Acta Cryst. (2007). E63, m2389-m2390 [ doi:10.1107/S1600536807040470 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-oxalato-![[kappa]](/logos/entities/kappa_rmgif.gif)
4O1,O2:O1',O2']The title polymer, [Mn(C2O4)(H2O)2]n, was synthesized by the reaction of manganese(II) nitrate tetrahydrate with a proton-transfer compound, (pipzH2)(ox) (where oxH2 is oxalic acid and pipz is piperazine), in aqueous solution. The structure features a six-coordinate Mn2+ ion located on a twofold rotation axis, with a distorted octahedral geometry [Mn-O = 2.1728 (8)-2.1914 (9) Å]. The bond angles show that the two coordinated water molecules are arranged trans. One-dimensional linear chains are formed through bis-bidentate oxalate ligands bridging the MnII ions. These structural units are held together by O-H
O hydrogen bonds. A neutron diffraction study of [Mn(-ox)(D2O)2]n, using powdered samples, has been published recently in the same space group [Sledzinska, Murasik & Fischer (1987). J. Phys. Solid State Phys. 20, 2247-2259]. However, it should be noted that an orthorhombic polymorph for the title polymer is also known [Huizing, van Hal, Kwestroo, Langereis & van Loosdregt (1977). Mater. Res. Bull. 12, 605-611; Lethbridge, Congreve, Esslemont, Slawin & Lightfoot (2003). J. Solid State Chem. 172, 212-218]. The present single-crystal X-ray study deals with the monoclinic polymorph. This phase is isostructural with the CoII analogue.
A solution of Mn(NO3)2·4H2O (125 mg, 0.5 mmol) in water (20 ml) was added to an aqueous solution of (pipzH2)(ox) (253 mg, 1.0 mmol) in water (20 ml) in a 2:1 molar ratio (oxH2 is oxalic acid and pipz is piperazine; see Aghabozorg et al., 2006). Colorless crystals of (I) were obtained after a few days at room temperature.
H atoms for the water molecule O3 were found in a difference map but their positions regularized with O—H bond lengths constrained to 0.95 Å. H atoms were constrained to ride on O3 and were refined with an isotropic displacement parameter fixed to Uiso(H) = 1.2 Ueq(O3).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL.
![[Figure 1]](./bh2112fig1thm.gif)
| Fig. 1. Molecular structure of compound (I), displacement ellipsoids are drawn at the 50% probability level. |
![[Figure 2]](./bh2112fig2thm.gif)
| Fig. 2. Crystal packing of the title compound (I), hydrogen bonds are shown as dashed lines. |
| [Mn(C2O4)(H2O1)2] | F000 = 356 |
| Mr = 178.99 | Dx = 2.288 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 3637 reflections |
| a = 11.7648 (14) Å | θ = 3.4–27.5º |
| b = 5.6550 (6) Å | µ = 2.49 mm−1 |
| c = 9.6367 (11) Å | T = 296 (2) K |
| β = 125.843 (6)º | Block, colourless |
| V = 519.71 (10) Å3 | 0.21 × 0.21 × 0.11 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 607 independent reflections |
| Radiation source: fine-focus sealed tube | 604 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.025 |
| Detector resolution: 100 pixels mm-1 | θmax = 27.7º |
| T = 296(2) K | θmin = 4.2º |
| ω scans | h = −15→15 |
| Absorption correction: multi-scan (SADABS; Bruker, 1998) | k = −7→6 |
| Tmin = 0.616, Tmax = 0.763 | l = −12→12 |
| 4187 measured reflections |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.016 | w = 1/[σ2(Fo2) + (0.0267P)2 + 0.4357P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.046 | (Δ/σ)max < 0.001 |
| S = 1.10 | Δρmax = 0.46 e Å−3 |
| 607 reflections | Δρmin = −0.40 e Å−3 |
| 43 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0173 (15) |
| Secondary atom site location: difference Fourier map |
| [Mn(C2O4)(H2O1)2] | V = 519.71 (10) Å3 |
| Mr = 178.99 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 11.7648 (14) Å | µ = 2.49 mm−1 |
| b = 5.6550 (6) Å | T = 296 (2) K |
| c = 9.6367 (11) Å | 0.21 × 0.21 × 0.11 mm |
| β = 125.843 (6)º |
