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In the title complex, [Sn(C2H5)2Cl2(C5H5N)2], the Sn atom lies on an inversion centre and is octahedrally coordinated by two Cl atoms, two ethyl C atoms and two pyridine N atoms in an all-trans configuration. The dihedral angle between the pyridine ring and the SnNCl plane is 22.4 (2)°.
Supporting information
CCDC reference: 143225
The title compound was prepared by addition of a solution of py in CH2Cl2 to
a solution of diethyltin dichloride in the same solvent. After 3 d of stirring
the solution was concentrated, and upon cooling crystals suitable for X-ray
analysis were obtained.
Hydrogen atoms were refined using riding model (HFIX 43 for aromatic, HFIX 23
for methylen and HFIX 137 for methyl group). Disorder of methyl group (C7) was
modelled by refinement of the occupancy factor at values that resulted to be
0.30 and 0.70. The C6—C7 distance was restrained to be close to 1.5 Å.
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELX97 (Sheldrick, 1997).
dichlorodiethylbis(pyridine)tin(IV)
top
Crystal data top
[SnCl2(C2H5)2(C5H5N)2] | F(000) = 808 |
Mr = 405.91 | Dx = 1.562 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.9828 (3) Å | Cell parameters from 39 reflections |
b = 9.6029 (2) Å | θ = 3–23° |
c = 14.0432 (2) Å | µ = 1.78 mm−1 |
β = 113.7640 (13)° | T = 293 K |
V = 1725.78 (6) Å3 | Block, colorless |
Z = 4 | 0.35 × 0.20 × 0.15 mm |
Data collection top
Siemens CCD diffractometer | 2128 independent reflections |
Radiation source: fine-focus sealed tube | 1459 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ω scans | θmax = 28.3°, θmin = 2.7° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −7→18 |
Tmin = 0.550, Tmax = 0.766 | k = −12→12 |
5824 measured reflections | l = −18→18 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.00 | Calculated w = 1/[σ2(Fo2) + (0.0354P)2] where P = (Fo2 + 2Fc2)/3 |
2128 reflections | (Δ/σ)max < 0.001 |
99 parameters | Δρmax = 0.60 e Å−3 |
1 restraint | Δρmin = −0.31 e Å−3 |
Crystal data top
[SnCl2(C2H5)2(C5H5N)2] | V = 1725.78 (6) Å3 |
Mr = 405.91 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.9828 (3) Å | µ = 1.78 mm−1 |
b = 9.6029 (2) Å | T = 293 K |
c = 14.0432 (2) Å | 0.35 × 0.20 × 0.15 mm |
β = 113.7640 (13)° | |
Data collection top
Siemens CCD diffractometer | 2128 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1459 reflections with I > 2σ(I) |
Tmin = 0.550, Tmax = 0.766 | Rint = 0.031 |
5824 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 1 restraint |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.60 e Å−3 |
2128 reflections | Δρmin = −0.31 e Å−3 |
99 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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Sn | 0.0000 | 0.0000 | 0.0000 | 0.04881 (12) | |
Cl | −0.06320 (8) | 0.21590 (11) | 0.06917 (7) | 0.0718 (3) | |
N | 0.1660 (2) | 0.0080 (3) | 0.1476 (2) | 0.0597 (7) | |
C1 | 0.2500 (3) | −0.0542 (4) | 0.1455 (3) | 0.0677 (9) | |
H1 | 0.2449 | −0.0964 | 0.0840 | 0.081* | |
C2 | 0.3437 (3) | −0.0590 (4) | 0.2299 (3) | 0.0790 (11) | |
H2 | 0.4010 | −0.1032 | 0.2256 | 0.095* | |
C3 | 0.3517 (3) | 0.0022 (4) | 0.3207 (4) | 0.0824 (13) | |
