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Acta Cryst. (2007). E63, m1567    [ doi:10.1107/S1600536807021174 ]

Bis(4-phenylpyridinium) tetrakis(nitrato-[kappa]2O,O')stannate(IV)

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

Abstract top

The asymmetric unit of the title compound, (C11H9N)2[Sn(NO3)4], consists of a mononuclear complex anion and two non-coordinated 4-phenylpyridinium cations. The SnIV atom, lying on a twofold rotation axis, is coordinated by eight O atoms of four NO3- anions. This mononuclear complex is further extended into a supramolecular network structure via non-classical hydrogen bonds between CH groups of cations and O atoms of neighbouring anions.

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 vapor 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 eight-coordinate environment of the Sn atom is completed by the eight O atoms of four NO3- (Table 1). The Sn—O bond lengths are in the range 2.466 (5) to 2.552 (5) Å. Hydrogen bonds

between C—H groups of free 4-phenylpyridinium and O atoms of neighboring molecules, with C···O distances of 3.032 (8) and 3.100 (8), generate a layered hydrogen-bonded network (Fig. 2 and Table 2). The non-classical hydrogen-bonding interactions link the mononuclear complex into a supramolecular network structure.

Related literature top

For related literature, see: Allen et al. (1987); Bandoli et al. (1992, 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 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-phenylpyridinium (62.8 mg, 0.4 mmol), nitric acid (0.2 mol/l, 4 ml) and ethanol (5 ml) 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 (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Atoms labeled with the suffix A and B are generated by the symmetry operation (-x + 2, y, -z + 3/2) and (-x + 3/2, -y + 5/2,-z + 2), respectively.
[Figure 2] Fig. 2. A packing diagram of (I), H-bonds with dashed lines.
Bis(4-phenylpyridinium) tetrakis(nitrato-κ2O,O')tin(IV) top
Crystal data top
(C11H9N)2[Sn(NO3)4]F(000) = 1352
Mr = 677.11Dx = 1.784 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8235 reflections
a = 20.121 (5) Åθ = 2.5–29.5°
b = 7.8112 (12) ŵ = 1.09 mm−1
c = 18.307 (5) ÅT = 273 K
β = 118.823 (9)°Plane, colourless
V = 2520.8 (10) Å30.40 × 0.33 × 0.21 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer		2495 independent reflections
Radiation source: fine-focus sealed tube2450 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.014
φ and ω scansθmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −24→25
Tmin = 0.656, Tmax = 0.801k = −9→9
8171 measured reflectionsl = −22→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)] = 0.035H-atom parameters constrained
wR(F2) = 0.123 w = 1/[σ2(Fo2) + (0.0667P)2 + 16.0815P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
