Potassium barium bismuth oxide

KBa₄Bi₃O crystallizes in the centrosymmetric tetragonal space group I4/mcm. In this compound, bismuth is present as two anionic species, i.e. Bi₂^4- dumbbells [Bi-Bi 3.113 (3) Å] and isolated Bi^3-. Atom Bi1 (Bi^3-) lies inside a bicapped square antiprism (2 × K and 8 × Ba). Atom Bi2, which forms the Bi₂^4- dumbbell, sits inside a bicapped distorted trigonal prism (2 × K and 6 × Ba). O atoms occupy tetra­hedral voids between Ba atoms.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: local program; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

Potassium Barium Bismuth oxide

Crystal data

KBa4Bi3O	Dx = 6.131 Mg m^−3
Mr = 1231.40	Mo Kα radiation, λ = 0.71069 Å
Tetragonal, I4/mcm	Cell parameters from 25 reflections
Hall symbol: -I 4 2c	θ = 9.1–18.5°
a = 8.960 (1) Å	µ = 51.30 mm^−1
c = 16.617 (4) Å	T = 293 K
V = 1334.0 (4) Å^3	Triangular wedge, metallic light grey
Z = 4	0.20 × 0.04 × 0.02 mm
F(000) = 2000

Data collection

Nonius CAD-4 diffractometer	381 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.057
Graphite monochromator	θmax = 30.0°, θmin = 2.5°
ω–θ scans	h = 0→8
Absorption correction: numerical (SHELX76; Sheldrick, 1976)	k = 0→12
Tmin = 0.102, Tmax = 0.436	l = 0→22
830 measured reflections	3 standard reflections every 100 reflections
495 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Calculated w = 1/[σ^2(Fo^2) + (0.0403P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.112	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 2.87 e Å^−3
495 reflections	Δρmin = −2.42 e Å^−3
18 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00031 (6)

Special details

Experimental. All computations were carried out on a PentiumII 266 computer.

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
Bi1	0.0000	0.0000	0.2500	0.0201 (5)
Bi2	0.62283 (10)	0.12283 (10)	0.0000	0.0178 (4)
Ba	−0.34395 (12)	0.15605 (12)	0.34522 (9)	0.0197 (4)
K	0.0000	0.0000	0.0000	0.023 (2)
O	0.5000	0.0000	0.2500	0.018 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.0149 (5)	0.0149 (5)	0.0306 (10)	0.000	0.000	0.000
Bi2	0.0164 (4)	0.0164 (4)	0.0206 (6)	−0.0023 (5)	0.000	0.000
Ba	0.0181 (5)	0.0181 (5)	0.0229 (7)	−0.0024 (5)	0.0005 (4)	0.0005 (4)
K	0.011 (3)	0.011 (3)	0.047 (7)	0.000	0.000	0.000
O	0.021 (10)	0.021 (10)	0.011 (14)	0.000	0.000	0.000

Geometric parameters (Å, º)

