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Acta Cryst. (2010). E66, m1163    [ doi:10.1107/S1600536810033167 ]

catena-Poly[[[aquapyridinezinc(II)]-[mu]2-3,3'-(p-phenylene)diacrylato] pyridine solvate]

D. Su, D. Song and Z. Fu

Abstract top

The title compound, {[Zn(C12H8O4)(C5H5N)(H2O)]·C5H5N}n, has been prepared by hydrothermal reaction. The ZnII atom is six-coordinated by four carboxylate O atoms of two p-phenylenediacrylate (ppda2-) ligands, one N atom of a pyridine molecule and one O atom of a water molecule in a distorted octahedral environment. The carboxylate groups of the ppda2- anions are in a bridging-chelating mode, in which two O atoms chelate one Zn2+ ion. These connections result in an extended chain structure. Parallel packing of the chains forms a two-dimensional network with intermolecular edge-to-face interactions. Further linkages between the layers through O-H...O hydrogen-bonding interactions result in a three-dimensional supramolecular architecture with one-dimensional rectanglar channels.

Comment top

Metal-organic frameworks (MOFs) became one of the most active research areas in chemistry and materials in recent years due to their intriguing variety of architectures as well as promising applications as functional materials (Li et al., 2009; Zhang et al., 2010). One of the current interesting topics is to rationally design and synthesize coordination polymers and supramolecular organization by coordinated covalent bonds or supramolecular contacts (Zeng et al., 2010; Jose et al., 2010). Herein, we report the synthesis and characterization of a new metal organic framework with three-dimensional supramolecular structural motif. In the title compound, the ZnII center is six-coordinated in a distorted octahedral geometry (Figure 1), surrounded by O1, O2, O4 from two ppda2- ligand and O5 from a water molecule in the equatorial plane, and N1, O3 of pyridine molecule and ppda2- ligand respectively in the axial position. The ppda2- anion adopts a bridging coordination mode, interconnect with the zinc ions forming a 1-D infinite chain. The shortest distance between the neighbour zinc centers is 15.26 Å. The parallel chains are arranged into a two-dimensional network by intermolecular edge-to-face C—H···pi interactions (Figure 2). Two neighboring pyridine molecules from adjacent chains are parallel and form a dihedral angle of 58.1° with the plane of uncoordinated pyridine molecule. C—H···pi interactions exist between uncoordinated pyridine molecule and coordinated pyridine molecules. The C19—H19A and C22—H22A groups point to the center of adjacent pyridine rings, with H···centroid distances 2.9408 (3) and 3.3096 (5) Å. These two-dimensional networks are further linked via interlayer strong O—H···O hydrogen-bonding interactions, forming a three-dimensional supramolecular architecture with one-dimensional rectangle-shaped channels along the a direction (Figure 3). The H1···O4 distance is 1.8628Å and the O5—H1···O4 bond angle is 171.58°. Guest pyridine molecules are situated in the cavities.

Related literature top

For the applications of metal-organic frameworks, see: Li et al. (2009); Zhang et al. (2010). For the rational design and synthesis of coordination polymers by coordinated covalent bonds or supramolecular contacts, see: Jose et al. (2010); Zeng et al. (2010). For a similar complex, see: Sun et al. (2009).

Experimental top

A mixture of H2ppda (0.0218 g, 0.1 mmol), Zn(OAc)2.2H2O (0.0219 g, 0.1 mmol), 4,4,-bpy (0.0156 g, 0.1 mmol), and py/H2O (1:3, 12 ml) was sealed in a 25 ml Teflon-lined bomb and heated at 353 K for 48 h. The reaction mixture was then allowed to cool to room temperature at a rate of 3 K/h. Colorless block-shape crystals were obtained.

