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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): m166.
Published online 2007 December 12. doi:  10.1107/S1600536807065142
PMCID: PMC2915102

Bis(μ-carboxyl­atoethyl­phospho­nato)bis­[aqua­(2,2′-bipyridine)manganese(II)]

Abstract

The title compound, [Mn2(HO3PCH2CH2COO)2(C8H8N2)2(H2O)2], was obtained by hydro­thermal synthesis. The manganese(II) ions are six-coordinate and are linked by two 2-carboxy­ethyl­phospho­nate ligands, forming a centrosymmetric dimer. The Mn ions adopts a distorted octahedral coordination geometry. The dimers are further linked by O—H(...)O hydrogen bonds and π–π stacking inter­actions [centroid–centroid distance 4.2754 (4) Å].

Related literature

For related literature, see: Clearfield (1998 [triangle]); Cheetham et al. (1999 [triangle]); Stock et al. (2000 [triangle]); Serpaggi & Férey (1999 [triangle]); Ying & Mao et al. (2004 [triangle]); Ying et al. (2007 [triangle]). For the isostructural Zn(II) complex, see: Ying et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0m166-scheme1.jpg

Experimental

Crystal data

  • [Mn2(C5H5O5P)2(C8H8N2)2(H2O)2]
  • M r = 762.36
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m166-efi1.jpg
  • a = 8.7553 (13) Å
  • b = 18.060 (3) Å
  • c = 20.682 (3) Å
  • V = 3270.3 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.94 mm−1
  • T = 293 (2) K
  • 0.32 × 0.30 × 0.26 mm

Data collection

  • Bruker APEX area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2002 [triangle]) T min = 0.754, T max = 0.796
  • 23111 measured reflections
  • 4057 independent reflections
  • 2893 reflections with I > 2σ(I)
  • R int = 0.038

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.090
  • S = 0.99
  • 4057 reflections
  • 208 parameters
  • H-atom parameters constrained
  • Δρmax = 0.47 e Å−3
  • Δρmin = −0.60 e Å−3

Data collection: SMART (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a [triangle]); molecular graphics: SHELXTL (Sheldrick, 1997b [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807065142/om2188sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807065142/om2188Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by Jiangxi Provincial Department of Education’s Project of Science and Technology (No. [2007]316).

supplementary crystallographic information

Comment

In recent years, metal phosphonates have been a rapid expansion research field due to their potential application in the area of catalysis, ion exchange, proton conductivity, intercalation chemistry, photochemistry and materials chemistry (Clearfield 1998). Many metal phosphonates have been reported (Cheetham et al., 1999; Stock et al., 2000; Serpaggi & Férey, 1999; Ying & Mao, 2004; Ying et al., 2006). Metal phosphonates can exhibit various kinds of structures. We report here the crystal structure of a new manganese(II) carboxyalkylphosphonate complex synthesized by the hydrothermal method.

The asymmetric unit of the title compound contains one manganese(II) ion, one doubly deprotonated 2-carboxyethylphosphonic acid ligand, one 2,2'-bipyridine and one coordinated water molecule. The manganese(II) ion is six-coordinated by one phosphonate oxygen atom, one water molecule, two carboxylate oxygen atoms and two N atoms from a 2,2'-bipyridine molecule. The Mn—O distances range from 2.0646 (12) to 2.3161 (14) Å and the Mn—N distances are 2.2437 (16) and 2.2890 (16) Å. Two manganese(II) ions are linked by two 2-carboxyethylphosphonic acid ligands forming a dimer (Fig. 1). The dimers are further interlinked by O—H···O hydrogen bonds and π-π stacking interactions to form a three-dimensional supermolecular structure (Fig. 2). The compound is isostructural with a zinc(II) complex which has been reported recently (Ying et al., 2007).

Experimental

A mixture of manganese(II) acetate (0.5 mmol, 0.120 g), 2-carboxyethylphosphonic acid (0.5 mmol, 0.076 g), and 2,2'-bipyridine (0.5 mmol, 0.079 g) in 10 ml of distilled water was sealed in an autoclave equipped with a Teflon liner (20 ml) and then heated at 150°C for 3 days. Crystals of the title compound were obtained.

Refinement

All hydrogen atoms were geometrically positioned with C—H = 0.93–0.98 Å, O—H = 0.82 Å, and refined in the riding-model approximation, with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(O).

