Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100001530/qa0220sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100001530/qa0220Isup2.hkl |
Tyrosine was dissolved in 15 ml of an aqueous solution containing sodium acetate (2 mmol) and potassium hydroxide (2 mmol), and salicylaldehyde (4 mmol) dissolved in 18 ml of ethanol was added. 14 ml of an aqueous solution of VOSO4 (4 mmol) were added slowly, followed by 1 ml of pyridine. The mixture was kept in a beaker covered with Parafilm at 277–279 K and after five weeks red–brown crystals of the title compound were separated.
K– and Na-atom sites were assigned on the basis of the observed electron density. H atoms of water molecules were refined with their 1–2 and 1–3 distances restrained to 0.9 (2) and 1.45 (4) Å, respectively. Crystallographic software was used through the OSCAIL interface of McArdle (1995).
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software (Enraf-Nonius, 1989); data reduction: SDP (Nonius, 1985); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick & Schneider, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick & Schneider, 1997).
K4Na2[V10O28]·10H2O | Z = 1 |
Mr = 1339.94 | F(000) = 652 |
Triclinic, P1 | Dx = 2.678 Mg m−3 |
a = 8.5893 (6) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 10.3543 (6) Å | Cell parameters from 25 reflections |
c = 10.9893 (6) Å | θ = 14.0–15.9° |
α = 69.194 (5)° | µ = 3.33 mm−1 |
β = 87.122 (5)° | T = 293 K |
γ = 66.172 (5)° | Prism, dark orange |
V = 830.75 (9) Å3 | 0.40 × 0.35 × 0.30 mm |
Nonius CAD-4 diffractometer | 4320 reflections with I > 2σ(I) |
Radiation source: Nonius FR-591 rotating anode generator | Rint = 0.033 |
Graphite monochromator | θmax = 30.0°, θmin = 2.0° |
ω–2θ scans | h = −12→0 |
Absorption correction: ψ scan (North et al., 1968) | k = −14→13 |
Tmin = 0.252, Tmax = 0.368 | l = −15→15 |
5134 measured reflections | 3 standard reflections every 60 min |
4832 independent reflections | intensity decay: 0.9% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.028 | All H-atom parameters refined |
wR(F2) = 0.074 | w = 1/[σ2(Fo2) + (0.032P)2 + 1.1139P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.010 |
4832 reflections | Δρmax = 1.06 e Å−3 |
284 parameters | Δρmin = −1.28 e Å−3 |
15 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0032 (4) |
K4Na2[V10O28]·10H2O | γ = 66.172 (5)° |
Mr = 1339.94 | V = 830.75 (9) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.5893 (6) Å | Mo Kα radiation |
b = 10.3543 (6) Å | µ = 3.33 mm−1 |
c = 10.9893 (6) Å | T = 293 K |
α = 69.194 (5)° | 0.40 × 0.35 × 0.30 mm |
β = 87.122 (5)° |
Nonius CAD-4 diffractometer | 4320 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.033 |
Tmin = 0.252, Tmax = 0.368 | 3 standard reflections every 60 min |
5134 measured reflections | intensity decay: 0.9% |
4832 independent reflections |
R[F2 > 2σ(F2)] = 0.028 | 15 restraints |
wR(F2) = 0.074 | All H-atom parameters refined |
S = 1.10 | Δρmax = 1.06 e Å−3 |
4832 reflections | Δρmin = −1.28 e Å−3 |
284 parameters |
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 | ||
V1 | 0.81086 (4) | 0.99951 (4) | 0.52006 (3) | 0.01349 (7) | |
V2 | 1.12315 (4) | 0.71476 (4) | 0.49940 (3) | 0.01603 (8) | |
V3 | 0.97440 (5) | 0.70792 (4) | 0.76604 (3) | 0.01836 (8) | |
V4 | 0.97047 (4) | 1.00558 (4) | 0.25469 (3) | 0.01601 (8) | |