2495 reflectionsΔρmax = 0.88 e Å−3
187 parametersΔρmin = −0.61 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0034 (4)
Crystal data top
(C11H9N)2[Sn(NO3)4]V = 2520.8 (10) Å3
Mr = 677.11Z = 4
Monoclinic, C2/cMo Kα radiation
a = 20.121 (5) ŵ = 1.09 mm−1
b = 7.8112 (12) ÅT = 273 K
c = 18.307 (5) Å0.40 × 0.33 × 0.21 mm
β = 118.823 (9)°
Data collection top
Bruker APEXII area-detector
diffractometer		2495 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2450 reflections with I > 2σ(I)
Tmin = 0.656, Tmax = 0.801Rint = 0.014
8171 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.035 w = 1/[σ2(Fo2) + (0.0667P)2 + 16.0815P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.123Δρmax = 0.88 e Å−3
S = 1.02Δρmin = −0.61 e Å−3
2495 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
Sn11.00000.33855 (4)0.75000.04796 (19)
O11.0921 (3)0.4420 (6)0.8900 (3)0.0671 (12)
O21.0826 (4)0.4129 (8)1.0028 (3)0.0948 (18)
O30.9970 (3)0.3046 (6)0.8849 (3)0.0675 (12)
O40.9294 (3)0.0724 (7)0.6688 (4)0.0773 (14)
O50.8183 (3)−0.0046 (7)0.6531 (4)0.0850 (15)
O60.8782 (3)0.2146 (6)0.7289 (3)0.0673 (12)
N11.0582 (3)0.3864 (7)0.9290 (3)0.0609 (13)
N20.8730 (3)0.0901 (7)0.6818 (3)0.0572 (12)
N30.9363 (3)0.6016 (7)0.7803 (3)0.0571 (12)
C10.9745 (4)0.7370 (8)0.8257 (4)0.0579 (14)
H11.02350.75410.83430.069*
C20.9464 (4)0.8528 (7)0.8605 (4)0.0557 (14)
H20.97580.94520.89100.067*
C30.8639 (4)0.5857 (9)0.7678 (4)0.0625 (15)
H30.83470.49530.73490.075*
C40.8316 (4)0.6929 (8)0.8002 (4)0.0582 (14)
H40.78210.67510.78980.070*
C50.8742 (4)0.8307 (7)0.8497 (4)0.0509 (13)
C60.8427 (3)0.9443 (7)0.8910 (4)0.0511 (12)
C70.7945 (4)0.8780 (8)0.9188 (4)0.0560 (14)
H70.78210.76220.91270.067*
C80.7654 (4)0.9871 (9)0.9554 (4)0.0624 (15)
H80.73310.94330.97380.075*
C90.7820 (4)1.1524 (7)0.9653 (4)0.0508 (13)
H90.76161.22260.99050.061*
C100.8271 (5)1.2168 (10)0.9397 (6)0.078 (2)
H100.83711.33360.94600.093*
C110.8606 (5)1.1178 (9)0.9033 (5)0.0704 (19)
H110.89411.16610.88760.084*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.0310 (3)0.0253 (2)0.0368 (3)0.0000.02356 (19)0.000
O10.062 (3)0.070 (3)0.076 (3)−0.012 (2)0.038 (2)0.001 (2)
O20.123 (5)0.095 (4)0.052 (3)−0.010 (4)0.031 (3)−0.005 (3)
O30.070 (3)0.073 (3)0.071 (3)−0.017 (2)0.043 (2)−0.005 (2)
O40.082 (3)0.066 (3)0.104 (4)−0.002 (3)0.060 (3)−0.016 (3)
O50.077 (3)0.076 (3)0.093 (4)−0.033 (3)0.033 (3)−0.018 (3)
O60.074 (3)0.058 (2)0.084 (3)−0.011 (2)0.051 (3)−0.019 (2)
N10.068 (3)0.057 (3)0.058 (3)−0.001 (3)0.030 (3)0.002 (2)
N20.061 (3)0.050 (3)0.063 (3)−0.006 (2)0.032 (2)−0.005 (2)
N30.063 (3)0.056 (3)0.065 (3)0.001 (2)0.041 (3)−0.003 (2)
C10.062 (4)0.050 (3)0.076 (4)−0.006 (3)0.046 (3)−0.006 (3)
C20.060 (4)0.051 (3)0.069 (4)−0.007 (2)0.041 (3)−0.007 (3)
C30.059 (4)0.063 (4)0.068 (4)−0.002 (3)0.033 (3)−0.016 (3)
C40.053 (3)0.062 (3)0.063 (3)0.000 (3)0.030 (3)−0.012 (3)
