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A thio­semicarbazone derivative, 2-acetyl­pyridine 4-phenyl­thio­semicarbazone, was prepared and complexed to Lewis acids, Sn(CH3)2X2, X = Cl and Br. The products, [SnX(C14H13N4S)(CH3)2], were characterized by single-crystal X-ray diffraction, and IR, NMR and Mössbauer spectroscopies. They are isomorphous and crystallize in the monoclinic space group P21/n. The structure determination revealed discrete neutral complexes with the SnIV atom in a distorted octahedral coordination geometry, with the halogeno ligand and the thio­semicarbazone derivative in the equatorial plane and the methyl groups in axial positions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199015450/fr1234sup1.cif
Contains datablocks global, (I), (II)

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015450/fr1234Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015450/fr1234IIsup3.hkl
Contains datablock gf2new

CCDC references: 142741; 142742

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. View of (I) with displacement ellipsoids plotted at 50% probability level.
(I) [2-acetylpyridine-(4-phenylthiosemicarbazonoato)- N,N,S)]-chloro-transdimethyl-tin(IV), top
Crystal data top
[Sn(C14H13N4S)Cl(CH3)2]F(000) = 904
Mr = 453.55Dx = 1.63 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 10.273 (2) ÅCell parameters from 25 reflections
b = 15.238 (2) Åθ = 10–18°
c = 11.976 (2) ŵ = 1.63 mm1
β = 95.63 (1)°T = 293 K
V = 1865.7 (5) Å3Prism, yellow
Z = 40.55 × 0.40 × 0.35 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
4243 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.025
Graphite monochromatorθmax = 30.0°, θmin = 2.4°
ω/2θ scansh = 1414
Absorption correction: ψ scan
(North et al., 1968)
k = 210
Tmin = 0.481, Tmax = 0.566l = 160
5664 measured reflections3 standard reflections every 120 min
5426 independent reflections intensity decay: 1.4%
Refinement top
Refinement on F2Primary atom site location: Patterson
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 1.07Calculated w = 1/[σ2(Fo2) + (0.0554P)2 + 0.8405P]
where P = (Fo2 + 2Fc2)/3
5426 reflections(Δ/σ)max < 0.001
211 parametersΔρmax = 0.99 e Å3
0 restraintsΔρmin = 0.56 e Å3
Crystal data top
[Sn(C14H13N4S)Cl(CH3)2]V = 1865.7 (5) Å3
Mr = 453.55Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.273 (2) ŵ = 1.63 mm1
b = 15.238 (2) ÅT = 293 K
c = 11.976 (2) Å0.55 × 0.40 × 0.35 mm
