metal-organic compounds
Bis(μ-2-carboxymethyl-2-hydroxybutanedioato)bis[diaquamanganese(II)]–1,2-bis(pyridin-4-yl)ethene–water (1/1/2)
aDepartment of Fine Chemistry, Seoul National University of Science & Technology, Seoul 139-743, Republic of Korea, bDepartment of Forest & Environment Resources, Kyungpook National University, Sangju 742-711, Republic of Korea, cDepartment of Forest Resources Development, Korea Forest Research Institute, Suwon 441-350, Republic of Korea, and dDepartment of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Republic of Korea
*Correspondence e-mail: chealkim@seoultech.ac.kr, ymeekim@ewha.ac.kr
The 2(C6H6O7)2(H2O)4]·C12H10N2·2H2O, contains half of the centrosymmetric Mn complex dimer, half of a 1,2-bis(pyridin-4-yl)ethene molecule, which lies across an inversion center, and one water molecule. Two citrate ligands bridge two MnII ions, and each MnII atom is coordinated by four O atoms from the citrate ligands (one from hydroxy and three from carboxylate groups) and two water O atoms, forming a distorted octahedral environment. In the crystal, O—H⋯O and O—H⋯N hydrogen bonds link the centrosymmetric dimers and lattice water molecules into a three-dimensional structure which is further stabilized by intermolecular π–π interactions [centroid–centroid distance = 3.959 (2) Å]. Weak C—H⋯O hydrogen bonding interactions are also observed.
of the title compound, [MnRelated literature
For interactions of metal ions with biologically active molecules, see: Daniele et al. (2008); Parkin (2004); Tshuva & Lippard (2004); Stoumpos et al. (2009). For manganese citrate and zinc citrate complexes, see: Hwang et al. (2012a,b). For related complexes, see: Yu et al. (2009); Kim et al. (2011).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); 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: SHELXTL.
Supporting information
10.1107/S1600536812047034/sj5281sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812047034/sj5281Isup2.hkl
Citric acid (19.4 mg, 0.1 mmol) and Zn(NO3)2.6H2O (30.4 mg, 0.1 mmol) were dissolved in 4 ml H2O and carefully layered by 4 ml of an acetonitrile solution of 1,2-bis(4-pyridyl)ethene (37.6 mg, 0.2 mmol). Suitable crystals of the title compound were obtained from this solution within two weeks.
H atoms bound to C were placed in calculated positions with C—H distances of 0.95 Å for aromatic C atoms and 0.99 Å for methylene C atoms. They were included in the
using the riding-motion approximation with Uiso(H) = 1.2Ueq(C). H atoms bound to O were located in difference Fourier maps and refined with their O–H distances restrained as follows and Uiso(H) = 1.2Ueq(O). Hydroxyl O—H = 0.860 (2) Å, coordinated water molecules O—H = 0.930 (2) Å the free water molecule O—H = 0.930 (2) Å.Data collection: SMART (Bruker, 1997); cell
SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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).Fig. 1. The structure of the title compound showing the atom numbering scheme. Displacement ellipsoids are shown at the 50% probability level. The labelled atoms are related to unlabelled atoms by the symmetry codes: [1 - x, 1 - y, 1 - z] for diaqua-bis-(citrato)di-manganese(II) complex and [2 - x, 2 - y,z] for the 1,2-bis(pyridin-4-yl)ethene molecule. |
[Mn2(C6H6O7)2(H2O)4]·C12H10N2·2H2O | Z = 1 |
Mr = 780.41 | F(000) = 402 |
Triclinic, P1 | Dx = 1.676 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.3970 (19) Å | Cell parameters from 11909 reflections |
b = 9.4580 (19) Å | θ = 2.7–27.6° |
c = 10.131 (2) Å | µ = 0.91 mm−1 |
α = 70.24 (3)° | T = 170 K |
β = 67.11 (3)° | Plate, colorless |
γ = 75.52 (3)° | 0.15 × 0.10 × 0.02 mm |
V = 773.3 (3) Å3 |
Bruker SMART CCD diffractometer | 2973 independent reflections |
Radiation source: fine-focus sealed tube | 2423 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −11→10 |
Tmin = 0.876, Tmax = 0.982 | k = −11→10 |
4358 measured reflections | l = −12→12 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0538P)2] where P = (Fo2 + 2Fc2)/3 |
2973 reflections | (Δ/σ)max = 0.001 |
241 parameters | Δρmax = 0.47 e Å−3 |
8 restraints | Δρmin = −0.63 e Å−3 |
[Mn2(C6H6O7)2(H2O)4]·C12H10N2·2H2O | γ = 75.52 (3)° |
Mr = 780.41 | V = 773.3 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.3970 (19) Å | Mo Kα radiation |
b = 9.4580 (19) Å | µ = 0.91 mm−1 |
c = 10.131 (2) Å | T = 170 K |
α = 70.24 (3)° | 0.15 × 0.10 × 0.02 mm |
β = 67.11 (3)° |
Bruker SMART CCD diffractometer | 2973 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 2423 reflections with I > 2σ(I) |
Tmin = 0.876, Tmax = 0.982 | Rint = 0.021 |
4358 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 8 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.47 e Å−3 |
2973 reflections | Δρmin = −0.63 e Å−3 |
241 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 | 0.59596 (4) | 0.68914 (4) | 0.60932 (4) | 0.01775 (14) | |
O1 | 0.4231 (2) | 0.51640 (19) | 0.72246 (19) | 0.0179 (4) | |
H1O | 0.435 (3) | 0.479 (3) | 0.652 (2) | 0.021* | |
O2 | 0.3899 (2) | 0.79755 (19) | 0.54416 (19) | 0.0226 (4) | |
O3 | 0.1299 (2) | 0.8203 (2) | 0.6391 (2) | 0.0306 (5) | |
O4 | 0.4605 (2) | 0.7549 (2) | 0.81346 (19) | 0.0248 (4) | |
O5 | 0.3362 (2) | 0.6926 (2) | 1.0561 (2) | 0.0289 (5) | |
H5O | 0.411 (2) | 0.731 (3) | 1.055 (3) | 0.035* | |
O6 | 0.3225 (2) | 0.4206 (2) | 0.56485 (19) | 0.0232 (4) | |
