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Acta Cryst. (2008). E64, m558    [ doi:10.1107/S1600536808006417 ]

Diaquabis(pyrazine-2-carboxylato-[kappa]2N1,O)manganese(II) dihydrate

H.-D. Xie, C.-Z. Xie and F.-F. Dang

Abstract top

In the title compound, [Mn(C5H3N2O2)2(H2O)2]·2H2O, the MnII atom, lying on an inversion centre, has a distorted octahedral environment and the molecules are linked by O-H...O and N-H...O hydrogen bonds to form a three-dimensional supramolecular structure.

Comment top

In the past decades, self-assembly processes involving metal ions and organic ligands directed by either metal coordination or hydrogen bonds have received a great deal of attention in the field of supramolecular chemistry and crystal engineering. Pyrazine carboxylic acids, containing O– or N– donors, are excellent bridging ligands when coordinated to transition metals and have been extensively studied as active ligands in the course of electron-transfer and magnetochemistry research (Klein et al., 1982; O'Connor et al., 1981). The cobalt(II), nickel(II), copper(II), zinc(II) and manganese(II) complexes of the 2-pyrazinecarboxylic acid ligand have been reported (Ciurtin et al., 2002; Dong et al., 2000; Ptasiewicz-Bak et al., 1995). Ptasiewicz-Bak et al. reported an orthorhombic manganese(II) dipyrazinate dihydrate complex (space group Fdd2), in which the coordination polyhedron around the MnII atom is a distorted octahedron with cis positioned water molecules. The title complex is another monomeric complex of MnII with the 2-pyrazinecarboxylic acid ligand, which is isostructrual to the cobalt(II) complex (Ptasiewicz-Bak et al., 1995).

The MnII atom sits on an inversion center and the coordination geometry for the MnII atom (Fig. 1) is distorted octahedral (Table 1). Each MnII atom is axially coordinated by water molecules and consists of an equatorial plane of two oxygen donors and two nitrogen donors from two chelating 2-pyrazinecarboxylato group. As a consequence of the reaction the carboxylic groups of the starting diacid in position 3 are decarboxylated while the coordinated carboxylic groups in 2-position are kept and are deprotonated. The title molecules are connected by the O—H···N and O—H···O hydrogen-bonding interactions (Fig. 2); see Table 2 for the geometric parameters describing these interactions.

Related literature top

For related literature, see: Ciurtin et al. (2002); Dong et al. (2000); Klein et al. (1982); O'Connor & Sinn (1981); Ptasiewicz-Bak et al. (1995).

Experimental top

A mixture of manganese(II) chloride tetrahydrate, (0.4 mmol, 79.2 mg), pyrazine-2,3-dicarboxylic acid (0.8 mmol, 134.5 mg), and H2O (1.0 mol, 18.0 ml) in the molar ratio of 1: 2: 2500 was sealed in a 40 ml stainless steel reactor with Teflon liner and directly heated to 160 °C, kept at 160 °C for 72 h, and then directly cooled to the room temperature. Light-yellow block-shaped crystals of the title complex were collected by filtration and washed with ethanol (2×5 ml) for the structural analysis.

