The first silver bis­muth borate, AgBi₂B₅O₁₁

The first silver bis­muth borate, AgBi₂B₅O₁₁ (silver dibismuth penta­borate), has been prepared via glass crystallization in the Ag₂O–Bi₂O₃–B₂O₃ system and characterized by single-crystal X-ray diffraction. Its structure is derived from that of centrosymmetric Bi₃B₅O₁₂ by ordered substitution of one Bi³⁺ ion for Ag⁺, which results in the disappearance of the mirror plane and inversion centre. Second harmonic generation (SHG) measurements confirm the acentric crystal structure. It is formed by [Bi₂B₅O₁₁]_∞ layers stretched along c and comprised of vertex-sharing B₅O₁₀ and BiO₃ groups which incorporate the Ag⁺ cations. The new compound was characterized by thermal analysis, high-temperature powder X-ray diffraction, and vibrational and UV–Vis–NIR (near infrared) spectroscopy. Its thermal expansion is strongly anisotropic due to the presence of rigid B₅O₁₀ groups aligned in a parallel manner. The minimal value is observed along their axis [parallel to c, α_c = 3.1 (1) × 10⁻⁶ K⁻¹], while maximal values are observed in the ab plane [α_a = 20.4 (2) and α_b = 7.8 (2) × 10⁻⁶ K⁻¹]. Upon heating, AgBi₂B₅O₁₁ starts to decay above 684 K due to partial reduction of silver; incongruent melting is observed at 861 K. According to density functional theory (DFT) band-structure cal­culations, the new compound is a semiconductor with an indirect energy gap of 3.57 eV, which agrees with the experimental data (absorption onset at 380 nm).

Computing details

Data collection: APEX2 (Bruker, 2003); cell refinement: APEX2 (Bruker, 2003); data reduction: APEX2 (Bruker, 2003); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007) and JANA2006(Petricek et al., 2014); molecular graphics: ATOMS (Dowty, 2003); software used to prepare material for publication: PLATON (Spek, 2009).

Silver dibismuth pentaborate

Crystal data

AgBi2B5O11	F(000) = 2608
Mr = 755.9	Dx = 5.379 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 83842 reflections
a = 13.2210 (3) Å	θ = 2.2–38.7°
b = 7.7792 (2) Å	µ = 39.75 mm^−1
c = 18.1515 (4) Å	T = 293 K
V = 1866.86 (8) Å^3	Prizm, colourless
Z = 8	0.24 × 0.13 × 0.07 mm

Data collection

Bruker APEXII CCD detector diffractometer	9998 independent reflections
Radiation source: X-ray tube	6350 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.113
ω and phi scans	θmax = 38.7°, θmin = 2.2°
Absorption correction: analytical (SADABS; Bruker, 2003)	h = −22→22
Tmin = 0.012, Tmax = 0.164	k = −12→12
83842 measured reflections	l = −31→31

Refinement

Refinement on F	1 constraint
R[F^2 > 2σ(F^2)] = 0.037	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
wR(F^2) = 0.042	(Δ/σ)max = 0.031
S = 0.99	Δρmax = 2.55 e Å^−3
9998 reflections	Δρmin = −1.80 e Å^−3
343 parameters	Absolute structure: 4716 of Friedel pairs used in the refinement
0 restraints	Absolute structure parameter: 0.006 (6)

