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Acta Cryst. (2007). E63, m2051-m2052    [ doi:10.1107/S1600536807031418 ]

Potassium (4-carboxypyridine-2,6-dicarboxylato)dioxidovanadate(V) monohydrate

A. A. Holder and D. VanDerveer

Abstract top

The title complex, K[V(C8H3NO6)O2]·H2O, was synthesized by reacting 4-carboxypyridine-2,6-dicarboxylic acid (contaminated as a potassium salt) with NH4VO3 in aqueous solution. The title complex, with a vanadium(V) metal center, is a distorted square-based pyramid. Its structure consists of chains of the anionic complexes in the direction of the b axis connected by potassium-oxygen interactions which range from 2.5981 (18) to 3.0909 (18) Å. These chains are linked to each other by hydrogen bonding between the O atoms of the complex and the water molecules.

Comment top

Pyridine-2,6-dicarboxylic acid (dipicolinic acid, abbreviated as H2dipic) has been found to be an interesting and versatile ligand for several reasons: (1) it can function as a tridentate ligand; (2) the carboxylate groups sometimes bridge two metal atoms (Cingi et al., 1971); (3) coordination to a metal atom can occur through dianionic (dipic2−) (Lukes & Jurecek, 1948, Dutta & Ghosh, 1967, Drew et al., 1970), monoanionic (Hdipic−) (Murtha & Walton, 1973, Gaw et al., 1971), or neutral (H2dipic) forms of this ligand (Drew et al., 1970). Based on these facts, a large number of divalent or trivalent transition metal and lanthanide(III) complexes of dipicolinic acid have been studied (Payne et al., 2007, Cassellato & Vigato, 1978, D'Ascenzo et al., 1978, Ghosh et al., 1978, Furst et al., 1978). Recently, a number of cobalt- and vanadium-containing complexes with either 4-hydroxypyridine-2,6-dicarboxylic acid or dipicolinic acid as ligand, were reported to be insulin-like in nature (Crans, Mahroof-Tahir et al., 2003, Crans, Yang et al., 2003, Crans et al., 2000, Yang et al., 2002)·As part of our interest in the coordination chemistry of analogues of dipicolinic acid, we now extend this chemistry to include the structural elucidation of the [VO2(dipic-CO2H]− anion. The title complex, with a vanadium(V) metal centre, is a distorted square-based pyramid.

Related literature top

For related literature, see: Cassellato & Vigato (1978); Crans et al. (2000); Crans, Mahroof-Tahir et al. (2003); Crans, Yang et al. (2003); D'Ascenzo et al. (1978); Drew et al. (1970); Dutta & Ghosh (1967); Furst et al. (1978); Gaw et al. (1971); Ghosh et al. (1978); Lukes & Jurecek (1948); Murtha & Walton (1973); Payne et al. (2007); Syper et al. (1980); Yang et al. (2002).

For related literature, see: Cingi et al. (1971).

Experimental top

H2dipic-CO2H was synthesized by the literature procedure (Syper et al., 1980). Deionized water (20 cm3) was added to a mixture of H2dipic-CO2H (3.15 g, 14.8 mmol) and NH4VO3 (1.74 g, 14.9 mmol) in a 50 cm3 beaker. The mixture was then heated to 353–363 K until the solution became clear yellow; while hot, the pH of the solution was reduced to 1.1 with 2 M HCl. The mixture was then heated for an additional 15 minutes and filtered to give a bright yellow-orange solution. Upon standing, a yellowish-white solid was formed. The crude product was filtered off and recrystallized from a minimum of hot water to give a solid, which was found to be the potassium salt, K[VO2(dipic-CO2H]·H2O, as confirmed by X-ray crystallography.

FT IR (cm−1): 3470 (br, ν (OH)), 1682 (versus, νas(CO2−)), and 928 (versus, ν (V=O)). 51V NMR (H2O): δ = −533 p.p.m.

