Interstitial defects in the van der Waals gap of Bi₂Se₃

Bi₂Se₃ is a thermoelectric material and a topological insulator. It is slightly conducting in its bulk due to the presence of defects and by controlling the defects different physical properties can be fine tuned. However, studies of the defects in this material are often contradicting or inconclusive. Here, the defect structure of Bi₂Se₃ is studied with a combination of techniques: high-resolution scanning transmission electron microscopy (HR-STEM), high-resolution energy-dispersive X-ray (HR-EDX) spectroscopy, precession electron diffraction tomography (PEDT), X-ray diffraction (XRD) and first-principles calculations using density functional theory (DFT). Based on these results, not only the observed defects are discussed, but also the discrepancies in results or possibilities across the techniques. STEM and EDX revealed interstitial defects with mainly Bi character in an octahedral coordination in the van der Waals gap, independent of the applied sample preparation method (focused ion beam milling or cryo-crushing). The inherent character of these defects is supported by their observation in the structure refinement of the EDT data. Moreover, the occupancy probability of the defects determined by EDT is inversely proportional to their corresponding DFT calculated formation energies. STEM also showed the migration of some atoms across and along the van der Waals gap. The kinetic barriers calculated using DFT suggest that some paths are possible at room temperature, while others are most probably beam induced.

Computing details

(I)

Crystal data

Bi2.318Se2.682	F(000) = 850
Mr = 696.19	Dx = 8.148 Mg m^−3
Trigonal, R3m	Electron radiation, λ = 0.0251 Å
Hall symbol: -R 3 2"	Cell parameters from 1513 reflections
a = 4.1407 Å	θ = 0.2–1.3°
c = 28.6564 Å	µ = 0 mm^−1
V = 425.50 Å^3	T = 293 K
Z = 3	Single Crystal

Data collection

TecnaiG2 diffractometer	θmax = 1.3°, θmin = 0.2°
2400 measured reflections	h = −7→7
1513 independent reflections	k = −7→7
687 reflections with I > 3σ(I)	l = −44→44

Refinement

Refinement on F	0 restraints
R[F^2 > 2σ(F^2)] = 0.149	0 constraints
wR(F^2) = 0.166	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
S = 6.57	(Δ/σ)max = 0.043
1513 reflections	Δρmax = 3.44 e Å^−3
7 parameters	Δρmin = −1.19 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Bi1	0	0	0.40045 (11)	0.0228 (3)*
Se1	0	0	0	0.0246 (15)*	0.87 (2)
Bi2	0	0	0	0.0246 (15)*	0.13 (2)
Se2	0	0	0.20997 (17)	0.0273 (13)*	0.906 (17)
Bi3	0	0	0.20997 (17)	0.0273 (13)*	0.094 (17)

Geometric parameters (Å, º)

Bi1—Bi2^i	3.068 (2)	Bi1—Bi3^v	2.883 (3)
Bi1—Bi2^ii	3.068 (2)	Bi1—Bi3^vi	2.883 (3)
Bi1—Bi2^iii	3.068 (2)	Se1—Bi2	0
Bi1—Se2^iv	2.883 (3)	Se2—Bi3	0
Bi1—Se2^v	2.883 (3)	Bi3—Bi3^vii	3.446 (5)
Bi1—Se2^vi	2.883 (3)	Bi3—Bi3^viii	3.446 (5)
Bi1—Bi3^iv	2.883 (3)	Bi3—Bi3^ix	3.446 (5)
Bi2^i—Bi1—Bi2^ii	84.87 (7)	Bi1^xi—Bi2—Bi1^xii	84.87 (5)
Bi2^i—Bi1—Bi2^iii	84.87 (7)	Bi1^xi—Bi2—Bi1^vii	95.13 (5)
Bi2^i—Bi1—Se2^iv	91.57 (6)	Bi1^xi—Bi2—Bi1^viii	180.0 (5)
Bi2^i—Bi1—Se2^v	91.57 (6)	Bi1^xi—Bi2—Bi1^ix	95.13 (5)
Bi2^i—Bi1—Se2^vi	175.17 (13)	Bi1^xi—Bi2—Se1	0
Bi2^i—Bi1—Bi3^iv	91.57 (6)	Bi1^xii—Bi2—Bi1^vii	180.0 (5)
Bi2^i—Bi1—Bi3^v	91.57 (6)	Bi1^xii—Bi2—Bi1^viii	95.13 (5)
Bi2^i—Bi1—Bi3^vi	175.17 (13)	Bi1^xii—Bi2—Bi1^ix	95.13 (5)
Bi2^ii—Bi1—Bi2^iii	84.87 (7)	Bi1^xii—Bi2—Se1	0
Bi2^ii—Bi1—Se2^iv	91.57 (6)	Bi1^vii—Bi2—Bi1^viii	84.87 (5)
Bi2^ii—Bi1—Se2^v	175.17 (13)	Bi1^vii—Bi2—Bi1^ix	84.87 (5)
Bi2^ii—Bi1—Se2^vi	91.57 (6)	Bi1^vii—Bi2—Se1	0
Bi2^ii—Bi1—Bi3^iv	91.57 (6)	Bi1^viii—Bi2—Bi1^ix	84.87 (5)
Bi2^ii—Bi1—Bi3^v	175.17 (13)	Bi1^viii—Bi2—Se1	0
Bi2^ii—Bi1—Bi3^vi	91.57 (6)	Bi1^ix—Bi2—Se1	0
Bi2^iii—Bi1—Se2^iv	175.17 (13)	Bi1^iv—Se2—Bi1^v	91.79 (12)
Bi2^iii—Bi1—Se2^v	91.57 (6)	Bi1^iv—Se2—Bi1^vi	91.79 (12)
Bi2^iii—Bi1—Se2^vi	91.57 (6)	Bi1^iv—Se2—Bi3	0
Bi2^iii—Bi1—Bi3^iv	175.17 (13)	Bi1^v—Se2—Bi1^vi	91.79 (12)
Bi2^iii—Bi1—Bi3^v	91.57 (6)	Bi1^v—Se2—Bi3	0
Bi2^iii—Bi1—Bi3^vi	91.57 (6)	Bi1^vi—Se2—Bi3	0
Se2^iv—Bi1—Se2^v	91.79 (11)	Bi1^iv—Bi3—Bi1^v	91.79 (12)
Se2^iv—Bi1—Se2^vi	91.79 (11)	Bi1^iv—Bi3—Bi1^vi	91.79 (12)
Se2^iv—Bi1—Bi3^iv	0.0 (5)	Bi1^iv—Bi3—Se2	0
Se2^iv—Bi1—Bi3^v	91.79 (11)	Bi1^iv—Bi3—Bi3^vii	96.60 (6)
Se2^iv—Bi1—Bi3^vi	91.79 (11)	Bi1^iv—Bi3—Bi3^viii	96.60 (6)
Se2^v—Bi1—Se2^vi	91.79 (11)	Bi1^iv—Bi3—Bi3^ix	167.91 (16)
Se2^v—Bi1—Bi3^iv	91.79 (11)	Bi1^v—Bi3—Bi1^vi	91.79 (12)
Se2^v—Bi1—Bi3^v	0.0 (5)	Bi1^v—Bi3—Se2	0
Se2^v—Bi1—Bi3^vi	91.79 (11)	Bi1^v—Bi3—Bi3^vii	96.60 (6)
Se2^vi—Bi1—Bi3^iv	91.79 (11)	Bi1^v—Bi3—Bi3^viii	167.91 (16)
Se2^vi—Bi1—Bi3^v	91.79 (11)	Bi1^v—Bi3—Bi3^ix	96.60 (6)
Se2^vi—Bi1—Bi3^vi	0.0 (5)	Bi1^vi—Bi3—Se2	0
Bi3^iv—Bi1—Bi3^v	91.79 (11)	Bi1^vi—Bi3—Bi3^vii	167.91 (16)
Bi3^iv—Bi1—Bi3^vi	91.79 (11)	Bi1^vi—Bi3—Bi3^viii	96.60 (6)
Bi3^v—Bi1—Bi3^vi	91.79 (11)	Bi1^vi—Bi3—Bi3^ix	96.60 (6)
Bi1^x—Bi2—Bi1^xi	84.87 (5)	Se2—Bi3—Bi3^vii	0
Bi1^x—Bi2—Bi1^xii	84.87 (5)	Se2—Bi3—Bi3^viii	0
Bi1^x—Bi2—Bi1^vii	95.13 (5)	Se2—Bi3—Bi3^ix	0
Bi1^x—Bi2—Bi1^viii	95.13 (5)	Bi3^vii—Bi3—Bi3^viii	73.85 (11)
Bi1^x—Bi2—Bi1^ix	180.0 (5)	Bi3^vii—Bi3—Bi3^ix	73.85 (11)
Bi1^x—Bi2—Se1	0	Bi3^viii—Bi3—Bi3^ix	73.85 (11)

Symmetry codes: (i) x−1/3, y−2/3, z+1/3; (ii) x−1/3, y+1/3, z+1/3; (iii) x+2/3, y+1/3, z+1/3; (iv) y−2/3, x−1/3, −z+2/3; (v) y+1/3, x−1/3, −z+2/3; (vi) y+1/3, x+2/3, −z+2/3; (vii) y−1/3, x−2/3, −z+1/3; (viii) y−1/3, x+1/3, −z+1/3; (ix) y+2/3, x+1/3, −z+1/3; (x) x−2/3, y−1/3, z−1/3; (xi) x+1/3, y−1/3, z−1/3; (xii) x+1/3, y+2/3, z−1/3.

(I_1)

Crystal data

Bi2.261Se2.740	F(000) = 809
Mr = 688.86	Dx = 8.076 Mg m^−3
Trigonal, R3m	Electron radiation, λ = 0.0251 Å
Hall symbol: -R 3 2"	Cell parameters from 1504 reflections
a = 4.1407 Å	θ = 0.2–1.3°
c = 28.6564 Å	µ = 0 mm^−1
V = 425.50 Å^3	T = 293 K
Z = 3	Single Crystal

Data collection

TecnaiG2 diffractometer	θmax = 1.3°, θmin = 0.2°
2400 measured reflections	h = −7→7
1504 independent reflections	k = −7→7
685 reflections with I > 3σ(I)	l = −44→44

Refinement

Refinement on F	0 restraints
R[F^2 > 2σ(F^2)] = 0.142	6 constraints
wR(F^2) = 0.159	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
S = 6.34	(Δ/σ)max = 0.042
1504 reflections	Δρmax = 3.60 e Å^−3
12 parameters	Δρmin = −1.18 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Bi1	0	0	0.40034 (11)	0.0225 (5)*	0.974 (10)
Se1	0	0	0	0.0243 (16)*	0.92 (3)
Bi2	0	0	0	0.0243 (16)*	0.08 (3)
Se2	0	0	0.2122 (5)	0.0268 (11)*	0.91 (2)
Bi3	0	0	0.198 (2)	0.0268 (11)*	0.09 (2)
Bi4	0	0	0.5	0.0268 (11)*	0.015 (6)
Bi5	0.333333	0.666667	0.606 (6)	0.0268 (11)*	0.019 (5)

Geometric parameters (Å, º)

