Nickel bis­muth boride, Ni23-xBixB6 [x = 2.44 (1)]

Berthebaud, D.; Sato, A.; Mori, T.

doi:10.1107/S1600536811000894

inorganic compounds

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Volume 67| Part 2| February 2011| Page i17

doi:10.1107/S1600536811000894

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Nickel bismuth boride, Ni_23-xBi_xB₆ [x = 2.44 (1)]

David Berthebaud,^a Akira Sato ^a and Takao Mori ^a ^*

^aNational Institute for Materials Science, Namiki 1-1, Tsukuba, 305-0044 Japan
^*Correspondence e-mail: mori.takao@nims.go.jp

(Received 2 November 2010; accepted 6 January 2011; online 15 January 2011)

The τ-boride Ni_23-xBi_xB₆ [x = 2.44 (1)] adopts a ternary variant of the cubic Cr₂₃C₆-type structure, with Ni₈ cubes and Ni₁₂ cuboctahedra arranged in a NaCl-type pattern. Two of the four independent metal sites (8c, $[\overline{4}]$ 3m symmetry; 4a, m $[\overline{3}]$ m symmetry) are occupied by a mixture of Ni and Bi atoms in a 0.106 (6):0.894 (6) and a 0.350 (7):0.650 (7) ratio, respectively.

Related literature

For the structure of Cr₂₃C₆, see: Westgren (1933 ). For other examples of τ-borides, which have more than 80 representatives, see: Villars & Calvert (1985 ). For ternary ordered variants, see: Hillebrecht & Ade (1998 ) for M₂₀M′₃B₆; Veremchuk et al. (2009 ) for M₂₁M′₂B₆. For isotypic cobalt-containing solid solutions Co_23-_xM'_xB₆, see: Kotzott et al. (2009 ).

Experimental

Crystal data

Ni_20.56Bi_2.44B₆
M_r = 1780.35
Cubic, $[F m \overline 3m ]$
a = 10.575 (5) Å
V = 1182.6 (10) Å³
Z = 4
Mo Kα radiation
μ = 67.81 mm⁻¹
T = 293 K
0.10 × 0.08 × 0.06 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.010, T_max = 0.067
6672 measured reflections
236 independent reflections
235 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.045
S = 1.16
236 reflections
15 parameters
Δρ_max = 2.18 e Å⁻³
Δρ_min = −2.22 e Å⁻³

Data collection: SMART (Bruker, 1999); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811000894/mg2107sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811000894/mg2107Isup2.hkl

checkCIF report

Comment top

Ni_23-_xBi_xB₆ belongs to a class of metal-rich compounds known as τ-borides, which are interesting ceramic materials. It is isostructural to numerous related M₂₀M'₃B₆ and M₂₁M'₂B₆ (M = 3d metal; M' = rare-earth, 4d, 5d, or main-group metal) phases, which adopt a ternary variant of the cubic Cr₂₃C₆-type structure (Westgren, 1933; Villars & Calvert, 1985; Hillebrecht & Ade, 1998; Veremchuk et al., 2009). Of the four metal sites, two (32f and 48h) are occupied exclusively by Ni atoms giving a NaCl-type arrangement of Ni₈ cubes and Ni₁₂ cuboctahedra, and two (4a and 8c) are occupied by a mixture of Ni and Bi atoms, resulting in the composition Ni_20.56Bi_2.44B₆ (Fig. 1). Mixed occupation of the 4a and 8c sites has also been previously reported in the Co-containing τ-borides Co_23-_xM'_xB₆ (Kotzott et al., 2009).

Related literature top

For the structure of Cr₂₃C₆, see: Westgren (1933). For other examples of τ-borides, which have more than 80 representatives, see: Villars & Calvert (1985). For ternary ordered variants, see: Hillebrecht & Ade (1998) for M₂₀M'₃B₆; Veremchuk et al. (2009) for M₂₁M'₂B₆. For isotypic cobalt-containing solid solutions Co_23-_xM'_xB₆, see: Kotzott et al. (2009).

