C-Methyl­calix[4]resorcinarene–1,4-bis­(pyridin-3-yl)-2,3-diaza-1,3-butadiene (1/2)

Konstantin A Udachin; Md Badruz Zaman; John A Ripmeester

doi:10.1107/S1600536811054717

. 2012 Jan 7;68(Pt 2):o261–o262. doi: 10.1107/S1600536811054717

C-Methylcalix[4]resorcinarene–1,4-bis(pyridin-3-yl)-2,3-diaza-1,3-butadiene (1/2)

Konstantin A Udachin ^a,^*, Md Badruz Zaman ^a,^b, John A Ripmeester ^a

PMCID: PMC3274953 PMID: 22346906

Abstract

In the title compound, 2C₁₂H₁₀N₄·C₃₂H₃₂O₈, the calixarene adopts a rctt conformation with dihedral angles of 138.40 (1) and 9.10 (1)° between the opposite rings. The dihedral angles between the rings of the pyridine derivative are 8.80 (1) and 9.20 (1)°. In the crystal, adjacent C-methylcalix[4]resorcinarene molecules are connected into columns parallel to [010] by O—H⋯O hydrogen bonds. O—H⋯N hydrogen bonds between the axial phenoxyl groups and bipyridine molecules link the columns into sheets parallel to (011), which are connected by O—H⋯N hydrogen bonds. Further O—H⋯N hydrogen bonds link the bipyridine and C-methylcalix[4]resorcinarene molecules, giving rise to a three-dimensional network.

Related literature

For the synthesis and structure of the 1,4-di-3-pyridyl-2,3-diaza-1,3-butadiene ligand, see: Ciurtin et al. (2001 ▶). For coordination polymers of 1,4-di-3-pyridyl-2,3-diaza-1,3-butadiene structures, see: Dong et al. (2004 ▶). For the structure of C-methylcalix[4]resorcinarene, see: Kuzmicz et al. (2010 ▶). For C-methylcalix[4]resorcinarene co-crystal structures, see: MacGillivray et al. (2001 ▶); Ma & Coppens (2004 ▶); Momose & Bosch (2010 ▶). For the stereochemistry of C-methylcalix[4]resorcinarene, see: Moore & Matthews (2009 ▶).

Experimental

Crystal data

2C₁₂H₁₀N₄·C₃₂H₃₂O₈
M _r = 965.06
Monoclinic,
a = 12.2998 (10) Å
b = 26.232 (2) Å
c = 16.1097 (13) Å
β = 109.324 (2)°
V = 4904.9 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 173 K
0.35 × 0.20 × 0.15 mm

Data collection

Bruker Kappa APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.970, T _max = 0.987
58266 measured reflections
12755 independent reflections
7952 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.131
S = 1.02
12755 reflections
656 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ATOMS (Dowty, 1999 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811054717/vm2143sup1.cif

e-68-0o261-sup1.cif^{(33KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811054717/vm2143Isup2.hkl

e-68-0o261-Isup2.hkl^{(623.6KB, 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
O1—H1⋯N4B	0.84	1.95	2.765 (2)	162
O2—H2⋯N1A	0.84	1.87	2.6986 (17)	167
O3—H3⋯O2ⁱ	0.84	1.99	2.8297 (17)	172
O4—H4⋯O5	0.84	2.15	2.9265 (17)	153
O5—H5⋯N4Aⁱⁱ	0.84	1.90	2.7338 (19)	175
O6—H6⋯N1Bⁱⁱ	0.84	1.95	2.7855 (19)	176
O7—H7⋯O6	0.84	2.14	2.9528 (18)	163
O8—H8⋯N2Bⁱⁱⁱ	0.84	2.11	2.947 (2)	174

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

supplementary crystallographic information

Comment

C-Methylcalix[4]resorcinarene is the simplest member of the resorcinarene compounds and assemblies by means of intermolecular hydrogen bonding (Kuzmicz et al., 2010). C-Methylcalix[4]resorcinarene has typically been crystallized with 4,4'-bipyridine type ligands to form solids with large cavities capable of including organic or inorganic guests (MacGillivray et al., 2001; Ma & Coppens, 2004; Momose & Bosch, 2010). We used bidentate Schiff-base ligands 1,4-di-3-pyridyl-2,3-diaza-1,3-butadiene (Dong et al., 2004) with C-methylcalix[4]resorcinarene and crystallized single-crystals using ethanol as solvent (Fig. 1).

Nearby C-methylcalix[4]resorcinarene molecules are connected into infinite columns parallel to the crystallographic [010] direction through two, center-of-symmetry-related, phenoxyl O–H···O hydrogen bonds per molecular pair [O3···O2 = 2.8297 (17) Å, O3–H3···O2 = 172.4 °]. As shown in Figure 2, O–H···N hydrogen bonds between the axial phenoxyl groups and bipyridine molecules link the columns into stair-like sheets parallel to the (011) plane [O2···N1A = 2.6986 (17)Å, O2–H2···N1A = 167.3 °; O1···N4B = 2.765 (2) Å, O1–H1···N4B = 162.3 °]. The sheets are connected with each other by a second set of bipyridylmolecules through O–H···N hydrogen bonds [O5···N4A = 2.7338 (19) Å, O5–H5···N4A = 174.9 °; O6···N1B = 2.7855 (19) Å, O6–H6···N1B = 175.9 °]. Additionally, zigzag –CH=N—N=CH– bridge of the bipyridine molecules and axial phenoxyl groups of C-methylcalix[4]resorcinarene molecules are also connected via O–H···N hydrogen bonds [O8···N2B = 2.947 (2) Å, O8–H8···N2B = 173.8 °] giving rise to a three-dimensional network.

Confirmation of calix[4]resorcinarene topology has been classified into four diffrent structures i.e. rccc (cone/crown), rcct (chair), rctt (diamond), rccc (boat) (Moore & Matthews, 2009). In the title compound, a pair of aromatic rings are almost coplanar, whereas the others are orthogonal at an angle of 88.1 and 95.7 ° from the plane facing the side-chains. This constructs an rctt conformation (Fig. 1).

Experimental

C-methylcalix[4]resorcinarene (0.05 mmol) and 1,4-di-3-pyridyl-2,3-diaza-1,3-butadiene (0.05 mmol) were dissolved in 3 ml and 1.5 ml of ethanol, respectively. After that, the mixture was heated to 100 ° C for 4 h in an oven, cooled to room temperature at a rate of 20 ° C per hour and kept few days at room temperature. Colorless, plate-like crystals were collected after 2/3 days.