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In the title compound, [Zn(CH5N3S)2](NO3)2, the zinc(II) ion is located on the twofold axis and chelated by two thiosemicarbazide ligands with Zn-S and Zn-N distances of 2.0904 (17) and 2.2672 (6) Å, respectively. Thus the central zinc(II) is four-coordinated and in a distorted tetrahedral geometry. The inter- and intramolecular hydrogen bonds formed between thiosemicarbazide ligands and nitrate anions assemble the molecules into a one-dimensional chain.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199012974/bk1501sup1.cif
Contains datablocks I, zncs

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199012974/bk1501Isup2.hkl
Contains datablock I

CCDC reference: 140935

Comment top

As a ligand with potential S and N donors, thiosemicarbazide is interesting not only because of the structural chemistry of its multifunction coordination modes, but also because of the formation of complexes with biological activities. The biological activities of complexes with thiourea derivatives have been well documented (Shen et al., 1998) and thiourea derivatives have been successfully screened for various biological actions (Antholine et al., 1982). We are interested in the crystal engineering of metal complexes with various intra- and intermolecular interactions (Su et al., 1998, 1999), and now report the crystal structure of [Zn(CH5N3S)2](NO3)2, (I).

The structure of the title compound consists of a cation [Zn(CH5N3S)2]2+ and two nitrate anions, which are joined together by two sets of intramolecular cyclic hydrogen bonding as shown in Fig. 1. The cation of the complex contains a distorted tetrahedral zinc(II) ion which is chelated by two bidendate thiosemicarbazide ligands though their sulfur and nitrogen atoms. There is a crystallographically imposed twofold axis passing through the central zinc(II) ion [symmetry code: (i) 1 − x, y, 1/2 − z]. The Zn—S and Zn—N distances show no remarkable features [2.0904 (17) and 2.2672 (6) Å, respectively], and the most deviation from the normal tetrahedral geometry was found from the N1—Zn1—S1 and S1i—Zn1—S1 angles [88.33 (5) and 134.26 (3)°, respectively].

It is interesting that the hydrogen bonding plays aa important role in the crystal packing. Both the coordinated and uncoordinated NH2 group, and the NH group of the thiosemicarbazide ligands are involved in hydrogen-bonding acting as hydrogen-bond donors with three oxygen atoms of nitrate as potential hydrogen-bond acceptors. As shown in Fig. 1 the N2 and N3 atoms form intramolecular cyclic hydrogen bonds with O2 and O1 atoms, and the N1 atom forms intermolecular hydrogen bond with O3ii (Table 1) as shown in Fig. 2. So the two nitrate anions bridge two [Zn(CH5N3S)2]2+ cations to form a tricyclic hydrogen-bonding motif which assembles the molecules into a one-dimensional chain.

Experimental top

The deep red crystals of the title compound were obtained from the reaction of hydrated Zn(NO3)2 with thiosemicarbazide in molar ratio of 1:2 in H2O-ethanol mixed solution at room temperature. The yield was 55%. Found: C 6.39, H 2.79, N 30.12; analysis calculated for C2H10N8O6S2Zn: C 6.46, H 2.71, N 30.15%. IR (KBr): 3367(s), 3295(s), 3288(s), 3142(s), 2987(m), 2945(m), 2635(w), 2425(w), 1771(w), 1630(s), 1447(m), 1391(s), 1349(s), 1285(s), 1215(m), 1131(s), 1046(m), 1018(m), 814(m), 716(m), 688(s), 629(w), 561(s), 456(w) cm−1.

Refinement top

The hydrogen atoms were located in a difference electron-density map and were included in refinement independently.

