catena-Poly[[[aqua­(glycine-κO)lithium]-μ-glycine-κ2 O:O′] bromide]

T Balakrishnan; K Ramamurthi; J Jeyakanthan; S Thamotharan

doi:10.1107/S1600536812050660

. 2012 Dec 19;69(Pt 1):m60–m61. doi: 10.1107/S1600536812050660

catena-Poly[[[aqua(glycine-κO)lithium]-μ-glycine-κ² O:O′] bromide]

T Balakrishnan ^a, K Ramamurthi ^b, J Jeyakanthan ^c, S Thamotharan ^d,^*

PMCID: PMC3588392 PMID: 23476353

Abstract

In the title coordination polymer, {[Li(C₂H₅NO₂)₂(H₂O)]Br}_n, the Li⁺ cation is coordinated by three carboxylate O atoms of zwitterionic glycine molecules and by a water molecule, forming a distorted tetrahedral geometry. One of the two glycine molecules bridges neighbouring complexes, forming an infinite chain parallel to the c axis. Polymeric chains are further linked by extensive hydrogen bonds involving the Br⁻ anions and glycine and water molecules, producing a three-dimensional network.

Related literature

For hydrogen-bonding motifs, see Bernstein et al. (1995 ▶). For glycine polymorphs, see: Marsh (1958 ▶); Iitaka (1960 ▶, 1961 ▶). For glycine with halogen and metal halogenides, see: Fleck (2008 ▶). For related structures, see: Müller et al. (1994 ▶); Baran et al. (2003 ▶, 2009 ▶); Fleck & Bohatý (2004 ▶); Fleck et al. (2006 ▶). For head-to-tail hydrogen bonds, see: Sharma et al. (2006 ▶); Selvaraj et al. (2007 ▶). graphic file with name e-69-00m60-scheme1.jpg

Experimental

Crystal data

[Li(C₂H₅NO₂)₂(H₂O)]Br
M _r = 255.01
Monoclinic,
a = 7.5396 (6) Å
b = 17.4173 (14) Å
c = 8.2726 (12) Å
β = 118.138 (7)°
V = 957.96 (18) Å³
Z = 4
Mo Kα radiation
μ = 4.28 mm⁻¹
T = 173 K
0.61 × 0.30 × 0.30 mm

Data collection

STOE IPDS diffractometer
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009 ▶) T _min = 0.217, T _max = 0.277
7515 measured reflections
1847 independent reflections
1520 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.021
wR(F ²) = 0.051
S = 0.96
1847 reflections
151 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: EXPOSE in IPDS (Stoe & Cie, 2000 ▶); cell refinement: CELL in IPDS; data reduction: INTEGRATE in IPDS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Click here for additional data file.^{(16.7KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812050660/aa2077sup1.cif

e-69-00m60-sup1.cif^{(16.7KB, cif)}

Click here for additional data file.^{(89.1KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812050660/aa2077Isup2.hkl

e-69-00m60-Isup2.hkl^{(89.1KB, 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
N1—H1A⋯O4ⁱ	0.94 (3)	1.83 (3)	2.774 (2)	176 (3)
N1—H1B⋯O1W ⁱⁱ	0.92 (4)	2.15 (4)	2.989 (3)	151 (2)
N1—H1C⋯Br1ⁱⁱⁱ	0.86 (3)	2.61 (3)	3.353 (2)	146 (3)
N2—H2A⋯Br1	0.81 (3)	2.48 (3)	3.283 (2)	170 (3)
N2—H2B⋯O1^iv	0.90 (3)	2.00 (3)	2.833 (3)	153 (2)
N2—H2C⋯O1^v	0.93 (3)	1.92 (3)	2.797 (2)	157 (3)
O1W—H1⋯O2^vi	0.82 (2)	1.88 (2)	2.692 (2)	172 (3)
O1W—H2⋯Br1^vii	0.83 (2)	2.48 (2)	3.2923 (17)	169 (3)

Open in a new tab

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

Acknowledgments

TB thanks the University Grants Commission (UGC) for the award of a Research Fellowship under the Faculty Improvement Programme (FIP). We are grateful to Professor Helen Stoeckli-Evans, University of Neuchâtel, Switzerland, for measuring the X-ray diffraction data. ST thanks the management of SASTRA University for their encouragement.

supplementary crystallographic information

Comment

The asymmetric unit of the title complex contains two glycine molecules, one Li cation, one Br^- anion and a water molecule (Fig. 1). The bond lengths and angles around the carboxylic groups of both glycine molecules indicate that they are deprotonated and each carboxylic group then carries a negative charge. The amino groups of the glycine molecules are protonated. The positive charge of the ammonium groups are compensated for by the negative charge of the carboxylate groups. The central Li atom is coordinated by a water molecule and three carboxylate oxygen atoms of the three glycine molecules, and has a distorted tetrahedral coordination geometry. One of the two glycine molecules acts as a bridging ligand connecting neighbouring complexes to an infinite chain parallel to the c axis (Fig. 2).

The ammonium group of one glycine molecule is involved in an intermolecular hydrogen bond (N1—H1A···O4) with an adjacent glycine molecule (Table 1). Another amino group of the second glycine molecule also participates in an intermolecular hydrogen bond (N2—H2B···O1) with a neighbouring carboxylate group of a glycine molecule. These two hydrogen bonds combined to produce C²₂(10) (Bernstein et al., 1995) chains that run parallel to the c axis. Adjacent C²₂(10) chains are connected by another N1···O1 hydrogen bond via hydrogen H2C. Two types of N2···O1 hydrogen bonds generate two ring motifs, R²₄(8) and R⁴₄(20), with C²₂(10) chains (Fig. 3). These two ring motifs are arranged alternately along the c axis.

Each polymer chain is interconnected with neighbouring polymeric chains via a hydrogen bond (N2—H2C···O1, Table 1) involving the ammonium group of glycine and a symmetry-related carboxylate group. This hydrogen bond produce two ring motifs R²₂(18) and R²₂(26). These two rings motifs are arranged alternately along the bc plane (Fig. 4). Four glycine molecules and two Li cations are involved in the former ring, while six glycines and four Li ions are involved in the latter motif. The Br^- anion acts as an acceptor for two different ammonium groups (atoms N1 and N2) of the glycine molecules. The water molecule acts as a donor for two different intermolecular hydrogen bonds with a carboxylate oxygen (O2) and the Br^- anion. The N1—H1C···Br1, O1W—H1···O2 and O1W—H2···Br1 hydrogen bonds held together to form a R⁴₆(18) ring motif (Fig. 5).

Experimental

A 1:1 stoichiometeric mixture of glycine and lithium bromide was dissolved in double distilled water. Colourless block-shaped single crystals were obtained after 2 weeks by slow evaporation.