Bis(2-phenyl­biguanidium) adipate tetra­hydrate

Irena Matulková; Ivana Císařová; Ivan Němec

doi:10.1107/S1600536810049925

. 2010 Dec 11;67(Pt 1):o118–o119. doi: 10.1107/S1600536810049925

Bis(2-phenylbiguanidium) adipate tetrahydrate

Irena Matulková ^a,^b,^*, Ivana Císařová ^a, Ivan Němec ^a

PMCID: PMC3050311 PMID: 21522629

Abstract

In the title salt, 2C₈H₁₂N₅ ⁺·C₆H₈O₄ ²⁻·4H₂O, the anion is located on a centre of symmetry. The observed supramolecular network of the crystal structure is produced by ten different hydrogen bonds of the N—H⋯N, N—H⋯O and O—H⋯O types. One additional O—H group is not connected to an acceptor site.

Related literature

For uses of biguanide complexes in medicine, see: Sirtori & Pasik (1994 ▶); Clement & Girreser (1999 ▶); Thompson et al. (1999 ▶); Ross et al. (2004 ▶); Woo et al. (1999 ▶); Watkins et al. (1987 ▶); Morain et al. (1994 ▶); Marchi et al. (1999 ▶); Shapiro et al. (1959a ▶,b ▶). The salts of biguanidium (1+) or (2+) cations have been tested for non-linear optical properties, see: Matulková et al. (2008 ▶, 2010 ▶); Martin et al. (1996 ▶); Martin & Pinkerton (1996 ▶); Pinkerton et al. (1978 ▶).

Experimental

Crystal data

2C₈H₁₂N₅ ⁺·C₆H₈O₄ ²⁻·4H₂O
M _r = 572.64
Triclinic,
a = 7.1560 (1) Å
b = 10.8670 (2) Å
c = 11.1410 (2) Å
α = 61.5590 (9)°
β = 88.682 (1)°
γ = 71.702 (1)°
V = 714.93 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 150 K
0.4 × 0.4 × 0.3 mm

Data collection

Nonius KappaCCD area-detector diffractometer
20455 measured reflections
3260 independent reflections
2953 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.093
S = 1.06
3260 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶) and DENZO (Otwinowski & Minor, 1997 ▶); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810049925/im2248sup1.cif

e-67-0o118-sup1.cif^{(18KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049925/im2248Isup2.hkl

e-67-0o118-Isup2.hkl^{(159.9KB, 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
N5—H1⋯O1	0.89	2.12	2.982 (1)	163
N2—H2A⋯O2ⁱ	0.94	1.92	2.837 (1)	168
N2—H2B⋯O2ⁱⁱ	0.88	2.07	2.855 (1)	149
N4—H4A⋯N3ⁱⁱⁱ	0.90	2.14	3.041 (1)	178
N4—H4B⋯O1W	0.92	2.23	2.998 (1)	141
N1—H5A⋯O1ⁱ	0.94	1.95	2.882 (1)	171
N5—H5B⋯O1W	0.92	2.03	2.897 (1)	158
O1W—H11⋯O1^iv	0.85	1.99	2.825 (1)	168
O1W—H12⋯O2W^v	0.92	1.86	2.781 (1)	174
O2W—H22⋯O2	0.93	1.89	2.797 (1)	165

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

Acknowledgments

This work was supported financially by the Czech Science Foundation (grant No. 203/09/0878) and is part of Long-term Research Plan of the Ministry of Education of the Czech Republic (No. MSM 0021620857).

supplementary crystallographic information

Comment

The wide area of application of biguanides involves the field of medical research (Sirtori & Pasik, 1994; Clement & Girreser, 1999), especially in the treatment of diabetes mellitus (N,N-dimethylbiguanide and N-phenylethylbiguanide) (Thompson et al., 1999; Ross et al., 2004; Woo et al., 1999). Biguanide derivatives are also used in the synthesis of antimalarial drugs (N-butylbiguanide) (Watkins et al., 1987), and in therapeutic treatment of pain, anxiety, memory disorders (Morain et al., 1994) and hypoglycaemic activity (Marchi et al., 1999; Sirtori & Pasik, 1994; Shapiro et al., 1959a, 1959b).