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

	x	y	z	Uiso*/Ueq
Bi1	0.60824 (3)	0.71542 (5)	0.40703 (2)	0.01617 (9)
Bi2	0.38139 (3)	0.51716 (4)	0.320446 (18)	0.01557 (8)
Bi3	0.13714 (3)	0.54085 (5)	0.61769 (2)	0.01636 (9)
Bi4	0.36116 (3)	0.72982 (5)	0.52786 (2)	0.01623 (10)
Ag1	0.38274 (7)	0.97671 (11)	0.32360 (6)	0.0264 (2)
Ag2	0.36692 (7)	0.50199 (11)	0.11168 (5)	0.0258 (2)
O1	0.1902 (7)	0.2640 (10)	0.3025 (6)	0.025 (3)
O2	0.4426 (7)	0.2546 (9)	0.6343 (6)	0.024 (3)
O3	0.3838 (5)	0.3134 (10)	0.7556 (4)	0.0185 (19)
O4	0.1321 (6)	0.1824 (11)	0.1844 (4)	0.022 (2)
O5	0.2143 (7)	0.7422 (9)	0.5690 (5)	0.022 (2)
O6	0.0787 (6)	0.4414 (10)	0.3750 (4)	0.021 (2)
O7	0.4583 (6)	0.7158 (10)	0.3738 (5)	0.021 (2)
O8	0.2681 (5)	0.2040 (11)	0.6671 (4)	0.021 (2)
O9	0.0139 (6)	0.3006 (11)	0.2697 (4)	0.021 (2)
O10	0.2699 (6)	0.7071 (10)	0.2972 (5)	0.024 (2)
O11	0.5660 (6)	0.5184 (9)	0.4883 (4)	0.022 (2)
O12	0.0598 (6)	0.1323 (9)	0.3754 (4)	0.018 (2)
O13	0.5684 (7)	0.2133 (10)	0.4887 (5)	0.023 (2)
O14	0.4535 (6)	0.5941 (10)	0.2182 (4)	0.025 (2)
O15	0.3124 (8)	0.2270 (9)	0.4481 (5)	0.027 (3)
O16	0.3048 (6)	0.5286 (9)	0.4514 (4)	0.020 (2)
O17	0.5595 (5)	0.9130 (9)	0.4870 (4)	0.0181 (19)
O18	0.2032 (5)	0.6027 (10)	0.7247 (4)	0.021 (2)
O19	0.3371 (6)	0.0741 (9)	0.5605 (4)	0.021 (2)
O20	0.3123 (6)	0.9246 (9)	0.4501 (5)	0.022 (2)
O21	0.3106 (6)	0.3810 (10)	0.5628 (4)	0.022 (2)
O22	0.9768 (6)	0.2771 (10)	0.1402 (5)	0.022 (2)
B1	0.0370 (9)	0.2533 (11)	0.1980 (8)	0.012 (3)
B2	0.2064 (8)	0.1809 (16)	0.2375 (6)	0.019 (3)
B3	0.2909 (10)	0.2357 (15)	0.7372 (9)	0.021 (3)
B4	0.4590 (8)	0.3242 (14)	0.7022 (6)	0.016 (3)
B5	0.5649 (8)	0.3667 (14)	0.4515 (6)	0.017 (3)
B6	0.0895 (9)	0.2849 (14)	0.3294 (7)	0.018 (3)
B7	0.3193 (9)	0.0755 (15)	0.4848 (7)	0.020 (3)
B8	0.3417 (10)	0.2231 (15)	0.6063 (6)	0.018 (3)
B9	0.5700 (8)	0.0599 (15)	0.4487 (6)	0.015 (3)
B10	0.3091 (9)	0.3804 (16)	0.4869 (7)	0.021 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.01471 (17)	0.01751 (15)	0.01628 (17)	0.00043 (12)	0.00033 (14)	0.00014 (16)
Bi2	0.01569 (14)	0.01625 (15)	0.01478 (14)	0.00040 (11)	−0.00070 (14)	−0.00080 (14)
Bi3	0.01577 (15)	0.01705 (16)	0.01628 (15)	0.00032 (11)	0.00077 (14)	0.00037 (14)
Bi4	0.01499 (18)	0.01682 (16)	0.01688 (17)	−0.00046 (11)	−0.00096 (14)	−0.00029 (16)
