Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802015799/tk6077sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802015799/tk6077Isup2.hkl |
CCDC reference: 198293
Key indicators
- Single-crystal synchrotron study
- T = 100 K
- Mean (C-C) = 0.018 Å
- H-atom completeness 49%
- R factor = 0.038
- wR factor = 0.103
- Data-to-parameter ratio = 20.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
ATOM_007 Alert A _atom_site_aniso_label is missing Unique label identifying the atom site.
Author response: All atoms were refined with isotropic thermal parameters. |
REFLT_03 From the CIF: _diffrn_reflns_theta_max 30.00 From the CIF: _reflns_number_total 3953 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 4709 Completeness (_total/calc) 83.95% Alert A: < 85% complete (theta max?) THETM_01 Alert A The value of sine(theta_max)/wavelength is less than 0.550 Calculated sin(theta_max)/wavelength = 0.5432
Author response: The CCD detector plate was placed as close to the crystal as was practicable (55 cm); this limited the maximum theta_max value. |
Alert Level C:
PLAT_202 Alert C Isotropic non-H Atoms in Anion/Solvent = 21 General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C12 H49 N5 O25 W6 Atom count from _chemical_formula_moiety: FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C12 H49 N5 O25 W6 Atom count from the _atom_site data: C12 H24 N5 O25 W6 ABSMU_01 Radiation type not identified. Calculation of _exptl_absorpt_correction_mu not performed. CELLZ_01 From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_sum C12 H49 N5 O25 W6 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 24.00 24.00 0.00 H 98.00 48.00 50.00 N 10.00 10.00 0.00 O 50.00 50.00 0.00 W 12.00 12.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional? CHEMW_03 From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_weight 1766.66 TEST: Calculate formula weight from _atom_site_* atom mass num sum O 16.00 25.00 399.97 H 1.01 24.00 24.19 C 12.01 12.00 144.13 N 14.01 5.00 70.04 W 183.85 6.00 1103.10 Calculated formula weight 1741.43 The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.99 <> 1.01
3 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The compound was prepared by the reaction of H2WO4 with diaminohexane in an ammonia (0.1 N) solution uder flowing nitrogen gas. The product was precipitated by evaporating to dryness at 353 K [Calc. N 3.96%, Found 3.71, 3.90%].