Bi1—Ba^i	3.7358 (9)	Ba—Bi2^xv	3.8034 (19)
Bi1—Ba^ii	3.7358 (8)	Ba—Ba^xix	3.955 (3)
Bi1—Ba^iii	3.7358 (9)	Ba—Ba^vii	3.960 (3)
Bi1—Ba^iv	3.7358 (9)	Ba—Ba^xx	4.223 (3)
Bi1—Ba^v	3.7358 (8)	Ba—Ba^ii	4.223 (3)
Bi1—Ba^vi	3.7358 (9)	Ba—K^viii	4.2506 (11)
Bi1—Ba^vii	3.7358 (9)	Ba—K^xxi	4.2506 (11)
Bi1—Ba	3.7358 (9)	K—Bi2^xxii	3.5541 (7)
Bi1—K^viii	4.1543 (10)	K—Bi2^xxiii	3.5542 (7)
Bi1—K	4.1543 (10)	K—Bi2^ix	3.5541 (7)
Bi2—Bi2^ix	3.113 (3)	K—Bi2^xvii	3.5541 (7)
Bi2—K^x	3.5541 (7)	K—Bi1^xxiv	4.1543 (10)
Bi2—K^xi	3.5541 (7)	K—Ba^xxv	4.2506 (11)
Bi2—Ba^xii	3.5982 (15)	K—Ba^v	4.2506 (11)
Bi2—Ba^xiii	3.5982 (16)	K—Ba^xxvi	4.2506 (11)
Bi2—Ba^v	3.5982 (16)	K—Ba^vii	4.2506 (11)
Bi2—Ba^xiv	3.5982 (16)	K—Ba^xii	4.2506 (11)
Bi2—Ba^xv	3.8034 (19)	K—Ba^xxvii	4.2506 (11)
Bi2—Ba^xvi	3.8034 (19)	O—Ba^xi	2.5325 (15)
Ba—O^xvii	2.5325 (15)	O—Ba^v	2.5325 (15)
Ba—Bi2^xviii	3.5982 (15)	O—Ba^xiv	2.5325 (15)
Ba—Bi2^viii	3.5982 (16)	O—Ba^iv	2.5325 (15)
Ba—Bi1^vii	3.7358 (9)
Ba^i—Bi1—Ba^ii	142.84 (4)	Bi2^xviii—Ba—Ba^xx	118.74 (3)
Ba^i—Bi1—Ba^iii	136.04 (4)	Bi2^viii—Ba—Ba^xx	94.35 (4)
Ba^ii—Bi1—Ba^iii	79.666 (17)	Bi1—Ba—Ba^xx	103.23 (5)
Ba^i—Bi1—Ba^iv	79.666 (17)	Bi1^vii—Ba—Ba^xx	55.58 (2)
Ba^ii—Bi1—Ba^iv	136.04 (4)	Bi2^xv—Ba—Ba^xx	148.394 (10)
Ba^iii—Bi1—Ba^iv	64.02 (4)	Ba^xix—Ba—Ba^xx	62.08 (2)
Ba^i—Bi1—Ba^v	64.02 (4)	Ba^vii—Ba—Ba^xx	71.50 (5)
Ba^ii—Bi1—Ba^v	129.88 (4)	O^xvii—Ba—Ba^ii	33.512 (18)
Ba^iii—Bi1—Ba^v	79.666 (17)	Bi2^xviii—Ba—Ba^ii	94.35 (4)
Ba^iv—Bi1—Ba^v	68.84 (5)	Bi2^viii—Ba—Ba^ii	118.74 (3)
Ba^i—Bi1—Ba^vi	129.88 (4)	Bi1—Ba—Ba^ii	55.58 (2)
Ba^ii—Bi1—Ba^vi	64.02 (4)	Bi1^vii—Ba—Ba^ii	103.23 (5)
Ba^iii—Bi1—Ba^vi	68.84 (5)	Bi2^xv—Ba—Ba^ii	148.394 (10)
Ba^iv—Bi1—Ba^vi	79.666 (17)	Ba^xix—Ba—Ba^ii	62.08 (2)
Ba^v—Bi1—Ba^vi	142.84 (4)	Ba^vii—Ba—Ba^ii	71.50 (5)
Ba^i—Bi1—Ba^vii	68.84 (5)	Ba^xx—Ba—Ba^ii	55.84 (4)
Ba^ii—Bi1—Ba^vii	79.666 (17)	O^xvii—Ba—K^viii	126.64 (2)
