Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803012054/ya6164sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803012054/ya6164Isup2.hkl |
CCDC reference: 204404
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.006 Å
- R factor = 0.067
- wR factor = 0.151
- Data-to-parameter ratio = 10.7
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level B:
ABSTM_02 Alert B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75 Tmin and Tmax reported: 0.390 0.862 Tmin' and Tmax expected: 0.786 0.899 RR' = 0.517 Please check that your absorption correction is appropriate.
Alert Level C:
PLAT_731 Alert C Bond Calc 0.87(3), Rep 0.860(10) ...... 3.00 su-Rat O1W -H1W2 1.555 1.555 PLAT_731 Alert C Bond Calc 0.85(3), Rep 0.850(10) ...... 3.00 su-Rat O2W -H2W1 1.555 1.555 PLAT_731 Alert C Bond Calc 0.84(3), Rep 0.840(10) ...... 3.00 su-Rat O2W -H2W2 1.555 1.555 PLAT_731 Alert C Bond Calc 0.85(4), Rep 0.850(10) ...... 4.00 su-Rat O3W -H3W1 1.555 1.555 PLAT_731 Alert C Bond Calc 0.85(4), Rep 0.850(10) ...... 4.00 su-Rat O3W -H3W2 1.555 1.555 PLAT_735 Alert C D-H Calc 0.87(3), Rep 0.860(10) ...... 3.00 su-Rat O1W -H1W2 1.555 1.555 PLAT_735 Alert C D-H Calc 0.85(3), Rep 0.850(10) ...... 3.00 su-Rat O1W -H1W1 1.555 1.555 PLAT_735 Alert C D-H Calc 0.85(3), Rep 0.850(10) ...... 3.00 su-Rat O2W -H2W1 1.555 1.555 PLAT_735 Alert C D-H Calc 0.84(3), Rep 0.840(10) ...... 3.00 su-Rat O2W -H2W2 1.555 1.555 PLAT_735 Alert C D-H Calc 0.85(4), Rep 0.850(10) ...... 4.00 su-Rat O3W -H3W1 1.555 1.555 PLAT_735 Alert C D-H Calc 0.85(4), Rep 0.850(10) ...... 4.00 su-Rat O3W -H3W2 1.555 1.555 PLAT_736 Alert C H...A Calc 1.94(3), Rep 1.940(10) ...... 3.00 su-Rat H1W1 -O5 1.555 1.545 PLAT_736 Alert C H...A Calc 1.87(3), Rep 1.870(10) ...... 3.00 su-Rat H2W1 -O2 1.555 1.655
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
13 Alert Level C = Please check
The compound was synthesized hydrothermally from the reaction of ammonium metavanadate (0.12 g, 1 mmol), triethylenetetraaminehexaacetic acid (0.15 g, 0.5 mmol) and sodium hydroxide (0.12 g, 3 mmol); the pH of the solution was approximately 7. The solution was heated in a steel bomb to 453 K and was kept at this temperature for 72 h. The bomb was then cooled to room temperature at the rate of 5 K per hour. Blue polyhedral crystals separated from the solution in about 50% yield.
One of the two independent Na atoms (Na1) is disordered over an inversion center at (1/2,0,1/2); the PART −1 command in SHELXL97 was used for its refinement. The water H atoms were located and refined subject to the O—H = 0.85 (1) and H···H = 1.39 (1) Å constraints; their temperature factors were set to 1.2 times those of the equivalent isotropic temperature factors of the parent O atoms. The C-bound H atoms were positioned geometrically (C—H = 0.97 Å) and were included in the refinement in the riding model approximation; their temperature factors were treated similarly as those of the water H atoms.
