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

Yi, J.; Hu, S.

doi:10.1107/S1600536809039671

organic compounds

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

Jianhong Yi ^a and Shuangqi Hu ^b ^*

^aSchool of Material Science and Engineering, North University of China, Taiyuan 030051, People's Republic of China, and ^bSchool of Chemical Engineering and Environment, North University of China, Taiyuan 030051, People's Republic of China
^*Correspondence e-mail: yijianhongnu@126.com

(Received 28 September 2009; accepted 29 September 2009; online 3 October 2009)

The molecule of the title compound, C₂₀H₂₀Br₂N₂O₂, lies on a twofold axis. It contains two stereogenic C atoms with R chirality and thus it is the enatiomerically pure R,R-diastereomer. There is an intramolecular O—H⋯N hydrogen bond.

Related literature

For the structure of 1,2-cyclohexanediamine, see: Yang et al., (2004 , 2007 ). For background to the use of chiral Salen compounds containing the 1,2-cyclohexanediamine motif in asymmetric catalytic synthesis, see: Canail & Sherrington (1999 ); Jacobsen (2000 ).

Experimental

Crystal data

C₂₀H₂₀Br₂N₂O₂
M_r = 480.20
Orthorhombic, P 2₁ 2₁ 2
a = 5.9323 (16) Å
b = 19.079 (5) Å
c = 9.009 (2) Å
V = 1019.7 (4) Å³
Z = 2
Mo Kα radiation
μ = 3.99 mm⁻¹
T = 298 K
0.28 × 0.21 × 0.15 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.401, T_max = 0.586
5912 measured reflections
1727 independent reflections
1449 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.089
S = 1.06
1727 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.39 e Å⁻³
Absolute structure: Flack (1983 ), 681 Friedel pairs
Flack parameter: 0.018 (18)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.91	2.611 (4)	143

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809039671/dn2493sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039671/dn2493Isup2.hkl

checkCIF report

Comment top

Chiral Salen compounds containing 1,2-cyclohexanediamine motif are widely used in the asymmetric catalytic synthesis (Canail & Sherrington, 1999; Jacobsen et al., 2000). Until now, only few single-crystal structures of chiral Salen compounds were reported. Some interesting compounds with 1,2-cyclohexanediamine have however been reported (Yang et al., 2004; 2007). In an attempt to form a Cd(II) complex with the (R,R)-4,4'-bromo-2,2'-[cyclohexane-1,2-diylbis (nitrilomethylidyne)]diphenol, we unexpectedly obtained the title compound (I) whose crystal structure is reported herein.

The molecular structure of (I) is built from two halves related through a two fold axix passing through the middle of the C8-C8ⁱ and C10-C10ⁱ bonds [(i)= 1-x, 2-y, z)] (Fig. 1). The stereogenic carbon C8 has the R chirality and so the molecule is the enantiomerically pure R,R diastereomer which confirms the synthetic patway used. This molecule is closely related to the (R,R)-N,N'-Bis(5-chlorosalicylidene)- 1,2-cyclohexanediamine compound (Yang et al., 2004).

Intramolecular O-H···N hydrogen bonds also exist in this molecule and thus stabilize the structure (Table 1).

Related literature top

For the structure of 1,2-cyclohexanediamine, see: Yang et al., (2004,2007). For backgroup to the use of chiral Salen compounds containing the 1,2-cyclohexanediamine motif in asymmetric catalytic synthesis, see: Canail & Sherrington (1999); Jacobsen (2000).

Experimental top

The title compound was synthesized according to the literature (Yang et al., 2004) using the reaction of (R,R)-1,2-cyclohexanediamine, Na₂SO₄, and 5-bromon–2-hydroxybenzaldehyde under mild condition. (R,R)-4,4'-Bromo-2,2'-[cyclohexane-1,2-diylbis (nitrilomethylidyne)]diphenol (0.52 g, 1 mmol) was added to a solution of Cd(AC)₂ .4H₂O(0.26g, 1mmol) in methanol(20mL). The mixture was heated for 20 hs under reflux with stirring. It was then filtered to give a clear solution, into which diethyl ether vapour was allowed to condense in a closed vessel. After being allowed to stand for a two weeks at room temperature, colorless single crystals were used to measure X-ray diffraction analysis.

