rac-2,2′-Bipiperidine-1,1′-diium dibromide

Laars, M.; Ausmees, K.; Kudrjashova, M.; Kanger, T.; Werner, F.

doi:10.1107/S1600536811016084

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1324

doi:10.1107/S1600536811016084

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rac-2,2′-Bipiperidine-1,1′-diium dibromide

Marju Laars,^a Kerti Ausmees,^a Marina Kudrjashova,^a Tõnis Kanger ^a and Franz Werner ^a ^*

^aTallinn University of Technology, Department of Chemistry, Akadeemia tee 15, 12618 Tallinn, Estonia
^*Correspondence e-mail: fwerner@chemnet.ee

(Received 10 April 2011; accepted 27 April 2011; online 7 May 2011)

In the title compound, C₁₀H₂₂N₂²⁺·2Br⁻, a precursor in the synthesis of organocatalysts, the bipiperidinium ion is located on a twofold rotation axis which passes through the mid-point of the central C—C bond. The piperidinium ring adopts a chair conformation. In the crystal, the cations are linked together by Br⁻ ions through N—H⋯Br hydrogen bonds, forming layers parallel to the ab plane.

Related literature

For the synthesis, see: Krumholz (1953 ); Herrmann et al. (2006 ). For the application of N-substituted enantiopure derivatives of the title compound in organocatalysis, see: Laars et al. (2008 ). For details of the Cu^II–catalysed Henry reaction, see: Noole et al. (2010 ). For related structures, see: Sato et al. (1982 ); Baran et al. (1992a ,b ); Intini et al. (2008 ).

Experimental

Crystal data

C₁₀H₂₂N₂²⁺·2Br⁻
M_r = 330.12
Monoclinic, C 2/c
a = 11.789 (2) Å
b = 10.6403 (18) Å
c = 11.6632 (17) Å
β = 107.687 (5)°
V = 1393.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 5.79 mm⁻¹
T = 300 K
0.40 × 0.30 × 0.20 mm

Data collection

Bruker SMART X2S diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.151, T_max = 0.391
4225 measured reflections
1225 independent reflections
1012 reflections with I > 2σ(I)
R_int = 0.068

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.093
S = 1.08
1224 reflections
70 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.94 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1NA⋯Br1ⁱ	0.95 (4)	2.36 (4)	3.293 (3)	168 (3)
N1—H1NB⋯Br1ⁱⁱ	0.92 (4)	2.34 (4)	3.228 (3)	162 (3)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x, -y, z-{\script{1\over 2}}]$ .

Data collection: GIS (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2009 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811016084/is2700sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811016084/is2700Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811016084/is2700Isup3.cml

checkCIF report

Comment top

N-substituted, enantiopure derivatives of the title phase, rac-2,2'-bipiperidine-1,1'-diium dibromide (I), catalyse stereoselectively both aldol reactions (Laars et al., 2008) and, in the form of their Cu^II–complexes, Henry (nitro-aldol) reactions (Noole et al., 2010).

Owing to the twofold axis, passing the centre of the bond C1—C1ⁱ (Fig. 1), Z'=0.5. Bond lengths and bond angles in the salt are normal. The piperidinium rings adopt chair conformation, with their least-squares planes (defined by their carbon and nitrogen atoms) twisted by about 77° against each other. Parallel to the (0 0 1) plane, the structure is made up of layers with a repeating distance of d₀₀₁/2 of cations, which are hydrogen-bound via bromide ions (Fig. 2).

Related literature top

For the synthesis, see: Krumholz (1953); Herrmann et al. (2006). For the application of N-substituted enantiopure derivatives of the title compound in organocatalysis, see: Laars et al. (2008). For details of the Cu^II–catalysed Henry reaction, see: Noole et al. (2010). For related structures, see: Sato et al. (1982); Baran et al. (1992a,b); Intini et al. (2008).

Experimental top

Single crystals of (I) were prepared from 2,2'-bipiperidine (Krumholz, 1953) according to Herrmann et al. (2006).

