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Acta Cryst. (2007). E63, m2185    [ doi:10.1107/S1600536807034496 ]

catena-Poly[[aqua(pyrazine-2-carboxylato-[kappa]2N1,O)manganese(II)]-[mu]-pyrazine-2-carboxylato-[kappa]3N1,O:N4]

Y.-X. Gao, L.-B. Wang, Y.-L. Niu and L.-J. Hao

Abstract top

The title compound, [Mn(C5H3N2O2)2(H2O)]n, prepared by hydrothermal synthesis, is isostructural with its FeII, CoII, NiII and CuII analogues. The asymmetric unit contains two bidendate pyrazine-2-carboxylate anions coordinated to MnII in the equatorial plane through one N and one O atom. The MnII atoms are linked into chains by the second N atom of one of the pyrazine-2-carboxylate anions coordinating to an axial site of a neighbouring MnII atom. The slightly distorted octahedral coordination around MnII is completed by a water molecule, which forms hydrogen bonds to link the chains into a three-dimensional structure. The investigated crystal was an inversion twin.

Comment top

The title compound, [Mn(C5H3N2O2)2(H2O)]n, is isostructural with its FeII, CoII, NiII, and CuII analogues (Hao & Liu, (2007); Hao, Mu & Liu, (2007); Gao et al. (2007a); Gao et al. (2007b)).

The MnII atom is coordinated in a bidentate fashion by two O and two N atoms from two independent pyrazine-2-carboxylate anions. The distorted octahedral coordiantion is completed by another N atom from a third pyrazine-2-carboxylate ligand, and by the O atom of a water molecule (Figure 1). The Mn—N and Mn—O bond lengths are in the range of 2.094 (3)–2.137 (3) and 2.010 (3)–2.072 (3) Å, respectively.

One pyrazine-2-carboxylate ligand coordinates to a neighbouring MnII atom via its second N atom, leading to a polymeric structure with zigzag chains extending parallel to the b axis (Figure 2). Hydrogen bonding between the water molecules stablizes the structure. The refined Flack parameter of 0.48 (3) indicates that the crystal is an inversion twin.

Related literature top

For the isostructural FeII, CoII, NiII and CuII analogues, see: Hao & Liu (2007); Hao, Mu & Liu (2007); Gao et al. (2007a,b).

Experimental top

All chemicals were used as purchased from Jinan Henghua Sci & Tec Co. Ltd. A mixture of Mn(CH3CO2)2 (0.5 mmol), KOH (0.5 mmol), 2-pyrazine carboxylic acid (0.5 mmol), EtOH (8 ml) and H2O (8 ml) in a 25 ml Teflon-lined stainless steel autoclave was kept at 413 K for 2 d. On cooling to room temperature, colourless crystals were obtained in a yield of 36%. Elemental analysis calculated: C 37.62, H 2.51, N 17.55%; found: C 37.56, H 2.47, N 17.51%.

Refinement top

H atoms on C atoms were placed geometrically and refined as riding atoms with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C). The H atoms of the water molecule were located from difference Fourier maps and were refined with distance restraints of O—H = 0.82 (1) Å and H···H = 1.38 (2) Å, and with Uiso(H) = 0.08 Å2. The refined Flack parameter (Flack, 1983) from 1086 Friedel pairs is 0.48 (3), indicating that the crystal is an inversion twin.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; 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.

