
Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035052/rz2159sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035052/rz2159Isup2.hkl |
CCDC reference: 657627
The tin complex of acetylpyrazine N(4)-ethylthiosemicarbazone was prepared by the following procedure: a solution of diphenyltin dichloride (0.69 g, 2 mmol) in 20 ml of dry methanol was added to a refluxing methanol solution (20 ml) of the ligand. The resulting mixture was refluxed for 1 h. Cooling followed by slow evaporation at room temperature produced yellow crystals (ca 75% yield), with a melting point 459–461 K. IR spectra were obtained in the 4000–400 cm-1 range in KBr pellets on a Nicolet 670 F T—IR spectrophotometer νN—H 3350, νC—N 1590, 1530(s), νC—S 850(s) cm-1).
H atoms on C were placed in idealized positions with C—H distances 0.95–0.99 Å and thereafter treated as riding. Uiso for H was assigned as 1.2 times Ueq of the attached C or N atoms (1.5 for methyl). A torsional parameter was refined for each methyl group. N—H hydrogen atom positions were refined.
There has been a steady growth of interest in the synthesis, structure and reactivity studies of metal complexes of heterocyclic thiosemicarbazones due to their biological and pharmacological properties (Ali & Livingstone, 1974; Campbell, 1975; Padhye & Kauffman, 1985). The unique feature is attributed to the tautomeric equilibrium present in the thiosemicarbazone moiety and thereby the coordinating ability with many metal ions. Among the non-transition metals, organotin(IV) derivatives are of special interest due to environmental, and medical issues (Barbieri et al., 1993; Bamgboye & Bamgboye, 1988; Casas et al., 1994, Casas et al., 1996, De Sousa et al., 2001). Continuing with this type of studies, we describe here the structure of a diphenyltin dichloride derivative of pyrazine-2-carbaldehyde N(4)-ethyl-3-thiosemicarbazone (I).
The tin atom of the diphenyl dichloride unit lies on an inversion center, and is coordinated in monodentate fashion by the pyrazine nitrogen atoms of two thiosemicarbazone ligands, unlike the normal bidentate/tridentate modes of coordination. The yellow-colored complex is built up of discrete molecules of acetylpyrazine thiosemicarbazone ligand with diphenyl tin dichloride with the two chlorine atoms and two phenyl groups occupying the four equatorial positions (trans to each other) of a distorted octahedron around the tin atom. The pyrazine groups are in the inverse position and trans to one another. The angles subtended by the adjacent atoms to tin are 89.75 (4)°, [C10—Sn—Cl1], 88.99 (4)° [N1—Sn1—C10] and 91.79 (3)° (N1—Sn1—Cl1] and the corresponding bond distances are Sn—C [2.1378 (12)], Sn—Cl [2.5483 (4)] and Sn—N [2.4033 (11) Å]. The Sn—N bond length value is in the range of 2.27 to 2.58, and is less than the van der Waals radii of the two atoms, 3.74 Å (Allen et al., 1979). The Sn—Cl bond is in the range of normal covalent radii (2.37–2.60 Å) (Casas et al., 1997, Davies, 1998). The bond length Sn—C (phenyl) is slightly shorter compared to the tin adduct reported 2.1424 (14) Å by us earlier (Venkatraman et al., 2004). The bond length Sn—C increases with an increase in coordination number from four [2.122 (11) Å] (in Ph2SnCl2) and higher as expected (Dey et al., 2003).
N–H groups usually serve as hydrogen-bond donors, however, no intermolecular hyrogen bonding is present in this structure. N–H group N5 forms an intramolecular hydrogen bond of graph set designation S(5) (Etter, 1990), with N3 as acceptor, N3···N5 2.609 (2) Å. In five-membered rings, the hydrogen-bonding geometry necessarily distorts greatly from linearity. The H···N3 distance is 2.15 (2) Å, and the angle about H is 109.9 (19)°. The other N–H group N4 is not involved in hydrogen bonding.
For related literature, see: Ali & Livingstone (1974); Allen et al. (1979); Bamgboye & Bamgboye (1988); Barbieri et al. (1993); Campbell (1975); Casas et al. (1994, 1996, 1997); Davies (1998); De Sousa, Francisco, Gambardella, Santos & Abras (2001); Dey et al. (2003); Etter (1990); Padhye & Kauffman (1985); Venkatraman et al. (2004).
Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
![]() | Fig. 1. Numbering scheme and displacement ellipsoids at the 50% level. H atoms are represented with arbitrary radius. Unlabelled atoms are related by the symmetry operation (1 - x, 1 - y, 1 - z). |
[Sn(C6H5)2Cl2(C9H13N5S)2] | F(000) = 804 |
Mr = 790.40 | Dx = 1.591 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6430 reflections |
a = 10.7262 (15) Å | θ = 2.5–35.6° |
b = 17.971 (3) Å | µ = 1.10 mm−1 |
c = 9.0868 (13) Å | T = 90 K |
β = 109.641 (6)° | Needle fragment, yellow |
V = 1649.7 (4) Å3 | 0.27 × 0.22 × 0.20 mm |
Z = 2 |
Nonius KappaCCD (with Oxford Cryosystems Cryostream cooler) diffractometer | 7475 independent reflections |
Radiation source: fine-focus sealed tube | 6422 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans with κ offsets | θmax = 35.6°, θmin = 2.7° |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | h = −17→17 |
Tmin = 0.755, Tmax = 0.810 | k = −25→29 |
24456 measured reflections | l = −14→14 |
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)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.071 | w = 1/[σ2(Fo2) + (0.0301P)2 + 1.1288P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
7475 reflections | Δρmax = 0.85 e Å−3 |
214 parameters | Δρmin = −1.29 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0022 (4) |
[Sn(C6H5)2Cl2(C9H13N5S)2] | V = 1649.7 (4) Å3 |
Mr = 790.40 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.7262 (15) Å | µ = 1.10 mm−1 |
b = 17.971 (3) Å | T = 90 K |
c = 9.0868 (13) Å | 0.27 × 0.22 × 0.20 mm |
β = 109.641 (6)° |
Nonius KappaCCD (with Oxford Cryosystems Cryostream cooler) diffractometer | 7475 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 6422 reflections with I > 2σ(I) |
Tmin = 0.755, Tmax = 0.810 | Rint = 0.026 |
24456 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.85 e Å−3 |
7475 reflections | Δρmin = −1.29 e Å−3 |
214 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 | ||
Sn1 | 0.5000 | 0.5000 | 0.5000 | 0.00677 (3) | |
Cl1 | 0.42470 (3) | 0.606662 (17) | 0.63487 (3) | 0.01054 (6) | |
S1 | −0.15561 (4) | 0.75620 (2) | 0.60254 (4) | 0.01438 (7) | |
N1 | 0.27549 (11) | 0.46903 (6) | 0.34850 (13) | 0.00969 (18) | |
N2 | 0.00894 (12) | 0.45016 (7) | 0.16677 (14) | 0.0129 (2) | |
N3 | −0.01068 (11) | 0.59622 (6) | 0.42005 (13) | 0.01122 (19) | |
N4 | −0.09760 (11) | 0.64282 (7) | 0.45362 (14) | 0.01177 (19) | |
H4N | −0.176 (2) | 0.6485 (12) | 0.391 (2) | 0.014* | |
N5 | 0.07887 (12) | 0.68918 (7) | 0.65242 (15) | 0.0152 (2) | |
H5N | 0.123 (2) | 0.6529 (13) | 0.620 (3) | 0.018* | |
C1 | 0.18071 (13) | 0.51177 (7) | 0.36914 (16) | 0.0111 (2) | |
H1 | 0.2044 | 0.5495 | 0.4468 | 0.013* | |
C2 | 0.23751 (13) | 0.41575 (8) | 0.23804 (16) | 0.0121 (2) | |
H2 | 0.3020 | 0.3837 | 0.2214 | 0.015* | |
C3 | 0.10492 (14) | 0.40721 (8) | 0.14829 (16) | 0.0137 (2) | |
