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Acta Cryst. (2007). E63, m2924    [ doi:10.1107/S1600536807054980 ]

Bis([mu]-2-pyridine-2,6-dicarboxylato)bis[aquadimethyltin(IV)]

M. Yang, R. Zhang and Y. Sun

Abstract top

The title dinuclear complex, [Sn2(CH3)4(C7H3NO4)2(H2O)2], lies on a crystallographic inversion center. The unique SnIV atom is coordinated in a slightly disorted pentagonal-bipyramidal geometry. The two symmetry-related SnIV atoms are connected via two asymmetric Sn-O-Sn bridges (Sn-O = 2.473 and 2.634 Å), such that an exactly planar Sn-O-Sn-O ring is formed.

Comment top

In recent years, organotin complexes have been attracting more and more attention due to their wide industrial applications and biological activities (Dubey & Roy, 2003). Organotin(IV) dicarboxylates have been studied in considerable detail, and in general the reported organotin dicarboxylates exist as dinuclear, one-dimensional zigzag chain and cyclic structures (Ma et al., 2005). Herein we report the structure of the title complex (Fig. 1). For the coordination of the SnIV atom, two C atoms of the methyl groups are in the apical positions[C—Sn—C = 167.1 (3)°], and four O atoms and one N atom are in the equatorial positions giving a slightly distorted pentagonal- bipyramidal environment. The Sn—O, Sn—N bond distances are comparable to those reported in the literature (Aizawa et al., 1996). The longest Sn—O distance is 2.634 (5)Å for Sn—Oi [symmetry code: (i) 1 − x, −y, 1 − z].

Related literature top

For related literature, see: Aizawa et al. (1996); Dubey & Roy (2003); Ma et al. (2005).

Experimental top

The reaction was carried out under N2 atmoshpere. 2,6-pyridinedicarboxylic acid (0.167 g, 1 mmol) was added to a solution of benzene(30 ml) with sodium ethoxide (0.136 g, 2 mmol)in a Schlenk flask. After stirring for 10 min, dimethyltin dichloride (0.220 g, 1 mmol) was added to the mixture. The mixture was kept at 313 K for 12 h. After cooling to room temperature, the solution was filtered. The solvent of the filtrate was gradually removed by evaporation under vacuum until a solid product was obtained. The solid was then recrystallized from diethyl ether. Colorless single crystals of the title complex were obtained after one week. Yield, 81%. Analysis calculated for C18H22N2O10Sn2: C 32.57, H 3.34, N, 4.22; found: C 32.36, H 3.22, N, 4.31. The elemental analyses were performed with PERKIN ELMER MODEL 2400 SERIES II.

Refinement top

All H atoms were placed geometrically idealized positions and treated as riding on their parent atoms, with aromatic C—H distances of 0.93 Å and methyl C—H distances of 0.96 Å. The Uiso(H) values were set at 1.2Ueq(C) for the aromatic H atoms and 1.5Ueq(C) for methyl H atoms.