Bi1—Bi2^i	3.066 (2)	Se2—Bi3	0.42 (6)
Bi1—Bi2^ii	3.066 (2)	Se2—Bi4^xi	2.724 (6)
Bi1—Bi2^iii	3.066 (2)	Se2—Bi4^xii	2.724 (6)
Bi1—Se2^iv	2.849 (7)	Se2—Bi4^xiii	2.724 (6)
Bi1—Se2^v	2.849 (7)	Se2—Bi5^xiv	2.95 (10)
Bi1—Se2^vi	2.849 (7)	Se2—Bi5^xi	2.95 (10)
Bi1—Bi3^iv	3.10 (4)	Se2—Bi5^xii	2.95 (10)
Bi1—Bi3^v	3.10 (4)	Bi3—Bi3^xv	2.98 (5)
Bi1—Bi3^vi	3.10 (4)	Bi3—Bi3^xvi	2.98 (5)
Bi1—Bi4	2.856 (3)	Bi3—Bi3^xvii	2.98 (5)
Bi1—Bi5^vii	2.397 (12)	Bi3—Bi4^xi	2.55 (2)
Bi1—Bi5^viii	2.397 (12)	Bi3—Bi4^xii	2.55 (2)
Bi1—Bi5^ix	2.397 (12)	Bi3—Bi4^xiii	2.55 (2)
Se1—Bi2	0	Bi3—Bi5^xiv	3.21 (11)
Se1—Bi5^x	1.75 (16)	Bi3—Bi5^xi	3.21 (11)
Se1—Bi5^iv	1.75 (16)	Bi3—Bi5^xii	3.21 (11)
Bi2—Bi5^x	1.75 (16)	Bi5—Bi5^xviii	3.5 (2)
Bi2—Bi5^iv	1.75 (16)
Bi2^i—Bi1—Bi2^ii	84.94 (7)	Se2—Bi3—Bi4^xii	110.3 (12)
Bi2^i—Bi1—Bi2^iii	84.94 (7)	Se2—Bi3—Bi4^xiii	110.3 (12)
Bi2^i—Bi1—Se2^iv	90.79 (16)	Se2—Bi3—Bi5^xiv	48 (2)
Bi2^i—Bi1—Se2^v	90.79 (16)	Se2—Bi3—Bi5^xi	48 (2)
Bi2^i—Bi1—Se2^vi	174.2 (2)	Se2—Bi3—Bi5^xii	48 (2)
Bi2^i—Bi1—Bi3^iv	95.6 (6)	Bi3^xv—Bi3—Bi3^xvi	88.2 (16)
Bi2^i—Bi1—Bi3^v	95.6 (6)	Bi3^xv—Bi3—Bi3^xvii	88.2 (16)
Bi2^i—Bi1—Bi3^vi	179.3 (8)	Bi3^xv—Bi3—Bi4^xi	54.3 (6)
Bi2^i—Bi1—Bi4	128.77 (5)	Bi3^xv—Bi3—Bi4^xii	54.3 (6)
Bi2^i—Bi1—Bi5^vii	35 (4)	Bi3^xv—Bi3—Bi4^xiii	123 (2)
Bi2^i—Bi1—Bi5^viii	110 (3)	Bi3^xv—Bi3—Bi5^xiv	78 (2)
Bi2^i—Bi1—Bi5^ix	110 (3)	Bi3^xv—Bi3—Bi5^xi	134.2 (7)
Bi2^ii—Bi1—Bi2^iii	84.94 (7)	Bi3^xv—Bi3—Bi5^xii	134.2 (7)
Bi2^ii—Bi1—Se2^iv	90.79 (16)	Bi3^xvi—Bi3—Bi3^xvii	88.2 (16)
Bi2^ii—Bi1—Se2^v	174.2 (2)	Bi3^xvi—Bi3—Bi4^xi	54.3 (6)
Bi2^ii—Bi1—Se2^vi	90.79 (16)	Bi3^xvi—Bi3—Bi4^xii	123 (2)
Bi2^ii—Bi1—Bi3^iv	95.6 (6)	Bi3^xvi—Bi3—Bi4^xiii	54.3 (6)
Bi2^ii—Bi1—Bi3^v	179.3 (8)	Bi3^xvi—Bi3—Bi5^xiv	134.2 (7)
Bi2^ii—Bi1—Bi3^vi	95.6 (6)	Bi3^xvi—Bi3—Bi5^xi	78 (2)
Bi2^ii—Bi1—Bi4	128.77 (5)	Bi3^xvi—Bi3—Bi5^xii	134.2 (7)
Bi2^ii—Bi1—Bi5^vii	110 (3)	Bi3^xvii—Bi3—Bi4^xi	123 (2)
Bi2^ii—Bi1—Bi5^viii	35 (4)	Bi3^xvii—Bi3—Bi4^xii	54.3 (6)
Bi2^ii—Bi1—Bi5^ix	110 (3)	Bi3^xvii—Bi3—Bi4^xiii	54.3 (6)
Bi2^iii—Bi1—Se2^iv	174.2 (2)	Bi3^xvii—Bi3—Bi5^xiv	134.2 (7)
Bi2^iii—Bi1—Se2^v	90.79 (16)	Bi3^xvii—Bi3—Bi5^xi	134.2 (7)
Bi2^iii—Bi1—Se2^vi	90.79 (16)	Bi3^xvii—Bi3—Bi5^xii	78 (2)
Bi2^iii—Bi1—Bi3^iv	179.3 (8)	Bi4^xi—Bi3—Bi4^xii	108.6 (13)
Bi2^iii—Bi1—Bi3^v	95.6 (6)	Bi4^xi—Bi3—Bi4^xiii	108.6 (13)
Bi2^iii—Bi1—Bi3^vi	95.6 (6)	Bi4^xi—Bi3—Bi5^xiv	83.3 (13)
Bi2^iii—Bi1—Bi4	128.77 (5)	Bi4^xi—Bi3—Bi5^xi	83.3 (13)
Bi2^iii—Bi1—Bi5^vii	110 (3)	Bi4^xi—Bi3—Bi5^xii	158 (3)
Bi2^iii—Bi1—Bi5^viii	110 (3)	Bi4^xii—Bi3—Bi4^xiii	108.6 (13)
Bi2^iii—Bi1—Bi5^ix	35 (4)	Bi4^xii—Bi3—Bi5^xiv	83.3 (13)
Se2^iv—Bi1—Se2^v	93.2 (2)	Bi4^xii—Bi3—Bi5^xi	158 (3)
Se2^iv—Bi1—Se2^vi	93.2 (2)	Bi4^xii—Bi3—Bi5^xii	83.3 (13)
Se2^iv—Bi1—Bi3^iv	6.5 (9)	Bi4^xiii—Bi3—Bi5^xiv	158 (3)
Se2^iv—Bi1—Bi3^v	88.7 (6)	Bi4^xiii—Bi3—Bi5^xi	83.3 (13)
Se2^iv—Bi1—Bi3^vi	88.7 (6)	Bi4^xiii—Bi3—Bi5^xii	83.3 (13)
Se2^iv—Bi1—Bi4	57.0 (2)	Bi5^xiv—Bi3—Bi5^xi	80 (3)
Se2^iv—Bi1—Bi5^vii	68 (2)	Bi5^xiv—Bi3—Bi5^xii	80 (3)
Se2^iv—Bi1—Bi5^viii	68 (2)	Bi5^xi—Bi3—Bi5^xii	80 (3)
Se2^iv—Bi1—Bi5^ix	151 (4)	Bi1—Bi4—Bi1^ix	180.0 (5)
Se2^v—Bi1—Se2^vi	93.2 (2)	Bi1—Bi4—Se2^i	118.6 (2)
Se2^v—Bi1—Bi3^iv	88.7 (6)	Bi1—Bi4—Se2^ii	118.6 (2)
Se2^v—Bi1—Bi3^v	6.5 (9)	Bi1—Bi4—Se2^iii	118.6 (2)
Se2^v—Bi1—Bi3^vi	88.7 (6)	Bi1—Bi4—Se2^iv	61.4 (2)
Se2^v—Bi1—Bi4	57.0 (2)	Bi1—Bi4—Se2^v	61.4 (2)
Se2^v—Bi1—Bi5^vii	68 (2)	Bi1—Bi4—Se2^vi	61.4 (2)
Se2^v—Bi1—Bi5^viii	151 (4)	Bi1—Bi4—Bi3^i	110.3 (12)
Se2^v—Bi1—Bi5^ix	68 (2)	Bi1—Bi4—Bi3^ii	110.3 (12)
Se2^vi—Bi1—Bi3^iv	88.7 (6)	Bi1—Bi4—Bi3^iii	110.3 (12)
Se2^vi—Bi1—Bi3^v	88.7 (6)	Bi1—Bi4—Bi3^iv	69.7 (12)
Se2^vi—Bi1—Bi3^vi	6.5 (9)	Bi1—Bi4—Bi3^v	69.7 (12)
Se2^vi—Bi1—Bi4	57.0 (2)	Bi1—Bi4—Bi3^vi	69.7 (12)
Se2^vi—Bi1—Bi5^vii	151 (4)	Bi1^ix—Bi4—Se2^i	61.4 (2)
Se2^vi—Bi1—Bi5^viii	68 (2)	Bi1^ix—Bi4—Se2^ii	61.4 (2)
Se2^vi—Bi1—Bi5^ix	68 (2)	Bi1^ix—Bi4—Se2^iii	61.4 (2)
Bi3^iv—Bi1—Bi3^v	83.9 (9)	Bi1^ix—Bi4—Se2^iv	118.6 (2)
Bi3^iv—Bi1—Bi3^vi	83.9 (9)	Bi1^ix—Bi4—Se2^v	118.6 (2)
Bi3^iv—Bi1—Bi4	50.5 (8)	Bi1^ix—Bi4—Se2^vi	118.6 (2)
Bi3^iv—Bi1—Bi5^vii	70 (3)	Bi1^ix—Bi4—Bi3^i	69.7 (12)
Bi3^iv—Bi1—Bi5^viii	70 (3)	Bi1^ix—Bi4—Bi3^ii	69.7 (12)
Bi3^iv—Bi1—Bi5^ix	145 (4)	Bi1^ix—Bi4—Bi3^iii	69.7 (12)
Bi3^v—Bi1—Bi3^vi	83.9 (9)	Bi1^ix—Bi4—Bi3^iv	110.3 (12)
Bi3^v—Bi1—Bi4	50.5 (8)	Bi1^ix—Bi4—Bi3^v	110.3 (12)
Bi3^v—Bi1—Bi5^vii	70 (3)	Bi1^ix—Bi4—Bi3^vi	110.3 (12)
Bi3^v—Bi1—Bi5^viii	145 (4)	Se2^i—Bi4—Se2^ii	98.9 (2)
Bi3^v—Bi1—Bi5^ix	70 (3)	Se2^i—Bi4—Se2^iii	98.9 (2)
Bi3^vi—Bi1—Bi4	50.5 (8)	Se2^i—Bi4—Se2^iv	81.1 (2)
Bi3^vi—Bi1—Bi5^vii	145 (4)	Se2^i—Bi4—Se2^v	81.1 (2)
Bi3^vi—Bi1—Bi5^viii	70 (3)	Se2^i—Bi4—Se2^vi	180.0 (5)
Bi3^vi—Bi1—Bi5^ix	70 (3)	Se2^i—Bi4—Bi3^i	8.3 (12)
Bi4—Bi1—Bi5^vii	94 (4)	Se2^i—Bi4—Bi3^ii	104.2 (8)
Bi4—Bi1—Bi5^viii	94 (4)	Se2^i—Bi4—Bi3^iii	104.2 (8)
Bi4—Bi1—Bi5^ix	94 (4)	Se2^i—Bi4—Bi3^iv	75.8 (8)
Bi5^vii—Bi1—Bi5^viii	119.5 (7)	Se2^i—Bi4—Bi3^v	75.8 (8)
Bi5^vii—Bi1—Bi5^ix	119.5 (7)	Se2^i—Bi4—Bi3^vi	171.7 (12)
Bi5^viii—Bi1—Bi5^ix	119.5 (7)	Se2^ii—Bi4—Se2^iii	98.9 (2)
Bi2—Se1—Bi5^x	0	Se2^ii—Bi4—Se2^iv	81.1 (2)
Bi2—Se1—Bi5^iv	0	Se2^ii—Bi4—Se2^v	180.0 (5)
Bi5^x—Se1—Bi5^iv	180.0 (5)	Se2^ii—Bi4—Se2^vi	81.1 (2)
Bi1^xi—Bi2—Bi1^xii	84.94 (5)	Se2^ii—Bi4—Bi3^i	104.2 (8)
Bi1^xi—Bi2—Bi1^xiii	84.94 (5)	Se2^ii—Bi4—Bi3^ii	8.3 (12)
Bi1^xi—Bi2—Bi1^xv	95.06 (5)	Se2^ii—Bi4—Bi3^iii	104.2 (8)
Bi1^xi—Bi2—Bi1^xvi	95.06 (5)	Se2^ii—Bi4—Bi3^iv	75.8 (8)
Bi1^xi—Bi2—Bi1^xvii	180.0 (5)	Se2^ii—Bi4—Bi3^v	171.7 (12)
Bi1^xi—Bi2—Se1	0	Se2^ii—Bi4—Bi3^vi	75.8 (8)
Bi1^xi—Bi2—Bi5^x	128.77 (5)	Se2^iii—Bi4—Se2^iv	180.0 (5)
Bi1^xi—Bi2—Bi5^iv	51.23 (5)	Se2^iii—Bi4—Se2^v	81.1 (2)
Bi1^xii—Bi2—Bi1^xiii	84.94 (5)	Se2^iii—Bi4—Se2^vi	81.1 (2)
Bi1^xii—Bi2—Bi1^xv	95.06 (5)	Se2^iii—Bi4—Bi3^i	104.2 (8)
Bi1^xii—Bi2—Bi1^xvi	180.0 (5)	Se2^iii—Bi4—Bi3^ii	104.2 (8)
Bi1^xii—Bi2—Bi1^xvii	95.06 (5)	Se2^iii—Bi4—Bi3^iii	8.3 (12)