H3 | 0.0813 | 0.3694 | 0.0707 | 0.016* | |
C4 | 0.04715 (13) | 0.50219 (7) | 0.27881 (15) | 0.00994 (19) | |
C5 | −0.05560 (13) | 0.55018 (7) | 0.30524 (15) | 0.0105 (2) | |
C6 | −0.19717 (13) | 0.54186 (8) | 0.20520 (17) | 0.0146 (2) | |
H6A | −0.2495 | 0.5267 | 0.2701 | 0.022* | |
H6B | −0.2045 | 0.5040 | 0.1251 | 0.022* | |
H6C | −0.2304 | 0.5895 | 0.1547 | 0.022* | |
C7 | −0.04970 (13) | 0.69445 (7) | 0.57094 (15) | 0.0115 (2) | |
C8 | 0.14983 (16) | 0.73660 (10) | 0.78438 (18) | 0.0208 (3) | |
H8A | 0.2195 | 0.7070 | 0.8615 | 0.025* | |
H8B | 0.0875 | 0.7544 | 0.8360 | 0.025* | |
C9 | 0.21281 (19) | 0.80299 (11) | 0.7342 (2) | 0.0301 (4) | |
H9A | 0.2716 | 0.7857 | 0.6788 | 0.045* | |
H9B | 0.2641 | 0.8316 | 0.8266 | 0.045* | |
H9C | 0.1435 | 0.8347 | 0.6647 | 0.045* | |
C10 | 0.50493 (12) | 0.57431 (7) | 0.31832 (14) | 0.00910 (19) | |
C11 | 0.56171 (13) | 0.64482 (7) | 0.35463 (15) | 0.0107 (2) | |
H11 | 0.5983 | 0.6599 | 0.4607 | 0.013* | |
C12 | 0.56497 (14) | 0.69314 (8) | 0.23604 (16) | 0.0137 (2) | |
H12 | 0.6054 | 0.7406 | 0.2616 | 0.016* | |
C13 | 0.50916 (14) | 0.67200 (8) | 0.08006 (16) | 0.0140 (2) | |
H13 | 0.5104 | 0.7052 | −0.0007 | 0.017* | |
C14 | 0.45164 (14) | 0.60209 (8) | 0.04319 (15) | 0.0130 (2) | |
H14 | 0.4130 | 0.5877 | −0.0631 | 0.016* | |
C15 | 0.45039 (13) | 0.55302 (7) | 0.16182 (15) | 0.0109 (2) | |
H15 | 0.4123 | 0.5050 | 0.1360 | 0.013* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.00730 (5) | 0.00772 (5) | 0.00631 (5) | 0.00094 (4) | 0.00365 (3) | 0.00064 (4) |
Cl1 | 0.01262 (12) | 0.01062 (12) | 0.00942 (11) | 0.00198 (10) | 0.00508 (9) | −0.00091 (9) |
S1 | 0.01682 (15) | 0.01227 (14) | 0.01643 (14) | 0.00014 (11) | 0.00872 (12) | −0.00298 (11) |
N1 | 0.0089 (4) | 0.0106 (4) | 0.0103 (4) | 0.0001 (3) | 0.0041 (3) | 0.0003 (3) |
N2 | 0.0121 (5) | 0.0136 (5) | 0.0128 (5) | −0.0004 (4) | 0.0039 (4) | −0.0032 (4) |
N3 | 0.0109 (4) | 0.0112 (4) | 0.0123 (4) | 0.0007 (4) | 0.0049 (4) | −0.0014 (4) |
N4 | 0.0098 (4) | 0.0125 (5) | 0.0130 (5) | 0.0012 (4) | 0.0038 (4) | −0.0025 (4) |
N5 | 0.0126 (5) | 0.0169 (5) | 0.0145 (5) | −0.0002 (4) | 0.0025 (4) | −0.0044 (4) |
C1 | 0.0097 (5) | 0.0118 (5) | 0.0122 (5) | −0.0002 (4) | 0.0042 (4) | −0.0017 (4) |
C2 | 0.0110 (5) | 0.0130 (5) | 0.0131 (5) | 0.0006 (4) | 0.0049 (4) | −0.0017 (4) |
C3 | 0.0134 (5) | 0.0137 (5) | 0.0140 (5) | −0.0002 (4) | 0.0046 (4) | −0.0040 (4) |
C4 | 0.0085 (5) | 0.0112 (5) | 0.0107 (5) | −0.0003 (4) | 0.0041 (4) | −0.0006 (4) |
C5 | 0.0088 (5) | 0.0113 (5) | 0.0118 (5) | −0.0003 (4) | 0.0038 (4) | −0.0006 (4) |
C6 | 0.0085 (5) | 0.0168 (6) | 0.0174 (6) | −0.0003 (4) | 0.0028 (4) | −0.0041 (5) |
C7 | 0.0136 (5) | 0.0115 (5) | 0.0108 (5) | −0.0015 (4) | 0.0059 (4) | −0.0004 (4) |
C8 | 0.0179 (6) | 0.0256 (7) | 0.0158 (6) | −0.0010 (6) | 0.0014 (5) | −0.0078 (5) |
