metal-organic compounds
(1,5-Diphenylthiocarbazonato-κS)trimethyltin(IV)
aDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein, 9300, South Africa, bDepartment of Chemistry, St Francis Xavier University, PO Box 5000, Antigonish, Nova Scotia B2G 2W5, Canada, and cDepartment of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4J3, Canada
*Correspondence e-mail: veschwkg@ufs.ac.za
In the title compound, [Sn(C13H11N4S)(CH3)3], the SnIV atom is coordinated by an S atom from the 1,5-diphenylthiocarbazonato (L) ligand [Sn—S 2.4710 (6) Å] and by three methyl groups [Sn—C 2.123 (3)–2.130 (2) Å] in a distorted tetrahedral geometry. The aromatic rings of the L ligand form a dihedral angle of 2.1 (1)°.
Related literature
For general background to dithizone and dithizonato metal complexes, see: Irving (1977). For the synthesis of dithizone, see: Pelkis et al. (1957). For structural aspects of dithizone and its oxidation products and observed solvatochromism and concentratochromism, see: Von Eschwege et al. (2011a). For related ligand and complex structures, see: Harrowfield et al. (1983); Kong & Wong (1999); Herbstein & Schwotzer (1984); Fernandes et al. (2002); Von Eschwege et al. (2008); Laing et al. (1971). For electrochemical studies of dithizone and its Hg complex, see: Von Eschwege & Swarts (2010); Von Eschwege et al. (2011b). For femto second laser spectroscopy studies on a photochromic dithizonatomercury complex, see: Schwoerer et al. (2011). For the weighting scheme, see: Carruthers & Watkin (1979).
Experimental
Crystal data
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Data collection: PROCESS-AUTO (Rigaku, 1998); cell PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: CRYSTALS (Watkin et al., 1999); molecular graphics: CrystalStructure; software used to prepare material for publication: CrystalStructure.
Supporting information
10.1107/S1600536812047216/cv5361sup1.cif
contains datablocks General, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812047216/cv5361Isup2.hkl
Solvents (AR) purchased from Merck and reagents from Sigma-Aldrich were used without further purification. Dithizone (0.1 g, 0.39 mmol) was dissolved in dry benzene (100 ml) and dimethylamino-trimethyltin (0.082 g, 0.394 mmol) was added under nitrogen. The solvent was removed under reduced pressure, yielding 0.157 g (97%) orange dithizonatotrimethyltin(IV), after crystallization from diethyl ether. The product proved to be unstable in most solvents, except benzene and diethyl ether. M.p. 134°C, λmax/nm (diethyl ether) 442, δH (300 MHz, C6D6, Spectrum A7)/p.p.m.: 0.47 (6 H, s, 2 × CH3), 0.54 (3 H, s, CH3), 6.85 – 8.09 (10 H, 3 × m, C6H5).
