1,1,4,4-Tetra­methyl­piperazinediium dibromide

Kärnä, M.; Lahtinen, M.; Valkonen, J.

doi:10.1107/S1600536809045139

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2952

https://doi.org/10.1107/S1600536809045139

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1,1,4,4-Tetramethylpiperazinediium dibromide

Minna Kärnä,^a Manu Lahtinen ^a ^* and Jussi Valkonen ^a

^aUniversity of Jyväskylä, Department of Chemistry, PO Box 35, FIN-40014 JY, Finland
^*Correspondence e-mail: manu.lahtinen@jyu.fi

(Received 23 October 2009; accepted 28 October 2009; online 31 October 2009)

A small quantity of the title compound, C₈H₂₀N₂²⁺·2Br⁻, was formed as a by-product in a reaction between a diamine and an alkyl bromide. The asymmetric unit contains half of a centrosymmetric dication and a bromide anion. In the crystal, weak intermolecular C—H⋯Br hydrogen bonds consolidate the crystal packing.

Related literature

For a possible synthetic route, see Creighton & Taylor (1987 ). For related structures, see; Linden et al. (1999 , 2002 ); Guo et al. (2007 ).

Experimental

Crystal data

C₈H₂₀N₂²⁺·2Br⁻
M_r = 304.08
Monoclinic, P 2₁ /c
a = 5.8769 (12) Å
b = 8.4584 (17) Å
c = 11.200 (2) Å
β = 92.79 (3)°
V = 556.07 (19) Å³
Z = 2
Mo Kα radiation
μ = 7.25 mm⁻¹
T = 123 K
0.24 × 0.16 × 0.16 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.296, T_max = 0.390
5032 measured reflections
1370 independent reflections
1223 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.061
S = 1.11
1370 reflections
95 parameters
All H-atom parameters refined
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.70 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯Br1ⁱ	0.96 (3)	2.88 (4)	3.816 (4)	165 (2)
C2—H2B⋯Br1	0.93 (3)	2.92 (4)	3.820 (4)	163 (2)
C2—H2C⋯Br1ⁱⁱ	0.98 (3)	2.83 (4)	3.770 (3)	161 (2)
C3—H3B⋯Br1ⁱⁱⁱ	1.00 (3)	2.84 (3)	3.806 (4)	163 (2)
C4—H4A⋯Br1^iv	0.93 (3)	2.92 (2)	3.566 (2)	127 (2)
C4—H4B⋯Br1ⁱⁱ	0.97 (3)	2.86 (5)	3.787 (2)	159 (2)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 1999 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ; Otwinowski et al., 2003 ); data reduction: DENZO-SMN; 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 I, global. DOI: https://doi.org/10.1107/S1600536809045139/cv2642sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809045139/cv2642Isup2.hkl

checkCIF report

Comment top

Low quantity of the title compound (Fig. 1) was formed as a byproduct in a synthesis between a tetramethylethylenediamine (TMEDA) and ethoxyethylbromide. Most probably residues of dibromoethane existed as an impurity on either of the starting materials as it is known that piperazinium can be formed by reacting TMEDA and 1,2-dibromoethane. The compound has been recrystallized from acetonitrile/methanol solvent and its crystal structure is reported here.

The asymmetric unit consists of one anion and half a cation. The C—H···Br distances vary from 2.826 (30) to 2.924 (20) Å. In the crystal, cations are packed columnary along a axis forming at the same time layers along b axis. The bromide anions are analogously packed between the cation layers. The structure is stabilized by weak intermolecular C—H···Br interactions. Cation conformation of this compound is similar to those previously reported tetraiodidocadmate and pentabromothallate salts.

Related literature top

For a possible synthetic route, see Creighton & Taylor (1987). For related structures, see; Linden et al. (1999, 2002); Guo et al. (2007).

Experimental top

The compound was a byproduct from a reaction between tetramethylenediamine and ethoxyethylbromide. Few crystals suitable for a single-crystal structure determination recrystallized from an acetonitrile-methanol solution.

Structure description top

For a possible synthetic route, see Creighton & Taylor (1987). For related structures, see; Linden et al. (1999, 2002); Guo et al. (2007).

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997; Otwinowski et al., 2003); data reduction: DENZO-SMN (Otwinowski & Minor, 1997; Otwinowski et al., 2003); 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. Left: The molecular structure of (I) showing 50% probability displacement ellipsoids and the atomic numbering [symmetry code: (i) -x + 1, y + 1/2, -z + 3/2]. Right: Spacefill presentation of location of eight bromides around a single dication. Six of the anions belong to the neighboring ion pairs.

