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In the title complex, [Zn(C12H6O4)(H2O)]n, a ZnII polymer based on naphthalene-1,8-dicarboxyl­ate (1,8-nap), the ZnII atoms adopt an elongated octa­hedral coordination geometry. A zigzag chain is formed by μ2-aqua ligands and μ2-carboxyl­ate groups of the 1,8-nap ligands. Adjacent parallel chains are further linked by 1,8-nap ligands, forming a twisted two-dimensional layer structure along the (100) plane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107047130/bg3055sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107047130/bg3055Isup2.hkl
Contains datablock I

CCDC reference: 669159

Comment top

Considerable efforts are currently devoted to the use of suitable multidentate ligands as building blocks to design metal-organic coordination polymers not only because such ligands can construct intriguing structural topologies (Yaghi et al., 1998; Hagrman et al., 1999), but also because of their potential properties for eventual application as functional materials (Piguet et al., 1997; Park et al., 2001). Molecular self-assembly has emerged as an attractive approach to the fabrication of new materials, and in the construction of one-, two- or three-dimensional frameworks, multidentate ligands are usually used to bridge metal centers into polymetric structures (Li et al., 1999; Zheng et al., 2003; Wen et al., 2005). It is well known that naphthyl-containing aromatic multicarboxylate ligands are versatile building blocks able to modify the structure and properties of these polymers owing to their variety of bridging abilities. Some structural reports on transition metal complexes containing naphthalenecarboxylic acid, such as naphthalene-1,4,5,8- tetracarboxylic dianhydride (Xu et al., 2005), naphthalene-1,4,5,8,- tetracarboxylic acid (Wang et al., 2005; Chen et al., 2005) and 1,4-naphthalenedicarboxylic acid (Zheng et al., 2005), have been reported in the literature. In the present paper, we report a new two-dimensional Zn complex, [Zn(1,8-nap)(H2O)]n, (I) (1,8-nap is naphthalene-1,8-dicarboxylate), as part of one of our current lines of work focusing on the use of 1,8-naphthalenecarboxylic anhydride, hydrolyzed under hydrothermal conditions into the naphthalene-1,8-dicarboxylate ligand, as a starting material to prepare novel coordination polymers. To the best of our knowledge, (I) is the first ZnII polymer containing the 1,8-nap ligand.

The X-ray diffraction study shows that the asymmetric unit of (I) is composed of one Zn atom, one µ4-1,8-nap ligand and one coordinated water molecule. As shown in Fig. 1, the ZnII center is six-coordinated by four carboxylate O atoms of four 1,8-nap ligands and two water molecules, and displays a slightly distorted [ZnO6] octahedral coordination geometry, with the three trans angles [170.58 (5), 170.66 (5) and 174.41 (4)°] deviating slightly from the ideal value of 180°. The four carboxylate O atoms form the equatorial plane of the octahedron [the sum of the angles is 360.0 (2)°], from which the Zn1 atom deviates slightly, by 0.018 Å. Finally, the two water O atoms occupy the axial positions, with an O—Zn—O angle of 174.41 (4)°. The Zn—Ocarboxy [2.0483 (13)–2.0921 (13) Å] and Zn—Owater [2.1330 (12)° and 2.1547 (12)°] distances are comparable to those found in other ZnII complexes with similar coordination (Kongshaug & Fjellvag, 2002; Chun et al., 2005; Muthu et al., 2001). The carboxylate groups of the 1,8-nap ligand act as µ2-bridges to link two Zn atoms, and as a result, each 1,8-nap is coordinated by four Zn atoms. The ligands are not planar, with the carboxylate groups and the naphthalene rings subtending dihedral angles of 45.8 (1) and 45.4 (1)°, respectively.

The ZnII centers in (I) are linked via µ2-aqua and µ2-carboxylate groups to generate a one-dimensional linear chain propagating along the b axis, with a Zn···Zn separation of 3.529 (1) Å (Fig. 2a). In this chain, the [ZnO6] octahedra are corner-sharing via µ2-aqua ligands. As shown in Fig. 2(b), two 1,8-nap ligands bridge simultaneously two dinuclear Zn units from two adjacent chains, thus further combining parallel chains into two-dimensional layers parallel to the (100) plane (Fig. 2c). The naphthalene ring systems of the ligands are located on opposite sides of the layer, and the dihedral angles between naphthalene systems from different sides are 59.?? (1)°.