V5 | 1.32986 (4) | 0.71094 (4) | 0.72355 (4) | 0.01809 (8) | |
O2 | 1.1596 (2) | 0.61295 (18) | 0.41017 (16) | 0.0236 (3) | |
O3 | 0.8942 (2) | 0.6027 (2) | 0.86523 (17) | 0.0292 (4) | |
O4 | 1.0054 (2) | 0.90210 (18) | 0.16651 (15) | 0.0231 (3) | |
O5 | 1.5240 (2) | 0.61032 (19) | 0.79070 (17) | 0.0271 (3) | |
O6 | 0.93052 (17) | 1.12532 (15) | 0.39354 (13) | 0.0140 (3) | |
O7 | 0.89665 (17) | 0.88038 (15) | 0.41290 (14) | 0.0148 (3) | |
O8 | 0.81796 (17) | 1.11693 (15) | 0.61964 (14) | 0.0146 (3) | |
O13 | 0.76500 (18) | 0.86770 (16) | 0.64264 (14) | 0.0176 (3) | |
O15 | 0.62465 (18) | 1.12507 (17) | 0.42806 (15) | 0.0180 (3) | |
O23 | 1.01890 (19) | 0.62951 (16) | 0.63169 (15) | 0.0192 (3) | |
O25 | 1.32989 (18) | 0.63232 (16) | 0.59548 (15) | 0.0189 (3) | |
O34 | 1.05651 (19) | 1.14232 (17) | 0.16503 (14) | 0.0191 (3) | |
O35 | 1.20537 (19) | 0.61595 (17) | 0.82557 (15) | 0.0203 (3) | |
O45 | 0.74827 (18) | 1.13821 (16) | 0.20181 (14) | 0.0185 (3) | |
K1 | 1.31538 (7) | 0.28838 (6) | 0.50606 (6) | 0.03117 (12) | |
K2 | 1.76536 (12) | 0.31748 (9) | 0.92721 (7) | 0.0624 (3) | |
Na1 | 0.57073 (12) | 0.83232 (11) | 0.13120 (9) | 0.0267 (2) | |
O1W | 1.2960 (2) | 1.0124 (2) | 0.01396 (18) | 0.0302 (4) | |
O2W | 0.4705 (2) | 1.0180 (2) | 0.7446 (2) | 0.0368 (4) | |
O3W | 1.1602 (3) | 0.3170 (2) | 0.7440 (2) | 0.0429 (5) | |
O4W | 1.4305 (3) | 0.3230 (2) | 0.9773 (2) | 0.0427 (5) | |
O5W | 0.5293 (3) | 1.3148 (2) | 0.7010 (3) | 0.0511 (6) | |
H11W | 1.229 (4) | 1.053 (4) | 0.064 (3) | 0.047 (10)* | |
H12W | 1.230 (4) | 1.012 (5) | −0.042 (3) | 0.067 (13)* | |
H21W | 0.564 (3) | 0.965 (3) | 0.719 (3) | 0.039 (9)* | |
H22W | 0.406 (4) | 0.968 (4) | 0.753 (4) | 0.047 (10)* | |
H31W | 1.103 (4) | 0.416 (2) | 0.718 (4) | 0.058 (11)* | |
H32W | 1.089 (4) | 0.276 (4) | 0.749 (4) | 0.067 (13)* | |
H41W | 1.347 (4) | 0.414 (3) | 0.939 (4) | 0.066 (13)* | |
H42W | 1.415 (6) | 0.289 (5) | 1.059 (2) | 0.081 (15)* | |
H51W | 0.615 (3) | 1.265 (3) | 0.667 (3) | 0.049 (10)* | |
H52W | 0.494 (4) | 1.413 (2) | 0.660 (3) | 0.054 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
V1 | 0.01202 (14) | 0.01221 (14) | 0.01500 (15) | −0.00463 (11) | 0.00070 (11) | −0.00394 (11) |
V2 | 0.01828 (16) | 0.01105 (14) | 0.01692 (16) | −0.00441 (12) | 0.00011 (12) | −0.00478 (12) |
V3 | 0.01893 (16) | 0.01500 (15) | 0.01711 (16) | −0.00706 (13) | 0.00116 (12) | −0.00126 (12) |
V4 | 0.01863 (16) | 0.01432 (15) | 0.01333 (15) | −0.00507 (12) | −0.00040 (12) | −0.00486 (12) |
V5 | 0.01524 (15) | 0.01448 (15) | 0.01869 (16) | −0.00318 (12) | −0.00345 (12) | −0.00231 (12) |
O2 | 0.0261 (8) | 0.0181 (7) | 0.0278 (8) | −0.0067 (6) | 0.0014 (6) | −0.0123 (6) |
O3 | 0.0318 (9) | 0.0267 (8) | 0.0257 (8) | −0.0158 (7) | 0.0056 (7) | −0.0019 (7) |
O4 | 0.0277 (8) | 0.0241 (8) | 0.0201 (7) | −0.0099 (6) | 0.0023 (6) | −0.0117 (6) |
O5 | 0.0204 (7) | 0.0228 (8) | 0.0298 (9) | −0.0028 (6) | −0.0067 (6) | −0.0064 (7) |
O6 | 0.0133 (6) | 0.0118 (6) | 0.0145 (6) | −0.0036 (5) | 0.0003 (5) | −0.0036 (5) |
O7 | 0.0144 (6) | 0.0130 (6) | 0.0168 (6) | −0.0054 (5) | 0.0005 (5) | −0.0053 (5) |
O8 | 0.0141 (6) | 0.0130 (6) | 0.0152 (6) | −0.0040 (5) | 0.0011 (5) | −0.0054 (5) |
O13 | 0.0166 (6) | 0.0164 (6) | 0.0183 (7) | −0.0074 (5) | 0.0019 (5) | −0.0040 (5) |
O15 | 0.0141 (6) | 0.0178 (7) | 0.0197 (7) | −0.0052 (5) | −0.0003 (5) | −0.0054 (5) |
