Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031340/bt2394sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031340/bt2394Isup2.hkl |
CCDC reference: 657520
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (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
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.
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).
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).
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.
[HgI2(C7H8N4S)2] | F(000) = 1496 |
Mr = 814.86 | Dx = 2.381 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C2yc | Cell parameters from 3233 reflections |
a = 18.973 (5) Å | θ = 2.4–27.8° |
b = 7.0494 (17) Å | µ = 9.69 mm−1 |
c = 17.454 (4) Å | T = 298 K |
β = 103.137 (3)° | Block, yellow |
V = 2273.4 (9) Å3 | 0.30 × 0.14 × 0.10 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2048 independent reflections |
Radiation source: fine-focus sealed tube | 1888 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
φ and ω scans | θmax = 25.3°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −22→22 |
Tmin = 0.159, Tmax = 0.444 | k = −8→8 |
5534 measured reflections | l = −16→20 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-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 reflections | Δρmax = 2.96 e Å−3 |
124 parameters | Δρmin = −2.79 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Bruker, 2001), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00154 (15) |
[HgI2(C7H8N4S)2] | V = 2273.4 (9) Å3 |
Mr = 814.86 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.973 (5) Å | µ = 9.69 mm−1 |
b = 7.0494 (17) Å | T = 298 K |
c = 17.454 (4) Å | 0.30 × 0.14 × 0.10 mm |
β = 103.137 (3)° |
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 = 0.444 | Rint = 0.030 |
5534 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0614P)2 + 22.4472P] where P = (Fo2 + 2Fc2)/3 |
2048 reflections | Δρmax = 2.96 e Å−3 |
124 parameters | Δρmin = −2.79 e Å−3 |
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 | ||
Hg1 | 1.0000 | 1.20675 (6) | 0.2500 | 0.0413 (2) | |
N1 | 0.8487 (3) | 0.6917 (8) | 0.2868 (4) | 0.0335 (13) | |
H1A | 0.8223 | 0.6719 | 0.2405 | 0.040* | |
N2 | 0.8486 (3) | 0.5658 (9) | 0.3465 (3) | 0.0327 (13) | |
N3 | 0.9329 (4) | 0.8690 (11) | 0.3721 (4) | 0.0516 (19) | |
H3A | 0.9334 | 0.7850 | 0.4079 | 0.062* | |
H3B | 0.9600 | 0.9678 | 0.3822 | 0.062* | |
N4 | 0.7574 (3) | 0.1331 (9) | 0.3603 (4) | 0.0353 (14) | |
C1 | 0.7530 (5) | −0.0075 (13) | 0.4107 (5) | 0.049 (2) | |
H1 | 0.7198 | −0.1046 | 0.3947 | 0.058* | |
C2 | 0.7963 (5) | −0.0124 (14) | 0.4856 (5) | 0.056 (2) | |
H2 | 0.7919 | −0.1119 | 0.5192 | 0.067* | |
C3 | 0.8452 (5) | 0.1268 (15) | 0.5106 (5) | 0.053 (2) | |
H3 | 0.8743 | 0.1246 | 0.5613 | 0.064* | |
C4 | 0.8511 (5) | 0.2720 (12) | 0.4596 (5) | 0.0402 (18) | |
H4 | 0.8844 | 0.3693 | 0.4751 | 0.048* | |
C5 | 0.8067 (4) | 0.2707 (10) | 0.3849 (4) | 0.0295 (14) | |
C6 | 0.8098 (4) | 0.4184 (10) | 0.3269 (4) | 0.0315 (15) | |
H6 | 0.7832 | 0.4048 | 0.2754 | 0.038* | |
C7 | 0.8907 (4) | 0.8463 (11) | 0.3019 (4) | 0.0348 (16) | |
S1 | 0.88321 (11) | 1.0065 (3) | 0.22652 (11) | 0.0399 (5) | |
I1 | 0.96424 (3) | 1.36465 (12) | 0.10320 (4) | 0.0687 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.0375 (3) | 0.0448 (3) | 0.0401 (3) | 0.000 | 0.00548 (18) | 0.000 |
N1 | 0.038 (3) | 0.035 (3) | 0.024 (3) | −0.007 (3) | −0.001 (3) | 0.006 (2) |
N2 | 0.033 (3) | 0.037 (3) | 0.024 (3) | −0.003 (3) | −0.002 (2) | 0.003 (3) |
N3 | 0.057 (4) | 0.049 (4) | 0.038 (4) | −0.021 (3) | −0.012 (3) | 0.007 (3) |
N4 | 0.036 (3) | 0.040 (3) | 0.028 (3) | −0.005 (3) | 0.002 (3) | 0.006 (3) |
