A one-dimensional inorganic–organic hybrid compound: catena-poly[ethyl­enediammonium [indate(III)-di-μ-hydrogenphosphato(V)-μ-hydroxido] monohydrate]

Abderrazzak Assani; Mohamed Saadi; Lahcen El Ammari

doi:10.1107/S160053681003240X

. 2010 Aug 28;66(Pt 9):m1065–m1066. doi: 10.1107/S160053681003240X

A one-dimensional inorganic–organic hybrid compound: catena-poly[ethylenediammonium [indate(III)-di-μ-hydrogenphosphato(V)-μ-hydroxido] monohydrate]

Abderrazzak Assani ^a, Mohamed Saadi ^a,^*, Lahcen El Ammari ^a

PMCID: PMC3007876 PMID: 21588488

Abstract

The title compound, (C₂H₁₀N₂)[In(HPO₄)₂(OH)]·H₂O, was synthesized under hydrothermal conditions. The structure of this hybrid compound consists of isolated inorganic chains with composition _∞[In(HPO₄)_4/2(OH)_2/2] running along [010]. The coordination of the In^III atom is distorted octahedral. The ethylenediammonium cation and the disordered water molecule (site-occupation factors = 0.7:0.3) ensure the cohesion of the structure via N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For properties of and background to indium phosphates, see: Forster & Cheetham (2003 ▶); Chen, Liu et al. (2006 ▶); Chen et al. (2007 ▶); Huang et al. (2010 ▶); Thirumurugan & Srinivasan (2003 ▶). For compounds with related structures, see: Chen, Yi et al. (2006 ▶); Li et al. (2006 ▶); Du et al. (2004 ▶). For background to bond-valence analysis, see: Brown & Altermatt (1985 ▶).

Experimental

Crystal data

(C₂H₁₀N₂)[In(HPO₄)₂(OH)]·H₂O
M _r = 403.92
Monoclinic,
a = 10.0702 (3) Å
b = 7.4896 (2) Å
c = 15.6007 (5) Å
β = 99.000 (1)°
V = 1162.15 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.36 mm⁻¹
T = 296 K
0.20 × 0.06 × 0.03 mm

Data collection

Bruker X8 APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.844, T _max = 0.932
13591 measured reflections
2771 independent reflections
2168 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.026
wR(F ²) = 0.067
S = 1.03
2771 reflections
162 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681003240X/wm2383sup1.cif

e-66-m1065-sup1.cif^{(17.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681003240X/wm2383Isup2.hkl

e-66-m1065-Isup2.hkl^{(136.1KB, hkl)}

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

Table 1. Selected bond lengths (Å).

In1—O9ⁱ	2.089 (2)
In1—O9	2.094 (2)
In1—O2ⁱ	2.135 (2)
In1—O3	2.148 (2)
In1—O6ⁱ	2.154 (2)
In1—O7	2.154 (2)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O5ⁱⁱ	0.82	1.78	2.595 (3)	174
O8—H8⋯O1	0.82	1.75	2.567 (4)	172
O9—H9⋯O10	0.86 (2)	1.93 (2)	2.780 (5)	170 (3)
O10—H10A⋯O1ⁱ	0.85	2.44	3.291 (5)	179
O10—H10B⋯O8ⁱⁱⁱ	0.87	2.35	2.911 (5)	122
N1—H11A⋯O3^iv	0.89	2.00	2.876 (4)	168
N1—H11B⋯O2ⁱ	0.89	2.51	3.137 (4)	128
N1—H11B⋯O10	0.89	2.43	3.114 (5)	133
N1—H11C⋯O4^v	0.89	2.41	3.011 (4)	125
N1—H11C⋯O1^v	0.89	1.98	2.823 (4)	158
N2—H22A⋯O5	0.89	1.87	2.750 (4)	170
N2—H22B⋯O6^vi	0.89	2.06	2.911 (4)	160
N2—H22C⋯O7^vii	0.89	2.05	2.892 (4)	158