All non-hydrogen atoms were refined with isotropic thermal parameters. H atoms on the 1,6-hexanediammonium carbon atoms were constrained in calculated positions (C—H 0.99 Å) to ride on their parent atom, with a Uiso 1.2 times the Ueq of the parent atom. No other H atoms were located. The largest residual electron density peak was located in the vicinity of the W atom.
Data collection: DENZO (Otinowski & Minor, 1997); cell refinement: DENZO; data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
2(NH4)4(C6H18N2)[H2W12O42].8H2O | Z = 2 |
Mr = 1766.66 | F(000) = 1582 |
Triclinic, P1 | Dx = 3.319 Mg m−3 |
a = 10.987 (2) Å | Synchrotron radiation, λ = 0.9204 Å |
b = 10.980 (2) Å | Cell parameters from 340 reflections |
c = 14.681 (3) Å | θ = 3.8–22.5° |
α = 85.99 (3)° | µ = 37.82 mm−1 |
β = 84.85 (3)° | T = 100 K |
γ = 87.69 (3)° | Plate, colourless |
V = 1758.6 (6) Å3 | 0.35 × 0.08 × 0.03 mm |
Quantum4 CCD detector diffractometer | 3953 independent reflections |
None monochromator | 3937 reflections with I > 2σ(I) |
Detector resolution: 4000 pixels mm-1 | Rint = 0.066 |
ϕ scan | θmax = 30.0°, θmin = 2.9° |
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997) | h = 0→11 |
Tmin = 0.033, Tmax = 0.389 | k = −11→10 |
3953 measured reflections | l = −14→15 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0454P)2 + 33.4374P] where P = (Fo2 + 2Fc2)/3 |
3953 reflections | (Δ/σ)max = 0.001 |
193 parameters | Δρmax = 2.74 e Å−3 |
0 restraints | Δρmin = −2.77 e Å−3 |
2(NH4)4(C6H18N2)[H2W12O42].8H2O | γ = 87.69 (3)° |
Mr = 1766.66 | V = 1758.6 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.987 (2) Å | Synchrotron radiation, λ = 0.9204 Å |
b = 10.980 (2) Å | µ = 37.82 mm−1 |
c = 14.681 (3) Å | T = 100 K |
α = 85.99 (3)° | 0.35 × 0.08 × 0.03 mm |
β = 84.85 (3)° |
Quantum4 CCD detector diffractometer | 3953 independent reflections |
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997) | 3937 reflections with I > 2σ(I) |
Tmin = 0.033, Tmax = 0.389 | Rint = 0.066 |
3953 measured reflections | θmax = 30.0° |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0454P)2 + 33.4374P] where P = (Fo2 + 2Fc2)/3 |
3953 reflections | Δρmax = 2.74 e Å−3 |
193 parameters | Δρmin = −2.77 e Å−3 |
Experimental. The incomplete shell of data is all the available data accessible using the highest wavelength possible on the NSLS X9B beamline, with the CCD detector plate placed as close to the crystal as was practicable (55 cm). Crystal decay was monitored and corrected by the inter-frame analysis (DENZO: Otwinowski & Minor (1997). |
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. |
x | y | z | Uiso*/Ueq | ||
W1 | 0.43522 (4) | 0.74176 (4) | 0.54171 (3) | 0.00210 (17)* | |
