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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): m1526.
Published online 2010 November 6. doi:  10.1107/S160053681004506X
PMCID: PMC3011441

Tetra­aqua­bis­[4-(pyrazin-2-ylsulfanylmeth­yl)benzoato]manganese(II) dihydrate

Abstract

The title compound, [Mn(C12H9N2O2S)2(H2O)4]·2H2O, has been synthesized with a flexible asymmetrical bridging ligand, 4-(pyrazin-2-ylsulfanylmeth­yl)benzoic acid (Hpztmb). The MnII ion exhibits a centrosymmetric octa­hedral geometry involving two carboxyl­ate O atoms of two different pztmb ligands and four O atoms of four coordinated water mol­ecules. The packing shows a three-dimensional supra­molecular network via O—H(...)O and O—H(...)N hydrogen bonds and π–π stacking inter­actions [centroid–centroid distances = 3.884 (8) and 4.034 (8) Å] between the benzene ring of one pztmb anion and the pyrazine ring of an adjacent anion.

Related literature

For background to the network topologies and applications of coordination polymers, see: Han et al. (2003 [triangle], 2005 [triangle], 2006 [triangle]); Zhao et al. (2002 [triangle]); Akutagawa & Nakamura (2000 [triangle]). For related syntheses and structures of a similar ligand (Hpmtmb), see: Han et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1526-scheme1.jpg

Experimental

Crystal data

  • [Mn(C12H9N2O2S)2(H2O)4]·2H2O
  • M r = 653.41
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1526-efi1.jpg
  • a = 16.587 (3) Å
  • b = 7.8928 (16) Å
  • c = 10.986 (2) Å
  • β = 94.38 (3)°
  • V = 1434.1 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.67 mm−1
  • T = 296 K
  • 0.20 × 0.15 × 0.14 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.865, T max = 0.925
  • 17310 measured reflections
  • 3425 independent reflections
  • 3114 reflections with I > 2Σ(I)
  • R int = 0.044

Refinement

  • R[F 2 > 2σ(F 2)] = 0.064
  • wR(F 2) = 0.229
  • S = 1.09
  • 3425 reflections
  • 188 parameters
  • H-atom parameters constrained
  • Δρmax = 0.40 e Å−3
  • Δρmin = −0.48 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2010) [triangle]; software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681004506X/pk2282sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681004506X/pk2282Isup2.hkl

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

Acknowledgments

This work was supported financially by College of Chemistry and Chemical Engineering, Pingdingshan University, China.

supplementary crystallographic information

Comment

It is common knowledge that the coordination geometry of the metal ion and the shape and bonding mode of the ligand are generally the primary considerations in metal-mediated self-assembly reactions. Relatively small changes in the bridging ligand can give rise to large variation in the overall structure of the assembly. Recently, some coordination polymers containing long and flexible monoanionic ligands with hybrid pyridyl or pyrimidyl and benzoic carboxylate moieties have been reported (Han et al. 2005; Han et al. 2006). To better understand the influence of N-heterocyclic ring on the resultant structure, we have been working on the architectures of polymeric structures containing a novel long and flexible ligand 4-(2-pyrazinylthiomethyl)benzoic acid (Hpztmb). As part of our ongoing investigation, a new complex, [Mn(pztmb)2(H2O)4].2H2O, was prepared and its structure has been determined.

The title compound comprises one MnII ion, two pztmb anions, four coordinated water molecules and two solvent water molecules (Fig.1). The MnII ion has a centrosymmetric octahedral geometry coordinated by four O atoms from four coordinated water molecules and two carboxylate O1 atoms from two different pztmb anion ligands. In the crystal structure, in addition to hydrogen-bonds between the carboxylate O2 atoms and the solvent water molecules, hydrogen-bonds exist between coordinated and solvent water molecules and between coordinated water molecules and carboxylate O2 atoms (Table 1). Moreover, the solvent water molecules and the non-coordinated N1 atoms of pyrazine rings form O—H···N hydrogen-bonds (H3WB···N1vi 1.91 Å). In addition, Two neighbouring pztmb anion ligands are parallel and arranged to enable π···π interaction (centroid-centroid distance of 4.034 (8) or 3.884 (8) Å) between the benzene ring of one pztmb anion and the pyrazine ring of an adjacent anion. Consequently, a variety of hydrogen-bonds and weak π···π interactions lead to a three-dimensional supramolecular network (Fig. 2).

Experimental

A mixture of Mn(NO3)2.6H2O (28.5 mg, 0.1 mmol) with Hpztmb (50 mg, 0.2 mmol) in 10 ml of H2O was sealed in a stainless-steel reactor with a Teflon liner and heated at 110 K for 72 h. A quantity of colorless single crystals were obtained after the solution was cooled to room temperature at a rate of 10 K/h.