Experimental top

A mixture of Ni, Bi, and B powders with nominal composition Ni₂₀Bi₃B₁₂ was pressed into a pellet and placed in an alumina crucible. It was melted under Ar gas at 1473 K for 6 h, cooled at 20 K h^-1 to 1273 K, and further cooled at 300 K h^-1 to room temperature. The sample contained crystals of the title compound, in the presence of binary nickel borides, as revealed by powder X-ray diffraction analysis.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. Structure of Ni_23-_xBi_xB₆ highlighting the arrangement of Ni₁₂ cuboctahedra (Ni3, 48 h) and Ni₈ cubes (Ni2, 32f). Displacement ellipsoids are drawn at the 60% probability level. Symmetry codes are defined in the footnote of the table of geometric parameters.

nickel bismuth boron (20.56/2.44/6) top

Crystal data top

B₆Bi_2.44Ni_20.56	D_x = 9.999 Mg m⁻³
M_r = 1780.35	Mo Kα radiation, λ = 0.71073 Å
Cubic, Fm3m	Cell parameters from 834 reflections
Hall symbol: -F 4 2 3	θ = 3.3–40.4°
a = 10.575 (5) Å	µ = 67.81 mm⁻¹
V = 1182.6 (10) Å³	T = 293 K
Z = 4	Prism, grey
F(000) = 3231	0.10 × 0.08 × 0.06 mm

Data collection top

Bruker SMART APEX CCD diffractometer	235 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ω scans	θ_max = 40.4°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −19→19
T_min = 0.010, T_max = 0.067	k = −19→19
6672 measured reflections	l = −17→19
236 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.020	w = 1/[σ²(F_o²) + (0.0165P)² + 39.3966P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.045	(Δ/σ)_max < 0.001
S = 1.16	Δρ_max = 2.18 e Å⁻³
236 reflections	Δρ_min = −2.22 e Å⁻³
15 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
0 restraints	Extinction coefficient: 0.00047 (4)

Crystal data top

B₆Bi_2.44Ni_20.56	Z = 4
M_r = 1780.35	Mo Kα radiation
Cubic, Fm3m	µ = 67.81 mm⁻¹
a = 10.575 (5) Å	T = 293 K
V = 1182.6 (10) Å³	0.10 × 0.08 × 0.06 mm

Data collection top

Bruker SMART APEX CCD diffractometer	236 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	235 reflections with I > 2σ(I)
T_min = 0.010, T_max = 0.067	R_int = 0.044
6672 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	0 restraints
wR(F²) = 0.045	w = 1/[σ²(F_o²) + (0.0165P)² + 39.3966P] where P = (F_o² + 2F_c²)/3
S = 1.16	Δρ_max = 2.18 e Å⁻³
236 reflections	Δρ_min = −2.22 e Å⁻³
15 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni2	0.38433 (4)	0.38433 (4)	0.38433 (4)	0.00939 (16)
Ni3	0	0.17150 (4)	0.17150 (4)	0.01007 (16)
Ni4	0.25	0.25	0.25	0.01036 (13)	0.106 (6)
Ni1	0	0	0	0.0092 (2)	0.349 (7)
Bi1	0.25	0.25	0.25	0.01036 (13)	0.894 (6)
Bi2	0	0	0	0.0092 (2)	0.650 (7)
B	0	0.2663 (7)	0	0.0109 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni2	0.00939 (16)	0.00939 (16)	0.00939 (16)	0.00036 (13)	0.00036 (13)	0.00036 (13)
Ni3	0.0116 (3)	0.00930 (19)	0.00930 (19)	0	0	−0.00020 (16)
Ni4	0.01036 (13)	0.01036 (13)	0.01036 (13)	0	0	0
Ni1	0.0092 (2)	0.0092 (2)	0.0092 (2)	0	0	0
Bi1	0.01036 (13)	0.01036 (13)	0.01036 (13)	0	0	0
Bi2	0.0092 (2)	0.0092 (2)	0.0092 (2)	0	0	0

