005 AÊ Rfactor = 0.054 wRfactor = 0.155

Data-to-parameter ratio = 15.9

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

#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved

In the title compound {systematic name: (R,R)-4,40

-dichloro-2,20_{-[cyclohexane-1,2-diylbis(nitrilomethylidyne)]diphenol},}

C20H20Cl2N2O2, there are two chiral C atoms and two

intramolecular OÐH N hydrogen bonds. The molecule lies

on a twofold rotation axis. The crystal structure is stabilized by

intermolecular OÐH O hydrogen bonds, which link the

molecules into one-dimensional helical chains along thebaxis.

Comment

Chiral salen compounds are important chiral ligands widely used in asymmetric catalytic synthesis (Canail & Sherrington, 1999; Jacobsen, 2000). The structure of chiral salen compounds has a crucial effect on enantioselectivity and activity in asymmetric catalytic reactions (Nicewiczet al., 2004; Yaoet al., 2001). Our research is focused on asymmetric synthesis cata-lysed by chiral salen±metal complexes (Zhu et al., 2004). In order to study the relationship between the structures and properties of such salen compounds, we have synthesized the chiral ligand (R,R)-N,N0

-bis(5-chloro-salicylidene)-1,2-cyclo-hexanediamine, (I), and present its crystal structure here.

The molecular structure of (I) (Fig. 1) contains two chiral C atoms in (R,R)-diastereomeric form, the molecule lying on a

twofold rotation axis. Intramolecular OÐH N hydrogen

bonds (Fig. 1, Table 1) are present.

The crystal packing is stabilized by intermolecular OÐ

H O hydrogen bonds (Table 1), which link the molecules

into one-dimensional helical chains along thebaxis (Fig. 2).

Experimental

Under nitrogen, a mixture of (R,R)-1,2-cyclohexanediamine (342 mg, 3 mmol), Na2SO4 (2 g) and 5-chloro-2-hydroxybenzaldehyde

(939 mg, 6 mmol) in absolute ethanol (10 ml) was re¯uxed for about 12 h to yield a yellow precipitate. The product was collected by vacuum ®ltration and washed with ethanol. The crude solid was dissolved in CH2Cl2(50 ml) and washed with water (210 ml) and

brine (10 ml). After drying over Na2SO4, the solvent was removed

under vacuum and a yellow solid was isolated in 85% yield (1.0 g). Yellow single crystals of (I) suitable for X-ray analysis were grown from a solution in hexane by slow evaporation of the solvent at room temperature over a period of about a week. Spectroscopic analysis:

1_{H NMR (300 MHz, CDCl}

3,, p.p.m.): 13.13 (s, 2H), 8.10 (s, 2H),

7.10±7.14 (dd,J= 2.0 and 8.8 Hz, 2H), 6.98±7.04 (d,J= 2.0 Hz, 2H), 6.75±6.78 (d,J= 8.8 Hz, 2H), 3.23±3.26 (m, 2H), 1.82±1.87 (m, 4H), 1.62±1.65 (m, 2H), 1.36±1.42 (m, 2H); IR (KBr,, cmÿ1_{): 3430, 2924,}

2856, 1633, 1478, 1371, 1282, 1185, 1293, 1034, 977; analysis calculated for C20H20Cl2N2O2(%): C 61.39, H 5.15, N 7.16; found: C 61.28, H

5.24, N 7.22.

Crystal data C20H20Cl2N2O2

Mr= 391.28

Orthorhombic,P21212

a= 18.990 (6) AÊ b= 5.829 (2) AÊ c= 8.839 (3) AÊ V= 978.4 (6) AÊ3

Z= 2

Dx= 1.328 Mg mÿ3

MoKradiation Cell parameters from 780

re¯ections = 2.5±25.0

= 0.35 mmÿ1

T= 293 (2) K Block, yellow 0.300.240.22 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer 'and!scans

Absorption correction: multi-scan (SADABS; Bruker, 2000) Tmin= 0.91,Tmax= 0.93

5037 measured re¯ections

1879 independent re¯ections 1554 re¯ections withI> 2(I) Rint= 0.058

max= 26.0

h=ÿ21!23 k=ÿ5!7 l=ÿ10!10 Refinement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.054}

wR(F2_{) = 0.155}

S= 1.05 1879 re¯ections 118 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0882P)2

+ 0.127P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.34 e AÊÿ3

min=ÿ0.20 e AÊÿ3

Absolute structure: Flack (1983), with 732 Friedel pairs Flack parameter = 0.13 (15)

Table 1

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A O1ÐH1B N1 0.85 2.03 2.599 (4) 124 O1ÐH1B O1i _{0.85 2.46 2.903 (5) 114} Symmetry code: (i) 1ÿx;1ÿy;z.