O23 | 0.0215 (7) | 0.0132 (6) | 0.0212 (7) | −0.0073 (5) | 0.0004 (5) | −0.0040 (5) |
O25 | 0.0169 (6) | 0.0130 (6) | 0.0219 (7) | −0.0020 (5) | −0.0010 (5) | −0.0054 (5) |
O34 | 0.0216 (7) | 0.0183 (7) | 0.0152 (6) | −0.0077 (6) | 0.0024 (5) | −0.0043 (5) |
O35 | 0.0211 (7) | 0.0151 (6) | 0.0179 (7) | −0.0055 (6) | −0.0021 (5) | −0.0003 (5) |
O45 | 0.0181 (7) | 0.0175 (7) | 0.0168 (7) | −0.0054 (5) | −0.0030 (5) | −0.0045 (5) |
K1 | 0.0296 (3) | 0.0270 (2) | 0.0378 (3) | −0.0107 (2) | 0.0032 (2) | −0.0141 (2) |
K2 | 0.0668 (5) | 0.0434 (4) | 0.0374 (4) | 0.0147 (3) | −0.0052 (3) | −0.0130 (3) |
Na1 | 0.0298 (5) | 0.0238 (4) | 0.0265 (5) | −0.0123 (4) | 0.0018 (4) | −0.0075 (4) |
O1W | 0.0250 (8) | 0.0381 (10) | 0.0239 (8) | −0.0100 (7) | 0.0032 (7) | −0.0110 (7) |
O2W | 0.0299 (9) | 0.0437 (11) | 0.0559 (13) | −0.0211 (9) | 0.0183 (9) | −0.0347 (10) |
O3W | 0.0377 (11) | 0.0196 (8) | 0.0636 (14) | −0.0086 (8) | −0.0177 (10) | −0.0072 (9) |
O4W | 0.0594 (14) | 0.0279 (10) | 0.0266 (10) | −0.0045 (9) | −0.0088 (9) | −0.0082 (8) |
O5W | 0.0537 (13) | 0.0235 (9) | 0.0639 (15) | −0.0127 (9) | 0.0389 (12) | −0.0106 (10) |
V1—O15 | 1.6790 (14) | O6—V5i | 2.2819 (14) |
V1—O13 | 1.7052 (15) | O6—V3i | 2.3597 (14) |
V1—O7 | 1.9135 (14) | O7—K1ii | 2.9097 (15) |
V1—O8 | 1.9213 (14) | O8—V4i | 1.9909 (14) |
V1—O6 | 2.0828 (14) | O8—V2i | 2.0076 (14) |
V1—O6i | 2.1276 (13) | O13—K1ii | 2.9411 (16) |
V1—V5i | 3.0515 (5) | O15—V5i | 2.0670 (15) |
V1—V3 | 3.0907 (5) | O15—K1iii | 2.7968 (15) |
V1—K1ii | 3.6599 (7) | O23—K1ii | 2.9679 (16) |
V1—K1iii | 4.0665 (7) | O34—V3i | 1.8789 (15) |
V2—O2 | 1.6147 (16) | O34—K2v | 3.1619 (17) |
V2—O23 | 1.8140 (16) | O35—K2iv | 3.0754 (18) |
V2—O25 | 1.8221 (15) | O45—V5i | 1.8897 (15) |
V2—O7 | 1.9903 (14) | O45—K2v | 2.9614 (17) |
V2—O8i | 2.0076 (14) | K1—O15viii | 2.7968 (15) |
V2—O6i | 2.2475 (14) | K1—O7ii | 2.9097 (15) |
V2—V4 | 3.0708 (5) | K1—O3W | 2.930 (3) |
V2—V5 | 3.0878 (5) | K1—O2Wviii | 2.934 (2) |
V2—K1ii | 3.7836 (7) | K1—O13ii | 2.9411 (16) |
V2—K1 | 4.0143 (7) | K1—O23ii | 2.9679 (16) |
V3—O3 | 1.5925 (17) | K1—O5Wviii | 3.043 (3) |
V3—O35 | 1.8525 (15) | K1—V1ii | 3.6599 (7) |
V3—O23 | 1.8787 (16) | K1—Na1ii | 3.7780 (12) |
V3—O34i | 1.8789 (15) | K1—V2ii | 3.7836 (7) |
V3—O13 | 2.0144 (15) | K1—V5vi | 3.8581 (7) |
V3—O6i | 2.3597 (14) | K2—O4vi | 2.8197 (17) |
V3—V5 | 3.0764 (5) | K2—O4W | 2.883 (3) |
V3—V4i | 3.1177 (5) | K2—O45ix | 2.9614 (17) |
V3—K1ii | 3.9658 (7) | K2—O35iv | 3.0754 (18) |
V3—K2iv | 4.0101 (10) | K2—O34ix | 3.1619 (17) |
V4—O4 | 1.6204 (15) | K2—O5Wviii | 3.300 (3) |
V4—O45 | 1.8146 (15) | K2—O3x | 3.398 (2) |
V4—O34 | 1.8174 (15) | K2—V4ix | 3.7773 (9) |
V4—O8i | 1.9909 (14) | K2—V5iv | 3.8160 (9) |
V4—O7 | 2.0143 (14) | K2—Na1ii | 3.9576 (15) |
V4—O6 | 2.2206 (14) | K2—V3iv | 4.0101 (10) |
V4—V5i | 3.1058 (5) | Na1—O5Wxi | 2.315 (2) |
V4—V3i | 3.1177 (5) | Na1—O4Wii | 2.320 (2) |
V4—K2v | 3.7773 (9) | Na1—O2Wxi | 2.324 (2) |
V5—O5 | 1.6077 (16) | Na1—O3Wii | 2.353 (2) |
V5—O35 | 1.8203 (16) | Na1—O1Wvii | 2.398 (2) |
V5—O25 | 1.8593 (15) | Na1—O1Wxii | 2.434 (2) |
V5—O45i | 1.8897 (15) | Na1—Na1xiii | 3.4175 (19) |
V5—O15i | 2.0670 (15) | Na1—K1ii | 3.7780 (12) |
V5—O6i | 2.2819 (14) | Na1—K2ii | 3.9576 (15) |
V5—V1i | 3.0515 (5) | O1W—Na1x | 2.398 (2) |
V5—V4i | 3.1058 (5) | O1W—Na1xii | 2.434 (2) |
V5—K2iv | 3.8160 (9) | O2W—Na1xi | 2.324 (2) |
