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Acta Cryst. (2007). E63, m1566    [ doi:10.1107/S1600536807020880 ]

Bis(4,4'-bipyridine-[kappa]N)tetrakis(nitrato-[kappa]2O,O')tin(IV)

H. Zhong, X.-R. Zeng, X.-M. Yang and Q.-Y. Luo

Abstract top

The SnIV atom in the title complex, [Sn(NO3)4(C10H8N2)2], is ten-coordinated by two N atoms of 4,4'-bipyridine ligands and eight O atoms of four NO3- ligands. The Sn atom lies on a crystallographic twofold rotation axis. The Sn-O bond lengths are in the range 2.378 (5)-2.538 (5) Å. The Sn-N bond length is 2.601 (5) Å. C-H...O hydrogen bonds link mononuclear complex molecules into a supramolecular network structure.

Comment top

In recent years, the researches on tin complexes draw increasing attention owning to their potential applications as photovoltaic materials, holographic recording system and biological activities (Jiang & Ozin, 1998; Valiukonis et al., 1986; Hencher et al., 1982; Bandoli et al., 1992, 1993), solar control devices (Nair & Nair, 1991) and semiconductor materials. Mononuclear or binuclear tin materials are important candidates as molecular precursors to prepare tin film materials by chemical vapour deposition (CVD)(Barone et al., 2002). We report herein the crystal structure of the title compound, (I).

In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). The ten-coordinate environment of the Sn atom is completed by two N atoms of 4,4'-bipyridine ligands and eight O atoms of four NO3- ligands (Table 1). The Sn—O bond lengths are in the range 2.378 (5) to 2.538 (5) Å. The Sn—N bond length is 2.601 (5) Å. The C—H···O hydrogen bonds link the mononuclear complex into a supramolecular network structure (Fig. 2).

Related literature top

For related literature, see: Allen et al. (1987); Bandoli et al. (1992); Bandoli et al. (1993); Barone et al. (2002); Hencher et al. (1982); Jiang & Ozin (1998); Nair & Nair (1991); Valiukonis et al. (1986).

Experimental top

Crystals of the title compound (I) were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb, which was then sealed. Tin dioxide (30.1 mg, 0.2 mmol), 4,4'-bipyridine (93.6 mg, 0.6 mmol), nitric acid (0.2 mol/l, 4 ml) and distilled water (2 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure for 7 d at 413 K and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colorless solution was decanted from small colorless crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature. Powder X-ray diffraction was conducted on the sample.