Ag1	0.0301 (4)	0.0271 (4)	0.0219 (4)	−0.0034 (3)	−0.0052 (4)	0.0058 (4)
Ag2	0.0279 (4)	0.0281 (4)	0.0214 (4)	0.0026 (3)	−0.0042 (3)	−0.0058 (4)
O1	0.017 (4)	0.037 (5)	0.020 (5)	−0.002 (3)	−0.001 (3)	−0.008 (3)
O2	0.019 (4)	0.033 (4)	0.021 (5)	−0.001 (3)	0.001 (3)	−0.006 (3)
O3	0.013 (3)	0.024 (4)	0.019 (3)	−0.006 (2)	0.000 (2)	0.004 (3)
O4	0.021 (4)	0.033 (4)	0.011 (3)	0.009 (3)	0.000 (2)	−0.006 (3)
O5	0.015 (4)	0.028 (4)	0.023 (4)	−0.001 (2)	0.011 (3)	0.002 (3)
O6	0.026 (4)	0.027 (4)	0.010 (3)	0.002 (3)	0.001 (2)	−0.001 (3)
O7	0.018 (4)	0.019 (3)	0.027 (4)	0.001 (3)	0.001 (3)	−0.006 (3)
O8	0.011 (3)	0.035 (4)	0.017 (3)	−0.009 (3)	−0.001 (2)	0.004 (3)
O9	0.014 (3)	0.038 (4)	0.013 (3)	0.004 (3)	0.000 (2)	−0.005 (3)
O10	0.024 (4)	0.029 (4)	0.019 (4)	0.008 (3)	−0.005 (3)	−0.001 (3)
O11	0.028 (4)	0.020 (4)	0.018 (3)	−0.003 (3)	−0.005 (3)	−0.001 (3)
O12	0.027 (4)	0.016 (3)	0.013 (3)	−0.002 (3)	−0.002 (3)	0.001 (3)
O13	0.031 (4)	0.020 (3)	0.017 (4)	−0.005 (3)	−0.004 (3)	−0.001 (3)
O14	0.020 (4)	0.039 (4)	0.016 (3)	−0.008 (3)	−0.001 (3)	0.003 (3)
O15	0.046 (6)	0.016 (3)	0.018 (4)	0.000 (3)	−0.003 (4)	−0.002 (3)
O16	0.020 (3)	0.019 (3)	0.021 (3)	−0.003 (2)	0.000 (3)	−0.003 (3)
O17	0.022 (3)	0.016 (3)	0.016 (3)	0.005 (2)	−0.001 (3)	0.006 (3)
O18	0.018 (3)	0.031 (4)	0.014 (3)	−0.006 (3)	−0.001 (2)	0.000 (3)
O19	0.034 (4)	0.016 (3)	0.013 (3)	0.002 (3)	0.006 (3)	−0.005 (3)
O20	0.027 (4)	0.012 (3)	0.026 (4)	−0.001 (2)	0.002 (3)	0.002 (3)
O21	0.026 (4)	0.019 (4)	0.022 (4)	0.001 (3)	0.001 (3)	−0.001 (3)
O22	0.013 (3)	0.037 (4)	0.016 (3)	0.006 (3)	−0.002 (3)	0.003 (3)
B1	0.013 (5)	0.009 (5)	0.014 (5)	0.003 (3)	−0.001 (4)	0.003 (3)
B2	0.011 (5)	0.032 (6)	0.014 (4)	−0.002 (4)	−0.003 (3)	−0.001 (4)
B3	0.018 (6)	0.023 (6)	0.020 (6)	−0.005 (4)	−0.006 (5)	−0.007 (4)
B4	0.016 (5)	0.016 (5)	0.015 (4)	−0.001 (3)	−0.001 (3)	0.000 (4)
B5	0.017 (5)	0.017 (5)	0.016 (5)	0.005 (3)	0.004 (4)	−0.003 (4)
B6	0.021 (5)	0.016 (5)	0.017 (5)	0.005 (3)	0.001 (4)	0.002 (5)
B7	0.025 (6)	0.018 (5)	0.017 (5)	−0.003 (4)	0.004 (4)	0.006 (4)
B8	0.026 (6)	0.023 (5)	0.007 (4)	−0.003 (4)	0.005 (4)	0.002 (4)
B9	0.019 (5)	0.020 (5)	0.007 (4)	−0.002 (4)	−0.004 (3)	0.002 (4)
B10	0.015 (5)	0.025 (6)	0.022 (6)	−0.003 (4)	0.011 (4)	−0.011 (5)

