Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101019643/iz1016sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101019643/iz1016Isup2.hkl |
Since the crystal melts congruently the top-seeded solution method was used. Bi2B8O15 contains two modifications. The low-temperature form was obtained by annealing the as-grown crystal.
The structure was refined as a racemic twin with components 0.81 (6) and 0.19 (6). 856 Friedel pairs were used. Because the anisotropic atomic displacement parameter (ADP) of the light atoms are very large in this kind of structure, the SHELXTL commands DELU, ISOR and SIMU (Bruker, 1997) were used for all atoms in the refinement to restrain their ADP parameters in the direction of the bond to be equal within a standard deviation 0.01; atoms closer than 1.7 Å were restrained with standard deviation 0.04 to have the same ADP components and to approximate isotropic behavior with standard deviation 0.1. The high R factor and large residual electron density is probably due to the poor crystal quality (Rint=0.072). Δρmax was located at the position x = 0.2966, y =0.2605, z = 0.115, 0.66 Å from Bi1 atom.
Data collection: XSCANS (Siemens,1996); cell refinement: XSCANS (Siemens,1996); data reduction: Bruker SHELXTL (Bruker,1997); program(s) used to solve structure: Bruker SHELXTL (Bruker,1997); program(s) used to refine structure: Bruker SHELXTL (Bruker,1997); molecular graphics: Bruker SHELXTL (Bruker,1997).
B8Bi2O15 | F(000) = 652 |
Mr = 744.44 | Dx = 4.152 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.3142 (7) Å | Cell parameters from 40 reflections |
b = 22.141 (4) Å | θ = 5.5–15.9° |
c = 6.4675 (10) Å | µ = 29.60 mm−1 |
β = 105.441 (11)° | T = 293 K |
V = 595.49 (16) Å3 | Prism, colourless |
Z = 2 | 0.10 × 0.10 × 0.09 mm |
Bruker P4 diffractometer | 2655 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.072 |
Graphite monochromator | θmax = 35.0°, θmin = 3.3° |
θ/2θ scans | h = −6→1 |
Absorption correction: ψ scan SCANS (Siemens,1996) | k = −35→1 |
Tmin = 0.05, Tmax = 0.07 | l = −10→10 |
3607 measured reflections | 3 standard reflections every 97 reflections |
2751 independent reflections | intensity decay: none |
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)] = 0.070 | w = 1/[σ2(Fo2) + (0.1457P)2 + 1.4317P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.171 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 11.45 e Å−3 |
2751 reflections | Δρmin = −6.20 e Å−3 |
227 parameters | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
341 restraints | Absolute structure parameter: 0.19 (6) |
B8Bi2O15 | V = 595.49 (16) Å3 |
Mr = 744.44 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 4.3142 (7) Å | µ = 29.60 mm−1 |
b = 22.141 (4) Å | T = 293 K |
c = 6.4675 (10) Å | 0.10 × 0.10 × 0.09 mm |
β = 105.441 (11)° |
