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The title compound, [Zn(C14H8O6S)(H2O)2]n, is the first reported metal complex of the 4,4′-sulfonyl­dibenzoate anion. The structure comprises zigzag chains of alternating [Zn(H2O)2]2+ and sulfonyl­dibenzoate units, the central Zn and S atoms of which lie on crystallographic twofold axes. The ZnII centre occupies a strongly distorted tetra­hedral environment [O—Zn—O = 83.30 (7)–136.19 (8)°], coordinated by the two water O atoms [Zn—O = 1.986 (2) Å] and one O atom from each of two carboxyl­ate groups [Zn—O = 1.9942 (19) Å], with much longer contacts to the other O atoms of these carboxyl­ates [Zn—O = 2.528 (2) Å]. Hydrogen bonds between carboxyl­ate O atoms and coordinated water mol­ecules in adjacent chains lead to the formation of a three-dimensional network structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107008244/bm3026sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107008244/bm3026Isup2.hkl
Contains datablock I

CCDC reference: 652498

Comment top

In recent years, much attention has been focused on the design and synthesis of supramolecular complexes because of their novel structural architectures and potential applications in catalysis, magnetism, ion exchange and non-linear optics (Atwood et al., 1996; Barton et al., 1999; Lo et al., 2000). The basic strategy for the synthesis of such compounds involves connecting metal-containing building blocks with various multidentate ligands. As an important family of these multidentate ligands, organic aromatic polycarboxylate ligands such as 1,2-benzenedicarboxylate, 1,3,5-benzenetricarboxylate, 3,3',4,4'-benzophenonetetracarboxylate and 1,2,4,5-benzenetetracarboxylate have been extensively employed in the preparation of such metal–organic complexes. These products exhibit both high dimensionality in their structures and interesting properties (Chui et al., 1999; Li et al., 1999; Zhang et al., 2004). Similarly, the 4,4'-sulfonyldibenzoate anion (hereinafter DSDC) can act as a versatile ligand for the construction of novel metal–organic hybrid compounds, due to the presence of two carboxylate functions and its structural flexibility. However, to the best of our knowledge, no metal complexes with DSDC have been reported to date. Therefore, with the aim of exploring the coordination chemistry of DSDC, the title complex, (I), was obtained from the hydrothermal reaction of 4,4'-sulfonylbis(methyl benzoate) with zinc acetate and sodium hydroxide.

As shown in Fig. 1, the Zn centres in (I) are four-coordinate in a highly distorted tetrahedral environment involving two O-donors of two DSDC ligands and two coordinated water molecules. The ZnII centre occupies a strongly distorted tetrahedral environment [O—Zn—O = 83.30 (7)–136.19 (8)°], coordinated by the two water O atoms [Zn—O = 1.986 (2) Å] and one O atom from each of two carboxylate groups [Zn—O = 1.9942 (19) Å], with much longer contacts to the other O atoms of these carboxylates [Zn—O = 2.528 (2) Å]. The bonded distances are in agreement with values reported in other zinc carboxylate complexes (Monge et al., 2005; Wang et al., 2006; He et al., 2006). The DSDC group acts as a bidentate ligand in this structure, with both carboxylate groups each coordinating in an essentially monodentate manner to the ZnII centres.

The structure of (I) comprises strongly zigzag chains of alternating [Zn(H2O)2]2+ and sulfonyldibenzoate units, with their respective Zn and S atoms lying on crystallographic twofold axes. The zigzag nature of the chains, which run along the [101] direction (Fig. 2), can be traced to the O3—Zn1—O3 and C1—S1—S1 angles of 99.67 (12) and 104.04 (17)°, respectively. The two benzene ring planes in the each DSDC ligand are almost perpendicular, with a dihedral angle of 80.99 (7)°, imparting a slight twist to the chains. The carboxylate group is not coplanar with the aromatic ring to which it is attached but is twisted from the mean plane through the aromatic ring by 21.7(s.u.?)°.

