Literature DB >> 21201835

A quaternary germanium(II) phosphate, Na[Ge(4)(PO(4))(3)].

Abstract

A new germanium(II) phosphate, sodium tetra-germanium tris-(phosphate), Na[Ge(4)(PO(4))(3)], has been synthesized by a solid-state reaction. The compound is isotypic with A[Sn(4)(PO(4))(3)] (A = Na, K, NH(4)). It features a [Ge(4)(PO(4))(3)](-) framework made up of GeO(3) pyramids and PO(4) tetra-hedra, which are linked by shared corners, yielding a three-dimensional structure. The crystal studied showed partial inversion twinning.

Entities: Chemical Disease Species

Year: 2008 PMID： 21201835 PMCID： PMC2960825 DOI： 10.1107/S1600536808003231

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

Open–framework series of isotypic tin(II) phosphates with general formula A[Sn4(PO4)3] (A = Na, K, NH4) were synthesized by hydrothermal methods (Ayyappan et al., 2000 ▶; Bontchev & Moore, 2004 ▶; Deng et al., 2004 ▶; Mao et al., 2004 ▶). For related literature, see: Brown & Altermatt (1985 ▶); Cheetham et al. (1999 ▶); Weakley & Watt (1979 ▶).

Experimental

Crystal data

Na[Ge4(PO4)3] M = 598.26 Trigonal, a = 9.377 (8) Å c = 23.48 (3) Å V = 1788 (3) Å3 Z = 6 Mo Kα radiation μ = 10.49 mm−1 T = 298 (2) K 0.2 × 0.13 × 0.1 mm

Data collection

Bruker SMART CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.488, T max = 1 (expected range = 0.171–0.350) 2164 measured reflections 639 independent reflections 567 reflections with I > 2σ(I) R int = 0.068

Refinement

R[F 2 > 2σ(F 2)] = 0.058 wR(F 2) = 0.133 S = 1.09 639 reflections 62 parameters 1 restraint Δρmax = 1.71 e Å−3 Δρmin = −1.06 e Å−3 Absolute structure: Flack (1983 ▶), 146 Friedel pairs Flack parameter: 0.23 (8) Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ATOMS (Dowty, 2005 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶). Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808003231/fi2055sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536808003231/fi2055Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Na[Ge₄(PO₄)₃]	Z = 6
M_r = 598.26	F₀₀₀ = 1680
Trigonal, R3c	D_x = 3.334 Mg m⁻³
Hall symbol: R 3 -2" c	Mo Kα radiation λ = 0.71073 Å
a = 9.377 (8) Å	Cell parameters from 2164 reflections
b = 9.377 (8) Å	θ = 3.1–28.3º
c = 23.48 (3) Å	µ = 10.49 mm⁻¹
α = 90º	T = 298 (2) K
β = 90º	Rod, colourless
γ = 120º	0.2 × 0.13 × 0.1 mm
V = 1788 (3) Å³

Bruker SMART CCD area-detector diffractometer	567 reflections with I > 2σ(I)
Monochromator: graphite	R_int = 0.068
T = 298(2) K	θ_max = 28.3º
φ and ω scans	θ_min = 3.1º
Absorption correction: multi-scan(SADABS; Bruker, 2000)	h = −11→6
T_min = 0.488, T_max = 1	k = −12→10
2164 measured reflections	l = −14→31
639 independent reflections

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.08P)²] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.058	(Δ/σ)_max = 0.017
wR(F²) = 0.133	Δρ_max = 1.71 e Å⁻³
S = 1.09	Δρ_min = −1.06 e Å⁻³
639 reflections	Extinction correction: none
62 parameters	Absolute structure: Flack (1983), 146 Friedel pairs
1 restraint	Flack parameter: 0.23 (8)
Primary atom site location: structure-invariant direct methods