The amino H atom was located on a difference map and isotropically refined. C-bound H atoms were placed in calculated positions [C—H = 0.93 Å], and refined as riding, with Uiso(H) = 1.2–1.5Ueq(C).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell
PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: CRYSTALS (Watkin et al., 1999); molecular graphics: CrystalStructure (Rigaku/MSC, 2002); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2002).Fig. 1. The molecular structure of the title compound showing the atomic numbering and 50% probability displacement ellipsoids. | |
Fig. 2. A portion of the molecular packing of the title compound. |
[Sn(C13H11N4S)(CH3)3] | F(000) = 840.00 |
Mr = 419.11 | Dx = 1.561 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2yn | Cell parameters from 16795 reflections |
a = 11.1058 (4) Å | θ = 3.0–27.6° |
b = 7.2672 (3) Å | µ = 1.55 mm−1 |
c = 22.5024 (9) Å | T = 223 K |
β = 101.0116 (11)° | Needle, orange |
V = 1782.69 (12) Å3 | 0.20 × 0.19 × 0.08 mm |
Z = 4 |
Rigaku SCXmini diffractometer | 3344 reflections with F2 > 2.0σ(F2) |
Detector resolution: 6.85 pixels mm-1 | Rint = 0.023 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | h = −14→14 |
Tmin = 0.751, Tmax = 0.886 | k = −9→9 |
17952 measured reflections | l = −29→28 |
4092 independent reflections |
Refinement on F | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.027 | Chebychev polynomial with 3 parameters (Carruthers & Watkin, 1979) 3.3785 -1.5365 2.4749 |
wR(F2) = 0.027 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 0.32 e Å−3 |
3344 reflections | Δρmin = −0.36 e Å−3 |
223 parameters |
[Sn(C13H11N4S)(CH3)3] | V = 1782.69 (12) Å3 |
Mr = 419.11 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.1058 (4) Å | µ = 1.55 mm−1 |
b = 7.2672 (3) Å | T = 223 K |
c = 22.5024 (9) Å | 0.20 × 0.19 × 0.08 mm |
β = 101.0116 (11)° |
Rigaku SCXmini diffractometer | 4092 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 3344 reflections with F2 > 2.0σ(F2) |
Tmin = 0.751, Tmax = 0.886 | Rint = 0.023 |
17952 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 223 parameters |
wR(F2) = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.32 e Å−3 |
3344 reflections | Δρmin = −0.36 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 was performed using reflections with F2 > 3.0 σ(F2). The weighted R-factor(wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Sn1 | 0.584750 (10) | 0.72516 (2) | 0.103690 (10) | 0.03181 (4) | |
S2 | 0.48283 (6) | 0.42282 (9) | 0.08476 (3) | 0.03382 (14) | |
N1 | 0.54036 (19) | 0.2246 (3) | 0.18902 (10) | 0.0345 (5) | |
N2 | 0.4294 (2) | 0.2702 (3) | 0.19760 (10) | 0.0376 (5) | |
N3 | 0.69296 (19) | 0.2259 (3) | 0.13655 (9) | 0.0342 (5) | |
N4 | 0.73146 (18) | 0.2866 (3) | 0.09132 (9) | 0.0327 (4) | |
C1 | 0.6418 (3) | 0.7378 (5) | 0.19937 (13) | 0.0556 (9) | |