Related literature top

For related literature, see: Chen et al. (2005); Chun et al. (2005); Hagrman et al. (1999); Li et al. (1999); Muthu et al. (2001); Park et al. (2001); Piguet et al. (1997); Wang et al. (2005); Wen et al. (2005); Xu et al. (2005); Yaghi et al. (1998); Zheng et al. (2003, 2005).

Experimental top

A mixture of 1,8-naphthalenecarboxylic anhydride (0.1982 g, 1 mmol), ZnSO4·7H2O (0.2857 g, 1 mmol), Na2CO3(0.053 g, 0.5 mmol) and water–ethanol (1:1, 16 ml) was sealed in a 25 ml stainless-steel reactor with a Telflon liner and was heated at 433 K for 3 d. On completion of the reaction, the reactor was cooled slowly to room temperature and the mixture was filtered, giving colorless single crystals suitable for X-ray analysis in 30% yield. Elemental analysis found: C 48.84, H 2.36, O 27.12%; calcualted for C12H8O5Zn: H 2.39, C 48.82, O 27.11%. IR (KBr, cm−1): 3052.63 (s), 1771.44 (s), 1739.21(s), 1619.59 (sh), 1511.94 (s), 1454.43 (s), 1388.66 (s), 845.35 (s), 775.57 (sh), 632.97 (s).

Refinement top

C-bound H atoms were positioned geometrically and included in the refinement using a riding model [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)]. Water H atoms were located in difference maps and their positions were refined isotropically, with distance restraints O—H = 0.85 (2) Å and H···H = 1.30 (2) Å; their Uiso(H) values were set to 1.5Ueq(O).

Computing details top

Data collection: APEXII (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL (Bruker, 2002).

Figures top
[Figure 1] Fig. 1. The coordination environment of the ZnII atom in (I), showing the atom-numbering scheme. Displacement ellipsoids are plotted at the 30% probability level. Atoms labelled with the suffixes a to f are at the symmetry positions (x, 1/2 − y, −1/2 + z), (1 − x, −y, 2 − z),(1 − x, 1/2 + y, 3/2 − z), (1 − x, −1/2 + y, 3/2 − z), (x, 1/2 − y, 1/2 + z), (1 − x, 1 − y, 1 − z), respectively.
[Figure 2] Fig. 2. (a) A view of the chain substructure in (I); (b) two dinuclear Zn units from two adjacent chains are bridged by two 1,8-nap ligands; (c) a view of the layered structure of (I).
catena-Poly[[µ-aqua-dizinc(II)]-bis(µ4-naphthalene-1,8-dicarboxylato)] top
Crystal data top
[Zn(C12H6O4)(H2O)]F(000) = 600
Mr = 297.55Dx = 1.855 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3771 reflections
a = 15.693 (3) Åθ = 2.6–27.5°
b = 7.0491 (14) ŵ = 2.31 mm1
c = 9.752 (2) ÅT = 296 K
β = 98.97 (3)°Sheet, colorless
V = 1065.6 (4) Å30.19 × 0.15 × 0.05 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer
2427 independent reflections
Radiation source: fine-focus sealed tube2134 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ω scansθmax = 27.5°, θmin = 2.6°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 2020
Tmin = 0.67, Tmax = 0.89k = 99
9526 measured reflectionsl = 1212
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) = 0.061H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0324P)2 + 0.3204P]
where P = (Fo2 + 2Fc2)/3
2427 reflections(Δ/σ)max = 0.001
169 parametersΔρmax = 0.41 e Å3
3 restraintsΔρmin = 0.43 e Å3
Crystal data top
[Zn(C12H6O4)(H2O)]V = 1065.6 (4) Å3
Mr = 297.55Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.693 (3) ŵ = 2.31 mm1
b = 7.0491 (14) ÅT = 296 K
c = 9.752 (2) Å0.19 × 0.15 × 0.05 mm
β = 98.97 (3)°
Data collection top
Bruker APEXII area-detector
diffractometer
2427 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
2134 reflections with I > 2σ(I)
Tmin = 0.67, Tmax = 0.89Rint = 0.025
9526 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0243 restraints
wR(F2) = 0.061H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.41 e Å3
2427 reflectionsΔρmin = 0.43 e Å3
169 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.

