trans-2,5-Di­methyl­piperazine-1,4-diium dinitrate

Gatfaoui, S.; Roisnel, T.; Dhaouadi, H.; Marouani, H.

doi:10.1107/S1600536814012100

organic compounds

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doi:10.1107/S1600536814012100

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trans-2,5-Dimethylpiperazine-1,4-diium dinitrate

Sofian Gatfaoui,^a Thierry Roisnel,^b Hassouna Dhaouadi ^c ^* and Houda Marouani ^a

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia, ^bCentre de Diffractométrie X, UMR 6226 CNRS, Unité Sciences Chimiques de Rennes, Université de Rennes I, 263 Avenue du Général Leclerc, 35042 Rennes, France, and ^cLaboratoire des Matériaux Utiles, Institut National de Recherche et d'Analyse Physico-chimique, Pole Technologique de Sidi-Thabet, 2020 Tunis, Tunisia
^*Correspondence e-mail: dhaouadihassouna@yahoo.fr

(Received 9 May 2014; accepted 25 May 2014; online 31 May 2014)

In the structure of the title salt, C₆H₁₆N₂²⁺·2NO₃⁻, the cations are connected to the anions through bifurcated N—H⋯(O,O) and weak C—H⋯O hydrogen bonds, generating corrugated layers parallel to the (100) plane. The organic cation is centrosymmetric and the diprotonated piperazine ring adopts a chair conformation, with the methyl groups occupying equatorial positions.

CCDC reference: 1005191

Related literature

For pharmacological properties of piperazine, see: Conrado et al. (2008 ). For related structures, see: Gatfaoui et al. (2013 , 2014a ,b ); Marouani et al. (2012 ); Kefi et al. (2013 ). For a complex of the title cation, see: Rother et al. (1997 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₆H₁₆N₂²⁺·2NO₃⁻
M_r = 240.23
Monoclinic, P 2₁ /c
a = 7.0357 (8) Å
b = 10.0277 (10) Å
c = 8.3112 (8) Å
β = 116.149 (8)°
V = 526.36 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 150 K
0.58 × 0.46 × 0.23 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.827, T_max = 0.970
4126 measured reflections
1195 independent reflections
1059 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.090
S = 1.11
1195 reflections
74 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ⁱ	0.90	1.99	2.8471 (14)	158
N2—H2A⋯O2ⁱⁱ	0.90	2.45	2.9899 (13)	119
N2—H2B⋯O1	0.90	2.07	2.9057 (13)	153
N2—H2B⋯O3	0.90	2.42	3.2172 (14)	149
C1—H1⋯O1ⁱⁱⁱ	0.98	2.50	3.2614 (14)	134
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (ii) -x, -y, -z-1; (iii) -x, -y, -z.

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg & Putz 2005 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and CRYSCAL (T. Roisnel, local program).

Supporting information

CCDC reference: 1005191

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814012100/bg2529sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814012100/bg2529Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814012100/bg2529Isup3.cml

checkCIF report

Comment top

Piperazine and its derivatives are widely used due to their interesting biological and pharmacology proprieties (Conrado et al., 2008). In this work, we report the preparation and the structural investigation of a new organic nitrate, C₆H₁₆N₂·(NO₃)₂ (I). The asymmetric unit of (I) is composed of a half trans-2,5-dimeyhylpipeazine-1,4-dium cations and one nitrate anion (Figure 1). In the structure, the cations are connected to the anions through bifurcated N—H···O(O) and weak C—H···O hydrogen bonds, generating a corrugated layers parallel to the (001) plane (Fig. 2).

Interatomic bond lengths and angles of the nitrate anions spread respectively within the ranges [1.2398 (13)–1.2706 (13) Å] and [118.65 (10)–121.73 (10)°]. These geometrical features have also been noticed in other crystal structures (Marouani et al., 2012; Kefi et al., 2013; Gatfaoui et al., 2013, 2014a,b). It is worth noting that the distance N1—O1 is significantly longer than the N1—O2 and N1—O3 distances because O1 is applied in three hydrogen bonds (table1) while O2 and O3 are applied in only one hydrogen bond. Inside such a structure, the complete organic entity is generated by inversion symmetry located at (0, 0, 0) and (0, 1/2, 1/2). So it is built up by only the half of the cation. Examination of the organic cations shows that the bond distances and angles show no significant difference from those obtained in other complex involving the same organic groups (Rother et al., 1997). The diprotonated piperazine ring adopts a chair conformation, with the methyl groups occupying an equatorial position, with puckering parameters: Q = 0.6083 Å, θ = 90 ° and ϕ = 166 ° (Cremer & Pople, 1975).

