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Acta Cryst. (2007). E63, m2205    [ doi:10.1107/S1600536807035209 ]

Poly[([mu]2-trans-di-4-pyridylethylene-[kappa]2N:N')([mu]2-fumarato-[kappa]2O:O')zinc(II)]

J.-Y. Xu, E. J. Hurtado, E. B. Lobkovsky and B. Chen

Abstract top

In the title compound, [Zn(C4H2O4)(C12H10N2)], the ZnII atom lies on a crystallographic twofold rotation axis in a distorted tetrahedral geometry. The ZnII ions are bridged by fumarate and trans-di-4-pyridylethylene to form a porous triply interpenetrated diamond-like metal-organic framework.

Comment top

Porous metal-organic frameworks (MOFs) self-assembled by the coordination of suitable metal ions/clusters with organic building blocks are of great interest for their potential applications in gas storage, separation, molecular recognition, magnetism and catalysis (Eddaoudi et al., 2001; Kitagawa et al., 2004; Yaghi et al., 2003; Janiak, 2003). Recently we have been interested in the construction of porous MOFs by making use of mixed organic linkers (Rather & Zaworotko, 2003; Chun et al., 2005; Ma et al., 2005; Chen et al., 2006). The title compound is one such MOF constructed from ZnII and the organic linkers fumarato and trans-di-4-pyridylethylene.

A small portion of the extended framework of (I) is shown in Fig. 1. Atom Zn1 is in a distorted tetrahedral geometry. These ZnII ions are bridged by fumarato and trans-di-4-pyridylethylene to form a porous triply-interpenetrated metal-organic framework with a diamond-like structure (Fig. 2).

Related literature top

For related literature, see: Chen et al. (2006); Chun et al. (2005); Eddaoudi et al. (2001); Janiak (2003); Kitagawa et al. (2004); Ma et al. (2005); Rather & Zaworotko (2003); Yaghi et al. (2003).

For related literature, see: Sluis & Spek (1990).

Experimental top

The title compound was synthesized by a hydrothermal reaction of Zn(NO3)2.6H2O, fumaric acid and trans-di-4-pyridylethylene (1:1:1 mole ratio) in DMF at 100 °C. Small, colorless crystals of the title compound formed and were collected in 38% yield.

Refinement top

All the hydrogen atoms were found in a difference Fourier map and refined isotropically.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker 2004); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A portion of the structure showing the labelling scheme of the asymmetric unit. Displacement ellipsoids are at the 50% probability level.
[Figure 2] Fig. 2. (a) Coordination geometry around Zn; (b) one 'diamond' unit; (c) schematic illustration of the triply-interpenetrated metal-organic framework; (d) packing of the metal-organic framework indicating its porous structure (Zn yellow; C gray; N blue; O red).
Poly[(µ2-trans-di-4-pyridylethylene-κ2N:N')(µ2-fumarato-\ κ2O:O')zinc(II)] top
Crystal data top
[Zn(C4H2O4)(C12H10N2)]F(000) = 736
Mr = 361.67Dx = 0.941 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8809 reflections
a = 8.8488 (8) Åθ = 2.4–32.0°
b = 21.5285 (19) ŵ = 0.98 mm−1
c = 13.5042 (11) ÅT = 173 K
β = 97.144 (4)°Block, colourless
V = 2552.6 (4) Å30.30 × 0.15 × 0.10 mm
Z = 4
Data collection top
Bruker X8 APEX II
diffractometer		5175 independent reflections
Radiation source: fine-focus sealed tube4435 reflections with I > 2σ(I)
graphiteRint = 0.031
Detector resolution: 18 pixels mm-1θmax = 34.2°, θmin = 1.9°
φ and ω scansh = −13→13
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		k = −33→33
Tmin = 0.759, Tmax = 0.909l = −18→21
25652 measured reflections
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)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0404P)2 + 0.1113P]
where P = (Fo2 + 2Fc2)/3
5175 reflections(Δ/σ)max < 0.001
106 parametersΔρmax = 0.31 e Å−3
0 restraintsΔρmin = −0.53 e Å−3
Crystal data top
[Zn(C4H2O4)(C12H10N2)]V = 2552.6 (4) Å3
Mr = 361.67Z = 4
Monoclinic, C2/cMo Kα radiation
a = 8.8488 (8) ŵ = 0.98 mm−1
b = 21.5285 (19) ÅT = 173 K
c = 13.5042 (11) Å0.30 × 0.15 × 0.10 mm
β = 97.144 (4)°
Data collection top
Bruker X8 APEX II
diffractometer		5175 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		4435 reflections with I > 2σ(I)
Tmin = 0.759, Tmax = 0.909Rint = 0.031
25652 measured reflectionsθmax = 34.2°
Refinement top
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.073Δρmax = 0.31 e Å−3
S = 1.09Δρmin = −0.53 e Å−3
5175 reflectionsAbsolute structure: ?
106 parametersFlack parameter: ?
0 restraintsRogers 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 > 2σ(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.