Refinement

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å, Uiso(H) = 1.2Ueq(C) for aromatic H, and C—H = 0.97 Å, Uiso(H) = 1.2Ueq(C) for CH2. Water H atoms were found in difference Fourier maps and initially included with a tight O—H restraint [0.85 Å]. In the final refinement, the positions of the water H atoms were fixed, with Uiso(H) = 1.2Ueq(O).

Figures

Fig. 1.
The molecular structure of the title compound, showing the atom-labelling scheme, with displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (i) - x, 1 - y, 2 - z.
Fig. 2.
Three-dimensional supramolecular structure of the title compound. Hydrogen atoms have been omitted for clarity. Dashed lines indicate hydrogen-bonds and π···π interactions

Crystal data

[Mn(C12H9N2O2S)2(H2O)4]·2H2OF(000) = 677.8
Mr = 653.41Dx = 1.513 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 786 reflections
a = 16.587 (3) Åθ = 1.9–27.9°
b = 7.8928 (16) ŵ = 0.67 mm1
c = 10.986 (2) ÅT = 296 K
β = 94.38 (3)°Prism, colourless
V = 1434.1 (5) Å30.2 × 0.15 × 0.14 mm
Z = 2

Data collection

Bruker SMART APEXII CCD area-detector diffractometer3425 independent reflections
Radiation source: fine-focus sealed tube3114 reflections with I > 2Σ(I)
graphiteRint = 0.044
ω scansθmax = 27.9°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −21→21
Tmin = 0.865, Tmax = 0.925k = −10→10
17310 measured reflectionsl = −14→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.064Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.229H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.1555P)2] where P = (Fo2 + 2Fc2)/3
3425 reflections(Δ/σ)max = 0.004
188 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = −0.47 e Å3

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*/UeqOcc. (<1)
Mn10.00000.50001.00000.0317 (3)
O10.12369 (15)0.5282 (3)0.9481 (2)0.0418 (6)
O20.09688 (13)0.6123 (3)0.7547 (2)0.0437 (6)
O1W−0.01101 (15)0.7678 (3)0.9589 (3)0.0536 (7)
H1WA0.00920.84550.98920.064*
H1WB−0.05700.83950.97050.064*
O2W0.04302 (15)0.5499 (4)1.1920 (2)0.0467 (6)
H2WA0.05030.64931.22060.056*
H2WB0.00760.49521.22780.056*
O3W0.88036 (15)0.0223 (3)0.9768 (2)0.0457 (6)
H3WA0.87720.06070.90100.055*
H3WB0.8305−0.00811.00130.055*
N20.65704 (18)0.7072 (4)0.7820 (3)0.0464 (7)
N10.74665 (19)0.5955 (5)0.5930 (3)0.0536 (8)
C10.14473 (17)0.5842 (4)0.8483 (3)0.0336 (6)
C20.23309 (18)0.6181 (4)0.8372 (3)0.0332 (7)
C30.25917 (19)0.7072 (4)0.7380 (3)0.0394 (7)
H30.22170.75110.67890.047*
C40.3410 (2)0.7298 (5)0.7279 (3)0.0442 (8)
H40.35800.79010.66180.053*
C50.39827 (19)0.6651 (4)0.8138 (3)0.0370 (7)
C60.3719 (2)0.5780 (5)0.9120 (3)0.0405 (7)
H60.40950.53390.97070.049*
C70.2902 (2)0.5554 (5)0.9244 (3)0.0391 (7)
H70.27340.49770.99180.047*
C80.4882 (2)0.6883 (5)0.8047 (3)0.0468 (8)
H8A0.51740.60710.85750.056*
H8B0.50370.80110.83270.056*
C90.6222 (2)0.6573 (4)0.6757 (3)0.0402 (7)
C100.6666 (2)0.6013 (5)0.5810 (3)0.0480 (9)
H100.63960.56720.50790.058*
C110.7822 (2)0.6467 (5)0.6995 (4)0.0517 (9)
H110.83830.64430.71140.062*
C120.7382 (2)0.7028 (5)0.7917 (4)0.0505 (9)
H120.76550.73930.86410.061*
S10.51581 (5)0.66040 (14)0.65082 (8)0.0518 (4)0.997 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Mn10.0279 (4)0.0358 (4)0.0321 (4)−0.0018 (2)0.0060 (3)−0.0009 (2)
O10.0301 (12)0.0581 (15)0.0384 (13)−0.0014 (10)0.0103 (10)0.0082 (10)
O20.0294 (12)0.0636 (16)0.0384 (13)0.0005 (10)0.0038 (9)0.0079 (10)
O1W0.0436 (15)0.0378 (13)0.0800 (19)0.0037 (10)0.0090 (13)0.0015 (13)
O2W0.0422 (14)0.0602 (15)0.0383 (13)−0.0095 (12)0.0065 (10)−0.0062 (11)
O3W0.0342 (13)0.0539 (15)0.0504 (16)−0.0006 (10)0.0127 (11)0.0088 (10)
N20.0366 (16)0.0584 (19)0.0453 (16)−0.0020 (13)0.0107 (12)0.0020 (13)
N10.0378 (17)0.070 (2)0.055 (2)0.0088 (15)0.0144 (14)0.0003 (16)
C10.0256 (14)0.0343 (16)0.0417 (17)0.0015 (11)0.0075 (12)0.0022 (12)
C20.0283 (15)0.0394 (16)0.0325 (15)0.0005 (12)0.0061 (11)−0.0008 (12)
C30.0289 (15)0.0491 (19)0.0405 (18)−0.0021 (13)0.0052 (12)0.0116 (14)
C40.0317 (17)0.058 (2)0.0437 (19)−0.0041 (14)0.0091 (13)0.0167 (15)
C50.0275 (15)0.0464 (17)0.0377 (16)−0.0029 (12)0.0056 (12)−0.0005 (13)
C60.0357 (17)0.051 (2)0.0347 (16)0.0029 (14)0.0036 (13)0.0043 (13)
C70.0365 (17)0.0490 (18)0.0326 (16)−0.0031 (14)0.0089 (13)0.0042 (13)
C80.0324 (17)0.069 (2)0.0404 (19)−0.0048 (15)0.0079 (14)−0.0002 (16)
C90.0343 (17)0.0464 (18)0.0411 (18)0.0000 (13)0.0101 (13)0.0034 (13)
C100.0401 (19)0.064 (2)0.0406 (19)0.0021 (16)0.0089 (15)−0.0023 (16)
C110.0275 (17)0.071 (3)0.057 (2)0.0069 (15)0.0097 (15)0.0095 (18)
C120.0387 (19)0.066 (2)0.047 (2)−0.0053 (16)0.0020 (15)0.0031 (17)
S10.0299 (5)0.0853 (8)0.0409 (6)0.0005 (4)0.0080 (4)−0.0027 (4)