Computing details top

Data collection: GIS (Bruker, 2010); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Cationic moiety in the crystal structure of the title compound together with the bromide ions bound to it through N—H···Br hydrogen bonds. Displacement ellipsoids for non–H atoms are drawn at the 50% probability level. Orange dashed lines indicate the hydrogen bonds. Symmetry codes: (i) -x, y, 1/2 - z; (ii) 1/2-x, 1/2 - y, 1 - z; (iii) x, -y, -1/2 + z; (iv) -1/2 + x, 1/2 - y, -1/2 + z; (v) -x, -y, 1 - z.

Fig. 2. Packing diagram of the title compound. Orange dashed lines indicate N—H···Br hydrogen bonds. H atoms not involved in the hydrogen bonds have been omitted for clarity.

rac-2,2'-Bipiperidine-1,1'-diium dibromide top

Crystal data top

C₁₀H₂₂N₂²⁺·2Br⁻	F(000) = 664
M_r = 330.12	D_x = 1.573 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1621 reflections
a = 11.789 (2) Å	θ = 2.6–24.9°
b = 10.6403 (18) Å	µ = 5.79 mm⁻¹
c = 11.6632 (17) Å	T = 300 K
β = 107.687 (5)°	Prism, colourless
V = 1393.9 (4) Å³	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection top

Bruker SMART X2S diffractometer	1225 independent reflections
Radiation source: XOS X-beam microfocus source	1012 reflections with I > 2σ(I)
Doubly curved silicon crystal monochromator	R_int = 0.068
ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→14
T_min = 0.151, T_max = 0.391	k = −12→12
4225 measured reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.P)² + 0.0285P] where P = (F_o² + 2F_c²)/3
1224 reflections	(Δ/σ)_max < 0.001
70 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.94 e Å⁻³

Crystal data top

C₁₀H₂₂N₂²⁺·2Br⁻	V = 1393.9 (4) Å³
M_r = 330.12	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 11.789 (2) Å	µ = 5.79 mm⁻¹
b = 10.6403 (18) Å	T = 300 K
c = 11.6632 (17) Å	0.40 × 0.30 × 0.20 mm
β = 107.687 (5)°

Data collection top

Bruker SMART X2S diffractometer	1225 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1012 reflections with I > 2σ(I)
T_min = 0.151, T_max = 0.391	R_int = 0.068
4225 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.47 e Å⁻³
1224 reflections	Δρ_min = −0.94 e Å⁻³
70 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Br1	0.19514 (3)	0.07309 (4)	0.77393 (4)	0.0429 (2)
N1	0.1066 (3)	0.1990 (3)	0.1590 (3)	0.0319 (7)
H1NA	0.156 (3)	0.271 (4)	0.183 (3)	0.038*
H1NB	0.146 (3)	0.132 (4)	0.202 (4)	0.038*
C1	−0.0106 (3)	0.2219 (3)	0.1814 (3)	0.0287 (8)
H1	−0.0630	0.1510	0.1473	0.034*
C2	−0.0661 (3)	0.3394 (4)	0.1136 (3)	0.0385 (9)
H2A	−0.1423	0.3553	0.1265	0.046*
H2B	−0.0148	0.4111	0.1438	0.046*
C3	−0.0836 (4)	0.3232 (5)	−0.0213 (4)	0.0524 (11)
H3A	−0.1393	0.2553	−0.0526	0.063*
H3B	−0.1169	0.3997	−0.0635	0.063*
C4	0.0349 (4)	0.2940 (4)	−0.0433 (3)	0.0489 (11)
H4A	0.0213	0.2782	−0.1284	0.059*
H4B	0.0872	0.3662	−0.0208	0.059*
C5	0.0944 (4)	0.1811 (4)	0.0280 (4)	0.0442 (10)
H5A	0.0474	0.1064	−0.0017	0.053*
H5B	0.1725	0.1694	0.0182	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0502 (3)	0.0283 (3)	0.0495 (4)	−0.01100 (16)	0.0142 (3)	−0.00332 (18)
N1	0.0415 (17)	0.0201 (16)	0.0361 (19)	0.0024 (14)	0.0146 (16)	0.0033 (15)
C1	0.0344 (18)	0.0208 (18)	0.031 (2)	−0.0017 (15)	0.0101 (16)	−0.0031 (17)
C2	0.042 (2)	0.034 (2)	0.037 (2)	0.0072 (18)	0.0088 (19)	0.0033 (19)
C3	0.069 (3)	0.053 (3)	0.029 (2)	0.006 (2)	0.005 (2)	0.004 (2)
C4	0.075 (3)	0.044 (3)	0.031 (2)	−0.004 (2)	0.020 (2)	0.000 (2)
C5	0.068 (3)	0.033 (2)	0.040 (2)	−0.006 (2)	0.030 (2)	−0.012 (2)

