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Acta Cryst. (2007). E63, m2400    [ doi:10.1107/S1600536807040172 ]

Poly[[hexaaquabis([mu]3-trans-propene-1,2,3-tricarboxylato)trimanganese(II)] 0.2-hydrate]

M.-S. Wang, G.-W. Zhou, G.-C. Guo and J.-S. Huang

Abstract top

The title compound, {[Mn3(C6H3O6)2(H2O)6]·0.2H2O}n, contains a three-dimensional open framework formed by each organic ligand [mu]3-bridging three six-coordinated MnII atoms (one of which resides on a twofold crystallographic axis). Uncoordinated water molecules are located in the channels of the framework along the c-axis direction. The primary O-H...O intermolecular interactions have O...O distances ranging from 2.680 (4) to 3.020 (13) Å and O-H...O angles ranging from 125 (4) to 179 (4)°.

Comment top

trans-Propene-1,2,3-tricarboxylic acid (trans-aconitic acid, H3L) is a weak competitive inhibitor of the action of aconitase in the famous Krebs cycle (Thomson et al., 1966). Villagranca et al. detected an aconitase-manganous trans-aconitate complex by nuclear magnetic resonance (NMR) studies in 1972 (Villafranca & Mildvan, 1972), after which Dargay et al. reported the crystal structure of potassium dihydrogen trans-aconitate KH2L and assumed that the active positions of L3− ions in the aconitase-manganous trans-aconitate complex was the same as those in KH2L (Dargay et al., 1972). We deem that it is helpful to understand the active mechanism by the direct synthesis and structural characterization of a Mn(II) complex of the L3− ligand. Herein, we report the synthesis and crystal structure of Mn3L2(H2O)6·0.2H2O (I, Scheme 1).

As shown in Fig. 1, the crystallographically independent unit of (I) consists of one L3− ligand, 1.5 MnII atoms as well as three coordinated water molecules. The Mn1 and Mn2 atoms are in special and general positions, respectively. The coordination geometry of Mn1 atom is characteristic of a triangular prism, in which O1, O2 and O5 atoms comprise the base planes. The Mn2 atom locates in a slightly distorted octahedral environment, in which three water molecules are arranged in a mer- fashion. The mean Mn2—O bond distance of 2.178 (3) Å is 0.080 (3) Å shorter than that of Mn1—O bonds. The L3− ligand is four coordinated by two Mn1 and two Mn2 atoms. The three carboxylate groups of L3− ligand show two kinds of coordination modes: one is µ2-syn,trans- for carboxylate groups with C4 and C5 atoms and the other µ2-syn,syn- for the third carboxylate group. Additionally, the 1- and 3-carboxylate groups of L3− ligand form an 8-membered ring. In our previous work, we have found 8 kinds of coordination modes for L3− ligand (Wang et al., 2004; Wang et al., 2005). The coordination modes of L3− ligand in present example differs from those previously found by our group, and represents a new type. The C1—C2 vinyl bond has a bond distance of 1.313 (5) Å, which is similar to the reported values by our group.

Fig. 2a depicts the 3-D metal-organic framework of (I) viewed along the b axis direction. This framework can be simplified as a (3,4)-connect network by treating the C2, C4 and C5 atoms in L3− ligand as well as Mn2 atoms as 3-connected nodes while Mn1 atoms as 4-connected nodes. The resulting (3,4)-connected network has a short vertex symbol of (4.6.8)2(4.10.12)2(62.102.142). Fig. 2 b shows a perspective view of the crystal structure of 1 along the c direction, which reveals an open metal-organic framework with channels hosting lattice water molecules. The O—H···O hydrogen bonds presented in the crystal structure are listed (Table 1). The O—H···O hydrogen bonds in the framework have O···O distances falling in the range of 2.680 (4)–2.921 (4) Å, which are shorter than those of host–guest hydrogen bonds (O4W—H···O3w, 3.02 (1) Å).

