The langbeinite-type barium vanadium(III) orthophosphate, Ba₃V₄(PO₄)₆

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 [V^IIIO₆].

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

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Computing details

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)

Crystal data

Ba3V4(PO4)6	Dx = 4.08 Mg m^−3
Mr = 1185.58	Mo Kα radiation, λ = 0.71073 Å
Cubic, P213	Cell parameters from 29 reflections
Hall symbol: P 2ac 2ab 3	θ = 2.9–30.0°
a = 9.8825 (7) Å	µ = 8.49 mm^−1
V = 965.16 (12) Å^3	T = 293 K
Z = 2	Cube, yellow–green
F(000) = 1084	0.1 × 0.1 × 0.1 mm

Data collection

Nonius KappaCCD diffractometer	930 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
CCD rotation images, thick slices scans	θmax = 30.0°, θmin = 2.9°
Absorption correction: numerical (HABITUS; Herrendorf, 1993)	h = −13→13
Tmin = 0.597, Tmax = 0.707	k = −13→13
22794 measured reflections	l = −13→13
930 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + 7.2584P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.027	(Δ/σ)max = 0.015
wR(F^2) = 0.059	Δρmax = 2.02 e Å^−3
S = 1.13	Δρmin = −1.90 e Å^−3
930 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
61 parameters	Extinction coefficient: 0.0237 (15)
1 restraint	Absolute structure: Flack (1983), 393 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (3)

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	Occ. (<1)
Ba1	0.06743 (4)	0.06743 (4)	0.06743 (4)	0.0182 (2)	0.772 (2)
Ba2	0.29438 (6)	0.29438 (6)	0.29438 (6)	0.0282 (3)	0.728 (2)
V1	0.58620 (7)	0.58620 (7)	0.58620 (7)	0.0073 (2)
V2	0.85303 (7)	0.85303 (7)	0.85303 (7)	0.0086 (2)
P	0.62570 (10)	0.46081 (10)	0.27168 (10)	0.0067 (2)
O1	0.6530 (4)	0.5015 (4)	0.4170 (4)	0.0216 (7)
O2	0.7572 (4)	0.4841 (4)	0.1930 (4)	0.0279 (9)
O3	0.5776 (4)	0.3136 (3)	0.2618 (4)	0.0218 (7)
O4	0.5218 (4)	0.5517 (4)	0.2037 (4)	0.0238 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.0182 (2)	0.0182 (2)	0.0182 (2)	0.00074 (13)	0.00074 (13)	0.00074 (13)
Ba2	0.0282 (3)	0.0282 (3)	0.0282 (3)	0.0107 (2)	0.0107 (2)	0.0107 (2)
V1	0.0073 (2)	0.0073 (2)	0.0073 (2)	−0.0006 (2)	−0.0006 (2)	−0.0006 (2)
V2	0.0086 (2)	0.0086 (2)	0.0086 (2)	0.0010 (2)	0.0010 (2)	0.0010 (2)
P	0.0068 (4)	0.0065 (4)	0.0068 (4)	0.0016 (3)	0.0005 (3)	0.0002 (3)
O1	0.0250 (17)	0.0280 (18)	0.0118 (15)	0.0032 (15)	−0.0028 (13)	−0.0119 (14)
O2	0.0211 (17)	0.032 (2)	0.031 (2)	0.0097 (15)	0.0193 (15)	0.0087 (16)
O3	0.0254 (18)	0.0099 (14)	0.0300 (18)	−0.0046 (13)	−0.0131 (16)	0.0040 (13)
O4	0.0232 (17)	0.0212 (18)	0.0270 (18)	0.0125 (14)	−0.0084 (15)	0.0011 (15)

Geometric parameters (Å, º)

