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Acta Cryst. (2007). E63, m1772    [ doi:10.1107/S1600536807025305 ]

catena-Poly[[[aquabis(4-chlorobenzoato-[kappa]2O,O')manganese(II)]-[mu]-4,4'-bipyridine-[kappa]2N:N']4,4'-bipyridine solvate]

D.-Y. Ma and G.-H. Deng

Abstract top

The title compound, {[Mn(C7H4ClO2)2(C10H8N2)(H2O)]·C10H8N2}n, is a manganese polymer constructed from 4-chlorobenzoate and 4,4'-bipyridine ligands. The Mn centre and coordinated water molecule lie on a twofold rotation axis. The MnII centre is in a distorted pentagonal-bipyramidal geometry, coordinated by four carboxylate O atoms from two symmetry-related 4-chlorobenzoate ligands, two N atoms from two symmetry-related 4,4'-bipyridine ligands (axial positions) and one water molecule. A polymeric structure results from the bridging character of the 4,4'-bipyridine ligands. A three-dimensional network is formed by these chains via O-H...O hydrogen bonds and [pi]-[pi] stacking interactions. The face-to-face and centroid-centroid distances between parallel 4-chlorobenzoic acids of neighboring complexes (-x, -y, -z) are 3.583 (3) and 3.703 (2) Å, respectively. The non-coordinated 4,4'-bipyridine molecule fills voids in the metal-organic framework, stabilizing the crystal structure.

Comment top

Increased attention is being focused on the design and synthesis of coordination networks or metal-organic frameworks (MOFs), owing to their attracting topologies and potential application in molecular recognition, gas storage, catalysis and luminescence (Yaghi et al., 1998; Abrahams et al., 1999; Desiraju, 2001). Some functional ligands, such as carboxylates, bipyridine or its derivatives, and mixtures of both carboxylate and bipyridine ligands have been successfully employed to construct MOFs (Dybtsev et al., 2004; Tao et al., 2000). To the best of our knowledge, hydrogen-bonding interactions between ligands are specific and directional, and have little dependence on the properties of metal ions, playing then a critical role in the structures and functions of the products. In this sense, 4-chlorobenzoic acid is an excellent candidate for the construction of supramolecular complexes, since it not only has multiple coordination modes but also can form regular hydrogen bonds, being both donor and acceptor (Gu et al., 2004). In the paper, we report a novel Mn polymer, (I), which is a three-dimensional architecture with MOF.

As depicted in Fig. 1, The Mn1 and O1w water molecules lie on special positions (3/4, y, 3/4) in space group P2/n, corresponding to a twofold symmetry axis. The MnII centre presents a pentagonal-bipyramidal geometry, which is defined by four carboxylate O atoms from two 4-chlorobenzoate ligands, two N atoms from two 4,4'-bipyridine ligands and one water molecule (Table 1). The same situation was observed in the compound [Cd(py)2(C7H4O2Cl)2(H2O)] (C7H4O2Cl = 4-chlorobenzoate, py = pyridine) (Rodesiler et al. 1985). The carboxylate groups of two opposite 4-chlorobenzoate ligands have a bidentate coordination mode to coordinate to the Mn atom, and the 4,4'-bipyiridine has a dihedral angle of 53.55 (3)° between two pyridine rings, and bridges Mn atoms along the [100] direction. The Mn···Mn separation along the chain is 11.690 (2) Å. The coordinated water molecules play an important role in the crystal packing: these one-dimensional chains are connected through O—H···O hydrogen bonds involving the water molecules as donors and the carboxylate O atoms as acceptors, forming a corrugated layer parallel to [100]. The shortest Mn···Mn separation is 6.151 (3) Å in the layer. Moreover these layers are assembled into a three-dimensional network via π–π stacking interactions which have dimensions of 12.252 × 8.367 Å2 and accommodate 4,4'-bipyridine molecules (Fig. 2). The face-to-face and centroid-centroid distances between parallel 4-chlorobenzoate ligands of neighboring complexes are 3.583 (3) and 3.703 (2) Å, respectively. The free 4,4'-bipyridine molecule is stabilized through C—H···π interactions [C17—H17···Cg1i = 2.84 (2) Å; C14—H14···Cg2ii = 2.97 (2) Å. Symmetry codes: (i) x, y, z; (ii): 1 - x,1 - y, -z; Cg1 is the centroid of ring N1/C8···C12; Cg2 is the centroid of ring C2···C7].

Related literature top

For related literature, see: Abrahams et al. (1999); Desiraju (2001); Dybtsev et al. (2004); Gu et al. (2004); Rodesiler et al. (1985); Tao et al. (2000); Yaghi et al. (1998).