All H atoms were positioned geometrically and re®ned using a riding model, with CÐH distances in the range 0.93±0.98 AÊ and an OÐH distance of 0.85 AÊ, and withUiso(H) = 1.2Ueq(C,O).

Data collection:SMART(Bruker, 2000); cell re®nement:SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to re®ne structure:SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL.

The authors are grateful to the National Natural Science Foundation of China for ®nancial support (grant Nos. 20102002 and 20332050).

References

Bruker (2000).SMART(Version 5.625),SAINT(Version 6.01),SHELXTL (Version 6.10) andSADABS(Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.

Canail, L. & Sherrington, D. C. (1999).Chem. Soc. Rev.28, 85±93. Flack, H. D. (1983).Acta Cryst.A39, 876±881.

Jacobsen, E. N. (2000).Acc. Chem. Res.33, 421±431.

Nicewicz, D. A., Yates, C. M. & Johnson, J. S. (2004).J. Org. Chem.69, 6548± 6555.

Yao, X. Q., Qiu, M., LuÈ, W., Chen, H. L. & Zheng, Z. (2001).Tetrahedron: Asymmetry,12, 197±204.

Zhu, C. J., Yang, M. H., Sun, J. T., Zhu, Y. H. & Pan, Y. (2004).Synlett,3, 465± 468.

Figure 2

The one-dimensional hydrogen-bonded helical chain in (I), viewed down thecaxis.

Figure 1

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sup-1

Acta Cryst. (2004). E60, o2397–o2398

supporting information

Acta Cryst. (2004). E60, o2397–o2398 [https://doi.org/10.1107/S1600536804029319]

(R,R)-N,N

′

-Bis(5-chlorosalicylidene)-1,2-cyclohexanediamine

Ming-Hua Yang, Yi-Zhi Li, Cheng-Jian Zhu, Yi Pan and Shan-Hui Liu

(R,R)-4,4′-dichloro-2,2′-[cyclohexane-1,2-diylbis(nitrilomethylidyne)]diphenol

Crystal data

C20H20Cl2N2O2

Mr = 391.28

Orthorhombic, P21212 Hall symbol: P 2 2ab a = 18.990 (6) Å b = 5.829 (2) Å c = 8.839 (3) Å V = 978.4 (6) Å3

Z = 2 F(000) = 408

Dx = 1.328 Mg m−3

Melting point = 465.2–467.2 K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 780 reflections θ = 2.5–25.0°

µ = 0.35 mm−1

T = 293 K Block, yellow

0.30 × 0.24 × 0.22 mm

Data collection

Bruker SMART Apex CCD area-detector diffractometer

Radiation source: sealed tube Graphite monochromator φ and ω scans

Absorption correction: multi-scan (SADABS; Bruker, 2000) Tmin = 0.91, Tmax = 0.93

5037 measured reflections 1879 independent reflections 1554 reflections with I > 2σ(I) Rint = 0.058

θmax = 26.0°, θmin = 2.1°

h = −21→23 k = −5→7 l = −10→10

Refinement

Refinement on F2 Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.054}

wR(F2_{) = 0.155}

S = 1.05 1879 reflections 118 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) + (0.0882P)2 + 0.127P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001 Δρmax = 0.34 e Å−3 Δρmin = −0.20 e Å−3

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.

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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