O7 | 0.0686 (2) | 0.4237 (2) | 0.6196 (2) | 0.0335 (5) | |
O8 | 0.7614 (2) | 0.5543 (2) | 0.7192 (2) | 0.0263 (4) | |
H8A | 0.8656 (9) | 0.526 (3) | 0.669 (3) | 0.032* | |
H8B | 0.736 (3) | 0.4655 (17) | 0.794 (2) | 0.032* | |
O9 | 0.7071 (2) | 0.8889 (2) | 0.5139 (2) | 0.0311 (5) | |
H9A | 0.8153 (4) | 0.881 (3) | 0.478 (3) | 0.037* | |
H9B | 0.671 (3) | 0.9920 (8) | 0.501 (3) | 0.037* | |
C1 | 0.2687 (3) | 0.6001 (3) | 0.7591 (3) | 0.0166 (5) | |
C2 | 0.2613 (3) | 0.7522 (3) | 0.6372 (3) | 0.0187 (5) | |
C3 | 0.2331 (3) | 0.6280 (3) | 0.9100 (3) | 0.0209 (6) | |
H3A | 0.1328 | 0.6957 | 0.9320 | 0.025* | |
H3B | 0.2183 | 0.5299 | 0.9871 | 0.025* | |
C4 | 0.3533 (3) | 0.6963 (3) | 0.9249 (3) | 0.0195 (5) | |
C5 | 0.1477 (3) | 0.5074 (3) | 0.7752 (3) | 0.0184 (5) | |
H5A | 0.1411 | 0.4199 | 0.8642 | 0.022* | |
H5B | 0.0447 | 0.5713 | 0.7934 | 0.022* | |
C6 | 0.1791 (3) | 0.4481 (3) | 0.6430 (3) | 0.0188 (5) | |
N11 | 0.5629 (3) | 0.8142 (2) | 0.0477 (2) | 0.0236 (5) | |
C14 | 0.6748 (3) | 0.8996 (3) | 0.1754 (3) | 0.0234 (6) | |
H14 | 0.6673 | 0.9197 | 0.2638 | 0.028* | |
C11 | 0.6896 (3) | 0.8400 (3) | −0.0763 (3) | 0.0257 (6) | |
H11 | 0.6931 | 0.8193 | −0.1630 | 0.031* | |
C12 | 0.8134 (3) | 0.8954 (3) | −0.0799 (3) | 0.0247 (6) | |
H12 | 0.9015 | 0.9128 | −0.1679 | 0.030* | |
C13 | 0.8076 (3) | 0.9261 (3) | 0.0493 (3) | 0.0216 (6) | |
C15 | 0.5544 (3) | 0.8440 (3) | 0.1713 (3) | 0.0244 (6) | |
H15 | 0.4641 | 0.8267 | 0.2572 | 0.029* | |
C16 | 0.9369 (3) | 0.9793 (3) | 0.0573 (3) | 0.0246 (6) | |
H16 | 0.9299 | 0.9845 | 0.1517 | 0.030* | |
O1W | 0.0209 (3) | 0.8324 (2) | 0.4096 (3) | 0.0387 (5) | |
H1WA | 0.030 (4) | 0.7316 (11) | 0.412 (4) | 0.046* | |
H1WB | 0.063 (4) | 0.826 (4) | 0.481 (3) | 0.046* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0180 (2) | 0.0188 (2) | 0.0175 (2) | −0.00517 (15) | −0.00514 (16) | −0.00525 (16) |
O1 | 0.0186 (9) | 0.0177 (9) | 0.0194 (9) | −0.0028 (7) | −0.0062 (8) | −0.0075 (7) |
O2 | 0.0221 (10) | 0.0213 (9) | 0.0203 (10) | −0.0057 (8) | −0.0052 (8) | −0.0009 (7) |
O3 | 0.0199 (10) | 0.0247 (10) | 0.0401 (12) | 0.0003 (8) | −0.0103 (9) | −0.0022 (9) |
O4 | 0.0250 (10) | 0.0303 (10) | 0.0222 (10) | −0.0116 (8) | −0.0026 (8) | −0.0114 (8) |
O5 | 0.0301 (11) | 0.0424 (12) | 0.0210 (10) | −0.0210 (9) | −0.0075 (9) | −0.0063 (9) |
O6 | 0.0178 (9) | 0.0307 (10) | 0.0245 (10) | −0.0041 (8) | −0.0045 (8) | −0.0140 (8) |
O7 | 0.0228 (11) | 0.0514 (13) | 0.0378 (12) | −0.0080 (9) | −0.0096 (9) | −0.0246 (10) |
O8 | 0.0207 (10) | 0.0309 (11) | 0.0215 (10) | −0.0038 (8) | −0.0063 (8) | −0.0008 (8) |
O9 | 0.0248 (11) | 0.0189 (10) | 0.0454 (13) | −0.0073 (8) | −0.0074 (9) | −0.0057 (9) |