W2 | 0.67251 (4) | 0.75027 (4) | 0.38351 (3) | 0.00252 (17)* | |
W3 | 0.41623 (4) | 0.62649 (4) | 0.33707 (3) | 0.00217 (17)* | |
W4 | 0.27348 (4) | 0.53869 (4) | 0.72785 (3) | 0.00295 (17)* | |
W5 | 0.75556 (4) | 0.66461 (4) | 0.61806 (3) | 0.00280 (17)* | |
W6 | 0.52814 (4) | 0.66651 (4) | 0.77835 (3) | 0.00332 (17)* | |
O1 | 0.3635 (7) | 0.7476 (7) | 0.4258 (5) | 0.0037 (17)* | |
O2 | 0.5685 (7) | 0.8384 (7) | 0.4662 (5) | 0.0047 (17)* | |
O3 | 0.5528 (7) | 0.7491 (7) | 0.3021 (5) | 0.0041 (17)* | |
O4 | 0.3629 (7) | 0.8694 (7) | 0.5872 (5) | 0.0062 (18)* | |
O5 | 0.3295 (7) | 0.6781 (7) | 0.2469 (5) | 0.0067 (18)* | |
O6 | 0.7707 (7) | 0.8614 (7) | 0.3341 (5) | 0.0070 (18)* | |
O7 | 0.5409 (6) | 0.6102 (7) | 0.4496 (5) | 0.0031 (17)* | |
O8 | 0.3424 (7) | 0.6147 (7) | 0.5896 (5) | 0.0050 (17)* | |
O9 | 0.5601 (6) | 0.7070 (7) | 0.6248 (5) | 0.0018 (17)* | |
O10 | 0.7575 (7) | 0.6916 (7) | 0.4907 (5) | 0.0044 (17)* | |
O11 | 0.7463 (7) | 0.6035 (7) | 0.3328 (5) | 0.0029 (17)* | |
O12 | 0.5262 (7) | 0.5124 (7) | 0.2769 (5) | 0.0041 (17)* | |
O13 | 0.3241 (7) | 0.5141 (7) | 0.4007 (5) | 0.0024 (17)* | |
O14 | 0.3584 (6) | 0.6831 (7) | 0.7578 (5) | 0.0027 (17)* | |
O15 | 0.6928 (7) | 0.6136 (7) | 0.7436 (5) | 0.0030 (17)* | |
O16 | 0.7938 (7) | 0.8110 (7) | 0.6442 (5) | 0.0058 (17)* | |
O17 | 0.8960 (7) | 0.5803 (7) | 0.6205 (5) | 0.0040 (17)* | |
O18 | 0.1338 (7) | 0.6131 (7) | 0.7143 (5) | 0.0065 (18)* | |
O19 | 0.2510 (7) | 0.4760 (7) | 0.8402 (5) | 0.0084 (18)* | |
O20 | 0.5481 (7) | 0.8205 (7) | 0.7935 (5) | 0.0048 (17)* | |
O21 | 0.5196 (7) | 0.5992 (7) | 0.8901 (5) | 0.0051 (17)* | |
O1W | 0.2264 (8) | 0.1242 (8) | 0.1278 (6) | 0.018 (2)* | |
O2W | 0.0211 (7) | 0.1956 (7) | 0.2419 (5) | 0.0114 (19)* | |
O3W | 0.9926 (8) | 0.8085 (8) | 0.2310 (6) | 0.016 (2)* | |
O4W | 1.2179 (8) | 0.9161 (8) | 0.2522 (6) | 0.019 (2)* | |
N7 | 0.3966 (9) | 0.0094 (10) | 0.3721 (7) | 0.015 (2)* | |
N1 | 0.7858 (9) | 1.0991 (10) | 0.2400 (7) | 0.012 (2)* | |
C1 | 0.7729 (11) | 1.0442 (11) | 0.1514 (8) | 0.010 (3)* | |
H1A | 0.6862 | 1.0513 | 0.1378 | 0.012* | |
H1B | 0.7967 | 0.9562 | 0.1572 | 0.012* | |
C2 | 0.8531 (11) | 1.1074 (11) | 0.0712 (8) | 0.011 (3)* | |
H2A | 0.9402 | 1.0907 | 0.0815 | 0.013* | |
H2B | 0.8377 | 1.0709 | 0.0137 | 0.013* | |
C3 | 0.8305 (11) | 1.2435 (11) | 0.0594 (8) | 0.012 (3)* | |
H3A | 0.8612 | 1.2821 | 0.1115 | 0.014* | |
H3B | 0.7413 | 1.2613 | 0.0610 | 0.014* | |
C4 | 0.8929 (12) | 1.3005 (12) | −0.0311 (9) | 0.016 (3)* | |
H4A | 0.9826 | 1.2963 | −0.0279 | 0.019* | |