Refinement top

H atoms were positioned geometrically, with C—H = 0.93 Å for aromatic H and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [symmetry code (A): 2 - x, y, 1 - z].
[Figure 2] Fig. 2. Packing diagram for (I) showing hydrogen bonds as dashed lines.
Bis(4,4'-bipyridine-κN)tetrakis(nitrato-κ2O,O')tin(IV) top
Crystal data top
[Sn(NO3)4(C10H8N2)2]F(000) = 1352
Mr = 679.10Dx = 1.879 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8336 reflections
a = 20.112 (6) Åθ = 2.4–29.3°
b = 7.813 (4) ŵ = 1.15 mm−1
c = 17.302 (9) ÅT = 273 K
β = 117.991 (7)°Plate, colourless
V = 2400.9 (18) Å30.40 × 0.33 × 0.21 mm
Z = 4
Data collection top
Bruker APEX II area-detector
diffractometer		2286 independent reflections
Radiation source: fine-focus sealed tube2249 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.014
φ and ω scansθmax = 26.1°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −24→24
Tmin = 0.656, Tmax = 0.797k = −9→9
7607 measured reflectionsl = −21→21
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)] = 0.034H-atom parameters constrained
wR(F2) = 0.120 w = 1/[σ2(Fo2) + (0.0667P)2 + 18.0815P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
2286 reflectionsΔρmax = 0.91 e Å−3
187 parametersΔρmin = −0.48 e Å−3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0039 (4)
Crystal data top
[Sn(NO3)4(C10H8N2)2]V = 2400.9 (18) Å3
Mr = 679.10Z = 4
Monoclinic, C2/cMo Kα radiation
a = 20.112 (6) ŵ = 1.15 mm−1
b = 7.813 (4) ÅT = 273 K
c = 17.302 (9) Å0.40 × 0.33 × 0.21 mm
β = 117.991 (7)°
Data collection top
Bruker APEX II area-detector
diffractometer		2286 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2249 reflections with I > 2σ(I)
Tmin = 0.656, Tmax = 0.797Rint = 0.014
7607 measured reflectionsθmax = 26.1°
Refinement top
R[F2 > 2σ(F2)] = 0.034 w = 1/[σ2(Fo2) + (0.0667P)2 + 18.0815P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.120Δρmax = 0.91 e Å−3
S = 1.08Δρmin = −0.48 e Å−3
2286 reflectionsAbsolute structure: ?
187 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
H-atom parameters constrained
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
Sn11.00000.33854 (5)0.75000.0270 (2)
O11.0922 (3)0.4420 (6)0.8899 (3)0.0648 (12)
O21.0826 (4)0.4128 (9)1.0030 (3)0.0938 (19)
O30.9970 (3)0.3044 (6)0.8849 (3)0.0653 (12)
O40.9294 (3)0.0723 (7)0.6688 (4)0.0745 (14)
O50.8183 (3)−0.0051 (7)0.6530 (4)0.0817 (15)
O60.8783 (3)0.2147 (6)0.7288 (3)0.0650 (12)
N11.0580 (3)0.3864 (7)0.9290 (4)0.0600 (13)
N20.8730 (3)0.0901 (7)0.6819 (3)0.0558 (12)
N30.9364 (3)0.6015 (7)0.7804 (3)0.0552 (12)
C10.9745 (4)0.7368 (8)0.8256 (4)0.0563 (15)
H11.02320.75270.83380.068*
C20.9464 (4)0.8529 (8)0.8606 (5)0.0543 (15)
H20.97510.94650.89150.065*
C30.8638 (4)0.5856 (9)0.7678 (4)0.0612 (16)
H30.83520.49390.73440.073*
C40.8315 (4)0.6930 (8)0.8003 (4)0.0571 (15)
H40.78230.67650.79030.068*
C50.8742 (4)0.8304 (7)0.8496 (4)0.0501 (14)
C60.8428 (3)0.9443 (8)0.8911 (4)0.0498 (13)
C70.7946 (4)0.8782 (9)0.9187 (4)0.0549 (14)
H70.78250.76240.91240.066*
C80.7653 (4)0.9862 (9)0.9554 (4)0.0604 (15)
H80.73240.94310.97450.073*
N40.7817 (4)1.1533 (7)0.9655 (4)0.0616 (15)
C90.8274 (5)1.2168 (10)0.9397 (6)0.075 (2)
H90.83781.33340.94640.090*
C100.8605 (5)1.1178 (9)0.9031 (5)0.0685 (19)
H100.89421.16480.88630.082*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.0322 (3)0.0257 (3)0.0323 (3)0.0000.0227 (2)0.000
O10.063 (3)0.072 (3)0.067 (3)−0.012 (2)0.037 (2)0.000 (2)
O20.128 (5)0.098 (4)0.043 (3)−0.012 (4)0.029 (3)−0.005 (3)
O30.072 (3)0.073 (3)0.063 (3)−0.018 (2)0.041 (2)−0.006 (2)
O40.084 (4)0.067 (3)0.092 (4)−0.002 (3)0.058 (3)−0.015 (3)
O50.079 (3)0.078 (3)0.082 (3)−0.034 (3)0.033 (3)−0.017 (3)