Although the diffraction data were collected up to a 2θ of 55°, the use of the reflections with 2θ > 50° led to an R-index higher than 0.070. The 2θ limit was therefore set to 50° in the final refinement.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-II (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
(Na+)2·C18H24N4O14V22−·6(H2O) | F(000) = 800 |
Mr = 776.37 | Dx = 1.756 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.7086 (2) Å | Cell parameters from 2808 reflections |
b = 10.5746 (3) Å | θ = 2.0–27.0° |
c = 20.9333 (5) Å | µ = 0.76 mm−1 |
β = 98.678 (1)° | T = 298 K |
V = 1468.02 (7) Å3 | Block, blue |
Z = 2 | 0.31 × 0.21 × 0.14 mm |
Bruker APEX area-detector diffractometer | 2485 independent reflections |
Radiation source: fine-focus sealed tube | 2162 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
ϕ and ω scan | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan SADABS (Sheldrick, 1996) | h = −5→7 |
Tmin = 0.390, Tmax = 0.862 | k = −12→11 |
7204 measured reflections | l = −13→24 |
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 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.151 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.21 | w = 1/[σ2(Fo2) + (0.0674P)2] where P = (Fo2 + 2Fc2)/3 |
2485 reflections | (Δ/σ)max < 0.001 |
232 parameters | Δρmax = 0.58 e Å−3 |
9 restraints | Δρmin = −0.35 e Å−3 |
(Na+)2·C18H24N4O14V22−·6(H2O) | V = 1468.02 (7) Å3 |
Mr = 776.37 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.7086 (2) Å | µ = 0.76 mm−1 |
b = 10.5746 (3) Å | T = 298 K |
c = 20.9333 (5) Å | 0.31 × 0.21 × 0.14 mm |
β = 98.678 (1)° |
Bruker APEX area-detector diffractometer | 2485 independent reflections |
Absorption correction: multi-scan SADABS (Sheldrick, 1996) | 2162 reflections with I > 2σ(I) |
Tmin = 0.390, Tmax = 0.862 | Rint = 0.054 |
7204 measured reflections |
R[F2 > 2σ(F2)] = 0.067 | 9 restraints |
wR(F2) = 0.151 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.21 | Δρmax = 0.58 e Å−3 |
2485 reflections | Δρmin = −0.35 e Å−3 |
232 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
V1 | 0.6958 (1) | 0.57000 (7) | 0.63400 (3) | 0.0230 (3) | |
Na1 | 0.497 (1) | 0.0280 (5) | 0.5121 (3) | 0.047 (2) | 0.50 |
Na2 | 1.0000 | 0.0000 | 0.5000 | 0.0411 (7) | |
O1 | 0.5956 (5) | 0.3946 (3) | 0.6452 (2) | 0.033 (1) | |
O2 | 0.5411 (5) | 0.2105 (4) | 0.5934 (2) | 0.052 (1) | |
O3 | 0.5910 (5) | 0.6197 (3) | 0.7146 (1) | 0.035 (1) | |
