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Acta Cryst. (2007). E63, m1870    [ doi:10.1107/S1600536807027237 ]

catena-Poly[[tri-n-butyltin(IV)]-[mu]-pyridine-3-carboxylato-[kappa]2N:O]

T.-D. Li and H.-Y. You

Abstract top

The asymmetric unit of the title compound, [Sn(C4H9)3(C6H4NO2)]n, consists of three butyl and one pyridine-3-carboxylate groups bonded to the Sn atom in a distorted trigonal-bipyramidal geometry. In the crystal structure, these units are linked to form an infinite one-dimensional polymeric chain structure. In one n-butyl chain three C atoms are disordered over two sites, and in another two C atoms are disordered over two sites.

Comment top

Self-assembled organotin derivatives of carboxylic acid ligands have been extensively studied due to their biological activities as well as their industrial and agricultural applications (Gielen et al., 1988). pyridine-3-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.

The asymmetric unit of the title compound, (I), (Fig. 1), consists of three butyl and one (pyridine-3-carboxylate) groups bonded to the tin atom, where the bond lengths and angles are generally within normal ranges (Allen et al., 1987).

The tin atom has a distorted trigonal bipyramidal geometry with atoms O1 and N1i of the pyridine-3-carboxylic acid [symmetry code: (i) x, y, z − 1], in axial and C atoms of the three butyl groups in equatorial positions, as in the similar compound (Ma et al., 2004).

In the crystal structure, (Fig. 2), the molecules are linked to form an infinite one-dimensional polymeric chain structure.

Related literature top

For general backgroud, see: Allen et al. (1987); Gielen et al. (1988). For related literature, see: Ma et al. (2004).

Experimental top

For the preparation of the title compound, a mixture of tri-n-butyltin oxide (596.1 mg, 2 mmol) and pyridine-3-carboxylic acid (246.2 mg, 2 mmol), in methanol (80 ml) was heated under reflux for 12 h. The resulting clear solution was evaporated under vacuum. The product was crystallized from ethanol (yield; 446.3 mg, 82%, m.p. 398 K).

