3-(1H-Imidazol-1-yl)propanaminium 2-carb­oxy-4,6-di­nitro­phenolate

Thammarse S Yamuna; Manpreet Kaur; Brian J Anderson; Jerry P Jasinski; HS Yathirajan

doi:10.1107/S1600536814003146

. 2014 Feb 19;70(Pt 3):o318–o319. doi: 10.1107/S1600536814003146

3-(1H-Imidazol-1-yl)propanaminium 2-carboxy-4,6-dinitrophenolate

Thammarse S Yamuna ^a, Manpreet Kaur ^a, Brian J Anderson ^b, Jerry P Jasinski ^b,^*, HS Yathirajan ^a

PMCID: PMC3998440 PMID: 24765018

Abstract

In the title salt, C₆H₁₂N₃ ⁺·C₇H₃N₂O₇ ⁻, the imidazole ring is planar, with a maximum deviation of 0.0013 (14) Å for the N attached to the propanaminium group. In the anion, a single intramolecular O—H⋯O hydrogen bond is observed. The mean planes of the nitro groups in the anion are twisted from the benzene ring mean plane making dihedral angles of 24.7 (9) and 3.9 (6)°. In the crystal, the ammonium H atoms form N—H⋯N and N—H⋯O hydrogen bonds, resulting in an infinite chain along [111]. In addition to the classical hydrogen bonds, weak C—H⋯O and π–π [centroid–centroid distance = 3.7124 (9) Å] interactions are also observed, which lead to the formation a three-dimensional supramolecular structure that links the chains into layers along the bc plane.

Related literature

For general background and the pharmacological properties of imidazole compounds, see: ten Have et al. (1997 ▶); Lombardino & Wiseman (1974 ▶); Jackson et al. (2000 ▶); Krezel (1998 ▶); Maier et al. (1989 ▶). For the related structures of substituted imidazoles, see: Dayananda et al. (2012 ▶); Hemamalini & Fun (2010 ▶); Jasinski et al. (2011 ▶); Wei et al. (2012 ▶); Yamuna et al. (2013 ▶).

Experimental

Crystal data

C₆H₁₂N₃ ⁺·C₇H₃N₂O₇ ⁻
M _r = 353.30
Triclinic,
a = 7.0109 (4) Å
b = 10.6617 (8) Å
c = 10.7454 (7) Å
α = 93.075 (6)°
β = 95.863 (5)°
γ = 104.944 (6)°
V = 769.30 (9) Å³
Z = 2
Cu Kα radiation
μ = 1.09 mm⁻¹
T = 173 K
0.22 × 0.14 × 0.12 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T _min = 0.925, T _max = 1.000
4664 measured reflections
2953 independent reflections
2582 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.122
S = 1.04
2953 reflections
229 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814003146/fj2659sup1.cif

e-70-0o318-sup1.cif^{(25.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814003146/fj2659Isup2.hkl

e-70-0o318-Isup2.hkl^{(162.1KB, hkl)}

Click here for additional data file.^{(6.3KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814003146/fj2659Isup3.cml

CCDC reference: 986378

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2B—H2B⋯O1B	0.84	1.66	2.4484 (15)	155
N3A—H3AA⋯N1A ⁱ	0.91	1.92	2.7987 (19)	162
N3A—H3AB⋯O1B ⁱⁱ	0.91	2.03	2.8153 (17)	144
N3A—H3AC⋯O3B ⁱⁱⁱ	0.91	2.07	2.9546 (17)	165
C4A—H4AB⋯O4B ^iv	0.99	2.53	3.3572 (19)	142

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

Acknowledgments

TSY thanks the University of Mysore for research facilities and is also grateful to the Principal, Maharani’s Science College for Women, Mysore, for giving permission to undertake research. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

1. Comment

Imidazole rings appear frequently in biologically active compounds, both natural and man-made (ten Have et al., 1997). Compounds with an imidazole ring system have many pharmacological properties and play important roles in biochemical processes (Lombardino & Wiseman, 1974). Most of the imidazole compounds are known as inhibitors of fungicides and herbicides, plant growth regulators and therapeutic agents (Maier et al., 1989), anticancer agents (Krezel, 1998) and bactericidal effects (Jackson et al., 2000). The crystal structures of some related compounds, viz ; 2-amino-5-methylpyridinium 2-hydroxy-3,5-dinitrobenzoate (Hemamalini et al., 2010); Cinnarizinium 3,5-dinitrosalicylate (Dayananda et al., 2012); Enrofloxacinium picrate (Jasinski et al., 2011); 3-(1H-imidazol-1-yl)propanaminium picrate (Yamuna et al., 2013); 3,5-dimethylpyrazolium 3,5-dinitrosalicylate (Wei et al., 2012), have been reported. In view of the importance of substituted imidazoles and organic acid–base adducts based on hydrogen bonding and receiving great attention in recent years, this paper reports the crystal structure of the title salt, (I), C₆H₁₂N₃⁺.C₇H₃N₂O₇^-.

The title salt, (I), C₆H₁₂N₃⁺.C₇H₃N₂O₇^-, crystallizes with one independent monocation (A) and monoanion (B) in the asymmetric unit (Fig. 1). In the cation the protonated imidazol-1-ium ring is planar (maximum deviation = 0.0013 (14)Å for N2A). In the anion, a single O—H···O intramolecular hydrogen bond is observed. Bond lengths are in normal ranges. The mean planes of the nitro groups in the anion are twisted from the phenyl ring mean plane with maximun angles of 24.7 (9)° and 3.9 (6)°, respectively. The hydrogen atoms on the terminal N atom of the cation form N—H···N and N—H···O intermolecular hydrogen bonds resulting in an infinite 1D chain along [1 1 1]. In the crystal, in addition to the classical hydrogen bonds, weak C—H···O (Table 1) and Cg1—Cg2 π—π intermolecular interactions are observed with an intercentroid distance of 3.7125 (9)Å (symmetry operation -x,1-y,-z; Cg1 and Cg2 are the centroids of the C1B–C6B and N1A/C1A/N2A/C3A/C2A rings) which contribute to crystal packing stability (Fig. 2).

2. Experimental

Commercially available 1-(3-aminopropyl)imidazole (0.5 g, 3.99 mmol) and 3,5 dinitrosalicylic acid (0.909 g, 3.99 mmol) were dissolved in 10 ml of methanol and stirred for 15 minutes at 308 K. X-ray quality crystals were formed on slow evaporation of methanol. (m.p.: 468- 475K).