Ammonium diphosphitoindate(III).

The crystal structure of the title compound, NH4[In(HPO3)2], is built up from In(III) cations (site symmetry 3m.) adopting an octa-hedral environment and two different phosphite anions (each with site symmetry 3m.) exhibiting a triangular-pyramidal geometry. Each InO6 octa-hedron shares its six apices with hydrogen phosphite groups. Reciprocally, each HPO3 group shares all its O atoms with three different metal cations, leading to [In(HPO3)2](-) layers which propagate in the ab plane. The ammonium cation likewise has site symmetry 3m.. In the structure, the cations are located between the [In(HPO3)2](-) layers of the host framework. The sheets are held together by hydrogen bonds formed between the NH4 (+) cations and the O atoms of the framework.

Related literature

For general background, see: Natarajan & Mandal (2008 ▶); Marcos et al. (1993 ▶). For related structures, see: Li et al. (2013 ▶); Hamchaoui et al. (2013 ▶); Giester (2000 ▶); Graeber & Rosen­zweig (1971 ▶). For potential applications of open-framework transition metal phosphates, see: Cheetham et al. (1999 ▶). For the synthesis of the first organically templated vanadium phosphite with an open framework, see: Bonavia et al. (1995 ▶). Structures of purely inorganic phosphite compounds have been evidenced with magnetic and non-magnetic cations (Marcos et al., 1993 ▶; Morris et al., 1994 ▶; Orive et al., 2011 ▶) while closely related structures can be obtained by replacing organic cations by inorganic ones as observed in the AMn3(HPO3)4 system [A = en (Fernández et al., 2000 ▶); A = K (Hamchaoui et al., 2009 ▶)].

Experimental

Crystal data

NH4[In(HPO3)2]

M = 292.82

Hexagonal,

a = 5.4705 (1) Å

c = 13.0895 (4) Å

V = 339.24 (1) Å3

Z = 2

Mo Kα radiation

μ = 3.93 mm−1

T = 293 K

0.10 × 0.05 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2002) ▶ T min = 0.66, T max = 0.92

7774 measured reflections

962 independent reflections

912 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.017

wR(F 2) = 0.041

S = 1.26

962 reflections

30 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.51 e Å−3

Δρmin = −1.39 e Å−3

Absolute structure: Flack (1983 ▶), 459 Friedel pairs

Flack parameter: −0.01 (2)

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DIRAX/LSQ (Duisenberg, 1992 ▶); data reduction: EVALCCD (Duisenberg, 1998 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681300771X/ru2050sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681300771X/ru2050Isup2.hkl

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

NH4[In(HPO3)2]	Dx = 2.867 Mg m−3
Mr = 292.82	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63mc	Cell parameters from 1590 reflections
a = 5.4705 (1) Å	θ = 2.9–42.1°
c = 13.0895 (4) Å	µ = 3.93 mm−1
V = 339.24 (1) Å3	T = 293 K
Z = 2	Block, colourless
F(000) = 280	0.1 × 0.05 × 0.02 mm

Nonius KappaCCD diffractometer	962 independent reflections
Radiation source: fine-focus sealed tube	912 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
CCD rotation images, thick slices scans	θmax = 42.0°, θmin = 4.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −10→9
Tmin = 0.66, Tmax = 0.92	k = −10→9
7774 measured reflections	l = −24→24

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.017	w = 1/[σ2(Fo2) + (0.0183P)2 + 0.0737P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.041	(Δ/σ)max = 0.003
S = 1.26	Δρmax = 0.51 e Å−3
962 reflections	Δρmin = −1.39 e Å−3
30 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
5 restraints	Extinction coefficient: 0.092 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 459 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: −0.01 (2)

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.

	x	y	z	Uiso*/Ueq
In1	−0.3333	0.3333	−0.5985	0.01029 (5)
P1	−0.6667	−0.3333	−0.47231 (7)	0.00954 (13)
P2	0.0000	0.0000	−0.65957 (6)	0.00968 (14)
O1	−0.15240 (16)	0.15240 (16)	−0.69716 (14)	0.0201 (3)
O2	−0.5126 (2)	−0.0252 (4)	−0.5013 (2)	0.0276 (4)
N1	−0.6667	−0.3333	−0.8024 (3)	0.0222 (7)
HP1	−0.6667	−0.3333	−0.378 (9)	0.027*
HP2	0.0000	0.0000	−0.553 (6)	0.027*
HN1	−0.5809 (18)	−0.162 (4)	−0.782 (3)	0.027*
HN2	−0.6667	−0.3333	−0.8705 (8)	0.027*

