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The title compound, K-GaSi-GIS, potassium gallium silicon oxide hydrate, was synthesized hydrothermally and its crystal structure was determined from data collected on a single crystal of dimensions 10 × 10 × 8 µm at a synchrotron X-ray source. The compound, which has the aluminosilicate (AlSi) zeolite gismondine (GIS) topology, Ca4[Al8Si8O32]·16H2O, crystallizes in the tetragonal space group I41/a. A disordered distribution of the framework Si/Ga sites leads to higher symmetry of the GIS-type network compared with the usual monoclinic symmetry in AlSi-GIS. Framework Ga substitution for Al in AlSi-GIS leads to substantial distortion of the crankshaft chains, reducing the effective pore dimensions and suggesting the possibility of pore-dimension control via partial framework-cation substitution.
Supporting information
Data collection: SMART (Bruker AXS, 1996); cell refinement: SMART; data reduction: SAINT (Bruker AXS, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CrystalMaker (Palmer, 2000); software used to prepare material for publication: SHELXL97.
Crystal data top
K5.76Ga5.76Si10.24O32·3.4H2O | Dx = 2.647 Mg m−3 |
Mr = 1484.40 | Synchrotron radiation, λ = 0.6430 Å |
Tetragonal, I41/a | Cell parameters from 5045 reflections |
Hall symbol: -I 4ad | θ = 2.6–30.6° |
a = 9.9639 (6) Å | µ = 5.20 mm−1 |
c = 9.3806 (9) Å | T = 298 K |
V = 931.3 (1) Å3 | Octahedral, colourless |
Z = 1 | 0.01 × 0.01 × 0.01 mm |
F(000) = 715 | |
Data collection top
Bruker SMART CCD area detector diffractometer | 939 independent reflections |
Radiation source: Synchrotron | 749 reflections with I > 2σ(I) |
Si(111) monochromator | Rint = 0.094 |
Detector resolution: 0.70 pixels mm-1 | θmax = 30.6°, θmin = 2.6° |
φ scans | h = −15→15 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −15→15 |
Tmin = 0.949, Tmax = 0.959 | l = −14→14 |
5111 measured reflections | |
Refinement top
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)] = 0.067 | H-atom parameters not defined |
wR(F2) = 0.156 | w = 1/[σ2(Fo2) + (0.046P)2 + 15.7958P] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max < 0.001 |
939 reflections | Δρmax = 1.19 e Å−3 |
47 parameters | Δρmin = −0.97 e Å−3 |
0 restraints | |
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. The individual site occupancies for Ga, Si, K1 and OW1 refined to
37, 64.6, 36 and 21% respectively. In conjunction with an established
empirical formula (K6Ga6Si10.5O36) from EPMA these were fixed to 36,
64, 36 and 21% level respectively in the final cycle of the refinement. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Ga1 | 0.32466 (8) | 0.62521 (8) | 0.08729 (8) | 0.0117 (2) | 0.36 |
Si1 | 0.32466 (8) | 0.62521 (8) | 0.08729 (8) | 0.0117 (2) | 0.64 |