O4 | 0.5859 (5) | 0.5860 (4) | 0.8190 (2) | 0.043 (1) | |
O5 | 0.8826 (5) | 0.7178 (3) | 0.6355 (1) | 0.029 (1) | |
O6 | 1.1590 (6) | 0.8212 (4) | 0.6765 (2) | 0.048 (1) | |
O7 | 0.5294 (5) | 0.6239 (3) | 0.5764 (2) | 0.036 (1) | |
O1w | 0.7775 (6) | −0.0575 (3) | 0.5700 (1) | 0.035 (1) | |
O2w | 1.1582 (6) | 0.1229 (4) | 0.5877 (2) | 0.047 (1) | |
O3w | 1.2957 (6) | −0.1370 (4) | 0.5565 (2) | 0.049 (1) | |
N1 | 0.8947 (5) | 0.4670 (3) | 0.5796 (2) | 0.020 (1) | |
N2 | 0.9500 (6) | 0.5210 (3) | 0.7160 (2) | 0.023 (1) | |
C1 | 0.7892 (7) | 0.3451 (4) | 0.5614 (2) | 0.027 (1) | |
C2 | 0.6302 (7) | 0.3125 (5) | 0.6032 (2) | 0.030 (1) | |
C3 | 0.8445 (7) | 0.4848 (5) | 0.7710 (2) | 0.031 (1) | |
C4 | 0.6604 (8) | 0.5687 (5) | 0.7694 (2) | 0.033 (1) | |
C5 | 1.0730 (7) | 0.6363 (5) | 0.7310 (2) | 0.028 (1) | |
C6 | 1.0411 (7) | 0.7339 (5) | 0.6778 (2) | 0.029 (1) | |
C7 | 1.0941 (7) | 0.4463 (4) | 0.6227 (2) | 0.022 (1) | |
C8 | 1.0664 (7) | 0.4166 (4) | 0.6918 (2) | 0.028 (1) | |
C9 | 0.9310 (7) | 0.5359 (4) | 0.5199 (2) | 0.024 (1) | |
H1w1 | 0.807 (7) | −0.131 (2) | 0.585 (2) | 0.042* | |
H1w2 | 0.803 (7) | −0.003 (3) | 0.601 (1) | 0.042* | |
H2w1 | 1.277 (4) | 0.152 (5) | 0.591 (2) | 0.057* | |
H2w2 | 1.132 (7) | 0.099 (5) | 0.624 (1) | 0.057* | |
H3w1 | 1.373 (7) | −0.201 (4) | 0.562 (2) | 0.058* | |
H3w2 | 1.239 (7) | −0.128 (5) | 0.590 (2) | 0.058* | |
H1a | 0.8881 | 0.2776 | 0.5648 | 0.032* | |
H1b | 0.7256 | 0.3498 | 0.5167 | 0.032* | |
H3a | 0.9339 | 0.4958 | 0.8116 | 0.037* | |
H3b | 0.8040 | 0.3967 | 0.7672 | 0.037* | |
H5a | 1.2144 | 0.6128 | 0.7388 | 0.034* | |
H5b | 1.0400 | 0.6736 | 0.7704 | 0.034* | |
H7a | 1.1764 | 0.5216 | 0.6223 | 0.026* | |
H7b | 1.1649 | 0.3769 | 0.6057 | 0.026* | |
H8a | 0.9946 | 0.3373 | 0.6933 | 0.033* | |
H8b | 1.1969 | 0.4085 | 0.7187 | 0.033* | |
H9a | 0.9911 | 0.6175 | 0.5322 | 0.029* | |
H9b | 0.8024 | 0.5512 | 0.4929 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
V1 | 0.0178 (5) | 0.0342 (5) | 0.0176 (4) | 0.0054 (3) | 0.0045 (3) | 0.0035 (3) |
Na1 | 0.035 (2) | 0.051 (5) | 0.052 (5) | 0.001 (3) | −0.001 (3) | 0.014 (3) |
Na2 | 0.032 (2) | 0.060 (2) | 0.033 (1) | −0.010 (1) | 0.011 (1) | −0.008 (1) |
O1 | 0.026 (2) | 0.040 (2) | 0.035 (2) | −0.004 (2) | 0.011 (2) | 0.003 (2) |
O2 | 0.037 (2) | 0.048 (2) | 0.072 (3) | −0.018 (2) | 0.017 (2) | −0.002 (2) |
O3 | 0.033 (2) | 0.052 (2) | 0.024 (2) | 0.018 (2) | 0.011 (2) | 0.004 (2) |