Refinement top

Positions of the water H atoms were determined from a difference Fourier map and their coordinates were refined freely. All remaining H atoms were geometrically positioned and allowed to ride on the corresponding non-H atom with C—H = 0.96 Å, O—H = 0.83 Å, and Uiso(H) = 1.2Ueq(C,O).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Displacement ellipsoid drawing (50% probability level) of the vanadate complex.
[Figure 2] Fig. 2. The complex-potassium network. [Symmetry codes: (A) −x, 1/2 + y, 1/2 − z; (B) −1/2 + x, 1/2 + y, z; (C) 1/2 + x, 1/2 + y, z.]
Potassium (4-carboxypyridine-2,6-dicarboxylato)dioxidovanadate(V) monohydrate top
Crystal data top
K[V(C8H3NO6)O2]·H2ODx = 1.985 Mg m−3
Mr = 349.17Mo Kα radiation, λ = 0.7107 Å
Orthorhombic, PbcaCell parameters from 8517 reflections
a = 7.8086 (16) Åθ = 3.1–26.4°
b = 16.342 (3) ŵ = 1.25 mm−1
c = 18.316 (4) ÅT = 153 K
V = 2337.2 (8) Å3Plate, colorless
Z = 80.50 × 0.50 × 0.12 mm
F(000) = 1392
Data collection top
Rigaku Mercury CCD
diffractometer		2099 independent reflections
Radiation source: Sealed Tube1951 reflections with I > 2σ(I)
Graphite MonochromatorRint = 0.034
Detector resolution: 14.6306 pixels mm-1θmax = 25.2°, θmin = 3.1°
ω scansh = −9→9
Absorption correction: multi-scan
(REQAB; Rigaku/MSC, 1999)		k = −19→19
Tmin = 0.573, Tmax = 0.864l = −21→21
17213 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H atoms treated by a mixture of independent and constrained refinement
S = 1.15 w = 1/[σ2(Fo2) + (0.0337P)2 + 2.9965P]
where P = (Fo2 + 2Fc2)/3
2099 reflections(Δ/σ)max = 0.001
190 parametersΔρmax = 0.38 e Å−3
0 restraintsΔρmin = −0.42 e Å−3
Crystal data top
K[V(C8H3NO6)O2]·H2OV = 2337.2 (8) Å3
Mr = 349.17Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 7.8086 (16) ŵ = 1.25 mm−1
b = 16.342 (3) ÅT = 153 K
c = 18.316 (4) Å0.50 × 0.50 × 0.12 mm
Data collection top
Rigaku Mercury CCD
diffractometer		2099 independent reflections
Absorption correction: multi-scan
(REQAB; Rigaku/MSC, 1999)		1951 reflections with I > 2σ(I)
Tmin = 0.573, Tmax = 0.864Rint = 0.034
17213 measured reflectionsθmax = 25.2°
Refinement top
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.079Δρmax = 0.38 e Å−3
S = 1.15Δρmin = −0.42 e Å−3
2099 reflectionsAbsolute structure: ?
190 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
V10.01940 (5)0.56611 (2)0.17052 (2)0.01377 (14)
K1−0.20989 (6)0.21723 (3)0.20644 (3)0.02000 (16)
O10.1877 (2)0.65071 (9)0.13611 (9)0.0165 (3)