Due to a complete solvent area disorder data were treated with the SQUEEZE routine of the PLATON software package (van der Sluis & Spek, 1990). The calculated density is for the MOF only and does not include the solvent.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.00000.147618 (6)0.25000.01800 (5)
O1−0.10470 (8)0.20659 (3)0.15521 (5)0.02760 (14)
O2−0.21011 (10)0.12225 (4)0.07903 (6)0.03675 (18)
N10.14390 (8)0.09472 (4)0.18136 (6)0.02206 (14)
C10.28693 (11)0.11406 (5)0.17539 (8)0.02768 (19)
H1A0.32170.15090.20960.033*
C20.38538 (11)0.08249 (5)0.12157 (8)0.0313 (2)
H2A0.48520.09800.11840.038*
C30.33737 (10)0.02748 (5)0.07150 (7)0.02544 (18)
C40.19073 (11)0.00652 (5)0.08083 (8)0.0301 (2)
H4A0.1550−0.03140.05040.036*
C50.09708 (11)0.04145 (5)0.13489 (8)0.02801 (19)
H5A−0.00350.02720.13920.034*
C60.43108 (11)−0.00836 (5)0.00942 (8)0.0300 (2)
H6A0.3902−0.0460−0.01910.036*
C7−0.18907 (11)0.17920 (4)0.08416 (7)0.02391 (17)
C8−0.26287 (11)0.22001 (5)0.00310 (7)0.02724 (18)
H8A−0.33300.2015−0.04740.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01940 (7)0.01775 (7)0.01692 (7)0.0000.00252 (5)0.000
O10.0334 (3)0.0235 (3)0.0233 (3)0.0000 (3)−0.0070 (3)0.0022 (2)
O20.0468 (5)0.0218 (4)0.0378 (4)−0.0040 (3)−0.0099 (3)0.0017 (3)
N10.0205 (3)0.0232 (4)0.0229 (3)−0.0019 (3)0.0045 (3)−0.0043 (3)
C10.0230 (4)0.0275 (5)0.0334 (5)−0.0056 (3)0.0071 (3)−0.0111 (4)
C20.0229 (4)0.0340 (5)0.0383 (5)−0.0071 (4)0.0094 (4)−0.0129 (4)
C30.0214 (4)0.0253 (4)0.0304 (4)−0.0030 (3)0.0064 (3)−0.0071 (3)
C40.0263 (4)0.0266 (5)0.0391 (5)−0.0059 (4)0.0112 (4)−0.0122 (4)
C50.0225 (4)0.0271 (5)0.0357 (5)−0.0049 (3)0.0089 (4)−0.0085 (4)
C60.0255 (4)0.0291 (5)0.0365 (5)−0.0036 (4)0.0079 (4)−0.0130 (4)
C70.0260 (4)0.0232 (4)0.0215 (4)0.0001 (3)−0.0009 (3)0.0022 (3)
C80.0302 (4)0.0272 (5)0.0218 (4)−0.0003 (4)−0.0068 (3)0.0002 (3)
Geometric parameters (Å, °) top
Zn1—O1i1.9529 (7)C2—H2A0.9500
Zn1—O11.9529 (7)C3—C41.3941 (13)
Zn1—N1i2.0177 (8)C3—C61.4693 (13)
Zn1—N12.0177 (8)C4—C51.3913 (13)
O1—C71.2837 (11)C4—H4A0.9500
O2—C71.2406 (13)C5—H5A0.9500
N1—C11.3444 (11)C6—C6ii1.3264 (19)
N1—C51.3475 (12)C6—H6A0.9500
C1—C21.3808 (13)C7—C81.4895 (13)
C1—H1A0.9500C8—C8iii1.316 (2)
C2—C31.4031 (14)C8—H8A0.9500
O1i—Zn1—O198.89 (4)C4—C3—C6118.63 (8)
O1i—Zn1—N1i109.93 (3)C2—C3—C6124.04 (8)
O1—Zn1—N1i113.14 (3)C5—C4—C3119.62 (9)
O1i—Zn1—N1113.14 (3)C5—C4—H4A120.2
O1—Zn1—N1109.93 (3)C3—C4—H4A120.2
N1i—Zn1—N1111.27 (5)N1—C5—C4122.39 (8)
C7—O1—Zn1112.06 (6)N1—C5—H5A118.8
C1—N1—C5118.22 (8)C4—C5—H5A118.8
C1—N1—Zn1120.35 (6)C6ii—C6—C3124.37 (12)
C5—N1—Zn1121.28 (6)C6ii—C6—H6A117.8
N1—C1—C2122.64 (9)C3—C6—H6A117.8
N1—C1—H1A118.7O2—C7—O1124.40 (8)
C2—C1—H1A118.7O2—C7—C8119.53 (8)
C1—C2—C3119.74 (9)O1—C7—C8116.06 (8)
C1—C2—H2A120.1C8iii—C8—C7124.20 (11)
C3—C2—H2A120.1C8iii—C8—H8A117.9
C4—C3—C2117.33 (8)C7—C8—H8A117.9
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x+1, −y, −z; (iii) −x−1/2, −y+1/2, −z.
Acknowledgements top