Experimental top

The title complex was prepared by addition of a stoichiometric amount of manganese acetate (20 mmol) and 4,4'-bipyridine (20 mmol) to a hot aqueous solution of 4-chlorobenzoic acid (20 mmol). The pH was then adjusted to 7.0–8.0 with NaOH (30 mmol). The resulting solution was filtered, and yellow single crystals were obtained at room temperature by slow evaporation of the solvent over several days.

Refinement top

Water H atom H1W was located in a difference map, while C-bonded H atoms were placed in calculated positions. All H atoms were refined using a riding model with constrained distances O—H = 0.82 Å, C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(carrier atom).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atomic numbering scheme. Non-H atoms are shown with 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. A packing view of (I) viewed along the b-axis.
catena-Poly[[[aquabis(4-chlorobenzoato-\ κ2O,O')manganese(II)]-µ-4,4'-bipyridine-\ κ2N:N'] 4,4'-bipyridine solvate] top
Crystal data top
[Mn(C7H4ClO2)2(C10H8N2)(H2O)]·C10H8N2F(000) = 714
Mr = 696.43Dx = 1.462 Mg m−3
Monoclinic, P2/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yacCell parameters from 2376 reflections
a = 11.6900 (3) Åθ = 2.2–28.0°
b = 6.1510 (2) ŵ = 0.64 mm−1
c = 22.5184 (6) ÅT = 293 K
β = 102.369 (2)°Block, yellow
V = 1581.61 (8) Å30.25 × 0.19 × 0.18 mm
Z = 2
Data collection top
Bruker APEXII
diffractometer		3115 independent reflections
Radiation source: fine-focus sealed tube2373 reflections with I > 2σ(I)
graphiteRint = 0.056
φ and ω scansθmax = 26.0°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −14→14
Tmin = 0.857, Tmax = 0.894k = −7→7
16828 measured reflectionsl = −27→27
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0451P)2 + 1.3366P]
where P = (Fo2 + 2Fc2)/3
3115 reflections(Δ/σ)max = 0.001
212 parametersΔρmax = 0.61 e Å−3
0 restraintsΔρmin = −0.56 e Å−3
Crystal data top
[Mn(C7H4ClO2)2(C10H8N2)(H2O)]·C10H8N2V = 1581.61 (8) Å3
Mr = 696.43Z = 2
Monoclinic, P2/nMo Kα radiation
a = 11.6900 (3) ŵ = 0.64 mm−1
b = 6.1510 (2) ÅT = 293 K
c = 22.5184 (6) Å0.25 × 0.19 × 0.18 mm
β = 102.369 (2)°
Data collection top
Bruker APEXII
diffractometer		2373 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		Rint = 0.056
Tmin = 0.857, Tmax = 0.894θmax = 26.0°
16828 measured reflectionsStandard reflections: 0
3115 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.047H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.118Δρmax = 0.61 e Å−3
S = 1.05Δρmin = −0.56 e Å−3
3115 reflectionsAbsolute structure: ?
212 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.7981 (2)0.7343 (5)0.86400 (12)0.0350 (6)
C20.8244 (2)0.8210 (5)0.92758 (12)0.0338 (6)
C30.7973 (3)1.0318 (5)0.93992 (14)0.0508 (8)
H30.76431.12410.90810.061*
C40.8186 (3)1.1078 (6)0.99910 (15)0.0587 (9)