Related literature top

For related literature, see: Dargay et al. (1972); Thomson et al. (1966); Villafranca & Mildvan (1972); Wang et al. (2004, 2005).

Experimental top

A mixture of H3L (174 mg, 1 mmol) and Na2CO3 (159 mg, 1.5 mmol) was added into 8 ml water and reacted until no air bubbles appeared, after which MnCl2·4H2O (297 mg, 1.5 mmol) and pyridine (0.08 ml, 1 mmol) were added and let them react for further several minutes. Pale-yellow prismatic crystals of (I) suitable for single-crystal X-ray diffraction analysis were obtained by evaporation of the final solution under ambient environment.

Refinement top

Water H atoms were located in a difference Fourier map and refined as riding in their located positions, with Uiso(H) = 1.5Ueq(O). The DFIX commands were used to restrain the O—H bond distances of water molecules (Table 1). Other H atoms were allowed to ride on their respective parent atoms with C—H distances of 0.93 and 0.97 Å for methyne and methylene groups, respectively, and were included in the refinement with isotropic displacement parameters Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXTL (Siemens, 1994); program(s) used to refine structure: SHELXTL (Siemens, 1994); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXTL (Siemens, 1994).

Figures top
[Figure 1] Fig. 1. ORTEP drawing with 30% probability displacement ellipsoids of the coordination environment of metal centers. Hydrogen atoms are omitted for clarity.
[Figure 2] Fig. 2. 3-D packing diagram viewed along the (a) b axis and (b) c axis directions. Hydrogen atoms are omitted for clarity.
Poly[[hexaaquabis(µ3-trans-propene-1,2,3-tricarboxylato)trimanganese(II)] 0.2-hydrate] top
Crystal data top
[Mn3(C6H3O6)2(H2O)6]·0.2H2OF000 = 1244
Mr = 618.69Dx = 2.011 Mg m−3
Monoclinic, C2/cMelting point: not measured K
Hall symbol: -C 2ycMo Kα radiation
λ = 0.71073 Å
a = 17.092 (7) ÅCell parameters from 3076 reflections
b = 9.602 (2) Åθ = 3.2–27.5º
c = 13.897 (5) ŵ = 1.92 mm−1
β = 116.367 (14)ºT = 293 (2) K
V = 2043.4 (12) Å3Prism, pale yellow
Z = 40.4 × 0.26 × 0.25 mm
Data collection top
Rigaku Mercury CCD
diffractometer		1896 independent reflections
Radiation source: rotating-anode generator1698 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.036
T = 293(2) Kθmax = 25.5º
ω scansθmin = 3.2º
Absorption correction: multi-scan
(SPHERE in CrystalClear; Rigaku, 2002)		h = −15→20
Tmin = 0.868, Tmax = 1.000k = −11→11