H4B | 0.8742 | 1.2521 | −0.0822 | 0.019* | |
C5 | 0.8512 (11) | 1.4340 (11) | −0.0512 (8) | 0.012 (3)* | |
H5A | 0.7627 | 1.4370 | −0.0597 | 0.014* | |
H5B | 0.8628 | 1.4805 | 0.0026 | 0.014* | |
C6 | 0.9192 (12) | 1.4956 (12) | −0.1355 (8) | 0.014 (3)* | |
H6A | 0.8875 | 1.5808 | −0.1445 | 0.017* | |
H6B | 1.0071 | 1.4978 | −0.1259 | 0.017* | |
N2 | 0.9046 (9) | 1.4289 (9) | −0.2201 (7) | 0.012 (2)* | |
N3 | 0.5613 (9) | 0.6362 (10) | 0.0734 (7) | 0.016 (2)* | |
C11 | 0.5691 (12) | 0.7707 (12) | 0.0708 (9) | 0.018 (3)* | |
H11A | 0.6406 | 0.7969 | 0.0292 | 0.022* | |
H11B | 0.5807 | 0.7958 | 0.1329 | 0.022* | |
C12 | 0.4544 (11) | 0.8318 (11) | 0.0380 (8) | 0.012 (3)* | |
H12A | 0.3835 | 0.8025 | 0.0789 | 0.015* | |
H12B | 0.4444 | 0.8064 | −0.0242 | 0.015* | |
C13 | 0.4525 (11) | 0.9708 (12) | 0.0349 (9) | 0.014 (3)* | |
H13A | 0.4662 | 0.9962 | 0.0965 | 0.017* | |
H13B | 0.3703 | 1.0025 | 0.0205 | 0.017* | |
N5 | 0.1151 (8) | 0.6115 (9) | 0.5068 (6) | 0.005 (2)* | |
C21 | 0.0709 (10) | 0.7224 (10) | 0.4535 (8) | 0.005 (3)* | |
H21A | −0.0123 | 0.7097 | 0.4359 | 0.006* | |
H21B | 0.1256 | 0.7369 | 0.3967 | 0.006* | |
C22 | 0.0686 (10) | 0.8338 (10) | 0.5112 (8) | 0.006 (3)* | |
H22A | 0.0274 | 0.8121 | 0.5726 | 0.007* | |
H22B | 0.1538 | 0.8539 | 0.5194 | 0.007* | |
C23 | 0.0034 (11) | 0.9473 (11) | 0.4690 (9) | 0.014 (3)* | |
H23A | 0.0475 | 0.9727 | 0.4094 | 0.017* | |
H23B | −0.0805 | 0.9265 | 0.4575 | 0.017* |
W1—O4 | 1.729 (8) | W5—O9 | 2.173 (7) |
W1—O8 | 1.824 (8) | W5—O13i | 2.224 (8) |
W1—O9 | 1.927 (7) | W6—O20 | 1.746 (8) |
W1—O1 | 1.935 (7) | W6—O21 | 1.748 (7) |
W1—O2 | 2.042 (8) | W6—O15 | 1.914 (7) |
W1—O7 | 2.263 (7) | W6—O14 | 1.916 (7) |
W2—O6 | 1.738 (8) | W6—O9 | 2.266 (7) |
W2—O3 | 1.856 (7) | W6—O12i | 2.298 (8) |
W2—O2 | 1.882 (7) | O11—W4i | 1.880 (8) |
W2—O11 | 1.940 (7) | O12—W4i | 2.245 (7) |
W2—O10 | 1.958 (7) | O12—W6i | 2.298 (8) |
W2—O7 | 2.262 (7) | O13—W5i | 2.224 (8) |
W3—O5 | 1.749 (7) | N1—C1 | 1.492 (16) |
W3—O13 | 1.786 (7) | C1—C2 | 1.547 (16) |
W3—O12 | 1.911 (7) | C2—C3 | 1.506 (17) |
W3—O1 | 1.961 (7) | C3—C4 | 1.544 (17) |
W3—O3 | 2.063 (8) | C4—C5 | 1.534 (17) |
W3—O7 | 2.233 (7) | C5—C6 | 1.518 (17) |
W4—O18 | 1.730 (7) | C6—N2 | 1.509 (16) |
W4—O19 | 1.742 (8) | N3—C11 | 1.481 (17) |
W4—O11i | 1.880 (8) | C11—C12 | 1.506 (17) |
W4—O14 | 1.967 (8) | C12—C13 | 1.523 (18) |
W4—O8 | 2.220 (7) | C13—C13ii | 1.52 (2) |
W4—O12i | 2.245 (7) | N5—C21 | 1.489 (14) |
W5—O16 | 1.754 (8) | C21—C22 | 1.534 (16) |
W5—O17 | 1.769 (7) | C22—C23 | 1.533 (16) |