H3 | 0.4143 | −0.0003 | 0.3794 | 0.099* | |
C4 | 0.2667 (3) | 0.0666 (5) | 0.3236 (3) | 0.0830 (12) | |
H4 | 0.2705 | 0.1095 | 0.3844 | 0.100* | |
C5 | 0.1750 (3) | 0.0682 (4) | 0.2360 (3) | 0.0707 (10) | |
H5 | 0.1171 | 0.1130 | 0.2386 | 0.085* | |
C6 | −0.0567 (4) | −0.1308 (5) | 0.0904 (3) | 0.1015 (15) | |
H6A1 | −0.0208 | −0.0883 | 0.0513 | 0.122* | 0.30 |
H6A2 | −0.0743 | −0.0680 | 0.1350 | 0.122* | 0.30 |
H6B1 | −0.0940 | −0.0648 | 0.1185 | 0.122* | 0.70 |
H6B2 | 0.0037 | −0.1620 | 0.1473 | 0.122* | 0.70 |
C7A | −0.0336 (17) | −0.2617 (13) | 0.1212 (13) | 0.114 (6) | 0.30 |
H7A1 | −0.0823 | −0.2957 | 0.1482 | 0.171* | 0.30 |
H7A2 | 0.0359 | −0.2661 | 0.1745 | 0.171* | 0.30 |
H7A3 | −0.0378 | −0.3180 | 0.0632 | 0.171* | 0.30 |
C7B | −0.1228 (7) | −0.2399 (10) | 0.0458 (7) | 0.154 (4) | 0.70 |
H7B1 | −0.0963 | −0.2934 | 0.0039 | 0.231* | 0.70 |
H7B2 | −0.1909 | −0.2046 | 0.0028 | 0.231* | 0.70 |
H7B3 | −0.1275 | −0.2980 | 0.0993 | 0.231* | 0.70 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sn | 0.04618 (18) | 0.0568 (2) | 0.04256 (17) | 0.00031 (15) | 0.01699 (13) | −0.00217 (14) |
Cl | 0.0636 (5) | 0.0795 (6) | 0.0643 (5) | 0.0088 (5) | 0.0175 (4) | −0.0177 (5) |
N | 0.0537 (16) | 0.0657 (17) | 0.0539 (15) | 0.0051 (14) | 0.0155 (13) | −0.0065 (13) |
C1 | 0.054 (2) | 0.077 (2) | 0.066 (2) | 0.0037 (19) | 0.0176 (18) | −0.0129 (19) |
C2 | 0.057 (2) | 0.083 (2) | 0.084 (3) | 0.012 (2) | 0.014 (2) | −0.010 (2) |
C3 | 0.060 (2) | 0.091 (3) | 0.070 (3) | 0.006 (2) | −0.0010 (19) | 0.001 (2) |
C4 | 0.080 (3) | 0.103 (3) | 0.051 (2) | 0.008 (3) | 0.010 (2) | −0.011 (2) |
C5 | 0.064 (2) | 0.084 (2) | 0.057 (2) | 0.012 (2) | 0.0165 (18) | −0.0118 (19) |
C6 | 0.124 (4) | 0.115 (4) | 0.085 (3) | −0.030 (3) | 0.062 (3) | 0.000 (3) |
C7A | 0.20 (2) | 0.061 (9) | 0.097 (12) | 0.009 (11) | 0.080 (13) | 0.034 (8) |
C7B | 0.150 (8) | 0.161 (9) | 0.141 (8) | −0.068 (7) | 0.047 (6) | 0.038 (7) |
Geometric parameters (Å, º) top
Sn—C6i | 2.151 (4) | N—C1 | 1.328 (5) |
Sn—C6 | 2.151 (4) | C1—C2 | 1.368 (5) |
Sn—Ni | 2.410 (3) | C2—C3 | 1.367 (6) |
Sn—N | 2.411 (3) | C3—C4 | 1.354 (6) |
Sn—Cl | 2.591 (1) | C4—C5 | 1.374 (5) |
Sn—Cli | 2.591 (1) | C6—C7A | 1.326 (11) |
N—C5 | 1.329 (4) | C6—C7B | 1.370 (8) |
| | | |
C6i—Sn—C6 | 180.0 | N—Sn—Cli | 89.6 (1) |
C6i—Sn—Ni | 88.1 (2) | Cl—Sn—Cli | 180.0 |
C6—Sn—Ni | 91.9 (2) | C5—N—C1 | 117.7 (3) |
C6i—Sn—N | 91.9 (2) | C5—N—Sn | 120.8 (2) |
C6—Sn—N | 88.1 (2) | C1—N—Sn | 121.3 (2) |
Ni—Sn—N | 180.0 | N—C1—C2 | 122.8 (4) |
C6i—Sn—Cl | 90.9 (1) | C3—C2—C1 | 118.9 (4) |
C6—Sn—Cl | 89.1 (1) | C4—C3—C2 | 118.8 (4) |
Ni—Sn—Cl | 89.6 (1) | C3—C4—C5 | 119.5 (4) |
N—Sn—Cl | 90.5 (1) | N—C5—C4 | 122.3 (4) |
C6i—Sn—Cli | 89.1 (1) | C7A—C6—C7B | 57.0 (9) |
C6—Sn—Cli | 90.9 (1) | C7A—C6—Sn | 130.3 (9) |
Ni—Sn—Cli | 90.5 (1) | C7B—C6—Sn | 121.2 (5) |
| | | |
C6i—Sn—N—C5 | 115.0 (3) | C2—C3—C4—C5 | 0.4 (7) |
C6—Sn—N—C5 | −65.0 (3) | C1—N—C5—C4 | −0.5 (6) |
Ni—Sn—N—C5 | 51 (8) | Sn—N—C5—C4 | 175.7 (3) |
Cl—Sn—N—C5 | 24.0 (3) | C3—C4—C5—N | 0.2 (7) |
Cli—Sn—N—C5 | −156.0 (3) | C6i—Sn—C6—C7A | 173 (8) |
C6i—Sn—N—C1 | −69.0 (3) | Ni—Sn—C6—C7A | 109.3 (12) |
C6—Sn—N—C1 | 111.0 (3) | N—Sn—C6—C7A | −70.7 (12) |
