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Acta Cryst. (2008). E64, m1286    [ doi:10.1107/S1600536808029073 ]

trans-Diaquabis[5-carboxy-2-(3-pyridyl)-1H-imidazole-4-carboxylato-[kappa]2N3,O4]manganese(II)

L.-Z. Chen

Abstract top

In the title compound, [Mn(C10H6N3O4)2(H2O)2], synthesized by hydrothermal reaction, the MnII ion lies on an inversion centre and displays a distorted octahedral coordination geometry defined by the two imidazole N atoms and two carboxylate O atoms of the two trans-standing chelate ligands, and two O atoms of the water molecules. A two-dimensional supramolecular architecture is formed via N-H...O, O-H...N and O-H...O hydrogen-bonding interactions.

Comment top

N-Heterocyclic carboxylic acids, such as imidazole-4,5-dicarboxylic acid, are recognized as efficient N,O-donors, exhibiting diverse modes of coordination (Zhang et al., 2004; Xiao et al., 2004; Lu et al., 2006). In this work, we have chosen 2-Pyridin-3-yl-1H-imidazole-4,5-dicarboxylic acid as the building block to obtain the title compound, and we present its crystal structure here. MnII ion lies on an inversion centre and displaying distorted octahedral coordination geometry defined by the two imidazole N atoms, two O toms of the carboxylate groups and two O atoms of the water molecules. The pyridine ring and imidazole rings are twisted from each other by a dihedral angle of 20.78 (2)° (Fig. 1). The crystal structure is stabilized by intermolecular O—H···N, O—H···O and N—H···O, hydrogen bonds. A two-dimensional supramolecular architecture is formed via hydrogen-bond interactions (Table 1 and Fig. 2).

Related literature top

For the chemistry of imidazoles, see: Xiao et al. (2004); Zhang et al. (2004); Lu et al. (2006).

Experimental top

A mixture of 2-Pyridin-3-yl-1H-imidazole-4,5-dicarboxylic acid (0.1 mmol, 23 mg) and MnCl2 (20 mg, 0.1 mmol) and water (1 ml) sealed in a glass tube was maintained at 100°C for 3 d then cooled to room temperature to obtain suitable single crystals for X-ray analysis.