As illustrated in Figs. 2 and 3, a major structural feature of (I) is the connection of adjacent zigzag chains via O—H···O hydrogen bonds. The water H atoms participate in hydrogen bonds with different carboxylate O atoms as acceptors, O1W—H1···O3 and O1W—H2···O2, to form a three-dimensional framework (Fig. 3). [From the Co-Editor: Please replace or merge Figs. 2 and 3 because of changes to the text.]

Related literature top

For related literature, see: Atwood et al. (1996); Barton et al. (1999); Chui et al. (1999); He et al. (2006); Li et al. (1999); Lo et al. (2000); Monge et al. (2005); Wang et al. (2006); Zhang et al. (2004).

Experimental top

Zn(CH3CO2)2·2H2O (0.111 g, 0.5 mmol), 4,4'-sulfonylbis(methyl benzoate) (0.168 g, 0.5 mmol) and NaOH (0.039 g, 1 mmol) in a 1:1:2 molar ratio, with water (15 ml), were placed in a 25 ml Teflon-lined stainless steel reactor and heated to 453 K for 76 h. When the reactor was cooled to room temperature over a period of 3 d, colourless prismatic [From the Co-Editor: Please specify the type of prism] single crystals of (I) suitable for X-ray diffraction were obtained.

Refinement top

All H atoms were placed in calculated positions [From the Co-Editor: Not possible for water H atoms - please clarify] and refined with isotropic displacement parameters, using a riding model. [From the Co-Editor: Not possible for water H atoms - please clarify.]