β = 95.63 (1)°
Data collection top
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 = 0.5663 standard reflections every 120 min
5664 measured reflections intensity decay: 1.4%
5426 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.99 e Å3
5426 reflectionsΔρmin = 0.56 e Å3
211 parameters
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
Sn0.227704 (19)0.076401 (13)0.290183 (16)0.04116 (7)
Cl0.24435 (10)0.14284 (7)0.49805 (7)0.0649 (2)
C10.4008 (4)0.0049 (3)0.3394 (3)0.0665 (10)
C20.1504 (4)0.2003 (2)0.2363 (4)0.0671 (10)
N10.3432 (3)0.0989 (2)0.1124 (2)0.0566 (7)
C30.3057 (3)0.0471 (2)0.0249 (2)0.0419 (6)
C40.3577 (4)0.0569 (2)0.0766 (3)0.0535 (8)
C50.4494 (4)0.1213 (3)0.0865 (3)0.0626 (9)
C60.4871 (4)0.1746 (3)0.0017 (4)0.0692 (10)
C70.4316 (4)0.1608 (3)0.0987 (4)0.0732 (11)
C80.2052 (3)0.0199 (2)0.0447 (2)0.0418 (6)
C90.1652 (4)0.0861 (2)0.0432 (3)0.0591 (9)
N20.1567 (2)0.01741 (16)0.14058 (19)0.0402 (5)
N30.0647 (3)0.08129 (16)0.1538 (2)0.0439 (5)
C100.0109 (3)0.07854 (17)0.2477 (2)0.0393 (5)
S0.04340 (8)0.00500 (5)0.35924 (6)0.04527 (17)
N40.0819 (3)0.13942 (18)0.2663 (2)0.0472 (6)
HN40.112 (4)0.129 (3)0.317 (3)0.057*
C110.1280 (3)0.21187 (19)0.2008 (2)0.0435 (6)
C120.2356 (3)0.2559 (2)0.2368 (3)0.0513 (7)
C130.2844 (4)0.3289 (3)0.1791 (3)0.0614 (9)
C140.2279 (5)0.3601 (3)0.0867 (3)0.0698 (11)
C150.1212 (5)0.3164 (3)0.0523 (3)0.0747 (12)
C160.0700 (4)0.2430 (2)0.1093 (3)0.0626 (9)
H1A0.37860.05420.35760.080*
H1B0.44670.03220.40400.080*
H1C0.45570.00430.27900.080*
H2A0.05670.19690.22550.081*
H2B0.18360.21620.16690.081*
H2C0.17600.24380.29220.081*
H40.33120.02060.13700.064*
H50.48590.12850.15400.075*
H60.54860.21870.00400.083*
H70.45700.19710.15940.088*
H9A0.09960.12390.01740.071*
H9B0.23990.12040.05840.071*
H9C0.13030.05680.11050.071*
H120.27400.23610.29940.062*
H130.35670.35770.20260.074*
H140.26130.40960.04850.084*
H150.08300.33660.01010.090*
H160.00300.21490.08610.075*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn0.04385 (11)0.04005 (11)0.04028 (11)0.00166 (8)0.00774 (7)0.00380 (8)
Cl0.0722 (5)0.0747 (6)0.0502 (4)0.0116 (5)0.0183 (4)0.0230 (4)
C10.0548 (19)0.085 (3)0.059 (2)0.0189 (19)0.0038 (16)0.0051 (19)
C20.086 (3)0.0456 (18)0.071 (2)0.0080 (18)0.013 (2)0.0070 (16)
N10.0599 (17)0.0648 (17)0.0472 (14)0.0192 (14)0.0149 (13)0.0059 (13)
C30.0429 (14)0.0437 (14)0.0399 (13)0.0039 (12)0.0074 (11)0.0046 (11)
