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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): m1065–m1066.
Published online 2010 August 28. doi:  10.1107/S160053681003240X
PMCID: PMC3007876

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

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 InIII 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 [triangle]); Chen, Liu et al. (2006 [triangle]); Chen et al. (2007 [triangle]); Huang et al. (2010 [triangle]); Thirumurugan & Srinivasan (2003 [triangle]). For compounds with related structures, see: Chen, Yi et al. (2006 [triangle]); Li et al. (2006 [triangle]); Du et al. (2004 [triangle]). For background to bond-valence analysis, see: Brown & Altermatt (1985 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1065-scheme1.jpg

Experimental

Crystal data

  • (C2H10N2)[In(HPO4)2(OH)]·H2O
  • M r = 403.92
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1065-efi1.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.59 e Å−3
  • Δρmin = −0.65 e Å−3

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

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

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 InIII+ and PV+ 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.

Refinement

All O-bound, N-bound and C-bound H atoms were initially located in a difference map and refined with O—H, N—H and C—H distance restraints of 0.82 (1) Å, 0.89 (1) Å and C–H 0.97 (1) Å, respectively. In a subsequent cycle they were refined in the riding model approximation with Uiso(H) set to 1.5Ueq(O) or (N) and Uiso(H) set to 1.2 Ueq(C). The refinement of the site occupancy of the O atoms of the water molecule shows full occupation. However, the electron density is distributed over two adjacent positions (O10 and O11). The refinement of the occupancy rates of these two positions led to a site occupancy factor of 0.7 for O10 and of 0.3 for O11, accompanied with considerable improvements in R and Rw factors.

From the synthetic conditions one might expect an incorporation of F- ions. The distinction by X-ray diffraction between F- and O2- is difficult. However, when the relevant OH positions were replaced by F-, a small worsening of the reliability factors was observed. Moreover, the clearly discernible proton positions in the difference Fourier maps point to OH rather than to F. Nevertheless, the existence of a very small amount of F- incorporated in the structure cannot be excluded.

Figures

Fig. 1.
ORTEP plot of the asymmetric unit of the (H3NCH2CH2NH3)[In(HPO4)2(OH)].H2O structure. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are indicated by dashed lines.
Fig. 2.
A three-dimensional polyhedral view of the crystal structure of the (H3NCH2CH2NH3)[In(HPO4)2(OH)].H2O.
Fig. 3.
A view of an inorganic chain built up from corner sharing indium octahedra linked by HPO4 tetraedra.

Crystal data

(C2H10N2)[In(HPO4)2(OH)]·H2OF(000) = 800
Mr = 403.92Dx = 2.309 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2771 reflections
a = 10.0702 (3) Åθ = 2.6–27.9°
b = 7.4896 (2) ŵ = 2.36 mm1
c = 15.6007 (5) ÅT = 296 K
β = 99.000 (1)°Plate, colourless
V = 1162.15 (6) Å30.20 × 0.06 × 0.03 mm
Z = 4

Data collection

Bruker X8 APEXII CCD area-detector diffractometer2771 independent reflections
Radiation source: fine-focus sealed tube2168 reflections with I > 2σ(I)
graphiteRint = 0.045
[var phi] and ω scansθmax = 27.9°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −13→13
Tmin = 0.844, Tmax = 0.932k = −9→9
13591 measured reflectionsl = −20→19