Geometric parameters (Å, º)

Bi1—O3^i	2.760 (7)	Ag2—O8^x	2.582 (8)
Bi1—O6^ii	2.760 (8)	Ag2—O11^i	2.414 (8)
Bi1—O7	2.073 (8)	Ag2—O14	2.358 (7)
Bi1—O10^ii	2.984 (8)	Ag2—O22^iv	2.664 (8)
Bi1—O11	2.199 (8)	B1—O4	1.394 (14)
Bi1—O12^iii	2.838 (7)	B1—O9	1.387 (16)
Bi1—O17	2.210 (7)	B1—O22^xii	1.330 (16)
Bi1—O20^ii	3.012 (8)	B2—O1	1.362 (15)
Bi2—O7	2.088 (8)	B2—O4	1.377 (13)
Bi2—O9^iii	3.167 (8)	B2—O18^xi	1.361 (13)
Bi2—O10	2.129 (8)	B3—O3	1.409 (15)
Bi2—O12^iii	2.813 (7)	B3—O8	1.331 (18)
Bi2—O14	2.171 (7)	B3—O10^xiii	1.372 (18)
Bi2—O16	2.586 (8)	B4—O2	1.363 (15)
Bi3—O5	2.067 (8)	B4—O3	1.391 (13)
Bi3—O13^iv	3.196 (8)	B4—O14^vi	1.352 (13)
Bi3—O17^v	2.610 (7)	B5—O11	1.355 (13)
Bi3—O18	2.183 (7)	B5—O12^iii	1.383 (13)
Bi3—O21	2.792 (8)	B5—O13	1.372 (14)
Bi3—O22^vi	2.107 (8)	B6—O1	1.428 (16)
Bi4—O4^vii	2.866 (7)	B6—O6	1.478 (14)
Bi4—O5	2.083 (9)	B6—O9	1.479 (15)
Bi4—O7	3.080 (9)	B6—O12	1.504 (14)
Bi4—O16	2.220 (7)	B7—O15	1.358 (14)
Bi4—O17	3.075 (7)	B7—O19	1.394 (14)
Bi4—O19^viii	2.762 (7)	B7—O20^xiv	1.336 (14)
Bi4—O20	2.169 (8)	B8—O2	1.449 (16)
Bi4—O21	2.865 (8)	B8—O8	1.479 (14)
Bi4—O22^ix	2.980 (8)	B8—O19	1.427 (14)
Ag1—O6^ii	2.826 (8)	B8—O21	1.517 (14)
Ag1—O7	2.438 (8)	B9—O6^iii	1.343 (12)
Ag1—O9^ii	2.639 (8)	B9—O13	1.397 (14)
Ag1—O10	2.618 (8)	B9—O17^xiv	1.344 (13)
Ag1—O18^x	2.341 (7)	B10—O15	1.387 (15)
Ag1—O20	2.510 (8)	B10—O16	1.322 (14)
Ag2—O5^xi	2.415 (8)	B10—O21	1.376 (15)
O3^i—Bi1—O6^ii	82.8 (2)	O7—Bi4—O22^ix	109.0 (2)
O3^i—Bi1—O7	75.3 (3)	O16—Bi4—O17	117.5 (2)
O3^i—Bi1—O10^ii	47.5 (2)	O16—Bi4—O19^viii	141.2 (2)
O3^i—Bi1—O11	128.4 (3)	O16—Bi4—O20	89.2 (3)
O3^i—Bi1—O12^iii	74.3 (2)	O16—Bi4—O21	52.6 (2)
O3^i—Bi1—O17	136.2 (2)	O16—Bi4—O22^ix	139.1 (2)
