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The thermo-physical properties of the nonlinear optical (NLO) crystal K3B6O10Br (KBB) were experimentally investigated, including specific heat, thermal conductivity, coefficient of thermal expansion and refractive index. The specific heat of KBB is lower than that of LiB3O5 and higher than that of other borate NLO crystals, such as β-BaB2O4, CsLiB6O10 and CsB3O5, and KBB manifests a high damage threshold because of its lower temperature gradient during laser pulse irradiation. The thermal expansion coefficients were obtained as αx = 5.09 × 10−6 K−1 and αz = 2.39 × 10−5 K−1, showing weaker anisotropy than those of commonly used NLO crystals. The temperature-dependent Sellmeier dispersion equations of the refractive indices were also obtained, and the phase-matching angles for second harmonic generation (SHG) at temperatures of 313, 343, 373, 403 and 433 K which were calculated from these equations are in good agreement with the experimental values. All results are indicative of the KBB crystal as a novel promising NLO crystal for high power SHG.
Supporting information
CCDC reference: 1448410
Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
Crystal data top
B6BrK3O10 | Dx = 2.670 Mg m−3 |
Mr = 422.07 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3m | Cell parameters from 1535 reflections |
a = 10.1252 (14) Å | θ = 3.3–24.9° |
c = 8.8687 (18) Å | µ = 5.15 mm−1 |
V = 787.4 (2) Å3 | T = 296 K |
Z = 3 | Block |
F(000) = 606 | 0.1 × 0.08 × 0.07 mm |
Data collection top
CCD area detector diffractometer | 338 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.035 |
Graphite monochromator | θmax = 25.0°, θmin = 3.3° |
phi and ω scans | h = −9→12 |
1495 measured reflections | k = −12→8 |
340 independent reflections | l = −10→10 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0091P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.019 | (Δ/σ)max < 0.001 |
wR(F2) = 0.045 | Δρmax = 0.34 e Å−3 |
S = 1.18 | Δρmin = −0.56 e Å−3 |
340 reflections | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
41 parameters | Extinction coefficient: 0.399 (17) |
1 restraint | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.030 (12) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 > 2sigma(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 | Uiso*/Ueq | |
Br1 | 0.0000 | 0.0000 | 0.99502 (7) | 0.0214 (4) | |
K1 | 0.18026 (6) | 0.36051 (12) | 0.88304 (12) | 0.0157 (3) | |
O1 | 0.0000 | 0.0000 | 0.5512 (7) | 0.0057 (11) | |
O2 | 0.44484 (16) | 0.55516 (16) | 1.0558 (4) | 0.0108 (7) | |
O3 | 0.2327 (2) | 0.2336 (2) | 0.6246 (3) | 0.0115 (6) | |
B1 | 0.0871 (2) | 0.1741 (5) | 0.5452 (6) | 0.0072 (10) | |