| Bruker SMART CCD area-detector diffractometer | 607 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 1998) | 604 reflections with I > 2σ(I) |
| Tmin = 0.616, Tmax = 0.763 | Rint = 0.025 |
| 4187 measured reflections |
| R[F2 > 2σ(F2)] = 0.016 | 43 parameters |
| wR(F2) = 0.046 | H-atom parameters constrained |
| S = 1.10 | Δρmax = 0.46 e Å−3 |
| 607 reflections | Δρmin = −0.40 e Å−3 |
| x | y | z | Uiso*/Ueq | ||
| Mn1 | 0.5000 | 0.56903 (4) | 0.7500 | 0.00841 (13) | |
| C1 | 0.55073 (12) | 1.07019 (17) | 0.85025 (14) | 0.0084 (2) | |
| O1 | 0.58713 (8) | 0.87221 (15) | 0.92326 (10) | 0.01030 (19) | |
| O2 | 0.58807 (8) | 1.26771 (14) | 0.92238 (10) | 0.00973 (19) | |
| O3 | 0.31804 (9) | 0.56581 (13) | 0.75879 (11) | 0.0116 (2) | |
| H3A | 0.2346 | 0.6137 | 0.6532 | 0.014* | |
| H3B | 0.3304 | 0.6569 | 0.8495 | 0.014* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mn1 | 0.01051 (17) | 0.00518 (17) | 0.00806 (17) | 0.000 | 0.00461 (13) | 0.000 |
| C1 | 0.0080 (5) | 0.0101 (6) | 0.0070 (6) | 0.0001 (3) | 0.0044 (5) | 0.0001 (3) |
| O1 | 0.0124 (4) | 0.0067 (4) | 0.0085 (4) | 0.0003 (3) | 0.0043 (3) | 0.0007 (3) |
| O2 | 0.0124 (4) | 0.0065 (4) | 0.0080 (4) | −0.0005 (3) | 0.0047 (3) | −0.0006 (3) |
| O3 | 0.0121 (4) | 0.0121 (4) | 0.0086 (4) | 0.0005 (3) | 0.0049 (4) | −0.0009 (3) |
| Mn1—O2i | 2.1728 (8) | C1—O2 | 1.2515 (13) |
| Mn1—O2ii | 2.1728 (8) | C1—O1 | 1.2566 (13) |
| Mn1—O1 | 2.1849 (9) | C1—C1iii | 1.567 (2) |
| Mn1—O1iii | 2.1849 (9) | O2—Mn1iv | 2.1728 (8) |
| Mn1—O3 | 2.1914 (9) | O3—H3A | 0.9501 |
| Mn1—O3iii | 2.1914 (9) | O3—H3B | 0.9500 |
| O2i—Mn1—O2ii | 76.70 (4) | O1—Mn1—O3iii | 90.24 (3) |
| O2i—Mn1—O1 | 179.57 (3) | O1iii—Mn1—O3iii | 90.50 (3) |
| O2ii—Mn1—O1 | 103.35 (3) | O3—Mn1—O3iii | 179.05 (4) |
| O2i—Mn1—O1iii | 103.35 (3) | O2—C1—O1 | 126.19 (11) |
| O2ii—Mn1—O1iii | 179.57 (3) | O2—C1—C1iii | 116.80 (6) |
| O1—Mn1—O1iii | 76.61 (4) | O1—C1—C1iii | 117.00 (6) |
| O2i—Mn1—O3 | 89.07 (3) | C1—O1—Mn1 | 114.69 (7) |
| O2ii—Mn1—O3 | 90.19 (3) | C1—O2—Mn1iv | 114.84 (7) |
| O1—Mn1—O3 | 90.50 (3) | Mn1—O3—H3A | 112.1 |
| O1iii—Mn1—O3 | 90.24 (3) | Mn1—O3—H3B | 113.9 |
| O2i—Mn1—O3iii | 90.19 (3) | H3A—O3—H3B | 109.6 |
| O2ii—Mn1—O3iii | 89.07 (3) | ||
| O2—C1—O1—Mn1 | −179.34 (9) | O3—Mn1—O1—C1 | −90.31 (8) |
| C1iii—C1—O1—Mn1 | 0.46 (15) | O3iii—Mn1—O1—C1 | 90.28 (8) |
| O2ii—Mn1—O1—C1 | 179.38 (7) | O1—C1—O2—Mn1iv | −179.48 (9) |
| O1iii—Mn1—O1—C1 | −0.18 (6) | C1iii—C1—O2—Mn1iv | 0.72 (15) |
| Symmetry codes: (i) −x+1, y−1, −z+3/2; (ii) x, y−1, z; (iii) −x+1, y, −z+3/2; (iv) x, y+1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3A···O1v | 0.95 | 1.85 | 2.7696 (12) | 162 |
| O3—H3B···O2vi | 0.95 | 1.86 | 2.7517 (12) | 155 |
| Symmetry codes: (v) x−1/2, −y+3/2, z−1/2; (vi) −x+1, −y+2, −z+2. |
| Mn1—O2i | 2.1728 (8) | Mn1—O3 | 2.1914 (9) |
| Mn1—O1 | 2.1849 (9) | ||
| O2ii—Mn1—O2i | 76.70 (4) | O2ii—Mn1—O3iii | 90.19 (3) |
| O2ii—Mn1—O1 | 179.57 (3) | O2i—Mn1—O3iii | 89.07 (3) |
| O2i—Mn1—O1 | 103.35 (3) | O1—Mn1—O3iii | 90.24 (3) |
| O2ii—Mn1—O1iii | 103.35 (3) | O1iii—Mn1—O3iii | 90.50 (3) |
| O2i—Mn1—O1iii | 179.57 (3) | O3—Mn1—O3iii | 179.05 (4) |
| O1—Mn1—O1iii | 76.61 (4) | C1—O1—Mn1 | 114.69 (7) |
| O2ii—Mn1—O3 | 89.07 (3) | C1—O2—Mn1iv | 114.84 (7) |
| O2i—Mn1—O3 | 90.19 (3) | Mn1—O3—H3A | 112.1 |
| O1—Mn1—O3 | 90.50 (3) | Mn1—O3—H3B | 113.9 |
| O1iii—Mn1—O3 | 90.24 (3) | H3A—O3—H3B | 109.6 |
| Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1, −z+3/2; (iii) −x+1, y, −z+3/2; (iv) x, y+1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3A···O1v | 0.95 | 1.85 | 2.7696 (12) | 162 |
| O3—H3B···O2vi | 0.95 | 1.86 | 2.7517 (12) | 155 |
| Symmetry codes: (v) x−1/2, −y+3/2, z−1/2; (vi) −x+1, −y+2, −z+2. |
Financial support from Ilam University and the Teacher Training University is gratefully acknowledged.