W5—O10 | 1.871 (7) | C23—C23iii | 1.52 (2) |
W5—O15 | 1.961 (7) | ||
O4—W1—O8 | 104.6 (3) | O16—W5—O17 | 103.2 (3) |
O4—W1—O9 | 100.8 (3) | O16—W5—O10 | 98.7 (3) |
O8—W1—O9 | 93.8 (3) | O17—W5—O10 | 97.4 (3) |
O4—W1—O1 | 99.6 (3) | O16—W5—O15 | 95.0 (3) |
O8—W1—O1 | 92.7 (3) | O17—W5—O15 | 95.9 (3) |
O9—W1—O1 | 156.3 (3) | O10—W5—O15 | 158.1 (3) |
O4—W1—O2 | 94.2 (3) | O16—W5—O9 | 94.4 (3) |
O8—W1—O2 | 161.1 (3) | O17—W5—O9 | 160.7 (3) |
O9—W1—O2 | 83.7 (3) | O10—W5—O9 | 87.4 (3) |
O1—W1—O2 | 82.8 (3) | O15—W5—O9 | 74.6 (3) |
O4—W1—O7 | 164.7 (3) | O16—W5—O13i | 169.8 (3) |
O8—W1—O7 | 88.2 (3) | O17—W5—O13i | 85.1 (3) |
O9—W1—O7 | 86.4 (3) | O10—W5—O13i | 85.9 (3) |
O1—W1—O7 | 71.0 (3) | O15—W5—O13i | 78.1 (3) |
O2—W1—O7 | 73.0 (3) | O9—W5—O13i | 76.7 (3) |
O6—W2—O3 | 103.7 (3) | O20—W6—O21 | 103.4 (3) |
O6—W2—O2 | 102.3 (3) | O20—W6—O15 | 100.8 (3) |
O3—W2—O2 | 91.9 (3) | O21—W6—O15 | 96.8 (3) |
O6—W2—O11 | 101.8 (3) | O20—W6—O14 | 96.3 (3) |
O3—W2—O11 | 89.0 (3) | O21—W6—O14 | 101.0 (3) |
O2—W2—O11 | 154.9 (3) | O15—W6—O14 | 151.7 (3) |
O6—W2—O10 | 100.9 (3) | O20—W6—O9 | 89.1 (3) |
O3—W2—O10 | 155.2 (3) | O21—W6—O9 | 165.5 (3) |
O2—W2—O10 | 85.7 (3) | O15—W6—O9 | 73.3 (3) |
O11—W2—O10 | 83.2 (3) | O14—W6—O9 | 84.6 (3) |
O6—W2—O7 | 178.3 (3) | O20—W6—O12i | 163.5 (3) |
O3—W2—O7 | 76.1 (3) | O21—W6—O12i | 90.9 (3) |
O2—W2—O7 | 76.0 (3) | O15—W6—O12i | 85.5 (3) |
O11—W2—O7 | 80.0 (3) | O14—W6—O12i | 72.5 (3) |
O10—W2—O7 | 79.4 (3) | O9—W6—O12i | 77.9 (3) |
O5—W3—O13 | 104.0 (3) | W1—O1—W3 | 119.6 (4) |
O5—W3—O12 | 100.4 (3) | W2—O2—W1 | 116.2 (4) |
O13—W3—O12 | 95.6 (3) | W2—O3—W3 | 115.7 (4) |
O5—W3—O1 | 100.0 (3) | W3—O7—W2 | 95.2 (3) |
O13—W3—O1 | 90.9 (3) | W3—O7—W1 | 97.0 (3) |
O12—W3—O1 | 156.3 (3) | W2—O7—W1 | 94.8 (3) |
O5—W3—O3 | 94.5 (3) | W1—O8—W4 | 137.1 (4) |
O13—W3—O3 | 161.1 (3) | W1—O9—W5 | 138.4 (4) |
O12—W3—O3 | 84.8 (3) | W1—O9—W6 | 125.9 (3) |
O1—W3—O3 | 81.8 (3) | W5—O9—W6 | 95.1 (3) |
O5—W3—O7 | 165.4 (3) | W5—O10—W2 | 149.0 (4) |
O13—W3—O7 | 88.2 (3) | W4i—O11—W2 | 148.1 (4) |
O12—W3—O7 | 86.2 (3) | W3—O12—W4i | 137.2 (4) |
O1—W3—O7 | 71.2 (3) | W3—O12—W6i | 125.4 (4) |
O3—W3—O7 | 72.9 (3) | W4i—O12—W6i | 94.8 (3) |
O18—W4—O19 | 101.4 (4) | W3—O13—W5i | 139.5 (4) |
O18—W4—O11i | 100.2 (3) | W6—O14—W4 | 118.9 (4) |
O19—W4—O11i | 98.2 (3) | W6—O15—W5 | 115.4 (4) |
O18—W4—O14 | 96.2 (3) | N1—C1—C2 | 111.9 (10) |
O19—W4—O14 | 95.9 (3) | C3—C2—C1 | 114.1 (10) |
O11i—W4—O14 | 155.8 (3) | C2—C3—C4 | 112.9 (10) |
O18—W4—O8 | 89.5 (3) | C5—C4—C3 | 112.6 (10) |
O19—W4—O8 | 168.2 (3) | C6—C5—C4 | 113.7 (10) |
