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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807021174/bq2015sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807021174/bq2015Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • Mean [sigma](C-C) = 0.011 Å
  • R factor = 0.035
  • wR factor = 0.123
  • Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT241_ALERT_2_B Check High Ueq as Compared to Neighbors for O4 PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for Sn1
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.96 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O1 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O3 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O6 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C10 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N2 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C9 PLAT331_ALERT_2_C Small Average Phenyl C-C Dist. C6 -C11 1.36 Ang. PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 11 PLAT480_ALERT_4_C Long H...A H-Bond Reported H1 .. O1 .. 2.74 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Sn1 (2) 2.12
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 9 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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).

Structure description 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.

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).

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 m3
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 mm1
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 = 2425
Tmin = 0.656, Tmax = 0.801k = 99
8171 measured reflectionsl = 2222
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 Å3
187 parametersΔρmin = 0.61 e Å3
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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.123H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0667P)2 + 16.0815P]
where P = (Fo2 + 2Fc2)/3
2495 reflectionsΔρmax = 0.88 e Å3
187 parametersΔρmin = 0.61 e Å3
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

Experimental details

Crystal data
Chemical formula(C11H9N)2[Sn(NO3)4]
Mr677.11
Crystal system, space groupMonoclinic, C2/c
Temperature (K)273
a, b, c (Å)20.121 (5), 7.8112 (12), 18.307 (5)
β (°) 118.823 (9)
V3)2520.8 (10)
Z4
Radiation typeMo Kα
µ (mm1)1.09
Crystal size (mm)0.40 × 0.33 × 0.21
Data collection
DiffractometerBruker APEXII area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.656, 0.801
No. of measured, independent and
observed [I > 2σ(I)] reflections
8171, 2495, 2450
Rint0.014
(sin θ/λ)max1)0.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.123, 1.02
No. of reflections2495
No. of parameters187
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0667P)2 + 16.0815P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.88, 0.61

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996), SHELXTL.

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
 

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