Geometric parameters (Å, º) top

Ni2—Bⁱ	2.133 (5)	Ni4—Ni3^xv	2.8927 (14)
Ni2—Bⁱⁱ	2.133 (5)	Ni4—Ni3^xi	2.8927 (14)
Ni2—Bⁱⁱⁱ	2.133 (5)	Ni4—Ni3^x	2.8927 (14)
Ni2—Ni2^iv	2.4465 (15)	Ni4—Ni3^vii	2.8927 (14)
Ni2—Ni2^v	2.4465 (15)	Ni4—Ni3^ix	2.8927 (14)
Ni2—Ni2^vi	2.4465 (15)	Ni4—Ni3^viii	2.8927 (14)
Ni2—Ni4	2.4604 (14)	Ni4—Ni3^xvi	2.8927 (14)
Ni2—Ni3^vii	2.6287 (13)	Ni1—Ni3^xx	2.5648 (14)
Ni2—Ni3^viii	2.6287 (13)	Ni1—Ni3^xxi	2.5648 (14)
Ni2—Ni3^ix	2.6287 (13)	Ni1—Ni3^xv	2.5648 (14)
Ni2—Ni3^x	2.6287 (13)	Ni1—Ni3^xxii	2.5648 (14)
Ni3—B	2.072 (4)	Ni1—Ni3^xi	2.5648 (14)
Ni3—B^xi	2.072 (4)	Ni1—Ni3^xxiii	2.5648 (14)
Ni3—Ni3^xii	2.3480 (17)	Ni1—Ni3^xxiv	2.5648 (14)
Ni3—Ni1	2.5648 (14)	Ni1—Ni3^xxv	2.5648 (14)
Ni3—Ni3^xiii	2.5648 (14)	Ni1—Ni3^xiv	2.5648 (14)
Ni3—Ni3^xiv	2.5648 (14)	Ni1—Ni3^xxvi	2.5648 (14)
Ni3—Ni3^xv	2.5648 (14)	Ni1—Ni3^xiii	2.5648 (14)
Ni3—Ni3^xi	2.5648 (14)	B—Ni3^xiii	2.072 (4)
Ni3—Ni2^xvi	2.6287 (13)	B—Ni3^xxiv	2.072 (4)
Ni3—Ni2^xvii	2.6287 (13)	B—Ni3^xv	2.072 (4)
Ni3—Ni2^xviii	2.6287 (13)	B—Ni2^xvii	2.133 (5)
Ni4—Ni2^xvii	2.4604 (14)	B—Ni2^xxvii	2.133 (5)
Ni4—Ni2^xix	2.4604 (14)	B—Ni2^xxviii	2.133 (5)
Ni4—Ni2^xvi	2.4604 (14)	B—Ni2^xviii	2.133 (5)