O11i—W4—O8 | 84.1 (3) | N2—C6—C5 | 111.4 (11) |
O14—W4—O8 | 78.4 (3) | N3—C11—C12 | 110.4 (10) |
O18—W4—O12i | 164.4 (3) | C11—C12—C13 | 114.4 (10) |
O19—W4—O12i | 90.9 (3) | C12—C13—C13ii | 114.2 (14) |
O11i—W4—O12i | 87.4 (3) | N5—C21—C22 | 110.1 (9) |
O14—W4—O12i | 72.8 (3) | C23—C22—C21 | 113.8 (10) |
O8—W4—O12i | 77.6 (3) | C23iii—C23—C22 | 112.0 (13) |
O4—W1—O1—W3 | 177.1 (4) | O17—W5—O9—W1 | −99.9 (10) |
O8—W1—O1—W3 | −77.5 (4) | O10—W5—O9—W1 | 5.4 (6) |
O9—W1—O1—W3 | 28.2 (10) | O15—W5—O9—W1 | −162.1 (7) |
O2—W1—O1—W3 | 84.1 (4) | O13i—W5—O9—W1 | −81.0 (6) |
O7—W1—O1—W3 | 9.6 (4) | O16—W5—O9—W6 | −85.4 (3) |
O5—W3—O1—W1 | −177.6 (4) | O17—W5—O9—W6 | 70.8 (10) |
O13—W3—O1—W1 | 78.1 (4) | O10—W5—O9—W6 | 176.0 (3) |
O12—W3—O1—W1 | −28.3 (10) | O15—W5—O9—W6 | 8.5 (3) |
O3—W3—O1—W1 | −84.4 (4) | O13i—W5—O9—W6 | 89.6 (3) |
O7—W3—O1—W1 | −9.7 (4) | O20—W6—O9—W1 | −95.0 (5) |
O6—W2—O2—W1 | −179.9 (4) | O21—W6—O9—W1 | 115.1 (12) |
O3—W2—O2—W1 | 75.7 (4) | O15—W6—O9—W1 | 163.5 (5) |
O11—W2—O2—W1 | −15.9 (9) | O14—W6—O9—W1 | 1.5 (5) |
O10—W2—O2—W1 | −79.6 (4) | O12i—W6—O9—W1 | 74.6 (4) |
O7—W2—O2—W1 | 0.6 (3) | O20—W6—O9—W5 | 92.7 (3) |
O4—W1—O2—W2 | −172.0 (4) | O21—W6—O9—W5 | −57.2 (13) |
O8—W1—O2—W2 | 4.4 (12) | O15—W6—O9—W5 | −8.8 (3) |
O9—W1—O2—W2 | 87.6 (4) | O14—W6—O9—W5 | −170.8 (3) |
O1—W1—O2—W2 | −72.8 (4) | O12i—W6—O9—W5 | −97.7 (3) |
O7—W1—O2—W2 | −0.6 (3) | O16—W5—O10—W2 | −83.9 (9) |
O6—W2—O3—W3 | 180.0 (4) | O17—W5—O10—W2 | 171.4 (8) |
O2—W2—O3—W3 | −76.8 (4) | O15—W5—O10—W2 | 44.3 (14) |
O11—W2—O3—W3 | 78.1 (4) | O9—W5—O10—W2 | 10.2 (9) |
O10—W2—O3—W3 | 6.8 (10) | O13i—W5—O10—W2 | 87.0 (9) |
O7—W2—O3—W3 | −1.8 (3) | O6—W2—O10—W5 | 121.9 (9) |
O5—W3—O3—W2 | 174.1 (4) | O3—W2—O10—W5 | −64.9 (13) |
O13—W3—O3—W2 | 6.5 (12) | O2—W2—O10—W5 | 20.2 (9) |
O12—W3—O3—W2 | −85.8 (4) | O11—W2—O10—W5 | −137.3 (9) |
O1—W3—O3—W2 | 74.7 (4) | O7—W2—O10—W5 | −56.3 (8) |
O7—W3—O3—W2 | 1.9 (3) | O6—W2—O11—W4i | −129.6 (8) |
O5—W3—O7—W2 | −33.4 (13) | O3—W2—O11—W4i | −25.8 (8) |
O13—W3—O7—W2 | −179.9 (3) | O2—W2—O11—W4i | 66.4 (11) |
O12—W3—O7—W2 | 84.3 (3) | O10—W2—O11—W4i | 130.7 (8) |
O1—W3—O7—W2 | −88.3 (3) | O7—W2—O11—W4i | 50.2 (7) |
O3—W3—O7—W2 | −1.4 (3) | O5—W3—O12—W4i | 137.5 (6) |
O5—W3—O7—W1 | 62.2 (13) | O13—W3—O12—W4i | −117.1 (6) |
O13—W3—O7—W1 | −84.3 (3) | O1—W3—O12—W4i | −11.8 (12) |
O12—W3—O7—W1 | 179.9 (3) | O3—W3—O12—W4i | 43.9 (5) |
O1—W3—O7—W1 | 7.3 (3) | O7—W3—O12—W4i | −29.3 (5) |
O3—W3—O7—W1 | 94.2 (3) | O5—W3—O12—W6i | −66.2 (5) |
O3—W2—O7—W3 | 1.5 (3) | O13—W3—O12—W6i | 39.2 (5) |
