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The novel title ZnII coordination polymer, poly[bis­([mu]-6-thioxo-1,6-dihydropyridine-3-carboxylato-[kappa]2S:O)zinc(II)], [Zn(C6H4NO2S)2]n, consists of two crystallographically independent zinc centers and two 6-mercaptonicotinate (Hmna-) ligands. Each ZnII atom is four-coordinated and lies at the center of a distorted tetra­hedral ZnS2O2 coordination polyhedron, bridged by four Hmna- ligands to form a two-dimensional (4,4)-network. Each Hmna- ion acts as a bridging bidentate ligand, coordinating to two ZnII atoms through the S atom and a carboxyl O atom. The metal centers reside on twofold rotation axes. The coordination mode of the S atoms and N-H...O hydrogen-bonding inter­actions between the protonated N atoms and the uncoordinated carboxyl O atoms give the extended structure a wavelike form.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107063962/sq3111sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107063962/sq3111Isup2.hkl
Contains datablock I

CCDC reference: 677207

Comment top

In recent years, research on coordination polymers has expanded rapidly because of their fascinating structural diversity and potential applications as functional materials (Batten & Robson, 1998; Moulton & Zaworotko, 2001). Multifunctional carboxylates and related species provide an effective means of designing novel hybrid materials with porous structures and other interesting properties (Kitagawa et al., 2004; Yaghi et al., 2003). In contrast with the large amount of work on ligands containing O or N donors, there have been fewer reports of studies based on organothiolate ligands. Three kinds of organothiolate ligands, viz. thiolatopyridine (Han et al., 2004; Su et al., 2000), thiolatocarboxylate (Cave et al., 2002) and thiolatopyridinecarboxylate (Humphrey et al., 2005, 2006) have been explored to construct structures with luminescent or magnetic properties. 6-Mercaptonicotinic acid (H2mna), which exists in solution as an equilibrium mixture of thiol and thione tautomeric forms, is an interesting ligand in the thiolatopyridinecarboxylate system because of its potential coordination possibilities, which include (a) an S,N-donor chelate and carboxyl uncoordinated mode (Nomiya et al., 2003), (b) an S,N-donor chelate and carboxyl multidentate mode (Humphrey et al., 2005, 2006), (c) an S,N-donor chelate and O,O-chelation bridging mode (Humphrey et al., 2005, 2006), (d) a single S-donor and carboxyl monodentate mode, and (e) an S,N-donor chelate and carboxyl monodentate mode. In addition, it can act not only as a hydrogen-bond donor but also as a hydrogen-bond acceptor, owing to the existence of deprotonated and/or protonated carboxyl groups and pyridine N atoms, as well as the thiol or thione group. These considerations prompted our interest in the structure patterns of the H2mna ligand. In this paper, we report the preparation and crystal structure of a novel two-dimensional coordination polymer, (I), formulated [Zn(Hmna)2]n.

The asymmetric unit of (I) consists of two zinc centers and two Hmna- ligands (Fig. 1). Each ZnII atom sits on a twofold rotation axis and is coordinated by two O atoms and two S atoms from four different Hmna- ligands in a typical distorted tetrahedral coordination geometry (Table 1). The bond lengths and angles involving Zn, O and S are similar to those in analogous zinc coordination polymers (Humphrey et al., 2004). The two Hmna- ligands in the asymmetric unit adopt the same coordination mode, i.e. the thione coordinates to the Zn atoms and the carboxyl group links the Zn atoms in a monodentate coordination fashion [mode (d) above]. To the best of our knowledge, (I) is the first example with this coordination mode (d) of the H2mna ligand. In the molecular structure, the C5—S1 and C11—S2 bond lengths [1.728 (3) and 1.723 (3) Å] are indicative of double bonds, similar to those in a number of structures reported previously (Chung et al., 2003; Lobana et al., 2005). The C5—S1—Zn1 and C11—S2—Zn2i [symmetry code: (i) -x + 1, -y + 1, -z + 1] bond angles are 100.44 (9) and 111.71 (9)°, respectively.