Geometric parameters (Å, °)

Mn1—O1W2.166 (3)C2—C31.394 (4)
Mn1—O1Wi2.166 (3)C3—C41.382 (4)
Mn1—O12.182 (2)C3—H30.9300
Mn1—O1i2.182 (2)C4—C51.385 (5)
Mn1—O2Wi2.210 (2)C4—H40.9300
Mn1—O2W2.210 (2)C5—C61.378 (4)
O1—C11.257 (4)C5—C81.513 (4)
O2—C11.269 (4)C6—C71.384 (5)
O1W—H1WA0.7630C6—H60.9300
O1W—H1WB0.9660C7—H70.9300
O2W—H2WA0.8502C8—S11.798 (4)
O2W—H2WB0.8498C8—H8A0.9700
O3W—H3WA0.8845C8—H8B0.9700
O3W—H3WB0.9213C9—C101.391 (5)
N2—C91.323 (5)C9—S11.766 (3)
N2—C121.343 (4)C10—H100.9300
N1—C101.324 (4)C11—C121.367 (5)
N1—C111.333 (5)C11—H110.9300
C1—C21.504 (4)C12—H120.9300
C2—C71.385 (4)
O1W—Mn1—O1Wi180.0C2—C3—H3120.2
O1W—Mn1—O184.97 (9)C3—C4—C5121.6 (3)
O1Wi—Mn1—O195.03 (9)C3—C4—H4119.2
O1W—Mn1—O1i95.03 (9)C5—C4—H4119.2
O1Wi—Mn1—O1i84.97 (9)C6—C5—C4118.4 (3)
O1—Mn1—O1i180.00 (4)C6—C5—C8119.1 (3)
O1W—Mn1—O2Wi87.65 (11)C4—C5—C8122.5 (3)
O1Wi—Mn1—O2Wi92.35 (11)C5—C6—C7120.9 (3)
O1—Mn1—O2Wi90.59 (9)C5—C6—H6119.5
O1i—Mn1—O2Wi89.41 (9)C7—C6—H6119.5
O1W—Mn1—O2W92.35 (11)C6—C7—C2120.6 (3)
O1Wi—Mn1—O2W87.65 (11)C6—C7—H7119.7
O1—Mn1—O2W89.41 (9)C2—C7—H7119.7
O1i—Mn1—O2W90.59 (9)C5—C8—S1111.8 (2)
O2Wi—Mn1—O2W180.000 (1)C5—C8—H8A109.3
C1—O1—Mn1126.4 (2)S1—C8—H8A109.3
Mn1—O1W—H1WA131.8C5—C8—H8B109.3
Mn1—O1W—H1WB126.8S1—C8—H8B109.3
H1WA—O1W—H1WB78.3H8A—C8—H8B107.9
Mn1—O2W—H2WA122.9N2—C9—C10122.3 (3)
Mn1—O2W—H2WB99.6N2—C9—S1119.7 (3)
H2WA—O2W—H2WB112.5C10—C9—S1118.0 (3)
H3WA—O3W—H3WB112.0N1—C10—C9121.4 (3)
C9—N2—C12115.5 (3)N1—C10—H10119.3
C10—N1—C11116.7 (3)C9—C10—H10119.3
O1—C1—O2124.8 (3)N1—C11—C12121.6 (3)
O1—C1—C2118.1 (3)N1—C11—H11119.2
O2—C1—C2117.2 (3)C12—C11—H11119.2
C7—C2—C3119.0 (3)N2—C12—C11122.6 (4)
C7—C2—C1120.0 (3)N2—C12—H12118.7
C3—C2—C1121.0 (3)C11—C12—H12118.7
C4—C3—C2119.6 (3)C9—S1—C8100.38 (16)
C4—C3—H3120.2
O1W—Mn1—O1—C1−56.0 (3)C5—C6—C7—C20.9 (5)
O1Wi—Mn1—O1—C1124.0 (3)C3—C2—C7—C6−1.2 (5)