Geometric parameters (Å, º) top

N1—C1	1.501 (4)	C2—H2A	0.9700
N1—C5	1.503 (5)	C3—C4	1.528 (5)
N1—H1NB	0.92 (4)	C3—H3A	0.9700
N1—H1NA	0.95 (4)	C3—H3B	0.9700
C1—C2	1.517 (5)	C4—C5	1.508 (6)
C1—C1ⁱ	1.542 (6)	C4—H4A	0.9700
C1—H1	0.9800	C4—H4B	0.9700
C2—C3	1.533 (5)	C5—H5A	0.9700
C2—H2B	0.9700	C5—H5B	0.9700

C1—N1—C5	112.9 (3)	C4—C3—C2	110.5 (3)
C1—N1—H1NB	112 (2)	C4—C3—H3A	109.5
C5—N1—H1NB	110 (2)	C2—C3—H3A	109.5
C1—N1—H1NA	109 (2)	C4—C3—H3B	109.5
C5—N1—H1NA	106 (2)	C2—C3—H3B	109.5
H1NB—N1—H1NA	107 (3)	H3A—C3—H3B	108.1
N1—C1—C2	108.5 (3)	C5—C4—C3	111.4 (3)
N1—C1—C1ⁱ	108.3 (3)	C5—C4—H4A	109.3
C2—C1—C1ⁱ	116.7 (2)	C3—C4—H4A	109.3
N1—C1—H1	107.7	C5—C4—H4B	109.3
C2—C1—H1	107.7	C3—C4—H4B	109.3
C1ⁱ—C1—H1	107.7	H4A—C4—H4B	108.0
C1—C2—C3	110.2 (3)	N1—C5—C4	110.2 (3)
C1—C2—H2B	109.6	N1—C5—H5A	109.6
C3—C2—H2B	109.6	C4—C5—H5A	109.6
C1—C2—H2A	109.6	N1—C5—H5B	109.6
C3—C2—H2A	109.6	C4—C5—H5B	109.6
H2B—C2—H2A	108.1	H5A—C5—H5B	108.1

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NA···Br1ⁱⁱ	0.95 (4)	2.36 (4)	3.293 (3)	168 (3)
N1—H1NB···Br1ⁱⁱⁱ	0.92 (4)	2.34 (4)	3.228 (3)	162 (3)

Symmetry codes: (ii) −x+1/2, −y+1/2, −z+1; (iii) x, −y, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₂₂N₂²⁺·2Br⁻
M_r	330.12
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	300
a, b, c (Å)	11.789 (2), 10.6403 (18), 11.6632 (17)
β (°)	107.687 (5)
V (Å³)	1393.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.79
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Bruker SMART X2S diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.151, 0.391
No. of measured, independent and observed [I > 2σ(I)] reflections	4225, 1225, 1012
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.093, 1.08
No. of reflections	1224
No. of parameters	70
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.94

Computer programs: GIS (Bruker, 2010), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NA···Br1ⁱ	0.95 (4)	2.36 (4)	3.293 (3)	168 (3)
N1—H1NB···Br1ⁱⁱ	0.92 (4)	2.34 (4)	3.228 (3)	162 (3)

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) x, −y, z−1/2.

Acknowledgements

The authors thank for funding grant agreement No. 229830 IC–UP2 under the 7^th Framework Programme of the European Commission, the EU European Regional Development Fund (3.2.0101.08–0017), the Estonian Science Foundation (grant No. 8289) and the Ministry of Education and Research (grant No. 0142725 s06).

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