Structure description top

Intramolecular O-H···N hydrogen bonds also exist in this molecule and thus stabilize the structure (Table 1).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Molecular view of (I) with the atom-labeling scheme. Ellipsoids are drawn at the the 30% probability level. H atoms are represented as small spheres of arbitrary radii. [Symmetric code: (i): -x+1, -y+2, z]

(R,R)-4,4'-Dibromo-2,2'-[cyclohexane-1,2- diylbis(nitrilomethylidyne)]diphenol top

Crystal data top

C₂₀H₂₀Br₂N₂O₂	F(000) = 480
M_r = 480.20	D_x = 1.564 Mg m⁻³
Orthorhombic, P2₁2₁2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 1727 reflections
a = 5.9323 (16) Å	θ = 2.1–24.9°
b = 19.079 (5) Å	µ = 3.99 mm⁻¹
c = 9.009 (2) Å	T = 298 K
V = 1019.7 (4) Å³	Block, colorless
Z = 2	0.28 × 0.21 × 0.15 mm

Data collection top

Bruker APEXII area-detector diffractometer	1727 independent reflections
Radiation source: fine-focus sealed tube	1449 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
φ and ω scans	θ_max = 24.7°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −6→0
T_min = 0.401, T_max = 0.586	k = −22→22
5912 measured reflections	l = −10→0

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0509P)² + 0.1466P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
1727 reflections	Δρ_max = 0.34 e Å⁻³
119 parameters	Δρ_min = −0.39 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 681 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.018 (18)

Crystal data top

C₂₀H₂₀Br₂N₂O₂	V = 1019.7 (4) Å³
M_r = 480.20	Z = 2
Orthorhombic, P2₁2₁2	Mo Kα radiation
a = 5.9323 (16) Å	µ = 3.99 mm⁻¹
b = 19.079 (5) Å	T = 298 K
c = 9.009 (2) Å	0.28 × 0.21 × 0.15 mm

Data collection top

Bruker APEXII area-detector diffractometer	1727 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1449 reflections with I > 2σ(I)
T_min = 0.401, T_max = 0.586	R_int = 0.024
5912 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.089	Δρ_max = 0.34 e Å⁻³
S = 1.06	Δρ_min = −0.39 e Å⁻³
1727 reflections	Absolute structure: Flack (1983), 681 Friedel pairs
119 parameters	Absolute structure parameter: 0.018 (18)
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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) top

	x	y	z	U_iso*/U_eq
Br1	0.48940 (8)	0.71173 (2)	0.82889 (4)	0.0863 (2)
N1	0.6206 (5)	0.93317 (14)	0.2921 (3)	0.0608 (8)
O1	0.9786 (5)	0.92461 (14)	0.4597 (4)	0.0835 (8)
H1	0.8927	0.9446	0.4023	0.125*
C1	0.6427 (6)	0.77902 (19)	0.7105 (4)	0.0572 (9)
C2	0.8549 (7)	0.7999 (2)	0.7508 (4)	0.0635 (10)
H2	0.9242	0.7810	0.8342	0.076*
C3	0.9636 (6)	0.8492 (2)	0.6663 (4)	0.0677 (10)
H3	1.1076	0.8637	0.6933	0.081*
C4	0.8627 (6)	0.87805 (17)	0.5409 (5)	0.0590 (9)
C5	0.6450 (6)	0.85674 (15)	0.5008 (4)	0.0505 (8)
C6	0.5368 (6)	0.80627 (17)	0.5877 (3)	0.0533 (8)
H6	0.3929	0.7911	0.5623	0.064*
C7	0.5283 (6)	0.88710 (17)	0.3743 (4)	0.0533 (8)
H7	0.3823	0.8725	0.3529	0.064*
C8	0.4952 (8)	0.95999 (17)	0.1642 (3)	0.0648 (9)
H8	0.3376	0.9450	0.1716	0.078*
C9	0.5975 (9)	0.9300 (2)	0.0232 (5)	0.0878 (15)
H9A	0.7580	0.9397	0.0222	0.105*
H9B	0.5779	0.8796	0.0228	0.105*
C10	0.4915 (13)	0.9604 (2)	−0.1149 (5)	0.1066 (17)
H10A	0.3342	0.9467	−0.1197	0.128*
H10B	0.5670	0.9418	−0.2020	0.128*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1059 (4)	0.0925 (3)	0.0605 (3)	−0.0117 (3)	0.0117 (3)	0.01235 (19)
N1	0.0651 (18)	0.0461 (16)	0.071 (2)	0.0081 (14)	−0.0010 (17)	0.0035 (15)
O1	0.0581 (16)	0.0651 (15)	0.127 (2)	−0.0141 (15)	0.001 (2)	0.0131 (15)
C1	0.069 (2)	0.057 (2)	0.0452 (18)	0.0034 (18)	0.0052 (17)	−0.0075 (15)
C2	0.070 (2)	0.069 (2)	0.0509 (19)	0.011 (2)	−0.0112 (19)	−0.0097 (19)
C3	0.051 (2)	0.071 (2)	0.081 (2)	0.0040 (18)	−0.011 (3)	−0.025 (2)
C4	0.054 (2)	0.0445 (18)	0.078 (2)	0.0002 (16)	0.001 (2)	−0.0103 (18)
C5	0.051 (2)	0.0417 (16)	0.058 (2)	0.0042 (14)	0.0024 (18)	−0.0087 (15)
C6	0.050 (2)	0.0580 (18)	0.0516 (17)	−0.0006 (16)	0.0032 (17)	−0.0140 (15)
C7	0.0488 (19)	0.0507 (18)	0.0604 (17)	0.0064 (17)	−0.0017 (18)	−0.0102 (14)
C8	0.074 (2)	0.0500 (17)	0.071 (2)	0.014 (2)	−0.003 (3)	0.0000 (16)
C9	0.126 (4)	0.061 (2)	0.076 (3)	0.030 (3)	−0.004 (3)	−0.007 (2)
C10	0.160 (5)	0.093 (3)	0.067 (2)	0.042 (4)	−0.003 (4)	−0.010 (2)