Refinement top

All H atoms were initially located in difference Fourier maps and were treated isotropically in the riding-model approximation with C—H = 0.93 Å, O—H = 0.85 Å, Uiso(H) = 1.5Ueq(O), and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of the title compound and the atomic numbering scheme, with atom labels and 35% probability displacement ellipsoids for non-H atoms (small spheres for the H atoms).
[Figure 2] Fig. 2. The packing of the title compound viewed down the b axis, showing the hydrogen bond donor-acceptor atoms. H atoms have been omitted for clarity.
Diaquabis(pyrazine-2-carboxylato-κ2N1,O)manganese(II) dihydrate top
Crystal data top
[Mn(C5H3N2O2)2(H2O)2]·2H2OF000 = 382
Mr = 373.19Dx = 1.633 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 931 reflections
a = 7.233 (2) Åθ = 3.0–26.4º
b = 13.003 (4) ŵ = 0.91 mm−1
c = 8.257 (3) ÅT = 293 (2) K
β = 102.207 (5)ºBlock, light-yellow
V = 759.1 (4) Å30.20 × 0.10 × 0.10 mm
Z = 2
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1552 independent reflections
Radiation source: fine-focus sealed tube1252 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.025
T = 293(2) Kθmax = 26.4º
φ and ω scansθmin = 3.0º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −7→9
Tmin = 0.838, Tmax = 0.914k = −16→15
4297 measured reflectionsl = −10→9
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.081  w = 1/[σ2(Fo2) + (0.0336P)2 + 0.3749P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
1552 reflectionsΔρmax = 0.33 e Å−3
106 parametersΔρmin = −0.23 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Mn(C5H3N2O2)2(H2O)2]·2H2OV = 759.1 (4) Å3
Mr = 373.19Z = 2
Monoclinic, P21/nMo Kα
a = 7.233 (2) ŵ = 0.91 mm−1
b = 13.003 (4) ÅT = 293 (2) K
c = 8.257 (3) Å0.20 × 0.10 × 0.10 mm
β = 102.207 (5)º
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1552 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		1252 reflections with I > 2σ(I)
Tmin = 0.838, Tmax = 0.914Rint = 0.025
4297 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.032106 parameters
wR(F2) = 0.081H-atom parameters constrained
S = 1.08Δρmax = 0.33 e Å−3
1552 reflectionsΔρmin = −0.23 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mn10.00000.50000.00000.02497 (15)
C20.3799 (3)0.50843 (18)0.2061 (3)0.0321 (5)
O10.2234 (2)0.40214 (13)−0.0110 (2)0.0374 (4)
N10.2126 (3)0.55522 (15)0.1991 (2)0.0344 (5)
C10.3768 (3)0.41836 (17)0.0906 (3)0.0316 (5)
C50.2082 (4)0.6331 (2)0.3022 (3)0.0449 (6)
H50.09400.66610.30150.054*
O20.5231 (2)0.36634 (14)0.1034 (2)0.0461 (5)
N20.5373 (3)0.62300 (17)0.4146 (3)0.0457 (5)
C30.5411 (3)0.5443 (2)0.3121 (3)0.0388 (6)
H30.65610.51230.31190.047*
C40.3699 (4)0.6661 (2)0.4106 (3)0.0495 (7)
H40.36120.72000.48270.059*
O30.0978 (2)0.60221 (15)−0.1543 (2)0.0554 (5)
H3A0.21450.6136−0.14970.083*
H3B0.03280.6326−0.23860.083*
O40.9068 (3)0.69223 (17)0.5751 (3)0.0703 (7)
H4B0.79310.67980.52660.105*
