supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2044    [ doi:10.1107/S1600536807031340 ]

Diiodidobis[(E)-1-(2-pyridylmethylene)thiosemicarbazone-[kappa]S]mercury(II)

Y.-J. Fan, J.-P. Ma and Z.-X. Sun

Abstract top

The reaction of mercury(II) iodide with (E)-1-(2-pyridylmethylene)thiosemicarbazone afforded the title complex, [HgI2(C7H8N4S)2]. The HgII centre, which lies on a twofold rotation axis, is coordinated by two S atoms and two Cl atoms in a distorted tetrahedral coordination geometry. N-H...I and N-H...N hydrogen bonds stabilize the crystal structure.

Comment top

Heterocyclic thiosemicarbazones, as well as their metal complexes, are currently under discussion because of their biological activity (Klayman et al., 1979). A number of studies dealing with complex formation properties and structures of thiosemicarbazones are published (French et al., 1970). (E)-1-(1-(pyridin-2-yl)methylene) thiosemicarbazone is synthesized by 1-(pyridin-2-yl)methylene and thiosemicarbazide forming an insoluble complex.

The Hg(II) center is coordinated by two S atoms and two Cl atoms in a distorted tetrahedral coordination geometry. N—H···I and N—H···N hydrogen bonds stabilize the crystal structure.

Related literature top

For related literature, see: French & Blanz (1970); Klayman et al. (1979).

Experimental top

An methanol solution (10 ml) of HgI2 (45.4 mg, 0.10 mmol) was slowly diffused into a ethanol solution (10 ml) of (E)-1-(1-(pyridin-2-yl)methylene)thiosemicarbazide (36.0 mg, 0.20 mmol). Yellow single crystals of (I) were obtained after the solution was allowed to stand at room temperature for one week.