Computing details top

Data collection: SMART (Bruker, 1996); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT (Bruker, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme for non-H atoms [symmetry code: (A) 1 − x, −y, 1 − z].
Bis(µ-2-pyridine-2,6-dicarboxylato)bis[aquadimethyltin(IV)] top
Crystal data top
[Sn2(CH3)4(C7H3NO4)2(H2O)2]F000 = 1296
Mr = 663.76Dx = 1.940 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2820 reflections
a = 11.319 (5) Åθ = 2.6–28.2º
b = 10.705 (4) ŵ = 2.25 mm−1
c = 18.768 (8) ÅT = 298 (2) K
β = 91.864 (5)ºBlock, colorless
V = 2272.9 (16) Å30.23 × 0.17 × 0.14 mm
Z = 4
Data collection top
Bruker SMART CCD area detector
diffractometer		1998 independent reflections
Radiation source: fine-focus sealed tube1645 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.059
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −13→13
Tmin = 0.625, Tmax = 0.743k = −12→12
5571 measured reflectionsl = −19→22
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.123  w = 1/[σ2(Fo2) + (0.077P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
1998 reflectionsΔρmax = 0.99 e Å−3
147 parametersΔρmin = −1.93 e Å−3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Sn2(CH3)4(C7H3NO4)2(H2O)2]V = 2272.9 (16) Å3
Mr = 663.76Z = 4
Monoclinic, C2/cMo Kα
a = 11.319 (5) ŵ = 2.25 mm−1
b = 10.705 (4) ÅT = 298 (2) K
c = 18.768 (8) Å0.23 × 0.17 × 0.14 mm
β = 91.864 (5)º
Data collection top
Bruker SMART CCD area detector
diffractometer		1998 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1645 reflections with I > 2σ(I)
Tmin = 0.625, Tmax = 0.743Rint = 0.059
5571 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0464 restraints
wR(F2) = 0.123H-atom parameters constrained
S = 1.00Δρmax = 0.99 e Å−3
1998 reflectionsΔρmin = −1.93 e Å−3
147 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
Sn10.39712 (4)0.01350 (4)0.59215 (2)0.0274 (2)
N10.4229 (4)0.2188 (4)0.6236 (3)0.0236 (11)
O10.5332 (4)0.1262 (4)0.5141 (2)0.0270 (10)
O20.5885 (5)0.3132 (4)0.4773 (3)0.0440 (13)
O30.2964 (5)0.0520 (5)0.6883 (3)0.0435 (12)
O40.2345 (6)0.1879 (5)0.7685 (3)0.0642 (18)
O50.2951 (4)−0.1711 (4)0.6116 (3)0.0415 (12)
H10.2831−0.19810.65340.062*
H20.3360−0.22630.59110.062*
C10.5411 (5)0.2409 (6)0.5194 (3)0.0261 (14)
C20.4850 (5)0.2990 (6)0.5842 (3)0.0255 (14)
C30.4904 (5)0.4248 (6)0.6008 (4)0.0329 (15)
H30.53410.47930.57350.039*
C40.4294 (7)0.4685 (7)0.6589 (4)0.0393 (17)
H40.43240.55270.67110.047*
C50.3639 (6)0.3850 (6)0.6986 (4)0.0315 (15)
H5A0.32210.41270.73740.038*
C60.3620 (5)0.2609 (6)0.6794 (3)0.0290 (14)
C70.2929 (6)0.1611 (6)0.7156 (4)0.0373 (17)
C80.2604 (5)0.0637 (7)0.5183 (4)0.0348 (16)
H8A0.29270.11190.48040.052*
H8B0.20220.11240.54190.052*
H8C0.2241−0.01050.49890.052*
C90.5481 (6)−0.0590 (8)0.6463 (4)0.0439 (18)
H9A0.5806−0.12570.61880.066*
H9B0.5265−0.09040.69200.066*
H9C0.60600.00590.65270.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.0322 (3)0.0288 (3)0.0212 (3)−0.00140 (17)0.0044 (2)−0.00003 (18)
N10.026 (3)0.029 (3)0.016 (3)0.000 (2)0.003 (2)0.000 (2)
O10.034 (2)0.029 (3)0.018 (2)−0.0059 (18)0.0012 (19)−0.0028 (18)
O20.063 (3)0.032 (3)0.038 (3)−0.013 (2)0.027 (3)−0.005 (2)
O30.062 (3)0.039 (3)0.030 (3)−0.009 (3)0.023 (2)−0.004 (2)
O40.104 (5)0.049 (3)0.043 (4)−0.015 (3)0.048 (3)−0.011 (3)
O50.062 (3)0.030 (3)0.034 (3)−0.001 (2)0.019 (2)0.001 (2)
C10.028 (3)0.028 (4)0.022 (3)−0.004 (3)0.001 (3)0.001 (3)