O2Wi—Mn1—O1—C131.6 (3)C1—C2—C7—C6176.6 (3)
O2W—Mn1—O1—C1−148.4 (3)C6—C5—C8—S1139.1 (3)
Mn1—O1—C1—O2−10.1 (5)C4—C5—C8—S1−41.8 (4)
Mn1—O1—C1—C2171.00 (19)C12—N2—C9—C101.1 (5)
O1—C1—C2—C713.5 (4)C12—N2—C9—S1−179.0 (3)
O2—C1—C2—C7−165.5 (3)C11—N1—C10—C9−0.4 (6)
O1—C1—C2—C3−168.7 (3)N2—C9—C10—N1−0.1 (6)
O2—C1—C2—C312.3 (5)S1—C9—C10—N1180.0 (3)
C7—C2—C3—C40.6 (5)C10—N1—C11—C12−0.1 (6)
C1—C2—C3—C4−177.2 (3)C9—N2—C12—C11−1.6 (6)
C2—C3—C4—C50.4 (6)N1—C11—C12—N21.2 (7)
C3—C4—C5—C6−0.8 (6)N2—C9—S1—C8−13.5 (3)
C3—C4—C5—C8−180.0 (3)C10—C9—S1—C8166.4 (3)
C4—C5—C6—C70.2 (5)C5—C8—S1—C9−170.0 (3)
C8—C5—C6—C7179.4 (3)

Symmetry codes: (i) −x, −y+1, −z+2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O3Wii0.762.122.776 (4)145
O1W—H1WB···O3Wiii0.971.782.716 (3)162
O2W—H2WA···O2iv0.852.062.878 (4)162
O2W—H2WB···O2i0.851.952.752 (3)157
O3W—H3WA···O2v0.881.842.696 (4)162
O3W—H3WB···N1vi0.921.912.801 (4)163

Symmetry codes: (ii) −x+1, −y+1, −z+2; (iii) x−1, y+1, z; (iv) x, −y+3/2, z+1/2; (i) −x, −y+1, −z+2; (v) −x+1, y−1/2, −z+3/2; (vi) x, −y+1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2282).

References

  • Akutagawa, T. & Nakamura, T. (2000). Coord. Chem. Rev.198, 297–311.
  • Brandenburg, K. (2010). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Han, L., Hong, M.-C., Wang, R.-H., Luo, J.-H., Lin, Z.-Z. & Yuan, D.-Q. (2003). Chem. Commun. pp. 2580–2581. [PubMed]
  • Han, L., Wang, R.-H., Yuan, D.-Q., Wu, B.-L., Luo, B.-Y. & Hong, M.-C. (2005). J. Mol. Struct.737, 55–59.
  • Han, L., Yuan, D.-Q., Wu, B.-L., Liu, C.-P. & Hong, M.-C. (2006). Inorg. Chim. Acta, 359, 2232–2240.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhao, Y.-J., Hong, M.-C., Sun, D.-F. & Cao, R. (2002). J. Chem. Soc. Dalton Trans, pp. 1354–1357.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography