Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199015450/fr1234sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015450/fr1234Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015450/fr1234IIsup3.hkl |
CCDC references: 142741; 142742
The compound 2-acetylpyridine-(4-phenylthiosemicarbazonoato), HAP4P, was prepared by refluxing equimolar ethanolic solutions of 4-phenylthiosemicarbazide and 2-acetylpyridine, for 30 min. A light yellow crystalline solid was obtained, with mp = 444–447 K.
To obtain the complexes, the ligand (0.20 mmol) dissolved in CH3OH (10 ml) was refluxed for 5 minutes. Then Sn(CH3)2X2 (0.21 mmol), X = Cl, Br, dissolved in CH3OH, was added and refluxed for 1 h. After cooling the solution and slow evaporation of the solvent, the crystalline compounds were obtained, with yields about 70%. The complex with Cl has mp = 443–445 K and with Br has mp = 440–452 K.
Elemental analysis using a HERAEUS CHN indicated: calculated for C14H14N4S: C 62.20, H 5.22, N 20.72%; observed C 60.86, H 5.09, N 20.32%; for C16H19ClN4SSn: calculated C 42.37, H 4.22, N 12.35%; observed: C 42.31, H 4.19, N 12.25%; for C16H19BrN4SSn: calculated C 38.59, H 3.85, N 11.25%; observed: C 37.07, H 3.55 N 11.12%.
The complexes were studied at room temperature by IR, 1H NMR and 119Sn Mössbauer (using a constant acceleration moving CaSnO3 source) spectroscopies.
The fractional atomic coordinates of HN4 atoms (for both compounds) were found in a difference Fourier map, calculated after convergence of the refinement with all other atoms, and refined. The final distances N4—HN4 are short, 0.72 (4) and 0.73 (5) Å respectively for the compounds with Cl and Br. The positions of all other H atoms were calculated with C—H distances 0.96 Å for methyl groups and 0.93 Å for others. The isotropic displacement parameter 20% greater than those of the heavy atom they are bonded to, were assigned to them. In the complex with Cl, the maximum and minimum electronic density residuals are, respectively, 0.89 and 0.73 Å from the Sn. In the complex with Br, the maximum is 0.94 Å from Sn and the minimum is 0.37 Å from H9A.
Data collection: CAD-4 Software (Enraf-Nonius, 1989) for (I); CAD-4 Software (ENRAF-NONIUS, 1989) for (II). Cell refinement: CAD-4 Software for (I); CAD-4 Software (ENRAF-NONIUS, 1989) for (II). For both compounds, data reduction: SDP (Frenz, 1978). Program(s) used to solve structure: SDP for (I); SDP (Frenz, 1978) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEPIII (Burnett & Johnson, 1996) for (I); ORTEP-III (Burnett & Johnson, 1996) for (II). Software used to prepare material for publication: SHELXL97 for (I); SHELXL97 (Sheldrick, 1997) for (II).
[Sn(C14H13N4S)Cl(CH3)2] | F(000) = 904 |
Mr = 453.55 | Dx = 1.63 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.273 (2) Å | Cell parameters from 25 reflections |
b = 15.238 (2) Å | θ = 10–18° |
c = 11.976 (2) Å | µ = 1.63 mm−1 |
β = 95.63 (1)° | T = 293 K |
V = 1865.7 (5) Å3 | Prism, yellow |
Z = 4 | 0.55 × 0.40 × 0.35 mm |
Enraf-Nonius CAD-4 diffractometer | 4243 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.025 |
Graphite monochromator | θmax = 30.0°, θmin = 2.4° |
ω/2θ scans | h = −14→14 |
Absorption correction: ψ scan (North et al., 1968) | k = −21→0 |