O2—W2—O7—W3 | 97.0 (3) | O1—W3—O12—W6i | 144.6 (6) |
O11—W2—O7—W3 | −89.9 (3) | O3—W3—O12—W6i | −159.8 (4) |
O10—W2—O7—W3 | −174.8 (3) | O7—W3—O12—W6i | 127.0 (4) |
O3—W2—O7—W1 | −96.0 (3) | O5—W3—O13—W5i | 61.9 (6) |
O2—W2—O7—W1 | −0.5 (3) | O12—W3—O13—W5i | −40.3 (6) |
O11—W2—O7—W1 | 172.6 (3) | O1—W3—O13—W5i | 162.5 (6) |
O10—W2—O7—W1 | 87.7 (3) | O3—W3—O13—W5i | −130.8 (8) |
O4—W1—O7—W3 | −61.0 (12) | O7—W3—O13—W5i | −126.4 (6) |
O8—W1—O7—W3 | 86.1 (3) | O20—W6—O14—W4 | 176.7 (4) |
O9—W1—O7—W3 | −179.9 (3) | O21—W6—O14—W4 | −78.4 (4) |
O1—W1—O7—W3 | −7.4 (3) | O15—W6—O14—W4 | 49.6 (8) |
O2—W1—O7—W3 | −95.5 (3) | O9—W6—O14—W4 | 88.1 (4) |
O4—W1—O7—W2 | 34.9 (13) | O12i—W6—O14—W4 | 9.1 (3) |
O8—W1—O7—W2 | −178.0 (3) | O18—W4—O14—W6 | −178.0 (4) |
O9—W1—O7—W2 | −84.1 (3) | O19—W4—O14—W6 | 79.9 (4) |
O1—W1—O7—W2 | 88.5 (3) | O11i—W4—O14—W6 | −45.5 (9) |
O2—W1—O7—W2 | 0.4 (2) | O8—W4—O14—W6 | −89.8 (4) |
O4—W1—O8—W4 | −55.0 (6) | O12i—W4—O14—W6 | −9.3 (4) |
O9—W1—O8—W4 | 47.3 (6) | O20—W6—O15—W5 | −75.0 (4) |
O1—W1—O8—W4 | −155.6 (6) | O21—W6—O15—W5 | 179.9 (4) |
O2—W1—O8—W4 | 128.8 (8) | O14—W6—O15—W5 | 51.1 (8) |
O7—W1—O8—W4 | 133.5 (6) | O9—W6—O15—W5 | 10.8 (3) |
O18—W4—O8—W1 | 99.1 (6) | O12i—W6—O15—W5 | 89.5 (4) |
O19—W4—O8—W1 | −58.7 (18) | O16—W5—O15—W6 | 82.0 (4) |
O11i—W4—O8—W1 | −160.6 (6) | O17—W5—O15—W6 | −174.1 (4) |
O14—W4—O8—W1 | 2.7 (5) | O10—W5—O15—W6 | −46.8 (10) |
O12i—W4—O8—W1 | −72.0 (6) | O9—W5—O15—W6 | −11.2 (4) |
O4—W1—O9—W5 | −132.6 (6) | O13i—W5—O15—W6 | −90.4 (4) |
O8—W1—O9—W5 | 121.8 (6) | N1—C1—C2—C3 | −55.3 (13) |
O1—W1—O9—W5 | 16.2 (12) | C1—C2—C3—C4 | −169.1 (10) |
O2—W1—O9—W5 | −39.5 (6) | C2—C3—C4—C5 | 169.6 (10) |
O7—W1—O9—W5 | 33.8 (6) | C3—C4—C5—C6 | 174.9 (11) |
O4—W1—O9—W6 | 59.0 (5) | C4—C5—C6—N2 | 58.7 (14) |
O8—W1—O9—W6 | −46.7 (5) | N3—C11—C12—C13 | 178.8 (10) |
O1—W1—O9—W6 | −152.2 (6) | C11—C12—C13—C13ii | 65.7 (17) |
O2—W1—O9—W6 | 152.1 (5) | N5—C21—C22—C23 | −169.7 (10) |
O7—W1—O9—W6 | −134.6 (4) | C21—C22—C23—C23iii | 176.6 (12) |
O16—W5—O9—W1 | 104.0 (6) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z; (iii) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | 2(NH4)4(C6H18N2)[H2W12O42].8H2O |
Mr | 1766.66 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 10.987 (2), 10.980 (2), 14.681 (3) |
α, β, γ (°) | 85.99 (3), 84.85 (3), 87.69 (3) |
V (Å3) | 1758.6 (6) |
Z | 2 |
Radiation type | Synchrotron, λ = 0.9204 Å |
µ (mm−1) | 37.82 |
Crystal size (mm) | 0.35 × 0.08 × 0.03 |
Data collection | |
Diffractometer | Quantum4 CCD detector diffractometer |