6731 measured reflectionsl = −16→16
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)] = 0.053H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.076  w = 1/[σ2(Fo2) + (0.008P)2 + 2.8742P]
where P = (Fo2 + 2Fc2)/3
S = 1.25(Δ/σ)max < 0.001
1896 reflectionsΔρmax = 0.38 e Å−3
176 parametersΔρmin = −0.42 e Å−3
8 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Mn3(C6H3O6)2(H2O)6]·0.2H2OV = 2043.4 (12) Å3
Mr = 618.69Z = 4
Monoclinic, C2/cMo Kα
a = 17.092 (7) ŵ = 1.92 mm−1
b = 9.602 (2) ÅT = 293 (2) K
c = 13.897 (5) Å0.4 × 0.26 × 0.25 mm
β = 116.367 (14)º
Data collection top
Rigaku Mercury CCD
diffractometer		1896 independent reflections
Absorption correction: multi-scan
(SPHERE in CrystalClear; Rigaku, 2002)		1698 reflections with I > 2σ(I)
Tmin = 0.868, Tmax = 1.000Rint = 0.036
6731 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0538 restraints
wR(F2) = 0.076H atoms treated by a mixture of
independent and constrained refinement
S = 1.25Δρmax = 0.38 e Å−3
1896 reflectionsΔρmin = −0.42 e Å−3
176 parameters
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*/UeqOcc. (<1)
Mn10.50000.49519 (8)0.75000.0217 (2)
Mn20.26523 (4)0.24539 (6)0.20029 (4)0.01995 (18)
O10.50955 (18)0.3760 (3)0.6094 (2)0.0342 (7)
O20.39711 (18)0.3454 (3)0.6427 (2)0.0308 (7)
O30.2886 (2)0.0620 (3)0.2988 (2)0.0360 (8)
O40.27903 (17)−0.0846 (2)0.41617 (19)0.0258 (7)
O50.53149 (17)0.3356 (3)0.3676 (2)0.0269 (7)
O60.38878 (16)0.3483 (3)0.30525 (19)0.0246 (7)
O1W0.1846 (2)0.3148 (3)0.2723 (3)0.0501 (9)
H10.173 (3)0.4081 (16)0.273 (4)0.075*
H20.155 (3)0.264 (4)0.303 (3)0.075*
O2W0.16551 (17)0.1042 (3)0.0844 (2)0.0344 (8)
H30.131 (2)0.058 (4)0.109 (3)0.052*
H40.1220 (17)0.115 (4)0.0161 (13)0.052*
O3W0.34376 (18)0.1518 (3)0.1290 (2)0.0306 (7)
H50.386 (2)0.213 (3)0.130 (3)0.046*
H60.314 (2)0.120 (4)0.0594 (14)0.046*
C10.3347 (3)0.1398 (4)0.4788 (3)0.0244 (9)
H1A0.30440.15930.51860.029*
C20.4077 (3)0.2074 (4)0.5017 (3)0.0235 (9)
C30.4660 (3)0.1831 (4)0.4463 (3)0.0214 (9)
H3A0.52600.17450.50080.026*
H3B0.44970.09550.40770.026*
C40.4613 (3)0.2976 (4)0.3683 (3)0.0181 (9)
C50.2982 (3)0.0326 (4)0.3917 (3)0.0234 (9)
C60.4398 (3)0.3152 (4)0.5901 (3)0.0221 (9)
O4W0.5000−0.033 (2)0.25000.060 (8)0.20
H70.447 (8)0.01 (2)0.22 (2)0.090*0.20
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0305 (5)0.0170 (4)0.0140 (4)0.0000.0068 (4)0.000
Mn20.0234 (3)0.0187 (3)0.0162 (3)−0.0010 (3)0.0075 (3)0.0022 (3)
O10.0338 (18)0.0360 (18)0.0361 (17)−0.0123 (15)0.0184 (15)−0.0127 (14)
