In K4Sn9, which crystallizes with a new structure type, the Sn atoms form isolated Wade nido-[Sn9]4- clusters of approximate C4v symmetry (monocapped square antiprisms), with Sn-Sn distances ranging from 2.9264 (9) to 3.348 (1) Å. The cluster anions are separated by K+ cations and are in a hexagonal close-packed arrangement.
Supporting information
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1968) and DRAWxtl (Finger & Kroeker, 1999); software used to prepare material for publication: SHELXL97.
Tetrapotassium nonastannide
top
Crystal data top
K4Sn9 | F(000) = 2104 |
Mr = 1224.61 | Dx = 4.165 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71070 Å |
a = 14.238 (2) Å | Cell parameters from 980 reflections |
b = 8.3554 (13) Å | θ = 2.7–28.8° |
c = 16.487 (3) Å | µ = 12.12 mm−1 |
β = 95.261 (3)° | T = 293 K |
V = 1953.2 (5) Å3 | Irregular, metallic light silver |
Z = 4 | 0.08 × 0.06 × 0.03 mm |
Data collection top
Bruker AXS CCD diffractometer | 4575 independent reflections |
Radiation source: fine-focus sealed tube | 3176 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scans | θmax = 28.0°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −18→18 |
Tmin = 0.432, Tmax = 0.695 | k = −11→9 |
11888 measured reflections | l = −21→16 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.027 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.058 | w = 1/[σ2(Fo2) + (0.0174P)2 + 3.425P] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max < 0.001 |
4575 reflections | Δρmax = 1.22 e Å−3 |
118 parameters | Δρmin = −0.85 e Å−3 |
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 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 | |
Sn1 | 0.29271 (4) | 0.61971 (7) | 0.24040 (4) | 0.04424 (15) | |
Sn2 | 0.12208 (4) | 0.60221 (6) | 0.12012 (3) | 0.03745 (13) | |
Sn3 | 0.18159 (4) | 0.32550 (6) | 0.25293 (3) | 0.03628 (13) | |
Sn4 | 0.39013 (4) | 0.31956 (7) | 0.20216 (3) | 0.03980 (14) | |
Sn5 | 0.32767 (4) | 0.61046 (6) | 0.06830 (4) | 0.04254 (14) | |
Sn6 | 0.07469 (3) | 0.25753 (6) | 0.09188 (3) | 0.03736 (13) | |
Sn7 | 0.17431 (4) | 0.43065 (7) | −0.03032 (3) | 0.04244 (14) | |
Sn8 | 0.35443 (4) | 0.26749 (6) | 0.02620 (3) | 0.03940 (14) | |
Sn9 | 0.25244 (4) | 0.07640 (6) | 0.14252 (3) | 0.03556 (13) | |
K1 | 0.07578 (12) | 0.5710 (2) | 0.76158 (11) | 0.0464 (5) | |
K2 | 0.50822 (13) | 0.4386 (2) | 0.38471 (11) | 0.0499 (5) | |
K3 | 0.16211 (14) | 0.5654 (2) | 0.44653 (12) | 0.0557 (5) | |