V5—K1vi | 3.8581 (7) | O2W—K1iii | 2.934 (2) |
O2—K1 | 2.8613 (17) | O3W—Na1ii | 2.353 (2) |
O3—K2vii | 3.398 (2) | O4W—Na1ii | 2.320 (2) |
O4—K2vi | 2.8197 (17) | O5W—Na1xi | 2.315 (2) |
O5—K2 | 2.7827 (17) | O5W—K1iii | 3.043 (3) |
O6—V1i | 2.1276 (13) | O5W—K2iii | 3.300 (3) |
O6—V2i | 2.2475 (14) | ||
O15—V1—O13 | 106.38 (7) | O15i—V5—K2iv | 131.13 (5) |
O15—V1—O7 | 98.08 (7) | O6i—V5—K2iv | 102.16 (4) |
O13—V1—O7 | 96.15 (7) | V1i—V5—K2iv | 125.554 (17) |
O15—V1—O8 | 97.10 (7) | V3—V5—K2iv | 70.220 (19) |
O13—V1—O8 | 97.06 (7) | V2—V5—K2iv | 131.09 (2) |
O7—V1—O8 | 156.18 (6) | V4i—V5—K2iv | 65.206 (15) |
O15—V1—O6 | 88.31 (6) | O5—V5—K1vi | 63.46 (7) |
O13—V1—O6 | 165.31 (6) | O35—V5—K1vi | 150.57 (5) |
O7—V1—O6 | 81.12 (6) | O25—V5—K1vi | 64.79 (5) |
O8—V1—O6 | 81.09 (6) | O45i—V5—K1vi | 117.53 (5) |
O15—V1—O6i | 166.79 (7) | O15i—V5—K1vi | 44.71 (4) |
O13—V1—O6i | 86.81 (6) | O6i—V5—K1vi | 109.31 (4) |
O7—V1—O6i | 80.82 (6) | V1i—V5—K1vi | 71.015 (14) |
O8—V1—O6i | 80.21 (6) | V3—V5—K1vi | 147.784 (16) |
O6—V1—O6i | 78.51 (6) | V2—V5—K1vi | 86.845 (14) |
O15—V1—V5i | 39.93 (5) | V4i—V5—K1vi | 126.360 (16) |
O13—V1—V5i | 146.31 (5) | K2iv—V5—K1vi | 141.86 (2) |
O7—V1—V5i | 90.49 (4) | V2—O2—K1 | 125.15 (8) |
O8—V1—V5i | 89.44 (4) | V3—O3—K2vii | 147.01 (10) |
O6—V1—V5i | 48.38 (4) | V4—O4—K2vi | 150.08 (9) |
O6i—V1—V5i | 126.88 (4) | V5—O5—K2 | 144.90 (10) |
O15—V1—V3 | 143.51 (5) | V1—O6—V1i | 101.49 (6) |
O13—V1—V3 | 37.14 (5) | V1—O6—V4 | 94.07 (5) |
O7—V1—V3 | 89.30 (4) | V1i—O6—V4 | 93.00 (5) |
O8—V1—V3 | 89.34 (4) | V1—O6—V2i | 93.82 (5) |
O6—V1—V3 | 128.18 (4) | V1i—O6—V2i | 92.31 (5) |
O6i—V1—V3 | 49.67 (4) | V4—O6—V2i | 169.43 (7) |
V5i—V1—V3 | 176.520 (15) | V1—O6—V5i | 88.59 (5) |
O15—V1—K1ii | 85.13 (5) | V1i—O6—V5i | 169.87 (7) |
O13—V1—K1ii | 52.19 (5) | V4—O6—V5i | 87.22 (5) |
O7—V1—K1ii | 52.17 (4) | V2i—O6—V5i | 85.95 (5) |
O8—V1—K1ii | 147.85 (5) | V1—O6—V3i | 171.60 (7) |
O6—V1—K1ii | 131.06 (4) | V1i—O6—V3i | 86.90 (5) |
O6i—V1—K1ii | 104.08 (4) | V4—O6—V3i | 85.74 (5) |
V5i—V1—K1ii | 111.119 (15) | V2i—O6—V3i | 85.43 (5) |
V3—V1—K1ii | 71.389 (14) | V5i—O6—V3i | 83.01 (5) |
O15—V1—K1iii | 32.37 (5) | V1—O7—V2 | 107.90 (7) |
O13—V1—K1iii | 86.04 (5) | V1—O7—V4 | 106.63 (6) |
O7—V1—K1iii | 125.97 (4) | V2—O7—V4 | 100.13 (6) |
O8—V1—K1iii | 74.76 (4) | V1—O7—K1ii | 96.53 (5) |
O6—V1—K1iii | 107.31 (4) | V2—O7—K1ii | 99.38 (5) |
O6i—V1—K1iii | 152.87 (4) | V4—O7—K1ii | 143.20 (6) |
V5i—V1—K1iii | 63.785 (14) | V1—O8—V4i | 107.47 (6) |
V3—V1—K1iii | 118.970 (15) | V1—O8—V2i | 107.28 (7) |
K1ii—V1—K1iii | 91.982 (14) | V4i—O8—V2i | 100.34 (6) |
O2—V2—O23 | 103.34 (8) | V1—O13—V3 | 112.12 (7) |
O2—V2—O25 | 102.01 (8) | V1—O13—K1ii | 100.55 (6) |
O23—V2—O25 | 95.48 (7) | V3—O13—K1ii | 104.76 (6) |
O2—V2—O7 | 100.76 (7) | V1—O15—V5i | 108.65 (7) |
O23—V2—O7 | 89.93 (6) | V1—O15—K1iii | 128.88 (8) |
O25—V2—O7 | 154.66 (6) | V5i—O15—K1iii | 103.96 (6) |
O2—V2—O8i | 99.83 (7) | V2—O23—V3 | 115.68 (8) |
O23—V2—O8i | 154.90 (6) | V2—O23—K1ii | 101.88 (6) |
O25—V2—O8i | 88.97 (6) | V3—O23—K1ii | 107.70 (6) |
O7—V2—O8i | 76.29 (6) | V2—O25—V5 | 114.02 (8) |
O2—V2—O6i | 174.71 (7) | V4—O34—V3i | 115.01 (8) |
O23—V2—O6i | 81.16 (6) | V4—O34—K2v | 94.83 (6) |
O25—V2—O6i | 80.13 (6) | V3i—O34—K2v | 102.40 (6) |
O7—V2—O6i | 76.27 (5) | V5—O35—V3 | 113.77 (8) |