C9 | 0.0241 (8) | 0.0331 (9) | 0.0333 (9) | −0.0137 (7) | 0.0102 (7) | −0.0156 (8) |
C10 | 0.0095 (5) | 0.0102 (5) | 0.0087 (5) | 0.0006 (4) | 0.0045 (4) | 0.0014 (4) |
C11 | 0.0112 (5) | 0.0103 (5) | 0.0119 (5) | 0.0003 (4) | 0.0053 (4) | 0.0007 (4) |
C12 | 0.0156 (6) | 0.0120 (5) | 0.0154 (6) | −0.0008 (4) | 0.0076 (5) | 0.0022 (4) |
C13 | 0.0155 (6) | 0.0154 (6) | 0.0130 (5) | 0.0010 (5) | 0.0072 (4) | 0.0049 (4) |
C14 | 0.0147 (5) | 0.0163 (6) | 0.0089 (5) | 0.0000 (5) | 0.0051 (4) | 0.0018 (4) |
C15 | 0.0117 (5) | 0.0127 (5) | 0.0088 (5) | −0.0007 (4) | 0.0043 (4) | 0.0006 (4) |
Sn1—C10i | 2.1378 (12) | C4—C5 | 1.4813 (18) |
Sn1—C10 | 2.1378 (12) | C5—C6 | 1.4921 (19) |
Sn1—N1i | 2.4032 (11) | C6—H6A | 0.9800 |
Sn1—N1 | 2.4033 (11) | C6—H6B | 0.9800 |
Sn1—Cl1i | 2.5483 (4) | C6—H6C | 0.9800 |
Sn1—Cl1 | 2.5483 (4) | C8—C9 | 1.515 (3) |
S1—C7 | 1.6804 (14) | C8—H8A | 0.9900 |
N1—C1 | 1.3367 (17) | C8—H8B | 0.9900 |
N1—C2 | 1.3473 (17) | C9—H9A | 0.9800 |
N2—C4 | 1.3411 (17) | C9—H9B | 0.9800 |
N2—C3 | 1.3416 (18) | C9—H9C | 0.9800 |
N3—C5 | 1.2912 (17) | C10—C11 | 1.3966 (18) |
N3—N4 | 1.3619 (16) | C10—C15 | 1.3971 (18) |
N4—C7 | 1.3759 (17) | C11—C12 | 1.3934 (18) |
N4—H4N | 0.85 (2) | C11—H11 | 0.9500 |
N5—C7 | 1.3314 (18) | C12—C13 | 1.393 (2) |
N5—C8 | 1.4593 (19) | C12—H12 | 0.9500 |
N5—H5N | 0.91 (2) | C13—C14 | 1.390 (2) |
C1—C4 | 1.4019 (18) | C13—H13 | 0.9500 |
C1—H1 | 0.9500 | C14—C15 | 1.3963 (18) |
C2—C3 | 1.3898 (19) | C14—H14 | 0.9500 |
C2—H2 | 0.9500 | C15—H15 | 0.9500 |
C3—H3 | 0.9500 | ||
C10i—Sn1—C10 | 180.0 | C4—C5—C6 | 120.21 (11) |
C10i—Sn1—N1i | 88.99 (4) | C5—C6—H6A | 109.5 |
C10—Sn1—N1i | 91.01 (4) | C5—C6—H6B | 109.5 |
C10i—Sn1—N1 | 91.01 (4) | H6A—C6—H6B | 109.5 |
C10—Sn1—N1 | 88.99 (4) | C5—C6—H6C | 109.5 |
N1i—Sn1—N1 | 180.0 | H6A—C6—H6C | 109.5 |
C10i—Sn1—Cl1i | 89.75 (4) | H6B—C6—H6C | 109.5 |
C10—Sn1—Cl1i | 90.25 (4) | N5—C7—N4 | 115.48 (12) |
N1i—Sn1—Cl1i | 91.79 (3) | N5—C7—S1 | 125.82 (11) |
N1—Sn1—Cl1i | 88.21 (3) | N4—C7—S1 | 118.68 (10) |
C10i—Sn1—Cl1 | 90.25 (4) | N5—C8—C9 | 112.00 (14) |
C10—Sn1—Cl1 | 89.75 (4) | N5—C8—H8A | 109.2 |
N1i—Sn1—Cl1 | 88.21 (3) | C9—C8—H8A | 109.2 |
N1—Sn1—Cl1 | 91.79 (3) | N5—C8—H8B | 109.2 |
Cl1i—Sn1—Cl1 | 180.0 | C9—C8—H8B | 109.2 |
C1—N1—C2 | 117.33 (11) | H8A—C8—H8B | 107.9 |
C1—N1—Sn1 | 116.71 (9) | C8—C9—H9A | 109.5 |
C2—N1—Sn1 | 125.82 (9) | C8—C9—H9B | 109.5 |
C4—N2—C3 | 116.40 (12) | H9A—C9—H9B | 109.5 |
C5—N3—N4 | 118.51 (11) | C8—C9—H9C | 109.5 |
N3—N4—C7 | 118.86 (11) | H9A—C9—H9C | 109.5 |
N3—N4—H4N | 121.2 (14) | H9B—C9—H9C | 109.5 |
C7—N4—H4N | 118.0 (14) | C11—C10—C15 | 119.28 (12) |
C7—N5—C8 | 124.90 (13) | C11—C10—Sn1 | 120.42 (9) |
C7—N5—H5N | 115.3 (14) | C15—C10—Sn1 | 120.29 (9) |
C8—N5—H5N | 119.8 (14) | C12—C11—C10 | 120.33 (12) |
N1—C1—C4 | 121.53 (12) | C12—C11—H11 | 119.8 |
N1—C1—H1 | 119.2 | C10—C11—H11 | 119.8 |