K4 | 0.61160 (13) | 0.4697 (2) | 0.14277 (11) | 0.0483 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sn1 | 0.0509 (4) | 0.0366 (3) | 0.0445 (4) | −0.0048 (3) | 0.0003 (3) | −0.0147 (2) |
Sn2 | 0.0362 (3) | 0.0318 (3) | 0.0455 (4) | 0.0073 (2) | 0.0100 (2) | −0.0015 (2) |
Sn3 | 0.0416 (3) | 0.0361 (3) | 0.0329 (3) | −0.0011 (2) | 0.0128 (2) | −0.0024 (2) |
Sn4 | 0.0302 (3) | 0.0431 (3) | 0.0442 (4) | 0.0024 (2) | −0.0065 (2) | −0.0066 (2) |
Sn5 | 0.0443 (3) | 0.0337 (3) | 0.0521 (4) | −0.0077 (2) | 0.0176 (3) | 0.0004 (2) |
Sn6 | 0.0281 (3) | 0.0384 (3) | 0.0458 (3) | −0.0065 (2) | 0.0046 (2) | −0.0048 (2) |
Sn7 | 0.0411 (3) | 0.0568 (4) | 0.0295 (3) | 0.0032 (3) | 0.0035 (2) | 0.0034 (2) |
Sn8 | 0.0472 (3) | 0.0373 (3) | 0.0363 (3) | 0.0140 (2) | 0.0176 (2) | 0.0065 (2) |
Sn9 | 0.0339 (3) | 0.0272 (3) | 0.0469 (3) | −0.0016 (2) | 0.0111 (2) | −0.0023 (2) |
K1 | 0.0444 (10) | 0.0439 (11) | 0.0535 (12) | 0.0068 (8) | 0.0183 (9) | −0.0017 (8) |
K2 | 0.0536 (12) | 0.0516 (12) | 0.0435 (12) | −0.0201 (9) | −0.0007 (9) | 0.0000 (8) |
K3 | 0.0570 (13) | 0.0637 (13) | 0.0454 (12) | 0.0131 (10) | −0.0007 (9) | 0.0058 (9) |
K4 | 0.0565 (12) | 0.0467 (11) | 0.0437 (11) | 0.0016 (9) | 0.0149 (9) | 0.0087 (8) |
Geometric parameters (Å, º) top
Sn1—Sn5 | 2.9264 (9) | Sn7—K1viii | 3.773 (2) |
Sn1—Sn3 | 2.9409 (8) | Sn7—K4vi | 3.8025 (19) |
Sn1—Sn4 | 2.9616 (9) | Sn7—K3iv | 4.165 (2) |
Sn1—Sn2 | 2.9955 (9) | Sn8—Sn9 | 2.9742 (8) |
Sn1—K4i | 3.6926 (19) | Sn8—K2v | 3.6061 (18) |
Sn1—K2 | 4.003 (2) | Sn8—K4vi | 3.6146 (18) |
Sn1—K3 | 4.046 (2) | Sn8—K2iv | 3.7604 (19) |
Sn1—K1ii | 4.0669 (19) | Sn8—K3iv | 4.038 (2) |
Sn2—Sn6 | 2.9847 (9) | Sn9—K1iv | 3.5499 (18) |
Sn2—Sn7 | 3.0163 (8) | Sn9—K3iv | 3.569 (2) |
Sn2—Sn5 | 3.1243 (9) | Sn9—K2v | 3.6632 (19) |
Sn2—Sn3 | 3.2431 (8) | Sn9—K4v | 3.977 (2) |
Sn2—K1ii | 3.6897 (19) | K1—Sn9ix | 3.5499 (18) |
Sn2—K1iii | 3.8526 (19) | K1—Sn3ix | 3.6472 (19) |
Sn2—K3ii | 4.065 (2) | K1—Sn6iii | 3.6647 (18) |
Sn3—Sn6 | 2.9913 (8) | K1—Sn2x | 3.6897 (19) |
Sn3—Sn9 | 3.0000 (8) | K1—Sn3iii | 3.7515 (19) |
Sn3—Sn4 | 3.1584 (9) | K1—Sn7xi | 3.772 (2) |
Sn3—K1iv | 3.6473 (19) | K1—Sn2iii | 3.8526 (19) |
Sn3—K1iii | 3.7514 (19) | K1—Sn6ix | 3.9183 (19) |
Sn3—K3 | 3.801 (2) | K1—Sn1x | 4.0669 (19) |
Sn4—Sn9 | 2.9299 (8) | K2—Sn8i | 3.6061 (18) |
Sn4—Sn8 | 2.9314 (9) | K2—Sn5v | 3.640 (2) |
Sn4—Sn5 | 3.3480 (9) | K2—Sn9i | 3.6632 (19) |
Sn4—K2 | 3.4565 (19) | K2—Sn8ix | 3.7604 (19) |
Sn4—K4 | 3.6113 (19) | K2—Sn4i | 3.8283 (19) |
Sn4—K2v | 3.8282 (19) | K3—Sn9ix | 3.569 (2) |
Sn4—K4v | 3.885 (2) | K3—Sn6xii | 3.735 (2) |