B2 | 0.2997 (5) | 0.1499 (2) | 0.6611 (6) | 0.0073 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0199 (4) | 0.0199 (4) | 0.0243 (5) | 0.0100 (2) | 0.000 | 0.000 |
K1 | 0.0136 (5) | 0.0188 (6) | 0.0165 (6) | 0.0094 (3) | −0.0021 (2) | −0.0043 (5) |
O1 | 0.0062 (16) | 0.0062 (16) | 0.005 (2) | 0.0031 (8) | 0.000 | 0.000 |
O2 | 0.0135 (11) | 0.0135 (11) | 0.0092 (14) | 0.0095 (14) | 0.0012 (6) | −0.0012 (6) |
O3 | 0.0087 (12) | 0.0096 (12) | 0.0151 (11) | 0.0037 (10) | −0.0059 (8) | −0.0021 (8) |
B1 | 0.0050 (16) | 0.006 (2) | 0.011 (3) | 0.0030 (11) | 0.0000 (9) | −0.0001 (17) |
B2 | 0.006 (3) | 0.0111 (18) | 0.003 (2) | 0.0031 (13) | 0.002 (3) | 0.0011 (13) |
Geometric parameters (Å, º) top
Br1—K1i | 3.3135 (12) | O1—B1 | 1.528 (4) |
Br1—K1 | 3.3135 (12) | O1—B1i | 1.528 (4) |
Br1—K1ii | 3.3135 (12) | O1—B1ii | 1.528 (4) |
Br1—K1iii | 3.3258 (13) | O2—B2iii | 1.374 (6) |
Br1—K1iv | 3.3258 (13) | O2—B1xi | 1.449 (6) |
Br1—K1v | 3.3258 (13) | O2—K1xii | 2.851 (2) |
K1—O3iii | 2.793 (2) | O3—B2 | 1.364 (3) |
K1—O3vi | 2.793 (2) | O3—B1 | 1.465 (3) |
K1—O3vii | 2.806 (3) | O3—K1xiii | 2.793 (2) |
K1—O3 | 2.806 (3) | B1—O2xiv | 1.449 (6) |
K1—O2 | 2.851 (2) | B1—O3vii | 1.465 (3) |
K1—O2viii | 2.851 (2) | B2—O3xv | 1.364 (3) |
K1—B2iii | 3.146 (3) | B2—O2xiii | 1.374 (6) |
K1—B2ix | 3.146 (3) | B2—K1xiii | 3.146 (3) |
K1—Br1x | 3.3258 (13) | B2—K1xvi | 3.146 (3) |
K1—B1 | 3.413 (5) | B2—K1ii | 3.531 (3) |
K1—B2i | 3.531 (3) | | |
| | | |
K1i—Br1—K1 | 111.42 (2) | O2—K1—B1 | 139.33 (7) |
K1i—Br1—K1ii | 111.42 (2) | O2viii—K1—B1 | 139.33 (7) |
K1—Br1—K1ii | 111.42 (2) | B2iii—K1—B1 | 116.07 (9) |
K1i—Br1—K1iii | 161.26 (4) | B2ix—K1—B1 | 116.07 (9) |
K1—Br1—K1iii | 77.987 (9) | Br1—K1—B1 | 78.83 (8) |
K1ii—Br1—K1iii | 77.988 (9) | Br1x—K1—B1 | 82.44 (8) |
K1i—Br1—K1iv | 77.987 (9) | O3iii—K1—B2i | 135.24 (8) |
K1—Br1—K1iv | 161.26 (4) | O3vi—K1—B2i | 57.51 (10) |
K1ii—Br1—K1iv | 77.988 (9) | O3vii—K1—B2i | 21.14 (9) |
K1iii—Br1—K1iv | 88.70 (3) | O3—K1—B2i | 66.84 (8) |
K1i—Br1—K1v | 77.987 (9) | O2—K1—B2i | 174.66 (9) |
K1—Br1—K1v | 77.987 (9) | O2viii—K1—B2i | 103.29 (10) |
K1ii—Br1—K1v | 161.26 (4) | B2iii—K1—B2i | 157.66 (16) |
K1iii—Br1—K1v | 88.70 (3) | B2ix—K1—B2i | 77.47 (3) |
K1iv—Br1—K1v | 88.70 (3) | Br1—K1—B2i | 70.61 (7) |
O3iii—K1—O3vi | 150.64 (11) | Br1x—K1—B2i | 95.35 (6) |
O3iii—K1—O3vii | 124.33 (9) | B1—K1—B2i | 42.28 (8) |
O3vi—K1—O3vii | 75.79 (3) | B1—O1—B1i | 119.88 (4) |
O3iii—K1—O3 | 75.79 (3) | B1—O1—B1ii | 119.88 (4) |
O3vi—K1—O3 | 124.33 (9) | B1i—O1—B1ii | 119.88 (4) |
O3vii—K1—O3 | 49.46 (9) | B2iii—O2—B1xi | 130.6 (4) |
O3iii—K1—O2 | 49.49 (7) | B2iii—O2—K1 | 89.11 (18) |
O3vi—K1—O2 | 119.97 (8) | B1xi—O2—K1 | 116.73 (11) |
O3vii—K1—O2 | 157.68 (8) | B2iii—O2—K1xii | 89.11 (18) |
O3—K1—O2 | 115.35 (7) | B1xi—O2—K1xii | 116.73 (11) |
O3iii—K1—O2viii | 119.97 (8) | K1—O2—K1xii | 109.25 (12) |
O3vi—K1—O2viii | 49.49 (7) | B2—O3—B1 | 124.8 (3) |
O3vii—K1—O2viii | 115.35 (7) | B2—O3—K1xiii | 91.8 (2) |
O3—K1—O2viii | 157.68 (8) | B1—O3—K1xiii | 128.1 (2) |
O2—K1—O2viii | 72.88 (12) | B2—O3—K1 | 111.0 (3) |
O3iii—K1—B2iii | 25.67 (8) | B1—O3—K1 | 101.46 (19) |
O3vi—K1—B2iii | 144.32 (10) | K1xiii—O3—K1 | 96.52 (6) |
O3vii—K1—B2iii | 139.71 (10) | O2xiv—B1—O3 | 110.7 (2) |
O3—K1—B2iii | 91.25 (11) | O2xiv—B1—O3vii | 110.7 (2) |
O2—K1—B2iii | 25.90 (11) | O3—B1—O3vii | 106.5 (3) |
O2viii—K1—B2iii | 98.78 (10) | O2xiv—B1—O1 | 109.2 (4) |
O3iii—K1—B2ix | 144.32 (10) | O3—B1—O1 | 109.8 (3) |
O3vi—K1—B2ix | 25.67 (8) | O3vii—B1—O1 | 109.8 (3) |
O3vii—K1—B2ix | 91.24 (11) | O2xiv—B1—K1 | 134.2 (3) |
O3—K1—B2ix | 139.71 (10) | O3—B1—K1 | 53.67 (18) |
O2—K1—B2ix | 98.78 (10) | O3vii—B1—K1 | 53.67 (18) |
O2viii—K1—B2ix | 25.90 (11) | O1—B1—K1 | 116.6 (4) |
B2iii—K1—B2ix | 124.67 (17) | O3xv—B2—O3 | 121.0 (4) |
O3iii—K1—Br1 | 81.07 (5) | O3xv—B2—O2xiii | 119.3 (2) |
O3vi—K1—Br1 | 81.07 (5) | O3—B2—O2xiii | 119.3 (2) |
O3vii—K1—Br1 | 82.32 (5) | O3xv—B2—K1xiii | 145.6 (3) |
O3—K1—Br1 | 82.32 (5) | O3—B2—K1xiii | 62.55 (16) |
O2—K1—Br1 | 114.20 (6) | O2xiii—B2—K1xiii | 64.99 (15) |
O2viii—K1—Br1 | 114.20 (6) | O3xv—B2—K1xvi | 62.55 (16) |
B2iii—K1—Br1 | 103.42 (6) | O3—B2—K1xvi | 145.6 (3) |
B2ix—K1—Br1 | 103.42 (6) | O2xiii—B2—K1xvi | 64.99 (15) |
O3iii—K1—Br1x | 102.20 (5) | K1xiii—B2—K1xvi | 95.29 (13) |
O3vi—K1—Br1x | 102.20 (5) | O3xv—B2—K1ii | 47.9 (2) |
O3vii—K1—Br1x | 80.67 (5) | O3—B2—K1ii | 132.8 (3) |
O3—K1—Br1x | 80.67 (5) | O2xiii—B2—K1ii | 93.0 (2) |
O2—K1—Br1x | 80.45 (6) | K1xiii—B2—K1ii | 157.65 (16) |
O2viii—K1—Br1x | 80.45 (6) | K1xvi—B2—K1ii | 77.23 (3) |
B2iii—K1—Br1x | 84.80 (8) | O3xv—B2—K1 | 132.8 (3) |
B2ix—K1—Br1x | 84.80 (8) | O3—B2—K1 | 47.9 (2) |
Br1—K1—Br1x | 161.26 (4) | O2xiii—B2—K1 | 93.0 (2) |
O3iii—K1—B1 | 99.58 (6) | K1xiii—B2—K1 | 77.23 (3) |
O3vi—K1—B1 | 99.58 (6) | K1xvi—B2—K1 | 157.66 (16) |
O3vii—K1—B1 | 24.87 (4) | K1ii—B2—K1 | 101.67 (13) |
O3—K1—B1 | 24.87 (4) | | |
Symmetry codes: (i) −y, x−y, z; (ii) −x+y, −x, z; (iii) −y+2/3, x−y+1/3, z+1/3; (iv) x−1/3, y−2/3, z+1/3; (v) −x+y−1/3, −x+1/3, z+1/3; (vi) x−1/3, x−y+1/3, z+1/3; (vii) −x+y, y, z; (viii) −x+y, −x+1, z; (ix) x−1/3, y+1/3, z+1/3; (x) x+1/3, y+2/3, z−1/3; (xi) −x+y+1/3, −x+2/3, z+2/3; (xii) −y+1, x−y+1, z; (xiii) −x+y+1/3, −x+2/3, z−1/3; (xiv) −y+2/3, x−y+1/3, z−2/3; (xv) x, x−y, z; (xvi) x+1/3, y−1/3, z−1/3. |
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