Benzene-1,3,5-tricarboxylic acid–1,2-bis­(1,2,4-triazol-4-yl)ethane–water (4/1/2)

Hesham A Habib; Christoph Janiak

doi:10.1107/S1600536808015808

. 2008 Jun 7;64(Pt 7):o1199. doi: 10.1107/S1600536808015808

Benzene-1,3,5-tricarboxylic acid–1,2-bis(1,2,4-triazol-4-yl)ethane–water (4/1/2)

Hesham A Habib ^a, Christoph Janiak ^a,^*

PMCID: PMC2961855 PMID: 21202840

Abstract

The title compound, 4C₉H₆O₆·C₆H₈N₆·2H₂O, crystallizes in a layer structure where each sheet is composed of anellated hydrogen-bonded rings of six distinct sizes: R ₂ ²(16), R ₃ ³(18), R ₄ ⁴(12), R ₄ ⁴(18), R ₄ ⁴(22) and R ₄ ⁴(25). The two largest rings, viz. R ₄ ⁴(22) and R ₄ ⁴(25), are associated with O—H⋯N bonds from the carboxyl groups to the triazole rings. The typical head-to-tail carboxyl–carboxyl R ₂ ²(8) motif is not observed.

Related literature

For related literature, see: Althoff et al. (2006 ▶); Dale & Elsegood (2004 ▶); Dale et al. (2004 ▶); Dorn et al. (2005 ▶, 2006 ▶); Du et al. (2005 ▶); Etter et al. (1990 ▶); Fan et al. (2005 ▶); Goldberg & Bernstein (2007 ▶); Janiak (2000 ▶); Shattock et al. (2005 ▶); Turner et al. (2008 ▶); Wang & Wang (2005 ▶); Wisser & Janiak (2007a ▶,b ▶).

Experimental

Crystal data

4C₉H₆O₆·C₆H₈N₆·2H₂O
M _r = 1040.76
Triclinic,
a = 9.7989 (1) Å
b = 10.7511 (2) Å
c = 12.6578 (2) Å
α = 108.801 (1)°
β = 98.737 (1)°
γ = 113.340 (1)°
V = 1097.44 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 203 (2) K
0.37 × 0.05 × 0.02 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.952, T _max = 0.997
20984 measured reflections
4824 independent reflections
3452 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.105
S = 1.02
4824 reflections
359 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Crystal Impact, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015808/kj2089sup1.cif

e-64-o1199-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015808/kj2089Isup2.hkl

e-64-o1199-Isup2.hkl^{(236.3KB, 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⋯O11ⁱ	0.92 (2)	1.67 (2)	2.594 (2)	175 (2)
O4—H4⋯O8	0.88 (2)	1.75 (2)	2.626 (2)	174 (2)
O6—H6⋯O1ⁱⁱ	0.91 (2)	1.84 (2)	2.699 (2)	157 (2)
O7—H7⋯N1	0.96 (2)	1.75 (2)	2.703 (2)	172 (2)
O9—H9⋯O13	0.91 (3)	1.63 (3)	2.531 (2)	170 (2)
O12—H12⋯N2ⁱⁱⁱ	0.90 (2)	1.76 (2)	2.644 (2)	167 (2)
O13—H13A⋯O10^iv	0.91 (2)	1.81 (3)	2.711 (2)	171 (2)
O13—H13B⋯O5	0.85 (3)	1.92 (3)	2.751 (2)	167 (2)

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

Acknowledgments

Support through DFG grant No. Ja466/14-1 is acknowledged.

supplementary crystallographic information

Comment

Hydrogen bonding within crystalline systems is of timely interest for the rational design of organized solids (Althoff et al., 2006; Dorn et al., 2005; Dorn et al. 2006; Wisser & Janiak, 2007a,b). Co-crystallization of benzene-di, -tri- and -tetra-carboxylic acids, like trimesic acid or hemimellitic acid with solvent molecules or nitrogen bases is the focus of permanent and recent research activities (Dale & Elsegood, 2004; Dale et al., 2004; Du et al., 2005; Fan et al., 2005; Goldberg & Bernstein, 2007; Shattock et al., 2005; Turner et al., 2008; Wang & Wang, 2005). Co-crystal structures of trimesic acid (benzene-1,3,5-tricarboxylic acid) have been reported with 2,5-bis(3- and 4-pyridyl)-1,3,4-oxadiazole (two-dimensional sheet, Du et al., 2005), 3,6-bis(3'-pyridyl)-1,2,4,5-tetrazine (one-dimensional ribbon, Wang & Wang, 2005), 1,2-bis(4-pyridyl)ethane (two-dimensional 6,3- and 10,3-network with interpenetration, Shattock et al., 2005), mono- and bis(methanol) (one-dimensional tape, Dale et al., 2004), acetic acid (Goldberg & Bernstein, 2007) and dihydrate (three-dimensional network, Fan et al., 2005).

The hydrogen-bonded sheet in the title compound contains several different motifs that engage all of the strong hydrogen bond donors and acceptors available (Fig. 1 and 2). The hydrogen bond distances in the sheet are spread over a narrow range, with D···A distances from 2.53 to 2.75 Å. The sheet is constructed of six distinct hydrogen-bonded rings of sizes R₂²(16), R₃³(18), R₄⁴(12), R₄⁴(18), R₄⁴(22) and R₄⁴(25), using Etter's graph set analysis (Etter et al., 1990). The two largest rings R₄⁴(22) and R₄⁴(25) are associated with the O—H···N bonds from the carboxylic acid groups to the triazole rings. All N1 and N2 nitrogen atoms of the 1,2-bis(1,2,4-triazol-4-yl)ethane molecule act as hydrogen-bond acceptors. The smallest ring R₄⁴(12) incorporates two water molecules and two carboxylic acid groups. The 18-membered R₃³(18) and R₄⁴(18) rings are constructed from one water molecule in combination with three and four carboxylic acid groups, respectively. These water and carboxylic acid containing motifs are different from those seen in the structure of the trimesic acid dihydrate (Fan et al., 2005). Also, formation of the common R₂²(8) head-to-tail carboxylic acid–acid graph-set motif is apparently prevented in the structure of the title compound by the water and the bis-triazole molecule. No relevant π–π or C—H···π interactions are found between molecules in adjacent sheets (Fig. 3) (Janiak, 2000).

Experimental

A mixture of trimesic acid, H₃btc (210 mg, 1.00 mmol), 1,2-bis(1,2,4-triazol-4-yl)ethane, btre (164 mg, 1.00 mmol) and water (15 ml) was stirred for 30 min at room temperature, transferred to a Teflon-lined stainless-steel autoclave and heated at 453 K for 3 d. Then the autoclave was cooled to room temperature at a rate of 2.8 K h^-1. A colorless crystalline product was filtered off, washed with distilled water and dried in air (yield 135 mg, 52% based on H₃btc). Elemental analysis C₂₁H₁₈N₃O₁₃ (520.38) calcd. C 48.47, H 3.49, N 8.07; found: C 47.84, H 3.49, N 8.02%.