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Acta Cryst. (2012). E68, m957    [ doi:10.1107/S1600536812027158 ]

Poly[tetraaqua([mu]6-9,10-dioxo-9,10-dihydroanthracene-1,4,5,8-tetracarboxylato)dimanganese(II)]

R. Xu and J.-L. Liu

Abstract top

The title complex, [Mn2(C18H4O10)(H2O)4]n, was synthesized from manganese(II) chloride tetrahydrate and 9,10-dioxo-9,10-dihydroanthracene-1,4,5,8-tetracarboxylic acid (H4AQTC) in water. The anthraquinone unit is located about a crystallographic center of inversion. Each asymmetric unit therefore contains one MnII atom, two water ligands and one half AQTC4- anion. The MnII atom is coordinated in a distorted octahedral geometry by four O atoms from three AQTC4- ligands and two water O atoms. Two of the carboxylate groups coordinate one MnII atom in a chelating mode, whereas the others each coordinate two MnII atoms. Each AQTC4- tetra-anion therefore coordinates six different MnII ions and, as a result, a three-dimensional coordination polymer is formed. O-H...O hydrogen bonds, some of them bifurcated, between water ligands and neighboring water or anthraquinone ligands are observed in the crystal structure.

Comment top

Porous solid materials, such as MOFs (metal-organic frameworks) have been widely studied for their potential applications in gas absorption, separation, catalysis and magnetic materials. Explorations of advanced porous materials for these applications are an intense subject of scientific research (Li et al.,1999; Li et al., 2012; Cheng et al., 2010; Hong et al., 2009; Miller & Gatteschi, 2011; Liu et al., 2010.) Herein we report the crystal structure of the title compound.

The molecular structure of (I) is illustrated in Fig. 1., a summary of the observed hydrogen bonds and the corresponding angles are given in Table 1.

Each asymmetric unit therefore contains one manganese(II) atom, two water ligands and one half AQTC4- ligand. The coordination sphere around manganese is distorted octahedral due to the coordination of four O atoms from three AQTC4- ligands and two O atoms from two water molecules. Two of the carboxylate groups coordinate one manganese in a chelating mode whereas the others each coordinate two manganese center. Each AQTC4- therefore coordinates six different manganese ions and as a result a three-dimensional coordination polymer is formed.

Related literature top

For general background to metal-organic frameworks, see: Li et al. (1999, 2012); Cheng et al. (2010); Hong et al. (2009); Miller & Gatteschi (2011); Liu et al. (2010).

Experimental top

A mixture of 9,10-dioxo-9,10-dihydroanthracene-1,4,5,8-tetracarboxylic acid (H4AQTC; 0.025 mmol, 9.8 mg) was added to distilled water (4 ml) and ultra-sounded for 10 min. The pH value of the mixture was then adjusted to 7.0 with sodium hydroxide (0.5 mol L-1), prior to the addition of manganese(II) chloride tetrahydrate (0.05 mmol, 9.9 mg). The reactants were placed in a Teflon-lined stainless steel vessel, heated for 3 days, and then cooled to ambient temperature over 12 h. The solution was exposed to air for three days leading to the precipitation of brown crystals (yield 10%).

