Acta Cryst. (2010). E66, m213-m214 [ doi:10.1107/S1600536810002953 ]
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3-2-oxidopyridinium-3-carboxylato)manganese(II)sodium(I)] monohydrate]In the crystal structure of the title compound, {[MnNa(C6H4NO3)3]·H2O}n, the MnII cation is located on a threefold rotation axis and is chelated by three 2-oxidopyridinium-3-carboxylate (opc) anions in an octahedal coordination. The NaI cation is located on a threefold rotation axis and is surrounded by six O atoms from three opc anions. The opc anions link the Mn and Na cations, forming a three-dimensional polymeric structure. The uncoordinated water molecule, located on a threefold rotation axis, is equally disordered over two sites. The three-dimensional network is consolidated by N-H
O hydrogen bonds.
2-Hydroxy-pyridine-3-carboxylic acid (0.13 g, 1 mmol), NaOH (0.04 g, 1 mmol), imidazole (0.14 g, 2 mmol) and Mn(NO3)2 (0.18 g, 1 mmol) and water (8 ml) and ethanol (2 ml) were sealed in a 25 ml stainless steel reactor with a Teflon liner. The reaction system was heated at 433 K for 9 h. After the mixture was cooled to room temperature the single crystals of the title complex were obtained.
The lattice water molecule is disordered over two sites with 0.5 occupancy for each component, the water H atom was placed in a chemical sensitive position and refined in a riding mode with Uiso(H) = 1.2Ueq(O1W). The H atom bonded to the pyridine N was located in a difference Fourier map and refined as riding in as-found relative position with Uiso(H) = 1.2Ueq(N). Other H atoms were placed in calculated positions with C—H = 0.93 and refined in riding mode with Uiso(H) = 1.2Ueq(C).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./ng2724fig1thm.gif)
| Fig. 1. The coordination environment around a Mn cation and a Na cation with 30% probability displacement ellipsoids (arbitrary spheres for H atoms) [symmetry codes: (i) 1-y, x-y, z; (ii) 1-x+y, 1-x, z]. |
| [MnNa(C6H4NO3)3]·H2O | Dx = 1.523 Mg m−3 |
| Mr = 510.25 | Mo Kα radiation, λ = 0.71073 Å |
| Trigonal, R3c | Cell parameters from 1286 reflections |
| Hall symbol: R 3 -2"c | θ = 2.6–25.0° |
| a = 10.1478 (18) Å | µ = 0.67 mm−1 |
| c = 37.420 (13) Å | T = 294 K |
| V = 3337.1 (15) Å3 | Prism, brown |
| Z = 6 | 0.33 × 0.28 × 0.26 mm |
| F(000) = 1554 |
| Rigaku R-AXIS RAPID IP diffractometer | 1315 independent reflections |
| Radiation source: fine-focus sealed tube | 1236 reflections with I > 2σ(I) |
| graphite | Rint = 0.027 |
| Detector resolution: 10.00 pixels mm-1 | θmax = 25.2°, θmin = 2.6° |
| ω scan | h = −11→11 |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −11→11 |
| Tmin = 0.822, Tmax = 0.840 | l = −44→44 |
| 6825 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
| wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0683P)2 + 0.0175P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.16 | (Δ/σ)max = 0.001 |
| 1315 reflections | Δρmax = 0.35 e Å−3 |
| 103 parameters | Δρmin = −0.49 e Å−3 |
| 1 restraint | Absolute structure: Flack (1983), 649 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: −0.01 (3) |
| [MnNa(C6H4NO3)3]·H2O | Z = 6 |
| Mr = 510.25 | Mo Kα radiation |
| Trigonal, R3c | µ = 0.67 mm−1 |
| a = 10.1478 (18) Å | T = 294 K |
| c = 37.420 (13) Å | 0.33 × 0.28 × 0.26 mm |
| V = 3337.1 (15) Å3 |
| Rigaku R-AXIS RAPID IP diffractometer | 1315 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1236 reflections with I > 2σ(I) |
| Tmin = 0.822, Tmax = 0.840 | Rint = 0.027 |
| 6825 measured reflections | θmax = 25.2° |
| R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
| wR(F2) = 0.099 | Δρmax = 0.35 e Å−3 |
| S = 1.16 | Δρmin = −0.49 e Å−3 |
| 1315 reflections | Absolute structure: Flack (1983), 649 Friedel pairs |
| 103 parameters | Flack parameter: −0.01 (3) |
| 1 restraint |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | Occ. (<1) | |
| Mn | 0.6667 | 0.3333 | 0.87519 (2) | 0.0258 (2) | |
| Na1 | 0.6667 | 0.3333 | 0.96375 (5) | 0.0283 (5) | |
| N1 | 0.7336 (3) | 0.0138 (3) | 0.93953 (7) | 0.0401 (6) | |
| H1N | 0.7655 | 0.0750 | 0.9589 | 0.048* | |
| O1 | 0.4925 (3) | −0.1044 (3) | 0.82611 (6) | 0.0464 (6) | |
| O2 | 0.5735 (3) | 0.1281 (3) | 0.84538 (6) | 0.0377 (6) | |
| O3 | 0.6999 (3) | 0.1941 (3) | 0.91404 (6) | 0.0425 (6) | |
| C1 | 0.5566 (3) | −0.0028 (3) | 0.84910 (7) | 0.0292 (6) | |
| C2 | 0.6173 (3) | −0.0412 (3) | 0.88206 (8) | 0.0321 (6) | |
| C3 | 0.6828 (3) | 0.0635 (3) | 0.91133 (8) | 0.0293 (6) | |
| C4 | 0.7283 (6) | −0.1207 (4) | 0.94099 (12) | 0.0596 (12) | |
| H4 | 0.7664 | −0.1454 | 0.9609 | 0.072* | |
| C5 | 0.6677 (6) | −0.2210 (4) | 0.91359 (12) | 0.0689 (13) | |
| H5 | 0.6651 | −0.3139 | 0.9141 | 0.083* | |
| C6 | 0.6092 (6) | −0.1799 (4) | 0.88440 (12) | 0.0581 (12) | |
| H6 | 0.5631 | −0.2494 | 0.8659 | 0.070* | |
| O1W | 0.6667 | 0.3333 | 0.6735 (14) | 0.26 (3) | 0.50 |
| H1W | 0.5895 | 0.3288 | 0.6601 | 0.310* | 0.6667 |
| O2W | 0.6667 | 0.3333 | 0.6459 (14) | 0.30 (3) | 0.50 |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mn | 0.0289 (3) | 0.0289 (3) | 0.0195 (4) | 0.01446 (13) | 0.000 | 0.000 |
| Na1 | 0.0312 (7) | 0.0312 (7) | 0.0225 (11) | 0.0156 (4) | 0.000 | 0.000 |
| N1 | 0.0555 (16) | 0.0401 (14) | 0.0283 (13) | 0.0266 (13) | −0.0171 (12) | −0.0075 (10) |
| O1 | 0.0624 (15) | 0.0393 (12) | 0.0297 (12) | 0.0195 (12) | −0.0221 (12) | −0.0113 (10) |
| O2 | 0.0536 (14) | 0.0337 (13) | 0.0250 (11) | 0.0213 (9) | −0.0148 (10) | −0.0030 (10) |
