Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031418/cf2108sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031418/cf2108Isup2.hkl |
CCDC reference: 657525
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.
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).
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.
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).
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.
K[V(C8H3NO6)O2]·H2O | Dx = 1.985 Mg m−3 |
Mr = 349.17 | Mo Kα radiation, λ = 0.7107 Å |
Orthorhombic, Pbca | Cell parameters from 8517 reflections |
a = 7.8086 (16) Å | θ = 3.1–26.4° |
b = 16.342 (3) Å | µ = 1.25 mm−1 |
c = 18.316 (4) Å | T = 153 K |
V = 2337.2 (8) Å3 | Plate, colorless |
Z = 8 | 0.50 × 0.50 × 0.12 mm |
F(000) = 1392 |
Rigaku Mercury CCD diffractometer | 2099 independent reflections |
Radiation source: Sealed Tube | 1951 reflections with I > 2σ(I) |
Graphite Monochromator monochromator | Rint = 0.034 |
Detector resolution: 14.6306 pixels mm-1 | θmax = 25.2°, θmin = 3.1° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (REQAB; Rigaku/MSC, 1999) | k = −19→19 |
Tmin = 0.573, Tmax = 0.864 | l = −21→21 |
17213 measured reflections |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H 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 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
K[V(C8H3NO6)O2]·H2O | V = 2337.2 (8) Å3 |
Mr = 349.17 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.8086 (16) Å | µ = 1.25 mm−1 |
b = 16.342 (3) Å | T = 153 K |
c = 18.316 (4) Å | 0.50 × 0.50 × 0.12 mm |
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 = 0.864 | Rint = 0.034 |
17213 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.15 | Δρmax = 0.38 e Å−3 |
2099 reflections | Δρmin = −0.42 e Å−3 |
190 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 | 0.01940 (5) | 0.56611 (2) | 0.17052 (2) | 0.01377 (14) | |
K1 | −0.20989 (6) | 0.21723 (3) | 0.20644 (3) | 0.02000 (16) | |
O1 | 0.1877 (2) | 0.65071 (9) | 0.13611 (9) | 0.0165 (3) | |
O2 | −0.0321 (2) | 0.45032 (10) | 0.19712 (9) | 0.0187 (4) | |
O3 | 0.4445 (2) | 0.67819 (10) | 0.08618 (9) | 0.0192 (4) | |
O4 | 0.0627 (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) | |
O7 | 0.7845 (2) | 0.40826 (10) | 0.03885 (9) | 0.0199 (4) | |
H7 | 0.8721 | 0.3804 | 0.0325 | 0.024* | |
O8 | 0.6847 (2) | 0.29294 (10) | 0.09009 (9) | 0.0219 (4) | |
O9 | 1.0655 (2) | 0.33250 (12) | 0.02454 (11) | 0.0209 (4) | |
H9A | 1.067 (5) | 0.288 (2) | 0.0436 (19) | 0.038 (10)* | |
H9B | 1.104 (5) | 0.333 (2) | −0.017 (2) | 0.058 (13)* | |
N1 | 0.2394 (2) | 0.50057 (11) | 0.14296 (10) | 0.0138 (4) | |
C1 | 0.3378 (3) | 0.63102 (14) | 0.11050 (12) | 0.0153 (5) | |
C2 | 0.3713 (3) | 0.54026 (14) | 0.11337 (12) | 0.0145 (5) | |
C3 | 0.5159 (3) | 0.49909 (14) | 0.09037 (12) | 0.0146 (5) | |
H3 | 0.6112 | 0.5277 | 0.0694 | 0.018* | |
C4 | 0.5181 (3) | 0.41440 (15) | 0.09881 (12) | 0.0157 (5) | |
