The structure of the title pentaborate, [Pb2(B5O9)Br] (dilead pentaborate bromide), known from powder data, has been refined based on single-crystal data (R = 0.034) and is discussed in terms of intercrossing anionic and cationic frameworks.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (O-B) = 0.019 Å
- R factor = 0.034
- wR factor = 0.080
- Data-to-parameter ratio = 29.2
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT220_ALERT_2_A Large Non-Solvent O Ueq(max)/Ueq(min) ... 5.67 Ratio
| Author Response: low quality of U values due to the presence of Pb and Br,
acentric space group, twinning, and pseudosymmetry...
|
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 31.00
From the CIF: _reflns_number_total 2544
Count of symmetry unique reflns 1488
Completeness (_total/calc) 170.97%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1056
Fraction of Friedel pairs measured 0.710
Are heavy atom types Z>Si present yes
1 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
0 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Crystal Impact, 2000); software used to prepare material for publication: SHELXL97.
Dilead pentaborate bromide
top
Crystal data top
[Pb2(B5O9)Br] | F(000) = 1184 |
Mr = 692.34 | Dx = 5.341 Mg m−3 |
Orthorhombic, Pnn2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2 -2n | Cell parameters from 4734 reflections |
a = 11.4935 (19) Å | θ = 3.5–36.0° |
b = 11.4717 (19) Å | µ = 43.73 mm−1 |
c = 6.5297 (11) Å | T = 293 K |
V = 860.9 (2) Å3 | Column, colourless |
Z = 4 | 0.13 × 0.03 × 0.02 mm |
Data collection top
Stoe IPDS-II diffractometer | 2544 independent reflections |
Radiation source: fine-focus sealed tube | 2429 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.068 |
Detector resolution: 150 pixels mm-1 | θmax = 31.0°, θmin = 3.6° |
ω scans | h = −12→16 |
Absorption correction: numerical (XPREP in SHELXTL; Sheldrick, 1996). | k = −16→16 |
Tmin = 0.093, Tmax = 0.387 | l = −8→9 |
7497 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0337P)2 + 13.5461P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.034 | (Δ/σ)max < 0.001 |
wR(F2) = 0.080 | Δρmax = 1.96 e Å−3 |
S = 1.06 | Δρmin = −2.13 e Å−3 |
2544 reflections | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
87 parameters | Extinction coefficient: 0.00036 (10) |