Bⁱ—Ni2—Bⁱⁱ	110.02 (17)	Ni3^xv—Ni4—Ni3^x	146.645 (15)
Bⁱ—Ni2—Bⁱⁱⁱ	110.02 (17)	Ni3^xi—Ni4—Ni3^x	116.245 (7)
Bⁱⁱ—Ni2—Bⁱⁱⁱ	110.02 (17)	Ni3—Ni4—Ni3^x	94.724 (4)
Bⁱ—Ni2—Ni2^iv	55.01 (9)	Ni2—Ni4—Ni3^vii	58.152 (3)
Bⁱⁱ—Ni2—Ni2^iv	125.82 (17)	Ni2^xvii—Ni4—Ni3^vii	149.209 (11)
Bⁱⁱⁱ—Ni2—Ni2^iv	55.01 (9)	Ni2^xix—Ni4—Ni3^vii	58.152 (3)
Bⁱ—Ni2—Ni2^v	125.82 (17)	Ni2^xvi—Ni4—Ni3^vii	101.320 (11)
Bⁱⁱ—Ni2—Ni2^v	55.01 (9)	Ni3^xv—Ni4—Ni3^vii	116.245 (7)
Bⁱⁱⁱ—Ni2—Ni2^v	55.01 (9)	Ni3^xi—Ni4—Ni3^vii	94.724 (4)
Ni2^iv—Ni2—Ni2^v	90	Ni3—Ni4—Ni3^vii	146.645 (15)
Bⁱ—Ni2—Ni2^vi	55.01 (9)	Ni3^x—Ni4—Ni3^vii	94.724 (4)
Bⁱⁱ—Ni2—Ni2^vi	55.01 (9)	Ni2—Ni4—Ni3^ix	58.152 (3)
Bⁱⁱⁱ—Ni2—Ni2^vi	125.82 (17)	Ni2^xvii—Ni4—Ni3^ix	149.209 (11)
Ni2^iv—Ni2—Ni2^vi	90	Ni2^xix—Ni4—Ni3^ix	101.320 (11)
Ni2^v—Ni2—Ni2^vi	90	Ni2^xvi—Ni4—Ni3^ix	58.152 (3)
Bⁱ—Ni2—Ni4	108.92 (17)	Ni3^xv—Ni4—Ni3^ix	146.645 (15)
Bⁱⁱ—Ni2—Ni4	108.92 (17)	Ni3^xi—Ni4—Ni3^ix	94.724 (4)
Bⁱⁱⁱ—Ni2—Ni4	108.92 (17)	Ni3—Ni4—Ni3^ix	116.245 (7)
Ni2^iv—Ni2—Ni4	125.3	Ni3^x—Ni4—Ni3^ix	47.89 (2)
Ni2^v—Ni2—Ni4	125.3	Ni3^vii—Ni4—Ni3^ix	52.632 (19)
Ni2^vi—Ni2—Ni4	125.3	Ni2—Ni4—Ni3^viii	58.152 (3)
Bⁱ—Ni2—Ni3^vii	153.13 (3)	Ni2^xvii—Ni4—Ni3^viii	58.152 (3)
Bⁱⁱ—Ni2—Ni3^vii	95.32 (6)	Ni2^xix—Ni4—Ni3^viii	149.209 (11)
Bⁱⁱⁱ—Ni2—Ni3^vii	50.27 (13)	Ni2^xvi—Ni4—Ni3^viii	101.320 (11)
Ni2^iv—Ni2—Ni3^vii	102.978 (14)	Ni3^xv—Ni4—Ni3^viii	116.245 (7)
Ni2^v—Ni2—Ni3^vii	62.268 (15)	Ni3^xi—Ni4—Ni3^viii	146.645 (15)
Ni2^vi—Ni2—Ni3^vii	148.889 (13)	Ni3—Ni4—Ni3^viii	94.724 (4)
Ni4—Ni2—Ni3^vii	69.188 (17)	Ni3^x—Ni4—Ni3^viii	52.632 (19)
Bⁱ—Ni2—Ni3^viii	50.27 (13)	Ni3^vii—Ni4—Ni3^viii	116.245 (7)
Bⁱⁱ—Ni2—Ni3^viii	95.32 (6)	Ni3^ix—Ni4—Ni3^viii	94.724 (4)
Bⁱⁱⁱ—Ni2—Ni3^viii	153.12 (3)	Ni2—Ni4—Ni3^xvi	58.152 (3)
Ni2^iv—Ni2—Ni3^viii	102.978 (14)	Ni2^xvii—Ni4—Ni3^xvi	101.320 (11)
Ni2^v—Ni2—Ni3^viii	148.889 (13)	Ni2^xix—Ni4—Ni3^xvi	58.152 (3)
Ni2^vi—Ni2—Ni3^viii	62.268 (15)	Ni2^xvi—Ni4—Ni3^xvi	149.209 (11)
Ni4—Ni2—Ni3^viii	69.188 (17)	Ni3^xv—Ni4—Ni3^xvi	94.724 (4)
Ni3^vii—Ni2—Ni3^viii	138.28 (3)	Ni3^xi—Ni4—Ni3^xvi	116.245 (7)
Bⁱ—Ni2—Ni3^ix	95.32 (6)	Ni3—Ni4—Ni3^xvi	146.645 (15)
Bⁱⁱ—Ni2—Ni3^ix	153.13 (3)	Ni3^x—Ni4—Ni3^xvi	116.245 (7)
Bⁱⁱⁱ—Ni2—Ni3^ix	50.27 (13)	Ni3^vii—Ni4—Ni3^xvi	47.89 (2)
Ni2^iv—Ni2—Ni3^ix	62.268 (15)	Ni3^ix—Ni4—Ni3^xvi	94.724 (4)
Ni2^v—Ni2—Ni3^ix	102.978 (14)	Ni3^viii—Ni4—Ni3^xvi	94.724 (4)
Ni2^vi—Ni2—Ni3^ix	148.889 (13)	Ni3—Ni1—Ni3^xx	120
Ni4—Ni2—Ni3^ix	69.188 (17)	Ni3—Ni1—Ni3^xxi	180.00 (3)