C2 | 0.7339 (2) | 0.7446 (3) | 0.05745 (14) | 0.0432 (7) | |
C3 | 0.4335 (2) | 0.8952 (3) | 0.06533 (13) | 0.0433 (7) | |
C4 | 0.5753 (2) | 0.2867 (3) | 0.14066 (11) | 0.0313 (5) | |
C5 | 0.3905 (2) | 0.2214 (3) | 0.25098 (10) | 0.0288 (5) | |
C6 | 0.2710 (2) | 0.2653 (3) | 0.25609 (11) | 0.0331 (5) | |
C7 | 0.2291 (2) | 0.2216 (3) | 0.30840 (12) | 0.0371 (6) | |
C8 | 0.3056 (2) | 0.1336 (4) | 0.35559 (11) | 0.0392 (6) | |
C9 | 0.4242 (2) | 0.0906 (3) | 0.35032 (11) | 0.0372 (6) | |
C10 | 0.4679 (2) | 0.1334 (3) | 0.29838 (11) | 0.0342 (6) | |
C11 | 0.8525 (2) | 0.2291 (3) | 0.08796 (11) | 0.0312 (5) | |
C12 | 0.8917 (2) | 0.2776 (3) | 0.03507 (11) | 0.0367 (6) | |
C13 | 1.0091 (2) | 0.2330 (4) | 0.02757 (13) | 0.0456 (7) | |
C14 | 1.0872 (2) | 0.1392 (4) | 0.07256 (15) | 0.0476 (8) | |
C15 | 1.0482 (2) | 0.0905 (4) | 0.12533 (14) | 0.0447 (7) | |
C16 | 0.9316 (2) | 0.1346 (3) | 0.13339 (12) | 0.0372 (6) | |
H1 | 0.6600 | 0.8589 | 0.2110 | 0.067* | |
H2 | 0.5792 | 0.6946 | 0.2178 | 0.067* | |
H3 | 0.7113 | 0.6652 | 0.2111 | 0.067* | |
H4 | 0.7433 | 0.8663 | 0.0463 | 0.052* | |
H5 | 0.8054 | 0.7050 | 0.0828 | 0.052* | |
H6 | 0.7185 | 0.6712 | 0.0230 | 0.052* | |
H7 | 0.3781 | 0.9004 | 0.0915 | 0.052* | |
H8 | 0.4615 | 1.0131 | 0.0594 | 0.052* | |
H9 | 0.3949 | 0.8462 | 0.0284 | 0.052* | |
H10 | 0.2194 | 0.3239 | 0.2243 | 0.040* | |
H11 | 0.1493 | 0.2516 | 0.3119 | 0.044* | |
H12 | 0.2772 | 0.1034 | 0.3907 | 0.047* | |
H13 | 0.4755 | 0.0319 | 0.3822 | 0.045* | |
H14 | 0.5479 | 0.1037 | 0.2952 | 0.041* | |
H15 | 0.8391 | 0.3401 | 0.0046 | 0.044* | |
H16 | 1.0354 | 0.2663 | −0.0078 | 0.055* | |
H17 | 1.1659 | 0.1088 | 0.0674 | 0.057* | |
H18 | 1.1011 | 0.0275 | 0.1556 | 0.054* | |
H19 | 0.9058 | 0.1015 | 0.1689 | 0.045* | |
H20 | 0.386 (3) | 0.335 (4) | 0.1727 (14) | 0.048 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.02999 (9) | 0.03258 (9) | 0.03273 (9) | 0.00214 (7) | 0.00567 (6) | 0.00547 (7) |
S2 | 0.0313 (2) | 0.0345 (3) | 0.0352 (3) | −0.0008 (2) | 0.0050 (2) | 0.0076 (2) |
N1 | 0.0357 (10) | 0.0341 (10) | 0.0367 (10) | 0.0043 (8) | 0.0142 (8) | 0.0069 (8) |
N2 | 0.0350 (10) | 0.0453 (12) | 0.0352 (10) | 0.0091 (9) | 0.0133 (8) | 0.0130 (9) |
N3 | 0.0337 (9) | 0.0347 (10) | 0.0360 (10) | 0.0022 (8) | 0.0112 (8) | 0.0070 (8) |
N4 | 0.0312 (9) | 0.0357 (10) | 0.0319 (9) | −0.0010 (8) | 0.0075 (7) | 0.0026 (8) |
C1 | 0.0575 (18) | 0.067 (2) | 0.0384 (14) | 0.0051 (15) | −0.0006 (12) | −0.0010 (14) |
C2 | 0.0373 (12) | 0.0429 (16) | 0.0514 (15) | −0.0042 (10) | 0.0133 (11) | 0.0021 (11) |
C3 | 0.0409 (14) | 0.0390 (14) | 0.0482 (15) | 0.0051 (11) | 0.0044 (12) | 0.0079 (11) |
C4 | 0.0313 (11) | 0.0298 (10) | 0.0343 (11) | 0.0013 (9) | 0.0102 (9) | 0.0046 (9) |