Figures

Fig. 1.
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Symmetry code: (i) 2 - x, -y, 1 - z.
Fig. 2.
Packing diagram of the title compound viewed along the a axis. Hydrogen atoms are omitted for clarity.

Crystal data

[Mn2(C5H5O5P1)2(C8H8N2)2(H2O)2]F000 = 1560
Mr = 762.36Dx = 1.548 Mg m3
Orthorhombic, PbcaMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 5461 reflections
a = 8.7553 (13) Åθ = 2.5–28.2º
b = 18.060 (3) ŵ = 0.94 mm1
c = 20.682 (3) ÅT = 293 (2) K
V = 3270.3 (8) Å3Block, colourless
Z = 40.32 × 0.30 × 0.26 mm

Data collection

Bruker APEX area-detector diffractometer4057 independent reflections
Radiation source: fine-focus sealed tube2893 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.038
T = 293(2) Kθmax = 28.3º
[var phi] and ω scansθmin = 2.0º
Absorption correction: multi-scan(SADABS; Sheldrick, 2002)h = −11→11
Tmin = 0.754, Tmax = 0.796k = −24→24
23111 measured reflectionsl = −27→27

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.090  w = 1/[σ2(Fo2) + (0.0521P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.001
4057 reflectionsΔρmax = 0.47 e Å3
208 parametersΔρmin = −0.60 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
Mn10.67540 (3)0.073021 (14)0.408219 (13)0.02994 (10)
P10.84779 (5)0.19961 (2)0.50438 (2)0.03026 (12)
N10.70029 (19)0.11228 (9)0.30583 (8)0.0409 (4)
N20.5539 (2)−0.01013 (9)0.34242 (7)0.0427 (4)
O10.71646 (15)0.22186 (7)0.55235 (6)0.0417 (3)
H1B0.63530.22400.53270.062*
O20.78629 (14)0.16537 (7)0.44369 (6)0.0364 (3)
O30.94774 (14)0.26603 (7)0.49251 (7)0.0441 (3)
O41.29300 (14)0.01457 (7)0.51674 (6)0.0378 (3)
O51.11488 (16)0.00513 (7)0.59060 (6)0.0419 (3)
O60.45857 (14)0.10698 (7)0.44337 (6)0.0415 (3)
H6A0.44910.15140.46580.050*
H6B0.37310.07750.43630.050*
C10.7756 (3)0.17412 (12)0.29085 (11)0.0538 (6)
H1A0.81820.20230.32390.065*
C20.7923 (3)0.19769 (14)0.22728 (12)0.0667 (7)
H2A0.84570.24080.21770.080*
C30.7284 (3)0.15608 (16)0.17906 (12)0.0703 (8)
H3A0.73760.17090.13620.084*
C40.6509 (3)0.09242 (14)0.19413 (11)0.0600 (7)
H4A0.60780.06360.16160.072*
C50.6375 (2)0.07146 (11)0.25805 (9)0.0402 (5)
C60.5559 (2)0.00356 (11)0.27852 (9)0.0412 (5)