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL96 (Sheldrick, 1996); software used to prepare material for publication: SHELXTL96.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) with displacement ellipsoids at the 30% probability level.
[Figure 2] Fig. 2. One-dimensional chain assembled from intra- and intermolecular hydrogen bonds.
(I) top
Crystal data top
[Zn(CH5N3S)2](NO3)2F(000) = 752
Mr = 371.67Dx = 2.098 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 11.165 (2) ÅCell parameters from 25 reflections
b = 7.605 (2) Åθ = 5–12.5°
c = 14.167 (3) ŵ = 2.48 mm1
β = 102.02 (3)°T = 293 K
V = 1176.5 (4) Å3Block, dark red
Z = 40.42 × 0.40 × 0.38 mm
Data collection top
Siemens R3m
diffractometer
1497 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.032
Graphite monochromatorθmax = 30.1°, θmin = 4.2°
ω scansh = 015
Absorption correction: ψ scan
(North et al., 1968)
k = 010
Tmin = 0.276, Tmax = 0.389l = 1919
1808 measured reflections3 standard reflections every 197 reflections
1728 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: DIFMAP
R[F2 > 2σ(F2)] = 0.029All H-atom parameters refined
wR(F2) = 0.074Calculated w = 1/[σ2(Fo2) + (0.0402P)2 + 0.5812P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
1728 reflectionsΔρmax = 0.36 e Å3
108 parametersΔρmin = 0.40 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0257 (12)
Crystal data top
[Zn(CH5N3S)2](NO3)2V = 1176.5 (4) Å3
Mr = 371.67Z = 4
Monoclinic, C2/cMo Kα radiation
a = 11.165 (2) ŵ = 2.48 mm1
b = 7.605 (2) ÅT = 293 K
c = 14.167 (3) Å0.42 × 0.40 × 0.38 mm
β = 102.02 (3)°
Data collection top
Siemens R3m
diffractometer
1497 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.032
Tmin = 0.276, Tmax = 0.3893 standard reflections every 197 reflections
1808 measured reflections intensity decay: none
1728 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.074All H-atom parameters refined
S = 1.08Δρmax = 0.36 e Å3
1728 reflectionsΔρmin = 0.40 e Å3
108 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.