The established H-bonds of types N—H···O(O) and C—H···O involve oxygen atoms of the nitrate anions as acceptors, and protonated nitrogen atoms and methine groups of the trans-2,5-dimethylpiperazine-1,4-diium as donors.

Related literature top

For pharmacological properties of piperazine, see: Conrado et al. (2008). For related structures, see: Gatfaoui et al. (2013, 2014a,b); Marouani et al. (2012); Kefi et al. (2013). For a complex of the title cation, see: Rother et al. (1997). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

An aqueous solution containing 2 mmol of HNO₃ in 10 ml of water was added to 1 mmol of trans-2,5-dimethylpiperazine in 20 ml of water. The obtained solution was stirred for 1 h, filtered and then left to stand at room temperature. Colorless single crystals of the title compound were obtained after some days.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Putz 2005); software used to prepare material for publication: WinGX (Farrugia, 2012) and CRYSCAL (T. Roisnel, local program).

Figures top

	Fig. 1. An ORTEP view of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are shown as dotted lines. Symmetry code: i: -x, -y, -z.
	Fig. 2. Projection of (I) along the a axis. The H-atoms not involved in H-bonding are omitted.

trans-2,5-Dimethylpiperazine-1,4-diium dinitrate top

Crystal data top

C₆H₁₆N₂²⁺·2NO₃⁻	F(000) = 256
M_r = 240.23	D_x = 1.516 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2153 reflections
a = 7.0357 (8) Å	θ = 3.4–27.4°
b = 10.0277 (10) Å	µ = 0.13 mm⁻¹
c = 8.3112 (8) Å	T = 150 K
β = 116.149 (8)°	Prism, colourless
V = 526.36 (9) Å³	0.58 × 0.46 × 0.23 mm
Z = 2

Data collection top

Bruker APEXII diffractometer	1059 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
CCD rotation images, thin slices scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −8→9
T_min = 0.827, T_max = 0.970	k = −9→12
4126 measured reflections	l = −10→10
1195 independent reflections

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0438P)² + 0.1423P] where P = (F_o² + 2F_c²)/3
1195 reflections	(Δ/σ)_max < 0.001
74 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₆H₁₆N₂²⁺·2NO₃⁻	V = 526.36 (9) Å³
M_r = 240.23	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.0357 (8) Å	µ = 0.13 mm⁻¹
b = 10.0277 (10) Å	T = 150 K
c = 8.3112 (8) Å	0.58 × 0.46 × 0.23 mm
β = 116.149 (8)°

Data collection top

Bruker APEXII diffractometer	1195 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	1059 reflections with I > 2σ(I)
T_min = 0.827, T_max = 0.970	R_int = 0.022
4126 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.11	Δρ_max = 0.30 e Å⁻³
1195 reflections	Δρ_min = −0.23 e Å⁻³
74 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
N1	0.20352 (15)	−0.09103 (10)	−0.37280 (12)	0.0173 (2)
O1	0.12714 (14)	−0.13760 (9)	−0.27150 (11)	0.0218 (2)
O2	0.24377 (15)	−0.16754 (10)	−0.47090 (11)	0.0255 (2)
O3	0.23709 (16)	0.03059 (9)	−0.36962 (13)	0.0312 (3)
N2	−0.02504 (15)	0.08866 (10)	−0.14298 (12)	0.0169 (2)
H2A	−0.0683	0.1671	−0.2001	0.020*
H2B	0.0282	0.0397	−0.2044	0.020*
C1	0.14685 (18)	0.11399 (12)	0.04232 (15)	0.0165 (3)
H1	0.0915	0.1730	0.1057	0.020*
C2	0.21154 (17)	−0.01747 (12)	0.14274 (15)	0.0176 (3)
H2C	0.2778	−0.0736	0.0869	0.021*
H2D	0.3146	−0.0007	0.2653	0.021*
C3	0.33291 (19)	0.18189 (13)	0.03060 (17)	0.0224 (3)
H3A	0.3930	0.1230	−0.0257	0.034*
H3B	0.4381	0.2036	0.1490	0.034*
H3C	0.2854	0.2621	−0.0389	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0184 (5)	0.0158 (5)	0.0155 (5)	0.0005 (4)	0.0054 (4)	0.0005 (4)
O1	0.0288 (5)	0.0212 (5)	0.0202 (4)	−0.0019 (3)	0.0153 (4)	−0.0007 (3)
O2	0.0331 (5)	0.0274 (5)	0.0203 (4)	0.0033 (4)	0.0158 (4)	−0.0025 (4)
O3	0.0356 (5)	0.0134 (5)	0.0400 (6)	−0.0040 (4)	0.0125 (4)	0.0023 (4)
N2	0.0199 (5)	0.0162 (5)	0.0150 (5)	0.0030 (4)	0.0081 (4)	0.0023 (4)
C1	0.0185 (5)	0.0144 (6)	0.0161 (5)	0.0018 (4)	0.0071 (4)	−0.0010 (4)
C2	0.0166 (5)	0.0168 (6)	0.0178 (5)	0.0020 (4)	0.0062 (4)	0.0016 (4)
C3	0.0207 (6)	0.0178 (6)	0.0287 (6)	0.0003 (5)	0.0112 (5)	0.0009 (5)

