Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199012974/bk1501sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199012974/bk1501Isup2.hkl |
CCDC reference: 140935
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.
The hydrogen atoms were located in a difference electron-density map and were included in refinement independently.
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.
Fig. 1. Molecular structure of (I) with displacement ellipsoids at the 30% probability level. | |
Fig. 2. One-dimensional chain assembled from intra- and intermolecular hydrogen bonds. |
[Zn(CH5N3S)2](NO3)2 | F(000) = 752 |
Mr = 371.67 | Dx = 2.098 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.165 (2) Å | Cell parameters from 25 reflections |
b = 7.605 (2) Å | θ = 5–12.5° |
c = 14.167 (3) Å | µ = 2.48 mm−1 |
β = 102.02 (3)° | T = 293 K |
V = 1176.5 (4) Å3 | Block, dark red |
Z = 4 | 0.42 × 0.40 × 0.38 mm |
Siemens R3m diffractometer | 1497 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 30.1°, θmin = 4.2° |
ω scans | h = 0→15 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→10 |
Tmin = 0.276, Tmax = 0.389 | l = −19→19 |
1808 measured reflections | 3 standard reflections every 197 reflections |
1728 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: DIFMAP |
R[F2 > 2σ(F2)] = 0.029 | All H-atom parameters refined |
wR(F2) = 0.074 | Calculated w = 1/[σ2(Fo2) + (0.0402P)2 + 0.5812P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
1728 reflections | Δρmax = 0.36 e Å−3 |
108 parameters | Δρmin = −0.40 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0257 (12) |
[Zn(CH5N3S)2](NO3)2 | V = 1176.5 (4) Å3 |
Mr = 371.67 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.165 (2) Å | µ = 2.48 mm−1 |
b = 7.605 (2) Å | T = 293 K |
c = 14.167 (3) Å | 0.42 × 0.40 × 0.38 mm |
β = 102.02 (3)° |
Siemens R3m diffractometer | 1497 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.032 |
Tmin = 0.276, Tmax = 0.389 | 3 standard reflections every 197 reflections |
1808 measured reflections | intensity decay: none |
1728 independent reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.074 | All H-atom parameters refined |
S = 1.08 | Δρmax = 0.36 e Å−3 |
1728 reflections | Δρmin = −0.40 e Å−3 |
108 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. 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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.5000 | 0.16827 (4) | 0.2500 | 0.03327 (13) | |
S1 | 0.44408 (4) | 0.28414 (7) | 0.38184 (3) | 0.03039 (13) | |
N1 | 0.63965 (16) | 0.0327 (2) | 0.34282 (11) | 0.0324 (3) | |
N2 | 0.64462 (15) | 0.0821 (2) | 0.43952 (11) | 0.0303 (3) | |
C1 | 0.56215 (15) | 0.1911 (2) | 0.46394 (12) | 0.0254 (3) | |
N3 | 0.57316 (19) | 0.2273 (3) | 0.55626 (12) | 0.0357 (4) | |
N4 | 0.82483 (13) | −0.0676 (2) | 0.66714 (11) | 0.0274 (3) | |
O1 | 0.77897 (14) | 0.0759 (2) | 0.68568 (11) | 0.0413 (3) | |
O2 | 0.83143 (13) | −0.1051 (2) | 0.58276 (10) | 0.0412 (3) | |
O3 | 0.86219 (18) | −0.1720 (2) | 0.73374 (12) | 0.0488 (4) | |
H1B | 0.630 (3) | −0.080 (4) | 0.339 (2) | 0.053 (8)* | |
H2 | 0.693 (2) | 0.043 (4) | 0.477 (2) | 0.045 (7)* | |
H3B | 0.623 (3) | 0.183 (3) | 0.589 (2) | 0.040 (7)* | |
H1A | 0.709 (2) | 0.057 (4) | 0.329 (2) | 0.046 (7)* | |
