catena-Poly[[diaqua­zinc(II)]-μ-4,4′-(methyl­enedioxy)­dibenzoato]

In the title complex, [Zn(C₁₅H₁₀O₆)(H₂O)₂]_n, the Zn^II 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...π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.032
• wR factor = 0.075
• Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   293.000
            Value of melting point given =     0.000
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        100 Ang.

Alert level G
PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 =          4
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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.

S2. Experimental

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.

S3. Refinement

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

Computing details

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

	Fig. 1. View of the local coordination of Zn(II) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	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]

Crystal data

[Zn(C15H10O6)(H2O)2]	F(000) = 396
Mr = 387.63	Dx = 1.705 Mg m^−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yc	Cell parameters from 3185 reflections
a = 13.496 (1) Å	θ = 2.1–27.4°
b = 4.931 (1) Å	µ = 1.67 mm^−1
c = 12.357 (1) Å	T = 293 K
β = 113.352 (1)°	Block, colourless
V = 755.0 (2) Å^3	0.21 × 0.19 × 0.15 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer	1696 independent reflections
Radiation source: fine-focus sealed tube	1461 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 10 pixels mm^-1	θmax = 27.5°, θmin = 3.3°
ω scans	h = −10→17
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −6→5
Tmin = 0.707, Tmax = 0.780	l = −15→15
4318 measured reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0304P)^2 + 0.2993P] where P = (Fo^2 + 2Fc^2)/3
1696 reflections	(Δ/σ)max < 0.001
118 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.0000	0.02532 (7)	0.2500	0.03611 (14)
O3	0.48509 (13)	1.0388 (3)	0.65056 (14)	0.0430 (4)
O4	0.06484 (17)	−0.2446 (4)	0.17945 (17)	0.0484 (5)
O2	0.07014 (13)	0.2515 (3)	0.46679 (14)	0.0420 (4)
O1	0.12200 (13)	0.2746 (3)	0.31887 (13)	0.0406 (4)
C5	0.39531 (18)	0.8759 (5)	0.60267 (19)	0.0351 (5)
C7	0.22564 (18)	0.6856 (4)	0.58165 (19)	0.0356 (5)
H7	0.1685	0.6754	0.6055	0.043*
C1	0.13275 (18)	0.3401 (4)	0.42419 (18)	0.0331 (5)
C8	0.5000	1.1980 (7)	0.7500	0.0451 (8)
H8A	0.4375	1.3138	0.7330	0.054*	0.50
H8B	0.5625	1.3138	0.7670	0.054*	0.50
C2	0.22362 (18)	0.5269 (4)	0.48823 (19)	0.0328 (5)
C6	0.31099 (19)	0.8591 (5)	0.6403 (2)	0.0379 (5)
H6	0.3119	0.9624	0.7037	0.046*
C3	0.3096 (2)	0.5481 (5)	0.4528 (2)	0.0434 (6)
H3	0.3092	0.4453	0.3896	0.052*
C4	0.3942 (2)	0.7180 (5)	0.5100 (2)	0.0447 (6)
H4	0.4515	0.7273	0.4863	0.054*
H2	0.069 (3)	−0.244 (7)	0.110 (3)	0.100 (13)*
H1	0.085 (2)	−0.374 (6)	0.210 (2)	0.046 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0455 (2)	0.0276 (2)	0.0380 (2)	0.000	0.01943 (18)	0.000
O3	0.0416 (9)	0.0491 (10)	0.0364 (9)	−0.0115 (8)	0.0132 (7)	0.0005 (7)
O4	0.0832 (14)	0.0311 (10)	0.0397 (10)	0.0128 (9)	0.0338 (10)	0.0040 (8)
O2	0.0471 (9)	0.0448 (9)	0.0359 (9)	−0.0096 (8)	0.0183 (7)	0.0003 (7)
O1	0.0538 (10)	0.0371 (9)	0.0338 (9)	−0.0057 (8)	0.0205 (8)	−0.0074 (7)
C5	0.0361 (12)	0.0332 (11)	0.0337 (12)	−0.0026 (10)	0.0114 (10)	0.0052 (10)
C7	0.0367 (12)	0.0370 (12)	0.0370 (12)	−0.0021 (10)	0.0189 (10)	−0.0009 (10)
C1	0.0404 (12)	0.0269 (10)	0.0293 (11)	0.0039 (9)	0.0110 (10)	0.0010 (9)
C8	0.045 (2)	0.0317 (17)	0.051 (2)	0.000	0.0109 (16)	0.000
C2	0.0379 (12)	0.0304 (11)	0.0301 (11)	−0.0009 (9)	0.0135 (9)	0.0015 (9)
C6	0.0445 (13)	0.0378 (12)	0.0338 (12)	−0.0033 (10)	0.0179 (11)	−0.0055 (10)
C3	0.0488 (14)	0.0483 (14)	0.0398 (13)	−0.0055 (12)	0.0246 (12)	−0.0078 (11)
C4	0.0447 (14)	0.0506 (14)	0.0483 (14)	−0.0037 (12)	0.0285 (12)	−0.0033 (12)

