Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025305/bh2104sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025305/bh2104Isup2.hkl |
CCDC reference: 650579
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.
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).
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].
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).
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.
Fig. 1. The structure of (I), showing the atomic numbering scheme. Non-H atoms are shown with 30% probability displacement ellipsoids. | |
Fig. 2. A packing view of (I) viewed along the b-axis. |
[Mn(C7H4ClO2)2(C10H8N2)(H2O)]·C10H8N2 | F(000) = 714 |
Mr = 696.43 | Dx = 1.462 Mg m−3 |
Monoclinic, P2/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yac | Cell parameters from 2376 reflections |
a = 11.6900 (3) Å | θ = 2.2–28.0° |
b = 6.1510 (2) Å | µ = 0.64 mm−1 |
c = 22.5184 (6) Å | T = 293 K |
β = 102.369 (2)° | Block, yellow |
V = 1581.61 (8) Å3 | 0.25 × 0.19 × 0.18 mm |
Z = 2 |
Bruker APEXII diffractometer | 3115 independent reflections |
Radiation source: fine-focus sealed tube | 2373 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
φ and ω scans | θmax = 26.0°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −14→14 |
Tmin = 0.857, Tmax = 0.894 | k = −7→7 |
16828 measured reflections | l = −27→27 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | H 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 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.56 e Å−3 |
[Mn(C7H4ClO2)2(C10H8N2)(H2O)]·C10H8N2 | V = 1581.61 (8) Å3 |
Mr = 696.43 | Z = 2 |
Monoclinic, P2/n | Mo Kα radiation |
a = 11.6900 (3) Å | µ = 0.64 mm−1 |
b = 6.1510 (2) Å | T = 293 K |
c = 22.5184 (6) Å | 0.25 × 0.19 × 0.18 mm |
β = 102.369 (2)° |
Bruker APEXII diffractometer | 3115 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2373 reflections with I > 2σ(I) |
Tmin = 0.857, Tmax = 0.894 | Rint = 0.056 |
16828 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.61 e Å−3 |
3115 reflections | Δρmin = −0.56 e Å−3 |
212 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.7981 (2) | 0.7343 (5) | 0.86400 (12) | 0.0350 (6) | |
C2 | 0.8244 (2) | 0.8210 (5) | 0.92758 (12) | 0.0338 (6) | |
C3 | 0.7973 (3) | 1.0318 (5) | 0.93992 (14) | 0.0508 (8) | |
H3 | 0.7643 | 1.1241 | 0.9081 | 0.061* | |
C4 | 0.8186 (3) | 1.1078 (6) | 0.99910 (15) | 0.0587 (9) | |
H4 | 0.7979 | 1.2489 | 1.0073 | 0.070* | |
C5 | 0.8706 (3) | 0.9728 (6) | 1.04552 (14) | 0.0490 (8) | |
C6 | 0.8995 (3) | 0.7654 (6) | 1.03456 (14) | 0.0604 (9) | |