C4—C1—H1 | 119.2 | C13—C12—C11 | 120.20 (13) |
N1—C2—C3 | 120.61 (12) | C13—C12—H12 | 119.9 |
N1—C2—H2 | 119.7 | C11—C12—H12 | 119.9 |
C3—C2—H2 | 119.7 | C14—C13—C12 | 119.72 (12) |
N2—C3—C2 | 122.68 (13) | C14—C13—H13 | 120.1 |
N2—C3—H3 | 118.7 | C12—C13—H13 | 120.1 |
C2—C3—H3 | 118.7 | C13—C14—C15 | 120.22 (12) |
N2—C4—C1 | 121.43 (12) | C13—C14—H14 | 119.9 |
N2—C4—C5 | 118.35 (11) | C15—C14—H14 | 119.9 |
C1—C4—C5 | 120.21 (12) | C14—C15—C10 | 120.23 (12) |
N3—C5—C4 | 114.09 (11) | C14—C15—H15 | 119.9 |
N3—C5—C6 | 125.69 (12) | C10—C15—H15 | 119.9 |
C10i—Sn1—N1—C1 | 91.62 (10) | N2—C4—C5—C6 | −2.00 (19) |
C10—Sn1—N1—C1 | −88.38 (10) | C1—C4—C5—C6 | 177.75 (13) |
Cl1i—Sn1—N1—C1 | −178.66 (9) | C8—N5—C7—N4 | −178.25 (14) |
Cl1—Sn1—N1—C1 | 1.34 (9) | C8—N5—C7—S1 | 0.2 (2) |
C10i—Sn1—N1—C2 | −92.92 (11) | N3—N4—C7—N5 | −6.22 (18) |
C10—Sn1—N1—C2 | 87.08 (11) | N3—N4—C7—S1 | 175.25 (10) |
Cl1i—Sn1—N1—C2 | −3.20 (10) | C7—N5—C8—C9 | −93.44 (18) |
Cl1—Sn1—N1—C2 | 176.80 (10) | N1i—Sn1—C10—C11 | −43.26 (10) |
C5—N3—N4—C7 | −176.94 (12) | N1—Sn1—C10—C11 | 136.74 (10) |
C2—N1—C1—C4 | −0.57 (19) | Cl1i—Sn1—C10—C11 | −135.05 (10) |
Sn1—N1—C1—C4 | 175.29 (10) | Cl1—Sn1—C10—C11 | 44.95 (10) |
C1—N1—C2—C3 | 1.13 (19) | N1i—Sn1—C10—C15 | 137.23 (10) |
Sn1—N1—C2—C3 | −174.31 (10) | N1—Sn1—C10—C15 | −42.77 (10) |
C4—N2—C3—C2 | −0.6 (2) | Cl1i—Sn1—C10—C15 | 45.44 (10) |
N1—C2—C3—N2 | −0.5 (2) | Cl1—Sn1—C10—C15 | −134.56 (10) |
C3—N2—C4—C1 | 1.20 (19) | C15—C10—C11—C12 | −0.57 (19) |
C3—N2—C4—C5 | −179.06 (12) | Sn1—C10—C11—C12 | 179.92 (10) |
N1—C1—C4—N2 | −0.6 (2) | C10—C11—C12—C13 | 1.3 (2) |
N1—C1—C4—C5 | 179.63 (12) | C11—C12—C13—C14 | −0.8 (2) |
N4—N3—C5—C4 | 179.97 (11) | C12—C13—C14—C15 | −0.4 (2) |
N4—N3—C5—C6 | −1.2 (2) | C13—C14—C15—C10 | 1.1 (2) |
N2—C4—C5—N3 | 176.87 (12) | C11—C10—C15—C14 | −0.62 (19) |
C1—C4—C5—N3 | −3.38 (18) | Sn1—C10—C15—C14 | 178.90 (10) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5N···N3 | 0.91 (2) | 2.16 (2) | 2.6093 (17) | 109.8 (16) |
Experimental details
Crystal data | |
Chemical formula | [Sn(C6H5)2Cl2(C9H13N5S)2] |
Mr | 790.40 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 90 |
a, b, c (Å) | 10.7262 (15), 17.971 (3), 9.0868 (13) |
β (°) | 109.641 (6) |
V (Å3) | 1649.7 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.10 |
Crystal size (mm) | 0.27 × 0.22 × 0.20 |
Data collection | |
Diffractometer | Nonius KappaCCD (with Oxford Cryosystems Cryostream cooler) |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.755, 0.810 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24456, 7475, 6422 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.819 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.071, 1.02 |
No. of reflections | 7475 |
No. of parameters | 214 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.85, −1.29 |