O8i—V2—O6i | 75.28 (5) | V5—O35—K2iv | 99.20 (7) |
O2—V2—V4 | 90.33 (6) | V3—O35—K2iv | 106.26 (7) |
O23—V2—V4 | 130.15 (5) | V4—O45—V5i | 113.94 (7) |
O25—V2—V4 | 128.60 (5) | V4—O45—K2v | 101.84 (6) |
O7—V2—V4 | 40.22 (4) | V5i—O45—K2v | 101.45 (6) |
O8i—V2—V4 | 39.63 (4) | O15viii—K1—O2 | 122.38 (5) |
O6i—V2—V4 | 84.59 (4) | O15viii—K1—O7ii | 112.26 (4) |
O2—V2—V5 | 135.16 (6) | O2—K1—O7ii | 119.89 (5) |
O23—V2—V5 | 83.51 (5) | O15viii—K1—O3W | 140.35 (5) |
O25—V2—V5 | 33.37 (5) | O2—K1—O3W | 83.44 (5) |
O7—V2—V5 | 123.74 (4) | O7ii—K1—O3W | 68.43 (5) |
O8i—V2—V5 | 86.87 (4) | O15viii—K1—O2Wviii | 78.18 (5) |
O6i—V2—V5 | 47.49 (3) | O2—K1—O2Wviii | 142.96 (5) |
V4—V2—V5 | 119.160 (15) | O7ii—K1—O2Wviii | 67.79 (5) |
O2—V2—K1ii | 83.13 (6) | O3W—K1—O2Wviii | 65.29 (5) |
O23—V2—K1ii | 50.14 (5) | O15viii—K1—O13ii | 73.60 (4) |
O25—V2—K1ii | 145.01 (5) | O2—K1—O13ii | 118.76 (5) |
O7—V2—K1ii | 49.35 (4) | O7ii—K1—O13ii | 54.87 (4) |
O8i—V2—K1ii | 124.65 (4) | O3W—K1—O13ii | 123.04 (5) |
O6i—V2—K1ii | 97.92 (4) | O2Wviii—K1—O13ii | 95.64 (5) |
V4—V2—K1ii | 85.470 (15) | O15viii—K1—O23ii | 121.37 (5) |
V5—V2—K1ii | 128.645 (16) | O2—K1—O23ii | 75.93 (5) |
O2—V2—K1 | 35.65 (6) | O7ii—K1—O23ii | 54.49 (4) |
O23—V2—K1 | 79.34 (5) | O3W—K1—O23ii | 92.15 (5) |
O25—V2—K1 | 78.51 (5) | O2Wviii—K1—O23ii | 122.28 (5) |
O7—V2—K1 | 126.83 (4) | O13ii—K1—O23ii | 51.92 (4) |
O8i—V2—K1 | 125.71 (4) | O15viii—K1—O5Wviii | 86.93 (5) |
O6i—V2—K1 | 149.38 (4) | O2—K1—O5Wviii | 84.96 (5) |
V4—V2—K1 | 125.974 (15) | O7ii—K1—O5Wviii | 122.61 (5) |
V5—V2—K1 | 106.688 (15) | O3W—K1—O5Wviii | 64.17 (6) |
K1ii—V2—K1 | 87.394 (14) | O2Wviii—K1—O5Wviii | 64.26 (5) |
O3—V3—O35 | 104.92 (8) | O13ii—K1—O5Wviii | 154.86 (5) |
O3—V3—O23 | 101.60 (8) | O23ii—K1—O5Wviii | 151.29 (5) |
O35—V3—O23 | 90.92 (7) | O15viii—K1—V1ii | 84.19 (3) |
O3—V3—O34i | 104.09 (8) | O2—K1—V1ii | 134.01 (4) |
O35—V3—O34i | 89.87 (7) | O7ii—K1—V1ii | 31.29 (3) |
O23—V3—O34i | 153.16 (7) | O3W—K1—V1ii | 98.76 (4) |
O3—V3—O13 | 100.72 (8) | O2Wviii—K1—V1ii | 73.12 (4) |
O35—V3—O13 | 154.35 (7) | O13ii—K1—V1ii | 27.26 (3) |
O23—V3—O13 | 83.21 (6) | O23ii—K1—V1ii | 58.11 (3) |
O34i—V3—O13 | 84.55 (6) | O5Wviii—K1—V1ii | 137.38 (4) |
O3—V3—O6i | 174.76 (8) | O15viii—K1—Na1ii | 102.23 (4) |
O35—V3—O6i | 80.19 (6) | O2—K1—Na1ii | 105.01 (4) |
O23—V3—O6i | 76.91 (6) | O7ii—K1—Na1ii | 84.83 (3) |
O34i—V3—O6i | 76.81 (6) | O3W—K1—Na1ii | 38.52 (4) |
O13—V3—O6i | 74.16 (5) | O2Wviii—K1—Na1ii | 37.95 (4) |
O3—V3—V5 | 137.67 (7) | O13ii—K1—Na1ii | 130.67 (4) |
O35—V3—V5 | 32.79 (5) | O23ii—K1—Na1ii | 127.93 (4) |
O23—V3—V5 | 82.87 (5) | O5Wviii—K1—Na1ii | 37.78 (4) |
O34i—V3—V5 | 83.37 (5) | V1ii—K1—Na1ii | 104.38 (2) |
O13—V3—V5 | 121.56 (4) | O15viii—K1—V2ii | 132.59 (4) |
O6i—V3—V5 | 47.41 (3) | O2—K1—V2ii | 89.79 (4) |
O3—V3—V1 | 131.45 (7) | O7ii—K1—V2ii | 31.27 (3) |
O35—V3—V1 | 123.61 (5) | O3W—K1—V2ii | 69.43 (4) |
O23—V3—V1 | 78.29 (5) | O2Wviii—K1—V2ii | 96.79 (4) |
O34i—V3—V1 | 78.99 (5) | O13ii—K1—V2ii | 59.88 (3) |
O13—V3—V1 | 30.74 (4) | O23ii—K1—V2ii | 27.98 (3) |
O6i—V3—V1 | 43.42 (3) | O5Wviii—K1—V2ii | 133.60 (4) |
V5—V3—V1 | 90.832 (14) | V1ii—K1—V2ii | 50.150 (11) |
O3—V3—V4i | 135.96 (7) | Na1ii—K1—V2ii | 101.17 (2) |
O35—V3—V4i | 80.84 (5) | O15viii—K1—V5vi | 31.33 (3) |
O23—V3—V4i | 122.16 (5) | O2—K1—V5vi | 91.39 (4) |
O34i—V3—V4i | 31.89 (5) | O7ii—K1—V5vi | 135.67 (3) |