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.067H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.031P)2 + 0.4367P] where P = (Fo2 + 2Fc2)/3
2771 reflections(Δ/σ)max = 0.001
162 parametersΔρmax = 0.59 e Å3
1 restraintΔρmin = −0.65 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
In10.247040 (19)0.02859 (3)0.250039 (14)0.01340 (8)
P10.12174 (8)−0.22253 (11)0.39952 (5)0.01587 (17)
P2−0.02212 (8)−0.22671 (10)0.15538 (5)0.01537 (17)
O1−0.0298 (2)−0.2219 (4)0.37808 (17)0.0389 (7)
O20.1861 (2)−0.3858 (3)0.36661 (15)0.0271 (5)
O30.1849 (2)−0.0520 (3)0.36984 (15)0.0271 (6)
O40.1498 (2)−0.2250 (3)0.50197 (14)0.0235 (5)
H40.2297−0.24490.51860.035*
O5−0.0986 (2)−0.2250 (3)0.06416 (15)0.0233 (5)
O60.0672 (2)−0.3905 (3)0.17185 (15)0.0246 (5)
O70.0595 (2)−0.0564 (3)0.17533 (16)0.0243 (5)
O8−0.1324 (2)−0.2335 (4)0.21683 (17)0.0366 (7)
H8−0.0965−0.22050.26730.055*
O90.3367 (2)−0.2199 (3)0.23619 (15)0.0174 (5)
H90.4156 (15)−0.208 (4)0.222 (2)0.026*
O100.5844 (4)−0.1357 (6)0.1893 (3)0.0634 (14)0.70
H10A0.5706−0.02850.17240.095*
H10B0.6316−0.23400.19450.095*
O110.5872 (10)−0.3060 (14)0.2029 (9)0.0634 (14)0.30
N10.3639 (3)−0.2375 (4)0.0340 (2)0.0309 (7)
H11A0.3562−0.32780.07010.046*
H11B0.4083−0.14820.06330.046*
H11C0.4086−0.2738−0.00760.046*
N20.0128 (3)−0.2744 (4)−0.0842 (2)0.0281 (7)
H22A−0.0222−0.2442−0.03720.042*
H22B−0.0317−0.3677−0.10980.042*
H22C0.0059−0.1828−0.12090.042*
C10.2296 (3)−0.1762 (5)−0.0048 (2)0.0276 (8)
H1A0.2376−0.0727−0.04100.033*
H1B0.1792−0.14140.04060.033*
C20.1563 (3)−0.3220 (5)−0.0585 (2)0.0300 (8)
H2A0.1972−0.3411−0.11010.036*
H2B0.1632−0.4322−0.02540.036*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
In10.01468 (13)0.00975 (12)0.01524 (12)−0.00045 (8)0.00069 (8)−0.00008 (8)
P10.0160 (4)0.0180 (4)0.0139 (4)0.0005 (3)0.0032 (3)−0.0003 (3)
P20.0134 (4)0.0151 (4)0.0162 (4)−0.0004 (3)−0.0022 (3)−0.0006 (3)
O10.0158 (12)0.081 (2)0.0204 (14)0.0028 (12)0.0031 (10)0.0022 (13)
O20.0413 (14)0.0192 (13)0.0237 (13)0.0033 (10)0.0145 (11)−0.0014 (9)
O30.0441 (15)0.0177 (13)0.0230 (14)−0.0017 (10)0.0159 (11)0.0001 (9)
O40.0207 (12)0.0355 (14)0.0144 (12)0.0046 (10)0.0035 (9)−0.0007 (9)
O50.0197 (12)0.0277 (13)0.0193 (12)−0.0008 (9)−0.0070 (9)0.0009 (9)
O60.0204 (11)0.0160 (12)0.0337 (14)0.0022 (9)−0.0077 (10)0.0014 (9)
O70.0203 (11)0.0156 (12)0.0335 (15)−0.0041 (9)−0.0064 (10)−0.0034 (9)
O80.0180 (13)0.068 (2)0.0241 (14)−0.0055 (12)0.0042 (11)−0.0058 (13)
O90.0156 (11)0.0103 (10)0.0279 (13)−0.0003 (8)0.0079 (9)0.0003 (9)
O100.035 (2)0.044 (2)0.119 (4)−0.003 (2)0.037 (2)−0.018 (3)
O110.035 (2)0.044 (2)0.119 (4)−0.003 (2)0.037 (2)−0.018 (3)
N10.0255 (16)0.0401 (19)0.0276 (18)−0.0053 (13)0.0055 (13)0.0052 (13)
N20.0241 (16)0.0328 (17)0.0243 (16)−0.0039 (12)−0.0058 (12)−0.0003 (12)
C10.0253 (18)0.0244 (19)0.032 (2)0.0018 (15)0.0003 (15)−0.0030 (15)
C20.0292 (19)0.0234 (19)0.036 (2)0.0025 (15)−0.0010 (16)−0.0070 (15)

Geometric parameters (Å, °)

