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Acta Cryst. (2007). E63, m2587    [ doi:10.1107/S1600536807044273 ]

catena-Poly[[trimethyltin(IV)]-[mu]-2-[(3-oxocyclohex-1-enyl)amino]benzoato-[kappa]2O:O']

F. T. Vieira, D. C. Menezes, G. M. de Lima, J. R. da S. Maia and N. L. Speziali

Abstract top

The Sn atom in the title compound, [Sn(CH3)3(C13H13NO3)]n, is five-coordinate in a trigonal-bipyramidal environment. An intramolecular N-H...O hydrogen bond is present.

Comment top

The reaction of 2-(3-oxocyclohex-1-enyl)benzoic acid (Vieira et al., 2007) with Sn(CH3)3Cl in the presence of triethylamine yielded the title complex. The X-ray crystallographic study revealed that it crystallizes forming an infinity double-polymeric chain structure, where the anionic ligand bridges two tin centre via the monodentate carboxylic moiety and the C═O fragment, Fig. 1. The structure possess one tin atom surrounded by three methyl groups and two oxygen atoms, describing an almost perfect trigonal bypiramid. The equatorial corners are occupied by the methyl groups and the axial positions by the oxygen atoms. The angles C1—Sn—C2 and O1—Sn—O3 are all near 120° and 180° as expected for a trigonal bypiramid.

Related literature top

For related literature, see: Vieira et al. (2007).

Experimental top

To a round-botton flask charged with 3-[(carboxyphenyl)amino]cyclohexen-2-one (1.0 g, 4.32 mmol) and triethylamine (0.6 ml, 4.32 mmol) dissolved in methanol (20 ml), was added trimethyltin chloride (0.86 g, 4.32 mmol). The X-ray quality crystals were obtained from a methanol/water (3:1) solution. IR (ν/cm−1): 473 (νSn—O). 1H NMR (δ, CDCl3): 8.63 d (C6), 8.0 m (C8, C9), 7.7 m (C7) 6.23 s (C16), 3.0 m (C14), 2.8 m (C12), 2.47 m (C13), 1.58 s (C1, 2, 3). 13C-NMR (δ, CDCl3): 199.5 (C15), 173.4 (C4), 162.5 (C11), 141.8 (C10), 133.9 (C6), 133.6 (C8), 124.3 (C5), 124.2 (C2), 101.58 (C7), 101.56 (C16), 37.5 (C14), 31.2 (C12), 22.8 (C13), 11.7 (C1, 2, 3), 119Sn-NMR (δ, CDCl3): 97.6, 119Sn Mossbauer (mm.s−1): δ 1.32, Δ 3.52, Elemental Analysis (%) for C16H21NO3Sn found (calc.): C 48.41 (48.76), H 5.37 (5.38), N 3.46 (3.55).

Refinement top

Fourier difference in the structure determination stage evidenced most of the H atoms in the structure; nevertheless, their positions were subsequently calculated and refined using a riding model approximation. All non-H atoms were refined anisotropically.