This research was supported by the China Pharmaceutical University (J—YX), the University of Texas–Pan American through a faculty research council award to BC, and in part by a Welch Foundation grant (BG-0017) to the Department of Chemistry.

references
References top

Bruker (2000). SHELXTL. Version 6.14. Bruker AXS Inc., Madison, Wisconsin, USA

Bruker (2004). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA

Chen, B., Liang, C., Yang, J., Contreras, D. S., Clancy, Y. L., Lobkovsky, E. B., Yaghi, O. M. & Dai, S. (2006). Angew. Chem. Int. Ed. 45, 1390–1393.

Chun, H., Dybtsev, D. N., Kim, H. & Kim, K. (2005). Chem. Eur. J. 11, 3521–3529.

Eddaoudi, M., Moler, D. B., Li, H., Chen, B., Reineke, T. M., O'Keeffe, M. & Yaghi, O. M. (2001). Acc. Chem. Res. 34, 319–330.

Janiak, C. (2003). Dalton Trans. pp. 2781–2804.

Kitagawa, S., Kitaura, R. & Noro, S. (2004). Angew. Chem. Int. Ed. 43, 2334–2375.

Ma, B.-Q., Mulfort, K. L. & Hupp, J. T. (2005). Inorg. Chem. 44, 4912–4914.

Rather, B. & Zaworotko, M. J. (2003). Chem. Commun. pp. 830–831.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sluis, P. van der & Spek, A. L. (1990). Acta Cryst. A46, 194–201.

Yaghi, O. M., O'Keeffe, M., Ockwig, N. W., Chae, H. K., Eddaoudi, M. & Kim, J. (2003). Nature (London), 423, 705–714.