| O3 | 0.0703 (17) | 0.0398 (13) | 0.0283 (12) | 0.0358 (13) | −0.0199 (12) | −0.0107 (11) |
| C1 | 0.0288 (14) | 0.0302 (16) | 0.0235 (13) | 0.0110 (12) | −0.0031 (12) | −0.0034 (12) |
| C2 | 0.0360 (14) | 0.0296 (14) | 0.0269 (15) | 0.0135 (13) | −0.0089 (12) | −0.0046 (12) |
| C3 | 0.0348 (15) | 0.0314 (15) | 0.0238 (13) | 0.0180 (13) | −0.0069 (11) | −0.0005 (11) |
| C4 | 0.094 (3) | 0.050 (2) | 0.044 (2) | 0.043 (2) | −0.031 (2) | −0.0023 (17) |
| C5 | 0.113 (4) | 0.042 (2) | 0.063 (2) | 0.047 (3) | −0.041 (2) | −0.011 (2) |
| C6 | 0.091 (3) | 0.0422 (19) | 0.048 (2) | 0.038 (2) | −0.034 (2) | −0.0189 (17) |
| O1W | 0.31 (4) | 0.31 (4) | 0.16 (4) | 0.15 (2) | 0.000 | 0.000 |
| O2W | 0.34 (5) | 0.34 (5) | 0.23 (6) | 0.17 (2) | 0.000 | 0.000 |
| Mn—O2 | 2.123 (3) | N1—H1N | 0.9033 |
| Mn—O2i | 2.123 (3) | O1—C1 | 1.247 (4) |
| Mn—O2ii | 2.123 (3) | O2—C1 | 1.260 (4) |
| Mn—O3 | 2.168 (2) | O3—C3 | 1.251 (4) |
| Mn—O3i | 2.168 (2) | C1—C2 | 1.514 (4) |
| Mn—O3ii | 2.168 (2) | C2—C6 | 1.370 (4) |
| Mn—Na1 | 3.314 (2) | C2—C3 | 1.437 (4) |
| Na1—O1iii | 2.331 (2) | C4—C5 | 1.356 (6) |
| Na1—O1iv | 2.331 (3) | C4—H4 | 0.9300 |
| Na1—O1v | 2.331 (2) | C5—C6 | 1.403 (6) |
| Na1—O3 | 2.459 (3) | C5—H5 | 0.9300 |
| Na1—O3i | 2.459 (3) | C6—H6 | 0.9300 |
| Na1—O3ii | 2.459 (3) | O1W—H1W | 0.9106 |
| N1—C4 | 1.339 (5) | O2W—H1W | 0.9294 |
| N1—C3 | 1.376 (4) | ||
| O2—Mn—O2i | 94.91 (9) | O3—Na1—O3ii | 69.00 (10) |
| O2—Mn—O2ii | 94.91 (9) | O3i—Na1—O3ii | 69.00 (10) |
| O2i—Mn—O2ii | 94.91 (9) | O1iii—Na1—Mn | 117.77 (8) |
| O2—Mn—O3 | 81.45 (8) | O1iv—Na1—Mn | 117.77 (8) |
| O2i—Mn—O3 | 105.70 (10) | O1v—Na1—Mn | 117.77 (8) |
| O2ii—Mn—O3 | 159.28 (9) | O3—Na1—Mn | 40.85 (6) |
| O2—Mn—O3i | 159.28 (9) | O3i—Na1—Mn | 40.85 (6) |
| O2i—Mn—O3i | 81.45 (8) | O3ii—Na1—Mn | 40.85 (6) |
| O2ii—Mn—O3i | 105.70 (10) | C4—N1—C3 | 125.0 (3) |
| O3—Mn—O3i | 79.96 (10) | C4—N1—H1N | 119.0 |
| O2—Mn—O3ii | 105.70 (11) | C3—N1—H1N | 115.8 |
| O2i—Mn—O3ii | 159.28 (9) | C1—O1—Na1vi | 163.8 (2) |
| O2ii—Mn—O3ii | 81.45 (8) | C1—O2—Mn | 137.3 (2) |
| O3—Mn—O3ii | 79.96 (10) | C3—O3—Mn | 130.64 (19) |
| O3i—Mn—O3ii | 79.96 (10) | C3—O3—Na1 | 133.1 (2) |
| O2—Mn—Na1 | 121.71 (7) | Mn—O3—Na1 | 91.26 (9) |
| O2i—Mn—Na1 | 121.71 (7) | O1—C1—O2 | 122.4 (3) |
| O2ii—Mn—Na1 | 121.71 (7) | O1—C1—C2 | 117.4 (3) |
| O3—Mn—Na1 | 47.89 (6) | O2—C1—C2 | 120.3 (3) |
| O3i—Mn—Na1 | 47.89 (7) | C6—C2—C3 | 118.6 (3) |
| O3ii—Mn—Na1 | 47.89 (6) | C6—C2—C1 | 119.5 (3) |
| O1iii—Na1—O1iv | 100.04 (10) | C3—C2—C1 | 121.8 (2) |
| O1iii—Na1—O1v | 100.04 (10) | O3—C3—N1 | 116.6 (3) |
| O1iv—Na1—O1v | 100.04 (10) | O3—C3—C2 | 127.8 (3) |
| O1iii—Na1—O3 | 149.83 (11) | N1—C3—C2 | 115.6 (2) |
| O1iv—Na1—O3 | 109.27 (10) | N1—C4—C5 | 120.4 (4) |
