Silver europium(III) polyphosphate

Abstract

Europium(III) silver polyphosphate, AgEu(PO₃)₄, was prepared by the flux method. The atomic arrangement is built up by infinite (PO₃)_n chains (periodicity of 4) extending along the c axis. These chains are joined to each other by EuO₈ dodeca­hedra. The Ag⁺ cations are located in the voids of this arrangement and are surrounded by five oxygen atoms in a distorted [4+1] coordination.

Related literature

For isotypic AgNd(PO₃)₄, see: Trunov et al. (1990 ▶). For related structures, see: Yamada et al. (1974 ▶); Hashimoto et al. (1991 ▶); Horchani et al. (2003 ▶); Durif (1995 ▶); Averbuch-Pouchot & Bagieu-Beucher (1987 ▶); Férid (2006 ▶).

Experimental

Crystal data

• AgEu(PO₃)₄

• M _r = 575.72

• Monoclinic,

• a = 9.9654 (3) Å

• b = 13.1445 (7) Å

• c = 7.2321 (3) Å

• β = 90.42 (1)°

• V = 947.31 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 9.37 mm⁻¹

• T = 298 (2) K

• 0.19 × 0.18 × 0.17 mm

Data collection

• Nonius KappaCCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.167, T _max = 0.201

• 3371 measured reflections

• 2019 independent reflections

• 1704 reflections with I > 2σ(I)

• R _int = 0.042

Refinement

• R[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 0.109

• S = 1.03

• 2019 reflections

• 164 parameters

• Δρ_max = 2.43 e Å⁻³

• Δρ_min = −2.06 e Å⁻³

Data collection: COLLECT (Nonius, 2001 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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

supplementary crystallographic information

Comment

In the last decades, investigation of the synthesis and characterization of rare earth polyphosphates has gained much attention due to their potential applications in diverse areas such as phosphors and laser materials (Yamada et al., 1974; Hashimoto et al., 1991; Horchani et al., 2003). In aim to study the condensed phosphates of rare earth and monovalent cations of general formula MILn(PO₃)₄ (with MI = monovalent cation)(Durif, 1995), (Ln = Eu, Er, Yb), we have synthesized single crystals of silver europium polyphosphate and investigated its crystalline structure. The atomic arrangement of this structure is characterized by a three-dimensional framework built of (PO₃)_n chains that are formed by corner-sharing of PO₄ tetrahedra. Eu3+ and Ag+ cations alternate in the middle of four such chains with Eu—Ag distances of 3.64 (7) Å (figures 1,3). The EuO₈ dodecahedra are isolated from each other and the distances Eu—O are arranged in interval 2.355 (5)- 2.508 (5)Å (figure 2). The polyphosphate chains display two types of distances, P—O terminal ranging from 1.479 (5) to 1.505 (5)Å and P—O bridging, ranging from 1.585 (5)to 1.609 (5)Å. These distances are comparable with those repoted for other condensed phosphates (Durif, 1995; Averbuch-Pouchot & Bagieu Beucher, 1987; Férid (2006). The structural study reported for silver neodymium polyphosphate AgNd(PO₃)₄ (Trunov et al., 1990) showed that the compound crystallize in the P2₁/n space group and has similar unit cell prameters compared to AgEu(PO₃)₄.

Experimental

Single crystals of AgEu(PO₃)₄ were prepared by flux method. A mixture of Ag₂CO₃ (3 g), EuCl_3.6H₂O (0.5 g) and H₃PO₄(85%, 17 ml), was progressively heated in a vitreous carbon crucible to 473 K for 12 h. The temperature was then raised and kept at 600 K for 16 days after that, the furnance was slowly cooled until the room temperature. The product was washed with boiling water to separate colorless single crystals from phosphoric acid.

Refinement

The highest peak and the deepest hole are located 1.22Å and 0.73 Å, respectively, from Ag and Eu.

Figures

Fig. 1.

: The structural arrangement of AgEu(PO3)4 along a axis.

Fig. 2.

: Projection of EuO8 dodecahedra viewed along [0 0 1] direction.

Fig. 3.

