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Acta Cryst. (2009). E65, m360    [ doi:10.1107/S1600536809006965 ]

catena-Poly[[diaquazinc(II)]-[mu]-4,4'-(methylenedioxy)dibenzoato]

L. Xu, Y. Guo and X. Yuan

Abstract top

In the title complex, [Zn(C15H10O6)(H2O)2]n, the ZnII atom is located on a twofold rotation axis and exhibits a distorted tetrahedral coordination environment defined by two O atoms from two 4,4'-(methylenedioxy)dibenzoate ligands and two O atoms from two coordinated water molecules. In the crystal structure, molecules are linked into a three-dimensional framework by O-H...O hydrogen bonds and C-H...[pi] interactions.

Comment top

Recently, the area of metal-organic framework materials has become one of the intense research activity for their fascinating structural diversities and potential applications in catalysis, nonlinear optics and molecular sensing. As an important family of multidentate O-donor ligands, organic aromatic polycarboxylate ligands have been extensively employed in the preparation of metal-organic complexes because of their potential properties and intriguing structural topologies (Han et al., 2009; Li et al., 2007; Chen et al., 2002). Herein, we report the structure of the title complex with bis(4-benzoateoxyl)methane and zinc, [Zn(C15H10O6)(H2O)2] (I).

Single-crystal X-ray diffraction analyses revealed Zn(II) is tetra-coordinated and exhibits tetrahedral coordination environment supplied by two bis(4-benzoateoxyl)methane O atoms and two water molecules (Fig. 1). The Zn—O bond lengthes are in the normal range (Table 1). The bis(4-benzoateoxyl)methane ligand adopts bidentate coordinated modes and bond with two zinc ions to form a chain. Adjacent chains are linked by O—H···O hydrogen bonds and C—H···π interactions into a three-dimensional supramolecular network structure (Fig. 2, Table 2).

Related literature top

For the potential properties and structural topologies of metal-organic complexes involving polycarboxylate ligands, see: Chen & Liu (2002); Han et al. (2009); Li et al. (2007). Cg3 is the centroid of the C2–C7 benzene ring.

Experimental top

Zinc(II) acetate dihydrate (0.066 g, 0.3 mol), bis(4-benzoateoxyl)methane (0.058 g, 0.2 mmol), sodium hydroxide (0.016 g, 0.4 mmol) and water (14 ml) were placed in a 23 ml Teflon-lined autoclave, and the autoclave was heated at 423 K for 3 d. After cooling slowly to room temperature at a rate of 10 K h-1, colourless crystals of (I) were obtained.

Refinement top

C-bound H atoms were treated as riding, with C—H = 0.93 and 0.97Å and Uiso(H) = 1.2 times Ueq(C). O-bound H atoms were located in a difference Fourier map and refined as riding in their as-found relative positions; Uiso(H) = 1.5Ueq(O).