Computing details top

Data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS (Siemens, 1991); data reduction: XSCANS (Siemens, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. Monomeric structure of poly-[trimethyltin-3-{(carboxyphenyl)amino} cyclohexen-2-one]
<it>catena</it>-Poly[[trimethyltin(IV)]-µ-2-[(3-oxocyclohex-1- enyl)amino]benzoato-κ2<it>O</it>:<it>O</it>'] top
Crystal data top
[Sn(CH3)3(C13H13NO3)]Dx = 1.534 Mg m−3
Mr = 394.03Melting point = 440–443 K
Orthorhombic, Fdd2Mo Kα radiation
λ = 0.71073 Å
a = 30.626 (5) ÅCell parameters from 26 reflections
b = 12.981 (2) Åθ = 11.8–12.5º
c = 17.164 (2) ŵ = 1.51 mm−1
V = 6823.6 (19) Å3T = 273 (2) K
Z = 16Prismatic, colourless
F000 = 31680.2 × 0.2 × 0.2 mm
Data collection top
Siemens P4 diffractometerRint = 0.039
Radiation source: fine-focus sealed tubeθmax = 25.0º
Monochromator: graphiteθmin = 2.1º
T = 273(2) Kh = −36→36
2θ/ω scansk = −15→11
Absorption correction: nonel = −19→12
7294 measured reflections3 standard reflections
2329 independent reflections every 97 reflections
2099 reflections with I > 2σ(I) intensity decay: 4%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of
independent and constrained refinement
R[F2 > 2σ(F2)] = 0.024  w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.087(Δ/σ)max < 0.001
S = 0.74Δρmax = 0.26 e Å−3
2329 reflectionsΔρmin = −0.37 e Å−3
193 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.04 (4)
Secondary atom site location: difference Fourier map
Crystal data top
[Sn(CH3)3(C13H13NO3)]V = 6823.6 (19) Å3
Mr = 394.03Z = 16
Orthorhombic, Fdd2Mo Kα
a = 30.626 (5) ŵ = 1.51 mm−1
b = 12.981 (2) ÅT = 273 (2) K
c = 17.164 (2) Å0.2 × 0.2 × 0.2 mm
Data collection top
Siemens P4 diffractometerRint = 0.039
Absorption correction: none3 standard reflections
7294 measured reflections every 97 reflections
2329 independent reflections intensity decay: 4%
2099 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.024H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.087Δρmax = 0.26 e Å−3
S = 0.74Δρmin = −0.37 e Å−3
2329 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs?
193 parametersFlack parameter: −0.04 (4)
1 restraint
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
Sn0.411524 (8)−0.002008 (19)0.26150 (5)0.05087 (14)
C10.43775 (19)0.1345 (4)0.2137 (4)0.0718 (15)
H1A0.43120.19150.24740.108*
H1B0.42510.14660.16340.108*
H1C0.46880.12760.20870.108*
C20.4509 (2)−0.0989 (5)0.3309 (4)0.0772 (16)
H2A0.4442−0.08800.38480.116*
H2B0.4811−0.08320.32180.116*
H2C0.4454−0.16950.31750.116*
C30.3535 (2)−0.0753 (5)0.2245 (4)0.089 (2)
H3A0.3308−0.06340.26220.134*
H3B0.3585−0.14800.21960.134*
H3C0.3447−0.04770.17510.134*
O10.38557 (11)0.0726 (2)0.3650 (2)0.0602 (8)
O20.33660 (11)0.1547 (2)0.2914 (2)0.0616 (9)
O30.44514 (15)−0.0706 (3)0.1396 (2)0.0771 (11)
C40.35365 (15)0.1367 (3)0.3546 (3)0.0513 (10)