O4 | 0.040 (2) | 0.068 (3) | 0.026 (2) | 0.007 (2) | 0.017 (2) | −0.001 (2) |
O5 | 0.031 (2) | 0.032 (2) | 0.024 (2) | −0.002 (2) | 0.002 (1) | 0.004 (1) |
O6 | 0.053 (3) | 0.052 (2) | 0.035 (2) | −0.021 (2) | −0.003 (2) | 0.005 (2) |
O7 | 0.026 (2) | 0.051 (2) | 0.030 (2) | 0.010 (2) | 0.001 (2) | 0.004 (2) |
O1w | 0.039 (2) | 0.037 (2) | 0.029 (2) | −0.004 (2) | 0.006 (2) | 0.006 (2) |
O2w | 0.040 (3) | 0.063 (3) | 0.042 (2) | −0.013 (2) | 0.016 (2) | −0.006 (2) |
O3w | 0.049 (3) | 0.053 (3) | 0.047 (2) | 0.010 (2) | 0.013 (2) | 0.005 (2) |
N1 | 0.018 (2) | 0.027 (2) | 0.016 (2) | 0.001 (2) | 0.003 (2) | 0.003 (2) |
N2 | 0.019 (2) | 0.033 (2) | 0.019 (2) | 0.004 (2) | 0.008 (2) | 0.003 (2) |
C1 | 0.025 (3) | 0.031 (3) | 0.024 (2) | −0.006 (2) | 0.004 (2) | −0.001 (2) |
C2 | 0.019 (3) | 0.037 (3) | 0.031 (2) | −0.003 (2) | −0.003 (2) | 0.009 (2) |
C3 | 0.026 (3) | 0.049 (3) | 0.018 (2) | 0.003 (2) | 0.007 (2) | 0.004 (2) |
C4 | 0.032 (3) | 0.038 (3) | 0.031 (2) | 0.002 (2) | 0.010 (2) | −0.003 (2) |
C5 | 0.020 (3) | 0.045 (3) | 0.019 (2) | 0.000 (2) | −0.001 (2) | −0.003 (2) |
C6 | 0.029 (3) | 0.036 (3) | 0.021 (2) | −0.005 (2) | 0.003 (2) | −0.007 (2) |
C7 | 0.014 (2) | 0.030 (2) | 0.022 (2) | 0.003 (2) | 0.004 (2) | 0.000 (2) |
C8 | 0.024 (3) | 0.036 (3) | 0.022 (2) | 0.006 (2) | 0.001 (2) | 0.006 (2) |
C9 | 0.024 (3) | 0.030 (3) | 0.018 (2) | 0.002 (2) | 0.005 (2) | 0.004 (2) |
V1—O1 | 1.998 (3) | N2—C5 | 1.479 (6) |
V1—O3 | 1.993 (3) | N2—C8 | 1.485 (6) |
V1—O5 | 2.001 (3) | N2—C3 | 1.489 (5) |
V1—O7 | 1.618 (3) | C1—C2 | 1.518 (6) |
V1—N1 | 2.174 (4) | C3—C4 | 1.517 (7) |
V1—N2 | 2.289 (4) | C5—C6 | 1.511 (6) |
Na1—O2 | 2.561 (6) | C7—C8 | 1.519 (6) |
Na1—O1w | 2.264 (8) | C9—C9iv | 1.536 (8) |
Na1—O1wi | 2.344 (8) | O1w—H1w1 | 0.85 (1) |
Na1—O3wii | 2.475 (9) | O1w—H1w2 | 0.86 (1) |
Na1—O3wiii | 2.433 (9) | O2w—H2w1 | 0.85 (1) |
Na2—O1w | 2.324 (3) | O2w—H2w2 | 0.84 (1) |
Na2—O1wiii | 2.324 (3) | O3w—H3w1 | 0.85 (1) |
Na2—O2w | 2.366 (4) | O3w—H3w2 | 0.85 (1) |
Na2—O2wiii | 2.366 (4) | C1—H1a | 0.97 |
Na2—O3w | 2.593 (4) | C1—H1b | 0.97 |
Na2—O3wiii | 2.593 (4) | C3—H3a | 0.97 |
O1—C2 | 1.281 (6) | C3—H3b | 0.97 |
O2—C2 | 1.235 (6) | C5—H5a | 0.97 |
O3—C4 | 1.289 (6) | C5—H5b | 0.97 |
O4—C4 | 1.232 (5) | C7—H7a | 0.97 |
O5—C6 | 1.288 (5) | C7—H7b | 0.97 |
O6—C6 | 1.219 (6) | C8—H8a | 0.97 |
N1—C1 | 1.492 (5) | C8—H8b | 0.97 |
