(−)-N,N′-Bis[(1S,2R,5S)-6,6-dimethyl-bicyclo­[3.1.1]heptan-2-ylmeth­yl]pyridine-2,6-dicarboxamide monohydrate

Sylvain Bernès; Francisco Javier Pérez-Flores; René Gutiérrez

doi:10.1107/S1600536808013652

. 2008 May 14;64(Pt 6):o1078–o1079. doi: 10.1107/S1600536808013652

(−)-N,N′-Bis[(1S,2R,5S)-6,6-dimethyl-bicyclo[3.1.1]heptan-2-ylmethyl]pyridine-2,6-dicarboxamide monohydrate

Sylvain Bernès ^a,^*, Francisco Javier Pérez-Flores ^b, René Gutiérrez ^b

PMCID: PMC2961349 PMID: 21202595

Abstract

The title compound, C₂₇H₃₉N₃O₂·H₂O, is a chiral pyridine-2,6-dicarboxamide derivative including cis-myrtanyl groups as amine substituents. The pyridine-2,6-dicarboxamide core approximates C ₂ point symmetry and a solvent water molecule lies on the pseudo-twofold axis. The water molecule serves both as acceptor and donor for efficient hydrogen bonds involving N—H and C=O functional groups as donor and acceptor groups, respectively. As a result, each water molecule in the crystal structure is tetrahedrally bonded to three symmetry-related molecules, forming a three-dimensional supramolecular network. Such an arrangement is a common feature found in the majority of X-ray-characterized symmetrically substituted pyridine-2,6-dicarboxamide derivatives.

Related literature

For background to the solvent–free synthesis used for the preparation of the title compound, see: Tanaka & Toda (2000 ▶); Vázquez et al. (2004 ▶); Tovar et al. (2007 ▶); Pérez-Flores & Gutiérrez (2008 ▶). For hydrates of pyridine-2,6-dicarboxamide derivatives, see: Yu et al. (1999 ▶); Qi et al. (2002 ▶); Jain et al. (2004 ▶); Odriozola et al. (2004 ▶).

Experimental

Crystal data

C₂₇H₃₉N₃O₂·H₂O
M _r = 455.63
Monoclinic,
a = 6.8476 (11) Å
b = 12.1101 (14) Å
c = 16.012 (2) Å
β = 91.173 (15)°
V = 1327.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 298 (1) K
0.6 × 0.6 × 0.2 mm

Data collection

Bruker P4 diffractometer
Absorption correction: none
6391 measured reflections
3180 independent reflections
2580 reflections with I > 2σ(I)
R _int = 0.035
3 standard reflections every 97 reflections intensity decay: 2%

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.107
S = 1.04
3180 reflections
319 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and POV-RAY (Cason, 2004 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013652/rk2088sup1.cif

e-64-o1078-sup1.cif^{(25.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808013652/rk2088Isup2.hkl

e-64-o1078-Isup2.hkl^{(156KB, 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—H2⋯O3	0.82 (2)	2.16 (2)	2.941 (3)	160 (2)
N3—H3⋯O3	0.86 (3)	2.19 (3)	3.017 (3)	159 (2)
O3—H31⋯O2ⁱ	0.87 (5)	1.90 (5)	2.756 (3)	167 (4)
O3—H32⋯O1ⁱⁱ	0.90 (4)	1.86 (5)	2.754 (3)	171 (3)

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

Acknowledgments

Partial support from VIEP–UAP (14/G/NAT/05) is acknowledged.

supplementary crystallographic information

Comment

Nowadays, reactions conducted in the absence of solvents under mild reaction conditions are becoming an important method in laboratories worldwide as an environment–friendly technique for the efficient syntheses of organic molecules. The main advantages of solvent-free organic synthesis are shorter reaction times, minimum waste and generally higher yields, operational simplicity as well as reduction of thermal degradative byproducts along with cleaner work–up (Tanaka & Toda, 2000). As part of an ongoing program aiming to develop simpler and eco–friendly methods for organic transformations under solvent–free conditions (Tovar et al., 2007; Vázquez et al., 2004), we engaged the preparation of chiral pincer ligands (Pérez-Flores & Gutiérrez, 2008). The title compound resulted from this research, by introducing chiral cis–myrtanyl groups as amine substituents.

The X–ray characterized monohydrate has the expected molecular geometry (Fig. 1). The pyridine–2,6–dicarboxamide core approximates a C₂ point symmetry, with the pseudo 2–fold axis passing through N1 and C24. The guest water molecule O3 is placed on the pseudo 2–fold axis and is involved in two N—H···O hydrogen bonds within the asymmetric unit (Fig. 1 and Table 1, lines 1 and 2). The same water molecule is a donor group for two C═O···H intermolecular hydrogen bonds of relatively strong strength (Table 1, lines 3 and 4). As a consequence, a three–dimensional supramolecular structure is formed in the crystal structure, with water molecules being bonded in a tetrahedral arrangement (Fig. 2) to three symmetry–related molecules. Such a feature seems to be common for symmetrically substituted pyridine–2,6–dicarboxamide derivatives. These compounds are generally crystallized as hydrates, and, at least for X–ray characterized compounds, water molecules form hydrogen bonds similar to those observed in the title molecule (e.g. Yu et al., 1999; Qi et al., 2002; Jain et al., 2004; Odriozola et al., 2004).

Experimental

Under solvent–free conditions, (-)-cis–myrtanylamine (0.38 g, 2.5 mmol) and 2,6–pyridinedicarbonyl dichloride (0.30 g, 1.5 mmol) were mixed at room temperature, giving a white solid. The crude was recrystallized from EtOH affording the corresponding dicarboxamide (98% yield).