Extensive hydrogen-bonding network and an unusual cation conformation in [tris­(hydroxy­meth­yl)methyl]­ammonium tetra­oxidorhenate(VII)

Małgorzata Hołyńska; Tadeusz Lis

doi:10.1107/S1600536809028797

. 2009 Jul 29;65(Pt 8):m998–m999. doi: 10.1107/S1600536809028797

Extensive hydrogen-bonding network and an unusual cation conformation in [tris(hydroxymethyl)methyl]ammonium tetraoxidorhenate(VII)

Małgorzata Hołyńska ^a,^*, Tadeusz Lis ^a

PMCID: PMC2977137 PMID: 21583437

Abstract

The title compound, (C₄H₁₂NO₃)[ReO₄], contains two cations and two anions in the asymmetric unit, related by a non-crystallographic centre of symmetry. The crystal structure is stabilized by an extensive hydrogen-bonding network with the formation of puckered layers perpendicular to [001]. In the tris(hydroxymethyl)ammonium cations, intramolecular O—H⋯O hydrogen bonds are present with the formation of an S ₁ ¹(6) graph-set motif. The crystal structure is further consolidated by N—H⋯O hydrogen bonds.

Related literature

For related structures, see: Castellari & Ottani (1997 ▶); Eilerman & Rudman (1980 ▶); Hołyńska & Lis (2004 ▶, 2008 ▶); Lock & Turner (1975 ▶); Marsh et al. (1998 ▶); Rudman et al. (1979 ▶, 1983 ▶); Shakked et al. (1980 ▶); Tusvik et al. (1999 ▶). For the dielectric properties of rhenates(VII) with organic ammonium cations, see: Czarnecki & Małuszyńska (2000 ▶). For graph-set notation, see: Etter et al. (1990 ▶). For the synthesis of rhenic(VII) acid, see: Johnson et al. (1967 ▶).

Experimental

Crystal data

(C₄H₁₂NO₃)[ReO₄]
M _r = 372.35
Orthorhombic,
a = 21.450 (5) Å
b = 6.867 (2) Å
c = 12.219 (4) Å
V = 1799.8 (9) Å³
Z = 8
Mo Kα radiation
μ = 13.51 mm⁻¹
T = 110 K
0.21 × 0.16 × 0.14 mm

Data collection

Oxford Diffraction KM-4-CCD diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006 ▶) T _min = 0.104, T _max = 0.268
24604 measured reflections
5888 independent reflections
5084 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.020
wR(F ²) = 0.034
S = 1.02
5888 reflections
245 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 2.00 e Å⁻³
Δρ_min = −1.27 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶) and SHELXTL-NT (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809028797/ez2176sup1.cif

e-65-0m998-sup1.cif^{(18.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028797/ez2176Isup2.hkl

e-65-0m998-Isup2.hkl^{(288.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Re1—O11	1.736 (2)
Re1—O21	1.728 (2)
Re1—O31	1.727 (2)
Re1—O41	1.702 (5)
Re2—O12	1.728 (4)
Re2—O22	1.730 (3)
Re2—O32	1.736 (3)
Re2—O42	1.726 (2)

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O41—Re1—O31	109.6 (2)
O41—Re1—O21	108.7 (2)
O31—Re1—O21	108.7 (2)
O41—Re1—O11	110.6 (2)
O31—Re1—O11	110.0 (2)
O21—Re1—O11	109.2 (2)
O42—Re2—O12	108.4 (2)
O42—Re2—O22	109.4 (2)
O12—Re2—O22	109.6 (2)
O42—Re2—O32	109.3 (2)
O12—Re2—O32	110.8 (2)
O22—Re2—O32	109.3 (2)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O21	0.91	2.03	2.858 (4)	150
N2—H2B⋯O111ⁱ	0.91	1.88	2.788 (4)	173
N2—H2C⋯O31ⁱⁱ	0.91	1.98	2.879 (4)	169
O112—H112⋯O212	0.84	2.12	2.773 (4)	134
O112—H112⋯O41	0.84	2.49	2.942 (4)	115
O212—H212⋯O32ⁱⁱ	0.84	1.89	2.721 (4)	168
O312—H312⋯O112ⁱⁱ	0.84	1.92	2.704 (4)	156
N1—H1A⋯O312ⁱⁱⁱ	0.91	1.83	2.738 (4)	176
N1—H1B⋯O42ⁱⁱ	0.91	2.05	2.872 (4)	150
N1—H1C⋯O22	0.91	1.98	2.862 (4)	164
O111—H111⋯O211^iv	0.84	1.89	2.681 (3)	157
O211—H211⋯O311	0.84	2.13	2.774 (4)	134
O211—H211⋯O12ⁱⁱ	0.84	2.54	2.960 (4)	112
O311—H311⋯O11	0.84	1.88	2.714 (4)	170