Computer programs: COLLECT (Nonius, 2000), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5N···N3 | 0.91 (2) | 2.16 (2) | 2.6093 (17) | 109.8 (16) |
There has been a steady growth of interest in the synthesis, structure and reactivity studies of metal complexes of heterocyclic thiosemicarbazones due to their biological and pharmacological properties (Ali & Livingstone, 1974; Campbell, 1975; Padhye & Kauffman, 1985). The unique feature is attributed to the tautomeric equilibrium present in the thiosemicarbazone moiety and thereby the coordinating ability with many metal ions. Among the non-transition metals, organotin(IV) derivatives are of special interest due to environmental, and medical issues (Barbieri et al., 1993; Bamgboye & Bamgboye, 1988; Casas et al., 1994, Casas et al., 1996, De Sousa et al., 2001). Continuing with this type of studies, we describe here the structure of a diphenyltin dichloride derivative of pyrazine-2-carbaldehyde N(4)-ethyl-3-thiosemicarbazone (I).
The tin atom of the diphenyl dichloride unit lies on an inversion center, and is coordinated in monodentate fashion by the pyrazine nitrogen atoms of two thiosemicarbazone ligands, unlike the normal bidentate/tridentate modes of coordination. The yellow-colored complex is built up of discrete molecules of acetylpyrazine thiosemicarbazone ligand with diphenyl tin dichloride with the two chlorine atoms and two phenyl groups occupying the four equatorial positions (trans to each other) of a distorted octahedron around the tin atom. The pyrazine groups are in the inverse position and trans to one another. The angles subtended by the adjacent atoms to tin are 89.75 (4)°, [C10—Sn—Cl1], 88.99 (4)° [N1—Sn1—C10] and 91.79 (3)° (N1—Sn1—Cl1] and the corresponding bond distances are Sn—C [2.1378 (12)], Sn—Cl [2.5483 (4)] and Sn—N [2.4033 (11) Å]. The Sn—N bond length value is in the range of 2.27 to 2.58, and is less than the van der Waals radii of the two atoms, 3.74 Å (Allen et al., 1979). The Sn—Cl bond is in the range of normal covalent radii (2.37–2.60 Å) (Casas et al., 1997, Davies, 1998). The bond length Sn—C (phenyl) is slightly shorter compared to the tin adduct reported 2.1424 (14) Å by us earlier (Venkatraman et al., 2004). The bond length Sn—C increases with an increase in coordination number from four [2.122 (11) Å] (in Ph2SnCl2) and higher as expected (Dey et al., 2003).
N–H groups usually serve as hydrogen-bond donors, however, no intermolecular hyrogen bonding is present in this structure. N–H group N5 forms an intramolecular hydrogen bond of graph set designation S(5) (Etter, 1990), with N3 as acceptor, N3···N5 2.609 (2) Å. In five-membered rings, the hydrogen-bonding geometry necessarily distorts greatly from linearity. The H···N3 distance is 2.15 (2) Å, and the angle about H is 109.9 (19)°. The other N–H group N4 is not involved in hydrogen bonding.