1,1,4,4-Tetramethylpiperazinediium dibromide top

Crystal data top

C₈H₂₀N₂²⁺·2Br⁻	F(000) = 304
M_r = 304.08	D_x = 1.816 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.8769 (12) Å	Cell parameters from 3094 reflections
b = 8.4584 (17) Å	θ = 0.4–28.3°
c = 11.200 (2) Å	µ = 7.25 mm⁻¹
β = 92.79 (3)°	T = 123 K
V = 556.07 (19) Å³	Block, colourless
Z = 2	0.24 × 0.16 × 0.16 mm

Data collection top

Bruker Kappa APEXII diffractometer	1370 independent reflections
Radiation source: fine-focus sealed tube	1223 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
φ and ω scans	θ_max = 28.2°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −6→7
T_min = 0.296, T_max = 0.390	k = −11→10
5032 measured reflections	l = −14→14

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)] = 0.025	Hydrogen site location: difference Fourier map
wR(F²) = 0.061	All H-atom parameters refined
S = 1.11	w = 1/[σ²(F_o²) + (0.0256P)² + 0.322P] where P = (F_o² + 2F_c²)/3
1370 reflections	(Δ/σ)_max = 0.001
95 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.70 e Å⁻³

Crystal data top

C₈H₂₀N₂²⁺·2Br⁻	V = 556.07 (19) Å³
M_r = 304.08	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.8769 (12) Å	µ = 7.25 mm⁻¹
b = 8.4584 (17) Å	T = 123 K
c = 11.200 (2) Å	0.24 × 0.16 × 0.16 mm
β = 92.79 (3)°

Data collection top

Bruker Kappa APEXII diffractometer	1370 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1223 reflections with I > 2σ(I)
T_min = 0.296, T_max = 0.390	R_int = 0.032
5032 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.061	All H-atom parameters refined
S = 1.11	Δρ_max = 0.38 e Å⁻³
1370 reflections	Δρ_min = −0.70 e Å⁻³
95 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
N1	0.5241 (3)	0.3260 (2)	0.48286 (16)	0.0111 (4)
C2	0.6413 (5)	0.1983 (3)	0.4148 (2)	0.0146 (5)
C3	0.3697 (5)	0.2474 (3)	0.5693 (2)	0.0155 (5)
C4	0.3920 (4)	0.4292 (3)	0.3948 (2)	0.0120 (4)
C5	0.2945 (4)	0.5749 (3)	0.4538 (2)	0.0117 (5)
Br1	0.89763 (4)	0.01387 (3)	0.702200 (19)	0.01391 (10)
H2A	0.524 (5)	0.137 (3)	0.374 (2)	0.017 (7)*
H2B	0.720 (5)	0.138 (3)	0.473 (2)	0.013 (7)*
H2C	0.733 (4)	0.252 (3)	0.356 (2)	0.011 (6)*
H3A	0.462 (5)	0.186 (3)	0.620 (2)	0.019 (7)*
H3B	0.292 (5)	0.333 (3)	0.614 (2)	0.020 (7)*
H3C	0.270 (5)	0.190 (3)	0.524 (3)	0.021 (8)*
H4A	0.272 (4)	0.370 (3)	0.360 (2)	0.010 (6)*
H4B	0.491 (5)	0.456 (3)	0.331 (2)	0.010 (6)*
H5A	0.182 (5)	0.546 (3)	0.519 (2)	0.013 (7)*
H5B	0.220 (4)	0.637 (3)	0.394 (2)	0.005 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0101 (10)	0.0108 (9)	0.0122 (9)	−0.0002 (7)	0.0004 (7)	−0.0004 (7)
C2	0.0186 (14)	0.0101 (11)	0.0149 (11)	0.0019 (10)	0.0000 (10)	−0.0024 (9)
C3	0.0157 (14)	0.0142 (12)	0.0168 (12)	−0.0011 (10)	0.0034 (10)	0.0033 (9)
C4	0.0128 (12)	0.0105 (10)	0.0122 (10)	0.0004 (9)	−0.0029 (9)	−0.0010 (9)
C5	0.0116 (12)	0.0095 (10)	0.0137 (11)	0.0019 (9)	−0.0034 (9)	−0.0011 (9)
Br1	0.01243 (16)	0.01658 (15)	0.01261 (14)	0.00082 (9)	−0.00030 (9)	−0.00037 (8)