C50.33861 (13)0.1881 (3)0.4283 (3)0.0444 (10)
C60.35136 (15)0.1499 (3)0.5001 (3)0.0558 (11)
H6A0.37030.09390.50210.067*
C70.33636 (18)0.1936 (5)0.5696 (3)0.0673 (15)
H7A0.34500.16700.61760.081*
C80.3084 (2)0.2772 (5)0.5656 (3)0.0643 (15)
H8A0.29770.30590.61150.077*
C90.29629 (16)0.3184 (4)0.4959 (3)0.0561 (11)
H9A0.27780.37530.49500.067*
C100.31093 (15)0.2770 (4)0.4268 (3)0.0474 (10)
N0.29828 (13)0.3157 (3)0.3544 (3)0.0510 (9)
H1N0.3021 (18)0.279 (5)0.310 (3)0.061*
C110.45673 (14)−0.3331 (3)0.0821 (3)0.0449 (10)
C120.47411 (17)−0.3229 (4)0.0014 (3)0.0594 (12)
H12A0.4622−0.3776−0.03060.071*
H12B0.5056−0.33100.00260.071*
C130.4631 (2)−0.2201 (4)−0.0352 (3)0.0703 (15)
H13A0.4799−0.2115−0.08270.084*
H13B0.4323−0.2187−0.04880.084*
C140.47305 (19)−0.1322 (4)0.0200 (4)0.0665 (14)
H14A0.4616−0.0688−0.00180.080*
H14B0.5045−0.12470.02450.080*
C150.45398 (15)−0.1476 (3)0.1002 (3)0.0528 (11)
C160.44788 (16)−0.2510 (3)0.1278 (3)0.0490 (11)
H16A0.4376−0.26170.17820.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn0.05684 (19)0.03705 (18)0.0587 (2)0.00106 (12)−0.00554 (19)0.00251 (11)
C10.098 (4)0.039 (2)0.079 (4)0.003 (2)0.014 (3)0.005 (2)
C20.094 (4)0.064 (3)0.073 (4)0.011 (3)0.001 (3)0.020 (3)
C30.084 (4)0.072 (4)0.112 (6)−0.009 (3)−0.016 (4)−0.026 (4)
O10.071 (2)0.0529 (19)0.057 (2)0.0084 (15)−0.0044 (17)0.0016 (15)
O20.091 (3)0.0457 (16)0.049 (2)0.0143 (15)−0.0092 (17)−0.0075 (14)
O30.117 (3)0.0449 (18)0.069 (2)0.0005 (19)0.007 (2)−0.0108 (19)
C40.068 (3)0.042 (2)0.044 (3)−0.012 (2)0.001 (2)0.001 (2)
C50.051 (3)0.038 (2)0.045 (2)−0.0123 (16)−0.0020 (18)−0.005 (2)
C60.059 (2)0.049 (2)0.059 (3)−0.0073 (18)−0.010 (2)0.011 (2)
C70.087 (4)0.072 (4)0.042 (3)−0.023 (3)−0.006 (2)0.016 (3)
C80.083 (4)0.063 (3)0.047 (3)−0.020 (3)0.019 (3)−0.006 (3)
C90.066 (3)0.048 (2)0.054 (3)−0.009 (2)0.002 (2)−0.009 (2)
C100.049 (2)0.043 (2)0.049 (3)−0.0119 (18)0.004 (2)−0.005 (2)
N0.067 (2)0.0390 (19)0.047 (2)−0.0001 (16)−0.0032 (18)−0.0048 (17)
C110.047 (2)0.038 (2)0.049 (3)−0.0034 (17)0.0002 (18)−0.0043 (19)
C120.077 (3)0.049 (2)0.053 (3)0.000 (2)0.016 (3)0.003 (3)
C130.102 (4)0.049 (3)0.061 (4)−0.003 (3)0.007 (3)0.006 (3)
C140.089 (4)0.047 (2)0.064 (4)−0.008 (2)0.009 (3)0.002 (3)
C150.059 (3)0.038 (2)0.061 (3)−0.0014 (18)0.004 (2)−0.008 (2)
C160.054 (3)0.043 (2)0.050 (3)0.0021 (16)0.004 (2)−0.0017 (17)
Geometric parameters (Å, °) top
Sn—C12.112 (5)C7—H7A0.9300
Sn—C22.111 (6)C8—C91.362 (8)
Sn—C32.113 (6)C8—H8A0.9300
Sn—O12.174 (4)C9—C101.377 (7)
Sn—O32.496 (4)C9—H9A0.9300
C1—H1A0.9600C10—N1.396 (7)
C1—H1B0.9600N—C11i1.376 (6)
C1—H1C0.9600N—H1N0.91 (6)
C2—H2A0.9600C11—C161.351 (6)
C2—H2B0.9600C11—Nii1.376 (6)
C2—H2C0.9600C11—C121.489 (7)
C3—H3A0.9600C12—C131.513 (8)
C3—H3B0.9600C12—H12A0.9700
C3—H3C0.9600C12—H12B0.9700
O1—C41.296 (5)C13—C141.515 (8)
O2—C41.227 (6)C13—H13A0.9700
O3—C151.237 (6)C13—H13B0.9700
C4—C51.503 (7)C14—C151.508 (8)
