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Langbeinite-type Ba3V4(PO4)6 has been crystallized from a stoichiometric melt starting from Ba(PO3)2 and V2O3. The crystal structure has been refined from single-crystal X-ray diffraction data. It consists of a vanadato(III)-phosphate network [V4(PO4)6]6-, which shows some resemblance to the NASICON structure type. A new method is presented for the visualization of this structural relationship. The single-crystal electronic spectrum of yellow-green Ba3V4(PO4)6 shows the absorption bands typical for the octahedral chromophore [VIIIO6].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804005689/br6140sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536804005689/br6140Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](P-O) = 0.004 Å
  • Disorder in solvent or counterion
  • R factor = 0.027
  • wR factor = 0.059
  • Data-to-parameter ratio = 15.2

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .... P PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 75.00 Perc.
Alert level G ABSTM02_ALERT_3_G The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.597 0.707 Tmin' and Tmax expected: 0.415 0.428 RR' = 0.870 Please check that your absorption correction is appropriate. REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 29.97 From the CIF: _reflns_number_total 930 Count of symmetry unique reflns 537 Completeness (_total/calc) 173.18% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 393 Fraction of Friedel pairs measured 0.732 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: COLLECT (Nonius, 2001); cell refinement: COLLECT and DENZO (Otwinowski & Minor, 1997); data reduction: COLLECT and DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS (Dowty, 2002); software used to prepare material for publication: WinGX (Farrugia, 1999).

(I) top
Crystal data top
Ba3V4(PO4)6Dx = 4.08 Mg m3
Mr = 1185.58Mo Kα radiation, λ = 0.71073 Å
Cubic, P213Cell parameters from 29 reflections
Hall symbol: P 2ac 2ab 3θ = 2.9–30.0°
a = 9.8825 (7) ŵ = 8.49 mm1
V = 965.16 (12) Å3T = 293 K
Z = 2Cube, yellow–green
F(000) = 10840.1 × 0.1 × 0.1 mm
Data collection top
Nonius KappaCCD
diffractometer
930 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
CCD rotation images, thick slices scansθmax = 30.0°, θmin = 2.9°
Absorption correction: numerical
(HABITUS; Herrendorf, 1993)
h = 1313
Tmin = 0.597, Tmax = 0.707k = 1313
22794 measured reflectionsl = 1313
930 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: full w = 1/[σ2(Fo2) + 7.2584P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.027(Δ/σ)max = 0.015
wR(F2) = 0.059Δρmax = 2.02 e Å3
S = 1.13Δρmin = 1.90 e Å3
930 reflectionsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
61 parametersExtinction coefficient: 0.0237 (15)
1 restraintAbsolute structure: Flack (1983), 393 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.02 (3)
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba10.06743 (4)0.06743 (4)0.06743 (4)0.0182 (2)0.772 (2)