From the Co-Editor: Please explain why the two O—H distances are so different. Please also supply details of O—H and C—H distances and Uiso(H) restraints used.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT and SHELXTL (Siemens, 1995); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are plotted at the 30% probability level. [Symmetry codes: (a) -1 - x, y, -3/2 - z; (b) -x, y, -1/2 - z; (c) 1 + x, y, 1 + z.]
[Figure 2] Fig. 2. A view of (I), showing how the chains are linked by hydrogen bonding into a three-dimensional network. Hydrogen bonds are depicted as dashed lines.
[Figure 3] Fig. 3. The network structure of (I), as seen from an alternative viewpoint. Hydrogen bonds are depicted as dashed lines.
catena-Poly[[diaquazinc(II)]-µ-4,4'-sulfonyldibenzoato-κ2O:O'] top
Crystal data top
[Zn(C14H8O6S)(H2O)2]F(000) = 412
Mr = 405.70Dx = 1.851 Mg m3
Monoclinic, P2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ycCell parameters from 310 reflections
a = 13.307 (2) Åθ = 3.4–27.5°
b = 5.0336 (5) ŵ = 1.87 mm1
c = 12.1142 (18) ÅT = 293 K
β = 116.218 (5)°Prism, colourless
V = 727.95 (17) Å30.30 × 0.10 × 0.03 mm
Z = 2
Data collection top
Bruker P4
diffractometer
1668 independent reflections
Radiation source: fine-focus sealed tube1454 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ω scansθmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1617
Tmin = 0.799, Tmax = 0.945k = 66
5356 measured reflectionsl = 1515
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0449P)2 + 0.496P]
where P = (Fo2 + 2Fc2)/3
1668 reflections(Δ/σ)max = 0.002
110 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.43 e Å3
Crystal data top
[Zn(C14H8O6S)(H2O)2]V = 727.95 (17) Å3
Mr = 405.70Z = 2
Monoclinic, P2/cMo Kα radiation
a = 13.307 (2) ŵ = 1.87 mm1
b = 5.0336 (5) ÅT = 293 K
c = 12.1142 (18) Å0.30 × 0.10 × 0.03 mm
β = 116.218 (5)°
Data collection top
Bruker P4
diffractometer
1668 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1454 reflections with I > 2σ(I)
Tmin = 0.799, Tmax = 0.945Rint = 0.034
5356 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.090H-atom parameters constrained
S = 1.02Δρmax = 0.35 e Å3
1668 reflectionsΔρmin = 0.43 e Å3
110 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.50000.06544 (8)0.25000.02921 (16)
S11.00001.11920 (17)0.75000.0245 (2)
O10.95911 (16)1.2624 (4)0.82475 (17)0.0333 (5)
O1W0.43397 (19)0.2093 (4)0.31598 (18)0.0404 (5)
H10.44310.16680.38510.048*
H20.41240.36010.27090.048*
O20.57593 (17)0.2490 (4)0.46605 (18)0.0369 (5)
O30.62737 (16)0.3210 (4)0.32013 (16)0.0315 (4)
C10.8918 (2)0.9027 (5)0.6537 (2)0.0246 (5)
C20.8021 (2)0.8548 (6)0.6798 (2)0.0297 (6)
H2A0.79750.93840.74580.036*
C30.7191 (2)0.6793 (6)0.6053 (2)0.0305 (6)
H3A0.65830.64470.62160.037*
C40.7264 (2)0.5561 (5)0.5072 (2)0.0249 (5)
C50.8155 (2)0.6106 (6)0.4804 (2)0.0310 (6)
H5A0.81910.53170.41280.037*
C60.8991 (2)0.7828 (6)0.5548 (2)0.0307 (6)
H6A0.95970.81780.53840.037*
C70.6383 (2)0.3636 (5)0.4294 (2)0.0268 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0281 (3)0.0200 (2)0.0372 (3)0.0000.0123 (2)0.000
S10.0232 (5)0.0219 (4)0.0243 (4)0.0000.0069 (4)0.000
O10.0320 (10)0.0287 (10)0.0365 (10)0.0021 (8)0.0128 (9)0.0074 (8)
O1W0.0640 (15)0.0269 (10)0.0353 (11)0.0108 (10)0.0266 (11)0.0061 (8)
O20.0371 (11)0.0358 (11)0.0342 (11)0.0115 (9)0.0124 (9)0.0005 (9)
O30.0330 (11)0.0312 (10)0.0270 (10)0.0038 (8)0.0102 (9)0.0073 (8)
C10.0249 (13)0.0226 (12)0.0225 (12)0.0002 (10)0.0070 (11)0.0003 (10)
C20.0323 (15)0.0319 (14)0.0276 (13)0.0043 (12)0.0158 (12)0.0078 (11)
C30.0290 (14)0.0343 (14)0.0316 (14)0.0069 (12)0.0166 (12)0.0055 (11)
C40.0257 (13)0.0216 (12)0.0234 (12)0.0002 (10)0.0071 (11)0.0004 (10)
C50.0329 (15)0.0348 (15)0.0264 (14)0.0041 (12)0.0141 (12)0.0065 (11)
C60.0294 (14)0.0363 (15)0.0291 (13)0.0060 (12)0.0154 (12)0.0043 (11)
C70.0266 (14)0.0221 (12)0.0246 (13)0.0046 (10)0.0049 (11)0.0019 (10)
Geometric parameters (Å, º) top
Zn1—O1Wi1.986 (2)O2—C71.243 (3)
Zn1—O1W1.986 (2)O3—C71.284 (3)
Zn1—O31.9942 (19)C1—C61.382 (4)
Zn1—O3i1.9942 (19)C1—C21.384 (4)
Zn1—O22.528 (2)C2—C31.391 (4)
Zn1—O2i2.528 (2)C2—H2A0.9300
Zn1—C72.613 (3)C3—C41.382 (4)
Zn1—C7i2.613 (3)C3—H3A0.9300
S1—O1ii1.4391 (19)C4—C51.388 (4)
S1—O11.4391 (19)C4—C71.492 (4)
S1—C11.771 (3)C5—C61.384 (4)
S1—C1ii1.771 (3)C5—H5A0.9300
O1W—H10.8199C6—H6A0.9300
O1W—H20.9045
O1Wi—Zn1—O1W91.73 (12)O1—S1—C1ii108.49 (11)
O1Wi—Zn1—O3100.18 (9)C1—S1—C1ii104.04 (17)
O1W—Zn1—O3136.19 (8)Zn1—O1W—H1109.7
O1Wi—Zn1—O3i136.19 (8)Zn1—O1W—H2114.8
O1W—Zn1—O3i100.18 (9)H1—O1W—H2134.4
O3—Zn1—O3i99.67 (11)C7—O2—Zn179.87 (15)
O1Wi—Zn1—O2128.74 (8)C7—O3—Zn1103.57 (17)
O1W—Zn1—O283.30 (7)C6—C1—C2121.3 (2)
O3—Zn1—O256.45 (7)C6—C1—S1119.5 (2)
O3i—Zn1—O294.65 (7)C2—C1—S1119.28 (19)
O1Wi—Zn1—O2i83.30 (7)C1—C2—C3118.8 (2)
O1W—Zn1—O2i128.74 (8)C1—C2—H2A120.6
O3—Zn1—O2i94.65 (7)C3—C2—H2A120.6
O3i—Zn1—O2i56.45 (7)C4—C3—C2120.3 (3)
O2—Zn1—O2i137.11 (9)C4—C3—H3A119.8
O1Wi—Zn1—C7117.42 (9)C2—C3—H3A119.8
O1W—Zn1—C7109.85 (8)C3—C4—C5120.3 (2)
O3—Zn1—C728.54 (8)C3—C4—C7120.0 (2)
O3i—Zn1—C797.91 (8)C5—C4—C7119.7 (2)
O2—Zn1—C727.91 (7)C6—C5—C4119.7 (2)
O2i—Zn1—C7117.62 (8)C6—C5—H5A120.2
O1Wi—Zn1—C7i109.85 (8)C4—C5—H5A120.2
O1W—Zn1—C7i117.42 (9)C5—C6—C1119.6 (3)
O3—Zn1—C7i97.91 (8)C5—C6—H6A120.2
O3i—Zn1—C7i28.54 (8)C1—C6—H6A120.2
O2—Zn1—C7i117.62 (8)O2—C7—O3120.1 (2)
O2i—Zn1—C7i27.91 (7)O2—C7—C4122.6 (2)
C7—Zn1—C7i109.89 (11)O3—C7—C4117.3 (2)
O1ii—S1—O1119.88 (17)O2—C7—Zn172.22 (15)
O1ii—S1—C1108.49 (11)O3—C7—Zn147.89 (13)
O1—S1—C1107.42 (12)C4—C7—Zn1165.2 (2)
O1ii—S1—C1ii107.42 (11)
Symmetry codes: (i) x+1, y, z+1/2; (ii) x+2, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1···O2iii0.821.972.709 (3)149
O1W—H2···O3iv0.901.892.790 (3)178
Symmetry codes: (iii) x+1, y, z+1; (iv) x+1, y1, z+1/2.