Tmin = 0.481, Tmax = 0.566 | l = −16→0 |
5664 measured reflections | 3 standard reflections every 120 min |
5426 independent reflections | intensity decay: 1.4% |
Refinement on F2 | Primary atom site location: Patterson |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Calculated w = 1/[σ2(Fo2) + (0.0554P)2 + 0.8405P] where P = (Fo2 + 2Fc2)/3 |
5426 reflections | (Δ/σ)max < 0.001 |
211 parameters | Δρmax = 0.99 e Å−3 |
0 restraints | Δρmin = −0.56 e Å−3 |
[Sn(C14H13N4S)Cl(CH3)2] | V = 1865.7 (5) Å3 |
Mr = 453.55 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.273 (2) Å | µ = 1.63 mm−1 |
b = 15.238 (2) Å | T = 293 K |
c = 11.976 (2) Å | 0.55 × 0.40 × 0.35 mm |
β = 95.63 (1)° |
Enraf-Nonius CAD-4 diffractometer | 4243 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.025 |
Tmin = 0.481, Tmax = 0.566 | 3 standard reflections every 120 min |
5664 measured reflections | intensity decay: 1.4% |
5426 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.102 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.99 e Å−3 |
5426 reflections | Δρmin = −0.56 e Å−3 |
211 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. |
x | y | z | Uiso*/Ueq | ||
Sn | 0.227704 (19) | 0.076401 (13) | 0.290183 (16) | 0.04116 (7) | |
Cl | 0.24435 (10) | 0.14284 (7) | 0.49805 (7) | 0.0649 (2) | |
C1 | 0.4008 (4) | 0.0049 (3) | 0.3394 (3) | 0.0665 (10) | |
C2 | 0.1504 (4) | 0.2003 (2) | 0.2363 (4) | 0.0671 (10) | |
N1 | 0.3432 (3) | 0.0989 (2) | 0.1124 (2) | 0.0566 (7) | |
C3 | 0.3057 (3) | 0.0471 (2) | 0.0249 (2) | 0.0419 (6) | |
C4 | 0.3577 (4) | 0.0569 (2) | −0.0766 (3) | 0.0535 (8) | |
C5 | 0.4494 (4) | 0.1213 (3) | −0.0865 (3) | 0.0626 (9) | |
C6 | 0.4871 (4) | 0.1746 (3) | 0.0017 (4) | 0.0692 (10) | |
C7 | 0.4316 (4) | 0.1608 (3) | 0.0987 (4) | 0.0732 (11) | |
C8 | 0.2052 (3) | −0.0199 (2) | 0.0447 (2) | 0.0418 (6) | |
C9 | 0.1652 (4) | −0.0861 (2) | −0.0432 (3) | 0.0591 (9) | |
N2 | 0.1567 (2) | −0.01741 (16) | 0.14058 (19) | 0.0402 (5) | |
N3 | 0.0647 (3) | −0.08129 (16) | 0.1538 (2) | 0.0439 (5) | |
C10 | 0.0109 (3) | −0.07854 (17) | 0.2477 (2) | 0.0393 (5) | |
S | 0.04340 (8) | −0.00500 (5) | 0.35924 (6) | 0.04527 (17) | |
N4 | −0.0819 (3) | −0.13942 (18) | 0.2663 (2) | 0.0472 (6) | |
HN4 | −0.112 (4) | −0.129 (3) | 0.317 (3) | 0.057* | |
C11 | −0.1280 (3) | −0.21187 (19) | 0.2008 (2) | 0.0435 (6) | |
C12 | −0.2356 (3) | −0.2559 (2) | 0.2368 (3) | 0.0513 (7) | |
C13 | −0.2844 (4) | −0.3289 (3) | 0.1791 (3) | 0.0614 (9) | |
C14 | −0.2279 (5) | −0.3601 (3) | 0.0867 (3) | 0.0698 (11) | |
C15 | −0.1212 (5) | −0.3164 (3) | 0.0523 (3) | 0.0747 (12) | |
C16 | −0.0700 (4) | −0.2430 (2) | 0.1093 (3) | 0.0626 (9) | |
H1A | 0.3786 | −0.0542 | 0.3576 | 0.080* | |
H1B | 0.4467 | 0.0322 | 0.4040 | 0.080* | |
H1C | 0.4557 | 0.0043 | 0.2790 | 0.080* | |
H2A | 0.0567 | 0.1969 | 0.2255 | 0.081* | |
H2B | 0.1836 | 0.2162 | 0.1669 | 0.081* | |
H2C | 0.1760 | 0.2438 | 0.2922 | 0.081* | |
H4 | 0.3312 | 0.0206 | −0.1370 | 0.064* | |
H5 | 0.4859 | 0.1285 | −0.1540 | 0.075* | |
H6 | 0.5486 | 0.2187 | −0.0040 | 0.083* | |
H7 | 0.4570 | 0.1971 | 0.1594 | 0.088* | |
H9A | 0.0996 | −0.1239 | −0.0174 | 0.071* | |
H9B | 0.2399 | −0.1204 | −0.0584 | 0.071* | |
H9C | 0.1303 | −0.0568 | −0.1105 | 0.071* | |
H12 | −0.2740 | −0.2361 | 0.2994 | 0.062* | |