Bi1^xii—Bi2—Se1	0	Se2^iii—Bi4—Bi3^iv	171.7 (12)
Bi1^xii—Bi2—Bi5^x	128.77 (5)	Se2^iii—Bi4—Bi3^v	75.8 (8)
Bi1^xii—Bi2—Bi5^iv	51.23 (5)	Se2^iii—Bi4—Bi3^vi	75.8 (8)
Bi1^xiii—Bi2—Bi1^xv	180.0 (5)	Se2^iv—Bi4—Se2^v	98.9 (2)
Bi1^xiii—Bi2—Bi1^xvi	95.06 (5)	Se2^iv—Bi4—Se2^vi	98.9 (2)
Bi1^xiii—Bi2—Bi1^xvii	95.06 (5)	Se2^iv—Bi4—Bi3^i	75.8 (8)
Bi1^xiii—Bi2—Se1	0	Se2^iv—Bi4—Bi3^ii	75.8 (8)
Bi1^xiii—Bi2—Bi5^x	128.77 (5)	Se2^iv—Bi4—Bi3^iii	171.7 (12)
Bi1^xiii—Bi2—Bi5^iv	51.23 (5)	Se2^iv—Bi4—Bi3^iv	8.3 (12)
Bi1^xv—Bi2—Bi1^xvi	84.94 (5)	Se2^iv—Bi4—Bi3^v	104.2 (8)
Bi1^xv—Bi2—Bi1^xvii	84.94 (5)	Se2^iv—Bi4—Bi3^vi	104.2 (8)
Bi1^xv—Bi2—Se1	0	Se2^v—Bi4—Se2^vi	98.9 (2)
Bi1^xv—Bi2—Bi5^x	51.23 (5)	Se2^v—Bi4—Bi3^i	75.8 (8)
Bi1^xv—Bi2—Bi5^iv	128.77 (5)	Se2^v—Bi4—Bi3^ii	171.7 (12)
Bi1^xvi—Bi2—Bi1^xvii	84.94 (5)	Se2^v—Bi4—Bi3^iii	75.8 (8)
Bi1^xvi—Bi2—Se1	0	Se2^v—Bi4—Bi3^iv	104.2 (8)
Bi1^xvi—Bi2—Bi5^x	51.23 (5)	Se2^v—Bi4—Bi3^v	8.3 (12)
Bi1^xvi—Bi2—Bi5^iv	128.77 (5)	Se2^v—Bi4—Bi3^vi	104.2 (8)
Bi1^xvii—Bi2—Se1	0	Se2^vi—Bi4—Bi3^i	171.7 (12)
Bi1^xvii—Bi2—Bi5^x	51.23 (5)	Se2^vi—Bi4—Bi3^ii	75.8 (8)
Bi1^xvii—Bi2—Bi5^iv	128.77 (5)	Se2^vi—Bi4—Bi3^iii	75.8 (8)
Se1—Bi2—Bi5^x	0	Se2^vi—Bi4—Bi3^iv	104.2 (8)
Se1—Bi2—Bi5^iv	0	Se2^vi—Bi4—Bi3^v	104.2 (8)
Bi5^x—Bi2—Bi5^iv	180.0 (5)	Se2^vi—Bi4—Bi3^vi	8.3 (12)
Bi1^iv—Se2—Bi1^v	93.2 (3)	Bi3^i—Bi4—Bi3^ii	108.6 (9)
Bi1^iv—Se2—Bi1^vi	93.2 (3)	Bi3^i—Bi4—Bi3^iii	108.6 (9)
Bi1^iv—Se2—Bi3	123.0 (2)	Bi3^i—Bi4—Bi3^iv	71.4 (9)
Bi1^iv—Se2—Bi4^xi	61.60 (6)	Bi3^i—Bi4—Bi3^v	71.4 (9)
Bi1^iv—Se2—Bi4^xii	128.97 (4)	Bi3^i—Bi4—Bi3^vi	180.0 (5)
Bi1^iv—Se2—Bi4^xiii	128.97 (4)	Bi3^ii—Bi4—Bi3^iii	108.6 (9)
Bi1^iv—Se2—Bi5^xiv	48.8 (7)	Bi3^ii—Bi4—Bi3^iv	71.4 (9)
Bi1^iv—Se2—Bi5^xi	48.8 (7)	Bi3^ii—Bi4—Bi3^v	180.0 (5)
Bi1^iv—Se2—Bi5^xii	111 (3)	Bi3^ii—Bi4—Bi3^vi	71.4 (9)
Bi1^v—Se2—Bi1^vi	93.2 (3)	Bi3^iii—Bi4—Bi3^iv	180.0 (5)
Bi1^v—Se2—Bi3	123.0 (2)	Bi3^iii—Bi4—Bi3^v	71.4 (9)
Bi1^v—Se2—Bi4^xi	128.97 (4)	Bi3^iii—Bi4—Bi3^vi	71.4 (9)
Bi1^v—Se2—Bi4^xii	61.60 (6)	Bi3^iv—Bi4—Bi3^v	108.6 (9)
Bi1^v—Se2—Bi4^xiii	128.97 (4)	Bi3^iv—Bi4—Bi3^vi	108.6 (9)
Bi1^v—Se2—Bi5^xiv	48.8 (7)	Bi3^v—Bi4—Bi3^vi	108.6 (9)
Bi1^v—Se2—Bi5^xi	111 (3)	Bi1^ix—Bi5—Bi1^xix	119.5 (10)
Bi1^v—Se2—Bi5^xii	48.8 (7)	Bi1^ix—Bi5—Bi1^xx	119.5 (10)
Bi1^vi—Se2—Bi3	123.0 (2)	Bi1^ix—Bi5—Se1^xxi	94 (4)
Bi1^vi—Se2—Bi4^xi	128.97 (4)	Bi1^ix—Bi5—Bi2^xxi	94 (4)
Bi1^vi—Se2—Bi4^xii	128.97 (4)	Bi1^ix—Bi5—Se2^ii	63.5 (17)
Bi1^vi—Se2—Bi4^xiii	61.60 (6)	Bi1^ix—Bi5—Se2^iii	63.5 (17)
Bi1^vi—Se2—Bi5^xiv	111 (3)	Bi1^ix—Bi5—Se2^xxii	140 (6)
Bi1^vi—Se2—Bi5^xi	48.8 (7)	Bi1^ix—Bi5—Bi3^ii	65 (2)
Bi1^vi—Se2—Bi5^xii	48.8 (7)	Bi1^ix—Bi5—Bi3^iii	65 (2)
Bi3—Se2—Bi4^xi	61.4 (2)	Bi1^ix—Bi5—Bi3^xxii	134 (6)
Bi3—Se2—Bi4^xii	61.4 (2)	Bi1^ix—Bi5—Bi5^xviii	94 (4)
Bi3—Se2—Bi4^xiii	61.4 (2)	Bi1^xix—Bi5—Bi1^xx	119.5 (10)
Bi3—Se2—Bi5^xiv	126 (3)	Bi1^xix—Bi5—Se1^xxi	94 (4)
Bi3—Se2—Bi5^xi	126 (3)	Bi1^xix—Bi5—Bi2^xxi	94 (4)
Bi3—Se2—Bi5^xii	126 (3)	Bi1^xix—Bi5—Se2^ii	63.5 (17)
Bi4^xi—Se2—Bi4^xii	98.9 (3)	Bi1^xix—Bi5—Se2^iii	140 (6)
Bi4^xi—Se2—Bi4^xiii	98.9 (3)	Bi1^xix—Bi5—Se2^xxii	63.5 (17)
Bi4^xi—Se2—Bi5^xiv	85.7 (17)	Bi1^xix—Bi5—Bi3^ii	65 (2)
Bi4^xi—Se2—Bi5^xi	85.7 (17)	Bi1^xix—Bi5—Bi3^iii	134 (6)
Bi4^xi—Se2—Bi5^xii	173 (3)	Bi1^xix—Bi5—Bi3^xxii	65 (2)
Bi4^xii—Se2—Bi4^xiii	98.9 (3)	Bi1^xix—Bi5—Bi5^xviii	94 (4)
Bi4^xii—Se2—Bi5^xiv	85.7 (17)	Bi1^xx—Bi5—Se1^xxi	94 (4)
Bi4^xii—Se2—Bi5^xi	173 (3)	Bi1^xx—Bi5—Bi2^xxi	94 (4)
Bi4^xii—Se2—Bi5^xii	85.7 (17)	Bi1^xx—Bi5—Se2^ii	140 (6)
Bi4^xiii—Se2—Bi5^xiv	173 (3)	Bi1^xx—Bi5—Se2^iii	63.5 (17)
Bi4^xiii—Se2—Bi5^xi	85.7 (17)	Bi1^xx—Bi5—Se2^xxii	63.5 (17)
Bi4^xiii—Se2—Bi5^xii	85.7 (17)	Bi1^xx—Bi5—Bi3^ii	134 (6)
Bi5^xiv—Se2—Bi5^xi	89 (3)	Bi1^xx—Bi5—Bi3^iii	65 (2)
Bi5^xiv—Se2—Bi5^xii	89 (3)	Bi1^xx—Bi5—Bi3^xxii	65 (2)
Bi5^xi—Se2—Bi5^xii	89 (3)	Bi1^xx—Bi5—Bi5^xviii	94 (4)
Bi1^iv—Bi3—Bi1^v	83.9 (12)	Se1^xxi—Bi5—Bi2^xxi	0.0 (5)
Bi1^iv—Bi3—Bi1^vi	83.9 (12)	Se1^xxi—Bi5—Se2^ii	126 (3)
Bi1^iv—Bi3—Se2	50.5 (8)	Se1^xxi—Bi5—Se2^iii	126 (3)
Bi1^iv—Bi3—Bi3^xv	93.9 (7)	Se1^xxi—Bi5—Se2^xxii	126 (3)
Bi1^iv—Bi3—Bi3^xvi	93.9 (7)	Se1^xxi—Bi5—Bi3^ii	132 (2)
Bi1^iv—Bi3—Bi3^xvii	177.1 (19)	Se1^xxi—Bi5—Bi3^iii	132 (2)
Bi1^iv—Bi3—Bi4^xi	59.8 (4)	Se1^xxi—Bi5—Bi3^xxii	132 (2)
Bi1^iv—Bi3—Bi4^xii	125.6 (7)	Se1^xxi—Bi5—Bi5^xviii	0.0 (5)
Bi1^iv—Bi3—Bi4^xiii	125.6 (7)	Bi2^xxi—Bi5—Se2^ii	126 (3)
Bi1^iv—Bi3—Bi5^xiv	44.6 (9)	Bi2^xxi—Bi5—Se2^iii	126 (3)
Bi1^iv—Bi3—Bi5^xi	44.6 (9)	Bi2^xxi—Bi5—Se2^xxii	126 (3)
Bi1^iv—Bi3—Bi5^xii	99 (3)	Bi2^xxi—Bi5—Bi3^ii	132 (2)
Bi1^v—Bi3—Bi1^vi	83.9 (12)	Bi2^xxi—Bi5—Bi3^iii	132 (2)
Bi1^v—Bi3—Se2	50.5 (8)	Bi2^xxi—Bi5—Bi3^xxii	132 (2)
Bi1^v—Bi3—Bi3^xv	93.9 (7)	Bi2^xxi—Bi5—Bi5^xviii	0.0 (5)
Bi1^v—Bi3—Bi3^xvi	177.1 (19)	Se2^ii—Bi5—Se2^iii	89 (4)
Bi1^v—Bi3—Bi3^xvii	93.9 (7)	Se2^ii—Bi5—Se2^xxii	89 (4)
Bi1^v—Bi3—Bi4^xi	125.6 (7)	Se2^ii—Bi5—Bi3^ii	6.1 (9)
Bi1^v—Bi3—Bi4^xii	59.8 (4)	Se2^ii—Bi5—Bi3^iii	85 (4)
Bi1^v—Bi3—Bi4^xiii	125.6 (7)	Se2^ii—Bi5—Bi3^xxii	85 (4)
Bi1^v—Bi3—Bi5^xiv	44.6 (9)	Se2^ii—Bi5—Bi5^xviii	126 (3)
Bi1^v—Bi3—Bi5^xi	99 (3)	Se2^iii—Bi5—Se2^xxii	89 (4)
Bi1^v—Bi3—Bi5^xii	44.6 (9)	Se2^iii—Bi5—Bi3^ii	85 (4)
Bi1^vi—Bi3—Se2	50.5 (8)	Se2^iii—Bi5—Bi3^iii	6.1 (9)
Bi1^vi—Bi3—Bi3^xv	177.1 (19)	Se2^iii—Bi5—Bi3^xxii	85 (4)
Bi1^vi—Bi3—Bi3^xvi	93.9 (7)	Se2^iii—Bi5—Bi5^xviii	126 (3)
Bi1^vi—Bi3—Bi3^xvii	93.9 (7)	Se2^xxii—Bi5—Bi3^ii	85 (4)
Bi1^vi—Bi3—Bi4^xi	125.6 (7)	Se2^xxii—Bi5—Bi3^iii	85 (4)
Bi1^vi—Bi3—Bi4^xii	125.6 (7)	Se2^xxii—Bi5—Bi3^xxii	6.1 (9)
Bi1^vi—Bi3—Bi4^xiii	59.8 (4)	Se2^xxii—Bi5—Bi5^xviii	126 (3)
Bi1^vi—Bi3—Bi5^xiv	99 (3)	Bi3^ii—Bi5—Bi3^iii	80 (3)
Bi1^vi—Bi3—Bi5^xi	44.6 (9)	Bi3^ii—Bi5—Bi3^xxii	80 (3)
Bi1^vi—Bi3—Bi5^xii	44.6 (9)	Bi3^ii—Bi5—Bi5^xviii	132 (2)
Se2—Bi3—Bi3^xv	126.5 (13)	Bi3^iii—Bi5—Bi3^xxii	80 (3)
Se2—Bi3—Bi3^xvi	126.5 (13)	Bi3^iii—Bi5—Bi5^xviii	132 (2)
Se2—Bi3—Bi3^xvii	126.5 (13)	Bi3^xxii—Bi5—Bi5^xviii	132 (2)
Se2—Bi3—Bi4^xi	110.3 (12)