The molecules of (I) form an extended two-dimensional network involving coordination frameworks of (4,4)-topology (Fig. 2). In the grid, the adjacent Zn···Zn distances (linked by Hmna- ligands) are 10.015 and 9.618 Å, so each 4 × 4 unit is an approximate rhombus. Considering the ZnII atoms as three-connected nodes, the corrugated metal-organic framework can be represented as a two-dimensional distorted sheet of (4,4)-topology in the ac plane. These layers are then stacked on top of each other to give rise to the final structure (Fig. 3).

There are some significant hydrogen-bonding interactions between the protonated N atoms of the Hmna- ligands (owing to the thiol–thione tautomerism) and the uncoordinated carboxyl O atoms (Table 2). The coordination mode of the S atoms and the hydrogen-bonding interactions lead the complex to form a wavelike extended structure along the (010) plane (Fig. 3).

Related literature top

For related literature, see: Batten & Robson (1998); Cave et al. (2002); Han et al. (2004); Humphrey et al. (2004); Kitagawa et al. (2004); Moulton & Zaworotko (2001); Nomiya et al. (2003); Su et al. (2000); Yaghi et al. (2003).

Experimental top

A mixture of Zn(CH3COO)2·2H2O (0.0658 g), H2mna (0.0466 g), NaOH (0.012 g) and water (10 ml) was stirred for 20 min in air. The mixture was then transferred to a 23 ml Teflon reactor and kept at 438 K for 3 d under autogenous pressure, then cooled to room temperature at a rate of 5 K h-1. Colorless block-like crystals of (I) were obtained; they were washed with distilled water and dried at room temperature (yield ca 50% based on Zn). Elemental analysis found: C 38.64, H 2.10, N 7.62%; calculated: C 38.57, H 2.16, N 7.50%.

Refinement top

All H atoms were generated geometrically and included as riding atoms, with C—H = 0.93 Å, N—H = 0.86 Å and Uiso(H)= 1.2Ueq(C,N).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: program (reference)?.

