Literature DB >> 21581464

Redetermination of the cubic struvite analogue Cs[Mg(OH(2))(6)](AsO(4)).

Abstract

In contrast to the previous refinement from photographic data [Ferrari et al. (1955 ▶). Gazz. Chim. Ital.84, 169-174], the present redetermination of the title compound, caesium hexa-aqua-magnesium arsenate(V), revealed the Cs atom to be on Wyckoff position 4d instead of Wyckoff position 4b of space group F3m. The structure can be derived from the halite structure. The centres of the complex [Mg(OH(2))(6)] octa-hedra and the AsO(4) tetra-hedra (both with 3m symmetry) are on the respective Na and Cl positions. The building units are connected to each other by O-H⋯O hydrogen bonds. The Cs(+) cations (3m symmetry) are located in the voids of this arrangement and exhibit a regular cubocta-hedral 12-coordination to the O atoms of the water mol-ecules. The O atom bonded to As has 2mm site symmetry (Wyckoff position 24f) and the water-mol-ecule O atom has m site symmetry (Wyckoff position 48h).

Entities: Chemical Disease Gene Species

Year: 2008 PMID： 21581464 PMCID： PMC2967843 DOI： 10.1107/S1600536808043171

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

Related literature

The crystal structure of struvite, NH4[Mg(OH2)6](PO4), was reported by Whitaker & Jeffery (1970a ▶,b ▶). Crystal growth of struvite-type compounds using the gel diffusion technique was reported by Banks et al. (1975 ▶). For isotypic structures, see: Carver et al. (2006 ▶) for Cs[Fe(OH2)6](PO4) and Massa et al. (2003 ▶) for the cubic form of dimorphic Cs[Mg(OH2)6](PO4). Isotypic struvite-type phases as well as analogues were recently surveyed by Weil (2008 ▶).

Experimental

Crystal data

Cs[Mg(OH2)6](AsO4) M = 404.24 Cubic, a = 10.1609 (5) Å V = 1049.05 (9) Å3 Z = 4 Mo Kα radiation μ = 6.75 mm−1 T = 293 (2) K 0.18 × 0.18 × 0.18 mm

Data collection

Enraf–Nonius CAD-4 diffractometer Absorption correction: integration (SHELXTL; Sheldrick, 2008 ▶) T min = 0.341, T max = 0.382 3332 measured reflections 208 independent reflections 207 reflections with I > 2σ(I) R int = 0.037 3 standard reflections frequency: 200 min intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.016 wR(F 2) = 0.038 S = 1.14 208 reflections 15 parameters 1 restraint H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.50 e Å−3 Δρmin = −0.48 e Å−3 Absolute structure: Flack (1983 ▶), 90 Friedel pairs Flack parameter: 0.01 (4) Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: HELENA implemented in PLATON (Spek, 2003 ▶); method used to solve structure: coordinates taken from an isotypic compound; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ATOMS (Dowty, 2004 ▶); software used to prepare material for publication: SHELXL97. Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808043171/hb2885sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043171/hb2885Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Cs[Mg(H₂O)₆](AsO₄)	D_x = 2.559 Mg m⁻³
M_r = 404.24	Mo Kα radiation, λ = 0.71073 Å
Cubic, F43m	Cell parameters from 25 reflections
Hall symbol: F -4 2 3	θ = 11.4–12.7°
a = 10.1609 (5) Å	µ = 6.75 mm⁻¹
V = 1049.05 (9) Å³	T = 293 K
Z = 4	Octahedron, colourless
F(000) = 768	0.18 × 0.18 × 0.18 mm

Enraf–Nonius CAD-4 diffractometer	207 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.037
graphite	θ_max = 30.9°, θ_min = 3.5°
ω/2θ scans	h = −14→14
Absorption correction: integration (SHELXTL; Sheldrick, 2008)	k = −14→14
T_min = 0.341, T_max = 0.382	l = −14→14
3332 measured reflections	3 standard reflections every 200 min
208 independent reflections	intensity decay: none

Refinement on F²	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ²(F_o²) + 5.0469P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.016	(Δ/σ)_max < 0.001
wR(F²) = 0.038	Δρ_max = 0.50 e Å⁻³
S = 1.14	Δρ_min = −0.48 e Å⁻³
208 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
15 parameters	Extinction coefficient: 0.00144 (17)
1 restraint	Absolute structure: Flack (1983), 90 Friedel pairs
Primary atom site location: isomorphous structure methods	Flack parameter: 0.01 (4)