Symmetry codes: (i) x−1/3, y−2/3, z+1/3; (ii) x−1/3, y+1/3, z+1/3; (iii) x+2/3, y+1/3, z+1/3; (iv) y−2/3, x−1/3, −z+2/3; (v) y+1/3, x−1/3, −z+2/3; (vi) y+1/3, x+2/3, −z+2/3; (vii) y−1, x−1, −z+1; (viii) y−1, x, −z+1; (ix) y, x, −z+1; (x) x−1/3, y−2/3, z−2/3; (xi) x−2/3, y−1/3, z−1/3; (xii) x+1/3, y−1/3, z−1/3; (xiii) x+1/3, y+2/3, z−1/3; (xiv) x−2/3, y−4/3, z−1/3; (xv) y−1/3, x−2/3, −z+1/3; (xvi) y−1/3, x+1/3, −z+1/3; (xvii) y+2/3, x+1/3, −z+1/3; (xviii) y−1/3, x+1/3, −z+4/3; (xix) y, x+1, −z+1; (xx) y+1, x+1, −z+1; (xxi) x+1/3, y+2/3, z+2/3; (xxii) x+2/3, y+4/3, z+1/3.

(I_2)

Crystal data

Bi2.318Se2.682	V = 425.24 (3) Å^3
Mr = 696.19	Z = 3
Trigonal, R3m	F(000) = 851
Hall symbol: -R 3 2"	Dx = 8.153 Mg m^−3
a = 4.14006 (10) Å	Cu Kα radiation
c = 28.6474 (12) Å	T = 293 K

Data collection

G670 diffractometer

2θmin = 4.003°, 2θmax = 99.992°

Refinement

Rp = 0.048	0 restraints
Rwp = 0.069	1 constraint
Rexp = 0.004	Weighting scheme based on measured s.u.'s
R(F) = 0.092	(Δ/σ)max = 0.028
9600 data points	Background function: 10 Legendre polynoms
Profile function: Pseudo-Voigt	Preferred orientation correction: March & Dollase
17 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Bi1	0	0	0.40045	0.0228*
Se1	0	0	0	0.0246*	0.87
Bi2	0	0	0	0.0246*	0.13
Se2	0	0	0.20997	0.0273*	0.906
Bi3	0	0	0.20997	0.0273*	0.094

Geometric parameters (Å, º)