O2−0.0321 (2)0.45032 (10)0.19712 (9)0.0187 (4)
O30.4445 (2)0.67819 (10)0.08618 (9)0.0192 (4)
O40.0627 (2)0.32230 (10)0.21357 (9)0.0203 (4)
O5−0.0230 (2)0.60987 (10)0.24834 (9)0.0192 (4)
O6−0.1336 (2)0.58848 (10)0.11431 (9)0.0207 (4)
O70.7845 (2)0.40826 (10)0.03885 (9)0.0199 (4)
H70.87210.38040.03250.024*
O80.6847 (2)0.29294 (10)0.09009 (9)0.0219 (4)
O91.0655 (2)0.33250 (12)0.02454 (11)0.0209 (4)
H9A1.067 (5)0.288 (2)0.0436 (19)0.038 (10)*
H9B1.104 (5)0.333 (2)−0.017 (2)0.058 (13)*
N10.2394 (2)0.50057 (11)0.14296 (10)0.0138 (4)
C10.3378 (3)0.63102 (14)0.11050 (12)0.0153 (5)
C20.3713 (3)0.54026 (14)0.11337 (12)0.0145 (5)
C30.5159 (3)0.49909 (14)0.09037 (12)0.0146 (5)
H30.61120.52770.06940.018*
C40.5181 (3)0.41440 (15)0.09881 (12)0.0157 (5)
C50.3811 (3)0.37328 (14)0.13113 (12)0.0162 (5)
H50.38280.31500.13770.019*
C60.2425 (3)0.42000 (14)0.15330 (12)0.0151 (5)
C70.0808 (3)0.39222 (14)0.19098 (13)0.0173 (5)
C80.6716 (3)0.36540 (14)0.07538 (12)0.0169 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
V10.0131 (2)0.0131 (2)0.0151 (2)0.00022 (14)0.00020 (15)−0.00044 (15)
K10.0174 (3)0.0170 (3)0.0256 (3)−0.00151 (19)−0.0029 (2)0.0042 (2)
O10.0159 (8)0.0123 (8)0.0212 (8)0.0005 (6)0.0008 (7)0.0006 (7)
O20.0163 (8)0.0155 (8)0.0244 (9)0.0001 (7)0.0035 (7)0.0029 (7)
O30.0183 (8)0.0152 (8)0.0242 (9)−0.0039 (7)0.0023 (7)0.0025 (7)
O40.0220 (9)0.0129 (9)0.0260 (9)−0.0027 (7)0.0025 (7)0.0023 (7)
O50.0211 (9)0.0174 (9)0.0191 (8)−0.0023 (7)0.0032 (7)−0.0016 (7)
O60.0182 (8)0.0208 (9)0.0230 (9)−0.0033 (7)−0.0042 (7)0.0044 (7)
O70.0165 (8)0.0204 (9)0.0228 (9)0.0025 (7)0.0029 (7)0.0001 (7)
O80.0241 (9)0.0184 (9)0.0231 (9)0.0042 (7)0.0006 (7)0.0025 (7)
O90.0223 (9)0.0196 (10)0.0208 (10)0.0035 (7)0.0036 (7)0.0025 (8)
N10.0158 (9)0.0128 (10)0.0128 (9)−0.0006 (7)−0.0003 (8)−0.0010 (7)
C10.0163 (11)0.0156 (12)0.0139 (11)0.0007 (9)−0.0012 (9)−0.0004 (9)
C20.0158 (11)0.0157 (11)0.0120 (11)−0.0031 (9)−0.0027 (9)−0.0003 (9)
C30.0156 (11)0.0156 (12)0.0127 (11)−0.0007 (9)−0.0008 (9)0.0002 (9)
C40.0167 (11)0.0197 (12)0.0106 (11)−0.0002 (9)−0.0032 (9)−0.0014 (9)
C50.0195 (12)0.0148 (11)0.0144 (11)−0.0002 (9)−0.0041 (9)0.0003 (9)
C60.0167 (11)0.0163 (12)0.0124 (10)−0.0023 (9)−0.0024 (9)0.0005 (9)
C70.0177 (11)0.0174 (13)0.0167 (11)−0.0037 (9)−0.0015 (9)−0.0008 (9)
C80.0167 (11)0.0190 (13)0.0148 (11)0.0014 (9)−0.0018 (9)−0.0010 (9)
Geometric parameters (Å, °) top
V1—O61.6187 (17)O5—K1vi2.6593 (17)
V1—O51.6287 (17)O5—K1ix2.8313 (18)
V1—O21.9949 (17)O6—K1ix2.9612 (19)