H13 | −0.3567 | −0.3577 | 0.2026 | 0.074* | |
H14 | −0.2613 | −0.4096 | 0.0485 | 0.084* | |
H15 | −0.0830 | −0.3366 | −0.0101 | 0.090* | |
H16 | 0.0030 | −0.2149 | 0.0861 | 0.075* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn | 0.04385 (11) | 0.04005 (11) | 0.04028 (11) | −0.00166 (8) | 0.00774 (7) | −0.00380 (8) |
Cl | 0.0722 (5) | 0.0747 (6) | 0.0502 (4) | −0.0116 (5) | 0.0183 (4) | −0.0230 (4) |
C1 | 0.0548 (19) | 0.085 (3) | 0.059 (2) | 0.0189 (19) | 0.0038 (16) | −0.0051 (19) |
C2 | 0.086 (3) | 0.0456 (18) | 0.071 (2) | 0.0080 (18) | 0.013 (2) | 0.0070 (16) |
N1 | 0.0599 (17) | 0.0648 (17) | 0.0472 (14) | −0.0192 (14) | 0.0149 (13) | −0.0059 (13) |
C3 | 0.0429 (14) | 0.0437 (14) | 0.0399 (13) | 0.0039 (12) | 0.0074 (11) | 0.0046 (11) |
C4 | 0.0600 (19) | 0.0560 (19) | 0.0466 (16) | 0.0027 (15) | 0.0158 (14) | 0.0036 (13) |
C5 | 0.062 (2) | 0.066 (2) | 0.065 (2) | 0.0036 (18) | 0.0314 (17) | 0.0178 (18) |
C6 | 0.065 (2) | 0.065 (2) | 0.081 (3) | −0.0168 (18) | 0.0252 (19) | 0.008 (2) |
C7 | 0.079 (3) | 0.077 (3) | 0.065 (2) | −0.035 (2) | 0.018 (2) | −0.007 (2) |
C8 | 0.0427 (14) | 0.0472 (15) | 0.0362 (12) | 0.0025 (12) | 0.0064 (10) | −0.0002 (11) |
C9 | 0.068 (2) | 0.065 (2) | 0.0459 (16) | −0.0151 (17) | 0.0140 (15) | −0.0136 (15) |
N2 | 0.0421 (12) | 0.0419 (12) | 0.0377 (11) | −0.0040 (10) | 0.0089 (9) | −0.0030 (9) |
N3 | 0.0512 (13) | 0.0402 (12) | 0.0419 (12) | −0.0110 (10) | 0.0123 (10) | −0.0050 (9) |
C10 | 0.0430 (13) | 0.0357 (12) | 0.0395 (13) | 0.0017 (11) | 0.0059 (10) | 0.0008 (10) |
S | 0.0511 (4) | 0.0450 (4) | 0.0419 (3) | −0.0048 (3) | 0.0153 (3) | −0.0075 (3) |
N4 | 0.0547 (15) | 0.0465 (14) | 0.0425 (13) | −0.0113 (12) | 0.0152 (11) | −0.0060 (11) |
C11 | 0.0506 (15) | 0.0397 (14) | 0.0401 (13) | −0.0046 (12) | 0.0039 (11) | 0.0018 (11) |
C12 | 0.0500 (16) | 0.0580 (19) | 0.0458 (15) | −0.0090 (14) | 0.0046 (13) | −0.0003 (14) |
C13 | 0.061 (2) | 0.062 (2) | 0.060 (2) | −0.0174 (17) | 0.0003 (16) | 0.0040 (16) |
C14 | 0.094 (3) | 0.056 (2) | 0.058 (2) | −0.023 (2) | −0.0004 (19) | −0.0094 (17) |
C15 | 0.112 (4) | 0.058 (2) | 0.058 (2) | −0.022 (2) | 0.027 (2) | −0.0133 (17) |
C16 | 0.087 (3) | 0.0482 (18) | 0.0563 (19) | −0.0201 (17) | 0.0263 (18) | −0.0096 (15) |
Sn—C1 | 2.120 (4) | C8—N2 | 1.296 (3) |
Sn—C2 | 2.124 (4) | C8—C9 | 1.487 (4) |
Sn—N2 | 2.351 (2) | C9—H9A | 0.9600 |
Sn—S | 2.4728 (8) | C9—H9B | 0.9600 |
Sn—N1 | 2.560 (3) | C9—H9C | 0.9600 |
Sn—Cl | 2.6772 (9) | N2—N3 | 1.377 (3) |
C1—H1A | 0.9600 | N3—C10 | 1.301 (3) |
C1—H1B | 0.9600 | C10—N4 | 1.364 (4) |
C1—H1C | 0.9600 | C10—S | 1.750 (3) |
C2—H2A | 0.9600 | N4—C11 | 1.409 (4) |
C2—H2B | 0.9600 | N4—HN4 | 0.72 (4) |
C2—H2C | 0.9600 | C11—C16 | 1.382 (4) |
N1—C7 | 1.331 (5) | C11—C12 | 1.397 (4) |
N1—C3 | 1.337 (4) | C12—C13 | 1.378 (5) |
C3—C4 | 1.384 (4) | C12—H12 | 0.9300 |
C3—C8 | 1.487 (4) | C13—C14 | 1.383 (6) |
C4—C5 | 1.374 (5) | C13—H13 | 0.9300 |
C4—H4 | 0.9300 | C14—C15 | 1.379 (6) |
C5—C6 | 1.358 (6) | C14—H14 | 0.9300 |
C5—H5 | 0.9300 | C15—C16 | 1.387 (5) |
C6—C7 | 1.360 (5) | C15—H15 | 0.9300 |
C6—H6 | 0.9300 | C16—H16 | 0.9300 |
C7—H7 | 0.9300 | ||
C1—Sn—C2 | 145.09 (18) | N1—C7—C6 | 124.3 (4) |
C1—Sn—N2 | 95.09 (13) | N1—C7—H7 | 117.9 |
C2—Sn—N2 | 103.31 (13) | C6—C7—H7 | 117.9 |
C1—Sn—S | 107.35 (13) | N2—C8—C9 | 122.9 (3) |