C1 | 0.0137 (12) | 0.0181 (12) | 0.0174 (13) | −0.0044 (10) | −0.0024 (10) | −0.0057 (10) |
C2 | 0.0184 (14) | 0.0182 (13) | 0.0219 (14) | −0.0024 (11) | −0.0080 (11) | −0.0071 (11) |
C3 | 0.0206 (14) | 0.0245 (14) | 0.0181 (13) | −0.0066 (11) | −0.0039 (11) | −0.0067 (11) |
C4 | 0.0196 (13) | 0.0184 (13) | 0.0213 (14) | −0.0009 (10) | −0.0071 (11) | −0.0073 (11) |
C5 | 0.0151 (13) | 0.0188 (13) | 0.0196 (13) | −0.0048 (10) | −0.0021 (10) | −0.0056 (10) |
C6 | 0.0175 (13) | 0.0183 (13) | 0.0209 (13) | −0.0072 (10) | −0.0055 (11) | −0.0033 (10) |
N11 | 0.0260 (13) | 0.0213 (11) | 0.0242 (12) | −0.0056 (10) | −0.0111 (10) | −0.0022 (10) |
C14 | 0.0304 (15) | 0.0202 (13) | 0.0228 (14) | −0.0049 (11) | −0.0129 (12) | −0.0040 (11) |
C11 | 0.0301 (15) | 0.0269 (15) | 0.0251 (15) | −0.0054 (12) | −0.0121 (12) | −0.0086 (12) |
C12 | 0.0240 (15) | 0.0284 (15) | 0.0246 (15) | −0.0045 (12) | −0.0090 (12) | −0.0088 (12) |
C13 | 0.0226 (14) | 0.0166 (13) | 0.0289 (15) | −0.0038 (11) | −0.0126 (12) | −0.0048 (11) |
C15 | 0.0266 (15) | 0.0223 (14) | 0.0243 (14) | −0.0057 (11) | −0.0096 (12) | −0.0033 (11) |
C16 | 0.0301 (16) | 0.0252 (14) | 0.0241 (14) | −0.0057 (12) | −0.0133 (12) | −0.0071 (12) |
O1W | 0.0384 (13) | 0.0336 (12) | 0.0503 (14) | −0.0040 (10) | −0.0209 (11) | −0.0123 (11) |
Mn1—O9 | 2.136 (2) | C1—C2 | 1.554 (3) |
Mn1—O6i | 2.1373 (18) | C3—C4 | 1.510 (3) |
Mn1—O8 | 2.163 (2) | C3—H3A | 0.9900 |
Mn1—O4 | 2.1701 (19) | C3—H3B | 0.9900 |
Mn1—O2 | 2.1864 (19) | C5—C6 | 1.521 (3) |
Mn1—O1 | 2.288 (2) | C5—H5A | 0.9900 |
O1—C1 | 1.440 (3) | C5—H5B | 0.9900 |
O1—H1O | 0.860 (2) | N11—C15 | 1.342 (3) |
O2—C2 | 1.278 (3) | N11—C11 | 1.352 (4) |
O3—C2 | 1.238 (3) | C14—C15 | 1.381 (4) |
O4—C4 | 1.252 (3) | C14—C13 | 1.397 (4) |
O5—C4 | 1.264 (3) | C14—H14 | 0.9500 |
O5—H5O | 0.861 (2) | C11—C12 | 1.373 (4) |
O6—C6 | 1.282 (3) | C11—H11 | 0.9500 |
O6—Mn1i | 2.1372 (18) | C12—C13 | 1.412 (4) |
O7—C6 | 1.239 (3) | C12—H12 | 0.9500 |
O8—H8A | 0.929 (2) | C13—C16 | 1.465 (4) |
O8—H8B | 0.930 (2) | C15—H15 | 0.9500 |
O9—H9A | 0.930 (2) | C16—C16ii | 1.328 (5) |
O9—H9B | 0.930 (2) | C16—H16 | 0.9500 |
C1—C5 | 1.532 (3) | O1W—H1WA | 0.930 (2) |
C1—C3 | 1.533 (3) | O1W—H1WB | 0.930 (2) |
O9—Mn1—O6i | 104.69 (8) | C4—C3—H3A | 108.1 |
O9—Mn1—O8 | 95.79 (8) | C1—C3—H3A | 108.1 |
O6i—Mn1—O8 | 95.74 (7) | C4—C3—H3B | 108.1 |
O9—Mn1—O4 | 91.93 (8) | C1—C3—H3B | 108.1 |
O6i—Mn1—O4 | 162.66 (7) | H3A—C3—H3B | 107.3 |
O8—Mn1—O4 | 87.30 (8) | O4—C4—O5 | 122.9 (2) |
O9—Mn1—O2 | 94.80 (8) | O4—C4—C3 | 121.5 (2) |
O6i—Mn1—O2 | 89.16 (7) | O5—C4—C3 | 115.6 (2) |
O8—Mn1—O2 | 166.80 (7) | C6—C5—C1 | 115.7 (2) |