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	U_iso*/U_eq
Ge1	1.0000	1.0000	0.07489 (10)	0.0243 (6)
Ge2	1.41201 (19)	1.47337 (17)	0.10322 (6)	0.0214 (4)
P1	1.3317 (4)	1.1233 (4)	0.14139 (17)	0.0190 (7)
Na1	0.6667	0.3333	0.0506 (4)	0.025 (2)
O1	1.4071 (13)	1.2667 (13)	0.0985 (4)	0.024 (2)
O2	1.1603 (13)	0.9917 (13)	0.1226 (5)	0.032 (2)
O3	1.6040 (13)	1.5600 (13)	0.1466 (4)	0.027 (2)
O4	1.5371 (12)	1.5216 (13)	0.0335 (4)	0.026 (2)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ge1	0.0271 (9)	0.0271 (9)	0.0187 (11)	0.0136 (4)	0.000	0.000
Ge2	0.0170 (8)	0.0212 (8)	0.0242 (6)	0.0083 (6)	−0.0022 (5)	−0.0022 (6)
P1	0.0169 (17)	0.0186 (17)	0.0205 (14)	0.0082 (14)	0.0026 (12)	0.0008 (12)
Na1	0.025 (3)	0.025 (3)	0.026 (5)	0.0125 (16)	0.000	0.000
O1	0.025 (5)	0.027 (6)	0.019 (4)	0.012 (5)	−0.005 (4)	0.000 (4)
O2	0.019 (5)	0.031 (6)	0.050 (6)	0.016 (5)	0.002 (4)	0.010 (5)
O3	0.027 (6)	0.028 (5)	0.020 (4)	0.009 (5)	0.000 (4)	−0.004 (4)
O4	0.018 (5)	0.024 (6)	0.019 (4)	−0.001 (4)	0.002 (4)	0.008 (4)

Ge1—O2	1.908 (10)	Na1—O1^viii	2.462 (11)
Ge1—O2ⁱ	1.908 (10)	Na1—O4^vii	2.627 (11)
Ge1—O2ⁱⁱ	1.908 (10)	Na1—O4ⁱⁱ	2.627 (11)
Ge1—Na1ⁱⁱⁱ	3.343 (11)	Na1—O4^viii	2.627 (11)
Ge2—O3	1.864 (10)	Na1—O2^ix	2.705 (13)
Ge2—O1	1.918 (11)	Na1—O2^x	2.705 (13)
Ge2—O4	1.931 (10)	Na1—O2^xi	2.705 (13)
Ge2—Na1^iv	3.477 (5)	Na1—P1^ix	3.254 (7)
P1—O2	1.522 (12)	Na1—P1^x	3.254 (7)
P1—O3^v	1.534 (11)	Na1—P1^xi	3.254 (7)
P1—O1	1.540 (11)	O1—Na1^iv	2.462 (11)
P1—O4^vi	1.540 (9)	O2—Na1ⁱⁱⁱ	2.705 (13)
P1—Na1ⁱⁱⁱ	3.254 (7)	O3—P1^xii	1.534 (11)
Na1—O1^vii	2.462 (11)	O4—P1^xiii	1.540 (9)
Na1—O1ⁱⁱ	2.462 (11)	O4—Na1^iv	2.627 (11)

