4-(2,3-Dimethyl­phen­yl)piperazin-1-ium chloride monohydrate

Imen Ben Gharbia; Riadh Kefi; Meher El Glaoui; Erwann Jeanneau; Cherif Ben Nasr

doi:10.1107/S1600536808019016

. 2008 Jun 28;64(Pt 7):o1361. doi: 10.1107/S1600536808019016

4-(2,3-Dimethylphenyl)piperazin-1-ium chloride monohydrate

Imen Ben Gharbia ^a, Riadh Kefi ^a, Meher El Glaoui ^a, Erwann Jeanneau ^b, Cherif Ben Nasr ^a,^*

PMCID: PMC2961679 PMID: 21202979

Abstract

The title compound, C₁₂H₁₉N₂ ⁺·Cl⁻·H₂O, contains a network of 4-(2,3-dimethylphenyl)piperazin-1-ium cations, water molecules and chloride anions. The crystal packing is influenced by O—H⋯Cl, N—H⋯Cl, N—H⋯O, C—H⋯O and C—H⋯Cl hydrogen bonds, resulting in structure with an open-framework architecture.

Related literature

For related literature, see: Ben Gharbia et al. (2005 ▶, 2007 ▶); Bernstein et al. (1995 ▶); Pajewski et al. (2004 ▶); Sessler et al. (2003 ▶); Schmidtchen & Berge (1997 ▶). For the refinement weighting scheme, see: Prince (1982 ▶); Watkin (1994 ▶).

Experimental

Crystal data

C₁₂H₁₉N₂ ⁺·Cl⁻·H₂O
M _r = 244.76
Triclinic,
a = 7.5439 (3) Å
b = 9.4204 (3) Å
c = 10.4347 (4) Å
α = 72.733 (2)°
β = 74.152 (2)°
γ = 70.250 (2)°
V = 654.05 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 150 K
0.13 × 0.12 × 0.09 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
5719 measured reflections
3073 independent reflections
2601 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.035
S = 1.10
2491 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: COLLECT (Nonius, 2001 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: CRYSTALS.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808019016/cf2207sup1.cif

e-64-o1361-sup1.cif^{(15.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808019016/cf2207Isup2.hkl

e-64-o1361-Isup2.hkl^{(136.9KB, hkl)}

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
N2—H3⋯Cl1	0.90	2.18	3.069 (1)	169
N2—H4⋯O1ⁱ	0.91	1.86	2.776 (2)	175
O1—H1⋯Cl1	0.82	2.32	3.120 (1)	165
O1—H2⋯Cl1ⁱⁱ	0.83	2.31	3.136 (1)	171
C10—H15⋯Cl1ⁱⁱⁱ	0.99	2.87	3.846 (1)	168
C12—H20⋯Cl1^iv	0.97	2.84	3.779 (3)	161
C12—H19⋯O1^v	0.99	2.73	3.448 (2)	130

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

Acknowledgments

We acknowledge support provided by the Secretary of State for Scientific Research and Technology of Tunisia.

supplementary crystallographic information

Comment

The coordination chemistry of anions is a fast-growing area of supramolecular chemistry (Schmidtchen & Berge, 1997), on account of the importance of anion binding, recognition and transport in many biochemical processes (Pajewski et al., 2004). Thus, the Cl^- anion has been successfully used to assemble double-helical motifs of various molecules (Sessler et al., 2003). Here a new member of this family, the title compound, is presented, which was obtained during our studies of the preparation of new organic hydrochloride compounds. As shown in Fig. 1, the asymmetric unit of the crystal structure of the title compound contains a 4-(2,3-dimethylphenyl)piperazin-1-ium cation, a chloride anion and a water molecule, associated in a hydrogen-bonded network. Two water molecules and two Cl^- anions are interconnected through O—H···Cl hydrogen bonds, forming an 8-membered ring with graph-set R₂⁴(8) Bernstein et al., 1995). These entities are connected to two antiparallel organic cations via N—H···Cl, N—H···O and C—H···Cl hydrogen-bonding interactions to construct a convoluted hydrogen-bonded chain which runs in the c-axis direction (Fig. 2). When projected along the b axis, the chains have a marked zigzag structure and somewhat resemble a helix (Fig. 3). In addition to the hydrogen-bonding associations to Cl1 and O1, the organic cations have a second role by linking these chains to each other to form layers parallel to the bc plane through C—H···O hydrogen bonds. Fig. 3 shows that these planes are interconnected by NH₂⁺ groups to form an open framework architecture through hydrogen-bond interactions. An examination of the organic group geometrical features shows that the carbon atoms in the benzene ring of the title compound have a good coplanarity and they form a conjugated ring with an average deviation of 0.013 Å. The mean value of the C—C bond lengths [1.3967 (17) Å], which is between a single bond and a double bond, agrees with that in phenylpiperazinium tetrachloridozincate(II) [1.384 (4) Å] (Ben Gharbia et al., 2005). The piperazine-1,4-diium ring of the title compound adopts a typical chair conformation and its geometric parameters [d_av(C—N) = 1.4818 (16) and d_av(C—C) = 1.5437 (17) Å] are in full agreement with those found in 4-(2,3-dimethylphenyl)piperazin-1-ium tetrachloridozincate(II) (Ben Gharbia et al., 2007).

Experimental

An aqueous 1M HCl solution and 1-(2,3-dimethylphenyl)piperazine in a 1:1 molar ratio were mixed and dissolved in sufficient ethanol. Crystals of (I) grew as the ethanol evaporated at 293 K over the course of a few days.