O4—Mn1—O2 | 84.48 (7) | C6—C5—H5A | 108.4 |
O9—Mn1—O1 | 166.09 (7) | C1—C5—H5A | 108.4 |
O6i—Mn1—O1 | 83.34 (7) | C6—C5—H5B | 108.4 |
O8—Mn1—O1 | 94.66 (7) | C1—C5—H5B | 108.4 |
O4—Mn1—O1 | 79.39 (7) | H5A—C5—H5B | 107.4 |
O2—Mn1—O1 | 73.70 (7) | O7—C6—O6 | 123.8 (2) |
C1—O1—Mn1 | 107.29 (13) | O7—C6—C5 | 119.6 (2) |
C1—O1—H1O | 107.4 (18) | O6—C6—C5 | 116.5 (2) |
Mn1—O1—H1O | 103.0 (18) | C15—N11—C11 | 120.3 (2) |
C2—O2—Mn1 | 115.41 (15) | C15—C14—C13 | 119.9 (2) |
C4—O4—Mn1 | 130.73 (16) | C15—C14—H14 | 120.1 |
C4—O5—H5O | 109 (2) | C13—C14—H14 | 120.1 |
C6—O6—Mn1i | 124.98 (16) | N11—C11—C12 | 121.7 (2) |
Mn1—O8—H8A | 123.5 (18) | N11—C11—H11 | 119.2 |
Mn1—O8—H8B | 120.1 (18) | C12—C11—H11 | 119.2 |
H8A—O8—H8B | 102 (2) | C11—C12—C13 | 119.0 (3) |
Mn1—O9—H9A | 120.1 (18) | C11—C12—H12 | 120.5 |
Mn1—O9—H9B | 134.0 (19) | C13—C12—H12 | 120.5 |
H9A—O9—H9B | 106 (3) | C14—C13—C12 | 118.2 (2) |
O1—C1—C5 | 110.87 (18) | C14—C13—C16 | 119.2 (2) |
O1—C1—C3 | 106.59 (19) | C12—C13—C16 | 122.6 (2) |
C5—C1—C3 | 108.3 (2) | N11—C15—C14 | 121.0 (3) |
O1—C1—C2 | 110.49 (19) | N11—C15—H15 | 119.5 |
C5—C1—C2 | 109.4 (2) | C14—C15—H15 | 119.5 |
C3—C1—C2 | 111.13 (19) | C16ii—C16—C13 | 124.9 (3) |
O3—C2—O2 | 125.2 (2) | C16ii—C16—H16 | 117.5 |
O3—C2—C1 | 116.8 (2) | C13—C16—H16 | 117.5 |
O2—C2—C1 | 118.0 (2) | H1WA—O1W—H1WB | 103 (3) |
C4—C3—C1 | 116.8 (2) | ||
O9—Mn1—O1—C1 | 1.5 (4) | C3—C1—C2—O2 | 103.5 (2) |
O6i—Mn1—O1—C1 | −124.70 (14) | O1—C1—C3—C4 | 51.3 (3) |
O8—Mn1—O1—C1 | 140.04 (14) | C5—C1—C3—C4 | 170.7 (2) |
O4—Mn1—O1—C1 | 53.67 (14) | C2—C1—C3—C4 | −69.1 (3) |
O2—Mn1—O1—C1 | −33.63 (13) | Mn1—O4—C4—O5 | 144.1 (2) |
O9—Mn1—O2—C2 | −144.09 (17) | Mn1—O4—C4—C3 | −37.3 (3) |
O6i—Mn1—O2—C2 | 111.24 (17) | C1—C3—C4—O4 | 13.8 (4) |
O8—Mn1—O2—C2 | −0.8 (4) | C1—C3—C4—O5 | −167.5 (2) |
O4—Mn1—O2—C2 | −52.61 (17) | O1—C1—C5—C6 | −54.3 (3) |
O1—Mn1—O2—C2 | 27.93 (16) | C3—C1—C5—C6 | −171.0 (2) |
O9—Mn1—O4—C4 | 173.5 (2) | C2—C1—C5—C6 | 67.8 (3) |
O6i—Mn1—O4—C4 | 9.9 (4) | Mn1i—O6—C6—O7 | −5.4 (4) |
O8—Mn1—O4—C4 | −90.8 (2) | Mn1i—O6—C6—C5 | 171.83 (15) |
O2—Mn1—O4—C4 | 78.9 (2) | C1—C5—C6—O7 | −153.2 (2) |
O1—Mn1—O4—C4 | 4.5 (2) | C1—C5—C6—O6 | 29.4 (3) |
Mn1—O1—C1—C5 | 156.94 (15) | C15—N11—C11—C12 | 0.7 (4) |
Mn1—O1—C1—C3 | −85.35 (18) | N11—C11—C12—C13 | −0.1 (4) |
Mn1—O1—C1—C2 | 35.5 (2) | C15—C14—C13—C12 | 0.3 (4) |
Mn1—O2—C2—O3 | 162.7 (2) | C15—C14—C13—C16 | −177.6 (2) |
Mn1—O2—C2—C1 | −16.8 (3) | C11—C12—C13—C14 | −0.4 (4) |
O1—C1—C2—O3 | 165.9 (2) | C11—C12—C13—C16 | 177.4 (2) |
C5—C1—C2—O3 | 43.6 (3) | C11—N11—C15—C14 | −0.8 (4) |
C3—C1—C2—O3 | −76.0 (3) | C13—C14—C15—N11 | 0.3 (4) |
O1—C1—C2—O2 | −14.6 (3) | C14—C13—C16—C16ii | −174.0 (3) |
