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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): m867.
Published online 2008 June 7. doi:  10.1107/S1600536808016139
PMCID: PMC2961826

Bis(5-methyl­pyrazine-2-carboxyl­ato)­diphenyl­tin(IV)

Abstract

In the mol­ecule of the title compound, [Sn(C6H5)2(C6H5N2O2)2], two O and one N atoms from the two 5-methyl­pyrazine-2-carboxyl­ate ligands and one C atom of a phenyl group form a distorted square-planar arrangement in the equatorial plane around the Sn atom, while the distorted octa­hedral coordination is completed by an N atom of one of the 5-methyl­pyrazine-2-carboxyl­ate ligands and a C atom of the other phenyl group in the axial positions. In the crystal structure, inter­molecular C—H(...)O hydrogen bonds link the mol­ecules into centrosymmetric dimers.

Related literature

For general background, see: Gielen et al. (1988 [triangle]). For related literature, see: Vollano et al. (1984 [triangle]); Ma et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0m867-scheme1.jpg

Experimental

Crystal data

  • [Sn(C6H5)2(C6H5N2O2)2]
  • M r = 547.13
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m867-efi1.jpg
  • a = 12.030 (4) Å
  • b = 14.658 (5) Å
  • c = 13.409 (5) Å
  • β = 91.872 (4)°
  • V = 2363.2 (14) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.12 mm−1
  • T = 298 (2) K
  • 0.45 × 0.43 × 0.18 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.633, T max = 0.824
  • 12010 measured reflections
  • 4166 independent reflections
  • 2732 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.132
  • S = 1.05
  • 4166 reflections
  • 298 parameters
  • H-atom parameters constrained
  • Δρmax = 0.56 e Å−3
  • Δρmin = −0.46 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1998 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808016139/hk2458sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808016139/hk2458Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We acknowledge the financial support of the Science Foundation of Shandong.

supplementary crystallographic information

Comment

Self-assembled organotin derivatives of carboxylic acid ligands have been extensively studied due to their biological activities (Gielen et al., 1988). 5-methylpyrazine-2-carboxylic acid is a good bridging ligand that can sometimes be used to generate unexpected and interesting coordination polymers, and small changes in experimental conditions can lead to very different architectures (Ma et al., 2004).

The molecule of the title compound, (I), (Fig. 1) consists of two phenyl and two (5-methylpyrazine-2-carboxylate) groups bonded to the Sn atom and has a monomeric structure. The two O and the one N atoms of the two 2-methylpyrazine -5-carboxylate ligands and the one C atom of the one phenyl group in the equatorial plane around the Sn atom form a distorted square-planar arrangement, while the distorted octahedral coordination is completed by the one N atom of the one 5-methylpyrazine-2-carboxylate ligand and the one C atom of the other phenyl group in the axial positions (Table 1 and Fig. 1). The Sn1-O1 [2.086 (4) Å] and Sn1-O3 [2.091 (4) Å] bonds are much shorter than the van der Waal's sum of 4.0 Å (Vollano et al., 1984).

In the crystal structure, intermolecular C-H···O hydrogen bonds (Table 2) link the molecules into centrosymmetric dimers (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, a mixture of diphenyltin dichloride (344 mg, 1.0 mmol), 5-methylpyrazine-2-carboxylic acid (276 mg, 2.0 mmol) and sodium ethoxide (136 mg, 2.0 mmol) in ethanol (80 ml) was heated under reflux for 12 h at 303 K. The resulting clear solution was evaporated under vacuum and the product recrystallized from a mixture of methanol to yield colorless, block-like crystals of (I) (yield; 377 mg, 69%, m.p. 459 K). Analysis, calculated for (I): C 52.68, H, 3.68; N 10.24%; found: C 52.96, H 3.87, N, 10.11%.

Refinement

H atoms were positioned geometrically, with C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C), where x = 1.5 for methyl H, and x = 1.2 for aromatic H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
A partial packing diagram of (I). Hydrogen bonds are shown as dashed lines.