: The sequence of PO4 tetrahedra in AgEu(PO3)4, with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) 1-x, 2-y, 2-z; (ii) 1-x/2, 2-y, 3-z]

Crystal data

AgEu(PO3)4	F(000) = 1064
Mr = 575.72	Dx = 4.037 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 9.9654 (3) Å	θ = 2.4–30.1°
b = 13.1445 (7) Å	µ = 9.37 mm−1
c = 7.2321 (3) Å	T = 298 K
β = 90.42 (1)°	Prism, colorless
V = 947.31 (7) Å3	0.19 × 0.18 × 0.17 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	2019 independent reflections
Radiation source: fine-focus sealed tube	1704 reflections with I > 2σ(I)
graphite	Rint = 0.042
φ and ω scans	θmax = 27.5°, θmin = 3.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.167, Tmax = 0.201	k = −16→15
3371 measured reflections	l = −9→9

Refinement

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)] = 0.042	w = 1/[σ2(Fo2) + (0.0685P)2 + 1.0941P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.109	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 2.42 e Å−3
2019 reflections	Δρmin = −2.06 e Å−3
164 parameters	Extinction correction: SHELXL08 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.00014 (2)

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 (Ų)

	x	y	z	Uiso*/Ueq
Eu	0.52254 (4)	0.78212 (2)	0.51227 (4)	0.01862 (19)
Ag	0.43355 (7)	0.77670 (5)	1.00017 (8)	0.0322 (2)
P1	0.25190 (18)	0.90008 (12)	1.2536 (2)	0.0168 (4)
P2	0.19511 (18)	0.87338 (12)	1.6486 (2)	0.0167 (4)
P3	0.79921 (18)	0.90983 (12)	1.2635 (2)	0.0172 (4)
P4	0.73739 (18)	0.88594 (12)	0.8738 (2)	0.0162 (4)
O1	0.1995 (5)	0.8356 (3)	1.1018 (6)	0.0241 (11)
O2	0.3997 (5)	0.8951 (4)	1.2904 (7)	0.0243 (11)
O3	0.2039 (5)	1.0133 (3)	1.2168 (7)	0.0240 (11)
O4	0.1629 (5)	0.8769 (3)	1.4335 (6)	0.0198 (10)
O5	0.3444 (5)	0.8678 (4)	1.6767 (7)	0.0218 (10)
O6	0.1062 (6)	0.7906 (3)	1.7231 (6)	0.0228 (11)
O7	0.8644 (5)	1.0214 (3)	1.2777 (7)	0.0193 (10)
O8	0.9144 (5)	0.8395 (3)	1.2329 (6)	0.0236 (10)
O9	0.7055 (5)	0.8919 (3)	1.4217 (6)	0.0218 (10)
O10	0.7085 (5)	0.9202 (3)	1.0822 (6)	0.0203 (10)
O11	0.8483 (5)	0.8097 (3)	0.8671 (7)	0.0218 (10)
O12	0.6047 (5)	0.8557 (3)	0.7933 (6)	0.0198 (10)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Eu	0.0183 (3)	0.0189 (2)	0.0186 (2)	−0.00063 (12)	−0.00048 (15)	−0.00108 (12)
Ag	0.0262 (4)	0.0456 (4)	0.0249 (3)	0.0034 (2)	0.0008 (2)	−0.0088 (2)
P1	0.0201 (9)	0.0138 (7)	0.0165 (7)	−0.0001 (6)	0.0005 (6)	0.0001 (6)
P2	0.0173 (9)	0.0155 (8)	0.0173 (8)	0.0007 (6)	−0.0001 (6)	−0.0002 (6)
P3	0.0206 (9)	0.0143 (7)	0.0168 (8)	0.0004 (6)	−0.0017 (6)	−0.0002 (6)
P4	0.0162 (9)	0.0160 (8)	0.0165 (8)	−0.0001 (6)	−0.0020 (6)	−0.0012 (6)
O1	0.034 (3)	0.019 (2)	0.019 (2)	0.004 (2)	−0.002 (2)	−0.0060 (19)
O2	0.023 (3)	0.026 (2)	0.023 (2)	0.000 (2)	−0.002 (2)	−0.002 (2)
O3	0.028 (3)	0.016 (2)	0.028 (3)	0.007 (2)	−0.004 (2)	0.0052 (19)
O4	0.019 (3)	0.025 (2)	0.016 (2)	0.0000 (19)	−0.0004 (18)	0.0039 (18)
O5	0.017 (3)	0.024 (2)	0.025 (2)	0.0021 (19)	−0.003 (2)	−0.007 (2)
O6	0.029 (3)	0.021 (2)	0.018 (2)	−0.005 (2)	0.000 (2)	0.0038 (18)
O7	0.013 (2)	0.014 (2)	0.031 (3)	−0.0005 (18)	0.0063 (19)	−0.003 (2)
O8	0.027 (3)	0.018 (2)	0.026 (2)	0.003 (2)	−0.001 (2)	−0.002 (2)
O9	0.027 (3)	0.023 (2)	0.016 (2)	−0.004 (2)	0.0040 (19)	−0.0026 (18)
O10	0.017 (2)	0.020 (2)	0.024 (2)	0.0009 (19)	−0.0016 (18)	−0.0023 (19)
O11	0.022 (3)	0.018 (2)	0.025 (2)	0.007 (2)	−0.001 (2)	0.002 (2)
O12	0.023 (3)	0.021 (2)	0.015 (2)	0.005 (2)	−0.0053 (19)	−0.0005 (18)