Refinement top

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C). The non-hydrogen atoms were refined anisotropically. 34 low-theta reflections were omitted from the data set. These Low-theta reflections which calculate large but have a near-zero Fobs, might have been obscured by the beamstop. They were omitted for a well refinement. A restraint was applied for the O5 and H2 atom with O5—H2 = 0.82 Å.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. View of the two-dimensional supramolecular layer of the title compound.
[Figure 3] Fig. 3. Three-dimensional supramolecular network of the title complex.
catena-Poly[[[aquapyridinezinc(II)]-µ2-3,3'-(p-\ phenylene)diacrylato] pyridine solvate] top
Crystal data top
[Zn(C12H8O4)(C5H5N)(H2O)]·C5H5NF(000) = 944
Mr = 457.77Dx = 1.446 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3657 reflections
a = 10.2132 (15) Åθ = 2.9–25.0°
b = 17.375 (3) ŵ = 1.20 mm−1
c = 12.8144 (19) ÅT = 110 K
β = 112.360 (2)°Block, colorless
V = 2103.0 (5) Å30.30 × 0.16 × 0.15 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		3657 independent reflections
Radiation source: fine-focus sealed tube2923 reflections with I > 2σ(I)
graphiteRint = 0.026
ω scansθmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −12→12
Tmin = 0.74, Tmax = 0.85k = −20→15
9012 measured reflectionsl = −11→15
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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.044P)2 + 1.4847P]
where P = (Fo2 + 2Fc2)/3
3657 reflections(Δ/σ)max < 0.001
267 parametersΔρmax = 0.91 e Å−3
1 restraintΔρmin = −0.81 e Å−3
Crystal data top
[Zn(C12H8O4)(C5H5N)(H2O)]·C5H5NV = 2103.0 (5) Å3
Mr = 457.77Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.2132 (15) ŵ = 1.20 mm−1
b = 17.375 (3) ÅT = 110 K
c = 12.8144 (19) Å0.30 × 0.16 × 0.15 mm
β = 112.360 (2)°
Data collection top
Bruker SMART CCD
diffractometer		3657 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2923 reflections with I > 2σ(I)
Tmin = 0.74, Tmax = 0.85Rint = 0.026
9012 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.035H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.088Δρmax = 0.91 e Å−3
S = 1.05Δρmin = −0.81 e Å−3
3657 reflectionsAbsolute structure: ?
267 parametersFlack parameter: ?
1 restraintRogers parameter: ?
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
N10.5178 (2)−0.01394 (13)0.75537 (18)0.0163 (5)
C180.9544 (3)0.03667 (18)0.3132 (2)0.0260 (7)
H18A0.93480.00540.36630.031*
Zn10.41999 (3)0.072906 (17)0.63842 (2)0.01285 (11)
C11.3097 (3)0.35091 (15)0.2483 (2)0.0145 (6)
O11.44021 (18)0.34052 (11)0.27971 (15)0.0177 (4)
O21.24483 (18)0.39778 (11)0.16907 (14)0.0149 (4)
O30.40900 (19)0.18631 (11)0.52712 (15)0.0193 (4)