H6 | 0.9350 | 0.6756 | 1.0664 | 0.072* | |
C7 | 0.8755 (3) | 0.6890 (5) | 0.97564 (13) | 0.0484 (8) | |
H7 | 0.8942 | 0.5461 | 0.9681 | 0.058* | |
C8 | 0.5015 (2) | 0.7563 (5) | 0.76962 (13) | 0.0399 (7) | |
H8 | 0.5481 | 0.8737 | 0.7858 | 0.048* | |
C9 | 0.3844 (2) | 0.7609 (5) | 0.77142 (13) | 0.0401 (7) | |
H9 | 0.3534 | 0.8803 | 0.7878 | 0.048* | |
C10 | 0.3131 (2) | 0.5870 (5) | 0.74867 (12) | 0.0344 (6) | |
C11 | 0.3641 (2) | 0.4174 (5) | 0.72347 (14) | 0.0427 (7) | |
H11 | 0.3195 | 0.2978 | 0.7072 | 0.051* | |
C12 | 0.4821 (2) | 0.4272 (5) | 0.72261 (14) | 0.0419 (7) | |
H12 | 0.5146 | 0.3127 | 0.7049 | 0.050* | |
C13 | 0.4107 (5) | 0.1163 (10) | 0.9169 (3) | 0.142 (3) | |
H13 | 0.3605 | −0.0024 | 0.9138 | 0.171* | |
C14 | 0.4212 (5) | 0.2464 (10) | 0.9674 (3) | 0.131 (3) | |
H14 | 0.3802 | 0.2129 | 0.9973 | 0.157* | |
C15 | 0.4926 (3) | 0.4267 (6) | 0.97334 (16) | 0.0558 (9) | |
C16 | 0.5512 (3) | 0.4561 (6) | 0.92726 (16) | 0.0666 (10) | |
H16 | 0.6021 | 0.5732 | 0.9287 | 0.080* | |
C17 | 0.5357 (4) | 0.3148 (7) | 0.87917 (17) | 0.0723 (11) | |
H17 | 0.5775 | 0.3405 | 0.8491 | 0.087* | |
Cl1 | 0.90101 (10) | 1.0741 (2) | 1.11973 (4) | 0.0800 (3) | |
Mn1 | 0.7500 | 0.58733 (9) | 0.7500 | 0.02869 (17) | |
N1 | 0.55156 (17) | 0.5918 (4) | 0.74588 (10) | 0.0339 (5) | |
N2 | 0.4661 (3) | 0.1464 (6) | 0.87269 (16) | 0.0844 (11) | |
O1 | 0.77094 (16) | 0.8643 (3) | 0.81989 (8) | 0.0410 (5) | |
O2 | 0.80153 (18) | 0.5331 (3) | 0.85538 (9) | 0.0449 (5) | |
O1W | 0.7500 | 0.2327 (5) | 0.7500 | 0.0453 (8) | |
H1W | 0.739 (3) | 0.153 (5) | 0.7201 (14) | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0252 (13) | 0.0471 (18) | 0.0325 (15) | −0.0041 (12) | 0.0061 (10) | 0.0015 (13) |
C2 | 0.0314 (14) | 0.0372 (15) | 0.0324 (15) | −0.0050 (11) | 0.0062 (11) | 0.0013 (12) |
C3 | 0.073 (2) | 0.0406 (19) | 0.0382 (17) | 0.0020 (16) | 0.0098 (15) | 0.0038 (14) |
C4 | 0.086 (3) | 0.0425 (19) | 0.051 (2) | −0.0058 (18) | 0.0204 (18) | −0.0099 (16) |
C5 | 0.0518 (19) | 0.061 (2) | 0.0335 (16) | −0.0141 (16) | 0.0079 (13) | −0.0091 (15) |
C6 | 0.071 (2) | 0.072 (3) | 0.0329 (17) | 0.0150 (19) | 0.0013 (15) | 0.0040 (17) |
C7 | 0.0569 (19) | 0.0455 (18) | 0.0403 (17) | 0.0102 (15) | 0.0047 (14) | 0.0033 (15) |
C8 | 0.0296 (14) | 0.0384 (16) | 0.0508 (17) | −0.0034 (12) | 0.0066 (12) | −0.0081 (14) |
C9 | 0.0288 (14) | 0.0401 (16) | 0.0510 (18) | 0.0019 (12) | 0.0079 (12) | −0.0091 (14) |
C10 | 0.0255 (13) | 0.0436 (16) | 0.0334 (14) | 0.0010 (12) | 0.0050 (10) | 0.0016 (13) |
C11 | 0.0306 (14) | 0.0416 (16) | 0.0547 (18) | −0.0064 (13) | 0.0062 (12) | −0.0160 (15) |