C20.020 (3)0.034 (4)0.022 (4)0.000 (2)0.000 (3)0.000 (3)
C30.031 (3)0.034 (4)0.034 (4)−0.006 (3)0.007 (3)−0.001 (3)
C40.048 (4)0.031 (4)0.039 (5)−0.002 (3)0.007 (4)−0.009 (3)
C50.032 (4)0.038 (4)0.025 (4)0.004 (3)0.003 (3)−0.007 (3)
C60.032 (3)0.033 (4)0.022 (3)−0.003 (3)0.002 (3)0.000 (3)
C70.050 (4)0.032 (4)0.031 (4)−0.004 (3)0.011 (3)−0.006 (3)
C80.030 (3)0.036 (4)0.039 (4)−0.004 (3)0.003 (3)0.006 (3)
C90.045 (4)0.064 (5)0.023 (4)0.007 (4)−0.005 (3)0.002 (4)
Geometric parameters (Å, °) top
Sn1—C92.108 (7)C1—C21.523 (8)
Sn1—C82.114 (6)C2—C31.383 (9)
Sn1—O32.204 (5)C3—C41.390 (10)
Sn1—N12.292 (5)C3—H30.9300
Sn1—O52.324 (5)C4—C51.394 (10)
Sn1—O12.473 (4)C4—H40.9300
Sn1—O1i2.634 (5)C5—C61.376 (9)
N1—C21.347 (7)C5—H5A0.9300
N1—C61.350 (8)C6—C71.499 (9)
O1—C11.235 (7)C8—H8A0.9600
O2—C11.241 (7)C8—H8B0.9600
O3—C71.277 (8)C8—H8C0.9600
O4—C71.245 (8)C9—H9A0.9600
O5—H10.8500C9—H9B0.9600
O5—H20.8500C9—H9C0.9600
C9—Sn1—C8167.1 (3)C3—C2—C1124.2 (6)
C9—Sn1—O396.1 (2)C2—C3—C4119.1 (6)
C8—Sn1—O395.9 (2)C2—C3—H3120.5
C9—Sn1—N197.7 (3)C4—C3—H3120.5
C8—Sn1—N190.6 (2)C3—C4—C5119.3 (6)
O3—Sn1—N171.02 (17)C3—C4—H4120.3
C9—Sn1—O590.6 (3)C5—C4—H4120.3
C8—Sn1—O587.8 (2)C6—C5—C4118.9 (6)
O3—Sn1—O575.95 (17)C6—C5—H5A120.6
N1—Sn1—O5146.58 (17)C4—C5—H5A120.6
C9—Sn1—O187.4 (2)N1—C6—C5121.4 (6)
C8—Sn1—O186.8 (2)N1—C6—C7113.5 (6)
O3—Sn1—O1137.91 (16)C5—C6—C7125.0 (6)
N1—Sn1—O166.95 (15)O4—C7—O3123.7 (6)
O5—Sn1—O1146.11 (15)O4—C7—C6119.7 (6)
C2—N1—C6120.1 (5)O3—C7—C6116.6 (6)
C2—N1—Sn1122.3 (4)Sn1—C8—H8A109.5
C6—N1—Sn1117.2 (4)Sn1—C8—H8B109.5
C1—O1—Sn1118.9 (4)H8A—C8—H8B109.5
C7—O3—Sn1121.5 (4)Sn1—C8—H8C109.5
Sn1—O5—H1121.9H8A—C8—H8C109.5
Sn1—O5—H2103.8H8B—C8—H8C109.5
H1—O5—H2106.7Sn1—C9—H9A109.5
O1—C1—O2126.9 (6)Sn1—C9—H9B109.5
O1—C1—C2116.0 (5)H9A—C9—H9B109.5
O2—C1—C2117.0 (6)Sn1—C9—H9C109.5
N1—C2—C3121.1 (6)H9A—C9—H9C109.5
N1—C2—C1114.7 (5)H9B—C9—H9C109.5
C9—Sn1—N1—C289.9 (5)Sn1—N1—C2—C3174.1 (5)
C8—Sn1—N1—C2−80.2 (5)C6—N1—C2—C1−175.2 (5)
O3—Sn1—N1—C2−176.3 (5)Sn1—N1—C2—C1−2.8 (7)
O5—Sn1—N1—C2−167.2 (4)O1—C1—C2—N1−6.6 (8)
O1—Sn1—N1—C26.1 (4)O2—C1—C2—N1172.5 (6)
C9—Sn1—N1—C6−97.5 (5)O1—C1—C2—C3176.6 (6)
C8—Sn1—N1—C692.5 (5)O2—C1—C2—C3−4.3 (10)
O3—Sn1—N1—C6−3.6 (4)N1—C2—C3—C4−0.6 (10)
O5—Sn1—N1—C65.5 (6)C1—C2—C3—C4176.0 (6)
O1—Sn1—N1—C6178.8 (5)C2—C3—C4—C5−0.4 (11)
C9—Sn1—O1—C1−109.6 (5)C3—C4—C5—C60.4 (10)
C8—Sn1—O1—C181.9 (5)C2—N1—C6—C5−1.6 (9)
O3—Sn1—O1—C1−13.4 (6)Sn1—N1—C6—C5−174.5 (5)
N1—Sn1—O1—C1−10.1 (4)C2—N1—C6—C7177.2 (5)
O5—Sn1—O1—C1163.3 (4)Sn1—N1—C6—C74.3 (7)
C9—Sn1—O3—C798.4 (6)C4—C5—C6—N10.6 (10)
C8—Sn1—O3—C7−86.3 (6)C4—C5—C6—C7−178.1 (7)
N1—Sn1—O3—C72.3 (5)Sn1—O3—C7—O4177.9 (6)
O5—Sn1—O3—C7−172.6 (6)Sn1—O3—C7—C6−0.8 (9)
O1—Sn1—O3—C75.5 (7)N1—C6—C7—O4178.8 (7)
Sn1—O1—C1—O2−166.9 (6)C5—C6—C7—O4−2.4 (11)
Sn1—O1—C1—C212.2 (7)N1—C6—C7—O3−2.4 (9)
C6—N1—C2—C31.7 (9)C5—C6—C7—O3176.4 (7)
Symmetry codes: (i) −x+1, −y, −z+1.
Acknowledgements top

The authors thank the National Natural Science Foundation of China (20271025) for financial support.

references
References top

Aizawa, S. I., Natsume, T., Hatano, K. & Funahashi, S. (1996). Inorg. Chim. Acta, 248, 215–224.

Bruker (1996). SMART and SAINT. Bruker AXS Inc. Madison, Wisconsin, USA.

Dubey, S. K. & Roy, U. (2003). Appl. Organomet. Chem. 17, 3–8.

Ma, C. L., Li, J. K., Zhang, R. F. & Wang, D. Q. (2005). Inorg. Chim. Acta, 358, 4575–4580.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc. Madison, Wisconsin, USA.