Ba^iii—Bi1—Ba^vii	129.88 (4)	Bi2^xviii—Ba—K^viii	53.06 (2)
Ba^iv—Bi1—Ba^vii	142.84 (4)	Bi2^viii—Ba—K^viii	92.51 (3)
Ba^v—Bi1—Ba^vii	79.666 (17)	Bi1—Ba—K^viii	62.294 (16)
Ba^vi—Bi1—Ba^vii	136.04 (4)	Bi1^vii—Ba—K^viii	143.04 (4)
Ba^i—Bi1—Ba	79.666 (17)	Bi2^xv—Ba—K^viii	52.011 (18)
Ba^ii—Bi1—Ba	68.84 (5)	Ba^xix—Ba—K^viii	106.264 (19)
Ba^iii—Bi1—Ba	142.84 (4)	Ba^vii—Ba—K^viii	108.37 (4)
Ba^iv—Bi1—Ba	129.88 (4)	Ba^xx—Ba—K^viii	158.99 (2)
Ba^v—Bi1—Ba	136.04 (4)	Ba^ii—Ba—K^viii	103.63 (3)
Ba^vi—Bi1—Ba	79.666 (17)	O^xvii—Ba—K^xxi	126.64 (2)
Ba^vii—Bi1—Ba	64.02 (4)	Bi2^xviii—Ba—K^xxi	92.51 (3)
Ba^i—Bi1—K^viii	64.94 (2)	Bi2^viii—Ba—K^xxi	53.06 (2)
Ba^ii—Bi1—K^viii	115.06 (2)	Bi1—Ba—K^xxi	143.04 (4)
Ba^iii—Bi1—K^viii	115.06 (2)	Bi1^vii—Ba—K^xxi	62.294 (16)
Ba^iv—Bi1—K^viii	64.94 (2)	Bi2^xv—Ba—K^xxi	52.011 (18)
Ba^v—Bi1—K^viii	115.06 (2)	Ba^xix—Ba—K^xxi	106.264 (19)
Ba^vi—Bi1—K^viii	64.94 (2)	Ba^vii—Ba—K^xxi	108.37 (4)
Ba^vii—Bi1—K^viii	115.06 (2)	Ba^xx—Ba—K^xxi	103.63 (3)
Ba—Bi1—K^viii	64.94 (2)	Ba^ii—Ba—K^xxi	158.99 (2)
Ba^i—Bi1—K	115.06 (2)	K^viii—Ba—K^xxi	96.36 (3)
Ba^ii—Bi1—K	64.94 (2)	Bi2^xxii—K—Bi2^xxiii	180.0
Ba^iii—Bi1—K	64.94 (2)	Bi2^xxii—K—Bi2^ix	90.0
Ba^iv—Bi1—K	115.06 (2)	Bi2^xxiii—K—Bi2^ix	90.0
Ba^v—Bi1—K	64.94 (2)	Bi2^xxii—K—Bi2^xvii	90.0
Ba^vi—Bi1—K	115.06 (2)	Bi2^xxiii—K—Bi2^xvii	90.0
Ba^vii—Bi1—K	64.94 (2)	Bi2^ix—K—Bi2^xvii	180.0
Ba—Bi1—K	115.06 (2)	Bi2^xxii—K—Bi1	90.0
K^viii—Bi1—K	180.0	Bi2^xxiii—K—Bi1	90.0
Bi2^ix—Bi2—K^x	116.962 (19)	Bi2^ix—K—Bi1	90.0
Bi2^ix—Bi2—K^xi	116.962 (19)	Bi2^xvii—K—Bi1	90.0
K^x—Bi2—K^xi	126.08 (4)	Bi2^xxii—K—Bi1^xxiv	90.0
Bi2^ix—Bi2—Ba^xii	64.37 (2)	Bi2^xxiii—K—Bi1^xxiv	90.0
K^x—Bi2—Ba^xii	72.921 (19)	Bi2^ix—K—Bi1^xxiv	90.0
K^xi—Bi2—Ba^xii	133.31 (2)	Bi2^xvii—K—Bi1^xxiv	90.0
Bi2^ix—Bi2—Ba^xiii	64.37 (2)	Bi1—K—Bi1^xxiv	180.0
K^x—Bi2—Ba^xiii	133.31 (2)	Bi2^xxii—K—Ba^xxv	122.50 (2)
K^xi—Bi2—Ba^xiii	72.921 (19)	Bi2^xxiii—K—Ba^xxv	57.50 (2)