Ba20.29438 (6)0.29438 (6)0.29438 (6)0.0282 (3)0.728 (2)
V10.58620 (7)0.58620 (7)0.58620 (7)0.0073 (2)
V20.85303 (7)0.85303 (7)0.85303 (7)0.0086 (2)
P0.62570 (10)0.46081 (10)0.27168 (10)0.0067 (2)
O10.6530 (4)0.5015 (4)0.4170 (4)0.0216 (7)
O20.7572 (4)0.4841 (4)0.1930 (4)0.0279 (9)
O30.5776 (4)0.3136 (3)0.2618 (4)0.0218 (7)
O40.5218 (4)0.5517 (4)0.2037 (4)0.0238 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.0182 (2)0.0182 (2)0.0182 (2)0.00074 (13)0.00074 (13)0.00074 (13)
Ba20.0282 (3)0.0282 (3)0.0282 (3)0.0107 (2)0.0107 (2)0.0107 (2)
V10.0073 (2)0.0073 (2)0.0073 (2)0.0006 (2)0.0006 (2)0.0006 (2)
V20.0086 (2)0.0086 (2)0.0086 (2)0.0010 (2)0.0010 (2)0.0010 (2)
P0.0068 (4)0.0065 (4)0.0068 (4)0.0016 (3)0.0005 (3)0.0002 (3)
O10.0250 (17)0.0280 (18)0.0118 (15)0.0032 (15)0.0028 (13)0.0119 (14)
O20.0211 (17)0.032 (2)0.031 (2)0.0097 (15)0.0193 (15)0.0087 (16)
O30.0254 (18)0.0099 (14)0.0300 (18)0.0046 (13)0.0131 (16)0.0040 (13)
O40.0232 (17)0.0212 (18)0.0270 (18)0.0125 (14)0.0084 (15)0.0011 (15)
Geometric parameters (Å, º) top
Ba1—O1i2.843 (4)V1—Ba1xii3.7492 (5)
Ba1—O1ii2.843 (4)V1—Ba1xiii3.7492 (5)
Ba1—O1iii2.843 (4)V1—Ba1xiv3.7492 (5)
Ba1—O4iv2.961 (4)V2—O4xv1.996 (3)
Ba1—O4v2.961 (4)V2—O4xvi1.996 (3)
Ba1—O4vi2.961 (4)V2—O4xvii1.996 (4)
Ba1—O2i3.047 (5)V2—O3x1.999 (3)
Ba1—O2ii3.047 (5)V2—O3ix1.999 (4)
Ba1—O2iii3.047 (5)V2—O3xi1.999 (3)
Ba1—O2iv3.225 (5)V2—Ba1xviii3.6699 (14)
Ba1—O2v3.225 (5)V2—Ba2xix3.8209 (6)
Ba1—O2vi3.225 (5)V2—Ba2xvii3.8210 (5)
Ba2—O32.824 (4)V2—Ba2xi3.8210 (6)
Ba2—O3vii2.824 (4)P—O11.516 (3)
Ba2—O3viii2.824 (4)P—O41.521 (3)
Ba2—O4i3.009 (4)P—O21.531 (4)
Ba2—O4ii3.009 (4)P—O31.534 (3)
Ba2—O4iii3.009 (4)P—Ba1xx3.4118 (11)
Ba2—O2i3.111 (4)P—Ba2xiv3.4521 (11)
Ba2—O2ii3.111 (4)P—Ba1xiv3.5826 (11)
Ba2—O2iii3.111 (4)O1—Ba1xiv2.843 (4)
Ba2—Pi3.4521 (11)O2—V1xxi1.998 (4)
Ba2—Piii3.4521 (11)O2—Ba1xiv3.047 (5)
Ba2—Pii3.4521 (11)O2—Ba2xiv3.111 (4)
V1—O1vii1.983 (3)O2—Ba1xx3.225 (5)
V1—O1viii1.983 (3)O3—V2xxi1.999 (3)
V1—O11.983 (3)O4—V2xxii1.996 (3)
V1—O2ix1.998 (4)O4—Ba1xx2.961 (4)
V1—O2x1.998 (4)O4—Ba2xiv3.009 (4)
V1—O2xi1.998 (4)
O1i—Ba1—O1ii100.53 (10)O3—Ba2—O4i82.07 (11)
O1i—Ba1—O1iii100.53 (10)O3vii—Ba2—O4i57.03 (9)
O1ii—Ba1—O1iii100.53 (10)O3viii—Ba2—O4i149.16 (10)
O1i—Ba1—O4iv96.08 (10)O3—Ba2—O4ii149.16 (10)
O1ii—Ba1—O4iv100.78 (11)O3vii—Ba2—O4ii82.07 (11)
O1iii—Ba1—O4iv149.99 (10)O3viii—Ba2—O4ii57.03 (9)
O1i—Ba1—O4v149.99 (10)O4i—Ba2—O4ii118.85 (2)
O1ii—Ba1—O4v96.08 (10)O3—Ba2—O4iii57.03 (9)
O1iii—Ba1—O4v100.78 (11)O3vii—Ba2—O4iii149.16 (10)
O4iv—Ba1—O4v56.07 (11)O3viii—Ba2—O4iii82.07 (11)
O1i—Ba1—O4vi100.78 (11)O4i—Ba2—O4iii118.85 (2)
O1ii—Ba1—O4vi149.99 (10)O4ii—Ba2—O4iii118.85 (2)
O1iii—Ba1—O4vi96.08 (10)O3—Ba2—O2i81.88 (11)
O4iv—Ba1—O4vi56.07 (11)O3vii—Ba2—O2i103.48 (10)
O4v—Ba1—O4vi56.07 (11)O3viii—Ba2—O2i162.86 (10)
O1i—Ba1—O2i48.95 (10)O4i—Ba2—O2i46.60 (10)
O1ii—Ba1—O2i114.21 (11)O4ii—Ba2—O2i128.91 (11)
O1iii—Ba1—O2i52.41 (10)O4iii—Ba2—O2i81.46 (10)