Refinement top

When the crystal structure was solved, the atoms C9, C10, C12, C13 and C14 were found to be disordered. During the refinement proccess, the occupancies of C9, C12 and C14 were kept fixed as C9 = 1/4, C9' = 3/4, C12 = 1/2, C12' = 1/2, C14 = 0.50 and C14' = 1/2, while the remainings were refined as C10 = 0.39 (3), C10' = 0.61 (3), C13 = 0.39 (3) and C13' = 0.61 (3). H atoms were positioned geometrically, with C—H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H atoms, 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 all other H atoms.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. A packing diagram for (I). H atoms have been omitted for clarity.
catena-Poly[[tri-n-butyltin(IV)]-µ-pyridine-3-carboxylato-κ2N:O] top
Crystal data top
[Sn(C4H9)3(C6H4NO2)]F000 = 848
Mr = 412.13Dx = 1.333 Mg m−3
Monoclinic, CcMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3313 reflections
a = 9.594 (4) Åθ = 2.3–28.1º
b = 24.286 (11) ŵ = 1.25 mm−1
c = 9.715 (4) ÅT = 298 (2) K
β = 114.864 (5)ºBlock, colorless
V = 2053.7 (15) Å30.53 × 0.46 × 0.41 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		3260 independent reflections
Radiation source: fine-focus sealed tube2741 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.037
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −11→9
Tmin = 0.529, Tmax = 0.597k = −28→22
5123 measured reflectionsl = −11→11
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.058  w = 1/[σ2(Fo2) + (0.1189P)2 + 1.6655P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.163(Δ/σ)max = 0.001
S = 1.00Δρmax = 1.41 e Å−3
3260 reflectionsΔρmin = −0.73 e Å−3
219 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1798 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.06 (10)
Crystal data top
[Sn(C4H9)3(C6H4NO2)]V = 2053.7 (15) Å3
Mr = 412.13Z = 4
Monoclinic, CcMo Kα
a = 9.594 (4) ŵ = 1.25 mm−1
b = 24.286 (11) ÅT = 298 (2) K
c = 9.715 (4) Å0.53 × 0.46 × 0.41 mm
β = 114.864 (5)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3260 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2741 reflections with I > 2σ(I)
Tmin = 0.529, Tmax = 0.597Rint = 0.037
5123 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.163Δρmax = 1.41 e Å−3
S = 1.00Δρmin = −0.73 e Å−3
3260 reflectionsAbsolute structure: Flack (1983), 1798 Friedel pairs
219 parametersFlack parameter: 0.06 (10)
? restraints
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*/UeqOcc. (<1)
Sn10.5451 (3)0.87521 (2)0.0427 (3)0.0500 (2)
O10.5354 (16)0.8687 (4)0.2610 (13)0.062 (3)
O20.6522 (12)0.9490 (3)0.3408 (10)0.076 (2)
N10.552 (2)0.8833 (5)0.779 (2)0.064 (4)