Geometric parameters (Å, º) top

Br1—C1	1.901 (4)	C5—C7	1.454 (5)
N1—C7	1.273 (5)	C6—H6	0.9300
N1—C8	1.464 (4)	C7—H7	0.9300
O1—C4	1.341 (4)	C8—C9	1.519 (5)
O1—H1	0.8200	C8—C8ⁱ	1.528 (7)
C1—C2	1.369 (6)	C8—H8	0.9800
C1—C6	1.375 (5)	C9—C10	1.510 (6)
C2—C3	1.371 (5)	C9—H9A	0.9700
C2—H2	0.9300	C9—H9B	0.9700
C3—C4	1.392 (5)	C10—C10ⁱ	1.515 (10)
C3—H3	0.9300	C10—H10A	0.9700
C4—C5	1.401 (5)	C10—H10B	0.9700
C5—C6	1.397 (5)

C7—N1—C8	118.7 (4)	N1—C7—H7	119.1
C4—O1—H1	109.5	C5—C7—H7	119.1
C2—C1—C6	121.5 (4)	N1—C8—C9	108.9 (3)
C2—C1—Br1	119.2 (3)	N1—C8—C8ⁱ	109.3 (3)
C6—C1—Br1	119.2 (3)	C9—C8—C8ⁱ	111.2 (3)
C1—C2—C3	119.0 (4)	N1—C8—H8	109.2
C1—C2—H2	120.5	C9—C8—H8	109.2
C3—C2—H2	120.5	C8ⁱ—C8—H8	109.2
C2—C3—C4	121.3 (4)	C10—C9—C8	112.2 (4)
C2—C3—H3	119.4	C10—C9—H9A	109.2
C4—C3—H3	119.4	C8—C9—H9A	109.2
O1—C4—C3	119.0 (4)	C10—C9—H9B	109.2
O1—C4—C5	121.6 (4)	C8—C9—H9B	109.2
C3—C4—C5	119.4 (4)	H9A—C9—H9B	107.9
C6—C5—C4	118.6 (3)	C9—C10—C10ⁱ	110.8 (5)
C6—C5—C7	119.6 (3)	C9—C10—H10A	109.5
C4—C5—C7	121.7 (3)	C10ⁱ—C10—H10A	109.5
C1—C6—C5	120.1 (3)	C9—C10—H10B	109.5
C1—C6—H6	119.9	C10ⁱ—C10—H10B	109.5
C5—C6—H6	119.9	H10A—C10—H10B	108.1
N1—C7—C5	121.8 (4)

Symmetry code: (i) −x+1, −y+2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.91	2.611 (4)	143

Experimental details

Crystal data
Chemical formula	C₂₀H₂₀Br₂N₂O₂
M_r	480.20
Crystal system, space group	Orthorhombic, P2₁2₁2
Temperature (K)	298
a, b, c (Å)	5.9323 (16), 19.079 (5), 9.009 (2)
V (Å³)	1019.7 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.99
Crystal size (mm)	0.28 × 0.21 × 0.15

Data collection
Diffractometer	Bruker APEXII area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.401, 0.586
No. of measured, independent and observed [I > 2σ(I)] reflections	5912, 1727, 1449
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.587

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.089, 1.06
No. of reflections	1727
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.39
Absolute structure	Flack (1983), 681 Friedel pairs
Absolute structure parameter	0.018 (18)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.91	2.611 (4)	143.2

Acknowledgements

The authors are grateful for funding from the Northern University of China.

References

Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc, Madison, Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Canail, L. & Sherrington, D. C. (1999). Chem. Soc. Rev. 28, 85–93. Web of Science CrossRef Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

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https://doi.org/10.1107/S1600536809039671

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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