Ba^xii—Bi2—Ba^xiii	66.67 (5)	Bi2^ix—K—Ba^xxv	125.98 (2)
Bi2^ix—Bi2—Ba^v	64.37 (2)	Bi2^xvii—K—Ba^xxv	54.02 (2)
K^x—Bi2—Ba^v	72.921 (19)	Bi1—K—Ba^xxv	127.235 (18)
K^xi—Bi2—Ba^v	133.31 (2)	Bi1^xxiv—K—Ba^xxv	52.765 (18)
Ba^xii—Bi2—Ba^v	91.25 (5)	Bi2^xxii—K—Ba^v	57.50 (2)
Ba^xiii—Bi2—Ba^v	128.74 (4)	Bi2^xxiii—K—Ba^v	122.50 (2)
Bi2^ix—Bi2—Ba^xiv	64.37 (2)	Bi2^ix—K—Ba^v	54.02 (2)
K^x—Bi2—Ba^xiv	133.31 (2)	Bi2^xvii—K—Ba^v	125.98 (2)
K^xi—Bi2—Ba^xiv	72.921 (19)	Bi1—K—Ba^v	52.765 (18)
Ba^xii—Bi2—Ba^xiv	128.74 (4)	Bi1^xxiv—K—Ba^v	127.235 (18)
Ba^xiii—Bi2—Ba^xiv	91.25 (5)	Ba^xxv—K—Ba^v	180.0
Ba^v—Bi2—Ba^xiv	66.67 (5)	Bi2^xxii—K—Ba^xxvi	125.98 (2)
Bi2^ix—Bi2—Ba^xv	137.45 (3)	Bi2^xxiii—K—Ba^xxvi	54.02 (2)
K^x—Bi2—Ba^xv	70.49 (2)	Bi2^ix—K—Ba^xxvi	57.50 (2)
K^xi—Bi2—Ba^xv	70.49 (2)	Bi2^xvii—K—Ba^xxvi	122.50 (2)
Ba^xii—Bi2—Ba^xv	143.32 (2)	Bi1—K—Ba^xxvi	127.235 (18)
Ba^xiii—Bi2—Ba^xv	143.32 (2)	Bi1^xxiv—K—Ba^xxvi	52.765 (18)
Ba^v—Bi2—Ba^xv	80.52 (3)	Ba^xxv—K—Ba^xxvi	68.523 (18)
Ba^xiv—Bi2—Ba^xv	80.52 (3)	Ba^v—K—Ba^xxvi	111.477 (18)
Bi2^ix—Bi2—Ba^xvi	137.45 (3)	Bi2^xxii—K—Ba^vii	54.02 (2)
K^x—Bi2—Ba^xvi	70.49 (2)	Bi2^xxiii—K—Ba^vii	125.98 (2)
K^xi—Bi2—Ba^xvi	70.49 (2)	Bi2^ix—K—Ba^vii	122.50 (2)
Ba^xii—Bi2—Ba^xvi	80.52 (3)	Bi2^xvii—K—Ba^vii	57.50 (2)
Ba^xiii—Bi2—Ba^xvi	80.52 (3)	Bi1—K—Ba^vii	52.765 (18)
Ba^v—Bi2—Ba^xvi	143.32 (2)	Bi1^xxiv—K—Ba^vii	127.235 (18)
Ba^xiv—Bi2—Ba^xvi	143.32 (2)	Ba^xxv—K—Ba^vii	111.477 (18)
Ba^xv—Bi2—Ba^xvi	85.10 (6)	Ba^v—K—Ba^vii	68.523 (18)
O^xvii—Ba—Bi2^xviii	91.00 (4)	Ba^xxvi—K—Ba^vii	180.0
O^xvii—Ba—Bi2^viii	91.00 (4)	Bi2^xxii—K—Ba^xii	57.50 (2)
Bi2^xviii—Ba—Bi2^viii	51.26 (4)	Bi2^xxiii—K—Ba^xii	122.50 (2)
O^xvii—Ba—Bi1	89.09 (3)	Bi2^ix—K—Ba^xii	54.02 (2)
Bi2^xviii—Ba—Bi1	96.38 (2)	Bi2^xvii—K—Ba^xii	125.98 (2)
Bi2^viii—Ba—Bi1	147.63 (3)	Bi1—K—Ba^xii	127.235 (18)
O^xvii—Ba—Bi1^vii	89.09 (3)	Bi1^xxiv—K—Ba^xii	52.765 (18)