N1—C9 | 1.498 (5) | C9—H9a | 0.97 |
N1—C7 | 1.513 (5) | C9—H9b | 0.97 |
O1—V1—O3 | 88.7 (1) | O2—C2—O1 | 125.0 (5) |
O1—V1—O5 | 160.8 (1) | O2—C2—C1 | 117.8 (4) |
O1—V1—O7 | 102.0 (2) | O1—C2—C1 | 117.2 (4) |
O1—V1—N1 | 80.8 (1) | N2—C3—C4 | 108.2 (4) |
O1—V1—N2 | 85.9 (1) | O4—C4—O3 | 123.4 (5) |
O3—V1—O5 | 94.6 (1) | O4—C4—C3 | 120.0 (4) |
O3—V1—O7 | 104.2 (2) | O3—C4—C3 | 116.6 (4) |
O3—V1—N1 | 154.0 (1) | N2—C5—C6 | 113.2 (4) |
O3—V1—N2 | 75.1 (1) | O6—C6—O5 | 123.9 (4) |
O5—V1—O7 | 95.5 (2) | O6—C6—C5 | 120.9 (4) |
O5—V1—N1 | 88.1 (1) | O5—C6—C5 | 115.3 (4) |
O5—V1—N2 | 76.8 (1) | N1—C7—C8 | 112.0 (3) |
O7—V1—N1 | 101.2 (1) | N2—C8—C7 | 108.5 (3) |
O7—V1—N2 | 172.1 (2) | N1—C9—C9iv | 113.5 (4) |
N1—V1—N2 | 80.4 (1) | Na1—O1w—H1w1 | 134 (3) |
O2—Na1—O1w | 86.7 (2) | Na2—O1w—H1w1 | 110 (3) |
O2—Na1—O1wi | 112.7 (3) | Na1i—O1w—H1w1 | 121 (3) |
O2—Na1—O3wii | 107.2 (3) | Na1—O1w—H1w2 | 101 (3) |
O2—Na1—O3wiii | 91.0 (2) | Na2—O1w—H1w2 | 103 (3) |
O1w—Na1—O1wi | 160.5 (2) | Na1i—O1w—H1w2 | 120 (3) |
O1w—Na1—O3wiii | 90.2 (3) | H1w1—O1w—H1w2 | 109 (2) |
O1w—Na1—O3wii | 88.5 (3) | Na2—O2w—H2w1 | 125 (3) |
O1wi—Na1—O3wii | 87.4 (3) | Na2—O2w—H2w2 | 114 (3) |
O1wi—Na1—O3wiii | 87.7 (3) | H2w1—O2w—H2w2 | 111 (2) |
O3wii—Na1—O3wiii | 161.6 (2) | Na1iii—O3w—H3w1 | 94 (3) |
O1w—Na2—O1wiii | 180.0 | Na1v—O3w—H3w1 | 105 (4) |
O1w—Na2—O2w | 84.9 (1) | Na2—O3w—H3w1 | 156 (4) |
O1w—Na2—O2wiii | 95.1 (1) | Na1iii—O3w—H3w2 | 143 (4) |
O1w—Na2—O3w | 95.0 (1) | Na1v—O3w—H3w2 | 124 (4) |
O1w—Na2—O3wiii | 85.1 (1) | Na2—O3w—H3w2 | 85 (3) |
O1wiii—Na2—O2w | 95.1 (1) | H3w1—O3w—H3w2 | 109 (2) |
O1wiii—Na2—O2wiii | 84.9 (1) | N1—C1—H1a | 108.9 |
O1wiii—Na2—O3w | 85.1 (1) | C2—C1—H1a | 108.9 |
O1wiii—Na2—O3wiii | 95.0 (1) | N1—C1—H1b | 108.9 |
O2w—Na2—O2wiii | 180.0 (1) | C2—C1—H1b | 108.9 |
O2w—Na2—O3wiii | 105.6 (1) | H1a—C1—H1b | 107.7 |
O2w—Na2—O3w | 74.4 (1) | N2—C3—H3a | 110.1 |
O2wiii—Na2—O3wiii | 74.4 (1) | C4—C3—H3a | 110.1 |
O2wiii—Na2—O3w | 105.6 (1) | N2—C3—H3b | 110.1 |
O3w—Na2—O3wiii | 180.0 (2) | C4—C3—H3b | 110.1 |
C2—O1—V1 | 116.8 (3) | H3a—C3—H3b | 108.4 |
C2—O2—Na1 | 140.6 (4) | N2—C5—H5a | 108.9 |
C4—O3—V1 | 121.1 (3) | C6—C5—H5a | 108.9 |
C6—O5—V1 | 124.4 (3) | N2—C5—H5b | 108.9 |
Na1—O1w—Na2 | 96.8 (2) | C6—C5—H5b | 108.9 |
Na2—O1w—Na1i | 90.7 (2) | H5a—C5—H5b | 107.7 |
Na1iii—O3w—Na2 | 86.0 (2) | N1—C7—H7a | 109.2 |
Na1v—O3w—Na2 | 81.9 (2) | C8—C7—H7a | 109.2 |
