Bis[2-amino-6-methyl­pyrimidin-4(1H)-one-κ2 N 3,O]dichloridocadmium(II)

Kamel Kaabi; Meher El Glaoui; P S Pereira Silva; M Ramos Silva; Cherif Ben Nasr

doi:10.1107/S1600536810035051

. 2010 Sep 8;66(Pt 10):m1225. doi: 10.1107/S1600536810035051

Bis[2-amino-6-methylpyrimidin-4(1H)-one-κ² N ³,O]dichloridocadmium(II)

Kamel Kaabi ^a, Meher El Glaoui ^a, P S Pereira Silva ^b, M Ramos Silva ^b, Cherif Ben Nasr ^a,^*

PMCID: PMC2983177 PMID: 21587381

Abstract

In the title compound, [CdCl₂(C₅H₇N₃O)₂], the Cd^II atom is six-coordinated by two heterocyclic N atoms [Cd—N = 2.261 (2) and 2.286 (2) Å] and two O atoms [Cd—O = 2.624 (2) and 2.692 (2) Å] from two bidentate chelate 2-amino-6-methylpyrimidin-4(1H)-one ligands and two chloride ions [Cd—Cl = 2.4674 (6) and 2.4893 (7) Å]. The crystal packing is characterized by an open-framework architecture with the crystal packing stabilized by intermolecular N—H⋯Cl and N—H⋯O hydrogen bonds.

Related literature

For common applications of materials with open framework structures, see: Yaghi et al. (2003 ▶); Kitagawa et al. (2004 ▶). For literature on metal-organic compounds, see: Kaabi et al. (2010 ▶). For a discussion of geometrical features in related structures, see: Min et al. (2009 ▶); Qing-Yan & Li (2005 ▶); Moloto et al. (2003 ▶).

Experimental

Crystal data

[CdCl₂(C₅H₇N₃O)₂]
M _r = 433.57
Monoclinic,
a = 17.4204 (5) Å
b = 7.5467 (2) Å
c = 25.4422 (6) Å
β = 106.1333 (11)°
V = 3213.07 (15) Å³
Z = 8
Mo Kα radiation
μ = 1.70 mm⁻¹
T = 293 K
0.32 × 0.20 × 0.13 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.676, T _max = 0.801
41891 measured reflections
4494 independent reflections
3924 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.108
S = 1.27
4494 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −1.06 e Å⁻³

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810035051/zs2058sup1.cif

e-66-m1225-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810035051/zs2058Isup2.hkl

e-66-m1225-Isup2.hkl^{(215.8KB, 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
N5—H5⋯O2Aⁱ	0.86	1.92	2.704 (3)	151
N6—H6A⋯Cl3	0.86	2.62	3.417 (3)	155
N6—H6B⋯O2Aⁱ	0.86	2.47	3.116 (3)	132
N6—H6B⋯Cl3ⁱ	0.86	2.80	3.383 (2)	127
N5A—H5A⋯O2ⁱⁱ	0.86	1.87	2.692 (2)	158
N6A—H6A1⋯Cl2	0.86	2.51	3.336 (3)	161
N6A—H6A2⋯Cl3ⁱⁱⁱ	0.86	2.73	3.430 (2)	139

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

Acknowledgments

This work was supported by the Fundação para a Ciência e a Tecnologia (FCT), under the scholarship SFRH/BD/38387/2008.

supplementary crystallographic information

Comment

Open framework crystalline solids containing micro or mesoporisity have been studied extensively in recent years, due to their intriguing structures and considerable technological importance in magnetic, luminescent, porous and catalytic materials (Yaghi, et al., 2003; Kitagawa, et al., 2004). In this work a new member of this family is presented, the title complex involving CdCl₂ and the ligand 2-amino-4-hydroxy-6-methylpyrimidine, [Cd(C₅H₇N₃O)₂Cl₂], (I) which was obtained during our studies on the preparation of new organometallic materials (Kaabi,et al., 2010).

In the atomic arrangement of the title compound, the distorted octahedral Cd environment comprises two chloride donor atoms and two N and two O donor atoms from two bidentate chelate organic ligands (Fig. 1). The bond distances around the Cd atom [Cd—N, 2.261 (2), 2.286 (2) Å; Cd—O, 2.624 (2), 2.692 (2) Å; Cd—Cl, 2.4674 (6), 2.4893 (7) Å] are normal (Min et al., 2009; Qing-Yan & Li, 2005; Moloto et al., 2003). The octahedra have intramolecular N—H···Cl hydrogen bonds and are interconnected by a set of N—H···Cl and N—H···O hydrogen bonds (Table 1) leading to the formation of a three-dimensional network structure (Fig. 2). Among the hydrogen bonds, one is three-centred [N6—H6B···(O2A,Cl3)]. The overall packing pattern, presented in Fig. 3, shows that the different components of the title material are arranged so as to create pores extending along the c axis and located at (0, 0, 0) and (1/2, 1/2, 0). Thus, this organic-inorganic hybrid open framework material could have potential application as a molecular sieve. An examination of the organic moiety features shows that the bond distances for C2—O2 [1.248 (3) Å] and C2A—O2A [1.255 (3) Å] clearly indicate two double bonds. This allows us to confirm that the first step of the preparation of the title compound consists of the transformation of the 2-amino-6-methyl-4-pyrimidinol into 2-amino-6-methylpyrimidin-4-(1H)-one. However, the present investigation clearly shows that the N6—C6 [1.332 (3) Å] and N6A—C6A [1.324 (3) Å] distances are approximately equal to that of a C=N double bond length, indicating that N3 and N6 nitrogen atoms of the amino group are probably in an sp² hybridization. These bond length features are consistent with imino resonance and suggest a large contribution from it to the stability of the title compound.

Experimental

A solution of CdCl₂ (37 mg, 0.2 mmol) in water (6 ml) was added dropwise to a solution of 2-amino-4-hydroxy-6-methylpyrimidine (50 mg, 0.4 mmol) in ethanol (6 ml). After stirring for 30 min, the mixture was filtered and the resultant solution allowed to evaporate at room temperature. Crystals of the title compound, which remained stable under normal conditions of temperature and humidity, were isolated after several days and subjected to X-ray diffraction analysis (yield 58%).