C2—Sn—S | 105.77 (12) | N2—C8—C3 | 117.0 (3) |
N2—Sn—S | 76.08 (6) | C9—C8—C3 | 120.1 (3) |
C1—Sn—N1 | 81.70 (13) | C8—C9—H9A | 109.5 |
C2—Sn—N1 | 79.54 (14) | C8—C9—H9B | 109.5 |
N2—Sn—N1 | 65.30 (9) | H9A—C9—H9B | 109.5 |
S—Sn—N1 | 141.06 (7) | C8—C9—H9C | 109.5 |
C1—Sn—Cl | 87.73 (11) | H9A—C9—H9C | 109.5 |
C2—Sn—Cl | 86.22 (12) | H9B—C9—H9C | 109.5 |
N2—Sn—Cl | 157.68 (6) | C8—N2—N3 | 114.2 (2) |
S—Sn—Cl | 81.94 (3) | C8—N2—Sn | 125.09 (19) |
N1—Sn—Cl | 136.90 (7) | N3—N2—Sn | 120.48 (17) |
Sn—C1—H1A | 109.5 | C10—N3—N2 | 115.5 (2) |
Sn—C1—H1B | 109.5 | N3—C10—N4 | 118.8 (3) |
H1A—C1—H1B | 109.5 | N3—C10—S | 127.9 (2) |
Sn—C1—H1C | 109.5 | N4—C10—S | 113.3 (2) |
H1A—C1—H1C | 109.5 | C10—S—Sn | 99.25 (10) |
H1B—C1—H1C | 109.5 | C10—N4—C11 | 130.1 (3) |
Sn—C2—H2A | 109.5 | C10—N4—HN4 | 111 (3) |
Sn—C2—H2B | 109.5 | C11—N4—HN4 | 119 (3) |
H2A—C2—H2B | 109.5 | C16—C11—C12 | 119.7 (3) |
Sn—C2—H2C | 109.5 | C16—C11—N4 | 124.2 (3) |
H2A—C2—H2C | 109.5 | C12—C11—N4 | 115.9 (3) |
H2B—C2—H2C | 109.5 | C13—C12—C11 | 119.5 (3) |
C7—N1—C3 | 118.0 (3) | C13—C12—H12 | 120.2 |
C7—N1—Sn | 125.1 (3) | C11—C12—H12 | 120.2 |
C3—N1—Sn | 116.8 (2) | C12—C13—C14 | 121.2 (3) |
N1—C3—C4 | 121.2 (3) | C12—C13—H13 | 119.4 |
N1—C3—C8 | 115.5 (3) | C14—C13—H13 | 119.4 |
C4—C3—C8 | 123.2 (3) | C15—C14—C13 | 118.8 (4) |
C5—C4—C3 | 118.7 (3) | C15—C14—H14 | 120.6 |
C5—C4—H4 | 120.7 | C13—C14—H14 | 120.6 |
C3—C4—H4 | 120.7 | C14—C15—C16 | 121.1 (4) |
C6—C5—C4 | 120.4 (3) | C14—C15—H15 | 119.4 |
C6—C5—H5 | 119.8 | C16—C15—H15 | 119.4 |
C4—C5—H5 | 119.8 | C11—C16—C15 | 119.6 (3) |
C5—C6—C7 | 117.5 (4) | C11—C16—H16 | 120.2 |
C5—C6—H6 | 121.3 | C15—C16—H16 | 120.2 |
C7—C6—H6 | 121.3 |
[SnBr(C14H13N4S)(CH3)2] | F(000) = 976 |
Mr = 497.92 | Dx = 1.764 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.1858 (9) Å | Cell parameters from 25 reflections |
b = 15.3819 (18) Å | θ = 10–19° |
c = 12.0726 (7) Å | µ = 3.61 mm−1 |
β = 97.560 (6)° | T = 293 K |
V = 1875.1 (3) Å3 | Prism, yellow |
Z = 4 | 0.22 × 0.20 × 0.10 mm |
Enraf-Nonius CAD-4 diffractometer | 3161 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.050 |
Graphite monochromator | θmax = 30.0°, θmin = 2.4° |
ω/2θ scans | h = −14→14 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→21 |
Tmin = 0.548, Tmax = 0.697 | l = 0→16 |
5663 measured reflections | 3 standard reflections every 120 min |
5433 independent reflections | intensity decay: 4.8% |
Refinement on F2 | Primary atom site location: Patterson |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Calculated w = 1/[σ2(Fo2) + (0.0298P)2 + 3.6976P] where P = (Fo2 + 2Fc2)/3 |
5433 reflections | (Δ/σ)max < 0.001 |
211 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.63 e Å−3 |
[SnBr(C14H13N4S)(CH3)2] | V = 1875.1 (3) Å3 |
Mr = 497.92 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.1858 (9) Å | µ = 3.61 mm−1 |
b = 15.3819 (18) Å | T = 293 K |
c = 12.0726 (7) Å | 0.22 × 0.20 × 0.10 mm |
β = 97.560 (6)° |
Enraf-Nonius CAD-4 diffractometer | 3161 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.050 |
Tmin = 0.548, Tmax = 0.697 | 3 standard reflections every 120 min |
5663 measured reflections | intensity decay: 4.8% |
5433 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.60 e Å−3 |
