2,2′-(Piperazine-1,4-di­yl)diethanaminium dibenzoate

Ignacy Cukrowski; Adedapo S Adeyinka; David C Liles

doi:10.1107/S1600536812030115

. 2012 Jul 7;68(Pt 8):o2389. doi: 10.1107/S1600536812030115

2,2′-(Piperazine-1,4-diyl)diethanaminium dibenzoate

Ignacy Cukrowski ^a,^*, Adedapo S Adeyinka ^a, David C Liles ^a

PMCID: PMC3414314 PMID: 22904847

Abstract

The asymmetric unit of the title salt C₈H₂₂N₄ ²⁺·2C₇H₅O₂ ⁻, comprises two independent pairs of half a 2,2′-(piperazine-1,4-diyl)diethanaminium dication plus a benzoate anion. The dications are symmetrical and lie across crystallographic centres of inversion. The crystal structure was refined as a two-component pseudo-merohedral twin using the twin law 001 0-10 100 [he domain fractions are 0.8645 (8) and 0.1355 (8)]. The anions and cations are linked by N—H⋯O hydrogen bonds and weak N—H⋯O intermolecular interactions to form infinite two-dimensional networks parallel to [101]. The conformation adopted by the cation in the crystal structure is very similar to that adopted by the same cation in the structures of the 2-hydroxybenzoate [Cukrowski et al. (2012 ▶). Acta Cryst, E68, o2387], the nitrate and the tetrahydrogen pentaborate salts.

Related literature

For the structures of the 2-hydroxybenzoate, the nitrate and the tetrahydrogen pentaborate salts of the 1,4-di(2-ammonioethyl)piperazine cation, see: Cukrowski et al. (2012 ▶); Junk & Smith (2005 ▶); Jiang et al. (2009 ▶), respectively.

Experimental

Crystal data

C₈H₂₂N₄ ²⁺·2C₇H₅O₂ ⁻
M _r = 416.52
Monoclinic,
a = 19.5300 (4) Å
b = 6.6694 (2) Å
c = 19.6178 (4) Å
β = 115.989 (1)°
V = 2296.89 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 180 K
0.28 × 0.23 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.910, T _max = 0.991
20137 measured reflections
5194 independent reflections
3970 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.110
S = 1.02
5194 reflections
290 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶), SCALEPACK and SORTAV (Blessing, 1995 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶), POV-RAY (Cason, 2004 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812030115/jj2134sup1.cif

e-68-o2389-sup1.cif^{(29.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812030115/jj2134Isup2.hkl

e-68-o2389-Isup2.hkl^{(254.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812030115/jj2134Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O15ⁱ	0.945 (18)	1.833 (19)	2.7739 (17)	173.0 (15)
N1—H1B⋯O15	0.902 (16)	1.895 (17)	2.7836 (15)	167.8 (14)
N1—H1B⋯O14	0.902 (16)	2.632 (16)	3.2580 (16)	127.2 (13)
N1—H1C⋯O14ⁱⁱ	0.925 (18)	1.887 (18)	2.7660 (16)	157.9 (14)
N1′—H1′A⋯O14′	0.882 (19)	1.857 (19)	2.7355 (17)	174.2 (15)
N1′—H1′B⋯O14′ⁱⁱⁱ	0.897 (17)	1.908 (17)	2.7836 (16)	164.8 (15)
N1′—H1′B⋯O15′ⁱⁱⁱ	0.897 (17)	2.533 (16)	3.1858 (16)	130.1 (13)
N1′—H1′C⋯O15′^iv	0.916 (18)	1.934 (18)	2.7585 (16)	148.8 (14)

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

The authors thank Dr John E. Davies of the University of Cambridge (England) for the data collection.

supplementary crystallographic information

Comment

The title compound [C₈H₂₂N₄²⁺ 2(C₇H₅O₂^-)] (1) was obtained as an unintended product during an attempt to prepare a benzoate salt of a singly protonated N,N'-di(2-aminoethyl)-2-aminoethane-1-ammonium ion (C₆H₁₉N₄⁺ C₇H₅O₂^-). This occurred because the starting material, instead of being pure N,N'-di(2-aminoethyl)-ethane-1,2-diamine, (C₆H₁₈N₄), was a mixture of that compound and 1,4-di(2-aminoethyl)piperazine (C₈H₂₂N₄) see Cukrowski, et al. (2012).

The asymmetric unit of the title compound, C₈H₂₂N₄²⁺, 2(C₇H₅O₂^-), 1, is a salt with two independent pairs of half a C₈H₂₂N₄²⁺ cation plus a C₇H₅O₂^- anion. The C₈H₂₂N₄²⁺ cations are symmetrical and lie across crystallographic centres of inversion (Fig. 1). The crystal structure was refined as a two-component pseudo- merohedral twin using the twin law 0 0 1 0 - 1 0 1 0 0. The fractional contribution refined to 0.1355 (8).

All three H atoms of each ammonium group in the cations of 1 are hydrogen bonded to the O atoms of the carboxylate groups of the anions. For each ammonium group, one H atom forms a bifurcated hydrogen bond to both of the O atoms of the carboxylate group of one anion, whereas the other two H atoms each form single hydrogen bonds to one O atom of the carboxylate group of each of two additional anions (Fig. 2). Thus both the O atoms of each carboxylate group are each acceptors for two hydrogen bonds. N—H···O hydrogen bonds and weak N—H···O intermolecular interactions link the cations and anions to form a two-dimensional network with layers parallel to the [101] plane (Fig. 2). Each of the two independent cation-anion pairs form the content of alternate network layers.

The conformation adopted by the C₈H₂₂N₄²⁺ cation in the crystal structure of 1 is very similar to the conformations adopted by the same cation in the crystal structures of the 2-hydroxybenzoate (Cukrowski, et al., 2012), the nitrate (Junk & Smith, 2005) and the tetrahydrogenpentaborate (Jiang, et al., 2009) salts despite the differences in the size and shape of the anions in the various structures.

Experimental

2 ml of a.3.32 M aqueous solution of what was claimed by the supplier (QinHuangDao JinLei Chemical Co.Ltd) to be N,N'-di(2-aminoethyl)-ethane-1,2-diamine, but which turned out to be a mixture of that compound (C₆H₁₈N₄, 6.64n mmol) and 1,4-di(2-aminoethyl)piperazine (C₈H₂₀N₄, 5.57(1-n) mmol) was added to 0.78 g of benzoic acid (6.96 mmol), resulting in a clear colourless solution. 0.2 ml of ethanol was added to the solution and the mixture was heated for 3 h at 70 °C. The solution was cooled to room temperature and then left covered for six days and then allowed to slowly evaporate by covering the container with perforated aluminium foil. Yellow crystals were obtained after four days of slow evaporation.