C40.0600 (19)0.0560 (19)0.0466 (16)0.0027 (15)0.0158 (14)0.0036 (13)
C50.062 (2)0.066 (2)0.065 (2)0.0036 (18)0.0314 (17)0.0178 (18)
C60.065 (2)0.065 (2)0.081 (3)0.0168 (18)0.0252 (19)0.008 (2)
C70.079 (3)0.077 (3)0.065 (2)0.035 (2)0.018 (2)0.007 (2)
C80.0427 (14)0.0472 (15)0.0362 (12)0.0025 (12)0.0064 (10)0.0002 (11)
C90.068 (2)0.065 (2)0.0459 (16)0.0151 (17)0.0140 (15)0.0136 (15)
N20.0421 (12)0.0419 (12)0.0377 (11)0.0040 (10)0.0089 (9)0.0030 (9)
N30.0512 (13)0.0402 (12)0.0419 (12)0.0110 (10)0.0123 (10)0.0050 (9)
C100.0430 (13)0.0357 (12)0.0395 (13)0.0017 (11)0.0059 (10)0.0008 (10)
S0.0511 (4)0.0450 (4)0.0419 (3)0.0048 (3)0.0153 (3)0.0075 (3)
N40.0547 (15)0.0465 (14)0.0425 (13)0.0113 (12)0.0152 (11)0.0060 (11)
C110.0506 (15)0.0397 (14)0.0401 (13)0.0046 (12)0.0039 (11)0.0018 (11)
C120.0500 (16)0.0580 (19)0.0458 (15)0.0090 (14)0.0046 (13)0.0003 (14)
C130.061 (2)0.062 (2)0.060 (2)0.0174 (17)0.0003 (16)0.0040 (16)
C140.094 (3)0.056 (2)0.058 (2)0.023 (2)0.0004 (19)0.0094 (17)
C150.112 (4)0.058 (2)0.058 (2)0.022 (2)0.027 (2)0.0133 (17)
C160.087 (3)0.0482 (18)0.0563 (19)0.0201 (17)0.0263 (18)0.0096 (15)
Geometric parameters (Å, º) top
Sn—C12.120 (4)C8—N21.296 (3)
Sn—C22.124 (4)C8—C91.487 (4)
Sn—N22.351 (2)C9—H9A0.9600
Sn—S2.4728 (8)C9—H9B0.9600
Sn—N12.560 (3)C9—H9C0.9600
Sn—Cl2.6772 (9)N2—N31.377 (3)
C1—H1A0.9600N3—C101.301 (3)
C1—H1B0.9600C10—N41.364 (4)
C1—H1C0.9600C10—S1.750 (3)
C2—H2A0.9600N4—C111.409 (4)
C2—H2B0.9600N4—HN40.72 (4)
C2—H2C0.9600C11—C161.382 (4)
N1—C71.331 (5)C11—C121.397 (4)
N1—C31.337 (4)C12—C131.378 (5)
C3—C41.384 (4)C12—H120.9300
C3—C81.487 (4)C13—C141.383 (6)
C4—C51.374 (5)C13—H130.9300
C4—H40.9300C14—C151.379 (6)
C5—C61.358 (6)C14—H140.9300
C5—H50.9300C15—C161.387 (5)
C6—C71.360 (5)C15—H150.9300
C6—H60.9300C16—H160.9300
C7—H70.9300
C1—Sn—C2145.09 (18)N1—C7—C6124.3 (4)
C1—Sn—N295.09 (13)N1—C7—H7117.9
C2—Sn—N2103.31 (13)C6—C7—H7117.9
C1—Sn—S107.35 (13)N2—C8—C9122.9 (3)
C2—Sn—S105.77 (12)N2—C8—C3117.0 (3)
N2—Sn—S76.08 (6)C9—C8—C3120.1 (3)
C1—Sn—N181.70 (13)C8—C9—H9A109.5
C2—Sn—N179.54 (14)C8—C9—H9B109.5
N2—Sn—N165.30 (9)H9A—C9—H9B109.5
S—Sn—N1141.06 (7)C8—C9—H9C109.5
C1—Sn—Cl87.73 (11)H9A—C9—H9C109.5
C2—Sn—Cl86.22 (12)H9B—C9—H9C109.5
N2—Sn—Cl157.68 (6)C8—N2—N3114.2 (2)
S—Sn—Cl81.94 (3)C8—N2—Sn125.09 (19)
N1—Sn—Cl136.90 (7)N3—N2—Sn120.48 (17)
Sn—C1—H1A109.5C10—N3—N2115.5 (2)
Sn—C1—H1B109.5N3—C10—N4118.8 (3)
H1A—C1—H1B109.5N3—C10—S127.9 (2)
Sn—C1—H1C109.5N4—C10—S113.3 (2)