O40.58751 (18)0.10624 (10)0.60053 (14)0.0148 (4)
O50.3145 (2)0.00368 (12)0.50538 (16)0.0183 (4)
H20.239 (3)0.0196 (18)0.451 (2)0.031 (9)*
H10.351 (4)−0.026 (2)0.476 (3)0.030 (10)*
C21.2295 (3)0.30907 (16)0.3060 (2)0.0155 (6)
H2A1.27360.26700.35390.019*
C31.0980 (3)0.32845 (15)0.2929 (2)0.0146 (6)
H3A1.05590.36920.24170.018*
C41.0110 (3)0.29379 (15)0.3489 (2)0.0144 (6)
C50.8720 (3)0.31994 (16)0.3217 (2)0.0167 (6)
H5A0.83690.36060.26880.020*
C60.7854 (3)0.28786 (16)0.3702 (2)0.0158 (6)
H6A0.69090.30580.34890.019*
C70.8350 (3)0.22904 (15)0.4506 (2)0.0137 (5)
C80.9737 (3)0.20268 (15)0.4779 (2)0.0137 (6)
H8A1.00890.16230.53130.016*
C91.0604 (3)0.23431 (15)0.4286 (2)0.0141 (5)
H9A1.15430.21570.44890.017*
C100.7473 (3)0.19340 (15)0.5051 (2)0.0138 (6)
H10A0.78870.15170.55480.017*
C110.6165 (3)0.21278 (15)0.4930 (2)0.0152 (6)
H11A0.57550.25760.45070.018*
C120.5322 (3)0.16709 (15)0.5429 (2)0.0141 (6)
C130.6192 (3)0.00035 (18)0.8551 (2)0.0309 (5)
H13A0.64820.05220.87390.037*
C140.6844 (4)−0.05630 (18)0.9326 (3)0.0360 (6)
H14A0.7576−0.04361.00270.043*
C150.6423 (4)−0.13168 (19)0.9073 (3)0.0345 (8)
H15A0.6827−0.17150.96070.041*
C160.5408 (4)−0.14810 (19)0.8033 (3)0.0360 (6)
H16A0.5118−0.19960.78170.043*
C170.4820 (4)−0.08740 (17)0.7307 (3)0.0309 (5)
H17A0.4116−0.09880.65880.037*
N21.0893 (3)0.05277 (14)0.3312 (2)0.0227 (6)
C191.1138 (3)0.09713 (18)0.2556 (3)0.0296 (7)
H19A1.20930.10910.26760.035*
C201.0086 (4)0.12641 (19)0.1615 (3)0.0344 (8)
H20A1.03090.15750.10950.041*
C210.8701 (3)0.1097 (2)0.1440 (3)0.0330 (8)
H21A0.79460.12960.08020.040*
C220.8431 (3)0.0636 (2)0.2209 (3)0.0343 (8)
H22A0.74850.05050.21020.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0178 (12)0.0153 (12)0.0166 (11)0.0013 (10)0.0073 (9)0.0012 (9)
C180.0300 (17)0.0237 (16)0.0258 (16)−0.0048 (13)0.0123 (14)0.0010 (13)
Zn10.01274 (17)0.01317 (17)0.01527 (17)0.00028 (13)0.00828 (12)0.00003 (13)
C10.0161 (14)0.0127 (14)0.0160 (13)−0.0010 (11)0.0075 (11)−0.0045 (11)
O10.0132 (10)0.0198 (10)0.0219 (10)0.0013 (8)0.0088 (8)0.0035 (8)
O20.0149 (9)0.0156 (9)0.0166 (9)−0.0006 (8)0.0087 (8)0.0029 (8)
O30.0166 (10)0.0215 (11)0.0244 (10)0.0026 (8)0.0130 (8)0.0056 (8)
O40.0153 (9)0.0145 (10)0.0174 (9)0.0008 (8)0.0093 (8)0.0014 (8)
O50.0181 (11)0.0179 (11)0.0179 (10)0.0039 (9)0.0058 (9)−0.0049 (9)
C20.0159 (14)0.0166 (14)0.0161 (13)0.0002 (11)0.0084 (11)0.0021 (11)
C30.0156 (13)0.0154 (14)0.0128 (13)−0.0010 (11)0.0055 (11)0.0009 (11)
C40.0127 (13)0.0178 (14)0.0131 (13)−0.0024 (11)0.0056 (11)−0.0018 (11)
C50.0175 (14)0.0161 (14)0.0157 (13)−0.0014 (11)0.0056 (11)0.0032 (11)
C60.0107 (13)0.0206 (15)0.0170 (13)0.0012 (11)0.0063 (11)−0.0006 (11)
C70.0124 (13)0.0158 (14)0.0134 (13)−0.0030 (11)0.0053 (10)−0.0021 (11)