Cl1 0.79252 (5) −0.0079 (2) 1.32170 (10) 0.1000 (4) C1 0.62495 (14) 0.3578 (5) 1.0577 (4) 0.0660 (8) C2 0.64605 (14) 0.1388 (5) 1.0135 (3) 0.0547 (7) C3 0.69842 (14) 0.0309 (5) 1.0955 (3) 0.0578 (6) H3A 0.7139 −0.1136 1.0658 0.069* C4 0.72761 (17) 0.1327 (6) 1.2188 (3) 0.0660 (8) C5 0.70625 (18) 0.3454 (6) 1.2646 (4) 0.0766 (9) H5A 0.7260 0.4128 1.3501 0.092* C6 0.65548 (18) 0.4585 (6) 1.1837 (4) 0.0757 (9) H6A 0.6413 0.6044 1.2136 0.091* C7 0.61448 (14) 0.0243 (5) 0.8846 (3) 0.0584 (7) H7A 0.6296 −0.1228 0.8599 0.070* C8 0.54043 (14) −0.0090 (6) 0.6741 (3) 0.0701 (8) H8A 0.5546 −0.1703 0.6809 0.084* N1 0.56724 (12) 0.1169 (4) 0.8047 (3) 0.0659 (7) O1 0.57601 (12) 0.4740 (4) 0.9799 (4) 0.0939 (8) H1B 0.5448 0.3877 0.9409 0.113* C9 0.57074 (19) 0.0973 (8) 0.5319 (4) 0.0953 (13) H9A 0.6214 0.0766 0.5313 0.114* H9B 0.5612 0.2608 0.5319 0.114* C10 0.5395 (2) −0.0100 (11) 0.3902 (5) 0.1173 (16) H10A 0.5584 0.0662 0.3015 0.141* H10B 0.5527 −0.1706 0.3853 0.141*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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Acta Cryst. (2004). E60, o2397–o2398

C4 0.0727 (17) 0.0739 (17) 0.0513 (15) −0.0003 (16) 0.0126 (13) 0.0079 (14) C1 0.0551 (15) 0.0565 (16) 0.087 (2) 0.0003 (14) 0.0159 (14) −0.0026 (16) C9 0.0695 (19) 0.127 (3) 0.089 (3) −0.031 (2) 0.0046 (18) 0.009 (2) C10 0.107 (3) 0.168 (4) 0.077 (2) −0.051 (3) 0.014 (2) −0.012 (3)

Geometric parameters (Å, º)

Cl1—C4 1.737 (3) C8—C8i _{1.539 (6)} C3—C4 1.359 (4) C8—H8A 0.9800 C3—C2 1.382 (4) C5—C4 1.366 (5) C3—H3A 0.9300 C5—H5A 0.9300 C7—N1 1.263 (4) O1—C1 1.340 (4) C7—C2 1.450 (4) O1—H1B 0.8498 C7—H7A 0.9300 C9—C10 1.520 (6) C2—C1 1.394 (4) C9—H9A 0.9700 C6—C5 1.370 (5) C9—H9B 0.9700 C6—C1 1.387 (5) C10—C10i _{1.505 (9)} C6—H6A 0.9300 C10—H10A 0.9700 C8—N1 1.460 (4) C10—H10B 0.9700 C8—C9 1.515 (5)

C4—C3—C2 121.0 (3) C6—C5—H5A 120.3 C4—C3—H3A 119.5 C1—O1—H1B 113.1 C2—C3—H3A 119.5 C3—C4—C5 120.9 (3) N1—C7—C2 122.4 (3) C3—C4—Cl1 120.2 (3) N1—C7—H7A 118.8 C5—C4—Cl1 118.9 (3) C2—C7—H7A 118.8 O1—C1—C6 119.2 (3) C3—C2—C1 118.5 (3) O1—C1—C2 121.2 (3) C3—C2—C7 120.0 (3) C6—C1—C2 119.5 (3) C1—C2—C7 121.5 (3) C8—C9—C10 111.5 (3) C5—C6—C1 120.7 (3) C8—C9—H9A 109.3 C5—C6—H6A 119.7 C10—C9—H9A 109.3 C1—C6—H6A 119.7 C8—C9—H9B 109.3 N1—C8—C9 108.5 (3) C10—C9—H9B 109.3 N1—C8—C8i _{108.3 (2) H9A—C9—H9B 108.0} C9—C8—C8i _{110.6 (2) C10}i_{—C10—C9 110.9 (4)} N1—C8—H8A 109.8 C10i_{—C10—H10A 109.5} C9—C8—H8A 109.8 C9—C10—H10A 109.5 C8i_{—C8—H8A 109.8 C10}i_{—C10—H10B 109.5} C7—N1—C8 118.4 (3) C9—C10—H10B 109.5 C4—C5—C6 119.4 (3) H10A—C10—H10B 108.0 C4—C5—H5A 120.3

Symmetry code: (i) −x+1, −y, z.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O1—H1B···O1ii _{0.85 2.46 2.903 (5) 114}