Ni—Sn—N—C1 | −133 (8) | Cl—Sn—C6—C7A | −161.1 (12) |
Cl—Sn—N—C1 | −159.9 (3) | Cli—Sn—C6—C7A | 18.9 (12) |
Cli—Sn—N—C1 | 20.1 (3) | C6i—Sn—C6—C7B | 102 (7) |
C5—N—C1—C2 | 0.3 (6) | Ni—Sn—C6—C7B | 38.1 (7) |
Sn—N—C1—C2 | −175.9 (3) | N—Sn—C6—C7B | −141.9 (7) |
N—C1—C2—C3 | 0.3 (7) | Cl—Sn—C6—C7B | 127.6 (7) |
C1—C2—C3—C4 | −0.6 (7) | Cli—Sn—C6—C7B | −52.4 (7) |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···Cli | 0.93 | 2.83 | 3.460 (4) | 126 |
C2—H2···Clii | 0.93 | 3.00 | 3.719 (5) | 136 |
C5—H5···Cl | 0.93 | 2.86 | 3.507 (4) | 128 |
Symmetry codes: (i) −x, −y, −z; (ii) x+1/2, y−1/2, z. |
Experimental details
Crystal data |
Chemical formula | [SnCl2(C2H5)2(C5H5N)2] |
Mr | 405.91 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 13.9828 (3), 9.6029 (2), 14.0432 (2) |
β (°) | 113.7640 (13) |
V (Å3) | 1725.78 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.78 |
Crystal size (mm) | 0.35 × 0.20 × 0.15 |
|
Data collection |
Diffractometer | Siemens CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.550, 0.766 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5824, 2128, 1459 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.666 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.077, 1.00 |
No. of reflections | 2128 |
No. of parameters | 99 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −0.31 |
Selected geometric parameters (Å, º) topSn—C6 | 2.151 (4) | Sn—N | 2.411 (3) |
Sn—Ni | 2.410 (3) | Sn—Cl | 2.591 (1) |
| | | |
C6i—Sn—N | 91.9 (2) | C6—Sn—Cl | 89.1 (1) |
C6—Sn—N | 88.1 (2) | Ni—Sn—Cl | 89.6 (1) |
C6i—Sn—Cl | 90.9 (1) | N—Sn—Cl | 90.5 (1) |
| | | |
Cl—Sn—C6—C7A | −161.1 (12) | Cl—Sn—C6—C7B | 127.6 (7) |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···Cli | 0.93 | 2.83 | 3.460 (4) | 126 |
C2—H2···Clii | 0.93 | 3.00 | 3.719 (5) | 136 |
C5—H5···Cl | 0.93 | 2.86 | 3.507 (4) | 128 |
Symmetry codes: (i) −x, −y, −z; (ii) x+1/2, y−1/2, z. |
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The antitumoral activity of diorganotin(IV) dihalide complexes with N-donor ligands (Yang & Guo, 1999) arouses interest in their structures. Surprisingly, despite the wide use of pyridine (py) as a ligand (Thornton, 1990), the only py complexes of this kind that have previously been characterized structurally are the methyl derivatives [SnMe2X2(py)2] (X = Cl, Br) (Aslanov et al., 1978). In view of this, and bearing in mind that spectral data for [SnEt2Cl2(py)2] suggest an all-trans octahedral structure (Van den Berghe et al., 1969) and that the Cambridge Structural Database contains no all-trans complexes of SnEt2Cl2 with N-donor ligands (Allen & Kennard, 1993), we have synthesized and determined the crystal and molecular structures of the title compound, (I). \sch
