Redetermination of AgPO(3).

Single crystals of silver(I) polyphosphate(V), AgPO(3), were prepared via a phospho-ric acid melt method using a solution of Ag(3)PO(4) in H(3)PO(4). In comparison with the previous study based on single-crystal Weissenberg photographs [Jost (1961 ▶). Acta Cryst. 14, 779-784], the results were mainly confirmed, but with much higher precision and with all displacement parameters refined anisotropically. The structure is built up from two types of distorted edge- and corner-sharing [AgO(5)] polyhedra, giving rise to multidirectional ribbons, and from two types of PO(4) tetra-hedra linked into meandering chains (PO(3))(n) spreading parallel to the b axis with a repeat unit of four tetra-hedra. The calculated bond-valence sum value of one of the two Ag(I) ions indicates a significant strain of the structure.

Related literature

For a previous crystallographic study of AgPO3, see: Jost (1961 ▶). For the isotypic A-form of the Kurrol salt NaPO3, see: McAdam et al. (1968 ▶). Properties of glassy silver phosphates have been reported by Portier et al. (1990 ▶) and Novita et al. (2009 ▶). For long-chain polyphosphates AgM III(PO3)4 (M III = La, Gd, Eu), see: El Masloumi et al. (2005 ▶); Naıli et al. (2006 ▶); Ayadi et al. (2009 ▶). For AgM II (PO3)3 (M II = Mg, Zn, Ba), see: Belharouak et al. (1999 ▶); for AgM I(PO3)2 (M I = K, Rb, Cs, Tl), see: Averbuch-Pouchot (1993 ▶). For background to the bond-valence method, see: Brown & Altermatt (1985 ▶).

Experimental

Crystal data

AgPO3

M = 186.84

Monoclinic,

a = 11.9335 (3) Å

b = 6.0667 (1) Å

c = 7.3278 (2) Å

β = 93.491 (2)°

V = 529.53 (2) Å3

Z = 8

Mo Kα radiation

μ = 7.96 mm−1

T = 293 K

0.10 × 0.08 × 0.04 mm

Data collection

Oxford Diffraction Xcalibur-3 CCD diffractometer

Absorption correction: multi-scan (Blessing, 1995 ▶) T min = 0.465, T max = 0.733

22720 measured reflections

2333 independent reflections

2208 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.058

S = 1.08

2333 reflections

92 parameters

Δρmax = 1.43 e Å−3

Δρmin = −1.86 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2006 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811003977/wm2454sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811003977/wm2454Isup2.hkl

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

AgPO3	F(000) = 688
Mr = 186.84	Dx = 4.687 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 22720 reflections
a = 11.9335 (3) Å	θ = 3.2–35.0°
b = 6.0667 (1) Å	µ = 7.96 mm−1
c = 7.3278 (2) Å	T = 293 K
β = 93.491 (2)°	Prism, colorless
V = 529.53 (2) Å3	0.10 × 0.08 × 0.04 mm
Z = 8

Oxford Diffraction Xcalibur-3 CCD diffractometer	2333 independent reflections
Radiation source: fine-focus sealed tube	2208 reflections with I > 2σ(I)
graphite	Rint = 0.042
φ and ω scans	θmax = 35°, θmin = 3.2°
Absorption correction: multi-scan (Blessing, 1995)	h = −19→19
Tmin = 0.465, Tmax = 0.733	k = −9→9
22720 measured reflections	l = −11→11

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024	w = 1/[σ2(Fo2) + (0.0212P)2 + 1.7313P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.058	(Δ/σ)max = 0.001
S = 1.08	Δρmax = 1.43 e Å−3
2333 reflections	Δρmin = −1.86 e Å−3
92 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
0 restraints	Extinction coefficient: 0.0034 (3)

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
Ag1	0.127313 (18)	0.33468 (3)	0.61230 (3)	0.02461 (6)
Ag2	0.03023 (2)	0.89757 (4)	0.77035 (3)	0.02748 (6)
P1	0.22766 (5)	0.81768 (10)	0.48624 (7)	0.01372 (10)
P2	0.11152 (5)	0.61417 (10)	0.18002 (8)	0.01331 (10)
O1	0.25346 (18)	0.6554 (3)	0.6355 (3)	0.0241 (4)
O2	0.22388 (14)	0.6980 (3)	0.2909 (2)	0.0179 (3)
O3	0.12509 (15)	0.9578 (3)	0.4956 (3)	0.0218 (3)
O4	0.16402 (14)	0.4679 (3)	0.0265 (2)	0.0169 (3)
O5	0.05294 (17)	0.7997 (3)	0.0843 (3)	0.0234 (3)
O6	0.04724 (16)	0.4744 (3)	0.3047 (3)	0.0220 (3)

	U11	U22	U33	U12	U13	U23
Ag1	0.02707 (10)	0.02043 (10)	0.02611 (10)	0.00056 (7)	−0.00023 (7)	0.00252 (7)
Ag2	0.03883 (12)	0.02340 (11)	0.02121 (9)	0.00423 (8)	0.01011 (8)	0.00068 (7)
P1	0.0138 (2)	0.0153 (2)	0.0121 (2)	−0.00206 (17)	0.00169 (16)	0.00000 (17)
P2	0.0124 (2)	0.0141 (2)	0.0134 (2)	0.00133 (17)	0.00096 (16)	−0.00069 (17)
O1	0.0312 (9)	0.0223 (9)	0.0183 (7)	−0.0081 (7)	−0.0021 (7)	0.0064 (6)
O2	0.0155 (6)	0.0225 (8)	0.0157 (6)	−0.0010 (6)	0.0008 (5)	−0.0059 (6)
O3	0.0169 (7)	0.0268 (9)	0.0220 (8)	0.0031 (6)	0.0041 (6)	−0.0047 (7)
O4	0.0161 (6)	0.0200 (8)	0.0145 (6)	0.0058 (6)	0.0000 (5)	−0.0042 (5)
O5	0.0278 (9)	0.0208 (8)	0.0211 (8)	0.0108 (7)	−0.0020 (6)	0.0000 (6)
O6	0.0218 (8)	0.0243 (9)	0.0204 (7)	−0.0050 (7)	0.0061 (6)	0.0000 (7)