Bruker P4 diffractometer | 2655 reflections with I > 2σ(I) |
Absorption correction: ψ scan SCANS (Siemens,1996) | Rint = 0.072 |
Tmin = 0.05, Tmax = 0.07 | 3 standard reflections every 97 reflections |
3607 measured reflections | intensity decay: none |
2751 independent reflections |
R[F2 > 2σ(F2)] = 0.070 | 341 restraints |
wR(F2) = 0.171 | Δρmax = 11.45 e Å−3 |
S = 1.07 | Δρmin = −6.20 e Å−3 |
2751 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
227 parameters | Absolute structure parameter: 0.19 (6) |
x | y | z | Uiso*/Ueq | ||
Bi2 | 0.82447 (12) | 0.64754 (3) | 0.66890 (8) | 0.01683 (14) | |
Bi1 | 0.61092 (13) | 0.78383 (3) | 0.89404 (8) | 0.01693 (14) | |
B1 | 0.442 (7) | 0.9889 (12) | 0.571 (3) | 0.031 (3) | |
B2 | 0.462 (8) | 0.9644 (13) | 0.208 (4) | 0.036 (3) | |
B3 | 0.693 (6) | 0.8982 (11) | 0.511 (3) | 0.027 (2) | |
B4 | 0.867 (4) | 0.7863 (10) | 0.480 (2) | 0.0159 (18) | |
B5 | 1.280 (4) | 0.7847 (12) | 0.265 (3) | 0.019 (2) | |
B6 | 0.573 (4) | 0.6447 (12) | 1.086 (3) | 0.0182 (19) | |
B7 | 0.147 (3) | 0.6475 (13) | 1.304 (3) | 0.018 (2) | |
B8 | 0.609 (7) | 0.5321 (12) | 1.089 (3) | 0.030 (3) | |
O1 | 0.357 (6) | 1.0016 (9) | 0.349 (2) | 0.038 (3) | |
O2 | 0.602 (5) | 0.9387 (9) | 0.650 (2) | 0.033 (3) | |
O3 | 0.632 (5) | 0.9103 (9) | 0.299 (2) | 0.035 (3) | |
O4 | 0.821 (4) | 0.8454 (7) | 0.5930 (19) | 0.0205 (17) | |
O5 | 1.180 (3) | 0.7842 (7) | 0.4473 (18) | 0.0177 (16) | |
O6 | 0.836 (3) | 0.7429 (7) | 0.649 (2) | 0.0175 (16) | |
O7 | 1.098 (3) | 0.7911 (9) | 1.057 (2) | 0.025 (2) | |
O8 | 0.610 (3) | 0.7813 (9) | 1.284 (2) | 0.0204 (19) | |
O9 | 0.829 (3) | 0.6540 (7) | 0.2850 (19) | 0.019 (2) | |
O10 | 0.339 (3) | 0.6410 (10) | 0.506 (2) | 0.024 (2) | |
O11 | 0.595 (3) | 0.6872 (8) | 0.9208 (19) | 0.0202 (17) | |
O12 | 0.251 (3) | 0.6488 (9) | 1.1206 (19) | 0.0195 (18) | |
O13 | 0.597 (4) | 0.5844 (7) | 0.987 (2) | 0.0233 (19) | |
O14 | 0.647 (5) | 0.5302 (9) | 1.307 (2) | 0.033 (3) | |
O15 | 0.580 (6) | 0.4758 (8) | 0.986 (2) | 0.036 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Bi2 | 0.0128 (2) | 0.0220 (2) | 0.0158 (2) | 0.00064 (19) | 0.00411 (15) | 0.00035 (17) |
Bi1 | 0.0127 (2) | 0.0226 (2) | 0.0155 (2) | 0.00083 (17) | 0.00382 (14) | 0.00052 (16) |
B1 | 0.051 (7) | 0.028 (6) | 0.016 (4) | 0.012 (6) | 0.013 (5) | −0.001 (5) |
B2 | 0.056 (8) | 0.036 (6) | 0.019 (5) | 0.012 (6) | 0.017 (5) | 0.000 (5) |
B3 | 0.038 (6) | 0.026 (4) | 0.018 (4) | 0.009 (5) | 0.011 (4) | 0.001 (4) |
B4 | 0.016 (4) | 0.016 (4) | 0.016 (4) | −0.003 (4) | 0.003 (3) | 0.000 (4) |
B5 | 0.016 (5) | 0.025 (6) | 0.016 (5) | −0.003 (6) | 0.003 (4) | −0.004 (6) |
B6 | 0.020 (4) | 0.022 (4) | 0.014 (4) | 0.000 (5) | 0.006 (3) | 0.002 (4) |
B7 | 0.005 (4) | 0.029 (6) | 0.018 (5) | −0.001 (5) | 0.001 (3) | −0.007 (6) |
B8 | 0.049 (7) | 0.026 (4) | 0.015 (4) | −0.008 (5) | 0.008 (5) | 0.001 (4) |