Ni3^vii—Ni2—Ni3^ix	58.40 (2)	Ni3^xx—Ni1—Ni3^xxi	60
Ni3^viii—Ni2—Ni3^ix	108.098 (18)	Ni3—Ni1—Ni3^xv	60
Bⁱ—Ni2—Ni3^x	50.27 (13)	Ni3^xx—Ni1—Ni3^xv	180.00 (3)
Bⁱⁱ—Ni2—Ni3^x	153.13 (3)	Ni3^xxi—Ni1—Ni3^xv	120
Bⁱⁱⁱ—Ni2—Ni3^x	95.32 (6)	Ni3—Ni1—Ni3^xxii	120
Ni2^iv—Ni2—Ni3^x	62.268 (15)	Ni3^xx—Ni1—Ni3^xxii	60
Ni2^v—Ni2—Ni3^x	148.889 (13)	Ni3^xxi—Ni1—Ni3^xxii	60
Ni2^vi—Ni2—Ni3^x	102.978 (14)	Ni3^xv—Ni1—Ni3^xxii	120
Ni4—Ni2—Ni3^x	69.188 (17)	Ni3—Ni1—Ni3^xi	60
Ni3^vii—Ni2—Ni3^x	108.098 (18)	Ni3^xx—Ni1—Ni3^xi	120
Ni3^viii—Ni2—Ni3^x	58.40 (2)	Ni3^xxi—Ni1—Ni3^xi	120
Ni3^ix—Ni2—Ni3^x	53.05 (2)	Ni3^xv—Ni1—Ni3^xi	60
B—Ni3—B^xi	147.8 (4)	Ni3^xxii—Ni1—Ni3^xi	180.00 (3)
B—Ni3—Ni3^xii	106.08 (19)	Ni3—Ni1—Ni3^xxiii	120
B^xi—Ni3—Ni3^xii	106.08 (19)	Ni3^xx—Ni1—Ni3^xxiii	90
B—Ni3—Ni1	73.92 (19)	Ni3^xxi—Ni1—Ni3^xxiii	60
B^xi—Ni3—Ni1	73.92 (19)	Ni3^xv—Ni1—Ni3^xxiii	90
Ni3^xii—Ni3—Ni1	180.00 (3)	Ni3^xxii—Ni1—Ni3^xxiii	120
B—Ni3—Ni3^xiii	51.76 (8)	Ni3^xi—Ni1—Ni3^xxiii	60
B^xi—Ni3—Ni3^xiii	110.00 (12)	Ni3—Ni1—Ni3^xxiv	90
Ni3^xii—Ni3—Ni3^xiii	120	Ni3^xx—Ni1—Ni3^xxiv	120
Ni1—Ni3—Ni3^xiii	60	Ni3^xxi—Ni1—Ni3^xxiv	90
B—Ni3—Ni3^xiv	110.00 (12)	Ni3^xv—Ni1—Ni3^xxiv	60
B^xi—Ni3—Ni3^xiv	51.76 (8)	Ni3^xxii—Ni1—Ni3^xxiv	60
Ni3^xii—Ni3—Ni3^xiv	120	Ni3^xi—Ni1—Ni3^xxiv	120
Ni1—Ni3—Ni3^xiv	60	Ni3^xxiii—Ni1—Ni3^xxiv	120
Ni3^xiii—Ni3—Ni3^xiv	60	Ni3—Ni1—Ni3^xxv	90
B—Ni3—Ni3^xv	51.76 (8)	Ni3^xx—Ni1—Ni3^xxv	60
B^xi—Ni3—Ni3^xv	110.00 (12)	Ni3^xxi—Ni1—Ni3^xxv	90
Ni3^xii—Ni3—Ni3^xv	120	Ni3^xv—Ni1—Ni3^xxv	120
Ni1—Ni3—Ni3^xv	60	Ni3^xxii—Ni1—Ni3^xxv	120
Ni3^xiii—Ni3—Ni3^xv	90	Ni3^xi—Ni1—Ni3^xxv	60
Ni3^xiv—Ni3—Ni3^xv	120	Ni3^xxiii—Ni1—Ni3^xxv	60
B—Ni3—Ni3^xi	110.00 (12)	Ni3^xxiv—Ni1—Ni3^xxv	180.00 (3)
B^xi—Ni3—Ni3^xi	51.76 (8)	Ni3—Ni1—Ni3^xiv	60
Ni3^xii—Ni3—Ni3^xi	120	Ni3^xx—Ni1—Ni3^xiv	60
Ni1—Ni3—Ni3^xi	60	Ni3^xxi—Ni1—Ni3^xiv	120
Ni3^xiii—Ni3—Ni3^xi	120	Ni3^xv—Ni1—Ni3^xiv	120
Ni3^xiv—Ni3—Ni3^xi	90	Ni3^xxii—Ni1—Ni3^xiv	90
Ni3^xv—Ni3—Ni3^xi	60	Ni3^xi—Ni1—Ni3^xiv	90
B—Ni3—Ni2^xvi	149.09 (8)	Ni3^xxiii—Ni1—Ni3^xiv	120
B^xi—Ni3—Ni2^xvi	52.37 (15)	Ni3^xxiv—Ni1—Ni3^xiv	120
Ni3^xii—Ni3—Ni2^xvi	63.474 (12)	Ni3^xxv—Ni1—Ni3^xiv	60
Ni1—Ni3—Ni2^xvi	116.526 (12)	Ni3—Ni1—Ni3^xxvi	120
Ni3^xiii—Ni3—Ni2^xvi	159.139 (17)	Ni3^xx—Ni1—Ni3^xxvi	120
Ni3^xiv—Ni3—Ni2^xvi	99.802 (17)	Ni3^xxi—Ni1—Ni3^xxvi	60
Ni3^xv—Ni3—Ni2^xvi	106.043 (14)	Ni3^xv—Ni1—Ni3^xxvi	60
Ni3^xi—Ni3—Ni2^xvi	60.801 (12)	Ni3^xxii—Ni1—Ni3^xxvi	90
B—Ni3—Ni2^xvii	52.37 (15)	Ni3^xi—Ni1—Ni3^xxvi	90
B^xi—Ni3—Ni2^xvii	149.09 (8)	Ni3^xxiii—Ni1—Ni3^xxvi	60