O20.0410 (18)0.0291 (17)0.0315 (17)−0.0117 (14)0.0246 (16)−0.0096 (13)
O30.068 (2)0.0178 (15)0.0192 (16)−0.0086 (15)0.0172 (16)−0.0011 (12)
O40.0398 (18)0.0149 (14)0.0187 (15)−0.0076 (13)0.0095 (14)0.0001 (12)
O50.0249 (16)0.0294 (16)0.0327 (16)0.0038 (13)0.0184 (14)0.0082 (13)
O60.0226 (16)0.0228 (15)0.0184 (14)0.0004 (12)0.0002 (13)0.0020 (12)
O1W0.082 (3)0.0256 (18)0.077 (2)−0.0053 (19)0.066 (2)−0.0007 (18)
O2W0.0234 (17)0.050 (2)0.0237 (16)−0.0148 (15)0.0053 (14)−0.0003 (15)
O3W0.0298 (18)0.0356 (18)0.0264 (16)−0.0067 (14)0.0123 (15)−0.0121 (14)
C10.035 (3)0.017 (2)0.021 (2)−0.0002 (19)0.013 (2)0.0011 (17)
C20.030 (2)0.017 (2)0.018 (2)0.0010 (18)0.0056 (19)0.0043 (17)
C30.027 (2)0.018 (2)0.020 (2)0.0072 (18)0.0104 (19)0.0047 (17)
C40.027 (2)0.013 (2)0.015 (2)0.0014 (17)0.0096 (19)−0.0040 (16)
C50.030 (2)0.019 (2)0.018 (2)−0.0017 (18)0.0071 (19)−0.0005 (18)
C60.029 (2)0.016 (2)0.017 (2)−0.0005 (18)0.005 (2)0.0014 (17)
O4W0.08 (2)0.023 (13)0.042 (15)0.000−0.008 (15)0.000
Geometric parameters (Å, °) top
Mn1—O5i2.195 (3)O5—C41.259 (4)
Mn1—O5ii2.195 (3)O5—Mn1ii2.195 (3)
Mn1—O22.248 (3)O6—C41.255 (4)
Mn1—O2iii2.248 (3)O1W—H10.919 (19)
Mn1—O12.332 (3)O1W—H20.95 (5)
Mn1—O1iii2.332 (3)O2W—H30.92 (4)
Mn1—C62.636 (4)O2W—H40.915 (19)
Mn1—C6iii2.636 (4)O3W—H50.93 (4)
Mn2—O1W2.137 (3)O3W—H60.92 (1)
Mn2—O32.156 (3)C1—C21.313 (5)
Mn2—O4iv2.183 (2)C1—C51.498 (5)
Mn2—O3W2.184 (3)C1—H1A0.9300
Mn2—O62.197 (3)C2—C61.511 (5)
Mn2—O2W2.213 (3)C2—C31.524 (5)
O1—C61.246 (4)C3—C41.521 (5)
O2—C61.274 (4)C3—H3A0.9700
O3—C51.259 (4)C3—H3B0.9700
O4—C51.260 (4)O4W—H70.928 (11)
O4—Mn2v2.183 (2)
O5i—Mn1—O5ii84.49 (14)O3W—Mn2—O2W81.25 (11)
O5i—Mn1—O2145.92 (10)O6—Mn2—O2W163.96 (11)
O5ii—Mn1—O296.82 (10)C6—O1—Mn189.6 (2)
O5i—Mn1—O2iii96.82 (10)C6—O2—Mn192.7 (2)
O5ii—Mn1—O2iii145.91 (10)C5—O3—Mn2137.5 (2)
O2—Mn1—O2iii100.48 (15)C5—O4—Mn2v120.9 (2)
O5i—Mn1—O1154.37 (10)C4—O5—Mn1ii107.5 (2)
O5ii—Mn1—O179.91 (10)C4—O6—Mn2130.5 (2)
O2—Mn1—O157.01 (10)Mn2—O1W—H1120 (3)
O2iii—Mn1—O185.24 (10)Mn2—O1W—H2130 (3)
O5i—Mn1—O1iii79.91 (10)H1—O1W—H2110 (4)
O5ii—Mn1—O1iii154.37 (10)Mn2—O2W—H3117 (2)
O2—Mn1—O1iii85.24 (10)Mn2—O2W—H4134 (3)
O2iii—Mn1—O1iii57.01 (10)H3—O2W—H495 (3)
O1—Mn1—O1iii121.24 (15)Mn2—O3W—H5111 (3)
O5i—Mn1—C6170.88 (11)Mn2—O3W—H6116 (3)
O5ii—Mn1—C689.03 (11)H5—O3W—H6107 (3)
O2—Mn1—C628.86 (10)C2—C1—C5123.1 (4)
O2iii—Mn1—C692.15 (11)C2—C1—H1A118.4
O1—Mn1—C628.19 (10)C5—C1—H1A118.4
O1iii—Mn1—C6103.78 (11)C1—C2—C6119.9 (4)