1 restraint | Absolute structure: Flack (1983), 1059 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (2) |
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 as pseudomerohedral (110) twin, twin ratio 31.2 (2)%. 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 | Uiso*/Ueq | |
Pb1 | 0.25762 (6) | 0.04280 (6) | 0.00433 (9) | 0.01489 (12) | |
Pb2 | 0.02631 (6) | 0.23505 (5) | −0.66205 (14) | 0.01614 (13) | |
Br1 | 0.0000 | 0.0000 | −0.9081 (5) | 0.0289 (6) | |
Br2 | 0.0000 | 0.5000 | −0.6476 (6) | 0.0259 (5) | |
O1 | 0.2376 (8) | 0.3135 (8) | −0.5784 (14) | 0.0030 (16)* | |
O2 | 0.2084 (8) | 0.4248 (8) | −0.173 (2) | 0.0108 (16)* | |
O3 | 0.2717 (8) | 0.2256 (9) | −0.2448 (16) | 0.0079 (19)* | |
O4 | 0.0686 (11) | 0.2753 (11) | −0.2398 (19) | 0.017 (2)* | |
O5 | 0.2790 (9) | 0.4487 (11) | −0.835 (2) | 0.015 (2)* | |
O6 | 0.3827 (9) | 0.2616 (9) | −0.8357 (17) | 0.0092 (18)* | |
O7 | 0.1785 (8) | 0.2698 (9) | −0.9231 (15) | 0.0046 (16)* | |
O8 | 0.4168 (8) | 0.2110 (9) | −0.4921 (18) | 0.0090 (16)* | |
O9 | 0.2339 (9) | 0.1103 (10) | −0.5577 (16) | 0.0106 (19)* | |
B1 | 0.2706 (13) | 0.3217 (14) | −0.795 (2) | 0.008 (3)* | |
B2 | 0.1803 (13) | 0.3009 (14) | −0.146 (3) | 0.012 (3)* | |
B3 | 0.2864 (14) | 0.2180 (15) | −0.460 (2) | 0.010 (3)* | |
B4 | 0.4556 (13) | 0.2354 (16) | −0.683 (3) | 0.011 (3)* | |
B5 | 0.2513 (15) | 0.4950 (14) | −0.019 (3) | 0.009 (3)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pb1 | 0.0172 (2) | 0.0170 (2) | 0.0105 (2) | 0.0011 (2) | 0.0010 (2) | 0.0004 (3) |
Pb2 | 0.0187 (2) | 0.0179 (2) | 0.0118 (3) | −0.0013 (2) | 0.0034 (3) | 0.0000 (3) |
Br1 | 0.0202 (12) | 0.0154 (10) | 0.0511 (19) | −0.0011 (10) | 0.000 | 0.000 |
Br2 | 0.0188 (11) | 0.0179 (10) | 0.0411 (16) | 0.0002 (8) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Pb1—O5i | 2.497 (13) | O1—Pb1viii | 2.686 (9) |
Pb1—O2i | 2.534 (12) | B2—O2 | 1.468 (19) |
Pb1—O3 | 2.659 (11) | B2—O3 | 1.504 (19) |
Pb1—O1i | 2.686 (9) | B2—O4 | 1.450 (19) |
Pb1—O7ii | 2.798 (10) | B2—O7ii | 1.50 (2) |
Pb1—O9ii | 2.975 (11) | O2—Pb1viii | 2.534 (12) |
Pb1—Br2i | 2.9977 (16) | B3—O1 | 1.453 (19) |
Pb1—Br1ii | 3.0554 (10) | B3—O3 | 1.417 (19) |
Pb1—O6ii | 3.076 (11) | B3—O8 | 1.516 (19) |
Pb1—B5i | 3.160 (19) | B3—O9 | 1.52 (2) |
Pb2—O7 | 2.475 (10) | B4—O4x | 1.358 (19) |
Pb2—O8iii | 2.571 (11) | B4—O6 | 1.34 (2) |
Pb2—O1 | 2.647 (9) | B4—O8 | 1.35 (2) |