C5 | 0.0316 (10) | 0.0256 (10) | 0.0308 (10) | −0.0018 (9) | 0.0096 (8) | 0.0020 (8) |
C6 | 0.0315 (11) | 0.0331 (12) | 0.0348 (11) | 0.0006 (9) | 0.0068 (9) | 0.0012 (9) |
C7 | 0.0305 (11) | 0.0404 (12) | 0.0432 (12) | −0.0035 (10) | 0.0144 (9) | −0.0032 (11) |
C8 | 0.0439 (14) | 0.0459 (15) | 0.0302 (12) | −0.0090 (11) | 0.0134 (10) | −0.0007 (10) |
C9 | 0.0442 (14) | 0.0370 (13) | 0.0284 (11) | −0.0020 (10) | 0.0020 (10) | 0.0046 (9) |
C10 | 0.0301 (11) | 0.0350 (12) | 0.0376 (12) | 0.0017 (9) | 0.0070 (9) | 0.0033 (10) |
C11 | 0.0339 (11) | 0.0290 (11) | 0.0313 (10) | −0.0021 (9) | 0.0077 (8) | −0.0034 (9) |
C12 | 0.0381 (12) | 0.0432 (13) | 0.0306 (11) | −0.0008 (11) | 0.0108 (9) | −0.0017 (10) |
C13 | 0.0467 (14) | 0.0540 (17) | 0.0416 (13) | −0.0017 (13) | 0.0221 (11) | −0.0056 (12) |
C14 | 0.0363 (14) | 0.0462 (16) | 0.0628 (18) | 0.0056 (11) | 0.0159 (12) | −0.0108 (14) |
C15 | 0.0404 (14) | 0.0387 (14) | 0.0528 (16) | 0.0080 (11) | 0.0036 (12) | 0.0023 (12) |
C16 | 0.0411 (13) | 0.0363 (13) | 0.0346 (12) | 0.0017 (10) | 0.0080 (10) | 0.0049 (10) |
Sn1—S2 | 2.4710 (6) | C15—C16 | 1.380 (4) |
Sn1—C1 | 2.127 (2) | N2—H20 | 0.82 (3) |
Sn1—C2 | 2.123 (3) | C1—H1 | 0.930 |
Sn1—C3 | 2.130 (2) | C1—H2 | 0.930 |
S2—C4 | 1.766 (2) | C1—H3 | 0.930 |
N1—N2 | 1.325 (3) | C2—H4 | 0.930 |
N1—C4 | 1.304 (3) | C2—H5 | 0.930 |
N2—C5 | 1.398 (3) | C2—H6 | 0.930 |
N3—N4 | 1.257 (3) | C3—H7 | 0.930 |
N3—C4 | 1.400 (3) | C3—H8 | 0.930 |
N4—C11 | 1.423 (3) | C3—H9 | 0.930 |
C5—C6 | 1.391 (3) | C6—H10 | 0.930 |
C5—C10 | 1.391 (3) | C7—H11 | 0.930 |
C6—C7 | 1.383 (3) | C8—H12 | 0.930 |
C7—C8 | 1.383 (3) | C9—H13 | 0.930 |
C8—C9 | 1.381 (4) | C10—H14 | 0.930 |
C9—C10 | 1.384 (3) | C12—H15 | 0.930 |
C11—C12 | 1.389 (3) | C13—H16 | 0.930 |
C11—C16 | 1.395 (3) | C14—H17 | 0.930 |
C12—C13 | 1.385 (4) | C15—H18 | 0.930 |
C13—C14 | 1.380 (4) | C16—H19 | 0.930 |
C14—C15 | 1.385 (4) | ||
C3···C4i | 3.526 (3) | H7···C8iv | 3.204 |
C4···C3ii | 3.526 (3) | H7···H4viii | 3.565 |
C13···C13iii | 3.599 (4) | H7···H11iv | 2.499 |
C13···C14iii | 3.552 (4) | H7···H12iv | 2.839 |
C14···C13iii | 3.552 (4) | H7···H15v | 3.399 |
Sn1···H11iv | 3.506 | H7···H17x | 2.766 |
S2···H6v | 3.045 | H8···S2i | 3.033 |
S2···H8ii | 3.033 | H8···N1i | 3.266 |
S2···H12iv | 3.314 | H8···N3i | 3.211 |
N1···H1ii | 2.970 | H8···N4i | 3.554 |
N1···H3vi | 3.237 | H8···C2viii | 3.542 |
N1···H7ii | 3.479 | H8···C3viii | 3.306 |
N1···H8ii | 3.266 | H8···C4i | 2.831 |
N2···H7ii | 3.568 | H8···H4viii | 3.088 |
N3···H1ii | 3.208 | H8···H6viii | 3.359 |
N3···H3vi | 3.419 | H8···H8viii | 2.963 |
N3···H4ii | 3.420 | H8···H9viii | 2.948 |
N3···H8ii | 3.211 | H8···H17x | 3.395 |
N4···H4ii | 3.228 | H9···N4v | 2.952 |
N4···H8ii | 3.554 | H9···C11v | 3.458 |
N4···H9v | 2.952 | H9···C12v | 3.354 |