Geometric parameters (Å, º)

Zn1—O1	1.9582 (18)	C7—C2	1.386 (3)
Zn1—O1^i	1.9582 (18)	C7—C6	1.387 (3)
Zn1—O4	1.975 (2)	C7—H7	0.9300
Zn1—O4^i	1.975 (2)	C1—C2	1.487 (3)
O3—C5	1.377 (3)	C8—O3^ii	1.404 (2)
O3—C8	1.404 (2)	C8—H8A	0.9700
O4—H2	0.88 (4)	C8—H8B	0.9700
O4—H1	0.74 (3)	C2—C3	1.396 (3)
O2—C1	1.239 (3)	C6—H6	0.9300
O1—C1	1.292 (3)	C3—C4	1.366 (3)
C5—C4	1.380 (3)	C3—H3	0.9300
C5—C6	1.392 (3)	C4—H4	0.9300
O1—Zn1—O1^i	102.26 (11)	O1—C1—C2	115.52 (19)
O1—Zn1—O4	99.87 (9)	O3—C8—O3^ii	112.0 (3)
O1^i—Zn1—O4	132.40 (8)	O3—C8—H8A	109.2
O1—Zn1—O4^i	132.40 (8)	O3^ii—C8—H8A	109.2
O1^i—Zn1—O4^i	99.87 (9)	O3—C8—H8B	109.2
O4—Zn1—O4^i	95.27 (13)	O3^ii—C8—H8B	109.2
C5—O3—C8	119.93 (16)	H8A—C8—H8B	107.9
Zn1—O4—H2	130 (2)	C7—C2—C3	118.3 (2)
Zn1—O4—H1	119 (2)	C7—C2—C1	122.2 (2)
H2—O4—H1	111 (3)	C3—C2—C1	119.5 (2)
C1—O1—Zn1	109.52 (14)	C7—C6—C5	118.8 (2)
O3—C5—C4	113.8 (2)	C7—C6—H6	120.6
O3—C5—C6	126.0 (2)	C5—C6—H6	120.6
C4—C5—C6	120.2 (2)	C4—C3—C2	120.8 (2)
C2—C7—C6	121.5 (2)	C4—C3—H3	119.6
C2—C7—H7	119.3	C2—C3—H3	119.6
C6—C7—H7	119.3	C3—C4—C5	120.4 (2)
O2—C1—O1	121.1 (2)	C3—C4—H4	119.8
O2—C1—C2	123.4 (2)	C5—C4—H4	119.8
O1^i—Zn1—O1—C1	86.84 (14)	O1—C1—C2—C7	158.0 (2)
O4—Zn1—O1—C1	−135.58 (15)	O2—C1—C2—C3	159.3 (2)
O4^i—Zn1—O1—C1	−29.01 (18)	O1—C1—C2—C3	−21.1 (3)
C8—O3—C5—C4	−176.2 (2)	C2—C7—C6—C5	1.0 (3)
C8—O3—C5—C6	3.1 (3)	O3—C5—C6—C7	179.5 (2)
Zn1—O1—C1—O2	−1.0 (3)	C4—C5—C6—C7	−1.2 (3)
Zn1—O1—C1—C2	179.28 (14)	C7—C2—C3—C4	0.9 (4)
C5—O3—C8—O3^ii	64.94 (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—C3	1.3 (4)

Symmetry codes: (i) −x, y, −z+1/2; (ii) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1···O1^iii	0.74 (3)	2.13 (3)	2.851 (3)	167 (3)
O4—H2···O2^iv	0.88 (4)	1.78 (4)	2.657 (3)	177 (4)
C8—H8A···Cg3^v	0.97	2.97	3.741 (3)	137
C8—H8B···Cg3^vi	0.97	2.97	3.741 (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.