Figures top
[Figure 1] Fig. 1. A view of the local coordination of ZnII, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 1, y, -z + 3/2; (iii) -x, y, -z + 1/2; (iv) x - 1, -y + 1, z - 1/2.]
[Figure 2] Fig. 2. The two-dimensional single-layer (4,4)-network in (I). The N—H···O hydrogen bonds are shown as dashed lines. H atoms bonded to C atoms have been omitted for clarity.
[Figure 3] Fig. 3. The view of the sine wave sheets in (I), along the (010) plane.
poly[bis(µ-6-mercaptonicotinato-κ2S:O)zinc(II)] top
Crystal data top
[Zn(C6H4NO2S)2]F(000) = 752
Mr = 373.69Dx = 1.828 Mg m3
Monoclinic, P2/cMo Kα radiation, λ = 0.71073 Å
a = 13.4079 (8) ÅCell parameters from 7030 reflections
b = 6.5765 (4) Åθ = 1.6–28.3°
c = 16.0390 (9) ŵ = 2.13 mm1
β = 106.283 (1)°T = 293 K
V = 1357.54 (14) Å3Block, colorless
Z = 40.23 × 0.19 × 0.14 mm
Data collection top
Bruker SMART APEXII CCD
diffractometer
3222 independent reflections
Radiation source: fine-focus sealed tube2531 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ϕ and ω scansθmax = 28.4°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 1517
Tmin = 0.640, Tmax = 0.755k = 78
8024 measured reflectionsl = 2120
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)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0499P)2]
where P = (Fo2 + 2Fc2)/3
3222 reflections(Δ/σ)max = 0.001
191 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
[Zn(C6H4NO2S)2]V = 1357.54 (14) Å3
Mr = 373.69Z = 4
Monoclinic, P2/cMo Kα radiation
a = 13.4079 (8) ŵ = 2.13 mm1
b = 6.5765 (4) ÅT = 293 K
c = 16.0390 (9) Å0.23 × 0.19 × 0.14 mm
β = 106.283 (1)°
Data collection top
Bruker SMART APEXII CCD
diffractometer
3222 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
2531 reflections with I > 2σ(I)
Tmin = 0.640, Tmax = 0.755Rint = 0.037
8024 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.094H-atom parameters constrained
S = 1.00Δρmax = 0.37 e Å3
3222 reflectionsΔρmin = 0.42 e Å3
191 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
Zn10.50000.34394 (6)0.75000.02530 (13)
Zn20.00000.21258 (6)0.25000.02685 (13)
S10.43938 (6)0.52761 (10)0.62292 (4)0.03456 (19)
S20.96122 (6)0.60438 (12)0.86184 (5)0.0372 (2)
O10.09182 (14)0.0180 (3)0.32820 (12)0.0341 (5)
O20.22106 (16)0.2440 (3)0.36875 (13)0.0369 (5)
O30.62239 (15)0.1658 (3)0.76481 (13)0.0344 (5)
O40.56008 (15)0.0335 (3)0.64862 (13)0.0381 (5)
N10.38953 (17)0.1566 (3)0.55170 (14)0.0265 (5)
H10.44910.11990.58470.032*
N20.79097 (16)0.4525 (3)0.74755 (14)0.0274 (5)
H20.79180.56320.71930.033*
C10.1796 (2)0.0782 (4)0.37571 (16)0.0274 (6)
C20.23661 (19)0.0677 (4)0.44346 (15)0.0236 (5)
C30.1986 (2)0.2630 (4)0.45163 (18)0.0302 (6)
H30.13230.29880.41840.036*
C40.2577 (2)0.4014 (4)0.50771 (17)0.0313 (6)
H40.23140.53050.51230.038*
C50.3580 (2)0.3503 (4)0.55854 (16)0.0264 (6)
C60.3333 (2)0.0187 (4)0.49645 (15)0.0261 (5)
H60.36000.11100.49400.031*
C70.6236 (2)0.0083 (4)0.71967 (17)0.0266 (6)
C80.7101 (2)0.1385 (4)0.75667 (17)0.0243 (5)
