4-Chloro­anilinium (4-chloro­phen­yl)guanidinium dichloride hemihydrate

Yanhua Zhang; Xiangyun Liu

doi:10.1107/S1600536810007774

. 2010 Mar 10;66(Pt 4):o790. doi: 10.1107/S1600536810007774

4-Chloroanilinium (4-chlorophenyl)guanidinium dichloride hemihydrate

Yanhua Zhang ^a,^*, Xiangyun Liu ^a

PMCID: PMC2983776 PMID: 21580629

Abstract

In the title hydrated molecular salt, C₆H₇ClN⁺·C₇H₉ClN₃ ⁺·2Cl⁻·0.5H₂O, the water O atom lies on a crystallographic twofold axis. In the crystal, intermolecular N—H⋯Cl and O—H⋯Cl hydrogen bonds form layers perpendicular to the ac plane in which both the water molecule and the chloride anion are involved in connecting the layers into a three-dimensional structure.

Related literature

For applications of guanidine-containing compounds, see: Yonehara & Otake (1966 ▶); Berlinck (1995 ▶); Gobbi & Frenking (1993 ▶). For related structures, see: Ploug-Sørenson & Andersen 1985 ▶; Kolev et al. (1997 ▶); Glidewell et al. (2005 ▶); Smith et al. (2005 ▶).

Experimental

Crystal data

C₆H₇ClN⁺·C₇H₉ClN₃ ⁺·2Cl⁻·0.5H₂O
M _r = 379.11
Monoclinic,
a = 41.297 (8) Å
b = 4.2089 (8) Å
c = 23.695 (5) Å
β = 120.164 (2)°
V = 3560.8 (12) Å³
Z = 8
Mo Kα radiation
μ = 0.67 mm⁻¹
T = 298 K
0.51 × 0.50 × 0.34 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.727, T _max = 0.805
8167 measured reflections
3078 independent reflections
2495 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.122
S = 1.03
3078 reflections
211 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810007774/hg2652sup1.cif

e-66-0o790-sup1.cif^{(18KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810007774/hg2652Isup2.hkl

e-66-0o790-Isup2.hkl^{(151.1KB, 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
O1—H14A⋯Cl1ⁱ	0.82 (2)	2.36 (2)	3.1797 (17)	177 (3)
N2—H2A⋯Cl2ⁱ	0.86	2.54	3.324 (2)	152
N3—H3A⋯Cl2ⁱ	0.86	2.48	3.281 (2)	155
N4—H4D⋯Cl2ⁱⁱ	0.82 (6)	2.39 (5)	3.185 (3)	164 (5)
N2—H2B⋯Cl2ⁱⁱⁱ	0.86	2.62	3.2457 (19)	131
N4—H4A⋯Cl1^iv	0.93 (6)	2.27 (6)	3.158 (3)	160 (5)
N1—H1A⋯Cl1^v	0.86	2.52	3.283 (2)	148

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

supplementary crystallographic information

Comment

The guanidine-containing compounds have been employed as anti-microbials and fungicides on a considerable scale(Yonehara & Otake, 1966). The drugs containing guanidine framework are not only easy to transport(Berlinck, 1995), but also make the functions of absorption and osmosis more selective due to the good solubility of their various acid salts in aqueous solution(Gobbi & Frenking, 1993). We report here the cocrystal structure of title compound.

Title compound crystallizes with one 4-chloropenylguanidinium cation , one 4-chloroanilinium cation, two chloride anion and half water molecular in the asymmetric unit (Fig. 1). All bond lengths and angles are normal (Ploug-Sørenson & Andersen, 1985; Kolev et al., 1997; Glidewell et al., 2005; Smith et al., 2005). The forces between cations and anions consist of hydrogen bonding and ion-pairing. Intermolecular N—H···Cl and O—H···Cl hydrogen bonds form layers perpendicular to the ac plane in which both the water molecule and the chloride anion are involved in structure extension (Table 1).

Experimental

The 4-chlorophenylguanidine (0.01 mol) was added to a solution of 4-chlorobenzenamine (0.01 mol) in ethanol (20 ml) and stirred half hour at room temperature. The mixture was adjusted to pH 2-3 with concentrated hydrochloric acid, and the desired products then precipitated, which was collected by filtration. Single crystals suitable for X-ray measurements were obtained by recrystallization from methanol and water (v/v 1:1) at room temperature for one week.