metal-organic compounds
Diaquabis(2-oxo-2H-chromene-3-carboxylato-κ2O2,O3)manganese(II)
aCollege of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, People's Republic of China
*Correspondence e-mail: xieyabo@bjut.edu.cn
In the title compound, [Mn(C10H5O4)2(H2O)2], the MnII atom lies on a crystallographic inversion center and is six-coordinated by two O atoms from water molecules in the axial positions and four O atoms from two deprotonated coumarin-3-carboxylic acid ligands in the equatorial plane. The overall coordination geometry is slightly distorted octahedral. The Mn—O bond distances vary between 2.0931 (12) and 2.2315 (13) Å. O—H⋯O hydrogen bonds between the H atoms of coordinated water molecules and the O atoms of the carboxylate groups link the complex molecules into two-dimensional layers parallel to the ab plane.
Related literature
For background to topological networks, see: Hu et al. (2010). For applications of manganese(II) complexes, see: Hazra et al. (2011), Kuschel et al. (2010); Yang et al. (2010). For related structures, see: Gao et al. (2010).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; 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: SHELXL97.
Supporting information
10.1107/S1600536811016667/sj5131sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811016667/sj5131Isup2.hkl
The title complex was synthesized by carefully layering a solution of MnSO4.H2O (16.9 mg, 0.1 mmol) in ethanol (10 ml) on top of a solution of coumarin-3-carboxylic acid (19.0 mg, 0.1 mmol) and LiOH (8.4 mg, 0.2 mmol) in H2O (10 ml) in a test-tube. After about one month at room temperature, yellow block-shaped single crystals suitable for X-ray investigation appeared at the boundary between the ethanol solution and the water layer with a yield of 25% (12.1 mg). FT—IR (KBr, cm-1): 788, 1028, 1183, 1285, 1388, 1457, 1585, 1662, 3214.
Carbon H atoms were placed geometrically (C—H = 0.93 Å) and treated as riding with Uiso(H) = 1.2Ueq(C). Water H atoms were located in a difference Fourier map. One was treated as riding in the subsequent
atoms, with O—H = 0.85 Å, the coordinates of the other were refined freely. For both i>Uiso(H) = 1.5Ueq(O).Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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: SHELXL97 (Sheldrick, 2008).[Mn(C10H5O4)2(H2O)2] | Z = 1 |
Mr = 469.25 | F(000) = 239 |
Triclinic, P1 | Dx = 1.746 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.7036 (13) Å | Cell parameters from 1947 reflections |
b = 6.9797 (14) Å | θ = 2.0–28.3° |
c = 10.424 (2) Å | µ = 0.80 mm−1 |
α = 93.28 (3)° | T = 293 K |
β = 90.67 (3)° | Block, yellow |
γ = 113.47 (3)° | 0.20 × 0.20 × 0.15 mm |
V = 446.33 (15) Å3 |
Bruker APEXII CCD diffractometer | 2021 independent reflections |
Radiation source: fine-focus sealed tube | 1905 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.009 |
ϕ and ω scans | θmax = 28.3°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −7→8 |
Tmin = 0.852, Tmax = 0.887 | k = −8→8 |
2811 measured reflections | l = −13→13 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.070 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.030P)2 + 0.2201P] where P = (Fo2 + 2Fc2)/3 |