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

Acknowledgments

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

supplementary crystallographic information

Comment

The research of new porous materials and open-framework structures in the hybrid inorganic-organic systems continues to be of great interest in the field of materials chemistry. Mainly, hybrid metal phosphates are extensively investigated due to their impressive diversity of structures which are strongly required for catalysis applications (Forster & Cheetham, 2003). Accordingly, in the past two decades, amine templated indium phosphates were in the focus of investigation, providing one-dimensional chain, two-dimensional layered and three-dimensonal open-framework structures with different In:P ratios (Chen et al. 2007; Chen, Liu et al. 2006; Thirumurugan & Srinivasan, 2003; Huang et al. 2010). In the present work, a new indium phosphate with a In:P ratio of 1:2, namely (H₃NCH₂CH₂NH₃)[In(HPO₄)₂(OH)]^.H₂O was hydrothermally synthesized and structurally characterized.

The asymmetric unit of the title compound is drawn in Fig. 1. A three-dimensional polyhedral view of its crystal structure is represented in Fig. 2. It shows InO₄(OH)₂ octahedra linked to PO₃OH tetrahedra by sharing corners in the way to build _∞[In(OH)_2/2(HPO₄)_4/2] chains running along [010]. Fig. 3 shows the InO₆ octahedra linked to another via their hydroxide vertices, giving rise to a one-dimensional linear chain. Adjacent octahedra are additionally interconnected by PO₃OH tetrahedra by sharing their terminal O atoms with four tetrahedra. A similar connectivity is observed in the structure of (C₄N₂H₁₂)[In₂(HPO₄)₂(H₂PO₄)₂F₂] (Chen, Yi et al., 2006).

The +III and +V oxidation states of the In and P atoms were confirmed by bond valence sum calculations (Brown & Altermatt, 1985). The calculated values for the two In^III+ and P^V+ ions are as expected, viz. 3.25 and 5.04, respectively. The values of the bond valence sums calculated for all oxygen atoms are: 1.33 and 1.34 for the terminal O atoms O1 and O5, 2.29, 2.30 and 2.26 for O4, O8 and O9, respectively, and 1.82 for all other O atoms except that of the water molecule (O10) which amounts to 2.12. The difference between these values is explained by the nature and the length of the P—O bonds. From the two tetrahedrally coordinated phosphorus atoms P1 and P2, each shares two O atoms with adjacent indium atoms (average distance P—O = 1.520 Å) and possesses one terminal P1═O1 = 1.510 (2) Å, P2═O5 = 1.509 (2) Å and one P1—O4H = 1.579 (2) Å, P2—O8H = 1.577 (2) Å bond. The terminal O atoms are involved in strong hydrogen bonds (see below) which likewise explains their low bond valence sum. These results are in good agreement with the framework formula and are in close agreement with those reported in the literature for similar indium phosphates (Li et al. 2006; Du et al. 2004).

The ethylenediammonum cation and the water molecules ensure the cohesion of the structure via N—H···O and O—H···O hydrogen bonds (Fig. 1, Table 2).

Experimental

Single crystals of the title compound were hydrothermally synthesized from a reaction mixture of indium oxide (In₂O₃; 0,388 g), phosphoric acid 85%_wt (H₃PO₄; 0,35 ml), ethylenediamine (NH₂(CH₂)₂NH₂; 0,3 ml) and water (H₂O; 10 ml). In addition, 40%_wt fluoric acid (HF; 0,1 ml) was added to the mixture to provide fluoride ions which can act as a mineralizing agent in the hydrothermal synthesis and can play a structure-directing role. The hydrothermal reaction was conducted in a 23 ml Teflon-lined autoclave under autogeneous pressure at 398 K for two days. The resulting product was filtered off, washed with deionized water and was dried in air. It consisted of a yellow powder in addition to a few colorless parallelepipedic crystals of the title compound.