Crystal data

[Sn(C6H5)2(C6H5N2O2)2]F000 = 1096
Mr = 547.13Dx = 1.538 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3659 reflections
a = 12.030 (4) Åθ = 2.2–24.0º
b = 14.658 (5) ŵ = 1.12 mm1
c = 13.409 (5) ÅT = 298 (2) K
β = 91.872 (4)ºBlock, colorless
V = 2363.2 (14) Å30.45 × 0.43 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer4166 independent reflections
Radiation source: fine-focus sealed tube2732 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.039
T = 298(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 2.1º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −12→14
Tmin = 0.633, Tmax = 0.824k = −17→14
12010 measured reflectionsl = −15→15

Refinement

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) = 0.132  w = 1/[σ2(Fo2) + (0.066P)2 + 2.0808P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
4166 reflectionsΔρmax = 0.56 e Å3
298 parametersΔρmin = −0.46 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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 > 2sigma(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)

xyzUiso*/Ueq
Sn10.03995 (3)0.25533 (2)0.90574 (3)0.04317 (17)
N10.0859 (4)0.2891 (3)1.0739 (3)0.0440 (11)
N20.1584 (4)0.3005 (4)1.2707 (4)0.0611 (13)
N3−0.1259 (4)0.2163 (3)0.9852 (3)0.0473 (11)
N4−0.3408 (5)0.1915 (4)1.0421 (5)0.0788 (17)
O10.0994 (3)0.1346 (2)0.9701 (3)0.0517 (10)
O20.1706 (4)0.0621 (3)1.1024 (4)0.0853 (15)
O3−0.0532 (3)0.3752 (2)0.9163 (3)0.0545 (10)
O4−0.2151 (4)0.4402 (3)0.9433 (4)0.0946 (16)
C10.1354 (5)0.1303 (4)1.0620 (5)0.0557 (15)
C20.1298 (5)0.2175 (4)1.1213 (4)0.0450 (13)
C30.1662 (5)0.2249 (4)1.2196 (5)0.0556 (15)
H30.19760.17401.25090.067*
C40.1149 (5)0.3732 (4)1.2234 (4)0.0541 (15)
C50.0804 (5)0.3667 (4)1.1242 (4)0.0488 (14)
H50.05250.41841.09180.059*
C60.1053 (6)0.4589 (4)1.2806 (5)0.082 (2)
H6A0.13370.44961.34760.122*
H6B0.02860.47671.28200.122*
H6C0.14740.50601.24940.122*
C7−0.1548 (5)0.3744 (4)0.9450 (5)0.0570 (16)
C8−0.1966 (5)0.2842 (4)0.9824 (4)0.0513 (14)
C9−0.3049 (6)0.2725 (5)1.0106 (6)0.075 (2)
H9−0.35370.32171.00780.090*
C10−0.2715 (6)0.1230 (5)1.0447 (5)0.0649 (18)
C11−0.1606 (5)0.1348 (4)1.0159 (4)0.0536 (15)
H11−0.11170.08571.01830.064*
C12−0.3116 (6)0.0326 (5)1.0790 (6)0.091 (2)
H12A−0.38850.03711.09530.136*
H12B−0.26850.01381.13690.136*
H12C−0.3037−0.01151.02670.136*
C13−0.0319 (4)0.1966 (4)0.7745 (4)0.0469 (13)
C14−0.0653 (5)0.1070 (4)0.7688 (5)0.0665 (17)
H14−0.05840.07040.82530.080*
C15−0.1086 (6)0.0704 (5)0.6821 (6)0.080 (2)
H15−0.12980.00940.68010.096*
C16−0.1207 (6)0.1231 (7)0.5990 (6)0.088 (2)
H16−0.15140.09830.54050.105*