C10.6275 (15)0.9254 (5)0.7557 (12)0.065 (2)
H10.67180.95040.83460.078*
C20.6459 (14)0.9350 (5)0.6238 (12)0.062 (2)
H20.70270.96480.61570.074*
C30.5757 (14)0.8981 (5)0.5027 (12)0.0552 (18)
C40.4984 (13)0.8535 (5)0.5264 (13)0.061 (2)
H40.45440.82730.45040.073*
C50.4862 (16)0.8476 (5)0.6631 (13)0.0630 (19)
H50.43100.81800.67540.076*
C60.5913 (15)0.9068 (5)0.3591 (14)0.0663 (19)
C70.4511 (18)0.7949 (5)−0.0192 (16)0.083 (2)
H7A0.34080.7973−0.05200.100*
H7B0.46880.7830−0.10580.100*
C80.5117 (19)0.7515 (5)0.1005 (18)0.095 (3)
H8A0.50090.76460.18990.114*
H8B0.62060.74710.12790.114*
C90.4371 (19)0.6958 (5)0.0598 (17)0.098 (3)0.25
H9A0.48650.67470.00810.118*0.25
H9B0.32980.7003−0.00940.118*0.25
C100.448 (6)0.6638 (16)0.200 (4)0.109 (7)0.39 (3)
H10A0.39920.62860.16970.163*0.39 (3)
H10B0.39730.68420.25080.163*0.39 (3)
H10C0.55390.65870.26830.163*0.39 (3)
C9'0.4371 (19)0.6958 (5)0.0598 (17)0.098 (3)0.75
H9'10.43350.6853−0.03800.118*0.75
H9'20.33180.69930.04760.118*0.75
C10'0.512 (4)0.6492 (11)0.170 (3)0.097 (6)0.61 (3)
H10D0.45520.61580.13140.145*0.61 (3)
H10E0.51130.65780.26650.145*0.61 (3)
H10F0.61560.64450.18250.145*0.61 (3)
C110.3914 (15)0.9411 (6)−0.0442 (16)0.081 (2)
H11A0.45210.9740−0.03540.097*
H11B0.33230.9344−0.15170.097*
C120.2810 (15)0.9542 (7)0.0208 (16)0.089 (2)0.50
H12A0.33100.97790.10840.107*0.50
H12B0.25250.92040.05540.107*0.50
C130.133 (3)0.983 (2)−0.093 (3)0.091 (4)0.39 (3)
H13A0.16271.0105−0.14860.109*0.39 (3)
H13B0.07010.9560−0.16540.109*0.39 (3)
C140.0394 (19)1.0105 (8)−0.025 (2)0.132 (4)0.50
H14A−0.05561.0228−0.10430.198*0.50
H14B0.09441.04150.03400.198*0.50
H14C0.01820.98490.03910.198*0.50
C12'0.2810 (15)0.9542 (7)0.0208 (16)0.089 (2)0.50
H12C0.33710.95580.13030.107*0.50
H12D0.20860.9240−0.00240.107*0.50
C13'0.188 (3)1.0082 (10)−0.032 (4)0.092 (3)0.61 (3)
H13C0.25111.03820.02840.110*0.61 (3)
H13D0.17191.0150−0.13660.110*0.61 (3)
C14'0.0394 (19)1.0105 (8)−0.025 (2)0.132 (4)0.50
H14D−0.00821.0454−0.06240.198*0.50
H14E0.05371.00590.07820.198*0.50
H14F−0.02530.9815−0.08620.198*0.50
C150.7867 (15)0.8816 (5)0.1302 (18)0.079 (2)
H15A0.81170.91510.09100.095*
H15B0.82720.88540.23950.095*
C160.8680 (14)0.8340 (6)0.0944 (18)0.094 (3)
H16A0.83380.8310−0.01450.112*
H16B0.84290.79990.13090.112*
C171.0445 (14)0.8435 (7)0.1717 (19)0.100 (3)
H17A1.06810.87680.13060.121*
H17B1.07560.84930.27940.121*
C181.1349 (18)0.7980 (8)0.152 (3)0.128 (6)
H18A1.24240.80560.20750.192*
H18B1.11180.79410.04590.192*
H18C1.10950.76450.18840.192*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.0625 (4)0.0587 (3)0.0297 (3)0.0009 (5)0.0204 (2)0.0023 (4)
O10.068 (6)0.075 (6)0.046 (7)−0.003 (4)0.027 (5)−0.001 (4)