C90.7883 (2)0.0983 (4)0.83314 (17)0.0308 (6)
H90.78780.02360.86240.037*
C100.8657 (2)0.2366 (4)0.86529 (19)0.0328 (6)
H100.91730.20800.91620.039*
C110.8679 (2)0.4216 (4)0.82207 (16)0.0269 (6)
C120.7140 (2)0.3202 (4)0.71574 (17)0.0258 (6)
H120.66240.35180.66520.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0258 (2)0.0236 (2)0.0238 (2)0.0000.00250 (18)0.000
Zn20.0208 (2)0.0254 (2)0.0292 (2)0.0000.00152 (18)0.000
S10.0449 (4)0.0236 (4)0.0269 (3)0.0092 (3)0.0036 (3)0.0022 (3)
S20.0365 (4)0.0373 (4)0.0313 (4)0.0139 (3)0.0014 (3)0.0040 (3)
O10.0256 (10)0.0308 (10)0.0363 (10)0.0035 (8)0.0072 (8)0.0020 (9)
O20.0400 (12)0.0268 (10)0.0350 (11)0.0014 (9)0.0042 (9)0.0072 (9)
O30.0322 (11)0.0321 (11)0.0358 (11)0.0077 (8)0.0046 (9)0.0092 (9)
O40.0295 (10)0.0336 (11)0.0419 (11)0.0067 (9)0.0054 (9)0.0101 (9)
N10.0210 (11)0.0274 (12)0.0258 (11)0.0004 (9)0.0022 (9)0.0013 (9)
N20.0283 (12)0.0208 (11)0.0310 (11)0.0008 (9)0.0050 (10)0.0037 (9)
C10.0288 (14)0.0272 (14)0.0232 (12)0.0076 (11)0.0025 (11)0.0022 (11)
C20.0222 (12)0.0240 (13)0.0218 (12)0.0011 (10)0.0017 (10)0.0001 (10)
C30.0239 (14)0.0324 (15)0.0289 (14)0.0054 (11)0.0016 (11)0.0003 (12)
C40.0357 (15)0.0233 (13)0.0314 (14)0.0068 (12)0.0037 (12)0.0013 (12)
C50.0309 (14)0.0236 (13)0.0209 (12)0.0021 (11)0.0011 (11)0.0010 (10)
C60.0293 (13)0.0227 (13)0.0232 (12)0.0000 (11)0.0024 (11)0.0030 (11)
C70.0219 (13)0.0261 (14)0.0322 (14)0.0002 (10)0.0079 (11)0.0015 (11)
C80.0227 (13)0.0231 (13)0.0276 (13)0.0000 (10)0.0082 (11)0.0013 (11)
C90.0309 (15)0.0290 (14)0.0307 (14)0.0004 (11)0.0058 (12)0.0080 (12)
C100.0262 (14)0.0359 (16)0.0306 (14)0.0024 (12)0.0012 (12)0.0059 (12)
C110.0231 (13)0.0281 (14)0.0274 (13)0.0014 (11)0.0036 (11)0.0011 (11)
C120.0221 (13)0.0260 (14)0.0267 (13)0.0005 (10)0.0023 (11)0.0014 (11)
Geometric parameters (Å, º) top
Zn1—O31.9757 (19)N2—C111.357 (3)
Zn1—O3i1.9757 (19)N2—H20.8600
Zn1—S12.3119 (7)C1—C21.490 (3)
Zn1—S1i2.3119 (7)C2—C61.374 (3)
Zn2—O1ii1.9648 (18)C2—C31.401 (4)
Zn2—O11.9648 (18)C3—C41.366 (4)
Zn2—S2iii2.3367 (8)C3—H30.9300
Zn2—S2iv2.3367 (8)C4—C51.404 (4)
S1—C51.728 (3)C4—H40.9300
S2—C111.723 (3)C6—H60.9300
S2—Zn2iv2.3367 (8)C7—C81.497 (3)
O1—C11.273 (3)C8—C121.372 (3)
O2—C11.243 (3)C8—C91.398 (4)
O3—C71.266 (3)C9—C101.367 (4)
O4—C71.247 (3)C9—H90.9300
N1—C61.342 (3)C10—C111.404 (4)
N1—C51.356 (3)C10—H100.9300
N1—H10.8600C12—H120.9300
N2—C121.337 (3)
O3—Zn1—O3i107.26 (12)C4—C3—H3119.6
O3—Zn1—S1119.38 (6)C2—C3—H3119.6
O3i—Zn1—S197.41 (6)C3—C4—C5120.5 (2)
O3—Zn1—S1i97.41 (6)C3—C4—H4119.8
O3i—Zn1—S1i119.38 (6)C5—C4—H4119.8
S1—Zn1—S1i117.00 (4)N1—C5—C4116.6 (2)
O1ii—Zn2—O198.72 (11)N1—C5—S1121.6 (2)
O1ii—Zn2—S2iii126.23 (6)C4—C5—S1121.8 (2)
O1—Zn2—S2iii94.59 (6)N1—C6—C2120.5 (2)
O1ii—Zn2—S2iv94.59 (6)N1—C6—H6119.7
O1—Zn2—S2iv126.23 (6)C2—C6—H6119.7
S2iii—Zn2—S2iv117.98 (4)O4—C7—O3126.0 (2)
C5—S1—Zn1100.44 (9)O4—C7—C8118.3 (2)
C11—S2—Zn2iv111.71 (9)O3—C7—C8115.7 (2)
C1—O1—Zn2119.22 (17)C12—C8—C9117.7 (2)
C7—O3—Zn1124.05 (17)C12—C8—C7120.1 (2)