C80.0174 (14)0.0106 (13)0.0106 (12)−0.0006 (11)0.0024 (11)0.0009 (10)
C90.0110 (13)0.0157 (14)0.0157 (13)0.0002 (11)0.0054 (10)−0.0028 (11)
C100.0155 (13)0.0143 (14)0.0104 (12)−0.0027 (11)0.0038 (10)−0.0003 (10)
C110.0190 (14)0.0118 (13)0.0163 (13)−0.0007 (11)0.0082 (11)0.0016 (11)
C120.0141 (14)0.0162 (14)0.0138 (13)−0.0026 (11)0.0073 (11)−0.0051 (11)
C130.0386 (13)0.0196 (12)0.0240 (11)−0.0022 (10)0.0002 (10)−0.0009 (9)
C140.0455 (14)0.0231 (12)0.0272 (12)−0.0026 (11)0.0000 (11)−0.0008 (10)
C150.047 (2)0.0245 (17)0.0240 (16)0.0069 (15)0.0042 (15)0.0071 (13)
C160.0455 (14)0.0231 (12)0.0272 (12)−0.0026 (11)0.0000 (11)−0.0008 (10)
C170.0386 (13)0.0196 (12)0.0240 (11)−0.0022 (10)0.0002 (10)−0.0009 (9)
N20.0251 (14)0.0194 (13)0.0230 (13)0.0037 (10)0.0084 (11)−0.0013 (10)
C190.0239 (16)0.0305 (18)0.0362 (18)−0.0024 (14)0.0135 (14)0.0017 (14)
C200.039 (2)0.0326 (19)0.0330 (18)0.0029 (15)0.0154 (15)0.0118 (15)
C210.0267 (17)0.0352 (19)0.0313 (17)0.0053 (15)0.0042 (14)0.0083 (15)
C220.0227 (17)0.039 (2)0.0382 (19)−0.0055 (15)0.0081 (15)0.0018 (16)
Geometric parameters (Å, °) top
N1—C131.327 (4)C5—H5A0.9500
N1—C171.332 (4)C6—C71.402 (4)
Zn1—N12.093 (2)C6—H6A0.9500
C18—N21.336 (4)C7—C81.401 (4)
C18—C221.374 (4)C7—C101.466 (4)
C18—H18A0.9500C8—C91.382 (4)
Zn1—O52.0288 (19)C8—H8A0.9500
Zn1—O42.0324 (18)C9—H9A0.9500
Zn1—O2i2.0368 (18)C10—C111.328 (4)
Zn1—O1i2.3019 (18)C10—H10A0.9500
Zn1—O32.4099 (19)C11—C121.484 (4)
Zn1—C1i2.492 (3)C11—H11A0.9500
Zn1—C122.560 (3)C13—C141.377 (4)
C1—O11.250 (3)C13—H13A0.9500
C1—O21.273 (3)C14—C151.378 (4)
C1—C21.485 (4)C14—H14A0.9500
C1—Zn1ii2.492 (3)C15—C161.371 (4)
O1—Zn1ii2.3019 (18)C15—H15A0.9500
O2—Zn1ii2.0368 (18)C16—C171.383 (4)
O3—C121.241 (3)C16—H16A0.9500
O4—C121.291 (3)C17—H17A0.9500
O5—H20.864 (18)N2—C191.334 (4)
O5—H10.80 (4)C19—C201.372 (4)
C2—C31.333 (4)C19—H19A0.9500
C2—H2A0.9500C20—C211.377 (5)
C3—C41.466 (4)C20—H20A0.9500
C3—H3A0.9500C21—C221.377 (5)
C4—C51.403 (4)C21—H21A0.9500
C4—C91.405 (4)C22—H22A0.9500
C5—C61.377 (4)
C13—N1—C17116.8 (2)C6—C5—C4121.3 (2)
C13—N1—Zn1122.7 (2)C6—C5—H5A119.3
C17—N1—Zn1120.53 (19)C4—C5—H5A119.3
N2—C18—C22122.6 (3)C5—C6—C7120.8 (2)
N2—C18—H18A118.7C5—C6—H6A119.6
C22—C18—H18A118.7C7—C6—H6A119.6
O5—Zn1—O4101.20 (8)C8—C7—C6118.0 (2)
O5—Zn1—O2i94.92 (8)C8—C7—C10119.1 (2)
O4—Zn1—O2i148.85 (8)C6—C7—C10122.9 (2)
N1—Zn1—O597.50 (9)C9—C8—C7121.3 (2)
O4—Zn1—N199.25 (8)C9—C8—H8A119.4
O2i—Zn1—N1104.90 (8)C7—C8—H8A119.4
O5—Zn1—O1i155.29 (8)C8—C9—C4120.6 (2)
O4—Zn1—O1i99.78 (7)C8—C9—H9A119.7
O1i—Zn1—O2i60.49 (7)C4—C9—H9A119.7
N1—Zn1—O1i91.86 (8)C11—C10—C7127.3 (2)
O5—Zn1—O395.57 (7)C11—C10—H10A116.3
O3—Zn1—O458.64 (7)C7—C10—H10A116.3
O2i—Zn1—O393.61 (7)C10—C11—C12122.5 (2)
N1—Zn1—O3156.24 (8)C10—C11—H11A118.8