Bi1—Bi2^i	3.0676 (2)	Bi1—Bi3^v	2.8827 (1)
Bi1—Bi2^ii	3.0676 (1)	Bi1—Bi3^vi	2.8827 (2)
Bi1—Bi2^iii	3.0676 (2)	Se1—Bi2	0
Bi1—Se2^iv	2.8827 (2)	Se2—Bi3	0
Bi1—Se2^v	2.8827 (1)	Bi3—Bi3^vii	3.4452 (2)
Bi1—Se2^vi	2.8827 (2)	Bi3—Bi3^viii	3.4452 (1)
Bi1—Bi3^iv	2.8827 (2)	Bi3—Bi3^ix	3.4452 (2)
Bi2^i—Bi1—Bi2^ii	84.878 (2)	Bi1^xi—Bi2—Bi1^xii	84.878 (2)
Bi2^i—Bi1—Bi2^iii	84.878 (3)	Bi1^xi—Bi2—Bi1^vii	95.122 (2)
Bi2^i—Bi1—Se2^iv	91.565 (3)	Bi1^xi—Bi2—Bi1^viii	180.0 (5)
Bi2^i—Bi1—Se2^v	91.565 (2)	Bi1^xi—Bi2—Bi1^ix	95.122 (2)
Bi2^i—Bi1—Se2^vi	175.17	Bi1^xi—Bi2—Se1	0
Bi2^i—Bi1—Bi3^iv	91.565 (3)	Bi1^xii—Bi2—Bi1^vii	180.0 (5)
Bi2^i—Bi1—Bi3^v	91.565 (2)	Bi1^xii—Bi2—Bi1^viii	95.122 (2)
Bi2^i—Bi1—Bi3^vi	175.17	Bi1^xii—Bi2—Bi1^ix	95.122 (3)
Bi2^ii—Bi1—Bi2^iii	84.878 (2)	Bi1^xii—Bi2—Se1	0
Bi2^ii—Bi1—Se2^iv	91.565 (2)	Bi1^vii—Bi2—Bi1^viii	84.878 (2)
Bi2^ii—Bi1—Se2^v	175.17	Bi1^vii—Bi2—Bi1^ix	84.878 (3)
Bi2^ii—Bi1—Se2^vi	91.565 (2)	Bi1^vii—Bi2—Se1	0
Bi2^ii—Bi1—Bi3^iv	91.565 (2)	Bi1^viii—Bi2—Bi1^ix	84.878 (2)
Bi2^ii—Bi1—Bi3^v	175.17	Bi1^viii—Bi2—Se1	0
Bi2^ii—Bi1—Bi3^vi	91.565 (2)	Bi1^ix—Bi2—Se1	0
Bi2^iii—Bi1—Se2^iv	175.17	Bi1^iv—Se2—Bi1^v	91.795 (2)
Bi2^iii—Bi1—Se2^v	91.565 (2)	Bi1^iv—Se2—Bi1^vi	91.795 (3)
Bi2^iii—Bi1—Se2^vi	91.565 (3)	Bi1^iv—Se2—Bi3	0
Bi2^iii—Bi1—Bi3^iv	175.17	Bi1^v—Se2—Bi1^vi	91.795 (2)
Bi2^iii—Bi1—Bi3^v	91.565 (2)	Bi1^v—Se2—Bi3	0
Bi2^iii—Bi1—Bi3^vi	91.565 (3)	Bi1^vi—Se2—Bi3	0
Se2^iv—Bi1—Se2^v	91.795 (2)	Bi1^iv—Bi3—Bi1^v	91.795 (2)
Se2^iv—Bi1—Se2^vi	91.795 (3)	Bi1^iv—Bi3—Bi1^vi	91.795 (3)
Se2^iv—Bi1—Bi3^iv	0.0 (5)	Bi1^iv—Bi3—Se2	0
Se2^iv—Bi1—Bi3^v	91.795 (2)	Bi1^iv—Bi3—Bi3^vii	96.598 (3)
Se2^iv—Bi1—Bi3^vi	91.795 (3)	Bi1^iv—Bi3—Bi3^viii	96.598 (2)
Se2^v—Bi1—Se2^vi	91.795 (2)	Bi1^iv—Bi3—Bi3^ix	167.9169 (1)
Se2^v—Bi1—Bi3^iv	91.795 (2)	Bi1^v—Bi3—Bi1^vi	91.795 (2)
Se2^v—Bi1—Bi3^v	0.0 (5)	Bi1^v—Bi3—Se2	0
Se2^v—Bi1—Bi3^vi	91.795 (2)	Bi1^v—Bi3—Bi3^vii	96.598 (2)
Se2^vi—Bi1—Bi3^iv	91.795 (3)	Bi1^v—Bi3—Bi3^viii	167.92
Se2^vi—Bi1—Bi3^v	91.795 (2)	Bi1^v—Bi3—Bi3^ix	96.598 (2)
Se2^vi—Bi1—Bi3^vi	0.0 (5)	Bi1^vi—Bi3—Se2	0
Bi3^iv—Bi1—Bi3^v	91.795 (2)	Bi1^vi—Bi3—Bi3^vii	167.9169 (1)
Bi3^iv—Bi1—Bi3^vi	91.795 (3)	Bi1^vi—Bi3—Bi3^viii	96.598 (2)
Bi3^v—Bi1—Bi3^vi	91.795 (2)	Bi1^vi—Bi3—Bi3^ix	96.598 (3)
Bi1^x—Bi2—Bi1^xi	84.878 (2)	Se2—Bi3—Bi3^vii	0
Bi1^x—Bi2—Bi1^xii	84.878 (3)	Se2—Bi3—Bi3^viii	0
Bi1^x—Bi2—Bi1^vii	95.122 (3)	Se2—Bi3—Bi3^ix	0
Bi1^x—Bi2—Bi1^viii	95.122 (2)	Bi3^vii—Bi3—Bi3^viii	73.862 (2)
Bi1^x—Bi2—Bi1^ix	180.0 (5)	Bi3^vii—Bi3—Bi3^ix	73.862 (3)
Bi1^x—Bi2—Se1	0	Bi3^viii—Bi3—Bi3^ix	73.862 (2)

Symmetry codes: (i) x−1/3, y−2/3, z+1/3; (ii) x−1/3, y+1/3, z+1/3; (iii) x+2/3, y+1/3, z+1/3; (iv) y−2/3, x−1/3, −z+2/3; (v) y+1/3, x−1/3, −z+2/3; (vi) y+1/3, x+2/3, −z+2/3; (vii) y−1/3, x−2/3, −z+1/3; (viii) y−1/3, x+1/3, −z+1/3; (ix) y+2/3, x+1/3, −z+1/3; (x) x−2/3, y−1/3, z−1/3; (xi) x+1/3, y−1/3, z−1/3; (xii) x+1/3, y+2/3, z−1/3.

(I_3)

Crystal data

Bi2.261Se2.740	V = 425.24 (3) Å^3
Mr = 688.86	Z = 3
Trigonal, R3m	F(000) = 842
Hall symbol: -R 3 2"	Dx = 8.081 Mg m^−3
a = 4.14004 (10) Å	Cu Kα radiation
c = 28.6479 (11) Å	T = 293 K

Data collection

G670 diffractometer

2θmin = 4.003°, 2θmax = 99.992°

Refinement

Rp = 0.046	0 restraints
Rwp = 0.067	1 constraint
Rexp = 0.004	Weighting scheme based on measured s.u.'s
R(F) = 0.085	(Δ/σ)max = 0.046
9600 data points	Background function: 10 Legendre polynoms
Profile function: Pseudo-Voigt	Preferred orientation correction: March & Dollase
18 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Bi1	0	0	0.40034	0.0225*	0.974
Se1	0	0	0	0.0243*	0.92
Bi2	0	0	0	0.0243*	0.08
Se2	0	0	0.2122	0.0268*	0.91
Bi3	0	0	0.198	0.0268*	0.09
Bi4	0	0	0.5	0.0268*	0.015
Bi5	0.333333	0.666667	0.606	0.0268*	0.019

Geometric parameters (Å, º)