O2—Ge1—O2ⁱ	89.0 (5)	O2^ix—Na1—O2^x	59.2 (4)
O2—Ge1—O2ⁱⁱ	89.0 (5)	O1^vii—Na1—O2^xi	135.5 (4)
O2ⁱ—Ge1—O2ⁱⁱ	89.0 (5)	O1ⁱⁱ—Na1—O2^xi	122.3 (4)
O2—Ge1—Na1ⁱⁱⁱ	54.0 (3)	O1^viii—Na1—O2^xi	83.0 (3)
O2ⁱ—Ge1—Na1ⁱⁱⁱ	54.0 (3)	O4^vii—Na1—O2^xi	77.9 (4)
O2ⁱⁱ—Ge1—Na1ⁱⁱⁱ	54.0 (3)	O4ⁱⁱ—Na1—O2^xi	113.5 (4)
O3—Ge2—O1	90.1 (5)	O4^viii—Na1—O2^xi	55.5 (3)
O3—Ge2—O4	91.2 (4)	O2^ix—Na1—O2^xi	59.2 (4)
O1—Ge2—O4	83.8 (4)	O2^x—Na1—O2^xi	59.2 (4)
O3—Ge2—Na1^iv	70.3 (3)	O1^vii—Na1—P1^ix	69.3 (2)
O1—Ge2—Na1^iv	43.3 (3)	O1ⁱⁱ—Na1—P1^ix	158.4 (3)
O4—Ge2—Na1^iv	48.4 (3)	O1^viii—Na1—P1^ix	100.0 (3)
O2—P1—O3^v	108.5 (6)	O4^vii—Na1—P1^ix	27.8 (2)
O2—P1—O1	110.8 (6)	O4ⁱⁱ—Na1—P1^ix	97.9 (3)
O3^v—P1—O1	110.5 (6)	O4^viii—Na1—P1^ix	119.8 (3)
O2—P1—O4^vi	108.4 (6)	O2^ix—Na1—P1^ix	27.7 (2)
O3^v—P1—O4^vi	109.1 (6)	O2^x—Na1—P1^ix	86.4 (3)
O1—P1—O4^vi	109.5 (6)	O2^xi—Na1—P1^ix	66.4 (3)
O2—P1—Na1ⁱⁱⁱ	55.7 (4)	O1^vii—Na1—P1^x	100.0 (3)
O3^v—P1—Na1ⁱⁱⁱ	122.1 (4)	O1ⁱⁱ—Na1—P1^x	69.3 (2)
O1—P1—Na1ⁱⁱⁱ	127.4 (4)	O1^viii—Na1—P1^x	158.4 (3)
O4^vi—P1—Na1ⁱⁱⁱ	52.8 (4)	O4^vii—Na1—P1^x	119.8 (3)
O1^vii—Na1—O1ⁱⁱ	100.8 (4)	O4ⁱⁱ—Na1—P1^x	27.8 (2)
O1^vii—Na1—O1^viii	100.8 (4)	O4^viii—Na1—P1^x	97.9 (3)
O1ⁱⁱ—Na1—O1^viii	100.8 (4)	O2^ix—Na1—P1^x	66.4 (3)
O1^vii—Na1—O4^vii	60.6 (3)	O2^x—Na1—P1^x	27.7 (2)
O1ⁱⁱ—Na1—O4^vii	159.5 (5)	O2^xi—Na1—P1^x	86.4 (3)
O1^viii—Na1—O4^vii	76.3 (3)	P1^ix—Na1—P1^x	92.9 (2)
O1^vii—Na1—O4ⁱⁱ	76.3 (3)	O1^vii—Na1—P1^xi	158.4 (3)
O1ⁱⁱ—Na1—O4ⁱⁱ	60.6 (3)	O1ⁱⁱ—Na1—P1^xi	100.0 (3)
O1^viii—Na1—O4ⁱⁱ	159.5 (5)	O1^viii—Na1—P1^xi	69.3 (2)
O4^vii—Na1—O4ⁱⁱ	117.71 (15)	O4^vii—Na1—P1^xi	97.9 (3)
O1^vii—Na1—O4^viii	159.5 (5)	O4ⁱⁱ—Na1—P1^xi	119.8 (3)
O1ⁱⁱ—Na1—O4^viii	76.3 (3)	O4^viii—Na1—P1^xi	27.8 (2)
O1^viii—Na1—O4^viii	60.6 (3)	O2^ix—Na1—P1^xi	86.4 (3)
O4^vii—Na1—O4^viii	117.71 (15)	O2^x—Na1—P1^xi	66.4 (3)
O4ⁱⁱ—Na1—O4^viii	117.71 (15)	O2^xi—Na1—P1^xi	27.7 (2)
O1^vii—Na1—O2^ix	83.0 (3)	P1^ix—Na1—P1^xi	92.9 (2)
O1ⁱⁱ—Na1—O2^ix	135.5 (4)	P1^x—Na1—P1^xi	92.9 (2)
O1^viii—Na1—O2^ix	122.3 (4)	P1—O1—Ge2	127.8 (6)
O4^vii—Na1—O2^ix	55.5 (3)	P1—O1—Na1^iv	118.9 (6)
O4ⁱⁱ—Na1—O2^ix	77.9 (4)	Ge2—O1—Na1^iv	104.4 (5)
O4^viii—Na1—O2^ix	113.5 (4)	P1—O2—Ge1	132.2 (6)
O1^vii—Na1—O2^x	122.3 (4)	P1—O2—Na1ⁱⁱⁱ	96.7 (5)
O1ⁱⁱ—Na1—O2^x	83.0 (3)	Ge1—O2—Na1ⁱⁱⁱ	91.2 (4)
O1^viii—Na1—O2^x	135.5 (4)	P1^xii—O3—Ge2	141.5 (7)
O4^vii—Na1—O2^x	113.5 (4)	P1^xiii—O4—Ge2	123.5 (6)
O4ⁱⁱ—Na1—O2^x	55.5 (3)	P1^xiii—O4—Na1^iv	99.4 (6)
O4^viii—Na1—O2^x	77.9 (4)	Ge2—O4—Na1^iv	98.3 (4)

2 in total

1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. Open-Framework Inorganic Materials.

Authors:
Journal: Angew Chem Int Ed Engl Date: 1999-11-15 Impact factor: 15.336

2 in total