H3A | 0.526 (2) | 0.290 (4) | 0.5668 (19) | 0.034 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0428 (2) | 0.0352 (2) | 0.02094 (16) | 0.000 | 0.00465 (11) | 0.000 |
S1 | 0.0284 (2) | 0.0364 (3) | 0.0253 (2) | 0.00584 (17) | 0.00333 (15) | 0.00001 (16) |
N1 | 0.0394 (8) | 0.0313 (9) | 0.0275 (7) | 0.0059 (7) | 0.0092 (6) | −0.0011 (6) |
N2 | 0.0317 (7) | 0.0348 (8) | 0.0234 (7) | 0.0078 (6) | 0.0030 (6) | 0.0023 (6) |
C1 | 0.0258 (7) | 0.0263 (8) | 0.0237 (7) | −0.0023 (6) | 0.0043 (6) | 0.0013 (6) |
N3 | 0.0380 (9) | 0.0446 (10) | 0.0229 (7) | 0.0081 (8) | 0.0032 (6) | −0.0013 (7) |
N4 | 0.0269 (6) | 0.0271 (7) | 0.0279 (7) | −0.0032 (5) | 0.0053 (5) | −0.0010 (5) |
O1 | 0.0424 (8) | 0.0356 (8) | 0.0437 (8) | 0.0095 (6) | 0.0039 (6) | −0.0068 (6) |
O2 | 0.0412 (7) | 0.0538 (9) | 0.0301 (7) | 0.0023 (7) | 0.0110 (6) | −0.0070 (6) |
O3 | 0.0668 (11) | 0.0361 (8) | 0.0387 (8) | 0.0010 (7) | 0.0003 (7) | 0.0093 (6) |
Zn1—N1i | 2.0904 (17) | N4—O3 | 1.237 (2) |
Zn1—N1 | 2.0904 (17) | N4—O2 | 1.246 (2) |
Zn1—S1i | 2.2672 (6) | N4—O1 | 1.256 (2) |
Zn1—S1 | 2.2672 (6) | N1—H1B | 0.86 (3) |
S1—C1 | 1.7184 (18) | N1—H1A | 0.86 (3) |
N1—N2 | 1.411 (2) | N2—H2 | 0.74 (3) |
N2—C1 | 1.337 (2) | N3—H3B | 0.73 (3) |
C1—N3 | 1.317 (2) | N3—H3A | 0.73 (3) |
N1i—Zn1—N1 | 120.88 (11) | C1—N2—N1 | 121.79 (15) |
N1i—Zn1—S1i | 88.33 (5) | N3—C1—N2 | 117.38 (17) |
N1—Zn1—S1i | 114.37 (5) | N3—C1—S1 | 119.06 (15) |
N1i—Zn1—S1 | 114.37 (5) | N2—C1—S1 | 123.56 (13) |
N1—Zn1—S1 | 88.33 (5) | O3—N4—O2 | 120.47 (17) |
S1i—Zn1—S1 | 134.26 (3) | O3—N4—O1 | 119.02 (17) |
C1—S1—Zn1 | 95.36 (6) | O2—N4—O1 | 120.50 (16) |
N2—N1—Zn1 | 110.65 (12) | ||
N1i—Zn1—S1—C1 | 127.38 (8) | Zn1—N1—N2—C1 | 4.8 (2) |
N1—Zn1—S1—C1 | 3.97 (8) | N1—N2—C1—N3 | 178.91 (17) |
S1i—Zn1—S1—C1 | −119.25 (6) | N1—N2—C1—S1 | −0.9 (3) |
N1i—Zn1—N1—N2 | −122.78 (14) | Zn1—S1—C1—N3 | 177.16 (15) |
S1i—Zn1—N1—N2 | 133.71 (12) | Zn1—S1—C1—N2 | −2.99 (16) |
S1—Zn1—N1—N2 | −5.16 (13) |
Symmetry code: (i) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···O1 | 0.73 (3) | 2.14 (3) | 2.866 (3) | 175 (3) |
N2—H2···O2 | 0.74 (3) | 2.22 (3) | 2.955 (2) | 174 (3) |
N1—H1B···O3ii | 0.86 (3) | 2.16 (3) | 2.948 (2) | 151 (3) |
Symmetry code: (ii) −x+3/2, −y−1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(CH5N3S)2](NO3)2 |
Mr | 371.67 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.165 (2), 7.605 (2), 14.167 (3) |
β (°) | 102.02 (3) |
V (Å3) | 1176.5 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.48 |
Crystal size (mm) | 0.42 × 0.40 × 0.38 |
Data collection | |
Diffractometer | Siemens R3m diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.276, 0.389 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1808, 1728, 1497 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.705 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.074, 1.08 |
No. of reflections | 1728 |
No. of parameters | 108 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.36, −0.40 |
Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL96 (Sheldrick, 1996), SHELXTL96.
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···O1 | 0.73 (3) | 2.14 (3) | 2.866 (3) | 175 (3) |
N2—H2···O2 | 0.74 (3) | 2.22 (3) | 2.955 (2) | 174 (3) |
N1—H1B···O3i | 0.86 (3) | 2.16 (3) | 2.948 (2) | 151 (3) |
Symmetry code: (i) −x+3/2, −y−1/2, −z+1. |
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.