C12 | 0.0318 (14) | 0.0459 (17) | 0.0485 (17) | −0.0020 (13) | 0.0099 (12) | −0.0146 (15) |
C13 | 0.133 (5) | 0.159 (6) | 0.162 (5) | −0.102 (4) | 0.090 (4) | −0.105 (5) |
C14 | 0.128 (4) | 0.155 (5) | 0.141 (5) | −0.097 (4) | 0.095 (4) | −0.095 (4) |
C15 | 0.0409 (17) | 0.065 (2) | 0.062 (2) | −0.0090 (16) | 0.0118 (15) | −0.0146 (18) |
C16 | 0.082 (3) | 0.065 (2) | 0.054 (2) | −0.023 (2) | 0.0162 (18) | −0.0051 (19) |
C17 | 0.090 (3) | 0.077 (3) | 0.052 (2) | −0.011 (2) | 0.020 (2) | −0.006 (2) |
Cl1 | 0.0960 (8) | 0.1026 (8) | 0.0397 (5) | −0.0174 (6) | 0.0111 (5) | −0.0241 (5) |
Mn1 | 0.0237 (3) | 0.0308 (3) | 0.0316 (3) | 0.000 | 0.0060 (2) | 0.000 |
N1 | 0.0239 (11) | 0.0406 (13) | 0.0376 (12) | −0.0009 (10) | 0.0072 (9) | −0.0041 (11) |
N2 | 0.081 (2) | 0.095 (3) | 0.079 (2) | −0.022 (2) | 0.0222 (19) | −0.036 (2) |
O1 | 0.0445 (11) | 0.0465 (12) | 0.0293 (10) | 0.0002 (9) | 0.0021 (8) | 0.0052 (9) |
O2 | 0.0595 (13) | 0.0372 (12) | 0.0389 (11) | −0.0051 (9) | 0.0128 (9) | −0.0038 (9) |
O1W | 0.068 (2) | 0.0307 (16) | 0.0358 (17) | 0.000 | 0.0072 (15) | 0.000 |
C1—O2 | 1.254 (4) | C11—H11 | 0.9300 |
C1—O1 | 1.262 (3) | C12—N1 | 1.333 (3) |
C1—C2 | 1.497 (4) | C12—H12 | 0.9300 |
C2—C3 | 1.377 (4) | C13—N2 | 1.311 (6) |
C2—C7 | 1.382 (4) | C13—C14 | 1.375 (6) |
C3—C4 | 1.383 (4) | C13—H13 | 0.9300 |
C3—H3 | 0.9300 | C14—C15 | 1.378 (5) |
C4—C5 | 1.371 (5) | C14—H14 | 0.9300 |
C4—H4 | 0.9300 | C15—C16 | 1.372 (5) |
C5—C6 | 1.356 (5) | C15—C15ii | 1.482 (7) |
C5—Cl1 | 1.747 (3) | C16—C17 | 1.370 (5) |
C6—C7 | 1.378 (4) | C16—H16 | 0.9300 |
C6—H6 | 0.9300 | C17—N2 | 1.306 (5) |
C7—H7 | 0.9300 | C17—H17 | 0.9300 |
C8—N1 | 1.336 (3) | Mn1—O1W | 2.181 (3) |
C8—C9 | 1.378 (4) | Mn1—O1 | 2.297 (2) |
C8—H8 | 0.9300 | Mn1—O1iii | 2.297 (2) |
C9—C10 | 1.385 (4) | Mn1—N1 | 2.302 (2) |
C9—H9 | 0.9300 | Mn1—N1iii | 2.302 (2) |
C10—C11 | 1.382 (4) | Mn1—O2iii | 2.344 (2) |
C10—C10i | 1.490 (5) | Mn1—O2 | 2.344 (2) |
C11—C12 | 1.385 (4) | O1W—H1W | 0.82 (3) |
O2—C1—O1 | 121.0 (3) | C13—C14—H14 | 120.2 |
O2—C1—C2 | 119.5 (3) | C15—C14—H14 | 120.2 |
O1—C1—C2 | 119.5 (3) | C16—C15—C14 | 115.0 (3) |
C3—C2—C7 | 118.3 (3) | C16—C15—C15ii | 122.8 (4) |
C3—C2—C1 | 121.3 (3) | C14—C15—C15ii | 122.1 (4) |
C7—C2—C1 | 120.3 (3) | C17—C16—C15 | 120.7 (4) |
C2—C3—C4 | 120.7 (3) | C17—C16—H16 | 119.6 |
C2—C3—H3 | 119.6 | C15—C16—H16 | 119.6 |
C4—C3—H3 | 119.6 | N2—C17—C16 | 124.4 (4) |
C5—C4—C3 | 119.3 (3) | N2—C17—H17 | 117.8 |
C5—C4—H4 | 120.4 | C16—C17—H17 | 117.8 |
C3—C4—H4 | 120.4 | O1W—Mn1—O1 | 137.89 (5) |
C6—C5—C4 | 121.2 (3) | O1W—Mn1—O1iii | 137.89 (5) |