O1 | 0.062 (7) | 0.034 (6) | 0.018 (4) | 0.013 (5) | 0.010 (5) | −0.001 (4) |
O2 | 0.047 (6) | 0.031 (5) | 0.019 (4) | 0.011 (5) | 0.007 (4) | −0.002 (4) |
O3 | 0.058 (7) | 0.035 (5) | 0.017 (4) | 0.011 (5) | 0.017 (4) | 0.004 (4) |
O4 | 0.026 (4) | 0.021 (3) | 0.015 (3) | 0.000 (4) | 0.007 (3) | −0.002 (3) |
O5 | 0.013 (3) | 0.022 (4) | 0.019 (4) | 0.003 (4) | 0.006 (3) | 0.000 (4) |
O6 | 0.016 (4) | 0.020 (3) | 0.019 (4) | 0.003 (3) | 0.007 (3) | 0.001 (3) |
O7 | 0.013 (4) | 0.045 (8) | 0.017 (4) | −0.002 (5) | 0.005 (3) | −0.001 (4) |
O8 | 0.015 (4) | 0.028 (6) | 0.018 (4) | 0.004 (5) | 0.004 (3) | 0.001 (4) |
O9 | 0.014 (4) | 0.029 (6) | 0.012 (4) | 0.005 (4) | 0.001 (3) | −0.002 (4) |
O10 | 0.011 (4) | 0.043 (8) | 0.015 (4) | −0.004 (5) | −0.001 (3) | −0.002 (5) |
O11 | 0.023 (4) | 0.025 (4) | 0.014 (3) | −0.001 (4) | 0.009 (3) | 0.001 (3) |
O12 | 0.009 (3) | 0.030 (5) | 0.020 (4) | −0.002 (4) | 0.004 (3) | −0.001 (4) |
O13 | 0.028 (5) | 0.026 (4) | 0.018 (4) | −0.001 (4) | 0.010 (4) | 0.000 (3) |
O14 | 0.054 (8) | 0.034 (6) | 0.012 (4) | −0.012 (6) | 0.011 (5) | −0.003 (4) |
O15 | 0.066 (9) | 0.028 (5) | 0.014 (4) | −0.009 (6) | 0.012 (5) | −0.004 (4) |
Bi2—O10 | 2.084 (12) | B4—O4 | 1.54 (2) |
Bi2—O6 | 2.117 (15) | B5—O5 | 1.36 (2) |
Bi2—O11 | 2.294 (13) | B5—O7v | 1.37 (2) |
Bi2—O9 | 2.493 (12) | B5—O8vi | 1.40 (2) |
Bi2—O10i | 2.700 (13) | B6—O11 | 1.45 (2) |
Bi2—Bi1 | 3.5763 (9) | B6—O12 | 1.47 (2) |
Bi1—O7 | 2.090 (13) | B6—O9vii | 1.47 (2) |
Bi1—O11 | 2.149 (17) | B6—O13 | 1.50 (3) |
Bi1—O6 | 2.259 (13) | B7—O9viii | 1.350 (19) |
Bi1—O8 | 2.522 (13) | B7—O10vii | 1.36 (2) |
Bi1—O7ii | 2.697 (13) | B7—O12 | 1.37 (2) |
Bi1—O4 | 2.722 (13) | B8—O13 | 1.32 (3) |
B1—O14iii | 1.33 (3) | B8—O14 | 1.38 (2) |
B1—O2 | 1.34 (3) | B8—O15 | 1.40 (3) |
B1—O1 | 1.41 (3) | O7—B5vii | 1.37 (2) |
B2—O15iv | 1.24 (3) | O7—Bi1i | 2.697 (13) |
B2—O1 | 1.39 (3) | O8—B5viii | 1.40 (2) |
B2—O3 | 1.44 (3) | O8—B4vii | 1.45 (2) |
B3—O4 | 1.34 (3) | O9—B7vi | 1.350 (19) |
B3—O3 | 1.36 (3) | O9—B6v | 1.47 (2) |
B3—O2 | 1.40 (3) | O10—B7v | 1.36 (2) |
B4—O5 | 1.42 (2) | O10—Bi2ii | 2.700 (13) |
B4—O8v | 1.45 (2) | O14—B1ix | 1.33 (3) |
B4—O6 | 1.49 (2) | O15—B2x | 1.24 (3) |
O10—Bi2—O6 | 94.3 (7) | O5—B4—O4 | 110.3 (15) |
O10—Bi2—O11 | 79.6 (5) | O8v—B4—O4 | 108.4 (14) |
O6—Bi2—O11 | 71.6 (5) | O6—B4—O4 | 98.9 (12) |
O10—Bi2—O9 | 77.0 (5) | O5—B5—O7v | 128.5 (15) |
O6—Bi2—O9 | 82.8 (5) | O5—B5—O8vi | 118.2 (13) |
O11—Bi2—O9 | 143.6 (5) | O7v—B5—O8vi | 113.2 (14) |
O10—Bi2—O10i | 128.3 (6) | O11—B6—O12 | 109.0 (17) |
O6—Bi2—O10i | 89.7 (6) | O11—B6—O9vii | 111.9 (17) |
O11—Bi2—O10i | 148.3 (5) | O12—B6—O9vii | 112.4 (14) |
O9—Bi2—O10i | 52.4 (4) | O11—B6—O13 | 103.9 (13) |
O10—Bi2—Bi1 | 86.0 (5) | O12—B6—O13 | 107.2 (18) |
O6—Bi2—Bi1 | 36.5 (3) | O9vii—B6—O13 | 112.1 (16) |
