Acta Cryst. (2007). E63, m2360 [ doi:10.1107/S1600536807039773 ]
![[mu]](/logos/entities/mu_rmgif.gif)
3-malonato--pyrazine-dimanganese(II)]The title compound, [Mn2(C3H2O4)2(C4H4N2)(H2O)2]n, is isostructural with its CoII, NiII, ZnII and CdII analogues, and the complex resides on a crystallographic centre of inversion (at the pyrazine ring centroid). The MnII atoms are linked via coordinated malonates, forming a two-dimensional network with cavities. These sheets are further connected into a three-dimensional network by bridging pyrazine ligands which have inversion symmetry. The coordination geometry around the MnII atom is a tetragonally elongated octahedron, with pyrazine N and aqua O atoms at the axial positions.
A mixture of manganese(II) sulfate (0.5 mmol), malonate acid (0.5 mmol), sodium hydroxide (1 mmol), pyrazine (1 mmol) and H2O (8 ml) in a 25 ml Teflon-lined stainless steel autoclave was heated at 443 K for two days, and then cooled to room temperature. block crystals of complex (I) were obtained with a yield of 22%. Anal. Calc. for C5H6NMnO5: C 27.91, H 2.79, N 6.51%; Found: C 27.88, H 2.75, N 6.47%.
All H atoms on C atoms were generated geometrically and treated as riding atoms with C—H= 0.93Å and Uiso(H)= 1.2 times Ueq(C). The H atoms of the water molecule were located from difference density maps and were refined with distance restraints of d(H–H) = 1.38 (2) Å, d(O–H) = 0.82 (1) Å.
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).
![[Figure 1]](./gg2036fig1thm.gif)
| Fig. 1. Atom labeling scheme for the title complex (I), showing 30% probability displacement ellipsoids for non-H atoms. Atoms labeled with i are at the symmetry position (−x + 1,-y,-z + 1). |
![[Figure 2]](./gg2036fig2thm.gif)
| Fig. 2. Packing diagram for the title complex along the c axis. |
| [Mn2(C3H2O4)2(C4H4N2)(H2O)2] | F000 = 432 |
| Mr = 430.10 | Dx = 1.908 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 1314 reflections |
| a = 7.0127 (10) Å | θ = 2.8–25.1º |
| b = 14.490 (2) Å | µ = 1.74 mm−1 |
| c = 7.3711 (10) Å | T = 293 (2) K |
| β = 92.182 (1)º | Block, colorless |
| V = 748.45 (18) Å3 | 0.36 × 0.28 × 0.24 mm |
| Z = 2 |
| Bruker APEX II CCD area-detector diffractometer | 1314 independent reflections |
| Radiation source: fine-focus sealed tube | 1103 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.023 |
| T = 293(2) K | θmax = 25.1º |
| φ and ω scans | θmin = 2.8º |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −8→3 |
| Tmin = 0.573, Tmax = 0.680 | k = −13→16 |
| 2397 measured reflections | l = −8→8 |
| 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)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.117 | w = 1/[σ2(Fo2) + (0.0636P)2 + 2.2589P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.00 | (Δ/σ)max = 0.013 |
| 1314 reflections | Δρmax = 0.72 e Å−3 |
| 116 parameters | Δρmin = −0.40 e Å−3 |
| 3 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.051 (5) |
| [Mn2(C3H2O4)2(C4H4N2)(H2O)2] | V = 748.45 (18) Å3 |
| Mr = 430.10 | Z = 2 |
| Monoclinic, P21/n | Mo Kα |
| a = 7.0127 (10) Å | µ = 1.74 mm−1 |
| b = 14.490 (2) Å | T = 293 (2) K |
| c = 7.3711 (10) Å | 0.36 × 0.28 × 0.24 mm |
| β = 92.182 (1)º |
| Bruker APEX II CCD area-detector diffractometer | 1314 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1103 reflections with I > 2σ(I) |
| Tmin = 0.573, Tmax = 0.680 | Rint = 0.023 |
| 2397 measured reflections |
| R[F2 > 2σ(F2)] = 0.045 | 3 restraints |
| wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.00 | Δρmax = 0.72 e Å−3 |
| 1314 reflections | Δρmin = −0.40 e Å−3 |