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
Cs1	0.7500	0.7500	0.7500	0.0599 (3)
Mg1	0.0000	0.0000	0.0000	0.0250 (6)
As1	0.2500	0.2500	0.2500	0.0201 (2)
O1	0.2031 (3)	0.0000	0.0000	0.0508 (8)
O2	0.34550 (19)	0.34550 (19)	0.34550 (19)	0.0269 (7)
H1	0.249 (3)	0.045 (2)	0.045 (2)	0.053 (12)*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs1	0.0599 (3)	0.0599 (3)	0.0599 (3)	0.000	0.000	0.000
Mg1	0.0250 (6)	0.0250 (6)	0.0250 (6)	0.000	0.000	0.000
As1	0.0201 (2)	0.0201 (2)	0.0201 (2)	0.000	0.000	0.000
O1	0.0259 (13)	0.0632 (13)	0.0632 (13)	0.000	0.000	−0.033 (2)
O2	0.0269 (7)	0.0269 (7)	0.0269 (7)	−0.0036 (7)	−0.0036 (7)	−0.0036 (7)

Cs1—O1ⁱ	3.6239 (5)	Mg1—O1^xiii	2.064 (3)
Cs1—O1ⁱⁱ	3.6239 (5)	Mg1—O1^xiv	2.064 (3)
Cs1—O1ⁱⁱⁱ	3.6239 (5)	Mg1—O1^xv	2.064 (3)
Cs1—O1^iv	3.6239 (5)	Mg1—O1^xvi	2.064 (3)
Cs1—O1^v	3.6239 (5)	Mg1—O1^xvii	2.064 (3)
Cs1—O1^vi	3.6239 (5)	Mg1—O1	2.064 (3)
Cs1—O1^vii	3.6239 (5)	As1—O2	1.681 (3)
Cs1—O1^viii	3.6239 (5)	As1—O2^xviii	1.681 (3)
Cs1—O1^ix	3.6239 (5)	As1—O2^xix	1.681 (3)
Cs1—O1^x	3.6239 (5)	As1—O2^xx	1.681 (3)
Cs1—O1^xi	3.6239 (5)	O1—H1	0.79 (2)
Cs1—O1^xii	3.6239 (5)