H1A—C1—H1C109.5C10—S—Sn99.25 (10)
H1B—C1—H1C109.5C10—N4—C11130.1 (3)
Sn—C2—H2A109.5C10—N4—HN4111 (3)
Sn—C2—H2B109.5C11—N4—HN4119 (3)
H2A—C2—H2B109.5C16—C11—C12119.7 (3)
Sn—C2—H2C109.5C16—C11—N4124.2 (3)
H2A—C2—H2C109.5C12—C11—N4115.9 (3)
H2B—C2—H2C109.5C13—C12—C11119.5 (3)
C7—N1—C3118.0 (3)C13—C12—H12120.2
C7—N1—Sn125.1 (3)C11—C12—H12120.2
C3—N1—Sn116.8 (2)C12—C13—C14121.2 (3)
N1—C3—C4121.2 (3)C12—C13—H13119.4
N1—C3—C8115.5 (3)C14—C13—H13119.4
C4—C3—C8123.2 (3)C15—C14—C13118.8 (4)
C5—C4—C3118.7 (3)C15—C14—H14120.6
C5—C4—H4120.7C13—C14—H14120.6
C3—C4—H4120.7C14—C15—C16121.1 (4)
C6—C5—C4120.4 (3)C14—C15—H15119.4
C6—C5—H5119.8C16—C15—H15119.4
C4—C5—H5119.8C11—C16—C15119.6 (3)
C5—C6—C7117.5 (4)C11—C16—H16120.2
C5—C6—H6121.3C15—C16—H16120.2
C7—C6—H6121.3
(II) [2-acetylpyridine-(4-phenylthiosemicarbazonoato)- N,N,S)]-bromo-transdimethyl-tin(IV), top
Crystal data top
[SnBr(C14H13N4S)(CH3)2]F(000) = 976
Mr = 497.92Dx = 1.764 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 10.1858 (9) ÅCell parameters from 25 reflections
b = 15.3819 (18) Åθ = 10–19°
c = 12.0726 (7) ŵ = 3.61 mm1
β = 97.560 (6)°T = 293 K
V = 1875.1 (3) Å3Prism, yellow
Z = 40.22 × 0.20 × 0.10 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
3161 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.050
Graphite monochromatorθmax = 30.0°, θmin = 2.4°
ω/2θ scansh = 1414
Absorption correction: ψ scan
(North et al., 1968)
k = 021
Tmin = 0.548, Tmax = 0.697l = 016
5663 measured reflections3 standard reflections every 120 min
5433 independent reflections intensity decay: 4.8%
Refinement top
Refinement on F2Primary atom site location: Patterson
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.05Calculated w = 1/[σ2(Fo2) + (0.0298P)2 + 3.6976P]
where P = (Fo2 + 2Fc2)/3
5433 reflections(Δ/σ)max < 0.001
211 parametersΔρmax = 0.60 e Å3
0 restraintsΔρmin = 0.63 e Å3
Crystal data top
[SnBr(C14H13N4S)(CH3)2]V = 1875.1 (3) Å3
Mr = 497.92Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.1858 (9) ŵ = 3.61 mm1
b = 15.3819 (18) ÅT = 293 K
c = 12.0726 (7) Å0.22 × 0.20 × 0.10 mm
β = 97.560 (6)°
Data collection top
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 = 0.6973 standard reflections every 120 min
5663 measured reflections intensity decay: 4.8%
5433 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.60 e Å3
5433 reflectionsΔρmin = 0.63 e Å3
211 parameters
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