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

Acknowledgments

Financial support from the Ministry of Science and Higher Education (project No. N204 130 32/3318) is acknowledged.

supplementary crystallographic information

Comment

The title compound was obtained as starting material for other syntheses (e.g. reaction with acethyl chloride - Hołyńska & Lis, 2008). It was chosen as the tris(hydroxymethyl)methylammonium cation gives rise to an extensive hydrogen bonding network, which allows for selective crystallization of products containing Re, reducing the risk of cocrystallization of impurities and crystal structure disorder. Moreover, rhenates(VII) with organic ammonium cations crystallizing in non-centrosymmetric space groups are promising materials with respect to their dielectric properties. For example, the previously discovered ferroelectric with a Curie temperature above room temperature is pyridinium rhenate(VII) (Czarnecki & Małuszyńska, 2000).

The title compound (1) is a product of the reaction of rhenic(VII) acid with tris(hydroxymethyl)methylamine (TRIS) in aqueous solution, comprising discrete tris(hydroxymethyl)methylammonium cations (protonated TRIS here denoted as TRISH⁺) and rhenate(VII) anions (Fig. 1, Scheme 1).

There are two symmetry-independent rhenate(VII) anions (containing atoms Re1 and Re2, respectively) with the expected (see e.g. Hołyńska & Lis, 2004 for example of rhenate(VII) anions in low symmetry environment) slightly distorted tetrahedral geometry. The Re—O bond lengths are listed in Table 1. Their values are consistent with those for other rhenates(VII), e.g. 1.723 (4) Å for potassium rhenate(VII) reported by Lock & Turner (1975). These bond lengths are not much affected by the presence of hydrogen bonds, as all rhenate(VII) O atoms participate in these interactions as acceptors (Table 2).

It is interesting to note that both symmetry-independent TRISH⁺ cations are of unusual conformation. Usually the cation symmetry is close to C₃ (e.g. Rudman et al., 1983) or even exactly threefold (as in [TRISH]Cl appearing in a preliminary report by Rudman et al., 1979) with no intramolecular hydrogen bonds. In (1) both cations exhibit the presence of such intramolecular hydrogen bond (Table 2) with the formation of a S₁¹(6) graph-set motif (Etter et al., 1990). The relevant N—C—C—O torsion angles are given in Table 1. Bond lengths characterizing the cations, among them the C—N bond length (which is longer than in the TRIS molecule - 1.477 (3) Å as reported for the neutral TRIS molecule by Eilerman & Rudman, 1980) are in accordance with the values reported for other structures (e.g. Castellari & Ottani, 1997). TRIS is a constituent of buffers used in biochemical studies in the pH range of 7–9 (Castellari & Ottani, 1997). Upon protonation it forms salts with biologically relevant anions (e.g. tris(hydroxymethyl)methylammonium deoxycholate reported by Tusvik et al., 1999), also a report on its interaction with nucleotides in the crystalline state is available (Shakked et al., 1980).

All cation ammonium and hydroxyl groups are donors in N—H···O or O—H···O hydrogen bonds, both to other TRISH⁺ cations or to rhenate(VII) anions. The shortest Re···Re distance is 4.210 (2) Å. Thus, puckered hydrogen-bonded layers perpendicular to [001] are formed (Fig. 2). The hydrogen bonding scheme stabilizing an individual layer is illustrated in Fig. 3.

Experimental

The title compound was obtained in the reaction of 0.19 g of tris(hydroxymethyl)methylamine (TRIS) with an excess of rhenic(VII) acid in aqueous solution, with slow evaporation leading to colourless crystals. The reaction was carried out in a quartz beaker. Rhenic(VII) acid was obtained according to the literature procedure (Johnson et al., 1967) in reaction of 0.3 g of metallic Re with an excess of a 30% aqueous hydrogen peroxide solution.