O20.117 (7)0.073 (5)0.060 (5)−0.028 (5)0.058 (5)−0.003 (4)
N10.086 (9)0.067 (7)0.052 (9)−0.011 (6)0.041 (8)−0.019 (6)
C10.088 (4)0.071 (4)0.043 (4)−0.006 (4)0.035 (3)−0.004 (3)
C20.084 (4)0.066 (4)0.042 (4)−0.007 (4)0.032 (3)−0.002 (3)
C30.077 (4)0.058 (4)0.039 (4)0.000 (3)0.034 (3)−0.005 (3)
C40.083 (4)0.073 (4)0.040 (4)−0.012 (3)0.039 (4)−0.007 (4)
C50.086 (4)0.075 (4)0.042 (4)−0.013 (4)0.040 (3)−0.002 (3)
C60.082 (4)0.077 (4)0.050 (3)0.002 (3)0.038 (3)0.007 (3)
C70.096 (5)0.087 (5)0.070 (4)−0.007 (4)0.038 (4)0.009 (4)
C80.103 (6)0.085 (5)0.086 (6)−0.006 (5)0.029 (5)0.016 (5)
C90.110 (5)0.090 (5)0.085 (5)−0.005 (4)0.032 (4)0.012 (4)
C100.115 (11)0.099 (10)0.099 (11)−0.004 (10)0.032 (10)0.018 (10)
C9'0.110 (5)0.090 (5)0.085 (5)−0.005 (4)0.032 (4)0.012 (4)
C10'0.110 (10)0.101 (10)0.086 (9)−0.004 (9)0.048 (8)0.013 (9)
C110.090 (4)0.092 (4)0.068 (4)0.016 (4)0.041 (4)0.014 (4)
C120.097 (4)0.100 (4)0.076 (4)0.019 (4)0.042 (4)0.009 (4)
C130.099 (6)0.104 (6)0.077 (6)0.018 (6)0.043 (5)0.010 (5)
C140.131 (7)0.132 (7)0.107 (7)0.018 (6)0.025 (6)0.012 (6)
C12'0.097 (4)0.100 (4)0.076 (4)0.019 (4)0.042 (4)0.009 (4)
C13'0.098 (6)0.104 (6)0.080 (6)0.018 (5)0.043 (5)0.011 (5)
C14'0.131 (7)0.132 (7)0.107 (7)0.018 (6)0.025 (6)0.012 (6)
C150.078 (4)0.097 (5)0.069 (5)0.001 (4)0.037 (4)0.007 (4)
C160.087 (5)0.109 (6)0.086 (6)0.002 (5)0.038 (5)0.005 (5)
C170.089 (6)0.121 (7)0.092 (7)−0.002 (6)0.039 (6)0.001 (6)
C180.097 (9)0.156 (12)0.119 (11)−0.003 (9)0.033 (9)−0.021 (10)
Geometric parameters (Å, °) top
Sn1—C112.099 (12)C10—H10C0.9600
Sn1—C152.112 (13)C10'—H10D0.9600
Sn1—C72.127 (13)C10'—H10E0.9600
Sn1—O12.167 (12)C10'—H10F0.9600
Sn1—N1i2.603 (16)C11—C121.477 (13)
Sn1—O23.186 (9)C11—H11A0.9700
O1—C61.274 (13)C11—H11B0.9700
O2—C61.230 (12)C12—C131.550 (17)
N1—C11.322 (19)C12—H12A0.9700
N1—C51.347 (18)C12—H12B0.9700
C1—C21.385 (15)C13—C141.480 (18)
C1—H10.9300C13—H13A0.9700
C2—C31.405 (15)C13—H13B0.9700
C2—H20.9300C13'—H13C0.9700
C3—C41.386 (16)C13'—H13D0.9700
C3—C61.479 (15)C14—H14A0.9600
C4—C51.388 (15)C14—H14B0.9600
C4—H40.9300C14—H14C0.9600
C5—H50.9300C15—C161.514 (14)
C7—C81.494 (14)C15—H15A0.9700
C7—H7A0.9700C15—H15B0.9700
C7—H7B0.9700C16—C171.554 (14)
C8—C91.504 (14)C16—H16A0.9700
C8—H8A0.9700C16—H16B0.9700
C8—H8B0.9700C17—C181.468 (15)
C9—C101.535 (18)C17—H17A0.9700
C9—H9A0.9700C17—H17B0.9700
C9—H9B0.9700C18—H18A0.9600
C10—H10A0.9600C18—H18B0.9600
C10—H10B0.9600C18—H18C0.9600
C11—Sn1—C15124.9 (5)H10A—C10—H10B109.5
C11—Sn1—C7116.3 (6)C9—C10—H10C109.5
C15—Sn1—C7116.4 (6)H10A—C10—H10C109.5
C11—Sn1—O197.9 (5)H10B—C10—H10C109.5
C15—Sn1—O195.9 (6)H10D—C10'—H10E109.5
C7—Sn1—O191.2 (5)H10D—C10'—H10F109.5