All the ionic crystal structures containing biguanide moieties are formed by relatively strong hydrogen bonds (Matulková et al., 2010; Matulková et al., 2008). These intermolecular and intramolecular hydrogen bonds can substantially affect the geometry of the biguanidium cations (Martin et al., 1996; Martin & Pinkerton, 1996; Pinkerton et al., 1978). It was found in general that, as the value of the angle between the planes (formed by three nitrogen atoms and one carbon atom) in the biguanide molecule increases, the bonding distances increase and thus the electron distribution changes.

The molecular conformation of the constituents of the title compound is illustrated in Fig. 1. Hydrogen bonds in the crystal structure are formed between N-phenylbiguanidium cations and adipate anions, between N-phenylbiguanidium cations and water molecules, as well as between the carboxylate functions and water molecules. Hydrogen-bonding geometries in the title compound are listed in Table 1 and are illustrated in Fig. 2. Additionally, two N-phenylbiguanidium cations form a dimer via two centrosymmetrically related N—H···N hydrogen bonds. These dimers are interconnected by adipate anions into a network further supported by hydrogen bonds involving water molecules. The lengths of the N—H···O hydrogen bonds range from 2.837 (1) to 3.000 (1) Å. O - H···O hydrogen bonds connect water molecules with adipate anions and range from 2.781 (1) to 2.825 (1) Å.

Experimental

Crystals of the title compound were obtained from a solution of 0.3 g of N-phenylbiguanide (98%, Aldrich) and 0.53 g of adipic acid (purum, Lachema) in 4 ml of water and 8 ml of methanol. The solution was left to crystallize at room temperature for several weeks. The colourless crystals obtained were filtered off, washed with methanol and dried in a vacuum desiccator over KOH (m.p. 350-352 K).

Infrared spectra were recorded at room temperature using DRIFTS and nujol or fluorolube mull techniques on a Nicolet Magna 760 FTIR spectrometer with 2 cm^-1 resolution (4 cm^-1 resolution in far IR region) and Happ-Genzel apodization in the 85–4000 cm^-1 region.

FTIR spectrum (cm^-1): 3623 w; 3377 m; 3307 m; 3139 m; 3072 m; 2923 m; 2723 m; 1650 s; 1632 s; 1600 m; 1582 m; 1555 m; 1494 vw; 1456 vw; 1409 s; 1365 sh; 1317 m; 1303 s; 1290 s; 1266 s; 1200 m; 1169 w; 1153 vw; 1139 w; 1122 w; 1073 w; 1065 w; 1026 vw; 1003 vw; 936 w; 926 w; 911 w; 860 vw; 835 vw; 799 vw; 772 w; 741 m; 722 m; 714 vw; 696 m; 673 vw; 640 vw; 623 vw; 581 wb; 541 vw; 497 w; 483 w; 389 w; 316 w; 280 w; 235 w; 179 w.

Raman spectra of polycrystalline samples were recorded at room temperature on a Nicolet Magna 760 FTIR spectrometer equipped with the Nicolet Nexus FT Raman module (2 cm^-1 resolution, Happ-Genzel apodization, 1064 nm Nd:YVO4 laser excitation, 450 mW power at the sample) in the 100–3700 cm^-1 region.

FT Raman spectrum (cm^-1): 3296 vw; 3196 wb; 3069 m; 3057 m; 2967 w; 2931 m; 2919 m; 2900 w; 2875 w; 1696 vw; 1647 vwb; 1601 s; 1586 m; 1545 w; 1515 w; 1494 m; 1444 w; 1424 m; 1411 m; 1362 vw; 1321 m; 1308 w; 1288 w; 1269 s; 1243 sh; 1229 sh; 1176 m; 1155 m; 1084 m; 1060 m; 1030 m; 1018 vw; 1003 vs; 991 vw; 963 vw; 936 m; 909 m; 885 m; 857 m; 775 w; 740 m; 728 w; 671 w; 638 w; 615 m; 539 m; 493 m; 482 w; 408 m; 388 m; 376 w; 274 m; 234 m; 183 m; 151 mb.