C5 | 0.3811 (3) | 0.37328 (14) | 0.13113 (12) | 0.0162 (5) | |
H5 | 0.3828 | 0.3150 | 0.1377 | 0.019* | |
C6 | 0.2425 (3) | 0.42000 (14) | 0.15330 (12) | 0.0151 (5) | |
C7 | 0.0808 (3) | 0.39222 (14) | 0.19098 (13) | 0.0173 (5) | |
C8 | 0.6716 (3) | 0.36540 (14) | 0.07538 (12) | 0.0169 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
V1 | 0.0131 (2) | 0.0131 (2) | 0.0151 (2) | 0.00022 (14) | 0.00020 (15) | −0.00044 (15) |
K1 | 0.0174 (3) | 0.0170 (3) | 0.0256 (3) | −0.00151 (19) | −0.0029 (2) | 0.0042 (2) |
O1 | 0.0159 (8) | 0.0123 (8) | 0.0212 (8) | 0.0005 (6) | 0.0008 (7) | 0.0006 (7) |
O2 | 0.0163 (8) | 0.0155 (8) | 0.0244 (9) | 0.0001 (7) | 0.0035 (7) | 0.0029 (7) |
O3 | 0.0183 (8) | 0.0152 (8) | 0.0242 (9) | −0.0039 (7) | 0.0023 (7) | 0.0025 (7) |
O4 | 0.0220 (9) | 0.0129 (9) | 0.0260 (9) | −0.0027 (7) | 0.0025 (7) | 0.0023 (7) |
O5 | 0.0211 (9) | 0.0174 (9) | 0.0191 (8) | −0.0023 (7) | 0.0032 (7) | −0.0016 (7) |
O6 | 0.0182 (8) | 0.0208 (9) | 0.0230 (9) | −0.0033 (7) | −0.0042 (7) | 0.0044 (7) |
O7 | 0.0165 (8) | 0.0204 (9) | 0.0228 (9) | 0.0025 (7) | 0.0029 (7) | 0.0001 (7) |
O8 | 0.0241 (9) | 0.0184 (9) | 0.0231 (9) | 0.0042 (7) | 0.0006 (7) | 0.0025 (7) |
O9 | 0.0223 (9) | 0.0196 (10) | 0.0208 (10) | 0.0035 (7) | 0.0036 (7) | 0.0025 (8) |
N1 | 0.0158 (9) | 0.0128 (10) | 0.0128 (9) | −0.0006 (7) | −0.0003 (8) | −0.0010 (7) |
C1 | 0.0163 (11) | 0.0156 (12) | 0.0139 (11) | 0.0007 (9) | −0.0012 (9) | −0.0004 (9) |
C2 | 0.0158 (11) | 0.0157 (11) | 0.0120 (11) | −0.0031 (9) | −0.0027 (9) | −0.0003 (9) |
C3 | 0.0156 (11) | 0.0156 (12) | 0.0127 (11) | −0.0007 (9) | −0.0008 (9) | 0.0002 (9) |
C4 | 0.0167 (11) | 0.0197 (12) | 0.0106 (11) | −0.0002 (9) | −0.0032 (9) | −0.0014 (9) |
C5 | 0.0195 (12) | 0.0148 (11) | 0.0144 (11) | −0.0002 (9) | −0.0041 (9) | 0.0003 (9) |
C6 | 0.0167 (11) | 0.0163 (12) | 0.0124 (10) | −0.0023 (9) | −0.0024 (9) | 0.0005 (9) |
C7 | 0.0177 (11) | 0.0174 (13) | 0.0167 (11) | −0.0037 (9) | −0.0015 (9) | −0.0008 (9) |
C8 | 0.0167 (11) | 0.0190 (13) | 0.0148 (11) | 0.0014 (9) | −0.0018 (9) | −0.0010 (9) |
V1—O6 | 1.6187 (17) | O5—K1vi | 2.6593 (17) |
V1—O5 | 1.6287 (17) | O5—K1ix | 2.8313 (18) |
V1—O2 | 1.9949 (17) | O6—K1ix | 2.9612 (19) |
V1—O1 | 2.0091 (17) | O7—C8 | 1.310 (3) |
V1—N1 | 2.086 (2) | O7—H7 | 0.830 |
K1—O8i | 2.5981 (18) | O8—C8 | 1.219 (3) |
K1—O5ii | 2.6593 (17) | O8—K1x | 2.5981 (18) |
K1—O4 | 2.7377 (18) | O9—H9A | 0.81 (4) |
K1—O5iii | 2.8313 (18) | O9—H9B | 0.81 (4) |
K1—O4iv | 2.8721 (18) | N1—C6 | 1.330 (3) |
K1—O6iii | 2.9612 (19) | N1—C2 | 1.332 (3) |
K1—O1ii | 3.0867 (18) | C1—C2 | 1.507 (3) |
K1—O3v | 3.0909 (18) | C2—C3 | 1.380 (3) |
O1—C1 | 1.303 (3) | C3—C4 | 1.393 (3) |
O1—K1vi | 3.0867 (18) | C3—H3 | 0.960 |
O2—C7 | 1.301 (3) | C4—C5 | 1.395 (3) |
O3—C1 | 1.219 (3) | C4—C8 | 1.504 (3) |
O3—K1vii | 3.0909 (18) | C5—C6 | 1.385 (3) |
O4—C7 | 1.224 (3) | C5—H5 | 0.960 |
O4—K1viii | 2.8721 (18) | C6—C7 | 1.509 (3) |
O6—V1—O5 | 107.90 (9) | V1—O1—K1vi | 89.19 (6) |