Absorption correction | Multi-scan DENZO-SMN (Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.033, 0.389 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3953, 3953, 3937 |
Rint | 0.066 |
θmax (°) | 30.0 |
(sin θ/λ)max (Å−1) | 0.543 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.103, 1.09 |
No. of reflections | 3953 |
No. of parameters | 193 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0454P)2 + 33.4374P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 2.74, −2.77 |
Computer programs: DENZO (Otinowski & Minor, 1997), DENZO, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
W1—O4 | 1.729 (8) | W1—O2 | 2.042 (8) |
W1—O8 | 1.824 (8) | W1—O7 | 2.263 (7) |
W1—O9 | 1.927 (7) | W6—O12i | 2.298 (8) |
W1—O1 | 1.935 (7) | O11—W4i | 1.880 (8) |
O4—W1—O8 | 104.6 (3) | O4—W1—O1 | 99.6 (3) |
O4—W1—O9 | 100.8 (3) | O8—W1—O1 | 92.7 (3) |
O8—W1—O9 | 93.8 (3) | O9—W1—O1 | 156.3 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
The title compound, (I), was prepared as part of a study into the use of organic amine inter-layer spacer molecules for inorganic oxide-layered compounds. The crystal structure comprises [H2W12O42]10− anions bound in an infinite three-dimensional network through hydrogen bonding with 1,6-hexanediammonium2+ and NH4+ cations and water molecules, as shown in Fig. 1. There are at least 34 contacts between the anion oxygen atoms, amine nitrogen atoms and water O atoms within normal hydrogen-bonding distances, e.g. O6···O3W 2.814 (12) Å. Other minor intermolecular interactions are also found, e.g. C11—H···O3 with C11···O3 3.38 (2) Å (Spek, 1990).
The anions are centrosymmetric, and the final cell composition is inferred from the analytical data and chemically reasonable refinement options, since the X-ray scattering of hydrogen atoms cannot be determined unambiguously in the presence of the W atoms. The atom-numbering scheme for the anion follows that in (NH4)10[H2W12O42].10H2O (Allman, 1971). A closely related six-ammonium cation (NH4)6[H6W12O42].10H2O structure has been reported by Averbuch-Pouchot et al. (1979) and a decasodium diglycine [H2W12O42]10− salt recently by Naruke et al. (2000).
The 1,6-hexanediammonium cations, which are aligned approximately along the c axial direction, can be considered to separate the anions by the length of the molecule along this axis. By contrast, the other 1,6-hexanediammonium cations, aligned along the b axis (end-on in Fig. 1), separate the anions by the width of the molecule. This pseudo-layer packing is reflected in the platey nature of the crystals.