| O1v—Na1—O3 | 82.12 (8) | N1—C4—H4 | 119.8 |
| O1iii—Na1—O3i | 82.12 (8) | C5—C4—H4 | 119.8 |
| O1iv—Na1—O3i | 149.83 (11) | C4—C5—C6 | 117.8 (3) |
| O1v—Na1—O3i | 109.27 (10) | C4—C5—H5 | 121.1 |
| O3—Na1—O3i | 69.00 (10) | C6—C5—H5 | 121.1 |
| O1iii—Na1—O3ii | 109.27 (10) | C2—C6—C5 | 122.5 (4) |
| O1iv—Na1—O3ii | 82.12 (8) | C2—C6—H6 | 118.7 |
| O1v—Na1—O3ii | 149.83 (11) | C5—C6—H6 | 118.7 |
| Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x+1, z; (iii) −x+y+4/3, y+2/3, z+1/6; (iv) −y+1/3, −x+2/3, z+1/6; (v) x+1/3, x−y−1/3, z+1/6; (vi) −x+y+2/3, y−2/3, z−1/6. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1N···O1v | 0.90 | 2.12 | 2.983 (4) | 161 |
| N1—H1N···O2v | 0.90 | 2.37 | 3.113 (4) | 140 |
| Symmetry codes: (v) x+1/3, x−y−1/3, z+1/6. |
| Mn—O2 | 2.123 (3) | Na1—O1i | 2.331 (2) |
| Mn—O3 | 2.168 (2) | Na1—O3 | 2.459 (3) |
| Symmetry codes: (i) −x+y+4/3, y+2/3, z+1/6. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1N···O1ii | 0.90 | 2.12 | 2.983 (4) | 161 |
| N1—H1N···O2ii | 0.90 | 2.37 | 3.113 (4) | 140 |
| Symmetry codes: (ii) x+1/3, x−y−1/3, z+1/6. |
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As a part of ongoing investigation on π-π stacking (Li et al., 2005), the title complex has been prepared in the laboratory and its crystal structure is reported here.
In the crystal structure the MnII cation is located in a three-fold ratation axis and is chelated by three 2-oxidopyridinium-3-carboxylate (opc) anions in a distorted anti-triprism geometry (Fig. 1). The NaI cation is located on the same three-fold rotation axis and is surrounded by six O atoms from three opc anions (Table 1). The opc anions link the Mn and Na cations to form the three dimensional polymeric structure.
The shorter C—O bond distance of 1.251 (4) Å is observed between the deprotonated hydroxy group and pyridinium ring. This is similar to those found in the related complexes of oxidopyridinium-carboxylate (Yao et al., 2004; Yan & Hu, 2007a,b; Wen & Liu, 2007; Zhang et al. 2009a,b), it is also consistent with that found in hydroxy-pyridinecarboxylate complex (Quintal et al. 2002). This finding suggests the electron delocalization between pyridine ring and hydroxy group. But this shorter C—O bond is much different from the C—O bond distance of ca. 1.35 Å between benzene ring and hydroxy-O atom found in hydroxy-benzencarboxylic acid (Munshi & Guru Row, 2006) and in hydroxy-benzenecarboxylate complexes of metals (Su & Xu, 2005; Li et al., 2005).
The lattice water molecule located on the three-fold rotation axis is disordered over two sites with o.5 occupancies for each component. The N—H···O hydrogen bondings are present in the polymeric structure. No π-π stacking is observed in the crystal structure.