O60.077 (3)0.059 (3)0.075 (3)−0.011 (2)0.049 (3)−0.018 (2)
N10.070 (4)0.058 (3)0.054 (3)−0.001 (3)0.031 (3)0.002 (2)
N20.063 (3)0.052 (3)0.057 (3)−0.006 (2)0.031 (3)−0.005 (2)
N30.065 (3)0.056 (3)0.057 (3)0.002 (2)0.039 (3)−0.003 (2)
C10.063 (4)0.051 (3)0.070 (4)−0.005 (3)0.044 (3)−0.006 (3)
C20.061 (4)0.051 (3)0.064 (4)−0.006 (3)0.041 (3)−0.008 (3)
C30.062 (4)0.062 (4)0.064 (4)−0.002 (3)0.033 (3)−0.015 (3)
C40.054 (4)0.063 (4)0.058 (3)0.001 (3)0.030 (3)−0.011 (3)
C50.059 (4)0.051 (3)0.050 (3)0.004 (2)0.033 (3)0.001 (2)
C60.054 (3)0.052 (3)0.051 (3)0.002 (3)0.031 (3)−0.002 (2)
C70.061 (4)0.055 (3)0.060 (3)−0.003 (3)0.038 (3)−0.007 (3)
C80.063 (4)0.068 (4)0.065 (4)−0.004 (3)0.042 (3)−0.007 (3)
N40.070 (4)0.064 (4)0.067 (3)0.005 (3)0.046 (3)−0.009 (2)
C90.103 (6)0.055 (4)0.098 (6)−0.007 (4)0.073 (5)−0.014 (4)
C100.094 (6)0.052 (3)0.090 (5)−0.007 (3)0.069 (5)−0.012 (3)
Geometric parameters (Å, º) top
Sn1—O12.396 (5)C1—H10.9300
Sn1—O32.378 (5)C2—C51.384 (9)
Sn1—O42.538 (5)C2—H20.9300
Sn1—O62.495 (5)C3—C41.335 (9)
Sn1—N32.601 (5)C3—H30.9300
Sn1—O3i2.378 (5)C4—C51.389 (9)
Sn1—O1i2.396 (5)C4—H40.9300
Sn1—O6i2.495 (5)C5—C61.460 (8)
Sn1—O4i2.538 (5)C6—C71.367 (9)
O1—N11.247 (7)C6—C101.392 (9)
O2—N11.154 (7)C7—C81.347 (9)
O3—N11.272 (8)C7—H70.9300
O4—N21.265 (7)C8—N41.338 (9)
O5—N21.223 (7)C8—H80.9300
O6—N21.240 (7)N4—C91.294 (10)
N3—C11.324 (9)C9—C101.355 (10)
N3—C31.378 (9)C9—H90.9300
C1—C21.353 (8)C10—H100.9300
O1—Sn1—O353.85 (16)O2—N1—O1118.7 (7)
O1—Sn1—O4143.36 (18)O2—N1—O3123.1 (6)
O1—Sn1—O6121.36 (15)O1—N1—O3118.2 (5)
O3—Sn1—O4100.75 (17)O5—N2—O6122.0 (6)
O3—Sn1—O668.01 (16)O5—N2—O4124.7 (6)
O4—Sn1—O649.13 (15)O6—N2—O4113.3 (5)
O1—Sn1—N375.55 (18)C1—N3—C3116.2 (5)
O3—Sn1—N369.45 (17)C1—N3—Sn1123.2 (4)
O4—Sn1—N3123.99 (18)C3—N3—Sn1118.9 (4)
O6—Sn1—N378.13 (17)N3—C1—C2123.5 (6)
O3—Sn1—O3i167.1 (2)N3—C1—H1118.2
O3—Sn1—O1i131.72 (17)C2—C1—H1118.2
O3i—Sn1—O1i53.85 (16)C1—C2—C5119.0 (6)
O3i—Sn1—O1131.72 (18)C1—C2—H2120.5
O1i—Sn1—O1140.6 (2)C5—C2—H2120.5
O3i—Sn1—O6106.71 (17)C4—C3—N3124.4 (6)
O1i—Sn1—O675.01 (17)C4—C3—H3117.8
O3—Sn1—O6i106.70 (17)N3—C3—H3117.8
O3i—Sn1—O6i68.01 (16)C3—C4—C5117.5 (7)
O1i—Sn1—O6i121.36 (15)C3—C4—H4121.2
O1—Sn1—O6i75.01 (17)C5—C4—H4121.2
O6—Sn1—O6i134.3 (2)C2—C5—C4119.2 (6)
O3i—Sn1—O468.27 (18)C2—C5—C6121.6 (6)
O1i—Sn1—O475.55 (18)C4—C5—C6119.2 (6)
O6i—Sn1—O491.07 (17)C7—C6—C10119.3 (6)
O3—Sn1—O4i68.28 (18)C7—C6—C5118.9 (6)
O3i—Sn1—O4i100.75 (17)C10—C6—C5121.8 (6)
O1i—Sn1—O4i143.36 (18)C8—C7—C6117.8 (6)
O1—Sn1—O4i75.55 (18)C8—C7—H7121.1
O6—Sn1—O4i91.07 (17)C6—C7—H7121.1
O6i—Sn1—O4i49.12 (15)N4—C8—C7122.5 (6)
O4—Sn1—O4i69.9 (3)N4—C8—H8118.8
O3i—Sn1—N3121.88 (16)C7—C8—H8118.8
O1i—Sn1—N373.54 (16)C9—N4—C8120.0 (6)
O6i—Sn1—N3144.95 (18)N4—C9—C10121.7 (7)
O4i—Sn1—N3137.37 (17)N4—C9—H9119.1
N1—O1—Sn193.9 (4)C10—C9—H9119.1
N1—O3—Sn194.0 (3)C9—C10—C6118.6 (7)
N2—O4—Sn197.3 (4)C9—C10—H10120.7
N2—O6—Sn1100.2 (4)C6—C10—H10120.7
Symmetry code: (i) −x+2, y, −z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O60.932.373.021 (8)127
C1—H1···O10.932.743.111 (9)105
Selected geometric parameters (Å, º) top
Sn1—O12.396 (5)Sn1—O62.495 (5)
Sn1—O32.378 (5)Sn1—N32.601 (5)
Sn1—O42.538 (5)
O1—Sn1—O353.85 (16)O4—Sn1—O649.13 (15)
O1—Sn1—O4143.36 (18)O1—Sn1—N375.55 (18)
O1—Sn1—O6121.36 (15)O3—Sn1—N369.45 (17)
O3—Sn1—O4100.75 (17)O4—Sn1—N3123.99 (18)
O3—Sn1—O668.01 (16)O6—Sn1—N378.13 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O60.932.373.021 (8)127
C1—H1···O10.932.743.111 (9)105
Acknowledgements top

This work was supported by the Science and Technology Bureau of Jian, Jiangxi Province of China (grant No. 20052817).

references
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