V1—O12.0091 (17)O7—C81.310 (3)
V1—N12.086 (2)O7—H70.830
K1—O8i2.5981 (18)O8—C81.219 (3)
K1—O5ii2.6593 (17)O8—K1x2.5981 (18)
K1—O42.7377 (18)O9—H9A0.81 (4)
K1—O5iii2.8313 (18)O9—H9B0.81 (4)
K1—O4iv2.8721 (18)N1—C61.330 (3)
K1—O6iii2.9612 (19)N1—C21.332 (3)
K1—O1ii3.0867 (18)C1—C21.507 (3)
K1—O3v3.0909 (18)C2—C31.380 (3)
O1—C11.303 (3)C3—C41.393 (3)
O1—K1vi3.0867 (18)C3—H30.960
O2—C71.301 (3)C4—C51.395 (3)
O3—C11.219 (3)C4—C81.504 (3)
O3—K1vii3.0909 (18)C5—C61.385 (3)
O4—C71.224 (3)C5—H50.960
O4—K1viii2.8721 (18)C6—C71.509 (3)
O6—V1—O5107.90 (9)V1—O1—K1vi89.19 (6)
O6—V1—O2102.76 (8)C7—O2—V1122.32 (15)
O5—V1—O299.31 (8)C1—O3—K1vii109.16 (14)
O6—V1—O197.34 (8)C7—O4—K1131.29 (15)
O5—V1—O196.06 (8)C7—O4—K1viii131.23 (15)
O2—V1—O1149.45 (7)K1—O4—K1viii97.47 (5)
O6—V1—N1124.72 (8)V1—O5—K1vi115.03 (8)
O5—V1—N1127.20 (8)V1—O5—K1ix100.65 (8)
O2—V1—N174.81 (7)K1vi—O5—K1ix100.33 (6)
O1—V1—N174.85 (7)V1—O6—K1ix95.89 (7)
O8i—K1—O5ii141.84 (6)C8—O7—H7109.5
O8i—K1—O489.24 (6)C8—O8—K1x132.11 (15)
O5ii—K1—O482.37 (5)H9A—O9—H9B114 (4)
O8i—K1—O5iii106.51 (6)C6—N1—C2121.7 (2)
O5ii—K1—O5iii90.61 (5)C6—N1—V1119.25 (16)
O4—K1—O5iii161.50 (5)C2—N1—V1119.01 (15)
O8i—K1—O4iv86.43 (5)O3—C1—O1126.2 (2)
O5ii—K1—O4iv131.19 (5)O3—C1—C2121.1 (2)
O4—K1—O4iv94.67 (5)O1—C1—C2112.74 (19)
O5iii—K1—O4iv77.10 (5)N1—C2—C3121.3 (2)
O8i—K1—O6iii74.94 (5)N1—C2—C1111.1 (2)
O5ii—K1—O6iii89.49 (5)C3—C2—C1127.7 (2)
O4—K1—O6iii142.54 (5)C2—C3—C4117.4 (2)
O5iii—K1—O6iii53.85 (5)C2—C3—H3121.3
O4iv—K1—O6iii117.40 (5)C4—C3—H3121.3
O8i—K1—O1ii162.14 (5)C3—C4—C5121.1 (2)
O5ii—K1—O1ii55.83 (5)C3—C4—C8120.5 (2)
O4—K1—O1ii97.63 (5)C5—C4—C8118.4 (2)
O5iii—K1—O1ii64.52 (5)C6—C5—C4117.3 (2)
O4iv—K1—O1ii76.63 (5)C6—C5—H5121.4
O6iii—K1—O1ii107.78 (5)C4—C5—H5121.4
O8i—K1—O3v74.10 (5)N1—C6—C5121.2 (2)
O5ii—K1—O3v68.11 (5)N1—C6—C7110.3 (2)
O4—K1—O3v69.04 (5)C5—C6—C7128.5 (2)
O5iii—K1—O3v123.99 (5)O4—C7—O2125.0 (2)
O4iv—K1—O3v154.36 (5)O4—C7—C6122.2 (2)
O6iii—K1—O3v73.98 (5)O2—C7—C6112.8 (2)
O1ii—K1—O3v123.75 (5)O8—C8—O7125.2 (2)
C1—O1—V1122.11 (14)O8—C8—C4121.4 (2)
C1—O1—K1vi111.89 (13)O7—C8—C4113.4 (2)
Symmetry codes: (i) x−1, y, z; (ii) −x, y−1/2, −z+1/2; (iii) −x−1/2, y−1/2, z; (iv) x−1/2, y, −z+1/2; (v) −x+1/2, y−1/2, z; (vi) −x, y+1/2, −z+1/2; (vii) −x+1/2, y+1/2, z; (viii) x+1/2, y, −z+1/2; (ix) −x−1/2, y+1/2, z; (x) x+1, y, z.
Table 1
Selected geometric parameters (Å) top
V1—O61.6187 (17)V1—O12.0091 (17)
V1—O51.6287 (17)V1—N12.086 (2)
V1—O21.9949 (17)
Acknowledgements top

