3-(1H-Imidazol-1-yl)propanaminium picrate

T S Yamuna; Jerry P Jasinski; Courtney E Duff; H S Yathirajan; Manpreet Kaur

doi:10.1107/S1600536813025646

. 2013 Sep 21;69(Pt 10):o1572–o1573. doi: 10.1107/S1600536813025646

3-(1H-Imidazol-1-yl)propanaminium picrate

T S Yamuna ^a, Jerry P Jasinski ^b,^*, Courtney E Duff ^b, H S Yathirajan ^a, Manpreet Kaur ^a

PMCID: PMC3790432 PMID: 24098251

Abstract

In the title salt [systematic name: 3-(1H-imidazol-1-yl)propanaminium 2,4,6-trinitrophenolate], C₆H₁₂N₃ ⁺·C₆H₂N₃O₇ ⁻, there are five independent cation–anion pairs (A, B, C, D, E) in the asymmetric unit. In the cation, the ammonium group is protonated with the aminopropyl group nearly at right angles to the mean plane of the imidazole ring showing C—N—C—C torsion angles ranging from 79.6 (2) to 99.79 (19)° in the five cations. The nitro groups in the anion are twisted from the benzene mean plane with maximum dihedral angles subtended by nitro substituents ortho to the phenolate O atom of 26.0 (2) and 37.3 (7) (A), 28.9 (5) and 35.3 (1) (B), 34.7 (7) and 36.9 (7) (C), 14.7 (4) and 36.9 (2) (D) and 33.1 (1) and 35.4 (3)° (E). In contrast, the nitro groups in the para positions lie much closer to the aromatic ring plane, subtending dihedral angles of 1.8 (3) (A), 3.5 (3) (B), 6.03 (C), 2.1 (3) (D) and 7.7 (1)° (E). Disorder is observed for one O atom of an ortho nitro group in anion D with an occupancy ratio of 0.53 (5):0.47 (5). In the crystal, N—H⋯O cation–anion and N—H⋯N cation–cation hydrogen bonds are observed, linking the ions into chains along [010]. In addition, weak C—H⋯O cation–anion interactions occur.

Related literature

For pharmacological properties of imidazole compounds, see: Lombardino & Wiseman (1974 ▶). For applications of substituted imidazoles, see: Maier et al. (1989a ▶,b ▶). For imidazole derivatives as anticancer agents, see: Krezel (1998 ▶). For electrostatic or hydrogen-bonding interactions in picric acid charge-transfer complexes, see: In et al. (1997 ▶). For imidazolium-based cation picrate salts as good candidates for energetic ionic salts, see: Jin et al. (2005 ▶). For the crystal structure of imidazolium picrate, see: Soriano-García et al. (1990 ▶) and for the structures of picrates of some other imidazole derivatives, see: Du & Zhao (2003 ▶); Dutkiewicz et al. (2011 ▶); MacDonald et al. (2005 ▶); Nardelli et al. (1987 ▶); Pi et al. (2009 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₆H₁₂N₃ ⁺·C₆H₂N₃O₇ ⁻
M _r = 354.29
Monoclinic,
a = 11.98275 (18) Å
b = 38.5234 (6) Å
c = 16.4239 (2) Å
β = 94.1970 (14)°
V = 7561.2 (2) Å³
Z = 20
Cu Kα radiation
μ = 1.13 mm⁻¹
T = 173 K
0.21 × 0.17 × 0.08 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T _min = 0.870, T _max = 1.000
52087 measured reflections
14795 independent reflections
12167 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.116
S = 1.02
14795 reflections
1197 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.29 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/S1600536813025646/sj5352sup1.cif

e-69-o1572-sup1.cif^{(80.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813025646/sj5352Isup2.hkl