H4A0.93410.75050.53980.105*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0141 (2)0.0262 (2)0.0330 (3)0.00080 (19)0.00120 (16)0.0019 (2)
C20.0266 (10)0.0339 (12)0.0354 (12)−0.0008 (10)0.0058 (9)0.0064 (10)
O10.0273 (8)0.0382 (10)0.0439 (10)−0.0004 (7)0.0009 (7)−0.0047 (8)
N10.0285 (10)0.0322 (11)0.0419 (11)0.0015 (8)0.0061 (8)0.0012 (9)
C10.0253 (11)0.0315 (12)0.0388 (13)−0.0017 (9)0.0081 (9)0.0025 (10)
C50.0421 (15)0.0396 (15)0.0527 (16)0.0052 (11)0.0098 (12)−0.0058 (12)
O20.0262 (9)0.0475 (11)0.0635 (12)0.0075 (8)0.0071 (8)−0.0069 (9)
N20.0465 (13)0.0424 (13)0.0438 (13)−0.0070 (10)−0.0005 (10)−0.0009 (10)
C30.0305 (12)0.0406 (13)0.0429 (14)−0.0025 (10)0.0022 (10)0.0032 (12)
C40.0584 (17)0.0384 (15)0.0495 (16)−0.0011 (13)0.0066 (13)−0.0080 (12)
O30.0276 (9)0.0690 (14)0.0664 (13)−0.0023 (8)0.0024 (9)0.0293 (11)
O40.0569 (13)0.0736 (16)0.0679 (14)−0.0166 (11)−0.0148 (11)0.0273 (12)
Geometric parameters (Å, °) top
Mn1—O32.0670 (18)C1—O21.242 (3)
Mn1—O3i2.0670 (18)C5—C41.382 (4)
Mn1—O1i2.0738 (16)C5—H50.9300
Mn1—O12.0738 (16)N2—C41.328 (4)
Mn1—N1i2.1246 (19)N2—C31.332 (3)
Mn1—N12.1246 (19)C3—H30.9300
C2—N11.345 (3)C4—H40.9300
C2—C31.383 (3)O3—H3A0.8500
C2—C11.507 (3)O3—H3B0.8500
O1—C11.259 (3)O4—H4B0.8500
N1—C51.328 (3)O4—H4A0.8501
O3—Mn1—O3i180.0C5—N1—Mn1129.97 (17)
O3—Mn1—O1i90.24 (7)C2—N1—Mn1112.20 (15)
O3i—Mn1—O1i89.76 (7)O2—C1—O1125.5 (2)
O3—Mn1—O189.76 (7)O2—C1—C2118.1 (2)
O3i—Mn1—O190.24 (7)O1—C1—C2116.42 (19)
O1i—Mn1—O1180.0N1—C5—C4121.3 (2)
O3—Mn1—N1i91.51 (8)N1—C5—H5119.3
O3i—Mn1—N1i88.49 (8)C4—C5—H5119.3
O1i—Mn1—N1i78.35 (7)C4—N2—C3116.7 (2)
O1—Mn1—N1i101.65 (7)N2—C3—C2122.2 (2)
O3—Mn1—N188.49 (8)N2—C3—H3118.9
O3i—Mn1—N191.51 (8)C2—C3—H3118.9
O1i—Mn1—N1101.65 (7)N2—C4—C5121.9 (3)
O1—Mn1—N178.35 (7)N2—C4—H4119.1
N1i—Mn1—N1180.00 (8)C5—C4—H4119.1
N1—C2—C3120.4 (2)Mn1—O3—H3A123.4
N1—C2—C1115.55 (19)Mn1—O3—H3B126.9
C3—C2—C1124.1 (2)H3A—O3—H3B109.2
C1—O1—Mn1116.93 (15)H4B—O4—H4A106.2
C5—N1—C2117.5 (2)
Symmetry codes: (i) −x, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3B···O4ii0.851.792.639 (3)176
O3—H3A···O2iii0.851.872.715 (2)171
O4—H4A···O2iv0.851.982.806 (3)164
O4—H4B···N20.852.032.865 (3)170
Symmetry codes: (ii) x−1, y, z−1; (iii) −x+1, −y+1, −z; (iv) −x+3/2, y+1/2, −z+1/2.
Table 1
Selected geometric parameters (Å, °) top
Mn1—O32.0670 (18)O1—C11.259 (3)
Mn1—O12.0738 (16)C1—O21.242 (3)
Mn1—N12.1246 (19)
O3—Mn1—O1i90.24 (7)O1—Mn1—N1i101.65 (7)
O3—Mn1—O189.76 (7)O3—Mn1—N188.49 (8)
O3—Mn1—N1i91.51 (8)O1—Mn1—N178.35 (7)
Symmetry codes: (i) −x, −y+1, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3B···O4ii0.851.792.639 (3)176
O3—H3A···O2iii0.851.872.715 (2)171
O4—H4A···O2iv0.851.982.806 (3)164
O4—H4B···N20.852.032.865 (3)170
Symmetry codes: (ii) x−1, y, z−1; (iii) −x+1, −y+1, −z; (iv) −x+3/2, y+1/2, −z+1/2.
Acknowledgements top

The authors acknowledge financial support from the National Natural Science Foundation of China (grant No. 50590402).

references
References top

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