C50.056 (3)0.051 (3)0.055 (3)0.004 (2)0.034 (3)0.001 (2)
C60.054 (3)0.051 (3)0.055 (3)0.002 (2)0.032 (3)−0.002 (2)
C70.058 (3)0.054 (3)0.066 (3)−0.003 (3)0.038 (3)−0.008 (3)
C80.060 (4)0.073 (4)0.070 (4)−0.002 (3)0.043 (3)−0.005 (3)
C90.056 (3)0.051 (3)0.061 (3)0.007 (2)0.040 (3)−0.011 (2)
C100.101 (6)0.053 (4)0.109 (6)−0.005 (4)0.074 (5)−0.015 (4)
C110.093 (5)0.052 (3)0.100 (5)−0.008 (3)0.073 (5)−0.013 (3)
Geometric parameters (Å, º) top
Sn1—O12.466 (5)C2—C51.379 (9)
Sn1—O32.514 (5)C2—H20.9300
Sn1—O42.552 (5)C3—C41.359 (9)
Sn1—O62.485 (5)C3—H30.9300
Sn1—O1i2.466 (5)C4—C51.402 (9)
Sn1—O6i2.485 (5)C4—H40.9300
Sn1—O3i2.514 (5)C5—C61.490 (8)
Sn1—O4i2.552 (5)C6—C111.393 (9)
O1—N11.278 (7)C6—C71.395 (8)
O2—N11.213 (7)C7—C81.377 (8)
O3—N11.271 (7)C7—H70.9300
O4—N21.276 (7)C8—C91.324 (9)
O5—N21.215 (7)C8—H80.9300
O6—N21.269 (7)C9—C101.306 (10)
N3—C11.336 (8)C9—H90.9300
N3—C31.367 (8)C10—C111.390 (9)
C1—C21.374 (8)C10—H100.9300
C1—H10.9300C11—H110.9300
O1—Sn1—O351.33 (15)O5—N2—O4123.7 (6)
O1—Sn1—O4143.24 (17)O6—N2—O4114.8 (5)
O1—Sn1—O6118.72 (15)C1—N3—C3115.0 (5)
O3—Sn1—O4102.50 (16)N3—C1—C2124.6 (6)
O6—Sn1—O367.87 (16)N3—C1—H1117.7
O6—Sn1—O450.34 (15)C2—C1—H1117.7
O1i—Sn1—O677.00 (17)C1—C2—C5119.4 (6)
O6i—Sn1—O6134.1 (2)C1—C2—H2120.3
O1i—Sn1—O3133.95 (16)C5—C2—H2120.3
O6i—Sn1—O3107.13 (17)C4—C3—N3124.5 (6)
O1—Sn1—O3i133.95 (16)C4—C3—H3117.8
O1i—Sn1—O3i51.33 (15)N3—C3—H3117.8
O6i—Sn1—O3i67.86 (16)C3—C4—C5118.9 (6)
O6—Sn1—O3i107.13 (17)C3—C4—H4120.6
O3—Sn1—O3i167.9 (2)C5—C4—H4120.6
O1—Sn1—O4i74.51 (18)C2—C5—C4117.5 (5)
O1i—Sn1—O4i143.24 (18)C2—C5—C6122.0 (5)
O6i—Sn1—O4i50.34 (15)C4—C5—C6120.5 (6)
O6—Sn1—O4i90.19 (17)C11—C6—C7118.3 (6)
O3—Sn1—O4i67.15 (17)C11—C6—C5121.4 (5)
O3i—Sn1—O4i102.50 (16)C7—C6—C5120.3 (5)
O1i—Sn1—O474.51 (18)C8—C7—C6118.8 (6)
O6i—Sn1—O490.19 (17)C8—C7—H7120.6
O1—Sn1—O1i141.7 (2)C6—C7—H7120.6
O1—Sn1—O6i77.00 (17)C9—C8—C7122.1 (6)
O1i—Sn1—O6i118.72 (15)C9—C8—H8118.9
O3i—Sn1—O467.15 (17)C7—C8—H8118.9
O4i—Sn1—O470.9 (3)C10—C9—C8119.9 (6)
N1—O1—Sn197.6 (4)C10—C9—H9120.0
N1—O3—Sn195.5 (3)C8—C9—H9120.0
N2—O4—Sn195.6 (3)C9—C10—C11122.7 (7)
N2—O6—Sn199.1 (3)C9—C10—H10118.6
O2—N1—O3122.7 (6)C11—C10—H10118.6
O2—N1—O1121.7 (6)C10—C11—C6118.1 (6)
O3—N1—O1115.6 (5)C10—C11—H11120.9
O5—N2—O6121.5 (6)C6—C11—H11120.9
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···O60.932.383.032 (8)127
C1—H1···O10.932.743.100 (8)104
Selected geometric parameters (Å, º) top
Sn1—O12.466 (5)Sn1—O42.552 (5)
Sn1—O32.514 (5)Sn1—O62.485 (5)
O1—Sn1—O351.33 (15)O3—Sn1—O4102.50 (16)
O1—Sn1—O4143.24 (17)O6—Sn1—O367.87 (16)
O1—Sn1—O6118.72 (15)O6—Sn1—O450.34 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O60.932.383.032 (8)127
C1—H1···O10.932.743.100 (8)104
Acknowledgements top

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

references
References top

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