C11—Sn1—N1i81.4 (5)H10E—C10'—H10F109.5
C15—Sn1—N1i85.0 (6)C12—C11—Sn1120.1 (9)
C7—Sn1—N1i88.5 (5)C12—C11—H11A107.3
O1—Sn1—N1i179.1 (8)Sn1—C11—H11A107.3
C11—Sn1—O280.8 (4)C12—C11—H11B107.3
C15—Sn1—O273.3 (4)Sn1—C11—H11B107.3
C7—Sn1—O2135.2 (4)H11A—C11—H11B106.9
O1—Sn1—O244.1 (3)C11—C12—C13113.4 (12)
N1i—Sn1—O2136.2 (3)C11—C12—H12A108.9
C6—O1—Sn1120.1 (9)C13—C12—H12A108.9
C6—O2—Sn170.8 (7)C11—C12—H12B108.9
C1—N1—C5117.1 (14)C13—C12—H12B108.9
N1—C1—C2125.2 (12)H12A—C12—H12B107.7
N1—C1—H1117.4C14—C13—C12115.6 (17)
C2—C1—H1117.4C14—C13—H13A108.4
C1—C2—C3117.7 (11)C12—C13—H13A108.4
C1—C2—H2121.2C14—C13—H13B108.4
C3—C2—H2121.2C12—C13—H13B108.4
C4—C3—C2117.4 (10)H13A—C13—H13B107.4
C4—C3—C6122.8 (10)H13C—C13'—H13D107.3
C2—C3—C6119.7 (10)C13—C14—H14A109.5
C3—C4—C5120.4 (11)C13—C14—H14B109.5
C3—C4—H4119.8H14A—C14—H14B109.5
C5—C4—H4119.8C13—C14—H14C109.5
N1—C5—C4122.1 (12)H14A—C14—H14C109.5
N1—C5—H5119.0H14B—C14—H14C109.5
C4—C5—H5119.0C16—C15—Sn1115.8 (9)
O2—C6—O1125.0 (12)C16—C15—H15A108.3
O2—C6—C3119.9 (11)Sn1—C15—H15A108.3
O1—C6—C3115.1 (10)C16—C15—H15B108.3
C8—C7—Sn1116.5 (10)Sn1—C15—H15B108.3
C8—C7—H7A108.2H15A—C15—H15B107.4
Sn1—C7—H7A108.2C15—C16—C17109.7 (11)
C8—C7—H7B108.2C15—C16—H16A109.7
Sn1—C7—H7B108.2C17—C16—H16A109.7
H7A—C7—H7B107.3C15—C16—H16B109.7
C7—C8—C9116.3 (12)C17—C16—H16B109.7
C7—C8—H8A108.2H16A—C16—H16B108.2
C9—C8—H8A108.2C18—C17—C16114.1 (13)
C7—C8—H8B108.2C18—C17—H17A108.7
C9—C8—H8B108.2C16—C17—H17A108.7
H8A—C8—H8B107.4C18—C17—H17B108.7
C8—C9—C10112.0 (16)C16—C17—H17B108.7
C8—C9—H9A109.2H17A—C17—H17B107.6
C10—C9—H9A109.2C17—C18—H18A109.5
C8—C9—H9B109.2C17—C18—H18B109.5
C10—C9—H9B109.2H18A—C18—H18B109.5
H9A—C9—H9B107.9C17—C18—H18C109.5
C9—C10—H10A109.5H18A—C18—H18C109.5
C9—C10—H10B109.5H18B—C18—H18C109.5
Symmetry codes: (i) x, y, z−1.
Table 1
Selected geometric parameters (Å, °) top
Sn1—C112.099 (12)Sn1—N1i2.603 (16)
Sn1—C152.112 (13)Sn1—O23.186 (9)
Sn1—C72.127 (13)
C11—Sn1—C15124.9 (5)O1—Sn1—N1i179.1 (8)
C11—Sn1—C7116.3 (6)C11—Sn1—O280.8 (4)
C15—Sn1—C7116.4 (6)C15—Sn1—O273.3 (4)
C11—Sn1—O197.9 (5)C7—Sn1—O2135.2 (4)
C15—Sn1—O195.9 (6)O1—Sn1—O244.1 (3)
C7—Sn1—O191.2 (5)N1i—Sn1—O2136.2 (3)
C11—Sn1—N1i81.4 (5)C6—O1—Sn1120.1 (9)
C15—Sn1—N1i85.0 (6)C6—O2—Sn170.8 (7)
C7—Sn1—N1i88.5 (5)
Symmetry codes: (i) x, y, z−1.
Acknowledgements top

We acknowledge the financial support of the Shandong Institute of Light Industry Science Foundation.

references
References top

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Gielen, M., Vanbellinghen, C., Gelan, J. & Willem, R. (1988). Bull. Soc. Chim. Belg. 97, 873–?. Final page?

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