Redetermination of Fe(2)[BP(3)O(12)].

Explorations of phases in the quaternary Fe(III)-B(III)-P(V)-O system prepared by the high temperature solution growth (HTSG) method led to single-crystal growth of anhydrous diiron(III) borotriphosphate, Fe(2)[BP(3)O(12)]. This phase has been synthesized previously as a microcrystalline material and its structure refined in space group P3 from powder X-ray diffraction data using the Rietveld method [Chen et al. (2004 ▶). J. Inorg. Mater.19, 429-432]. In the current single-crystal study, it was shown that the correct space group is P6(3)/m. The three-dimensional structure of the title compound is built up from FeO(6) octa-hedra (3.. symmetry), trigonal-planar BO(3) groups ( symmetry) and PO(4) tetra-hedra (m.. symmetry). Two FeO(6) octa-hedra form Fe(2)O(9) dimers via face-sharing, while the anionic BO(3) and PO(4) groups are connected via corner-sharing to build up the [BP(3)O(12)](6-) anion. Both units are inter-connected via corner-sharing.

Related literature

Reviews on the crystal chemistry of borophosphates were given by Kniep et al. (1998 ▶) and Ewald et al. (2007 ▶). For the previous powder study of Fe2[BP3O12], see: Chen et al. (2004 ▶). For the structure of a related borophosphate, see: Zhao et al. (2009 ▶). Meisel et al. (2004 ▶) have reported the structure of V2[BP3O12] and Mi et al. (2000 ▶) that of Cr2[BP3O12].

Experimental

Crystal data

Fe2[BP3O12]

M = 407.42

Hexagonal,

a = 8.0347 (8) Å

c = 7.4163 (13) Å

V = 414.63 (9) Å3

Z = 2

Mo Kα radiation

μ = 4.15 mm−1

T = 293 K

0.15 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury70 CCD diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.575, T max = 0.819

3247 measured reflections

345 independent reflections

338 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.072

S = 1.07

345 reflections

33 parameters

Δρmax = 0.58 e Å−3

Δρmin = −0.78 e Å−3

Data collection: CrystalClear (Rigaku, 2004 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2004 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810029818/wm2377sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029818/wm2377Isup2.hkl

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

Fe2[BP3O12]	Dx = 3.263 Mg m−3
Mr = 407.42	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63/m	Cell parameters from 1049 reflections
Hall symbol: -P 6c	θ = 4.0–27.4°
a = 8.0347 (8) Å	µ = 4.15 mm−1
c = 7.4163 (13) Å	T = 293 K
V = 414.63 (9) Å3	Prism, light-red
Z = 2	0.15 × 0.05 × 0.05 mm
F(000) = 396

Rigaku Mercury70 CCD diffractometer	345 independent reflections
Radiation source: fine-focus sealed tube	338 reflections with I > 2σ(I)
Graphite Monochromator	Rint = 0.042
Detector resolution: 14.6306 pixels mm-1	θmax = 27.4°, θmin = 2.9°
ω scans	h = −10→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −10→10
Tmin = 0.575, Tmax = 0.819	l = −9→6
3247 measured reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.035	Secondary atom site location: difference Fourier map
wR(F2) = 0.072	w = 1/[σ2(Fo2) + (0.0168P)2 + 3.P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
345 reflections	Δρmax = 0.58 e Å−3
33 parameters	Δρmin = −0.78 e Å−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
Fe1	0.6667	0.3333	0.45190 (12)	0.0072 (3)
P1	1.04513 (17)	0.68473 (17)	0.2500	0.0064 (3)
O2	0.8735 (5)	0.4782 (5)	0.2500	0.0080 (7)
O1	0.9428 (5)	0.8099 (5)	0.2500	0.0097 (8)
B1	1.0000	1.0000	0.2500	0.0101 (19)
O3	1.1626 (3)	0.7289 (3)	0.4200 (4)	0.0115 (6)

	U11	U22	U33	U12	U13	U23
Fe1	0.0076 (3)	0.0076 (3)	0.0063 (5)	0.00381 (15)	0.000	0.000
P1	0.0055 (6)	0.0057 (6)	0.0077 (7)	0.0025 (5)	0.000	0.000
O2	0.0067 (15)	0.0059 (16)	0.0099 (19)	0.0021 (13)	0.000	0.000
O1	0.0060 (16)	0.0056 (16)	0.017 (2)	0.0022 (13)	0.000	0.000
B1	0.008 (2)	0.008 (2)	0.014 (5)	0.0040 (12)	0.000	0.000
O3	0.0116 (12)	0.0115 (12)	0.0127 (15)	0.0066 (10)	−0.0045 (11)	−0.0019 (10)

Fe1—O3i	1.929 (2)	P1—O2	1.538 (3)
Fe1—O3ii	1.929 (2)	P1—O1	1.586 (3)
Fe1—O3iii	1.929 (2)	O2—Fe1iv	2.103 (2)
Fe1—O2iv	2.103 (2)	O1—B1	1.357 (3)
Fe1—O2	2.103 (2)	B1—O1vii	1.357 (3)
Fe1—O2v	2.103 (2)	B1—O1viii	1.357 (3)
P1—O3	1.507 (3)	O3—Fe1i	1.929 (2)
P1—O3vi	1.507 (3)
O3i—Fe1—O3ii	97.83 (11)	O3—P1—O3vi	113.6 (2)
O3i—Fe1—O3iii	97.83 (11)	O3—P1—O2	111.85 (12)
O3ii—Fe1—O3iii	97.83 (11)	O3vi—P1—O2	111.85 (12)
O3i—Fe1—O2iv	93.65 (11)	O3—P1—O1	108.24 (12)
O3ii—Fe1—O2iv	91.53 (11)	O3vi—P1—O1	108.24 (12)
O3iii—Fe1—O2iv	164.04 (11)	O2—P1—O1	102.37 (18)
O3i—Fe1—O2	91.53 (11)	P1—O2—Fe1	129.13 (10)
O3ii—Fe1—O2	164.04 (11)	P1—O2—Fe1iv	129.14 (10)
O3iii—Fe1—O2	93.65 (11)	Fe1—O2—Fe1iv	90.78 (13)
O2iv—Fe1—O2	74.92 (10)	B1—O1—P1	136.3 (3)
O3i—Fe1—O2v	164.04 (11)	O1vii—B1—O1viii	120.000 (1)
O3ii—Fe1—O2v	93.65 (11)	O1vii—B1—O1	120.000 (1)
O3iii—Fe1—O2v	91.53 (11)	O1viii—B1—O1	120.000 (1)
O2iv—Fe1—O2v	74.92 (10)	P1—O3—Fe1i	142.54 (17)
O2—Fe1—O2v	74.92 (10)

Table 1

Selected bond lengths (Å)

Fe1—O3i	1.929 (2)
Fe1—O2	2.103 (2)
P1—O3	1.507 (3)
P1—O2	1.538 (3)
P1—O1	1.586 (3)
O1—B1	1.357 (3)

Symmetry code: (i) .