In1—O9i2.089 (2)O9—H90.862 (17)
In1—O92.094 (2)O10—O111.293 (12)
In1—O2i2.135 (2)O10—H10A0.8496
In1—O32.148 (2)O10—H10B0.8728
In1—O6i2.154 (2)O11—H10B0.7256
In1—O72.154 (2)N1—C11.466 (4)
P1—O11.510 (3)N1—H11A0.8900
P1—O21.511 (2)N1—H11B0.8900
P1—O31.530 (2)N1—H11C0.8900
P1—O41.579 (2)N2—C21.481 (4)
P2—O51.509 (2)N2—H22A0.8900
P2—O61.519 (2)N2—H22B0.8900
P2—O71.523 (2)N2—H22C0.8900
P2—O81.577 (3)C1—C21.498 (5)
O2—In1ii2.135 (2)C1—H1A0.9700
O4—H40.8200C1—H1B0.9700
O6—In1ii2.154 (2)C2—H2A0.9700
O8—H80.8200C2—H2B0.9700
O9—In1ii2.089 (2)
O9i—In1—O9178.25 (5)P2—O8—H8109.5
O9i—In1—O2i90.18 (9)In1ii—O9—In1127.09 (10)
O9—In1—O2i88.87 (9)In1ii—O9—H9122 (2)
O9i—In1—O389.24 (8)In1—O9—H9111 (2)
O9—In1—O391.66 (8)O11—O10—H10A169.0
O2i—In1—O3178.07 (9)O11—O10—H10B32.4
O9i—In1—O6i90.97 (8)H10A—O10—H10B152.4
O9—In1—O6i87.60 (8)O10—O11—H10B40.1
O2i—In1—O6i92.06 (9)C1—N1—H11A109.5
O3—In1—O6i86.11 (9)C1—N1—H11B109.5
O9i—In1—O789.32 (8)H11A—N1—H11B109.5
O9—In1—O792.14 (8)C1—N1—H11C109.5
O2i—In1—O789.67 (9)H11A—N1—H11C109.5
O3—In1—O792.16 (9)H11B—N1—H11C109.5
O6i—In1—O7178.24 (9)C2—N2—H22A109.5
O1—P1—O2113.55 (15)C2—N2—H22B109.5
O1—P1—O3112.56 (15)H22A—N2—H22B109.5
O2—P1—O3110.60 (13)C2—N2—H22C109.5
O1—P1—O4103.80 (13)H22A—N2—H22C109.5
O2—P1—O4108.44 (13)H22B—N2—H22C109.5
O3—P1—O4107.41 (14)N1—C1—C2110.2 (3)
O5—P2—O6111.58 (13)N1—C1—H1A109.6
O5—P2—O7111.43 (13)C2—C1—H1A109.6
O6—P2—O7110.81 (13)N1—C1—H1B109.6
O5—P2—O8105.63 (14)C2—C1—H1B109.6
O6—P2—O8109.01 (15)H1A—C1—H1B108.1
O7—P2—O8108.16 (14)N2—C2—C1110.5 (3)
P1—O2—In1ii137.89 (14)N2—C2—H2A109.5
P1—O3—In1133.57 (14)C1—C2—H2A109.5
P1—O4—H4109.5N2—C2—H2B109.5
P2—O6—In1ii139.63 (14)C1—C2—H2B109.5
P2—O7—In1139.23 (14)H2A—C2—H2B108.1

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O4—H4···O5iii0.821.782.595 (3)174
O8—H8···O10.821.752.567 (4)172
O9—H9···O100.86 (2)1.93 (2)2.780 (5)170 (3)
O10—H10A···O1iv0.852.443.291 (5)179
O10—H10B···O8v0.872.352.911 (5)122
N1—H11A···O3ii0.892.002.876 (4)168
N1—H11B···O2iv0.892.513.137 (4)128
N1—H11B···O100.892.433.114 (5)133
N1—H11C···O4vi0.892.413.011 (4)125
N1—H11C···O1vi0.891.982.823 (4)158
N2—H22A···O50.891.872.750 (4)170
N2—H22B···O6vii0.892.062.911 (4)160
N2—H22C···O7viii0.892.052.892 (4)158

Symmetry codes: (iii) x+1/2, −y−1/2, z+1/2; (iv) −x+1/2, y+1/2, −z+1/2; (v) x+1, y, z; (ii) −x+1/2, y−1/2, −z+1/2; (vi) x+1/2, −y−1/2, z−1/2; (vii) −x, −y−1, −z; (viii) −x, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2383).

References

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