Refinement top

All non-hydrogen atoms were refined anisotropically. H atoms of the H2O ligands were determined in difference Fourier maps and refined isotropically with distance restraints for O9—H5 and O9—H6 of 0.82 Å. H atoms of AQTC4- ligands calculated in idealized positions with C—H = 0.93 Å and refined as riding atoms, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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. One repeating unit of the coordination polymer, showing displacement ellipsoids at the 30% probability level. [Symmetry codes: (#1) x + 1,-y,-z + 1; (#2) x + 1,y + 1/2,-z + 1/2; (#3) x + 1,-y + 1,-z + 1; (#4) x + 1,y - 1/2,-z + 1/2.]
[Figure 2] Fig. 2. A view of the crystal structure of the title compound.
Poly[tetraaqua(µ6-9,10-dioxo-9,10-dihydroanthracene-1,4,5,8- tetracarboxylato)dimanganese(II)] top
Crystal data top
[Mn2(C18H4O10)(H2O)4]F(000) = 564
Mr = 562.16Dx = 2.034 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5133 reflections
a = 11.2255 (16) Åθ = 2.2–27.6°
b = 8.4153 (13) ŵ = 1.46 mm−1
c = 9.7252 (14) ÅT = 273 K
β = 92.355 (2)°Block, brown
V = 917.9 (2) Å30.46 × 0.32 × 0.26 mm
Z = 2
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		1609 independent reflections
Radiation source: fine-focus sealed tube1499 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.065
phi and ω scansθmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −12→13
Tmin = 0.553, Tmax = 0.702k = −10→7
4340 measured reflectionsl = −11→11
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)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0357P)2 + 0.3487P]
where P = (Fo2 + 2Fc2)/3
1609 reflections(Δ/σ)max < 0.001
170 parametersΔρmax = 0.35 e Å−3
2 restraintsΔρmin = −0.41 e Å−3
Crystal data top
[Mn2(C18H4O10)(H2O)4]V = 917.9 (2) Å3
Mr = 562.16Z = 2
Monoclinic, P21/cMo Kα radiation
a = 11.2255 (16) ŵ = 1.46 mm−1
b = 8.4153 (13) ÅT = 273 K
c = 9.7252 (14) Å0.46 × 0.32 × 0.26 mm
β = 92.355 (2)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		1609 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		1499 reflections with I > 2σ(I)
Tmin = 0.553, Tmax = 0.702Rint = 0.065
4340 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.076Δρmax = 0.35 e Å−3
S = 1.08Δρmin = −0.41 e Å−3
1609 reflectionsAbsolute structure: ?
170 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
C10.32095 (18)0.3515 (2)0.3203 (2)0.0199 (4)
C20.44180 (17)0.2999 (2)0.37593 (19)0.0182 (4)
C30.47029 (17)0.1544 (2)0.43842 (19)0.0174 (4)
C40.58569 (16)0.1290 (2)0.49497 (19)0.0168 (4)
C50.67291 (17)0.2464 (2)0.4857 (2)0.0176 (4)
C60.64515 (18)0.3863 (2)0.4181 (2)0.0214 (4)
H10.70360.46320.40810.026*
C70.53093 (18)0.4128 (2)0.3654 (2)0.0214 (4)
H20.51330.50870.32170.026*