Bi2^xviii—Ba—Bi1^vii	147.63 (3)	Ba^xxv—K—Ba^xii	105.53 (4)
Bi2^viii—Ba—Bi1^vii	96.38 (2)	Ba^v—K—Ba^xii	74.47 (4)
Bi1—Ba—Bi1^vii	115.98 (4)	Ba^xxvi—K—Ba^xii	68.523 (18)
O^xvii—Ba—Bi2^xv	176.12 (6)	Ba^vii—K—Ba^xii	111.477 (18)
Bi2^xviii—Ba—Bi2^xv	85.50 (4)	Bi2^xxii—K—Ba^xxvii	54.02 (2)
Bi2^viii—Ba—Bi2^xv	85.50 (4)	Bi2^xxiii—K—Ba^xxvii	125.98 (2)
Bi1—Ba—Bi2^xv	92.96 (3)	Bi2^ix—K—Ba^xxvii	122.50 (2)
Bi1^vii—Ba—Bi2^xv	92.96 (3)	Bi2^xvii—K—Ba^xxvii	57.50 (2)
O^xvii—Ba—Ba^xix	38.67 (3)	Bi1—K—Ba^xxvii	127.235 (18)
Bi2^xviii—Ba—Ba^xix	56.66 (2)	Bi1^xxiv—K—Ba^xxvii	52.765 (18)
Bi2^viii—Ba—Ba^xix	56.66 (2)	Ba^xxv—K—Ba^xxvii	68.523 (18)
Bi1—Ba—Ba^xix	108.58 (2)	Ba^v—K—Ba^xxvii	111.477 (18)
Bi1^vii—Ba—Ba^xix	108.58 (2)	Ba^xxvi—K—Ba^xxvii	105.53 (4)
Bi2^xv—Ba—Ba^xix	137.45 (3)	Ba^vii—K—Ba^xxvii	74.47 (4)
O^xvii—Ba—Ba^vii	88.29 (6)	Ba^xii—K—Ba^xxvii	68.523 (18)
Bi2^xviii—Ba—Ba^vii	154.36 (2)	Ba^xi—O—Ba^v	112.98 (4)
Bi2^viii—Ba—Ba^vii	154.36 (2)	Ba^xi—O—Ba^xiv	112.98 (4)
Bi1—Ba—Ba^vii	57.992 (19)	Ba^v—O—Ba^xiv	102.67 (7)
Bi1^vii—Ba—Ba^vii	57.992 (19)	Ba^xi—O—Ba^iv	102.67 (7)
Bi2^xv—Ba—Ba^vii	95.59 (6)	Ba^v—O—Ba^iv	112.98 (4)
Ba^xix—Ba—Ba^vii	126.96 (4)	Ba^xiv—O—Ba^iv	112.98 (4)
O^xvii—Ba—Ba^xx	33.512 (18)

Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x, −y, −z+1/2; (iii) x+1/2, y−1/2, −z+1/2; (iv) −x, −y, z; (v) −x, y, −z+1/2; (vi) −x−1/2, y−1/2, z; (vii) −x−1/2, −y+1/2, −z+1/2; (viii) −x, y, z+1/2; (ix) −x+1, −y, −z; (x) −x+1/2, y+1/2, z; (xi) x+1, y, z; (xii) −x, y, z−1/2; (xiii) x+1, −y, z−1/2; (xiv) x+1, −y, −z+1/2; (xv) −x+1/2, −y+1/2, −z+1/2; (xvi) −x+1/2, −y+1/2, z−1/2; (xvii) x−1, y, z; (xviii) x−1, −y, −z+1/2; (xix) −x−1, −y, z; (xx) −x−1, y, −z+1/2; (xxi) x−1/2, y+1/2, z+1/2; (xxii) x−1/2, −y+1/2, −z; (xxiii) −x+1/2, y−1/2, z; (xxiv) −x, −y, −z; (xxv) x, −y, z−1/2; (xxvi) x+1/2, y−1/2, z−1/2; (xxvii) −x−1/2, −y+1/2, z−1/2.