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The crystal structure of the title compound, [Zn(C5H5NS)4](NO3)2, consists of a [Zn(C5H5NS)4]2+ (C5H5NS is pyridinium-2-thiol­ate) cation and two nitrate anions. The central ZnII atom lies at a site with imposed \overline 4 symmetry and is surrounded by four S atoms [Zn—S = 2.3371 (5) Å] from four symmetrical pyridinium-2-thiol­ate ligands in a distorted tetrahedral geometry. There are N—H...O hydrogen-bonding interactions between the pyridinium-2-thiol­ate ligands and nitrate O atoms. In addition, π–π interactions via aromatic N-containing ligands are discussed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104008042/na1653sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104008042/na1653Isup2.hkl
Contains datablock I

CCDC reference: 243571

Comment top

The pyridine-2-thiol [PySH, (I)] ligand gives rise to an extensive chemistry with structural diversity, since it can coordinate both in the `thiolate' and the tautomeric `thione' [(II)] forms. Some structural reports on transition metal complexes containing the PySH ligand have appeared in the literature, in which the PySH ligand binds in monodentate (Lobana et al., 1998), bidentate chelating (Block et al., 1991), bidentate bridging (Lobana et al., 1999) or doubly bridging modes (Hong et al., 1999). Here, we report the synthesis and structural characterization of the title compound, (III), a mononuclear zinc compound. \sch

The present X-ray single-crystal diffraction study reveals that the crystal structure of (III) contains a discrete [Zn(C5H5NS)4]2+ cation and two nitrate anions. As illustrated in Fig. 1, the Zn atom displays a distorted tetrahedral geometry, and each Zn atom is coordinated by four S atoms [Zn—S 2.3372 (5) Å] from pyridinium-2-thiolate ligands. The cations and anions are further linked by hydrogen bonding between pyridinium-2-thiolate ligands and nitrate O atoms.

Although the PySH ligand has two coordination sites, only the S atom bonds to the metal ion in (III). This Zn[S4] coordination in (III) is also of interest because it clearly demonstrates the preference for S coordination over N coordination, an observation that is in accord with the prevalence of tetrahedral Zn[S4] coordination in zinc enzymes (Vallee & Auld, 1993; Holm et al., 1996; Lipscomb & Sträter, 1996).

A most interesting structural feature of (III) is that it presents a regular motif along the c axis. As shown in Fig. 2, open `cavities' are constructed by the cations, and the nitrate anions proportionately occupy these cavities to form a carpet-like framework structure.

In addition, it is worth noting that there are relatively short distances [centroid separation 3.484 (2), interplanar spacing 3.359 (1) and centroid shift 0.92 (9) Å] between a pyridine-ring plane and the symmetry-related plane at (3/2 − x, 3/2 − y, 1/2 − z) in an adjacent cation, implying strong ππ interactions in (III). According to Janiak (2000), these ππ interactions should be assigned to an offset stacking. ππ stacking is an important motif in forming extended structures, from low-dimensional to multi-dimensional. In (III), ππ interactions and hydrogen-bonding interactions lead to the formation of a three-dimensional network structure.

Experimental top

A mixture of pyridine-2-carboxylic acid (0.062 g, 0.5 mmol) and Zn(NO3)2·6H2O (0.149 g, 0.5 mmol) was dissolved in a mixed solution of MeOH-H2O (3:2 v/v, 25 ml) and stirred at 333 K for 30 min. PySH (0.056 g, 0.5 mmol) was then added and the resulting mixture was stirred continuously for 1 h. Green prism crystals of (III) were obtained by slow evaporation of the solution at room temperature.