Computing details top

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

Figures top
[Figure 1] Fig. 1. View of the local coordination of Zn(II) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A packing diagram for the three-dimensional supramolecular framework via O—H···O interactions. The view direction is parallel to the a axis. Hydrogen bonds are indicated by dashed lines.
catena-Poly[[diaquazinc(II)]-µ-4,4'-(methylenedioxy)dibenzoato] top
Crystal data top
[Zn(C15H10O6)(H2O)2]F(000) = 396
Mr = 387.63Dx = 1.705 Mg m−3
Monoclinic, P2/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ycCell parameters from 3185 reflections
a = 13.496 (1) Åθ = 2.1–27.4°
b = 4.931 (1) ŵ = 1.67 mm−1
c = 12.357 (1) ÅT = 293 K
β = 113.352 (1)°Block, colourless
V = 755.0 (2) Å30.21 × 0.19 × 0.15 mm
Z = 2
Data collection top
Rigaku R-AXIS RAPID
diffractometer		1696 independent reflections
Radiation source: fine-focus sealed tube1461 reflections with I > 2σ(I)
graphiteRint = 0.027
Detector resolution: 10 pixels mm-1θmax = 27.5°, θmin = 3.3°
ω scansh = −10→17
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −6→5
Tmin = 0.707, Tmax = 0.780l = −15→15
4318 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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0304P)2 + 0.2993P]
where P = (Fo2 + 2Fc2)/3
1696 reflections(Δ/σ)max < 0.001
118 parametersΔρmax = 0.25 e Å−3
0 restraintsΔρmin = −0.30 e Å−3
Crystal data top
[Zn(C15H10O6)(H2O)2]V = 755.0 (2) Å3
Mr = 387.63Z = 2
Monoclinic, P2/cMo Kα radiation
a = 13.496 (1) ŵ = 1.67 mm−1
b = 4.931 (1) ÅT = 293 K
c = 12.357 (1) Å0.21 × 0.19 × 0.15 mm
β = 113.352 (1)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		1696 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		1461 reflections with I > 2σ(I)
Tmin = 0.707, Tmax = 0.780Rint = 0.027
4318 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.075Δρmax = 0.25 e Å−3
S = 1.06Δρmin = −0.30 e Å−3
1696 reflectionsAbsolute structure: ?
118 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 > 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*/UeqOcc. (<1)
Zn10.00000.02532 (7)0.25000.03611 (14)
O30.48509 (13)1.0388 (3)0.65056 (14)0.0430 (4)
O40.06484 (17)−0.2446 (4)0.17945 (17)0.0484 (5)
O20.07014 (13)0.2515 (3)0.46679 (14)0.0420 (4)
O10.12200 (13)0.2746 (3)0.31887 (13)0.0406 (4)
C50.39531 (18)0.8759 (5)0.60267 (19)0.0351 (5)
C70.22564 (18)0.6856 (4)0.58165 (19)0.0356 (5)
H70.16850.67540.60550.043*
C10.13275 (18)0.3401 (4)0.42419 (18)0.0331 (5)
C80.50001.1980 (7)0.75000.0451 (8)
H8A0.43751.31380.73300.054*0.50
H8B0.56251.31380.76700.054*0.50
C20.22362 (18)0.5269 (4)0.48823 (19)0.0328 (5)
C60.31099 (19)0.8591 (5)0.6403 (2)0.0379 (5)
H60.31190.96240.70370.046*
C30.3096 (2)0.5481 (5)0.4528 (2)0.0434 (6)
H30.30920.44530.38960.052*
C40.3942 (2)0.7180 (5)0.5100 (2)0.0447 (6)
H40.45150.72730.48630.054*
H20.069 (3)−0.244 (7)0.110 (3)0.100 (13)*
H10.085 (2)−0.374 (6)0.210 (2)0.046 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0455 (2)0.0276 (2)0.0380 (2)0.0000.01943 (18)0.000
O30.0416 (9)0.0491 (10)0.0364 (9)−0.0115 (8)0.0132 (7)0.0005 (7)
O40.0832 (14)0.0311 (10)0.0397 (10)0.0128 (9)0.0338 (10)0.0040 (8)
O20.0471 (9)0.0448 (9)0.0359 (9)−0.0096 (8)0.0183 (7)0.0003 (7)
O10.0538 (10)0.0371 (9)0.0338 (9)−0.0057 (8)0.0205 (8)−0.0074 (7)