Bi1—Bi2^i	3.0656 (2)	Se2—Bi3	0.4068 (1)
Bi1—Bi2^ii	3.0656 (1)	Se2—Bi4^xi	2.7230 (1)
Bi1—Bi2^iii	3.0656 (2)	Se2—Bi4^xii	2.7230 (1)
Bi1—Se2^iv	2.8492 (1)	Se2—Bi4^xiii	2.7230 (1)
Bi1—Se2^v	2.8492 (1)	Se2—Bi5^xiv	2.9519 (2)
Bi1—Se2^vi	2.8492 (1)	Se2—Bi5^xi	2.9520 (1)
Bi1—Bi3^iv	3.0895 (2)	Se2—Bi5^xii	2.9519 (2)
Bi1—Bi3^v	3.0895 (1)	Bi3—Bi3^xv	2.9894 (2)
Bi1—Bi3^vi	3.0895 (2)	Bi3—Bi3^xvi	2.9894 (1)
Bi1—Bi4	2.8551 (2)	Bi3—Bi3^xvii	2.9894 (2)
Bi1—Bi5^vii	2.3971 (2)	Bi3—Bi4^xi	2.5532 (2)
Bi1—Bi5^viii	2.3971 (1)	Bi3—Bi4^xii	2.5532 (1)
Bi1—Bi5^ix	2.3971 (2)	Bi3—Bi4^xiii	2.5532 (2)
Se1—Bi2	0	Bi3—Bi5^xiv	3.2076 (2)
Se1—Bi5^x	1.7380 (1)	Bi3—Bi5^xi	3.2076 (1)
Se1—Bi5^iv	1.7380 (1)	Bi3—Bi5^xii	3.2076 (2)
Bi2—Bi5^x	1.7380 (1)	Bi5—Bi5^xviii	3.4760 (3)
Bi2—Bi5^iv	1.7380 (1)
Bi2^i—Bi1—Bi2^ii	84.944 (2)	Se2—Bi3—Bi4^xii	110.5831 (8)
Bi2^i—Bi1—Bi2^iii	84.944 (3)	Se2—Bi3—Bi4^xiii	110.5831 (10)
Bi2^i—Bi1—Se2^iv	90.787 (2)	Se2—Bi3—Bi5^xiv	48.1745 (15)
Bi2^i—Bi1—Se2^v	90.787 (2)	Se2—Bi3—Bi5^xi	48.1745 (12)
Bi2^i—Bi1—Se2^vi	174.2	Se2—Bi3—Bi5^xii	48.1745 (15)
Bi2^i—Bi1—Bi3^iv	95.458 (3)	Bi3^xv—Bi3—Bi3^xvi	87.650 (2)
Bi2^i—Bi1—Bi3^v	95.458 (2)	Bi3^xv—Bi3—Bi3^xvii	87.650 (3)
Bi2^i—Bi1—Bi3^vi	179.45	Bi3^xv—Bi3—Bi4^xi	54.1684 (11)
Bi2^i—Bi1—Bi4	128.7678 (15)	Bi3^xv—Bi3—Bi4^xii	54.1684 (17)
Bi2^i—Bi1—Bi5^vii	34.4225 (12)	Bi3^xv—Bi3—Bi4^xiii	122.507 (2)
Bi2^i—Bi1—Bi5^viii	109.9549 (16)	Bi3^xv—Bi3—Bi5^xiv	78.735 (3)
Bi2^i—Bi1—Bi5^ix	109.9549 (16)	Bi3^xv—Bi3—Bi5^xi	134.2991 (17)
Bi2^ii—Bi1—Bi2^iii	84.944 (2)	Bi3^xv—Bi3—Bi5^xii	134.2992 (11)
Bi2^ii—Bi1—Se2^iv	90.787 (2)	Bi3^xvi—Bi3—Bi3^xvii	87.650 (2)
Bi2^ii—Bi1—Se2^v	174.2	Bi3^xvi—Bi3—Bi4^xi	54.1684 (16)
Bi2^ii—Bi1—Se2^vi	90.787 (2)	Bi3^xvi—Bi3—Bi4^xii	122.5074 (19)
Bi2^ii—Bi1—Bi3^iv	95.458 (2)	Bi3^xvi—Bi3—Bi4^xiii	54.1684 (16)
Bi2^ii—Bi1—Bi3^v	179.45	Bi3^xvi—Bi3—Bi5^xiv	134.2991 (17)
Bi2^ii—Bi1—Bi3^vi	95.458 (2)	Bi3^xvi—Bi3—Bi5^xi	78.735 (2)
Bi2^ii—Bi1—Bi4	128.7678 (12)	Bi3^xvi—Bi3—Bi5^xii	134.2991 (17)
Bi2^ii—Bi1—Bi5^vii	109.9549 (16)	Bi3^xvii—Bi3—Bi4^xi	122.507 (2)
Bi2^ii—Bi1—Bi5^viii	34.4225 (10)	Bi3^xvii—Bi3—Bi4^xii	54.1684 (17)
Bi2^ii—Bi1—Bi5^ix	109.9549 (16)	Bi3^xvii—Bi3—Bi4^xiii	54.1684 (11)
Bi2^iii—Bi1—Se2^iv	174.2	Bi3^xvii—Bi3—Bi5^xiv	134.2992 (11)
Bi2^iii—Bi1—Se2^v	90.787 (2)	Bi3^xvii—Bi3—Bi5^xi	134.2991 (17)
Bi2^iii—Bi1—Se2^vi	90.787 (2)	Bi3^xvii—Bi3—Bi5^xii	78.735 (3)
Bi2^iii—Bi1—Bi3^iv	179.45	Bi4^xi—Bi3—Bi4^xii	108.3368 (19)
Bi2^iii—Bi1—Bi3^v	95.458 (2)	Bi4^xi—Bi3—Bi4^xiii	108.337 (2)
Bi2^iii—Bi1—Bi3^vi	95.458 (3)	Bi4^xi—Bi3—Bi5^xiv	83.433 (2)
Bi2^iii—Bi1—Bi4	128.7678 (15)	Bi4^xi—Bi3—Bi5^xi	83.4334 (19)
Bi2^iii—Bi1—Bi5^vii	109.9549 (16)	Bi4^xi—Bi3—Bi5^xii	158.7576 (5)
Bi2^iii—Bi1—Bi5^viii	109.9549 (16)	Bi4^xii—Bi3—Bi4^xiii	108.3368 (19)
Bi2^iii—Bi1—Bi5^ix	34.4225 (12)	Bi4^xii—Bi3—Bi5^xiv	83.4335 (19)
Se2^iv—Bi1—Se2^v	93.194 (2)	Bi4^xii—Bi3—Bi5^xi	158.7576 (4)
Se2^iv—Bi1—Se2^vi	93.194 (2)	Bi4^xii—Bi3—Bi5^xii	83.4335 (19)
Se2^iv—Bi1—Bi3^iv	6.3421 (1)	Bi4^xiii—Bi3—Bi5^xiv	158.7576 (5)
Se2^iv—Bi1—Bi3^v	88.838 (2)	Bi4^xiii—Bi3—Bi5^xi	83.4334 (19)
Se2^iv—Bi1—Bi3^vi	88.838 (2)	Bi4^xiii—Bi3—Bi5^xii	83.433 (2)
Se2^iv—Bi1—Bi4	57.0275 (14)	Bi5^xiv—Bi3—Bi5^xi	80.383 (2)
Se2^iv—Bi1—Bi5^vii	67.8506 (16)	Bi5^xiv—Bi3—Bi5^xii	80.383 (3)
Se2^iv—Bi1—Bi5^viii	67.8505 (17)	Bi5^xi—Bi3—Bi5^xii	80.383 (2)
Se2^iv—Bi1—Bi5^ix	151.3728 (11)	Bi1—Bi4—Bi1^ix	180.0 (5)
Se2^v—Bi1—Se2^vi	93.194 (2)	Bi1—Bi4—Se2^i	118.6227 (13)
Se2^v—Bi1—Bi3^iv	88.838 (2)	Bi1—Bi4—Se2^ii	118.6227 (10)
Se2^v—Bi1—Bi3^v	6.34	Bi1—Bi4—Se2^iii	118.6227 (13)
Se2^v—Bi1—Bi3^vi	88.838 (2)	Bi1—Bi4—Se2^iv	61.3773 (13)
Se2^v—Bi1—Bi4	57.0275 (11)	Bi1—Bi4—Se2^v	61.3773 (10)
Se2^v—Bi1—Bi5^vii	67.8505 (17)	Bi1—Bi4—Se2^vi	61.3773 (13)
Se2^v—Bi1—Bi5^viii	151.3728 (9)	Bi1—Bi4—Bi3^i	110.5832 (10)
Se2^v—Bi1—Bi5^ix	67.8505 (17)	Bi1—Bi4—Bi3^ii	110.5832 (8)
Se2^vi—Bi1—Bi3^iv	88.838 (2)	Bi1—Bi4—Bi3^iii	110.5832 (10)
Se2^vi—Bi1—Bi3^v	88.838 (2)	Bi1—Bi4—Bi3^iv	69.4168 (10)
Se2^vi—Bi1—Bi3^vi	6.3421 (1)	Bi1—Bi4—Bi3^v	69.4168 (8)
Se2^vi—Bi1—Bi4	57.0275 (14)	Bi1—Bi4—Bi3^vi	69.4168 (10)
Se2^vi—Bi1—Bi5^vii	151.3728 (11)	Bi1^ix—Bi4—Se2^i	61.3773 (13)
Se2^vi—Bi1—Bi5^viii	67.8505 (17)	Bi1^ix—Bi4—Se2^ii	61.3773 (10)
Se2^vi—Bi1—Bi5^ix	67.8506 (16)	Bi1^ix—Bi4—Se2^iii	61.3773 (13)
Bi3^iv—Bi1—Bi3^v	84.138 (2)	Bi1^ix—Bi4—Se2^iv	118.6227 (13)
Bi3^iv—Bi1—Bi3^vi	84.138 (3)	Bi1^ix—Bi4—Se2^v	118.6227 (10)
Bi3^iv—Bi1—Bi4	50.6853 (15)	Bi1^ix—Bi4—Se2^vi	118.6227 (13)
Bi3^iv—Bi1—Bi5^vii	70.2619 (16)	Bi1^ix—Bi4—Bi3^i	69.4168 (10)
Bi3^iv—Bi1—Bi5^viii	70.2619 (16)	Bi1^ix—Bi4—Bi3^ii	69.4168 (8)
Bi3^iv—Bi1—Bi5^ix	145.0307 (12)	Bi1^ix—Bi4—Bi3^iii	69.4168 (10)
Bi3^v—Bi1—Bi3^vi	84.138 (2)	Bi1^ix—Bi4—Bi3^iv	110.5832 (10)
Bi3^v—Bi1—Bi4	50.6853 (12)	Bi1^ix—Bi4—Bi3^v	110.5832 (8)
Bi3^v—Bi1—Bi5^vii	70.2618 (15)	Bi1^ix—Bi4—Bi3^vi	110.5832 (10)
Bi3^v—Bi1—Bi5^viii	145.0307 (10)	Se2^i—Bi4—Se2^ii	98.962 (2)
Bi3^v—Bi1—Bi5^ix	70.2618 (15)	Se2^i—Bi4—Se2^iii	98.962 (2)
Bi3^vi—Bi1—Bi4	50.6853 (15)	Se2^i—Bi4—Se2^iv	81.038 (2)
Bi3^vi—Bi1—Bi5^vii	145.0307 (12)	Se2^i—Bi4—Se2^v	81.038 (2)
Bi3^vi—Bi1—Bi5^viii	70.2619 (16)	Se2^i—Bi4—Se2^vi	180.0 (5)
Bi3^vi—Bi1—Bi5^ix	70.2619 (16)	Se2^i—Bi4—Bi3^i	8.0395 (3)
Bi4—Bi1—Bi5^vii	94.3454 (2)	Se2^i—Bi4—Bi3^ii	104.0320 (19)
Bi4—Bi1—Bi5^viii	94.3454 (2)	Se2^i—Bi4—Bi3^iii	104.032 (2)
Bi4—Bi1—Bi5^ix	94.3454 (2)	Se2^i—Bi4—Bi3^iv	75.968 (2)
Bi5^vii—Bi1—Bi5^viii	119.432 (2)	Se2^i—Bi4—Bi3^v	75.9680 (19)
Bi5^vii—Bi1—Bi5^ix	119.4318 (16)	Se2^i—Bi4—Bi3^vi	171.9605 (3)
Bi5^viii—Bi1—Bi5^ix	119.432 (2)	Se2^ii—Bi4—Se2^iii	98.962 (2)
Bi2—Se1—Bi5^x	0	Se2^ii—Bi4—Se2^iv	81.038 (2)
Bi2—Se1—Bi5^iv	0	Se2^ii—Bi4—Se2^v	180.0 (5)
Bi5^x—Se1—Bi5^iv	180.0 (5)	Se2^ii—Bi4—Se2^vi	81.038 (2)
Bi1^xi—Bi2—Bi1^xii	84.944 (2)	Se2^ii—Bi4—Bi3^i	104.0320 (19)
Bi1^xi—Bi2—Bi1^xiii	84.944 (3)	Se2^ii—Bi4—Bi3^ii	8.0395 (2)
Bi1^xi—Bi2—Bi1^xv	95.056 (3)	Se2^ii—Bi4—Bi3^iii	104.0320 (19)
Bi1^xi—Bi2—Bi1^xvi	95.056 (2)	Se2^ii—Bi4—Bi3^iv	75.9680 (19)
Bi1^xi—Bi2—Bi1^xvii	180.0 (5)	Se2^ii—Bi4—Bi3^v	171.9605 (2)
Bi1^xi—Bi2—Se1	0	Se2^ii—Bi4—Bi3^vi	75.9680 (19)
Bi1^xi—Bi2—Bi5^x	128.7678 (15)	Se2^iii—Bi4—Se2^iv	180.0 (5)
Bi1^xi—Bi2—Bi5^iv	51.2322 (15)	Se2^iii—Bi4—Se2^v	81.038 (2)
Bi1^xii—Bi2—Bi1^xiii	84.944 (2)	Se2^iii—Bi4—Se2^vi	81.038 (2)
Bi1^xii—Bi2—Bi1^xv	95.056 (2)	Se2^iii—Bi4—Bi3^i	104.032 (2)
Bi1^xii—Bi2—Bi1^xvi	180.0 (5)	Se2^iii—Bi4—Bi3^ii	104.0320 (19)
Bi1^xii—Bi2—Bi1^xvii	95.056 (2)	Se2^iii—Bi4—Bi3^iii	8.0395 (3)
Bi1^xii—Bi2—Se1	0	Se2^iii—Bi4—Bi3^iv	171.9604 (3)