C17−0.0877 (6)0.2125 (7)0.6012 (5)0.083 (2)
H17−0.09530.24870.54440.100*
C18−0.0427 (5)0.2482 (4)0.6896 (5)0.0645 (18)
H18−0.01940.30870.69110.077*
C190.1901 (5)0.3181 (4)0.8612 (4)0.0556 (15)
C200.2684 (7)0.2621 (5)0.8185 (7)0.084 (2)
H200.25410.19980.81420.101*
C210.3653 (7)0.2945 (8)0.7828 (7)0.111 (3)
H210.41560.25570.75290.134*
C220.3867 (8)0.3866 (7)0.7921 (6)0.104 (2)
H220.45370.40960.77010.124*
C230.3137 (7)0.4438 (6)0.8320 (6)0.090 (2)
H230.32860.50600.83650.108*
C240.2133 (6)0.4077 (5)0.8671 (5)0.0750 (19)
H240.16200.44690.89500.090*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Sn10.0388 (2)0.0483 (3)0.0423 (2)0.00011 (17)−0.00113 (16)0.00171 (17)
N10.040 (3)0.046 (2)0.046 (3)−0.006 (2)0.001 (2)0.003 (2)
N20.058 (3)0.075 (4)0.050 (3)−0.005 (3)−0.006 (2)0.004 (3)
N30.045 (3)0.049 (3)0.048 (3)0.000 (2)−0.001 (2)−0.003 (2)
N40.068 (4)0.081 (4)0.090 (4)0.002 (3)0.025 (3)−0.005 (3)
O10.054 (2)0.047 (2)0.055 (2)0.0109 (17)−0.0018 (19)−0.0026 (17)
O20.121 (4)0.052 (3)0.081 (3)0.018 (3)−0.015 (3)0.012 (2)
O30.058 (3)0.046 (2)0.059 (2)0.0037 (18)−0.009 (2)0.0066 (17)
O40.080 (4)0.067 (3)0.136 (5)0.030 (3)0.001 (3)0.006 (3)
C10.051 (4)0.053 (4)0.063 (4)0.004 (3)−0.005 (3)0.011 (3)
C20.044 (3)0.049 (3)0.042 (3)−0.003 (3)0.002 (3)0.006 (3)
C30.051 (4)0.063 (4)0.052 (4)0.000 (3)−0.006 (3)0.011 (3)
C40.053 (4)0.063 (4)0.046 (3)−0.008 (3)−0.003 (3)−0.006 (3)
C50.044 (3)0.048 (3)0.053 (3)−0.004 (2)−0.001 (3)0.000 (3)
C60.096 (6)0.081 (5)0.068 (5)−0.004 (4)−0.004 (4)−0.023 (4)
C70.053 (4)0.057 (4)0.061 (4)0.015 (3)−0.005 (3)−0.003 (3)
C80.044 (4)0.059 (3)0.051 (3)0.007 (3)0.004 (3)−0.015 (3)
C90.060 (5)0.080 (5)0.085 (5)0.023 (4)0.008 (4)−0.003 (4)
C100.064 (5)0.075 (5)0.057 (4)−0.014 (4)0.018 (3)−0.013 (3)
C110.054 (4)0.053 (4)0.055 (4)−0.003 (3)0.009 (3)−0.005 (3)
C120.087 (6)0.098 (6)0.090 (6)−0.033 (4)0.032 (4)0.002 (4)
C130.039 (3)0.057 (4)0.045 (3)−0.005 (3)−0.001 (3)−0.003 (3)
C140.065 (4)0.065 (4)0.069 (4)−0.005 (3)−0.015 (3)−0.007 (3)
C150.074 (5)0.071 (5)0.095 (6)−0.006 (4)−0.017 (4)−0.027 (4)
C160.059 (5)0.132 (8)0.072 (5)−0.004 (5)−0.004 (4)−0.036 (5)
C170.062 (5)0.143 (7)0.044 (4)−0.010 (5)−0.001 (3)0.004 (4)
C180.051 (4)0.095 (5)0.047 (4)−0.015 (3)0.002 (3)0.006 (3)
C190.051 (3)0.066 (4)0.050 (3)−0.007 (3)−0.001 (3)0.001 (3)
C200.069 (5)0.089 (5)0.095 (5)−0.006 (4)0.026 (4)0.003 (4)
C210.077 (5)0.147 (6)0.112 (6)−0.008 (5)0.042 (4)−0.001 (5)
C220.082 (5)0.130 (6)0.099 (5)−0.030 (5)0.015 (4)0.003 (5)
C230.097 (5)0.096 (5)0.077 (5)−0.038 (4)0.006 (4)0.002 (4)
C240.073 (4)0.089 (5)0.063 (4)−0.023 (4)0.003 (3)0.007 (3)