C5—C61.384 (7)C14—H14A0.9700
C5—C101.432 (7)C14—H14B0.9700
C6—C71.400 (8)C15—C161.436 (6)
C6—H6A0.9300C16—H16A0.9300
C7—C81.384 (9)
C1—Sn—C2120.1 (3)C6—C7—H7A120.7
C1—Sn—C3125.5 (3)C9—C8—C7121.3 (5)
C2—Sn—C3112.5 (3)C9—C8—H8A119.3
C1—Sn—O194.73 (19)C7—C8—H8A119.3
C2—Sn—O190.8 (2)C8—C9—C10121.0 (5)
C3—Sn—O197.9 (2)C8—C9—H9A119.5
C1—Sn—O379.46 (19)C10—C9—H9A119.5
C2—Sn—O391.4 (2)C9—C10—N122.4 (5)
C3—Sn—O386.3 (2)C9—C10—C5119.5 (5)
O1—Sn—O3174.13 (13)N—C10—C5118.1 (4)
Sn—C1—H1A109.5C11i—N—C10128.5 (4)
Sn—C1—H1B109.5C11i—N—H1N106 (4)
H1A—C1—H1B109.5C10—N—H1N122 (4)
Sn—C1—H1C109.5C16—C11—Nii124.6 (4)
H1A—C1—H1C109.5C16—C11—C12122.8 (4)
H1B—C1—H1C109.5Nii—C11—C12112.6 (4)
Sn—C2—H2A109.5C11—C12—C13112.7 (4)
Sn—C2—H2B109.5C11—C12—H12A109.1
H2A—C2—H2B109.5C13—C12—H12A109.1
Sn—C2—H2C109.5C11—C12—H12B109.1
H2A—C2—H2C109.5C13—C12—H12B109.1
H2B—C2—H2C109.5H12A—C12—H12B107.8
Sn—C3—H3A109.5C14—C13—C12111.0 (5)
Sn—C3—H3B109.5C14—C13—H13A109.4
H3A—C3—H3B109.5C12—C13—H13A109.4
Sn—C3—H3C109.5C14—C13—H13B109.4
H3A—C3—H3C109.5C12—C13—H13B109.4
H3B—C3—H3C109.5H13A—C13—H13B108.0
C4—O1—Sn116.7 (3)C13—C14—C15113.1 (4)
C15—O3—Sn146.8 (4)C13—C14—H14A109.0
O2—C4—O1124.4 (4)C15—C14—H14A109.0
O2—C4—C5122.0 (4)C13—C14—H14B109.0
O1—C4—C5113.6 (4)C15—C14—H14B109.0
C6—C5—C10118.1 (4)H14A—C14—H14B107.8
C6—C5—C4120.2 (4)O3—C15—C16123.1 (5)
C10—C5—C4121.6 (4)O3—C15—C14118.5 (4)
C5—C6—C7121.4 (4)C16—C15—C14118.4 (4)
C5—C6—H6A119.3C11—C16—C15121.3 (4)
C7—C6—H6A119.3C11—C16—H16A119.4
C8—C7—C6118.6 (5)C15—C16—H16A119.4
C8—C7—H7A120.7
Symmetry codes: (i) −x+3/4, y+3/4, z+1/4; (ii) −x+3/4, y−3/4, z−1/4.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N—H1N···O20.91 (6)1.96 (6)2.631 (5)129 (5)
Table 1
Selected geometric parameters (Å, °) top
Sn—C12.112 (5)Sn—O32.496 (4)
Sn—C22.111 (6)C10—N1.396 (7)
Sn—C32.113 (6)N—C11i1.376 (6)
Sn—O12.174 (4)
C1—Sn—C2120.1 (3)C1—Sn—O379.46 (19)
C1—Sn—C3125.5 (3)C2—Sn—O391.4 (2)
C2—Sn—C3112.5 (3)C3—Sn—O386.3 (2)
C1—Sn—O194.73 (19)O1—Sn—O3174.13 (13)
C2—Sn—O190.8 (2)C11i—N—C10128.5 (4)
C3—Sn—O197.9 (2)
Symmetry codes: (i) −x+3/4, y+3/4, z+1/4.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N—H1N···O20.91 (6)1.96 (6)2.631 (5)129 (5)
Acknowledgements top

This work was supported by the Brazilian agency CNPq.

references
References top

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Sheldrick, G. M. (1990). SHELXTL/PC. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. [Please check added reference and correct as necessary]

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. [Please check added reference and correct as necessary]

Siemens (1991). XSCANS User's Manual. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. [Please check added reference and correct as necessary]

Vieira, F. T., Menezes, D. C., de Lima, G. M. & Speziali, N. L. (2007). Acta Cryst. E63, o3376–?.