Refinement top

All H atoms attached to C atoms, O atoms and N atoms except H5B were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic), O—H = 0.82 Å and N—H = 0.86 Å with Uiso(H) = 1.2Ueq(C and N) or Uiso(H) = 1.5Ueq(O). H5B atom of H2O were located in difference Fourier maps.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Unlabelled atoms are related to labelled atoms by the symmetry code ( -x+1, -y+1, -z).
[Figure 2] Fig. 2. The crystal packing of the title compound viewed along the b axis and all hydrogen atoms not involved in hydrogen bonding (dashed lines) were omitted for clarity.
trans-Diaquabis[5-carboxy-2-(3-pyridyl)-1H-imidazole-4- carboxylato-κ2N3,O4]manganese(II) top
Crystal data top
[Mn(C10H6N3O4)2(H2O)2]Z = 1
Mr = 555.33F(000) = 283
Triclinic, P1Dx = 1.745 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.9574 (7) ÅCell parameters from 1463 reflections
b = 8.5636 (7) Åθ = 3.1–27.5°
c = 9.4409 (16) ŵ = 0.70 mm−1
α = 81.90 (3)°T = 298 K
β = 83.42 (4)°Block, colourless
γ = 72.10 (2)°0.25 × 0.20 × 0.20 mm
V = 528.41 (11) Å3
Data collection top
Rigaku Mercury2
diffractometer		2378 independent reflections
Radiation source: fine-focus sealed tube1871 reflections with I > 2σ(I)
graphiteRint = 0.029
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 2.5°
ω scansh = −8→8
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −11→11
Tmin = 0.845, Tmax = 0.869l = −12→12
5416 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.165H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.1003P)2 + 0.0122P]
where P = (Fo2 + 2Fc2)/3
2378 reflections(Δ/σ)max < 0.001
175 parametersΔρmax = 0.54 e Å−3
2 restraintsΔρmin = −0.44 e Å−3
Crystal data top
[Mn(C10H6N3O4)2(H2O)2]γ = 72.10 (2)°
Mr = 555.33V = 528.41 (11) Å3
Triclinic, P1Z = 1
a = 6.9574 (7) ÅMo Kα radiation
b = 8.5636 (7) ŵ = 0.70 mm−1
c = 9.4409 (16) ÅT = 298 K
α = 81.90 (3)°0.25 × 0.20 × 0.20 mm
β = 83.42 (4)°
Data collection top
Rigaku Mercury2
diffractometer		2378 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		1871 reflections with I > 2σ(I)
Tmin = 0.845, Tmax = 0.869Rint = 0.029
5416 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.047H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.165Δρmax = 0.54 e Å−3
S = 1.11Δρmin = −0.44 e Å−3
2378 reflectionsAbsolute structure: ?
175 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
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
Mn10.50000.50000.00000.0299 (2)
C10.3266 (4)0.8677 (4)−0.0160 (3)0.0290 (6)
C20.2634 (4)0.8148 (3)0.1332 (3)0.0253 (6)
C30.1577 (4)0.9082 (3)0.2405 (3)0.0260 (6)
C40.0487 (5)1.0861 (4)0.2425 (3)0.0308 (6)
C50.2472 (4)0.6428 (3)0.3206 (3)0.0229 (5)
C60.2698 (4)0.4926 (3)0.4203 (3)0.0253 (6)
C70.3049 (5)0.3401 (4)0.3713 (3)0.0336 (7)
H7A0.31200.33140.27370.040*