C1 | 0.049 (5) | 0.049 (5) | 0.045 (5) | −0.013 (4) | 0.005 (4) | 0.009 (4) |
C2 | 0.069 (6) | 0.059 (5) | 0.039 (5) | −0.008 (5) | 0.009 (4) | 0.026 (4) |
C3 | 0.060 (5) | 0.068 (6) | 0.026 (4) | −0.007 (5) | −0.002 (4) | 0.014 (4) |
C4 | 0.046 (4) | 0.048 (4) | 0.024 (4) | −0.009 (4) | 0.000 (3) | 0.003 (3) |
C5 | 0.031 (4) | 0.033 (4) | 0.024 (3) | 0.000 (3) | 0.006 (3) | 0.003 (3) |
C6 | 0.032 (4) | 0.040 (4) | 0.021 (3) | −0.001 (3) | 0.003 (3) | 0.002 (3) |
C7 | 0.031 (4) | 0.045 (4) | 0.027 (4) | −0.002 (3) | 0.002 (3) | 0.000 (3) |
S1 | 0.0424 (10) | 0.0455 (11) | 0.0285 (9) | −0.0139 (8) | 0.0011 (8) | 0.0061 (8) |
I1 | 0.0479 (4) | 0.0830 (5) | 0.0693 (5) | −0.0013 (3) | 0.0009 (3) | 0.0441 (4) |
Hg1—S1 | 2.5803 (19) | N4—C5 | 1.348 (10) |
Hg1—S1i | 2.5803 (19) | C1—C2 | 1.377 (13) |
Hg1—I1i | 2.7340 (8) | C1—H1 | 0.9300 |
Hg1—I1 | 2.7340 (8) | C2—C3 | 1.353 (14) |
N1—C7 | 1.340 (10) | C2—H2 | 0.9300 |
N1—N2 | 1.369 (8) | C3—C4 | 1.378 (12) |
N1—H1A | 0.8600 | C3—H3 | 0.9300 |
N2—C6 | 1.275 (9) | C4—C5 | 1.382 (11) |
N3—C7 | 1.312 (10) | C4—H4 | 0.9300 |
N3—H3A | 0.8600 | C5—C6 | 1.462 (10) |
N3—H3B | 0.8600 | C6—H6 | 0.9300 |
N4—C1 | 1.341 (11) | C7—S1 | 1.715 (8) |
S1—Hg1—S1i | 113.68 (10) | C3—C2—H2 | 119.8 |
S1—Hg1—I1i | 113.13 (5) | C1—C2—H2 | 119.8 |
S1i—Hg1—I1i | 93.02 (4) | C2—C3—C4 | 118.7 (8) |
S1—Hg1—I1 | 93.02 (4) | C2—C3—H3 | 120.6 |
S1i—Hg1—I1 | 113.13 (5) | C4—C3—H3 | 120.6 |
I1i—Hg1—I1 | 131.95 (4) | C3—C4—C5 | 118.9 (8) |
C7—N1—N2 | 118.8 (6) | C3—C4—H4 | 120.6 |
C7—N1—H1A | 120.6 | C5—C4—H4 | 120.6 |
N2—N1—H1A | 120.6 | N4—C5—C4 | 122.4 (7) |
C6—N2—N1 | 115.1 (6) | N4—C5—C6 | 115.2 (6) |
C7—N3—H3A | 120.0 | C4—C5—C6 | 122.4 (7) |
C7—N3—H3B | 120.0 | N2—C6—C5 | 120.4 (6) |
H3A—N3—H3B | 120.0 | N2—C6—H6 | 119.8 |
C1—N4—C5 | 117.7 (7) | C5—C6—H6 | 119.8 |
N4—C1—C2 | 121.9 (8) | N3—C7—N1 | 119.4 (7) |
N4—C1—H1 | 119.0 | N3—C7—S1 | 124.3 (6) |
C2—C1—H1 | 119.0 | N1—C7—S1 | 116.3 (5) |
C3—C2—C1 | 120.4 (8) | C7—S1—Hg1 | 108.7 (3) |
C7—N1—N2—C6 | −177.2 (7) | N4—C5—C6—N2 | 172.4 (7) |
C5—N4—C1—C2 | 0.7 (13) | C4—C5—C6—N2 | −7.7 (11) |
N4—C1—C2—C3 | 0.0 (16) | N2—N1—C7—N3 | 3.0 (11) |
C1—C2—C3—C4 | −0.5 (16) | N2—N1—C7—S1 | −175.4 (5) |
C2—C3—C4—C5 | 0.3 (15) | N3—C7—S1—Hg1 | 24.2 (8) |
C1—N4—C5—C4 | −0.9 (11) | N1—C7—S1—Hg1 | −157.5 (5) |
C1—N4—C5—C6 | 179.1 (7) | S1i—Hg1—S1—C7 | 52.4 (3) |
C3—C4—C5—N4 | 0.4 (13) | I1i—Hg1—S1—C7 | −52.0 (3) |
C3—C4—C5—C6 | −179.5 (8) | I1—Hg1—S1—C7 | 169.3 (3) |
N1—N2—C6—C5 | 178.3 (6) |
Symmetry code: (i) −x+2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···I1i | 0.86 | 3.13 | 3.978 (7) | 169 |
N1—H1A···N4ii | 0.86 | 2.06 | 2.910 (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] |
Mr | 814.86 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 18.973 (5), 7.0494 (17), 17.454 (4) |
β (°) | 103.137 (3) |
V (Å3) | 2273.4 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 9.69 |
Crystal size (mm) | 0.30 × 0.14 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.159, 0.444 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5534, 2048, 1888 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.110, 1.06 |
No. of reflections | 2048 |
No. of parameters | 124 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0614P)2 + 22.4472P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 2.96, −2.79 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXTL (Bruker, 2001), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···I1i | 0.86 | 3.13 | 3.978 (7) | 169.4 |
N1—H1A···N4ii | 0.86 | 2.06 | 2.910 (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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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.