Ba1—O1^i	2.843 (4)	V1—Ba1^xii	3.7492 (5)
Ba1—O1^ii	2.843 (4)	V1—Ba1^xiii	3.7492 (5)
Ba1—O1^iii	2.843 (4)	V1—Ba1^xiv	3.7492 (5)
Ba1—O4^iv	2.961 (4)	V2—O4^xv	1.996 (3)
Ba1—O4^v	2.961 (4)	V2—O4^xvi	1.996 (3)
Ba1—O4^vi	2.961 (4)	V2—O4^xvii	1.996 (4)
Ba1—O2^i	3.047 (5)	V2—O3^x	1.999 (3)
Ba1—O2^ii	3.047 (5)	V2—O3^ix	1.999 (4)
Ba1—O2^iii	3.047 (5)	V2—O3^xi	1.999 (3)
Ba1—O2^iv	3.225 (5)	V2—Ba1^xviii	3.6699 (14)
Ba1—O2^v	3.225 (5)	V2—Ba2^xix	3.8209 (6)
Ba1—O2^vi	3.225 (5)	V2—Ba2^xvii	3.8210 (5)
Ba2—O3	2.824 (4)	V2—Ba2^xi	3.8210 (6)
Ba2—O3^vii	2.824 (4)	P—O1	1.516 (3)
Ba2—O3^viii	2.824 (4)	P—O4	1.521 (3)
Ba2—O4^i	3.009 (4)	P—O2	1.531 (4)
Ba2—O4^ii	3.009 (4)	P—O3	1.534 (3)
Ba2—O4^iii	3.009 (4)	P—Ba1^xx	3.4118 (11)
Ba2—O2^i	3.111 (4)	P—Ba2^xiv	3.4521 (11)
Ba2—O2^ii	3.111 (4)	P—Ba1^xiv	3.5826 (11)
Ba2—O2^iii	3.111 (4)	O1—Ba1^xiv	2.843 (4)
Ba2—P^i	3.4521 (11)	O2—V1^xxi	1.998 (4)
Ba2—P^iii	3.4521 (11)	O2—Ba1^xiv	3.047 (5)
Ba2—P^ii	3.4521 (11)	O2—Ba2^xiv	3.111 (4)
V1—O1^vii	1.983 (3)	O2—Ba1^xx	3.225 (5)
V1—O1^viii	1.983 (3)	O3—V2^xxi	1.999 (3)
V1—O1	1.983 (3)	O4—V2^xxii	1.996 (3)
V1—O2^ix	1.998 (4)	O4—Ba1^xx	2.961 (4)
V1—O2^x	1.998 (4)	O4—Ba2^xiv	3.009 (4)
V1—O2^xi	1.998 (4)
O1^i—Ba1—O1^ii	100.53 (10)	O3—Ba2—O4^i	82.07 (11)
O1^i—Ba1—O1^iii	100.53 (10)	O3^vii—Ba2—O4^i	57.03 (9)
O1^ii—Ba1—O1^iii	100.53 (10)	O3^viii—Ba2—O4^i	149.16 (10)
O1^i—Ba1—O4^iv	96.08 (10)	O3—Ba2—O4^ii	149.16 (10)
O1^ii—Ba1—O4^iv	100.78 (11)	O3^vii—Ba2—O4^ii	82.07 (11)
O1^iii—Ba1—O4^iv	149.99 (10)	O3^viii—Ba2—O4^ii	57.03 (9)
O1^i—Ba1—O4^v	149.99 (10)	O4^i—Ba2—O4^ii	118.85 (2)
O1^ii—Ba1—O4^v	96.08 (10)	O3—Ba2—O4^iii	57.03 (9)
O1^iii—Ba1—O4^v	100.78 (11)	O3^vii—Ba2—O4^iii	149.16 (10)
O4^iv—Ba1—O4^v	56.07 (11)	O3^viii—Ba2—O4^iii	82.07 (11)
O1^i—Ba1—O4^vi	100.78 (11)	O4^i—Ba2—O4^iii	118.85 (2)
O1^ii—Ba1—O4^vi	149.99 (10)	O4^ii—Ba2—O4^iii	118.85 (2)
O1^iii—Ba1—O4^vi	96.08 (10)	O3—Ba2—O2^i	81.88 (11)
O4^iv—Ba1—O4^vi	56.07 (11)	O3^vii—Ba2—O2^i	103.48 (10)
O4^v—Ba1—O4^vi	56.07 (11)	O3^viii—Ba2—O2^i	162.86 (10)
O1^i—Ba1—O2^i	48.95 (10)	O4^i—Ba2—O2^i	46.60 (10)
O1^ii—Ba1—O2^i	114.21 (11)	O4^ii—Ba2—O2^i	128.91 (11)
O1^iii—Ba1—O2^i	52.41 (10)	O4^iii—Ba2—O2^i	81.46 (10)
O4^iv—Ba1—O2^i	133.01 (11)	O3—Ba2—O2^ii	162.86 (10)
O4^v—Ba1—O2^i	141.46 (11)	O3^vii—Ba2—O2^ii	81.88 (11)
O4^vi—Ba1—O2^i	95.73 (10)	O3^viii—Ba2—O2^ii	103.48 (10)
O1^i—Ba1—O2^ii	52.41 (10)	O4^i—Ba2—O2^ii	81.46 (10)
O1^ii—Ba1—O2^ii	48.95 (10)	O4^ii—Ba2—O2^ii	46.60 (10)
O1^iii—Ba1—O2^ii	114.21 (11)	O4^iii—Ba2—O2^ii	128.91 (11)