O4iv—Ba1—O2i133.01 (11)O3—Ba2—O2ii162.86 (10)
O4v—Ba1—O2i141.46 (11)O3vii—Ba2—O2ii81.88 (11)
O4vi—Ba1—O2i95.73 (10)O3viii—Ba2—O2ii103.48 (10)
O1i—Ba1—O2ii52.41 (10)O4i—Ba2—O2ii81.46 (10)
O1ii—Ba1—O2ii48.95 (10)O4ii—Ba2—O2ii46.60 (10)
O1iii—Ba1—O2ii114.21 (11)O4iii—Ba2—O2ii128.91 (11)
O4iv—Ba1—O2ii95.73 (10)O2i—Ba2—O2ii83.37 (13)
O4v—Ba1—O2ii133.01 (11)O3—Ba2—O2iii103.48 (10)
O4vi—Ba1—O2ii141.46 (11)O3vii—Ba2—O2iii162.86 (10)
O2i—Ba1—O2ii85.52 (11)O3viii—Ba2—O2iii81.88 (11)
O1i—Ba1—O2iii114.21 (11)O4i—Ba2—O2iii128.91 (11)
O1ii—Ba1—O2iii52.41 (10)O4ii—Ba2—O2iii81.46 (10)
O1iii—Ba1—O2iii48.95 (10)O4iii—Ba2—O2iii46.60 (10)
O4iv—Ba1—O2iii141.46 (11)O2i—Ba2—O2iii83.37 (13)
O4v—Ba1—O2iii95.73 (10)O2ii—Ba2—O2iii83.37 (13)
O4vi—Ba1—O2iii133.01 (11)O1vii—V1—O1viii93.73 (16)
O2i—Ba1—O2iii85.52 (11)O1vii—V1—O193.73 (16)
O2ii—Ba1—O2iii85.52 (11)O1viii—V1—O193.73 (16)
O1i—Ba1—O2iv56.07 (10)O1vii—V1—O2ix81.84 (18)
O1ii—Ba1—O2iv86.51 (10)O1viii—V1—O2ix92.35 (17)
O1iii—Ba1—O2iv156.56 (10)O1—V1—O2ix172.71 (18)
O4iv—Ba1—O2iv45.87 (9)O1vii—V1—O2x92.35 (17)
O4v—Ba1—O2iv100.65 (10)O1viii—V1—O2x172.71 (18)
O4vi—Ba1—O2iv88.09 (10)O1—V1—O2x81.84 (18)
O2i—Ba1—O2iv104.277 (10)O2ix—V1—O2x92.50 (16)
O2ii—Ba1—O2iv54.72 (14)O1vii—V1—O2xi172.71 (18)
O2iii—Ba1—O2iv137.20 (7)O1viii—V1—O2xi81.84 (18)
O1i—Ba1—O2v156.56 (10)O1—V1—O2xi92.35 (17)
O1ii—Ba1—O2v56.07 (10)O2ix—V1—O2xi92.50 (16)
O1iii—Ba1—O2v86.51 (10)O2x—V1—O2xi92.50 (16)
O4iv—Ba1—O2v88.09 (10)O4xv—V2—O4xvi88.44 (17)
O4v—Ba1—O2v45.87 (9)O4xv—V2—O4xvii88.44 (17)
O4vi—Ba1—O2v100.65 (10)O4xvi—V2—O4xvii88.44 (17)
O2i—Ba1—O2v137.20 (7)O4xv—V2—O3x88.61 (15)
O2ii—Ba1—O2v104.277 (10)O4xvi—V2—O3x176.20 (17)
O2iii—Ba1—O2v54.72 (14)O4xvii—V2—O3x89.08 (17)
O2iv—Ba1—O2v115.46 (5)O4xv—V2—O3ix89.08 (17)
O1i—Ba1—O2vi86.51 (10)O4xvi—V2—O3ix88.61 (15)
O1ii—Ba1—O2vi156.56 (10)O4xvii—V2—O3ix176.20 (17)
O1iii—Ba1—O2vi56.07 (10)O3x—V2—O3ix93.75 (17)
O4iv—Ba1—O2vi100.65 (10)O4xv—V2—O3xi176.20 (17)
O4v—Ba1—O2vi88.09 (10)O4xvi—V2—O3xi89.08 (17)
O4vi—Ba1—O2vi45.87 (9)O4xvii—V2—O3xi88.61 (15)
O2i—Ba1—O2vi54.72 (14)O3x—V2—O3xi93.75 (17)
O2ii—Ba1—O2vi137.20 (7)O3ix—V2—O3xi93.75 (17)
O2iii—Ba1—O2vi104.277 (10)O1—P—O4112.5 (2)
O2iv—Ba1—O2vi115.46 (5)O1—P—O2106.9 (2)
O2v—Ba1—O2vi115.46 (5)O4—P—O2105.1 (2)
O3—Ba2—O3vii93.11 (11)O1—P—O3111.5 (2)
O3—Ba2—O3viii93.11 (11)O4—P—O3108.8 (2)
O3vii—Ba2—O3viii93.11 (11)O2—P—O3111.9 (2)
Symmetry codes: (i) z+1/2, x+1, y1/2; (ii) y1/2, z+1/2, x+1; (iii) x+1, y1/2, z+1/2; (iv) z, x1/2, y+1/2; (v) y+1/2, z, x1/2; (vi) x1/2, y+1/2, z; (vii) z, x, y; (viii) y, z, x; (ix) y+1, z+1/2, x+3/2; (x) z+1/2, x+3/2, y+1; (xi) x+3/2, y+1, z+1/2; (xii) x+1/2, y+1, z+1/2; (xiii) x+1/2, y+1/2, z+1; (xiv) x+1, y+1/2, z+1/2; (xv) z+1, x+1/2, y+3/2; (xvi) y+3/2, z+1, x+1/2; (xvii) x+1/2, y+3/2, z+1; (xviii) x+1, y+1, z+1; (xix) x+1, y+1/2, z+3/2; (xx) x+1/2, y+1/2, z; (xxi) x+3/2, y+1, z1/2; (xxii) x1/2, y+3/2, z+1.
 

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