5433 reflections | Δρmin = −0.63 e Å−3 |
211 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. |
x | y | z | Uiso*/Ueq | ||
Sn | 0.22808 (3) | 0.07334 (2) | 0.28115 (3) | 0.03828 (10) | |
Br | 0.25249 (6) | 0.14109 (4) | 0.50777 (5) | 0.05845 (18) | |
C1 | 0.4046 (5) | 0.0043 (4) | 0.3327 (5) | 0.0590 (15) | |
C2 | 0.1492 (7) | 0.1973 (4) | 0.2348 (5) | 0.0656 (17) | |
N1 | 0.3364 (5) | 0.0985 (3) | 0.1076 (4) | 0.0521 (12) | |
C3 | 0.3003 (5) | 0.0455 (3) | 0.0216 (4) | 0.0383 (11) | |
C4 | 0.3522 (6) | 0.0544 (4) | −0.0784 (5) | 0.0538 (14) | |
C5 | 0.4428 (6) | 0.1207 (4) | −0.0877 (6) | 0.0622 (17) | |
C6 | 0.4785 (6) | 0.1745 (4) | −0.0001 (6) | 0.0641 (17) | |
C7 | 0.4247 (6) | 0.1611 (4) | 0.0958 (6) | 0.0649 (17) | |
C8 | 0.2032 (5) | −0.0221 (3) | 0.0395 (4) | 0.0370 (10) | |
C9 | 0.1629 (6) | −0.0896 (4) | −0.0466 (5) | 0.0556 (15) | |
N2 | 0.1541 (4) | −0.0198 (2) | 0.1344 (3) | 0.0358 (9) | |
N3 | 0.0637 (4) | −0.0840 (2) | 0.1468 (3) | 0.0395 (9) | |
C10 | 0.0124 (5) | −0.0815 (3) | 0.2415 (4) | 0.0371 (10) | |
S | 0.04525 (13) | −0.00743 (8) | 0.35047 (10) | 0.0409 (3) | |
N4 | −0.0776 (4) | −0.1430 (3) | 0.2587 (3) | 0.0416 (10) | |
HN4 | −0.105 (6) | −0.136 (4) | 0.311 (5) | 0.050* | |
C11 | −0.1261 (5) | −0.2157 (3) | 0.1936 (4) | 0.0393 (11) | |
C12 | −0.2307 (6) | −0.2606 (3) | 0.2289 (4) | 0.0484 (13) | |
C13 | −0.2818 (6) | −0.3332 (4) | 0.1724 (5) | 0.0558 (14) | |
C14 | −0.2282 (7) | −0.3637 (4) | 0.0809 (5) | 0.0639 (17) | |
C15 | −0.1234 (7) | −0.3198 (4) | 0.0464 (5) | 0.0673 (18) | |
C16 | −0.0714 (6) | −0.2461 (4) | 0.1026 (5) | 0.0556 (15) | |
H1A | 0.3834 | −0.0529 | 0.3568 | 0.071* | |
H1B | 0.4554 | 0.0346 | 0.3934 | 0.071* | |
H1C | 0.4554 | −0.0002 | 0.2713 | 0.071* | |
H2A | 0.2152 | 0.2410 | 0.2554 | 0.079* | |
H2B | 0.0735 | 0.2082 | 0.2724 | 0.079* | |
H2C | 0.1232 | 0.1989 | 0.1554 | 0.079* | |
H4 | 0.3269 | 0.0169 | −0.1378 | 0.065* | |
H5 | 0.4789 | 0.1281 | −0.1539 | 0.075* | |
H6 | 0.5382 | 0.2195 | −0.0054 | 0.077* | |
H7 | 0.4508 | 0.1973 | 0.1564 | 0.078* | |
H9A | 0.0966 | −0.1264 | −0.0216 | 0.067* | |
H9B | 0.2386 | −0.1239 | −0.0583 | 0.067* | |
H9C | 0.1276 | −0.0619 | −0.1154 | 0.067* | |
H12 | −0.2668 | −0.2414 | 0.2914 | 0.058* | |
H13 | −0.3532 | −0.3621 | 0.1963 | 0.067* | |
H14 | −0.2624 | −0.4131 | 0.0431 | 0.077* | |
H15 | −0.0866 | −0.3397 | −0.0155 | 0.081* | |
H16 | 0.0001 | −0.2174 | 0.0788 | 0.067* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn | 0.04041 (18) | 0.03608 (17) | 0.03917 (18) | −0.00284 (16) | 0.00836 (13) | −0.00249 (15) |
Br | 0.0643 (4) | 0.0658 (4) | 0.0491 (3) | −0.0100 (3) | 0.0219 (3) | −0.0212 (3) |
C1 | 0.049 (3) | 0.077 (4) | 0.051 (3) | 0.016 (3) | 0.007 (3) | −0.009 (3) |
C2 | 0.087 (5) | 0.039 (3) | 0.072 (4) | −0.001 (3) | 0.014 (4) | 0.007 (3) |
N1 | 0.055 (3) | 0.059 (3) | 0.044 (3) | −0.022 (2) | 0.014 (2) | −0.006 (2) |
C3 | 0.045 (3) | 0.036 (2) | 0.036 (3) | 0.003 (2) | 0.009 (2) | 0.005 (2) |
C4 | 0.052 (3) | 0.065 (4) | 0.049 (3) | 0.002 (3) | 0.019 (3) | 0.001 (3) |
C5 | 0.061 (4) | 0.059 (4) | 0.072 (4) | 0.001 (3) | 0.030 (3) | 0.021 (3) |
C6 | 0.058 (4) | 0.061 (4) | 0.077 (4) | −0.020 (3) | 0.023 (3) | 0.005 (3) |
C7 | 0.061 (4) | 0.069 (4) | 0.067 (4) | −0.027 (3) | 0.018 (3) | −0.008 (3) |