Sn5—Sn8 | 2.9812 (9) | K3—Sn6ix | 3.889 (2) |
Sn5—Sn7 | 3.0029 (9) | K3—Sn5x | 4.007 (2) |
Sn5—K2i | 3.640 (2) | K3—Sn8ix | 4.038 (2) |
Sn5—K4vi | 3.723 (2) | K3—Sn2x | 4.065 (2) |
Sn5—K3ii | 4.007 (2) | K3—Sn7ix | 4.165 (2) |
Sn6—Sn7 | 2.9475 (8) | K4—Sn8vi | 3.6145 (18) |
Sn6—Sn9 | 3.0008 (8) | K4—Sn1v | 3.6926 (19) |
Sn6—K1iii | 3.6646 (18) | K4—Sn5vi | 3.723 (2) |
Sn6—K3vii | 3.735 (2) | K4—Sn7vi | 3.8025 (19) |
Sn6—K3iv | 3.889 (2) | K4—Sn4i | 3.885 (2) |
Sn6—K1iv | 3.9183 (19) | K4—Sn9i | 3.977 (2) |
Sn7—Sn8 | 2.9775 (8) | | |
| | | |
Sn5—Sn1—Sn3 | 100.75 (2) | Sn3—Sn4—Sn5 | 87.933 (19) |
Sn5—Sn1—Sn4 | 69.30 (2) | Sn1—Sn5—Sn8 | 106.73 (2) |
Sn3—Sn1—Sn4 | 64.70 (2) | Sn1—Sn5—Sn7 | 111.00 (2) |
Sn5—Sn1—Sn2 | 63.67 (2) | Sn8—Sn5—Sn7 | 59.68 (2) |
Sn3—Sn1—Sn2 | 66.222 (19) | Sn1—Sn5—Sn2 | 59.240 (19) |
Sn4—Sn1—Sn2 | 100.66 (2) | Sn8—Sn5—Sn2 | 100.69 (2) |
Sn6—Sn2—Sn1 | 107.96 (2) | Sn7—Sn5—Sn2 | 58.94 (2) |
Sn6—Sn2—Sn7 | 58.832 (19) | Sn7—Sn6—Sn2 | 61.118 (19) |
Sn1—Sn2—Sn7 | 108.75 (2) | Sn7—Sn6—Sn3 | 106.02 (2) |
Sn6—Sn2—Sn5 | 100.53 (2) | Sn2—Sn6—Sn3 | 65.734 (18) |
Sn1—Sn2—Sn5 | 57.09 (2) | Sn7—Sn6—Sn9 | 89.49 (2) |
Sn7—Sn2—Sn5 | 58.523 (18) | Sn2—Sn6—Sn9 | 105.69 (2) |
Sn6—Sn2—Sn3 | 57.232 (19) | Sn3—Sn6—Sn9 | 60.087 (18) |
Sn1—Sn2—Sn3 | 56.081 (18) | Sn6—Sn7—Sn8 | 90.92 (2) |
Sn7—Sn2—Sn3 | 98.49 (2) | Sn6—Sn7—Sn5 | 104.30 (2) |
Sn5—Sn2—Sn3 | 90.40 (2) | Sn8—Sn7—Sn5 | 59.80 (2) |
Sn1—Sn3—Sn6 | 109.24 (2) | Sn6—Sn7—Sn2 | 60.05 (2) |
Sn1—Sn3—Sn9 | 108.92 (2) | Sn8—Sn7—Sn2 | 103.32 (2) |
Sn6—Sn3—Sn9 | 60.114 (19) | Sn5—Sn7—Sn2 | 62.54 (2) |
Sn1—Sn3—Sn4 | 57.968 (19) | Sn4—Sn8—Sn9 | 59.482 (19) |
Sn6—Sn3—Sn4 | 100.13 (2) | Sn4—Sn8—Sn7 | 107.94 (2) |
Sn9—Sn3—Sn4 | 56.747 (17) | Sn9—Sn8—Sn7 | 89.44 (2) |
Sn1—Sn3—Sn2 | 57.696 (19) | Sn4—Sn8—Sn5 | 68.97 (2) |
Sn6—Sn3—Sn2 | 57.035 (19) | Sn9—Sn8—Sn5 | 106.59 (2) |
Sn9—Sn3—Sn2 | 99.58 (2) | Sn7—Sn8—Sn5 | 60.525 (19) |
Sn4—Sn3—Sn2 | 91.49 (2) | Sn4—Sn9—Sn8 | 59.53 (2) |
Sn9—Sn4—Sn8 | 60.985 (18) | Sn4—Sn9—Sn3 | 64.35 (2) |
Sn9—Sn4—Sn1 | 110.28 (2) | Sn8—Sn9—Sn3 | 103.30 (2) |
Sn8—Sn4—Sn1 | 107.11 (2) | Sn4—Sn9—Sn6 | 105.36 (2) |
Sn9—Sn4—Sn3 | 58.900 (18) | Sn8—Sn9—Sn6 | 89.95 (2) |
Sn8—Sn4—Sn3 | 100.53 (2) | Sn3—Sn9—Sn6 | 59.800 (19) |
Sn1—Sn4—Sn3 | 57.332 (19) | | |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+3/2, z−1/2; (iii) −x, −y+1, −z+1; (iv) x, −y+1/2, z−1/2; (v) −x+1, y−1/2, −z+1/2; (vi) −x+1, −y+1, −z; (vii) −x, y−1/2, −z+1/2; (viii) x, y, z−1; (ix) x, −y+1/2, z+1/2; (x) x, −y+3/2, z+1/2; (xi) x, y, z+1; (xii) −x, y+1/2, −z+1/2. |