O11—Bi2—Bi1 | 35.0 (4) | O9viii—B7—O10vii | 116.1 (14) |
O9—Bi2—Bi1 | 115.4 (4) | O9viii—B7—O12 | 118.5 (14) |
O10i—Bi2—Bi1 | 122.1 (4) | O10vii—B7—O12 | 125.3 (13) |
O7—Bi1—O11 | 94.9 (7) | O13—B8—O14 | 121 (2) |
O7—Bi1—O6 | 79.8 (5) | O13—B8—O15 | 123.8 (17) |
O11—Bi1—O6 | 71.7 (5) | O14—B8—O15 | 115.4 (19) |
O7—Bi1—O8 | 76.5 (5) | B2—O1—B1 | 120 (2) |
O11—Bi1—O8 | 83.6 (5) | B1—O2—B3 | 119.3 (16) |
O6—Bi1—O8 | 143.9 (5) | B3—O3—B2 | 121.0 (17) |
O7—Bi1—O7ii | 128.2 (6) | B3—O4—B4 | 130.4 (14) |
O11—Bi1—O7ii | 88.9 (6) | B3—O4—Bi1 | 122.6 (12) |
O6—Bi1—O7ii | 148.1 (5) | B4—O4—Bi1 | 91.3 (9) |
O8—Bi1—O7ii | 52.5 (4) | B5—O5—B4 | 131.4 (13) |
O7—Bi1—O4 | 80.8 (5) | B4—O6—Bi2 | 134.4 (11) |
O11—Bi1—O4 | 125.4 (4) | B4—O6—Bi1 | 113.2 (11) |
O6—Bi1—O4 | 54.0 (5) | Bi2—O6—Bi1 | 109.6 (6) |
O8—Bi1—O4 | 144.6 (5) | B5vii—O7—Bi1 | 136.1 (12) |
O7ii—Bi1—O4 | 135.5 (5) | B5vii—O7—Bi1i | 93.6 (10) |
O7—Bi1—Bi2 | 86.4 (5) | Bi1—O7—Bi1i | 128.2 (6) |
O11—Bi1—Bi2 | 37.8 (3) | B5viii—O8—B4vii | 126.5 (13) |
O6—Bi1—Bi2 | 33.9 (4) | B5viii—O8—Bi1 | 100.6 (9) |
O8—Bi1—Bi2 | 117.2 (4) | B4vii—O8—Bi1 | 132.0 (10) |
O7ii—Bi1—Bi2 | 122.5 (4) | B7vi—O9—B6v | 125.0 (13) |
O4—Bi1—Bi2 | 87.8 (3) | B7vi—O9—Bi2 | 100.5 (9) |
O14iii—B1—O2 | 122.9 (19) | B6v—O9—Bi2 | 131.2 (10) |
O14iii—B1—O1 | 115 (2) | B7v—O10—Bi2 | 138.7 (11) |
O2—B1—O1 | 121.7 (18) | B7v—O10—Bi2ii | 91.0 (9) |
O15iv—B2—O1 | 124 (2) | Bi2—O10—Bi2ii | 128.3 (6) |
O15iv—B2—O3 | 120 (2) | B6—O11—Bi1 | 135.8 (12) |
O1—B2—O3 | 116.4 (19) | B6—O11—Bi2 | 113.7 (12) |
O4—B3—O3 | 121.4 (18) | Bi1—O11—Bi2 | 107.2 (6) |
O4—B3—O2 | 117.6 (16) | B7—O12—B6 | 132.1 (14) |
O3—B3—O2 | 120.8 (19) | B8—O13—B6 | 124.6 (15) |
O5—B4—O8v | 113.6 (13) | B1ix—O14—B8 | 131 (2) |
O5—B4—O6 | 111.3 (14) | B2x—O15—B8 | 129 (2) |
O8v—B4—O6 | 113.3 (14) |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) −x+1, y+1/2, −z+2; (iv) −x+1, y+1/2, −z+1; (v) x, y, z−1; (vi) x+1, y, z−1; (vii) x, y, z+1; (viii) x−1, y, z+1; (ix) −x+1, y−1/2, −z+2; (x) −x+1, y−1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | B8Bi2O15 |
Mr | 744.44 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 4.3142 (7), 22.141 (4), 6.4675 (10) |
β (°) | 105.441 (11) |
V (Å3) | 595.49 (16) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 29.60 |
Crystal size (mm) | 0.10 × 0.10 × 0.09 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan SCANS (Siemens,1996) |
Tmin, Tmax | 0.05, 0.07 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3607, 2751, 2655 |
Rint | 0.072 |
(sin θ/λ)max (Å−1) | 0.807 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.070, 0.171, 1.07 |
No. of reflections | 2751 |
No. of parameters | 227 |
No. of restraints | 341 |
Δρmax, Δρmin (e Å−3) | 11.45, −6.20 |
Absolute structure | Flack H D (1983), Acta Cryst. A39, 876-881 |