C8 | 0.036 (2) | 0.044 (3) | 0.032 (2) | 0.001 (2) | 0.0103 (19) | −0.003 (2) |
C9 | 0.064 (4) | 0.058 (4) | 0.047 (3) | −0.004 (3) | 0.019 (3) | −0.006 (3) |
N2 | 0.039 (2) | 0.033 (2) | 0.036 (2) | −0.0014 (17) | 0.0116 (17) | −0.0013 (16) |
N3 | 0.051 (2) | 0.034 (2) | 0.035 (2) | −0.0084 (19) | 0.0114 (18) | −0.0046 (17) |
C10 | 0.037 (2) | 0.032 (2) | 0.043 (3) | −0.002 (2) | 0.006 (2) | −0.001 (2) |
S | 0.0465 (7) | 0.0404 (6) | 0.0385 (6) | −0.0069 (6) | 0.0157 (5) | −0.0074 (5) |
N4 | 0.051 (3) | 0.040 (2) | 0.035 (2) | −0.013 (2) | 0.0121 (19) | −0.0063 (19) |
C11 | 0.048 (3) | 0.034 (2) | 0.036 (3) | −0.004 (2) | 0.007 (2) | 0.002 (2) |
C12 | 0.056 (3) | 0.050 (3) | 0.041 (3) | −0.014 (3) | 0.009 (2) | −0.003 (2) |
C13 | 0.059 (4) | 0.054 (3) | 0.054 (3) | −0.016 (3) | 0.009 (3) | −0.004 (3) |
C14 | 0.087 (5) | 0.047 (3) | 0.057 (4) | −0.012 (3) | 0.006 (3) | −0.006 (3) |
C15 | 0.101 (5) | 0.047 (3) | 0.059 (4) | −0.017 (3) | 0.032 (4) | −0.016 (3) |
C16 | 0.072 (4) | 0.046 (3) | 0.054 (3) | −0.018 (3) | 0.027 (3) | −0.009 (3) |
Sn—C1 | 2.111 (5) | C8—N2 | 1.310 (6) |
Sn—C2 | 2.115 (6) | C8—C9 | 1.487 (7) |
Sn—N2 | 2.325 (4) | C9—H9A | 0.9600 |
Sn—S | 2.4743 (12) | C9—H9B | 0.9600 |
Sn—N1 | 2.523 (4) | C9—H9C | 0.9600 |
Sn—Br | 2.9075 (6) | N2—N3 | 1.371 (5) |
C1—H1A | 0.9600 | N3—C10 | 1.319 (6) |
C1—H1B | 0.9600 | C10—N4 | 1.353 (6) |
C1—H1C | 0.9600 | C10—S | 1.739 (5) |
C2—H2A | 0.9600 | N4—C11 | 1.417 (6) |
C2—H2B | 0.9600 | N4—HN4 | 0.73 (5) |
C2—H2C | 0.9600 | C11—C16 | 1.378 (7) |
N1—C3 | 1.333 (6) | C11—C12 | 1.383 (7) |
N1—C7 | 1.338 (7) | C12—C13 | 1.375 (7) |
C3—C4 | 1.387 (7) | C12—H12 | 0.9300 |
C3—C8 | 1.470 (7) | C13—C14 | 1.378 (8) |
C4—C5 | 1.390 (8) | C13—H13 | 0.9300 |
C4—H4 | 0.9300 | C14—C15 | 1.373 (8) |
C5—C6 | 1.354 (9) | C14—H14 | 0.9300 |
C5—H5 | 0.9300 | C15—C16 | 1.389 (8) |
C6—C7 | 1.360 (8) | C15—H15 | 0.9300 |
C6—H6 | 0.9300 | C16—H16 | 0.9300 |
C7—H7 | 0.9300 | ||
C1—Sn—C2 | 144.2 (3) | N1—C7—C6 | 123.4 (6) |
C1—Sn—N2 | 95.3 (2) | N1—C7—H7 | 118.3 |
C2—Sn—N2 | 106.3 (2) | C6—C7—H7 | 118.3 |
C1—Sn—S | 107.31 (18) | N2—C8—C3 | 116.8 (4) |
C2—Sn—S | 105.40 (18) | N2—C8—C9 | 121.9 (4) |
N2—Sn—S | 76.43 (10) | C3—C8—C9 | 121.3 (4) |
C1—Sn—N1 | 82.7 (2) | C8—C9—H9A | 109.5 |
C2—Sn—N1 | 80.4 (2) | C8—C9—H9B | 109.5 |
N2—Sn—N1 | 66.12 (14) | H9A—C9—H9B | 109.5 |
S—Sn—N1 | 142.07 (10) | C8—C9—H9C | 109.5 |
C1—Sn—Br | 86.49 (16) | H9A—C9—H9C | 109.5 |
C2—Sn—Br | 84.76 (18) | H9B—C9—H9C | 109.5 |
N2—Sn—Br | 156.45 (9) | C8—N2—N3 | 114.5 (4) |
S—Sn—Br | 80.60 (3) | C8—N2—Sn | 124.1 (3) |
N1—Sn—Br | 137.21 (10) | N3—N2—Sn | 121.0 (3) |
Sn—C1—H1A | 109.5 | C10—N3—N2 | 114.9 (4) |
Sn—C1—H1B | 109.5 | N3—C10—N4 | 117.8 (4) |
H1A—C1—H1B | 109.5 | N3—C10—S | 128.1 (4) |
Sn—C1—H1C | 109.5 | N4—C10—S | 114.1 (3) |
H1A—C1—H1C | 109.5 | C10—S—Sn | 98.71 (16) |
H1B—C1—H1C | 109.5 | C10—N4—C11 | 131.3 (4) |
Sn—C2—H2A | 109.5 | C10—N4—HN4 | 112 (5) |
Sn—C2—H2B | 109.5 | C11—N4—HN4 | 117 (5) |
H2A—C2—H2B | 109.5 | C16—C11—C12 | 118.9 (5) |
Sn—C2—H2C | 109.5 | C16—C11—N4 | 124.2 (5) |
H2A—C2—H2C | 109.5 | C12—C11—N4 | 116.7 (4) |
H2B—C2—H2C | 109.5 | C13—C12—C11 | 120.7 (5) |
C3—N1—C7 | 118.5 (5) | C13—C12—H12 | 119.7 |
C3—N1—Sn | 116.5 (3) | C11—C12—H12 | 119.7 |
C7—N1—Sn | 124.9 (4) | C14—C13—C12 | 120.7 (6) |