C1···H11iv | 3.196 | H9···H4viii | 2.926 |
C1···H14vii | 3.561 | H9···H8viii | 2.948 |
C1···H19vii | 3.263 | H9···H12iv | 3.379 |
C2···H8viii | 3.542 | H9···H15v | 2.898 |
C2···H16ix | 2.985 | H9···H17x | 3.426 |
C2···H17ix | 3.386 | H10···C5iv | 3.225 |
C3···H4viii | 3.360 | H10···C6iv | 3.236 |
C3···H8viii | 3.306 | H10···C7iv | 3.063 |
C3···H11iv | 3.247 | H10···C8iv | 2.861 |
C3···H12iv | 3.441 | H10···C9iv | 2.845 |
C3···H15v | 3.570 | H10···C10iv | 3.039 |
C3···H17x | 3.362 | H10···C15xii | 3.136 |
C4···H1ii | 3.534 | H10···H11iv | 3.592 |
C4···H8ii | 2.831 | H10···H12iv | 3.296 |
C5···H10xi | 3.225 | H10···H13iv | 3.276 |
C5···H18vii | 3.050 | H10···H14iv | 3.555 |
C6···H10xi | 3.236 | H10···H18xii | 2.826 |
C6···H18xii | 3.168 | H10···H18vii | 3.378 |
C6···H18vii | 2.919 | H11···Sn1xi | 3.506 |
C7···H2xi | 3.367 | H11···C1xi | 3.196 |
C7···H7xi | 3.034 | H11···C3xi | 3.247 |
C7···H10xi | 3.063 | H11···H1xi | 3.464 |
C7···H18vii | 2.927 | H11···H2xi | 2.532 |
C7···H20xi | 3.15 (3) | H11···H7xi | 2.499 |
C8···H7xi | 3.204 | H11···H10xi | 3.592 |
C8···H10xi | 2.861 | H11···H18vii | 3.386 |
C8···H15xiii | 3.308 | H11···H20xi | 3.079 |
C8···H18vii | 3.071 | H12···S2xi | 3.314 |
C8···H20xi | 3.02 (3) | H12···C3xi | 3.441 |
C9···H5vi | 3.202 | H12···C12xiii | 3.368 |
C9···H10xi | 2.845 | H12···H7xi | 2.839 |
C9···H16xiii | 3.361 | H12···H9xi | 3.379 |
C9···H18vii | 3.188 | H12···H10xi | 3.296 |
C10···H5vi | 3.345 | H12···H15xiii | 2.558 |
C10···H10xi | 3.039 | H12···H16xiii | 3.440 |
C10···H18vii | 3.189 | H12···H18vii | 3.598 |
C11···H4ii | 2.978 | H12···H20xi | 2.853 |
C11···H9v | 3.458 | H13···C11vi | 2.907 |
C11···H13vii | 2.907 | H13···C12vi | 2.830 |
C12···H4ii | 3.446 | H13···C13vi | 2.956 |
C12···H9v | 3.354 | H13···C14vi | 3.152 |
C12···H12xiv | 3.368 | H13···C15vi | 3.221 |
C12···H13vii | 2.830 | H13···C16vi | 3.109 |
C12···H16ix | 3.494 | H13···H5vi | 2.719 |
C13···H4ix | 3.548 | H13···H10xi | 3.276 |
C13···H5ix | 3.545 | H13···H15vi | 3.266 |
C13···H6ix | 3.499 | H13···H15xiii | 3.514 |
C13···H13vii | 2.956 | H13···H16vi | 3.444 |
C13···H17iii | 3.596 | H13···H16xiii | 2.845 |
C14···H4ix | 3.553 | H14···C1vi | 3.561 |
C14···H6ix | 3.599 | H14···H1ii | 3.033 |
C14···H13vii | 3.152 | H14···H2ii | 3.496 |
C14···H16iii | 3.450 | H14···H3vi | 2.742 |
C15···H10xv | 3.136 | H14···H5vi | 3.004 |
C15···H13vii | 3.221 | H14···H10xi | 3.555 |
C16···H2vi | 3.401 | H15···C3v | 3.570 |
C16···H4ii | 3.232 | H15···C8xiv | 3.308 |
C16···H5ii | 3.521 | H15···H7v | 3.399 |
C16···H13vii | 3.109 | H15···H9v | 2.898 |
H1···N1i | 2.970 | H15···H12xiv | 2.558 |
H1···N3i | 3.208 | H15···H13vii | 3.266 |
H1···C4i | 3.534 | H15···H13xiv | 3.514 |
H1···H3vii | 3.019 | H15···H16ix | 3.177 |
H1···H11iv | 3.464 | H16···C2ix | 2.985 |