O3^i—Bi1—O20^ii	101.2 (2)	O17—Bi4—O19^viii	72.6 (2)
O6^ii—Bi1—O7	78.6 (3)	O17—Bi4—O20	76.9 (2)
O6^ii—Bi1—O10^ii	76.4 (2)	O17—Bi4—O21	133.7 (2)
O6^ii—Bi1—O11	141.2 (2)	O17—Bi4—O22^ix	59.7 (2)
O6^ii—Bi1—O12^iii	147.9 (2)	O19^viii—Bi4—O20	55.1 (2)
O6^ii—Bi1—O17	54.9 (2)	O19^viii—Bi4—O21	147.6 (2)
O6^ii—Bi1—O20^ii	122.1 (2)	O19^viii—Bi4—O22^ix	79.4 (2)
O7—Bi1—O10^ii	119.4 (3)	O20—Bi4—O21	137.4 (3)
O7—Bi1—O11	87.3 (3)	O20—Bi4—O22^ix	125.0 (3)
O7—Bi1—O12^iii	74.1 (3)	O21—Bi4—O22^ix	97.7 (2)
O7—Bi1—O17	84.9 (3)	O6^ii—Ag1—O7	71.9 (2)
O7—Bi1—O20^ii	158.9 (2)	O6^ii—Ag1—O9^ii	51.1 (2)
O10^ii—Bi1—O11	140.4 (3)	O6^ii—Ag1—O10	139.8 (2)
O10^ii—Bi1—O12^iii	102.7 (2)	O6^ii—Ag1—O18^x	127.1 (2)
O10^ii—Bi1—O17	120.5 (2)	O6^ii—Ag1—O20	94.3 (2)
O10^ii—Bi1—O20^ii	66.7 (2)	O7—Ag1—O9^ii	114.6 (3)
O11—Bi1—O12^iii	54.1 (2)	O7—Ag1—O10	68.6 (3)
O11—Bi1—O17	88.3 (3)	O7—Ag1—O18^x	146.5 (3)
O11—Bi1—O20^ii	78.5 (3)	O7—Ag1—O20	71.1 (3)
O12^iii—Bi1—O17	136.9 (2)	O9^ii—Ag1—O10	146.4 (3)
O12^iii—Bi1—O20^ii	84.8 (2)	O9^ii—Ag1—O18^x	76.1 (2)
O17—Bi1—O20^ii	110.0 (2)	O9^ii—Ag1—O20	133.5 (2)
O7—Bi2—O9^iii	116.3 (3)	O10—Ag1—O18^x	85.3 (3)
O7—Bi2—O10	85.1 (3)	O10—Ag1—O20	80.0 (2)
O7—Bi2—O12^iii	74.5 (3)	O18^x—Ag1—O20	126.1 (2)
O7—Bi2—O14	88.8 (3)	O5^xi—Ag2—O8^x	109.1 (3)
O7—Bi2—O16	74.9 (3)	O5^xi—Ag2—O11^i	79.1 (3)
O9^iii—Bi2—O10	150.1 (3)	O5^xi—Ag2—O14	137.1 (3)
O9^iii—Bi2—O12^iii	46.89 (19)	O5^xi—Ag2—O22^iv	67.8 (3)
O9^iii—Bi2—O14	74.0 (3)	O8^x—Ag2—O11^i	130.9 (3)
O9^iii—Bi2—O16	120.7 (2)	O8^x—Ag2—O14	80.3 (3)
O10—Bi2—O12^iii	159.7 (3)	O8^x—Ag2—O22^iv	142.9 (3)
O10—Bi2—O14	86.8 (3)	O11^i—Ag2—O14	127.0 (3)
O10—Bi2—O16	83.5 (3)	O11^i—Ag2—O22^iv	85.8 (3)
O12^iii—Bi2—O14	92.8 (2)	O14—Ag2—O22^iv	79.9 (3)
O12^iii—Bi2—O16	90.9 (2)	O4—B1—O9	118.0 (10)