O1ⁱ—Cs1—O1ⁱⁱ	47.49 (8)	O1ⁱⁱⁱ—Cs1—O1^xi	72.12 (8)
O1ⁱ—Cs1—O1ⁱⁱⁱ	47.49 (8)	O1^iv—Cs1—O1^xi	47.49 (8)
O1ⁱⁱ—Cs1—O1ⁱⁱⁱ	47.49 (8)	O1^v—Cs1—O1^xi	90.991 (13)
O1ⁱ—Cs1—O1^iv	164.89 (10)	O1^vi—Cs1—O1^xi	119.429 (8)
O1ⁱⁱ—Cs1—O1^iv	119.430 (7)	O1^vii—Cs1—O1^xi	72.12 (8)
O1ⁱⁱⁱ—Cs1—O1^iv	119.429 (7)	O1^viii—Cs1—O1^xi	119.429 (7)
O1ⁱ—Cs1—O1^v	119.429 (8)	O1^ix—Cs1—O1^xi	47.49 (8)
O1ⁱⁱ—Cs1—O1^v	164.89 (10)	O1^x—Cs1—O1^xi	164.89 (10)
O1ⁱⁱⁱ—Cs1—O1^v	119.429 (7)	O1ⁱ—Cs1—O1^xii	72.12 (8)
O1^iv—Cs1—O1^v	72.12 (8)	O1ⁱⁱ—Cs1—O1^xii	119.429 (7)
O1ⁱ—Cs1—O1^vi	119.429 (8)	O1ⁱⁱⁱ—Cs1—O1^xii	90.991 (13)
O1ⁱⁱ—Cs1—O1^vi	119.429 (8)	O1^iv—Cs1—O1^xii	119.429 (8)
O1ⁱⁱⁱ—Cs1—O1^vi	164.89 (10)	O1^v—Cs1—O1^xii	47.49 (8)
O1^iv—Cs1—O1^vi	72.12 (8)	O1^vi—Cs1—O1^xii	90.991 (13)
O1^v—Cs1—O1^vi	72.12 (8)	O1^vii—Cs1—O1^xii	47.49 (8)
O1ⁱ—Cs1—O1^vii	90.991 (13)	O1^viii—Cs1—O1^xii	119.429 (7)
O1ⁱⁱ—Cs1—O1^vii	119.430 (7)	O1^ix—Cs1—O1^xii	164.89 (10)
O1ⁱⁱⁱ—Cs1—O1^vii	72.12 (8)	O1^x—Cs1—O1^xii	72.12 (8)
O1^iv—Cs1—O1^vii	90.991 (13)	O1^xi—Cs1—O1^xii	119.429 (8)
O1^v—Cs1—O1^vii	47.49 (8)	O1^xiii—Mg1—O1^xiv	180.0
O1^vi—Cs1—O1^vii	119.429 (8)	O1^xiii—Mg1—O1^xv	90.0
O1ⁱ—Cs1—O1^viii	90.991 (13)	O1^xiv—Mg1—O1^xv	90.0
O1ⁱⁱ—Cs1—O1^viii	72.12 (8)	O1^xiii—Mg1—O1^xvi	90.0
O1ⁱⁱⁱ—Cs1—O1^viii	119.430 (7)	O1^xiv—Mg1—O1^xvi	90.0
O1^iv—Cs1—O1^viii	90.991 (13)	O1^xv—Mg1—O1^xvi	180.0
O1^v—Cs1—O1^viii	119.429 (8)	O1^xiii—Mg1—O1^xvii	90.0
O1^vi—Cs1—O1^viii	47.49 (8)	O1^xiv—Mg1—O1^xvii	90.0
O1^vii—Cs1—O1^viii	164.89 (10)	O1^xv—Mg1—O1^xvii	90.0
O1ⁱ—Cs1—O1^ix	119.429 (7)	O1^xvi—Mg1—O1^xvii	90.0
O1ⁱⁱ—Cs1—O1^ix	72.12 (8)	O1^xiii—Mg1—O1	90.0
O1ⁱⁱⁱ—Cs1—O1^ix	90.991 (13)	O1^xiv—Mg1—O1	90.0
O1^iv—Cs1—O1^ix	47.49 (8)	O1^xv—Mg1—O1	90.0
O1^v—Cs1—O1^ix	119.429 (8)	O1^xvi—Mg1—O1	90.0
O1^vi—Cs1—O1^ix	90.991 (13)	O1^xvii—Mg1—O1	180.0
O1^vii—Cs1—O1^ix	119.429 (8)	O2—As1—O2^xviii	109.5
O1^viii—Cs1—O1^ix	72.12 (8)	O2—As1—O2^xix	109.471 (1)
O1ⁱ—Cs1—O1^x	72.12 (8)	O2^xviii—As1—O2^xix	109.5
O1ⁱⁱ—Cs1—O1^x	90.991 (13)	O2—As1—O2^xx	109.5
O1ⁱⁱⁱ—Cs1—O1^x	119.430 (7)	O2^xviii—As1—O2^xx	109.5
O1^iv—Cs1—O1^x	119.429 (8)	O2^xix—As1—O2^xx	109.5
O1^v—Cs1—O1^x	90.991 (13)	Mg1—O1—Cs1^xxi	97.56 (5)
O1^vi—Cs1—O1^x	47.49 (8)	Mg1—O1—Cs1^xxii	97.56 (5)
O1^vii—Cs1—O1^x	119.429 (7)	Cs1^xxi—O1—Cs1^xxii	164.89 (10)
O1^viii—Cs1—O1^x	47.49 (8)	Mg1—O1—H1	126 (3)
O1^ix—Cs1—O1^x	119.429 (7)	Cs1^xxi—O1—H1	85.6 (3)
O1ⁱ—Cs1—O1^xi	119.430 (7)	Cs1^xxii—O1—H1	85.6 (3)
O1ⁱⁱ—Cs1—O1^xi	90.991 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^xix	0.79 (2)	1.86 (2)	2.650 (2)	176 (4)

Table 1

Selected bond lengths (Å)

Cs1—O1ⁱ	3.6239 (5)
Mg1—O1	2.064 (3)
As1—O2	1.681 (3)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱⁱ	0.79 (2)	1.86 (2)	2.650 (2)	176 (4)

Symmetry code: (ii) .

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1. A short history of SHELX.

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

2. Spectroscopic, magnetochemical, and crystallographic study of cesium iron phosphate hexahydrate: characterization of the electronic structure of the iron(II) hexa-aqua cation in a quasicubic environment.

Authors: Graham Carver; Christopher Dobe; Thomas B Jensen; Philip L W Tregenna-Piggott; Stefan Janssen; Eckhard Bill; Garry J McIntyre; Anne-Laure Barra
Journal: Inorg Chem Date: 2006-06-12 Impact factor: 5.165

3. A new cubic form of caesium hexaaquamagnesium phosphate, Cs[Mg(H2O)6](PO4).

Authors: Werner Massa; Olga V Yakubovich; Olga V Dimitrova
Journal: Acta Crystallogr C Date: 2003-07-31 Impact factor: 1.172

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