Aghabozorg, H., Ghadermazi, M. & Sheshmani, S. (2006). Acta Cryst. E62, o3287–o3289.
Bacsa, J., Eve, D. & Dunbar, K. R. (2005). Acta Cryst. C61, m58–m60.
Bruker (1998). SADABS (Version 2004/1), SAINT (Version 6.01) and SMART (Version 5.059). Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2005). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA.
Castillo, O., Luque, A., Lloret, F. & Román, P. (2001). Inorg. Chem. Commun. 4, 350–353.
Chiozzone, R., Gonzalez, R., Kremer, C., De Munno, G., Armentano, D., Lloret, F., Julve, M. & Faus, J. (2003). Inorg. Chem. 42, 1064–1069.
Deyrieux, R., Berro, C. & Peneloux, A. (1973). Bull. Soc. Chim. Fr. 1, 25–34.
Fu, X., Wang, C. & Li, M. (2005). Acta Cryst. E61, m1348–m1349.
Huizing, A., van Hal, H. A. M., Kwestroo, W., Langereis, C. & van Loosdregt, P. C. (1977). Mater. Res. Bull. 12, 605–611.
Lethbridge, Z. A. D., Congreve, A. F., Esslemont, E., Slawin, A. M. Z. & Lightfoot, P. (2003). J. Solid State Chem. 172, 212–218.
Marinescu, G., Lescouëzec, R., Armentano, D., De Munno, G., Andruh, M., Uriel, S., Llusar, R., Lloret, F. & Julve, M. (2002). Inorg. Chim. Acta, 336, 46–54.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Sledzinska, I., Murasik, A. & Fischer, P. (1987). J. Phys. Solid State Phys. 20, 2247–2259.
Verdaguer, M. (2001). Polyhedron, 20, 1115–1128.
Wu, W.-Y., Song, Y., Li, Y.-Z. & You, X.-Z. (2005). Inorg. Chem. Commun. 8, 732–736.
Oxalato-bridged coordination compounds have played a key role in the theoretical and experimental development of areas such as molecular magnetism (Verdaguer, 2001) and crystal engineering (Marinescu et al., 2002). It has been established that two crystal hydrates are formed in this system MnC2O4·2H2O and MnC2O4·3H2O. Both crystal hydrates differ in color and structure. The white α-MnC2O4·2H2O is monoclinic, space group C2/c (Deyrieux et al., 1973), while the pink-colored MnC2O4·3H2O is orthorhombic, space group Pcca (Huizing et al., 1977, Fu et al., 2005; Wu et al., 2005). However, the paper published by Deyrieux et al. does not include atomic coordinates. A neutron diffraction study for MnC2O4·two-dimensional2O, using powdered samples, has been published recently (Sledzinska et al., 1987). It is noticeable that an orthorhombic polymorphs for the title polymer is also known (Huizing et al., 1977; Lethbridge et al.., 2003;). In this way, our X-ray study deals with the monoclinic polymorph. It is expected that the difference in the crystal lattice of the compounds and the different way of bonding of water molecules would affect some properties, such as a thermal stability, oxidation, and magnetic behavior. The wide variety of coordination modes of the oxalate anion with different metals allows the use of metal-oxalato units as excellent building blocks to construct a great diversity of homo- and heterometallic structural frameworks ranging from discrete polymeric entities (Chiozzone et al., 2003) to one-, two- and three-dimensional networks (Castillo et al. 2001).
Figure 1 shows that the O3 and O3d atoms of the two coordinated water molecules occupy the axial positions, while O1, O1d, O2a and O2c atoms of bridging oxalate ligands form the equatorial plane. The O3—Mn—O3d angle is almost linear, 179.05 (4)°. Therefore, coordination sphere around the MnII center, placed on a twofold symmetry axis, is almost octahedral. The torsion angles show that the oxalate ligand is planar. Also, the result shows that one-dimensional linear chains are formed in the crystal structure through bridging bis-bidentate oxalate ligands. The bond angles show that the two coordinated water molecules are arranged trans. A remarkable feature in the crystal structure of (I) is the presence of strong O—H···O hydrogen bonds, connecting one-dimensional chains in the crystal structure (Fig. 2). The title complex is isomorphous to the corresponding CoII-based polymer (Bacsa et al., 2005).