O5i—Mn1—C6iii89.03 (11)C1—C2—C3124.4 (4)
O5ii—Mn1—C6iii170.88 (11)C6—C2—C3115.6 (3)
O2—Mn1—C6iii92.15 (11)C4—C3—C2114.1 (3)
O2iii—Mn1—C6iii28.86 (10)C4—C3—H3A108.7
O1—Mn1—C6iii103.78 (11)C2—C3—H3A108.7
O1iii—Mn1—C6iii28.19 (10)C4—C3—H3B108.7
C6—Mn1—C6iii98.09 (16)C2—C3—H3B108.7
O1W—Mn2—O386.19 (12)H3A—C3—H3B107.6
O1W—Mn2—O4iv91.76 (12)O6—C4—O5122.1 (3)
O3—Mn2—O4iv170.60 (10)O6—C4—C3120.1 (3)
O1W—Mn2—O3W173.89 (11)O5—C4—C3117.8 (3)
O3—Mn2—O3W88.53 (11)O3—C5—O4123.1 (3)
O4iv—Mn2—O3W92.97 (11)O3—C5—C1119.5 (3)
O1W—Mn2—O6100.26 (12)O4—C5—C1117.4 (3)
O3—Mn2—O695.35 (10)O1—C6—O2120.5 (3)
O4iv—Mn2—O694.04 (10)O1—C6—C2117.6 (4)
O3W—Mn2—O683.28 (10)O2—C6—C2121.9 (4)
O1W—Mn2—O2W94.79 (13)O1—C6—Mn162.2 (2)
O3—Mn2—O2W80.06 (11)O2—C6—Mn158.41 (19)
O4iv—Mn2—O2W90.99 (10)C2—C6—Mn1177.6 (3)
Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, y, −z+3/2; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x+1/2, y−1/2, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1···O3iv0.919 (19)2.05 (4)2.687 (4)125 (4)
O1W—H2···O2vi0.93 (5)1.75 (5)2.680 (4)176 (5)
O2W—H3···O1vii0.92 (4)2.18 (3)2.843 (4)129 (3)
O2W—H4···O5vii0.915 (19)2.011 (11)2.921 (4)173 (4)
O3W—H6···O4viii0.92 (1)1.838 (15)2.735 (4)163 (4)
O3W—H5···O5ix0.93 (4)1.83 (3)2.751 (4)179 (4)
O4W—H7···O3W0.92 (1)2.12 (7)3.020 (13)162
Symmetry codes: (iv) −x+1/2, y+1/2, −z+1/2; (vi) −x+1/2, −y+1/2, −z+1; (vii) x−1/2, −y+1/2, z−1/2; (viii) x, −y, z−1/2; (ix) −x+1, y, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1···O3i0.919 (19)2.05 (4)2.687 (4)125 (4)
O1W—H2···O2ii0.93 (5)1.75 (5)2.680 (4)176 (5)
O2W—H3···O1iii0.92 (4)2.18 (3)2.843 (4)129 (3)
O2W—H4···O5iii0.915 (19)2.011 (11)2.921 (4)173 (4)
O3W—H6···O4iv0.92 (1)1.838 (15)2.735 (4)163 (4)
O3W—H5···O5v0.93 (4)1.83 (3)2.751 (4)179 (4)
O4W—H7···O3W0.92 (1)2.12 (7)3.020 (13)162
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1/2, −y+1/2, −z+1; (iii) x−1/2, −y+1/2, z−1/2; (iv) x, −y, z−1/2; (v) −x+1, y, −z+1/2.
Acknowledgements top

We gratefully acknowledge the financial support by the NSF of Fujian Province (2004 J039 and 2006 J0275).

references
References top

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Villafranca, J. J. & Mildvan, A. S. (1972). J. Biol. Chem. 247, 3454–3463.

Wang, M. S., Guo, G. C., Cai, L. Z., Chen, W. T., Liu, B., Wu, A. Q. & Huang, J. S. (2004). Dalton Trans. pp. 2230–2236.

Wang, M. S., Guo, G. C., Fu, M. L., Xu, L., Cai, L. Z. & Huang, J. S. (2005). Dalton Trans. pp. 2899–2907.