O13—V3—V4i | 81.29 (4) | O3W—K1—V5vi | 152.08 (4) |
O6i—V3—V4i | 45.26 (3) | O2Wviii—K1—V5vi | 106.79 (4) |
V5—V3—V4i | 60.183 (12) | O13ii—K1—V5vi | 83.43 (3) |
V1—V3—V4i | 61.077 (12) | O23ii—K1—V5vi | 113.24 (4) |
O3—V3—K1ii | 84.22 (7) | O5Wviii—K1—V5vi | 88.09 (4) |
O35—V3—K1ii | 136.19 (5) | V1ii—K1—V5vi | 104.390 (16) |
O23—V3—K1ii | 45.48 (5) | Na1ii—K1—V5vi | 118.73 (2) |
O34i—V3—K1ii | 130.10 (5) | V2ii—K1—V5vi | 138.190 (18) |
O13—V3—K1ii | 45.82 (4) | O5—K2—O4vi | 130.10 (6) |
O6i—V3—K1ii | 91.27 (4) | O5—K2—O4W | 72.15 (6) |
V5—V3—K1ii | 122.892 (16) | O4vi—K2—O4W | 118.95 (6) |
V1—V3—K1ii | 60.999 (13) | O5—K2—O45ix | 123.43 (6) |
V4i—V3—K1ii | 122.022 (15) | O4vi—K2—O45ix | 103.65 (5) |
O3—V3—K2iv | 89.01 (7) | O4W—K2—O45ix | 66.61 (5) |
O35—V3—K2iv | 47.41 (5) | O5—K2—O35iv | 93.48 (5) |
O23—V3—K2iv | 138.22 (5) | O4vi—K2—O35iv | 131.48 (5) |
O34i—V3—K2iv | 50.36 (5) | O4W—K2—O35iv | 91.17 (5) |
O13—V3—K2iv | 134.79 (5) | O45ix—K2—O35iv | 51.91 (4) |
O6i—V3—K2iv | 95.43 (4) | O5—K2—O34ix | 139.60 (6) |
V5—V3—K2iv | 63.568 (17) | O4vi—K2—O34ix | 81.62 (5) |
V1—V3—K2iv | 123.520 (18) | O4W—K2—O34ix | 118.17 (6) |
V4i—V3—K2iv | 62.534 (17) | O45ix—K2—O34ix | 51.64 (4) |
K1ii—V3—K2iv | 173.05 (2) | O35iv—K2—O34ix | 49.97 (4) |
O4—V4—O45 | 102.88 (8) | O5—K2—O5Wviii | 70.03 (5) |
O4—V4—O34 | 102.79 (8) | O4vi—K2—O5Wviii | 75.39 (5) |
O45—V4—O34 | 94.78 (7) | O4W—K2—O5Wviii | 60.42 (6) |
O4—V4—O8i | 99.48 (7) | O45ix—K2—O5Wviii | 116.16 (6) |
O45—V4—O8i | 155.08 (6) | O35iv—K2—O5Wviii | 150.03 (5) |
O34—V4—O8i | 90.84 (6) | O34ix—K2—O5Wviii | 150.27 (5) |
O4—V4—O7 | 99.29 (7) | O5—K2—O3x | 63.33 (5) |
O45—V4—O7 | 89.45 (6) | O4vi—K2—O3x | 109.23 (6) |
O34—V4—O7 | 155.94 (6) | O4W—K2—O3x | 128.55 (6) |
O8i—V4—O7 | 76.13 (6) | O45ix—K2—O3x | 119.25 (5) |
O4—V4—O6 | 174.08 (7) | O35iv—K2—O3x | 68.10 (5) |
O45—V4—O6 | 80.33 (6) | O34ix—K2—O3x | 84.42 (5) |
O34—V4—O6 | 81.75 (6) | O5Wviii—K2—O3x | 120.75 (5) |
O8i—V4—O6 | 76.49 (5) | O5—K2—V4ix | 147.76 (5) |
O7—V4—O6 | 75.64 (5) | O4vi—K2—V4ix | 82.13 (4) |
O4—V4—V2 | 89.18 (6) | O4W—K2—V4ix | 92.67 (5) |
O45—V4—V2 | 129.10 (5) | O45ix—K2—V4ix | 28.05 (3) |
O34—V4—V2 | 130.87 (5) | O35iv—K2—V4ix | 57.70 (3) |
O8i—V4—V2 | 40.03 (4) | O34ix—K2—V4ix | 28.65 (3) |
O7—V4—V2 | 39.65 (4) | O5Wviii—K2—V4ix | 127.41 (5) |
O6—V4—V2 | 84.95 (4) | O3x—K2—V4ix | 111.41 (4) |
O4—V4—V5i | 136.49 (6) | O5—K2—V5iv | 99.53 (4) |
O45—V4—V5i | 33.79 (5) | O4vi—K2—V5iv | 130.22 (4) |
O34—V4—V5i | 83.45 (5) | O4W—K2—V5iv | 67.48 (4) |
O8i—V4—V5i | 123.68 (4) | O45ix—K2—V5iv | 29.03 (3) |
O7—V4—V5i | 87.11 (4) | O35iv—K2—V5iv | 28.09 (3) |
O6—V4—V5i | 47.21 (4) | O34ix—K2—V5iv | 57.69 (3) |
V2—V4—V5i | 119.319 (15) | O5Wviii—K2—V5iv | 127.63 (5) |
O4—V4—V3i | 135.80 (6) | O3x—K2—V5iv | 95.12 (4) |
O45—V4—V3i | 84.29 (5) | V4ix—K2—V5iv | 48.284 (13) |
O34—V4—V3i | 33.10 (5) | O5—K2—Na1ii | 87.78 (5) |
O8i—V4—V3i | 87.34 (4) | O4vi—K2—Na1ii | 84.38 (4) |
O7—V4—V3i | 124.58 (4) | O4W—K2—Na1ii | 35.44 (5) |
O6—V4—V3i | 49.00 (4) | O45ix—K2—Na1ii | 80.42 (4) |
V2—V4—V3i | 120.110 (14) | O35iv—K2—Na1ii | 122.59 (4) |
V5i—V4—V3i | 59.248 (12) | O34ix—K2—Na1ii | 124.13 (4) |
O4—V4—K2v | 81.14 (6) | O5Wviii—K2—Na1ii | 35.77 (4) |
O45—V4—K2v | 50.11 (5) | O3x—K2—Na1ii | 150.56 (4) |
O34—V4—K2v | 56.52 (5) | V4ix—K2—Na1ii | 95.95 (3) |