Geometric parameters (Å, °)

Eu—O11i	2.355 (5)	P2—O4	1.587 (5)
Eu—O12	2.390 (4)	P2—O7vi	1.598 (5)
Eu—O9ii	2.420 (5)	P3—O8	1.492 (5)
Eu—O5ii	2.422 (5)	P3—O9	1.500 (5)
Eu—O1iii	2.430 (5)	P3—O10	1.593 (5)
Eu—O6iv	2.451 (5)	P3—O7	1.607 (5)
Eu—O2ii	2.500 (5)	P4—O11	1.493 (5)
Eu—O8i	2.508 (5)	P4—O12	1.495 (5)
Eu—Ag	3.6453 (7)	P4—O3vii	1.592 (5)
Eu—Agii	3.8025 (7)	P4—O10	1.602 (5)
Ag—O8i	2.470 (5)	O1—Euviii	2.430 (5)
Ag—O12	2.503 (5)	O2—Euv	2.500 (5)
Ag—O6iii	2.511 (5)	O3—P4vii	1.592 (5)
Ag—O1	2.570 (5)	O5—Euv	2.422 (5)
Ag—Euv	3.8025 (7)	O6—Euix	2.451 (5)
P1—O1	1.479 (5)	O6—Agviii	2.511 (5)
P1—O2	1.496 (6)	O7—P2vi	1.598 (5)
P1—O3	1.585 (5)	O8—Agx	2.470 (5)
P1—O4	1.609 (5)	O8—Eux	2.508 (5)
P2—O5	1.502 (5)	O9—Euv	2.420 (5)
P2—O6	1.505 (5)	O11—Eux	2.355 (5)
O11i—Eu—O12	146.43 (17)	O12—Ag—Eu	40.66 (10)
O11i—Eu—O9ii	137.70 (16)	O6iii—Ag—Eu	117.27 (12)
O12—Eu—O9ii	74.62 (16)	O1—Ag—Eu	119.92 (10)
O11i—Eu—O5ii	85.21 (16)	O8i—Ag—Euv	142.17 (11)
O12—Eu—O5ii	69.01 (16)	O12—Ag—Euv	114.81 (10)
O9ii—Eu—O5ii	114.34 (16)	O6iii—Ag—Euv	39.40 (11)
O11i—Eu—O1iii	108.89 (17)	O1—Ag—Euv	85.49 (10)
O12—Eu—O1iii	77.74 (15)	Eu—Ag—Euv	152.34 (2)
O9ii—Eu—O1iii	84.55 (16)	O1—P1—O2	116.6 (3)
O5ii—Eu—O1iii	134.29 (16)	O1—P1—O3	108.0 (3)
O11i—Eu—O6iv	70.99 (18)	O2—P1—O3	111.5 (3)
O12—Eu—O6iv	140.07 (18)	O1—P1—O4	107.3 (3)
O9ii—Eu—O6iv	74.93 (16)	O2—P1—O4	113.3 (3)
O5ii—Eu—O6iv	148.82 (17)	O3—P1—O4	98.4 (3)
O1iii—Eu—O6iv	74.24 (16)	O5—P2—O6	120.1 (3)
O11i—Eu—O2ii	70.26 (16)	O5—P2—O4	109.1 (3)
O12—Eu—O2ii	117.94 (15)	O6—P2—O4	104.9 (3)
O9ii—Eu—O2ii	80.70 (17)	O5—P2—O7vi	111.5 (3)
O5ii—Eu—O2ii	71.45 (17)	O6—P2—O7vi	106.6 (3)
O1iii—Eu—O2ii	154.17 (16)	O4—P2—O7vi	103.2 (3)
