Melaminium perchlorate monohydrate

Min Min Zhao; Ping Ping Shi

doi:10.1107/S160053681001857X

. 2010 May 26;66(Pt 6):o1463. doi: 10.1107/S160053681001857X

Melaminium perchlorate monohydrate

Min Min Zhao ^a,^*, Ping Ping Shi ^a

PMCID: PMC2979602 PMID: 21579531

Abstract

In the title hydrated salt, 2,4,6-triamino-1,3,5-triazin-1-ium perchlorate monohydrate, C₃H₇N₆ ⁺·ClO₄ ⁻·H₂O, the constituents are linked via hydrogen bonds of the O—H⋯O, N—H⋯O, N—H⋯N and N—H⋯Cl types. All the H atoms of the melaminium cation are involved in the hydrogen bonds. The melaminium residues are interconnected by four N—H⋯N hydrogen bonds, forming chains parallel to (111). The ribbons are interconnected by other hydrogen bonds as well as by π–π interactions [centroid–centroid distance = 3.8097 (7) Å].

Related literature

For similar organic acid–base compounds, see: Martin & Pinkerton (1995 ▶); Perpétuo & Janczak (2006 ▶). For their ferroelectric properties, see: Hang et al. (2009 ▶), Li et al. (2008 ▶). For impedance studies, see; Uthrakumar et al. (2008 ▶).

Experimental

Crystal data

C₃H₇N₆ ⁺·ClO₄ ⁻·H₂O
M _r = 244.61
Triclinic,
a = 5.654 (4) Å
b = 7.553 (7) Å
c = 11.893 (10) Å
α = 102.72 (4)°
β = 94.58 (3)°
γ = 110.78 (2)°
V = 456.1 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.916, T _max = 0.916
4902 measured reflections
2051 independent reflections
1719 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.091
S = 0.90
2051 reflections
163 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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: PRPKAPPA (Ferguson, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681001857X/ng2764sup1.cif

e-66-o1463-sup1.cif^{(15KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681001857X/ng2764Isup2.hkl

e-66-o1463-Isup2.hkl^{(100.9KB, 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
O5—H5B⋯O4	0.85 (1)	2.16 (1)	2.960 (3)	158 (2)
O5—H5B⋯O5ⁱ	0.85 (1)	2.64 (2)	3.081 (3)	114 (2)
O5—H5A⋯O3ⁱⁱ	0.84 (1)	2.16 (1)	2.883 (3)	144 (2)
O5—H5A⋯O2ⁱⁱⁱ	0.84 (1)	2.38 (2)	2.867 (3)	117 (1)
N1—H1B⋯O1^iv	0.86 (1)	2.19 (1)	2.890 (2)	139 (2)
N1—H1B⋯O5^iv	0.86 (1)	2.48 (2)	3.146 (3)	135 (2)
N1—H1A⋯N6^v	0.86 (1)	2.14 (1)	2.998 (3)	178 (2)
N2—H2B⋯O4ⁱⁱ	0.86 (1)	2.31 (1)	3.086 (3)	151 (2)
N2—H2B⋯O2^vi	0.86 (1)	2.56 (2)	3.108 (3)	123 (2)
N2—H2A⋯O2ⁱⁱⁱ	0.86 (1)	2.20 (1)	2.979 (3)	150 (2)
N2—H2A⋯Cl1ⁱⁱⁱ	0.86 (1)	2.99 (1)	3.792 (3)	157 (2)
N3—H3B⋯N5^vii	0.85 (1)	2.23 (1)	3.084 (3)	173 (2)
N3—H3A⋯O1^viii	0.86 (1)	2.19 (1)	3.029 (3)	168 (2)
N4—H4A⋯O5^iv	0.84 (1)	1.90 (1)	2.723 (2)	168 (2)

Open in a new tab

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

Acknowledgments

The authors are grateful to the starter fund of Southeast University for financial support to buy the X-ray diffractometer.

supplementary crystallographic information

Comment

The melamine molecule and its organic and inorganic complexes or salts were widely researched by ancient Chemists (Martin et al. 1995; Perpétuo & Janczak, 2006). This study is a part of systematic investigation of dielectric ferroelectric materials, including organic ligands (Li et al., 2008), metal-organic coordination compounds (Hang et al., 2009) and organic inorganic hybrid. Melaminium monoperchlorate monohydrate has no dielectric disuniform from 90 K to 430 K, (m.p. > 470 K).

The asymmetric unit of the title compound is composed of cationic (C₃H₇N₆⁺), anionic (ClO₄^-) and one dissociative water molecular(Fig 1). The melaminium cation is protonated at only one melamine ring N atom. The six-membered aromatic ring of melaminium residues exhibit distortions from the regular hexagonal form. The internal C—N—C angle at the protonated N atom(119.41 (14) °) is greater than the other two C—N—C angles of the ring(115.45 (14) ° and 115.48 (14) °) and the internal N—C—N angles involving the nonprotonated ring N atoms (126.09 (15) °) are obviously greater than those containing protonated and non-protonated N atoms(121.65 (15) ° and 121.88 (15) °).

Fig. 2 shows a view down the c axis. The melaminium cations are interconnected by four N—H···N hydrogen bonds, forming ribbons parallel to (1 1 1). The ribbons are interconnected by other hydrogen bonds as well as by π-electron ring - π-electron ring interactions with the distance between the centroids of the neighbour melaminium rings (1-x,1-y,1-z) equal to 3.8097 Å. Melamine and its derivatives and organic and inorganic complexes or salts can develop well defined non-covalent supramolecular architectures via multiple hydrogen bonds. The hydrogen bonds are summarized in Tab. 1. The H atom of the protonated ring N atom (H4a) is donated to the water molecule, being involved in a strong N—H···O hydrogen bond. The other amine H atoms are involved in N—H···O, N—H···N and N—H···Cl hydrogen bonds. ClO₄^- anions take part in electrostatics equilibrium with the melaminium cations. They are also involved in N—H···O, O—H···O, and N—H···Cl hydrogen bonds.

Experimental

Single crystals of melaminium monoperchlorate monohydrate are prepared by slow evaporation at room temperature of an water solution of melamine and perchloric acid.

Dielectric studies (capacitance and dielectric loss measurements) were performed on powder samples which have been pressed into tablets on the surfaces of which a conducting carbon glue was deposited. The automatic impedance TongHui2828 Analyzer has been used (Uthrakumar et al., 2008). In the measured temperature ranges (90 K to 450 K, m.p. > 470 K), the title structure showed no dielectric disuniform.