Refinement top

All H atoms were included in calculated positions with N—H = 0.86, C—H = 0.93 and were included in the final cycles of refinement using a riding model with Uiso(H) = 1.2Ueq(N,C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The diagram of the complex with atom numbering, showing 30% probability displacement ellipsoids [Symmetry code: (i) -x + 2, y, -z + 1/2].
[Figure 2] Fig. 2. A diagram showing the N—H···I and N—H···N hydrogen bonding arrangement [Symmetry codes: (i) -x + 2, y, -z + 1/2; (ii) -x + 3/2, y + 1/2, -z + 1/2].
[Figure 3] Fig. 3. A diagram showing crystal structure (view along the c axis).
Diiodidobis[(E)-1-(2-pyridylmethylene)thiosemicarbazone-κS]mercury(II) top
Crystal data top
[HgI2(C7H8N4S)2]F(000) = 1496
Mr = 814.86Dx = 2.381 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C2ycCell parameters from 3233 reflections
a = 18.973 (5) Åθ = 2.4–27.8°
b = 7.0494 (17) ŵ = 9.69 mm−1
c = 17.454 (4) ÅT = 298 K
β = 103.137 (3)°Block, yellow
V = 2273.4 (9) Å30.30 × 0.14 × 0.10 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		2048 independent reflections
Radiation source: fine-focus sealed tube1888 reflections with I > 2σ(I)
graphiteRint = 0.030
φ and ω scansθmax = 25.3°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		h = −22→22
Tmin = 0.159, Tmax = 0.444k = −8→8
5534 measured reflectionsl = −16→20
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.110 w = 1/[σ2(Fo2) + (0.0614P)2 + 22.4472P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
2048 reflectionsΔρmax = 2.96 e Å−3
124 parametersΔρmin = −2.79 e Å−3
0 restraintsExtinction correction: SHELXTL (Bruker, 2001), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00154 (15)
Crystal data top
[HgI2(C7H8N4S)2]V = 2273.4 (9) Å3
Mr = 814.86Z = 4
Monoclinic, C2/cMo Kα radiation
a = 18.973 (5) ŵ = 9.69 mm−1
b = 7.0494 (17) ÅT = 298 K
c = 17.454 (4) Å0.30 × 0.14 × 0.10 mm
β = 103.137 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2048 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		1888 reflections with I > 2σ(I)
Tmin = 0.159, Tmax = 0.444Rint = 0.030
5534 measured reflectionsθmax = 25.3°
Refinement top
R[F2 > 2σ(F2)] = 0.042 w = 1/[σ2(Fo2) + (0.0614P)2 + 22.4472P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.110Δρmax = 2.96 e Å−3
S = 1.06Δρmin = −2.79 e Å−3
2048 reflectionsAbsolute structure: ?
124 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
H-atom parameters constrained
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
Hg11.00001.20675 (6)0.25000.0413 (2)
N10.8487 (3)0.6917 (8)0.2868 (4)0.0335 (13)
H1A0.82230.67190.24050.040*
N20.8486 (3)0.5658 (9)0.3465 (3)0.0327 (13)
N30.9329 (4)0.8690 (11)0.3721 (4)0.0516 (19)
H3A0.93340.78500.40790.062*
H3B0.96000.96780.38220.062*
N40.7574 (3)0.1331 (9)0.3603 (4)0.0353 (14)
C10.7530 (5)−0.0075 (13)0.4107 (5)0.049 (2)
H10.7198−0.10460.39470.058*
C20.7963 (5)−0.0124 (14)0.4856 (5)0.056 (2)
H20.7919−0.11190.51920.067*
C30.8452 (5)0.1268 (15)0.5106 (5)0.053 (2)
H30.87430.12460.56130.064*
C40.8511 (5)0.2720 (12)0.4596 (5)0.0402 (18)
H40.88440.36930.47510.048*
C50.8067 (4)0.2707 (10)0.3849 (4)0.0295 (14)
C60.8098 (4)0.4184 (10)0.3269 (4)0.0315 (15)
H60.78320.40480.27540.038*
C70.8907 (4)0.8463 (11)0.3019 (4)0.0348 (16)
S10.88321 (11)1.0065 (3)0.22652 (11)0.0399 (5)
I10.96424 (3)1.36465 (12)0.10320 (4)0.0687 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.0375 (3)0.0448 (3)0.0401 (3)0.0000.00548 (18)0.000
N10.038 (3)0.035 (3)0.024 (3)−0.007 (3)−0.001 (3)0.006 (2)
N20.033 (3)0.037 (3)0.024 (3)−0.003 (3)−0.002 (2)0.003 (3)
N30.057 (4)0.049 (4)0.038 (4)−0.021 (3)−0.012 (3)0.007 (3)
N40.036 (3)0.040 (3)0.028 (3)−0.005 (3)0.002 (3)0.006 (3)
C10.049 (5)0.049 (5)0.045 (5)−0.013 (4)0.005 (4)0.009 (4)
C20.069 (6)0.059 (5)0.039 (5)−0.008 (5)0.009 (4)0.026 (4)
C30.060 (5)0.068 (6)0.026 (4)−0.007 (5)−0.002 (4)0.014 (4)
C40.046 (4)0.048 (4)0.024 (4)−0.009 (4)0.000 (3)0.003 (3)
C50.031 (4)0.033 (4)0.024 (3)0.000 (3)0.006 (3)0.003 (3)
C60.032 (4)0.040 (4)0.021 (3)−0.001 (3)0.003 (3)0.002 (3)
C70.031 (4)0.045 (4)0.027 (4)−0.002 (3)0.002 (3)0.000 (3)
S10.0424 (10)0.0455 (11)0.0285 (9)−0.0139 (8)0.0011 (8)0.0061 (8)
I10.0479 (4)0.0830 (5)0.0693 (5)−0.0013 (3)0.0009 (3)0.0441 (4)
Geometric parameters (Å, °) top
Hg1—S12.5803 (19)N4—C51.348 (10)
Hg1—S1i2.5803 (19)C1—C21.377 (13)
Hg1—I1i2.7340 (8)C1—H10.9300
Hg1—I12.7340 (8)C2—C31.353 (14)
N1—C71.340 (10)C2—H20.9300
N1—N21.369 (8)C3—C41.378 (12)
N1—H1A0.8600C3—H30.9300
N2—C61.275 (9)C4—C51.382 (11)
N3—C71.312 (10)C4—H40.9300
N3—H3A0.8600C5—C61.462 (10)
N3—H3B0.8600C6—H60.9300
N4—C11.341 (11)C7—S11.715 (8)
S1—Hg1—S1i113.68 (10)C3—C2—H2119.8
S1—Hg1—I1i113.13 (5)C1—C2—H2119.8
S1i—Hg1—I1i93.02 (4)C2—C3—C4118.7 (8)
S1—Hg1—I193.02 (4)C2—C3—H3120.6
S1i—Hg1—I1113.13 (5)C4—C3—H3120.6
I1i—Hg1—I1131.95 (4)C3—C4—C5118.9 (8)
C7—N1—N2118.8 (6)C3—C4—H4120.6
C7—N1—H1A120.6C5—C4—H4120.6
N2—N1—H1A120.6N4—C5—C4122.4 (7)
C6—N2—N1115.1 (6)N4—C5—C6115.2 (6)
C7—N3—H3A120.0C4—C5—C6122.4 (7)
C7—N3—H3B120.0N2—C6—C5120.4 (6)
H3A—N3—H3B120.0N2—C6—H6119.8
C1—N4—C5117.7 (7)C5—C6—H6119.8
N4—C1—C2121.9 (8)N3—C7—N1119.4 (7)
N4—C1—H1119.0N3—C7—S1124.3 (6)
C2—C1—H1119.0N1—C7—S1116.3 (5)
C3—C2—C1120.4 (8)C7—S1—Hg1108.7 (3)
C7—N1—N2—C6−177.2 (7)N4—C5—C6—N2172.4 (7)
C5—N4—C1—C20.7 (13)C4—C5—C6—N2−7.7 (11)
N4—C1—C2—C30.0 (16)N2—N1—C7—N33.0 (11)
C1—C2—C3—C4−0.5 (16)N2—N1—C7—S1−175.4 (5)
C2—C3—C4—C50.3 (15)N3—C7—S1—Hg124.2 (8)
C1—N4—C5—C4−0.9 (11)N1—C7—S1—Hg1−157.5 (5)
C1—N4—C5—C6179.1 (7)S1i—Hg1—S1—C752.4 (3)
C3—C4—C5—N40.4 (13)I1i—Hg1—S1—C7−52.0 (3)
C3—C4—C5—C6−179.5 (8)I1—Hg1—S1—C7169.3 (3)
N1—N2—C6—C5178.3 (6)
Symmetry codes: (i) −x+2, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···I1i0.863.133.978 (7)169
N1—H1A···N4ii0.862.062.910 (9)169
Symmetry codes: (i) −x+2, y, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···I1i0.863.133.978 (7)169
N1—H1A···N4ii0.862.062.910 (9)169
Symmetry codes: (i) −x+2, y, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2.
Acknowledgements top

The authors thank the Science Research Foundation of Jinan University (grant No. y0622) for support.

references
References top

Bruker (1997). SMART (Version 5.6), SAINT (Version 5.06a) and SADABS (Version?). Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA.

French, F. A. & Blanz, E. Jr (1970). J. Med. Chem. 13, 1117–1124.

Klayman, D. L., Scovill, J. P., Bartosevich, J. F. & Mason, C. L. (1979). J. Med. Chem. 22, 1367–1373.