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
Zn10.500473 (12)0.10066 (3)0.740690 (19)0.01488 (8)
O10.60470 (8)0.01324 (19)1.17533 (13)0.0208 (3)
O20.59277 (8)0.29719 (19)1.12717 (12)0.0198 (3)
O30.60664 (8)0.01144 (19)0.87537 (12)0.0206 (3)
O40.59344 (8)0.29812 (19)0.91846 (12)0.0199 (3)
O50.49977 (9)0.15646 (17)0.62521 (12)0.0162 (2)
H5A0.5419 (10)0.165 (3)0.587 (2)0.024*
H5B0.4572 (11)0.168 (3)0.560 (2)0.024*
C10.77386 (13)0.2970 (3)1.1946 (2)0.0296 (4)
H1A0.74460.39811.22700.036*
C20.86478 (14)0.2982 (4)1.2141 (3)0.0397 (6)
H2A0.89510.40031.25800.048*
C30.90778 (14)0.1501 (3)1.1687 (2)0.0358 (5)
H3A0.96780.14931.18560.043*
C40.86338 (12)0.0035 (3)1.0961 (2)0.0259 (4)
C50.77130 (11)0.0019 (3)1.07022 (17)0.0183 (4)
C60.72804 (12)0.1488 (3)1.12855 (19)0.0194 (4)
C70.63408 (11)0.1423 (2)1.14177 (17)0.0159 (3)
C80.90848 (14)0.1577 (3)1.0485 (2)0.0346 (5)
H8A0.96840.15901.06630.041*
C90.86620 (14)0.3033 (4)0.9776 (3)0.0384 (5)
H9A0.89690.40540.94980.046*
C100.77538 (13)0.3001 (3)0.9459 (2)0.0303 (5)
H10A0.74670.39980.89610.036*
C110.72874 (12)0.1520 (3)0.98756 (19)0.0192 (4)
C120.63531 (11)0.1445 (2)0.92458 (17)0.0159 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01674 (12)0.01272 (12)0.01520 (11)0.00009 (8)0.00258 (8)0.00013 (7)
O10.0197 (6)0.0202 (7)0.0241 (6)0.0017 (5)0.0083 (5)0.0006 (5)
O20.0195 (7)0.0195 (6)0.0209 (6)0.0033 (5)0.0046 (5)0.0011 (5)
O30.0199 (6)0.0200 (7)0.0203 (6)0.0014 (5)0.0017 (5)0.0011 (5)
O40.0204 (7)0.0195 (6)0.0193 (6)0.0039 (5)0.0014 (5)0.0021 (5)
O50.0186 (6)0.0150 (6)0.0153 (6)0.0002 (5)0.0034 (5)0.0013 (5)
C10.0232 (10)0.0275 (11)0.0382 (11)0.0033 (9)0.0048 (8)0.0111 (9)
C20.0228 (11)0.0407 (13)0.0543 (14)0.0110 (10)0.0013 (10)0.0179 (11)
C30.0145 (10)0.0470 (14)0.0443 (13)0.0055 (9)0.0002 (9)0.0086 (10)
C40.0170 (9)0.0331 (11)0.0270 (9)0.0003 (8)0.0015 (7)0.0019 (8)
C50.0149 (8)0.0207 (9)0.0187 (8)0.0001 (7)0.0012 (6)0.0021 (7)
C60.0172 (9)0.0215 (9)0.0194 (8)0.0012 (7)0.0030 (7)0.0007 (7)
C70.0163 (9)0.0207 (9)0.0106 (7)0.0003 (7)0.0021 (6)0.0027 (6)
C80.0154 (10)0.0454 (14)0.0423 (12)0.0065 (9)0.0026 (8)0.0053 (10)
C90.0240 (11)0.0392 (13)0.0513 (14)0.0127 (10)0.0033 (10)0.0128 (11)
C100.0243 (11)0.0272 (11)0.0383 (11)0.0042 (9)0.0016 (8)0.0096 (9)
C110.0168 (9)0.0206 (9)0.0197 (8)0.0002 (7)0.0016 (7)0.0012 (7)
C120.0169 (9)0.0197 (9)0.0114 (7)0.0007 (7)0.0030 (6)0.0022 (6)
Geometric parameters (Å, º) top
Zn1—O1i2.0483 (13)C2—H2A0.9300
Zn1—O32.0529 (13)C3—C41.417 (3)
Zn1—O2ii2.0837 (13)C3—H3A0.9300
Zn1—O4iii2.0921 (13)C4—C81.414 (3)
Zn1—O52.1330 (12)C4—C51.428 (2)
Zn1—O5iii2.1547 (12)C5—C61.426 (3)
O1—C71.252 (2)C5—C111.431 (2)
O2—C71.267 (2)C6—C71.501 (3)
O3—C121.254 (2)C8—C91.352 (3)
O4—C121.263 (2)C8—H8A0.9300