Ag1—O3i	2.441 (2)	P1—O4vii	1.5889 (17)
Ag1—O1	2.460 (2)	P1—O2	1.6033 (17)
Ag1—O6ii	2.491 (2)	P2—O5	1.479 (2)
Ag1—O1iii	2.511 (2)	P2—O6	1.4924 (19)
Ag1—O6	2.540 (2)	P2—O4	1.5909 (17)
Ag1—Ag2i	3.1431 (3)	P2—O2	1.6074 (18)
Ag2—O5iv	2.3708 (19)	O1—Ag1viii	2.511 (2)
Ag2—O5v	2.3756 (19)	O3—Ag1vi	2.441 (2)
Ag2—O3	2.3968 (19)	O4—P1ix	1.5889 (17)
Ag2—O6ii	2.487 (2)	O5—Ag2iv	2.3708 (19)
Ag2—O3iv	2.750 (2)	O5—Ag2x	2.3756 (19)
Ag2—Ag1vi	3.1431 (3)	O6—Ag2ii	2.487 (2)
P1—O1	1.490 (2)	O6—Ag1ii	2.491 (2)
P1—O3	1.4952 (19)
O3i—Ag1—O1	139.36 (7)	O3—P1—O4vii	110.36 (11)
O3i—Ag1—O6ii	121.99 (6)	O1—P1—O2	110.46 (11)
O1—Ag1—O6ii	97.63 (7)	O3—P1—O2	108.66 (10)
O3i—Ag1—O1iii	81.11 (6)	O4vii—P1—O2	100.72 (9)
O1—Ag1—O1iii	88.56 (4)	O5—P2—O6	118.48 (12)
O6ii—Ag1—O1iii	117.80 (6)	O5—P2—O4	106.52 (10)
O3i—Ag1—O6	90.36 (7)	O6—P2—O4	110.79 (11)
O1—Ag1—O6	89.59 (6)	O5—P2—O2	110.76 (12)
O6ii—Ag1—O6	77.68 (6)	O6—P2—O2	108.33 (10)
O1iii—Ag1—O6	164.51 (6)	O4—P2—O2	100.46 (9)
O3i—Ag1—Ag2i	48.87 (5)	P1—O1—Ag1	111.96 (11)
O1—Ag1—Ag2i	151.61 (4)	P1—O1—Ag1viii	109.67 (10)
O6ii—Ag1—Ag2i	88.27 (5)	Ag1—O1—Ag1viii	135.28 (8)
O1iii—Ag1—Ag2i	64.42 (5)	P1—O2—P2	124.88 (11)
O6—Ag1—Ag2i	118.78 (4)	P1—O3—Ag2	112.45 (11)
O5iv—Ag2—O5v	77.57 (7)	P1—O3—Ag1vi	123.86 (11)
O5iv—Ag2—O3	119.43 (7)	Ag2—O3—Ag1vi	81.04 (6)
O5v—Ag2—O3	145.04 (7)	P1ix—O4—P2	135.91 (11)
O5iv—Ag2—O6ii	129.94 (7)	P2—O5—Ag2iv	125.12 (11)
O5v—Ag2—O6ii	90.36 (7)	P2—O5—Ag2x	132.23 (11)
O3—Ag2—O6ii	98.10 (6)	Ag2iv—O5—Ag2x	102.43 (7)
O5iv—Ag2—Ag1vi	71.68 (5)	P2—O6—Ag2ii	125.33 (11)
O5v—Ag2—Ag1vi	123.01 (5)	P2—O6—Ag1ii	110.73 (11)
O3—Ag2—Ag1vi	50.09 (5)	Ag2ii—O6—Ag1ii	99.83 (6)
O6ii—Ag2—Ag1vi	145.52 (4)	P2—O6—Ag1	123.59 (11)
O1—P1—O3	118.36 (12)	Ag2ii—O6—Ag1	90.46 (7)
O1—P1—O4vii	106.84 (10)	Ag1ii—O6—Ag1	102.32 (6)

Ag1—O3i	2.441 (2)
Ag1—O1	2.460 (2)
Ag1—O6ii	2.491 (2)
Ag1—O1iii	2.511 (2)
Ag1—O6	2.540 (2)
Ag2—O5iv	2.3708 (19)
Ag2—O5v	2.3756 (19)
Ag2—O3	2.3968 (19)
Ag2—O6ii	2.487 (2)
Ag2—O3iv	2.750 (2)
P1—O1	1.490 (2)
P1—O3	1.4952 (19)
P1—O4vi	1.5889 (17)
P1—O2	1.6033 (17)
P2—O5	1.479 (2)
P2—O6	1.4924 (19)
P2—O4	1.5909 (17)
P2—O2	1.6074 (18)

P1—O2—P2	124.88 (11)
P1vii—O4—P2	135.91 (11)

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