C70.4850 (3)−0.04431 (14)0.23502 (10)0.0582 (6)
H7A0.4878−0.03450.19090.070*
C80.4116 (3)−0.10562 (16)0.25773 (12)0.0758 (8)
H8A0.3634−0.13770.22910.091*
C90.4089 (3)−0.12002 (14)0.32312 (12)0.0773 (9)
H9A0.3599−0.16160.33960.093*
C100.4818 (3)−0.07028 (12)0.36322 (11)0.0632 (7)
H10A0.4803−0.07940.40750.076*
C111.0934 (2)0.10444 (10)0.51376 (9)0.0380 (4)
H11A1.06510.09300.46950.046*
H11B1.16710.14450.51230.046*
C121.1699 (2)0.03742 (10)0.54257 (9)0.0314 (4)
C130.9522 (2)0.13154 (10)0.54921 (9)0.0393 (4)
H13A0.98280.15260.59040.047*
H13B0.88600.08970.55800.047*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Mn10.03305 (17)0.02699 (15)0.02977 (16)0.00015 (11)−0.00014 (11)0.00075 (11)
P10.0241 (2)0.0261 (2)0.0406 (3)0.00079 (18)−0.0006 (2)−0.00313 (19)
N10.0446 (10)0.0396 (9)0.0386 (9)0.0034 (7)0.0020 (8)0.0085 (7)
N20.0506 (11)0.0449 (10)0.0325 (9)−0.0091 (8)−0.0030 (8)0.0000 (7)
O10.0308 (7)0.0512 (8)0.0430 (8)0.0083 (6)0.0008 (6)−0.0065 (6)
O20.0366 (7)0.0329 (7)0.0396 (7)−0.0046 (5)−0.0019 (6)−0.0030 (6)
O30.0311 (7)0.0292 (7)0.0719 (10)−0.0051 (5)−0.0002 (7)−0.0057 (6)
O40.0338 (7)0.0338 (7)0.0457 (8)0.0075 (6)0.0078 (6)0.0066 (6)
O50.0443 (8)0.0411 (8)0.0403 (8)0.0082 (6)0.0105 (7)0.0098 (6)
O60.0337 (7)0.0318 (7)0.0591 (8)−0.0018 (6)0.0060 (6)−0.0074 (6)
C10.0614 (15)0.0473 (13)0.0527 (13)−0.0027 (11)0.0044 (12)0.0119 (11)
C20.0764 (19)0.0570 (15)0.0667 (17)0.0022 (13)0.0152 (14)0.0280 (13)
C30.092 (2)0.0752 (18)0.0435 (13)0.0132 (15)0.0154 (14)0.0201 (13)
C40.0825 (19)0.0638 (15)0.0337 (11)0.0127 (13)0.0043 (11)0.0085 (11)
C50.0437 (11)0.0464 (11)0.0305 (10)0.0134 (9)0.0009 (8)0.0031 (9)
C60.0420 (12)0.0462 (11)0.0354 (10)0.0080 (9)−0.0041 (9)−0.0008 (9)
C70.0699 (16)0.0699 (15)0.0348 (12)−0.0029 (13)−0.0109 (11)−0.0052 (11)
C80.092 (2)0.0759 (18)0.0590 (16)−0.0260 (17)−0.0192 (16)−0.0155 (14)
C90.102 (2)0.0702 (17)0.0596 (16)−0.0440 (17)−0.0095 (16)−0.0037 (13)
C100.0830 (18)0.0629 (15)0.0437 (12)−0.0296 (14)−0.0059 (12)0.0006 (11)
C110.0330 (10)0.0335 (10)0.0475 (11)0.0045 (8)0.0011 (9)0.0085 (8)
C120.0310 (10)0.0264 (9)0.0367 (10)−0.0005 (7)−0.0034 (8)−0.0027 (8)
C130.0378 (11)0.0378 (10)0.0422 (11)0.0106 (8)0.0002 (9)0.0008 (8)