Experimental details

Crystal data
Chemical formula[Zn(C14H8O6S)(H2O)2]
Mr405.70
Crystal system, space groupMonoclinic, P2/c
Temperature (K)293
a, b, c (Å)13.307 (2), 5.0336 (5), 12.1142 (18)
β (°) 116.218 (5)
V3)727.95 (17)
Z2
Radiation typeMo Kα
µ (mm1)1.87
Crystal size (mm)0.30 × 0.10 × 0.03
Data collection
DiffractometerBruker P4
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.799, 0.945
No. of measured, independent and
observed [I > 2σ(I)] reflections
5356, 1668, 1454
Rint0.034
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.090, 1.02
No. of reflections1668
No. of parameters110
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.35, 0.43

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SAINT and SHELXTL (Siemens, 1995), SHELXTL.

Selected geometric parameters (Å, º) top
Zn1—O1W1.986 (2)Zn1—O22.528 (2)
Zn1—O31.9942 (19)
O1Wi—Zn1—O1W91.73 (12)O3—Zn1—O3i99.67 (11)
O1Wi—Zn1—O3100.18 (9)O1Wi—Zn1—O2128.74 (8)
O1W—Zn1—O3136.19 (8)O1W—Zn1—O283.30 (7)
O1Wi—Zn1—O3i136.19 (8)O3—Zn1—O256.45 (7)
O1W—Zn1—O3i100.18 (9)
Symmetry code: (i) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1···O2ii0.821.972.709 (3)149.1
O1W—H2···O3iii0.901.892.790 (3)178.0
Symmetry codes: (ii) x+1, y, z+1; (iii) x+1, y1, z+1/2.
 

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