Pb2—O6iv | 2.695 (11) | B5—O2 | 1.38 (2) |
Pb2—O4 | 2.838 (13) | B5—O5ii | 1.36 (2) |
Pb2—O9 | 2.864 (11) | B5—O9xi | 1.358 (19) |
Pb2—O3iii | 3.010 (10) | O3—Pb2xii | 3.010 (10) |
Pb2—Br2 | 3.0559 (8) | O4—B4iv | 1.358 (19) |
Pb2—B1 | 3.104 (15) | O5—B5vi | 1.36 (2) |
Pb2—Br1 | 3.153 (2) | O5—Pb1viii | 2.497 (13) |
Br1—Pb1v | 3.0554 (10) | O6—Pb2x | 2.695 (11) |
Br1—Pb1vi | 3.0554 (10) | O6—Pb1vi | 3.076 (11) |
Br1—Pb2vii | 3.1532 (19) | O7—B2vi | 1.50 (2) |
Br2—Pb1viii | 2.9977 (16) | O7—Pb1vi | 2.798 (10) |
Br2—Pb1iii | 2.9977 (16) | O8—Pb2xii | 2.571 (11) |
Br2—Pb2ix | 3.0559 (8) | O9—B5xiii | 1.358 (19) |
B1—O1 | 1.470 (18) | O9—Pb1vi | 2.975 (11) |
B1—O5 | 1.48 (2) | B1—Pb1viii | 3.220 (16) |
B1—O6 | 1.485 (18) | B4—Pb2x | 3.25 (2) |
B1—O7 | 1.473 (18) | B5—Pb1viii | 3.160 (19) |
| | | |
O5i—Pb1—O2i | 122.1 (4) | B2—O3—Pb1 | 98.6 (9) |
O5i—Pb1—O3 | 79.0 (4) | B3—O3—Pb2xii | 94.1 (8) |
O2i—Pb1—O3 | 157.0 (3) | B2—O3—Pb2xii | 121.1 (8) |
O5i—Pb1—O1i | 53.3 (3) | Pb1—O3—Pb2xii | 93.9 (3) |
O2i—Pb1—O1i | 68.9 (3) | B4iv—O4—B2 | 138.5 (15) |
O3—Pb1—O1i | 130.4 (3) | B4iv—O4—Pb2 | 95.0 (11) |
O5i—Pb1—O7ii | 119.8 (3) | B2—O4—Pb2 | 126.4 (10) |
O2i—Pb1—O7ii | 114.0 (3) | B5vi—O5—B1 | 121.5 (13) |
O3—Pb1—O7ii | 52.4 (3) | B5vi—O5—Pb1viii | 125.4 (10) |
O1i—Pb1—O7ii | 162.2 (3) | B1—O5—Pb1viii | 105.2 (9) |
O5i—Pb1—O9ii | 161.5 (3) | B4—O6—B1 | 121.0 (13) |
O2i—Pb1—O9ii | 49.8 (3) | B4—O6—Pb2x | 102.2 (9) |
O3—Pb1—O9ii | 112.8 (3) | B1—O6—Pb2x | 131.6 (9) |
O1i—Pb1—O9ii | 116.8 (3) | B4—O6—Pb1vi | 111.3 (10) |
O7ii—Pb1—O9ii | 64.2 (3) | B1—O6—Pb1vi | 91.9 (8) |
O5i—Pb1—Br2i | 78.0 (3) | Pb2x—O6—Pb1vi | 91.7 (3) |
O2i—Pb1—Br2i | 92.5 (2) | B1—O7—B2vi | 116.3 (11) |
O3—Pb1—Br2i | 82.6 (2) | B1—O7—Pb2 | 100.6 (8) |
O1i—Pb1—Br2i | 75.76 (19) | B2vi—O7—Pb2 | 135.8 (8) |
O7ii—Pb1—Br2i | 120.7 (2) | Pb1viii—Br2—Pb2 | 94.66 (3) |
O9ii—Pb1—Br2i | 116.5 (2) | Pb1iii—Br2—Pb2 | 86.52 (3) |
O5i—Pb1—Br1ii | 86.2 (3) | Pb1viii—Br2—Pb2ix | 86.52 (3) |
O2i—Pb1—Br1ii | 84.7 (2) | Pb1iii—Br2—Pb2ix | 94.66 (3) |
O3—Pb1—Br1ii | 107.5 (2) | Pb2—Br2—Pb2ix | 176.46 (16) |
O1i—Pb1—Br1ii | 84.26 (19) | B3—O1—B1 | 117.5 (11) |
O7ii—Pb1—Br1ii | 78.6 (2) | B3—O1—Pb2 | 102.0 (8) |
O9ii—Pb1—Br1ii | 76.9 (2) | B1—O1—Pb2 | 93.4 (7) |
Br2i—Pb1—Br1ii | 159.43 (5) | B3—O1—Pb1viii | 128.5 (8) |
O5i—Pb1—O6ii | 137.1 (3) | B1—O1—Pb1viii | 97.2 (8) |