H40.79791.24891.00730.070*
C50.8706 (3)0.9728 (6)1.04552 (14)0.0490 (8)
C60.8995 (3)0.7654 (6)1.03456 (14)0.0604 (9)
H60.93500.67561.06640.072*
C70.8755 (3)0.6890 (5)0.97564 (13)0.0484 (8)
H70.89420.54610.96810.058*
C80.5015 (2)0.7563 (5)0.76962 (13)0.0399 (7)
H80.54810.87370.78580.048*
C90.3844 (2)0.7609 (5)0.77142 (13)0.0401 (7)
H90.35340.88030.78780.048*
C100.3131 (2)0.5870 (5)0.74867 (12)0.0344 (6)
C110.3641 (2)0.4174 (5)0.72347 (14)0.0427 (7)
H110.31950.29780.70720.051*
C120.4821 (2)0.4272 (5)0.72261 (14)0.0419 (7)
H120.51460.31270.70490.050*
C130.4107 (5)0.1163 (10)0.9169 (3)0.142 (3)
H130.3605−0.00240.91380.171*
C140.4212 (5)0.2464 (10)0.9674 (3)0.131 (3)
H140.38020.21290.99730.157*
C150.4926 (3)0.4267 (6)0.97334 (16)0.0558 (9)
C160.5512 (3)0.4561 (6)0.92726 (16)0.0666 (10)
H160.60210.57320.92870.080*
C170.5357 (4)0.3148 (7)0.87917 (17)0.0723 (11)
H170.57750.34050.84910.087*
Cl10.90101 (10)1.0741 (2)1.11973 (4)0.0800 (3)
Mn10.75000.58733 (9)0.75000.02869 (17)
N10.55156 (17)0.5918 (4)0.74588 (10)0.0339 (5)
N20.4661 (3)0.1464 (6)0.87269 (16)0.0844 (11)
O10.77094 (16)0.8643 (3)0.81989 (8)0.0410 (5)
O20.80153 (18)0.5331 (3)0.85538 (9)0.0449 (5)
O1W0.75000.2327 (5)0.75000.0453 (8)
H1W0.739 (3)0.153 (5)0.7201 (14)0.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0252 (13)0.0471 (18)0.0325 (15)−0.0041 (12)0.0061 (10)0.0015 (13)
C20.0314 (14)0.0372 (15)0.0324 (15)−0.0050 (11)0.0062 (11)0.0013 (12)
C30.073 (2)0.0406 (19)0.0382 (17)0.0020 (16)0.0098 (15)0.0038 (14)
C40.086 (3)0.0425 (19)0.051 (2)−0.0058 (18)0.0204 (18)−0.0099 (16)
C50.0518 (19)0.061 (2)0.0335 (16)−0.0141 (16)0.0079 (13)−0.0091 (15)
C60.071 (2)0.072 (3)0.0329 (17)0.0150 (19)0.0013 (15)0.0040 (17)
C70.0569 (19)0.0455 (18)0.0403 (17)0.0102 (15)0.0047 (14)0.0033 (15)
C80.0296 (14)0.0384 (16)0.0508 (17)−0.0034 (12)0.0066 (12)−0.0081 (14)
C90.0288 (14)0.0401 (16)0.0510 (18)0.0019 (12)0.0079 (12)−0.0091 (14)
C100.0255 (13)0.0436 (16)0.0334 (14)0.0010 (12)0.0050 (10)0.0016 (13)
C110.0306 (14)0.0416 (16)0.0547 (18)−0.0064 (13)0.0062 (12)−0.0160 (15)
C120.0318 (14)0.0459 (17)0.0485 (17)−0.0020 (13)0.0099 (12)−0.0146 (15)
C130.133 (5)0.159 (6)0.162 (5)−0.102 (4)0.090 (4)−0.105 (5)
C140.128 (4)0.155 (5)0.141 (5)−0.097 (4)0.095 (4)−0.095 (4)
C150.0409 (17)0.065 (2)0.062 (2)−0.0090 (16)0.0118 (15)−0.0146 (18)
C160.082 (3)0.065 (2)0.054 (2)−0.023 (2)0.0162 (18)−0.0051 (19)
C170.090 (3)0.077 (3)0.052 (2)−0.011 (2)0.020 (2)−0.006 (2)
Cl10.0960 (8)0.1026 (8)0.0397 (5)−0.0174 (6)0.0111 (5)−0.0241 (5)
Mn10.0237 (3)0.0308 (3)0.0316 (3)0.0000.0060 (2)0.000
N10.0239 (11)0.0406 (13)0.0376 (12)−0.0009 (10)0.0072 (9)−0.0041 (11)
N20.081 (2)0.095 (3)0.079 (2)−0.022 (2)0.0222 (19)−0.036 (2)
O10.0445 (11)0.0465 (12)0.0293 (10)0.0002 (9)0.0021 (8)0.0052 (9)
O20.0595 (13)0.0372 (12)0.0389 (11)−0.0051 (9)0.0128 (9)−0.0038 (9)
O1W0.068 (2)0.0307 (16)0.0358 (17)0.0000.0072 (15)0.000