C1—N1—C9 | 109.8 (3) | N1—C7—H7b | 109.2 |
C1—N1—C7 | 111.7 (3) | C8—C7—H7b | 109.2 |
C9—N1—C7 | 109.2 (3) | H7a—C7—H7b | 107.9 |
C1—N1—V1 | 105.1 (3) | N2—C8—H8a | 110.0 |
C9—N1—V1 | 112.6 (3) | C7—C8—H8a | 110.0 |
C7—N1—V1 | 108.5 (2) | N2—C8—H8b | 110.0 |
C5—N2—C8 | 112.3 (4) | C7—C8—H8b | 110.0 |
C5—N2—C3 | 111.3 (3) | H8a—C8—H8b | 108.4 |
C8—N2—C3 | 114.1 (3) | N1—C9—H9a | 108.9 |
C5—N2—V1 | 107.5 (3) | C9iv—C9—H9a | 108.9 |
C8—N2—V1 | 106.4 (2) | N1—C9—H9b | 108.9 |
C3—N2—V1 | 104.5 (3) | C9iv—C9—H9b | 108.9 |
N1—C1—C2 | 113.4 (4) | H9a—C9—H9b | 107.7 |
O7—V1—O1—C2 | 77.5 (3) | N2—V1—N1—C9 | −131.5 (3) |
O3—V1—O1—C2 | −178.2 (3) | O7—V1—N1—C7 | 161.6 (3) |
O5—V1—O1—C2 | −77.7 (5) | O3—V1—N1—C7 | −30.4 (5) |
N1—V1—O1—C2 | −22.1 (3) | O1—V1—N1—C7 | −97.9 (3) |
N2—V1—O1—C2 | −103.1 (3) | O5—V1—N1—C7 | 66.3 (3) |
O1w—Na1—O2—C2 | 86.5 (6) | N2—V1—N1—C7 | −10.6 (2) |
O1wi—Na1—O2—C2 | −91.6 (6) | O3—V1—N2—C5 | −86.1 (3) |
O3wiii—Na1—O2—C2 | −3.6 (6) | O1—V1—N2—C5 | −175.9 (3) |
O3wii—Na1—O2—C2 | 173.9 (5) | O5—V1—N2—C5 | 12.4 (3) |
O7—V1—O3—C4 | 164.4 (4) | N1—V1—N2—C5 | 102.8 (3) |
O1—V1—O3—C4 | 62.3 (4) | O3—V1—N2—C8 | 153.3 (3) |
O5—V1—O3—C4 | −98.7 (4) | O1—V1—N2—C8 | 63.6 (3) |
N1—V1—O3—C4 | −3.5 (6) | O5—V1—N2—C8 | −108.1 (3) |
N2—V1—O3—C4 | −23.8 (4) | N1—V1—N2—C8 | −17.8 (3) |
O7—V1—O5—C6 | 173.3 (3) | O3—V1—N2—C3 | 32.2 (3) |
O3—V1—O5—C6 | 68.5 (3) | O1—V1—N2—C3 | −57.5 (3) |
O1—V1—O5—C6 | −31.0 (6) | O5—V1—N2—C3 | 130.8 (3) |
N1—V1—O5—C6 | −85.6 (3) | N1—V1—N2—C3 | −138.9 (3) |
N2—V1—O5—C6 | −5.0 (3) | C9—N1—C1—C2 | −141.3 (4) |
O1wi—Na1—O1w—Na2 | 73 (1) | C7—N1—C1—C2 | 97.5 (4) |
O3wiii—Na1—O1w—Na2 | −11.2 (2) | V1—N1—C1—C2 | −20.0 (4) |
O3wii—Na1—O1w—Na2 | 150.5 (2) | Na1—O2—C2—O1 | 168.4 (4) |
O2—Na1—O1w—Na2 | −102.1 (2) | Na1—O2—C2—C1 | −9.9 (8) |
O3wiii—Na1—O1w—Na1i | −84 (1) | V1—O1—C2—O2 | −161.9 (4) |
O3wii—Na1—O1w—Na1i | 78 (1) | V1—O1—C2—C1 | 16.4 (5) |
O2—Na1—O1w—Na1i | −175 (1) | N1—C1—C2—O2 | −177.1 (4) |
O2w—Na2—O1w—Na1 | 116.7 (2) | N1—C1—C2—O1 | 4.6 (6) |
O2wiii—Na2—O1w—Na1 | −63.3 (2) | C5—N2—C3—C4 | 79.3 (5) |
O3wiii—Na2—O1w—Na1 | 10.5 (2) | C8—N2—C3—C4 | −152.4 (4) |
O3w—Na2—O1w—Na1 | −169.5 (2) | V1—N2—C3—C4 | −36.5 (4) |
O2w—Na2—O1w—Na1i | 135.3 (2) | V1—O3—C4—O4 | −171.8 (4) |
O2wiii—Na2—O1w—Na1i | −44.7 (2) | V1—O3—C4—C3 | 8.7 (6) |
O3wiii—Na2—O1w—Na1i | 29.1 (2) | N2—C3—C4—O4 | −157.0 (4) |
O3w—Na2—O1w—Na1i | −150.9 (2) | N2—C3—C4—O3 | 22.4 (6) |
O1w—Na2—O3w—Na1iii | −170.3 (2) | C8—N2—C5—C6 | 98.8 (4) |
O1wiii—Na2—O3w—Na1iii | 9.7 (2) | C3—N2—C5—C6 | −131.9 (4) |
O2w—Na2—O3w—Na1iii | −87.0 (2) | V1—N2—C5—C6 | −18.0 (4) |
O2wiii—Na2—O3w—Na1iii | 93.0 (2) | V1—O5—C6—O6 | 176.5 (4) |
O1w—Na2—O3w—Na1v | −152.3 (2) | V1—O5—C6—C5 | −4.1 (5) |
O1wiii—Na2—O3w—Na1v | 27.7 (2) | N2—C5—C6—O6 | −164.7 (4) |
O2w—Na2—O3w—Na1v | −69.0 (2) | N2—C5—C6—O5 | 15.8 (6) |
O2wiii—Na2—O3w—Na1v | 111.0 (2) | C1—N1—C7—C8 | −76.8 (4) |
O7—V1—N1—C1 | −78.9 (3) | C9—N1—C7—C8 | 161.5 (4) |
O3—V1—N1—C1 | 89.2 (4) | V1—N1—C7—C8 | 38.6 (4) |
O1—V1—N1—C1 | 21.7 (2) | C5—N2—C8—C7 | −74.6 (4) |
O5—V1—N1—C1 | −174.1 (3) | C3—N2—C8—C7 | 157.6 (4) |
N2—V1—N1—C1 | 109.0 (3) | V1—N2—C8—C7 | 42.8 (4) |
O7—V1—N1—C9 | 40.7 (3) | N1—C7—C8—N2 | −56.4 (5) |
O3—V1—N1—C9 | −151.3 (3) | C1—N1—C9—C9iv | −62.5 (6) |
O1—V1—N1—C9 | 141.2 (3) | C7—N1—C9—C9iv | 60.2 (6) |
O5—V1—N1—C9 | −54.6 (3) | V1—N1—C9—C9iv | −179.3 (4) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z; (iii) −x+2, −y, −z+1; (iv) −x+2, −y+1, −z+1; (v) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1w—H1w2···O4vi | 0.86 (1) | 1.98 (2) | 2.811 (5) | 164 (4) |
O1w—H1w1···O5vii | 0.85 (1) | 1.94 (1) | 2.782 (4) | 170 (4) |
O2w—H2w1···O2v | 0.85 (1) | 1.87 (1) | 2.716 (5) | 176 (5) |
O2w—H2w2···O4vi | 0.84 (1) | 2.03 (3) | 2.760 (5) | 145 (5) |
O3w—H3w1···O7viii | 0.85 (1) | 2.12 (2) | 2.971 (5) | 172 (5) |
O3w—H3w2···O6vii | 0.85 (1) | 2.04 (2) | 2.836 (5) | 156 (4) |
Symmetry codes: (v) x+1, y, z; (vi) −x+3/2, y−1/2, −z+3/2; (vii) x, y−1, z; (viii) x+1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | (Na+)2·C18H24N4O14V22−·6(H2O) |
Mr | 776.37 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 6.7086 (2), 10.5746 (3), 20.9333 (5) |
β (°) | 98.678 (1) |
V (Å3) | 1468.02 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.76 |
Crystal size (mm) | 0.31 × 0.21 × 0.14 |
Data collection | |
Diffractometer | Bruker APEX area-detector diffractometer |
Absorption correction | Multi-scan SADABS (Sheldrick, 1996) |
Tmin, Tmax | 0.390, 0.862 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7204, 2485, 2162 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.151, 1.21 |
No. of reflections | 2485 |
No. of parameters | 232 |
No. of restraints | 9 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.58, −0.35 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-II (Johnson, 1976).
V1—O1 | 1.998 (3) | Na1—O1w | 2.264 (8) |
V1—O3 | 1.993 (3) | Na1—O1wi | 2.344 (8) |
V1—O5 | 2.001 (3) | Na1—O3wii | 2.475 (9) |
V1—O7 | 1.618 (3) | Na1—O3wiii | 2.433 (9) |
V1—N1 | 2.174 (4) | Na2—O1w | 2.324 (3) |
V1—N2 | 2.289 (4) | Na2—O2w | 2.366 (4) |
Na1—O2 | 2.561 (6) | Na2—O3w | 2.593 (4) |
O1—V1—O3 | 88.7 (1) | N1—V1—N2 | 80.4 (1) |
O1—V1—O5 | 160.8 (1) | O2—Na1—O1w | 86.7 (2) |
O1—V1—O7 | 102.0 (2) | O2—Na1—O1wi | 112.7 (3) |
O1—V1—N1 | 80.8 (1) | O2—Na1—O3wii | 107.2 (3) |
O1—V1—N2 | 85.9 (1) | O2—Na1—O3wiii | 91.0 (2) |
O3—V1—O5 | 94.6 (1) | O1w—Na1—O1wi | 160.5 (2) |
O3—V1—O7 | 104.2 (2) | O1w—Na1—O3wiii | 90.2 (3) |
O3—V1—N1 | 154.0 (1) | O1w—Na1—O3wii | 88.5 (3) |
O3—V1—N2 | 75.1 (1) | O1wi—Na1—O3wii | 87.4 (3) |
O5—V1—O7 | 95.5 (2) | O1wi—Na1—O3wiii | 87.7 (3) |
O5—V1—N1 | 88.1 (1) | O3wii—Na1—O3wiii | 161.6 (2) |
O5—V1—N2 | 76.8 (1) | O1w—Na2—O2w | 84.9 (1) |
O7—V1—N1 | 101.2 (1) | O1w—Na2—O3w | 95.0 (1) |
O7—V1—N2 | 172.1 (2) | O2w—Na2—O3w | 74.4 (1) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z; (iii) −x+2, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1w—H1w2···O4iv | 0.86 (1) | 1.98 (2) | 2.811 (5) | 164 (4) |
O1w—H1w1···O5v | 0.85 (1) | 1.94 (1) | 2.782 (4) | 170 (4) |
O2w—H2w1···O2vi | 0.85 (1) | 1.87 (1) | 2.716 (5) | 176 (5) |
O2w—H2w2···O4iv | 0.84 (1) | 2.03 (3) | 2.760 (5) | 145 (5) |
O3w—H3w1···O7vii | 0.85 (1) | 2.12 (2) | 2.971 (5) | 172 (5) |
O3w—H3w2···O6v | 0.85 (1) | 2.04 (2) | 2.836 (5) | 156 (4) |
Symmetry codes: (iv) −x+3/2, y−1/2, −z+3/2; (v) x, y−1, z; (vi) x+1, y, z; (vii) x+1, y−1, z. |
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We have recently reported several heterometallic coordination compounds in which main-group metal atoms are linked to transition metals through carboxylato groups (Long et al., 2002; Ren et al., 2002). Sodium µ-triethylenetetraaminehexaacetatodi[oxovanadate] was reported earlier as a decahydrate (Fallon & Gatehouse, 1976). In this paper, we report the structure of the hexahydrate form, (I), of this complex,
The dinuclear anion and both Na+ cations occupy special positions at inversion centers (one of the Na+ cations is disordered in the vicinity of the inversion center). The V(IV) atom has an octahedral coordination environment, defined by the vanadyl oxo atom, two N and three O atoms of the aminoacetato anion (Fig. 1). The V=O double-bond distance [V1=O7 1.618 (3) Å] is significantly shorter than the other three covalent V—O bonds [1.993 (3), 1.998 (3), 2.001 (3) Å]. The V—N bond trans to the V=O bond [V1—N2 2.289 (4) Å] is somewhat longer than the other V—N bond [V1—N1 2.174 (4) Å]. The distances are similar to those found in the decahydrate, and the geometry of the V atom is also the same. In the decahydrate, the V=O double bond is 1.605 (8) Å; the V—N bond trans to the vanadyl bond is 2.294 (7) Å (Fallon & Gatehouse, 1976).
One of the Na+ cations (Na2) is coordinated by six water molecules whereas the other (Na1) is only penta-coordinate. Four of the neighbors of the Na1 atom are water O atoms bridging it to the Na2 atom, the fifth being a carbonyl O atom belonging to the aminoacid ligand (Fig. 2). The bridging pattern gives rise to a tightly-held network structure. The packing of the hexahydrate is more compact than that of the decahydrate, as noted from the higher density.
The blue colour of the title complex leaves no doubt that the V atom oxidation state is 4+. It is not clear, however, what is the exact nature of the reducing agent in the process of its synthesis from metavanadate where V has an oxidation state of 5. One may guess, though, that under hydrothermal condition the carboxylate group or even water may exhibit redox activity.