O6—V1—O2 | 102.76 (8) | C7—O2—V1 | 122.32 (15) |
O5—V1—O2 | 99.31 (8) | C1—O3—K1vii | 109.16 (14) |
O6—V1—O1 | 97.34 (8) | C7—O4—K1 | 131.29 (15) |
O5—V1—O1 | 96.06 (8) | C7—O4—K1viii | 131.23 (15) |
O2—V1—O1 | 149.45 (7) | K1—O4—K1viii | 97.47 (5) |
O6—V1—N1 | 124.72 (8) | V1—O5—K1vi | 115.03 (8) |
O5—V1—N1 | 127.20 (8) | V1—O5—K1ix | 100.65 (8) |
O2—V1—N1 | 74.81 (7) | K1vi—O5—K1ix | 100.33 (6) |
O1—V1—N1 | 74.85 (7) | V1—O6—K1ix | 95.89 (7) |
O8i—K1—O5ii | 141.84 (6) | C8—O7—H7 | 109.5 |
O8i—K1—O4 | 89.24 (6) | C8—O8—K1x | 132.11 (15) |
O5ii—K1—O4 | 82.37 (5) | H9A—O9—H9B | 114 (4) |
O8i—K1—O5iii | 106.51 (6) | C6—N1—C2 | 121.7 (2) |
O5ii—K1—O5iii | 90.61 (5) | C6—N1—V1 | 119.25 (16) |
O4—K1—O5iii | 161.50 (5) | C2—N1—V1 | 119.01 (15) |
O8i—K1—O4iv | 86.43 (5) | O3—C1—O1 | 126.2 (2) |
O5ii—K1—O4iv | 131.19 (5) | O3—C1—C2 | 121.1 (2) |
O4—K1—O4iv | 94.67 (5) | O1—C1—C2 | 112.74 (19) |
O5iii—K1—O4iv | 77.10 (5) | N1—C2—C3 | 121.3 (2) |
O8i—K1—O6iii | 74.94 (5) | N1—C2—C1 | 111.1 (2) |
O5ii—K1—O6iii | 89.49 (5) | C3—C2—C1 | 127.7 (2) |
O4—K1—O6iii | 142.54 (5) | C2—C3—C4 | 117.4 (2) |
O5iii—K1—O6iii | 53.85 (5) | C2—C3—H3 | 121.3 |
O4iv—K1—O6iii | 117.40 (5) | C4—C3—H3 | 121.3 |
O8i—K1—O1ii | 162.14 (5) | C3—C4—C5 | 121.1 (2) |
O5ii—K1—O1ii | 55.83 (5) | C3—C4—C8 | 120.5 (2) |
O4—K1—O1ii | 97.63 (5) | C5—C4—C8 | 118.4 (2) |
O5iii—K1—O1ii | 64.52 (5) | C6—C5—C4 | 117.3 (2) |
O4iv—K1—O1ii | 76.63 (5) | C6—C5—H5 | 121.4 |
O6iii—K1—O1ii | 107.78 (5) | C4—C5—H5 | 121.4 |
O8i—K1—O3v | 74.10 (5) | N1—C6—C5 | 121.2 (2) |
O5ii—K1—O3v | 68.11 (5) | N1—C6—C7 | 110.3 (2) |
O4—K1—O3v | 69.04 (5) | C5—C6—C7 | 128.5 (2) |
O5iii—K1—O3v | 123.99 (5) | O4—C7—O2 | 125.0 (2) |
O4iv—K1—O3v | 154.36 (5) | O4—C7—C6 | 122.2 (2) |
O6iii—K1—O3v | 73.98 (5) | O2—C7—C6 | 112.8 (2) |
O1ii—K1—O3v | 123.75 (5) | O8—C8—O7 | 125.2 (2) |
C1—O1—V1 | 122.11 (14) | O8—C8—C4 | 121.4 (2) |
C1—O1—K1vi | 111.89 (13) | O7—C8—C4 | 113.4 (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. |
Experimental details
Crystal data | |
Chemical formula | K[V(C8H3NO6)O2]·H2O |
Mr | 349.17 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 153 |
a, b, c (Å) | 7.8086 (16), 16.342 (3), 18.316 (4) |
V (Å3) | 2337.2 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.25 |
Crystal size (mm) | 0.50 × 0.50 × 0.12 |
Data collection | |
Diffractometer | Rigaku Mercury CCD |
Absorption correction | Multi-scan (REQAB; Rigaku/MSC, 1999) |
Tmin, Tmax | 0.573, 0.864 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17213, 2099, 1951 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.079, 1.15 |
No. of reflections | 2099 |
No. of parameters | 190 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.38, −0.42 |
Computer programs: CrystalClear (Rigaku/MSC, 2006), CrystalClear, SHELXTL (Bruker, 2000), SHELXTL.
V1—O6 | 1.6187 (17) | V1—O1 | 2.0091 (17) |
V1—O5 | 1.6287 (17) | V1—N1 | 2.086 (2) |
V1—O2 | 1.9949 (17) |
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.