Geometric parameters (Å, °) top
C1—O21.254 (4)C11—H110.9300
C1—O11.262 (3)C12—N11.333 (3)
C1—C21.497 (4)C12—H120.9300
C2—C31.377 (4)C13—N21.311 (6)
C2—C71.382 (4)C13—C141.375 (6)
C3—C41.383 (4)C13—H130.9300
C3—H30.9300C14—C151.378 (5)
C4—C51.371 (5)C14—H140.9300
C4—H40.9300C15—C161.372 (5)
C5—C61.356 (5)C15—C15ii1.482 (7)
C5—Cl11.747 (3)C16—C171.370 (5)
C6—C71.378 (4)C16—H160.9300
C6—H60.9300C17—N21.306 (5)
C7—H70.9300C17—H170.9300
C8—N11.336 (3)Mn1—O1W2.181 (3)
C8—C91.378 (4)Mn1—O12.297 (2)
C8—H80.9300Mn1—O1iii2.297 (2)
C9—C101.385 (4)Mn1—N12.302 (2)
C9—H90.9300Mn1—N1iii2.302 (2)
C10—C111.382 (4)Mn1—O2iii2.344 (2)
C10—C10i1.490 (5)Mn1—O22.344 (2)
C11—C121.385 (4)O1W—H1W0.82 (3)
O2—C1—O1121.0 (3)C13—C14—H14120.2
O2—C1—C2119.5 (3)C15—C14—H14120.2
O1—C1—C2119.5 (3)C16—C15—C14115.0 (3)
C3—C2—C7118.3 (3)C16—C15—C15ii122.8 (4)
C3—C2—C1121.3 (3)C14—C15—C15ii122.1 (4)
C7—C2—C1120.3 (3)C17—C16—C15120.7 (4)
C2—C3—C4120.7 (3)C17—C16—H16119.6
C2—C3—H3119.6C15—C16—H16119.6
C4—C3—H3119.6N2—C17—C16124.4 (4)
C5—C4—C3119.3 (3)N2—C17—H17117.8
C5—C4—H4120.4C16—C17—H17117.8
C3—C4—H4120.4O1W—Mn1—O1137.89 (5)
C6—C5—C4121.2 (3)O1W—Mn1—O1iii137.89 (5)
C6—C5—Cl1120.2 (3)O1—Mn1—O1iii84.22 (10)
C4—C5—Cl1118.6 (3)O1W—Mn1—N190.69 (6)
C5—C6—C7119.3 (3)O1—Mn1—N188.70 (7)
C5—C6—H6120.4O1iii—Mn1—N190.28 (7)
C7—C6—H6120.4O1W—Mn1—N1iii90.69 (6)
C6—C7—C2121.2 (3)O1—Mn1—N1iii90.28 (8)
C6—C7—H7119.4O1iii—Mn1—N1iii88.70 (7)
C2—C7—H7119.4N1—Mn1—N1iii178.62 (12)
N1—C8—C9123.4 (3)O1W—Mn1—O2iii81.82 (5)
N1—C8—H8118.3O1—Mn1—O2iii139.99 (7)
C9—C8—H8118.3O1iii—Mn1—O2iii56.30 (7)
C8—C9—C10119.7 (3)N1—Mn1—O2iii85.56 (7)
C8—C9—H9120.1N1iii—Mn1—O2iii94.63 (7)
C10—C9—H9120.1O1W—Mn1—O281.82 (5)
C11—C10—C9117.2 (2)O1—Mn1—O256.30 (7)
C11—C10—C10i122.29 (19)O1iii—Mn1—O2139.99 (7)
C9—C10—C10i120.50 (19)N1—Mn1—O294.63 (7)
C10—C11—C12119.4 (3)N1iii—Mn1—O285.56 (7)
C10—C11—H11120.3O2iii—Mn1—O2163.65 (10)
C12—C11—H11120.3C12—N1—C8116.8 (2)
N1—C12—C11123.5 (3)C12—N1—Mn1122.04 (18)
N1—C12—H12118.2C8—N1—Mn1121.13 (18)
C11—C12—H12118.2C17—N2—C13115.1 (4)
N2—C13—C14125.1 (4)C1—O1—Mn192.36 (17)
N2—C13—H13117.5C1—O2—Mn190.38 (16)
C14—C13—H13117.5Mn1—O1W—H1W127 (2)
C13—C14—C15119.6 (4)
Symmetry codes: (i) −x+1/2, y, −z+3/2; (ii) −x+1, −y+1, −z+2; (iii) −x+3/2, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O1iv0.82 (3)1.98 (3)2.740 (3)153 (3)
C8—H8···O10.932.553.181 (3)125
Symmetry codes: (iv) −x+3/2, y−1, −z+3/2.
Table 1
Selected geometric parameters (°) top
N1—Mn1—O294.63 (7)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O1i0.82 (3)1.98 (3)2.740 (3)153 (3)
C8—H8···O10.932.553.181 (3)125
Symmetry codes: (i) −x+3/2, y−1, −z+3/2.
Acknowledgements top

The authors acknowledge South China University of Technology for supporting this work.

references
References top

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