O2i—Pb1—O6ii | 94.7 (3) | Pb2—O1—Pb1viii | 113.1 (3) |
O3—Pb1—O6ii | 62.3 (3) | B5—O2—B2 | 123.9 (14) |
O1i—Pb1—O6ii | 149.1 (3) | B5—O2—Pb1viii | 103.8 (9) |
O7ii—Pb1—O6ii | 48.3 (3) | B2—O2—Pb1viii | 130.6 (11) |
O9ii—Pb1—O6ii | 60.3 (3) | B3—O3—B2 | 122.8 (13) |
Br2i—Pb1—O6ii | 79.1 (2) | B3—O3—Pb1 | 124.4 (10) |
Br1ii—Pb1—O6ii | 121.4 (2) | B2—O3—Pb1 | 98.6 (9) |
O5i—Pb1—B5i | 142.3 (4) | B3—O3—Pb2xii | 94.1 (8) |
O2i—Pb1—B5i | 25.1 (4) | B2—O3—Pb2xii | 121.1 (8) |
O3—Pb1—B5i | 137.8 (4) | Pb1—O3—Pb2xii | 93.9 (3) |
O1i—Pb1—B5i | 91.6 (4) | B4iv—O4—B2 | 138.5 (15) |
O7ii—Pb1—B5i | 89.1 (4) | B4iv—O4—Pb2 | 95.0 (11) |
O9ii—Pb1—B5i | 25.3 (4) | B2—O4—Pb2 | 126.4 (10) |
Br2i—Pb1—B5i | 109.1 (3) | B5vi—O5—B1 | 121.5 (13) |
Br1ii—Pb1—B5i | 75.9 (3) | B5vi—O5—Pb1viii | 125.4 (10) |
O6ii—Pb1—B5i | 79.8 (4) | B1—O5—Pb1viii | 105.2 (9) |
O7—Pb2—O8iii | 74.3 (3) | B4—O6—B1 | 121.0 (13) |
O7—Pb2—O1 | 55.9 (3) | B4—O6—Pb2x | 102.2 (9) |
O8iii—Pb2—O1 | 122.7 (3) | B1—O6—Pb2x | 131.6 (9) |
O7—Pb2—O6iv | 167.2 (3) | B4—O6—Pb1vi | 111.3 (10) |
O8iii—Pb2—O6iv | 111.1 (3) | B1—O6—Pb1vi | 91.9 (8) |
O1—Pb2—O6iv | 113.2 (3) | Pb2x—O6—Pb1vi | 91.7 (3) |
O7—Pb2—O4 | 121.4 (3) | B1—O7—B2vi | 116.3 (11) |
O8iii—Pb2—O4 | 149.2 (3) | B1—O7—Pb2 | 100.6 (8) |
O1—Pb2—O4 | 65.6 (3) | B2vi—O7—Pb2 | 135.8 (8) |
O6iv—Pb2—O4 | 48.3 (3) | B1—O7—Pb1vi | 103.8 (8) |
O7—Pb2—O9 | 69.8 (3) | B2vi—O7—Pb1vi | 93.0 (7) |
O8iii—Pb2—O9 | 136.7 (3) | Pb2—O7—Pb1vi | 101.3 (3) |
O1—Pb2—O9 | 49.9 (3) | B4—O8—B3 | 116.3 (12) |
O6iv—Pb2—O9 | 109.2 (3) | B4—O8—Pb2xii | 124.1 (9) |
O4—Pb2—O9 | 73.0 (4) | B3—O8—Pb2xii | 110.8 (8) |
O7—Pb2—O3iii | 122.7 (3) | B5xiii—O9—B3 | 131.8 (13) |
O8iii—Pb2—O3iii | 48.5 (3) | B5xiii—O9—Pb2 | 129.5 (10) |
O1—Pb2—O3iii | 151.4 (3) | B3—O9—Pb2 | 91.4 (8) |
O6iv—Pb2—O3iii | 62.9 (3) | B5xiii—O9—Pb1vi | 85.0 (9) |
O4—Pb2—O3iii | 108.5 (3) | B3—O9—Pb1vi | 125.5 (8) |
O9—Pb2—O3iii | 158.0 (3) | Pb2—O9—Pb1vi | 88.7 (3) |
O7—Pb2—Br2 | 86.1 (2) | O1—B1—O7 | 109.5 (11) |
O8iii—Pb2—Br2 | 74.8 (2) | O1—B1—O5 | 104.2 (12) |
O1—Pb2—Br2 | 75.3 (2) | O7—B1—O5 | 110.3 (12) |
O6iv—Pb2—Br2 | 84.3 (2) | O1—B1—O6 | 111.4 (12) |
O4—Pb2—Br2 | 79.9 (3) | O7—B1—O6 | 109.6 (12) |
O9—Pb2—Br2 | 124.9 (2) | O5—B1—O6 | 111.7 (11) |
O3iii—Pb2—Br2 | 76.1 (2) | O1—B1—Pb2 | 58.3 (6) |
O7—Pb2—B1 | 27.8 (4) | O7—B1—Pb2 | 51.6 (6) |
