4-Carbamoylpyridin-1-ium 2,2,2-tri­chloro­acetate–isonicotinamide (1/1)

Franc Perdih

doi:10.1107/S1600536812037002

. 2012 Aug 31;68(Pt 9):o2818. doi: 10.1107/S1600536812037002

4-Carbamoylpyridin-1-ium 2,2,2-trichloroacetate–isonicotinamide (1/1)

Franc Perdih ^a,^b,^*

PMCID: PMC3435842 PMID: 22969688

Abstract

In the crystal structure of the title 1:1 co-crystal, C₆H₇N₂O⁺·C₂Cl₃O₂ ⁻·C₆H₆N₂O, the amide groups of the 4-carbamoylpyridin-1-ium ion and the isonicotinamide molecule are twisted out of the plane of the aromatic ring with C—C—C—N torsion angles of 21.5 (4) and −33.5 (4)°, respectively. The 4-carbamoylpyridin-1-ium and isonicotinamide amide groups form R ₂ ²(8) hydrogen-bonded dimers via N—H⋯O=C interactions. The two remaining amide H atoms (i) link dimers via the cation to an isonicotinamide and (ii) from the isonicotinamide to a trichloroacetate anion. The pyridinium H atom also forms an N—H⋯O hydrogen bond with the trichloroacetate anion. Due to the extended hydrogen bonding, including C—H⋯O and C—H⋯Cl interactions, all components in the structure aggregate into a three-dimensional supramolecular framework.

Related literature

For applications of co-crystals, see: Karki et al. (2009 ▶); Friščić & Jones (2010 ▶). For related structures, see: Madeley et al. (2011 ▶).

Experimental

Crystal data

C₆H₇N₂O⁺·C₂Cl₃O₂ ⁻·C₆H₆N₂O
M _r = 407.63
Orthorhombic,
a = 13.7910 (3) Å
b = 22.6680 (5) Å
c = 5.6340 (1) Å
V = 1761.27 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.55 mm⁻¹
T = 293 K
0.4 × 0.1 × 0.1 mm

Data collection

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.811, T _max = 0.947
16297 measured reflections
4017 independent reflections
3575 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.04
wR(F ²) = 0.091
S = 1.04
4017 reflections
241 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.57 e Å⁻³
Absolute structure: Flack (1983) ▶, 1791 Friedel pairs
Flack parameter: 0.01 (6)

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812037002/gg2095sup1.cif

e-68-o2818-sup1.cif^{(24.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812037002/gg2095Isup2.hkl

e-68-o2818-Isup2.hkl^{(192.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812037002/gg2095Isup3.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
N1—H15⋯O2ⁱ	0.90 (3)	1.78 (3)	2.679 (3)	175 (3)
N2—H16A⋯N3ⁱⁱ	0.87 (3)	2.11 (3)	2.958 (3)	164 (3)
N2—H16B⋯O3	0.90 (4)	1.99 (4)	2.887 (3)	178 (3)
N4—H17A⋯O4	0.91 (4)	2.08 (4)	2.972 (3)	167 (4)
N4—H17B⋯O1	0.89 (4)	1.98 (4)	2.839 (3)	160 (3)
C1—H1⋯O1ⁱ	0.93	2.58	3.211 (3)	126
C2—H2⋯O4ⁱⁱⁱ	0.93	2.55	3.358 (3)	146
C7—H7⋯O3^iv	0.93	2.58	3.489 (3)	166
C11—H11⋯Cl2^v	0.93	2.82	3.711 (3)	162

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

Acknowledgments

The author thanks the Ministry of Education, Science, Culture and Sport of the Republic of Slovenia and the Slovenian Research Agency for financial support through grants P1–0230–0175 as well as the EN–FIST Centre of Excellence, Dunajska 156, 1000 Ljubljana, Slovenia for use of the Supernova diffractometer.

supplementary crystallographic information

Comment

Co-crystals have attracted much attention in recent years owing to their contributions to crystal engineering and pharmaceutical chemistry. They were found to be useful in improving the stability, solubility, dissolution rate and mechanical properties (Karki et al., 2009; Friščić & Jones, 2010). Here we present the structure obtained by reacting isonicotinamide and trichloroacetic acid in 2:1 molar ratio.

The asymmetric unit of (I) consists of one 4-carbamoylpyridin-1-ium cation, one trichloroacetate anion and one isonicotinamide molecule (Fig. 1). The amide groups of 4-carbamoylpyridin-1-ium ion and isonicotinamide molecule are twisted out of the plane of the aromatic ring with a C—C—C—N torsion angle of 21.5 (4)° and -33.5 (4)°, respectively. Similar twisting was observed for example in isonicotinamide–2-naphthoic acid (1/1) (Madeley et al., 2011). Aromatic rings of 4-carbamoylpyridin-1-ium ion and isonicotinamide molecule are not coplanar, but are inclined by 35.05 (12)°. In the crystal, all the components of the structure are associated via the extended system of hydrogen bonds (N—H···O and N—H···N) and weak C—H···O and C—H···Cl interactions into extended three-dimensional supramolecular framework (Figs. 2, 3). The 4-carbamoylpyridin-1-ium ion is hydrogen bonded via N—H···O hydrogen bonding of the pyridinium unit to the trichloroacetate ion. The amide groups from 4-carbamoylpyridin-1-ium and isonicotinamide form a dimer via N—H···O hydrogen bonding, that is a typical supramolecular hydrogen-bonded synthon observed for amide-amide homodimers. Furthermore, the amide group of the cation is hydrogen bonded to the pyridine unit of isonicotinamide and the amide group of the isonicotinamide is hydrogen bonded to the trichloroacetate ion.

Experimental

Crystals of the title compound were obtained by slow evaporation of a 2:1 mol. mixture of isonicotinamide and trichloroacetic acid in methanol at room temperature.