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Acta Cryst. (2008). E64, m166    [ doi:10.1107/S1600536807065142 ]

Bis([mu]-carboxylatoethylphosphonato)bis[aqua(2,2'-bipyridine)manganese(II)]

S.-M. Ying, Y. Chen, Q.-Y. Luo, Y.-P. Xv and D.-S. Liu

Abstract top

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 [pi]-[pi] stacking interactions [centroid-centroid distance 4.2754 (4) Å].

Comment top

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).

Related literature top

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

complex, see: Ying et al. (2006).

Experimental top

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 top

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).

Computing details top

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

Figures top
[Figure 1] 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.
[Figure 2] Fig. 2. Packing diagram of the title compound viewed along the a axis. Hydrogen atoms are omitted for clarity.
Bis(µ-carboxylatoethylphosphonato)bis[aqua(2,2'-bipyridine)manganese(II)] top
Crystal data top
[Mn2(C5H5O5P1)2(C8H8N2)2(H2O)2]F000 = 1560
Mr = 762.36Dx = 1.548 Mg m−3
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 mm−1
c = 20.682 (3) ÅT = 293 (2) K
V = 3270.3 (8) Å3Block, colourless
Z = 40.32 × 0.30 × 0.26 mm
Data collection top
Bruker APEX area-detector
diffractometer		4057 independent reflections
Radiation source: fine-focus sealed tube2893 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.038
T = 293(2) Kθmax = 28.3º
φ 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 top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-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 Å−3
208 parametersΔρmin = −0.60 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Mn2(C5H5O5P1)2(C8H8N2)2(H2O)2]V = 3270.3 (8) Å3
Mr = 762.36Z = 4
Orthorhombic, PbcaMo Kα
a = 8.7553 (13) ŵ = 0.94 mm−1
b = 18.060 (3) ÅT = 293 (2) K
c = 20.682 (3) Å0.32 × 0.30 × 0.26 mm
Data collection top
Bruker APEX area-detector
diffractometer		4057 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)		2893 reflections with I > 2σ(I)
Tmin = 0.754, Tmax = 0.796Rint = 0.038
23111 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.030208 parameters
wR(F2) = 0.090H-atom parameters constrained
S = 0.99Δρmax = 0.47 e Å−3
4057 reflectionsΔρmin = −0.60 e Å−3
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
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O6—H6B···O4i0.932.132.6813 (18)117
O1—H1B···O3ii0.821.732.5385 (19)167
Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+1/2, −z+1.
Acknowledgements top

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

references
References top

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