C50.0361 (12)0.0332 (11)0.0337 (12)−0.0026 (10)0.0114 (10)0.0052 (10)
C70.0367 (12)0.0370 (12)0.0370 (12)−0.0021 (10)0.0189 (10)−0.0009 (10)
C10.0404 (12)0.0269 (10)0.0293 (11)0.0039 (9)0.0110 (10)0.0010 (9)
C80.045 (2)0.0317 (17)0.051 (2)0.0000.0109 (16)0.000
C20.0379 (12)0.0304 (11)0.0301 (11)−0.0009 (9)0.0135 (9)0.0015 (9)
C60.0445 (13)0.0378 (12)0.0338 (12)−0.0033 (10)0.0179 (11)−0.0055 (10)
C30.0488 (14)0.0483 (14)0.0398 (13)−0.0055 (12)0.0246 (12)−0.0078 (11)
C40.0447 (14)0.0506 (14)0.0483 (14)−0.0037 (12)0.0285 (12)−0.0033 (12)
Geometric parameters (Å, °) top
Zn1—O11.9582 (18)C7—C21.386 (3)
Zn1—O1i1.9582 (18)C7—C61.387 (3)
Zn1—O41.975 (2)C7—H70.9300
Zn1—O4i1.975 (2)C1—C21.487 (3)
O3—C51.377 (3)C8—O3ii1.404 (2)
O3—C81.404 (2)C8—H8A0.9700
O4—H20.88 (4)C8—H8B0.9700
O4—H10.74 (3)C2—C31.396 (3)
O2—C11.239 (3)C6—H60.9300
O1—C11.292 (3)C3—C41.366 (3)
C5—C41.380 (3)C3—H30.9300
C5—C61.392 (3)C4—H40.9300
O1—Zn1—O1i102.26 (11)O1—C1—C2115.52 (19)
O1—Zn1—O499.87 (9)O3—C8—O3ii112.0 (3)
O1i—Zn1—O4132.40 (8)O3—C8—H8A109.2
O1—Zn1—O4i132.40 (8)O3ii—C8—H8A109.2
O1i—Zn1—O4i99.87 (9)O3—C8—H8B109.2
O4—Zn1—O4i95.27 (13)O3ii—C8—H8B109.2
C5—O3—C8119.93 (16)H8A—C8—H8B107.9
Zn1—O4—H2130 (2)C7—C2—C3118.3 (2)
Zn1—O4—H1119 (2)C7—C2—C1122.2 (2)
H2—O4—H1111 (3)C3—C2—C1119.5 (2)
C1—O1—Zn1109.52 (14)C7—C6—C5118.8 (2)
O3—C5—C4113.8 (2)C7—C6—H6120.6
O3—C5—C6126.0 (2)C5—C6—H6120.6
C4—C5—C6120.2 (2)C4—C3—C2120.8 (2)
C2—C7—C6121.5 (2)C4—C3—H3119.6
C2—C7—H7119.3C2—C3—H3119.6
C6—C7—H7119.3C3—C4—C5120.4 (2)
O2—C1—O1121.1 (2)C3—C4—H4119.8
O2—C1—C2123.4 (2)C5—C4—H4119.8
O1i—Zn1—O1—C186.84 (14)O1—C1—C2—C7158.0 (2)
O4—Zn1—O1—C1−135.58 (15)O2—C1—C2—C3159.3 (2)
O4i—Zn1—O1—C1−29.01 (18)O1—C1—C2—C3−21.1 (3)
C8—O3—C5—C4−176.2 (2)C2—C7—C6—C51.0 (3)
C8—O3—C5—C63.1 (3)O3—C5—C6—C7179.5 (2)
Zn1—O1—C1—O2−1.0 (3)C4—C5—C6—C7−1.2 (3)
Zn1—O1—C1—C2179.28 (14)C7—C2—C3—C40.9 (4)
C5—O3—C8—O3ii64.94 (16)C1—C2—C3—C4−180.0 (2)
C6—C7—C2—C3−0.9 (3)C2—C3—C4—C5−1.2 (4)
C6—C7—C2—C1−179.9 (2)O3—C5—C4—C3−179.3 (2)
O2—C1—C2—C7−21.7 (3)C6—C5—C4—C31.3 (4)
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x+1, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H1···O1iii0.74 (3)2.13 (3)2.851 (3)167 (3)
O4—H2···O2iv0.88 (4)1.78 (4)2.657 (3)177 (4)
C8—H8A···Cg3v0.972.973.741 (3)137
C8—H8B···Cg3vi0.972.973.741 (3)137
Symmetry codes: (iii) x, y−1, z; (iv) x, −y, z−1/2; (v) x, y+1, z; (vi) −x+1, y+1, −z+3/2.
Table 1
Selected geometric parameters (Å, °) top
Zn1—O11.9582 (18)Zn1—O41.975 (2)
O1—Zn1—O1i102.26 (11)O1i—Zn1—O4132.40 (8)
O1—Zn1—O499.87 (9)O4—Zn1—O4i95.27 (13)
Symmetry codes: (i) −x, y, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H1···O1ii0.74 (3)2.13 (3)2.851 (3)167 (3)
O4—H2···O2iii0.88 (4)1.78 (4)2.657 (3)177 (4)
C8—H8A···Cg3iv0.972.973.741 (3)137
C8—H8B···Cg3v0.972.973.741 (3)137
Symmetry codes: (ii) x, y−1, z; (iii) x, −y, z−1/2; (iv) x, y+1, z; (v) −x+1, y+1, −z+3/2.
Acknowledgements top

The authors thank the Key Project of the Chinese Ministry of Education (No. 308008) and the Analysis and Testing Foundation of Northeast Normal University for financial support.

references
References top

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Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.

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