O8iii—Pb2—B1 | 97.5 (4) | O5—B1—Pb2 | 115.0 (9) |
O1—Pb2—B1 | 28.2 (4) | O6—B1—Pb2 | 133.3 (9) |
O6iv—Pb2—B1 | 140.5 (4) | O1—B1—Pb1viii | 55.9 (6) |
O4—Pb2—B1 | 93.8 (4) | O7—B1—Pb1viii | 126.2 (9) |
O9—Pb2—B1 | 58.2 (4) | O5—B1—Pb1viii | 48.5 (7) |
O3iii—Pb2—B1 | 141.4 (4) | O6—B1—Pb1viii | 124.1 (9) |
Br2—Pb2—B1 | 77.3 (3) | Pb2—B1—Pb1viii | 89.4 (4) |
O7—Pb2—Br1 | 81.6 (2) | O4—B2—O2 | 109.9 (13) |
O8iii—Pb2—Br1 | 74.4 (2) | O4—B2—O7ii | 110.4 (12) |
O1—Pb2—Br1 | 118.9 (2) | O2—B2—O7ii | 110.4 (14) |
O6iv—Pb2—Br1 | 110.9 (2) | O4—B2—O3 | 108.8 (13) |
O4—Pb2—Br1 | 130.6 (3) | O2—B2—O3 | 110.5 (12) |
O9—Pb2—Br1 | 76.9 (2) | O7ii—B2—O3 | 106.7 (12) |
O3iii—Pb2—Br1 | 86.8 (2) | O4—B2—Pb1 | 100.7 (9) |
Br2—Pb2—Br1 | 148.95 (10) | O2—B2—Pb1 | 149.2 (10) |
B1—Pb2—Br1 | 102.6 (3) | O7ii—B2—Pb1 | 59.5 (6) |
Pb1v—Br1—Pb1vi | 158.42 (14) | O3—B2—Pb1 | 54.2 (7) |
Pb1v—Br1—Pb2 | 109.01 (4) | O3—B3—O1 | 115.8 (13) |
Pb1vi—Br1—Pb2 | 82.24 (3) | O3—B3—O8 | 105.0 (12) |
Pb1v—Br1—Pb2vii | 82.24 (3) | O1—B3—O8 | 110.3 (12) |
Pb1vi—Br1—Pb2vii | 109.01 (4) | O3—B3—O9 | 114.8 (13) |
Pb2—Br1—Pb2vii | 118.74 (11) | O1—B3—O9 | 103.7 (11) |
Pb1viii—Br2—Pb1iii | 141.35 (15) | O8—B3—O9 | 107.0 (11) |
Pb1viii—Br2—Pb2 | 94.66 (3) | O3—B3—Pb2 | 106.7 (9) |
Pb1iii—Br2—Pb2 | 86.52 (3) | O1—B3—Pb2 | 52.3 (6) |
Pb1viii—Br2—Pb2ix | 86.52 (3) | O8—B3—Pb2 | 148.2 (10) |
Pb1iii—Br2—Pb2ix | 94.66 (3) | O9—B3—Pb2 | 61.0 (7) |
Pb2—Br2—Pb2ix | 176.46 (16) | O6—B4—O8 | 121.9 (13) |
B3—O1—B1 | 117.5 (11) | O6—B4—O4x | 114.5 (17) |
B3—O1—Pb2 | 102.0 (8) | O8—B4—O4x | 123.4 (16) |
B1—O1—Pb2 | 93.4 (7) | O6—B4—Pb2x | 54.1 (9) |
B3—O1—Pb1viii | 128.5 (8) | O8—B4—Pb2x | 172.2 (11) |
B1—O1—Pb1viii | 97.2 (8) | O4x—B4—Pb2x | 60.4 (10) |
Pb2—O1—Pb1viii | 113.1 (3) | O5ii—B5—O9xi | 121.1 (15) |
B5—O2—B2 | 123.9 (14) | O5ii—B5—O2 | 120.3 (14) |
B5—O2—Pb1viii | 103.8 (9) | O9xi—B5—O2 | 118.7 (15) |
B2—O2—Pb1viii | 130.6 (11) | O5ii—B5—Pb1viii | 162.0 (11) |
B3—O3—B2 | 122.8 (13) | O9xi—B5—Pb1viii | 69.7 (9) |
B3—O3—Pb1 | 124.4 (10) | O2—B5—Pb1viii | 51.1 (8) |
Symmetry codes: (i) −x+1/2, y−1/2, z+1/2; (ii) x, y, z+1; (iii) x−1/2, −y+1/2, z−1/2; (iv) x−1/2, −y+1/2, z+1/2; (v) −x, −y, z−1; (vi) x, y, z−1; (vii) −x, −y, z; (viii) −x+1/2, y+1/2, z−1/2; (ix) −x, −y+1, z; (x) x+1/2, −y+1/2, z−1/2; (xi) −x+1/2, y+1/2, z+1/2; (xii) x+1/2, −y+1/2, z+1/2; (xiii) −x+1/2, y−1/2, z−1/2. |