Ni3^xii—Ni3—Ni2^xvii	63.474 (12)	Ni3^xxiv—Ni1—Ni3^xxvi	60
Ni1—Ni3—Ni2^xvii	116.526 (12)	Ni3^xxv—Ni1—Ni3^xxvi	120
Ni3^xiii—Ni3—Ni2^xvii	99.802 (17)	Ni3^xiv—Ni1—Ni3^xxvi	180.00 (3)
Ni3^xiv—Ni3—Ni2^xvii	159.139 (17)	Ni3—Ni1—Ni3^xiii	60
Ni3^xv—Ni3—Ni2^xvii	60.801 (12)	Ni3^xx—Ni1—Ni3^xiii	90
Ni3^xi—Ni3—Ni2^xvii	106.043 (14)	Ni3^xxi—Ni1—Ni3^xiii	120
Ni2^xvi—Ni3—Ni2^xvii	99.67 (3)	Ni3^xv—Ni1—Ni3^xiii	90
B—Ni3—Ni2^xviii	52.37 (15)	Ni3^xxii—Ni1—Ni3^xiii	60
B^xi—Ni3—Ni2^xviii	149.09 (8)	Ni3^xi—Ni1—Ni3^xiii	120
Ni3^xii—Ni3—Ni2^xviii	63.474 (12)	Ni3^xxiii—Ni1—Ni3^xiii	180.00 (3)
Ni1—Ni3—Ni2^xviii	116.526 (12)	Ni3^xxiv—Ni1—Ni3^xiii	60
Ni3^xiii—Ni3—Ni2^xviii	60.801 (12)	Ni3^xxv—Ni1—Ni3^xiii	120
Ni3^xiv—Ni3—Ni2^xviii	106.043 (14)	Ni3^xiv—Ni1—Ni3^xiii	60
Ni3^xv—Ni3—Ni2^xviii	99.802 (17)	Ni3^xxvi—Ni1—Ni3^xiii	120
Ni3^xi—Ni3—Ni2^xviii	159.139 (17)	Ni3^xiii—B—Ni3^xxiv	76.47 (16)
Ni2^xvi—Ni3—Ni2^xviii	126.95 (2)	Ni3^xiii—B—Ni3	76.47 (16)
Ni2^xvii—Ni3—Ni2^xviii	55.46 (3)	Ni3^xxiv—B—Ni3	122.2 (4)
Ni2—Ni4—Ni2^xvii	109.5	Ni3^xiii—B—Ni3^xv	122.2 (4)
Ni2—Ni4—Ni2^xix	109.5	Ni3^xxiv—B—Ni3^xv	76.47 (16)
Ni2^xvii—Ni4—Ni2^xix	109.5	Ni3—B—Ni3^xv	76.47 (16)
Ni2—Ni4—Ni2^xvi	109.5	Ni3^xiii—B—Ni2^xvii	141.71 (6)
Ni2^xvii—Ni4—Ni2^xvi	109.5	Ni3^xxiv—B—Ni2^xvii	141.71 (6)
Ni2^xix—Ni4—Ni2^xvi	109.5	Ni3—B—Ni2^xvii	77.36 (3)
Ni2—Ni4—Ni3^xv	149.209 (11)	Ni3^xv—B—Ni2^xvii	77.36 (3)
Ni2^xvii—Ni4—Ni3^xv	58.152 (3)	Ni3^xiii—B—Ni2^xxvii	77.36 (3)
Ni2^xix—Ni4—Ni3^xv	58.152 (3)	Ni3^xxiv—B—Ni2^xxvii	77.36 (3)
Ni2^xvi—Ni4—Ni3^xv	101.320 (11)	Ni3—B—Ni2^xxvii	141.71 (6)
Ni2—Ni4—Ni3^xi	149.209 (11)	Ni3^xv—B—Ni2^xxvii	141.71 (6)
Ni2^xvii—Ni4—Ni3^xi	101.320 (11)	Ni2^xvii—B—Ni2^xxvii	108.4 (3)
Ni2^xix—Ni4—Ni3^xi	58.152 (3)	Ni3^xiii—B—Ni2^xxviii	141.71 (6)
Ni2^xvi—Ni4—Ni3^xi	58.152 (3)	Ni3^xxiv—B—Ni2^xxviii	77.36 (3)
Ni3^xv—Ni4—Ni3^xi	52.632 (19)	Ni3—B—Ni2^xxviii	141.71 (6)
Ni2—Ni4—Ni3	149.209 (11)	Ni3^xv—B—Ni2^xxviii	77.36 (3)
Ni2^xvii—Ni4—Ni3	58.152 (3)	Ni2^xvii—B—Ni2^xxviii	69.97 (17)
Ni2^xix—Ni4—Ni3	101.320 (11)	Ni2^xxvii—B—Ni2^xxviii	69.97 (17)
Ni2^xvi—Ni4—Ni3	58.152 (3)	Ni3^xiii—B—Ni2^xviii	77.36 (3)
Ni3^xv—Ni4—Ni3	52.632 (19)	Ni3^xxiv—B—Ni2^xviii	141.71 (6)
Ni3^xi—Ni4—Ni3	52.632 (19)	Ni3—B—Ni2^xviii	77.36 (3)
Ni2—Ni4—Ni3^x	58.152 (3)	Ni3^xv—B—Ni2^xviii	141.71 (6)
Ni2^xvii—Ni4—Ni3^x	101.320 (11)	Ni2^xvii—B—Ni2^xviii	69.97 (17)
Ni2^xix—Ni4—Ni3^x	149.209 (11)	Ni2^xxvii—B—Ni2^xviii	69.97 (17)
Ni2^xvi—Ni4—Ni3^x	58.152 (3)	Ni2^xxviii—B—Ni2^xviii	108.4 (3)