| 116 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 | ||
| C3 | 0.5846 (7) | 0.3318 (3) | 0.7561 (7) | 0.0344 (11) | |
| C4 | 0.6125 (8) | 0.3910 (4) | 0.5887 (7) | 0.0432 (12) | |
| H4A | 0.7407 | 0.4162 | 0.5951 | 0.052* | |
| H4B | 0.5240 | 0.4424 | 0.5904 | 0.052* | |
| C5 | 0.5834 (7) | 0.3404 (3) | 0.4123 (7) | 0.0348 (11) | |
| C2 | 0.4526 (8) | 0.0744 (4) | 0.5906 (8) | 0.0507 (14) | |
| H2 | 0.4135 | 0.1258 | 0.6549 | 0.061* | |
| C1 | 0.6785 (7) | −0.0046 (4) | 0.4448 (8) | 0.0468 (13) | |
| H1 | 0.8016 | −0.0106 | 0.4036 | 0.056* | |
| Mn1 | 0.83760 (8) | 0.19134 (4) | 0.58103 (7) | 0.0172 (3) | |
| N1 | 0.6323 (6) | 0.0717 (3) | 0.5372 (6) | 0.0389 (10) | |
| O2 | 0.6638 (5) | 0.2528 (3) | 0.7693 (5) | 0.0433 (9) | |
| O5 | 0.4862 (5) | 0.3675 (2) | 0.8747 (5) | 0.0435 (9) | |
| O3 | 0.6698 (5) | 0.2644 (3) | 0.3903 (5) | 0.0464 (9) | |
| O4 | 0.4753 (5) | 0.3775 (2) | 0.2943 (5) | 0.0427 (9) | |
| O1 | 1.0317 (6) | 0.3107 (3) | 0.5859 (5) | 0.0473 (9) | |
| H2W | 1.087 (8) | 0.313 (5) | 0.489 (4) | 0.080* | |
| H1W | 1.104 (7) | 0.303 (5) | 0.675 (5) | 0.080* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C3 | 0.038 (2) | 0.031 (3) | 0.034 (2) | 0.000 (2) | 0.0003 (19) | −0.005 (2) |
| C4 | 0.060 (3) | 0.035 (3) | 0.034 (3) | 0.005 (2) | 0.003 (2) | 0.000 (2) |
| C5 | 0.039 (2) | 0.029 (3) | 0.036 (3) | 0.003 (2) | 0.005 (2) | 0.004 (2) |
| C2 | 0.048 (3) | 0.042 (3) | 0.063 (4) | −0.006 (3) | 0.018 (3) | −0.014 (3) |
| C1 | 0.041 (3) | 0.037 (3) | 0.063 (4) | −0.002 (2) | 0.012 (2) | −0.009 (3) |
| Mn1 | 0.0218 (4) | 0.0155 (4) | 0.0144 (4) | 0.0007 (2) | 0.0018 (2) | −0.0006 (2) |
| N1 | 0.039 (2) | 0.036 (2) | 0.042 (2) | −0.0017 (18) | 0.0021 (17) | −0.0012 (19) |
| O2 | 0.056 (2) | 0.039 (2) | 0.0350 (19) | 0.0076 (17) | 0.0117 (16) | 0.0031 (15) |
| O5 | 0.049 (2) | 0.040 (2) | 0.043 (2) | 0.0044 (16) | 0.0172 (16) | −0.0004 (17) |
| O3 | 0.058 (2) | 0.045 (2) | 0.0355 (19) | 0.0118 (18) | −0.0044 (16) | −0.0029 (16) |
| O4 | 0.053 (2) | 0.0347 (19) | 0.0399 (19) | 0.0032 (17) | −0.0064 (16) | 0.0032 (16) |
| O1 | 0.051 (2) | 0.055 (2) | 0.037 (2) | −0.0021 (18) | 0.0019 (16) | 0.0004 (18) |
| C3—O5 | 1.246 (6) | C1—C2i | 1.386 (8) |
| C3—O2 | 1.275 (6) | C1—H1 | 0.9300 |
| C3—C4 | 1.521 (7) | Mn1—O5ii | 2.060 (3) |
| C4—C5 | 1.500 (7) | Mn1—O4iii | 2.070 (4) |
| C4—H4A | 0.9700 | Mn1—O3 | 2.087 (4) |
| C4—H4B | 0.9700 | Mn1—O2 | 2.082 (3) |
| C5—O4 | 1.254 (6) | Mn1—O1 | 2.200 (4) |
| C5—O3 | 1.270 (7) | Mn1—N1 | 2.269 (4) |
| C2—N1 | 1.335 (7) | O5—Mn1iv | 2.060 (3) |
| C2—C1i | 1.386 (8) | O4—Mn1v | 2.070 (4) |
| C2—H2 | 0.9300 | O1—H2W | 0.83 (4) |
| C1—N1 | 1.344 (7) | O1—H1W | 0.82 (4) |
| O5—C3—O2 | 124.7 (5) | O4iii—Mn1—O2 | 88.18 (14) |
| O5—C3—C4 | 115.3 (4) | O3—Mn1—O2 | 84.41 (14) |
| O2—C3—C4 | 119.9 (4) | O5ii—Mn1—O1 | 90.42 (14) |
| C3—C4—C5 | 114.2 (4) | O4iii—Mn1—O1 | 95.52 (14) |
| C3—C4—H4A | 108.7 | O3—Mn1—O1 | 86.84 (16) |
| C5—C4—H4A | 108.7 | O2—Mn1—O1 | 91.75 (15) |
| C3—C4—H4B | 108.7 | O5ii—Mn1—N1 | 85.11 (15) |
| C5—C4—H4B | 108.7 | O4iii—Mn1—N1 | 90.85 (15) |
| H4A—C4—H4B | 107.6 | O3—Mn1—N1 | 87.32 (16) |
| O4—C5—O3 | 124.2 (5) | O2—Mn1—N1 | 92.14 (15) |
| O4—C5—C4 | 116.8 (4) | O1—Mn1—N1 | 172.65 (15) |
| O3—C5—C4 | 119.0 (4) | C2—N1—C1 | 115.0 (4) |
| N1—C2—C1i | 123.3 (5) | C2—N1—Mn1 | 122.4 (4) |
| N1—C2—H2 | 118.3 | C1—N1—Mn1 | 122.4 (3) |
| C1i—C2—H2 | 118.3 | C3—O2—Mn1 | 126.7 (3) |
| N1—C1—C2i | 121.7 (5) | C3—O5—Mn1iv | 131.0 (3) |
| N1—C1—H1 | 119.2 | C5—O3—Mn1 | 127.8 (3) |
| C2i—C1—H1 | 119.2 | C5—O4—Mn1v | 124.9 (3) |