O8i—V4—K2v | 146.06 (5) | V5iv—K2—Na1ii | 95.20 (3) |
O7—V4—K2v | 137.60 (4) | O5—K2—V3iv | 112.54 (4) |
O6—V4—K2v | 104.64 (4) | O4vi—K2—V3iv | 106.14 (4) |
V2—V4—K2v | 169.35 (2) | O4W—K2—V3iv | 113.67 (5) |
V5i—V4—K2v | 66.510 (16) | O45ix—K2—V3iv | 56.92 (3) |
V3i—V4—K2v | 70.383 (19) | O35iv—K2—V3iv | 26.33 (3) |
O5—V5—O35 | 105.10 (8) | O34ix—K2—V3iv | 27.23 (3) |
O5—V5—O25 | 100.58 (8) | O5Wviii—K2—V3iv | 173.05 (5) |
O35—V5—O25 | 93.10 (7) | O3x—K2—V3iv | 65.45 (4) |
O5—V5—O45i | 102.48 (8) | V4ix—K2—V3iv | 47.084 (12) |
O35—V5—O45i | 90.89 (7) | V5iv—K2—V3iv | 46.212 (12) |
O25—V5—O45i | 154.67 (6) | Na1ii—K2—V3iv | 137.29 (3) |
O5—V5—O15i | 97.45 (8) | O5Wxi—Na1—O4Wii | 85.01 (9) |
O35—V5—O15i | 157.44 (6) | O5Wxi—Na1—O2Wxi | 86.54 (9) |
O25—V5—O15i | 83.43 (6) | O4Wii—Na1—O2Wxi | 169.82 (9) |
O45i—V5—O15i | 83.35 (6) | O5Wxi—Na1—O3Wii | 85.66 (10) |
O5—V5—O6i | 171.89 (8) | O4Wii—Na1—O3Wii | 99.87 (8) |
O35—V5—O6i | 83.01 (6) | O2Wxi—Na1—O3Wii | 85.11 (8) |
O25—V5—O6i | 78.47 (6) | O5Wxi—Na1—O1Wvii | 96.50 (9) |
O45i—V5—O6i | 77.22 (6) | O4Wii—Na1—O1Wvii | 88.19 (8) |
O15i—V5—O6i | 74.45 (5) | O2Wxi—Na1—O1Wvii | 87.14 (8) |
O5—V5—V1i | 128.87 (7) | O3Wii—Na1—O1Wvii | 171.82 (8) |
O35—V5—V1i | 126.04 (5) | O5Wxi—Na1—O1Wxii | 169.80 (10) |
O25—V5—V1i | 78.97 (5) | O4Wii—Na1—O1Wxii | 103.13 (8) |
O45i—V5—V1i | 78.48 (5) | O2Wxi—Na1—O1Wxii | 85.91 (8) |
O15i—V5—V1i | 31.42 (4) | O3Wii—Na1—O1Wxii | 86.87 (8) |
O6i—V5—V1i | 43.03 (4) | O1Wvii—Na1—O1Wxii | 89.96 (7) |
O5—V5—V3 | 138.52 (7) | O5Wxi—Na1—Na1xiii | 141.28 (8) |
O35—V5—V3 | 33.44 (5) | O4Wii—Na1—Na1xiii | 98.02 (7) |
O25—V5—V3 | 85.31 (5) | O2Wxi—Na1—Na1xiii | 85.07 (7) |
O45i—V5—V3 | 84.34 (5) | O3Wii—Na1—Na1xiii | 130.97 (8) |
O15i—V5—V3 | 124.03 (4) | O1Wvii—Na1—Na1xiii | 45.41 (5) |
O6i—V5—V3 | 49.58 (4) | O1Wxii—Na1—Na1xiii | 44.56 (5) |
V1i—V5—V3 | 92.608 (14) | O5Wxi—Na1—K1ii | 53.62 (8) |
O5—V5—V2 | 133.17 (7) | O4Wii—Na1—K1ii | 126.32 (6) |
O35—V5—V2 | 82.90 (5) | O2Wxi—Na1—K1ii | 50.93 (6) |
O25—V5—V2 | 32.62 (4) | O3Wii—Na1—K1ii | 50.84 (7) |
O45i—V5—V2 | 123.77 (5) | O1Wvii—Na1—K1ii | 124.80 (6) |
O15i—V5—V2 | 82.29 (4) | O1Wxii—Na1—K1ii | 116.18 (5) |
O6i—V5—V2 | 46.56 (3) | Na1xiii—Na1—K1ii | 135.61 (4) |
V1i—V5—V2 | 62.050 (12) | O5Wxi—Na1—K2ii | 56.44 (8) |
V3—V5—V2 | 60.950 (12) | O4Wii—Na1—K2ii | 46.10 (7) |
O5—V5—V4i | 134.74 (6) | O2Wxi—Na1—K2ii | 123.94 (6) |
O35—V5—V4i | 81.62 (5) | O3Wii—Na1—K2ii | 126.02 (6) |
O25—V5—V4i | 124.04 (5) | O1Wvii—Na1—K2ii | 61.01 (5) |
O45i—V5—V4i | 32.28 (4) | O1Wxii—Na1—K2ii | 133.75 (6) |
O15i—V5—V4i | 81.95 (4) | Na1xiii—Na1—K2ii | 98.77 (4) |
O6i—V5—V4i | 45.57 (3) | K1ii—Na1—K2ii | 110.03 (3) |
V1i—V5—V4i | 61.541 (12) | Na1x—O1W—Na1xii | 90.04 (7) |
V3—V5—V4i | 60.568 (12) | Na1xi—O2W—K1iii | 91.12 (7) |
V2—V5—V4i | 91.833 (14) | Na1ii—O3W—K1 | 90.64 (8) |
O5—V5—K2iv | 83.31 (7) | Na1ii—O4W—K2 | 98.46 (8) |
O35—V5—K2iv | 52.71 (5) | Na1xi—O5W—K1iii | 88.60 (9) |
O25—V5—K2iv | 144.80 (5) | Na1xi—O5W—K2iii | 87.79 (9) |
O45i—V5—K2iv | 49.52 (5) | K1iii—O5W—K2iii | 175.68 (8) |
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x−1, y+1, z; (iv) −x+3, −y+1, −z+2; (v) x−1, y+1, z−1; (vi) −x+3, −y+1, −z+1; (vii) x−1, y, z; (viii) x+1, y−1, z; (ix) x+1, y−1, z+1; (x) x+1, y, z; (xi) −x+1, −y+2, −z+1; (xii) −x+2, −y+2, −z; (xiii) −x+1, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | K4Na2[V10O28]·10H2O |