C80.79987 (17)0.2271 (2)0.5408 (2)0.0187 (4)
C90.38273 (18)0.0223 (2)0.4344 (2)0.0173 (4)
Mn10.14215 (3)0.50978 (3)0.21336 (3)0.02054 (15)
O10.31881 (13)0.4118 (2)0.20209 (15)0.0305 (4)
O20.23044 (12)0.35278 (18)0.39148 (15)0.0261 (4)
O30.87242 (12)0.15778 (18)0.46563 (15)0.0245 (3)
O60.82943 (13)0.28802 (18)0.65405 (15)0.0274 (4)
O70.28972 (13)0.03344 (17)0.36714 (16)0.0244 (4)
O80.09489 (15)0.2961 (2)0.08600 (17)0.0267 (4)
O9−0.04028 (17)0.5190 (3)0.2639 (2)0.0489 (6)
H30.143 (3)0.273 (4)0.034 (3)0.053 (10)*
H40.024 (3)0.306 (4)0.042 (4)0.068 (10)*
H5−0.064 (3)0.590 (3)0.312 (3)0.079 (13)*
H6−0.091 (3)0.457 (5)0.239 (5)0.114 (17)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0197 (10)0.0151 (10)0.0247 (11)−0.0006 (8)−0.0031 (8)0.0011 (8)
C20.0176 (10)0.0206 (10)0.0166 (10)0.0002 (8)0.0007 (7)0.0003 (8)
C30.0157 (9)0.0201 (10)0.0163 (10)0.0020 (8)0.0004 (7)−0.0001 (8)
C40.0171 (9)0.0186 (10)0.0147 (10)0.0016 (8)−0.0007 (7)−0.0010 (7)
C50.0172 (10)0.0191 (10)0.0163 (10)0.0015 (8)−0.0002 (7)−0.0031 (8)
C60.0183 (10)0.0225 (11)0.0233 (11)−0.0042 (8)0.0000 (8)0.0011 (8)
C70.0223 (10)0.0191 (10)0.0225 (10)0.0012 (8)−0.0008 (8)0.0042 (8)
C80.0177 (10)0.0154 (10)0.0228 (11)−0.0029 (8)−0.0027 (8)0.0029 (8)
C90.0158 (10)0.0183 (10)0.0178 (10)0.0016 (8)0.0002 (8)−0.0015 (8)
Mn10.0173 (2)0.0225 (2)0.0215 (2)0.00180 (12)−0.00320 (14)−0.00052 (12)
O10.0221 (8)0.0426 (10)0.0265 (8)0.0031 (7)−0.0023 (6)0.0113 (7)
O20.0205 (8)0.0280 (8)0.0299 (8)0.0030 (6)0.0035 (6)0.0038 (6)
O30.0166 (7)0.0319 (8)0.0247 (8)0.0000 (6)−0.0016 (6)−0.0063 (6)
O60.0260 (8)0.0289 (8)0.0266 (8)−0.0003 (7)−0.0069 (6)−0.0097 (7)
O70.0183 (8)0.0225 (7)0.0315 (9)0.0000 (6)−0.0105 (6)0.0041 (6)
O80.0185 (8)0.0339 (9)0.0276 (9)0.0005 (7)−0.0007 (7)−0.0065 (7)
O90.0217 (9)0.0638 (14)0.0617 (14)−0.0095 (9)0.0059 (9)−0.0353 (11)
Geometric parameters (Å, º) top
C1—O21.253 (3)C8—O31.260 (2)
C1—O11.256 (2)C9—O71.212 (2)
C1—C21.504 (3)C9—C4i1.483 (3)
C2—C71.386 (3)Mn1—O92.1270 (19)
C2—C31.398 (3)Mn1—O3ii2.1412 (15)
C3—C41.403 (3)Mn1—O6iii2.1508 (15)
C3—C91.483 (3)Mn1—O12.1547 (15)
C4—C51.396 (3)Mn1—O82.2350 (16)
C4—C9i1.483 (3)Mn1—O22.3637 (15)
C5—C61.378 (3)O3—Mn1iv2.1412 (15)
C5—C81.511 (3)O6—Mn1iii2.1508 (15)
C6—C71.379 (3)O8—H30.78 (3)
C6—H10.9300O8—H40.89 (4)
C7—H20.9300O9—H50.812 (10)
C8—O61.247 (2)O9—H60.809 (10)
O2—C1—O1121.11 (18)C4i—C9—C3119.05 (17)
O2—C1—C2122.96 (18)O9—Mn1—O3ii97.16 (8)
O1—C1—C2115.40 (17)O9—Mn1—O6iii87.31 (7)
C7—C2—C3118.63 (18)O3ii—Mn1—O6iii91.81 (6)
C7—C2—C1114.76 (17)O9—Mn1—O1157.30 (8)
C3—C2—C1126.59 (18)O3ii—Mn1—O1102.77 (5)
C2—C3—C4119.69 (18)O6iii—Mn1—O1102.67 (6)
C2—C3—C9120.34 (17)O9—Mn1—O887.05 (7)
C4—C3—C9119.75 (18)O3ii—Mn1—O890.52 (6)
C5—C4—C3120.36 (18)O6iii—Mn1—O8174.13 (6)
C5—C4—C9i118.84 (17)O1—Mn1—O882.05 (6)
C3—C4—C9i120.80 (17)O9—Mn1—O2103.28 (8)
C6—C5—C4119.34 (17)O3ii—Mn1—O2159.49 (5)
C6—C5—C8116.90 (17)O6iii—Mn1—O287.45 (6)
C4—C5—C8123.71 (17)O1—Mn1—O257.61 (5)
C5—C6—C7120.24 (19)O8—Mn1—O292.25 (6)
C5—C6—H1119.9C1—O1—Mn195.23 (12)
C7—C6—H1119.9C1—O2—Mn185.71 (12)
C6—C7—C2121.64 (19)C8—O3—Mn1iv135.36 (13)
C6—C7—H2119.2C8—O6—Mn1iii151.88 (14)
C2—C7—H2119.2Mn1—O8—H3114 (2)
O6—C8—O3123.22 (18)Mn1—O8—H4112 (2)
O6—C8—C5118.82 (17)H3—O8—H4110 (3)
O3—C8—C5117.82 (17)Mn1—O9—H5120 (3)
O7—C9—C4i120.01 (18)Mn1—O9—H6126 (4)
O7—C9—C3120.77 (18)H5—O9—H6114 (5)
O2—C1—C2—C7−122.6 (2)C4—C5—C8—O384.0 (2)
O1—C1—C2—C749.1 (3)C2—C3—C9—O76.4 (3)
O2—C1—C2—C355.6 (3)C4—C3—C9—O7−168.17 (19)
O1—C1—C2—C3−132.7 (2)C2—C3—C9—C4i−178.27 (17)
C7—C2—C3—C43.3 (3)C4—C3—C9—C4i7.1 (3)
C1—C2—C3—C4−174.94 (18)O2—C1—O1—Mn16.2 (2)
C7—C2—C3—C9−171.33 (17)C2—C1—O1—Mn1−165.70 (15)
C1—C2—C3—C910.5 (3)O9—Mn1—O1—C1−39.0 (2)
C2—C3—C4—C5−1.8 (3)O3ii—Mn1—O1—C1170.17 (12)
C9—C3—C4—C5172.81 (17)O6iii—Mn1—O1—C175.34 (13)
C2—C3—C4—C9i178.11 (17)O8—Mn1—O1—C1−101.11 (13)
C9—C3—C4—C9i−7.3 (3)O2—Mn1—O1—C1−3.32 (11)
C3—C4—C5—C6−1.2 (3)O1—C1—O2—Mn1−5.63 (19)
C9i—C4—C5—C6178.86 (18)C2—C1—O2—Mn1165.63 (18)
C3—C4—C5—C8−178.52 (18)O9—Mn1—O2—C1169.94 (12)
C9i—C4—C5—C81.6 (3)O3ii—Mn1—O2—C1−15.1 (2)
C4—C5—C6—C72.8 (3)O6iii—Mn1—O2—C1−103.43 (12)
C8—C5—C6—C7−179.76 (18)O1—Mn1—O2—C13.32 (11)
C5—C6—C7—C2−1.3 (3)O8—Mn1—O2—C182.44 (12)
C3—C2—C7—C6−1.8 (3)O6—C8—O3—Mn1iv168.36 (14)
C1—C2—C7—C6176.64 (19)C5—C8—O3—Mn1iv−15.9 (3)
C6—C5—C8—O682.5 (2)O3—C8—O6—Mn1iii112.0 (3)
C4—C5—C8—O6−100.1 (2)C5—C8—O6—Mn1iii−63.7 (4)
C6—C5—C8—O3−93.4 (2)
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+1, −y+1, −z+1; (iv) −x+1, y−1/2, −z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O8—H3···O2v0.78 (3)2.03 (3)2.775 (2)160 (3)
O8—H4···O3vi0.89 (4)1.86 (4)2.742 (2)174 (3)
O8—H4···O6vi0.89 (4)2.60 (3)3.159 (2)121 (3)
O9—H5···O8vii0.81 (1)2.03 (1)2.832 (3)168 (4)
O9—H6···O6vi0.81 (1)2.38 (2)3.135 (3)157 (5)
O9—H6···O7vii0.81 (1)2.50 (4)3.031 (3)124 (4)
Symmetry codes: (v) x, −y+1/2, z−1/2; (vi) x−1, −y+1/2, z−1/2; (vii) −x, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O8—H3···O2i0.78 (3)2.03 (3)2.775 (2)160 (3)
O8—H4···O3ii0.89 (4)1.86 (4)2.742 (2)174 (3)
O8—H4···O6ii0.89 (4)2.60 (3)3.159 (2)121 (3)
O9—H5···O8iii0.812 (10)2.033 (13)2.832 (3)168 (4)
O9—H6···O6ii0.809 (10)2.38 (2)3.135 (3)157 (5)
O9—H6···O7iii0.809 (10)2.50 (4)3.031 (3)124 (4)
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x−1, −y+1/2, z−1/2; (iii) −x, y+1/2, −z+1/2.
Acknowledgements top

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

references
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