The molecular structure and atomic numbering scheme of (I) are shown in Figure 1. The Sn atom is octahedrally coordinated by two Cl atoms, two ethyl C atoms and two py N atoms in all-trans configuration with the Sn atom at a centre of symmetry. Comparison of the Sn—C, Sn—Cl and Sn—N bond lengths with those of similar [SnR2Cl2L2] complexes (as noted above, no data are available for other all-trans [SnEt2Cl2L2] complexes). [R = methyl; L = pyridine; 2.15 (2); 2.570 (1); 2.39 (2) Å (Aslanov et al., 1978); L = imidazole; 2.110 (3); 2.5955 (7); 2.312 (2) Å (García-Martínez et al., 1990); L = N-methylimidazole; 2.118 (5); 2.571 (3); 2.329 (5) Å (Bardi et al., 1984); L = 2-chloroimidazole; 2.134 (4); 2.591 (2); 2.380 (4) Å (Casellato et al., 1995); L = indazole; 2.12 (1); 2.590 (3); 2.377 (6) Å (Alvarez Boo et al., 1997); L = 3-methyladenine; 2.121 (4); 2.596 (1); 2.384 (3) Å (Hazell et al., 1997); L = pyrazole; 2.114 (13); 2.570 (3); 2.338 (6) Å (Valle et al., 1987); L = 4-bromopyrazole; 2.129 (5); 2.563 (2); 2.359 (4) Å (Casellato et al., 1995); L = 4-methylpyrazole; 2.128 (6); 2.572 (2); 2.351 (5) Å (Gioia Lobbia et al., 1996); L = 3,5-dimethylpyrazole; 2.11 (1), 2.12 (1); 2.581 (2); 2.379 (6) Å (Graziani et al., 1982); L = 3,4,5-trimethylpyrazole; 2.128 (5), 2.125 (5); 2.563 (4), 2.596 (5); 2.38 (2), 2.37 (2) Å (Calogero et al., 1996); R = ethyl; L = pyridine; 2.151 (4); 2.591 (1); 2.410 (3), 2.411 (3) Å this work; R = vinyl; L = pyrazole; 2.103 (13); 2.565 (2); 2.322 (5) Å (Peruzzo et al., 1989); R = butyl; L = pyrazole; 2.131 (5), 2.149 (5); 2.592 (4), 2.587 (4); 2.329 (5), 2.388 (5) Å (Sánchez-González et al., 1992); R = phenyl; L = pyrazole; 2.146 (7), 2.140 (8); 2.526 (2), 2.536 (2); 2.315 (6), 2.341 (6) Å (Casas et al., 1996); L = thiazole; 2.154 (8), 2.158 (8); 2.508 (3), 2.569 (3); 2.368 (8), 2.370 (8) Å (Alvarez Boo et al., 1996)] shows that the Sn—N bond is the longest so far reported, and the Sn—C and Sn—Cl bond lengths are also near the upper ends of the corresponding ranges.
The pyridine ring exhibits negligible deviation from the best least-squares plane. The bond lengths in the ring are slightly different from those found in [SnMe2X2(py)2] (Aslanov et al., 1978), but the large s.u.'s of the latter preclude detailed comparison. The dihedral angle between the py ring and the SnNCl plane is 22.4 (2)°. In the pyrazole complexes mentioned above, and in those of some of its derivatives, the orientation of the ring with respect to the SnNCl plane is essentially determined by the formation of intramolecular N—H···Cl hydrogen bonds. Since the C1—H and C5—H groups contiguous to the py N atom in [SnEt2Cl2(py)2] are positionally equivalent to the N—H groups in pyrazole, it is possible that in this case ring orientation may be determined by C—H···Cl interactions [C5···Cl 3.507 (4); H5···Cl 2.86 Å; C5—H5···Cl 128°; C1···Cli 3.460 (4) Å; H1···Cli 2.83 Å; C1—H1···Cli 126°; i = -x, -y, -z] (Steiner, 1998).
With regard to the molecular packing, the crystal may be described as composed of two kinds of molecule layers, A and B. The N—Sn—N axes of all the molecules have the same orientation, but the molecules of type A layers are rotated 90° about this axis with respect to those type B layers. Type A layers comprise molecules lying at the vertices and centres of the ab faces of the unit cell, and type B layers molecules lying at the centre of the cell and the centres of the sides oriented in the c direction. Intermolecular C—H···Cl interactions [C2···Clii 3.719 (5) Å; H2···Clii 3.00 Å; C2—H2···Clii 136°; ii = x + 1/2, y - 1/2, z] can contribute to the stability of this molecular packing.