Geometric parameters (Å, °)

Mn1—O22.0646 (12)C1—H1A0.9300
Mn1—O62.1233 (13)C2—C31.368 (4)
Mn1—O4i2.2334 (13)C2—H2A0.9300
Mn1—N12.2437 (16)C3—C41.371 (4)
Mn1—N22.2890 (16)C3—H3A0.9300
Mn1—O5i2.3161 (14)C4—C51.380 (3)
Mn1—C12i2.6170 (18)C4—H4A0.9300
P1—O21.4993 (13)C5—C61.481 (3)
P1—O31.5050 (13)C6—C71.394 (3)
P1—O11.5710 (13)C7—C81.364 (3)
P1—C131.7909 (18)C7—H7A0.9300
N1—C11.334 (2)C8—C91.377 (3)
N1—C51.350 (3)C8—H8A0.9300
N2—C101.328 (2)C9—C101.379 (3)
N2—C61.345 (2)C9—H9A0.9300
O1—H1B0.8200C10—H10A0.9300
O4—C121.272 (2)C11—C121.506 (2)
O4—Mn1i2.2334 (13)C11—C131.518 (2)
O5—C121.248 (2)C11—H11A0.9700
O5—Mn1i2.3161 (14)C11—H11B0.9700
O6—H6A0.9300C12—Mn1i2.6170 (18)
O6—H6B0.9300C13—H13A0.9700
C1—C21.390 (3)C13—H13B0.9700
O2—Mn1—O693.75 (5)C3—C2—H2A120.7
O2—Mn1—O4i105.49 (5)C1—C2—H2A120.7
O6—Mn1—O4i94.44 (5)C2—C3—C4119.8 (2)
O2—Mn1—N191.97 (6)C2—C3—H3A120.1
O6—Mn1—N1108.58 (6)C4—C3—H3A120.1
O4i—Mn1—N1150.19 (5)C3—C4—C5119.3 (2)
O2—Mn1—N2163.71 (5)C3—C4—H4A120.3
O6—Mn1—N288.71 (6)C5—C4—H4A120.3
O4i—Mn1—N290.35 (6)N1—C5—C4121.1 (2)
N1—Mn1—N272.02 (6)N1—C5—C6116.05 (16)
O2—Mn1—O5i96.64 (5)C4—C5—C6122.8 (2)
O6—Mn1—O5i151.79 (5)N2—C6—C7120.96 (19)
O4i—Mn1—O5i57.51 (4)N2—C6—C5116.09 (17)
N1—Mn1—O5i97.21 (5)C7—C6—C5122.95 (18)
N2—Mn1—O5i88.57 (6)C8—C7—C6119.4 (2)
O2—Mn1—C12i103.54 (5)C8—C7—H7A120.3
O6—Mn1—C12i123.35 (6)C6—C7—H7A120.3
O4i—Mn1—C12i29.05 (5)C7—C8—C9120.0 (2)
N1—Mn1—C12i123.89 (6)C7—C8—H8A120.0
N2—Mn1—C12i88.38 (6)C9—C8—H8A120.0
O5i—Mn1—C12i28.49 (5)C8—C9—C10117.4 (2)
O2—P1—O3113.64 (8)C8—C9—H9A121.3
O2—P1—O1111.80 (8)C10—C9—H9A121.3
O3—P1—O1108.95 (8)N2—C10—C9123.9 (2)
O2—P1—C13109.49 (8)N2—C10—H10A118.0
O3—P1—C13109.55 (9)C9—C10—H10A118.0
O1—P1—C13102.85 (8)C12—C11—C13115.46 (16)
C1—N1—C5119.24 (18)C12—C11—H11A108.4
C1—N1—Mn1122.14 (15)C13—C11—H11A108.4
C5—N1—Mn1118.61 (13)C12—C11—H11B108.4
C10—N2—C6118.37 (18)C13—C11—H11B108.4
C10—N2—Mn1124.41 (14)H11A—C11—H11B107.5
C6—N2—Mn1117.22 (13)O5—C12—O4120.64 (17)
P1—O1—H1B109.5O5—C12—C11121.25 (16)
P1—O2—Mn1143.09 (8)O4—C12—C11118.11 (16)
C12—O4—Mn1i92.45 (11)O5—C12—Mn1i62.24 (10)
C12—O5—Mn1i89.27 (11)O4—C12—Mn1i58.50 (9)
Mn1—O6—H6A120.0C11—C12—Mn1i175.17 (13)
Mn1—O6—H6B120.0C11—C13—P1112.77 (13)
H6A—O6—H6B120.0C11—C13—H13A109.0
N1—C1—C2121.9 (2)P1—C13—H13A109.0
N1—C1—H1A119.1C11—C13—H13B109.0
C2—C1—H1A119.1P1—C13—H13B109.0
C3—C2—C1118.6 (2)H13A—C13—H13B107.8

Symmetry codes: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O6—H6B···O4ii0.932.132.6813 (18)117
O1—H1B···O3iii0.821.732.5385 (19)167

Symmetry codes: (ii) x−1, y, z; (iii) x−1/2, −y+1/2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: OM2188).

References

  • Bruker (2004). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cheetham, A. K., Férey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed.38, 3268–3292. [PubMed]
  • Clearfield, A. (1998). Progress in Inorganic Chemistry, Vol. 47, edited by K. D. Karlin, pp. 371–510. New York: John Wiley & Sons Inc.
  • Serpaggi, F. & Férey, G. (1999). Inorg. Chem.38, 4741–4744. [PubMed]
  • Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Sheldrick, G. M. (1997b). SHELXTL Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2002). SADABS Version 2.03. University of Göttingen, Germany.
  • Stock, N., Frey, S. A., Stucky, G. D. & Cheetham, A. K. (2000). J. Chem. Soc. Dalton Trans. pp. 4292–4296.
  • Ying, S.-M., Li, X.-F., Chen, W.-T., Liu, D.-S. & Liu, J.-H. (2007). Acta Cryst. E63, m555–m557.
  • Ying, S.-M. & Mao, J.-G. (2004). Eur. J. Inorg. Chem. pp. 1270–1276.
  • Ying, S.-M., Zeng, X.-R., Fang, X.-N., Li, X.-F. & Liu, D.-S. (2006). Inorg. Chim. Acta, 359, 1589–1593.

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