Sn0.22808 (3)0.07334 (2)0.28115 (3)0.03828 (10)
Br0.25249 (6)0.14109 (4)0.50777 (5)0.05845 (18)
C10.4046 (5)0.0043 (4)0.3327 (5)0.0590 (15)
C20.1492 (7)0.1973 (4)0.2348 (5)0.0656 (17)
N10.3364 (5)0.0985 (3)0.1076 (4)0.0521 (12)
C30.3003 (5)0.0455 (3)0.0216 (4)0.0383 (11)
C40.3522 (6)0.0544 (4)0.0784 (5)0.0538 (14)
C50.4428 (6)0.1207 (4)0.0877 (6)0.0622 (17)
C60.4785 (6)0.1745 (4)0.0001 (6)0.0641 (17)
C70.4247 (6)0.1611 (4)0.0958 (6)0.0649 (17)
C80.2032 (5)0.0221 (3)0.0395 (4)0.0370 (10)
C90.1629 (6)0.0896 (4)0.0466 (5)0.0556 (15)
N20.1541 (4)0.0198 (2)0.1344 (3)0.0358 (9)
N30.0637 (4)0.0840 (2)0.1468 (3)0.0395 (9)
C100.0124 (5)0.0815 (3)0.2415 (4)0.0371 (10)
S0.04525 (13)0.00743 (8)0.35047 (10)0.0409 (3)
N40.0776 (4)0.1430 (3)0.2587 (3)0.0416 (10)
HN40.105 (6)0.136 (4)0.311 (5)0.050*
C110.1261 (5)0.2157 (3)0.1936 (4)0.0393 (11)
C120.2307 (6)0.2606 (3)0.2289 (4)0.0484 (13)
C130.2818 (6)0.3332 (4)0.1724 (5)0.0558 (14)
C140.2282 (7)0.3637 (4)0.0809 (5)0.0639 (17)
C150.1234 (7)0.3198 (4)0.0464 (5)0.0673 (18)
C160.0714 (6)0.2461 (4)0.1026 (5)0.0556 (15)
H1A0.38340.05290.35680.071*
H1B0.45540.03460.39340.071*
H1C0.45540.00020.27130.071*
H2A0.21520.24100.25540.079*
H2B0.07350.20820.27240.079*
H2C0.12320.19890.15540.079*
H40.32690.01690.13780.065*
H50.47890.12810.15390.075*
H60.53820.21950.00540.077*
H70.45080.19730.15640.078*
H9A0.09660.12640.02160.067*
H9B0.23860.12390.05830.067*
H9C0.12760.06190.11540.067*
H120.26680.24140.29140.058*
H130.35320.36210.19630.067*
H140.26240.41310.04310.077*
H150.08660.33970.01550.081*
H160.00010.21740.07880.067*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn0.04041 (18)0.03608 (17)0.03917 (18)0.00284 (16)0.00836 (13)0.00249 (15)
Br0.0643 (4)0.0658 (4)0.0491 (3)0.0100 (3)0.0219 (3)0.0212 (3)
C10.049 (3)0.077 (4)0.051 (3)0.016 (3)0.007 (3)0.009 (3)
C20.087 (5)0.039 (3)0.072 (4)0.001 (3)0.014 (4)0.007 (3)
N10.055 (3)0.059 (3)0.044 (3)0.022 (2)0.014 (2)0.006 (2)
C30.045 (3)0.036 (2)0.036 (3)0.003 (2)0.009 (2)0.005 (2)
C40.052 (3)0.065 (4)0.049 (3)0.002 (3)0.019 (3)0.001 (3)
C50.061 (4)0.059 (4)0.072 (4)0.001 (3)0.030 (3)0.021 (3)
C60.058 (4)0.061 (4)0.077 (4)0.020 (3)0.023 (3)0.005 (3)
C70.061 (4)0.069 (4)0.067 (4)0.027 (3)0.018 (3)0.008 (3)
C80.036 (2)0.044 (3)0.032 (2)0.001 (2)0.0103 (19)0.003 (2)
C90.064 (4)0.058 (4)0.047 (3)0.004 (3)0.019 (3)0.006 (3)
N20.039 (2)0.033 (2)0.036 (2)0.0014 (17)0.0116 (17)0.0013 (16)
