Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104008042/na1653sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104008042/na1653Isup2.hkl |
CCDC reference: 243571
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.
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.
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.
[Zn(C5H5NS)4](NO3)2 | Dx = 1.669 Mg m−3 |
Mr = 634.03 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/acd | Cell parameters from 6926 reflections |
a = 18.534 (3) Å | θ = 2.2–25.0° |
c = 14.693 (4) Å | µ = 1.35 mm−1 |
V = 5047.2 (18) Å3 | T = 293 K |
Z = 8 | Prism, green |
F(000) = 2592 | 0.38 × 0.38 × 0.30 mm |
Bruker P4 diffractometer | 1112 independent reflections |
Radiation source: fine-focus sealed tube | 1109 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −22→19 |
Tmin = 0.629, Tmax = 0.666 | k = −15→22 |
14775 measured reflections | l = −17→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.020 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.055 | H-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 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
[Zn(C5H5NS)4](NO3)2 | Z = 8 |
Mr = 634.03 | Mo Kα radiation |
Tetragonal, I41/acd | µ = 1.35 mm−1 |
a = 18.534 (3) Å | T = 293 K |
c = 14.693 (4) Å | 0.38 × 0.38 × 0.30 mm |
V = 5047.2 (18) Å3 |
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 = 0.666 | Rint = 0.015 |
14775 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.055 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.22 e Å−3 |
1112 reflections | Δρmin = −0.18 e Å−3 |
85 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 1.0000 | 0.7500 | 0.1250 | 0.01406 (13) | |
S1 | 0.93817 (2) | 0.841221 (18) | 0.20232 (3) | 0.01800 (13) | |
N1 | 0.81742 (7) | 0.84327 (6) | 0.29729 (8) | 0.0168 (3) | |
H1A | 0.8163 | 0.8874 | 0.2791 | 0.020* | |
N2 | 0.72374 (11) | 1.0000 | 0.2500 | 0.0243 (4) | |
C1 | 0.87340 (7) | 0.80120 (8) | 0.26986 (9) | 0.0146 (3) | |
C2 | 0.87332 (8) | 0.72961 (8) | 0.29978 (10) | 0.0187 (3) | |
H2A | 0.9106 | 0.6988 | 0.2828 | 0.022* | |
C3 | 0.81836 (8) | 0.70443 (8) | 0.35419 (10) | 0.0199 (3) | |
H3A | 0.8185 | 0.6566 | 0.3733 | 0.024* | |
C4 | 0.76245 (9) | 0.75003 (8) | 0.38085 (9) | 0.0186 (3) | |
H4A | 0.7253 | 0.7333 | 0.4178 | 0.022* | |
C5 | 0.76344 (8) | 0.81981 (8) | 0.35151 (10) | 0.0199 (3) | |
H5A | 0.7269 | 0.8513 | 0.3688 | 0.024* | |
O1 | 0.69078 (7) | 0.94232 (6) | 0.25438 (11) | 0.0437 (4) | |
O2 | 0.79245 (9) | 1.0000 | 0.2500 | 0.0338 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.01293 (15) | 0.01293 (15) | 0.0163 (2) | 0.000 | 0.000 | 0.000 |
S1 | 0.0179 (2) | 0.0121 (2) | 0.0240 (2) | 0.00034 (13) | 0.00425 (14) | −0.00054 (14) |
N1 | 0.0163 (6) | 0.0134 (6) | 0.0207 (6) | 0.0019 (5) | −0.0007 (5) | −0.0015 (5) |
N2 | 0.0260 (10) | 0.0159 (9) | 0.0311 (10) | 0.000 | 0.000 | −0.0017 (8) |
C1 | 0.0131 (7) | 0.0170 (7) | 0.0138 (7) | 0.0007 (5) | −0.0028 (5) | −0.0039 (5) |