2021 reflections | (Δ/σ)max = 0.002 |
146 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
[Mn(C10H5O4)2(H2O)2] | γ = 113.47 (3)° |
Mr = 469.25 | V = 446.33 (15) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.7036 (13) Å | Mo Kα radiation |
b = 6.9797 (14) Å | µ = 0.80 mm−1 |
c = 10.424 (2) Å | T = 293 K |
α = 93.28 (3)° | 0.20 × 0.20 × 0.15 mm |
β = 90.67 (3)° |
Bruker APEXII CCD diffractometer | 2021 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 1905 reflections with I > 2σ(I) |
Tmin = 0.852, Tmax = 0.887 | Rint = 0.009 |
2811 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.070 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.27 e Å−3 |
2021 reflections | Δρmin = −0.25 e Å−3 |
146 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.0000 | 0.5000 | 0.5000 | 0.02451 (10) | |
O1 | 0.20420 (17) | 0.69142 (18) | 0.12393 (10) | 0.0279 (2) | |
O1W | −0.00060 (19) | 0.21428 (19) | 0.40159 (11) | 0.0308 (2) | |
H1WA | 0.0974 | 0.1872 | 0.4325 | 0.046* | |
O2 | 0.06195 (17) | 0.64929 (19) | 0.31264 (11) | 0.0311 (3) | |
O3 | 0.34009 (16) | 0.63381 (18) | 0.51888 (10) | 0.0290 (2) | |
O4 | 0.67461 (16) | 0.86812 (18) | 0.49213 (11) | 0.0307 (3) | |
C1 | 0.7033 (3) | 0.7877 (3) | −0.12676 (17) | 0.0377 (4) | |
H1A | 0.8140 | 0.8088 | −0.1842 | 0.045* | |
C2 | 0.7458 (3) | 0.7881 (3) | 0.00281 (16) | 0.0327 (3) | |
H2A | 0.8845 | 0.8080 | 0.0326 | 0.039* | |
C3 | 0.5793 (2) | 0.7581 (2) | 0.09021 (14) | 0.0255 (3) | |
C4 | 0.3735 (2) | 0.7261 (2) | 0.04195 (14) | 0.0254 (3) | |
C5 | 0.3284 (3) | 0.7240 (3) | −0.08835 (15) | 0.0332 (4) | |
H5A | 0.1893 | 0.7017 | −0.1186 | 0.040* | |
C6 | 0.4953 (3) | 0.7559 (3) | −0.17236 (16) | 0.0377 (4) | |
H6A | 0.4685 | 0.7562 | −0.2601 | 0.045* | |
C7 | 0.6108 (2) | 0.7651 (2) | 0.22644 (14) | 0.0253 (3) | |
H7A | 0.7483 | 0.7901 | 0.2607 | 0.030* | |
C8 | 0.4463 (2) | 0.7363 (2) | 0.30689 (13) | 0.0218 (3) | |
C9 | 0.2290 (2) | 0.6896 (2) | 0.25373 (14) | 0.0230 (3) | |
C10 | 0.4883 (2) | 0.7473 (2) | 0.45064 (14) | 0.0223 (3) | |
H1WB | −0.110 (4) | 0.112 (4) | 0.418 (2) | 0.057 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.01647 (15) | 0.02948 (18) | 0.02242 (17) | 0.00348 (12) | 0.00291 (11) | 0.00327 (12) |
O1 | 0.0219 (5) | 0.0382 (6) | 0.0210 (5) | 0.0088 (4) | −0.0001 (4) | 0.0052 (4) |
O1W | 0.0233 (5) | 0.0326 (6) | 0.0332 (6) | 0.0077 (5) | 0.0017 (4) | 0.0022 (5) |
O2 | 0.0191 (5) | 0.0457 (7) | 0.0274 (6) | 0.0107 (5) | 0.0038 (4) | 0.0102 (5) |
O3 | 0.0188 (5) | 0.0397 (6) | 0.0220 (5) | 0.0042 (4) | 0.0017 (4) | 0.0066 (4) |
O4 | 0.0185 (5) | 0.0351 (6) | 0.0297 (6) | 0.0014 (4) | −0.0035 (4) | 0.0037 (5) |
C1 | 0.0473 (10) | 0.0351 (9) | 0.0282 (8) | 0.0133 (7) | 0.0157 (7) | 0.0038 (7) |
C2 | 0.0310 (8) | 0.0342 (8) | 0.0307 (8) | 0.0104 (6) | 0.0093 (6) | 0.0030 (6) |
C3 | 0.0263 (7) | 0.0253 (7) | 0.0223 (7) | 0.0073 (6) | 0.0042 (5) | 0.0030 (5) |
C4 | 0.0271 (7) | 0.0236 (7) | 0.0223 (7) | 0.0066 (6) | 0.0033 (5) | 0.0030 (5) |
C5 | 0.0389 (9) | 0.0324 (8) | 0.0242 (8) | 0.0101 (7) | −0.0031 (6) | 0.0016 (6) |
C6 | 0.0558 (11) | 0.0332 (8) | 0.0199 (7) | 0.0133 (8) | 0.0046 (7) | 0.0020 (6) |
C7 | 0.0202 (6) | 0.0277 (7) | 0.0257 (7) | 0.0072 (5) | 0.0007 (5) | 0.0020 (6) |