Geometric parameters (Å, º) top

N1—O2	1.2398 (13)	C1—C2	1.5188 (17)
N1—O3	1.2403 (14)	C1—H1	0.9800
N1—O1	1.2706 (13)	C2—N2ⁱ	1.4945 (15)
N2—C2ⁱ	1.4945 (15)	C2—H2C	0.9700
N2—C1	1.5024 (14)	C2—H2D	0.9700
N2—H2A	0.9000	C3—H3A	0.9600
N2—H2B	0.9000	C3—H3B	0.9600
C1—C3	1.5163 (17)	C3—H3C	0.9600

O2—N1—O3	121.73 (10)	C2—C1—H1	108.8
O2—N1—O1	119.62 (10)	N2ⁱ—C2—C1	111.39 (9)
O3—N1—O1	118.65 (10)	N2ⁱ—C2—H2C	109.4
C2ⁱ—N2—C1	112.95 (9)	C1—C2—H2C	109.4
C2ⁱ—N2—H2A	109.0	N2ⁱ—C2—H2D	109.4
C1—N2—H2A	109.0	C1—C2—H2D	109.4
C2ⁱ—N2—H2B	109.0	H2C—C2—H2D	108.0
C1—N2—H2B	109.0	C1—C3—H3A	109.5
H2A—N2—H2B	107.8	C1—C3—H3B	109.5
N2—C1—C3	109.74 (9)	H3A—C3—H3B	109.5
N2—C1—C2	109.11 (9)	C1—C3—H3C	109.5
C3—C1—C2	111.53 (10)	H3A—C3—H3C	109.5
N2—C1—H1	108.8	H3B—C3—H3C	109.5
C3—C1—H1	108.8

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱⁱ	0.90	1.99	2.8471 (14)	158
N2—H2A···O2ⁱⁱⁱ	0.90	2.45	2.9899 (13)	119
N2—H2B···O1	0.90	2.07	2.9057 (13)	153
N2—H2B···O3	0.90	2.42	3.2172 (14)	149
C1—H1···O1ⁱ	0.98	2.50	3.2614 (14)	134

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.90	1.99	2.8471 (14)	157.7
N2—H2A···O2ⁱⁱ	0.90	2.45	2.9899 (13)	118.5
N2—H2B···O1	0.90	2.07	2.9057 (13)	153.2
N2—H2B···O3	0.90	2.42	3.2172 (14)	148.5
C1—H1···O1ⁱⁱⁱ	0.98	2.50	3.2614 (14)	134.2

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

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal impact GbR, Bonn, Germany. Google Scholar
Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Conrado, D. J., Verli, H., Neves, G., Fraga, C. A., Barreiro, E. J., Rates, S. M. & Dalla-Costa, T. (2008). J. Pharm. Pharmacol. 60, 699–707. Web of Science CrossRef PubMed CAS Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gatfaoui, S., Dhaouadi, H., Roisnel, T., Rzaigui, M. & Marouani, H. (2014a). Acta Cryst. E70, o398–o399. CSD CrossRef CAS IUCr Journals Google Scholar
Gatfaoui, S., Marouani, H. & Rzaigui, M. (2013). Acta Cryst. E69, o1453. CSD CrossRef IUCr Journals Google Scholar
Gatfaoui, S., Rzaigui, M. & Marouani, H. (2014b). Acta Cryst. E70, o198. CSD CrossRef IUCr Journals Google Scholar
Kefi, C., Marouani, H. & Rzaigui, M. (2013). Acta Cryst. E69, o1475. CSD CrossRef IUCr Journals Google Scholar
Marouani, H., Raouafi, N., Toumi Akriche, S., Al-Deyab, S. S. & Rzaigui, M. (2012). E-J. Chem. 9, 772–779. CrossRef CAS Google Scholar
Rother, G., Worzala, H. & Bentrup, U. (1997). Z. Kristallogr. New Cryst. Struct. 212, 199. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 6| June 2014| Page o725

doi:10.1107/S1600536814012100

Open

access