The one-dimensional coordination polymer poly[tetra­kis­[(4-chloro­phen­yl)methanaminium] [cadmate-μ-cyclo­hexa­phospho­rato]]

Sonia Abid; S Salem Al-Deyab; Mohamed Rzaigui

doi:10.1107/S160053681104133X

. 2011 Oct 22;67(Pt 11):m1549–m1550. doi: 10.1107/S160053681104133X

The one-dimensional coordination polymer poly[tetrakis[(4-chlorophenyl)methanaminium] [cadmate-μ-cyclohexaphosphorato]]

Sonia Abid ^a,^*, S Salem Al-Deyab ^b, Mohamed Rzaigui ^a

PMCID: PMC3246971 PMID: 22219791

Abstract

Cyclohexaphosphoric acid (P₆O₁₈H₆) reacts with cadmium carbonate and 4-chlorobenzylamine (CBA) to give the mononuclear title complex, (C₇H₉ClN)₄[Cd(P₆O₁₈)]_n, in which the Cd^II atom, lying on an inversion centre, has an octahedral coordination built of six O atoms of two centrosymmetric P₆O₁₈ rings. Each P₆O₁₈ ligand acts as a bridge, linking two Cd^II atoms and forming an anionic coordination polymer [Cd(P₆O₁₈)⁴⁻]_n extending along [010]. Adjacent polymeric chains are connected through N—H⋯O and C—H⋯O hydrogen bonds, generating a three-dimensional supramolecular network.

Related literature

For the crystal chemistry of condensed phosphates, see: Averbuch-Pouchot & Durif (1996 ▶); Durif (2005 ▶). For general background to supramolecular complexes, see: Kolotuchin et al. (1995 ▶); Tong et al. (1999 ▶). For Cl⋯Cl interactions, see: Hathwar et al. (2010 ▶) and for π–π interactions, see: Janiak et al. (2000 ▶). For the synthesis, see: Schülke & Kayser (1985 ▶). For related structures, see: Du et al. (2010 ▶); Hu et al. (2008 ▶); Kontturi et al. (2005 ▶); Man et al. (2006 ▶).

Experimental

Crystal data

(C₇H₉ClN)₄[Cd(P₆O₁₈)]
M _r = 1156.63
Triclinic,
a = 8.021 (4) Å
b = 8.1696 (16) Å
c = 17.919 (3) Å
α = 87.31 (5)°
β = 88.914 (19)°
γ = 70.100 (3)°
V = 1102.9 (6) Å³
Z = 1
Mo Kα radiation
μ = 1.03 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.18 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
3873 measured reflections
3770 independent reflections
3506 reflections with I > 2σ(I)
R _int = 0.009
2 standard reflections every 120 min intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.074
S = 1.14
3770 reflections
277 parameters
H-atom parameters constrained
Δρ_max = 0.76 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681104133X/ff2028sup1.cif

e-67-m1549-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681104133X/ff2028Isup2.hkl

e-67-m1549-Isup2.hkl^{(181.1KB, 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⋯O1	0.89	1.91	2.785 (3)	167
N1—H1B⋯O6ⁱ	0.89	1.88	2.740 (3)	162
N1—H1C⋯O9ⁱⁱ	0.89	1.93	2.809 (4)	168
N2—H2A⋯O2	0.89	1.96	2.814 (4)	160
N2—H2B⋯O5ⁱⁱ	0.89	2.19	2.866 (3)	133
N2—H2C⋯O1ⁱⁱⁱ	0.89	1.95	2.824 (3)	169
C3—H3⋯O1^iv	0.93	2.56	3.339 (5)	142
C13—H13⋯O6ⁱⁱ	0.93	2.53	3.394 (4)	154
C14—H14B⋯O3^v	0.97	2.56	3.410 (4)	147

