Very stable crystals of the title compound, (CH
6N
3)
8[PtW
6O
24], containing the well known A-type Anderson–Evans heteropolyoxotungstate structure, were obtained by hydrothermal reaction. All O atoms in the polyanion form strong N—H
O hydrogen bonds with all N atoms of the guanidinium ions. The [PtW
6O
24]
8− anion has
S6 (
) symmetry, with a Pt—O bond length of 2.016 (9) Å, and three types of W—O bonds, with distances of 1.74 (1) and 1.78 (1) (O
t), 1.95 (1) (O
b), and 2.17 (1) (O
c) Å.
Supporting information
CCDC reference: 206741
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (N-C) = 0.024 Å
- R factor = 0.049
- wR factor = 0.106
- Data-to-parameter ratio = 17.0
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Data collection: STADI4 (Stoe & Cie, 1996); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).
Crystal data top
(CH6N3)8[PtW6O24] | Dx = 3.387 Mg m−3 |
Mr = 2162.89 | Mo Kα radiation, λ = 0.71069 Å |
Hexagonal, R3 | Cell parameters from 25 reflections |
Hall symbol: -R 3 | θ = 13.7–15.7° |
a = 12.928 (2) Å | µ = 19.59 mm−1 |
c = 21.981 (5) Å | T = 298 K |
V = 3181.6 (10) Å3 | Cubic, yellow |
Z = 3 | 0.10 × 0.10 × 0.10 mm |
F(000) = 2934 | |
Data collection top
Stoe STADI4 diffractometer | 1108 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
ω/2–θ scans | h = −16→8 |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1996) | k = 0→16 |
Tmin = 0.120, Tmax = 0.143 | l = 0→28 |
1629 measured reflections | 3 standard reflections every 60 min |
1629 independent reflections | intensity decay: 3.5% |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.18 | w = 1/[σ2(Fo2) + (0.0325P)2 + 60.3628P] where P = (Fo2 + 2Fc2)/3 |
1629 reflections | (Δ/σ)max < 0.001 |
96 parameters | Δρmax = 1.46 e Å−3 |
0 restraints | Δρmin = −2.72 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 | |
Pt | 0.0000 | 0.0000 | 0.0000 | 0.0113 (3) | |
W | −0.18149 (5) | 0.10481 (5) | 0.00160 (3) | 0.01744 (17) | |
Oc | −0.0221 (9) | 0.1236 (9) | 0.0449 (4) | 0.0172 (19) | |
Ob | −0.0468 (9) | 0.2294 (9) | −0.0431 (5) | 0.020 (2) | |
Ot1 | −0.2872 (10) | 0.0929 (10) | −0.0541 (5) | 0.030 (3) | |
Ot2 | −0.1935 (10) | 0.1915 (11) | 0.0585 (5) | 0.031 (3) | |
C1 | −0.1038 (17) | 0.4444 (17) | 0.1332 (8) | 0.036 (4) | |
C2 | −0.3333 | 0.3333 | −0.0785 (16) | 0.039 (8) | |
N1 | −0.0599 (15) | 0.3850 (14) | 0.1615 (7) | 0.040 (4) | |
H1A | −0.0633 | 0.3795 | 0.2005 | 0.049* | |
H1B | −0.0278 | 0.3517 | 0.1409 | 0.049* | |
N2 | −0.0943 (17) | 0.4541 (14) | 0.0730 (6) | 0.046 (5) | |
H2A | −0.0600 | 0.4219 | 0.0534 | 0.055* | |
H2B | −0.1224 | 0.4925 | 0.0537 | 0.055* | |
N3 | −0.1537 (12) | 0.4966 (13) | 0.1633 (6) | 0.030 (3) | |
H3A | −0.1581 | 0.4923 | 0.2023 | 0.036* | |