C80.3291 (5)0.2013 (4)0.4703 (3)0.0369 (7)
H8A0.35920.09720.43990.044*
C90.3080 (5)0.2195 (4)0.6156 (3)0.0345 (7)
H9A0.32150.12610.68170.041*
N30.2692 (4)0.3661 (3)0.6640 (3)0.0332 (6)
C110.2491 (5)0.4986 (4)0.5688 (3)0.0300 (6)
H11A0.21960.60100.60250.036*
N10.3172 (3)0.6504 (3)0.1834 (2)0.0255 (5)
N20.1531 (4)0.7971 (3)0.3573 (2)0.0269 (5)
H2A0.09920.82070.44120.032*
O10.4330 (4)0.7595 (3)−0.0912 (2)0.0380 (5)
O20.2722 (4)1.0220 (3)−0.0599 (2)0.0408 (6)
O30.0641 (4)1.1816 (3)0.1292 (2)0.0397 (6)
H30.16021.13480.07640.060*
O4−0.0526 (4)1.1310 (3)0.3540 (2)0.0457 (6)
O50.7793 (4)0.5087 (3)0.0738 (2)0.0414 (6)
H50.75440.55390.14760.062*
H5B0.867 (5)0.416 (3)0.083 (3)0.042 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0369 (4)0.0247 (4)0.0204 (3)0.0026 (3)0.0007 (3)−0.0056 (2)
C10.0337 (15)0.0254 (14)0.0204 (13)0.0004 (11)0.0015 (11)−0.0017 (10)
C20.0307 (14)0.0207 (13)0.0197 (13)−0.0006 (10)−0.0005 (11)−0.0035 (10)
C30.0315 (14)0.0231 (14)0.0205 (12)−0.0040 (11)0.0015 (11)−0.0049 (10)
C40.0366 (16)0.0242 (14)0.0257 (14)0.0005 (12)−0.0005 (12)−0.0061 (11)
C50.0233 (13)0.0235 (13)0.0184 (12)−0.0021 (10)0.0020 (10)−0.0047 (9)
C60.0270 (13)0.0265 (14)0.0208 (13)−0.0063 (11)0.0028 (11)−0.0041 (10)
C70.0455 (17)0.0288 (15)0.0212 (14)−0.0052 (13)0.0077 (13)−0.0064 (11)
C80.0493 (19)0.0225 (14)0.0336 (16)−0.0033 (12)−0.0003 (14)−0.0048 (11)
C90.0404 (17)0.0279 (15)0.0303 (16)−0.0074 (13)0.0003 (13)0.0039 (12)
N30.0419 (15)0.0327 (13)0.0209 (12)−0.0075 (11)0.0023 (10)−0.0012 (9)
C110.0388 (16)0.0271 (14)0.0226 (14)−0.0065 (12)−0.0030 (12)−0.0041 (11)
N10.0310 (12)0.0214 (11)0.0200 (11)−0.0021 (9)−0.0007 (10)−0.0028 (9)
N20.0334 (12)0.0246 (12)0.0185 (11)−0.0032 (10)0.0038 (9)−0.0058 (8)
O10.0503 (14)0.0304 (11)0.0210 (10)0.0023 (10)0.0077 (9)−0.0028 (8)
O20.0578 (14)0.0251 (11)0.0257 (11)0.0011 (10)0.0082 (10)0.0035 (8)
O30.0508 (14)0.0229 (11)0.0330 (12)0.0038 (9)0.0059 (10)−0.0031 (8)
O40.0650 (16)0.0303 (12)0.0291 (12)0.0059 (11)0.0040 (11)−0.0123 (9)
O50.0423 (13)0.0434 (14)0.0309 (12)0.0012 (11)−0.0015 (10)−0.0119 (10)
Geometric parameters (Å, °) top
Mn1—O5i2.163 (2)C5—N21.356 (3)
Mn1—O52.163 (2)C5—C61.460 (4)
Mn1—O1i2.194 (2)C6—C71.389 (4)
Mn1—O12.194 (2)C6—C111.399 (4)
Mn1—N1i2.322 (2)C7—C81.383 (4)
Mn1—N12.322 (2)C7—H7A0.9300
C1—O11.246 (3)C8—C91.388 (4)
C1—O21.279 (3)C8—H8A0.9300
C1—C21.477 (4)C9—N31.335 (4)
C2—N11.370 (3)C9—H9A0.9300
C2—C31.380 (4)N3—C111.326 (4)
C3—N21.355 (3)C11—H11A0.9300
C3—C41.480 (4)N2—H2A0.8600
C4—O41.238 (3)O3—H30.8200
C4—O31.267 (4)O5—H50.8200
C5—N11.331 (3)O5—H5B0.839 (17)
O5i—Mn1—O5180.00 (11)N2—C5—C6123.9 (2)
O5i—Mn1—O1i90.51 (10)C7—C6—C11117.7 (3)
O5—Mn1—O1i89.49 (10)C7—C6—C5121.3 (2)
O5i—Mn1—O189.49 (10)C11—C6—C5121.0 (2)
O5—Mn1—O190.51 (10)C8—C7—C6118.9 (3)
O1i—Mn1—O1180.0C8—C7—H7A120.6
O5i—Mn1—N1i90.00 (8)C6—C7—H7A120.6