N1—C3—C4 | 121.3 (5) | C14—C13—H13 | 119.7 |
N1—C3—C8 | 116.1 (4) | C12—C13—H13 | 119.7 |
C4—C3—C8 | 122.6 (5) | C15—C14—C13 | 118.8 (6) |
C5—C4—C3 | 118.4 (6) | C15—C14—H14 | 120.6 |
C5—C4—H4 | 120.8 | C13—C14—H14 | 120.6 |
C3—C4—H4 | 120.8 | C14—C15—C16 | 120.9 (6) |
C6—C5—C4 | 119.9 (6) | C14—C15—H15 | 119.5 |
C6—C5—H5 | 120.1 | C16—C15—H15 | 119.5 |
C4—C5—H5 | 120.1 | C11—C16—C15 | 119.9 (5) |
C5—C6—C7 | 118.4 (6) | C11—C16—H16 | 120.0 |
C5—C6—H6 | 120.8 | C15—C16—H16 | 120.0 |
C7—C6—H6 | 120.8 |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Sn(C14H13N4S)Cl(CH3)2] | [SnBr(C14H13N4S)(CH3)2] |
Mr | 453.55 | 497.92 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 10.273 (2), 15.238 (2), 11.976 (2) | 10.1858 (9), 15.3819 (18), 12.0726 (7) |
β (°) | 95.63 (1) | 97.560 (6) |
V (Å3) | 1865.7 (5) | 1875.1 (3) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.63 | 3.61 |
Crystal size (mm) | 0.55 × 0.40 × 0.35 | 0.22 × 0.20 × 0.10 |
Data collection | ||
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.481, 0.566 | 0.548, 0.697 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5664, 5426, 4243 | 5663, 5433, 3161 |
Rint | 0.025 | 0.050 |
(sin θ/λ)max (Å−1) | 0.703 | 0.702 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.102, 1.07 | 0.040, 0.106, 1.05 |
No. of reflections | 5426 | 5433 |
No. of parameters | 211 | 211 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.99, −0.56 | 0.60, −0.63 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software (ENRAF-NONIUS, 1989), CAD-4 Software, SDP (Frenz, 1978), SDP, SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), ORTEP-III (Burnett & Johnson, 1996), SHELXL97.
Sn—C1 | 2.120 (4) | N1—C3 | 1.337 (4) |
Sn—C2 | 2.124 (4) | C3—C8 | 1.487 (4) |
Sn—N2 | 2.351 (2) | C8—N2 | 1.296 (3) |
Sn—S | 2.4728 (8) | N2—N3 | 1.377 (3) |
Sn—N1 | 2.560 (3) | N3—C10 | 1.301 (3) |
Sn—Cl | 2.6772 (9) | C10—S | 1.750 (3) |
N1—C7 | 1.331 (5) | ||
C1—Sn—C2 | 145.09 (18) | C1—Sn—Cl | 87.73 (11) |
C1—Sn—N2 | 95.09 (13) | C2—Sn—Cl | 86.22 (12) |
C2—Sn—N2 | 103.31 (13) | S—Sn—Cl | 81.94 (3) |
C1—Sn—S | 107.35 (13) | N1—Sn—Cl | 136.90 (7) |
C2—Sn—S | 105.77 (12) | C8—N2—N3 | 114.2 (2) |
N2—Sn—S | 76.08 (6) | C8—N2—Sn | 125.09 (19) |
C1—Sn—N1 | 81.70 (13) | N3—N2—Sn | 120.48 (17) |
C2—Sn—N1 | 79.54 (14) | C10—N3—N2 | 115.5 (2) |
N2—Sn—N1 | 65.30 (9) | N3—C10—S | 127.9 (2) |
Sn—C1 | 2.111 (5) | N1—C7 | 1.338 (7) |
Sn—C2 | 2.115 (6) | C3—C8 | 1.470 (7) |
Sn—N2 | 2.325 (4) | C8—N2 | 1.310 (6) |
Sn—S | 2.4743 (12) | N2—N3 | 1.371 (5) |
Sn—N1 | 2.523 (4) | N3—C10 | 1.319 (6) |
Sn—Br | 2.9075 (6) | C10—S | 1.739 (5) |
N1—C3 | 1.333 (6) | ||
C1—Sn—C2 | 144.2 (3) | C1—Sn—Br | 86.49 (16) |
C1—Sn—N2 | 95.3 (2) | C2—Sn—Br | 84.76 (18) |
C2—Sn—N2 | 106.3 (2) | S—Sn—Br | 80.60 (3) |
C1—Sn—S | 107.31 (18) | N1—Sn—Br | 137.21 (10) |
C2—Sn—S | 105.40 (18) | C8—N2—N3 | 114.5 (4) |
N2—Sn—S | 76.43 (10) | C8—N2—Sn | 124.1 (3) |
C1—Sn—N1 | 82.7 (2) | N3—N2—Sn | 121.0 (3) |
C2—Sn—N1 | 80.4 (2) | C10—N3—N2 | 114.9 (4) |
N2—Sn—N1 | 66.12 (14) | N3—C10—S | 128.1 (4) |
S—Sn—N1 | 142.07 (10) |
N,N,S-tridentate-N(4)-heterocyclic thiosemicarbazones derived from 2-formyl and 2-acetylpyridine, include important classes of compounds with biological activity (West et al., 1998; Labib et al., 1996; West et al., 1991).