C2 | 0.0181 (8) | 0.0187 (7) | 0.0193 (7) | 0.0047 (6) | −0.0001 (6) | 0.0000 (6) |
C3 | 0.0212 (8) | 0.0188 (7) | 0.0197 (7) | 0.0017 (6) | −0.0010 (6) | 0.0037 (6) |
C4 | 0.0150 (8) | 0.0255 (9) | 0.0153 (7) | −0.0002 (6) | −0.0003 (5) | 0.0008 (6) |
C5 | 0.0146 (7) | 0.0239 (8) | 0.0212 (7) | 0.0036 (6) | 0.0003 (6) | −0.0040 (6) |
O1 | 0.0378 (7) | 0.0171 (6) | 0.0761 (10) | −0.0083 (5) | −0.0204 (7) | 0.0086 (6) |
O2 | 0.0197 (8) | 0.0396 (10) | 0.0422 (10) | 0.000 | 0.000 | −0.0052 (8) |
Zn1—S1i | 2.3371 (5) | N2—O2 | 1.274 (3) |
Zn1—S1ii | 2.3371 (5) | C1—C2 | 1.398 (2) |
Zn1—S1 | 2.3371 (5) | C2—C3 | 1.377 (2) |
Zn1—S1iii | 2.3371 (5) | C2—H2A | 0.9300 |
S1—C1 | 1.7252 (15) | C3—C4 | 1.393 (2) |
N1—C5 | 1.351 (2) | C3—H3A | 0.9300 |
N1—C1 | 1.3590 (18) | C4—C5 | 1.363 (2) |
N1—H1A | 0.8600 | C4—H4A | 0.9300 |
N2—O1 | 1.2330 (16) | C5—H5A | 0.9300 |
N2—O1iv | 1.2330 (16) | ||
S1i—Zn1—S1ii | 103.666 (10) | N1—C1—S1 | 117.08 (11) |
S1i—Zn1—S1 | 103.666 (10) | C2—C1—S1 | 126.14 (11) |
S1ii—Zn1—S1 | 121.84 (2) | C3—C2—C1 | 120.35 (14) |
S1i—Zn1—S1iii | 121.84 (2) | C3—C2—H2A | 119.8 |
S1ii—Zn1—S1iii | 103.666 (10) | C1—C2—H2A | 119.8 |
S1—Zn1—S1iii | 103.666 (10) | C2—C3—C4 | 120.53 (14) |
C1—S1—Zn1 | 108.05 (5) | C2—C3—H3A | 119.7 |
C5—N1—C1 | 123.75 (13) | C4—C3—H3A | 119.7 |
C5—N1—H1A | 118.1 | C5—C4—C3 | 118.45 (14) |
C1—N1—H1A | 118.1 | C5—C4—H4A | 120.8 |
O1—N2—O1iv | 120.6 (2) | C3—C4—H4A | 120.8 |
O1—N2—O2 | 119.70 (10) | N1—C5—C4 | 120.13 (14) |
O1iv—N2—O2 | 119.70 (10) | N1—C5—H5A | 119.9 |
N1—C1—C2 | 116.78 (13) | C4—C5—H5A | 119.9 |
Symmetry codes: (i) y+1/4, −x+7/4, −z+1/4; (ii) −x+2, −y+3/2, z; (iii) −y+7/4, x−1/4, −z+1/4; (iv) x, −y+2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C5H5NS)4](NO3)2 |
Mr | 634.03 |
Crystal system, space group | Tetragonal, I41/acd |
Temperature (K) | 293 |
a, c (Å) | 18.534 (3), 14.693 (4) |
V (Å3) | 5047.2 (18) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.35 |
Crystal size (mm) | 0.38 × 0.38 × 0.30 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.629, 0.666 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14775, 1112, 1109 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.055, 1.03 |
No. of reflections | 1112 |
No. of parameters | 85 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.18 |
Computer programs: SMART (Siemens, 1996), SMART and SAINT (Siemens,1994), XPREP in SHELXTL (Siemens, 1994), SHELXTL.
Zn1—S1 | 2.3371 (5) | ||
S1i—Zn1—S1 | 103.666 (10) | C1—S1—Zn1 | 108.05 (5) |
S1ii—Zn1—S1 | 121.84 (2) |
Symmetry codes: (i) y+1/4, −x+7/4, −z+1/4; (ii) −x+2, −y+3/2, z. |
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 π–π interactions in (III). According to Janiak (2000), these π–π interactions should be assigned to an offset stacking. π–π stacking is an important motif in forming extended structures, from low-dimensional to multi-dimensional. In (III), π–π interactions and hydrogen-bonding interactions lead to the formation of a three-dimensional network structure.