Absolute structure parameter | 0.19 (6) |
Computer programs: XSCANS (Siemens,1996), Bruker SHELXTL (Bruker,1997).
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The growing field of nonlinear optical (NLO) research and applications still requires new materials for developing new laser sources and extending applications. Much effort has been spent on developing the borate series. Among them, β-BaB2O4 (BBO), LiB3O5 (LBO), YCa4(BO3)3O (YCOB) and BiB3O6 (BIBO), have been studied as promising NLO crystals (Becker, 1998). The B atom usually coordinates with either three or four O atoms forming BO3 or BO4 groups, where the electronic orbitals are hybridized to a planar sp2 or a three-dimensional sp3 configuration. The structural unit can comprise several different BmOn groups through different combinations, such as the B3O6 group in BBO, the B3O7 group in LBO, and a combination of BO3 and BO4 groups as in BIBO (Xue & Zhang, 1997). Levin & McDaniel (1962) investigated the binary system Bi2O3—B2O3, and described Bi2B8O15 for the first time. Based on their study, the authors have grown a low-temperature form of Bi2B8O15 single crystals. To our best knowledge, Bi2B8O15 has not been grown as a single-crystal in the past.
The crystal structure of Bi2B8O15 is shown in Fig. 1. The three-dimensional framework of the structure is composed of two principal components; (a) Bi atoms of fivefold and sixfold coordination, (b) BO3 triangles, (c) B3O6 planar rings, and (d) BO4 tetrahedra. The BiO5 and BiO6 polyhedra are linked to B3O6 rings via BO3 triangles or BO4 tetrahedra. The ratio of BO3 triangles and BO4 tetrahedra is 3:1. The lone-pair electrons are supposedly located near the Bi cation (Hellwig et al., 1999).
The crystal consists of nearly planar B3O6 rings bonded through Bi cations as shown in Fig. 2. The average B—O distances in B3O6 six-membered rings is 1.39 Å. The B2—O3 bond length [1.44 (3) Å] is significantly longer than others, including B3—O3 [1.36 (3) Å] and B1—O2 [1.34 (3) Å]. The average B—O—B angle is 120.8(X)° with the angles B1—O2—B3 [119.3 (16)°] and B3—O3—B2 [121.0 (17)°] showing the the largest deviation. The Bi atom has a distorted octahedral coordination, with the average Bi—O distance of 2.396(X)Å.
The anionic group theory (Chen & Wu, 1989) revealed that the B3O6 groups in BBO play an important role contributing to its excellent NLO responses. Accordingly, the NLO-active clusters in Bi2B8O15 should be B3O6 rings. The additional presence of distorted BiO6 and BiO5 polyhedra and lone-pair electrons of Bi may enhance the NLO effect (Zhang & Wang, 1996). The structural features indicated above show that the Bi2B8O15 is a potential NLO crystal, and in fact, the authors observed a strong second harmonic generation (SHG) effect by the irradiation of infrared light.