C5—C1—C2—O2 | −136.9 (2) | C12—C13—C16—C16ii | 8.2 (5) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···O3iii | 0.95 | 2.48 | 3.344 (4) | 151 |
C11—H11···O4iv | 0.95 | 2.53 | 3.143 (3) | 123 |
O9—H9B···O3v | 0.93 (1) | 2.56 (3) | 3.113 (3) | 118 (2) |
O9—H9B···O2v | 0.93 (1) | 1.88 (1) | 2.803 (3) | 175 (3) |
O9—H9A···O1Wvi | 0.93 (1) | 1.78 (1) | 2.695 (3) | 170 (3) |
O8—H8B···O5vii | 0.93 (1) | 1.78 (1) | 2.707 (3) | 173 (3) |
O8—H8A···O7vi | 0.93 (1) | 1.87 (1) | 2.769 (3) | 163 (3) |
O5—H5O···N11viii | 0.86 (1) | 1.76 (1) | 2.625 (3) | 178 (3) |
O1W—H1WB···O3 | 0.93 (1) | 1.92 (1) | 2.843 (3) | 175 (3) |
O1—H1O···O6 | 0.86 (1) | 1.88 (2) | 2.616 (2) | 143 (2) |
O1W—H1WA···O7ix | 0.93 (1) | 2.08 (2) | 2.891 (3) | 145 (3) |
Symmetry codes: (iii) x+1, y, z−1; (iv) x, y, z−1; (v) −x+1, −y+2, −z+1; (vi) x+1, y, z; (vii) −x+1, −y+1, −z+2; (viii) x, y, z+1; (ix) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mn2(C6H6O7)2(H2O)4]·C12H10N2·2H2O |
Mr | 780.41 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 170 |
a, b, c (Å) | 9.3970 (19), 9.4580 (19), 10.131 (2) |
α, β, γ (°) | 70.24 (3), 67.11 (3), 75.52 (3) |
V (Å3) | 773.3 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.91 |
Crystal size (mm) | 0.15 × 0.10 × 0.02 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.876, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4358, 2973, 2423 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.098, 1.08 |
No. of reflections | 2973 |
No. of parameters | 241 |
No. of restraints | 8 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.47, −0.63 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···O3i | 0.95 | 2.48 | 3.344 (4) | 151.3 |
C11—H11···O4ii | 0.95 | 2.53 | 3.143 (3) | 122.8 |
O9—H9B···O3iii | 0.930 (2) | 2.56 (3) | 3.113 (3) | 118 (2) |
O9—H9B···O2iii | 0.930 (2) | 1.876 (4) | 2.803 (3) | 175 (3) |
O9—H9A···O1Wiv | 0.930 (2) | 1.776 (6) | 2.695 (3) | 170 (3) |
O8—H8B···O5v | 0.930 (2) | 1.782 (5) | 2.707 (3) | 173 (3) |
O8—H8A···O7iv | 0.929 (2) | 1.868 (9) | 2.769 (3) | 163 (3) |
O5—H5O···N11vi | 0.861 (2) | 1.764 (4) | 2.625 (3) | 178 (3) |
O1W—H1WB···O3 | 0.930 (2) | 1.916 (5) | 2.843 (3) | 175 (3) |
O1—H1O···O6 | 0.860 (2) | 1.880 (17) | 2.616 (2) | 143 (2) |
O1W—H1WA···O7vii | 0.930 (2) | 2.082 (19) | 2.891 (3) | 145 (3) |
Symmetry codes: (i) x+1, y, z−1; (ii) x, y, z−1; (iii) −x+1, −y+2, −z+1; (iv) x+1, y, z; (v) −x+1, −y+1, −z+2; (vi) x, y, z+1; (vii) −x, −y+1, −z+1. |
Acknowledgements
Financial support from Forest Science & Technology Projects (S121012L080111) and the Converging Research Center Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2012001725) is gratefully acknowledged.