| O5ii—Mn1—O4iii | 97.27 (15) | Mn1—O1—H2W | 109 (5) |
| O5ii—Mn1—O3 | 90.03 (15) | Mn1—O1—H1W | 105 (5) |
| O4iii—Mn1—O3 | 172.30 (14) | H2W—O1—H1W | 114 (3) |
| O5ii—Mn1—O2 | 173.92 (15) |
| Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) x−1/2, −y+1/2, z+1/2; (v) x−1/2, −y+1/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H2W···O2ii | 0.83 (4) | 1.97 (4) | 2.705 (5) | 148 (7) |
| O1—H1W···O3iii | 0.82 (4) | 1.90 (4) | 2.644 (5) | 149 (7) |
| Symmetry codes: (ii) x+1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H2W···O2i | 0.83 (4) | 1.97 (4) | 2.705 (5) | 148 (7) |
| O1—H1W···O3ii | 0.82 (4) | 1.90 (4) | 2.644 (5) | 149 (7) |
| Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) x+1/2, −y+1/2, z+1/2. |
Bruker (2001). SAINT-Plus, SHELXTL and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.
Chung, L., Rajan, K. S., Merdinger, E. & Crecz, N. (1971). Biophys. J. 11, 469–475.
Delgado, F. S., Hemandez-Molina, M., Sanchiz, J., Ruiz-Perez, C., Rodriguez-Martin, Y., Lopez, T., Lioret, F. & Julve, M. (2004). CrystEngComm, 6, 106–109.
Delgado, F. S., Sanchiz, J., Ruiz-Perez, C., Lloret, F. & Julve, M. (2003). CrystEngComm, 5, 280–286.
Kim, Y., Lee, E. & Jung, D. Y. (2001). Chem. Mater. 13, 2684–2699.
Liu, Y., Dou, J., Wang, D., Ma, G. & Li, D. (2005). Acta Cryst. E61, m1834–m1836.
Mao, H. Y., Zhang, C. Z., Li, G., Zhang, H. Y., Hou, H. W., Li, L. J., Wu, Q. G., Zhu, Y. & Wang, E. B. (2004). Discuss. Faraday Soc. pp. 3918–3919.
Okabe, N. & Oya, N. (2000). Acta Cryst. C56, 1416–1417.
Pocker, Y. & Fong, C. T. O. (1980). Biochemistry, 19, 2045–2049.
Scapin, G., Reddy, S. G., Zheng, R. & Blanchard, J. S. (1997). Biochemistry, 36, 1508–15088.
Serre, C., Marrot, J. & Ferey, G. (2005). Inorg. Chem. 44, 654–658.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Zhang, X. T., Lu, C. Z., Zhang, Q. Z., Lu, S. F., Yang, W. B., Liu, J. C. & Zhuang, H. H. (2003). Eur. J. Inorg. Chem. pp. 1181–11816 Please check date; 2007 in text.
In recent years, dicarboxylic acids have been widely used as polydentate ligands, which undergo various metal chelation reactions to form transition or rare earth metal complexes with interesting properties in materials science and in biological systems (Church et al., 1971; Okabe & Oya, 2000; Serre et al., 2005; Pocker & Fong, 1980; Scapin et al., 1997). For example, Kim et al. (2001) focused on the syntheses of transition metal complexes containing benzene dicarboxylate and rigid aromatic pyridine ligands in order to study their electronic conductivity and magnetic properties. The importance of transition metal dicarboxylate complexes in materials science and biological systems prompted us to pursue synthetic strategies for these compounds, using malonate as a polydentate ligand and pyrazine as a rigid aromatic ligand. In this paper, we report the synthesis and X-ray crystal structure analysis of the title compound, [Mn2(C3H2O4)2(C4H4N2)(H2O)2]n.
The MnII atom has sixfold coordination, chelated by two O atoms from one malonate ligand to form a six-membered boat-type ring, and by two O atoms from two neighbouring malonates, one aqua molecule and one N atom from the bridging pyrazine ligand (Fig. 1). The Mn—O(carboxylate) and Mn—N bond lengths are in the range 2.060 (4) to 2.220 (4) and 2.269 (4) Å, respectively.
The packing diagram is shown in Fig. 2. If the pyrazine bridges are neglected, a two-dimensional network is formed by the [Mn(malonate)(H2O)] moieties parallel to the (010) plane. There are hydrogen bonds (Table 2) between the aqua and malonate ligands in this network.