N30.051 (2)0.034 (2)0.035 (2)0.0084 (19)0.0114 (18)0.0046 (17)
C100.037 (2)0.032 (2)0.043 (3)0.002 (2)0.006 (2)0.001 (2)
S0.0465 (7)0.0404 (6)0.0385 (6)0.0069 (6)0.0157 (5)0.0074 (5)
N40.051 (3)0.040 (2)0.035 (2)0.013 (2)0.0121 (19)0.0063 (19)
C110.048 (3)0.034 (2)0.036 (3)0.004 (2)0.007 (2)0.002 (2)
C120.056 (3)0.050 (3)0.041 (3)0.014 (3)0.009 (2)0.003 (2)
C130.059 (4)0.054 (3)0.054 (3)0.016 (3)0.009 (3)0.004 (3)
C140.087 (5)0.047 (3)0.057 (4)0.012 (3)0.006 (3)0.006 (3)
C150.101 (5)0.047 (3)0.059 (4)0.017 (3)0.032 (4)0.016 (3)
C160.072 (4)0.046 (3)0.054 (3)0.018 (3)0.027 (3)0.009 (3)
Geometric parameters (Å, º) top
Sn—C12.111 (5)C8—N21.310 (6)
Sn—C22.115 (6)C8—C91.487 (7)
Sn—N22.325 (4)C9—H9A0.9600
Sn—S2.4743 (12)C9—H9B0.9600
Sn—N12.523 (4)C9—H9C0.9600
Sn—Br2.9075 (6)N2—N31.371 (5)
C1—H1A0.9600N3—C101.319 (6)
C1—H1B0.9600C10—N41.353 (6)
C1—H1C0.9600C10—S1.739 (5)
C2—H2A0.9600N4—C111.417 (6)
C2—H2B0.9600N4—HN40.73 (5)
C2—H2C0.9600C11—C161.378 (7)
N1—C31.333 (6)C11—C121.383 (7)
N1—C71.338 (7)C12—C131.375 (7)
C3—C41.387 (7)C12—H120.9300
C3—C81.470 (7)C13—C141.378 (8)
C4—C51.390 (8)C13—H130.9300
C4—H40.9300C14—C151.373 (8)
C5—C61.354 (9)C14—H140.9300
C5—H50.9300C15—C161.389 (8)
C6—C71.360 (8)C15—H150.9300
C6—H60.9300C16—H160.9300
C7—H70.9300
C1—Sn—C2144.2 (3)N1—C7—C6123.4 (6)
C1—Sn—N295.3 (2)N1—C7—H7118.3
C2—Sn—N2106.3 (2)C6—C7—H7118.3
C1—Sn—S107.31 (18)N2—C8—C3116.8 (4)
C2—Sn—S105.40 (18)N2—C8—C9121.9 (4)
N2—Sn—S76.43 (10)C3—C8—C9121.3 (4)
C1—Sn—N182.7 (2)C8—C9—H9A109.5
C2—Sn—N180.4 (2)C8—C9—H9B109.5
N2—Sn—N166.12 (14)H9A—C9—H9B109.5
S—Sn—N1142.07 (10)C8—C9—H9C109.5
C1—Sn—Br86.49 (16)H9A—C9—H9C109.5
C2—Sn—Br84.76 (18)H9B—C9—H9C109.5
N2—Sn—Br156.45 (9)C8—N2—N3114.5 (4)
S—Sn—Br80.60 (3)C8—N2—Sn124.1 (3)
N1—Sn—Br137.21 (10)N3—N2—Sn121.0 (3)
Sn—C1—H1A109.5C10—N3—N2114.9 (4)
Sn—C1—H1B109.5N3—C10—N4117.8 (4)
H1A—C1—H1B109.5N3—C10—S128.1 (4)
Sn—C1—H1C109.5N4—C10—S114.1 (3)
H1A—C1—H1C109.5C10—S—Sn98.71 (16)
H1B—C1—H1C109.5C10—N4—C11131.3 (4)
Sn—C2—H2A109.5C10—N4—HN4112 (5)
Sn—C2—H2B109.5C11—N4—HN4117 (5)
H2A—C2—H2B109.5C16—C11—C12118.9 (5)
Sn—C2—H2C109.5C16—C11—N4124.2 (5)
H2A—C2—H2C109.5C12—C11—N4116.7 (4)
H2B—C2—H2C109.5C13—C12—C11120.7 (5)
C3—N1—C7118.5 (5)C13—C12—H12119.7
C3—N1—Sn116.5 (3)C11—C12—H12119.7
C7—N1—Sn124.9 (4)C14—C13—C12120.7 (6)
N1—C3—C4121.3 (5)C14—C13—H13119.7
N1—C3—C8116.1 (4)C12—C13—H13119.7
C4—C3—C8122.6 (5)C15—C14—C13118.8 (6)
C5—C4—C3118.4 (6)C15—C14—H14120.6