C6—C5—Cl1 | 120.2 (3) | O1—Mn1—O1iii | 84.22 (10) |
C4—C5—Cl1 | 118.6 (3) | O1W—Mn1—N1 | 90.69 (6) |
C5—C6—C7 | 119.3 (3) | O1—Mn1—N1 | 88.70 (7) |
C5—C6—H6 | 120.4 | O1iii—Mn1—N1 | 90.28 (7) |
C7—C6—H6 | 120.4 | O1W—Mn1—N1iii | 90.69 (6) |
C6—C7—C2 | 121.2 (3) | O1—Mn1—N1iii | 90.28 (8) |
C6—C7—H7 | 119.4 | O1iii—Mn1—N1iii | 88.70 (7) |
C2—C7—H7 | 119.4 | N1—Mn1—N1iii | 178.62 (12) |
N1—C8—C9 | 123.4 (3) | O1W—Mn1—O2iii | 81.82 (5) |
N1—C8—H8 | 118.3 | O1—Mn1—O2iii | 139.99 (7) |
C9—C8—H8 | 118.3 | O1iii—Mn1—O2iii | 56.30 (7) |
C8—C9—C10 | 119.7 (3) | N1—Mn1—O2iii | 85.56 (7) |
C8—C9—H9 | 120.1 | N1iii—Mn1—O2iii | 94.63 (7) |
C10—C9—H9 | 120.1 | O1W—Mn1—O2 | 81.82 (5) |
C11—C10—C9 | 117.2 (2) | O1—Mn1—O2 | 56.30 (7) |
C11—C10—C10i | 122.29 (19) | O1iii—Mn1—O2 | 139.99 (7) |
C9—C10—C10i | 120.50 (19) | N1—Mn1—O2 | 94.63 (7) |
C10—C11—C12 | 119.4 (3) | N1iii—Mn1—O2 | 85.56 (7) |
C10—C11—H11 | 120.3 | O2iii—Mn1—O2 | 163.65 (10) |
C12—C11—H11 | 120.3 | C12—N1—C8 | 116.8 (2) |
N1—C12—C11 | 123.5 (3) | C12—N1—Mn1 | 122.04 (18) |
N1—C12—H12 | 118.2 | C8—N1—Mn1 | 121.13 (18) |
C11—C12—H12 | 118.2 | C17—N2—C13 | 115.1 (4) |
N2—C13—C14 | 125.1 (4) | C1—O1—Mn1 | 92.36 (17) |
N2—C13—H13 | 117.5 | C1—O2—Mn1 | 90.38 (16) |
C14—C13—H13 | 117.5 | Mn1—O1W—H1W | 127 (2) |
C13—C14—C15 | 119.6 (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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O1iv | 0.82 (3) | 1.98 (3) | 2.740 (3) | 153 (3) |
C8—H8···O1 | 0.93 | 2.55 | 3.181 (3) | 125 |
Symmetry code: (iv) −x+3/2, y−1, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C7H4ClO2)2(C10H8N2)(H2O)]·C10H8N2 |
Mr | 696.43 |
Crystal system, space group | Monoclinic, P2/n |
Temperature (K) | 293 |
a, b, c (Å) | 11.6900 (3), 6.1510 (2), 22.5184 (6) |
β (°) | 102.369 (2) |
V (Å3) | 1581.61 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.64 |
Crystal size (mm) | 0.25 × 0.19 × 0.18 |
Data collection | |
Diffractometer | Bruker APEXII |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.857, 0.894 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16828, 3115, 2373 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.118, 1.05 |
No. of reflections | 3115 |
No. of parameters | 212 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.61, −0.56 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2004), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O1i | 0.82 (3) | 1.98 (3) | 2.740 (3) | 153 (3) |
C8—H8···O1 | 0.93 | 2.55 | 3.181 (3) | 125.0 |
Symmetry code: (i) −x+3/2, y−1, −z+3/2. |
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].