Bi1^xii—Bi2—Bi5^x	128.7679 (12)	Se2^iii—Bi4—Bi3^v	75.9680 (19)
Bi1^xii—Bi2—Bi5^iv	51.2321 (12)	Se2^iii—Bi4—Bi3^vi	75.968 (2)
Bi1^xiii—Bi2—Bi1^xv	180.0 (5)	Se2^iv—Bi4—Se2^v	98.962 (2)
Bi1^xiii—Bi2—Bi1^xvi	95.056 (2)	Se2^iv—Bi4—Se2^vi	98.962 (2)
Bi1^xiii—Bi2—Bi1^xvii	95.056 (3)	Se2^iv—Bi4—Bi3^i	75.968 (2)
Bi1^xiii—Bi2—Se1	0	Se2^iv—Bi4—Bi3^ii	75.9680 (19)
Bi1^xiii—Bi2—Bi5^x	128.7678 (15)	Se2^iv—Bi4—Bi3^iii	171.9605 (3)
Bi1^xiii—Bi2—Bi5^iv	51.2322 (15)	Se2^iv—Bi4—Bi3^iv	8.0395 (3)
Bi1^xv—Bi2—Bi1^xvi	84.944 (2)	Se2^iv—Bi4—Bi3^v	104.0320 (19)
Bi1^xv—Bi2—Bi1^xvii	84.944 (3)	Se2^iv—Bi4—Bi3^vi	104.032 (2)
Bi1^xv—Bi2—Se1	0	Se2^v—Bi4—Se2^vi	98.962 (2)
Bi1^xv—Bi2—Bi5^x	51.2322 (15)	Se2^v—Bi4—Bi3^i	75.9680 (19)
Bi1^xv—Bi2—Bi5^iv	128.7678 (15)	Se2^v—Bi4—Bi3^ii	171.9605 (2)
Bi1^xvi—Bi2—Bi1^xvii	84.944 (2)	Se2^v—Bi4—Bi3^iii	75.9680 (19)
Bi1^xvi—Bi2—Se1	0	Se2^v—Bi4—Bi3^iv	104.0320 (19)
Bi1^xvi—Bi2—Bi5^x	51.2321 (12)	Se2^v—Bi4—Bi3^v	8.0395 (2)
Bi1^xvi—Bi2—Bi5^iv	128.7679 (12)	Se2^v—Bi4—Bi3^vi	104.0320 (19)
Bi1^xvii—Bi2—Se1	0	Se2^vi—Bi4—Bi3^i	171.9605 (3)
Bi1^xvii—Bi2—Bi5^x	51.2322 (15)	Se2^vi—Bi4—Bi3^ii	75.9680 (19)
Bi1^xvii—Bi2—Bi5^iv	128.7678 (15)	Se2^vi—Bi4—Bi3^iii	75.968 (2)
Se1—Bi2—Bi5^x	0	Se2^vi—Bi4—Bi3^iv	104.032 (2)
Se1—Bi2—Bi5^iv	0	Se2^vi—Bi4—Bi3^v	104.0320 (19)
Bi5^x—Bi2—Bi5^iv	180.0 (5)	Se2^vi—Bi4—Bi3^vi	8.0395 (3)
Bi1^iv—Se2—Bi1^v	93.194 (2)	Bi3^i—Bi4—Bi3^ii	108.3367 (19)
Bi1^iv—Se2—Bi1^vi	93.194 (2)	Bi3^i—Bi4—Bi3^iii	108.337 (2)
Bi1^iv—Se2—Bi3	122.9725 (14)	Bi3^i—Bi4—Bi3^iv	71.663 (2)
Bi1^iv—Se2—Bi4^xi	61.595 (3)	Bi3^i—Bi4—Bi3^v	71.6633 (19)
Bi1^iv—Se2—Bi4^xii	128.9701 (18)	Bi3^i—Bi4—Bi3^vi	180.0 (5)
Bi1^iv—Se2—Bi4^xiii	128.9701 (12)	Bi3^ii—Bi4—Bi3^iii	108.3367 (19)
Bi1^iv—Se2—Bi5^xiv	48.7750 (11)	Bi3^ii—Bi4—Bi3^iv	71.6633 (19)
Bi1^iv—Se2—Bi5^xi	48.7751 (17)	Bi3^ii—Bi4—Bi3^v	180.0 (5)
Bi1^iv—Se2—Bi5^xii	111.096 (3)	Bi3^ii—Bi4—Bi3^vi	71.6633 (19)
Bi1^v—Se2—Bi1^vi	93.194 (2)	Bi3^iii—Bi4—Bi3^iv	180.0 (5)
Bi1^v—Se2—Bi3	122.9725 (11)	Bi3^iii—Bi4—Bi3^v	71.6633 (19)
Bi1^v—Se2—Bi4^xi	128.9701 (18)	Bi3^iii—Bi4—Bi3^vi	71.663 (2)
Bi1^v—Se2—Bi4^xii	61.595 (2)	Bi3^iv—Bi4—Bi3^v	108.3367 (19)
Bi1^v—Se2—Bi4^xiii	128.9701 (18)	Bi3^iv—Bi4—Bi3^vi	108.337 (2)
Bi1^v—Se2—Bi5^xiv	48.7751 (17)	Bi3^v—Bi4—Bi3^vi	108.3367 (19)
Bi1^v—Se2—Bi5^xi	111.096 (2)	Bi1^ix—Bi5—Bi1^xix	119.432 (2)
Bi1^v—Se2—Bi5^xii	48.7751 (17)	Bi1^ix—Bi5—Bi1^xx	119.4318 (16)
Bi1^vi—Se2—Bi3	122.9725 (14)	Bi1^ix—Bi5—Se1^xxi	94.3453 (2)
Bi1^vi—Se2—Bi4^xi	128.9701 (12)	Bi1^ix—Bi5—Bi2^xxi	94.3453 (2)
Bi1^vi—Se2—Bi4^xii	128.9701 (18)	Bi1^ix—Bi5—Se2^ii	63.3744 (14)
Bi1^vi—Se2—Bi4^xiii	61.595 (3)	Bi1^ix—Bi5—Se2^iii	63.3744 (16)
Bi1^vi—Se2—Bi5^xiv	111.096 (3)	Bi1^ix—Bi5—Se2^xxii	139.7233 (17)
Bi1^vi—Se2—Bi5^xi	48.7751 (17)	Bi1^ix—Bi5—Bi3^ii	65.0362 (13)
Bi1^vi—Se2—Bi5^xii	48.7750 (11)	Bi1^ix—Bi5—Bi3^iii	65.0361 (14)
Bi3—Se2—Bi4^xi	61.3773 (13)	Bi1^ix—Bi5—Bi3^xxii	133.8291 (17)
Bi3—Se2—Bi4^xii	61.3773 (10)	Bi1^ix—Bi5—Bi5^xviii	94.3453 (2)
Bi3—Se2—Bi4^xiii	61.3773 (13)	Bi1^xix—Bi5—Bi1^xx	119.432 (2)
Bi3—Se2—Bi5^xiv	125.9314 (14)	Bi1^xix—Bi5—Se1^xxi	94.3454 (2)
Bi3—Se2—Bi5^xi	125.9313 (11)	Bi1^xix—Bi5—Bi2^xxi	94.3454 (2)
Bi3—Se2—Bi5^xii	125.9314 (14)	Bi1^xix—Bi5—Se2^ii	63.3744 (16)
Bi4^xi—Se2—Bi4^xii	98.962 (2)	Bi1^xix—Bi5—Se2^iii	139.7233 (13)
Bi4^xi—Se2—Bi4^xiii	98.962 (2)	Bi1^xix—Bi5—Se2^xxii	63.3744 (16)
Bi4^xi—Se2—Bi5^xiv	85.740 (2)	Bi1^xix—Bi5—Bi3^ii	65.0362 (15)
Bi4^xi—Se2—Bi5^xi	85.740 (2)	Bi1^xix—Bi5—Bi3^iii	133.8292 (14)
Bi4^xi—Se2—Bi5^xii	172.6913 (2)	Bi1^xix—Bi5—Bi3^xxii	65.0362 (15)
Bi4^xii—Se2—Bi4^xiii	98.962 (2)	Bi1^xix—Bi5—Bi5^xviii	94.3455 (2)
Bi4^xii—Se2—Bi5^xiv	85.740 (2)	Bi1^xx—Bi5—Se1^xxi	94.3453 (2)
Bi4^xii—Se2—Bi5^xi	172.6914 (1)	Bi1^xx—Bi5—Bi2^xxi	94.3453 (2)
Bi4^xii—Se2—Bi5^xii	85.740 (2)	Bi1^xx—Bi5—Se2^ii	139.7233 (17)
Bi4^xiii—Se2—Bi5^xiv	172.6913 (2)	Bi1^xx—Bi5—Se2^iii	63.3744 (16)
Bi4^xiii—Se2—Bi5^xi	85.740 (2)	Bi1^xx—Bi5—Se2^xxii	63.3744 (14)
Bi4^xiii—Se2—Bi5^xii	85.740 (2)	Bi1^xx—Bi5—Bi3^ii	133.8291 (17)
Bi5^xiv—Se2—Bi5^xi	89.053 (2)	Bi1^xx—Bi5—Bi3^iii	65.0362 (14)
Bi5^xiv—Se2—Bi5^xii	89.053 (3)	Bi1^xx—Bi5—Bi3^xxii	65.0362 (13)
Bi5^xi—Se2—Bi5^xii	89.053 (2)	Bi1^xx—Bi5—Bi5^xviii	94.3453 (2)
Bi1^iv—Bi3—Bi1^v	84.138 (2)	Se1^xxi—Bi5—Bi2^xxi	0.0 (5)
Bi1^iv—Bi3—Bi1^vi	84.138 (3)	Se1^xxi—Bi5—Se2^ii	125.9314 (14)
Bi1^iv—Bi3—Se2	50.6853 (15)	Se1^xxi—Bi5—Se2^iii	125.9312 (11)
Bi1^iv—Bi3—Bi3^xv	94.082 (3)	Se1^xxi—Bi5—Se2^xxii	125.9314 (14)
Bi1^iv—Bi3—Bi3^xvi	94.082 (2)	Se1^xxi—Bi5—Bi3^ii	131.8256 (15)
Bi1^iv—Bi3—Bi3^xvii	177.59	Se1^xxi—Bi5—Bi3^iii	131.8254 (12)
Bi1^iv—Bi3—Bi4^xi	59.898 (2)	Se1^xxi—Bi5—Bi3^xxii	131.8256 (15)
Bi1^iv—Bi3—Bi4^xii	125.7952 (16)	Se1^xxi—Bi5—Bi5^xviii	0.0 (5)
Bi1^iv—Bi3—Bi4^xiii	125.7952 (11)	Bi2^xxi—Bi5—Se2^ii	125.9314 (14)
Bi1^iv—Bi3—Bi5^xiv	44.7019 (11)	Bi2^xxi—Bi5—Se2^iii	125.9312 (11)
Bi1^iv—Bi3—Bi5^xi	44.7020 (17)	Bi2^xxi—Bi5—Se2^xxii	125.9314 (14)
Bi1^iv—Bi3—Bi5^xii	98.860 (3)	Bi2^xxi—Bi5—Bi3^ii	131.8256 (15)
Bi1^v—Bi3—Bi1^vi	84.138 (2)	Bi2^xxi—Bi5—Bi3^iii	131.8254 (12)
Bi1^v—Bi3—Se2	50.6853 (12)	Bi2^xxi—Bi5—Bi3^xxii	131.8256 (15)
Bi1^v—Bi3—Bi3^xv	94.082 (2)	Bi2^xxi—Bi5—Bi5^xviii	0.0 (5)
Bi1^v—Bi3—Bi3^xvi	177.59	Se2^ii—Bi5—Se2^iii	89.053 (2)
Bi1^v—Bi3—Bi3^xvii	94.082 (2)	Se2^ii—Bi5—Se2^xxii	89.053 (3)
Bi1^v—Bi3—Bi4^xi	125.7952 (16)	Se2^ii—Bi5—Bi3^ii	5.89
Bi1^v—Bi3—Bi4^xii	59.898 (2)	Se2^ii—Bi5—Bi3^iii	84.858 (2)
Bi1^v—Bi3—Bi4^xiii	125.7952 (16)	Se2^ii—Bi5—Bi3^xxii	84.858 (3)
Bi1^v—Bi3—Bi5^xiv	44.7020 (17)	Se2^ii—Bi5—Bi5^xviii	125.9314 (14)
Bi1^v—Bi3—Bi5^xi	98.860 (2)	Se2^iii—Bi5—Se2^xxii	89.053 (2)
Bi1^v—Bi3—Bi5^xii	44.7020 (17)	Se2^iii—Bi5—Bi3^ii	84.858 (2)
Bi1^vi—Bi3—Se2	50.6853 (15)	Se2^iii—Bi5—Bi3^iii	5.89
Bi1^vi—Bi3—Bi3^xv	177.59	Se2^iii—Bi5—Bi3^xxii	84.858 (2)
Bi1^vi—Bi3—Bi3^xvi	94.082 (2)	Se2^iii—Bi5—Bi5^xviii	125.9312 (11)
Bi1^vi—Bi3—Bi3^xvii	94.082 (3)	Se2^xxii—Bi5—Bi3^ii	84.858 (3)
Bi1^vi—Bi3—Bi4^xi	125.7952 (11)	Se2^xxii—Bi5—Bi3^iii	84.858 (2)
Bi1^vi—Bi3—Bi4^xii	125.7952 (16)	Se2^xxii—Bi5—Bi3^xxii	5.89
Bi1^vi—Bi3—Bi4^xiii	59.898 (2)	Se2^xxii—Bi5—Bi5^xviii	125.9314 (14)
Bi1^vi—Bi3—Bi5^xiv	98.860 (3)	Bi3^ii—Bi5—Bi3^iii	80.383 (2)
Bi1^vi—Bi3—Bi5^xi	44.7020 (17)	Bi3^ii—Bi5—Bi3^xxii	80.383 (3)
Bi1^vi—Bi3—Bi5^xii	44.7019 (11)	Bi3^ii—Bi5—Bi5^xviii	131.8256 (15)
Se2—Bi3—Bi3^xv	126.9095 (14)	Bi3^iii—Bi5—Bi3^xxii	80.383 (2)
Se2—Bi3—Bi3^xvi	126.9095 (11)	Bi3^iii—Bi5—Bi5^xviii	131.8254 (12)
Se2—Bi3—Bi3^xvii	126.9095 (14)	Bi3^xxii—Bi5—Bi5^xviii	131.8256 (15)
Se2—Bi3—Bi4^xi	110.5831 (10)