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

Experimental details

Crystal data
Chemical formula	B₆Bi_2.44Ni_20.56
M_r	1780.35
Crystal system, space group	Cubic, Fm3m
Temperature (K)	293
a (Å)	10.575 (5)
V (Å³)	1182.6 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	67.81
Crystal size (mm)	0.10 × 0.08 × 0.06

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.010, 0.067
No. of measured, independent and observed [I > 2σ(I)] reflections	6672, 236, 235
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.912

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.045, 1.16
No. of reflections	236
No. of parameters	15
	w = 1/[σ²(F_o²) + (0.0165P)² + 39.3966P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	2.18, −2.22

Computer programs: SMART (Bruker, 1999), SAINT-Plus (Bruker, 1999), SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2005), WinGX (Farrugia, 1999).

Acknowledgements

This work was supported in part by a grant from AOARD (AOARD 104144).

References

Brandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (1999). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Hillebrecht, H. & Ade, M. (1998). Angew. Chem. Int. Ed. 37, 935–938. CrossRef CAS Google Scholar
Kotzott, D., Ade, M. & Hillebrecht, H. (2009). J. Solid State Chem. 182, 538–546. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Veremchuk, I., Gumeniuk, R., Prots, Yu., Schnelle, W., Burkhardt, U., Rosner, H., Kuz'ma, Yu., & Leithe-Jasper, A. (2009). Solid State Sci. 11, 507–512. Web of Science CrossRef CAS Google Scholar
Villars, P. & Calvert, L. D. (1985). Pearson's Handbook of Crystallographic Data for Intermetallics Phases. Metals Park, Ohio: American Society for Metals. Google Scholar
Westgren, A. (1933). Nature (London), 132, 480–481. CrossRef CAS Google Scholar