C8 | 0.0186 (6) | 0.0237 (7) | 0.0210 (7) | 0.0060 (5) | 0.0001 (5) | 0.0022 (5) |
C9 | 0.0217 (7) | 0.0241 (7) | 0.0213 (7) | 0.0066 (5) | 0.0009 (5) | 0.0049 (5) |
C10 | 0.0174 (6) | 0.0258 (7) | 0.0224 (7) | 0.0074 (5) | 0.0000 (5) | 0.0016 (5) |
Mn1—O3 | 2.0931 (12) | C1—C6 | 1.395 (3) |
Mn1—O3i | 2.0931 (12) | C1—H1A | 0.9300 |
Mn1—O1W | 2.1884 (13) | C2—C3 | 1.407 (2) |
Mn1—O1Wi | 2.1884 (13) | C2—H2A | 0.9300 |
Mn1—O2i | 2.2315 (13) | C3—C4 | 1.389 (2) |
Mn1—O2 | 2.2315 (13) | C3—C7 | 1.429 (2) |
O1—C9 | 1.3626 (17) | C4—C5 | 1.386 (2) |
O1—C4 | 1.3802 (18) | C5—C6 | 1.384 (3) |
O1W—H1WA | 0.8200 | C5—H5A | 0.9300 |
O1W—H1WB | 0.82 (3) | C6—H6A | 0.9300 |
O2—C9 | 1.2225 (18) | C7—C8 | 1.351 (2) |
O3—C10 | 1.2549 (18) | C7—H7A | 0.9300 |
O4—C10 | 1.2509 (17) | C8—C9 | 1.4555 (19) |
C1—C2 | 1.377 (2) | C8—C10 | 1.5133 (19) |
O3—Mn1—O3i | 180.0 | C3—C2—H2A | 120.0 |
O3—Mn1—O1W | 91.96 (5) | C4—C3—C2 | 118.33 (14) |
O3i—Mn1—O1W | 88.04 (5) | C4—C3—C7 | 117.86 (14) |
O3—Mn1—O1Wi | 88.04 (5) | C2—C3—C7 | 123.78 (14) |
O3i—Mn1—O1Wi | 91.96 (5) | O1—C4—C5 | 117.46 (14) |
O1W—Mn1—O1Wi | 180.00 (6) | O1—C4—C3 | 120.28 (13) |
O3—Mn1—O2i | 97.12 (5) | C5—C4—C3 | 122.25 (15) |
O3i—Mn1—O2i | 82.88 (5) | C4—C5—C6 | 118.39 (16) |
O1W—Mn1—O2i | 91.16 (5) | C4—C5—H5A | 120.8 |
O1Wi—Mn1—O2i | 88.84 (5) | C6—C5—H5A | 120.8 |
O3—Mn1—O2 | 82.88 (5) | C5—C6—C1 | 120.65 (16) |
O3i—Mn1—O2 | 97.12 (5) | C5—C6—H6A | 119.7 |
O1W—Mn1—O2 | 88.84 (5) | C1—C6—H6A | 119.7 |
O1Wi—Mn1—O2 | 91.16 (5) | C8—C7—C3 | 121.79 (14) |
O2i—Mn1—O2 | 180.0 | C8—C7—H7A | 119.1 |
C9—O1—C4 | 122.73 (12) | C3—C7—H7A | 119.1 |
Mn1—O1W—H1WA | 109.5 | C7—C8—C9 | 119.37 (13) |
Mn1—O1W—H1WB | 110.8 (17) | C7—C8—C10 | 119.84 (13) |
H1WA—O1W—H1WB | 102.0 | C9—C8—C10 | 120.77 (12) |
C9—O2—Mn1 | 124.45 (10) | O2—C9—O1 | 114.86 (13) |
C10—O3—Mn1 | 133.91 (10) | O2—C9—C8 | 127.35 (14) |
C2—C1—C6 | 120.41 (16) | O1—C9—C8 | 117.78 (13) |
C2—C1—H1A | 119.8 | O4—C10—O3 | 124.70 (14) |
C6—C1—H1A | 119.8 | O4—C10—C8 | 116.15 (13) |
C1—C2—C3 | 119.96 (16) | O3—C10—C8 | 119.13 (12) |
C1—C2—H2A | 120.0 | ||
O3—Mn1—O2—C9 | 25.72 (12) | C2—C1—C6—C5 | −0.1 (3) |
O3i—Mn1—O2—C9 | −154.28 (12) | C4—C3—C7—C8 | 1.7 (2) |
O1W—Mn1—O2—C9 | −66.40 (13) | C2—C3—C7—C8 | 179.71 (15) |
O1Wi—Mn1—O2—C9 | 113.60 (13) | C3—C7—C8—C9 | 2.2 (2) |
O1W—Mn1—O3—C10 | 90.62 (15) | C3—C7—C8—C10 | −179.37 (13) |
O1Wi—Mn1—O3—C10 | −89.38 (15) | Mn1—O2—C9—O1 | 152.34 (10) |
O2i—Mn1—O3—C10 | −177.97 (14) | Mn1—O2—C9—C8 | −28.2 (2) |
O2—Mn1—O3—C10 | 2.03 (14) | C4—O1—C9—O2 | −177.49 (13) |
C6—C1—C2—C3 | −0.6 (3) | C4—O1—C9—C8 | 3.0 (2) |
C1—C2—C3—C4 | 0.8 (2) | C7—C8—C9—O2 | 176.00 (15) |
C1—C2—C3—C7 | −177.20 (15) | C10—C8—C9—O2 | −2.4 (2) |
C9—O1—C4—C5 | 179.93 (14) | C7—C8—C9—O1 | −4.5 (2) |
C9—O1—C4—C3 | 1.0 (2) | C10—C8—C9—O1 | 177.09 (12) |
C2—C3—C4—O1 | 178.54 (13) | Mn1—O3—C10—O4 | 155.33 (12) |
C7—C3—C4—O1 | −3.3 (2) | Mn1—O3—C10—C8 | −26.6 (2) |
C2—C3—C4—C5 | −0.4 (2) | C7—C8—C10—O4 | 31.1 (2) |
C7—C3—C4—C5 | 177.76 (14) | C9—C8—C10—O4 | −150.50 (14) |
O1—C4—C5—C6 | −179.23 (14) | C7—C8—C10—O3 | −147.10 (15) |
C3—C4—C5—C6 | −0.3 (2) | C9—C8—C10—O3 | 31.3 (2) |