Refinement top

All H atoms were located theoretically, with C—H distances of 0.93 Å and an N—H distance of 0.86 Å, and treated as riding, with Uiso(H) = 1.2Ueq(C,N). Please check added text.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens,1994); data reduction: XPREP in SHELXTL (Siemens, 1994); 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. A view of the structure of (III), showing 30% probability displacement ellipsoids [symmetry codes: (a) 7/4 − y, x − 1/4, 1/4 − z; (b) 2 − x, 3/2 − y, z; (c) 1/4 + y, 7/4 − x, 1/4 − z; (d) x, 2 − y, 1/2 − z].
[Figure 2] Fig. 2. The crystal packing in (III), viewed along the c axis, showing the carpet-like structure. H atoms have been omitted for clarity. Zn atoms are shown as sky-blue spheres, S as yellow, C as off-white, N as dark blue and O as red.
Tetrakis(pyridinium-2-thiolato)zinc(II) dinitrate top
Crystal data top
[Zn(C5H5NS)4](NO3)2Dx = 1.669 Mg m3
Mr = 634.03Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/acdCell parameters from 6926 reflections
a = 18.534 (3) Åθ = 2.2–25.0°
c = 14.693 (4) ŵ = 1.35 mm1
V = 5047.2 (18) Å3T = 293 K
Z = 8Prism, green
F(000) = 25920.38 × 0.38 × 0.30 mm
Data collection top
Bruker P4
diffractometer
1112 independent reflections
Radiation source: fine-focus sealed tube1109 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 2219
Tmin = 0.629, Tmax = 0.666k = 1522
14775 measured reflectionsl = 1717
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)] = 0.020Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.055H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0319P)2 + 6.9441P]
where P = (Fo2 + 2Fc2)/3
1112 reflections(Δ/σ)max = 0.003
85 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
[Zn(C5H5NS)4](NO3)2Z = 8
Mr = 634.03Mo Kα radiation
Tetragonal, I41/acdµ = 1.35 mm1
a = 18.534 (3) ÅT = 293 K
c = 14.693 (4) Å0.38 × 0.38 × 0.30 mm
V = 5047.2 (18) Å3
Data collection top
Bruker P4
diffractometer
1112 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
1109 reflections with I > 2σ(I)
Tmin = 0.629, Tmax = 0.666Rint = 0.015
14775 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0200 restraints
wR(F2) = 0.055H-atom parameters constrained
S = 1.03Δρmax = 0.22 e Å3
1112 reflectionsΔρmin = 0.18 e Å3
85 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
Zn11.00000.75000.12500.01406 (13)
S10.93817 (2)0.841221 (18)0.20232 (3)0.01800 (13)
N10.81742 (7)0.84327 (6)0.29729 (8)0.0168 (3)
H1A0.81630.88740.27910.020*
N20.72374 (11)1.00000.25000.0243 (4)
C10.87340 (7)0.80120 (8)0.26986 (9)0.0146 (3)
C20.87332 (8)0.72961 (8)0.29978 (10)0.0187 (3)
H2A0.91060.69880.28280.022*
C30.81836 (8)0.70443 (8)0.35419 (10)0.0199 (3)
H3A0.81850.65660.37330.024*
C40.76245 (9)0.75003 (8)0.38085 (9)0.0186 (3)
H4A0.72530.73330.41780.022*
C50.76344 (8)0.81981 (8)0.35151 (10)0.0199 (3)
H5A0.72690.85130.36880.024*
O10.69078 (7)0.94232 (6)0.25438 (11)0.0437 (4)
O20.79245 (9)1.00000.25000.0338 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01293 (15)0.01293 (15)0.0163 (2)0.0000.0000.000
S10.0179 (2)0.0121 (2)0.0240 (2)0.00034 (13)0.00425 (14)0.00054 (14)
N10.0163 (6)0.0134 (6)0.0207 (6)0.0019 (5)0.0007 (5)0.0015 (5)
N20.0260 (10)0.0159 (9)0.0311 (10)0.0000.0000.0017 (8)
C10.0131 (7)0.0170 (7)0.0138 (7)0.0007 (5)0.0028 (5)0.0039 (5)
C20.0181 (8)0.0187 (7)0.0193 (7)0.0047 (6)0.0001 (6)0.0000 (6)
C30.0212 (8)0.0188 (7)0.0197 (7)0.0017 (6)0.0010 (6)0.0037 (6)
C40.0150 (8)0.0255 (9)0.0153 (7)0.0002 (6)0.0003 (5)0.0008 (6)
C50.0146 (7)0.0239 (8)0.0212 (7)0.0036 (6)0.0003 (6)0.0040 (6)
O10.0378 (7)0.0171 (6)0.0761 (10)0.0083 (5)0.0204 (7)0.0086 (6)
O20.0197 (8)0.0396 (10)0.0422 (10)0.0000.0000.0052 (8)
Geometric parameters (Å, º) top
Zn1—S1i2.3371 (5)N2—O21.274 (3)
Zn1—S1ii2.3371 (5)C1—C21.398 (2)
Zn1—S12.3371 (5)C2—C31.377 (2)
Zn1—S1iii2.3371 (5)C2—H2A0.9300
S1—C11.7252 (15)C3—C41.393 (2)
N1—C51.351 (2)C3—H3A0.9300
N1—C11.3590 (18)C4—C51.363 (2)
N1—H1A0.8600C4—H4A0.9300
N2—O11.2330 (16)C5—H5A0.9300
N2—O1iv1.2330 (16)
S1i—Zn1—S1ii103.666 (10)N1—C1—S1117.08 (11)
S1i—Zn1—S1103.666 (10)C2—C1—S1126.14 (11)
S1ii—Zn1—S1121.84 (2)C3—C2—C1120.35 (14)
S1i—Zn1—S1iii121.84 (2)C3—C2—H2A119.8
S1ii—Zn1—S1iii103.666 (10)C1—C2—H2A119.8
S1—Zn1—S1iii103.666 (10)C2—C3—C4120.53 (14)
C1—S1—Zn1108.05 (5)C2—C3—H3A119.7
C5—N1—C1123.75 (13)C4—C3—H3A119.7
C5—N1—H1A118.1C5—C4—C3118.45 (14)
C1—N1—H1A118.1C5—C4—H4A120.8
O1—N2—O1iv120.6 (2)C3—C4—H4A120.8
O1—N2—O2119.70 (10)N1—C5—C4120.13 (14)
O1iv—N2—O2119.70 (10)N1—C5—H5A119.9
N1—C1—C2116.78 (13)C4—C5—H5A119.9
Symmetry codes: (i) y+1/4, x+7/4, z+1/4; (ii) x+2, y+3/2, z; (iii) y+7/4, x1/4, z+1/4; (iv) x, y+2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O20.862.183.0223 (13)168

Experimental details

Crystal data
Chemical formula[Zn(C5H5NS)4](NO3)2
Mr634.03
Crystal system, space groupTetragonal, I41/acd
Temperature (K)293
a, c (Å)18.534 (3), 14.693 (4)
V3)5047.2 (18)
Z8
Radiation typeMo Kα
µ (mm1)1.35
Crystal size (mm)0.38 × 0.38 × 0.30
Data collection
DiffractometerBruker P4
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.629, 0.666
No. of measured, independent and
observed [I > 2σ(I)] reflections
14775, 1112, 1109
Rint0.015
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.055, 1.03
No. of reflections1112
No. of parameters85
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.22, 0.18

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

Selected geometric parameters (Å, º) top
Zn1—S12.3371 (5)
S1i—Zn1—S1103.666 (10)C1—S1—Zn1108.05 (5)
S1ii—Zn1—S1121.84 (2)
Symmetry codes: (i) y+1/4, x+7/4, z+1/4; (ii) x+2, y+3/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O20.862.183.0223 (13)168
 

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