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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031340/bt2394sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031340/bt2394Isup2.hkl
Contains datablock I

CCDC reference: 657520

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.012 Å
  • R factor = 0.042
  • wR factor = 0.110
  • Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.86 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Hg1 - S1 .. 9.13 su PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.17 PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 12 PLAT420_ALERT_2_C D-H Without Acceptor N3 - H3B ... ? PLAT480_ALERT_4_C Long H...A H-Bond Reported H3B .. I1 .. 3.13 Ang.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.855 Tmax scaled 0.380 Tmin scaled 0.136 PLAT794_ALERT_5_G Check Predicted Bond Valency for Hg1 (2) 2.43
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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).

Structure description 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.

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

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 m3
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 mm1
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)
Graphite monochromatorRint = 0.030
φ and ω scansθmax = 25.3°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 2222
Tmin = 0.159, Tmax = 0.444k = 88
5534 measured reflectionsl = 1620
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 Å3
124 parametersΔρmin = 2.79 e Å3
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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.110H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0614P)2 + 22.4472P]
where P = (Fo2 + 2Fc2)/3
2048 reflectionsΔρmax = 2.96 e Å3
124 parametersΔρmin = 2.79 e Å3
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)
H10.71980.10460.39470.058*
C20.7963 (5)0.0124 (14)0.4856 (5)0.056 (2)
H20.79190.11190.51920.067*
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, º) 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—C6177.2 (7)N4—C5—C6—N2172.4 (7)
C5—N4—C1—C20.7 (13)C4—C5—C6—N27.7 (11)
N4—C1—C2—C30.0 (16)N2—N1—C7—N33.0 (11)
C1—C2—C3—C40.5 (16)N2—N1—C7—S1175.4 (5)
C2—C3—C4—C50.3 (15)N3—C7—S1—Hg124.2 (8)
C1—N4—C5—C40.9 (11)N1—C7—S1—Hg1157.5 (5)
C1—N4—C5—C6179.1 (7)S1i—Hg1—S1—C752.4 (3)
C3—C4—C5—N40.4 (13)I1i—Hg1—S1—C752.0 (3)
C3—C4—C5—C6179.5 (8)I1—Hg1—S1—C7169.3 (3)
N1—N2—C6—C5178.3 (6)
Symmetry code: (i) x+2, y, z+1/2.
Hydrogen-bond geometry (Å, º) 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.

Experimental details

Crystal data
Chemical formula[HgI2(C7H8N4S)2]
Mr814.86
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)18.973 (5), 7.0494 (17), 17.454 (4)
β (°) 103.137 (3)
V3)2273.4 (9)
Z4
Radiation typeMo Kα
µ (mm1)9.69
Crystal size (mm)0.30 × 0.14 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.159, 0.444
No. of measured, independent and
observed [I > 2σ(I)] reflections
5534, 2048, 1888
Rint0.030
(sin θ/λ)max1)0.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.110, 1.06
No. of reflections2048
No. of parameters124
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0614P)2 + 22.4472P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)2.96, 2.79

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXTL (Bruker, 2001), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···I1i0.863.133.978 (7)169.4
N1—H1A···N4ii0.862.062.910 (9)168.9
Symmetry codes: (i) x+2, y, z+1/2; (ii) x+3/2, y+1/2, z+1/2.
 

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