O5—H5A0.813 (15)C9—C101.411 (3)
O5—H5B0.851 (15)C9—H9A0.9300
C1—C61.370 (3)C10—C111.372 (3)
C1—C21.410 (3)C10—H10A0.9300
C1—H1A0.9300C11—C121.500 (2)
C2—C31.354 (3)
O1i—Zn1—O3106.03 (5)C2—C3—C4121.4 (2)
O1i—Zn1—O2ii170.58 (5)C2—C3—H3A119.3
O3—Zn1—O2ii83.33 (5)C4—C3—H3A119.3
O1i—Zn1—O4iii83.16 (5)C8—C4—C3121.30 (18)
O3—Zn1—O4iii170.66 (5)C8—C4—C5119.51 (18)
O2ii—Zn1—O4iii87.46 (5)C3—C4—C5119.19 (18)
O1i—Zn1—O590.99 (5)C6—C5—C4117.84 (16)
O3—Zn1—O590.82 (5)C6—C5—C11124.49 (16)
O2ii—Zn1—O587.71 (5)C4—C5—C11117.67 (17)
O4iii—Zn1—O587.31 (5)C1—C6—C5120.51 (18)
O1i—Zn1—O5iii85.33 (5)C1—C6—C7115.71 (17)
O3—Zn1—O5iii86.17 (5)C5—C6—C7123.12 (16)
O2ii—Zn1—O5iii96.60 (5)O1—C7—O2125.55 (16)
O4iii—Zn1—O5iii96.41 (5)O1—C7—C6117.14 (15)
O5—Zn1—O5iii174.41 (4)O2—C7—C6117.13 (15)
C7—O1—Zn1i136.07 (12)C9—C8—C4121.4 (2)
C7—O2—Zn1iv128.62 (11)C9—C8—H8A119.3
C12—O3—Zn1136.07 (12)C4—C8—H8A119.3
C12—O4—Zn1v128.94 (11)C8—C9—C10119.9 (2)
Zn1—O5—Zn1v110.80 (6)C8—C9—H9A120.1
Zn1—O5—H5A111.6 (15)C10—C9—H9A120.1
Zn1v—O5—H5A107.7 (16)C11—C10—C9121.0 (2)
Zn1—O5—H5B114.6 (14)C11—C10—H10A119.5
Zn1v—O5—H5B107.4 (15)C9—C10—H10A119.5
H5A—O5—H5B104.4 (18)C10—C11—C5120.36 (17)
C6—C1—C2120.9 (2)C10—C11—C12116.00 (16)
C6—C1—H1A119.5C5—C11—C12123.04 (16)
C2—C1—H1A119.5O3—C12—O4125.46 (16)
C3—C2—C1119.8 (2)O3—C12—C11117.22 (15)
C3—C2—H2A120.1O4—C12—C11117.19 (15)
C1—C2—H2A120.1
O1i—Zn1—O3—C1258.13 (17)Zn1iv—O2—C7—O136.1 (2)
O2ii—Zn1—O3—C12120.73 (17)Zn1iv—O2—C7—C6138.90 (13)
O5—Zn1—O3—C1233.14 (17)C1—C6—C7—O1131.74 (18)
O5iii—Zn1—O3—C12142.15 (17)C5—C6—C7—O138.9 (2)
O1i—Zn1—O5—Zn1v52.77 (7)C1—C6—C7—O243.7 (2)
O3—Zn1—O5—Zn1v53.28 (7)C5—C6—C7—O2145.67 (17)
O2ii—Zn1—O5—Zn1v136.57 (7)C3—C4—C8—C9179.2 (2)
O4iii—Zn1—O5—Zn1v135.87 (7)C5—C4—C8—C90.6 (3)
C6—C1—C2—C30.9 (4)C4—C8—C9—C102.1 (4)
C1—C2—C3—C42.8 (4)C8—C9—C10—C110.8 (4)
C2—C3—C4—C8179.8 (2)C9—C10—C11—C53.1 (3)
C2—C3—C4—C50.0 (3)C9—C10—C11—C12168.3 (2)
C8—C4—C5—C6175.51 (19)C6—C5—C11—C10174.26 (18)
C3—C4—C5—C64.7 (3)C4—C5—C11—C105.7 (3)
C8—C4—C5—C114.4 (3)C6—C5—C11—C1215.0 (3)
C3—C4—C5—C11175.36 (19)C4—C5—C11—C12165.10 (17)
C2—C1—C6—C54.0 (3)Zn1—O3—C12—O413.4 (3)
C2—C1—C6—C7166.9 (2)Zn1—O3—C12—C11162.28 (12)
C4—C5—C6—C16.7 (3)Zn1v—O4—C12—O335.0 (3)
C11—C5—C6—C1173.39 (18)Zn1v—O4—C12—C11140.68 (13)
C4—C5—C6—C7163.57 (17)C10—C11—C12—O3131.44 (19)
C11—C5—C6—C716.4 (3)C5—C11—C12—O339.7 (2)
Zn1i—O1—C7—O215.3 (3)C10—C11—C12—O444.6 (2)
Zn1i—O1—C7—C6159.64 (12)C5—C11—C12—O4144.23 (17)
Symmetry codes: (i) x+1, y, z+2; (ii) x, y+1/2, z1/2; (iii) x+1, y+1/2, z+3/2; (iv) x, y+1/2, z+1/2; (v) x+1, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O4vi0.81 (2)1.96 (2)2.6931 (19)151 (2)
O5—H5B···O2v0.85 (2)1.89 (2)2.6757 (19)153 (2)
Symmetry codes: (v) x+1, y1/2, z+3/2; (vi) x, y1/2, z1/2.