Figures top
[Figure 1] Fig. 1. Asymmetric unit of the title compound expanded to show the complete coordination sphere of MnII. Displacement ellipsoids are shown at 30% probability for non-H atoms. Symmetry code (I): 1 - x, 1/2 + y, 1/2 - z.
[Figure 2] Fig. 2. View of the [Mn(C5H3N2O2)2(H2O)]n coordination polymer.
catena-Poly[[aqua(pyrazine-2-carboxylato-κ2N1,O)manganese(II)]- µ-pyrazine-2-carboxylato-κ3-κ2N1,O:N4] top
Crystal data top
[Mn(C5H3N2O2)2(H2O)]F(000) = 644
Mr = 319.14Dx = 1.844 Mg m−3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2661 reflections
a = 7.722 (1) Åθ = 2.5–28.0°
b = 10.0002 (1) ŵ = 1.18 mm−1
c = 14.8836 (1) ÅT = 293 K
V = 1149.33 (15) Å3Cube, colourless
Z = 40.10 × 0.10 × 0.10 mm
Data collection top
Bruker APEX II CCD
diffractometer		2661 independent reflections
Radiation source: fine-focus sealed tube2367 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
φ and ω scansθmax = 28.0°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −9→10
Tmin = 0.891, Tmax = 0.891k = −12→13
7188 measured reflectionsl = −15→19
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)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.101 w = 1/[σ2(Fo2) + (0.059P)2 + 0.7652P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2661 reflectionsΔρmax = 1.02 e Å−3
187 parametersΔρmin = −0.33 e Å−3
3 restraintsAbsolute structure: Flack (1983), 1086 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.48 (3)
Crystal data top
[Mn(C5H3N2O2)2(H2O)]V = 1149.33 (15) Å3
Mr = 319.14Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.722 (1) ŵ = 1.18 mm−1
b = 10.0002 (1) ÅT = 293 K
c = 14.8836 (1) Å0.10 × 0.10 × 0.10 mm
Data collection top
Bruker APEX II CCD
diffractometer		2661 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2367 reflections with I > 2σ(I)
Tmin = 0.891, Tmax = 0.891Rint = 0.032
7188 measured reflectionsθmax = 28.0°
Refinement top
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.101Δρmax = 1.02 e Å−3
S = 1.00Δρmin = −0.33 e Å−3
2661 reflectionsAbsolute structure: Flack (1983), 1086 Friedel pairs
187 parametersFlack parameter: 0.48 (3)
3 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1−0.1432 (6)0.5282 (4)−0.0196 (3)0.0336 (9)
C20.0370 (5)0.5738 (4)−0.0409 (3)0.0328 (9)
C30.0750 (6)0.6650 (4)−0.1082 (3)0.0431 (10)
H3−0.01600.7017−0.14080.052*
C40.3581 (6)0.6483 (4)−0.0792 (3)0.0432 (10)
H40.47240.6719−0.09080.052*
C50.3240 (6)0.5575 (4)−0.0107 (3)0.0366 (9)
H50.41530.52330.02290.044*
C60.3050 (5)0.1913 (4)0.1834 (3)0.0277 (8)
C70.1282 (5)0.1459 (4)0.2115 (2)0.0270 (7)
C8−0.1645 (5)0.1694 (4)0.2000 (3)0.0353 (10)
H8−0.26150.20980.17490.042*
C10−0.1851 (5)0.0674 (4)0.2636 (3)0.0327 (9)
H10−0.29640.04210.28050.039*
C110.1061 (5)0.0419 (4)0.2732 (3)0.0307 (9)
H110.2031−0.00240.29530.037*
H1W0.006 (5)0.240 (6)−0.056 (3)0.080*
H2W0.156 (5)0.178 (5)−0.028 (4)0.080*
Mn10.07321 (6)0.36583 (5)0.09074 (3)0.01617 (13)
N1−0.0492 (4)0.0050 (3)0.3010 (2)0.0293 (7)
N2−0.0065 (4)0.2087 (3)0.1753 (2)0.0303 (7)
N30.1645 (4)0.5190 (3)0.0073 (2)0.0299 (7)
N40.2341 (5)0.7020 (4)−0.1282 (3)0.0505 (10)
O10.0814 (5)0.2346 (3)−0.01690 (19)0.0399 (7)
O2−0.1538 (4)0.4351 (3)0.04084 (19)0.0333 (6)
O3−0.2617 (4)0.5807 (4)−0.0589 (3)0.0567 (9)
O40.3053 (3)0.2971 (3)0.13085 (18)0.0315 (6)
O50.4313 (4)0.1305 (3)0.20942 (19)0.0415 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.029 (2)0.036 (2)0.036 (2)−0.0012 (17)−0.0035 (17)0.0013 (17)
C20.035 (2)0.033 (2)0.030 (2)0.0042 (17)−0.0003 (16)−0.0001 (16)
C30.033 (2)0.048 (2)0.049 (3)0.002 (2)−0.005 (2)0.0146 (18)
C40.035 (2)0.044 (2)0.051 (3)−0.002 (2)0.005 (2)0.009 (2)
C50.032 (2)0.037 (2)0.041 (2)0.0014 (18)−0.0017 (18)0.0019 (17)