O4^iv—Ba1—O2^ii	95.73 (10)	O2^i—Ba2—O2^ii	83.37 (13)
O4^v—Ba1—O2^ii	133.01 (11)	O3—Ba2—O2^iii	103.48 (10)
O4^vi—Ba1—O2^ii	141.46 (11)	O3^vii—Ba2—O2^iii	162.86 (10)
O2^i—Ba1—O2^ii	85.52 (11)	O3^viii—Ba2—O2^iii	81.88 (11)
O1^i—Ba1—O2^iii	114.21 (11)	O4^i—Ba2—O2^iii	128.91 (11)
O1^ii—Ba1—O2^iii	52.41 (10)	O4^ii—Ba2—O2^iii	81.46 (10)
O1^iii—Ba1—O2^iii	48.95 (10)	O4^iii—Ba2—O2^iii	46.60 (10)
O4^iv—Ba1—O2^iii	141.46 (11)	O2^i—Ba2—O2^iii	83.37 (13)
O4^v—Ba1—O2^iii	95.73 (10)	O2^ii—Ba2—O2^iii	83.37 (13)
O4^vi—Ba1—O2^iii	133.01 (11)	O1^vii—V1—O1^viii	93.73 (16)
O2^i—Ba1—O2^iii	85.52 (11)	O1^vii—V1—O1	93.73 (16)
O2^ii—Ba1—O2^iii	85.52 (11)	O1^viii—V1—O1	93.73 (16)
O1^i—Ba1—O2^iv	56.07 (10)	O1^vii—V1—O2^ix	81.84 (18)
O1^ii—Ba1—O2^iv	86.51 (10)	O1^viii—V1—O2^ix	92.35 (17)
O1^iii—Ba1—O2^iv	156.56 (10)	O1—V1—O2^ix	172.71 (18)
O4^iv—Ba1—O2^iv	45.87 (9)	O1^vii—V1—O2^x	92.35 (17)
O4^v—Ba1—O2^iv	100.65 (10)	O1^viii—V1—O2^x	172.71 (18)
O4^vi—Ba1—O2^iv	88.09 (10)	O1—V1—O2^x	81.84 (18)
O2^i—Ba1—O2^iv	104.277 (10)	O2^ix—V1—O2^x	92.50 (16)
O2^ii—Ba1—O2^iv	54.72 (14)	O1^vii—V1—O2^xi	172.71 (18)
O2^iii—Ba1—O2^iv	137.20 (7)	O1^viii—V1—O2^xi	81.84 (18)
O1^i—Ba1—O2^v	156.56 (10)	O1—V1—O2^xi	92.35 (17)
O1^ii—Ba1—O2^v	56.07 (10)	O2^ix—V1—O2^xi	92.50 (16)
O1^iii—Ba1—O2^v	86.51 (10)	O2^x—V1—O2^xi	92.50 (16)
O4^iv—Ba1—O2^v	88.09 (10)	O4^xv—V2—O4^xvi	88.44 (17)
O4^v—Ba1—O2^v	45.87 (9)	O4^xv—V2—O4^xvii	88.44 (17)
O4^vi—Ba1—O2^v	100.65 (10)	O4^xvi—V2—O4^xvii	88.44 (17)
O2^i—Ba1—O2^v	137.20 (7)	O4^xv—V2—O3^x	88.61 (15)
O2^ii—Ba1—O2^v	104.277 (10)	O4^xvi—V2—O3^x	176.20 (17)
O2^iii—Ba1—O2^v	54.72 (14)	O4^xvii—V2—O3^x	89.08 (17)
O2^iv—Ba1—O2^v	115.46 (5)	O4^xv—V2—O3^ix	89.08 (17)
O1^i—Ba1—O2^vi	86.51 (10)	O4^xvi—V2—O3^ix	88.61 (15)
O1^ii—Ba1—O2^vi	156.56 (10)	O4^xvii—V2—O3^ix	176.20 (17)
O1^iii—Ba1—O2^vi	56.07 (10)	O3^x—V2—O3^ix	93.75 (17)
O4^iv—Ba1—O2^vi	100.65 (10)	O4^xv—V2—O3^xi	176.20 (17)
O4^v—Ba1—O2^vi	88.09 (10)	O4^xvi—V2—O3^xi	89.08 (17)
O4^vi—Ba1—O2^vi	45.87 (9)	O4^xvii—V2—O3^xi	88.61 (15)
O2^i—Ba1—O2^vi	54.72 (14)	O3^x—V2—O3^xi	93.75 (17)
O2^ii—Ba1—O2^vi	137.20 (7)	O3^ix—V2—O3^xi	93.75 (17)
O2^iii—Ba1—O2^vi	104.277 (10)	O1—P—O4	112.5 (2)
O2^iv—Ba1—O2^vi	115.46 (5)	O1—P—O2	106.9 (2)
O2^v—Ba1—O2^vi	115.46 (5)	O4—P—O2	105.1 (2)
O3—Ba2—O3^vii	93.11 (11)	O1—P—O3	111.5 (2)
O3—Ba2—O3^viii	93.11 (11)	O4—P—O3	108.8 (2)
O3^vii—Ba2—O3^viii	93.11 (11)	O2—P—O3	111.9 (2)

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