O6iv—Eu—O2ii	81.49 (16)	O8—P3—O9	120.0 (3)
O11i—Eu—O8i	68.78 (16)	O8—P3—O10	111.3 (3)
O12—Eu—O8i	82.12 (15)	O9—P3—O10	106.8 (3)
O9ii—Eu—O8i	151.72 (16)	O8—P3—O7	105.3 (3)
O5ii—Eu—O8i	70.38 (16)	O9—P3—O7	110.4 (3)
O1iii—Eu—O8i	74.87 (16)	O10—P3—O7	101.6 (3)
O6iv—Eu—O8i	116.40 (15)	O11—P4—O12	117.5 (3)
O2ii—Eu—O8i	125.20 (17)	O11—P4—O3vii	105.7 (3)
O11i—Eu—Ag	103.74 (12)	O12—P4—O3vii	112.8 (3)
O12—Eu—Ag	43.03 (12)	O11—P4—O10	111.0 (3)
O9ii—Eu—Ag	117.57 (11)	O12—P4—O10	106.1 (3)
O5ii—Eu—Ag	49.41 (11)	O3vii—P4—O10	102.9 (3)
O1iii—Eu—Ag	84.88 (11)	P1—O1—Euviii	144.5 (3)
O6iv—Eu—Ag	154.81 (10)	P1—O1—Ag	93.9 (3)
O2ii—Eu—Ag	120.77 (12)	Euviii—O1—Ag	112.98 (17)
O8i—Eu—Ag	42.51 (10)	P1—O2—Euv	128.1 (3)
O11i—Eu—Agii	52.44 (12)	P1—O3—P4vii	137.7 (4)
O12—Eu—Agii	155.75 (11)	P2—O4—P1	133.6 (3)
O9ii—Eu—Agii	85.32 (11)	P2—O5—Euv	133.2 (3)
O5ii—Eu—Agii	108.69 (11)	P2—O6—Euix	142.4 (3)
O1iii—Eu—Agii	114.28 (11)	P2—O6—Agviii	115.3 (2)
O6iv—Eu—Agii	40.55 (12)	Euix—O6—Agviii	100.06 (18)
O2ii—Eu—Agii	43.64 (11)	P2vi—O7—P3	131.3 (3)
O8i—Eu—Agii	120.64 (11)	P3—O8—Agx	108.8 (3)
Ag—Eu—Agii	152.34 (2)	P3—O8—Eux	145.5 (3)
O8i—Ag—O12	80.67 (15)	Agx—O8—Eux	94.16 (15)
O8i—Ag—O6iii	109.46 (15)	P3—O9—Euv	140.7 (3)
O12—Ag—O6iii	93.64 (16)	P3—O10—P4	130.2 (3)
O8i—Ag—O1	110.19 (16)	P4—O11—Eux	150.8 (3)
O12—Ag—O1	132.06 (14)	P4—O12—Eu	137.3 (3)
O6iii—Ag—O1	122.79 (16)	P4—O12—Ag	118.8 (2)
O8i—Ag—Eu	43.33 (11)	Eu—O12—Ag	96.31 (16)

Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) x, y, z−1; (iii) x+1/2, −y+3/2, z−1/2; (iv) x+1/2, −y+3/2, z−3/2; (v) x, y, z+1; (vi) −x+1, −y+2, −z+3; (vii) −x+1, −y+2, −z+2; (viii) x−1/2, −y+3/2, z+1/2; (ix) x−1/2, −y+3/2, z+3/2; (x) x+1/2, −y+3/2, z+1/2.