AAH thanks The University of Southern Mississippi for a startup grant (DE00977), which was very valuable in making this structural elucidation viable. AAH also thanks Dr William Jarrett for acquiring the 51V NMR spectrum.

references
References top

Bruker (2000). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Cassellato, U. & Vigato, P. A. (1978). Coord. Chem. Rev. 26, 85–159.

Cingi, M. B., Villa, A. C., Guastini, C. & Nardelli, M. (1971). Gazz. Chim. Ital. 101, 825–832.

Crans, D. C., Mahroof-Tahir, M., Johnson, M. D., Wilkins, P. C., Yang, L., Robbins, K., Johnson, A., Alfano, J. A., Godzala, M. E., Austin, L. T. & Willsky, G. R. (2003). Inorg. Chim. Acta, 356, 365–378.

Crans, D. C., Yang, L., Alfano, J. A., Chi, L.-H., Jin, W., Mahroof-Tahir, M., Robbins, K., Toloue, M. M., Chan, L. K., Plante, A. J., Grayson, R. Z. & Willsky, G. R. (2003). Coord. Chem. Rev. 237, 13–22.

Crans, D. C., Yang, L., Jakusch, T. & Kiss, T. (2000). Inorg. Chem. 39, 4409–4416.

D'Ascenzo, G., Marino, A., Sabbatini, M. & Bica, T. (1978). Thermochim. Acta, 25, 325–332.

Drew, M. G. B., Matthews, R. W. & Walton, R. A. (1970). J. Chem. Soc. A, pp. 1405–1410.

Dutta, R. L. & Ghosh, S. (1967). J. Indian Chem. Soc. 44, 273–289.

Furst, W., Gouzerch, P. & Jeannin, Y. (1978). J. Coord. Chem. 8, 237–243.

Gaw, H., Robinson, W. R. & Walton, R. W. (1971). Inorg. Nucl. Chem. Lett. 7, 695–699.

Ghosh, S., Banerjee, T. K. & Ray, P. K. (1978). J. Indian Chem. Soc. 55, 610–611.

Lukes, R. & Jurecek, M. (1948). Collect. Czech. Chem. Commun. 13, 131–160.

Murtha, D. P. & Walton, R. A. (1973). Inorg. Chem. 12, 1278–1282.

Payne, V. C. R., Headley, O. S. C., Stibrany, R. T., Maragh, P. T., Dasgupta, T. P., Newton, A. M. & Holder, A. A. (2007). J. Chem. Crystallogr. 37, 309–314.

Rigaku/MSC (1999). REQAB. Rigaku/MSC, The Woodlands, Texas, USA.

Rigaku/MSC (2006). CrystalClear. Version 1.3. Rigaku/MSC, The Woodlands, Texas, USA.

Syper, L., Kloc, K. & Mlochowski, J. (1980). Tetrahedron, 36, 123–129.

Yang, L., Crans, D. C., Miller, S. M., la Cour, A., Anderson, O. P., Kaszynski, P. M., Godzala, M. E., Austin, L. D. & Willsky, G. R. (2002). Inorg. Chem. 41, 4859–4871.