Mr | 1339.94 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.5893 (6), 10.3543 (6), 10.9893 (6) |
α, β, γ (°) | 69.194 (5), 87.122 (5), 66.172 (5) |
V (Å3) | 830.75 (9) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 3.33 |
Crystal size (mm) | 0.40 × 0.35 × 0.30 |
Data collection | |
Diffractometer | Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.252, 0.368 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5134, 4832, 4320 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.702 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.074, 1.10 |
No. of reflections | 4832 |
No. of parameters | 284 |
No. of restraints | 15 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 1.06, −1.28 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), SDP (Nonius, 1985), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick & Schneider, 1997), ORTEPIII (Burnett & Johnson, 1996).
V1—O15 | 1.6790 (14) | V3—O35 | 1.8525 (15) |
V1—O13 | 1.7052 (15) | V3—O23 | 1.8787 (16) |
V1—O7 | 1.9135 (14) | V3—O34i | 1.8789 (15) |
V1—O8 | 1.9213 (14) | V3—O13 | 2.0144 (15) |
V1—O6 | 2.0828 (14) | V3—O6i | 2.3597 (14) |
V1—O6i | 2.1276 (13) | V4—O4 | 1.6204 (15) |
V1—V5i | 3.0515 (5) | V4—O45 | 1.8146 (15) |
V1—V3 | 3.0907 (5) | V4—O34 | 1.8174 (15) |
V2—O2 | 1.6147 (16) | V4—O8i | 1.9909 (14) |
V2—O23 | 1.8140 (16) | V4—O7 | 2.0143 (14) |
V2—O25 | 1.8221 (15) | V5—O5 | 1.6077 (16) |
V2—O7 | 1.9903 (14) | V5—O35 | 1.8203 (16) |
V2—O8i | 2.0076 (14) | V5—O25 | 1.8593 (15) |
V2—O6i | 2.2475 (14) | V5—O45i | 1.8897 (15) |
V2—V4 | 3.0708 (5) | V5—O15i | 2.0670 (15) |
V2—V5 | 3.0878 (5) | V5—O6i | 2.2819 (14) |
V3—O3 | 1.5925 (17) |
Symmetry code: (i) −x+2, −y+2, −z+1. |
In the course of our work with Schiff base vanadium complexes, several polyoxovanadates formed, particularly crystalline decavanadates (Cavaco et al., 1995; Costa Pessoa et al., 1998, 1999). In the present case, we isolated the title compound, (I), while attempting to obtain N-salicylidenetyrosinate (sal–Tyr) oxovanadium complexes. The hydrolysis of vanadium(V) is very complex, but by combination of potentiometric and 51V NMR spectroscopy, its speciation was determined in the whole pH range (Pettersson et al., 1983). In the slightly acid pH range (3.0–5.5), yellow–orange decavanadates [HnV10O28](6-n)- form. The hydrolysis of vanadium(IV) is also quite complex. On increasing the pH starting in the acid range, VIVO2+ hydroxide precipitates in the pH range 4–8 (Boas & Costa Pessoa, 1987). In the present case, the pH is ~5, but the sal–Tyr ligand coordinates to VIVO2+ and hinders the precipitation of the hydroxide. The VO(sal–Tyr) complex is soluble, it does not precipitate and the formation of a compound of VV may then be explained by the slow oxidation of VIVO2+ by atmospheric oxygen. Decavanadates being the dominant VV species at pH ~5 therefore form slowly as crystalline compounds. This explains why several decavanadate salts have been obtained by our group under relatively similar conditions. In particular, this compound is isostructural with the disodium tetraammonium salt (Cavaco et al., 1995), with the replacement of NH4+ by K+ ions. Valence bond calculations show that all V—O and V═O bond distances are consistent with the non-protonation of the decavanadate ion, thus confirming the assumed overall charge of -6.