C5—C4—H4120.8C13—C14—H14120.6
C3—C4—H4120.8C14—C15—C16120.9 (6)
C6—C5—C4119.9 (6)C14—C15—H15119.5
C6—C5—H5120.1C16—C15—H15119.5
C4—C5—H5120.1C11—C16—C15119.9 (5)
C5—C6—C7118.4 (6)C11—C16—H16120.0
C5—C6—H6120.8C15—C16—H16120.0
C7—C6—H6120.8

Experimental details

(I)(II)
Crystal data
Chemical formula[Sn(C14H13N4S)Cl(CH3)2][SnBr(C14H13N4S)(CH3)2]
Mr453.55497.92
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/n
Temperature (K)293293
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)
V3)1865.7 (5)1875.1 (3)
Z44
Radiation typeMo KαMo Kα
µ (mm1)1.633.61
Crystal size (mm)0.55 × 0.40 × 0.350.22 × 0.20 × 0.10
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Enraf-Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
ψ scan
(North et al., 1968)
Tmin, Tmax0.481, 0.5660.548, 0.697
No. of measured, independent and
observed [I > 2σ(I)] reflections
5664, 5426, 4243 5663, 5433, 3161
Rint0.0250.050
(sin θ/λ)max1)0.7030.702
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.102, 1.07 0.040, 0.106, 1.05
No. of reflections54265433
No. of parameters211211
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.99, 0.560.60, 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.

Selected geometric parameters (Å, º) for (I) top
Sn—C12.120 (4)N1—C31.337 (4)
Sn—C22.124 (4)C3—C81.487 (4)
Sn—N22.351 (2)C8—N21.296 (3)
Sn—S2.4728 (8)N2—N31.377 (3)
Sn—N12.560 (3)N3—C101.301 (3)
Sn—Cl2.6772 (9)C10—S1.750 (3)
N1—C71.331 (5)
C1—Sn—C2145.09 (18)C1—Sn—Cl87.73 (11)
C1—Sn—N295.09 (13)C2—Sn—Cl86.22 (12)
C2—Sn—N2103.31 (13)S—Sn—Cl81.94 (3)
C1—Sn—S107.35 (13)N1—Sn—Cl136.90 (7)
C2—Sn—S105.77 (12)C8—N2—N3114.2 (2)
N2—Sn—S76.08 (6)C8—N2—Sn125.09 (19)
C1—Sn—N181.70 (13)N3—N2—Sn120.48 (17)
C2—Sn—N179.54 (14)C10—N3—N2115.5 (2)
N2—Sn—N165.30 (9)N3—C10—S127.9 (2)
Selected geometric parameters (Å, º) for (II) top
Sn—C12.111 (5)N1—C71.338 (7)
Sn—C22.115 (6)C3—C81.470 (7)
Sn—N22.325 (4)C8—N21.310 (6)
Sn—S2.4743 (12)N2—N31.371 (5)
Sn—N12.523 (4)N3—C101.319 (6)
Sn—Br2.9075 (6)C10—S1.739 (5)
N1—C31.333 (6)
C1—Sn—C2144.2 (3)C1—Sn—Br86.49 (16)
C1—Sn—N295.3 (2)C2—Sn—Br84.76 (18)
C2—Sn—N2106.3 (2)S—Sn—Br80.60 (3)
C1—Sn—S107.31 (18)N1—Sn—Br137.21 (10)
C2—Sn—S105.40 (18)C8—N2—N3114.5 (4)
N2—Sn—S76.43 (10)C8—N2—Sn124.1 (3)
C1—Sn—N182.7 (2)N3—N2—Sn121.0 (3)
C2—Sn—N180.4 (2)C10—N3—N2114.9 (4)
N2—Sn—N166.12 (14)N3—C10—S128.1 (4)
S—Sn—N1142.07 (10)
 

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