C6—N1—C5123.9 (2)C9—C8—C7122.2 (2)
C6—N1—H1118.0C10—C9—C8120.6 (2)
C5—N1—H1118.0C10—C9—H9119.7
C12—N2—C11123.6 (2)C8—C9—H9119.7
C12—N2—H2118.2C9—C10—C11120.6 (2)
C11—N2—H2118.2C9—C10—H10119.7
O2—C1—O1125.5 (2)C11—C10—H10119.7
O2—C1—C2118.7 (2)N2—C11—C10116.6 (2)
O1—C1—C2115.8 (2)N2—C11—S2121.0 (2)
C6—C2—C3117.5 (2)C10—C11—S2122.4 (2)
C6—C2—C1120.1 (2)N2—C12—C8120.9 (2)
C3—C2—C1122.2 (2)N2—C12—H12119.5
C4—C3—C2120.9 (2)C8—C12—H12119.5
O3—Zn1—S1—C586.43 (12)Zn1—S1—C5—C4134.3 (2)
O3i—Zn1—S1—C528.19 (12)C5—N1—C6—C21.4 (4)
S1i—Zn1—S1—C5156.63 (10)C3—C2—C6—N12.0 (4)
O1ii—Zn2—O1—C1161.8 (2)C1—C2—C6—N1173.4 (2)
S2iii—Zn2—O1—C170.4 (2)Zn1—O3—C7—O417.5 (4)
S2iv—Zn2—O1—C159.5 (2)Zn1—O3—C7—C8162.43 (17)
O3i—Zn1—O3—C743.26 (19)O4—C7—C8—C124.5 (4)
S1—Zn1—O3—C766.0 (2)O3—C7—C8—C12175.4 (2)
S1i—Zn1—O3—C7167.2 (2)O4—C7—C8—C9176.0 (3)
Zn2—O1—C1—O211.3 (4)O3—C7—C8—C94.1 (4)
Zn2—O1—C1—C2170.07 (16)C12—C8—C9—C100.0 (4)
O2—C1—C2—C60.4 (4)C7—C8—C9—C10179.6 (3)
O1—C1—C2—C6178.3 (2)C8—C9—C10—C110.0 (4)
O2—C1—C2—C3175.5 (3)C12—N2—C11—C101.7 (4)
O1—C1—C2—C33.2 (4)C12—N2—C11—S2176.9 (2)
C6—C2—C3—C42.7 (4)C9—C10—C11—N20.8 (4)
C1—C2—C3—C4172.6 (2)C9—C10—C11—S2177.8 (2)
C2—C3—C4—C50.1 (4)Zn2iv—S2—C11—N233.3 (2)
C6—N1—C5—C43.9 (4)Zn2iv—S2—C11—C10148.2 (2)
C6—N1—C5—S1173.3 (2)C11—N2—C12—C81.8 (4)
C3—C4—C5—N13.1 (4)C9—C8—C12—N20.9 (4)
C3—C4—C5—S1174.2 (2)C7—C8—C12—N2179.6 (2)
Zn1—S1—C5—N148.5 (2)
Symmetry codes: (i) x+1, y, z+3/2; (ii) x, y, z+1/2; (iii) x1, y+1, z1/2; (iv) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O40.861.852.686 (3)163
N2—H2···O2iv0.861.872.706 (3)164
Symmetry code: (iv) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Zn(C6H4NO2S)2]
Mr373.69
Crystal system, space groupMonoclinic, P2/c
Temperature (K)293
a, b, c (Å)13.4079 (8), 6.5765 (4), 16.0390 (9)
β (°) 106.283 (1)
V3)1357.54 (14)
Z4
Radiation typeMo Kα
µ (mm1)2.13
Crystal size (mm)0.23 × 0.19 × 0.14
Data collection
DiffractometerBruker SMART APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.640, 0.755
No. of measured, independent and
observed [I > 2σ(I)] reflections
8024, 3222, 2531
Rint0.037
(sin θ/λ)max1)0.670
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.094, 1.00
No. of reflections3222
No. of parameters191
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.37, 0.42

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990), program (reference)?.

Selected geometric parameters (Å, º) top
Zn1—O31.9757 (19)Zn2—O11.9648 (18)
Zn1—S12.3119 (7)Zn2—S2i2.3367 (8)
O3—Zn1—O3ii107.26 (12)O1iii—Zn2—O198.72 (11)
O3—Zn1—S1119.38 (6)O1—Zn2—S2iv94.59 (6)
O3ii—Zn1—S197.41 (6)O1—Zn2—S2i126.23 (6)
S1—Zn1—S1ii117.00 (4)S2iv—Zn2—S2i117.98 (4)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z+3/2; (iii) x, y, z+1/2; (iv) x1, y+1, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O40.861.852.686 (3)163.2
N2—H2···O2i0.861.872.706 (3)164.0
Symmetry code: (i) x+1, y+1, z+1.
 

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