The structure was solved by direct method and all non-H atoms were refined by full-matrix least-squares method (Sheldrick, 1990) with anisotropic displacement parameters.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.50000.16827 (4)0.25000.03327 (13)
S10.44408 (4)0.28414 (7)0.38184 (3)0.03039 (13)
N10.63965 (16)0.0327 (2)0.34282 (11)0.0324 (3)
N20.64462 (15)0.0821 (2)0.43952 (11)0.0303 (3)
C10.56215 (15)0.1911 (2)0.46394 (12)0.0254 (3)
N30.57316 (19)0.2273 (3)0.55626 (12)0.0357 (4)
N40.82483 (13)0.0676 (2)0.66714 (11)0.0274 (3)
O10.77897 (14)0.0759 (2)0.68568 (11)0.0413 (3)
O20.83143 (13)0.1051 (2)0.58276 (10)0.0412 (3)
O30.86219 (18)0.1720 (2)0.73374 (12)0.0488 (4)
H1B0.630 (3)0.080 (4)0.339 (2)0.053 (8)*
H20.693 (2)0.043 (4)0.477 (2)0.045 (7)*
H3B0.623 (3)0.183 (3)0.589 (2)0.040 (7)*
H1A0.709 (2)0.057 (4)0.329 (2)0.046 (7)*
H3A0.526 (2)0.290 (4)0.5668 (19)0.034 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0428 (2)0.0352 (2)0.02094 (16)0.0000.00465 (11)0.000
S10.0284 (2)0.0364 (3)0.0253 (2)0.00584 (17)0.00333 (15)0.00001 (16)
N10.0394 (8)0.0313 (9)0.0275 (7)0.0059 (7)0.0092 (6)0.0011 (6)
N20.0317 (7)0.0348 (8)0.0234 (7)0.0078 (6)0.0030 (6)0.0023 (6)
C10.0258 (7)0.0263 (8)0.0237 (7)0.0023 (6)0.0043 (6)0.0013 (6)
N30.0380 (9)0.0446 (10)0.0229 (7)0.0081 (8)0.0032 (6)0.0013 (7)
N40.0269 (6)0.0271 (7)0.0279 (7)0.0032 (5)0.0053 (5)0.0010 (5)
O10.0424 (8)0.0356 (8)0.0437 (8)0.0095 (6)0.0039 (6)0.0068 (6)
O20.0412 (7)0.0538 (9)0.0301 (7)0.0023 (7)0.0110 (6)0.0070 (6)
O30.0668 (11)0.0361 (8)0.0387 (8)0.0010 (7)0.0003 (7)0.0093 (6)
Geometric parameters (Å, º) top
Zn1—N1i2.0904 (17)N4—O31.237 (2)
Zn1—N12.0904 (17)N4—O21.246 (2)
Zn1—S1i2.2672 (6)N4—O11.256 (2)
Zn1—S12.2672 (6)N1—H1B0.86 (3)
S1—C11.7184 (18)N1—H1A0.86 (3)
N1—N21.411 (2)N2—H20.74 (3)
N2—C11.337 (2)N3—H3B0.73 (3)
C1—N31.317 (2)N3—H3A0.73 (3)
N1i—Zn1—N1120.88 (11)C1—N2—N1121.79 (15)
N1i—Zn1—S1i88.33 (5)N3—C1—N2117.38 (17)
N1—Zn1—S1i114.37 (5)N3—C1—S1119.06 (15)
N1i—Zn1—S1114.37 (5)N2—C1—S1123.56 (13)
N1—Zn1—S188.33 (5)O3—N4—O2120.47 (17)
S1i—Zn1—S1134.26 (3)O3—N4—O1119.02 (17)
C1—S1—Zn195.36 (6)O2—N4—O1120.50 (16)
N2—N1—Zn1110.65 (12)
N1i—Zn1—S1—C1127.38 (8)Zn1—N1—N2—C14.8 (2)
N1—Zn1—S1—C13.97 (8)N1—N2—C1—N3178.91 (17)
S1i—Zn1—S1—C1119.25 (6)N1—N2—C1—S10.9 (3)
N1i—Zn1—N1—N2122.78 (14)Zn1—S1—C1—N3177.16 (15)
S1i—Zn1—N1—N2133.71 (12)Zn1—S1—C1—N22.99 (16)
S1—Zn1—N1—N25.16 (13)
Symmetry code: (i) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O10.73 (3)2.14 (3)2.866 (3)175 (3)
N2—H2···O20.74 (3)2.22 (3)2.955 (2)174 (3)
N1—H1B···O3ii0.86 (3)2.16 (3)2.948 (2)151 (3)
Symmetry code: (ii) x+3/2, y1/2, z+1.

Experimental details

Crystal data
Chemical formula[Zn(CH5N3S)2](NO3)2
Mr371.67
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)11.165 (2), 7.605 (2), 14.167 (3)
β (°) 102.02 (3)
V3)1176.5 (4)
Z4
Radiation typeMo Kα
µ (mm1)2.48
Crystal size (mm)0.42 × 0.40 × 0.38
Data collection
DiffractometerSiemens R3m
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.276, 0.389
No. of measured, independent and
observed [I > 2σ(I)] reflections
1808, 1728, 1497
Rint0.032
(sin θ/λ)max1)0.705
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.074, 1.08
No. of reflections1728
No. of parameters108
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.36, 0.40

Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL96 (Sheldrick, 1996), SHELXTL96.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O10.73 (3)2.14 (3)2.866 (3)175 (3)
N2—H2···O20.74 (3)2.22 (3)2.955 (2)174 (3)
N1—H1B···O3i0.86 (3)2.16 (3)2.948 (2)151 (3)
Symmetry code: (i) x+3/2, y1/2, z+1.
 

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