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

supplementary crystallographic information

Comment

The key to successful construction of supramolecular architecture is the control and manipulation of coordination bonds an non-covalent interactions by carefully selecting the coordination geometry of the metal atoms and the organic ligands containing appropriate functional groups (such as polyphosphoric acid and polyamine) (Kolotuchin et al., 1995). Up to now, a large number of supramolecular complexes with various dimensions and topologies have been achieved through judicious choice of linkers and metal ions (Tong et al., 1999). The approach to supramolecular framework employed in this work is to use the hexafunctional linker P₆O₁₈^6- that is of strong coordinating ability and suitable hydrogen bond acceptor. The 4-chlorobenzylamine (CBA) is used to create possibly π-π packing interactions between the aromatic rings and Cl—Cl interactions, which could facilitate the formation of ordered and non-interpenetrated open frameworks. In this contribution, we report the self-assembly of Cd^II with P₆O₁₈^6- in the presence of template (CBA) into a supramolecular open framework material [Cd(P₆O₁₈^6-)]_n.4n(CABH) (Scheme I). Single-crystal X-ray diffraction study of this compound shows that the asymmetric unit contains half of cadmium atom, half of a cycle P₆O₁₈ and two crystallographically independent 4-chlorobenzylammonium (CBAH) cations (Fig. 1). The Cd atom locates on an inversion centre and is coordinated by six O atoms. The CdO₆ octahedron, sharing six vertex oxygen atoms with two adjacent P₆O₁₈ rings, is slightly distorted compared to other cases (Du et al., 2010; Kontturi et al., 2005; Man et al., 2006; Hu et al., 2008). Bond distances Cd—O range from 2.230 (2) to 2.353 (7)Å and angles O—Cd—O range from 83.53 (8) to 88.19 (7) °. The P₆O₁₈ units display average P–O distances of 1.540 A and P–P distances of 2.967 Å, values usually found in other condensed anions (Averbuch-Pouchot & Durif, 1996). The values of the P—P—P angles, varying from 87.13 (1) to 128.55 (1)°, are in the range of values observed with other cyclohexaphosphates (Durif, 2005). As shown in Fig. 2, the Cd^II atoms are bridged by P₆O₁₈ rings to form infinite 1-D coordination polymers [Cd(P₆O₁₈)]n parallel to the b axis. Fig. 3 shows the supramolecular open framework structure built of the infinite zigzag chains linked by hydrogen bonds of types N(C)—H···O ranging from 2.714 (3) to 3.410 (4) Å, established by the protonated amine (CBAH). The phenyl rings of these organic molecules are planar, with a mean plane deviation of 0.0043 Å and are parallel with a dihedral angle of 4.94°. The orientations of the –CH₂—NH₃⁺ substituent in the two cations (CBAH) are distinct, as seen from the following torsion angles: N1—C7—C1—C2 = 13.1 (3) and N2—C14—C8—C9 = 118.3 (17)°. The supramolecular framework structure is further stabilized by electrostatic strengths, Cl–Cl interactions [4.051 Å] (Hathwar et al., 2010). The inter-planar distance between nearby phenyl rings is in the vicinity of 4.165 Å, which is longer than 3.80 Å, value required for the formation of π–π interactions (Janiak et al., 2000).

Experimental

The chemicals used to prepare the title compounds include CdCO₃, 4-chlorobenzylamine (CBA) and H₆P₆O₁₈. Both first reagents were commercially available (Accros), the third one was produced from Li₆P₆O₁₈.6H₂O, which is prepared by the process of Schülke (Schülke & Kayser, 1985) and protonated with an ion-exchange resin (Amberlite IR 120) in its H-state. An aqueous solution of H₆P₆O₁₈ (5 mmol, 15 ml) was added dropwise to a stirred mixture of CdCO₃ (0.86 g, 5 mmol), 4-chlorobenzylamine (2.45 ml, 20 mmol)and C₂H₅OH (50 ml). The obtained solution was allowed to stand in air at room temperature until formation of single crystals of the title complex.