catena-Poly[[[aqua­bis(4-chloro­benzoato-κ²O,O′)manganese(II)]-μ-4,4′-bipyridine-κ²N:N′]4,4′-bipyridine solvate]

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 Mn^II 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 π–π 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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.047
• wR factor = 0.118
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found





Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT128_ALERT_4_C Non-standard setting of Space group P2/c    ....    P2/n
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C5
PLAT243_ALERT_4_C High  'Solvent' Ueq as Compared to Neighbors for        C13
PLAT243_ALERT_4_C High  'Solvent' Ueq as Compared to Neighbors for        C14
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N2
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C15
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       3.24

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1         (2)       1.89

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

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 Mn^II 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 Ų 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

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).

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2U_eq(carrier atom).

Computing details

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

	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.

catena-Poly[[[aquabis(4-chlorobenzoato-\k²O,O')manganese(II)]-µ-4,4'-bipyridine-\k²N:N'] 4,4'-bipyridine solvate]

Crystal data

[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) Å^3	0.25 × 0.19 × 0.18 mm
Z = 2

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0451P)^2 + 1.3366P] where P = (Fo^2 + 2Fc^2)/3
3115 reflections	(Δ/σ)max = 0.001
212 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.56 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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

Geometric parameters (Å, º)

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—C15^ii	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—O1^iii	2.297 (2)
C9—C10	1.385 (4)	Mn1—N1	2.302 (2)
C9—H9	0.9300	Mn1—N1^iii	2.302 (2)
C10—C11	1.382 (4)	Mn1—O2^iii	2.344 (2)
C10—C10^i	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—C15^ii	122.8 (4)
C3—C2—C1	121.3 (3)	C14—C15—C15^ii	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—O1^iii	137.89 (5)
C6—C5—Cl1	120.2 (3)	O1—Mn1—O1^iii	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	O1^iii—Mn1—N1	90.28 (7)
C7—C6—H6	120.4	O1W—Mn1—N1^iii	90.69 (6)
C6—C7—C2	121.2 (3)	O1—Mn1—N1^iii	90.28 (8)
C6—C7—H7	119.4	O1^iii—Mn1—N1^iii	88.70 (7)
C2—C7—H7	119.4	N1—Mn1—N1^iii	178.62 (12)
N1—C8—C9	123.4 (3)	O1W—Mn1—O2^iii	81.82 (5)
N1—C8—H8	118.3	O1—Mn1—O2^iii	139.99 (7)
C9—C8—H8	118.3	O1^iii—Mn1—O2^iii	56.30 (7)
C8—C9—C10	119.7 (3)	N1—Mn1—O2^iii	85.56 (7)
C8—C9—H9	120.1	N1^iii—Mn1—O2^iii	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—C10^i	122.29 (19)	O1^iii—Mn1—O2	139.99 (7)
C9—C10—C10^i	120.50 (19)	N1—Mn1—O2	94.63 (7)
C10—C11—C12	119.4 (3)	N1^iii—Mn1—O2	85.56 (7)
C10—C11—H11	120.3	O2^iii—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.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O1^iv	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.