O1 | 0.3199 (6) | 0.7937 (5) | 0.0689 (5) | 0.0363 (10) | |
O2 | 0.3218 (5) | 0.5660 (4) | −0.0810 (5) | 0.0327 (10) | |
K1 | 0.1712 (12) | 0.7056 (7) | −0.2649 (6) | 0.099 (3) | 0.36 |
OW1 | 0.057 (3) | 0.731 (3) | −0.215 (3) | 0.057 (8) | 0.21 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ga1 | 0.0121 (4) | 0.0124 (4) | 0.0107 (3) | −0.0002 (3) | 0.0028 (3) | −0.0017 (3) |
Si1 | 0.0121 (4) | 0.0124 (4) | 0.0107 (3) | −0.0002 (3) | 0.0028 (3) | −0.0017 (3) |
O1 | 0.052 (3) | 0.023 (2) | 0.034 (2) | 0.0019 (19) | −0.006 (2) | −0.0013 (18) |
O2 | 0.049 (3) | 0.023 (2) | 0.0257 (19) | 0.0059 (18) | 0.009 (2) | −0.0019 (16) |
K1 | 0.210 (11) | 0.054 (4) | 0.033 (3) | 0.057 (5) | −0.002 (4) | 0.017 (3) |
OW1 | 0.09 (2) | 0.023 (12) | 0.053 (15) | 0.000 (13) | 0.026 (15) | −0.003 (11) |
Geometric parameters (Å, º) top
Ga1—O1i | 1.673 (5) | K1—K1iii | 1.82 (2) |
Ga1—O2ii | 1.684 (4) | K1—OW1vii | 2.43 (4) |
Ga1—O2 | 1.686 (5) | K1—O2iii | 2.697 (7) |
Ga1—O1 | 1.688 (5) | K1—OW1iii | 2.76 (4) |
Ga1—K1iii | 3.462 (5) | K1—OW1viii | 2.84 (3) |
Ga1—K1iv | 3.576 (7) | K1—O1iii | 2.852 (8) |
Ga1—K1ii | 3.584 (7) | K1—OW1v | 2.89 (3) |
Ga1—K1 | 3.728 (6) | K1—O1v | 3.066 (11) |
Ga1—K1v | 3.768 (6) | K1—O2ix | 3.178 (8) |
Ga1—K1vi | 3.979 (7) | K1—Ga1iii | 3.462 (5) |
K1—O2 | 2.676 (8) | OW1—OW1vii | 1.25 (7) |
K1—OW1 | 1.23 (3) | | |
| | | |
O1i—Ga1—O2ii | 108.0 (2) | OW1—K1—OW1iii | 148.9 (12) |
O1i—Ga1—O2 | 113.0 (3) | K1iii—K1—OW1iii | 20.4 (6) |
O2ii—Ga1—O2 | 107.5 (3) | OW1vii—K1—OW1iii | 150.6 (11) |
O1i—Ga1—O1 | 113.8 (4) | O2—K1—OW1iii | 67.4 (6) |
O2ii—Ga1—O1 | 109.7 (3) | O2iii—K1—OW1iii | 75.3 (6) |
O2—Ga1—O1 | 104.6 (2) | OW1—K1—OW1viii | 32.8 (19) |
O1i—Ga1—K1iii | 127.6 (3) | K1iii—K1—OW1viii | 99.4 (8) |
O2ii—Ga1—K1iii | 124.1 (3) | OW1vii—K1—OW1viii | 42.0 (10) |
O2—Ga1—K1iii | 49.66 (19) | O2—K1—OW1viii | 89.8 (7) |
O1—Ga1—K1iii | 55.0 (2) | O2iii—K1—OW1viii | 96.6 (8) |
O1i—Ga1—K1iv | 58.9 (3) | OW1iii—K1—OW1viii | 118.8 (10) |
O2ii—Ga1—K1iv | 62.7 (2) | OW1—K1—O1iii | 113.5 (16) |
O2—Ga1—K1iv | 92.32 (18) | K1iii—K1—O1iii | 97.2 (5) |
O1—Ga1—K1iv | 163.05 (19) | OW1vii—K1—O1iii | 102.5 (7) |
K1iii—Ga1—K1iv | 141.93 (13) | O2—K1—O1iii | 128.9 (3) |
O1i—Ga1—K1ii | 124.4 (3) | O2iii—K1—O1iii | 57.43 (17) |
O2ii—Ga1—K1ii | 45.1 (2) | OW1iii—K1—O1iii | 84.6 (7) |
O2—Ga1—K1ii | 62.4 (2) | OW1viii—K1—O1iii | 141.2 (7) |
O1—Ga1—K1ii | 121.0 (3) | OW1—K1—OW1v | 30.2 (17) |
K1iii—Ga1—K1ii | 93.0 (3) | K1iii—K1—OW1v | 118.4 (7) |
K1iv—Ga1—K1ii | 65.79 (2) | OW1vii—K1—OW1v | 41.4 (9) |
O1i—Ga1—K1 | 149.2 (2) | O2—K1—OW1v | 81.8 (6) |
O2ii—Ga1—K1 | 97.5 (2) | O2iii—K1—OW1v | 117.6 (7) |
O2—Ga1—K1 | 40.35 (19) | OW1iii—K1—OW1v | 134.3 (11) |
O1—Ga1—K1 | 71.6 (2) | OW1viii—K1—OW1v | 25.1 (14) |
K1iii—Ga1—K1 | 29.1 (4) | O1iii—K1—OW1v | 140.5 (7) |
