Nicotinamide–2,2,2-trifluoro­ethanol (2/1)

Julie Bardin; Alan R Kennedy; Li Ven Wong; Blair F Johnston; Alastair J Florence

doi:10.1107/S1600536809007594

. 2009 Mar 11;65(Pt 4):o727–o728. doi: 10.1107/S1600536809007594

Nicotinamide–2,2,2-trifluoroethanol (2/1)

Julie Bardin ^a, Alan R Kennedy ^b, Li Ven Wong ^a, Blair F Johnston ^a, Alastair J Florence ^a,^*

PMCID: PMC2968831 PMID: 21582462

Abstract

The nicotinamide (NA) molecules of the title compound, 2C₆H₆N₂O·C₂H₃F₃O, form centrosymmetric R ² ₂(8) hydrogen-bonded dimers via N—H⋯O contacts. The asymmetric unit contains two molecules of NA and one trifluoroethanol molecule disordered over two sites of equal occupancy. The packing consists of alternating layers of nicotinamide dimers and disordered 2,2,2-trifluoroethanol molecules stacking in the c-axis direction. Intramolecular C—H⋯O and intermolecular N—H⋯N, O—H⋯N, C—H⋯N, C—H⋯O and C—H⋯F interactions are present.

Related literature

For nicotinamide polymorphs, see: Wright & King (1954 ▶); Miwa et al. (1999 ▶); Hino et al. (2001 ▶). For nicotinamide co-crystals and salts, see: Fleischman et al. (2003 ▶); Koman et al. (2003 ▶); Athimoolam & Natarajan (2007a ▶,b ▶); Berry et al. (2008 ▶). For graph-set motifs, see: Etter (1990 ▶). For initial identification using multi-sample foil transmission X-ray powder diffraction analysis, see: Florence et al. (2003 ▶).

Experimental

Crystal data

2C₆H₆N₂O·C₂H₃F₃O
M _r = 344.30
Triclinic,
a = 5.0472 (3) Å
b = 11.2930 (7) Å
c = 15.0877 (10) Å
α = 107.002 (3)°
β = 96.636 (3)°
γ = 95.753 (3)°
V = 808.70 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 123 K
0.15 × 0.10 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▶) T _min = 0.903, T _max = 0.998
15936 measured reflections
4008 independent reflections
3416 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.114
S = 1.04
4008 reflections
260 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809007594/fl2234sup1.cif

e-65-0o727-sup1.cif^{(24.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809007594/fl2234Isup2.hkl

e-65-0o727-Isup2.hkl^{(196.4KB, 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
N2—H1N⋯N3ⁱ	0.897 (16)	2.122 (16)	2.9994 (15)	165.7 (15)
N2—H2N⋯O1ⁱⁱ	0.898 (16)	2.013 (16)	2.9093 (13)	176.8 (14)
N4—H3N⋯O2ⁱⁱⁱ	0.877 (16)	2.047 (16)	2.9139 (13)	170.1 (16)
O3—H3O⋯N1^iv	0.84	1.91	2.7511 (15)	178
N4—H4N⋯O1^v	0.878 (17)	2.222 (17)	3.0867 (14)	168.4 (15)
C1—H1⋯N3ⁱ	0.95	2.51	3.4220 (16)	161
C3—H3⋯O2^vi	0.95	2.40	3.0103 (15)	122
C5—H5⋯F3A^vii	0.95	2.46	3.408 (7)	177
C7—H7⋯O1^v	0.95	2.36	3.2118 (14)	149
C11—H11⋯O3	0.95	2.50	3.2590 (16)	137

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

Acknowledgments

The authors thank the University of Strathclyde for funding JB, the Basic Technology programme of the UK Research Councils for project funding under the Control and Prediction of the Organic Solid State (www.cposs.org.uk), and the Glasgow Centre for Physical Organic Chemistry for access to single-crystal diffraction facilities.

supplementary crystallographic information

Comment

The crystal structure of nicotinamide (NA) was first reported in 1954 (Wright & King, 1954; Miwa et al., 1999) and a number of polymorphic forms have also been identified (Hino et al., 2001). In recent years NA has also been investigated as a pharmaceutically acceptable co-crystal former to modify the crystal structure and physico-chemical properties of drug compounds including carbamazepine (Fleischman et al., 2003), salicylic acid and both racemic and S(+)-ibuprofen (Berry et al., 2008). Crystal structures of 3,5-dinitrosalicylate (Koman et al., 2003) as well as 2R,3R-tartrate and trifluoroacetate (Athimoolam & Natarajan, 2007a and Athimoolam & Natarajan, 2007b) salts of NA have also been reported.

In the 2,2,2-trifluoroethanol (TFE) hemisolvate reported here, the molecules crystallize in space group P1 with two molecules of NA and one molecule of TFE in the asymetric unit (Fig. 1). Both independent NA molecules form centro-symmetric R²₂(8) (Etter, 1990) dimer motifs via N—H..O hydrogen bonds (Table 1). The anti-oriented hydrogen atoms on both amide groups form further contacts between adjacent non-symmetry equivalent dimers, either to the aromatic nitrogen, N3 (N2—H1N···N3) or the carbonyl oxygen atom, O1 (N4—H4N···O1).This gives rise to a two-dimensional hydrogen bonded layer of nicotinamide dimers lying parallel to the a-b plane. The remaining aromatic acceptor nitrogen atom, N1, forms an N—H···O hydrogen bond to the solvent molecule producing a structure with alternating layers of NA dimers and TFE that stack in the direction of the c-axis (Fig. 2). The structure is further stabilized by six weak C—H···O and C—H···F interactions (Table 1). The CF₃atoms of the TFE molecule are disordered over two sites with equal occupancies.

Experimental

The novel structure reported here was discovered during a study of solvate formation in organic compounds with a range of fluorinated solvents. A crystalline sample was obtained by isothermal evaporation at 263 K from a saturated TFE solution held on a Reactarray RM2 crystalliser. Identification of the novel phase was initially made using multi-sample foil transmission X-ray powder diffraction analysis (Florence et al., 2003) and a suitable single-crystal for structure determination was selected from the sample.