O1i—Zn1—O384.33 (7)C12—C11—H11A118.8
O5—Zn1—C1i125.46 (8)O3—C12—O4120.6 (2)
O4—Zn1—C1i125.88 (8)O3—C12—C11120.3 (2)
O2i—Zn1—C1i30.61 (8)O4—C12—C11119.0 (2)
N1—Zn1—C1i99.99 (8)O3—C12—Zn168.89 (14)
O1i—Zn1—C1i29.89 (7)O4—C12—Zn151.76 (12)
O3—Zn1—C1i88.32 (7)C11—C12—Zn1170.73 (19)
O5—Zn1—C1299.68 (8)N1—C13—C14123.2 (3)
O4—Zn1—C1229.91 (8)N1—C13—H13A118.4
O2i—Zn1—C12121.19 (8)C14—C13—H13A118.4
N1—Zn1—C12128.66 (9)C13—C14—C15119.1 (3)
O1i—Zn1—C1292.05 (7)C13—C14—H14A120.4
O3—Zn1—C1228.72 (7)C15—C14—H14A120.4
C1i—Zn1—C12108.13 (8)C16—C15—C14118.7 (3)
O1—C1—O2121.1 (2)C16—C15—H15A120.7
O1—C1—C2119.4 (2)C14—C15—H15A120.7
O2—C1—C2119.4 (2)C15—C16—C17118.0 (3)
O1—C1—Zn1ii66.61 (14)C15—C16—H16A121.0
O2—C1—Zn1ii54.53 (12)C17—C16—H16A121.0
C2—C1—Zn1ii173.96 (19)N1—C17—C16124.2 (3)
C1—O1—Zn1ii83.50 (15)N1—C17—H17A117.9
C1—O2—Zn1ii94.86 (15)C16—C17—H17A117.9
C12—O3—Zn182.39 (15)C19—N2—C18117.5 (3)
C12—O4—Zn198.33 (15)N2—C19—C20123.5 (3)
Zn1—O5—H2121 (2)N2—C19—H19A118.3
Zn1—O5—H1125 (2)C20—C19—H19A118.3
H2—O5—H1105 (3)C19—C20—C21118.5 (3)
C3—C2—C1122.3 (3)C19—C20—H20A120.7
C3—C2—H2A118.8C21—C20—H20A120.7
C1—C2—H2A118.8C20—C21—C22118.7 (3)
C2—C3—C4127.2 (3)C20—C21—H21A120.7
C2—C3—H3A116.4C22—C21—H21A120.7
C4—C3—H3A116.4C21—C22—C18119.2 (3)
C5—C4—C9117.9 (2)C21—C22—H22A120.4
C5—C4—C3119.3 (2)C18—C22—H22A120.4
C9—C4—C3122.8 (2)
Symmetry codes: (i) x−1, −y+1/2, z+1/2; (ii) x+1, −y+1/2, z−1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H1···O4iii0.80 (4)1.94 (4)2.743 (4)172 (4)
Symmetry codes: (iii) −x+1, −y, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Zn1—N12.093 (2)Zn1—O1i2.3019 (18)
Zn1—O52.0288 (19)Zn1—O32.4099 (19)
Zn1—O42.0324 (18)Zn1—C1i2.492 (3)
Zn1—O2i2.0368 (18)Zn1—C122.560 (3)
N1—Zn1—O597.50 (9)O3—Zn1—O458.64 (7)
O1i—Zn1—O2i60.49 (7)
Symmetry codes: (i) x−1, −y+1/2, z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H1···O4ii0.80 (4)1.94 (4)2.743 (4)172 (4)
Symmetry codes: (ii) −x+1, −y, −z+1.
Acknowledgements top

The authors thank the NNSFC (No. 20701014), the Fundamental Research Funds for the Central Universities (2009ZM0030) and the SRP program of the SCUT for financial support.

references
References top

Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Jose, J. C., Herbert, H. & Miguel, P. H. (2010). Inorg. Chim. Acta, 363, 1179–1185.

Li, J. R., Kuppler, R. J. & Zhou, H. C. (2009). Chem. Soc. Rev. 3838, 1477–1504.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Sun, Q., Yue, Q., Zhang, J. Y., Wang, L., Li, X. & Gao, E. Q. (2009). Cryst. Growth Des. 9, 2310–2317.

Zeng, F. H., Ni, J., Wang, Q. G. & Xie, Y. S. (2010). Cryst. Growth Des. 10, 1611–1622.

Zhang, L., Yao, Y. L., Che, Y. X. & Zheng, J. M. (2010). Cryst. Growth Des. 10, 528–533.