Geometric parameters (Å, °)

Sn1—O12.086 (4)C9—H90.9300
Sn1—O32.091 (4)C10—C111.411 (8)
Sn1—C132.117 (5)C10—C121.488 (9)
Sn1—C192.130 (6)C11—H110.9300
Sn1—N12.357 (4)C12—H12A0.9600
Sn1—N32.363 (5)C12—H12B0.9600
N1—C51.324 (7)C12—H12C0.9600
N1—C21.328 (7)C13—C181.370 (8)
N2—C31.308 (8)C13—C141.375 (8)
N2—C41.338 (7)C14—C151.368 (9)
N3—C81.309 (7)C14—H140.9300
N3—C111.335 (7)C15—C161.360 (10)
N4—C101.305 (8)C15—H150.9300
N4—C91.336 (9)C16—C171.370 (10)
O1—C11.294 (7)C16—H160.9300
O2—C11.207 (6)C17—C181.389 (10)
O3—C71.292 (7)C17—H170.9300
O4—C71.207 (7)C18—H180.9300
C1—C21.508 (8)C19—C241.344 (9)
C2—C31.379 (8)C19—C201.387 (9)
C3—H30.9300C20—C211.361 (11)
C4—C51.384 (7)C20—H200.9300
C4—C61.477 (8)C21—C221.380 (12)
C5—H50.9300C21—H210.9300
C6—H6A0.9600C22—C231.339 (11)
C6—H6B0.9600C22—H220.9300
C6—H6C0.9600C23—C241.413 (9)
C7—C81.506 (9)C23—H230.9300
C8—C91.379 (9)C24—H240.9300
O1—Sn1—O3149.56 (15)N4—C9—C8121.0 (6)
O1—Sn1—C1397.14 (18)N4—C9—H9119.5
O3—Sn1—C13101.11 (18)C8—C9—H9119.5
O1—Sn1—C19101.5 (2)N4—C10—C11120.5 (6)
O3—Sn1—C1996.7 (2)N4—C10—C12118.7 (6)
C13—Sn1—C19105.6 (2)C11—C10—C12120.8 (6)
O1—Sn1—N173.49 (15)N3—C11—C10120.2 (6)
O3—Sn1—N182.40 (15)N3—C11—H11119.9
C13—Sn1—N1163.15 (18)C10—C11—H11119.9
C19—Sn1—N190.17 (18)C10—C12—H12A109.5
O1—Sn1—N383.74 (16)C10—C12—H12B109.5
O3—Sn1—N373.16 (16)H12A—C12—H12B109.5
C13—Sn1—N387.08 (18)C10—C12—H12C109.5
C19—Sn1—N3165.3 (2)H12A—C12—H12C109.5
N1—Sn1—N378.12 (15)H12B—C12—H12C109.5
C5—N1—C2117.4 (5)C18—C13—C14117.5 (6)
C5—N1—Sn1130.8 (4)C18—C13—Sn1119.5 (4)
C2—N1—Sn1111.6 (4)C14—C13—Sn1123.0 (4)
C3—N2—C4117.5 (5)C15—C14—C13121.7 (7)
C8—N3—C11118.7 (5)C15—C14—H14119.2
C8—N3—Sn1111.1 (4)C13—C14—H14119.2
C11—N3—Sn1129.3 (4)C16—C15—C14120.1 (7)
C10—N4—C9118.7 (6)C16—C15—H15119.9
C1—O1—Sn1122.3 (3)C14—C15—H15119.9
C7—O3—Sn1121.8 (3)C15—C16—C17120.2 (7)
O2—C1—O1124.7 (6)C15—C16—H16119.9
O2—C1—C2119.0 (6)C17—C16—H16119.9
O1—C1—C2116.2 (5)C16—C17—C18118.9 (7)
N1—C2—C3120.2 (5)C16—C17—H17120.5
N1—C2—C1116.2 (5)C18—C17—H17120.5
C3—C2—C1123.5 (5)C13—C18—C17121.7 (7)
N2—C3—C2122.7 (6)C13—C18—H18119.2
N2—C3—H3118.6C17—C18—H18119.2
C2—C3—H3118.6C24—C19—C20117.4 (6)
N2—C4—C5120.0 (5)C24—C19—Sn1125.6 (5)
N2—C4—C6117.9 (5)C20—C19—Sn1116.9 (5)
C5—C4—C6122.1 (6)C21—C20—C19122.6 (8)
N1—C5—C4122.0 (5)C21—C20—H20118.7
N1—C5—H5119.0C19—C20—H20118.7
C4—C5—H5119.0C20—C21—C22118.0 (9)
C4—C6—H6A109.5C20—C21—H21121.0
C4—C6—H6B109.5C22—C21—H21121.0
H6A—C6—H6B109.5C23—C22—C21121.8 (9)
C4—C6—H6C109.5C23—C22—H22119.1
H6A—C6—H6C109.5C21—C22—H22119.1
H6B—C6—H6C109.5C22—C23—C24118.5 (8)
O4—C7—O3124.2 (6)C22—C23—H23120.7
O4—C7—C8120.0 (6)C24—C23—H23120.7
O3—C7—C8115.9 (5)C19—C24—C23121.6 (7)
N3—C8—C9121.1 (6)C19—C24—H24119.2
N3—C8—C7116.9 (5)C23—C24—H24119.2
C9—C8—C7122.0 (6)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C12—H12C···O2i0.962.513.315 (3)142
C14—H14···O2i0.932.573.298 (3)135

Symmetry codes: (i) −x, −y, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2458).

References

  • Bruker (1998). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Gielen, M., Vanbellinghen, C., Gelan, J. & Willem, R. (1988). Bull. Soc. Chim. Belg.97, 873–876.
  • Ma, C. L., Han, Y. F., Zhang, R. F. & Wang, D. Q. (2004). Dalton Trans. pp. 1832–1840. [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Vollano, J. F., Day, R. O. & Holmes, R. R. (1984). Organometallics, 3, 745–750.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography