Butane-1,2,3,4-tetra­carb­oxy­lic acid–1,10-phenanthroline–water (1/2/2)

Hong-lin Zhu

doi:10.1107/S1600536811021398

. 2011 Jun 11;67(Pt 7):o1626. doi: 10.1107/S1600536811021398

Butane-1,2,3,4-tetracarboxylic acid–1,10-phenanthroline–water (1/2/2)

Hong-lin Zhu ^a,^*

PMCID: PMC3151845 PMID: 21837032

Abstract

The asymmetric unit of the title compound, 2C₁₂H₈N₂·C₈H₁₀O₈·2H₂O, contains one 1,10-phenanthroline molecule, one half-molecule of butane-1,2,3,4-tetracarboxylic acid (H₄BTC) and a water molecule, with the complete tetra-acid generated by crystallographic inversion symmetry. Intermolecular O—H⋯O hydrogen bonds and π–π stacking interactions [centroid–centroid distances = 3.672 (2) and 3.708 (2) Å form an extensive three-dimensional network, which consolidates the crystal packing.

Related literature

For the use of H₄BTC as a ligand in metal–organic coordination complexes, see: Delgado et al. (2007 ▶); Liu et al. (2008 ▶); Xu et al. (2010 ▶); Zhu et al. (2011 ▶). For co-crystals involving H₄BTC, see: Cheng et al. (2009 ▶); Najafpour et al. (2008 ▶). For details of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

2C₁₂H₈N₂·C₈H₁₀O₈·2H₂O
M _r = 630.60
Triclinic,
a = 7.9472 (16) Å
b = 9.884 (2) Å
c = 10.628 (2) Å
α = 84.37 (3)°
β = 70.12 (3)°
γ = 72.72 (3)°
V = 749.7 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.58 × 0.34 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.950, T _max = 0.990
7400 measured reflections
3396 independent reflections
1960 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.188
S = 1.17
3396 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811021398/sj5157sup1.cif

e-67-o1626-sup1.cif^{(16.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021398/sj5157Isup2.hkl

e-67-o1626-Isup2.hkl^{(166.5KB, 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—H1A⋯O5ⁱⁱⁱ	0.87	1.70	2.565 (3)	172
O4—H4A⋯N2	0.86	1.90	2.723 (3)	159
O5—H5B⋯O2^iv	0.88	1.98	2.817 (3)	160
O5—H5C⋯N1	0.85	2.09	2.858 (3)	149

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Symmetry codes: (iii) Inline graphic ; (iv) .

Acknowledgments

This project was supported by the K. C. Wong Magna Fund of Ningbo University.

supplementary crystallographic information

Comment

Systems with butane-1,2,3,4-tetracarboxylic acid (H₄BTC) as a ligand have been widely studied (Delgado et al., 2007; Liu et al., 2008; Xu et al., 2010; Zhu et al., 2011). A search of the Cambridge structural database (version 5.32, May 2011) (Allen, 2002) showed that most of the literature dealing with butane-1,2,3,4-tetracarboxylic acid concentrated on metal-organic coordination complexes. In contrast, utilization of the butane-1,2,3,4-tetracarboxylic acid seems relatively limited in the construction of co-crystals (Cheng et al., 2009; Najafpour et al., 2008). In this paper, we report the structure of the title cocrystal.

The asymmetric unit of the title cocrystal consists of one 1,10-phenanthroline, unit one half molecule of butane-1,2,3,4-tetracarboxylic acid and a water molecule as depicted in Figure 1. The present 1,10-phenanthroline molecule preserves a nearly perfect coplanarity with a maximum deviation from the best fit meanplane 0.123 (1) Å. The carboxylato group with C1 and C4 atoms is gauche with the C1–C2–C3–C4 torsion angle being 63.35 (2)°. These values agree well with reported structures (Cheng et al., 2009; Najafpour et al., 2008;). The butane-1,2,3,4-tetracarboxylic acid molecules and water molecules are interlinked via O–H···O hydrogen bonds to generate a 1-dimensional supramolecular chain (Figure 2), which is further interconnected by interchain O–H···N hydrogen bonds to construct a 2-dimensional layer parallel to the (001) plane (Figure 3). The resulting layers are arranged in such a way that the 1,10-phenanthroline ligands are each sandwiched between two antiparallel phen neighbors from different adjacent layers, and the mean interplanar distances between the neighboring phen ligands are 3.67 Å and 3.71 Å, suggesting significant intermolecular face-to-face π–π stacking interactions. Such interlayer interactions are regarded as the driving forces to assemble the layers into a three-dimensional supramolecular architecture as shown in Figure 4.

Experimental

All chemicals were obtained from commerical sources and were used as obtained. 1,10-phenanthroline (0.1983 g, 1.00 mmol) was added to a stirred mixture solution of butane-1,2,3,4-tetracarboxylic acid (0.1173 g, 0.50 mmol) in 10 ml H₂O and 10 ml me thanol, and the resulting mixture was stirred for 30 min. Colorless crystals were obtained from the solution after standing at room temperature for two months.