K1iv—Ga1—K1 | 123.11 (12) | OW1—K1—O1v | 82.5 (15) |
K1ii—Ga1—K1 | 64.22 (11) | K1iii—K1—O1v | 144.7 (6) |
O1i—Ga1—K1v | 145.0 (2) | OW1vii—K1—O1v | 82.7 (7) |
O2ii—Ga1—K1v | 39.71 (19) | O2—K1—O1v | 82.7 (2) |
O2—Ga1—K1v | 76.8 (2) | O2iii—K1—O1v | 132.7 (3) |
O1—Ga1—K1v | 94.4 (3) | OW1iii—K1—O1v | 126.7 (6) |
K1iii—Ga1—K1v | 85.08 (14) | OW1viii—K1—O1v | 103.4 (7) |
K1iv—Ga1—K1v | 88.2 (4) | O1iii—K1—O1v | 81.4 (2) |
K1ii—Ga1—K1v | 28.6 (4) | OW1v—K1—O1v | 78.8 (7) |
K1—Ga1—K1v | 57.8 (3) | OW1—K1—O2ix | 131.4 (14) |
O1i—Ga1—K1vi | 38.0 (2) | K1iii—K1—O2ix | 93.5 (5) |
O2ii—Ga1—K1vi | 79.02 (18) | OW1vii—K1—O2ix | 133.9 (7) |
O2—Ga1—K1vi | 147.5 (2) | O2—K1—O2ix | 54.51 (13) |
O1—Ga1—K1vi | 102.8 (2) | O2iii—K1—O2ix | 128.1 (3) |
K1iii—Ga1—K1vi | 150.6 (3) | OW1iii—K1—O2ix | 75.3 (6) |
K1iv—Ga1—K1vi | 61.69 (11) | OW1viii—K1—O2ix | 135.0 (8) |
K1ii—Ga1—K1vi | 116.13 (11) | O1iii—K1—O2ix | 78.1 (2) |
K1—Ga1—K1vi | 172.1 (2) | OW1v—K1—O2ix | 113.6 (7) |
K1v—Ga1—K1vi | 118.32 (13) | O1v—K1—O2ix | 51.52 (16) |
Si1x—O1—Ga1 | 135.8 (3) | OW1—K1—Ga1iii | 103.6 (14) |
Si1x—O1—K1iii | 120.9 (3) | K1iii—K1—Ga1iii | 83.6 (4) |
Ga1—O1—K1iii | 96.0 (2) | OW1vii—K1—Ga1iii | 92.8 (7) |
Si1x—O1—K1viii | 93.3 (3) | O2—K1—Ga1iii | 144.0 (4) |
Ga1—O1—K1viii | 117.0 (3) | O2iii—K1—Ga1iii | 28.46 (11) |
K1iii—O1—K1viii | 82.1 (2) | OW1iii—K1—Ga1iii | 79.7 (7) |
Si1ix—O2—Ga1 | 135.4 (3) | OW1viii—K1—Ga1iii | 119.7 (8) |
Si1ix—O2—K1 | 108.5 (3) | O1iii—K1—Ga1iii | 29.01 (11) |
Ga1—O2—K1 | 115.6 (3) | OW1v—K1—Ga1iii | 133.6 (6) |
Si1ix—O2—K1iii | 116.8 (3) | O1v—K1—Ga1iii | 107.3 (2) |
Ga1—O2—K1iii | 101.9 (2) | O2ix—K1—Ga1iii | 104.3 (2) |
K1—O2—K1iii | 39.7 (5) | K1—OW1—OW1vii | 157.6 (16) |
Si1ix—O2—K1ii | 89.2 (3) | K1—OW1—K1vii | 147 (2) |
Ga1—O2—K1ii | 89.5 (2) | OW1vii—OW1—K1vii | 11.1 (8) |
K1—O2—K1ii | 82.78 (17) | K1—OW1—K1iii | 31.1 (12) |
K1iii—O2—K1ii | 120.7 (5) | OW1vii—OW1—K1iii | 149 (3) |
OW1—K1—K1iii | 128.5 (16) | K1vii—OW1—K1iii | 148.0 (12) |
OW1—K1—OW1vii | 11.3 (10) | K1—OW1—K1v | 120.3 (17) |
K1iii—K1—OW1vii | 131.2 (8) | OW1vii—OW1—K1v | 79.5 (19) |
OW1—K1—O2 | 112.0 (14) | K1vii—OW1—K1v | 86.4 (9) |
K1iii—K1—O2 | 70.8 (4) | K1iii—OW1—K1v | 121.7 (12) |
OW1vii—K1—O2 | 123.0 (7) | K1—OW1—K1viii | 117 (2) |
OW1—K1—O2iii | 92.9 (13) | OW1vii—OW1—K1viii | 75.4 (15) |
K1iii—K1—O2iii | 69.5 (4) | K1vii—OW1—K1viii | 85.4 (8) |
OW1vii—K1—O2iii | 84.5 (7) | K1iii—OW1—K1viii | 87.0 (10) |
O2—K1—O2iii | 140.3 (5) | K1v—OW1—K1viii | 75.9 (7) |
Symmetry codes: (i) −y+5/4, x+1/4, −z+1/4; (ii) −y+3/4, x+1/4, z+1/4; (iii) −x+1/2, −y+3/2, −z−1/2; (iv) −x+1/2, −y+1, z+1/2; (v) y−3/4, −x+3/4, −z−1/4; (vi) y−1/4, −x+3/4, z+3/4; (vii) −x, −y+3/2, z; (viii) −y+3/4, x+3/4, −z−1/4; (ix) y−1/4, −x+3/4, z−1/4; (x) y−1/4, −x+5/4, −z+1/4. |
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