e-69-o1572-Isup2.hkl^{(809.8KB, hkl)}

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

Supplementary material file. DOI: 10.1107/S1600536813025646/sj5352Isup3.cml

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
N6A—H6AA⋯O3E ⁱ	0.85 (2)	2.06 (2)	2.8943 (18)	167.5 (18)
N6A—H6AB⋯O3D ⁱⁱ	0.91 (2)	2.08 (2)	2.8671 (18)	143.1 (16)
N6A—H6AB⋯O4D ⁱⁱ	0.91 (2)	2.25 (2)	2.961 (2)	134.6 (15)
N6A—H6AC⋯N4C	0.95 (2)	1.87 (2)	2.8157 (19)	172.5 (18)
N6B—H6BA⋯O3B ⁱⁱⁱ	0.92 (2)	2.117 (19)	2.8728 (17)	138.5 (15)
N6B—H6BA⋯O4B ⁱⁱⁱ	0.92 (2)	2.268 (19)	3.006 (2)	136.6 (15)
N6B—H6BB⋯O3B	0.89 (2)	2.00 (2)	2.8502 (17)	161.0 (19)
N6B—H6BC⋯N4A ^iv	0.92 (2)	1.88 (2)	2.7988 (19)	173.4 (17)
N6C—H6CA⋯O2C ^v	0.85 (2)	2.305 (18)	2.8334 (19)	120.9 (15)
N6C—H6CA⋯O3C ^v	0.85 (2)	2.10 (2)	2.8944 (18)	155.4 (17)
N6C—H6CB⋯O3A ^vi	0.89 (2)	2.174 (19)	2.9145 (18)	140.2 (16)
N6C—H6CB⋯O4A ^vi	0.89 (2)	2.270 (19)	2.986 (2)	137.3 (15)
N6C—H6CC⋯N4D ^vi	0.92 (2)	1.91 (2)	2.8179 (19)	167.6 (17)
N6D—H6DA⋯O2A ^vii	0.89 (2)	2.361 (19)	2.9631 (19)	124.9 (15)
N6D—H6DA⋯O3A ^vii	0.89 (2)	2.06 (2)	2.8340 (17)	145.0 (16)
N6D—H6DB⋯O3C ^vi	0.89 (2)	2.16 (2)	2.9171 (17)	142.0 (17)
N6D—H6DB⋯O4C ^vi	0.89 (2)	2.27 (2)	2.9323 (19)	130.5 (16)
N6D—H6DC⋯N4E	0.89 (2)	1.91 (2)	2.7932 (19)	174.0 (17)
N6E—H6EA⋯O2D ^viii	0.91 (2)	2.32 (2)	2.973 (2)	128.7 (17)
N6E—H6EA⋯O3D ^viii	0.91 (2)	2.06 (2)	2.8527 (18)	145.4 (18)
N6E—H6EB⋯O3E	0.87 (2)	2.19 (2)	2.9056 (18)	139.6 (17)
N6E—H6EB⋯O4E	0.87 (2)	2.33 (2)	3.010 (2)	135.3 (16)
N6E—H6EC⋯N4B ^viii	0.93 (2)	1.85 (2)	2.7750 (19)	174.0 (19)
C8A—H8A⋯O2B ^ix	0.95	2.46	3.0887 (19)	123
C9A—H9A⋯O5E	0.95	2.43	3.243 (2)	144
C12A—H12B⋯O7A ^ix	0.99	2.46	3.313 (2)	145
C9B—H9B⋯O5B ⁱ	0.95	2.37	3.224 (2)	150
C12B—H12D⋯O7C ^vi	0.99	2.47	3.335 (2)	145
C8C—H8C⋯O5C ^vi	0.95	2.33	3.194 (2)	152
C9C—H9C⋯O2E ⁱ	0.95	2.49	3.105 (2)	123
C7D—H7D⋯O5A ^vi	0.95	2.35	3.233 (2)	155
C11D—H11H⋯O6A ^vi	0.99	2.55	3.421 (2)	147
C12D—H12G⋯O6B ^vii	0.99	2.43	3.238 (2)	139
C9E—H9E⋯O5D ⁱⁱ	0.95	2.27	3.162 (6)	156
C9E—H9E⋯O5DA ⁱⁱ	0.95	2.56	3.357 (17)	141
C12E—H12I⋯O6E ^viii	0.99	2.34	3.186 (2)	142

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) .

Acknowledgments

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

supplementary crystallographic information

1. Comment

Compounds with an imidazole ring system have many pharmacological properties and play important roles in biochemical processes (Lombardino & Wiseman, 1974). Many imidazole derivatives are characterized as inhibitors of fungicides and herbicides, plant growth regulators and therapeutic agents (Maier et al., 1989a,b). Imidazole derivatives are also used as potential anticancer agents (Krezel, 1998) and display a broad spectrum of pharmacological activities. It is well known that picric acid forms charge transfer molecular complexes with a number of aromatic compounds such as aromatic amines through electrostatic or hydrogen bonding interactions (In et al., 1997). Picric acid is a polynitrogen compound with explosive character and imidazolium-based cation picrate salts are good candidates for energetic ionic salts (Jin et al., 2005).

The crystal structures of some imidazolium picrates have been reported, for instance imidazolium picrate itself (Soriano-García et al., 1990), also two solvates (hydrate and ethanolate) of 2-aminohistamine dipicrate (Nardelli et al., 1987), 4-hydroxy methylimidazolium picrate (Du & Zhao, 2003), two polymorphs of betaine bis(diimidazolium) dipicrate (MacDonald et al., 2005) and 3-benzyl-1-methyl-imidazolium picrate (Pi et al., 2009). Recently, we have reported the crystal structure of 2-methylimidazolium picrate (Dutkiewicz et al., 2011).

In view of the importance of imidazoles, this paper reports the crystal structure of the title salt, C₆H₁₂N₃⁺ . C₆H₂N₃O₇^-, (I).

In (I), there are five cation-anion independent pairs (A, B, C, D, E) in the asymmetric unit. For clarity only the C cation-anion pair is displayed in Fig. 1. In the cation the ammonium group is protonated with the aminopropyl group nearly at right angles to the imidazole ring showing C/N/C/C torsion angles ranging from 79.6 (2)° to 99.79 (19)° in the five cations. Bond lengths are in normal ranges (Allen et al., 1987). The nitro groups in the anion are twisted from the benzene mean plane with maximum dihedral angles subtended by nitro substituents ortho to phenolate oxygen of 26.0 (2)°, 37,3(7)° (A); 28,9(5)°, 35.3 (1)° (B); 34.7 (7)°, 36.9 (7)° (C); 14.7 (4)°, 36.9 (2)° (D); 33.1 (1)°, 35.4 (3)° (E). In contrast the nitro groups in the para positions lie much closer to the aromatic ring plane with angles 1.8 (3)° (A); 3.5 (3)° (B); 6.03° (C); 2.1 (3)° (D); 7.7 (1)° (E), respectively. Disorder is observed in atom O5D, an ortho nitro group in anion D, with an occupancy ratio of 0.53 (5):0.47 (5). In the crystal, N—H···O cation-anion and N—H···N cation-cation hydrogen bonds (Table 1) are observed linking the ions into chains along [0 1 0] (Fig. 2). In addition, weak C—H···O cation-anion intermolecular interactions also contribute to packing stability.

2. Experimental

Commercially available 1-(3-aminopropyl)imidazole (0.5 g, 3.99 mmol) and picric acid (1.19 g, 3.99 mmol) were dissolved in 10 ml of ethanol and stirred for 5 minutes at room temperature. After 30 mins, crystals were formed on evaporation of ethanol (m.p.: 370–373 K).