O14—Bi2—O16	161.6 (3)	O4—B1—O22^xii	117.0 (11)
O5—Bi3—O13^iv	107.2 (3)	O9—B1—O22^xii	124.9 (10)
O5—Bi3—O17^v	72.6 (3)	O1—B2—O4	119.4 (9)
O5—Bi3—O18	90.9 (3)	O1—B2—O18^xi	119.9 (9)
O5—Bi3—O21	77.3 (3)	O4—B2—O18^xi	120.6 (9)
O5—Bi3—O22^vi	85.8 (3)	O3—B3—O8	120.2 (12)
O13^iv—Bi3—O17^v	46.2 (2)	O3—B3—O10^xiii	113.1 (12)
O13^iv—Bi3—O18	154.4 (2)	O8—B3—O10^xiii	126.7 (11)
O13^iv—Bi3—O21	72.3 (2)	O2—B4—O3	119.5 (9)
O13^iv—Bi3—O22^vi	110.7 (3)	O2—B4—O14^vi	121.1 (9)
O17^v—Bi3—O18	159.3 (2)	O3—B4—O14^vi	119.4 (9)
O17^v—Bi3—O21	93.4 (2)	O11—B5—O12^iii	119.1 (9)
O17^v—Bi3—O22^vi	78.6 (3)	O11—B5—O13	121.0 (10)
O18—Bi3—O21	95.0 (2)	O12^iii—B5—O13	119.9 (9)
O18—Bi3—O22^vi	88.0 (3)	O1—B6—O6	112.1 (9)
O21—Bi3—O22^vi	162.8 (3)	O1—B6—O9	112.9 (10)
O4^vii—Bi4—O5	71.3 (3)	O1—B6—O12	110.0 (8)
O4^vii—Bi4—O7	152.0 (2)	O6—B6—O9	106.1 (8)
O4^vii—Bi4—O16	122.6 (3)	O6—B6—O12	108.3 (9)
O4^vii—Bi4—O17	105.8 (2)	O9—B6—O12	107.2 (8)
O4^vii—Bi4—O19^viii	85.2 (2)	O15—B7—O19	120.1 (10)
O4^vii—Bi4—O20	138.1 (3)	O15—B7—O20^xiv	121.8 (11)
O4^vii—Bi4—O21	70.5 (2)	O19—B7—O20^xiv	118.1 (10)
O4^vii—Bi4—O22^ix	46.8 (2)	O2—B8—O8	111.1 (9)
O5—Bi4—O7	135.7 (3)	O2—B8—O19	112.4 (10)
O5—Bi4—O16	86.8 (3)	O2—B8—O21	107.2 (9)
O5—Bi4—O17	149.3 (2)	O8—B8—O19	108.9 (9)
O5—Bi4—O19^viii	76.7 (3)	O8—B8—O21	107.0 (9)
O5—Bi4—O20	85.6 (3)	O19—B8—O21	110.1 (9)
O5—Bi4—O21	75.3 (3)	O6^iii—B9—O13	121.7 (9)
O5—Bi4—O22^ix	114.8 (3)	O6^iii—B9—O17^xiv	121.2 (9)
O7—Bi4—O16	63.1 (2)	O13—B9—O17^xiv	117.1 (9)
O7—Bi4—O17	56.1 (2)	O15—B10—O16	120.2 (11)
O7—Bi4—O19^viii	106.1 (2)	O15—B10—O21	120.8 (10)
O7—Bi4—O20	63.8 (3)	O16—B10—O21	119.0 (10)
O7—Bi4—O21	105.3 (2)

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