The chelating behavior of N,N,S-tridentate thiosemicarbazones revealed three coordination modes. They can act as a neutral N(azomethine), S-bidentate ligand (Barbieri et al., 1993) and as anionic (1-) one, bonded through N, N, S or through N(azomethine), S (Bamgboye & Bamgboye, 1988; Labib et al., 1996).
The structure determination of the compounds [SnAP4P(CH3)2Cl] and [SnAP4P(CH3)2Br], where HAP4P = 2-acetylpyridine-(4-phenylthiosemicarbazone), confirmed that they are isomorphous. The chloro derivative is shown at Figure 1. The crystal structure is built up by discrete molecules. The SnIV has a strongly distorted octahedral coordination geometry, with the equatorial plane occupied by the halogen and the thiosemicarbazone derivative. The methyl groups are at the apical positions. Selected bond parameters are given in Tables 1 and 2.
IR spectroscopy of the free ligand and the complexes revealed: (i) the disappearance of the ν(N—H) absorption at 3167 cm−1 as a consequence of the deprotonation of HAP4P for complexation through N2, (ii) the ν(C=N) at 1597, 1528 cm−1 absorption bands found in the free ligand are shifted to 1594, 1549 cm−1 in the chloro complex and to 1595, 1531 cm−1 in the bromo complex, confirming coordination via N2 (Labib et al., 1996), (iii) the ν(C=S) vibrations in the free ligand at 1287, 1218 cm−1 are shifted to lower frequencies by 35–69 cm−1. The same trend is exhibited by the absorption at 896 cm−1 attributed to ν(C=S), found in the spectra of both complexes at 852 cm−1. These observations and the appearance of bands with ν(C—S) character at 762 cm−1 in the spectra of the complexes suggest coordination through thiocarbonyl sulfur (Ferrari et al., 1991). The far infrared spectral bands observed at 355 and 410 cm−1 for [SnAP4P(CH3)2Cl], at 353 and 410 cm−1 for [SnAP4P(CH3)2Br] were tentatively assigned to ν(Sn—N) and ν(Sn—S) modes, respectively (Barbieri et al., 1993; Casas et al., 1994).
The 1H NMR (200 MHz) spectrum in CDCl3 of the chloro derivative showed two singlets in the methyl region, at 1.60 and 1.18 p.p.m. [2J(119Sn—CH3) = 96.4 Hz] due to two magnetically non-equivalent methyl groups bonded in N=C—CH3 and Sn—CH3, respectively. The spectrum in CCl4 of [SnBr(CH3)2AP4P] showed similar singlets at 1.56 and 2.48 p.p.m. [2J(119Sn—CH3) = 73.0 Hz].
Similar results were reported for trigonal bipyramidal complexes, with analogous coordination geometry [Me2SnCl2ImSOMe] [ImSOMe = 1-methyl-2-(methylsulfinyl)imidazol] and [Me2SnClFPT] (FPT = 2-formylpyridine thiosemicarbazone) (Sousa et al., 1996; Labib et al., 1996). In these cases, the tin-proton coupling constants, 2J(119Sn—CH3), are 91.45 (acetone-d6) and 96.0 Hz (DMSO-d6), respectively. These data suggest that probably in solution, these complexes, which are penta-coordinated and have ambidentate ligands, have a strong intramolecular interaction Sn—N(py).
The isomer shifts (δ) of the complexes ([SnAP4P(CH3)2Cl]: 1.38 mm/s, [SnAP4P(CH3)2Br]: 1.42 mm/s) are lower than the values observed for the parent acids: (CH3)2SnCl2: 1.49 mm/s, (CH3)2SnBr2: 1.59 mm/s), as a result of rehybridization to a higher coordination for Sn(IV) in the complexes, leading to a participation smaller than 25% for s orbital (Sousa et al., 1996; Stocker & Sano, 1968). The lower isomer shift value for chloro complex compared to the bromo one, is consistent with the electronegativity of the present ligands.
The quadrupole splittings (Δ) (3.35 mm/s for [SnAP4P(CH3)2Cl]; 3.40 mm/s for [SnAP4P(CH3)2Br]) are very close, indicating the charge distributions around the tin nucleus are similar and highly asymmetric, with highly distorted geometries.