	U11	U22	U33	U12	U13	U23
In1	0.00741 (6)	0.00741 (6)	0.01606 (8)	0.00371 (3)	0.000	0.000
P1	0.00840 (19)	0.00840 (19)	0.0118 (3)	0.00420 (9)	0.000	0.000
P2	0.00826 (19)	0.00826 (19)	0.0125 (4)	0.00413 (9)	0.000	0.000
O1	0.0275 (7)	0.0275 (7)	0.0188 (6)	0.0240 (8)	−0.0001 (2)	0.0001 (2)
O2	0.0282 (7)	0.0120 (7)	0.0374 (9)	0.0060 (4)	0.0053 (4)	0.0106 (7)
N1	0.0232 (10)	0.0232 (10)	0.0203 (16)	0.0116 (5)	0.000	0.000

In1—O2i	2.1226 (19)	P1—O2iii	1.5082 (18)
In1—O2	2.1226 (19)	P1—O2	1.5082 (18)
In1—O2ii	2.1226 (19)	P1—O2iv	1.5082 (18)
In1—O1	2.1461 (17)	P2—O1v	1.5255 (16)
In1—O1ii	2.1461 (17)	P2—O1vi	1.5255 (16)
In1—O1i	2.1461 (17)	P2—O1	1.5255 (15)
O2i—In1—O2	87.75 (10)	O2ii—In1—O1i	92.35 (6)
O2i—In1—O2ii	87.75 (10)	O1—In1—O1i	87.55 (7)
O2—In1—O2ii	87.75 (10)	O1ii—In1—O1i	87.55 (7)
O2i—In1—O1	92.35 (6)	O2iii—P1—O2	113.89 (9)
O2—In1—O1	92.35 (6)	O2iii—P1—O2iv	113.89 (9)
O2ii—In1—O1	179.86 (9)	O2—P1—O2iv	113.89 (9)
O2i—In1—O1ii	179.86 (9)	O1v—P2—O1vi	110.12 (7)
O2—In1—O1ii	92.35 (6)	O1v—P2—O1	110.12 (7)
O2ii—In1—O1ii	92.35 (6)	O1vi—P2—O1	110.12 (7)
O1—In1—O1ii	87.55 (7)	P2—O1—In1	124.21 (11)
O2i—In1—O1i	92.35 (6)	P1—O2—In1	157.74 (17)
O2—In1—O1i	179.86 (10)

D—H···A	D—H	H···A	D···A	D—H···A
N1—HN1···O1	0.86 (2)	2.38 (2)	3.066 (2)	138 (2)
N1—HN1···O1ii	0.86 (2)	2.38 (2)	3.066 (2)	138 (2)
N1—HN2···O2vii	0.89 (1)	2.41 (1)	3.109 (4)	135 (1)
N1—HN2···O2viii	0.89 (1)	2.41 (1)	3.109 (4)	135 (1)
N1—HN2···O2ix	0.89 (1)	2.41 (1)	3.109 (4)	135 (1)
N1—HN2···O2x	0.89 (1)	2.41 (1)	3.109 (4)	135 (1)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—HN1⋯O1	0.86 (2)	2.38 (2)	3.066 (2)	138 (2)
N1—HN1⋯O1i	0.86 (2)	2.38 (2)	3.066 (2)	138 (2)
N1—HN2⋯O2ii	0.89 (1)	2.41 (1)	3.109 (4)	135 (1)
N1—HN2⋯O2iii	0.89 (1)	2.41 (1)	3.109 (4)	135 (1)
N1—HN2⋯O2iv	0.89 (1)	2.41 (1)	3.109 (4)	135 (1)
N1—HN2⋯O2v	0.89 (1)	2.41 (1)	3.109 (4)	135 (1)

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