Symmetry codes: (i) x−1/3, y−2/3, z+1/3; (ii) x−1/3, y+1/3, z+1/3; (iii) x+2/3, y+1/3, z+1/3; (iv) y−2/3, x−1/3, −z+2/3; (v) y+1/3, x−1/3, −z+2/3; (vi) y+1/3, x+2/3, −z+2/3; (vii) y−1, x−1, −z+1; (viii) y−1, x, −z+1; (ix) y, x, −z+1; (x) x−1/3, y−2/3, z−2/3; (xi) x−2/3, y−1/3, z−1/3; (xii) x+1/3, y−1/3, z−1/3; (xiii) x+1/3, y+2/3, z−1/3; (xiv) x−2/3, y−4/3, z−1/3; (xv) y−1/3, x−2/3, −z+1/3; (xvi) y−1/3, x+1/3, −z+1/3; (xvii) y+2/3, x+1/3, −z+1/3; (xviii) y−1/3, x+1/3, −z+4/3; (xix) y, x+1, −z+1; (xx) y+1, x+1, −z+1; (xxi) x+1/3, y+2/3, z+2/3; (xxii) x+2/3, y+4/3, z+1/3.

(I_4)

Crystal data

Bi2.032Se2.968	V = 425.54 (1) Å^3
Mr = 659.00	Z = 3
Trigonal, R3m	F(000) = 809
Hall symbol: -R 3 2"	Dx = 7.715 Mg m^−3
a = 4.14078 (4) Å	Cu Kα radiation
c = 28.6579 (6) Å	T = 293 K

Data collection

G670 diffractometer

2θmin = 4.003°, 2θmax = 99.992°

Refinement

Rp = 0.037	0 restraints
Rwp = 0.054	0 constraints
Rexp = 0.004	Weighting scheme based on measured s.u.'s
R(F) = 0.064	(Δ/σ)max = 2.676
9600 data points	Background function: 10 Legendre polynoms
Profile function: Pseudo-Voigt	Preferred orientation correction: March & Dollase
18 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Bi1	0	0	0.40037 (4)	0.0092 (3)*
Se1	0	0	0	0.0105 (7)*
Se2	0	0	0.21063 (6)	0.0105 (7)*	0.984 (3)
Bi3	0	0	0.21063 (6)	0.0105*	0.016 (3)

Geometric parameters (Å, º)

Bi1—Se2^i	2.8742 (12)	Bi1—Bi3^iii	2.8742 (12)
Bi1—Se2^ii	2.8742 (12)	Se2—Bi3	0
Bi1—Se2^iii	2.8742 (12)	Bi3—Bi3^iv	3.4733 (18)
Bi1—Bi3^i	2.8742 (12)	Bi3—Bi3^v	3.4733 (18)
Bi1—Bi3^ii	2.8742 (12)	Bi3—Bi3^vi	3.4733 (18)
Se2^i—Bi1—Se2^ii	92.17 (4)	Bi1^i—Bi3—Bi1^ii	92.17 (4)
Se2^i—Bi1—Se2^iii	92.17 (4)	Bi1^i—Bi3—Bi1^iii	92.17 (4)
Se2^i—Bi1—Bi3^i	0.0 (5)	Bi1^i—Bi3—Se2	0
Se2^i—Bi1—Bi3^ii	92.17 (4)	Bi1^i—Bi3—Bi3^iv	96.69 (2)
Se2^i—Bi1—Bi3^iii	92.17 (4)	Bi1^i—Bi3—Bi3^v	96.69 (2)
Se2^ii—Bi1—Se2^iii	92.17 (4)	Bi1^i—Bi3—Bi3^vi	167.21 (6)
Se2^ii—Bi1—Bi3^i	92.17 (4)	Bi1^ii—Bi3—Bi1^iii	92.17 (4)
Se2^ii—Bi1—Bi3^ii	0.0 (5)	Bi1^ii—Bi3—Se2	0
Se2^ii—Bi1—Bi3^iii	92.17 (4)	Bi1^ii—Bi3—Bi3^iv	96.69 (2)
Se2^iii—Bi1—Bi3^i	92.17 (4)	Bi1^ii—Bi3—Bi3^v	167.21 (6)
Se2^iii—Bi1—Bi3^ii	92.17 (4)	Bi1^ii—Bi3—Bi3^vi	96.69 (2)
Se2^iii—Bi1—Bi3^iii	0.0 (5)	Bi1^iii—Bi3—Se2	0
Bi3^i—Bi1—Bi3^ii	92.17 (4)	Bi1^iii—Bi3—Bi3^iv	167.21 (6)
Bi3^i—Bi1—Bi3^iii	92.17 (4)	Bi1^iii—Bi3—Bi3^v	96.69 (2)
Bi3^ii—Bi1—Bi3^iii	92.17 (4)	Bi1^iii—Bi3—Bi3^vi	96.69 (2)
Bi1^i—Se2—Bi1^ii	92.17 (4)	Se2—Bi3—Bi3^iv	0
Bi1^i—Se2—Bi1^iii	92.17 (4)	Se2—Bi3—Bi3^v	0
Bi1^i—Se2—Bi3	0	Se2—Bi3—Bi3^vi	0
Bi1^ii—Se2—Bi1^iii	92.17 (4)	Bi3^iv—Bi3—Bi3^v	73.18 (4)
Bi1^ii—Se2—Bi3	0	Bi3^iv—Bi3—Bi3^vi	73.18 (4)
Bi1^iii—Se2—Bi3	0	Bi3^v—Bi3—Bi3^vi	73.18 (4)

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

(I_5)

Crystal data

Bi2.024Se2.976	V = 425.50 (1) Å^3
Mr = 657.96	Z = 3
Trigonal, R3m	F(000) = 810
Hall symbol: -R 3 2"	Dx = 7.703 Mg m^−3
a = 4.14070 (3) Å	Cu Kα radiation
c = 28.6564 (6) Å	T = 293 K

Data collection

G670 diffractometer

2θmin = 4.003°, 2θmax = 99.992°

Refinement

Rp = 0.031	0 restraints
Rwp = 0.047	0 constraints
Rexp = 0.004	Weighting scheme based on measured s.u.'s
R(F) = 0.044	(Δ/σ)max = 0.234
9600 data points	Background function: 10 Legendre polynoms
Profile function: Pseudo-Voigt	Preferred orientation correction: March & Dollase
20 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Bi1	0	0	0.40052 (4)	0.0112 (4)
Se1	0	0	0	0.0192 (9)
Se2	0	0	0.21014 (7)	0.0192 (9)	0.988 (2)
Bi3	0	0	0.21014 (7)	0.0192	0.012 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.0034 (3)	0.0034 (3)	0.0267 (9)	0.00168 (17)	0	0
Se1	0.0044 (6)	0.0044 (6)	0.049 (2)	0.0022 (3)	0	0
Se2	0.0044 (6)	0.0044 (6)	0.049 (2)	0.0022 (3)	0	0
Bi3	0.00436	0.00436	0.048738	0.00218	0	0

Geometric parameters (Å, º)

Bi1—Se2^i	2.8793 (12)	Bi1—Bi3^iii	2.8793 (12)
Bi1—Se2^ii	2.8793 (12)	Se2—Bi3	0
Bi1—Se2^iii	2.8793 (12)	Bi3—Bi3^iv	3.4530 (19)
Bi1—Bi3^i	2.8793 (12)	Bi3—Bi3^v	3.4530 (19)
Bi1—Bi3^ii	2.8793 (12)	Bi3—Bi3^vi	3.4530 (19)
Se2^i—Bi1—Se2^ii	91.95 (4)	Bi1^i—Bi3—Bi1^ii	91.95 (5)
Se2^i—Bi1—Se2^iii	91.95 (4)	Bi1^i—Bi3—Bi1^iii	91.95 (5)
Se2^i—Bi1—Bi3^i	0.0 (5)	Bi1^i—Bi3—Se2	0
Se2^i—Bi1—Bi3^ii	91.95 (4)	Bi1^i—Bi3—Bi3^iv	96.59 (2)
Se2^i—Bi1—Bi3^iii	91.95 (4)	Bi1^i—Bi3—Bi3^v	96.59 (2)
Se2^ii—Bi1—Se2^iii	91.95 (4)	Bi1^i—Bi3—Bi3^vi	167.69 (6)
Se2^ii—Bi1—Bi3^i	91.95 (4)	Bi1^ii—Bi3—Bi1^iii	91.95 (5)
Se2^ii—Bi1—Bi3^ii	0.0 (5)	Bi1^ii—Bi3—Se2	0
Se2^ii—Bi1—Bi3^iii	91.95 (4)	Bi1^ii—Bi3—Bi3^iv	96.59 (2)
Se2^iii—Bi1—Bi3^i	91.95 (4)	Bi1^ii—Bi3—Bi3^v	167.69 (6)
Se2^iii—Bi1—Bi3^ii	91.95 (4)	Bi1^ii—Bi3—Bi3^vi	96.59 (2)
Se2^iii—Bi1—Bi3^iii	0.0 (5)	Bi1^iii—Bi3—Se2	0
Bi3^i—Bi1—Bi3^ii	91.95 (4)	Bi1^iii—Bi3—Bi3^iv	167.69 (6)
Bi3^i—Bi1—Bi3^iii	91.95 (4)	Bi1^iii—Bi3—Bi3^v	96.59 (2)
Bi3^ii—Bi1—Bi3^iii	91.95 (4)	Bi1^iii—Bi3—Bi3^vi	96.59 (2)
Bi1^i—Se2—Bi1^ii	91.95 (5)	Se2—Bi3—Bi3^iv	0
Bi1^i—Se2—Bi1^iii	91.95 (5)	Se2—Bi3—Bi3^v	0
Bi1^i—Se2—Bi3	0	Se2—Bi3—Bi3^vi	0
Bi1^ii—Se2—Bi1^iii	91.95 (5)	Bi3^iv—Bi3—Bi3^v	73.68 (4)
Bi1^ii—Se2—Bi3	0	Bi3^iv—Bi3—Bi3^vi	73.68 (4)
Bi1^iii—Se2—Bi3	0	Bi3^v—Bi3—Bi3^vi	73.68 (4)

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