H1···H14i | 3.033 | H16···C9xiv | 3.361 |
H1···H19i | 3.529 | H16···C12ix | 3.494 |
H1···H19vii | 3.477 | H16···C14iii | 3.450 |
H2···C7iv | 3.367 | H16···H4ix | 2.921 |
H2···C16vii | 3.401 | H16···H5ix | 2.676 |
H2···H11iv | 2.532 | H16···H6ix | 2.855 |
H2···H14i | 3.496 | H16···H12xiv | 3.440 |
H2···H19vii | 2.612 | H16···H13vii | 3.444 |
H3···N1vii | 3.237 | H16···H13xiv | 2.845 |
H3···N3vii | 3.419 | H16···H15ix | 3.177 |
H3···H1vi | 3.019 | H16···H16ix | 3.519 |
H3···H14vii | 2.742 | H17···C2ix | 3.386 |
H3···H19vii | 3.247 | H17···C3xvi | 3.362 |
H4···N3i | 3.420 | H17···C13iii | 3.596 |
H4···N4i | 3.228 | H17···H4ix | 2.931 |
H4···C3viii | 3.360 | H17···H6ix | 3.057 |
H4···C11i | 2.978 | H17···H7xvi | 2.766 |
H4···C12i | 3.446 | H17···H8xvi | 3.395 |
H4···C13ix | 3.548 | H17···H9xvi | 3.426 |
H4···C14ix | 3.553 | H17···H20xv | 3.479 |
H4···C16i | 3.232 | H18···C5vi | 3.050 |
H4···H7viii | 3.565 | H18···C6xv | 3.168 |
H4···H8viii | 3.088 | H18···C6vi | 2.919 |
H4···H9viii | 2.926 | H18···C7vi | 2.927 |
H4···H16ix | 2.921 | H18···C8vi | 3.071 |
H4···H17ix | 2.931 | H18···C9vi | 3.188 |
H4···H19i | 3.448 | H18···C10vi | 3.189 |
H5···C9vii | 3.202 | H18···H10xv | 2.826 |
H5···C10vii | 3.345 | H18···H10vi | 3.378 |
H5···C13ix | 3.545 | H18···H11vi | 3.386 |
H5···C16i | 3.521 | H18···H12vi | 3.598 |
H5···H13vii | 2.719 | H19···C1vi | 3.263 |
H5···H14vii | 3.004 | H19···H1ii | 3.529 |
H5···H16ix | 2.676 | H19···H1vi | 3.477 |
H5···H19i | 3.532 | H19···H2vi | 2.612 |
H6···S2v | 3.045 | H19···H3vi | 3.247 |
H6···C13ix | 3.499 | H19···H4ii | 3.448 |
H6···C14ix | 3.599 | H19···H5ii | 3.532 |
H6···H8viii | 3.359 | H20···C7iv | 3.15 (3) |
H6···H16ix | 2.855 | H20···C8iv | 3.02 (3) |
H6···H17ix | 3.057 | H20···H11iv | 3.079 |
H7···N1i | 3.479 | H20···H12iv | 2.853 |
H7···N2i | 3.568 | H20···H17xii | 3.479 |
H7···C7iv | 3.034 | ||
S2—Sn1—C1 | 104.53 (9) | H1—C1—H2 | 109.5 |
S2—Sn1—C2 | 110.46 (7) | H1—C1—H3 | 109.5 |
S2—Sn1—C3 | 98.40 (7) | H2—C1—H3 | 109.5 |
C1—Sn1—C2 | 112.56 (12) | Sn1—C2—H4 | 109.5 |
C1—Sn1—C3 | 116.40 (12) | Sn1—C2—H5 | 109.5 |
C2—Sn1—C3 | 113.04 (11) | Sn1—C2—H6 | 109.5 |
Sn1—S2—C4 | 100.97 (8) | H4—C2—H5 | 109.5 |
N2—N1—C4 | 117.9 (2) | H4—C2—H6 | 109.5 |
N1—N2—C5 | 120.7 (2) | H5—C2—H6 | 109.5 |
N4—N3—C4 | 114.15 (19) | Sn1—C3—H7 | 109.5 |
N3—N4—C11 | 114.26 (19) | Sn1—C3—H8 | 109.5 |
S2—C4—N1 | 124.29 (18) | Sn1—C3—H9 | 109.5 |
S2—C4—N3 | 123.56 (18) | H7—C3—H8 | 109.5 |
N1—C4—N3 | 112.1 (2) | H7—C3—H9 | 109.5 |
N2—C5—C6 | 118.0 (2) | H8—C3—H9 | 109.5 |
N2—C5—C10 | 121.9 (2) | C5—C6—H10 | 120.0 |
C6—C5—C10 | 120.1 (2) | C7—C6—H10 | 120.0 |
C5—C6—C7 | 120.0 (2) | C6—C7—H11 | 119.9 |
C6—C7—C8 | 120.2 (2) | C8—C7—H11 | 119.9 |
C7—C8—C9 | 119.6 (2) | C7—C8—H12 | 120.2 |
C8—C9—C10 | 121.1 (2) | C9—C8—H12 | 120.2 |