Geometric parameters (Å, º) top

N1—C4	1.505 (3)	C3—H3B	1.01 (3)
N1—C5ⁱ	1.506 (3)	C3—H3C	0.90 (3)
N1—C2	1.507 (3)	C4—C5	1.524 (3)
N1—C3	1.512 (3)	C4—H4A	0.93 (3)
C2—H2A	0.96 (3)	C4—H4B	0.97 (3)
C2—H2B	0.93 (3)	C5—N1ⁱ	1.506 (3)
C2—H2C	0.99 (3)	C5—H5A	1.04 (3)
C3—H3A	0.93 (3)	C5—H5B	0.94 (2)

C4—N1—C5ⁱ	108.49 (18)	N1—C3—H3C	105.5 (18)
C4—N1—C2	108.52 (17)	H3A—C3—H3C	113 (2)
C5ⁱ—N1—C2	107.85 (18)	H3B—C3—H3C	112 (2)
C4—N1—C3	111.58 (19)	N1—C4—C5	112.19 (18)
C5ⁱ—N1—C3	112.09 (17)	N1—C4—H4A	108.5 (16)
C2—N1—C3	108.19 (18)	C5—C4—H4A	108.6 (16)
N1—C2—H2A	107.1 (16)	N1—C4—H4B	108.0 (16)
N1—C2—H2B	105.1 (16)	C5—C4—H4B	112.5 (15)
H2A—C2—H2B	111 (2)	H4A—C4—H4B	107 (2)
N1—C2—H2C	106.7 (15)	N1ⁱ—C5—C4	112.47 (19)
H2A—C2—H2C	109 (2)	N1ⁱ—C5—H5A	104.9 (15)
H2B—C2—H2C	117 (2)	C4—C5—H5A	112.6 (15)
N1—C3—H3A	106.8 (18)	N1ⁱ—C5—H5B	108.7 (15)
N1—C3—H3B	107.6 (15)	C4—C5—H5B	108.2 (14)
H3A—C3—H3B	112 (2)	H5A—C5—H5B	110 (2)

C5ⁱ—N1—C4—C5	−55.1 (3)	C3—N1—C4—C5	68.8 (2)
C2—N1—C4—C5	−172.1 (2)	N1—C4—C5—N1ⁱ	57.4 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Br1ⁱⁱ	0.96 (3)	2.88 (4)	3.816 (4)	165 (2)
C2—H2B···Br1	0.93 (3)	2.92 (4)	3.820 (4)	163 (2)
C2—H2C···Br1ⁱⁱⁱ	0.98 (3)	2.83 (4)	3.770 (3)	161 (2)
C3—H3B···Br1^iv	1.00 (3)	2.84 (3)	3.806 (4)	163 (2)
C4—H4A···Br1^v	0.93 (3)	2.92 (2)	3.566 (2)	127 (2)
C4—H4B···Br1ⁱⁱⁱ	0.97 (3)	2.86 (5)	3.787 (2)	159 (2)

Symmetry codes: (ii) −x+1, −y, −z+1; (iii) x, −y+1/2, z−1/2; (iv) −x+1, y+1/2, −z+3/2; (v) x−1, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₈H₂₀N₂²⁺·2Br⁻
M_r	304.08
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	5.8769 (12), 8.4584 (17), 11.200 (2)
β (°)	92.79 (3)
V (Å³)	556.07 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	7.25
Crystal size (mm)	0.24 × 0.16 × 0.16

Data collection
Diffractometer	Bruker Kappa APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.296, 0.390
No. of measured, independent and observed [I > 2σ(I)] reflections	5032, 1370, 1223
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.061, 1.11
No. of reflections	1370
No. of parameters	95
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.70

Computer programs: COLLECT (Nonius, 1999), DENZO-SMN (Otwinowski & Minor, 1997; Otwinowski et al., 2003), 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
C2—H2A···Br1ⁱ	0.96 (3)	2.88 (4)	3.816 (4)	165 (2)
C2—H2B···Br1	0.93 (3)	2.92 (4)	3.820 (4)	163 (2)
C2—H2C···Br1ⁱⁱ	0.98 (3)	2.83 (4)	3.770 (3)	161 (2)
C3—H3B···Br1ⁱⁱⁱ	1.00 (3)	2.84 (3)	3.806 (4)	163 (2)
C4—H4A···Br1^iv	0.93 (3)	2.92 (2)	3.566 (2)	127 (2)
C4—H4B···Br1ⁱⁱ	0.97 (3)	2.86 (5)	3.787 (2)	159 (2)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z−1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) x−1, −y+1/2, z−1/2.

Acknowledgements

The authors thank the Inorganic Materials Chemistry Graduate Program and the Magnus Ehrnrooth Foundation for financial support.

References

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