C60.0222 (18)0.0309 (18)0.0300 (19)−0.0004 (15)−0.0003 (14)−0.0031 (15)
C70.0266 (17)0.0282 (18)0.0262 (17)0.0032 (15)0.0021 (13)−0.0009 (16)
C80.0233 (19)0.042 (3)0.040 (2)−0.0008 (18)−0.0011 (17)0.0003 (18)
C100.027 (2)0.033 (2)0.038 (2)−0.0034 (17)0.0000 (16)0.0052 (17)
C110.027 (2)0.0339 (19)0.0308 (19)0.0019 (16)0.0003 (16)0.0025 (16)
Mn10.0136 (2)0.0179 (2)0.0170 (2)−0.00008 (19)0.00074 (19)0.00062 (19)
N10.0295 (17)0.0290 (15)0.0293 (15)−0.0008 (14)−0.0005 (14)0.0049 (13)
N20.0247 (15)0.0327 (17)0.0334 (18)−0.0010 (14)0.0014 (14)−0.0021 (14)
N30.0293 (17)0.0296 (17)0.0307 (17)−0.0006 (14)−0.0006 (14)0.0019 (13)
N40.042 (2)0.055 (2)0.055 (2)−0.007 (2)0.0056 (19)0.019 (2)
O10.0371 (16)0.0445 (16)0.0383 (15)0.0116 (16)−0.0078 (14)−0.0132 (13)
O20.0231 (13)0.0360 (15)0.0407 (16)−0.0022 (12)0.0007 (12)−0.0003 (13)
O30.0314 (17)0.076 (2)0.063 (2)0.0063 (17)−0.0064 (15)0.0208 (19)
O40.0267 (14)0.0359 (15)0.0321 (14)−0.0014 (12)0.0022 (11)0.0018 (12)
O50.0258 (13)0.0494 (16)0.0492 (16)0.0051 (17)−0.0006 (13)0.0100 (14)
Geometric parameters (Å, º) top
C1—O31.206 (5)C8—N21.334 (5)
C1—O21.297 (5)C8—C101.401 (6)
C1—C21.498 (6)C8—H80.930
C2—N31.335 (5)C10—N11.341 (5)
C2—C31.387 (6)C10—H100.930
C3—N41.317 (6)C11—N11.321 (5)
C3—H30.930C11—H110.930
C4—N41.318 (6)Mn1—O42.010 (3)
C4—C51.390 (6)Mn1—O22.026 (3)
C4—H40.930Mn1—O12.072 (3)
C5—N31.318 (5)Mn1—N32.094 (3)
C5—H50.930Mn1—N22.106 (3)
C6—O51.213 (5)Mn1—N1i2.137 (3)
C6—O41.315 (5)N1—Mn1ii2.137 (3)
C6—C71.498 (5)O1—H1W0.83 (4)
C7—N21.329 (5)O1—H2W0.82 (4)
C7—C111.399 (5)
O3—C1—O2126.9 (4)O4—Mn1—O2175.74 (12)
O3—C1—C2118.0 (4)O4—Mn1—O189.19 (12)
O2—C1—C2115.1 (3)O2—Mn1—O187.68 (12)
N3—C2—C3120.1 (4)O4—Mn1—N397.25 (12)
N3—C2—C1116.5 (3)O2—Mn1—N379.85 (12)
C3—C2—C1123.3 (4)O1—Mn1—N389.68 (13)
N4—C3—C2123.0 (4)O4—Mn1—N280.08 (12)
N4—C3—H3118.5O2—Mn1—N2102.79 (12)
C2—C3—H3118.5O1—Mn1—N289.91 (13)
N4—C4—C5122.3 (4)N3—Mn1—N2177.31 (14)
N4—C4—H4118.9O4—Mn1—N1i94.36 (12)
C5—C4—H4118.9O2—Mn1—N1i88.78 (12)
N3—C5—C4121.1 (4)O1—Mn1—N1i176.45 (14)
N3—C5—H5119.4N3—Mn1—N1i90.00 (13)
C4—C5—H5119.4N2—Mn1—N1i90.57 (12)
O5—C6—O4126.3 (4)C11—N1—C10116.8 (3)
O5—C6—C7119.5 (3)C11—N1—Mn1ii119.7 (3)
O4—C6—C7114.3 (3)C10—N1—Mn1ii123.2 (3)
N2—C7—C11121.5 (3)C7—N2—C8117.7 (3)
N2—C7—C6117.2 (3)C7—N2—Mn1111.4 (3)
C11—C7—C6121.3 (3)C8—N2—Mn1130.7 (3)
N2—C8—C10120.3 (4)C5—N3—C2117.4 (3)
N2—C8—H8119.8C5—N3—Mn1130.5 (3)
C10—C8—H8119.8C2—N3—Mn1111.7 (3)
N1—C10—C8122.0 (4)C3—N4—C4116.0 (4)
N1—C10—H10119.0Mn1—O1—H1W119 (3)
C8—C10—H10119.0Mn1—O1—H2W128 (3)
N1—C11—C7121.6 (3)H1W—O1—H2W113 (3)
N1—C11—H11119.2C1—O2—Mn1116.4 (3)
C7—C11—H11119.2C6—O4—Mn1116.7 (2)
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1W···O4iii0.83 (4)1.94 (2)2.742 (4)162 (6)
O1—H2W···O2iv0.82 (4)1.86 (1)2.681 (4)171 (5)
Symmetry codes: (iii) x−1/2, −y+1/2, −z; (iv) x+1/2, −y+1/2, −z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1W···O4i0.83 (4)1.94 (2)2.742 (4)162 (6)
O1—H2W···O2ii0.82 (4)1.862 (12)2.681 (4)171 (5)
Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) x+1/2, −y+1/2, −z.
Acknowledgements top

The authors thank the NSFC (grant No. 20501017) and Tonghua Teachers' College.

references
References top

Bruker (2001). SAINT-Plus, SADABS and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Gao, Y.-X., Wang, L.-B., Niu, Y.-L. & Hao, L.-J. (2007a). Acta Cryst. E63, m1882–?.

Gao, Y.-X., Wang, L.-B., Niu, Y.-L. & Hao, L.-J. (2007b). Acta Cryst. E63, m2006–?.

Hao, L.-J. & Liu, T.-T. (2007). Acta Cryst. E63, m169–m171.

Hao, L.-J., Mu, C.-H. & Liu, T.-T. (2007). Acta Cryst. E63, m281–m283.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.