C5—C10—C9 | 119.1 (2) | C8—C9—H13 | 119.5 |
N4—C11—C12 | 115.2 (2) | C10—C9—H13 | 119.5 |
N4—C11—C16 | 125.1 (2) | C5—C10—H14 | 120.5 |
C12—C11—C16 | 119.7 (2) | C9—C10—H14 | 120.5 |
C11—C12—C13 | 120.1 (2) | C11—C12—H15 | 119.9 |
C12—C13—C14 | 120.0 (2) | C13—C12—H15 | 119.9 |
C13—C14—C15 | 120.0 (2) | C12—C13—H16 | 120.0 |
C14—C15—C16 | 120.5 (2) | C14—C13—H16 | 120.0 |
C11—C16—C15 | 119.6 (2) | C13—C14—H17 | 120.0 |
N1—N2—H20 | 119 (2) | C15—C14—H17 | 120.0 |
C5—N2—H20 | 120 (2) | C14—C15—H18 | 119.7 |
Sn1—C1—H1 | 109.5 | C16—C15—H18 | 119.7 |
Sn1—C1—H2 | 109.5 | C11—C16—H19 | 120.2 |
Sn1—C1—H3 | 109.5 | C15—C16—H19 | 120.2 |
C(1)—Sn(1)—S(2)—C(4) | −36.42 (13) | N(2)—C(5)—C(10)—C(9) | 179.3 (2) |
C(2)—Sn(1)—S(2)—C(4) | 84.89 (12) | C(6)—C(5)—C(10)—C(9) | −0.0 (3) |
C(3)—Sn(1)—S(2)—C(4) | −156.59 (12) | C(10)—C(5)—C(6)—C(7) | 0.1 (2) |
Sn(1)—S(2)—C(4)—N(1) | 108.4 (2) | C(5)—C(6)—C(7)—C(8) | −0.3 (3) |
Sn(1)—S(2)—C(4)—N(3) | −74.7 (2) | C(6)—C(7)—C(8)—C(9) | 0.4 (4) |
N(2)—N(1)—C(4)—S(2) | −1.7 (3) | C(7)—C(8)—C(9)—C(10) | −0.3 (4) |
N(2)—N(1)—C(4)—N(3) | −178.9 (2) | C(8)—C(9)—C(10)—C(5) | 0.1 (3) |
C(4)—N(1)—N(2)—C(5) | −174.5 (2) | N(4)—C(11)—C(12)—C(13) | 178.3 (2) |
N(1)—N(2)—C(5)—C(6) | −176.9 (2) | N(4)—C(11)—C(16)—C(15) | −178.3 (2) |
N(1)—N(2)—C(5)—C(10) | 3.8 (3) | C(12)—C(11)—C(16)—C(15) | 0.1 (3) |
N(4)—N(3)—C(4)—S(2) | 4.5 (3) | C(16)—C(11)—C(12)—C(13) | −0.3 (3) |
N(4)—N(3)—C(4)—N(1) | −178.3 (2) | C(11)—C(12)—C(13)—C(14) | 0.4 (4) |
C(4)—N(3)—N(4)—C(11) | 178.29 (19) | C(12)—C(13)—C(14)—C(15) | −0.3 (4) |
N(3)—N(4)—C(11)—C(12) | 173.2 (2) | C(13)—C(14)—C(15)—C(16) | 0.1 (3) |
N(3)—N(4)—C(11)—C(16) | −8.3 (3) | C(14)—C(15)—C(16)—C(11) | −0.0 (3) |
N(2)—C(5)—C(6)—C(7) | −179.2 (2) |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) −x+2, −y, −z; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x+1, −y+1, −z; (vi) −x+3/2, y−1/2, −z+1/2; (vii) −x+3/2, y+1/2, −z+1/2; (viii) −x+1, −y+2, −z; (ix) −x+2, −y+1, −z; (x) x−1, y+1, z; (xi) −x+1/2, y−1/2, −z+1/2; (xii) x−1, y, z; (xiii) x−1/2, −y+1/2, z+1/2; (xiv) x+1/2, −y+1/2, z−1/2; (xv) x+1, y, z; (xvi) x+1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Sn(C13H11N4S)(CH3)3] |
Mr | 419.11 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 223 |
a, b, c (Å) | 11.1058 (4), 7.2672 (3), 22.5024 (9) |
β (°) | 101.0116 (11) |
V (Å3) | 1782.69 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.55 |
Crystal size (mm) | 0.20 × 0.19 × 0.08 |
Data collection | |
Diffractometer | Rigaku SCXmini diffractometer |
Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
Tmin, Tmax | 0.751, 0.886 |
No. of measured, independent and observed [F2 > 2.0σ(F2)] reflections | 17952, 4092, 3344 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.027, 1.07 |