References
Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Daniele, P. G., Foti, C., Gianguzza, A., Prenesti, E. & Sammartano, S. (2008). Coord. Chem. Rev. 252, 1093–1107. Web of Science CrossRef CAS Google Scholar
Hwang, I. H., Kim, P.-G., Kim, C. & Kim, Y. (2012a). Acta Cryst. E68, m1116–m1117. CSD CrossRef IUCr Journals Google Scholar
Hwang, I. H., Kim, P.-G., Kim, C. & Kim, Y. (2012b). Acta Cryst. E68, m1305–m1306. CSD CrossRef IUCr Journals Google Scholar
Kim, J. H., Kim, C. & Kim, Y. (2011). Acta Cryst. E67, m3–m4. Web of Science CrossRef IUCr Journals Google Scholar
Parkin, G. (2004). Chem. Rev. 104, 699–767. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoumpos, C. C., Gass, I. A., Milios, C. J., Lalioti, N., Terzis, A., Aromi, G., Teat, S. J., Brechin, E. K. & Perlepes, S. P. (2009). Dalton Trans. pp. 307–317. Web of Science CSD CrossRef Google Scholar
Tshuva, E. Y. & Lippard, S. J. (2004). Chem. Rev. 104, 987–1012. Web of Science CrossRef PubMed CAS Google Scholar
Yu, S. M., Shin, D. H., Kim, P.-G., Kim, C. & Kim, Y. (2009). Acta Cryst. E65, m1045–m1046. Web of Science CSD CrossRef IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Complexes involving citric acid have often been used as models to examine the interaction between transition metal ions with biologically active molecules (Daniele et al., 2008; Parkin, 2004; Tshuva & Lippard, 2004; Stoumpos et al., 2009). Quite recently, our group has reported two novel compounds from the reaction of manganese(II) and zinc(II) nitrates as the building blocks and citric acid as the ligand (Hwang, et al., 2012a,b). In order to study the effects of spacer ligands on the interaction between transition metal ions with citric acid (Yu, et al., 2009; Kim, et al., 2011), in this work, we have attempted to employ 1,2-bis(4-pyridyl)ethene as a spacer source. We report here the resulting structure in which the 1,2-bis(4-pyridyl)ethene molecule does not function as a spacer but co-crystallises with the Mn complex to form bis(µ-2-carboxymethyl-2-hydroxybutanedioato)bis[diaquamanganese(II)]– 1,2-bis(pyridin-4-yl)ethene–water(1/1/2).
The molecular structure of the title compound is shown in Fig. 1. The asymmetric unit of the title compound, C24H34Mn2N2O20, contains half of the centrosymmetric Mn complex dimer, half of a 1,2-bis(pyridin-4-yl)ethene molecule, which lies across an inversion center, and one water molecule. Two citrate ligands bridge two MnII ions, and each MnII is coordinated by four oxygen atoms from the citrate ligands (one hydroxyl and three carboxylate, with one bridging) and two water oxygen atoms, forming a distorted octahedral environment. In the crystal, O—H···O hydrogen bonds link the centrosymmetric dimers and lattice water molecules into a three-dimensional structure. The crystal structure is further stabilized by intermolecular π-π interactions [centroid = C11–C15/N11; centroid–centroid distance = 3.959 (2) Å symmetry code: 1 - x, 2 - y, z].