O5—Mn1—N1i90.00 (8)C7—C8—C9119.2 (3)
O1i—Mn1—N1i74.86 (8)C7—C8—H8A120.4
O1—Mn1—N1i105.14 (8)C9—C8—H8A120.4
O5i—Mn1—N190.00 (8)N3—C9—C8122.5 (3)
O5—Mn1—N190.00 (8)N3—C9—H9A118.8
O1i—Mn1—N1105.14 (8)C8—C9—H9A118.8
O1—Mn1—N174.86 (8)C11—N3—C9118.2 (3)
N1i—Mn1—N1180.0N3—C11—C6123.5 (3)
O1—C1—O2123.7 (3)N3—C11—H11A118.2
O1—C1—C2118.1 (3)C6—C11—H11A118.2
O2—C1—C2118.2 (3)C5—N1—C2105.7 (2)
N1—C2—C3110.3 (2)C5—N1—Mn1145.47 (18)
N1—C2—C1119.8 (2)C2—N1—Mn1108.75 (16)
C3—C2—C1129.9 (3)C3—N2—C5109.1 (2)
N2—C3—C2104.8 (2)C3—N2—H2A125.5
N2—C3—C4121.9 (2)C5—N2—H2A125.5
C2—C3—C4133.1 (3)C1—O1—Mn1118.36 (18)
O4—C4—O3124.5 (3)C4—O3—H3109.5
O4—C4—C3117.8 (3)Mn1—O5—H5109.5
O3—C4—C3117.7 (2)Mn1—O5—H5B113 (2)
N1—C5—N2110.0 (2)H5—O5—H5B112.4
N1—C5—C6126.0 (2)
O1—C1—C2—N1−1.9 (4)C6—C5—N1—C2−179.2 (3)
O2—C1—C2—N1179.4 (3)N2—C5—N1—Mn1176.6 (2)
O1—C1—C2—C3175.6 (3)C6—C5—N1—Mn1−2.2 (5)
O2—C1—C2—C3−3.1 (5)C3—C2—N1—C5−0.6 (3)
N1—C2—C3—N21.4 (3)C1—C2—N1—C5177.3 (3)
C1—C2—C3—N2−176.2 (3)C3—C2—N1—Mn1−178.84 (19)
N1—C2—C3—C4−173.1 (3)C1—C2—N1—Mn1−0.9 (3)
C1—C2—C3—C49.3 (6)O5i—Mn1—N1—C595.6 (3)
N2—C3—C4—O4−1.9 (5)O5—Mn1—N1—C5−84.4 (3)
C2—C3—C4—O4171.9 (3)O1i—Mn1—N1—C55.0 (4)
N2—C3—C4—O3178.8 (3)O1—Mn1—N1—C5−175.0 (4)
C2—C3—C4—O3−7.4 (5)O5i—Mn1—N1—C2−87.49 (19)
N1—C5—C6—C7−22.7 (4)O5—Mn1—N1—C292.51 (19)
N2—C5—C6—C7158.6 (3)O1i—Mn1—N1—C2−178.01 (18)
N1—C5—C6—C11159.7 (3)O1—Mn1—N1—C21.99 (18)
N2—C5—C6—C11−18.9 (4)C2—C3—N2—C5−1.7 (3)
C11—C6—C7—C8−3.7 (4)C4—C3—N2—C5173.6 (3)
C5—C6—C7—C8178.7 (3)N1—C5—N2—C31.4 (3)
C6—C7—C8—C93.1 (5)C6—C5—N2—C3−179.8 (2)
C7—C8—C9—N3−1.4 (5)O2—C1—O1—Mn1−177.4 (2)
C8—C9—N3—C110.4 (5)C2—C1—O1—Mn13.9 (4)
C9—N3—C11—C6−1.1 (5)O5i—Mn1—O1—C186.8 (2)
C7—C6—C11—N32.8 (4)O5—Mn1—O1—C1−93.2 (2)
C5—C6—C11—N3−179.6 (3)N1i—Mn1—O1—C1176.7 (2)
N2—C5—N1—C2−0.4 (3)N1—Mn1—O1—C1−3.3 (2)
Symmetry codes: (i) −x+1, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O4ii0.862.002.840 (3)164.
O5—H5···N3iii0.821.972.779 (3)171.
O5—H5B···O3iv0.84 (2)2.07 (2)2.908 (3)173 (3)
O3—H3···O20.821.692.456 (3)155.
Symmetry codes: (ii) −x, −y+2, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x+1, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O4i0.862.002.840 (3)164.
O5—H5···N3ii0.821.972.779 (3)171.
O5—H5B···O3iii0.84 (2)2.07 (2)2.908 (3)173 (3)
O3—H3···O20.821.692.456 (3)155.
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y−1, z.
Acknowledgements top

This work was supported by a start-up grant from Southeast University to Professor Ren-Gen Xiong.

references
References top

Lu, W.-G., Su, C.-Y., Lu, T.-B., Jiang, L. & Chen, J.-M. (2006). J. Am. Chem. Soc. 128, 34–35.

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Xiao, H.-P., Li, X.-H. & Shi, Q. (2004). Acta Cryst. E60, m1519–m1521.

Zhang, X.-M., Fang, R.-Q., Wu, H.-S. & Ng, S. W. (2004). Acta Cryst. E60, m12–m13.