No. of reflections | 3344 |
No. of parameters | 223 |
No. of restraints | ? |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.36 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), CRYSTALS (Watkin et al., 1999).
Acknowledgements
We acknowledge the Central Research Fund of the University of the Free State for financial assistance.
References
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During a study of the reactions of dimethylamino-trimethyltin, orange crystals of the title compound suitable for X-ray crystallography, were isolated from a diethyl ether solution. The structure revealed distorted tetrahedral coordination geometry around tin, with S—Sn—C bond angles 110.5 (4)°, 105.0 (4)° and 98.0 (9)°. Contrary to most bidentate metal-dithizonate complexes, but with the exception of one ligand in In(HDz)3 (Harrowfield et al., 1983) and in an osmium carbonyl cluster compound (Kong & Wong, 1999), coordination of dithizone to trimethyltin(IV) was found to be monodentate, through the sulfur atom alone. The dithizonate ligand clearly illustrates a high degree of planarity, with the ligand backbone being linear, comparable to that of uncoordinated dithizone (Herbstein & Schwotzer, 1984). The Sn—S bond length of 2.4710 (6) Å agrees well with the value of 2.433 (2) Å in a related compound, 4,6-dimethylpyrimidine-2-thione triphenyltin(IV),Ph3Sn(Me2Pymt), reported by Fernandes et al. (2002). The less bulky pyrimidine-thione ligand, however, is bidentately coordinated to Sn through both sulfur and nitrogen, forming a four-membered ring, as opposed to the usual 5-membered metal-dithizonate rings, as seen in PhHgHDz (Von Eschwege et al., 2008). In the case of Me3Sn(HDz), the metal lies completely outside the ligand plane, whereas in most other metal dithizonates the carbon-sulfur-metal angle is in the direction of the nitrogen (N4) that does not carry the imine proton, H2 (Laing et al., 1971). The three methyl carbons, being at bond distances of 2.13 (2) Å, hold the metal in the sterically more favourable out-of-plane position. Bond lengths along the ligand backbone are neither typically single nor double bond in character. However, the N3—N4 bond length of 1.267 (9) Å and the N1—C1 bond length of 1.308 (9) Å are close to typical double bond lengths of 1.25 Å and 1.29 Å respectively. Even the N1—N2 bond (1.327 (14) Å), which is expected to be a single bond, has more double bond character than single. N—N single bonds are typically 1.45 Å in length. The N3—C1 bond length of 1.40 (2) Å is shorter than an N—C single bond length of 1.47 Å. Observed deviation from single and double bond distances is further evidence of the high degree of electron delocalization along the dithizonate backbone.