C4—C5—C6—C1 | 0.5 (3) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4ii | 0.82 | 1.89 | 2.7113 (17) | 178 |
O1W—H1WB···O4iii | 0.82 (3) | 1.95 (3) | 2.755 (2) | 167 (2) |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x−1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C10H5O4)2(H2O)2] |
Mr | 469.25 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.7036 (13), 6.9797 (14), 10.424 (2) |
α, β, γ (°) | 93.28 (3), 90.67 (3), 113.47 (3) |
V (Å3) | 446.33 (15) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.80 |
Crystal size (mm) | 0.20 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.852, 0.887 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2811, 2021, 1905 |
Rint | 0.009 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.070, 1.07 |
No. of reflections | 2021 |
No. of parameters | 146 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.25 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4i | 0.82 | 1.89 | 2.7113 (17) | 178 |
O1W—H1WB···O4ii | 0.82 (3) | 1.95 (3) | 2.755 (2) | 167 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y−1, z. |
Acknowledgements
This work was supported by the National Natural Science Foundation of China (No.21075114), the Science and Technology Development Project of the Beijing Education Committee and the Special Environmental Protection Fund for Public Welfare Project (201009015), the Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the jurisdiction of the Beijing Municipality (PHR 201107104) and the Ninth Technology Fund for Postgraduates of Beijing University of Technology (ykj-2011-5406).
References
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In the past decades, numerous papers dealing with manganese(II) complexes have been published due to their fascinating structural diversity (Hu et al., 2010) and potential applications in the areas of catalysis (Kuschel et al., 2010), gas adsorption (Hazra et al., 2011) and magnetism (Yang et al., 2010). Herein, we report the synthesis and crystal structure of a new mononuclear manganese complex coordinated by coumarin-3-carboxylic acid.
In the title compound, [Mn(C10H5O4)2(H2O)2], each manganese(II) atom lies on a crystallographic inversion center and is six-coordinated by two O atoms from water molecules in the axial positions and four O atoms from two deprotonated coumarin-3-carboxylic acid ligands in the equatorial plane to exhibits a slightly distorted octahedral geometry. Angles around the Mn(II) atom vary between 82.88 (5)° and 97.12 (5)°. The Mn—O bond distances between the Mn(II) atom and the O atoms vary between 2.0931 (12) and 2.2315 (13) Å, all of which are comparable to those reported for other manganese-oxygen donor complexes (e.g. Gao et al., 2010). The (C1/C2/C3/C4/C5/C6) and (C4/C3/C7/C8/C9/O1) rings are almost coplanar with a dihedral angle of 1.847 (6)° between them. The dihedral angle between the C10/C8/C9/O2 and O2/Mn/O3 planes is 25.803 (7)°. O—H···O hydrogen bonds between the hydrogen atoms of the coordinated water molecules and the O atoms of the carboxyl groups [O(1 W)—H(1 W A)···O(4), 2.711 (2) Å, O(1 W)—H(1WB)···O(4), 2.755 (2) Å] join the complexes into two-dimensional layers parallel the ab plane (Table 1, Fig. 2).