Experimental details

Crystal data
Chemical formula[Zn(C12H6O4)(H2O)]
Mr297.55
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)15.693 (3), 7.0491 (14), 9.752 (2)
β (°) 98.97 (3)
V3)1065.6 (4)
Z4
Radiation typeMo Kα
µ (mm1)2.31
Crystal size (mm)0.19 × 0.15 × 0.05
Data collection
DiffractometerBruker APEXII area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.67, 0.89
No. of measured, independent and
observed [I > 2σ(I)] reflections
9526, 2427, 2134
Rint0.025
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.061, 1.07
No. of reflections2427
No. of parameters169
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.41, 0.43

Computer programs: APEXII (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002).

Selected bond lengths (Å) top
Zn1—O1i2.0483 (13)Zn1—O4iii2.0921 (13)
Zn1—O32.0529 (13)Zn1—O52.1330 (12)
Zn1—O2ii2.0837 (13)Zn1—O5iii2.1547 (12)
Symmetry codes: (i) x+1, y, z+2; (ii) x, y+1/2, z1/2; (iii) x+1, y+1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O4iv0.813 (15)1.955 (18)2.6931 (19)151 (2)
O5—H5B···O2v0.851 (15)1.888 (17)2.6757 (19)153 (2)
Symmetry codes: (iv) x, y1/2, z1/2; (v) x+1, y1/2, z+3/2.
 

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