Bis(tetra­methyl­amonium) bis­(2,4,5-carboxy­benzoate)–benzene-1,2,4,5-tetra­carboxylic acid (1/1)

Luís Cunha-Silva; Penka I Girginova; Tito Trindade; João Rocha; Jacek Klinowski; Filipe A Almeida Paz

doi:10.1107/S1600536807062381

. 2007 Dec 6;64(Pt 1):o69–o70. doi: 10.1107/S1600536807062381

Bis(tetramethylamonium) bis(2,4,5-carboxybenzoate)–benzene-1,2,4,5-tetracarboxylic acid (1/1)

Luís Cunha-Silva ^a, Penka I Girginova ^a, Tito Trindade ^a, João Rocha ^a, Jacek Klinowski ^b, Filipe A Almeida Paz ^a,^*

PMCID: PMC2915027 PMID: 21200946

Abstract

The asymmetric unit of the title compound, 2C₄H₁₂N⁺·2C₁₀H₅O₈ ⁻·C₁₀H₆O₈, consists of a tetramethylamonium cation, an anion derived from the singly deprotonated pyromellitic acid anion, 2,4,5-carboxybenzoate (H₃bta⁻), and one-half of a benzene-1,2,4,5-tetracarboxylic acid (H₄bta) molecule, which has the centroid of the aromatic ring positioned at a crystallographic centre of inversion. The H₄bta and H₃bta⁻ residues are involved in an extensive intermolecular O—H⋯O hydrogen-bonding network, which leads to a three-dimensional supramolecular structure containing one-dimensional channels running parallel to the [001] crystallographic direction. These channels house the tetramethylamonium cations.

Related literature

For general background on supramolecular assemblies of organic molecules mediated by hydrogen bonds, see: Dale et al. (2004 ▶); Fabelo et al. (2005 ▶); Ruiz-Pérez et al. (2004 ▶); Steed & Atwood (2000 ▶). For literature relevant to this communication and published by our group, see: Cunha-Silva et al. (2007 ▶); Paz & Klinowski (2003 ▶); Paz et al. (2002 ▶); Shi et al. (2007 ▶). For the Cambridge Structural Database, see: Allen (2002 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶)

Experimental

Crystal data

2C₄H₁₂N⁺·2C₁₀H₅O₈ ⁻·C₁₀H₆O₈
M _r = 908.72
Monoclinic,
a = 9.4282 (4) Å
b = 18.7286 (8) Å
c = 11.3175 (5) Å
β = 107.053 (2)°
V = 1910.55 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 150 (2) K
0.14 × 0.12 × 0.12 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ▶) T _min = 0.982, T _max = 0.984
19608 measured reflections
3736 independent reflections
2523 reflections with I > 2σ(I)
R _int = 0.061

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.099
S = 1.00
3736 reflections
308 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: APEX2; data reduction: SAINT-Plus (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Bruker 2001 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807062381/sj2444sup1.cif

e-64-00o69-sup1.cif^{(21.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062381/sj2444Isup2.hkl

e-64-00o69-Isup2.hkl^{(183.2KB, 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
O2—H2⋯O6ⁱ	0.959 (10)	1.637 (11)	2.5885 (18)	171 (2)
O4—H4⋯O11ⁱⁱ	0.941 (10)	1.806 (12)	2.7166 (19)	162 (2)
O7—H7⋯O6	0.962 (10)	1.483 (10)	2.4334 (19)	169 (2)
O10—H10⋯O5ⁱⁱⁱ	0.938 (10)	1.764 (11)	2.6890 (18)	168 (2)
O12—H12⋯O8^iv	0.957 (10)	1.600 (11)	2.5308 (19)	163 (2)

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

Acknowledgments

We are grateful to Fundação para a Ciência e Tecnologia (FCT, Portugal) for their general financial support (POCI-PPCDT/QUI/58377/2004, supported by FEDER) and for the postdoctoral and PhD research grants Nos. SFRH/BPD/14410/2003 (to LCS) and SFRH/BD/17968/2004 (to PIG.).

supplementary crystallographic information

Comment

Crystal Engineers aim to design functional materials with overall properties which are uniquely directed by the physical and chemical properties of the employed building blocks. In this context, an important strategy used to control the self-assembly processes is based on the use of reliable intermolecular interactions, such as strong and highly directional hydrogen bonds (Steed & Atwood, 2000). Pyromellitic acid (benzene-1,2,4,5-tetracarboxylic acid, H₄bta) has been widely used in the isolation of novel organic crystals, as revealed by a systematic search of the Cambridge Structural Database (Version 5.28, 3 updates - August 2007; Allen, 2002). Indeed, the four symmetrically located carboxylic acid groups confer on this organic molecule predictable and interesting supramolecular properties (Ruiz-Pérez et al., 2004; Fabelo et al., 2005; Dale et al., 2004). As part of our on-going research in the field of Crystal Engineering (Cunha-Silva et al., 2007; Shi et al., 2007), in particular in the use of organic ligands based on carboxylic acid groups (Paz & Klinowski, 2003; Paz et al., 2002), we have recently isolated the title compound, [NMe₄]⁺₂(H₃bta)^-₂.(H₄bta), as a secondary product.

The asymmetric unit of I comprises one [NMe₄]⁺cation, one H₃bta^- anion and half of a H₄bta molecule which has the centroid of the aromatic ring (C_g) positioned at a crystallographic centre of inversion (Figure 1). H₃bta^- anions (moiety type A) and H₄bta molecules (moiety type B) close pack along the [001] direction of the unit cell in a AABAAB_∞ alternate fashion, mediated by a series of weak π···π offset stacking interactions having C_g···C_g distances of 3.762 (2) Å (for A···A), 3.927 (2) Å (for A···B) and 3.910 (2) Å (for B···A). However, the crystal packing of I is essentially mediated by the extensive hydrogen bonding network composed of strong and highly directional O—H···O hydrogen bonds involving the two crystallographic independent residues of pyromellitic acid (Table 1). Indeed, while each H₄bta molecule interacts with six neighbouring H₃bta^- anions, each H₃bta^- is instead connected to three H₄bta plus another two symmetry-related H₃bta^-. The resulting complicated hydrogen bond connectivity leads to the formation of supramolecular R₅⁵(31) rings (Bernstein et al., 1995), which are further interconnected into helices running parallel to the [001] direction of the unit cell (Figure 2 and Table 1). This supramolecular arrangement distributes the H₃bta^- and H₄bta chemical moieties in such a way that the anionic framework contains a one-dimensional channels (also running parallel to the [001] direction) which houses the charge-balancing [NMe₄]⁺ cations (Figure 3). Besides the electrostatic interactions, these cationic moieties are further stabilized inside the channels by a series of weak C—H···O interactions, with C···O distances ranging from 3.161 (3) to 3.663 (3) Å (not shown).

Experimental

2,6-Dihydroxybenzoic acid (0.308 g, 2 mmol) and benzene-1,2,4,5-tetracarboxylic acid (0.510 g, 2 mmol) were mixed in distilled water (ca 20 ml). Tetramethylamonium hydroxide (solution of 25%; 2 mmol) and manganese chloride tetrahydrate (0.101 g, 0.5 mmol) were added, and the resulting mixture was refluxed for 5 h. The solvent from the final pale yellow solution was allowed to slowly evaporate, at ambient temperature, over a period of 10 months. Large single-crystals of the title compound, suitable for X-ray diffraction, were directly harvested from the crystallization vial.