H3B | −0.1818 | 0.5349 | 0.1438 | 0.036* | |
N4 | −0.4163 (15) | 0.2181 (16) | −0.0808 (9) | 0.057 (5) | |
H4A | −0.3953 | 0.1647 | −0.0838 | 0.069* | |
H4B | −0.4907 | 0.1970 | −0.0793 | 0.069* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt | 0.0103 (4) | 0.0103 (4) | 0.0132 (6) | 0.00515 (19) | 0.000 | 0.000 |
W | 0.0157 (3) | 0.0180 (3) | 0.0210 (3) | 0.0103 (3) | −0.0004 (3) | −0.0013 (3) |
Oc | 0.015 (5) | 0.016 (5) | 0.020 (5) | 0.007 (4) | −0.005 (4) | −0.007 (4) |
Ob | 0.012 (5) | 0.018 (5) | 0.024 (6) | 0.004 (4) | −0.002 (4) | 0.001 (4) |
Ot1 | 0.029 (7) | 0.032 (7) | 0.039 (7) | 0.023 (6) | −0.015 (5) | −0.004 (5) |
Ot2 | 0.027 (6) | 0.033 (7) | 0.030 (6) | 0.012 (6) | 0.006 (5) | −0.009 (5) |
C1 | 0.043 (11) | 0.039 (11) | 0.027 (9) | 0.022 (9) | 0.000 (8) | −0.006 (7) |
C2 | 0.032 (11) | 0.032 (11) | 0.05 (2) | 0.016 (5) | 0.000 | 0.000 |
N1 | 0.065 (11) | 0.045 (10) | 0.029 (8) | 0.040 (9) | −0.014 (8) | −0.001 (7) |
N2 | 0.096 (15) | 0.051 (10) | 0.019 (7) | 0.058 (11) | 0.008 (8) | 0.008 (7) |
N3 | 0.044 (9) | 0.046 (9) | 0.014 (6) | 0.033 (8) | 0.000 (6) | −0.002 (6) |
N4 | 0.032 (10) | 0.044 (11) | 0.099 (15) | 0.022 (9) | 0.003 (10) | −0.005 (11) |
Geometric parameters (Å, º) top
W—Wi | 3.2443 (7) | W—Oc | 2.17 (1) |
Pt—W | 3.2437 (7) | C1—N1 | 1.32 (2) |
Pt—Oc | 2.016 (9) | C1—N2 | 1.33 (2) |
W—Ot1 | 1.78 (1) | C1—N3 | 1.32 (2) |
W—Ot2 | 1.74 (1) | C2—N4 | 1.33 (2) |
W—Ob | 1.95 (1) | | |
| | | |
Ocii—Pt—Ociii | 81.9 (3) | Ot2—W—Oc | 89.9 (5) |
Ocii—Pt—Oc | 180.0 (7) | Ot1—W—Oc | 162.6 (5) |
Ociii—Pt—Oc | 98.1 (3) | Obiv—W—Oc | 89.5 (4) |
Ot2—W—Ot1 | 103.8 (5) | Ob—W—Oc | 73.8 (4) |
Ot2—W—Obiv | 95.7 (5) | Ociv—W—Oc | 75.0 (5) |
Ot1—W—Obiv | 99.6 (5) | Pt—W—Wi | 60.0 |
Ot2—W—Ob | 99.2 (5) | N1—C1—N3 | 122 (2) |
Ot1—W—Ob | 93.1 (5) | N1—C1—N2 | 119 (2) |
Obiv—W—Ob | 157.5 (6) | N3—C1—N2 | 120 (2) |
Ot2—W—Ociv | 161.5 (5) | N4v—C2—N4 | 119.9 (2) |
Ot1—W—Ociv | 93.2 (4) | N4v—C2—N4vi | 119.9 (2) |
Obiv—W—Ociv | 74.0 (4) | N4—C2—N4vi | 119.9 (2) |
Ob—W—Ociv | 87.0 (4) | | |
Symmetry codes: (i) y, −x+y, −z; (ii) −x, −y, −z; (iii) −x+y, −x, z; (iv) x−y, x, −z; (v) −y, x−y+1, z; (vi) −x+y−1, −x, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Obvii | 0.86 | 1.97 | 2.83 (2) | 175 |
N1—H1B···Ot1i | 0.86 | 2.37 | 3.10 (2) | 142 |
N2—H2A···Ot1i | 0.86 | 2.30 | 3.04 (3) | 145 |
N2—H2B···Ot2v | 0.86 | 2.18 | 2.94 (2) | 147 |
N2—H2A···Ot2 | 0.86 | 2.59 | 2.99 (2) | 109 |
N3—H3A···Ocviii | 0.86 | 1.99 | 2.83 (2) | 165 |
N3—H3B···Ot2v | 0.86 | 2.18 | 2.94 (2) | 148 |
N4—H4A···Ot1 | 0.86 | 2.13 | 2.91 (2) | 150 |
Symmetry codes: (i) y, −x+y, −z; (v) −y, x−y+1, z; (vii) −x+y−1/3, −x+1/3, z+1/3; (viii) y−1/3, −x+y+1/3, −z+1/3. |